#### Sample records for surfaces geochemical complexities

1. Mineral Surfaces, Geochemical Complexities, and the Origins of Life

PubMed Central

Hazen, Robert M.; Sverjensky, Dimitri A.

2010-01-01

Crystalline surfaces of common rock-forming minerals are likely to have played several important roles in life’s geochemical origins. Transition metal sulfides and oxides promote a variety of organic reactions, including nitrogen reduction, hydroformylation, amination, and Fischer-Tropsch-type synthesis. Fine-grained clay minerals and hydroxides facilitate lipid self-organization and condensation polymerization reactions, notably of RNA monomers. Surfaces of common rock-forming oxides, silicates, and carbonates select and concentrate specific amino acids, sugars, and other molecular species, while potentially enhancing their thermal stabilities. Chiral surfaces of these minerals also have been shown to separate left- and right-handed molecules. Thus, mineral surfaces may have contributed centrally to the linked prebiotic problems of containment and organization by promoting the transition from a dilute prebiotic “soup” to highly ordered local domains of key biomolecules. PMID:20452963

2. Geochemical processes at mineral surfaces

SciTech Connect

Davis, J.A.; Hayes, K.F.

1986-01-01

This volume includes 32 papers which were presented at a symposium on geochemical processes at mineral-water interfaces in 1985 and which bring to bear on this area a very wide range of expertise. The discontinuities in properties which occur at the mineral-water interface have profound effects on the movement of naturally occurring ions. Weathering and precipitation processes control the concentrations and speciation of ions in natural waters and the movements of these within the hydrosphere; both classes of processes take place at mineral-water interfaces. After an introductory overview, the book is divided into seven major sections, each dealing with one of the aspects of the processes occurring at the mineral-water interface. Five papers deal with the physical properties of the mineral-water interface; these represent a well-balanced mix of experimental and theoretical (mathematical modeling) work. Adsorption phenomena are dealt with in another five papers; these are largely experimental in character. Ion-exchange processes are discussed in four papers, one of which addresses the use of relaxation methods to study ion exchange kinetics at the microscopic level. Spectroscopic techniques (including electron-spin resonance and Moessbauer spectroscopy) are utilized in four papers. Chemical reactions, mainly redox processes, at mineral-water interfaces are treated in four papers, one of which deals with non-biological organic reactions. Solid-solution formation and equilibria are the subjects of another set of four articles, and the last group of papers deals with the processes involved in precipitation and dissolution, including weathering.

3. Research-derived insights into surface geochemical hydrocarbon exploration

USGS Publications Warehouse

Price, L.C.

1996-01-01

Research studies based on foreland basins (mainly in eastern Colorado) examined three surface geochemical exploration (SGE) methods as possible hydrocarbon (HC) exploration techniques. The first method, microbial soil surveying, has high potential as an exploration tool, especially hi development and enhanced recovery operations. Integrative adsorption, the second technique, is not effective as a quantitative SGE method because water, carbon dioxide, nitrous oxide, unsaturated hydrocarbons, and organic compounds are collected by the adsorbent (activated charcoal) much more strongly than covalently bonded microseeping Q-Cs thermogenic HCs. Qualitative comparisons (pattern recognition) of C8+ mass spectra cannot gauge HC gas microseepage that involves only the Q-Cs HCs. The third method, soil cakite surveying, also has no potential as an exploration tool. Soil calcite concentrations had patterns with pronounced areal contrasts, but these patterns had no geometric relationship to surface traces of established or potential production, that is, the patterns were random. Microscopic examination of thousands of soils revealed that soil calcite was an uncrystallized caliche coating soil particles. During its precipitation, caliche captures or occludes any gases, elements, or compounds in its immediate vicinity. Thus, increased signal intensity of some SGE methods should depend on increasing soil calcite concentrations. Analyses substantiate this hypothesis. Because soil calcite has no utility as a surface exploration tool, any surface method that depends on soil calcite has a diminished utility as an SGE tool. Isotopic analyses of soil calcites revealed carbonate carbon ??13C values of -4.0 to +2.07co (indicating a strong influence of atmospheric CO2) as opposed to expected values of-45 to -30%c if the carbonate carbon had originated from microbial oxidation of microseeping HC gases. These analyses confirm a surface origin for this soil calcite (caliche), which is not

4. Surface complexation modeling

Technology Transfer Automated Retrieval System (TEKTRAN)

Adsorption-desorption reactions are important processes that affect the transport of contaminants in the environment. Surface complexation models are chemical models that can account for the effects of variable chemical conditions, such as pH, on adsorption reactions. These models define specific ...

5. Predictive Surface Complexation Modeling

SciTech Connect

Sverjensky, Dimitri A.

2016-11-29

Surface complexation plays an important role in the equilibria and kinetics of processes controlling the compositions of soilwaters and groundwaters, the fate of contaminants in groundwaters, and the subsurface storage of CO2 and nuclear waste. Over the last several decades, many dozens of individual experimental studies have addressed aspects of surface complexation that have contributed to an increased understanding of its role in natural systems. However, there has been no previous attempt to develop a model of surface complexation that can be used to link all the experimental studies in order to place them on a predictive basis. Overall, my research has successfully integrated the results of the work of many experimentalists published over several decades. For the first time in studies of the geochemistry of the mineral-water interface, a practical predictive capability for modeling has become available. The predictive correlations developed in my research now enable extrapolations of experimental studies to provide estimates of surface chemistry for systems not yet studied experimentally and for natural and anthropogenically perturbed systems.

6. Zonation of the Newry Igneous Complex, Northern Ireland, based on geochemical and geophysical data

Anderson, P. E.; Cooper, M. R.; Stevenson, C. T.; Hastie, A. R.; Hoggett, M.; Inman, J.; Meighan, I. G.; Hurley, C.; Reavy, R. J.; Ellam, R. M.

2016-09-01

The Late Caledonian Newry Igneous Complex (NIC), Northern Ireland, comprises three largely granodioritic plutons, together with an intermediate-ultramafic body at its northeastern end. New whole-rock geochemical data, petrological classifications, and published data, including recent Tellus aeromagnetic and radiometric results, have been used to establish 15 distinct zones across the four bodies of the NIC. These become broadly younger to the southwest of the complex and toward the centres of individual plutons. In places, zones are defined by both current compositional data (geochemistry and petrology) and Tellus results. This is particularly clear at the eastern edge of the NIC, where a thorium-elevated airborne radiometric signature occurs alongside distinct concentrations of various elements from geochemistry. However, in the northeastern-most pluton of the NIC, a prominent ring-shaped aeromagnetic anomaly occurs independent of any observed surface compositional variation, and thus the zones in this area are defined by aeromagnetic data only. The origins of this and other aeromagnetic anomalies are as yet undetermined, although in places, these closely correspond to facies at the surface. The derived zonation for the NIC supports incremental emplacement of the complex as separate, distinct magma pulses. Each pulse is thought to have originated from the same fractionally crystallising source that periodically underwent mixing with more basic magma.

7. On the bioavailability of trace metals in surface sediments: a combined geochemical and biological approach.

PubMed

Roosa, Stéphanie; Prygiel, Emilie; Lesven, Ludovic; Wattiez, Ruddy; Gillan, David; Ferrari, Benoît J D; Criquet, Justine; Billon, Gabriel

2016-06-01

The bioavailability of metals was estimated in three river sediments (Sensée, Scarpe, and Deûle Rivers) impacted by different levels of Cu, Cd, Pb, and Zn (Northern France). For that, a combination of geochemistry and biological responses (bacteria and chironomids) was used. The results obtained illustrate the complexity of the notion of "bioavailability." Indeed, geochemical indexes suggested a low toxicity, even in surface sediments with high concentrations of total metals and a predicted severe effect levels for the organisms. This was also suggested by the abundance of total bacteria as determined by DAPI counts, with high bacterial cell numbers even in contaminated areas. However, a fraction of metals may be bioavailable as it was shown for chironomid larvae which were able to accumulate an important quantity of metals in surface sediments within just a few days.We concluded that (1) the best approach to estimate bioavailability in the selected sediments is a combination of geochemical and biological approaches and that (2) the sediments in the Deûle and Scarpe Rivers are highly contaminated and may impact bacterial populations but also benthic invertebrates.

8. Surface complexation of antimony on kaolinite.

PubMed

Rakshit, Sudipta; Sarkar, Dibyendu; Datta, Rupali

2015-01-01

9. Geochemical signatures of the oceanic complexes in southern Central America

Gazel, E.; Herzberg, C. T.; Carr, M. J.; Denyer, P.

2006-12-01

The Pacific coast of Costa Rica and western Panama is famous for wide occurrence of oceanic crust that represent fragmentary and disrupted Jurassic to Miocene sequences with a very complicated geological and geotectonic histories. In Northern Costa Rica, the Santa Elena Nappe of ultramafic and mafic associations overthrusts the Santa Rosa Accretionary Complex. The Nicoya Complex represents pre-Campanian Caribbean Large Igneous Province (CLIP) segments that crop out in the Nicoya Peninsula and the basement of the Herradura Block. The Tortugal Komatiitic-like Suite represents an accreted seamount section. The Tulin Formation (Maastrichtian to Lower Eocene) forms the main edifice of an accreted oceanic island of the Herradura Block. The Quepos Block was formed by the accretion of a late Cretaceous-Paleocene seamount. In the Osa and Burica peninsulas, Caño Island and Golfito area, a series of Upper Cretaceous to Eocene accreted CLIP and seamount blocks crop out. In western Panama, the oceanic rocks range from Upper Cretaceous to Miocene and their geochemistry show ocean island and CLIP signatures. These oceanic complexes are result of accretionary processes rather than tectonic erosion, even though this last process is currently active in the Middle American Trench. The mafic and ultramafic associations of Santa Elena Nappe and Murcielago Islands represent a supra-subduction complex with a subduction modified NMORB source. The Nicoya Complex, Herradura Basement, and CLIP rocks from Osa, Golfito, Burica and W Panamá were probably formed from high-degree melts of a NMORB source modified by the Galapagos hot-spot plume. The presence of rocks with an ocean island signature from Upper Cretaceous to Lower Miocene suggests the continuous arrivals of Galapagos hot-spot seamount tracks. Mantle reservoirs of the CLIP rocks and ocean islands trend to HIMU (high U/Pb), while Santa Elena rocks trend toward depleted reservoirs (DM). CLIP signature is characterized by high 206Pb

10. Geochemical and spectral characterization of naturally altered rock surfaces

NASA Technical Reports Server (NTRS)

Chang, L. L. Y.; Sommer, S. E.; Buckingham, W. F.

1981-01-01

The possibility of using the visible-near infrared region for compositional analysis of remotely sensed rock surfaces is studied. This would allow mapping rock type both on the Earth's surface and on other planetary surfaces. Reflectance spectroscopy, economic geology, optical depth determination, and X-ray diffraction mineralogy are discussed.

11. Soil Iodine Determination in Deccan Syneclise, India: Implications for Near Surface Geochemical Hydrocarbon Prospecting

SciTech Connect

Mani, Devleena; Kumar, T. Satish; Rasheed, M. A.; Patil, D. J.; Dayal, A. M.; Rao, T. Gnaneshwar; Balaram, V.

2011-03-15

The association of iodine with organic matter in sedimentary basins is well documented. High iodine concentration in soils overlying oil and gas fields and areas with hydrocarbon microseepage has been observed and used as a geochemical exploratory tool for hydrocarbons in a few studies. In this study, we measure iodine concentration in soil samples collected from parts of Deccan Syneclise in the west central India to investigate its potential application as a geochemical indicator for hydrocarbons. The Deccan Syneclise consists of rifted depositional sites with Gondwana-Mesozoic sediments up to 3.5 km concealed under the Deccan Traps and is considered prospective for hydrocarbons. The concentration of iodine in soil samples is determined using ICP-MS and the values range between 1.1 and 19.3 ppm. High iodine values are characteristic of the northern part of the sampled region. The total organic carbon (TOC) content of the soil samples range between 0.1 and 1.3%. The TOC correlates poorly with the soil iodine (r{sup 2} < 1), indicating a lack of association of iodine with the surficial organic matter and the possibility of interaction between the seeping hydrocarbons and soil iodine. Further, the distribution pattern of iodine compares well with two surface geochemical indicators: the adsorbed light gaseous hydrocarbons (methane through butane) and the propane-oxidizing bacterial populations in the soil. The integration of geochemical observations show the occurrence of elevated values in the northern part of the study area, which is also coincident with the presence of exposed dyke swarms that probably serve as conduits for hydrocarbon microseepage. The corroboration of iodine with existing geological, geophysical, and geochemical data suggests its efficacy as one of the potential tool in surface geochemical exploration of hydrocarbons. Our study supports Deccan Syneclise to be promising in terms of its hydrocarbon prospects.

12. Application of statistical quality control measures for near-surface geochemical petroleum exploration

Belt, John Q.; Rice, Gary K.

2002-02-01

There are four major quality control measures that can apply to geochemical petroleum exploration data: statistical quality control charts, data reproducibility-Juran approach, ethane composition index, and hydrocarbon cross plots. Statistical quality control, or SQC, charts reflect the quality-performance of the analytical process composed of equipment, instrumentation, and operator technique. An unstable process is detected through assignable causes using SQC charts. Knowing data variability is paramount to tying geochemical data over time for in-fill samples and/or project extensions. The Juran approach is a statistical tool used to help determine the ability of a process to maintain itself within the limits of set specifications for reproducing geochemical data. Ethane composition index, or ECI, is a statistical calculation based on near-surface, light hydrocarbon measurements that help differentiate thermogenic, petroleum sources at depth. The ECI data are integrated with subsurface geological information, and/or seismic survey data to determine lower-risk drilling locations. Hydrocarbon cross plots are visual correlation techniques that compare two hydrocarbons within a similar hydrocarbon suite (e.g., ethane versus propane, benzene versus toluene, or 2-ring aromatics versus 3-ring aromatics). Cross plots help determine contamination, multiple petroleum sources, and low-quality data versus high-quality data indigenous to different geochemical exploration tools. When integrated with geomorphology, subsurface geology, and seismic survey data high-quality geochemical data provides beneficial information for developing a petroleum exploration model. High-quality data is the key to the successful application of geochemistry in petroleum exploration modeling. The ability to produce high-quality, geochemical data requires the application of quality control measures reflective of a well managed ISO 9000 quality system. Statistical quality control charts, Juran

13. Geochemical heterogeneity in a small, stratigraphically complex moraine aquifer system (Ontario, Canada): Interpretation of flow and recharge using multiple geochemical parameters

USGS Publications Warehouse

Stotler, R.L.; Frape, S.K.; El Mugammar, H.T.; Johnston, C.; Judd-Henrey, I.; Harvey, F.E.; Drimmie, R.; Jones, J.P.

2011-01-01

The Waterloo Moraine is a stratigraphically complex system and is the major water supply to the cities of Kitchener and Waterloo in Ontario, Canada. Despite over 30 years of investigation, no attempt has been made to unify existing geochemical data into a single database. A composite view of the moraine geochemistry has been created using the available geochemical information, and a framework created for geochemical data synthesis of other similar flow systems. Regionally, fluid chemistry is highly heterogeneous, with large variations in both water type and total dissolved solids content. Locally, upper aquifer units are affected by nitrate and chloride from fertilizer and road salt. Typical upper-aquifer fluid chemistry is dominated by calcium, magnesium, and bicarbonate, a result of calcite and dolomite dissolution. Evidence also suggests that ion exchange and diffusion from tills and bedrock units accounts for some elevated sodium concentrations. Locally, hydraulic "windows" cross connect upper and lower aquifer units, which are typically separated by a clay till. Lower aquifer units are also affected by dedolomitization, mixing with bedrock water, and locally, upward diffusion of solutes from the bedrock aquifers. A map of areas where aquifer units are geochemically similar was constructed to highlight areas with potential hydraulic windows. ?? 2010 Springer-Verlag.

14. Establishing geochemical background variation and threshold values for 59 elements in Australian surface soil.

PubMed

Reimann, Clemens; de Caritat, Patrice

2017-02-01

During the National Geochemical Survey of Australia over 1300 top (0-10cm depth) and bottom (~60-80cm depth) sediment samples (including ~10% field duplicates) were collected from the outlet of 1186 catchments covering 81% of the continent at an average sample density of 1 site/5200km(2). The <2mm fraction of these samples was analysed for 59 elements by ICP-MS following an aqua regia digestion. Results are used here to establish the geochemical background variation of these elements, including potentially toxic elements (PTEs), in Australian surface soil. Different methods of obtaining geochemical threshold values, which differentiate between background and those samples with unusually high element concentrations and requiring attention, are presented and compared to Western Australia's 'ecological investigation levels' (EILs) established for 14 PTEs. For Mn and V these EILs are so low that an unrealistically large proportion (~24%) of the sampled sites would need investigation in Australia. For the 12 remaining elements (As, Ba, Cd, Co, Cr, Cu, Hg, Mo, Ni, Pb, Sn and Zn) few sample sites require investigation and as most of these are located far from human activity centres, they potentially suggest either minor local contamination or mineral exploration potential rather than pollution. No major diffuse source of contamination by PTEs affects Australian soil at the continental scale. Of the statistical methods used to establish geochemical threshold values, the most pertinent results come from identifying breaks in cumulative probability distributions, the Tukey inner fence and the 98th percentile. Geochemical threshold values for 59 elements, including emerging 'high-tech' critical elements such as lanthanides, Be, Ga or Ge, for which no EILs currently exist, are presented.

15. Geochemical baseline distribution of harmful elements in the surface soils of Campania region.

Albanese, Stefano; Lima, Annamaria; Qu, Chengkai; Cicchella, Domenico; Buccianti, Antonella; De Vivo, Benedetto

2015-04-01

Environmental geochemical mapping has assumed an increasing relevance and the separation of values to discriminate between anthropogenic pollution and natural (geogenic) sources has become crucial to address environmental problems affecting the quality of life of human beings. In the last decade, a number of geochemical prospecting projects, mostly focused on surface soils (topsoils), were carried out at different scales (from regional to local) across the whole Campania region (Italy) to characterize the distribution of both harmful elements and persistent organic pollutants (POP) in the environment and to generating a valuable database to serve as reference in developing geomedical studies. During the 2014, a database reporting the distribution of 53 chemical elements in 3536 topsoil samples, collected across the whole region, was completed. The geochemical data, after necessary quality controls, were georeferenced and processed in a geochemistry dedicated GIS software named GEODAS. For each considered element a complete set of maps was generated to depict both the discrete and the spatially continuous (interpolated) distribution of elemental concentrations across the region. The interpolated maps were generated using the Multifractal Inverse Distance eighted (MIDW) algorithm. Subsequently, the S-A method, also implemented in GEODAS, was applied to MIDW maps to eliminate spatially limited anomalies from the original grid and to generate the distribution patterns of geochemical baselines for each element. For a selected group of elements geochemical data were also treated by means of a Compositional Data Analysis (CoDA) aiming at investigating the regionalised structure of the data by considering the joint behaviour of several elements constituting for each sample its whole composition. A regional environmental risk assessment was run on the basis of the regional distribution of heavy metals in soil, land use types and population. The risk assessment produced a

16. Selected Geochemical Data for Modeling Near-Surface Processes in Mineral Systems

USGS Publications Warehouse

Giles, Stuart A.; Granitto, Matthew; Eppinger, Robert G.

2009-01-01

The database herein was initiated, designed, and populated to collect and integrate geochemical, geologic, and mineral deposit data in an organized manner to facilitate geoenvironmental mineral deposit modeling. The Microsoft Access database contains data on a variety of mineral deposit types that have variable environmental effects when exposed at the ground surface by mining or natural processes. The data tables describe quantitative and qualitative geochemical analyses determined by 134 analytical laboratory and field methods for over 11,000 heavy-mineral concentrate, rock, sediment, soil, vegetation, and water samples. The database also provides geographic information on geology, climate, ecoregion, and site contamination levels for over 3,000 field sites in North America.

17. Surface water geochemical and isotopic variations in an area of accelerating Marcellus Shale gas development.

PubMed

2014-12-01

Water samples were collected from 50 streams in an area of accelerating shale gas development in the eastern U.S.A. The geochemical/isotopic characteristics show no correlation with the five categories of Marcellus Shale production. The sub-watersheds with the greatest density of Marcellus Shale development have also undergone extensive coal mining. Hence, geochemical/isotopic compositions were used to understand sources of salinity and effects of coal mining and shale gas development in the area. The data indicates that while some streams appear to be impacted by mine drainage; none appear to have received sustained contribution from deep brines or produced waters associated with shale gas production. However, it is important to note that our interpretations are based on one time synoptic base flow sampling of a few sampling stations and hence do account potential intermittent changes in chemistry that may result from major/minor spills or specific mine discharges on the surface water chemistry.

18. Evaluating sensitivity of complex electrical methods for monitoring CO2 intrusion into a shallow groundwater system and associated geochemical transformations

Dafflon, B.; Wu, Y.; Hubbard, S. S.; Birkholzer, J. T.; Daley, T. M.; Pugh, J. D.; Peterson, J.; Trautz, R. C.

2011-12-01

A risk factor of CO2 storage in deep geological formations includes its potential to leak into shallow formations and impact groundwater geochemistry and quality. In particular, CO2 decreases groundwater pH, which can potentially mobilize naturally occurring trace metals and ions commonly absorbed to or contained in sediments. Here, geophysical studies (primarily complex electrical method) are being carried out at both laboratory and field scales to evaluate the sensitivity of geophysical methods for monitoring dissolved CO2 distribution and geochemical transformations that may impact water quality. Our research is performed in association with a field test that is exploring the effects of dissolved CO2 intrusion on groundwater geochemistry. Laboratory experiments using site sediments (silica sand and some fraction of clay minerals) and groundwater were initially conducted under field relevant CO2 partial pressures (pCO2). A significant pH drop was observed with inline sensors with concurrent changes in fluid conductivity caused by CO2 dissolution. Electrical resistivity and electrical phase responses correlated well with the CO2 dissolution process at various pCO2. Specifically, resistivity decreased initially at low pCO2 condition resulting from CO2 dissolution followed by a slight rebound because of the transition of bicarbonate into non-dissociated carbonic acid at lower pH slightly reducing the total concentration of dissociated species. Continuous electrical phase decreases were also observed, which are interpreted to be driven by the decrease of surface charge density (due to the decrease of pH, which approaches the PZC of the sediments). In general, laboratory experiments revealed the sensitivity of electrical signals to CO2 intrusion into groundwater formations and can be used to guide field data interpretation. Cross well complex electrical data are currently being collected periodically throughout a field experiment involving the controlled release of

19. Monitoring CO2 intrusion and associated geochemical transformations in a shallow groundwater system using complex electrical methods.

PubMed

Dafflon, Baptiste; Wu, Yuxin; Hubbard, Susan S; Birkholzer, Jens T; Daley, Thomas M; Pugh, John D; Peterson, John E; Trautz, Robert C

2013-01-02

The risk of CO(2) leakage from a properly permitted deep geologic storage facility is expected to be very low. However, if leakage occurs it could potentially impact potable groundwater quality. Dissolved CO(2) in groundwater decreases pH, which can mobilize naturally occurring trace metals commonly contained in aquifer sediments. Observing such processes requires adequate monitoring strategies. Here, we use laboratory and field experiments to explore the sensitivity of time-lapse complex resistivity responses for remotely monitoring dissolved CO(2) distribution and geochemical transformations that may impact groundwater quality. Results show that electrical resistivity and phase responses correlate well with dissolved CO(2) injection processes. Specifically, resistivity initially decreases due to increase of bicarbonate and dissolved species. As pH continues to decrease, the resistivity rebounds toward initial conditions due to the transition of bicarbonate into nondissociated carbonic acid, which reduces the total concentration of dissociated species and thus the water conductivity. An electrical phase decrease is also observed, which is interpreted to be driven by the decrease of surface charge density as well as potential mineral dissolution and ion exchange. Both laboratory and field experiments demonstrate the potential of field complex resistivity method for remotely monitoring changes in groundwater quality due to CO(2) leakage.

20. Robustness surfaces of complex networks

Manzano, Marc; Sahneh, Faryad; Scoglio, Caterina; Calle, Eusebi; Marzo, Jose Luis

2014-09-01

Despite the robustness of complex networks has been extensively studied in the last decade, there still lacks a unifying framework able to embrace all the proposed metrics. In the literature there are two open issues related to this gap: (a) how to dimension several metrics to allow their summation and (b) how to weight each of the metrics. In this work we propose a solution for the two aforementioned problems by defining the R*-value and introducing the concept of robustness surface (Ω). The rationale of our proposal is to make use of Principal Component Analysis (PCA). We firstly adjust to 1 the initial robustness of a network. Secondly, we find the most informative robustness metric under a specific failure scenario. Then, we repeat the process for several percentage of failures and different realizations of the failure process. Lastly, we join these values to form the robustness surface, which allows the visual assessment of network robustness variability. Results show that a network presents different robustness surfaces (i.e., dissimilar shapes) depending on the failure scenario and the set of metrics. In addition, the robustness surface allows the robustness of different networks to be compared.

1. Emplacement and geochemical evolution of highly evolved syenites investigated by a combined structural and geochemical field study: The lujavrites of the Ilímaussaq complex, SW Greenland

Ratschbacher, Barbara C.; Marks, Michael A. W.; Bons, Paul D.; Wenzel, Thomas; Markl, Gregor

2015-08-01

Structural mapping and the combined study of magmatic to solid-state deformation textures and mineral compositions in highly evolved nepheline syenites (lujavrites) of the alkaline to peralkaline Ilímaussaq complex (South Greenland) reveal detailed insight into the emplacement and geochemical evolution of the melts they crystallized from. Based on magmatic to solid-state flow textures such as foliations and lineations, we propose that the investigated rock sequence forms a sill-like structure with a steep feeder zone that flattens out over a short distance and intrudes into less evolved overlying units as sub-horizontal sheets by roof uplift. Systematic compositional variation of early-magmatic eudialyte-group minerals (EGM) in the investigated rock sequence monitors the geochemical evolution of the lujavrite-forming melt(s). The chlorine contents of EGM decrease successively upwards within the rock sequence, which probably indicates a successive increase of water activity during differentiation, consistent with a change from sodic pyroxene (aegirine) to sodic amphibole (arfvedsonite) in the mineral assemblage. Both REE contents and Fe/Mn ratios of EGM are promising differentiation indicators, which increase and decrease, respectively, upwards within the sequence due to fractional crystallization. This closed-system evolution is interrupted by a shift towards less evolved melt compositions in one lujavrite unit, for which we assume magma recharge. Our study demonstrates the strength of a combined structural and petrological approach to understand the petrogenesis of an igneous body in more detail and highlights their close connection.

2. Structurally Complex Surface of Europa

NASA Technical Reports Server (NTRS)

1997-01-01

This is a composite of two images of Jupiter's icy moon Europa obtained from a range of 2119 miles (3410 kilometers) by the Galileo spacecraft during its fourth orbit around Jupiter and its first close pass of Europa. The mosaic spans 11 miles by 30 miles (17 km by 49 km) and shows features as small as 230 feet (70 meters) across. This mosaic is the first very high resolution image data obtained of Europa, and has a resolution more than 50 times better than the best Voyager coverage and 500 times better than Voyager coverage in this area. The mosaic shows the surface of Europa to be structurally complex. The sun illuminates the scene from the right, revealing complex overlapping ridges and fractures in the upper and lower portions of the mosaic, and rugged, more chaotic terrain in the center. Lateral faulting is revealed where ridges show offsets along their lengths (upper left of the picture). Missing ridge segments indicate obliteration of pre-existing materials and emplacement of new terrain (center of the mosaic). Only a small number of impact craters can be seen, indicating the surface is not geologically ancient.

The Jet Propulsion Laboratory, Pasadena, CA manages the mission for NASA's Office of Space Science, Washington, DC.

This image and other images and data received from Galileo are posted on the Galileo mission home page on the World Wide Web at http://galileo.jpl.nasa.gov. Background information and educational context for the images can be found at URL http://www.jpl.nasa.gov/galileo/sepo

3. The effects of sorting by aeolian processes on the geochemical characteristics of surface materials: a wind tunnel experiment

Wang, Xunming; Lang, Lili; Hua, Ting; Zhang, Caixia; Li, Hui

2017-03-01

The geochemical characteristics of aeolian and surface materials in potential source areas of dust are frequently employed in environmental reconstructions as proxies of past climate and as source tracers of aeolian sediments deposited in downwind areas. However, variations in the geochemical characteristics of these aeolian deposits that result from near-surface winds are currently poorly understood. In this study, we collected surface samples from the Ala Shan Plateau (a major potential dust source area in Central Asia) to determine the influence of aeolian processes on the geochemical characteristics of aeolian transported materials. Correlation analyses show that compared with surface materials, the elements in transported materials (e.g., Cu, As, Pb, Mn, Zn, Al, Ca, Fe, Ga, K, Mg, P, Rb, Co, Cr, Na, Nb, Si, and Zr) were subjected to significant sorting by aeolian processes, and the sorting also varied among different particle size fractions and elements. Variations in wind velocity were significantly correlated with the contents of Cr, Ga, Sr, Ca, Y, Nd, Zr, Nb, Ba, and Al, and with the Zr/Al, Zr/Rb, K/Ca, Sr/Ca, Rb/Sr, and Ca/Al ratios. Given the great variation in the geochemical characteristics of materials transported under different aeolian processes relative to those of the source materials, these results indicate that considerable uncertainty may be introduced to analyses by using surface materials to trace the potential source areas of aeolian deposits that accumulate in downwind areas.

4. Surface complexation modeling of americium sorption onto volcanic tuff.

PubMed

Ding, M; Kelkar, S; Meijer, A

2014-10-01

Results of a surface complexation model (SCM) for americium sorption on volcanic rocks (devitrified and zeolitic tuff) are presented. The model was developed using PHREEQC and based on laboratory data for americium sorption on quartz. Available data for sorption of americium on quartz as a function of pH in dilute groundwater can be modeled with two surface reactions involving an americium sulfate and an americium carbonate complex. It was assumed in applying the model to volcanic rocks from Yucca Mountain, that the surface properties of volcanic rocks can be represented by a quartz surface. Using groundwaters compositionally representative of Yucca Mountain, americium sorption distribution coefficient (Kd, L/Kg) values were calculated as function of pH. These Kd values are close to the experimentally determined Kd values for americium sorption on volcanic rocks, decreasing with increasing pH in the pH range from 7 to 9. The surface complexation constants, derived in this study, allow prediction of sorption of americium in a natural complex system, taking into account the inherent uncertainty associated with geochemical conditions that occur along transport pathways.

5. Arsenic transport between surface and groundwater in a moderately reducing zone: Geochemical approach

Khaska, Mahmoud; Le Gal La Salle, Corinne; Verdoux, Patrick

2015-04-01

Arsenic contamination represents a major risk to human health as one of the most prominent environmental causes of cancer mortality. Mining activities, particularly those involving arsenic rich ores have an impact on the environment and on human health that may persist for many decades after mine closure. The relationships between As released from alluvial aquifer in the vicinity of the sulfide-rich mine dumps was demonstrated with geochemical and isotopic tracers (major and traces elements, 87Sr/86Sr, 18O, 2H). Strontium isotopes were used to trace the transport of As downstream from a As rich tailing dam. Increasing As and Fe concentrations in surface water are explained by As release associated with alluvial groundwater discharge to the stream. This process occurs in a moderately reduced section of the stream downgradient from the sulfide-rich tailing dam. High As, total Fe and low Eh in groundwater confirm the discharge of alluvial groundwater and explain its impact on surface water. Transport of As between surface and groundwater can be described as follows: 1- Subsurface moderately reducing conditions prevail in groundwater downgradient from the tailing dams. This suggests a flux of reduced water from sulfide-rich tailing dams which is characterized by its high As and Fe content resulting from the reduction of Fe-sulfides. 2- Upon mixing with surface water, oxidizing conditions prevails and precipitate as Fe hydroxide on the stream bed. As and Sr subsequently adsorbed on the Fe -oxyhydroxide surface. This process contributes to the immobilization of As in surface water. Remaining dissolved As in surface water can be re-introduced in alluvial groundwater downstream of the reducing zone.

6. Combined geological and surface geochemical methods discovered Agaritta and Brady Creek Fields, Concho County, Texas

SciTech Connect

Saunders, D.F.; Burson, K.R.; Thompson, C.K. ); Brown, J.J. )

1993-07-01

From December 1987 to March 1991, 25 prospects in the lower King sand (Upper Pennsylvanian Cisco) play in Concho County, Texas, were tested by several operators. They used combinations of subsurface geology, reconnaissance airborne gas sensing, surface radiometrics, soil magnetic susceptibility, and soil-gas hydrocarbon measurements to define prospects. Six new King sand discoveries or extensions and three deeper Goen discoveries resulted in a 36% exploratory success rate. The total exploration and development cost was approximately $0.67/bbl of proven producing oil reserves. Final locations for the discovery wells on each of the nine successful prospects were selected primarily on the basis of combined subsurface geology and surface geochemical data. As examples, we present information about the discovery of Brady Creek and Agaritta fields. Agaritta field is one of the two largest of the new-field discoveries, with estimated proven producing recoverable reserves of 6 million bbl of oil. Its discovery was based on a combination of (1) regional subsurface geologic projection, (2) airborne hydrocarbon sensing, (3) interstitial soil-gas hydrocarbon data, (4) soil magnetic-susceptibility measurements, and (5) surface potassium and uranium concentrations measured by gamma-ray spectrometry. 7. Geochemical surface anomaly distribution above active hydrocarbon source beds: Anadarko Deep example SciTech Connect Harnett, R.A. 1991-08-01 Surface geochemical surveys were run on all available county roads across the deep part of the Anadarko basin in Caddo, Custer, and Washita Counties, Oklahoma. In the Anadarko Deep there are three major mature petroleum source horizons: Woodford, Springer-Morrow, and Middle-Upper Pennsylvanian marine shales. In most of the area surveyed, the Woodford is post mature. However, the Springer-Morrow and Middle-Upper Pennsylvanian horizons are currently in the oil and/or thermal gas-generating windows. Surface gamma-ray surveys were run over 1,708 mi in T8-9N, R13-19W to see if there were areas of discrete detectable microseep alteration (anomalies) or whether the entire generating area would be without anomalous contrast. Data were analyzed and anomalies were noted. The anomalies were then plotted against the position of major structural elements and drilling results. Discrete areas of anomalies were noted, many coincident with established production. More importantly, large areas were seen to be without anomalies. It is most probable that the detectable microseeps at the surface are associated with gathered concentrations of hydrocarbons at depth since the entire area was not found to be anomalous. 8. Seasonal distribution and geochemical fractionation of heavy metals from surface sediment in a tropical estuary of Jeneberang River, Indonesia. PubMed Najamuddin; Prartono, Tri; Sanusi, Harpasis S; Nurjaya, I Wayan 2016-10-15 Lead (Pb) and zinc (Zn) concentrations from surface sediments were determined at 17 stations in riverine, estuarine, and marine environments during the wet and dry seasons. The geochemical fractionations were obtained by a sequential extraction procedure in five geochemical forms: exchangeable, bound to carbonate, iron-manganese oxide, organic, and residual fractions. The concentrations of Pb and Zn in the water were higher during the wet season than the dry season and higher in the riverine and marine samples than the estuarine samples. Following geochemical fractionation, the metals were found mainly in the residual fraction. The results indicated that the concentrations were influenced by season, with the sources of Pb and Zn derived mainly from rivers and natural sources. The contamination status in the estuary of the Jeneberang River was classified as weak to moderate pollution and the risk level to aquatic biota attributed was no risk to low risk. 9. The geochemical nature of the Archean Ancient Gneiss Complex and Granodiorite Suite, Swaziland: a preliminary study USGS Publications Warehouse Hunter, D.R.; Barker, F.; Millard, H.T. 1978-01-01 The Ancient Gneiss Complex (AGC) of Swaziland, an Archean gray gneiss complex, lies southeast and south of the Barberton greenstone belt and includes the most structurally complex and highly metamorphosed portions of the eastern Kaapvaal craton. The AGC is not precisely dated but apparently is older than 3.4 Ga. The AGC consists of three major units: (a) a bimodal suite of closely interlayered siliceous, low-K gneisses and metabasalt; (b) homogeneous tonalite gneiss; and (c) interlayered siliceous microcline gneiss, metabasalt, and minor metasedimentary rocks - termed the metamorphite suite. A geologically younger gabbro-diorite-tonalite-trondhjemite suite, the Granodiorite Suite, is spatially associated with the AGC and intrusive into it. The bimodal suite consists largely of two types of low-K siliceous gneiss: one has SiO2 14%, low Rb/Sr ratios, and depleted heavy rare earth elements (REE's); the other has SiO2 > 75%, Al2O3 < 13%, high Rb/Sr ratios, and relatively abundant REE's except for negative Eu anomalies. The interlayered metabasalt ranges from komatiitic to tholeiitic compositions. Lenses of quartz monzonitic gneiss of K2O/Na2O close to 1 form a minor part of the bimodal suite. Tonalitic to trondhjemitic migmatite locally is abundant and has major-element abundances similar to those of non-migmatitic varieties. The siliceous gneisses of the metamorphic suite show low Al2O, K2O/Na2O ratios of about 1, high Rb/Sr ratios, moderate REE abundances and negative Eu anomalies. K/Rb ratios of siliceous gneisses of the bimodal suite are very low (???130); of the tonalitic gneiss, low (???225); of the siliceous gneiss of the metamorphite suite, moderate (???300); and of the Granodiorite Suite, high (???400). Rocks of the AGC differ geochemically in several ways from the siliceous volcanic and hypabyssal rocks of the Upper Onverwacht Group and from the diapirs of tonalite and trondhjemite that intrude the Swaziland Group. ?? 1978. 10. Petrogenesis of the Sabongari alkaline complex, cameroon line (central Africa): Preliminary petrological and geochemical constraints NASA Astrophysics Data System (ADS) Njonfang, Emmanuel; Tchoneng, Gilbert Tchuenté; Cozzupoli, Domenico; Lucci, Federico 2013-07-01 The petrography, mineral chemistry and geochemical features of the Sabongari alkaline complex are presented and discussed in this paper with the aim of constraining its petrogenesis and comparing it with other alkaline complexes of the Cameroon Line. The complex is mainly made up of felsic rocks: (i) granites predominate and include pyroxene-amphibole (the most abundant), amphibole-biotite, biotite and pyroxene types; (ii) syenites are subordinate and comprise amphibole-pyroxene and amphibole-biotite quartz syenites; (iii) pyroxene-amphibole-biotite trachyte and (iv) relatively abundant rhyolite. The minor basic and intermediate terms associated with felsic rocks consist of basanites, microdiorite and monzodioites. Two groups of pyroxene bearing rocks are distinguished: a basanite-trachyte-granite (Group 1) bimodal series (SiO2 gap: 44 and 63 wt.%) and a basanite-microdiorite-monzodiorite-syenite-granite (Group 2) less pronounced bimodal series (reduced SiO2 gap: 56-67 wt.%). Both are metaluminous to peralkaline whereas felsic rocks bare of pyroxene (Group 3) are metaluminous to peraluminous. The Group 1 basanite is SiO2-undersaturated (modal analcite in the groundmass and 11.04 wt.% normative nepheline); its Ni (240 ppm) and Cr (450 ppm) contents, near mantle values, indicate its most primitive character. The Group 2 basanite is rather slightly SiO2-saturated (1.56 wt.% normative hypersthene), a marker of its high crustal contamination (low Nb/Y-high Rb/Y). The La/Yb and Gd/Yb values of both basanites (1: 19.47 and 2.92; 2: 9.09 and 2.23) suggest their common parental magma composition, and their crystallization through two episodes of partial melting (2% and 3% respectively) of a lherzolite mantle source with <4% residual garnet. The effects of crustal contamination were selectively felt in the values of HFSE/LREE, LREE/LILE and LREE/HFSE ratios, known as indicators. Similar features have been recently obtained in the felsic lavas of the Cameroon Volcanic Line. 11. Geochemical evidence for a complex origin for the Kelso dunes, Mojave National Preserve, California USA USGS Publications Warehouse Muhs, Daniel; Lancaster, Nicholas; Skipp, Gary L. 2017-01-01 The Kelso Dune field in southern California is intriguing because although it is of limited areal extent (~ 100 km2), it has a wide variety of dune forms and contains many active dunes (~ 40 km2), which is unusual in the Mojave Desert. Studies over the past eight decades have concluded that the dunes are derived primarily from a single source, Mojave River alluvium, under a dominant, westerly-to-northwesterly wind regime. The majority of these studies did not, however, present data to support the Mojave River as the only source. We conducted mineralogical and geochemical studies of most of the 14 geomorphically defined dune groups of the Kelso Dune field as well as potential sand sources, alluvial sediments from the surrounding mountain ranges. Results indicate that sands in the nine western dune groups have K/Rb and K/Ba (primarily from K-feldspar) compositions that are indistinguishable from Mojave River alluvium (westerly/northwesterly winds) and Budweiser Wash alluvium (southwesterly winds), permitting an interpretation of two sources. In contrast, sands from the five eastern dune groups have K/Rb and K/Ba values that indicate significant inputs from alluvial fan deposits of the Providence Mountains. This requires either rare winds from the east or southeast or, more likely, aeolian reworking of distal Providence Mountain fan sediments by winds from the west, at a rate greater than input from the Mojave River or other western sources. The results indicate that even a small dune field can have a complex origin, either from seasonally varying winds or complex alluvial-fan-dune interaction. Application of K/Rb and K/Ba in K-feldspar as a provenance indicator could be used in many of the world's ergs or sand seas, where dune origins are still not well understood or are controversial. Four examples are given from Africa and the Middle East where such an approach could yield useful new information about dune sand provenance. 12. Geochemical characteristics and origin of the Lebowa Granite Suite, Bushveld Complex USGS Publications Warehouse Hill, M.; Barker, F.; Hunter, D.; Knight, R. 1996-01-01 The ??? 2052-Ma Lebowa Granite Suite (LGS) represents the culminating phase of an Early Proterozoic magmatic cycle in the Central Transvaal area of the Kaapvaal Province. Following extrusion of at least 200,000 km3 of intermediate to acid volcanics (Rooiberg Felsite), mafic and ultramafic magmas intruded at 2065 Ma to form the Rustenburg Layered Suite (RLS). The LGS includes the Nebo, Makhutso, Bobbejaankop, Lease, and Klipkloof granites. The Nebo Granite intruded the Rooiberg Felsite as sheets up to 4 km thick above the RLS. Smaller stocks of the other granites crosscut the Nebo. We determined major- and trace-element compositions and oxygen, Rb-Sr, and Sm-Nd isotope ratios for samples of: Nebo Granite; Rooiberg Felsite; granophyre and granophyric granite; Makhutso, Bobbejaankop, and Lease granites; and feldspar porphyry from areas throughout the exposed area of the LGS (Dennilton, Verena Balmoral, Enkeldoorn, Sekhukhune Plateau, Zaaiplaats-Potgeitersrus, and Western Transvaal). Coherent floor-to-roof geochemical trends exist in some areas, although it is not possible to model them convincingly. Regional variations in geochemistry exist and likely are related to source variations in the estimated 200,000 km3 of the Nebo Granite sheets. ??18O for the LGS range from +5.9??? to +9.5???; if these are approximate primary magmatic values, pelitic sediments cannot have been an important source for the LGS. The Rb-Sr isotope system has been altered, a finding consistent with previous studies. A mineral isochron for Nebo Granite near Dennilton yields a York regression age of 1995 ?? 99 Ma, with initial 143Nd/144Nd = 0.50978??8 and ???CHUR=-5.12. Samples from the Sekhukhune Plateau have higher 143Nd/144Nd ratios than do Dennilton-area samples, suggesting that the former originated from older or less LREE-enriched sources. We suggest that intrusion of mafic to ultramafic magmas at depth in the continental crust triggered melting of Archean quartzofeldspathic crystalline 13. Surface geochemical survey for geothermal exploration in the south-east zone of Tenerife Island, Canary Islands NASA Astrophysics Data System (ADS) Diaz Requejo, M.; Marrero, R.; Padron, E.; Melian, G.; Guerrero, V.; Hernandez Perez, P. A.; Perez, N.; Hidalgo, R. 2009-12-01 Water and gas sampling of natural discharges are the most common type of geochemical surveys for geothermal exploration. However, these natural discharges are generally scarces at geothermal exploration areas where the extent of the field is not known. Therefore, soil-volatile (Hg, As, Sb, NH3 and B) and soil-gas surveys (222Rn, CO2, He, H2, CH4, O2, Ar) are becoming a useful geochemical tool to identify permeable areas and potential upflow or boiling zones. These surveys can also help to delineate the margins of a geothermal system, and therefore often complement geophysical surveys particularly where the interpretation of geophysical data shows some difficulties. During July and August, 2008, a surface geochemical survey was undertaken in a ~120 km2 area at the south-east slope of Tenerife Island, Spain. In order to obtain a representative distribution of the whole study area, during the field work a total of 577 sampling points were performed. In-situ measurement of radon (222Rn) and thoron (220Rn) activities together with Hg0 and H2S gas concentration and CO2 and H2S soil effluxes were performed at each sampling point. At the same time, gas samples were taken from the soil atmosphere at 40 cm depth for subsequent chemical analysis by means of micro-gas chromatography and quadrupole mass spectrometry (He, H2, Ne, N2, CO2, CH4, Ar and CO2). At least two geochemical anomalous zones have been identified in the present work: (A) one close to Siete Fuentes-Fasnia historical vents (1704-1705 AD) and (B) located on the southwestern limit of the study area. Relatively high concentrations of H2 and ΔHe as well as high H2/Ar and He/CO2 ratios were observed at both zones, indicating a clear evidence of the existence of an upflow zone with an important contribution of endogenous gases. The existence of a volcanic-hydrothermal system coupled with a vertical permeability structures in both zones could explain these geochemical anomalies observed in the surface environment 14. Geochemical speciation and pollution assessment of heavy metals in surface sediments from Nansi Lake, China. PubMed Yang, Liyuan; Wang, Longfeng; Wang, Yunqian; Zhang, Wei 2015-05-01 Sixteen surface sediment samples were collected from Nansi Lake to analyze geochemical speciation of heavy metals including Cd, As, Pb, Cr, and Zn, assess their pollution level, and determine the spatial distribution of the non-residual fraction. Results showed that Cd had higher concentrations in water-soluble and exchangeable fractions. As and Pb were mainly observed as humic acid and reducible fractions among the non-residual fractions, while Cr and Zn were mostly locked up in a residual fraction. The mean pollution index (P i) values revealed that the lower lake generally had a higher enrichment degree than the upper lake. Cd (2.73) and As (2.05) were in moderate level of pollution, while the pollution of Pb (1.80), Cr (1.27), and Zn (1.02) appeared at low-level pollution. The calculated pollution load index (PLI) suggested the upper lake suffered from borderline moderate pollution, while the lower lake showed moderate to heavy pollution. Spatial principle component analysis showed that the first principal component (PC1) including Cd, As, and Pb could explain 56.18 % of the non-residual fraction. High values of PC1 were observed mostly in the southern part of Weishan Lake, which indicated greater bioavailability and toxicity of Cd, As, and Pb in this area. 15. Lithological and geochemical typification of surface bottom sediments in the Kara Sea NASA Astrophysics Data System (ADS) Rusakov, V. Yu.; Kuzhmina, T. G.; Levitan, M. A.; Toropchenova, E. S.; Zhylkina, A. V. 2017-01-01 The Kara Sea is part of the Western Arctic shelf of Eurasia. The deposition of sediments in this shallow sea is largely determined by solid runoff from two great Siberian rivers (the Yenisei and Ob) and the glacial periods when the sea area repeatedly (during the Quaternary) dried up and was covered by continental glaciers. The rise of the World Ocean due to Holocene warming resulted in a significant expansion of the sea area to the south and complete degradation of the ice sheet. In this article, new data on the geochemical composition of the surface (0- to 2-cm) layer of sea-bottom sediments are considered, which reflects the spatial distribution of marine sediments during the maximum sea level. Cluster analysis of the variance for 24 chemical elements reveals sediment chemotypes, and critical analysis of their relationship with lithotypes is performed. The presented data have been collected on cruises of the R/V Akademik Boris Petrov in 2000, 2001, and 2003 and the R/V Akademik Mstislav Keldysh in 2015. 16. The hydrothermal system of the Domuyo volcanic complex (Argentina): A conceptual model based on new geochemical and isotopic evidences NASA Astrophysics Data System (ADS) Tassi, F.; Liccioli, C.; Agusto, M.; Chiodini, G.; Vaselli, O.; Calabrese, S.; Pecoraino, G.; Tempesti, L.; Caponi, C.; Fiebig, J.; Caliro, S.; Caselli, A. 2016-12-01 The Domuyo volcanic complex (Neuquén Province, Argentina) hosts one of the most promising geothermal systems of Patagonia, giving rise to thermal manifestations discharging hot and Cl--rich fluids. This study reports a complete geochemical dataset of gas and water samples collected in three years (2013, 2014 and 2015) from the main fluid discharges of this area. The chemical and isotopic composition (δD-H2O and δ18O-H2O) of waters indicates that rainwater and snow melting are the primary recharge of a hydrothermal reservoir located at relative shallow depth (400-600 m) possibly connected to a second deeper (2-3 km) reservoir. Reactive magmatic gases are completely scrubbed by the hydrothermal aquifer(s), whereas interaction of meteoric waters at the surface causes a significant air contamination and dilution of the fluid discharges located along the creeks at the foothill of the Cerro Domuyo edifice. Thermal discharges located at relatively high altitude ( 3150 m a.s.l.), namely Bramadora, are less affected by this process, as also shown by their relatively high R/Ra values (up to 6.91) pointing to the occurrence of an actively degassing magma batch located at an unknown depth. Gas and solute geothermometry suggests equilibrium temperatures up to 220-240 °C likely referred to the shallower hydrothermal reservoir. These results, confirming the promising indications of the preliminary surveys carried out in the 1980‧s, provide useful information for a reliable estimation of the geothermal potential of this extinct volcanic system, although a detailed geophysical measurements is required for the correct estimation of depth and dimensions of the fluid reservoir(s). 17. An index of floodplain surface complexity USGS Publications Warehouse Scown, Murray W.; Thoms, Martin C.; DeJager, Nathan R. 2016-01-01 Floodplain surface topography is an important component of floodplain ecosystems. It is the primary physical template upon which ecosystem processes are acted out, and complexity in this template can contribute to the high biodiversity and productivity of floodplain ecosystems. There has been a limited appreciation of floodplain surface complexity because of the traditional focus on temporal variability in floodplains as well as limitations to quantifying spatial complexity. An index of floodplain surface complexity (FSC) is developed in this paper and applied to eight floodplains from different geographic settings. The index is based on two key indicators of complexity, variability in surface geometry (VSG) and the spatial organisation of surface conditions (SPO), and was determined at three sampling scales. FSC, VSG, and SPO varied between the eight floodplains and these differences depended upon sampling scale. Relationships between these measures of spatial complexity and seven geomorphological and hydrological drivers were investigated. There was a significant decline in all complexity measures with increasing floodplain width, which was explained by either a power, logarithmic, or exponential function. There was an initial rapid decline in surface complexity as floodplain width increased from 1.5 to 5 km, followed by little change in floodplains wider than 10 km. VSG also increased significantly with increasing sediment yield. No significant relationships were determined between any of the four hydrological variables and floodplain surface complexity. 18. Mineralogical and geochemical characteristics of BERYL (AQUAMARINE) from the Erongo Volcanic Complex, Namibia NASA Astrophysics Data System (ADS) Lum, Jullieta Enone; Viljoen, Fanus; Cairncross, Bruce; Frei, Dirk 2016-12-01 The granite hosted pegmatites of the Erongo Volcanic Complex in central Namibia are well known for the wide variety of minerals present, of considerable interest to mineral collectors. These include (amongst others) often spectacular, museum quality examples of beryl, schorl, jeremejevite, fluorite, quartz, goethite and cassiterite. The locality is particularly recognized for hosting a variety of beryl types, including green, yellow (heliodor), colorless (goshenite) and blue/greenish blue (aquamarine) variants. Comprehensive geochemical studies of the Erongo beryls are very limited. The present contribution serves to document the visual characteristics (colour, colour zoning, inclusion content) as well as the major and trace element chemistry of 42 blue, two green and one colorless beryl from Erongo, and to compare these with other localities worldwide. The beryls from Erongo are generally subhedral to euhedral with a well-formed prismatic habit. Idiomorphic crystals, characterised by strong hexagonal prisms, are common. Beryl is commonly associated with schorl, quartz, muscovite, alkali feldspar, plagioclase feldspar, iron oxides, foitite, rossmanite and cassiterite. Aquamarines range from pale blue to deep blue or greenish blue, with marked colour zoning seen in a number of samples. One of the two green beryls examined is of a medium green colour, and is heavily included, while the other specimen has a pale yellowish green colour. The goshenite sample is colourless, clear, and transparent. Numerous cracks are present in the samples examined, and these are usually filled by iron oxides. Inclusions species encountered in the beryl samples are schorl, quartz, muscovite, feldspar, iron oxides and cassiterite, clearly reflective of the host pegmatite mineralogy. Aquamarine and green beryl contain iron as the main chromophore while goshenite is devoid of chromophores. Fe contents in beryl increase with colour intensity, consistent with the known chromatic effects of Fe 19. An index of floodplain surface complexity NASA Astrophysics Data System (ADS) Scown, M. W.; Thoms, M. C.; De Jager, N. R. 2015-04-01 Floodplain surface topography is an important component of floodplain ecosystems. It is the primary physical template upon which ecosystem processes are acted out. There has been a limited appreciation of floodplain surface complexity because of the traditional focus on temporal variability in floodplains as well as limitations to quantifying spatial complexity. An index of floodplain surface complexity (FSC) is developed in this paper and applied to eight floodplains from different geographic settings. The index is based on the two key indicators of complexity; variability in surface geometry (VSG) and the spatial organization of surface conditions (SOC) and was determined at three sampling scales. Relationships between these measures of spatial complexity and environmental drivers, namely; flow variability (mean daily discharge [Q], the coefficient of variation of daily discharge [QCV], the coefficient of variation of mean annual discharge [QCVAnn], the coefficient of variation of maximum annual discharge [QCVMax]), sediment yield (SY), valley slope (Vs), and floodplain width (Fpw) were examined. FSC, VSG, and SOC varied between the eight floodplains and this was dependent upon sampling scale. All complexity values declined with increasing Fpw in either a power, logarithmic, or exponential function. There was little change in surface complexity with floodplain widths greater than 10 km. VSG was significantly related to SY and no significant relationships were determined between any of the hydrological variables and floodplain surface complexity. 20. Geochemical signature of land-based activities in Caribbean coral surface samples USGS Publications Warehouse Prouty, N.G.; Hughen, K.A.; Carilli, J. 2008-01-01 Anthropogenic threats, such as increased sedimentation, agrochemical run-off, coastal development, tourism, and overfishing, are of great concern to the Mesoamerican Caribbean Reef System (MACR). Trace metals in corals can be used to quantify and monitor the impact of these land-based activities. Surface coral samples from the MACR were investigated for trace metal signatures resulting from relative differences in water quality. Samples were analyzed at three spatial scales (colony, reef, and regional) as part of a hierarchical multi-scale survey. A primary goal of the paper is to elucidate the extrapolation of information between fine-scale variation at the colony or reef scale and broad-scale patterns at the regional scale. Of the 18 metals measured, five yielded statistical differences at the colony and/or reef scale, suggesting fine-scale spatial heterogeneity not conducive to regional interpretation. Five metals yielded a statistical difference at the regional scale with an absence of a statistical difference at either the colony or reef scale. These metals are barium (Ba), manganese (Mn), chromium (Cr), copper (Cu), and antimony (Sb). The most robust geochemical indicators of land-based activities are coral Ba and Mn concentrations, which are elevated in samples from the southern region of the Gulf of Honduras relative to those from the Turneffe Islands. These findings are consistent with the occurrence of the most significant watersheds in the MACR from southern Belize to Honduras, which contribute sediment-laden freshwater to the coastal zone primarily as a result of human alteration to the landscape (e.g., deforestation and agricultural practices). Elevated levels of Cu and Sb were found in samples from Honduras and may be linked to industrial shipping activities where copper-antimony additives are commonly used in antifouling paints. Results from this study strongly demonstrate the impact of terrestrial runoff and anthropogenic activities on coastal water 1. Geochemical signature of land-based activities in Caribbean coral surface samples NASA Astrophysics Data System (ADS) Prouty, N. G.; Hughen, K. A.; Carilli, J. 2008-12-01 Anthropogenic threats, such as increased sedimentation, agrochemical run-off, coastal development, tourism, and overfishing, are of great concern to the Mesoamerican Caribbean Reef System (MACR). Trace metals in corals can be used to quantify and monitor the impact of these land-based activities. Surface coral samples from the MACR were investigated for trace metal signatures resulting from relative differences in water quality. Samples were analyzed at three spatial scales (colony, reef, and regional) as part of a hierarchical multi-scale survey. A primary goal of the paper is to elucidate the extrapolation of information between fine-scale variation at the colony or reef scale and broad-scale patterns at the regional scale. Of the 18 metals measured, five yielded statistical differences at the colony and/or reef scale, suggesting fine-scale spatial heterogeneity not conducive to regional interpretation. Five metals yielded a statistical difference at the regional scale with an absence of a statistical difference at either the colony or reef scale. These metals are barium (Ba), manganese (Mn), chromium (Cr), copper (Cu), and antimony (Sb). The most robust geochemical indicators of land-based activities are coral Ba and Mn concentrations, which are elevated in samples from the southern region of the Gulf of Honduras relative to those from the Turneffe Islands. These findings are consistent with the occurrence of the most significant watersheds in the MACR from southern Belize to Honduras, which contribute sediment-laden freshwater to the coastal zone primarily as a result of human alteration to the landscape (e.g., deforestation and agricultural practices). Elevated levels of Cu and Sb were found in samples from Honduras and may be linked to industrial shipping activities where copper-antimony additives are commonly used in antifouling paints. Results from this study strongly demonstrate the impact of terrestrial runoff and anthropogenic activities on coastal water 2. Final Report: Molecular Basis for Microbial Adhesion and Geochemical Surface Reactions: A Study Across Scales SciTech Connect Dixon, David Adams 2013-06-27 Computational chemistry was used to help provide a molecular level description of the interactions of Gram-negative microbial membranes with subsurface materials. The goal is to develop a better understanding of the molecular processes involved in microbial metal binding, microbial attachment to mineral surfaces, and, eventually, oxidation/reduction reactions (electron transfer) that can occur at these surfaces and are mediated by the bacterial exterior surface. The project focused on the interaction of the outer microbial membrane, which is dominated by an exterior lipopolysaccharide (LPS) portion, of Pseudomonas aeruginosa with the mineral goethite and with solvated ions in the environment. This was originally a collaborative project with T.P. Straatsma and B. Lowery of the Pacific Northwest National Laboratory. The University of Alabama effort used electronic structure calculations to predict the molecular behavior of ions in solution and the behavior of the sugars which form a critical part of the LPS. The interactions of the sugars with metal ions are expected to dominate much of the microscopic structure and transport phenomena in the LPS. This work, in combination with the molecular dynamics simulations of Straatsma and the experimental electrochemistry and microscopy measurements of Lowry, both at PNNL, is providing new insights into the detailed molecular behavior of these membranes in geochemical environments. The effort at The University of Alabama has three components: solvation energies and structures of ions in solution, prediction of the acidity of the critical groups in the sugars in the LPS, and binding of metal ions to the sugar anions. An important aspect of the structure of the LPS membrane as well as ion transport in the LPS is the ability of the sugar side groups such as the carboxylic acids and the phosphates to bind positively charged ions. We are studying the acidity of the acidic side groups in order to better understand the ability of 3. Geochemical characteristics of hydrous basaltic magmas due to assimilation and fractional crystallization: the Ikoma gabbroic complex, southwest Japan NASA Astrophysics Data System (ADS) Koizumi, N.; Okudaira, T.; Ogawa, D.; Yamashita, K.; Suda, Y. 2016-10-01 To clarify the processes that occur in hydrous basaltic magma chambers, we have undertaken detailed petrological and geochemical analyses of mafic and intermediate rocks from the Ikoma gabbroic complex, southwest Japan. The complex consists mainly of hornblende gabbros, hornblende gabbronorites, and hornblende leucogabbros. The hornblende leucogabbros are characterized by low TiO2 and high CaO contents, whereas the hornblende gabbronorites have high TiO2 and low CaO contents. The initial 87Sr/86Sr ratios (SrI) of the hornblende gabbronorites and hornblende gabbros are higher than those of the hornblende leucogabbros and plagioclase, and they may have resulted from a higher degree of assimilation of metasediments. The geochemical features of the hornblende leucogabbros and hornblende gabbronorites can be explained by accumulation of plagioclase and ilmenite, respectively, in a hybrid magma that formed by chemical interaction between mafic magma and metasediment, whereas the hornblende gabbros were produced by a high degree of crustal assimilation and fractional crystallization of this hybrid magma. As a result of the density differences between crystals and melt, the Ikoma gabbroic rocks formed by the accumulation of plagioclase in the middle of the magma chamber and by the accumulation of ilmenite in the bottom of the chamber. Taking into account the subsequent assimilation and fractional crystallization, our observations suggest an enriched mantle (SrI = ~0.7071) as the source material for the Ikoma gabbros. 4. Geochemical forms and seasonal variations of phosphorus in surface sediments of the East China Sea shelf NASA Astrophysics Data System (ADS) Zhou, Fengxia; Gao, Xuelu; Yuan, Huamao; Song, Jinming; Chen, Chen-Tung Arthur; Lui, Hon-Kit; Zhang, Yong 2016-07-01 Geochemical characteristics of phosphorus (P) in the surface sediments of the East China Sea shelf (ECSS) were studied in spring and autumn, 2014. Distributions, seasonal variations, transformations and their influencing factors were discussed. Besides, burial fluxes of P in different seasons were also calculated. Five operationally defined forms of P, namely exchangeable or loosely sorbed P (Ads-P), iron-bound P (Fe-P), authigenic P (Au-P), detrital apatite plus other inorganic P (De-P) and organic P (OP), were obtained using a sequential extraction procedure. Generally, the concentrations of Ads-P, Fe-P, Au-P and OP decreased seaward and the concentrations of De-P increased seaward in both seasons. In spring, the average concentrations of Ads-P, Fe-P, Au-P, De-P and OP were 13.8 ± 5.0, 21.9 ± 7.6, 148.5 ± 44.5, 153.1 ± 55.8 and 91.7 ± 21.5 μg g- 1, respectively. The corresponding concentrations in autumn were 11.4 ± 4.3, 20.0 ± 10.9, 170.4 ± 53.6, 225.6 ± 101.7 and 77.1 ± 33.9 μg g- 1, respectively. The average percentages of P fractions in total P (TP) in spring and autumn were both in the order: De-P > Au-P > OP > Fe-P > Ads-P. The average concentrations of Bio-available P (Bio-P) were 127.4 ± 31.4 μg g- 1 in spring and 108.5 ± 47.2 μg g- 1 in autumn, accounting for 29.8% ± 7.3% and 21.5% ± 8.2% of corresponding TP, respectively. Seasonal variations of the primary production, hydrodynamic conditions, hypoxia and other environmental conditions were responsible for the seasonal variations of different phosphorus forms. The calculation of burial fluxes reflected that, in most parts of the studied area, TP had relative high burial fluxes in autumn, while Bio-P had relatively high burial fluxes in spring. The burial fluxes of other phosphorus forms also showed different seasonal variations in different parts of the studied area. 5. Geochemical modeling research related to the surface disposal of processed oil shale solid waste. [Elements and compounds in oil shale wastes SciTech Connect Reddy, K. J.; Drever, J. I. 1987-10-01 Several geochemical codes are available in the literature to model chemical processes such as oxidation-reduction, precipitation-dissolution, formation of solution complex, adsorption, and ion exchange. However, these models differ in the environments to which they apply. The objective of this research was to evaluate the applicability of existing geochemical codes to predict water quality from an oil shale solid waste environment. We selected EQ3/EQ6, GEOCHEM, MINTEQ, PHREEQE, SOLMNEQ, and WATEQFC geochemical models for further evaluation. We concluded that all these models lack thermodynamic data for minerals and solution complexes which are important for oil shale solid waste studies. Selection of any one of the models would require development of a more reliable thermodynamic database, and this report describes the initiation of that work. So far, critical evaluation of thermodynamic data has been completed for Sr, F, Mo, and Se. 64 refs., 15 tabs. 6. Geochemical recognition of a captured back-arc basin metabasaltic complex, southwestern Oregon USGS Publications Warehouse Donato, M.M. 1991-01-01 An extensive fault-bounded amphibolite terrane of Late Jurassic (145 ?? 2 Ma) metamorphic age occurring in the northeastern Klamath Mountains of southern Oregon has been recognized as the remnants of an ancient back-arc basin. In spite of thorough metamorphic recrystallization under amphibolite-facies conditions, the amphibolite locally displays relict igneous textures which suggest that the protoliths included basaltic dikes or sills, shallow diabase intrusions, and gabbros. The geochemical data, together with the present-day geologic context, indicate that the tectonic setting of eruption/intrusion was probably within a back-arc basin that existed inboard (east) of a pre-Nevadan volcanic arc. The basalt (now amphibolite) and the overlying sediments (now the May Creek Schist) were metamorphosed and deformed during accretion to North America during the Late Jurassic Nevadan orogeny. -from Author 7. Bridging arsenate surface complexes on the hematite (012) surface. SciTech Connect Catalano, J. G.; Zhang, Z.; Park, C.; Fenter, P.; Bedzyk, M. J.; Chemistry; Northwestern Univ. 2007-04-15 The fate of the oxoanion arsenate in diverse systems is strongly affected by its adsorption on the surfaces of iron (oxyhydr)oxide minerals. Predicting this behavior in the environment requires an understanding of the mechanisms of arsenate adsorption. In this study, the binding site and adsorption geometry of arsenate on the hematite (012) surface is investigated. The structure and termination of the hematite (012)-water interface were determined by high resolution X-ray reflectivity, revealing that two distinct terminations exist in a roughly 3:1 proportion. The occurrence of multiple terminations appears to be a result of sample preparation, and is not intrinsic to the hematite (012) surface. X-ray standing wave (XSW) measurements were used to determine the registry of adsorbed arsenate to the hematite structure, and thus the binding site and geometry of the resulting surface complex. Arsenate forms a bridging bidentate complex on two adjacent singly coordinated oxygen groups on each of the two distinct terminations present at the hematite surface. Although this geometry is consistent with that seen in past studies, the derived As-Fe distances are longer, the result of the topology of the FeO6 octahedra on the (012) surface. As EXAFS-derived As-Fe distances are often used to determine the adsorption mechanism in environmental samples (e.g., mine tailings, contaminated sediments), this demonstrates the importance of considering the possible sorbent surface structures and arrangements of adsorbates when interpreting such data. As multiple functional groups are present and multiple binding geometries are possible on the hematite (012) surface, the XSW data suggest that formation of bridging bidentate surface complexes on singly coordinated oxygen sites is the preferred adsorption mechanism on this and most other hematite surfaces (provided those surfaces contain adjacent singly coordinated oxygen groups). These measurements also constrain the likely reaction 8. Global Geochemical Variation on the Lunar Surface: A Three-Element Approach NASA Technical Reports Server (NTRS) Thomsen, D. R.; Lawrence, D. J.; Vaniman, D.; Feldman, W. C.; Elphic, R. C.; Barraclough, B. L.; Maurice, S.; Lucey, P. G.; Binder, A. B. 1999-01-01 We present a method for displaying the relative abundances of three important elements (Th, Fe, and Ti) on the same map projection of the lunar surface. Using Th-, Fe-, and Ti-elemental abundances from orbital geochemical data and assigning each element a primary color, a false-color map of the lunar surface was created. This approach is similar to the ternary diagram approach presented by Davis and Spudis with some important differences, discussed later. For the present maps, Th abundances were measured by the Lunar Prospector (LP) Gamma-Ray Spectrometer(GRS).The new LPGRS low-altitude dataset was used in this analysis. Iron and Ti weight percentages were based on Clementine spectral reflectance data smoothed to the LP low altitude footprint. This method of presentation was designed to aid in the location and recognition of three principal lunar compositions: ferroan anorthosite (FAN), mare basalts (MB), and the Mg suite/ KREEP-rich rocks on the lunar surface, with special emphasis on the highlands and specific impact basins. In addition to the recognition of these endmember rock compositions, this method is an attempt to examine the relationship between elemental compositions that do not conform readily to previously accepted or observed endmember rocks in various specific regions of interest, including eastern highlands regions centered on 150 deg longitude, and a northern highlands Th-rich region observed. The LP low-altitude data has full width at half-maximum spatial resolution of about 40 km. The Clementine spectral reflectance datasets were adapted using an equal-area, gaussian smoothing routine to this footprint. In addition, these datasets, reported in weight percent of FeO and of Ti02, were adjusted to Fe and Ti weight percentages. Each dataset was then assigned one of the three primary colors: blue for Th, red for Fe, and green for Ti. For each element, the data range was normalized to represent the ratio of each point to the maximum in the dataset. (To 9. Surface Complexation Modelling in Metal-Mineral-Bacteria Systems NASA Astrophysics Data System (ADS) Johnson, K. J.; Fein, J. B. 2002-12-01 The reactive surfaces of bacteria and minerals can determine the fate, transport, and bioavailability of aqueous heavy metal cations. Geochemical models are instrumental in accurately accounting for the partitioning of the metals between mineral surfaces and bacteria cell walls. Previous research has shown that surface complexation modelling (SCM) is accurate in two-component systems (metal:mineral and metal:bacteria); however, the ability of SCMs to account for metal distribution in mixed metal-mineral-bacteria systems has not been tested. In this study, we measure aqueous Cd distributions in water-bacteria-mineral systems, and compare these observations with predicted distributions based on a surface complexation modelling approach. We measured Cd adsorption in 2- and 3-component batch adsorption experiments. In the 2-component experiments, we measured the extent of adsorption of 10 ppm aqueous Cd onto either a bacterial or hydrous ferric oxide sorbent. The metal:bacteria experiments contained 1 g/L (wet wt.) of B. subtilis, and were conducted as a function of pH; the metal:mineral experiments were conducted as a function of both pH and HFO content. Two types of 3-component Cd adsorption experiments were also conducted in which both mineral powder and bacteria were present as sorbents: 1) one in which the HFO was physically but not chemically isolated from the system using sealed dialysis tubing, and 2) others where the HFO, Cd and B. subtilis were all in physical contact. The dialysis tubing approach enabled the direct determination of the concentration of Cd on each sorbing surface, after separation and acidification of each sorbent. The experiments indicate that both bacteria and mineral surfaces can dominate adsorption in the system, depending on pH and bacteria:mineral ratio. The stability constants, determined using the data from the 2-component systems, along with those for other surface and aqueous species in the systems, were used with FITEQL to 10. Geochemical behaviour of palladium in soils and Pd/PdO model substances in the presence of the organic complexing agents L-methionine and citric acid. PubMed Zereini, Fathi; Wiseman, Clare L S; Vang, My; Albers, Peter; Schneider, Wolfgang; Schindl, Roland; Leopold, Kerstin 2016-01-01 Risk assessments of platinum group metal (PGE) emissions, notably those of platinum (Pt), palladium (Pd) and rhodium (Rh), have been mostly based on data regarding the metallic forms used in vehicular exhaust converters, known to be virtually biologically inert and immobile. To adequately assess the potential impacts of PGE, however, data on the chemical behaviour of these metals under ambient conditions post-emission is needed. Complexing agents with a high affinity for metals in the environment are hypothesized to contribute to an increased bioaccessibility of PGE. The purpose of this study is to examine the modulating effects of the organic complexing agents, L-methionine and citric acid, on the geochemical behavior of Pd in soils and model substances (Pd black and PdO). Batch experimental tests were conducted with soils and model substances to examine the impacts of the concentration of complexing agents, pH and length of extraction period on Pd solubility and its chemical transformation. Particle surface chemistry was examined using X-ray photoelectron spectroscopy (XPS) on samples treated with solutions under various conditions, including low and high O2 levels. Pd was observed to be more soluble in the presence of organic complexing agents, compared to Pt and Rh. Pd in soils was more readily solubilized with organic complexing agents compared to the model substances. After 7 days of extraction, L-methionine (0.1 M) treated soil and Pd black samples, for instance, had mean soluble Pd fractions of 12.4 ± 5.9% and 0.554 ± 0.024%, respectively. Surface chemistry analyses (XPS) confirmed the oxidation of metallic Pd surfaces when treated with organic complexing agents. The type of organic complexing agent used for experimental purposes was observed to be the most important factor influencing solubility, followed by solution pH and time of extraction. The results demonstrate that metallic Pd can be transformed into more bioaccessible species in the presence of 11. Exciton coupling of surface complexes on a nanocrystal surface. PubMed Xu, Xiangxing; Ji, Jianwei; Wang, Guan; You, Xiaozeng 2014-08-25 Exciton coupling may arise when chromophores are brought into close spatial proximity. Herein the intra-nanocrystal exciton coupling of the surface complexes formed by coordination of 8-hydroxyquinoline to ZnS nanocrystals (NCs) is reported. It is studied by absorption, photoluminescence (PL), PL excitation (PLE), and PL lifetime measurements. The exciton coupling of the surface complexes tunes the PL color and broadens the absorption and PLE windows of the NCs, and thus is a potential strategy for improving the light-harvesting efficiency of NC solar cells and photocatalysts. 12. Hydrological sulfur cycling in the volcanic complex of Valles Caldera - geochemical and astrobiological implications for Mars NASA Astrophysics Data System (ADS) Szynkiewicz, A.; Borrok, D. M.; Vaniman, D. T.; Goff, F. 2012-12-01 Sulfate minerals on the Martian surface provide compelling evidence of past fluid movement, chemistry, and potential habitability. However, we are uncertain about the relative influence of concurrent volcanic sulfur emissions, aqueous sulfide weathering, and climate conditions on the sulfur cycle, and we poorly understand the hydrological cycle of sulfur transport on Mars. Therefore, the goal of our research is to describe and quantify the active and historical hydrological sulfur cycle in the Valles Caldera, a ≤ 1.25 Myr giant, circular, volcanic complex located in northern New Mexico, and to compare this to available data for the sulfur cycle on Mars. The rocks of Valles Caldera (e.g., rhyolite lavas and pyroclastic deposits, intracaldera sediments and breccias, pre-caldera dacite and andesite, etc.) show wide variations in S content from 0.003 up to 3.41 wt% in fresh to hydrothermally altered units, respectively (Goff et al. 2007). Additionally, an acid-sulfate hot spring system issues from the western flank of the resurgent dome inside Valles Caldera and significantly increases the sulfate concentrations in local springs (up to 3,000 mg/L; Szynkiewicz et al. 2012). Using historical USGS stream flow measurements and sulfate concentrations (1958 to 1990), we calculated that in average ~16.4 tons of dissolved sulfate is annually removed from this volcanic system via the hydrological cycle. Initial S isotope mass balance calculations indicate that ~70 % of the dissolved sulfate (~11.5 tons/year) is likely contributed by the acid-sulfate hot springs and ~30 % (~4.9 tons/year) comes from dissolution/oxidation of S-enriched bedrock and atmospheric wet deposition. Although the acid-sulfate hot spring system is an ideal habitat for microbial S metabolism, the preservation of S isotope biosignatures is poor in geological samples because of prevailing contributions of S species from magmatic sources. In the next step of our research, we will 1) quantify the present 13. Geochemical recognition of a captured back-arc basin metabasaltic complex, southwestern Oregon SciTech Connect Donato, M.M. ) 1991-09-01 An extensive fault-bounded amphibolite terrane of Late Jurassic (145 {plus minus} 2 Ma) metamorphic age occurring in the northeastern Klamath Mountains of southern Oregon has been recognized as the remnants of an ancient back-arc basin. In spite of through metamorphic recrystallization under amphibolite-facies conditions, the amphibolite locally displays relict igneous textures which suggest that the protoliths included basaltic dikes or sills, shallow diabase intrusions, and gabbros. The major- and minor-element chemistry of the amphibolite indicates that some alteration of original compositions has occurred. Nevertheless, certain elements (e.g. Zr, Ti, Y, Hf, P, Th, Ta, and the REE) were probably immobile and retain their original igneous abundances, Chondrite-normalized REE patterns are similar to those of mid-ocean ridge basalt (MORB): concave-downward and flat or slightly LREE-depleted, with abundances about six to 30 times chondritic values. Patterns are slightly LREE-enriched and HREE-depleted relative to average MORB. Most samples plot in or near MORB fields in tectonomagmatic discrimination diagrams, but relative enrichment in Th, and the LREE suggest the involvement of subduction-related fluids in magma genesis. In this regard, the amphibolite is very similar to some back-arc basin basalts. The geochemical data, together with the present-day geologic context, indicate that the tectonic setting of eruption/intrusion was probably within a back-arc basin that existed inboard (east) of a pre-Nevadan volcanic arc. The basalt (now amphibolite) and the overlying sediments (now the May Creek Schist) were metamorphosed and deformed during accretion to North America during the Late Jurassic Nevadan orogeny. 14. Geochemical investigation of Archaean Bimodal and Dwalile metamorphic suites, Ancient Gneiss Complex, Swaziland USGS Publications Warehouse Hunter, D.R.; Barker, F.; Millard, H.T. 1984-01-01 The bimodal suite (BMS) comprises leucotonalitic and trondhjemitic gneisses interlayered with amphibolites. Based on geochemical parameters three main groups of siliceous gneiss are recognized: (i) SiO2 14%, and fractionated light rare-earth element (REE) and flat heavy REE patterns; (ii) SiO2 and Al2O3 contents similar to (i) but with strongly fractionated REE patterns with steep heavy REE slopes; (iii) SiO2 > 73%, Al2O3 < 14%, Zr ??? 500 ppm and high contents of total REE having fractionated light REE and flat heavy REE patterns with large negative Eu anomalies. The interlayered amphibolites have major element abundances similar to those of basaltic komatiites, Mg-tholeiites and Fe-rich tholeiites. The former have gently sloping REE patterns, whereas the Mg-tholeiites have non-uniform REE patterns ranging from flat (??? 10 times chondrite) to strongly light REE-enriched. The Fe-rich amphibolites have flat REE patterns at 20-30 times chondrite. The Dwalile metamorphic suite, which is preserved in the keels of synforms within the BMS, includes peridotitic komatiites that have depleted light REE patterns similar to those of compositionally similar volcanics in the Onverwacht Group, Barberton, basaltic komatiites and tholeiites. The basaltic komatiites have REE patterns parallel to those of the BMS basaltic komatiites but with lower total REE contents. The Dwalile tholeiites have flat REE patterns. The basic and ultrabasic liquids were derived by partial melting of a mantle source which may have been heterogeneous or the heterogeneity may have resulted from sequential melting of the mantle source. The Fe-rich amphibolites were derived either from liquids generated at shallow levels or from liquids generated at depth which subsequently underwent extensive fractionation. ?? 1984. 15. Geochemical mapping of the lunar surface using laser-induced ion mass spectrometry from landers and rovers NASA Astrophysics Data System (ADS) Funsten, H. O.; Elphic, R. C.; Blacic, J. D.; Borovsky, J. E.; McComas, D. J.; Nordholt, J. E. In-situ lunar geochemical assessment is essential when remotely prospecting for lunar resources or characterizing the mineralogy of a lunar site. We discuss a technique for lunar geochemical mapping from landed platforms using Laser-induced Ion Mass Spectrometry (LIMS). In this technique, a focused diode-pumped Nd:YAG laser on an lunar lander or rover vaporizes a thin layer of a soil or rock target located at a range of 1 to 100 m. The vapor is ionized through electron heating by inverse Bremsstrahlung, and the expanding plasma cloud contains information about the target composition. Ions in this plasma are analyzed using specialized time-of-flight ion mass spectrometry, providing detailed composition analysis of the lunar surface. In considering this technique, we discuss the effects on the ion trajectories of ambient electric and magnetic fields and present a high sensitivity, high mass-resolution mass spectrometer that is capable of detecting low atomic mass abundances, trace elements, and isotopic variations. 16. Geochemical and mineralogical characteristics of the Yonghwa phoscorite-carbonatite complex, South Korea, and genetic implications NASA Astrophysics Data System (ADS) Seo, Jieun; Choi, Seon-Gyu; Park, Jung-Woo; Whattam, Scott; Kim, Dong Woo; Ryu, In-Chang; Oh, Chang Whan 2016-10-01 The Yonghwa phoscorite-carbonatite complex occurs as an isolated individual body with an inclined pipe shape within the Precambrian Gyeonggi Massif, South Korea. The phoscorite consists mainly of olivine, apatite, magnetite, carbonates, amphibole, and phlogopite, and can be subdivided into two types, olivine-rich and apatite-rich. The carbonatite is composed of calcite, Mg-rich dolomite, Fe-rich dolomite, magnetite, apatite, and/or siderite. Intensive fenitization occurred along the boundary between the complex and the wall rocks of leucocratic banded gneiss and garnet-bearing metabasite. The paragenetic sequences of the phoscorite-carbonatite complex demonstrate that the early crystallization of silicate minerals was followed by the crystallization of carbonates as the carbonatitic melt cooled. Magnetite occurs within the complex, and the carbonatites have Fe contents that are higher than typical ferrocarbonatites, due to the high magnetite contents. The rare earth elements (REEs) in the phoscorites and carbonatites are weakly fractionated and show enrichments of LREEs and Nb relative to HREEs. Furthermore, the apatites reflect the fractionated trends of LREEs relative to HREEs. Phoscorite apatites are enriched in Sr and show substitutions between Ca and Sr. Mica chemistry reflects the evolutionary trend of Fe2 + and Mg2 + in the phoscorite-carbonatite melt without Al substitution. Micas exhibit high values of Mg# in the phoscorite-carbonatite complex, but lower values in fenites. Via thermodynamic analysis, the early stability fields of magnetite-pyrrhotite-graphite-carbonate assemblages indicate that the Yonghwa phoscorite and carbonatite crystallized under conditions of 600 °C, 2 kbar, and XCO2 = 0.2. Afterward, melts underwent an evolution to the late stability fields of magnetite-pyrite-pyrrhotite-ilmenite assemblages. The δ13C and δ18O isotopic compositions of carbonates in the Yonghwa phoscorite-carbonatite complex are - 8.2‰ to - 3.4‰ and 6.6 to 11 17. Origin of late Archean granite: geochemical evidence from the Vermilion Granitic Complex of northern Minnesota USGS Publications Warehouse Day, W.C.; Weiblen, P.W. 1986-01-01 The 2,700-Ma Vermilion Granitic Complex of northern Minnesota is a granite-migmatite terrane composed of supracrustal metasedimentary rocks, mafic rocks, tonalitic and granodioritic plutonic rocks, and granite. The metasedimentary rocks are predominantly graywacke, which has been regionally metamorphosed to garnet-sillimanite-muscovite-bearing biotite schist, and has locally undergone anatexis. The mafic rocks form early phases within the complex and are of two types: (1) basaltic amphibolite, and (2) monzodiorite and essexite rich in large ion lithophile elements (LILE). The members of the early plutonic suite form small bodies that intrude the metasedimentary rocks and mafic rocks, producing an early migmatite. The granite is of two distinct varieties: (1) white garnet-muscovite-biotite leucogranite (S-type; Chappell and White 1974) and (2) grayish-pink biotite-magnetite Lac La Croix Granite (I-type). The leucogranite occurs in the early migmatite and in paragneissic portions of the complex, whereas the Lac La Croix Granite is a late-stage intrusive phase that invades the early migmatite and metasediment (producing a late migmatite) and forms a batholith. This study focuses specifically on the origin of granite in the Vermilion Granitic Complex. Chemical mass-balance calculations suggest that the S-type two-mica leucogranite had a metagraywacke source, and that the I-type Lac La Croix Granite formed via partial fusion of calc-alkaline tonalitic material, which may have been similar to rocks of the early plutonic suite. This model is satisfactory for petrogenesis of similar Late Archean post-kinematic granites throughout the Canadian Shield. ?? 1986 Springer-Verlag. 18. Origin of late Archean granite: geochemical evidence from the Vermilion Granitic Complex of northern Minnesota NASA Astrophysics Data System (ADS) Day, Warren C.; Weiblen, P. W. 1986-07-01 The 2,700-Ma Vermilion Granitic Complex of northern Minnesota is a granite-migmatite terrane composed of supracrustal metasedimentary rocks, mafic rocks, tonalitic and granodioritic plutonic rocks, and granite. The metasedimentary rocks are predominantly graywacke, which has been regionally metamorphosed to garnet-sillimanite-muscovite-bearing biotite schist, and has locally undergone anatexis. The mafic rocks form early phases within the complex and are of two types: (1) basaltic amphibolite, and (2) monzodiorite and essexite rich in large ion lithophile elements (LILE). The members of the early plutonic suite form small bodies that intrude the metasedimentary rocks and mafic rocks, producing an early migmatite. The granite is of two distinct varieties: (1) white garnet-muscovite-biotite leucogranite ( S-type; Chappell and White 1974) and (2) grayish-pink biotite-magnetite Lac La Croix Granite ( I-type). The leucogranite occurs in the early migmatite and in paragneissic portions of the complex, whereas the Lac La Croix Granite is a late-stage intrusive phase that invades the early migmatite and metasediment (producing a late migmatite) and forms a batholith. This study focuses specifically on the origin of granite in the Vermilion Granitic Complex. Chemical mass-balance calculations suggest that the S-type two-mica leucogranite had a metagraywacke source, and that the I-type Lac La Croix Granite formed via partial fusion of calc-alkaline tonalitic material, which may have been similar to rocks of the early plutonic suite. This model is satisfactory for petrogenesis of similar Late Archean post-kinematic granites throughout the Canadian Shield. 19. Colloidal Nanocrystals Fluoresced by Surface Coordination Complexes PubMed Central Wang, Guan; Ji, Jianwei; Zhang, Xinwen; Zhang, Yan; Wang, Qiangbin; You, Xiaozeng; Xu, Xiangxing 2014-01-01 Colloidal Nanocrystals (NCs) with fluorescence originating from surface complexes are successfully prepared. The components of these NCs range from insulator, semiconductor to metal, with either pure phase, doped or core/shell structures. The photoluminescence of these NCs can be reversibly tuned across the visible to infrared spectrum, and even allow multi-color emission. A light emitting device is fabricated and a new in vivo cell imaging method is performed to demonstrate the power of this technology for emerging applications. PMID:24970242 20. Colloidal nanocrystals fluoresced by surface coordination complexes. PubMed Wang, Guan; Ji, Jianwei; Zhang, Xinwen; Zhang, Yan; Wang, Qiangbin; You, Xiaozeng; Xu, Xiangxing 2014-06-27 Colloidal Nanocrystals (NCs) with fluorescence originating from surface complexes are successfully prepared. The components of these NCs range from insulator, semiconductor to metal, with either pure phase, doped or core/shell structures. The photoluminescence of these NCs can be reversibly tuned across the visible to infrared spectrum, and even allow multi-color emission. A light emitting device is fabricated and a new in vivo cell imaging method is performed to demonstrate the power of this technology for emerging applications. 1. Contributions of natural arsenic sources to surface waters on a high grade arsenic-geochemical anomaly (French Massif Central). PubMed Bossy, A; Grosbois, C; Hendershot, W; Beauchemin, S; Crouzet, C; Bril, H 2012-08-15 The subwatershed studied drains a non-exploited area of the St-Yrieix-la-Perche gold mining district (French Massif Central) and it is located on an arsenic (As) geochemical anomaly. In this context, it is important to know the geochemical processes involved in the transfer of As from solid environmental compartments to the aquatic system. The stream showed a temporal variation of dissolved As (As(d)) content from 69.4 μg.L(-1) in the low flow period to 7.5 μg.L(-1) in the high flow period. Upstream, ground- and wetland waters had As(d) concentrations up to 215 and 169 μg.L(-1), respectively. The main representative As sources were determined at the subwatershed scale with in-situ monitoring of major and trace element contents in different waters and single extraction experiments. The As sources to stream water could be regrouped into two components: (i) one As-rich group (mainly in the low flow period) with groundwater, gallery exploration outlet waters and wetland waters, and (ii) one As-poor group (mainly in the high flow period) with rainwaters and soil solutions. In the soil profile, As(d) showed a significant decrease from 52.4 μg.L(-1) in the 0-5 cm superficial soil horizon to 14.4 μg.L(-1) in the 135-165 cm deep soil horizon. This decrease may be related to pedogenic processes and suggests an evolution of As-bearing phase stability through the soil profile. Quantification of As(d) fluxes at the subwatershed scale showed that groundwater was the major input (>80%) of As(d) to surface water. Moreover, natural weathering of the As-rich solid phases showed an impact on the As release, mainly from superficial soil horizons with runoff contributing about 5% to As input in surface water. 2. Pyrochlores from the Lueshe carbonatite complex (Democratic Republic of Congo): a geochemical record of different alteration stages NASA Astrophysics Data System (ADS) Nasraoui, M.; Bilal, E. 2000-04-01 Magmatic pyrochlores from the Lueshe syenite-carbonatite complex from the northeastern part of Democratic Republic of Congo (ex-Zaı̈re) are characterized by Ta/Nb ratios in an increasing order from pyroxenite, calcite-carbonatite (sövite), silicate xenoliths (nodules) to syenite. Substitutions involving Nb, Ta, Ti and REE have been precisely described. Hydrothermal alteration of Lueshe pyrochlore involves the substitution of Na ++F -=VA+VY and Ca+O=VA+VY (VA=A-site vacancy and VY=Y-site vacancy). In calcite carbonatite, hydrothermal alteration of pyrochlore took place during and after the precipitation of ancylite-(Ce), strontianite, celestite, baryte and fayalite according to a fluid composition of relatively low pH, aNa +, aCa 2+ and aHF, and high aSr 2+ and aLREE 3+. The supergene alteration is characterized by complete leaching of Na, Ca and F and partial incorporation of K, Ba, Sr and Ce resulting in the formation of kali-, bario-, strontio- and ceriopyrochlore respectively. The Na-poor pyrochlore may be an intermediate variety corresponding to an alteration stage between the hydrothermal and weathered pyrochlores. The IR spectroscopic study has indicated that the weathered pyrochlore is a hydrated variety containing two bands of OH vibration modes at 3413 and 1630 cm -1. During hydrothermal and supergene alterations, the cations at B-site remain relatively constant. The variable chemical compositions of the pyrochlores from the Lueshe complex represent geochemical memories of the different alteration conditions including the variation in the oxidation-reduction environment. 3. The geochemical characteristics of Haiyang A-type granite complex in Shandong, eastern China NASA Astrophysics Data System (ADS) Li, He; Ling, Ming-xing; Ding, Xing; Zhang, Hong; Li, Cong-ying; Liu, Dun-yi; Sun, Wei-dong 2014-07-01 Haiyang granite complex consists of K-feldspar granite and syenite, with a total exposure area of ~ 600 km2. The K-feldspar granite is metaluminous (A/CNK = 0.70 to 0.99) and the syenite is slightly peraluminous (A/CNK = 1.01 to 1.10), both of which have typical characteristics of A-type granite with high total alkali contents and FeOT/(FeOT + MgO) ratios. Zircon U-Pb age are 116.8 ± 1.7 Ma and 115.8 ± 2.2 Ma, for the K-feldspar granite and the syenite, respectively. This is consistent with field observation that the syenite intruded into the K-feldspar granite. Varied zircon O isotope (5.65-7.78‰ for K-feldspar granite and 4.68-7.08‰ for syenite) with peak values that are marginally higher than those of mantle zircon reflects important mantle contributions. These together with large variation of zircon εHf(t) values of K-feldspar granite (- 22.4 to - 15.6) and syenite (- 24.6 to - 13.5), can best be explained by the involvement of at least two components, e.g., enriched lithospheric mantle +/- subducted materials, and upwelling asthenosphere. Apatite has right decline REE pattern. The apatite from K-feldspar granite has higher Cl contents than those of syenite, implying more influence from a subduction released fluid in K-feldspar granite source. This distinction is supported by the systematically higher oxygen fugacity of K-feldspar granite as indicated by zircon Ce4 +/Ce3 + ratios. In the Yb/Ta-Y/Nb, Ce/Nb-Y/Nb diagrams, both K-feldspar granite and syenite plot in A1-type, with K-feldspar granite plotting closer to A2. In the Nb-Y-3Ga and Nb-Y-Ce charts, syenite plots near the boundary between A1 and A2, whereas some K-feldspar granite samples plot in A2 field, indicating a tendency of transition originally from A2 to A1. In general A1 granites form in intraplate settings, whereas A2 granite forms in post-collision. It is likely that mantle components metasomatized by subduction released fluids are easier to be partially melted, forming K-feldspar granite 4. Petrological and geochemical constraints on granitoid formation: The Waldoboro Pluton Complex, Maine SciTech Connect Barton, M. . Dept. of Geological Science); Sidle, W.S. ) 1992-01-01 The Waldoboro Pluton Complex (WPC) comprises seven units ranging from qtz-diorite to aplite. The country rocks are biotite-rich metagraywackes with minor shales mostly belonging to the Proterozoic Z-Ordovician Bucksport Formation. Field evidence strongly suggests that the WPC formed in-situ: contacts with the country rock are cryptic, transitional and concordant; restitic minerals in the granitoids are identical to those in the country rocks; prolific metasedimentary enclaves in the WPC are locally derived. Major and trace element data for country rock and the most voluminous units of the WPC define consistent linear trends suggesting limited melt segregation and retention of a high proportion of restite. Mixing models and partial melting models require 54--76% melting for generation of the gneissic granites and two-mica granites. Garnet-biotite geothermometry and garnet-Al[sub 2]SiO[sub 5]-SiO[sub 2]-plagioclase geobarometry indicate that the WPC formed at T = 740--780 C and P = 0.4--0.7 GPa. Published experimental data show that < 50% melting is likely under these conditions if melting is controlled by dehydration reactions. Bucksport lithologies contain < 20% biotite, suggesting that the maximum amount of melt that could have formed by dehydration melting is < 20%, even if all biotite was consumed during melting. It seems probable that a free fluid phase was required to generate the WPC. Migmatization is apparent in all lithologies (including amphibolites) in the vicinity of the WPC, consistent with fluid-present melting. Fluid may have ingressed along the St. George thrust, but the source of the fluid is unknown. 5. Mineralogical, geochemical, and magnetic signatures of surface sediments from the Canadian Beaufort Shelf and Amundsen Gulf (Canadian Arctic) NASA Astrophysics Data System (ADS) Gamboa, Adriana; Montero-Serrano, Jean-Carlos; St-Onge, Guillaume; Rochon, André; Desiage, Pierre-Arnaud 2017-02-01 Mineralogical, geochemical, magnetic, and siliciclastic grain-size signatures of 34 surface sediment samples from the Mackenzie-Beaufort Sea Slope and Amundsen Gulf were studied in order to better constrain the redox status, detrital particle provenance, and sediment dynamics in the western Canadian Arctic. Redox-sensitive elements (Mn, Fe, V, Cr, Zn) indicate that modern sedimentary deposition within the Mackenzie-Beaufort Sea Slope and Amundsen Gulf took place under oxic bottom-water conditions, with more turbulent mixing conditions and thus a well-oxygenated water column prevailing within the Amundsen Gulf. The analytical data obtained, combined with multivariate statistical (notably, principal component and fuzzy c-means clustering analyses) and spatial analyses, allowed the division of the study area into four provinces with distinct sedimentary compositions: (1) the Mackenzie Trough-Canadian Beaufort Shelf with high phyllosilicate-Fe oxide-magnetite and Al-K-Ti-Fe-Cr-V-Zn-P contents; (2) Southwestern Banks Island, characterized by high dolomite-K-feldspar and Ca-Mg-LOI contents; (3) the Central Amundsen Gulf, a transitional zone typified by intermediate phyllosilicate-magnetite-K-feldspar-dolomite and Al-K-Ti-Fe-Mn-V-Zn-Sr-Ca-Mg-LOI contents; and (4) mud volcanoes on the Canadian Beaufort Shelf distinguished by poorly sorted coarse-silt with high quartz-plagioclase-authigenic carbonate and Si-Zr contents, as well as high magnetic susceptibility. Our results also confirm that the present-day sedimentary dynamics on the Canadian Beaufort Shelf is mainly controlled by sediment supply from the Mackenzie River. Overall, these insights provide a basis for future studies using mineralogical, geochemical, and magnetic signatures of Canadian Arctic sediments in order to reconstruct past variations in sediment inputs and transport pathways related to late Quaternary climate and oceanographic changes. 6. The Mount Manengouba, a complex volcano of the Cameroon Line: Volcanic history, petrological and geochemical features NASA Astrophysics Data System (ADS) Pouclet, André; Kagou Dongmo, Armand; Bardintzeff, Jacques-Marie; Wandji, Pierre; Chakam Tagheu, Pulchérie; Nkouathio, David; Bellon, Hervé; Ruffet, Gilles 2014-09-01 The volcanic story of Mount Manengouba is related to four chronological stages: (1) forming of the early Manengouba shield volcano between 1.55 and 0.94 Ma, (2) building of the Eboga strato-cone between 0.94 and 0.89 Ma, (3) caldera collapse and silicic extrusions of the Elengoum Complex between 0.89 and 0.70 Ma, and (4) intra-caldera and flank activity between 0.45 and 0.11 Ma. The volume of the volcano is calculated at 320 km3 ± 5%. The volcanic rocks are attributed to two magmatic outputs. The first and main magma generation produced the shield volcano, the strato-cone, and the syn- to post-caldera extrusions, displaying a complete series from basanites to trachytes (magmatic Group 1). The second magma generation is limited to the late and flank activity evolving from basanites to trachy-phonolite (magmatic Group 2). Both magmatic groups belong to the under-saturated alkaline sodic series. Petrological calculations locate the magmatic reservoir between 37 and 39 km in the upper mantle for the Group 1 lavas, and between 42 and 44 km for the Group 2 lavas. Trachytes were generated in a secondary crustal reservoir. Magmatic series evolve with medium to low pressure fractional crystallization of olivine, pyroxene, oxides, feldspar, and apatite. Significant crustal assimilation is evidenced in trachytes. The magma of Group 1 was generated with 3-6% of partial melting of a moderately enriched source containing 3-7% of garnet. Melting took place in the spinel to garnet transition zone located at 70-90 km and around 25 kb. The magma of Group 2 resulted from a slightly higher partial melting from a less garnet-rich source that indicates uprising of the melting column in the upper part of transition zone. Sr, Nd, and Pb isotope data of the Manengouba rocks and neighboring lavas are analyzed and compared with those of the mafic lavas of the CVL. Three source components are distinguished: a depleted component originated from the asthenospheric swell, a radiogenic component 7. Application of the surface complexation concept to complex mineral assemblages USGS Publications Warehouse Davis, J.A.; Coston, J.A.; Kent, D.B.; Fuller, C.C. 1998-01-01 Two types of modeling approaches are illustrated for describing inorganic contaminant adsorption in aqueous environments: (a) the component additivity approach and (b) the generalized composite approach. Each approach is applied to simulate Zn2+ adsorption by a well-characterized sediment collected from an aquifer at Cape Cod, MA. Zn2+ adsorption by the sediment was studied in laboratory batch experiments with a range of pH and Zn(II) concentrations selected to encompass conditions observed in the aquifer. In the generalized composite approach, one, and two-site surface complexation model parameters were calibrated with the experimental data using FITEQL. The pH dependence of Zn2+ adsorption was simulated without explicit representation of electrostatic energy terms. Surface acidity constants and ion pair formation by major electrolyte ions were also not required in the model thereby minimizing the number of fitted parameters. Predictions of Zn2+ adsorption with the component additivity modeling approach did not simulate the experimental data adequately without manipulation of surface area or site density parameter values. To apply the component additivity approach to environmental sorbents, further research is needed to better characterize the composition of sediment surface coatings. The generalized composite modeling approach requires less information and can be viewed as more practical for application within solute transport models. With only three adjustable parameters, this approach could simulate Zn2+ adsorption over a range of chemical conditions that would cause several orders of magnitude variation in the distribution coefficient (K(d)) for Zn2+ within the aquifer.Two types of modeling approaches are illustrated for describing inorganic contaminant adsorption in aqueous environments: (a) the component additivity approach and (b) the generalized composite approach. Each approach is applied to simulate Zn2+ adsorption by a well-characterized sediment 8. Soft Landing of Complex Molecules on Surfaces * NASA Astrophysics Data System (ADS) Johnson, Grant E.; Hu, Qichi; Laskin, Julia 2011-07-01 Soft and reactive landing of mass-selected ions onto surfaces has become a topic of substantial interest due to its promising potential for the highly controlled preparation of materials. For example, there are possible applications in the production of peptide and protein microarrays for use in high-throughput screening, protein separation and conformational enrichment of peptides, redox protein characterization, thin-film production, and the preparation of catalysts through deposition of clusters and organometallic complexes. Soft landing overcomes many of the limitations associated with conventional thin-film production techniques and offers unprecedented selectivity and specificity of preparation of deposited species. This review discusses the fundamental aspects of soft and reactive landing of mass-selected ions on surfaces that pertain to applications of these techniques in biomaterials, molecular electronics, catalysis, and interfacial chemistry. 9. Surface complexation clues to dolomite growth SciTech Connect Brady, P.V.; Krumhansl, J.L.; Papenguth, H.W. 1996-02-01 Calcium and magnesium adsorb in near-stoichiometric proportions to dolomite over wide ranges in [Ca{sup 2+}]/[Mg{sup 2+}], ionic strength, and solution composition pointing to minimal mixing of metal cations between the CaCO{sub 3} and MgCO{sub 3} layer edges exposed at the dolomite surface. Near-neutral pH Mg and Ca adsorb as hydrated ions, or, in sulfate-rich solutions, as metal sulfate complexes. Near-stoichiometric adsorption of Ca and Mg points to dehydration and subsequent carbonation of adsorbed Mg as the likely rate-limiting step for dolomite growth at near-Earth surface conditions. We propose that one path for dolomite growth from low-temperature natural waters is through the initial adsorption of Mg-sulfate complexes onto either (1) growing dolomite crystals or (2) rate-limiting dolomite nucleii. Field relations, as well as homogeneous synthesis at low temperatures (25{degrees}C < T < 100{degrees}C) support this hypothesis and provide a mechanistic explanation for dolomite growth from sulfate-rich natural waters. 36 refs. 10. Geochemical assessment of light gaseous hydrocarbons in near-surface soils of Kutch-Saurashtra: Implication for hydrocarbon prospects NASA Astrophysics Data System (ADS) Rao, P. Lakshmi Srinivasa; Madhavi, T.; Srinu, D.; Kalpana, M. S.; Patil, D. J.; Dayal, A. M. 2013-02-01 Light hydrocarbons in soil have been used as direct indicators in geochemical hydrocarbon exploration, which remains an unconventional path in the petroleum industry. The occurrence of adsorbed soil gases, methane and heavier homologues were recorded in the near-surface soil samples collected from Kutch-Saurashtra, India. Soil gas alkanes were interpreted to be derived from deep-seated hydrocarbon sources and have migrated to the surface through structural discontinuities. The source of hydrocarbons is assessed to be thermogenic and could have been primarily derived from humic organic matter with partial contribution from sapropelic matter. Gas chromatographic analyses of hydrocarbons desorbed from soil samples through acid extraction technique showed the presence of methane through n-butane and the observed concentrations (in ppb) vary from: methane (C1) from 4-291, ethane (C2) from 0-84, propane (C3) from 0-37, i-butane (iC4) from 0-5 and n-butane (nC4) from 0-4. Carbon isotopes measured for methane and ethane by GC-C-IRMS, range between -42.9‰ to -13.3‰ (Pee Dee Belemnite - PDB) and -21.2‰ to -12.4‰ (PDB), respectively. The increased occurrence of hydrocarbons in the areas near Anjar of Kutch and the area south to Rajkot of Saurashtra signifies the area potential for oil and gas. 11. Post-Eocene volcanics of the Abazar district, Qazvin, Iran: Mineralogical and geochemical evidence for a complex magmatic evolution NASA Astrophysics Data System (ADS) Asiabanha, A.; Bardintzeff, J. M.; Kananian, A.; Rahimi, G. 2012-02-01 The style of volcanism of post-Eocene volcanism in the Alborz zone of northern Iran is different to that of Eocene volcanism (Karaj Formation). Indeed, the volcanic succession of the Abazar district, located in a narrow volcanic strip within the Alborz magmatic assemblage, is characterized by distinct mineralogical and chemical compositions linked to a complex magmatic evolution. The succession was produced by explosive eruptions followed by effusive eruptions. Two main volcanic events are recognized: (1) a thin rhyolitic ignimbritic sheet underlain by a thicker lithic breccia, and (2) lava flows including shoshonite, latite, and andesite that overlie the first event across a reddish soil horizon. Plagioclase in shoshonite (An 48-92) shows normal zoning, whereas plagioclase in latite and andesite (An 48-75) has a similar composition but shows reverse and oscillatory zoning. QUILF temperature calculations for shoshonites and andesites yield temperatures of 1035 °C and 1029 °C, respectively. The geothermometers proposed by Ridolfi et al. (2010) and Holland and Blundy (1994) yield temperatures of 960 °C and 944 °C for latitic lava, respectively. The samples of volcanic rock show a typical geochemical signature of the continental arc regime, but the andesites clearly differ from the shoshonites, the latites and the rhyolites. The mineralogical and chemical characteristics of these rocks are explained by the following petrogenesis: (1) intrusion of a hot, mantle-depth mafic (shoshonitic) magma, which differentiated in the magma chamber to produce a latitic and then a rhyolitic liquid; (2) rhyolitic ignimbritic eruptions from the top of the magma chamber, following by shoshonitic and then latitic extrusions; (3) magma mingling between the latitic and andesitic magmas, as indicated by the occurrence of andesite clasts within the latite; and (4) andesitic effusions. The youngest volcanic events in the Alborz zone show a close chemical relationship with continental arc 12. MOSAIC: An organic geochemical and sedimentological database for marine surface sediments NASA Astrophysics Data System (ADS) Tavagna, Maria Luisa; Usman, Muhammed; De Avelar, Silvania; Eglinton, Timothy 2015-04-01 Modern ocean sediments serve as the interface between the biosphere and the geosphere, play a key role in biogeochemical cycles and provide a window on how contemporary processes are written into the sedimentary record. Research over past decades has resulted in a wealth of information on the content and composition of organic matter in marine sediments, with ever-more sophisticated techniques continuing to yield information of greater detail and as an accelerating pace. However, there has been no attempt to synthesize this wealth of information. We are establishing a new database that incorporates information relevant to local, regional and global-scale assessment of the content, source and fate of organic materials accumulating in contemporary marine sediments. In the MOSAIC (Modern Ocean Sediment Archive and Inventory of Carbon) database, particular emphasis is placed on molecular and isotopic information, coupled with relevant contextual information (e.g., sedimentological properties) relevant to elucidating factors that influence the efficiency and nature of organic matter burial. The main features of MOSAIC include: (i) Emphasis on continental margin sediments as major loci of carbon burial, and as the interface between terrestrial and oceanic realms; (ii) Bulk to molecular-level organic geochemical properties and parameters, including concentration and isotopic compositions; (iii) Inclusion of extensive contextual data regarding the depositional setting, in particular with respect to sedimentological and redox characteristics. The ultimate goal is to create an open-access instrument, available on the web, to be utilized for research and education by the international community who can both contribute to, and interrogate the database. The submission will be accomplished by means of a pre-configured table available on the MOSAIC webpage. The information on the filled tables will be checked and eventually imported, via the Structural Query Language (SQL), into 13. Molecular Basis for Microbial Adhesion to Geochemical Surfaces: Computer Simulation of Pseudomonas aeruginosa Adhesion to Goethite PubMed Central Shroll, Robert M.; Straatsma, T. P. 2003-01-01 The adhesion of Pseudomonas aeruginosa to the goethite mineral is investigated using classical molecular simulation. A fragment model for goethite has been integrated into a fully atomistic membrane model. Properties for the resulting system are evaluated for a 1.5-ns simulation in the isothermal-isobaric ensemble. The response of the membrane to the presence of the mineral is investigated. Radial distribution functions are used to present an average picture of the hydrogen bonding. Orientational vectors, assigned to the saccharide groups, reveal the extent of the mineral's perturbations on the membrane. Significant structural changes were observed for the outermost saccharide groups, several of which rotate to form hydrogen bonds with the mineral surface. The structure of the inner core, and the corresponding integrity of the membrane, is maintained. The mineral surface dehydrates slightly in the presence of the membrane as saccharide hydroxyl groups compete with water molecules for hydrogen-bonding sites on its surface. PMID:12609878 14. Geochemical Relations between Surface Water and Groundwater In Fractured Rock In Nevada County, CA NASA Astrophysics Data System (ADS) Soltero, E. 2013-12-01 The Sierra Nevada foothills in the South Yuba River basin Nevada County, CA is underlain by plutonic, metabasic rocks of pre-Tertiary age. Fifty-six water samples from five sites were analyzed for spatial and temporal variations using stable isotopes of water and major element chemistry. Hydrogeochemical data from surface water and groundwater indicate site specific, depth related spatial variations. Temporal variations are evident in most surface water data and absent in most groundwater data. Data for 18O and deuterium (D) plot close to the global meteoric water line confirming a meteoric source and minimal subsequent evaporative fractionation or effects of gas-water-rock interactions. An altitude effect presented in surface and groundwater data as a 0.1 per mil decrease in δ 18O and a 0.5- 0.7 per mil decrease in δ D per 30.5 meter (100ft) increase between 305 and 884 meters (1,000 and 2,900 feet) in elevation. Major element chemistry was dominated by sodium, magnesium, and calcium bicarbonate in dilute concentrations. Most groundwater data had higher Ca/Na (1.8:1), Ca/Mg (4:3), and HCO3- /Cl- (3:1) ratios than surface water data from the same site, indicative of local gas-water-rock interactions or mixing of infiltrating water with other groundwater sources. Most deep groundwater data (>91 meters or 300ft) had similar Ca/Na (0.9:1), and higher Ca/Mg (1.6:1) and HCO3- /Cl- (1.6:1) ratios than shallow groundwater data. Most groundwater samples were under saturated or close to saturation with respect to calcite. Aqueous speciation modeling, EQ3NR version 7.2c, adjusted for lab conditions, indicated acceptable charge balance relations. Most water data are consistent with fracture flow in the granitic and metamorphic rocks of the region. Data suggest a precipitation dominated hydrologic regime where local surface waters are related to local groundwaters. Most data indicate that infiltration by way of secondary porosity contributes to groundwater production in 15. Surface water types in the Western Canadian Arctic: geochemical evolution and aquatic carbon transport NASA Astrophysics Data System (ADS) Dean, Joshua F.; Billett, Mike F.; Dinsmore, Kerry J.; Lessels, Jason S.; Street, Lorna; Washbourne, Ian; Subke, Jens-Arne; Tetzlaff, Doerthe; Baxter, Robert; Wookey, Philip A. 2015-04-01 Arctic surface waters are a substantial conduit for terrestrial C flow as well as a potential source of GHGs to the atmosphere - a significant positive feedback to global climate warming and a key component of the net ecosystem carbon balance in permafrost regions. As temperatures rise in the Arctic, permafrost thaw deepens releasing C from the landscape into the aquatic system making streams and lakes increasingly important conduits and reactors of both allochthonous and autochthonous C. The HYDRA project ('Permafrost catchments in transition: hydrological controls on carbon cycling and greenhouse gas budgets'), aims to quantify the assimilation of C and the controls of C movement between the plant-soil-water-atmosphere continuum. The specific aspect of the project presented here considers the different aquatic pathways in warming Arctic permafrost catchments, and the potential role that they play in GHG emissions and aquatic C cycling. This study presents the surface water geochemistry of Siksik Creek, a small ( 16. Mineral Ecology: Surface Specific Colonization and Geochemical Drivers of Biofilm Accumulation, Composition, and Phylogeny PubMed Central Jones, Aaron A.; Bennett, Philip C. 2017-01-01 This study tests the hypothesis that surface composition influences microbial community structure and growth of biofilms. We used laboratory biofilm reactors (inoculated with a diverse subsurface community) to explore the phylogenetic and taxonomic variability in microbial communities as a function of surface type (carbonate, silicate, aluminosilicate), media pH, and carbon and phosphate availability. Using high-throughput pyrosequencing, we found that surface type significantly controlled ~70–90% of the variance in phylogenetic diversity regardless of environmental pressures. Consistent patterns also emerged in the taxonomy of specific guilds (sulfur-oxidizers/reducers, Gram-positives, acidophiles) due to variations in media chemistry. Media phosphate availability was a key property associated with variation in phylogeny and taxonomy of whole reactors and was negatively correlated with biofilm accumulation and α-diversity (species richness and evenness). However, mineral-bound phosphate limitations were correlated with less biofilm. Carbon added to the media was correlated with a significant increase in biofilm accumulation and overall α-diversity. Additionally, planktonic communities were phylogenetically distant from those in biofilms. All treatments harbored structurally (taxonomically and phylogenetically) distinct microbial communities. Selective advantages within each treatment encouraged growth and revealed the presence of hundreds of additional operational taxonomix units (OTU), representing distinct consortiums of microorganisms. Ultimately, these results provide evidence that mineral/rock composition significantly influences microbial community structure, diversity, membership, phylogenetic variability, and biofilm growth in subsurface communities. 17. Combined geological and surface geochemical methods discover Agaritta and Brady Creek fields, Concho County, Texas SciTech Connect Saunders, D.F.; Burson, K.R.; Thompson, C.K. ); Brown, J.J. ) 1992-04-01 From December 1987 to March 1991, 25 prospects in the lower King Sandstone (Upper Pennsylvanian Cisco) play in Concho County, Texas, were tested by several operators. They used combinations of subsurface geology, reconnaissance airborne gas sensing, surface radiometrics, soil magnetic susceptibility, and soil gas hydrocarbon measurements to define prospects. Six new King Sandstone field discoveries or extensions and three deeper pay Goen Limestone field discoveries resulted in a 36% exploratory success rate. The total exploration and development cost was approximately$0.67 per bbl of proven producing oil reserves. As examples, the authors present the discovery of Brady Creek and Agaritta fields. Agaritta field is one of the two largest of the new field discoveries with estimated proven producing recoverable reserves of 6,000,000 BO. Its discovery was based on a combination of (1) airborne hydrocarbon sensing, (2) interstitial soil gas hydrocarbon data, (3) soil magnetic susceptibility measurements, and (4) surface potassium and uranium concentrations measured by gamma-ray spectrometry. Interstitial soil gas hydrocarbon anomalies combined with soil magnetic susceptibility anomalies provided the best detailed surface guidance to Agaritta field. These were supported locally by radiometric anomalies. The Brady Creek field is interpreted to be a possible crevasse splay deposit. The Aggaritta field is interpreted to be a point bar deposit. Both fields are stratigraphic traps.

18. Identification of complex molecules at surfaces

Green, F. M.; Dell, E. J.; Gilmore, I. S.; Seah, M. P.

2008-04-01

In this study, we develop a simple method using the SMILES molecular structure format to simulate fragmentation pathways in secondary ion mass spectrometry (SIMS). These pathways are found to have good agreement with fragmentation pathways identified using G-SIMS-FPM (Fragmentation Pathway Mapping) using the two examples of folic acid and Irganox 1010. G-SIMS is an easy-to-use method that considerably simplifies complex static SIMS spectra. G-SIMS-FPM allows the molecular structure to be re-assembled by following fragmentation pathways as the G-SIMS surface plasma temperature is varied. The simulated pathways help reduce the wide choice of possible structures faced by analysts as the molecular structure is reassembled, leading to more reliable molecular identification. A rapid method to establish a foundation database of simulated pathways using the community and a web-based system is proposed.

19. Heavy metal assessment using geochemical and statistical tools in the surface sediments of Vembanad Lake, Southwest Coast of India.

PubMed

Selvam, A Paneer; Priya, S Laxmi; Banerjee, Kakolee; Hariharan, G; Purvaja, R; Ramesh, R

2012-10-01

The geochemical distribution and enrichment of ten heavy metals in the surface sediments of Vembanad Lake, southwest coast of India was evaluated. Sediment samples from 47 stations in the Lake were collected during dry and wet seasons in 2008 and examined for heavy metal content (Al, Fe, Mn, Cr, Zn, Ni, Pb, Cu, Co, Cd), organic carbon, and sediment texture. Statistically significant spatial variation was observed among all sediment variables, but negligible significant seasonal variation was observed. Correlation analysis showed that the metal content of sediments was mainly regulated by organic carbon, Fe oxy-hydroxides, and grain size. Principal component analysis was used to reduce the 14 sediment variables into three factors that reveal distinct origins or accumulation mechanisms controlling the chemical composition in the study area. Pollution intensity of the Vembanad Lake was measured using the enrichment factor and the pollution load index. Severe and moderately severe enrichment of Cd and Zn in the north estuary with minor enrichment of Pb and Cr were observed, which reflects the intensity of the anthropogenic inputs related to industrial discharge into this system. The results of pollution load index reveal that the sediment was heavily polluted in northern arm and moderately polluted in the extreme end and port region of the southern arm of the lake. A comparison with sediment quality guideline quotient was also made, indicating that there may be some ecotoxicological risk to benthic organisms in these sediments.

20. Remote sensing and geochemical investigations of selected surface processes in Egypt and Missouri

Crombie, Mary Katherine

This thesis consists of three studies of surface processes on Earth: 1. Age and isotopic constraints of pluvial episodes in the Western Desert of Egypt. North Africa has undergone drastic climatic change over the past several hundred thousand years. Timing of humid intervals called pluvials was investigated by uranium- series disequilibrium dating of travertines from the Kurkur Oasis, Western Desert, Egypt. Stable oxygen isotopes of the travertines were used in equilibrium oxygen isotope fractionation calculations indicating the Kurkur travertines have δ18O values similar to ancient Western Desert groundwaters (~[- ]11/perthous). The ages of the of the travertines correspond to times of monsoonal maxima, eustatic sea level high stands and interglacial maxima. Increased precipitation, recharge of Western Desert groundwaters, and resultant travertine deposition are interpreted to be consequences of Milankovitch cycle forcing, through enhanced Atlantic and Indian Ocean monsoons during periods of enhanced northern summer insolation. 2. Identification of soil moisture as an environmental risk factor for filariasis in Egypt. Bancroftian filariasis is a deforming illness transmitted by mosquitoes (Culex. pipiens) and caused by the parasite Wuchereria bancrofti (WHO technical report 821; Neva and Brown, 1994). Environmental variables, such as humidity, play an important role in the transmission cycle of filariasis. Landsat Thematic Mapper data were used to model the surface soil moisture conditions of the southern Nile Delta region of Egypt as a proxy for environmental humidity. Filariasis infection rates were found to be negligible for areas with low surface soil moisture availability (>20%). Variable infection rates were observed for regions with higher surface soil moisture content, possibly due to anthropogenic influences such as insect control and the use of anti- filarial drugs. 3. Monitoring of Pb aerosol fallout in the vicinity of the Glover smelter, Southeastern

1. Maghemite soil nodules reveal the impact of fire on mineralogical and geochemical differentiation at the Earth's surface

Löhr, Stefan C.; Murphy, David T.; Nothdurft, Luke D.; Bolhar, Robert; Piazolo, Sandra; Siegel, Coralie

2017-03-01

Fires occur frequently over large parts of the Earth's surface. They potentially exert a significant influence on the mineralogical and geochemical characteristics of an environment that is otherwise considered to be dominated by low temperature processes. We test this hypothesis by comparing the mineralogy and geochemistry of (i) magnetic, iron-rich soil nodules, (ii) non-magnetic iron soil nodules and (iii) a published dataset of surficial sediments from eastern Australia. Maghemite-rich nodules are present in soils from around the world. It has been argued that they are thermal alteration products of non-magnetic precursors, but this remains controversial. We use detailed petrographic and mineralogical analyses to demonstrate that maghemite occurs as part of a high temperature mineral assemblage including hematite and χ-alumina, within a magnetic nodule microfabric indicative of fire-induced dehydroxylation and sintering of non-magnetic precursors at temperatures of up to 600 °C. The genetic link between magnetic and non-magnetic nodules means that their comparison offers insights into the geochemical impact of fire. Our results show that magnetic nodules are depleted in Si, Y, Zr and HREE but enriched in Fe and Cr relative to non-magnetic nodules that occur in close spatial proximity. Magnetic nodules also show variable but distinctly low Y/Ho (21.4 ± 0.4) and Zr/Hf (29.3 ± 0.8) as well as anomalously low La relative to the other LREE. In situ laser ablation analyses show that this is largely due to the presence of χ-alumina that is depleted in HREEs and has extremely low Y/Ho (mainly <20), as well as the low Zr/Hf of χ-alumina and the maghemite-hematite matrix, with no involvement from zircon. We propose a multi-stage process of formation where fire transforms non-magnetic nodule precursors into proto-magnetic nodules. This is associated with thermal transformation of clays as well as Fe and Al oxyhydroxides, followed by isochemical segregation into a

2. Diatom and Geochemical Constraints on Pliocene Sea Surface Conditions on the Wilkes Land Margin, East Antarctica

Riesselman, C. R.; Taylor-Silva, B.

2015-12-01

The mid-Pliocene is the most recent interval in Earth's history to sustain global temperatures within the range of warming predicted for the 21st century, providing an appealing analog with which to examine the changes we might encounter in the coming century. Diatom-based Southern Ocean sea surface and sea ice reconstructions by the USGS Pliocene Research Interpretations and Synoptic Mapping (PRISM) Group suggest an average +2° summer SST anomaly during the 3.3-3.0 Ma interval relative to modern. Here, we present a reconstruction of Pliocene sea surface conditions from a marine sediment core collected at IODP Site U1361, on the continental rise of the Wilkes Land margin. U1361 biogenic silica concentrations document the alternation of diatom-rich and diatom-poor lithologies; we interpret 8 diatom-rich mudstones within this sequence to record interglacial conditions between 3.8 and 2.8 Ma, across the transition from obliquity control to precession control on East Antarctic ice volumes. This progression also preserves 3 packages of interglacial sediments within the 3.3-3.0 PRISM interval, providing an opportunity for direct comparison to proximal PRISM site Eltanin 50-28. Diatom assemblages in both cores are characterized by Fragilariopsis barronii and Rouxia antarctica, extinct species with an inferred ecological preference for waters south of the polar front. However F. weaveri, an extinct diatom with inferred preference for more northerly waters and moderate abundance in E50-28, has not been identified at U1361. This may indicate that the polar frontal zone migrated across E50-28 (62° 54'S) but remained north of U1361 (64° 25'S) during the mid-Pliocene. This interpretation is bolstered by the low abundance of extant polar front species (e.g., Thalassiosira oliverana, T. lentiginosa) at U1361; these diatoms dominate the E50-28 assemblage. In contrast, the U1361 assemblage includes a number of extant sea ice indicators (F. sublinearis, F. curta, Chaetoceros

3. The cancrinite-syenite/carbonatite complex of Lueshe, Kivu/NE-Zaire: petrographic and geochemical studies and its economic significance

Maravic, H. v.; Morteani, G.; Roethe, G.

The Luesche cancrinite-syenite/carbonatite complex is located in NE-Zaire about 50 km SSW of Lake Edward. The alkaline rocks have intruded metamorphic rocks of Burundian age (1.100 m.y.). The country rocks are quartzites and mica schists bearing chlorite, garnet, Kyanite and staurolite, which indicates P-T conditions of some 4 kbar and 430-500°C, maximum 6 kbar and 620°C. The K/Ar age of the biotites from the carbonatite is found to be 516 m.y. The core of the alkaline complex is composed of cancrinite-syenites which vary from place to place with respect to the contents of garnet, amphibole, aegirine, sodalite and cancrinite. Significant variations of the pyrochlore content are also observed. The core is surrounded by fine grained calcitic carbonatite (alvikite) which often shows a banded texture and grades into coarse grained calcitic carbonatite (søvite). In the SE of the søvite ring there is a separate dolomitic carbonatite body (beforsite) while at the contacts between the alkaline rocks and the country rocks a wide range of low to high grade fenites enriched in Na or K occurs. Within the alkaline complex the highest niobium values are found associated with metasomatic rocks of the contact zones such as carbosyenites, pyroxentic rocks and fenites. The main niobium mineral is a Ca, Na-pyrochlore enriched in Ti and/or Sr. The geochemical distribution patterns of the major elements as well as of the trace elements, especially the REE, suggests that the carbonatites are of primary magmatic origin derived from mantle material which was affected by later remobilizations, most likely as a result of postmagmatic hydrothermal solutions. Regarding the cancrinite-syenites, there is no evidence for a comagmatic formation with the carbonatites. They are rather of subcrustal origin; formed in the course of various metasomatic processes where the alkalic carbonate melts or volatile carbonate phases interacted with the metamorphic country rocks to form rheomorphic syenites

4. Geochemical Assessment of Trace Element Pollution in Surface Sediments from the Georges River, Southern Sydney, Australia.

PubMed

Alyazichi, Yasir M; Jones, Brian G; McLean, Errol; Pease, Joel; Brown, Heidi

2017-02-01

Measurement of elevated trace elements is an important component of environmental assessment and management of estuarine marine sediments in systems adjacent to concentrated human activity. The present study surveys the estuarine sediments in selected tributary bays, creeks, and the upper segments of the Georges River system, NSW, Australia, which flows into the Tasman Sea through Botany Bay. A total of 146 surface sediment samples were analysed by X-ray fluorescence. Potential pollution of sediments was evaluated using potential load index, modified degree of contamination, and potential ecological risk index. The spatial distribution of trace elements varies between sites. Variable sources of contamination, including runoff from catchment areas, and emissions from watercraft and boatyards are contributing sources. Bay morphologies and their interactions with catchment and tidal flows play significant roles in the distribution of trace elements. The greatest concentration of trace elements occurs around discharge points and in the inner parts of bays that have high percentages of mud particles and organic matter. The lowest contamination by trace elements was found in sandy sediments along the shoreline and edges of the bays. Trace element distributions decline in concentration in residential-free areas and reach background levels in deeper sediment cores. The concentrations of trace elements were controlled by discharge points from the catchment area, marine boat activities, bay morphology, and sediment types (sand, silt, and clay). The highest pollutant concentrations are the result of past legal, but uncontrolled, discharge of waste from manufacturing into Salt Pan Creek.

5. Geochemical diversity of shergottite basalts: Mixing and fractionation, and their relation to Mars surface basalts

Treiman, Allan H.; Filiberto, Justin

2015-04-01

The chemical compositions of shergottite meteorites, basaltic rocks from Mars, provide a broad view of the origins and differentiation of these Martian magmas. The shergottite basalts are subdivided based on their Al contents: high-Al basalts (Al > 5% wt) are distinct from low-Al basalts and olivine-phyric basalts (both with Al < 4.5% wt). Abundance ratios of highly incompatible elements (e.g., Th, La) are comparable in all the shergottites. Abundances of less incompatible elements (e.g., Ti, Lu, Hf) in olivine-phyric and low-Al basalts correlate well with each other, but the element abundance ratios are not constant; this suggests mixing between components, both depleted and enriched. High-Al shergottites deviate from these trends consistent with silicate mineral fractionation. The "depleted" component is similar to the Yamato-980459 magma; approximately, 67% crystal fractionation of this magma would yield a melt with trace element abundances like QUE 94201. The "enriched" component is like the parent magma for NWA 1068; approximately, 30% crystal fractionation from it would yield a melt with trace element abundances like the Los Angeles shergottite. This component mixing is consistent with radiogenic isotope and oxygen fugacity data. These mixing relations are consistent with the compositions of many of the Gusev crater basalts analyzed on Mars by the Spirit rover (although with only a few elements to compare). Other Mars basalts fall off the mixing relations (e.g., Wishstone at Gusev, Gale crater rocks). Their compositions imply that basalt source areas in Mars include significant complexities that are not present in the source areas for the shergottite basalts.

6. Geochemical Signature of Land-based Activities in Caribbean Coral Surface Samples

Prouty, N. G.; Hughen, K.; Carilli, J.

2007-12-01

Anthropogenic threats to the Mesoamerican Caribbean Reef Ecoregion, resulting from increased sedimentation, agrochemical run-off, coastal development, tourism and overfishing, are of great concern for future coral reef health and sustainability. Abundances of trace metal in corals can be used to monitor and identify the impact of land-based activities on the reef itself. In this study we demonstrate that surface coral samples from four sites in the Mesoamerican Caribbean Reef Ecoregion, Turneffe Atoll, Sapodilla Cayes and Honduras Bay Islands (Utila and Cayos Cochinos), yield statistically different chemical signatures due to their water quality and relative distance from pollution sources. Specifically, samples from the Sapodilla Cayes and the Bay Islands of Honduras yield elevated Ba/Ca and Mn/Ca levels, indicative of greater exposure to sediment-laden runoff form the south. In a similar manner, elevated coral Pb/Ca and Zn/Ca, and Sb/Ca and Cu/Ca values can be linked to mining activities and the use of antifouling paints, respectively. In addition, site heterogeneity was investigated by analyzing replicate cores at a single site from different colonies. We show that regional variability within the Sapodilla Cayes Marine Reserve can be explained by relative location and orientation within the reef and distance from the continental shelf. Our results indicate good reproducibility for the majority of trace metals investigated (not including Sr/Ca or Mg/Ca), suggesting that local environmental changes such as seawater chemistry, and not climate, is the dominant influence on the metal/Ca ratios.

7. Parameterizing surface wind speed over complex topography

Helbig, N.; Mott, R.; Herwijnen, A.; Winstral, A.; Jonas, T.

2017-01-01

Subgrid parameterizations are used in coarse-scale meteorological and land surface models to account for the impact of unresolved topography on wind speed. While various parameterizations have been suggested, these were generally validated on a limited number of measurements in specific geographical areas. We used high-resolution wind fields to investigate which terrain parameters most affect near-surface wind speed over complex topography under neutral conditions. Wind fields were simulated using the Advanced Regional Prediction System (ARPS) on Gaussian random fields as model topographies to cover a wide range of terrain characteristics. We computed coarse-scale wind speed, i.e., a spatial average over the large grid cell accounting for influence of unresolved topography, using a previously suggested subgrid parameterization for the sky view factor. We only require correlation length of subgrid topographic features and mean square slope in the coarse grid cell. Computed coarse-scale wind speed compared well with domain-averaged ARPS wind speed. To further statistically downscale coarse-scale wind speed, we use local, fine-scale topographic parameters, namely, the Laplacian of terrain elevations and mean square slope. Both parameters showed large correlations with fine-scale ARPS wind speed. Comparing downscaled numerical weather prediction wind speed with measurements from a large number of stations throughout Switzerland resulted in overall improved correlations and distribution statistics. Since we used a large number of model topographies to derive the subgrid parameterization and the downscaling framework, both are not scale dependent nor bound to a specific geographic region. Both can readily be implemented since they are based on easy to derive terrain parameters.

8. Scale-Dependent Rates of Uranyl Surface Complexation Reaction in Sediments

SciTech Connect

Liu, Chongxuan; Shang, Jianying; Kerisit, Sebastien N.; Zachara, John M.; Zhu, Weihuang

2013-03-15

Scale-dependency of uranyl[U(VI)] surface complexation rates was investigated in stirred flow-cell and column systems using a U(VI)-contaminated sediment from the US Department of Energy, Hanford site, WA. The experimental results were used to estimate the apparent rate of U(VI) surface complexation at the grain-scale and in porous media. Numerical simulations using molecular, pore-scale, and continuum models were performed to provide insights into and to estimate the rate constants of U(VI) surface complexation at the different scales. The results showed that the grain-scale rate constant of U(VI) surface complexation was over 3 to 10 orders of magnitude smaller, dependent on the temporal scale, than the rate constant calculated using the molecular simulations. The grain-scale rate was faster initially and slower with time, showing the temporal scale-dependency. The largest rate constant at the grain-scale decreased additional 2 orders of magnitude when the rate was scaled to the porous media in the column. The scaling effect from the grain-scale to the porous media became less important for the slower sorption sites. Pore-scale simulations revealed the importance of coupled mass transport and reactions in both intragranular and inter-granular domains, which caused both spatial and temporal dependence of U(VI) surface complexation rates in the sediment. Pore-scale simulations also revealed a new rate-limiting mechanism in the intragranular porous domains that the rate of coupled diffusion and surface complexation reaction was slower than either process alone. The results provided important implications for developing models to scale geochemical/biogeochemical reactions.

9. Characterization of surface-water quality in the S-Line Canal and potential geochemical reactions from storage of surface water in the Basalt aquifer near Fallon, Nevada

USGS Publications Warehouse

Welch, Alan H.; Maurer, Douglas K.; Lico, Michael S.; McCormack, John K.

2005-01-01

The Fallon basalt aquifer serves as the sole source of municipal water supply for the Lahontan Valley in west-central Nevada. Principal users include the City of Fallon, Naval Air Station Fallon, and the Fallon Paiute-Shoshone Tribe. Pumpage from the aquifer increased from about 1,700 acre-feet per year in the early 1970's to more than 3,000 acre-feet per year in the late 1990's, and has been accompanied by declines in water levels and changes in water quality. Storage of surface water in the basalt may mitigate the effects of pumpage, but may cause undesirable changes in water chemistry. In May 2001, the U.S. Geological Survey began a study, in cooperation with the Fallon Paiute-Shoshone Tribe, to characterize the surface-water quality of the S-Line Canal, a likely source of water for augmenting recharge. Because arsenic concentrations in ground water of the basalt aquifer exceed drinking water standards, the potential for arsenic release to artificial recharge was explored by using geochemical modeling. Model results suggest that arsenic release may increase concentrations to levels that could limit the use of artificial recharge. Field-based experiments are needed to evaluate the underlying model assumptions.

10. GEOQUÌMICO : an interactive tool for comparing sorption conceptual models (surface complexation modeling verus K[D]).

SciTech Connect

Hammond, Glenn E.; Cygan, Randall Timothy

2007-11-01

Within reactive geochemical transport, several conceptual models exist for simulating sorption processes in the subsurface. Historically, the K{sub D} approach has been the method of choice due to ease of implementation within a reactive transport model and straightforward comparison with experimental data. However, for modeling complex sorption phenomenon (e.g. sorption of radionuclides onto mineral surfaces), this approach does not systematically account for variations in location, time, or chemical conditions, and more sophisticated methods such as a surface complexation model (SCM) must be utilized. It is critical to determine which conceptual model to use; that is, when the material variation becomes important to regulatory decisions. The geochemical transport tool GEOQUIMICO has been developed to assist in this decision-making process. GEOQUIMICO provides a user-friendly framework for comparing the accuracy and performance of sorption conceptual models. The model currently supports the K{sub D} and SCM conceptual models. The code is written in the object-oriented Java programming language to facilitate model development and improve code portability. The basic theory underlying geochemical transport and the sorption conceptual models noted above is presented in this report. Explanations are provided of how these physicochemical processes are instrumented in GEOQUIMICO and a brief verification study comparing GEOQUIMICO results to data found in the literature is given.

11. Utilizing hydrologic, statistical, and geochemical tools to assess uranium mobility in surface and near-surface environments

Naftz, D. L.; Walton-Day, K. E.; Fuller, C.; Dam, W. L.; Briggs, M. A.; Snyder, T.

2015-12-01

Legacy uranium (U) mining and processing activities have resulted in soil and water contamination on Federal, state, and tribal lands in the western United States. Sites include legacy mill sites associated with U extraction now managed by the Department of Energy and thousands of waste dumps associated with U exploration, mining, and processing. Recently (2012), over 400,000 hectares of federally managed land in northern Arizona was withdrawn from consideration of mining for a 20-year period to protect the Grand Canyon watershed from potentially adverse effects of U mineral exploration and development. Ore from active and recently active U mines in the Colorado Plateau, the Henry Mountains Complex, and the Arizona Strip is transported to the only currently (2015) active conventional mill site in the western United States, located in Utah. Previous and ongoing U.S. Geological Survey assessments to examine U mobility at a variety of legacy and active sites associated with ore exploration, extraction, and processing will be presented as field-scale examples. Topics associated with site investigations will include: (1) offsite migration of radionuclides associated with the operation of the White Mesa U mill; (2) long-term contaminant transport from legacy U waste dumps on Bureau of Land Management regulated land in Utah; (3) application of incremental soil sampling techniques to determine pre- and post-mining radionuclide levels associated with planned and operating U mines in northern Arizona; (4) application of fiber optic digital temperature sensing equipment to identify areas where shallow groundwater containing elevated U levels may be discharging to a river adjacent to a reclaimed mill site in central Wyoming; and (5) field-scale manipulation of groundwater chemistry to limit U migration from a legacy upgrader site in southeastern Utah.

12. Uranyl adsorption and surface speciation at the imogolite-water interface: Self-consistent spectroscopic and surface complexation models

USGS Publications Warehouse

Arai, Y.; McBeath, M.; Bargar, J.R.; Joye, J.; Davis, J.A.

2006-01-01

Macro- and molecular-scale knowledge of uranyl (U(VI)) partitioning reactions with soil/sediment mineral components is important in predicting U(VI) transport processes in the vadose zone and aquifers. In this study, U(VI) reactivity and surface speciation on a poorly crystalline aluminosilicate mineral, synthetic imogolite, were investigated using batch adsorption experiments, X-ray absorption spectroscopy (XAS), and surface complexation modeling. U(VI) uptake on imogolite surfaces was greatest at pH ???7-8 (I = 0.1 M NaNO3 solution, suspension density = 0.4 g/L [U(VI)]i = 0.01-30 ??M, equilibration with air). Uranyl uptake decreased with increasing sodium nitrate concentration in the range from 0.02 to 0.5 M. XAS analyses show that two U(VI) inner-sphere (bidentate mononuclear coordination on outer-wall aluminol groups) and one outer-sphere surface species are present on the imogolite surface, and the distribution of the surface species is pH dependent. At pH 8.8, bis-carbonato inner-sphere and tris-carbonato outer-sphere surface species are present. At pH 7, bis- and non-carbonato inner-sphere surface species co-exist, and the fraction of bis-carbonato species increases slightly with increasing I (0.1-0.5 M). At pH 5.3, U(VI) non-carbonato bidentate mononuclear surface species predominate (69%). A triple layer surface complexation model was developed with surface species that are consistent with the XAS analyses and macroscopic adsorption data. The proton stoichiometry of surface reactions was determined from both the pH dependence of U(VI) adsorption data in pH regions of surface species predominance and from bond-valence calculations. The bis-carbonato species required a distribution of surface charge between the surface and ?? charge planes in order to be consistent with both the spectroscopic and macroscopic adsorption data. This research indicates that U(VI)-carbonato ternary species on poorly crystalline aluminosilicate mineral surfaces may be important in

13. Combined Use of GIS, Hydrostratigraphic, Geochemical, and Multi-Isotope Analysis for Groundwater Preservation and Development in a Complex Karst Setting

Murgulet, D.; Cook, M. R.

2011-12-01

The complex stratigraphy and geologic structure characteristic to fractured karst aquifers underlying an urban part of the north-central Alabama Valley and Ridge Setting make the development and protection of groundwater sources difficult. In this area, population growth accompanied by increased impervious surfaces, storm water runoff, contaminants, subsidence, and pumping rates have rendered the groundwater resource. The potential for aquifer recharge and flow conditions were evaluated in order to determine the current and future alternative water sources available in this area. Geochemical and multi-isotope techniques were coupled with hydrostratigraphic and geomorphic spatial (GIS) analyses to determine the primary mechanisms controlling recharge and flow and evaluate seasonal impacts on groundwater resources and recharge environments. Groundwater samples, collected in summer and fall (2010) from wells developed in the Bangor Limestone and Tuscumbia Fort Payne aquifers (north-central Alabama), were analyzed for major ions, stable isotopes of oxygen (δ^18O), hydrogen (δD), and carbon (δ^13C), and anthropogenic isotopes such as chlorofluorocarbon (CFCs) and sulphur hexafluoride (SF_6). Stable isotope investigations suggest that recharge occurs under relatively closed conditions, with fast percolation rates in short periods (characteristic to karst aquifers) and low evaporation rates during the colder seasons. The average δ^13C value (-11.4±2% PDB, n=9) lies near the combined average δ^13C values of soil CO_2 and the carbonate. Therefore, groundwater δ^13C signature is mainly controlled by two factors: soil CO_2 and carbonate dissolution. Static water levels decrease over the summer causing drawdowns (2 to 5.2 meters) in all the production wells and a slight shift of the δ^18O and δD values towards a more positive member (summer range--δ^18O: -5.1±0.1 to -5.7±0.1% VSMOW, n=11; δD: -25.0±1 to -30.6±1% VSMOW, n=11 and fall range--δ^18O: -4.8±0.1 to

14. A geochemical constraint on the formation process of a manganese carbonate nodule in the siliceous mudstone of the Jurassic accretionary complex in the Mino Belt, Japan

Nakada, Ryoichi; Shirai, Taka'aki; Takahashi, Satoshi; Suzuki, Noritoshi; Ogawa, Kazuhiro; Takahashi, Yoshio

2014-12-01

Manganese (Mn) carbonate nodules, which differ from seafloor Mn nodules mainly composed of MnO2, are occasionally embedded in the form of a lens shape in the Jurassic accretionary complexes, such as the Mino Belt in Japan. The interpretation of the formation process of Mn carbonate is still controversial, particularly concerning whether the Mn carbonate was formed primarily or secondarily. In this study, a fresh Mn carbonate nodule incorporated into the red siliceous mudstone was collected for geochemical and sedimentological analysis. The optical observation of thin sections indicates that the Mn carbonate nodules are composed of abraded grains of rhodochrosite spherule with radiolarians and are sedimentary embedded in siliceous mudstone. Microfossil radiolarians from the Mn carbonate nodules and the host red siliceous mudstone are dated as the Bajocian, but the radiolarians in the nodules are somewhat older than those in the host red siliceous mudstone. Geochemical analysis using the X-ray absorption near-edge structure on Ce indicates the dominance of trivalent Ce at present, despite the observation of a positive Ce anomaly in the PAAS-normalized REE pattern of Mn carbonate. The REE adsorption experiment on synthesized MnCO3 does not show any distinctive positive Ce anomaly, and a thermodynamic calculation suggests the possible coexistence of rhodochrosite and spontaneous oxidation of Ce. A leaching experiment that can selectively decompose the carbonate phase demonstrated no Ce anomaly in the carbonate phase of the Mn carbonate and a poor contribution to the bulk REE concentration. The carbon isotope data of Mn carbonate nodule implied the dominance of inorganic marine carbonate origin with small contribution of organic decomposition. The most plausible account of all of the observational and geochemical results is that the rhodochrosite grains were primarily formed on the depositional site and subsequently transferred to a different site, where siliceous

15. Petrogenesis of coeval silica-saturated and silica-undersaturated alkaline rocks: Mineralogical and geochemical evidence from the Saima alkaline complex, NE China

Zhu, Yu-Sheng; Yang, Jin-Hui; Sun, Jin-Feng; Zhang, Ji-Heng; Wu, Fu-Yuan

2016-03-01

A combined study of zircon U-Pb ages, mineral chemistry, whole-rock elements and Sr-Nd-Hf isotopes was carried out for the Saima alkaline complex in the northeastern China, in order to investigate the source and petrogenesis of coeval silica-saturated and silica-undersaturated alkaline rocks. The Saima alkaline complex consists of nepheline syenites, quartz-bearing syenites and alkaline volcanic rocks (i.e., phonolite and trachyte), with minor mafic dikes and carbonatitic veins. Laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) and secondary ion mass spectrometry (SIMS) zircon U-Pb dating gives consistent ages of 230-224 Ma for these rocks, suggesting that they are coeval. All alkaline rocks in the Saima complex are enriched in large ion lithophile elements (LILEs) and light rare earth elements (LREEs), and depleted in high field strength elements (HFSEs) with significant negative Nb, Ta and Ti anomalies. Geochemical data and Sr-Nd-Hf isotopic compositions indicate that the various alkaline rocks were all derived from partial melting of an ancient, re-enriched lithospheric mantle in the garnet stability field, but experienced variable siliceous- or carbonate-rich crustal contamination. Based on petrographic evidence, mineral compositions, and whole-rock geochemical data, two distinct magmatic evolutionary trends are proposed to explain the coeval emplacement of the various rock types within the Saima alkaline complex. The silica-undersaturated rocks (nepheline syenites and phonolites) result from alkali feldspar + apatite + titanite crystal fractionation of an alkaline mafic parental melt combined with assimilation of marine carbonate host rocks. In contrast, the generation of silica-saturated rocks (quartz-bearing syenites and trachytes) may be attributed to subsequent and continued clinopyroxene + apatite + biotite crystal fractionation coupled with assimilation of siliceous sediments.

16. Geochemical processes in ground water resulting from surface mining of coal at the Big Sky and West Decker Mine areas, southeastern Montana

USGS Publications Warehouse

Clark, D.W.

1995-01-01

A potential hydrologic effect of surface mining of coal in southeastern Montana is a change in the quality of ground water. Dissolved-solids concen- trations in water in spoils aquifers generally are larger than concentrations in water in the coal aquifers they replaced; however, laboratory experiments have indicated that concentrations can decrease if ground water flows from coal-mine spoils to coal. This study was conducted to determine if decreases in concentrations occur onsite and, if so, which geochemical processes caused the decreases. Solid-phase core samples of spoils, unmined over- burden, and coal, and ground-water samples were collected from 16 observation wells at two mine areas. In the Big Sky Mine area, changes in ground- water chemistry along a flow path from an upgradient coal aquifer to a spoils aquifer probably were a result of dedolomitization. Dissolved-solids concentrations were unchanged as water flowed from a spoils aquifer to a downgradient coal aquifer. In the West Decker Mine area, dissolved-solids concentrations apparently decreased from about 4,100 to 2,100 milligrams per liter as water moved along an inferred flow path from a spoils aquifer to a downgradient coal aquifer. Geochemical models were used to analyze changes in water chemistry on the basis of results of solid-phase and aqueous geochemical characteristics. Geochemical processes postulated to result in the apparent decrease in dissolved-solids concentrations along this inferred flow path include bacterial reduction of sulfate, reverse cation exchange within the coal, and precipitation of carbonate and iron-sulfide minerals.

17. Surface complexation modeling of Cd(II) sorption to montmorillonite, bacteria, and their composite

Wang, Ning; Du, Huihui; Huang, Qiaoyun; Cai, Peng; Rong, Xingmin; Feng, Xionghan; Chen, Wenli

2016-10-01

Surface complexation modeling (SCM) has emerged as a powerful tool for simulating heavy metal adsorption processes on the surface of soil solid components under different geochemical conditions. The component additivity (CA) approach is one of the strategies that have been widely used in multicomponent systems. In this study, potentiometric titration, isothermal adsorption, zeta potential measurement, and extended X-ray absorption fine-structure (EXAFS) spectra analysis were conducted to investigate Cd adsorption on 2 : 1 clay mineral montmorillonite, on Gram-positive bacteria Bacillus subtilis, and their mineral-organic composite. We developed constant capacitance models of Cd adsorption on montmorillonite, bacterial cells, and mineral-organic composite. The adsorption behavior of Cd on the surface of the composite was well explained by CA-SCM. Some deviations were observed from the model simulations at pH < 5, where the values predicted by the model were lower than the experimental results. The Cd complexes of X2Cd, SOCd+, R-COOCd+, and R-POCd+ were the predominant species on the composite surface over the pH range of 3 to 8. The distribution ratio of the adsorbed Cd between montmorillonite and bacterial fractions in the composite as predicted by CA-SCM closely coincided with the estimated value of EXAFS at pH 6. The model could be useful for the prediction of heavy metal distribution at the interface of multicomponents and their risk evaluation in soils and associated environments.

18. Motion of clusters on complex surfaces

Alkis, Sabri; Krause, Jeffrey; Cheng, Hai-Ping

2007-03-01

Polymer and organic molecule assemblies have been investigated intensely in the past decade, due to their vast range of applications in nano-molecular electronics and as bio-sensors. In particular, self-assembled monolyers (SAMs) of alkanethiol on the Au(111) surface are used widely in surface studies because they are simple structurally, stable thermodynamically and have well-defined order. In this project, inspired by recent experiments, we use classical molecular dynamics simulations to study motions of Agn clusters with various sizes on the alkanthiol SAMs. We report detailed results on dynamics, diffusion, and sintering processes of these nano-clusters.

19. Mineralogical and geochemical evidence for hydrothermal activity at the west wall of 12°50′N core complex (Mid-Atlantic ridge): a new ultramafic-hosted seafloor hydrothermal deposit?

USGS Publications Warehouse

Dekov, Vesselin; Boycheva, Tanya; Halenius, Ulf; Billstrom, Kjell; Kamenov, George D.; Shanks, Wayne C.; Stummeyer, Jens

2011-01-01

Dredging along the west wall of the core complex at 12°50′N Mid-Atlantic Ridge sampled a number of black oxyhydroxide crusts and breccias cemented by black and dark brown oxyhydroxide matrix. Black crusts found on top of basalt clasts (rubble) are mainly composed of Mn-oxides (birnessite, 10-Å manganates) with thin films of nontronite and X-ray amorphous FeOOH on their surfaces. Their chemical composition (low trace- and rare earth-element contents, high Li and Ag concentrations, rare earth element distribution patterns with negative both Ce and Eu anomalies), Sr–Nd–Pb-isotope systematic and O-isotope data suggest low-temperature (~ 20 °C) hydrothermal deposition from a diffuse vent area on the seafloor. Mineralogical, petrographic and geochemical investigations of the breccias showed the rock clasts were hydrothermally altered fragments of MORBs. Despite the substantial mineralogical changes caused by the alteration the Sr–Nd–Pb-isotope ratios have not been significantly affected by this process. The basalt clasts are cemented by dark brown and black matrix. Dark brown cement exhibits geochemical features (very low trace- and rare earth- element contents, high U concentration, rare earth element distribution pattern with high positive Eu anomaly) and Nd–Pb-isotope systematics (similar to that of MORB) suggesting that the precursor was a primary, high-temperature Fe-sulfide, which was eventually altered to goethite at ambient seawater conditions. The data presented in this work points towards the possible existence of high- and low-temperature hydrothermal activity at the west wall of the core complex at 12°50′N Mid-Atlantic Ridge. Tectonic setting at the site implies that the proposed hydrothermal field is possibly ultramafic-hosted.

20. Peat porewaters have contrasting geochemical fingerprints for groundwater recharge and discharge due to matrix diffusion in a large, northern bog-fen complex

Levy, Zeno F.; Siegel, Donald I.; Glaser, Paul H.; Samson, Scott D.; Dasgupta, Soumitri S.

2016-10-01

Although northern peatlands represent a globally significant reservoir for carbon, considerable uncertainty exists concerning solute transport systems within large (>1000 km2) peat deposits. We therefore delineated geochemical gradients linked to groundwater recharge and discharge along a 6 km transect within the 1200 km2 Red Lake Peatland of northwestern Minnesota. We used ratios of Ca/Mg and 87Sr/86Sr to distinguish discharge of calcareous groundwater (∼1.4 and 0.7155, respectively) to the peatland from the mineral substratum along a topographic gradient from a bog crest downslope to an internal fen water track and bog islands. In contrast, the stable isotopes of the porewaters (δ18O from -12.8 ‰ to -7.8 ‰) show that the active pore-spaces in these peat profiles have been flushed by recharge from the near-surface peat. We hypothesize that back-diffusion of groundwater-derived solutes from the peat matrix to active pore-spaces has allowed the geochemical signal from paleo-hydrogeologic discharge to persist into the current regime of dilute recharge. This effect has not been observed previously on the landform-scale and has important implications for carbon cycling in peatlands.

1. Geochemical characterization of surface water and spring water in SE Kashmir Valley, western Himalaya: Implications to water-rock interaction

Jeelani, Gh; Bhat, Nadeem A.; Shivanna, K.; Bhat, M. Y.

2011-10-01

Water samples from precipitation, glacier melt, snow melt, glacial lake, streams and karst springs were collected across SE of Kashmir Valley, to understand the hydrogeochemical processes governing the evolution of the water in a natural and non-industrial area of western Himalayas. The time series data on solute chemistry suggest that the hydrochemical processes controlling the chemistry of spring waters is more complex than the surface water. This is attributed to more time available for infiltrating water to interact with the diverse host lithology. Total dissolved solids (TDS), in general, increases with decrease in altitude. However, high TDS of some streams at higher altitudes and low TDS of some springs at lower altitudes indicated contribution of high TDS waters from glacial lakes and low TDS waters from streams, respectively. The results show that some karst springs are recharged by surface water; Achabalnag by the Bringi stream and Andernag and Martandnag by the Liddar stream. Calcite dissolution, dedolomitization and silicate weathering were found to be the main processes controlling the chemistry of the spring waters and calcite dissolution as the dominant process in controlling the chemistry of the surface waters. The spring waters were undersaturated with respect to calcite and dolomite in most of the seasons except in November, which is attributed to the replenishment of the CO2 by recharging waters during most of the seasons.

2. Surface complexation of Pb(II) by hexagonal birnessite nanoparticles

SciTech Connect

Kwon, K.; Refson, K.; Sposito, G.

2010-10-15

Natural hexagonal birnessite is a poorly-crystalline layer type Mn(IV) oxide precipitated by bacteria and fungi which has a particularly high adsorption affinity for Pb(II). X-ray spectroscopic studies have shown that Pb(II) forms strong inner-sphere surface complexes mainly at two sites on hexagonal birnessite nanoparticles: triple corner-sharing (TCS) complexes on Mn(IV) vacancies in the interlayers and double edge-sharing (DES) complexes on lateral edge surfaces. Although the TCS surface complex has been well characterized by spectroscopy, some important questions remain about the structure and stability of the complexes occurring on the edge surfaces. First-principles simulation techniques such as density functional theory (DFT) offer a useful way to address these questions by providing complementary information that is difficult to obtain by spectroscopy. Following this computational approach, we used spin-polarized DFT to perform total-energy-minimization geometry optimizations of several possible Pb(II) surface complexes on model birnessite nanoparticles similar to those that have been studied experimentally. We first validated our DFT calculations by geometry optimizations of (1) the Pb-Mn oxyhydroxide mineral, quenselite (PbMnO{sub 2}OH), and (2) the TCS surface complex, finding good agreement with experimental structural data while uncovering new information about bonding and stability. Our geometry optimizations of several protonated variants of the DES surface complex led us to conclude that the observed edge-surface species is very likely to be this complex if the singly-coordinated terminal O that binds to Pb(II) is protonated. Our geometry optimizations also revealed that an unhydrated double corner-sharing (DCS) species that has been proposed as an alternative to the DES complex is intrinsically unstable on nanoparticle edge surfaces, but could become stabilized if the local coordination environment is well-hydrated. A significant similarity exists

3. Surface complexation of Pb(II) by hexagonal birnessite nanoparticles

Kwon, Kideok D.; Refson, Keith; Sposito, Garrison

2010-12-01

Natural hexagonal birnessite is a poorly crystalline layer type Mn(IV) oxide precipitated by bacteria and fungi which has a particularly high adsorption affinity for Pb(II). X-ray spectroscopic studies have shown that Pb(II) forms strong inner-sphere surface complexes mainly at two sites on hexagonal birnessite nanoparticles: triple corner-sharing (TCS) complexes on Mn(IV) vacancies in the interlayers and double edge-sharing (DES) complexes on lateral edge surfaces. Although the TCS surface complex has been well characterized by spectroscopy, some important questions remain about the structure and stability of the complexes occurring on the edge surfaces. First-principles simulation techniques such as density functional theory (DFT) offer a useful way to address these questions by providing complementary information that is difficult to obtain by spectroscopy. Following this computational approach, we used spin-polarized DFT to perform total-energy-minimization geometry optimizations of several possible Pb(II) surface complexes on model birnessite nanoparticles similar to those that have been studied experimentally. We first validated our DFT calculations by geometry optimizations of (1) the Pb-Mn oxyhydroxide mineral, quenselite (PbMnO 2OH), and (2) the TCS surface complex, finding good agreement with experimental structural data while uncovering new information about bonding and stability. Our geometry optimizations of several protonated variants of the DES surface complex led us to conclude that the observed edge-surface species is very likely to be this complex if the singly coordinated terminal O that binds to Pb(II) is protonated. Our geometry optimizations also revealed that an unhydrated double corner-sharing (DCS) species that has been proposed as an alternative to the DES complex is intrinsically unstable on nanoparticle edge surfaces, but could become stabilized if the local coordination environment is well-hydrated. A significant similarity exists in

4. Subduction- and non-subduction-related igneous rocks in the Central European Variscides: geochemical and Nd isotope evidence from the Kłodzko Metamorphic Complex, Polish Sudetes

Kryza, Ryszard; Mazur, Stanisław; Pin, Christian

2003-11-01

The Kłodzko Metamorphic Complex (KMC) in the Central Sudetes is a composite outcrop of pre-Upper Devonian metasedimentary and metaigneous rocks, formed of several thrust units. The metaigneous rocks are geochemically diversified, and were interpreted to reflect a complex geodynamic setting of emplacement. The association of large amounts of felsic and mafic rocks is reminiscent of the model of Cambro-Ordovician bimodal, rift-related suites developed along the northern periphery of Gondwana. However, the felsic rocks are potash-poor, calc-alkaline in character, while the associated mafic rocks are, in part, metagabbros and cumulates resembling N-MORB, which is consistent with neither typical ensialic rift nor evolved MOR tectonic environments. Combined with published data, our new geochemical and Nd isotope results show that the metabasic rocks of the northeastern part of the KMC, not associated with felsic volcanics, are of within-plate type, with an ɛNd 400 (assuming approximate youngest possible Silurian/Devonian age) of +6.8, typical of magmas derived from time-integrated depleted mantle sources. The metagabbros of the southwestern part of the KMC (associated with felsic rocks) range from slightly enriched to depleted rocks, and their ɛNd 560 (assuming a Neoproterozoic age, K. Turniak, personal communication) scatters from +2.2 to +8.6, suggesting that hybrid sources and/or variable degrees of crustal contamination of a strongly depleted mantle source were involved. The intermediate and acidic rocks are peraluminous to metaluminous rhyolites, rhyodatites/dacites, and andesites (and volcaniclastics), with Na 2O > K 2O and large negative anomalies of Nb, Sr, and Ti. Their highly variable, but distinctly positive, ɛNd 560 values (from +2.9 to +8.6, mostly clustered around +5.5) overlap those measured in the associated metagabbros, thereby substantiating close genetic relationships. Metarhyolites produced by crustal melting are conspicuously missing. A

5. Effect on Groundwater Quality from Proximal Surface Water Bodies and Effect on Arsenic Distribution in Bangladesh: Geochemical Controls

Barua, S.; Kulkarni, H.; Mladenov, N.; Khan, M. A.; Mahfuz, M.; Ahmed, K. M.; Datta, S.

2014-12-01

Matlab is one of the areas in SE Bangladesh highly affected with elevated concentrations of dissolved As in drinking waters. Matlab is stratigraphically composed of thick floodplain deposits of Holocene age overlying Plio-Pleistocene grey fine to coarse sands with considerable clay (Dupi Tila). The dissolved As concentrations in the studied area ranged from <1 to 3644 μg/l and more than 70% of functioning tubewells exceeded the WHO guideline of 10 μg/l. To test the hypothesis that young labile organic carbon (LOC) accelerates As release in reducing aquifer systems as long as As-bearing iron oxides/hydroxides are available, we collected 19 groundwater (depths from 14 to 240 m) and 9 surface water (8 pond and 1 canal in proximity to the piezeometer nests) samples from 4 nests in north and south Matlab, respectively, during monsoon months (Jun-Jul, 2014). Dissolved organic carbon (DOC), fluorescent properties of dissolved organic matter (DOM) and fecal indicator bacteria (FIB) (e.g., E. coli) counts using field ColilertTM test kits were undertaken to understand the chemical character and potential sources of dissolved organic matter (DOM) in groundwater and surface waters. DOC concentrations were high (1.5-12.2 mg/l) in shallow aquifers (14-33 m) where dissolved As ranged from 100-500 µg/l. DOC concentrations were lower (0.7-4.2 mg/l) in intermediate to deeper depths (52-240 m) with lower As concentrations of 0-50 µg/l. In surface water bodies, the range of DOC was 2.9-8.1 mg/l. MPN based analyses for both ground and surface waters indicate the frequency of E. coli detection in shallow well waters (MPN= 3.6-74.1) was high as well as in ponds and canals (MPN= 8.5-433.4). Microbial activity in groundwater was lower than in unprotected surface waters. Freshness index (β:α), humification index (HIX), fluorescence source index (FI) values showed that DOM in shallow and surface water bodies was distinct from deep groundwater. Concurrent with the lower DOC in deeper

6. Near-surface electromagnetic, rock magnetic, and geochemical fingerprinting of submarine freshwater seepage at Eckernförde Bay (SW Baltic Sea)

Müller, Hendrik; von Dobeneck, Tilo; Nehmiz, Wiebke; Hamer, Kay

2011-04-01

Submarine groundwater discharge in coastal settings can massively modify the hydraulic and geochemical conditions of the seafloor. Resulting local anomalies in the morphology and physical properties of surface sediments are usually explored with seismo-acoustic imaging techniques. Controlled source electromagnetic imaging offers an innovative dual approach to seep characterization by its ability to detect pore-water electrical conductivity, hence salinity, as well as sediment magnetic susceptibility, hence preservation or diagenetic alteration of iron oxides. The newly developed electromagnetic (EM) profiler Neridis II successfully realized this concept for a first time with a high-resolution survey of freshwater seeps in Eckernförde Bay (SW Baltic Sea). We demonstrate that EM profiling, complemented and validated by acoustic as well as sample-based rock magnetic and geochemical methods, can create a crisp and revealing fingerprint image of freshwater seepage and related reductive alteration of near-surface sediments. Our findings imply that (1) freshwater penetrates the pore space of Holocene mud sediments by both diffuse and focused advection, (2) pockmarks are marked by focused freshwater seepage, underlying sand highs, reduced mud thickness, higher porosity, fining of grain size, and anoxic conditions, (3) depletion of Fe oxides, especially magnetite, is more pervasive within pockmarks due to higher concentrations of organic and sulfidic reaction partners, and (4) freshwater advection reduces sediment magnetic susceptibility by a combination of pore-water injection (dilution) and magnetite reduction (depletion). The conductivity vs. susceptibility biplot resolves subtle lateral litho- and hydrofacies variations.

7. Surface Complexation Modeling of Radionuclide Sorption in the Saturated Zone of Yucca Mountain Rocks

Ding, M.; Kelkar, S.; Fabryka-Martin, J. T.; Caporuscio, F. A.; Meijer, A.

2008-12-01

The U.S. DOE is preparing to submit a license application to the Nuclear Regulatory Commission (NRC) to create a geologic repository at the Yucca Mountain, Nevada, for the disposal of spent nuclear fuel and high- level radioactive waste. In the event of a radionuclide release, the ground water beneath the Yucca Mountain is the primary medium through which most radionuclides might move from the geologic repository to the accessible environment. Sorption of radionuclides onto rock surfaces is one of the important processes affecting the transport in the saturated zone of Yucca Mountain (SZ). For this reason, a considerable experimental effort has been devoted over the last two decades to the measurements of sorption distribution coefficients (Kd) for various radionuclides in rock samples from the vicinity of the repository site at the Yucca Mountain. Despite the quantity and quality of the data, they are strictly valid only under the experimental conditions at which they were measured, whereas the Kd distributions used as inputs in performance assessment calculations need to represent the range of geochemical conditions and rock types expected to occur along the transport pathways. Hence geochemical modeling was used to calculate and predict chemical speciation of elements of interest in solid and solution under a variety of different conditions. The computer code PHREEQC v2.3 and the thermodynamic database PHREEQCDATA025.DAT were used for this geochemical modeling. The modeling provides a basis for extrapolating the experimentally derived Kd's, and provides improved understanding of the underlying sorption mechanisms, thus justifying and defending the Kd's selected for further radionuclide transport modeling development. This presentation focuses on the elements Am, U, Np and Pu which sorb in the SZ primarily via surface complexation reactions. We discuss quantitatively the influence of groundwater compositions, rock surface area, binding constants, and

8. Surface Complexation Modeling of Radionuclide Sorption in the Saturated Zone of Yucca Mountain Rocks

Ding, M.; Kelkar, S.; Fabryka-Martin, J.; Caporuscio, F.; Meijer, A.

2007-12-01

The U.S. DOE is preparing to submit a license application to the Nuclear Regulatory Commission (NRC) to create a geologic repository at the Yucca Mountain, Nevada, for the disposal of spent nuclear fuel and high-level radioactive waste. In the event of a radionuclide release, the ground water beneath the Yucca Mountain is the primary medium through which most radionuclides might move from the geologic repository to the accessible environment. Sorption of radionuclides onto rock surfaces in the saturated zone of Yucca Mountain (SZ) is one of the most important processes retarding their release to the accessible environment. For this reason, a considerable experimental effort has been devoted over the last two decades to the measurements of sorption distribution coefficients (Kd) for various radionuclides in rock samples from the vicinity of the repository site at the Yucca Mountain. Despite the quantity and quality of the data, they are strictly valid only under the experimental conditions at which they were measured, whereas the Kd distributions used as inputs in performance assessment calculations need to represent the range of geochemical conditions and rock types expected to occur along the transport pathways. Hence geochemical modeling was used to calculate and predict chemical speciation of elements of interest in solid and solution under a variety of different conditions. The computer code PHREEQC v2.3 and the thermodynamic database PHREEQCDATA025.DAT were used for this geochemical modeling. The modeling provides a basis for extrapolating the experimentally derived Kd's, and provides improved understanding of the underlying sorption mechanisms, thus justifying and defending the Kd's selected for further radionuclide transport modeling development. This presentation focuses on the elements Am, U, Np and Pu which sorb in the SZ primarily via surface complexation reactions. We discuss quantitatively the influence of groundwater compositions, rock surface area

9. Analysis of gold(I/III)-complexes by HPLC-ICP-MS demonstrates gold(III) stability in surface waters.

PubMed

Ta, Christine; Reith, Frank; Brugger, Joël; Pring, Allan; Lenehan, Claire E

2014-05-20

Understanding the form in which gold is transported in surface- and groundwaters underpins our understanding of gold dispersion and (bio)geochemical cycling. Yet, to date, there are no direct techniques capable of identifying the oxidation state and complexation of gold in natural waters. We present a reversed phase ion-pairing HPLC-ICP-MS method for the separation and determination of aqueous gold(III)-chloro-hydroxyl, gold(III)-bromo-hydroxyl, gold(I)-thiosulfate, and gold(I)-cyanide complexes. Detection limits for the gold species range from 0.05 to 0.30 μg L(-1). The [Au(CN)2](-) gold cyanide complex was detected in five of six waters from tailings and adjacent monitoring bores of working gold mines. Contrary to thermodynamic predictions, evidence was obtained for the existence of Au(III)-complexes in circumneutral, hypersaline waters of a natural lake overlying a gold deposit in Western Australia. This first direct evidence for the existence and stability of Au(III)-complexes in natural surface waters suggests that Au(III)-complexes may be important for the transport and biogeochemical cycling of gold in surface environments. Overall, these results show that near-μg L(-1) enrichments of Au in environmental waters result from metastable ligands (e.g., CN(-)) as well as kinetically controlled redox processes leading to the stability of highly soluble Au(III)-complexes.

10. Metrology of complex astigmatic surfaces for astronomical optics

Rolt, Stephen; Kirby, Andrew K.; Robertson, David J.

2010-07-01

This paper will focus on the metrology of multiple complex surfaces that are to be integrated into the KBand Multi- Object Spectrograph (KMOS). KMOS is a multi-field astronomical spectrograph designed for integration with the 8.2m diameter European Southern Observatory Very Large Telescope (VLT). There are 1080 separate optical surfaces in the design, many of them complex freeform surfaces. Optical surfaces were manufactured in aluminium by precision freeform diamond machining. This flexible technique allows the fabrication of extremely complex surfaces with an accuracy of better than 15 nm RMS over a 20 mm aperture, giving the designer great freedom in generating powerful and unorthodox designs. However, the complexity of these freeform surfaces poses a challenge to their accurate characterisation. This paper will discuss in detail the metrology of a specific freeform component in the instrument. The form of these complex astigmatic surfaces was measured using spherical wavefronts by adapting a tilted Twyman-Green Interferometer arrangement. There are eight separate designs for this type of component, each with a different orientation and magnitude of astigmatism. Careful mechanical fixturing is essential to align the astigmatic axis to the test set up. The impact of mechanical tolerances on measurement uncertainty will be discussed in detail.

11. Floodplain complexity and surface metrics: influences of scale and geomorphology

USGS Publications Warehouse

Scown, Murray W.; Thoms, Martin C.; DeJager, Nathan R.

2015-01-01

Many studies of fluvial geomorphology and landscape ecology examine a single river or landscape, thus lack generality, making it difficult to develop a general understanding of the linkages between landscape patterns and larger-scale driving variables. We examined the spatial complexity of eight floodplain surfaces in widely different geographic settings and determined how patterns measured at different scales relate to different environmental drivers. Floodplain surface complexity is defined as having highly variable surface conditions that are also highly organised in space. These two components of floodplain surface complexity were measured across multiple sampling scales from LiDAR-derived DEMs. The surface character and variability of each floodplain were measured using four surface metrics; namely, standard deviation, skewness, coefficient of variation, and standard deviation of curvature from a series of moving window analyses ranging from 50 to 1000 m in radius. The spatial organisation of each floodplain surface was measured using spatial correlograms of the four surface metrics. Surface character, variability, and spatial organisation differed among the eight floodplains; and random, fragmented, highly patchy, and simple gradient spatial patterns were exhibited, depending upon the metric and window size. Differences in surface character and variability among the floodplains became statistically stronger with increasing sampling scale (window size), as did their associations with environmental variables. Sediment yield was consistently associated with differences in surface character and variability, as were flow discharge and variability at smaller sampling scales. Floodplain width was associated with differences in the spatial organization of surface conditions at smaller sampling scales, while valley slope was weakly associated with differences in spatial organisation at larger scales. A comparison of floodplain landscape patterns measured at different

12. Mars Geochemical Instrument (MarGI): An instrument for the analysis of the Martian surface and the search for evidence of life

NASA Technical Reports Server (NTRS)

Kojiro, Daniel R.; Mancinelli, Rocco; Martin, Joe; Holland, Paul M.; Stimac, Robert M.; Kaye, William J.

2005-01-01

The Mars Geochemical Instrument, MarGI, was developed to provide a comprehensive analysis of the rocks and surface material on Mars. The instrument combines Differential Thermal Analysis (DTA) with miniature Gas Chromatography-Ion Mobility Spectrometry (GC-IMS) to identify minerals, the presence and state of water, and organic compounds. Miniature pyrolysis ovens are used to both, conduct DTA analysis of soil or crushed rocks samples, and pyrolyze the samples at temperatures up to 1000 degrees C for GC-IMS analysis of the released gases. This combination of analytical processes and techniques, which can characterize the mineralogy of the rocks and soil, and identify and quantify volatiles released during pyrolysis, has applications across a wide range of target sites including comets, planets, asteroids, and moons such as Titan and Europa. The MarGI analytical approach evolved from the Cometary Ice and Dust Experiment (CIDEX) selected to fly on the Comet Rendezvous Asteroid Flyby Mission (CRAF).

13. Trace metal contamination in surface sediments of intertidal zone from Qinhuangdao, China, revealed by geochemical and magnetic approaches: Distribution, sources, and health risk assessment.

PubMed

Zhu, Zongmin; Xue, Junhui; Deng, Yuzhen; Chen, Lin; Liu, Jiangfeng

2016-04-15

Based on geochemical and magnetic approaches, the distribution, sources, and health risk of trace metals in surface sediments from a seashore tourist city were investigated. A significant correlation was found between magnetic susceptibility (χ) and trace metals, which suggested that levels of trace metals in the sediments can be effectively depicted by the magnetic approach. The spatial distribution of χ and trace metals matched well with the city layout with relatively higher values being found in the port and busy tourist areas. This result, together with enrichment factors (EFs) and Tomlinson pollution load index (PLI) of metals, suggested that the influence of human activities on the coastal environment was noticeable. Principal component analysis (PCA) indicated that trace metals in the sediments were derived from both anthropogenic and natural sources. Noncarcinogenic risk assessment showed that there was no potential health risk of exposure to metals by means of ingestion or inhalation.

14. Complexity and Fermi surface deformation in compressed lithium

Rodriguez-Prieto, A.; Bergara, A.; Silkin, V. M.; Echenique, P. M.

2006-11-01

Recently reported structural complexity and enhanced temperature superconducting transitions in lithium under pressure have increased the interest in light alkalies, otherwise considered as simple and well-known systems under normal conditions. Here we present an analysis of the pressure-induced Fermi surface deformation in lithium and its relation to the observed complexity. According to our calculations, the Fermi surface becomes increasingly anisotropic with pressure and at 8GPa contacts the Brillouin zone boundary inducing a Hume-Rothery mechanism explaining the bcc-fcc transition. Around 30GPa increasing cooper-like necks and an extended nesting are observed in the Fermi surface in the fcc phase, enhancing the electronic susceptibility response function and inducing a strong phonon softening. This softening, besides preluding the transition to complex structures and providing a better understanding of the observed superconductivity, is expected to induce other yet unexplored anomalies in compressed lithium.

15. Geochronological and geochemical constraints on the origin of clastic meta-sedimentary rocks associated with the Yuanjiacun BIF from the Lüliang Complex, North China

Wang, Changle; Zhang, Lianchang; Dai, Yanpei; Lan, Caiyun

2015-01-01

The Lüliang Complex is situated in the central part of the western margin of the Trans-North China Orogen (TNCO) in the North China Craton (NCC), and consists of metamorphic volcanic and sedimentary rocks and granitoid intrusions. The Yuanjiacun Formation metasediments occupy roughly the lowest part of the Lüliang Group and are mainly represented by well-bedded meta-pelites (chlorite schists and sericite-chlorite phyllites), banded iron formations (BIFs) and meta-arenites (sericite schists), which have undergone greenschist-facies metamorphism. The youngest group of detrital zircons from the meta-arenite samples constrains their maximum depositional age at ~ 2350 Ma. In combination with previous geochronological studies on meta-volcanic rocks in the overlying Jinzhouyu Formation, the depositional age of the Yuanjiacun Formation can be constrained between 2350 and 2215 Ma. The metasediments have suffered varying degrees of source weathering, measured using widely employed weathering indices (e.g., CIA, CIW, PIA and Th/U ratios). Source rocks of the low-Al meta-pelites have undergone severe chemical weathering, whereas those of the meta-arenites and high-Al meta-pelites have suffered relatively moderate chemical weathering. Significant secondary K addition is recognized in the A-CN-K diagram for most of the studied samples. Diagnostic geochemical features like the Al2O3/TiO2 values, trace element ratios (e.g., Th/Sc) and REE patterns, suggest that the meta-arenites and high-Al meta-pelites are predominantly derived from felsic igneous sources, whereas the low-Al meta-pelites are sourced mainly from mafic rocks. Coupled with Nd isotopic data, it is proposed that the meta-arenites and high-Al meta-pelites were sedimentary erosion products of the less differential felsic terrain (likely the old upper continental crust). The low-Al meta-pelites, however, have geochemical affinities with both pelite- and BIF-like components, suggesting that they were mixtures of these

16. Unusual evolution of silica-under- and -oversaturated alkaline rocks in the Cenozoic Ambohimirahavavy Complex (Madagascar): Mineralogical and geochemical evidence

Estrade, Guillaume; Béziat, Didier; Salvi, Stefano; Tiepolo, Massimo; Paquette, Jean-Louis; Rakotovao, Soatsitohaina

2014-10-01

The almost unknown Ambohimirahavavy ring complex in the Cenozoic alkaline province of northwestern Madagascar has recently attracted considerable interest because of the discovery of important rare-metal mineralization. The complex consists of arc-shaped bodies made up of silica-under- and -oversaturated syenites and extremely evolved peralkaline granitic dykes, as well as several mafic to felsic volcanic units, including basalt, phonolite and trachyte, all of which have an alkaline affinity. Uranium-lead zircon ages of 24.2 ± 0.6 Ma and 23.5 ± 6.8 Ma have been obtained for nepheline syenites and peralkaline granitic dykes, respectively, which, together with field data and ages of neighboring complexes, support emplacement controlled by regional lithospheric structures, rather than an evolving hot spot. Whole-rock major and trace-element and Sr-Nd isotopic data for the mafic suite suggest that the parental melt of this complex was generated by low degrees of melting of a metasomatized mantle source with residual amphibole. Fractional crystallization of this alkali basaltic melt likely produced the silica-undersaturated suite. We propose that the silica-oversaturated suite evolved from the undersaturated melt after contamination of the latter by crustal material. Further evolution to peralkaline compositions in both suites is attributed mainly to plagioclase and alkali feldspar segregation. Nepheline and feldspar compositions, as well as considerations of mineral equilibria among mafic silicates and Fe-Ti oxide minerals indicate crystallization temperatures of 1000 to 700 °C and an oxygen fugacity of 0.4 to 0.8 log units below the fayalite-magnetite-quartz (FMQ) buffer at 1 kbar for the silica-undersaturated melt, and temperatures of 860 to 570 °C and an oxygen fugacity of 1.5 to 3.8 log units below FMQ for the oversaturated syenitic melt. The undersaturated melt evolved towards a more peralkaline composition. Crystallization of arfvedsonite plus aegirine

17. Deduction of static surface roughness from complex excess attenuation.

PubMed

Nichols, Andrew; Attenborough, Keith; Taherzadeh, Shahram

2011-03-01

Data for complex excess attenuation have been used to determine the effective surface admittance and hence characteristic roughness size of a surface comprising a random distribution of semi-cylindrical rods on an acoustically hard plane. The inversion for roughness size is based on a simplified boss model. The technique is shown to be effective to within 4%, up to a threshold roughness packing density of 32%, above which the interaction between scattering elements appears to exceed that allowed by the model.

18. Surface grid generation for complex three-dimensional geometries

Luh, Raymond Ching-Chung

1988-10-01

An outline is presented for the creation of surface grids from primitive geometry data such as obtained from CAD/CAM systems. The general procedure is applicable to any geometry including full aircraft with wing, nacelle, and empennage. When developed in an interactive graphics environment, a code based on this procedure is expected to substantially improve the turn around time for generating surface grids on complex geometries. Results are shown for a general hypersonic airplane geometry.

19. Sensitivity of geological, geochemical and hydrologic parameters in complex reactive transport systems for in-situ uranium bioremediation

Yang, G.; Maher, K.; Caers, J.

2015-12-01

Groundwater contamination associated with remediated uranium mill tailings is a challenging environmental problem, particularly within the Colorado River Basin. To examine the effectiveness of in-situ bioremediation of U(VI), acetate injection has been proposed and tested at the Rifle pilot site. There have been several geologic modeling and simulated contaminant transport investigations, to evaluate the potential outcomes of the process and identify crucial factors for successful uranium reduction. Ultimately, findings from these studies would contribute to accurate predictions of the efficacy of uranium reduction. However, all these previous studies have considered limited model complexities, either because of the concern that data is too sparse to resolve such complex systems or because some parameters are assumed to be less important. Such simplified initial modeling, however, limits the predictive power of the model. Moreover, previous studies have not yet focused on spatial heterogeneity of various modeling components and its impact on the spatial distribution of the immobilized uranium (U(IV)). In this study, we study the impact of uncertainty on 21 parameters on model responses by means of recently developed distance-based global sensitivity analysis (DGSA), to study the main effects and interactions of parameters of various types. The 21 parameters include, for example, spatial variability of initial uranium concentration, mean hydraulic conductivity, and variogram structures of hydraulic conductivity. DGSA allows for studying multi-variate model responses based on spatial and non-spatial model parameters. When calculating the distances between model responses, in addition to the overall uranium reduction efficacy, we also considered the spatial profiles of the immobilized uranium concentration as target response. Results show that the mean hydraulic conductivity and the mineral reaction rate are the two most sensitive parameters with regard to the overall

20. Surface complexation modeling or organic acid sorption to goethite

SciTech Connect

Evanko, C.R.; Dzombak, D.A.

1999-06-15

Surface complexation modeling was performed using the Generalized Two-Layer Model for a series of low molecular weight organic acids. Sorption of these organic acids to goethite was investigated in a previous study to assess the influence of particular structural features on sorption. Here, the ability to describe the observed sorption behavior for compounds with similar structural features using surface complexation modeling was investigated. A set of surface reactions and equilibrium constants yielding optimal data fits was obtained for each organic acid over a range of total sorbate concentrations. Surface complexation modeling successfully described sorption of a number of the simple organic acids, but an additional hydrophobic component was needed to describe sorption behavior of some compounds with significant hydrophobic character. These compounds exhibited sorption behavior of some compounds with significant hydrophobic character. These compounds exhibited sorption behavior that was inconsistent with ligand exchange mechanisms since sorption behavior of some compounds with significant hydrophobic character. These compounds exhibited sorption behavior that was inconsistent with ligand exchange mechanisms since sorption did not decrease with increasing total sorbate concentration and/or exceeded surface site saturation. Hydrophobic interactions appeared to be most significant for the compound containing a 5-carbon aliphatic chain. Comparison of optimized equilibrium constants for similar surface species showed that model results were consistent with observed sorption behavior: equilibrium constants were highest for compounds having adjacent carboxylic groups, lower for compounds with adjacent phenolic groups, and lowest for compounds with phenolic groups in the ortho position relative to a carboxylic group. Surface complexation modeling was also performed to fit sorption data for Suwannee River fulvic acid. The data could be described well using reactions and

1. Surface Complexation Modeling of Organic Acid Sorption to Goethite.

PubMed

Evanko; Dzombak

1999-06-15

Surface complexation modeling was performed using the Generalized Two-Layer Model for a series of low molecular weight organic acids. Sorption of these organic acids to goethite was investigated in a previous study to assess the influence of particular structural features on sorption. Here, the ability to describe the observed sorption behavior for compounds with similar structural features using surface complexation modeling was investigated. A set of surface reactions and equilibrium constants yielding optimal data fits was obtained for each organic acid over a range of total sorbate concentrations. Surface complexation modeling successfully described sorption of a number of the simple organic acids, but an additional hydrophobic component was needed to describe sorption behavior of some compounds with significant hydrophobic character. These compounds exhibited sorption behavior that was inconsistent with ligand exchange mechanisms since sorption did not decrease with increasing total sorbate concentration and/or exceeded surface site saturation. Hydrophobic interactions appeared to be most significant for the compound containing a 5-carbon aliphatic chain. Comparison of optimized equilibrium constants for similar surface species showed that model results were consistent with observed sorption behavior: equilibrium constants were highest for compounds having adjacent carboxylic groups, lower for compounds with adjacent phenolic groups, and lowest for compounds with phenolic groups in the ortho position relative to a carboxylic group. Surface complexation modeling was also performed to fit sorption data for Suwannee River fulvic acid. The data could be described well using reactions and constants similar to those for pyromellitic acid. This four-carboxyl group compound may be useful as a model for fulvic acid with respect to sorption. Other simple organic acids having multiple carboxylic and phenolic functional groups were identified as potential models for humic

2. A Comparative Analysis of the Influence of Surface Mining on Hydrological and Geochemical Response of Selected Headwater Streams in the Elk Valley, British Columbia, Canada.

Carey, S. K.; Shatilla, N. J.; Szmudrowska, B.; Rastelli, J.; Wellen, C.

2014-12-01

Surface mining is a common method of accessing coal. Blasting of overburden rock allows access to mineable ore. In high-elevation environments, the removed overburden rock is deposited in adjacent valleys as waste rock spoils. As part of a multi-year R&D program examining the influence of surface mining on watershed hydrological and water quality responses in the Elk Valley, British Columbia, this study reports on how surface mining affects streamflow hydrological and geochemical response at four reference and four mine-influenced catchments. The hydrology of this environment is dominated by snowmelt and steep topographic gradients. Flows were attenuated in mine-influenced catchments, with spring freshet delayed and more muted responses to precipitation events observed. Dissolved ions were an order of magnitude greater in mine-influenced streams, with more dilution-based responses to flows compared with chemostatic behavior observed in reference streams. Stable isotope signatures in stream water suggested that in both mine-influenced and reference watersheds, stream water was derived from well mixed groundwater as annual variability of stream isotope signatures was dampened compared with precipitation signatures. However, deflection of stream isotopes in response to precipitation were more apparent in reference watersheds. As a group, mine influenced catchments had a heavier isotope signature than reference watersheds, suggesting an enhanced influence of rainfall on recharge. Transit time distributions indicate existing waste rock spoils increase the average time water takes to move through the catchment.

3. Surface complexation of organic arsenic on nanocrystalline titanium oxide.

PubMed

Jing, Chuanyong; Meng, Xiaoguang; Liu, Suqin; Baidas, Salem; Patraju, Ravi; Christodoulatos, Christos; Korfiatis, George P

2005-10-01

The adsorption mechanisms of monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) on nanocrystalline titanium oxide (TiO2) were investigated with X-ray absorption spectroscopy (XAS), surface charge and zeta potential measurements, adsorption edge, and surface complexation modeling. XAS data demonstrated that MMA and DMA formed bidentate and monodentate inner sphere complexes with the TiO2 surface, respectively. The charge and zeta potential behaviors of TiO2 as a function of ionic strength suggested that the point of zero charge (PZC) and isoelectric point (IEP) of TiO2 were identical at pH 5.8. Adsorption of MMA and DMA on TiO2 shifted the IEP to pH 4.1 and 4.8, respectively, indicating the formation of negatively charged surface complexes. A satisfactory interpretation of the experimental data was provided by the charge distribution (CD) multi-site complexation (MUSIC) model with the triple plane option under the constraint of the XAS evidence.

4. A complex origin for the Kelso Dunes, Mojave National Preserve, California, USA: A case study using a simple geochemical method with global applications

Muhs, Daniel R.; Lancaster, Nicholas; Skipp, Gary L.

2017-01-01

The Kelso Dune field in southern California is intriguing because although it is of limited areal extent ( 100 km2), it has a wide variety of dune forms and contains many active dunes ( 40 km2), which is unusual in the Mojave Desert. Studies over the past eight decades have concluded that the dunes are derived primarily from a single source, Mojave River alluvium, under a dominant, westerly-to-northwesterly wind regime. The majority of these studies did not, however, present data to support the Mojave River as the only source. We conducted mineralogical and geochemical studies of most of the 14 geomorphically defined dune groups of the Kelso Dune field as well as potential sand sources, alluvial sediments from the surrounding mountain ranges. Results indicate that sands in the nine western dune groups have K/Rb and K/Ba (primarily from K-feldspar) compositions that are indistinguishable from Mojave River alluvium (westerly/northwesterly winds) and Budweiser Wash alluvium (southwesterly winds), permitting an interpretation of two sources. In contrast, sands from the five eastern dune groups have K/Rb and K/Ba values that indicate significant inputs from alluvial fan deposits of the Providence Mountains. This requires either rare winds from the east or southeast or, more likely, aeolian reworking of distal Providence Mountain fan sediments by winds from the west, at a rate greater than input from the Mojave River or other western sources. The results indicate that even a small dune field can have a complex origin, either from seasonally varying winds or complex alluvial-fan-dune interaction. Application of K/Rb and K/Ba in K-feldspar as a provenance indicator could be used in many of the world's ergs or sand seas, where dune origins are still not well understood or are controversial. Four examples are given from Africa and the Middle East where such an approach could yield useful new information about dune sand provenance.

5. Prelimilary Geological and Geochemical Data from the Cangaldag Complex (Kastamonu-Turkey): Implications for the Geodynamic Evolution of the Central Pontides

Cimen, Okay; Sayit, Kaan; Goncuoglu, M. Cemal

2015-04-01

The Cangaldag Complex, one of the tectonic units lying in the Central Pontides of the Sakarya Composite Terrane, comprises variably deformed and metamorphosed rocks of mostly magmatic origin. These lithologies include both extrusive and intrusive varieties as well as volcaniclastic types, with a wide range of compositions from felsic to mafic. Petrographically the complex consists of diverse rock types, including basalt, tuff, diabase, gabbro, andesite, and rhyo-dacite. The mafic lithologies generally appear to be affected by greenschist facies metamorphism with typical assemblage of ab+act+chl+ep. A well-developed schistosity is observed in some cases. The dacitic types are generally slightly metamorphic, displaying porphyritic textures with quartz and feldspar phenocrysts embedded in a fine-grained groundmass. Mylonitic varieties of this type are also found. On the basis of geochemistry, the Cangaldag samples are of sub-alkaline character and represented by both primitive and evolved members. All rock types are variably depleted in Nb compared to LREE, similar to the lavas from subduction-related tectonic settings. In N-MORB normalized plots, the primitive members are separated into 3 groups on the basis of levels of enrichment. The first group display highly depleted characteristics akin to boninitic lavas. The second group is relatively enriched compared to the first group but still depleted than N-MORB. The third group, however, is the most enriched among the three, whose level of enrichment is around N-MORB. The overall geochemical features suggest that the Cangaldag meta-igneous rocks have been generated in an intra-oceanic system with the involvement of a subduction-modified mantle source. The chemistry of the primitive members further indicate that the melt generation within the Cangaldag Unit probably occurred on both arc and back-arc regions of the Intra-Pontide supra-subduction zone.

6. Arc-continent collision and the formation of continental crust: A new geochemical and isotopic record from the Ordovician Tyrone Igneous Complex, Ireland

USGS Publications Warehouse

Draut, Amy E.; Clift, Peter D.; Amato, Jeffrey M.; Blusztajn, Jerzy; Schouten, Hans

2009-01-01

Collisions between oceanic island-arc terranes and passive continental margins are thought to have been important in the formation of continental crust throughout much of Earth's history. Magmatic evolution during this stage of the plate-tectonic cycle is evident in several areas of the Ordovician Grampian-Taconic orogen, as we demonstrate in the first detailed geochemical study of the Tyrone Igneous Complex, Ireland. New U-Pb zircon dating yields ages of 493 2 Ma from a primitive mafic intrusion, indicating intra-oceanic subduction in Tremadoc time, and 475 10 Ma from a light rare earth element (LREE)-enriched tonalite intrusion that incorporated Laurentian continental material by early Arenig time (Early Ordovician, Stage 2) during arc-continent collision. Notably, LREE enrichment in volcanism and silicic intrusions of the Tyrone Igneous Complex exceeds that of average Dalradian (Laurentian) continental material that would have been thrust under the colliding forearc and potentially recycled into arc magmatism. This implies that crystal fractionation, in addition to magmatic mixing and assimilation, was important to the formation of new crust in the Grampian-Taconic orogeny. Because similar super-enrichment of orogenic melts occurred elsewhere in the Caledonides in the British Isles and Newfoundland, the addition of new, highly enriched melt to this accreted arc terrane was apparently widespread spatially and temporally. Such super-enrichment of magmatism, especially if accompanied by loss of corresponding lower crustal residues, supports the theory that arc-continent collision plays an important role in altering bulk crustal composition toward typical values for ancient continental crust. ?? 2009 Geological Society of London.

7. Metal-organic complexes in geochemical processes: Calculation of standard partial molal thermodynamic properties of aqueous acetate complexes at high pressures and temperatures

Shock, Everett L.; Koretsky, Carla M.

1993-10-01

Estimates of standard partial molal properties at high temperatures and pressures for aqueous acetate complexes of major and trace elements in geologic fluids were made with the aid of experimental data from the literature and correlation algorithms. A system of correlation expressions allows the incorporation of all available experimental data, but also allows estimates in the absence of any measurements. Likely uncertainties for each type of estimate were assessed. Thermodynamic data and equation of state parameters permit calculation of standard partial molal properties including dissociation constants for 114 acetate complexes. Incorporation of many of these dissociation constants with those for hydroxide, chloride, and sulfate complexes demonstrate that acetate complexes are ineffectual in transporting major rock forming elements or trace metals in sedimentary basin brines. In contrast, these complexes could be considerably more efficient in metal transport in low salinity groundwater solutions with elevated concentrations of organic solutes. Calculations indicate that up to 40% of the acetate may be present as sodium and calcium complexes in basin brines with total salinities around 1.0 molal.

8. Pre-collisional, Tonian (ca. 790 Ma) continental arc magmatism in southern Mantiqueira Province, Brazil: Geochemical and isotopic constraints from the Várzea do Capivarita Complex

Martil, Mariana Maturano Dias; de Fátima Bitencourt, Maria; Nardi, Lauro Valentim Stoll; Koester, Edinei; Pimentel, Márcio Martins

2017-03-01

This paper focuses on the pre-collisional mature arc magmatism (ca. 790 Ma) recorded in orthogneisses from the Várzea do Capivarita Complex (VCC), southern Mantiqueira Province (PM), Brazil. The complex comprises ortho- and paragneisses tectonically interleaved during a transpressive high grade regime (ca. 650 Ma), possibly related to oblique collision. The VCC orthogneisses are metaluminous to peraluminous calc-alkaline rocks, with high 87Sr/86Sr(i) ratios from 0.71628 to 0.72509 and εNd(790) values from - 7.19 to - 10.06. The VCC magmatism is correlated with other ca. 800 Ma arc sequences from southern PM, as the Porongos Metamorphic Complex (PMC) metavolcanic rocks and the orthogneisses from Cerro Bori (CB), Uruguay. All associations show signatures typical of accretionary orogens, TDM and Meso to Paleoproteroic inheritance ages, and strong evidence of crustal assimilation/contamination. Their high K contents, and the tendency to move toward the post-collisional field in geotectonic diagrams suggest that they were generated in thick-crust, mature arc environments. In contrast, the CB sequence exhibits a less mature continental-arc character, suggestive of thinner crust or shorter distance to the active margin. VCC and CB orthogneisses, and part of the PMC metavolcanic rocks may be interpreted as part of the same magmatism, or at least as fragments of similar magmatic arcs. However, VCC magmatism is distinct from continental arc sequences in the São Gabriel Block (ca. 700-750 Ma). Isotope signatures for this younger magmatism indicate major contribution of Neoproterozoic juvenile sources, with only little amounts of reworked, old continental crust. Geochemical and Sr-Nd signatures presented in this paper suggest that at least part of the PMC metavolcanic rocks are the protoliths of the VCC orthogneisses. This, together with the isotope evidence of similarity between VCC and PMC igneous and sedimentary fractions, corroborates the hypothesis that the VCC and PMC

9. Determining the geochemical structure of the mantle from surface isotope distribution patterns? Insights from Ne and He isotopes and abundance ratios

Stroncik, N.; Niedermann, S.; Schnabel, E.; Erzinger, J.

2011-12-01

It is a common procedure among geochemists to use surface distribution patterns of e.g. Sr, Nd, Pb or He isotopes of lavas erupted at oceanic islands to map the geochemical structure of the Earth's mantle. Advances in noble gas mass spectrometry within the last decade resulting in an increasing availability of Ne isotope data sets allow us to test the strength of this approach. 4He and 21Ne are coupled through the same parent nuclides and therefore should show analogous isotope distribution patterns. Here we present He and Ne fusion data of fresh olivines derived from Big Island, Hawaii, together with He and Ne fusion data of fresh glasses from the Easter Seamount Chain (ESC), indicating that the observed isotope distribution patterns are mainly controlled by melting and shallow mixing processes. He isotopic ratios of the investigated olivines vary from MORB-like (8 ± 1 RA) to ratios more typical for a primitive mantle source (up to 20 and 26 RA for Hawaii and the ESC, respectively; RA = atmospheric 3He/4He ratio of 1.39 x 10-6). In contrast, all Ne isotope data plot within error limits along the Loihi-Kilauea line in a Ne three-isotope diagram. The Loihi-Kilauea line is regarded to be typical for a primitive mantle source. Thus, the Ne isotope data are inconsistent with any kind of zoned plume model or even a heterogeneous mantle source. The combined He and Ne data show that these He and Ne isotope systematics are produced by a pre-degassing fractionation process and subsequent melt mixing. Basically, this process causes a He deficit in melts generated by the plume, as shown by 3He/22NeS below current estimates of solar or planetary composition and 4He/21Ne* lower than the production ratio, making the He isotopic composition more susceptible to changes than the Ne isotopic composition. This can best be explained by a model in which He is fractionated from Ne during formation of melts from a plume (or enriched parts of a plume) at low melting degrees, which

10. Surface active complexes formed between keratin polypeptides and ionic surfactants.

PubMed

Pan, Fang; Lu, Zhiming; Tucker, Ian; Hosking, Sarah; Petkov, Jordan; Lu, Jian R

2016-12-15

Keratins are a group of important proteins in skin and hair and as biomaterials they can provide desirable properties such as strength, biocompatibility, and moisture regaining and retaining. The aim of this work is to develop water-soluble keratin polypeptides from sheep wool and then explore how their surface adsorption behaves with and without surfactants. Successful preparation of keratin samples was demonstrated by identification of the key components from gel electrophoresis and the reproducible production of gram scale samples with and without SDS (sodium dodecylsulphate) during wool fibre dissolution. SDS micelles could reduce the formation of disulphide bonds between keratins during extraction, reducing inter-molecular crosslinking and improving keratin polypeptide solubility. However, Zeta potential measurements of the two polypeptide batches demonstrated almost identical pH dependent surface charge distributions with isoelectric points around pH 3.5, showing complete removal of SDS during purification by dialysis. In spite of different solubility from the two batches of keratin samples prepared, very similar adsorption and aggregation behavior was revealed from surface tension measurements and dynamic light scattering. Mixing of keratin polypeptides with SDS and C12TAB (dodecyltrimethylammonium bromide) led to the formation of keratin-surfactant complexes that were substantially more effective at reducing surface tension than the polypeptides alone, showing great promise in the delivery of keratin polypeptides via the surface active complexes. Neutron reflection measurements revealed the coexistence of surfactant and keratin polypeptides at the interface, thus providing the structural support to the observed surface tension changes associated with the formation of the surface active complexes.

11. The Development and Study of Surface Bound Ruthenium Organometallic Complexes

Abbott, Geoffrey Reuben

The focus of this project has been on the use of mono-diimine ruthenium organometallic complexes, of the general structure [H(Ru)(CO)(L)2(L') 2][PF6] (L=PPh3, DPPENE and L'=Bpy, DcBpy, MBpyC, Phen, AminoPhen) bound to surfaces as luminescent probes. Both biological and inorganic/organic hybrid surfaces have been studied. The complexes were characterized both bound and unbound using standard analytical techniques such as NMR, IR and X-ray crystallography, as well as through several photophysical methods as well. Initially the study focused on how the photophyscial properties of the complexes were affected by incorporation into biological membranes. It was found that by conjugating the probes to a more rigid cholesterol moiety that luminescence was conserved, compared to conjugation with a far more flexible lipid moiety, where luminescence was either lost or reduced. Both the cholesterol and lipid conjugates were able to insert into a lipid membrane, and in the more rigid environment some of the lipid conjugates regained some of their luminescence, but often blue shifted and reduced, depending on the conjugation site. Silica Polyamine Composites (SPCs) were a hybrid material developed in the Rosenberg Lab as useful metal separation materials, that could be easily modified, and had several benefits over current commercially available polymers, or inorganic materials. These SPCs also provided an opportunity for the development of a heterogeneous platform for luminescent complexes as either catalysts or sensors. Upon binding of the luminescent Ru complexes to the surface no loss, or major change in luminescence was seen, however, when bound to the rigid surface a significant increase in excited state lifetime was measured. It is likely that through binding and interacting with the surface that the complexes lost non-radiative decay pathways, resulting in the increase in lifetime, however, these interactions do not seem to affect the energy level of the MLCT band in a

12. Geochemical background and ecological risk of heavy metals in surface sediments from the west Zhoushan Fishing Ground of East China Sea.

PubMed

Xu, Gang; Liu, Jian; Pei, Shaofeng; Hu, Gang; Kong, Xianghuai

2015-12-01

Surface sediment grain size as well as the spatial distribution, pollution status, and source identification of heavy metals in the west Zhoushan Fishing Ground (ZFG) of the East China Sea were analyzed to study the geochemical background concentrations of heavy metals and to assess their potential ecological risk. Our results show that surface sediments in the eastern part of study area were mainly composed of sand-sized components. Spatial distributions of heavy metals were mainly controlled by grain size and terrigenous materials, and their concentrations in the coarsest grain sediments formed primarily during the Holocene transgressive period could represent the element background values of our study area. Contamination factor suggests that there was no pollution of Pb, Zn, and Cr generally in our study area and slight pollution of Cu, Cd, and As (especially Cu) at some stations. In addition, ecological harm coefficient indicates that the ecological risk of each heavy metal, except for Cd, at two stations was low as well. These results are consistent with the pollution load index and ecological risk index, which suggest both the overall level of pollution and the overall ecological risk of six studied metals in sediment were relatively low in our study area. Enrichment factor indicates that the heavy metals came mostly from the natural source. Summarily, the quality level of sediment in our study area was relatively good, and heavy metals in sediments could not exert threat to aquatic lives in the ZFG until now.

13. SEDIMENT GEOCHEMICAL MODEL

EPA Science Inventory

Until recently, sediment geochemical models (diagenetic models) have been only able to explain sedimentary flux and concentration profiles for a few simplified geochemical cycles (e.g., nitrogen, carbon and sulfur). However with advances in numerical methods, increased accuracy ...

14. Geochemical constraints on the evolution of mafic and felsic rocks in the Bathani volcanic and volcano-sedimentary sequence of Chotanagpur Granite Gneiss Complex

2014-06-01

The Bathani volcanic and volcano-sedimentary (BVS) sequence is a volcanic and volcano-sedimentary sequence, best exposed near Bathani village in Gaya district of Bihar. It is located in the northern fringe of the Chotanagpur Granite Gneiss Complex (CGGC). The volcano-sedimentary unit comprises of garnet-mica schist, rhyolite, tuff, banded iron formation (BIF) and chert bands with carbonate rocks as enclaves within the rhyolite and the differentiated volcanic sequence comprises of rhyolite, andesite, pillow basalt, massive basalt, tuff and mafic pyroclasts. Emplacement of diverse felsic and mafic rocks together testifies for a multi-stage and multi-source magmatism for the area. The presence of pillow basalt marks the eruption of these rocks in a subaqueous environment. Intermittent eruption of mafic and felsic magmas resulted in the formation of rhyolite, mafic pyroclasts, and tuff. Mixing and mingling of the felsic and mafic magmas resulted in the hybrid rock andesite. Granites are emplaced later, cross-cutting the volcanic sequence and are probably products of fractional crystallization of basaltic magma. The present work characterizes the geochemical characteristics of the magmatic rocks comprising of basalt, andesite, rhyolite, tuff, and granite of the area. Tholeiitic trend for basalt and calc-alkaline affinities of andesite, rhyolite and granite is consistent with their generation in an island arc, subduction related setting. The rocks of the BVS sequence probably mark the collision of the northern and southern Indian blocks during Proterozoic period. The explosive submarine volcanism may be related to culmination of the collision of the aforementioned blocks during the Neoproterozoic (1.0 Ga) as the Grenvillian metamorphism is well established in various parts of CGGC.

15. Convective instabilities in complex systems with partly free surface

Schwabe, Dietrich

2007-04-01

Experiments and observations and some selected theoretical studies of thermocapillary instabilities are reviewed and presented together with new unpublished work. We start with simple idealized model systems of pure thermocapillarity and add to them more complex features like gravity forces, temperature gradients inclined to the free surface, static and dynamic surface deformations, solutocapillary effects and reacting or moving crystal boundaries (like during unidirectional solidification). Many effects and instabilities are demonstrated in video clips which can be downloaded from http://meyweb.physik.uni-giessen.de/1_Forschung/crystalgrowth/video/homepage.html. We try to point out the relationship of thermocapillary instabilities in the more complex systems with those in theoretical studies where the names of these instabilities have been coined.

16. Global geochemical problems

NASA Technical Reports Server (NTRS)

Harriss, R. C.

1980-01-01

Application of remote sensing techniques to the solution of geochemical problems is considered with emphasis on the 'carbon-cycle'. The problem of carbon dioxide sinks and the areal extent of coral reefs are treated. In order to assess the problems cited it is suggested that remote sensing techniques be utilized to: (1)monitor globally the carbonate and bicarbonate concentrations in surface waters of the world ocean; (2)monitor the freshwater and oceanic biomass and associated dissolved organic carbon; (3) inventory the coral reef areas and types and the associated oceanographic climatic conditions; and (4)measure the heavy metal fluxes from forested and vegetated areas, from volcanos, from different types of crustal rocks, from soils, and from sea surfaces.

17. Atmospheric and Science Complexity Effects on Surface Bidirectional Reflectance

NASA Technical Reports Server (NTRS)

Diner, D. J. (Principal Investigator); Martonchik, J. V.; Sythe, W. D.; Hessom, C.

1985-01-01

Among the tools used in passive remote sensing of Earth resources in the visible and near-infrared spectral regions are measurements of spectral signature and bidirectional reflectance functions (BDRFs). Determination of surface properties using these observables is complicated by a number of factors, including: (1) mixing of surface components, such as soil and vegetation, (2) multiple reflections of radiation due to complex geometry, such as in crop canopies, and (3) atmospheric effects. In order to bridge the diversity in these different approaches, there is a need for a fundamental physical understanding of the influence of the various effects and a quantiative measure of their relative importance. In particular, we consider scene complexity effects using the example of reflection by vegetative surfaces. The interaction of sunlight with a crop canopy and interpretation of the spectral and angular dependence of the emergent radiation is basically a multidimensional radiative transfer problem. The complex canopy geometry, underlying soil cover, and presence of diffuse as well as collimated illumination will modify the reflectance characteristics of the canopy relative to those of the individual elements.

18. Thiol surface complexation on growing CdS clusters

SciTech Connect

Swayambunathan, V.; Hayes, D.; Schmidt, K.H.; Liao, Y.X.; Meisel, D. )

1990-05-09

The growth of small CdS colloidal particles has been initiated by pulse radiolytic release of sulfide from thiol (3-mercapto-1,2-propanediol, RSH) in the presence of Cd{sup 2+} ions. The kinetics and stoichiometry of the ensuring reactions were followed by conductivity, absorption spectroscopy, and light-scattering techniques. The final CdS product has been identified by electron diffraction. The formation of Cd-thiolate complexes at the surface of the particles is indicated by conductivity and by energy dispersive analysis of X-ray (EDAX) results. The rate of formation of CdS clusters is strongly pH dependent due to the pH effect on the stability of Dd{sup 2+}/HS{sup {minus}} complexes. At low pHs (4.0-5.3) the growth mechanism is proposed to be primarily a cluster-molecule process. At this pH range Cd{sup 2+} ions at the CdS particle surface complex with thiolate ions stronger than in the bulk of the solution. The size control of the particles by thiols is proposed to result from a competition of thiolate ions with HS{sup {minus}} ions for cadmium ions at the surface of the growing particles.

19. Geochemical processes controlling mobilization of arsenic and trace elements in shallow aquifers and surface waters in the Antequera and Poopó mining regions, Bolivian Altiplano

Ramos Ramos, Oswaldo Eduardo; Rötting, Tobias S.; French, Megan; Sracek, Ondra; Bundschuh, Jochen; Quintanilla, Jorge; Bhattacharya, Prosun

2014-10-01

A geochemical approach was applied to understand the factors controlling the mobilization of As and trace elements (TEs) in mining areas of the Poopó and Antequera River sub-basins on the Bolivian Altiplano. A total of 52 samples (surface, groundwater and geothermal water) were collected during the rainy season (2009). Arsenic, Cd and Mn concentrations exceed World Health Organization (WHO) drinking water guidelines and Bolivian regulations for drinking water in 28 groundwater samples, but Cu, Ni, Pb and Zn do not. Arsenic, Cd, Mn, Pb and Zn concentrations exceed World Health Organization guidelines for drinking water and Bolivian regulations Class A standard for discharge to water bodies in 20 surface water samples, whereas levels of Cu do not, and Ni and Fe rarely exceed regulation and guideline values. Factor analysis was applied to 18 hydrochemical parameters of 52 samples. Five factors for groundwater (plagioclase weathering, dissolution of gypsum and halite, TEs mobilization at acidic pH, sulfide oxidation, and release of As) account for 86.5% of the total variance for Antequera and 83.9% for Poopó sub-basins. Four factors for surface water data (weathering and mobilization of TEs influenced by pH, dissolution of evaporate salts, neutralization of acid mine drainage, and As release due to dissolution of Mn and Fe oxides) account for 91% of the total variance in Antequera and 96% in Poopó sub-basins. The As and TEs mobilized in these regions could affect the local water sources, which is a prevalent concern with respect to water resource management in this semi-arid Altiplano region. Presence of both natural and anthropogenic sources of contamination requires careful monitoring of water quality.

20. Exploring complex networks via topological embedding on surfaces.

PubMed

Aste, Tomaso; Gramatica, Ruggero; Di Matteo, T

2012-09-01

We demonstrate that graphs embedded on surfaces are a powerful and practical tool to generate, to characterize, and to simulate networks with a broad range of properties. Any network can be embedded on a surface with sufficiently high genus and therefore the study of topologically embedded graphs is non-restrictive. We show that the local properties of the network are affected by the surface genus which determines the average degree, which influences the degree distribution, and which controls the clustering coefficient. The global properties of the graph are also strongly affected by the surface genus which is constraining the degree of interwovenness, changing the scaling properties of the network from large-world kind (small genus) to small- and ultrasmall-world kind (large genus). Two elementary moves allow the exploration of all networks embeddable on a given surface and naturally introduce a tool to develop a statistical mechanics description for these networks. Within such a framework, we study the properties of topologically embedded graphs which dynamically tend to lower their energy towards a ground state with a given reference degree distribution. We show that the cooling dynamics between high and low "temperatures" is strongly affected by the surface genus with the manifestation of a glass-like transition occurring when the distance from the reference distribution is low. We prove, with examples, that topologically embedded graphs can be built in a way to contain arbitrary complex networks as subgraphs. This method opens a new avenue to build geometrically embedded networks on hyperbolic manifolds.

1. Overview of Mars surface geochemical diversity through Alpha Particle X-Ray Spectrometer data multidimensional analysis: First attempt at modeling rock alteration

Tréguier, Erwan; d'Uston, Claude; Pinet, Patrick C.; Berger, Gilles; Toplis, Michael J.; McCoy, Timothy J.; Gellert, Ralf; Brückner, Johannes

2008-11-01

Principal component analysis and a hierarchical clustering method have been employed to describe and quantify the compositional variability of Martian rocks and soils measured by the Alpha Particle X-Ray Spectrometers onboard the Mars Exploration Rovers. A robust classification of samples emerges which defines distinct rock classes and sheds light on the petrogenetic relationships between rocks. This is particularly useful in the case of rocks from Gusev Crater, where significant chemical diversity is observed. This approach also highlights that compositional variability of rocks at Meridiani is dominated by variations in sulfur content; the relative proportions of other elements remaining approximately constant. For soils, variations in Fe concentration dominate because of the presence of hematite-rich berry''-bearing samples. On the basis of this observation, a simple geochemical model of acid fog alteration of Martian basalts has been tested, assuming either equivalent alteration of all phases or preferential alteration of certain phases (thus taking into account kinetic considerations). The results show that for certain ranges of SO3/basalt, many of the compositional and mineralogical features measured at both sites may be explained. The secondary mineralogy and bulk rock compositions predicted by the model are broadly consistent with rock and soil compositions from Gusev and Meridiani, especially if the role of brine circulation and evaporation are considered. Although agreement is not perfect, comparison of observations and models argues in favor of variable interaction of the Martian surface with sour gas, explaining the high local abundance of sulfates, for example.

2. Neptunium (V) Adsorption to a Halophilic Bacterium Under High Ionic Strength Conditions: A Surface Complexation Modeling Approach

SciTech Connect

Ams, David A

2012-06-11

Rationale for experimental design: Np(V) -- important as analog for Pu(V) and for HLW scenarios; High ionic strength -- relevant to salt-based repositories such as the WIPP; Halophilic microorganisms -- representative of high ionic strength environments. For the first time showed: Significant adsorbant to halophilic microorganisms over entire pH range under high ionic strength conditions; Strong influence of ionic strength with increasing adsorption with increasing ionic strength (in contrast to trends of previous low ionic strength studies); Effect of aqueous Np(V) and bacterial surface site speciation on adsorption; and Developed thermodynamic models that can be incorporated into geochemical speciation models to aid in the prediction of the fate and transport of Np(V) in more complex systems.

3. Geochemical speciation and risk assessment of heavy metals in the surface sediments of Jemberau Lake, Tasik Chini, Malaysia

Krishnankutty, Nimisha; Idris, Mushrifah; Hamzah, Firdaus Mohamad; Vijayan, Neethu

2016-11-01

The mine tailings from the iron ore mining in Jemberau catchment, Tasik Chini is directly seeping into Laut Jemberau. The caustic red sludge which consists of trace amounts of heavy metals from the mining site is also being washed and ultimately gets accumulated in the lake sediment. Under favorable conditions, the heavy metals are remobilized to the aquatic system, causing danger to the benthic organisms. Hence, a risk assessment study of surface sediment was conducted at Laut Jemberau, Tasik Chini. The results suggested that Mn, Co, and Cd are the most easily exchangeable metals in the sediment. Among these metals, the concentration of Mn (mean value = 12.04 ppm ± 13.25) is higher and it has adverse effect on aquatic biota. The risk assessment code (RAC) results also identified that the risk associated with Co, Cd, Mn are highly dangerous due to its high bioavailability and labiality in Jemberau aquatic system. The closer vicinity of mining site poses higher risk in comparative to other sampling stations. The geoaccumulation index (Igeo) shows that level of contamination in surface sediment due to anthropogenic activities is extremely higher especially in S2- near to mining site.

4. Dynamic surface tension analysis of dodecyl sulfate association complexes.

PubMed

Quigley, W W; Nabi, A; Prazen, B J; Lenghor, N; Grudpan, K; Synovec, R E

2001-09-13

First, a novel calibration method is used to expand the current understanding of spherical drop growth and elongation that occurs during on-line measurements of surface pressure using the dynamic surface tension detector (DSTD). Using a novel surface tension calibration method, the drop radius is calculated as a function of time from experimental drop pressure data and compared to the theoretical drop radius calculated from volumetric flow rate. From this comparison, the drop volume at which the drop shape starts to deviate ( approximately 4 mul) from a spherical shape is readily observed and deviates more significantly by approximately 6 mul drop volume (5% deviation in the ideal spherical drop radius) for the capillary sensing tip employed in the DSTD. From this assessment of drop shape, an experimental method for precise drop detachment referred to as pneumatic drop detachment is employed at a drop volume of 2 mul (two second drops at 60 mul/min) in order to provide rapid dynamic surface tension measurements via the novel on-line calibration methodology. Second, the DSTD is used to observe and study kinetic information for surface-active molecules and association complexes adsorbing to an air-liquid drop interface. Dynamic surface tension measurements are made for sodium dodecyl sulfate (SDS) in the absence and presence of either tetra butyl ammonium (TBA) or chromium (III). Sensitive, indirect detection of chromium and other multiply charged metals at low concentrations is also investigated. The DSTD is utilized in examining the dynamic nature of SDS: cation association at the air-liquid interface of a growing drop. Either TBA or Cr(III) were found to substantially enhance the surface tension lowering of dodecyl sulfate (DS), but the surface tension lowering is accompanied by a considerable kinetic dependence. Essentially, the surface tension lowering of these DS: cation complexes is found to be a fairly slow process in the context of the two second DSTD

5. Geochemical Analyses of Surface and Shallow Gas Flux and Composition Over a Proposed Carbon Sequestration Site in Eastern Kentucky

SciTech Connect

Thomas Parris; Michael Solis; Kathryn Takacs

2009-12-31

Using soil gas chemistry to detect leakage from underground reservoirs (i.e. microseepage) requires that the natural range of soil gas flux and chemistry be fully characterized. To meet this need, soil gas flux (CO{sub 2}, CH{sub 4}) and the bulk (CO{sub 2}, CH{sub 4}) and isotopic chemistry ({delta}{sup 13}C-CO2) of shallow soil gases (<1 m, 3.3 ft) were measured at 25 locations distributed among two active oil and gas fields, an active strip mine, and a relatively undisturbed research forest in eastern Kentucky. The measurements apportion the biologic, atmospheric, and geologic influences on soil gas composition under varying degrees of human surface disturbance. The measurements also highlight potential challenges in using soil gas chemistry as a monitoring tool where the surface cover consists of reclaimed mine land or is underlain by shallow coals. For example, enrichment of ({delta}{sup 13}C-CO2) and high CH{sub 4} concentrations in soils have been historically used as indicators of microseepage, but in the reclaimed mine lands similar soil chemistry characteristics likely result from dissolution of carbonate cement in siliciclastic clasts having {delta}{sup 13}C values close to 0{per_thousand} and degassing of coal fragments. The gases accumulate in the reclaimed mine land soils because intense compaction reduces soil permeability, thereby impeding equilibration with the atmosphere. Consequently, the reclaimed mine lands provide a false microseepage anomaly. Further potential challenges arise from low permeability zones associated with compacted soils in reclaimed mine lands and shallow coals in undisturbed areas that might impede upward gas migration. To investigate the effect of these materials on gas migration and composition, four 10 m (33 ft) deep monitoring wells were drilled in reclaimed mine material and in undisturbed soils with and without coals. The wells, configured with sampling zones at discrete intervals, show the persistence of some of the

6. Geochemical and geo-statistical assessment of selected heavy metals in the surface sediments of the Gorgan Bay, Iran.

PubMed

Bastami, Kazem Darvish; Bagheri, Hossein; Haghparast, Sarah; Soltani, Farzaneh; Hamzehpoor, Ali; Bastami, Mousa Darvish

2012-12-01

We investigated heavy metal concentrations of zinc (Zn), copper (Cu), chromium (Cr), and lead (Pb), their spatial distribution and enrichment factor index in surface sediments of the Gorgan Bay. Sediment Quality Guidelines were also applied to assess adverse biological effects of these metals. Heavy metals were determined by inductively coupled plasma-mass spectroscopy (ICP-MS). The results indicated mean concentrations (ppm) of heavy metals were (mean±S.D.) Pb: 11.5±4.88, Cu: 18±8.83, Zn: 42±22.15 and Cr: 32±15.19. Based on Enrichment index, the Gorgan Bay is a low-enriched to non-enriched bay. Heavy metal contents were lower than the standard limits of PEL, ERL, and ERM that reveal no threatening influence of the metals in the Bay.

7. Complex Behavior of Caffeine Crystallites on Muscovite Mica Surfaces

PubMed Central

2015-01-01

Defined fabrication of organic thin films is highly desired in technological, as well as pharmaceutical, applications since morphology and crystal structure are directly linked to physical, electrical, and optical properties. Within this work, the directed growth of caffeine deposited by hot wall epitaxy (HWE) on muscovite mica is studied. Optical and atomic force microscopy measurements reveal the presence of caffeine needles exhibiting a preferable alignment in the azimuthal directions with respect to the orientation of the defined mica surface. Specular X-ray diffraction and X-ray diffraction pole figure measurements give evidence that the β-polymorphic form of caffeine forms on the mica surface. All results consent that caffeine molecules have an edge-on conformation i.e. minimizing their interaction area with the surface. Furthermore, the azimuthal alignment of the long caffeine needle axis takes place along the [11̅0], [100], and [110] real space directions of mica; needles are observed every 60° azimuthally. While mica has a complex surface structure with mirror planes and lowered oxygen rows, the slightly disturbed 3-fold symmetry dictates the crystal alignment. This is different to previous findings for solution cast caffeine growth on mica. For HWE the needles align solely along the mica main directions whereby solution cast needles show an additional needle splitting due to a different alignment of caffeine with respect to the surface. PMID:26366127

8. Photoelectrochemical etching of gallium nitride surface by complexation dissolution mechanism

Zhang, Miao-Rong; Hou, Fei; Wang, Zu-Gang; Zhang, Shao-Hui; Pan, Ge-Bo

2017-07-01

Gallium nitride (GaN) surface was etched by 0.3 M ethylenediamine tetraacetic acid disodium (EDTA-2Na) via photoelectrochemical etching technique. SEM images reveal the etched GaN surface becomes rough and irregular. The pore density is up to 1.9 × 109 per square centimeter after simple acid post-treatment. The difference of XPS spectra of Ga 3d, N 1s and O 1s between the non-etched and freshly etched GaN surfaces can be attributed to the formation of Ga-EDTA complex at the etching interface between GaN and EDTA-2Na. The proposed complexation dissolution mechanism can be broadly applicable to almost all neutral etchants under the prerequisite of strong light and electric field. From the point of view of environment, safety and energy, EDTA-2Na has obvious advantages over conventionally corrosive etchants. Moreover, as the further and deeper study of such nearly neutral etchants, GaN etching technology has better application prospect in photoelectric micro-device fabrication.

9. Structure-geochemical zoning of Topolninsk gold-ore field (Gorny Altai)

Timkin, T. V.; Lavrov, D. S.; Askanakova, O. Y.; Korotchenko, T. V.

2014-08-01

Geochemical zoning of prospective mineable gold-bearing skarns was carried out. The geochemical field abnormal structures of different hierarchy levels associated with gold- skarn formations were revealed. The interrelation between the structure of ore-geochemical fields and associated ring structures was studied. Complex structure-geochemical criteria for gold mineralization prospecting and evaluation were proposed.

10. Geochemical studies of Fe, Mn, Co, As, Cr, Sb, Zn, Sc and V in surface sediments from Jiaozhou Bay

Wu, Run; Li, Pei-Quan; Miao, Lu-Tian; Zhang, Shu-Xin; Tian, Wei-Zhi

1994-12-01

The contents of nearly forty-elements in surface sediments in Jiaozhou Bay were determined using a Neutron Activation Analysis Technique (Grancini, et al., 1976; Li Peiquan et al., 1985, 1986; Li Xiuxia et al., 1986). This paper's detailed discussion on only nine elements (Fe, Mn, Co, Cr, Sc, As, Sb, Zn and V) includes their distributions, concentrations, correlationships, material sources, background, etc. Based on Zavaristski's classification method, Fe, Mn, Co, Cr and V belong to the second group; As and Sb to the eighth groups: Sc and Zn to the third and sixth groups. It was found that their notably good correlationship is mainly due to the similarity of their ionic structures and that their variation is controlled by the Fe content (except Mn). The source of sediments is mainly terristrial material, and the composition of sediment is similar to that of shale and shale+clay. The contents for a large number of elements are within the scope of the background level, but there still is pollution of Zn and Cr, at least in a few stations.

11. Zinc surface complexes on birnessite: A density functional theory study

SciTech Connect

Kwon, Kideok D.; Refson, Keith; Sposito, Garrison

2009-01-05

Biogeochemical cycling of zinc is strongly influenced by sorption on birnessite minerals (layer-type MnO2), which are found in diverse terrestrial and aquatic environments. Zinc has been observed to form both tetrahedral (Zn{sup IV}) and octahedral (Zn{sup VI}) triple-corner-sharing surface complexes (TCS) at Mn(IV) vacancy sites in hexagonal birnessite. The octahedral complex is expected to be similar to that of Zn in the Mn oxide mineral, chalcophanite (ZnMn{sub 3}O{sub 7} {center_dot} 3H{sub 2}O), but the reason for the occurrence of the four-coordinate Zn surface species remains unclear. We address this issue computationally using spin-polarized Density Functional Theory (DFT) to examine the Zn{sub IV}-TCS and Zn{sup VI}-TCS species. Structural parameters obtained by DFT geometry optimization were in excellent agreement with available experimental data on Zn-birnessites. Total energy, magnetic moments, and electron-overlap populations obtained by DFT for isolated Zn{sup IV}-TCS revealed that this species is stable in birnessite without a need for Mn(III) substitution in the octahedral sheet and that it is more effective in reducing undersaturation of surface O at a Mn vacancy than is Zn{sub VI}-TCS. Comparison between geometry-optimized ZnMn{sub 3}O{sub 7} {center_dot} 3H{sub 2}O (chalcophanite) and the hypothetical monohydrate mineral, ZnMn{sub 3}O{sub 7} {center_dot} H{sub 2}O, which contains only tetrahedral Zn, showed that the hydration state of Zn significantly affects birnessite structural stability. Finally, our study also revealed that, relative to their positions in an ideal vacancy-free MnO{sub 2}, Mn nearest to Zn in a TCS surface complex move toward the vacancy by 0.08-0.11 {angstrom}, while surface O bordering the vacancy move away from it by 0.16-0.21 {angstrom}, in agreement with recent X-ray absorption spectroscopic analyses.

12. Geochemical and isotopic constraints on the age and origin of the Nidar Ophiolitic Complex, Ladakh, India: Implications for the Neo-Tethyan subduction along the Indus suture zone

Ahmad, T.; Tanaka, T.; Sachan, H. K.; Asahara, Y.; Islam, R.; Khanna, P. P.

2008-04-01

The Nidar ophiolite complex is exposed within the Indus suture zone in eastern Ladakh, India. The suture zone is considered to represent remnant Neo-Tethyan Ocean that closed via subduction as the Indian plate moved northward with respect to the Asian plate. The two plates ultimately collided during the Middle Eocene. The Nidar ophiolite complex comprises a sequence of ultra-mafic rocks at the base, gabbroic rocks in the middle and volcano-sedimentary assemblage on the top. Earlier studies considered the Nidar ophiolite complex to represent an oceanic floor sequence based on lithological assemblage. However, present study, based on new mineral and whole rock geochemical and isotopic data (on bulk rocks and mineral separates) indicate their generation and emplacement in an intra-oceanic subduction environment. The plutonic and volcanic rocks have nearly flat to slightly depleted rare earth element (REE) patterns. The gabbroic rocks, in particular, show strong positive Sr and Eu anomalies in their REE and spidergram patterns, probably indicating plagioclase accumulation. Depletion in high field strength elements (HFSE) in the spidergram patterns may be related to stabilization of phases retaining the HFSE in the subducting slab and / or fractional crystallization of titano-magnetite phases. The high radiogenic Nd- and low radiogenic Sr-isotopic ratios for these rocks exclude any influence of continental material in their genesis, implying an intra-oceanic environment. Nine point mineral-whole rock Sm-Nd isochron corresponds to an age of 140 ± 32 Ma with an initial 143Nd/ 144Nd of 0.513835 ± 0.000053 ( ENdt = + 7.4). This age is consistent with the precise Early Cretaceous age of Hauterivian (132 ± 2 to 127 ± 1.6 Ma) to Aptian (121 ± 1.4 to 112 ±1.1 Ma) for the overlying volcano-sedimentary (radiolarian bearing chert) sequences based on well-preserved radiolarian fossils (Kojima, S., Ahmad, T., Tanaka, T., Bagati, T.N., Mishra, M., Kumar, R. Islam, R., Khanna, P

13. Multifractal interpolation and spectrum-area fractal modeling of stream sediment geochemical data: Implications for mapping exploration targets

Parsa, Mohammad; Maghsoudi, Abbas; Yousefi, Mahyar; Carranza, Emmanuel John M.

2017-04-01

The spectrum-area (S-A) fractal model is a powerful tool for decomposition of complex anomaly patterns of gridded geochemical data. Ordinary moving average interpolation techniques are commonly being used for gridding geochemical data; however, these methods suffer from two major drawbacks of (1) ignoring the locally high values and (2) smoothing the interpolated surface. Multifractal moving average interpolation methods have been developed to overcome the shortcomings of ordinary moving average methods. This study seeks to compare two sets of multifractal and ordinary gridded geochemical data using success rate curves and applies the S-A fractal model to decompose anomalous geochemical patterns. A set of stream sediment geochemical data in Ahar area, NW Iran, was used as a case study. Then, a mineralization-related multi-element geochemical signature was gridded by ordinary and multifractal approaches and considered for further analyses. The S-A fractal method was applied to decompose anomaly and background components of the resultant multi-element geochemical signature. Exploration targets were delimited and further evaluated using two bivariate statistical procedures of Student's t-value and normalized density index. The results revealed that (a) application of multifractal gridded data enhances the predicting ability of geochemical signatures, (b) application of S-A fractal model on multifractal gridded data allows for superior discrimination of geochemical anomalies, and (c) the multi-element geochemical anomalies in the Ahar area related to porphyry-Cu deposits were properly delineated through sequence application of multifractal interpolation and S-A fractal model.

14. Complex copolymers for mobility control, water purification, and surface activity

SciTech Connect

Meister, J.J.

1988-05-01

Many processes that are basic to the extraction of natural resources are facilitated by addition of polymers. To be useful, the polymers must meet an interrelated list of chemical and physical properties as well as economic criteria. Two important properties demanded of the polymers are: 1. Rheology. Polymers are often added to change solvent or process flow properties. The addition of polymers almost always causes non-Newtonian flow behavior in the resulting fluid. Methods of controlling surface behavior are to: 1) create polar and nonpolar regions in the molecule thus producing a hydrophilic-lipophilic balance in the molecule, 2) charge the molecule by introducing ionic sites with the same or opposite charge as the boundary, or 3) introduce or remove functional groups in the molecule which produce binding reactions, such as a) hydrogen bond creation of b) nitrogen lone-pair donation, with the surface. This multitude of properties the polymer must possess dictate that better polymer performance is obtained from materials with complicated structures. Such polymers are complex polymers: random copolymers, block copolymers, graft copolymers, micellizing copolymers, and network copolymers. There has been a dramatic increase in the past decade in the number and complexity of these copolymers and it is these newly discovered polymers and their chemistry which will be described here. The synthesis, analysis, and testing of these polymers, with particular emphasis on those polymers designed for enhanced oil recovery, is presented.

15. Contaminant Organic Complexes: Their Structure and Energetics in Surface Decontamination

SciTech Connect

Samuel Traina; Shankar Sharma

2005-07-12

The Department of Energy has a goal of decontaminating an estimated 180,000 metric tons of metal wastes in various surplus facilities. Uranium (U) and other radioactive actinides and lanthanides are embedded within the mixed oxide structures of the passivity layers of corroded iron and steel. These toxic metals can be dissolved out of the surface layers by a naturally occurring bacterial siderophore called Desferrioxamine B (DFB). DFB is a trihydroxamate ligand with one amine and three hydroxamate groups, which chelates with metals through hydroxamate coordination. Complexation of DFB with U can be utilized in decontamination strategy of the passivity layers. Therefore, we have been studying reactions of uranyl U(VI) with zerovalent iron (Fe0) followed by dissolution by DFB. The objectives were to determine the structure and speciation of solution and solid phases of U and to assess the effectiveness of DVB in U dissolution.

16. Surface Complexation of Neptunium(V) with Goethite

SciTech Connect

Jerden, James L.; Kropf, A. Jeremy

2007-07-01

Batch adsorption experiments in which neptunium-bearing solutions were reacted with goethite (alpha-FeOOH) have been performed to study uptake mechanisms in sodium chloride and calcium-bearing sodium silicate solutions. This paper presents results identifying and quantifying the mechanisms by which neptunium is adsorbed as a function of pH and reaction time (aging). Also presented are results from tests in which neptunium is reacted with goethite in the presence of other cations (uranyl and calcium) that may compete with neptunium for sorption sites. The desorption of neptunium from goethite has been studied by re-suspending the neptunium-loaded goethite samples in solutions containing no neptunium. Selected reacted sorbent samples were analyzed by x-ray absorption spectroscopy (XAS) to determine the oxidation state and molecular speciation of the adsorbed neptunium. Results have been used to establish the pH adsorption edge of neptunium on goethite in sodium chloride and calcium-bearing sodium silicate solutions. The results indicate that neptunium uptake on goethite reaches 95% at a pH of approximately 7 and begins to decrease at pH values greater than 8.5. Distribution coefficients for neptunium sorption range from less than 1000 (moles/kg){sub sorbed} / (moles/kg){sub solution} at pH less than 5.0 to greater than 10,000 (moles/kg){sub sorbed} / (moles/kg){sub solution} at pH greater than 7.0. Distribution coefficients as high as 100,000 (moles/kg){sub sorbed} / (moles/kg){sub solution} were recorded for the tests done in calcite equilibrated sodium silicate solutions. XAS results show that neptunium complexes with the goethite surface mainly as Np(V) (although Np(IV) is prevalent in some of the longer-duration sorption tests). The neptunium adsorbed to goethite shows Np-O bond length of approximately 1.8 angstroms which is representative of the Np-O axial bond in the neptunyl(V) complex. This neptunyl(V) ion is coordinated to 5 or 6 equatorial oxygens with Np

17. Surface complexation model of uranyl sorption on Georgia kaolinite

USGS Publications Warehouse

Payne, T.E.; Davis, J.A.; Lumpkin, G.R.; Chisari, R.; Waite, T.D.

2004-01-01

The adsorption of uranyl on standard Georgia kaolinites (KGa-1 and KGa-1B) was studied as a function of pH (3-10), total U (1 and 10 ??mol/l), and mass loading of clay (4 and 40 g/l). The uptake of uranyl in air-equilibrated systems increased with pH and reached a maximum in the near-neutral pH range. At higher pH values, the sorption decreased due to the presence of aqueous uranyl carbonate complexes. One kaolinite sample was examined after the uranyl uptake experiments by transmission electron microscopy (TEM), using energy dispersive X-ray spectroscopy (EDS) to determine the U content. It was found that uranium was preferentially adsorbed by Ti-rich impurity phases (predominantly anatase), which are present in the kaolinite samples. Uranyl sorption on the Georgia kaolinites was simulated with U sorption reactions on both titanol and aluminol sites, using a simple non-electrostatic surface complexation model (SCM). The relative amounts of U-binding >TiOH and >AlOH sites were estimated from the TEM/EDS results. A ternary uranyl carbonate complex on the titanol site improved the fit to the experimental data in the higher pH range. The final model contained only three optimised log K values, and was able to simulate adsorption data across a wide range of experimental conditions. The >TiOH (anatase) sites appear to play an important role in retaining U at low uranyl concentrations. As kaolinite often contains trace TiO2, its presence may need to be taken into account when modelling the results of sorption experiments with radionuclides or trace metals on kaolinite. ?? 2004 Elsevier B.V. All rights reserved.

18. Eocene Granitoids of the Okhotsk Complex in Sakhalin Island, Russian Far East: Petrogenesis and tectonic implications from zircon U-Pb ages, geochemical and Sr-Nd isotopic characteristics

Liao, Jia Ping; Alexandrov, Igor; Jahn, Bor-ming

2016-04-01

Sakhalin Island represents an important part of the Western Pacific Orogenic Belt (or "Nipponides"). The island comprises several accreted terrains that have recorded strike-slip displacements and block rotations from Cretaceous to Tertiary. These terrains include fore-arc basins, accretionary complexes and island arc assemblages. The stratigraphic features of most terrains can be correlated to those of Hokkaido Island of Japan. However, little research has been undertaken on the magmatic activities on Sakhalin, so a direct comparison of crustal development and tectonic activities with Hokkaido has not been fulfilled. We intend to study the petrogenesis of granitic complexes of Sakhalin to resolve this problem. In this work, we present new results of age determination and geochemical analyses of the Okhotsk Complex and discuss the tectonic implications. The Okhotsk complex is one of the three main granitoid complexes in Sakhalin Island. It intruded into the Ozersk accretionary terrain that is composed of island arc assemblages and marine sediments and has traveled northward and accreted to Sakhalin Island in Eocene. Eleven samples from the Okhotsk Complex, including 7 granitoids, 1 enclave, 2 rhyolites, and 1 dacite, were subject to zircon U-Pb dating, whole-rock geochemical and Sr-Nd isotopic analyses. The results show that the entire complex was emplaced within 42 to 44 Ma. The 7 granitoids are slightly peraluminous, ferroan, and alkali-calcic. The REE abundances of granitoids show consistent patterns with weak LREE enrichment and negative Eu anomaly. The spidergrams show negative Ta-Nb-Ti anomaly as expected in most granitoids. They possess transitional characteristics between I- and A-type granites. For isotopic signatures, the granitoids have ɛNd(t) values of +2.8 to +3.7, initial 87Sr/86Sr ratios of 0.7047 to 0.7050, and Sm-Nd model ages (TDM-1) of 700-1100 Ma. The middle Eocene magmatic episode (42-44 Ma) of the Okhotsk Complex can find its counterpart in

19. Geochemical methods of prospecting for hydrocarbons

SciTech Connect

Duchscherer, W. Jr.

1980-12-01

Because the commonly used reflection-seismograph exploration technique misses many marginal low-relief structural prospects and regardless of its electronic computer sophistication, overlooks almost all stratigraphic traps, the hydrocarbon exploration industry should take a look at geochemical prospecting methods, which detect geochemical anomalies in the near-surface soils by measuring the thermal dissociation of the soil carbonates that are found overlying hydrocarbon accumulations. To promote understanding of such prospecting techniques, Geochemical Surveys reviews the methods used, the soil-alteration patterns, the lateral and vertical migration of hydrocarbon gases, the halo phenomenon (a ring or annual anomaly), the geochemical modification of sediments, and the data-interpretation and exploration procedures involved in a carbonate ..delta.. C analysis, which measures the residual, stable, cumulative effect of hydrocarbon migration.

20. Surface x-ray diffraction of complex metal oxide surfaces and interfaces--a new era

SciTech Connect

Schlepuetz, C. M.; Willmott, P. R.; Pauli, S. A.; Herger, R.; Martoccia, D.; Bjoerck, M.; Kumah, D.; Clarke, R.; Yacoby, Y.

2009-01-29

The availability of high-brilliance hard x-ray synchrotron radiation and the advent of novel photon counting area detectors have brought surface x-ray diffraction (SXRD) into a new era. It is now possible to record large numbers of structure factors with much improved reliability within reasonable beamtime durations. As a result, structural determination of the surfaces and interfaces of complex crystallographic systems and heterostructures has now become feasible, especially in conjunction with phase-retrieval methods. It is thereby hoped that detailed structural information will shed light on the unusual physical properties of these systems. Complex metal oxide systems investigated at the Materials Science beamline of the Swiss Light Source, including the surface of SrTiO{sub 3}, the interface between LaAlO{sub 3} and SrTiO{sub 3}, and the structure of YBa{sub 2}Cu{sub 3}O{sub 7} grown on NdGaO{sub 3}, SrTiO{sub 3}, and (LaSr)(AlTa)O{sub 3} will be presented as examples of what is now possible using SXRD.

1. Surface complexation studied via combined grazing-incidence EXAFS and surface diffraction: Arsenate on hematite (0001) and (10-12)

USGS Publications Warehouse

Waychunas, G.; Trainor, T.; Eng, P.; Catalano, J.; Brown, G.; Davis, J.; Rogers, J.; Bargar, J.

2005-01-01

X-ray diffraction [crystal-truncation-rod (CTR)] studies of the surface structure of moisture-equilibrated hematite reveal sites for complexation not present on the bulk oxygen-terminated surface, and impose constraints on the types of inner-sphere sorption topologies. We have used this improved model of the hematite surface to analyze grazing-incidence EXAFS results for arsenate sorption on the c(0001) and r(10-12) surfaces measured in two electric vector polarizations. This work shows that the reconfiguration of the surface under moist conditions is responsible for an increased adsorption density of arsenate complexes on the (0001) surface relative to predicted ideal termination, and an abundance of "edge-sharing" bidentate complexes on both studied surfaces. We consider possible limitations on combining the methods due to differing surface sensitivities, and discuss further analysis possibilities using both methods. ?? Springer-Verlag 2005.

2. Complexity in Surfaces of Densest Packings for Families of Polyhedra

Chen, Elizabeth R.; Klotsa, Daphne; Engel, Michael; Damasceno, Pablo F.; Glotzer, Sharon C.

2014-01-01

Packings of hard polyhedra have been studied for centuries due to their mathematical aesthetic and more recently for their applications in fields such as nanoscience, granular and colloidal matter, and biology. In all these fields, particle shape is important for structure and properties, especially upon crowding. Here, we explore packing as a function of shape. By combining simulations and analytic calculations, we study three two-parameter families of hard polyhedra and report an extensive and systematic analysis of the densest known packings of more than 55 000 convex shapes. The three families have the symmetries of triangle groups (icosahedral, octahedral, tetrahedral) and interpolate between various symmetric solids (Platonic, Archimedean, Catalan). We find optimal (maximum) packing-density surfaces that reveal unexpected richness and complexity, containing as many as 132 different structures within a single family. Our results demonstrate the importance of thinking about shape not as a static property of an object, in the context of packings, but rather as but one point in a higher-dimensional shape space whose neighbors in that space may have identical or markedly different packings. Finally, we present and interpret our packing results in a consistent and generally applicable way by proposing a method to distinguish regions of packings and classify types of transitions between them.

3. Localization of Pathology on Complex Architecture Building Surfaces

Sidiropoulos, A. A.; Lakakis, K. N.; Mouza, V. K.

2017-02-01

The technology of 3D laser scanning is considered as one of the most common methods for heritage documentation. The point clouds that are being produced provide information of high detail, both geometric and thematic. There are various studies that examine techniques of the best exploitation of this information. In this study, an algorithm of pathology localization, such as cracks and fissures, on complex building surfaces is being tested. The algorithm makes use of the points' position in the point cloud and tries to distinguish them in two groups-patterns; pathology and non-pathology. The extraction of the geometric information that is being used for recognizing the pattern of the points is being accomplished via Principal Component Analysis (PCA) in user-specified neighborhoods in the whole point cloud. The implementation of PCA leads to the definition of the normal vector at each point of the cloud. Two tests that operate separately examine both local and global geometric criteria among the points and conclude which of them should be categorized as pathology. The proposed algorithm was tested on parts of the Gazi Evrenos Baths masonry, which are located at the city of Giannitsa at Northern Greece.

4. Interplay between fluid flow and fault-fracture mesh generation within underthrust sediments: Geochemical evidence from the Chrystalls Beach Complex, New Zealand

Fagereng, Å.; Harris, C.

2014-02-01

The Chrystalls Beach Complex, in the Otago Schist on the South Island of New Zealand, is a mélange comprising sheared trench-fill sediments and fragments of oceanic crust. It represents an exhumed analogue for underthrust sediments actively deforming along modern subduction thrust interfaces. The mélange is cross-cut by a fault-fracture mesh, comprising subvertical extension veins and subhorizontal slickenfibre-coated shear surfaces. Both shear and extension veins have a ‘crack-seal’ microstructure indicating episodic growth. Shear veins are associated with pressure solution selvages along the shear surface, whereas wall rock alteration is not observed adjacent to extension veins. Electron microprobe analyses of selvage seams indicate dissolution of silica from the immediate surroundings of slickenfibre shear veins, and therefore these slickenfibres probably grew by local dissolution-precipitation of silica. On the contrary, no depletion or addition of silica is detected around extension veins, indicating these veins grew by precipitation from advecting fluids. Oxygen isotope ratios measured in vein quartz show that shear and extension veins both precipitated from an aqueous fluid with 7 %° < δ18O < 10 %°, consistent with a fluid derived from low-grade metamorphic dehydration reactions. Fluid pressure therefore probably increased as fluids were introduced to a relatively impermeable mélange with increasing metamorphic grade and decreasing porosity. Fault-fracture mesh generation therefore involved localized shear assisted by dissolution-precipitation creep and concomitant extension fracturing. This led in turn to transient permeability associated with a fluid pressure drop, allowing episodic vein growth. This process may be analogous to geophysically observed episodic tremor and slow slip, which also involves a mixture of deformation styles that, put together, achieve shear slip along the subduction thrust interface.

5. Unravelling the complex interaction between mantle and crustal magmas encoded in the lavas of San Vincenzo (Tuscany, Italy). Part II: Geochemical overview and modelling

Ridolfi, Filippo; Renzulli, Alberto; Perugini, Diego; Cesare, Bernardo; Braga, Roberto; Del Moro, Stefano

2016-02-01

This work reports a geochemical overview and modelling of the lavas erupted ~ 4.4 Ma ago at San Vincenzo (Tuscan Magmatic Province, TMP). Although these lavas cover a relatively small area (~ 10 km2), they show very large geochemical variations caused by the interaction of mantle-derived and crustal-anatectic magmas. The lavas consist of peraluminous rhyolites (87Sr/86Sr(i) up to 0.726) hosting primarily variably sized magmatic enclaves with shoshonite/latite compositions (87Sr/86Sr(i) down to 0.708). New whole-rock data for a large shoshonite enclave show high concentrations of LREE, LILE, and tetravalent HFSE, coupled with pentavalent HFSE depletions and enrichments in compatible elements such as Cr and Co. The chondrite-normalised REE pattern is strongly fractionated and characterised by a negative Eu anomaly (Eu/Eu* = 0.79). Hybridisation and AFC models suggest that the shoshonite enclave is the result of 12% rhyolite contamination of a mantle-derived magma akin to the potassic trachybasalt/shoshonite lavas of Capraia Island (~ 4.6 Ma; TMP), following an 18.5% assimilation of Late Triassic metasediments (13% evaporite and 5.5% carbonate) and 56% fractionation of clinopyroxene (39%), plagioclase (10%), and biotite (7%). Each rhyolite sample is characterised by mineral-scale isotopic disequilibria (e.g., 87Sr/86Sr(i) = 0.711-0.726), glass inclusions with large K2O/Na2O variations (1.1-3.4) and a poli-thermobarometric history of crustal melt production at eutectic conditions. A multi-parametric approach accounting for K2O/Na2O (1.3-2.2), 87Sr/86Sr(i) (0.713-0.725), Sr (104-311 ppm) and Rb (294-403 ppm) whole-rock variations, allowed us to divide the anatectic (A) rhyolites into five groups (A1, A2.1, A2.2, A2.3, A3). Group A1 shows the highest 87Sr/86Sr(i) ratios and the lowest values of Sr, K2O/Na2O and Rb. It is related to A2.1 and A3 rhyolites by positive K2O/Na2O-Rb and K2O/Na2O-FeO correlations. These three rhyolite groups crop out in the south of San

6. Pb-Sr-Nd isotope study of the 100- to 2700-Ma old alkalic rock-carbonatite complexes in the Canadian shield: inferences on the geochemical and structural evolution of the mantle

SciTech Connect

Kwon, S.T.

1986-01-01

The isotopic signatures of young continental alkalic complexes (CAC) display a remarkable similarity to those of oceanic island basalts (OIB). A study of Sr isotopic evolution showed that the mantle, presumably similar to the source of OIB, beneath the shield appears to have been depleted in large ion lithophile elements (LILE) and to have remained as a closed system since ca. 3000 Ma ago. The present investigations apply Pb and Nd as well as Sr isotopic systems for those complexes to study the secular geochemical evolution of the mantle over the past 2700 million years, and address the question of the processes responsible for the geochemical heterogeneity of the mantle. The data suggest: (1) Like Sr, Pb and Nd isotopic data indicate LILE depleted sources for the southern Canadian shield CAC over at least the past 1900 Ma. (2) Sr, Nd and Pb are compatible with an age of ca. 3000 Ma for the depleted source. (3) In contrast to Sr, and probably Nd, the Pb isotopic data cannot be explained by a closed system model for the depleted mantle source. (4) Coherent fractionation patterns are observed in the mantle sources of CAC since at least 1900 Ma ago: higher U/Pb and Sm/Nd, and lower Th/U and Rb/Sr ratios versus lower U/Pb and Sm/Nd, and higher Th/U and Rb/Sr ratios, indicating OlB-like sources for CAC. (5) The inverse correlation between /sup 206/Pb//sup 204/Pb and /sup 87/Sr//sup 86/Sr initial ratios permit calculation of apparent mean earth Pb isotope ratios with time, which yield 8.35 for the present day /sup 238/U//sup 204/Pb ratio, and 17.82 for /sup 206/Pb//sup 204/Pb. (6) A model for the geochemical and structural evolution of the mantle is based on the diverging isotopic evolution of the midocean ridge basalts (MORB) and OlB sources.

7. Surfaces of Al-based complex metallic alloys: atomic structure, thin film growth and reactivity

PubMed Central

Ledieu, Julian; Gaudry, Émilie; Fournée, Vincent

2014-01-01

We present a review on recent work performed on periodic complex metallic alloy (CMA) surfaces. The electronic and crystallographic structures of clean pseudo-tenfold, pseudo-twofold, sixfold surfaces will be presented along with the recent findings on CMA of lower structural complexity, i.e. with a smaller unit cell. The use of CMA surfaces as templates for thin film growth and the formation of surface alloy will also be introduced. The reactivity of these complex surfaces and their impact in the field of heterogeneous catalysis will be discussed. Finally, common trends among these systems will be highlighted when possible and future challenges will be examined. PMID:27877673

8. Principles of landscape-geochemical studies in the zones contaminated by technogenical radionuclides for ecological and geochemical mapping

Korobova, Elena; Romanov, Sergey

2013-04-01

Efficiency of landscape-geochemical approach was proved to be helpful in spatial and temporal evaluation of the Chernobyl radionuclide distribution in the environment. The peculiarity of such approach is in hierarchical consideration of factors responsible for radionuclide redistribution and behavior in a system of inter-incorporated landscape-geochemical structures of the local and regional scales with due regard to the density of the initial fallout and patterns of radionuclide migration in soil-water-plant systems. The approach has been applied in the studies of distribution of Cs-137, Sr-90 and some other radionuclides in soils and vegetation cover and in evaluation of contribution of the stable iodine supply in soils to spatial variation of risk of thyroid cancer in areas subjected to radioiodine contamination after the Chernobyl accident. The main feature of the proposed approach is simultaneous consideration of two types of spatial heterogeneities: firstly, the inhomogeneity of external radiation exposure due to a complex structure of the contamination field, and, secondly, the landscape geochemical heterogeneity of the affected area, so that the resultant effect of radionuclide impact could significantly vary in space. The main idea of risk assessment in this respect was to reproduce as accurately as possible the result of interference of two surfaces in the form of risk map. The approach, although it demands to overcome a number of methodological difficulties, allows to solve the problems associated with spatially adequate protection of the affected population and optimization of the use of contaminated areas. In general it can serve the basis for development of the idea of the two-level structure of modern radiobiogeochemical provinces formed by superposition of the natural geochemical structures and the fields of technogenic contamination accompanied by the corresponding peculiar and integral biological reactions.

9. Spectra over complex terrain in the surface layer

SciTech Connect

Panofsky, H.A.; Dutton, J.A.; Larko, D.; Lipschutz, R.; Stone, G.

1982-09-01

For design and control of Wind Energy Conversion Systems (WECS), the spectral distribution of wind speeds over frequencies needs to be known as well as velocity variances. Velocity spectra and other velocity statistics are estimated over three types of complex terrain: on tops of hills or escarpments; on land a short distance downwind from a water body; and over rolling farm land. The most important characteristics of turbulence models over uniform terrain are summarized briefly. Theoretical aspects of spectral characteristics over complex terrain are discussed, followed by detailed observations over complex terrain and procedures for their estimation. A theory is presented for calculation of response of engineering systems to wind fluctuations. (LEW)

10. A Novel Field Apparatus for Conducting Linked Geochemical-Microbiological Experiments in Shallow Sediments

Smith, E. W.; Voytek, M. A.; McGuire, J. T.; Cozzarelli, I. M.; Kneeshaw, T. A.; Baez-Cazull, S. E.

2008-12-01

Collecting in-situ experimental data for microbially mediated geochemical reactions is complex because it is difficult to assess the impact of the heterogeneity of natural systems. Specifically it is often difficult to constrain the degree of interaction between the pore water collected for geochemical analysis and a sampled microbial population. The newly developed apparatus, called a Native Organism Geochemical Experimentation Enclosure (NOGEE), provides the means to measure changes in well defined geochemical solutions that have been in direct contact with a known in-situ microbial population. The sampling apparatus is similar to a drive-point well. A short screened chamber (~60 ml) at the tip houses a polycarbonate sponge, which serves as a substrate for colonization by native microorganisms when it is open to the surrounding sediment. Following a colonization period dependent on season and temperature, the sponge chamber is closed to the surrounding environment by lowering an inner pipe and amended test solutions are introduced from the surface via tubing. An advantage to this method over laboratory microcosms is that the in-situ setting provides a natural, intrinsic control over environmental variables and minimizes disturbance to the system. To date, NOGEE's have been used to evaluate kinetic controls on sulfate reduction. Experimental results showed changing rates of sulfate reduction coincident with changes in microbial population and demonstrate the utility of using NOGEEs to quantify linkages between geochemistry and microbiology in complex natural environments.

11. Uranium(VI) adsorption to ferrihydrite: Application of a surface complexation model

USGS Publications Warehouse

Waite, T.D.; Davis, J.A.; Payne, T.E.; Waychunas, G.A.; Xu, N.

1994-01-01

A study of U(VI) adsorption by ferrihydrite was conducted over a wide range of U(VI) concentrations, pH, and at two partial pressures of carbon dioxide. A two-site (strong- and weak-affinity sites, FesOH and FewOH, respectively) surface complexation model was able to describe the experimental data well over a wide range of conditions, with only one species formed with each site type: an inner-sphere, mononuclear, bidentate complex of the type (FeO2)UO2. The existence of such a surface species was supported by results of uranium EXAFS spectroscopy performed on two samples with U(VI) adsorption density in the upper range observed in this study (10 and 18% occupancy of total surface sites). Adsorption data in the alkaline pH range suggested the existence of a second surface species, modeled as a ternary surface complex with UO2CO30 binding to a bidentate surface site. Previous surface complexation models for U(VI) adsorption have proposed surface species that are identical to the predominant aqueous species, e.g., multinuclear hydrolysis complexes or several U(VI)-carbonate complexes. The results demonstrate that the speciation of adsorbed U(VI) may be constrained by the coordination environment at the surface, giving rise to surface speciation for U(VI) that is significantly less complex than aqueous speciation.

12. Uranium(VI) adsorption to ferrihydrite: Application of a surface complexation model

USGS Publications Warehouse

Waite, T.D.; Davis, J.A.; Payne, T.E.; Waychunas, G.A.; Xu, N.

1994-01-01

A study of U(VI) adsorption by ferrihydrite was conducted over a wide range of U(VI) concentrations, pH, and at two partial pressures of carbon dioxide. A two-site (strong- and weak-affinity sites, FesOH and FewOH, respectively) surface complexation model was able to describe the experimental data well over a wide range of conditions, with only one species formed with each site type: an inner-sphere, mononuclear, bidentate complex of the type (FeO2)UO2. The existence of such a surface species was supported by results of uranium EXAFS spectroscopy performed on two samples with U(VI) adsorption density in the upper range observed in this study (10 and 18% occupancy of total surface sites). Adsorption data in the alkaline pH range suggested the existence of a second surface species, modeled as a ternary surface complex with UO2CO30 binding to a bidentate surface site. Previous surface complexation models for U(VI) adsorption have proposed surface species that are identical to the predominant aqueous species, e.g., multinuclear hydrolysis complexes or several U(VI)-carbonate complexes. The results demonstrate that the speciation of adsorbed U(VI) may be constrained by the coordination environment at the surface, giving rise to surface speciation for U(VI) that is significantly less complex than aqueous speciation. ?? 1994.

13. Surface complexation modeling of U(VI) adsorption by aquifer sediments from a former mill tailings site at Rifle, Colorado

SciTech Connect

Hyun, S. P.; Fox, Patricia M.; Davis, James A.; Campbell, Kate M.; Hayes, Kim F.; Long, Philip E.

2009-12-15

U(VI) adsorption by two aquifer sediment samples was studied under oxic conditions as a function of pH, U(VI), Ca, and dissolved carbonate concentration. Background-A (BKG-A) sediment was collected upstream of a former uranium mill-tailings site at Rifle, Colorado, and Little Rusty Composite (LRC) was collected on site but with low U contamination. Batch adsorption experiments were performed using artificial groundwater solutions prepared to simulate the field groundwater composition in equilibrium with specific partial pressures of carbon dioxide. To encompass the geochemical conditions of the alluvial aquifer at the site, the experimental conditions ranged from 6.8×10-8 to 10-5 M in [U(VI)]tot, 7.2 to 8.0 in pH, 3.0×10-3 to 6.0×10-3 M in [Ca2+], and 0.05 to 2.6% in partial pressure of carbon dioxide. The sediment was extracted with a dilute bicarbonate/carbonate solution to determine the background labile U(VI) already present in the sediment. A semi-empirical surface complexation model was developed to describe U(VI) adsorption using FITEQL4. The non-electrostatic, generalized composite surface complexation model successfully simulated U(VI) adsorption over the range of groundwater conditions at the Old Rifle site, using a two-site, two-reaction fitting scheme. The sensitivity of model parameters to background U(VI) concentration on the two samples was evaluated. U(VI) adsorption experiments were also performed using a sand fraction of BKG-A separated through repeated sonication and wet-sieving. Surface area normalized Kd for the bulk and sand fraction indicated similar reactivity for both. The surface complexation model developed in this work is expected to contribute to the prediction of fate and transport of U(VI) in the alluvial aquifer at the Old Rifle site, and to assist in the simulation of biostimulation field experiments performed at the site.

14. Surface complexation modeling of U(VI) adsorption by aquifer sediments from a former mill tailings site at Rifle, Colorado.

PubMed

Hyun, Sung Pil; Fox, Patricia M; Davis, James A; Campbell, Kate M; Hayes, Kim F; Long, Philip E

2009-12-15

A study of U(VI) adsorption by aquifer sediment samples from a former uranium mill tailings site at Rifle, Colorado, was conducted under oxic conditions as a function of pH, U(VI), Ca, and dissolved carbonate concentration. Batch adsorption experiments were performed using <2 mm size sediment fractions, a sand-sized fraction, and artificial groundwater solutions prepared to simulate the field groundwater composition. To encompass the geochemical conditions of the alluvial aquifer at the site, the experimental conditions ranged from 6.8 x 10(-8) to 10(-5) M in [U(VI)](tot), 7.2 to 8.0 in pH, 3.0 x 10(-3) to 6.0 x 10(-3) M in [Ca(2+)], and 0.05 to 2.6% in partial pressure of carbon dioxide. Surface area normalized U(VI) adsorption K(d) values for the sand and <2 mm sediment fraction were similar, suggesting a similar reactive surface coating on both fractions. A two-site two-reaction, nonelectrostatic generalized composite surface complexation model was developed and successfully simulated the U(VI) adsorption data. The model successfully predicted U(VI) adsorption observed from a multilevel sampling well installed at the site. A comparison of the model with the one developed previously for a uranium mill tailings site at Naturita, Colorado, indicated that possible calcite nonequilibrium of dissolved calcium concentration should be evaluated. The modeling results also illustrate the importance of the range of data used in deriving the best fit model parameters.

15. Surface complexation modeling of U(VI) adsorption by aquifer sediments from a former mill tailings site at Rifle, Colorado

USGS Publications Warehouse

Hyun, S.P.; Fox, P.M.; Davis, J.A.; Campbell, K.M.; Hayes, K.F.; Long, P.E.

2009-01-01

A study of U(VI) adsorption by aquifer sediment samples from a former uranium mill tailings site at Rifle, Colorado, was conducted under oxic conditions as a function of pH, U(VI), Ca, and dissolved carbonate concentration. Batch adsorption experiments were performed using <2mm size sediment fractions, a sand-sized fraction, and artificial groundwater solutions prepared to simulate the field groundwater composition. To encompass the geochemical conditions of the alluvial aquifer at the site, the experimental conditions ranged from 6.8 ?? 10-8 to 10-5 M in [U(VI)]tot, 7.2 to 8.0 in pH, 3.0 ?? 10-3 to 6.0 ?? 10 -3 M in [Ca2+], and 0.05 to 2.6% in partial pressure of carbon dioxide. Surface area normalized U(VI) adsorption Kd values for the sand and <2 mm sediment fraction were similar, suggesting a similar reactive surface coating on both fractions. A two-site two-reaction, nonelectrostatic generalized composite surface complexation model was developed and successfully simulated the U(VI) adsorption data. The model successfully predicted U(VI) adsorption observed from a multilevel sampling well installed at the site. A comparison of the model with the one developed previously for a uranium mill tailings site at Naturita, Colorado, indicated that possible calcite nonequilibrium of dissolved calcium concentration should be evaluated. The modeling results also illustrate the importance of the range of data used in deriving the best fit model parameters. ?? 2009 American Chemical Society.

16. Shape index distribution based local surface complexity applied to the human cortex

PubMed Central

Kim, Sun Hyung; Fonov, Vladimir; Collins, D. Louis; Gerig, Guido; Styner, Martin A.

2015-01-01

The quantification of local surface complexity in the human cortex has shown to be of interest in investigating population differences as well as developmental changes in neurodegenerative or neurodevelopment diseases. We propose a novel assessment method that represents local complexity as the difference between the observed distributions of local surface topology to its best-fit basic topology model within a given local neighborhood. This distribution difference is estimated via Earth Move Distance (EMD) over the histogram within the local neighborhood of the surface topology quantified via the Shape Index (SI) measure. The EMD scores have a range from simple complexity (0.0), which indicates a consistent local surface topology, up to high complexity (1.0), which indicates a highly variable local surface topology. The basic topology models are categorized as 9 geometric situation modeling situations such as crowns, ridges and fundi of cortical gyro and sulci. We apply a geodesic kernel to calculate the local SI histrogram distribution within a given region. In our experiments, we obtained the results of local complexity that shows generally higher complexity in the gyral/sulcal wall regions and lower complexity in some gyral ridges and lowest complexity in sulcal fundus areas. In addition, we show expected, preliminary results of increased surface complexity across most of the cortical surface within the first years of postnatal life, hypothesized to be due to the changes such as development of sulcal pits. PMID:26028803

17. Geochemical behaviour of rare earths in Vitis vinifera grafted onto different rootstocks and growing on several soils.

PubMed

Censi, P; Saiano, F; Pisciotta, A; Tuzzolino, N

2014-03-01

The geochemical behaviour of lanthanides and yttrium (Rare Earth Elements, REEs) has been investigated mainly in geological systems where these elements represent the best proxies of processes involving the occurrence of an interface between different media. This behaviour is assessed according to features recorded in sequences of REE concentrations along the REE series normalised with respect to a reference material. In this study, the geochemical behaviour of REE was investigated in different parts of Vitis vinifera specimens grown off-soil, on soils of different nature and grafted onto several rootstocks in order to evaluate effects induced by these changes. The results indicated that roots are the plant organs where REEs are preferentially concentrated, in particular elements from Sm to Ho (middle REE, MREE) whereas Eu enrichments occur in aerial parts. The geochemical behaviour of REE suggests that MREE enrichments in roots are due to preferential MREE interactions with biological membranes or to surface complexation with newly formed phosphates. Eu-positive anomalies suggest that Eu(3+) can form stable organic complexes in place of Ca(2+) in several biological processes in xylem fluids. The possibility that Eu mobility in these fluids can be enhanced by its reductive speciation as Eu(2+) cannot be ruled out. The assessment of the geochemical behaviour of REE according to the theory of the Tetrad Effect carried out confirms that REEs coming from soil are scavenged onto root tissues or mineral surfaces whereas their behaviour in aerial parts of V. vinifera is driven by dissolved complexation.

18. A universal surface complexation framework for modeling proton binding onto bacterial surfaces in geologic settings

USGS Publications Warehouse

Borrok, D.; Turner, B.F.; Fein, J.B.

2005-01-01

Adsorption onto bacterial cell walls can significantly affect the speciation and mobility of aqueous metal cations in many geologic settings. However, a unified thermodynamic framework for describing bacterial adsorption reactions does not exist. This problem originates from the numerous approaches that have been chosen for modeling bacterial surface protonation reactions. In this study, we compile all currently available potentiometric titration datasets for individual bacterial species, bacterial consortia, and bacterial cell wall components. Using a consistent, four discrete site, non-electrostatic surface complexation model, we determine total functional group site densities for all suitable datasets, and present an averaged set of 'universal' thermodynamic proton binding and site density parameters for modeling bacterial adsorption reactions in geologic systems. Modeling results demonstrate that the total concentrations of proton-active functional group sites for the 36 bacterial species and consortia tested are remarkably similar, averaging 3.2 ?? 1.0 (1??) ?? 10-4 moles/wet gram. Examination of the uncertainties involved in the development of proton-binding modeling parameters suggests that ignoring factors such as bacterial species, ionic strength, temperature, and growth conditions introduces relatively small error compared to the unavoidable uncertainty associated with the determination of cell abundances in realistic geologic systems. Hence, we propose that reasonable estimates of the extent of bacterial cell wall deprotonation can be made using averaged thermodynamic modeling parameters from all of the experiments that are considered in this study, regardless of bacterial species used, ionic strength, temperature, or growth condition of the experiment. The average site densities for the four discrete sites are 1.1 ?? 0.7 ?? 10-4, 9.1 ?? 3.8 ?? 10-5, 5.3 ?? 2.1 ?? 10-5, and 6.6 ?? 3.0 ?? 10-5 moles/wet gram bacteria for the sites with pKa values of 3

19. Antimicrobial ruthenium complex coating on the surface of titanium alloy. High efficiency anticorrosion protection of ruthenium complex.

PubMed

El-Gamel, Nadia E A; Fekry, Amany M

2015-08-01

A ruthenium complex was prepared and structurally characterized using various techniques. Antibacterial and antifungal activities of ruthenium complex were evaluated. High significant antimicrobial activity against Escherichia coli, Staphylococcus aureus and Candida albicans was recorded. Minor cytotoxicity records were reported at the highest concentration level using MTT assay. The influence of Cu(II), Cr(III), Fe(III) and Ru(III) metal ions of salen Schiff base on the corrosion resistance of Ti-alloy in 0.5M HCl was studied. In vitro corrosion resistance was investigated using electrochemical impedance spectroscopy (EIS) measurements and confirmed by surface examination via scanning electron microscope (SEM) technique. Both impedance and phase angle maximum (θ(max)) values were at maximum in the case of the ruthenium complex with promising antibacterial and antifungal activities. The surface film created by the ruthenium complex was highly resistant against attack or deterioration by bacteria. The EIS study showed high impedance values for the ruthenium complex with increasing exposure time up to 8 days. SEM images showed uniform distribution and adsorption of Ru(III) ions on Ti-alloy surface. The ruthenium complex, as a model of organic-inorganic hybrid complex, offered new prospects with desired properties in industrial and medical applications.

20. Surface Complexation at the TiO(2) (anatase)/Aqueous Solution Interface: Chemisorption of Catechol.

PubMed

Rodríguez; Blesa; Regazzoni

1996-01-15

Catechol adsorbs at the TiO(2) (anatase)/aqueous solution interface forming inner-sphere surface complexes. The UV-visible differential reflectance spectrum of surface titanium-catecholate complexes presents a band centered at 420 nm which corresponds to the ligand to metal charge transfer transition within the surface complexes. At pH values below pK(a1), the surface excess of catechol is almost insensitive toward pH and presents a Langmuirian dependence with the concentration of uncomplexed catechol. The ratio Gamma(max):N(S) (N(S) being the measured density of available OH surface groups) indicates a prevailing 1 to 2 ligand exchange adsorption stoichiometry. In the range pH >/= pK(a1), the catechol surface excess decreases markedly with increasing pH. Formation of 1 to 1 surface complexes produces an excess of negative surface charge that is revealed by the shift of the iep to lower pH values. The reported data, which are supplemented with information on the charging behavior of TiO(2) suspended in indifferent electrolyte solutions, are interpreted in terms of the multi-site surface complexation model. In this model, two types of surface OH groups are considered: identical withTiOH(1/3-) and identical withOH(1/3+). Although both surface groups undergo protonation-deprotonation reactions, only identical withTiOH(1/3-) are prone to chemisorption.

1. The origin of the 1.73-1.70 Ga anorogenic Ulkan volcano-plutonic complex, Siberian platform, Russia: inferences from geochronological, geochemical and Nd-Sr-Pb isotopic data

USGS Publications Warehouse

Larin, A.M.; Amelin, Yu. V.; Neymark, L.A.; Krymsky, R. Sh

1997-01-01

The Ulkan volcano-plutonic complex, a part of a 750 km Bilyakchian-Ulkan anorogenic belt, is located in the eastern part of the Archean-Paleoproterozoic Aldan shield. The tectonic position and geochemistry indicate that the Ulkan Complex is a typical A-type or intraplate magmatic association. The felsic volcanics of the Uian Group and granitoids of the North Uchur Massif, the major igneous components of the Ulkan Complex, have U-Pb zircon and monazite ages between 1721±1 Ma and 1703±18 Ma. Together with the spatially associated 1736±6 Ma Dzhugdzhur anorthosite massif, the Ulkan Complex forms a typical Proterozoic anorthosite-granite-volcanic association with the minimum duration of formation of 12 m.y. Initial εNd values between 0 and 1.1, similar for the Uian felsic volcanics, early granitoid phases of the North Uchur Massif and high-grade metamorphic basement rocks, indicate, along with geochemical data, that the crustal source of the Ulkan parental magmas may be similar to the basement rocks. The higher εNd(T) values of -0.3 to +1.9 in the later North Uchur granitoids and associated ore-bearing metasomatites, and relatively low time-integrated Rb/Sr, U/Pb, and Th/U estimated for their sources, may demonstrate involvement of variable amounts of a depleted mantle-derived component in the generation of later phases of the North Uchur Massif. The preferred model of formation of magmas parental to the Ulkan Complex involves thermal interaction of an uprising mantle diapir with Paleoproterozoic lower crust, which was accompanied by chemical interaction between a fluid derived from the diapir, with the lower crustal rocks.

2. Supported organometallic complexes, surface chemistry, spectroscopy, and catalysis

SciTech Connect

Marks, T.J.

1993-04-01

Goal is to elucidate and understand the surface chemistry and catalytic properties of well-defined, highly-reactive organometallic molecules (principally based upon abundant actinide, lanthanide, and early transition elements) adsorbed on metal oxides and halides. Nature of adsorbed species is probed by a battery of chemical and physicochemical techniques, to understand the nature of the molecule-surface coordination chemistry and how this can give rise to extremely high catalytic activity. A complementary objective is to delineate the scope and mechanisms of the heterogeneous catalytic reactions, as well as to relate them both conceptually and functionally to model systems generated in solution.

3. New geologic mapping combined with geochemical, paleomagnetic, and high-precision 40Ar/39Ar analyses reveal multiple overlapping calderas formed 16.4-15.7 Ma at High Rock caldera complex, northwestern Nevada

Coble, M. A.; Mahood, G. A.

2012-12-01

We present new evidence from 1:100,000- and 1:24,000-scale geologic mapping for the presence of at least four overlapping calderas, 24 to 40 km in diameter, that formed in an interval of only 0.7 m.y. during the mid-Miocene at High Rock caldera complex in northwest Nevada and southern Oregon. In total, an estimated minimum volume of ~725 km3 of rhyolitic magma erupted from the complex between 16.5 and 15.5 Ma, covering an area of ~9,000 km2. Rapid eruption of numerous units at volumetric rates as high as 3,000-4,000 km3/m.y., strong welding of lithic-poor ignimbrites, extensive vapor-phase alteration of lavas and ignimbrites alike, a limited range of phenocryst content and assemblage, silicification along faults, and a lack of well-exposed stratigraphic sections has hindered previous reconnaissance-scale mapping and identification of caldera centers. Calderas are located based on truncation of precaldera rhyolitic lavas by caldera topographic walls, by arcuate patterns of rhyolite lavas that erupted along buried caldera ring faults, and by the presence of pumiceous caldera lake sediments. We attribute formation of the Virgin Valley, Badger Mountain, Hanging Rock, and Cottonwood Creek Calderas to collapse on eruption, respectively, of the ca. 16.37 Ma Idaho Canyon Tuff, the 16.34 Ma Summit Lake Tuff, the 16.0 Ma Soldier Meadows Tuff, and the 15.7 Ma Tuff of Yellow Rock Canyon. Additional smaller-volume pyroclastic units erupted during emplacement of geochemically similar rhyolitic lavas. More than 60 new 40Ar/39Ar ages were obtained on ignimbrites, fall deposits, and rhyolitic, trachytic and basaltic lavas. Many of the eruptive units in the HRCC differ in age by less than 100 k.y., which, at ca. 16 Ma, requires precision at the 1-2‰ (2σ standard error) level to distinguish units using 40Ar/39Ar geochronology. The high-precision of the analyses of sanidine in the rhyolites, coupled with geochemical and paleomagnetic measurements, allowed us to correlate far

4. Geochemical Data for Stream-Sediment, Surface-Water, Rock, and Vegetation Samples from Red Mountain (Dry Creek), an Unmined Volcanogenic Massive Sulfide Deposit in the Bonnifield District, Alaska Range, East-Central Alaska

USGS Publications Warehouse

Giles, Stuart A.; Eppinger, Robert G.; Granitto, Matthew; Zelenak, Philip P.; Adams, Monique G.; Anthony, Michael W.; Briggs, Paul H.; Gough, Larry P.; Hageman, Philip L.; Hammarstrom, Jane M.; Horton, John D.; Sutley, Stephan J.; Theodorakos, Peter M.; Wolf, Ruth E.

2007-01-01

North-central and northeast Nevada contains numerous large plutons and smaller stocks but also contains many small, shallowly emplaced intrusive bodies, including dikes, sills, and intrusive lava dome complexes. Decades of geologic investigations in the study area demonstrate that many ore deposits, representing diverse ore deposit types, are spatially, and probably temporally and genetically, associated with these igneous intrusions. However, despite the number and importance of igneous instrusions in the study area, no synthesis of geochemical data available for these rocks has been completed. This report presents a synthesis of composition and age data for these rocks. The product represents the first phases of an effort to evaluate the time-space-compositional evolution of Mesozoic and Cenozoic magmatism in the study area and identify genetic associations between magmatism and mineralizing processes in this region.

5. Geochemical Interpretation of Collision Volcanism

Pearce, Julian

2014-05-01

collision type with extreme LILE and significant HFSE enrichment relative to MORB and with large negative Nb-Ta and Ti anomalies. Post-collision volcanism is usually ascribed to combinations of slab detachment, delamination, and slab roll back (orogenic) and extension (post-orogenic). The magma source is typically conductively-heated, sub-continental mantle lithosphere with composition and depth of melting depending on the nature and evolution of the collision zone in question. Geochemical patterns may be similar to those of syn-collision basalts or of intraplate, continental basalts - or transitional between these. This variability in space and time, though problematic for geochemical fingerprinting, can give clues to the polarity and development of the collision zone, for example by highlighting the distribution of subduction-modified mantle lithosphere and hence of pre-collision subduction zones. One characteristic common to this setting is a high crustal input resulting from the presence of a hot, thick 'crustal chemical filter' which is evident on geochemical projections that highlight AFC-type processes. Using this, and other, geochemical features it is possible to develop methodologies to at least partly see through the complexity of collision terranes.

6. Integral Solution for Diffraction Problems Involving Conducting Surfaces with Complex Geometries. 1. Theory

DTIC Science & Technology

1988-02-01

involving conducting surfaces with complex geometries. I. Theory Mohamed F. El-Hewle and Richard 1. Cook Franh !. Seiler Research Laboratory, U.S. Air...can be generalized to a surface of an arbi- mittance are then employed with the new geometry- and trary coordinate function as follows. At a surface

7. Efficient modelling of droplet dynamics on complex surfaces

Karapetsas, George; Chamakos, Nikolaos T.; Papathanasiou, Athanasios G.

2016-03-01

This work investigates the dynamics of droplet interaction with smooth or structured solid surfaces using a novel sharp-interface scheme which allows the efficient modelling of multiple dynamic contact lines. The liquid-gas and liquid-solid interfaces are treated in a unified context and the dynamic contact angle emerges simply due to the combined action of the disjoining and capillary pressure, and viscous stresses without the need of an explicit boundary condition or any requirement for the predefinition of the number and position of the contact lines. The latter, as it is shown, renders the model able to handle interfacial flows with topological changes, e.g. in the case of an impinging droplet on a structured surface. Then it is possible to predict, depending on the impact velocity, whether the droplet will fully or partially impregnate the structures of the solid, or will result in a ‘fakir’, i.e. suspended, state. In the case of a droplet sliding on an inclined substrate, we also demonstrate the built-in capability of our model to provide a prediction for either static or dynamic contact angle hysteresis. We focus our study on hydrophobic surfaces and examine the effect of the geometrical characteristics of the solid surface. It is shown that the presence of air inclusions trapped in the micro-structure of a hydrophobic substrate (Cassie-Baxter state) result in the decrease of contact angle hysteresis and in the increase of the droplet migration velocity in agreement with experimental observations for super-hydrophobic surfaces. Moreover, we perform 3D simulations which are in line with the 2D ones regarding the droplet mobility and also indicate that the contact angle hysteresis may be significantly affected by the directionality of the structures with respect to the droplet motion.

8. Efficient modelling of droplet dynamics on complex surfaces.

PubMed

Karapetsas, George; Chamakos, Nikolaos T; Papathanasiou, Athanasios G

2016-03-02

This work investigates the dynamics of droplet interaction with smooth or structured solid surfaces using a novel sharp-interface scheme which allows the efficient modelling of multiple dynamic contact lines. The liquid-gas and liquid-solid interfaces are treated in a unified context and the dynamic contact angle emerges simply due to the combined action of the disjoining and capillary pressure, and viscous stresses without the need of an explicit boundary condition or any requirement for the predefinition of the number and position of the contact lines. The latter, as it is shown, renders the model able to handle interfacial flows with topological changes, e.g. in the case of an impinging droplet on a structured surface. Then it is possible to predict, depending on the impact velocity, whether the droplet will fully or partially impregnate the structures of the solid, or will result in a 'fakir', i.e. suspended, state. In the case of a droplet sliding on an inclined substrate, we also demonstrate the built-in capability of our model to provide a prediction for either static or dynamic contact angle hysteresis. We focus our study on hydrophobic surfaces and examine the effect of the geometrical characteristics of the solid surface. It is shown that the presence of air inclusions trapped in the micro-structure of a hydrophobic substrate (Cassie-Baxter state) result in the decrease of contact angle hysteresis and in the increase of the droplet migration velocity in agreement with experimental observations for super-hydrophobic surfaces. Moreover, we perform 3D simulations which are in line with the 2D ones regarding the droplet mobility and also indicate that the contact angle hysteresis may be significantly affected by the directionality of the structures with respect to the droplet motion.

9. Hydrological and geochemical investigations of selenium behavior at Kesterson Reservoir

SciTech Connect

Benson, S.M.; Tokunaga, T.K.; Zawislanski, P.; Yee, A.W.; Daggett, J.S.; Oldfather, J.M.; Tsao, L.; Johannis, P.W.

1990-10-01

From 1985 to the present we have studied the behavior of selenium in various habitats and environments at Kesterson reservoir, shifting emphasis as remedial actions altered the physical setting. Investigations have evaluated the efficacy of several remedial alternatives, from innovative techniques relying on the complex geochemical behavior of selenium alternatives, from innovative techniques relying on the complex geochemical behavior of selenium in aquatic environments to conventional excavation schemes. Results of these studies supported two cost-effective remedial measures; drain water deliveries were terminated in 1986 and, in 1988, 1 million cubic yards of soil were imported and used to fill the low lying areas of the former Kesterson Reservoir. To date, these two actions appear to have eliminated the aquatic habitat that caused waterfowl death and deformity at Kesterson from the early 1980's to 1987. Biological, surface water and groundwater monitoring data collected by the USBR indicate that Kesterson is now a much safer environment than in past years when drainage water containing 300{mu}g/l of selenium was delivered to the Reservoir. The continued presence of a large inventory of selenium within the upper portions of unfilled areas of Kesterson Reservoir and immediately below the fill material requires that a continued awareness of the status of this inventory be maintained and improved upon. 83 refs., 130 figs., 19 tabs.

10. Using Electron Distributions to Probe Energy Surfaces at Complex R

Macek, J. H.; Ovchinnikov, S. Yu.

1997-04-01

The hidden crossing theory describes ion-atom collisions(S. Yu. Ovchinnikov and E. A. Solovév, Comments At. Mol. Phys. 22) 69 (1988). in terms of a single function \\varepsilon(R) defined for all complex R, where R is the distance between target and projectile nuclei. Conventional adiabatic energy curves \\varepsilon_n(R) represent different branches of \\varepsilon(R) at real, positive R. Electron distributions are computed by evaluating a phase integral along an appropriate path in the complex R-plane. The real part of the phase oscillates rapidly for a class of transitions that proceed via the "top of barrier" mechanism. Electron distributions oscillate owing to interfrence between σ and π transitions, and this oscillation relates closely to the real part of \\varepsilon(R) for complex R. The oscillation rate is in qualitative agreement with measurements (R. Döner, K. Khemliche, M. H. Prior, C. L. Cocke, J. A. Gary, R. E. Olson, V. Mergel, J. Ullrich and H. Schmidt-Böking, Phys. Rev. Lett.77), 1024 (1996).

11. Probing Potential Energy Surface Exploration Strategies for Complex Systems.

PubMed

N'Tsouaglo, Gawonou Kokou; Béland, Laurent Karim; Joly, Jean-François; Brommer, Peter; Mousseau, Normand; Pochet, Pascal

2015-04-14

The efficiency of minimum-energy configuration searching algorithms is closely linked to the energy landscape structure of complex systems, yet these algorithms often include a number of steps of which the effect is not always clear. Decoupling these steps and their impacts can allow us to better understand both their role and the nature of complex energy landscape. Here, we consider a family of minimum-energy algorithms based, directly or indirectly, on the well-known Bell-Evans-Polanyi (BEP) principle. Comparing trajectories generated with BEP-based algorithms to kinetically correct off-lattice kinetic Monte Carlo schemes allow us to confirm that the BEP principle does not hold for complex systems since forward and reverse energy barriers are completely uncorrelated. As would be expected, following the lowest available energy barrier leads to rapid trapping. This is why BEP-based methods require also a direct handling of visited basins or barriers. Comparing the efficiency of these methods with a thermodynamical handling of low-energy barriers, we show that most of the efficiency of the BEP-like methods lie first and foremost in the basin management rather than in the BEP-like step.

12. Surface chemistry of the linear chromium chain complex on GaN(0001)

SciTech Connect

Lung, C.-H.; Peng, S.-M.; Chang, C.-C.

2004-09-01

Better understanding about the chemistry of the organometallic chain complexes reacting on the solid surface can foster concepts of nanowire fabrication which are central to the continued advance of the electronic and optoelectronic industries. In this study, the adsorption and thermal reactivity of a trinuclear chromium chain complex, tetrakis (2,2{sup '}-dipyridylamino)chromium(VI) chloride, on the GaN(0001) surface were investigated using x-ray photoelectron spectroscopy, temperature-programmed desorption, and static secondary ion mass spectrometry in order to obtain some insight into the bonding changes involved in the reaction of the linear metal chain complex on the compound semiconductor surface. One of the two terminal Cr-Cl bonds of the complex may be cleaved upon adsorption at 110 K, leading to the formation of the Ga-Cl bonds on the surface, although some complexes remained intact upon adsorption and bonded strongly to the surface. No ligand was dissociated from the chromium chain complex during the adsorption. The Cl-cleaved complex residue preserved its original chemical configuration. Both the Cl-cleaved and the intact complexes in the first layer were stable on the surface in the substrate temperature range between 110 and 260 K. A partial decomposition in which some ligands were dissociated from the adsorbed complex took place before the substrate temperature reaching 400 K. Additional Cr-Cl bonds were disrupted, resulting in a larger population of Ga-Cl bonds on the surface. Further thermal reaction at higher temperatures led to the dominance of the Ga-Cl bonding for the Cl presence on the surface. Surface etching of Ga by the dissociated Cl atoms started at a substrate temperature of {approx}525 K and the etching rate reached its maximum at {approx}590 K.

13. Geochronology and isotopic-geochemical characteristics of magmatic complexes of gold-silver ore-magmatic structures in the Chukotka sector of the Russian Arctic coast

Sakhno, V. G.; Grigoriev, N. V.; Kurashko, V. V.

2016-05-01

The first results of SHRIMP dating of magmatic complexes and associated gold-silver deposits and ore occurrences (Kupol, Dvoinoe, Moroshka, and others) in the Chukotka sector of the Russian Arctic coast are discussed. The petrological and isotopic-geochronological data are used for reconstructing their formation conditions.

14. Theory of polyelectrolyte adsorption on heterogeneously charged surfaces applied to soluble protein-polyelectrolyte complexes

de Vries, R.; Weinbreck, F.; de Kruif, C. G.

2003-03-01

Existing theoretical approaches to polymer adsorption on heterogeneous surfaces are applied to the problems of polyelectrolyte and polyampholyte adsorption on randomly charged surfaces. Also, analytical estimates are developed for the critical pH at which weakly charged polyelectrolytes and globular proteins start forming soluble complexes. Below a critical salt concentration, soluble complexes form "on the wrong side" of the protein isoelectric point due to the heterogeneity of the protein surface charge distribution. The analytical estimates are consistent with experimental data on soluble complexes in mixtures of gum arabic and whey protein isolate.

15. Intersections of potential energy surfaces of short-lived states: the complex analogue of conical intersections.

PubMed

Feuerbacher, Sven; Sommerfeld, Thomas; Cederbaum, Lorenz S

2004-02-15

Whereas conical intersections between potential energy surfaces of bound states are well known, the interaction of short-lived states has been investigated only rarely. Here, we present several systematically constructed model Hamiltonians to study the topology of intersecting complex potential energy surfaces describing short-lived states: We find the general phenomenon of doubly intersecting complex energy surfaces, i.e., there are two points instead of one as in the case of bound states where the potential energy surfaces coalesce. In addition, seams of intersections of the respective real and imaginary parts of the potential energy surfaces emanate from these two points. Using the Sigma* and Pi* resonance states of the chloroethene anion as a practical example, we demonstrate that our complete linear model Hamiltonian is able to reproduce all phenomena found in explicitly calculated ab initio complex potential energy surfaces.

16. Surface-water-quality assessment of the upper Illinois River basin in Illinois, Indiana, and Wisconsin; spatial distribution of geochemicals in the fine fraction of streambed sediment, 1987

USGS Publications Warehouse

Fitzpatrick, Faith A.; Arnold, Terri L.; Colman, John A.

1998-01-01

Geochemical data for the upper Illinois River Basin are presented for concentrations of 39 elements in streambed sediment collected by the U.S. Geological Survey in the fall of 1987. These data were collected as part of the pilot phase of the National Water-Quality Assessment Program. A total of 372 sites were sampled, with 238 sites located on first- and second-order streams, and 134 sites located on main stems. Spatial distribution maps and exceedance probability plots are presented for aluminum, antimony, arsenic, barium, beryllium, boron, cadmium, calcium, carbon (total, inorganic, and organic), cerium, chromium, cobalt, copper, gallium, iron, lanthanum, lead, lithium, magnesium, manganese, mercury, molybdenum, neodymium, nickel, niobium, phosphorus, potassium, scandium, selenium, silver, sodium, strontium, sulfur, thorium, titanium, uranium, vanadium, yttrium, and zinc. For spatial distribution maps, concentrations of the elements are grouped into four ranges bounded by the minimum concentration, the 10th, 50th, and 90th percentiles, and the maximum concentrations. These ranges were selected to highlight streambed sediment with very low or very high element concentrations relative to the rest of the streambed sediment in the upper Illinois River Basin. Exceedance probability plots for each element display the differences, if any, in distributions between high- and low-order streams and may be helpful in determining differences between background and elevated concentrations.

17. Geochemical Reaction Mechanism Discovery from Molecular Simulation

DOE PAGES

Stack, Andrew G.; Kent, Paul R. C.

2014-11-10

Methods to explore reactions using computer simulation are becoming increasingly quantitative, versatile, and robust. In this review, a rationale for how molecular simulation can help build better geochemical kinetics models is first given. We summarize some common methods that geochemists use to simulate reaction mechanisms, specifically classical molecular dynamics and quantum chemical methods and discuss their strengths and weaknesses. Useful tools such as umbrella sampling and metadynamics that enable one to explore reactions are discussed. Several case studies wherein geochemists have used these tools to understand reaction mechanisms are presented, including water exchange and sorption on aqueous species and mineralmore » surfaces, surface charging, crystal growth and dissolution, and electron transfer. The impact that molecular simulation has had on our understanding of geochemical reactivity are highlighted in each case. In the future, it is anticipated that molecular simulation of geochemical reaction mechanisms will become more commonplace as a tool to validate and interpret experimental data, and provide a check on the plausibility of geochemical kinetic models.« less

18. Geochemical Reaction Mechanism Discovery from Molecular Simulation

SciTech Connect

Stack, Andrew G.; Kent, Paul R. C.

2014-11-10

Methods to explore reactions using computer simulation are becoming increasingly quantitative, versatile, and robust. In this review, a rationale for how molecular simulation can help build better geochemical kinetics models is first given. We summarize some common methods that geochemists use to simulate reaction mechanisms, specifically classical molecular dynamics and quantum chemical methods and discuss their strengths and weaknesses. Useful tools such as umbrella sampling and metadynamics that enable one to explore reactions are discussed. Several case studies wherein geochemists have used these tools to understand reaction mechanisms are presented, including water exchange and sorption on aqueous species and mineral surfaces, surface charging, crystal growth and dissolution, and electron transfer. The impact that molecular simulation has had on our understanding of geochemical reactivity are highlighted in each case. In the future, it is anticipated that molecular simulation of geochemical reaction mechanisms will become more commonplace as a tool to validate and interpret experimental data, and provide a check on the plausibility of geochemical kinetic models.

19. Petrogenesis of the igneous Mucajaí AMG complex, northern Amazonian craton — Geochemical, U-Pb geochronological, and Nd-Hf-O isotopic constraints

Heinonen, A. P.; Fraga, L. M.; Rämö, O. T.; Dall'Agnol, R.; Mänttäri, I.; Andersen, T.

2012-10-01

The ca. 1525 Ma igneous Mucajaí anorthosite-monzonite-granite (AMG) complex in northern Brazil is a rare manifestation of Mesoproterozoic intraplate magmatism in the northern Amazonian Craton. The complex comprises a two-phase rapakivi granite batholith with subordinate quartz-fayalite monzonites and syenites and the closely associated Repartimento anorthosite. Zircon U-Pb (ID-TIMS) geochronology reveals that the anorthosite (1526 ± 2 Ma), monzonite (1526 ± 2 Ma), and the main-phase biotite-hornblende granite (1527 ± 2 Ma) of the complex intruded the Paleoproterozoic (~ 1.94 Ga) country rocks simultaneously at ~ 1526 Ma and that the more evolved biotite granite is marginally younger at 1519 ± 2 Ma. Intraplate magmatism in the Mucajaí region was relatively short-lived and lasted 12 million years (1529-1517 Ma) at maximum. The Nd (whole-rock, ID-TIMS; ɛNd from - 1.9 to - 2.8), Hf (zircon, LAM-ICP-MS; ɛHf from - 2.0 to - 3.1), and O (zircon, SIMS; δ18O from 6.1 to 7.0‰) isotopic compositions of the studied rocks are fairly uniform but still reveal a small degree of isotopic heterogeneity in the Paleoproterozoic crust enclosing the complex. The small isotopic differences observed in the two types of rapakivi granites (biotite-hornblende granite and biotite granite) may result either from an isotopically heterogeneous lower crustal source or, more likely, from contamination of the granitic magma derived from a lower crustal source during prolonged residence at upper crustal levels.

20. The IUGS/IAGC Task Group on Global Geochemical Baselines

USGS Publications Warehouse

Smith, David B.; Wang, Xueqiu; Reeder, Shaun; Demetriades, Alecos

2012-01-01

The Task Group on Global Geochemical Baselines, operating under the auspices of both the International Union of Geological Sciences (IUGS) and the International Association of Geochemistry (IAGC), has the long-term goal of establishing a global geochemical database to document the concentration and distribution of chemical elements in the Earth’s surface or near-surface environment. The database and accompanying element distribution maps represent a geochemical baseline against which future human-induced or natural changes to the chemistry of the land surface may be recognized and quantified. In order to accomplish this long-term goal, the activities of the Task Group include: (1) developing partnerships with countries conducting broad-scale geochemical mapping studies; (2) providing consultation and training in the form of workshops and short courses; (3) organizing periodic international symposia to foster communication among the geochemical mapping community; (4) developing criteria for certifying those projects whose data are acceptable in a global geochemical database; (5) acting as a repository for data collected by those projects meeting the criteria for standardization; (6) preparing complete metadata for the certified projects; and (7) preparing, ultimately, a global geochemical database. This paper summarizes the history and accomplishments of the Task Group since its first predecessor project was established in 1988.

1. Geochemical and Sr-Nd-Hf-O-C isotopic constraints on the origin of the Neoproterozoic Qieganbulake ultramafic-carbonatite complex from the Tarim Block, Northwest China

Ye, Hai-Min; Li, Xian-Hua; Lan, Zhong-Wu

2013-12-01

The Qieganbulake ultramafic-carbonatite complex located within the northeastern margin of the Tarim Block of Northwest China hosts the world's second largest vermiculite deposit. Field observations, radiometric dating results and Sr-Nd-Hf isotopes reveal that the parental magmas of the carbonatite and ultramafic rocks are cogenetic and formed synchronously at ~ 810 Ma. They are characterized by unusually enriched Sr-Nd-Hf isotopic compositions (ISr = 0.70570-0.70762, εNd(t) = - 7.7 to - 12.5, and εHf(t) = - 6.7 to - 12.9), indicating that the parent magmas were derived mainly from a subcontinental mantle source that had been metasomatised by subduction processes. Higher δ13C (- 3.65 to - 4.11‰) values compared to primary magmatic carbonate (- 8 to - 4‰) argue for incorporation of recycled inorganic carbon derived from subducted oceanic crusts. The carbonatites and clinopyroxenties define two distinct differentiation trends, which suggest that liquid immiscibility rather than crystal fractionation controlled the petrogenetic process. Pyroxenities have clearly higher apatite ISr and δ18O values than coexisting carbonatites, indicating involvement of crustal components during their emplacement. The Qieganbulake complex is closely associated in time and space with the mid-Neoproterozoic Rodinia breakup event triggered by mantle plume activities in the Tarim Block. Therefore, the mantle plume likely induced partial malting of, and likely mixed with, the metasomatized subcontinental lithospheric mantle, to form the Qieganbulake ultramafic-carbonatite complex.

2. Kinetics of Uranium(VI) Desorption from Contaminated Sediments: Effect of Geochemical Conditions and Model Evaluation

SciTech Connect

Liu, Chongxuan; Shi, Zhenqing; Zachara, John M.

2009-09-01

Stirred-flow cell experiments were performed to investigate the kinetics of uranyl [U(VI)] desorption from a contaminated sediment collected from the Hanford 300 Area at the US Department of Energy (DOE) Hanford Site, Washington. Three influent solutions of variable pH, Ca and carbonate concentrations that affected U(VI) aqueous and surface speciation were used under dynamic flow conditions to evaluate the effect of geochemical conditions on the rate of U(VI) desorption. The measured rate of U(VI) desorption varied with solution chemical composition that evolved as a result of thermodynamic and kinetic interactions between the influent solutions and sediment. The solution chemical composition that led to a lower equilibrium U(VI) sorption to the solid phase yielded a faster desorption rate. The experimental results were used to evaluate a multi-rate, surface complexation model (SCM) that has been proposed to describe U(VI) desorption kinetics in the Hanford sediment that contained complex sorbed U(VI) species in mass transfer limited domains. The model was modified and supplemented by including multi-rate, ion exchange reactions to describe the geochemical interactions between the solutions and sediment. With the same set of model parameters, the modified model reasonably well described the evolution of major ions and the rates of U(VI) desorption under variable geochemical and flow conditions, implying that the multi-rate SCM is an effective way to describe U(VI) desorption kinetics in subsurface sediments.

3. Geochemical modeling: a review

SciTech Connect

Jenne, E.A.

1981-06-01

Two general families of geochemical models presently exist. The ion speciation-solubility group of geochemical models contain submodels to first calculate a distribution of aqueous species and to secondly test the hypothesis that the water is near equilibrium with particular solid phases. These models may or may not calculate the adsorption of dissolved constituents and simulate the dissolution and precipitation (mass transfer) of solid phases. Another family of geochemical models, the reaction path models, simulates the stepwise precipitation of solid phases as a result of reacting specified amounts of water and rock. Reaction path models first perform an aqueous speciation of the dissolved constituents of the water, test solubility hypotheses, then perform the reaction path modeling. Certain improvements in the present versions of these models would enhance their value and usefulness to applications in nuclear-waste isolation, etc. Mass-transfer calculations of limited extent are certainly within the capabilities of state-of-the-art models. However, the reaction path models require an expansion of their thermodynamic data bases and systematic validation before they are generally accepted.

4. Process for using surface strain measurements to obtain operational loads for complex structures

NASA Technical Reports Server (NTRS)

Richards, William Lance (Inventor); Ko, William L. (Inventor)

2010-01-01

The invention is an improved process for using surface strain data to obtain real-time, operational loads data for complex structures that significantly reduces the time and cost versus current methods.

5. Early Jurassic subduction of the Paleo-Pacific Ocean in NE China: Petrologic and geochemical evidence from the Tumen mafic intrusive complex

Guo, Feng; Li, Hongxia; Fan, Weiming; Li, Jingyan; Zhao, Liang; Huang, Miwei; Xu, Wenliang

2015-05-01

Subduction of the Paleo-Pacific Oceanic Plate is widely considered to have caused extensive Mesozoic magmatism, lithospheric deformation and mineralization in East Asia. However, it is still unclear when this subduction began. Here we report an Early Jurassic (~ 187 Ma) mafic intrusive complex (including olivine norite, gabbro, and diorite) from the Tumen area in NE China. The olivine norite contains a mineral assemblage of olivine, pyroxene, Ca-plagioclase, and hornblende that crystallized in a water-saturated parental magma. The rocks in the complex show variable degrees of plagioclase and ferromagnesian mineral accumulation as reflected by positive Sr and Eu anomalies in primitive mantle-normalized incompatible element patterns. Mass-balance calculations indicate that the parental magma was calc-alkaline with arc-type trace element features (i.e., large ion incompatible and light rare earth element enrichment and Nb-Ta depletion). It also had Sr-Nd-Hf isotopic compositions (87Sr/86Sr(i) = 0.7042 to 0.7044, εNd(t) = + 2.5 to + 3.5 and εHf(t) = + 8.4 to + 10.5) similar to those of modern arc basalts. The parental magma was likely derived from 5 to 20% melting of a mantle wedge metasomatized by an addition of 3-4% hydrous sediment melt from the subducting Paleo-Pacific Oceanic slab. The Tumen mafic intrusive complex, together with other contemporaneous mafic intrusions, I-type granitoids, and felsic lavas, constitutes an Early Jurassic N-S-trending arc magmatic belt that was formed by westward subduction of the Paleo-Pacific Ocean.

6. Integrating geochemical (surface waters, stream sediments) and biological (diatoms) approaches to assess AMD environmental impact in a pyritic mining area: Aljustrel (Alentejo, Portugal).

PubMed

Luís, Ana Teresa; Durães, Nuno; de Almeida, Salomé Fernandes Pinheiro; da Silva, Eduardo Ferreira

2016-04-01

Aljustrel mines were classified as having high environmental hazard due to their large tailings volume and high metal concentrations in waters and sediments. To assess acid mine drainage impacted systems whose environmental conditions change quickly, the use of biological indicators with short generation time such as diatoms is advantageous. This study combined geochemical and diatom data, whose results were highlighted in 3 groups: Group 1, with low pH (1.9-5.1) and high metal/metalloid (Al, As, Cd, Co, Cu, Fe, Mn, Ni, Pb, Zn; 0.65-1032 mg/L) and SO4 (405-39124 mg/L) concentrations. An acidophilic species, Pinnularia aljustrelica, was perfectly adapted to the adverse conditions; in contrast, teratological forms of Eunotia exigua were found, showing that metal toxicity affected this species. The low availability of metals/metalloids in sediments of this group indicates that metals/metalloids of the exchangeable fractions had been solubilized, which in fact enables metal/metalloid diatom uptake and consequently the occurrence of teratologies; Group 2, with sites of near neutral pH (5.0-6.8) and intermediate metal/metalloid (0.002-6 mg/L) and SO4 (302-2179 mg/L) concentrations; this enabled the existence of typical species of uncontaminated streams (Brachysira neglectissima, Achnanthidium minutissimum); Group 3, with samples from unimpacted sites, showing low metal/metalloid (0-0.8 mg/L) and SO4 (10-315 mg/L) concentrations, high pH (7.0-8.4) and Cl contents (10-2119 mg/L) and the presence of brackish to marine species (Entomoneis paludosa). For similar conditions of acidity, differences in diversity, abundance and teratologies of diatoms can be explained by the levels of metals/metalloids.

7. Structural, geochemical and geochronological analysis of metasedimentary and metavolcanic rocks of the Coatlaco area, Acatlán Complex, southern Mexico

Grodzicki, K. R.; Nance, R. D.; Keppie, J. D.; Dostal, J.; Murphy, J. B.

2008-12-01

Low-grade, siliciclastic metasedimentary and mafic metavolcanic rocks near Coatlaco, southern Mexico, form part of the Acatlán Complex, which has been interpreted as a vestige of either the Iapetus or Rheic Oceans. They form two tectonically interleaved units, the Canoas unit consisting of interbedded psammites and pelites, and the Coatlaco unit made up of interbedded quartzite and tholeiitic, within-plate, pillow basalts. Detrital zircons in these two units yielded different age population peaks: Ordovician (459 ± 14 Ma) and ca. 900-1250 Ma detrital zircons in the Canoas unit, and 357 ± 35 Ma, 563 ± 22 Ma, 837 ± 28 Ma, and 1156 ± 74 Ma in the Coatlaco unit. Whereas a source for the Paleozoic zircons may be found in the Acatlán Complex, and provenance for the ca. 900-1250 Ma zircons is likely the adjacent Oaxacan Complex, the Neoproterozoic zircons probably have a more exotic source in Amazonia. The contrasting age populations in the Canoas and Coatlaco units may be due to either (a) different ages of deposition, post-453 ± 6 Ma and post-Devonian, respectively; or (b) contemporaneous deposition in distinct environments; continental margin vs. oceanic with currents perpendicular and parallel to the margin, respectively. The Canoas unit was deformed by four phases of deformation: D 1 and D 2 produced NE-SW, steeply dipping, composite, axial planar solution cleavages (S CN1 and S CN2) with variably plunging, tight-isoclinal folds (F CN1 and F CN2) under lower greenschist facies metamorphic conditions; D 3 produced a sub-vertical, NE-SW, crenulation cleavage parallel to the axial planes of open to close folds, whose plunges show a NE-SW great circle distribution. D 4 produced small, vertically plunging chevron and kink folds (F CN4) in the pelitic rocks. The Coatlaco basalts are massive, lack deformational fabrics, and were altered under greenschist facies metamorphic conditions. The Coatlaco quartzites, in contrast, record two phases of deformation; (i) an S

8. Crystal mat-formation as an igneous layering-forming process: Textural and geochemical evidence from the 'lower layered' nepheline syenite sequence of the Ilímaussaq complex, South Greenland

Lindhuber, Matthias J.; Marks, Michael A. W.; Bons, Paul D.; Wenzel, Thomas; Markl, Gregor

2015-05-01

The lower layered nepheline syenite sequence (kakortokites) of the Mesoproterozoic alkaline to peralkaline Ilímaussaq complex, South Greenland shows spectacular rhythmic meter-scale igneous layering. The 29 exposed units have sharp contacts against each other and each of these units consists of three modally graded layers dominated by arfvedsonitic amphibole, eudialyte-group minerals, and alkali feldspar, respectively. This study uses field observations on changes in mineral orientation, recurrent mineral textures, compositional data from eudialyte-group minerals and amphibole, and settling rate calculations based on a modified Stokes' equation to explain the igneous layering of the kakortokites. We propose that the three major cumulus minerals (amphibole, eudialyte s.l., and alkali feldspar) were separated from each other by density contrasts, resulting in modally graded layers within each unit. The densest of these three minerals (amphibole) formed crystal mats within the cooling magma body. These crystal mats acted as barriers that inhibited large-scale vertical migration of melts and crystals with increasing effectiveness over time. The sub-volumes of magma captured in between the crystal mats evolved largely as geochemically independent sub-systems, as indicated by the observed trends in mineral composition.

9. Geochemical and isotopic constraints on the petrogenesis of the Puesto La Peña undersaturated potassic complex, Mendoza province, Argentina: Geodynamic implications

Zappettini, Eduardo O.; Villar, Luisa M.; Hernández, Laura B.; Santos, João O.

2013-03-01

Major and trace element and radiogenic and stable isotope data are reported for the Miocene Puesto La Peña undersaturated potassic complex, located in the Argentine Precordillera. The complex is composed of a pyroxenite core surrounded by a malignite-borolanite association, followed by radial and ring dikes composed of alkaline lamprophyres, tephrite to phonolite and intermediate varieties, porphyritic microledmorite, benmoreite, alkaline trachyte and a swarm of ultrabasic ouachitite dikes. Late trachytic to phonolitic volcanic necks and associated dikes crop out surrounding the malignitic-borolanitic massif. Major and trace element data are consistent with their derivation by partial melting from an enriched, probably lithospheric, metasomatized heterogeneous mantle involving spinel- and garnet-facies mantle sources. The trace element and isotope data indicate that all rock types are derived from a common parental magma and are thus cogenetic. Sr, Nd and Pb variations in the different studied lithologies are restricted, except for the evidence of Sr decoupling in the ouachitite samples. Their Sr-Nd isotope compositions follow the "mantle array" defined by oceanic basalts, within the OIB field, consistent with an intraplate depleted source. The genesis of the ouachitite is interpreted to be related to mixing between asthenospheric magma and melts from the lower lithosphere consisting of K-rich metasomatic layers. The Dupal like Pb isotopes signature suggests a mantle modification by introduction of continental crust material in the upper mantle; this is consistent with the Sr-Nd isotope data from the late silica-undersaturated felsic dikes and volcanic necks. Multistage mantle extraction would have occurred by the end of Neoproterozoic to lower Paleozoic times as indicated by the isotopic data. Partial melting was initiated by mantle upwelling decompression during lithosphere extension. Back-arc extensional conditions during the latest Early Miocene (19 Ma

10. Geometric and kinematic analysis, and geochemical study of the Corbin Gneiss Complex and its associated sheared rocks in the Blue Ridge of NW Georgia

SciTech Connect

Gargi, S.P.

1985-01-01

The Corbin Gneiss Complex forms the core of the Salem Church anticlinorium in the Blue Ridge of NW Georgia, and is composed of quartz monzodiorite (Corbin gneiss) and pyroxene-biotite diorite. The observed foliation and the presence of thin zones of ultramylonites and phyllonites in the rocks of the gneiss complex are the result of the ductile shearing. Subsequent to the development of the mylonitic foliation these rocks were subjected for four episodes of flexural slip folding. The first generation folds were associated with the formation of the Salem Church anticlinorium. The northeasterly striking axial planes and the southeasterly plunging fold axes of the last three systems of folds suggest that these folds were formed on the southeasterly dipping foliation planes of the Salem Church anticlinorium. The trace element study of the pyroxene-biotite diorite, the Corbin gneiss (quartz monzodiorite) including its variably sheared equivalents shows that these rocks originated from independent sources by primary petrogenetic processes, and do not show any mixing relationship. The whole rock Rb-Sr isochron of the ultramylonitic Corbin gneiss yields an age of 296 +/- 4 Ma and an initial /sup 87/Sr//sup 86/Sr ratio of 0.7208 +/- 7. The much younger age of the ultramylonite in comparison to that of the unsheared Corbin gneiss (age approx. 1 Ga) is the result of resetting of the Rb-Sr systematics of the latter due to shearing, and denotes the minimum age limit of the shearing. A two point whole rock isochron of the diorite gives an apparent age of 1.22 Ga and an initial /sup 87/Sr//sup 86/Sr ratio of 0.7036. The total crustal age of the diorite is slightly greater than the Corbin gneiss.

11. Geobiochemistry: Placing Biochemistry in Its Geochemical Context

Shock, E.; Boyer, G. M.; Canovas, P. A., III; Prasad, A.; Dick, J. M.

2014-12-01

Goals of geobiochemistry include simultaneously evaluating the relative stabilities of microbial cells and minerals, and predicting how the composition of biomolecules can change in response to the progress of geochemical reactions. Recent developments in theoretical geochemistry make it possible to predict standard thermodynamic properties of proteins, nucleotides, lipids, and many metabolites including the constituents of the citric acid cycle, at all temperatures and pressures where life is known to occur, and beyond. Combining these predictions with constraints from geochemical data makes it possible to assess the relative stabilities of biomolecules. Resulting independent predictions of the environmental occurrence of homologous proteins and lipid side-chains can be compared with observations from metagenomic and metalipidomic data to quantify geochemical driving forces that shape the composition of biomolecules. In addition, the energetic costs of generating biomolecules from within a diverse range of habitable environments can be evaluated in terms of prevailing geochemical variables. Comparisons of geochemical bioenergetic calculations across habitats leads to the generalization that the availability of H2 determines the cost of autotrophic biosynthesis relative to the aquatic environment external to microbial cells, and that pH, temperature, pressure, and availability of C, N, P, and S are typically secondary. Increasingly reduced conditions, which are determined by reactions of water with mineral surfaces and mineral assemblages, allow many biosynthetic reactions to shift from costing energy to releasing energy. Protein and lipid synthesis, as well as the reverse citric acid cycle, become energy-releasing processes under these conditions. The resulting energy balances that determine habitability contrast dramatically with assumptions derived from oxic surface conditions, such as those where human biochemistry operates.

12. VARIABLE BOUND-SITE CHARGING CONTRIBUTIONS TO SURFACE COMPLEXATION MASS ACTION EXPRESSIONS

EPA Science Inventory

One and two pK models of surface complexation reactions between reactive surface sites (>SOH) and the proton (H+) use mass action expressions of the form: Ka={[>SOHn-1z-1]g>SOH(0-1)aH+EXP(-xeY/kT)}/{[>SOHnz]g>SOH(n)} where Ka=the acidity constant, [ ]=reactive species concentrati...

13. Cell Surface Expression and Function of the Macromolecular C1 Complex on the Surface of Human Monocytes

PubMed Central

Hosszu, Kinga K.; Valentino, Alisa; Ji, Yan; Matkovic, Mara; Pednekar, Lina; Rehage, Nina; Tumma, Nithin; Peerschke, Ellinor I. B.; Ghebrehiwet, Berhane

2011-01-01

The synthesis of the subunits of the C1 complex (C1q, C1s, C1r), and its regulator C1 inhibitor (C1-Inh) by human monocytes has been previously established. However, surface expression of these molecules by monocytes has not been shown. Using flow cytometry and antigen-capture enzyme-linked immunosorbent assay, we show here for the first time that, in addition to C1q, peripheral blood monocytes, and the monocyte-derived U937 cells express C1s and C1r, as well as Factor B and C1-Inh on their surface. C1s and C1r immunoprecipitated with C1q, suggesting that at least some of the C1q on these cells is part of the C1 complex. Furthermore, the C1 complex on U937 cells was able to trigger complement activation via the classical pathway. The presence of C1-Inh may ensure that an unwarranted autoactivation of the C1 complex does not take place. Since C1-Inh closely monitors the activation of the C1 complex in a sterile or infectious inflammatory environment, further elucidation of the role of C1 complex is crucial to dissect its function in monocyte, dendritic cell, and T cell activities, and its implications in host defense and tolerance. PMID:22566921

14. Surface estimation methods with phased-arrays for adaptive ultrasonic imaging in complex components

Robert, S.; Calmon, P.; Calvo, M.; Le Jeune, L.; Iakovleva, E.

2015-03-01

Immersion ultrasonic testing of structures with complex geometries may be significantly improved by using phased-arrays and specific adaptive algorithms that allow to image flaws under a complex and unknown interface. In this context, this paper presents a comparative study of different Surface Estimation Methods (SEM) available in the CIVA software and used for adaptive imaging. These methods are based either on time-of-flight measurements or on image processing. We also introduce a generalized adaptive method where flaws may be fully imaged with half-skip modes. In this method, both the surface and the back-wall of a complex structure are estimated before imaging flaws.

15. Surface complexation model for strontium sorption to amorphous silica and goethite

PubMed Central

Carroll, Susan A; Roberts, Sarah K; Criscenti, Louise J; O'Day, Peggy A

2008-01-01

Strontium sorption to amorphous silica and goethite was measured as a function of pH and dissolved strontium and carbonate concentrations at 25°C. Strontium sorption gradually increases from 0 to 100% from pH 6 to 10 for both phases and requires multiple outer-sphere surface complexes to fit the data. All data are modeled using the triple layer model and the site-occupancy standard state; unless stated otherwise all strontium complexes are mononuclear. Strontium sorption to amorphous silica in the presence and absence of dissolved carbonate can be fit with tetradentate Sr2+ and SrOH+ complexes on the β-plane and a monodentate Sr2+complex on the diffuse plane to account for strontium sorption at low ionic strength. Strontium sorption to goethite in the absence of dissolved carbonate can be fit with monodentate and tetradentate SrOH+ complexes and a tetradentate binuclear Sr2+ species on the β-plane. The binuclear complex is needed to account for enhanced sorption at hgh strontium surface loadings. In the presence of dissolved carbonate additional monodentate Sr2+ and SrOH+ carbonate surface complexes on the β-plane are needed to fit strontium sorption to goethite. Modeling strontium sorption as outer-sphere complexes is consistent with quantitative analysis of extended X-ray absorption fine structure (EXAFS) on selected sorption samples that show a single first shell of oxygen atoms around strontium indicating hydrated surface complexes at the amorphous silica and goethite surfaces. Strontium surface complexation equilibrium constants determined in this study combined with other alkaline earth surface complexation constants are used to recalibrate a predictive model based on Born solvation and crystal-chemistry theory. The model is accurate to about 0.7 log K units. More studies are needed to determine the dependence of alkaline earth sorption on ionic strength and dissolved carbonate and sulfate concentrations for the development of a robust surface

16. Surface Complexation Model for Strontium Sorption to Amorphous Silica and Goethite

SciTech Connect

Carroll, S; Robers, S; Criscenti, L; O'Day, P

2007-11-30

Strontium sorption to amorphous silica and goethite was measured as a function of pH and dissolved strontium and carbonate concentrations at 25 C. Strontium sorption gradually increases from 0 to 100% from pH 6 to 10 for both phases and requires multiple outer-sphere surface complexes to fit the data. All data are modeled using the triple layer model and the site-occupancy standard state; unless stated otherwise all strontium complexes are mononuclear. Strontium sorption to amorphous silica in the presence and absence of dissolved carbonate can be fit with tetradentate Sr{sup 2+} and SrOH{sup +} complexes on the {beta}-plane and a monodentate Sr{sup 2+} complex on the diffuse plane to account for strontium sorption at low ionic strength. Strontium sorption to goethite in the absence of dissolved carbonate can be fit with monodentate and tetradentate SrOH{sup +} complexes and a tetradentate binuclear Sr{sup 2+} species on the {beta}-plane. The binuclear complex is needed to account for enhanced sorption at high strontium surface loadings. In the presence of dissolved carbonate additional monodentate Sr{sup 2+} and SrOH{sup +} carbonate surface complexes on the {beta}-plane are needed to fit strontium sorption to goethite. Modeling strontium sorption as outer-sphere complexes is consistent with quantitative analysis of extended X-ray absorption fine structure (EXAFS) on selected sorption samples that show a single first shell of oxygen atoms around strontium indicating hydrated surface complexes at the amorphous silica and goethite surfaces. Strontium surface complexation equilibrium constants determined in this study combined with other alkaline earth surface complexation constants are used to recalibrate a predictive model based on Born solvation and crystal-chemistry theory. The model is accurate to about 0.7 log K units. More studies are needed to determine the dependence of alkaline earth sorption on ionic strength and dissolved carbonate and sulfate

17. Cork-resin ablative insulation for complex surfaces and method for applying the same

NASA Technical Reports Server (NTRS)

Walker, H. M.; Sharpe, M. H.; Simpson, W. G. (Inventor)

1980-01-01

A method of applying cork-resin ablative insulation material to complex curved surfaces is disclosed. The material is prepared by mixing finely divided cork with a B-stage curable thermosetting resin, forming the resulting mixture into a block, B-stage curing the resin-containing block, and slicing the block into sheets. The B-stage cured sheet is shaped to conform to the surface being insulated, and further curing is then performed. Curing of the resins only to B-stage before shaping enables application of sheet material to complex curved surfaces and avoids limitations and disadvantages presented in handling of fully cured sheet material.

18. Complex dielectric constant of various biomolecules as a function of wavelength using surface plasmon resonance

Paliwal, Ayushi; Tomar, Monika; Gupta, Vinay

2014-07-01

Present study focuses on determination of complex dielectric constant of biomolecules as function of frequency by means of surface plasmon resonance (SPR) technique without losing their biofunctionality. Surface plasmon modes have been excited in Kretschmann configuration at interface of ZnO-Au thin films. Various biomolecules (glucose oxidase, cholesterol oxidase, urease, and uricase) have been immobilized successfully on surface of ZnO thin film by electrostatic interaction. SPR reflectance curves for all biomolecules were recorded separately at different wavelengths (407-635 nm). Complex dielectric constant was determined by fitting the experimental SPR data with Fresnel's equations. Dielectric constant of all biomolecules shows frequency dispersion and attributed to ionic polarization.

19. U(VI)-kaolinite surface complexation in absence and presence of humic acid studied by TRLFS.

PubMed

Krepelova, Adela; Brendler, Vinzenz; Sachs, Susanne; Baumann, Nils; Bernhard, Gert

2007-09-01

Time-resolved laser-induced fluorescence spectroscopy (TRLFS) was applied to study the U(VI) surface complexes on kaolinite in the presence and absence of humic acid (HA). Two uranyl surface species with fluorescence lifetimes of 5.9 +/- 1.4 and 42.5 +/- 3.4 micros and 4.4 +/- 1.2 and 30.9 +/- 7.2 micros were identified in the binary (U(VI)-kaolinite) and ternary system (U(VI)-HA-kaolinite), respectively. The fluorescence spectra of adsorbed uranyl surface species are described with six and five fluorescence emission bands in the binary and ternary system, respectively. The positions of peak maxima are shifted significantly to higher wavelengths compared to the free uranyl ion in perchlorate medium. HA has no influence on positions of the fluorescence emission bands. In the binary system, both surface species can be attributed to adsorbed bidentate mononuclear surface complexes, which differ in the number of water molecules in their coordination environment. In the ternary system, U(VI) prefers direct binding on kaolinite rather than via HA, but it is sorbed as a uranyl-humate complex. Consequently, the hydration shell of the U(VI) surface complexes is displaced with complexed HA, which is simultaneously distributed between kaolinite particles. Aluminol binding sites are assumed to control the sorption of U(VI) onto kaolinite.

20. Shallow groundwater monitoring at the SACROC oilfield, Scurry County, TX: good news for geologic storage of CO2 despite a complex hydrogeologic and geochemical setting (Invited)

Smyth, R. C.; Romanak, K.; Yang, C.; Hovorka, S.

2009-12-01

The SACROC water study is the first comprehensive research project with application to geologic storage (GS) of CO2 that focuses on collection and interpretation of field measurements of groundwater (water level and water chemistry data). CO2 has been injected for enhanced oil recovery at the SACROC oilfield in Scurry County, TX since 1972. Hence, we have a perfect natural laboratory and an analog for monitoring future commercial CO2 sequestration sites. Kinder Morgan currently operates the SACROC oilfield where over 150 million metric tons (MMT) of CO2 has been injected for EOR at ~2 km depth; over 75 MMT of the CO2 has been produced and re-injected. CO2 is assumed to be trapped in the deep subsurface at SACROC. The goals of monitoring shallow groundwater over CO2 injection sites are to (1) confirm that CO2 has remained in the deep subsurface and (2) assess impacts to water quality if CO2 were to migrate upward along conduit flow paths (e.g. leaking well bores). We collected groundwater and stratigraphic data within an ~3,000 km2 area centered on SACROC to establish regional variability prior to assessing potential impacts to groundwater from CO2 injection. Groundwater data include results from five sampling trips between June 2006 and November 2008, and a compilation of historical data from the Texas Water Development Board database, dating back to 1936. Sources of complexity that contribute to data interpretation challenges include: (1) regional historic oilfield activity, (2) multiple freshwater-bearing strata in the regional Dockum aquifer, (3) sampled wells screened in shallowest (30 m), deepest (150 m), or across both water-bearing zones, (4) variable discharge rate of sampled wells (<5 to >250 gpm), (5) groundwater flow divide that bisects SACROC, (6) variable aquifer recharge mechanisms, (7) temporal variability in groundwater levels and chemistry, (8) cation exchange, (9) presence of biogenically-produced CO2 in aquifer, and (10) incongruent dissolution

1. Multiple Plasmodium falciparum Merozoite Surface Protein 1 Complexes Mediate Merozoite Binding to Human Erythrocytes.

PubMed

Lin, Clara S; Uboldi, Alessandro D; Epp, Christian; Bujard, Hermann; Tsuboi, Takafumi; Czabotar, Peter E; Cowman, Alan F

2016-04-01

Successful invasion of human erythrocytes byPlasmodium falciparummerozoites is required for infection of the host and parasite survival. The early stages of invasion are mediated via merozoite surface proteins that interact with human erythrocytes. The nature of these interactions are currently not well understood, but it is known that merozoite surface protein 1 (MSP1) is critical for successful erythrocyte invasion. Here we show that the peripheral merozoite surface proteins MSP3, MSP6, MSPDBL1, MSPDBL2, and MSP7 bind directly to MSP1, but independently of each other, to form multiple forms of the MSP1 complex on the parasite surface. These complexes have overlapping functions that interact directly with human erythrocytes. We also show that targeting the p83 fragment of MSP1 using inhibitory antibodies inhibits all forms of MSP1 complexes and disrupts parasite growthin vitro.

2. Coupling geochemical, mineralogical and microbiological approaches to assess the health of contaminated soil around the Almalyk mining and smelter complex, Uzbekistan.

PubMed

Shukurov, Nosir; Kodirov, Obidjon; Peitzsch, Mirko; Kersten, Michael; Pen-Mouratov, Stanislav; Steinberger, Yosef

2014-04-01

This study describes the impact of airborne pollution resulting from mining and smelting activities on the soils of the Almalyk mining and industrial area (NE Uzbekistan). Samples were collected along a transect downwind of the industrial area. Enriched contents of some metals were found in the upper soil layers near the metallurgical complex (Zn≤3010 mg kg(-1), Pb≤630 mg kg(-1), Cd≤30 mg kg(-1)) which suggests that these metals were derived from local stack emissions. The morphology and internal microstructure of metal-bearing spherical particles found in the heavy mineral fraction suggest that these particles were probably a result of inefficient flue gas cleaning technique of the smelter. The highest metal concentrations were found also in soil solutions and exchangeable solid fractions from the first three locations, and decreased with increasing distance from the pollution source along transect. Thermodynamic equilibrium calculations suggest that the mobile metal pool in the contaminated soil is mainly controlled by dissolution of metal carbonates formed as weathering product of the metalliferous particles. The health of the microbiological soil ecosystem was assessed by measurements of basal respiration, nematode abundance, biomass-related C and N content, and microbial metabolic quotient qCO2. Significant correlations were found between the dissolved metal content and the microbiological health parameters, a negative one for Cmic/Corg ratio, and a positive one for qCO2. A negative correlation was found between the amount of nematodes and the metal contents suggesting that the contaminated soil has significant impact on the functioning of the microbiological community. A better understanding of the spatial variations in the whole ecosystem functioning due to airborne impact could be very useful for establishing suitable land use and best management practices for the polluted areas.

3. Modulation of proteins adsorption onto the surface of chitosan complexed with anionic copolymers. Real time analysis by surface plasmon resonance.

PubMed

Aguilar, María R; Gallardo, Alberto; Lechuga, Laura M; Calle, Ana; San Román, Julio

2004-07-14

The interpolyelectrolyte complex formation between chitosan and anionic polyacrylic derivatives, bearing sulfonic moieties, as well as the protein adsorption onto the chitosan/polyacrylic complexes were studied by surface plasmon resonance (SPR) optical biosensor. This unique technique allows a real time monitoring of different surface molecular interactions with very high sensitivity. The acrylic macromolecules are two families of copolymers of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) and, respectively, 2-hydroxyethylmethacrylate (HEMA) and N,N'-dimethylacrylamide (DMAA). The complexation process was evaluated through the SPR measurements resulting from the flowing of polyacrylic aqueous solution over the sensor previously coated with chitosan. The SPR was able to differentiate strong ionic bonds from other weak and reversible interactions. By means of the coated sensors (uncomplexed and the whole series of complexed chitosan), SPR cold be used for a simple "in vitro" protein adsorption analysis, by flowing aqueous solutions of albumin and fibrinogen. While both proteins were adsorbed on the uncomplexed chitosan, the complexed coatings exhibited different and very promising behaviors. In particular, they showed no adsorption or only selective adsorption of albumin.

4. Surface organometallic chemistry of tin: Reactivity of tetraalkyltin complexes and tributyltin hydride toward silica

SciTech Connect

Nedez, C.; Theolier, A.; Lefebvre, F.; Choplin, A.; Basset, J.M. ); Joly, J.F. )

1993-01-27

Tetraalkyltin complexes, SnR[sub 4] (R = Me, Et, i-Pr, Bu), and tributylhydridotin were reacted with the surface of partially dehydroxylated silica. Interaction between the complexes and the silica surface was followed by IR and [sup 13]C and [sup 119]Sn MAS NMR spectroscopies and analysis of the evolved gases. At room temperature, all the studied complexes are physisorbed: a hydrogen-type bonding between the terminal methyl group of the alkyl ligands and/or the hydride ligand and the surface silanol groups is evidenced. Above 100[degrees]C, with silica dehydroxylated at 500[degrees]C (SiO[sub 2](500)), a reaction occurs, leading to the formation at 200[degrees]C of essentially one surface complex,-SiO-SnR[sub 3] (1) with evolution of 1 mol of alkane per mol of surface tin. 1 is already formed at room temperature by reaction of silica with Bu[sub 3]SnH; the reaction is slow and liberates 1 mol of H[sub 2]/mol of surface Sn. At low surface coverage, and for R [ne] Me, the alkyl ligands of 1 are folded toward the surface, interacting with it via hydrogen-type bonding. The same interaction and reaction are observed when the surface of silica is less dehydroxylated, SiO[sub 2](200): nevertheless 1 is less stable, probably due to the availability of surface silanol groups in the neighborhood of 1. 28 refs., 9 figs., 1 tab.

5. Surface-Induced Changes in the Thermochromic Transformation of an Ionic Liquid Cobalt Thiocyanate Complex

PubMed Central

2017-01-01

We demonstrate that a thermodynamic complex equilibrium within an ionic liquid film can be significantly influenced by the presence of the liquid–vacuum interface. Using surface-sensitive X-ray photoelectron spectroscopy, we find that the temperature-driven transition from the blue-colored tetrahedral [Co(II) (NCS)4]2– to the red-colored octahedral [Co(II) (NCS)6]4– complex already occurs within the outermost nanometers at around +4 °C as compared with −25 °C in the bulk. This thermochromic transformation in the near-surface region goes along with a loss in preferential surface orientation of free [SCN]− anions and with a pronounced decrease in the complex density; both effects are attributed to the formation of a weakly bound solvation shell around the [Co(II) (NCS)6]4– anion, leading to an effective complex dilution. Our results are not only relevant for high-surface area thin film systems, such as in sensor and catalysis applications, but also shed light on the role of ionic liquid surfaces in particular and liquid surfaces in general. PMID:28212033

6. Surface-Induced Changes in the Thermochromic Transformation of an Ionic Liquid Cobalt Thiocyanate Complex.

PubMed

May, Benjamin; Hönle, Michael; Heller, Bettina; Greco, Francesco; Bhuin, Radha; Steinrück, Hans-Peter; Maier, Florian

2017-02-23

We demonstrate that a thermodynamic complex equilibrium within an ionic liquid film can be significantly influenced by the presence of the liquid-vacuum interface. Using surface-sensitive X-ray photoelectron spectroscopy, we find that the temperature-driven transition from the blue-colored tetrahedral [Co(II) (NCS)4](2-) to the red-colored octahedral [Co(II) (NCS)6](4-) complex already occurs within the outermost nanometers at around +4 °C as compared with -25 °C in the bulk. This thermochromic transformation in the near-surface region goes along with a loss in preferential surface orientation of free [SCN](-) anions and with a pronounced decrease in the complex density; both effects are attributed to the formation of a weakly bound solvation shell around the [Co(II) (NCS)6](4-) anion, leading to an effective complex dilution. Our results are not only relevant for high-surface area thin film systems, such as in sensor and catalysis applications, but also shed light on the role of ionic liquid surfaces in particular and liquid surfaces in general.

7. Managing complexity in simulations of land surface and near-surface processes

SciTech Connect

Coon, Ethan T.; Moulton, J. David; Painter, Scott L.

2016-01-12

Increasing computing power and the growing role of simulation in Earth systems science have led to an increase in the number and complexity of processes in modern simulators. We present a multiphysics framework that specifies interfaces for coupled processes and automates weak and strong coupling strategies to manage this complexity. Process management is enabled by viewing the system of equations as a tree, where individual equations are associated with leaf nodes and coupling strategies with internal nodes. A dynamically generated dependency graph connects a variable to its dependencies, streamlining and automating model evaluation, easing model development, and ensuring models are modular and flexible. Additionally, the dependency graph is used to ensure that data requirements are consistent between all processes in a given simulation. Here we discuss the design and implementation of these concepts within the Arcos framework, and demonstrate their use for verification testing and hypothesis evaluation in numerical experiments.

8. Managing complexity in simulations of land surface and near-surface processes

DOE PAGES

Coon, Ethan T.; Moulton, J. David; Painter, Scott L.

2016-01-12

Increasing computing power and the growing role of simulation in Earth systems science have led to an increase in the number and complexity of processes in modern simulators. We present a multiphysics framework that specifies interfaces for coupled processes and automates weak and strong coupling strategies to manage this complexity. Process management is enabled by viewing the system of equations as a tree, where individual equations are associated with leaf nodes and coupling strategies with internal nodes. A dynamically generated dependency graph connects a variable to its dependencies, streamlining and automating model evaluation, easing model development, and ensuring models aremore » modular and flexible. Additionally, the dependency graph is used to ensure that data requirements are consistent between all processes in a given simulation. Here we discuss the design and implementation of these concepts within the Arcos framework, and demonstrate their use for verification testing and hypothesis evaluation in numerical experiments.« less

9. Cationic and anionic polyelectrolyte complexes of xylan and chitosan. Interaction with lignocellulosic surfaces.

PubMed

Mocchiutti, Paulina; Schnell, Carla N; Rossi, Gerardo D; Peresin, María S; Zanuttini, Miguel A; Galván, María V

2016-10-05

Cationic (CatPECs) and anionic (AnPECs) polyelectrolyte complexes from xylan and chitosan were formed, characterized and adsorbed onto unbleached fibers for improving the papermaking properties. They were prepared at a level of 30% of neutralization charge ratio by modifying the order of addition of polyelectrolytes and the ionic strength (0.01N and 0.1N NaCl). The charge density, colloidal stability and particle size of polyelectrolyte complexes (PECs) was measured using polyelectrolyte titration method, Turbiscan and Zetasizer Nano equipments, respectively. All the complexes were stable even after seven days from PEC formation. DRIFT spectra of complexes were also analyzed. The adsorption behavior of them onto cellulose nanofibrils model surfaces was studied using quartz crystal microbalance with dissipation monitoring, and surface plasmon resonance. It was found that the PEC layers were viscoelastic and highly hydrated. Finally, it is shown that the adsorbed PECs onto cellulosic fibers markedly improved the tensile and crushing strengths of paper.

10. Complex organic molecules at metal surfaces: bonding, organisation and chirality [review article

Barlow, S. M.; Raval, R.

2003-08-01

Surface science techniques have now reached a stage of maturity that has enabled their successful deployment in the study of complex adsorption systems. A particular example of this success has been the understanding that has been gained regarding the behaviour of multi-functional organic molecules at metal surfaces. These organic-metal systems show enormous diversity, starting from their local description which can vary in terms of chemical structure, orientation and bonding. Additionally, in many cases, these complex organic molecules self-organise into beautiful, ordered superstructures held together by networks of intermolecular bonds. Both these aspects enable a single organic molecule-metal system to exhibit a wide-ranging and flexible approach to its environment, leading to a variety of adsorption phases, according to the prevailing temperature and coverage conditions. In this review we have attempted to capture this complexity by constructing adsorption phase diagrams from the available literature for complex carboxylic acids, amino acids, anhydrides and ring systems, all deposited under controlled conditions onto defined metal surfaces. These provide an accessible, pictorial basis of the adsorption phases which are then discussed further in the text of the review. Finally, interest has recently focused on the property of chirality that can be bestowed at an achiral metal surface by the adsorption of these complex organic molecules. The creation of such architectures offers the opportunity for ultimate stereocontrol of reactions and responses at surfaces. We have, therefore, specifically examined the various ways in which chirality can be expressed at a surface and provide a framework for classifying chiral hierarchies that are manifested at surfaces, with particular attention being paid to the progression of chirality from a local to a global level.

11. Complex metallic surface phases in the Al/Cu(111) system: An experimental and computational study

Duguet, T.; Gaudry, E.; Deniozou, T.; Ledieu, J.; de Weerd, M. C.; Belmonte, T.; Dubois, J. M.; Fournée, V.

2009-11-01

The growth of complex intermetallics as surface alloys is investigated by annealing Al thin films deposited on Cu(111) substrate in ultrahigh vacuum. Already at room temperature, the large lattice mismatch between Al and Cu results in interfacial intermixing. Upon annealing, various phases are formed by diffusion depending on the thickness of the Al films and the annealing temperature. The surface structures are characterized by scanning tunneling microscopy, low-energy electron diffraction, and x-ray photoelectron spectroscopy. Three different superlattice phases are identified as well as the complex Hume-Rothery γ-Al4Cu9 phase. The epitaxial relationships between the surface phases and the Cu(111) substrate are determined. We further investigate the electronic structure of the γ phase by density functional calculations. Experimental valence bands are compared to calculated density of states and simulated STM images are used to identify possible bulk planes appearing as surface termination.

12. Toroidal surface complexes of bacteriophage {phi}12 are responsible for host-cell attachment

SciTech Connect

Leo-Macias, Alejandra; Katz, Garrett; Wei Hui; Alimova, Alexandra; Katz, A.; Rice, William J.; Diaz-Avalos, Ruben; Hu Guobin; Stokes, David L.; Gottlieb, Paul

2011-06-05

Cryo-electron tomography and subtomogram averaging are utilized to determine that the bacteriophage {phi}12, a member of the Cystoviridae family, contains surface complexes that are toroidal in shape, are composed of six globular domains with six-fold symmetry, and have a discrete density connecting them to the virus membrane-envelope surface. The lack of this kind of spike in a reassortant of {phi}12 demonstrates that the gene for the hexameric spike is located in {phi}12's medium length genome segment, likely to the P3 open reading frames which are the proteins involved in viral-host cell attachment. Based on this and on protein mass estimates derived from the obtained averaged structure, it is suggested that each of the globular domains is most likely composed of a total of four copies of P3a and/or P3c proteins. Our findings may have implications in the study of the evolution of the cystovirus species in regard to their host specificity. - Research Highlights: > Subtomogram averaging reveals enhanced detail of a {phi}12 cystovirus surface protein complex. > The surface protein complex has a toroidal shape and six-fold symmetry. > It is encoded by the medium-size genome segment. > The proteins of the surface complex most likely are one copy of P3a and three copies of P3c.

13. Surface-induced dissociation of small molecules, peptides, and non-covalent protein complexes.

PubMed

Wysocki, Vicki H; Joyce, Karen E; Jones, Christopher M; Beardsley, Richard L

2008-02-01

This article provides a perspective on collisions of ions with surfaces, including surface-induced dissociation (SID) and reactive ion scattering spectrometry (RISS). The content is organized into sections on surface-induced dissociation of small ions, surface characterization of organic thin films by collision of well-characterized ions into surfaces, the use of SID to probe peptide fragmentation, and the dissociation of large non-covalent complexes by SID. Examples are given from the literature with a focus on experiments from the authors' laboratory. The article is not a comprehensive review but is designed to provide the reader with an overview of the types of results possible by collisions of ions into surfaces.

14. Surface-Induced Dissociation of Small Molecules, Peptides, and Non-covalent Protein Complexes

PubMed Central

Wysocki, Vicki H.; Joyce, Karen E.; Jones, Christopher M.; Beardsley, Richard L.

2009-01-01

This article provides a perspective on collisions of ions with surfaces, including surface-induced dissociation (SID) and reactive ion scattering spectrometry (RISS). The content is organized into sections on surface-induced dissociation of small ions, surface characterization of organic thin films by collision of well-characterized ions into surfaces, the use of SID to probe peptide fragmentation, and the dissociation of large non-covalent complexes by SID. Examples are given from the literature with a focus on experiments from the authors’ laboratory. The article is not a comprehensive review but is designed to provide the reader with an overview of the types of results possible by collisions of ions into surfaces. PMID:18191578

15. [Microbial geochemical calcium cycle].

PubMed

Zavarzin, G A

2002-01-01

The participation of microorganisms in the geochemical calcium cycle is the most important factor maintaining neutral conditions on the Earth. This cycle has profound influence on the fate of inorganic carbon, and, thereby, on the removal of CO2 from the atmosphere. The major part of calcium deposits was formed in the Precambrian, when prokaryotic biosphere predominated. After that, calcium recycling based on biogenic deposition by skeletal organisms became the main process. Among prokaryotes, only a few representatives, e.g., cyanobacteria, exhibit a special calcium function. The geochemical calcium cycle is made possible by the universal features of bacteria involved in biologically mediated reactions and is determined by the activities of microbial communities. In the prokaryotic system, the calcium cycle begins with the leaching of igneous rock predominantly through the action of the community of organotrophic organisms. The release of carbon dioxide to the soil air by organotrophic aerobes leads to leaching with carbonic acid and soda salinization. Under anoxic conditions, of major importance is the organic acid production by primary anaerobes (fermentative microorganisms). Calcium carbonate is precipitated by secondary anaerobes (sulfate reducers) and to a smaller degree by methanogens. The role of the cyanobacterial community in carbonate deposition is exposed by stromatolites, which are the most common organo-sedimentary Precambrian structures. Deposition of carbonates in cyanobacterial mats as a consequence of photoassimilation of CO2 does not appear to be a significant process. It is argued that carbonates were deposited at the boundary between the "soda continent", which emerged as a result of subaerial leaching with carbonic acid, and the ocean containing Ca2+. Such ecotones provided favorable conditions for the development of the benthic cyanobacterial community, which was a precursor of stromatolites.

16. Geochemical Speciation Mass Transfer

SciTech Connect

1985-12-01

PHREEQC is designed to model geochemical reactions. Based on an ion association aqueous model, PHREEQC can calculate pH, redox potential, and mass transfer as a function of reaction progress. It can be used to describe geochemical processes for both far-field and near-field performance assessment and to evaluate data acquisition needs and test data. It can also calculate the composition of solutions in equilibrium with multiple phases. The data base, including elements, aqueous species, and mineral phases, is independent of the program and is completely user-definable. PHREEQC requires thermodynamic data for each solid, gaseous, or dissolved chemical species being modeled. The two data bases, PREPHR and DEQPAK7, supplied with PHREEQC are for testing purposes only and should not be applied to real problems without first being carefully examined. The conceptual model embodied in PHREEQC is the ion-association model of Pearson and Noronha. In this model a set of mass action equations are established for each ion pair (and controlling solid phases when making mass transfer calculations) along with a set of mass balance equations for each element considered. These sets of equations are coupled using activity coefficient values for each aqueous species and solved using a continued fraction approach for the mass balances combined with a modified Newton-Raphson technique for all other equations. The activity coefficient expressions in PHREEQC include the extended Debye-Huckel, WATEQ Debye-Huckel, and Davies equations from the original United States Geological Survey version of the program. The auxiliary preprocessor program PHTL, which is derived from EQTL, converts EQ3/6 thermodynamic data to PHREEQC format so that the two programs can be compared. PHREEQC can be used to determine solubility limits on the radionuclides present in the waste form. These solubility constraints may be input to the WAPPA leach model.

17. Hydrogeologic and geochemical characterization and evaluation of two arroyos for managed aquifer recharge by surface infiltration in the Pojoaque River Basin, Santa Fe County, New Mexico, 2014–15

USGS Publications Warehouse

Robertson, Andrew J.; Cordova, Jeffrey; Teeple, Andrew; Payne, Jason; Carruth, Rob

2017-02-22

In order to provide long-term storage of diverted surface water from the Rio Grande as part of the Aamodt water rights settlement, managed aquifer recharge by surface infiltration in Pojoaque River Basin arroyos was proposed as an option. The initial hydrogeologic and geochemical characterization of two arroyos located within the Pojoaque River Basin was performed in 2014 and 2015 in cooperation with the Bureau of Reclamation to evaluate the potential suitability of these two arroyos as sites for managed aquifer recharge through surface infiltration.The selected reaches were high-gradient (average 3.0–3.5 percent) braided channels filled with unconsolidated sand and gravel-sized deposits that were generally 30–50 feet thick. Saturation was not observed in the unconsolidated channel sands in four subsurface borings but was found at 7–60 feet below the contact between the unconsolidated channel sands and the bedrock. The poorly to well-cemented alluvial deposits that make up the bedrock underlying the unconsolidated channel material is the Tesuque Formation. The individual beds of the Tesuque Formation are reported to be highly heterogeneous and anisotropic, and the bedrock at the site was observed to have variable moisture and large changes in lithology. Surface electrical-resistivity geophysical survey methods showed a sharp contrast between the electrically resistive unconsolidated channel sands and the highly conductive bedrock; however, because of the high conductivity, the resistivity methods were not able to image the water table or preferential flow paths (if they existed) in the bedrock.Infiltration rates measured by double-ring and bulk infiltration tests on a variety of channel morphologies in the study reaches were extremely large (9.7–94.5 feet per day), indicating that the channels could potentially accommodate as much as 6.6 cubic feet per second of applied water without generating surface runoff out of the reach; however, the small volume

18. Detection of surface breaking fatigue crack on a complex aircraft structure with Rayleigh surface waves

Na, Jeong K.; Blackshire, James L.; Kuhr, Samuel J.

2009-03-01

As part of an on-going, multi-year effort focused on developing a practical structural health monitoring (SHM) sensor for critical structural components in aircraft, a miniature Rayleigh surface wave sensor has been developed and tested. The sensor was specifically designed to detect localized, deterministic cracking in targeted locations in critical locations where fatigue cracking is prevalent. A representative aircraft component was used in the present investigation. Miniature interdigital transducers (IDTs) operating in the low megahertz frequency range were designed, fabricated, and tested on compact tension (CT) fatigue specimens in the laboratory before they were strategically placed on the structure, where surface wave signals were monitored in both pitch-catch and pulse-echo detection modes simultaneously. Under a high-cycle fatigue loading to the structure, the IDT sensors performed well with three of the sensors successfully detecting the existence of a critical fatigue crack. Visual and eddy current inspection methods subsequently verified the presence of the crack and its location. In this paper, the entire effort from the design and characterization of the IDT sensors to the final fatigue test on an actual aircraft part is discussed.

19. Geochemical partitioning and pollution assessment of Ni and V as indicator of oil pollution in surface sediments from Shadegan wildlife refuge, Iran.

PubMed

Chaharlang, Behnam Heidari; Bakhtiari, Alireza Riyahi; Mohammadi, Jahangard; Farshchi, Parvin

2016-10-15

The total concentrations and chemical partitioning of Ni, V and Fe have been assessed in surface sediments from 160 sites along the Shadegan wildlife refuge. The results showed that the average total level of Ni, V and Fe in surface sediments were 45.08±12.09, 25.25±20.8 and 25,979.01±6917.91μg/g dw, respectively. On the average, the chemical speciation of Ni, V and Fe in most stations were in the order of residual>oxidisable-organic>acid-reducible>exchangeable. In all fractions, the residual was accounted the highest proportion for the metals analyzed. Among the non-residual phases, the proportion of heavy metals in organic matter fraction was higher than other phases collected from all locations. The comparison between measured values in this study and some fresh water sediment quality guidelines indicated that the levels of nickel would be expected to sporadically cause harmful biological impacts on biota in the Shadegan wildlife refuge.

20. Communication: Structure, formation, and equilibration of ensembles of Ag-S complexes on an Ag surface

SciTech Connect

Russell, Selena M.; Kim, Yousoo; Liu, Da-Jiang; Evans, J. W.; Thiel, P. A.

2013-02-15

We have utilized conditions of very low temperature (4.7 K) and very low sulfur coverage to isolate and identify Ag-S complexes that exist on the Ag(111) surface. The experimental conditions are such that the complexes form at temperatures above the temperature of observation. These complexes can be regarded as polymeric chains of varying length, with an Ag4S pyramid at the core of each monomeric unit. Steps may catalyze the formation of the chains and this mechanism may be reflected in the chain length distribution.

1. Surface complexation modeling for predicting solid phase arsenic concentrations in the sediments of the Mississippi River Valley alluvial aquifer, Arkansas, USA

USGS Publications Warehouse

Sharif, M.S.U.; Davis, R.K.; Steele, K.F.; Kim, B.; Hays, P.D.; Kresse, T.M.; Fazio, J.A.

2011-01-01

The potential health impact of As in drinking water supply systems in the Mississippi River Valley alluvial aquifer in the state of Arkansas, USA is significant. In this context it is important to understand the occurrence, distribution and mobilization of As in the Mississippi River Valley alluvial aquifer. Application of surface complexation models (SCMs) to predict the sorption behavior of As and hydrous Fe oxides (HFO) in the laboratory has increased in the last decade. However, the application of SCMs to predict the sorption of As in natural sediments has not often been reported, and such applications are greatly constrained by the lack of site-specific model parameters. Attempts have been made to use SCMs considering a component additivity (CA) approach which accounts for relative abundances of pure phases in natural sediments, followed by the addition of SCM parameters individually for each phase. Although few reliable and internally consistent sorption databases related to HFO exist, the use of SCMs using laboratory-derived sorption databases to predict the mobility of As in natural sediments has increased. This study is an attempt to evaluate the ability of the SCMs using the geochemical code PHREEQC to predict solid phase As in the sediments of the Mississippi River Valley alluvial aquifer in Arkansas. The SCM option of the double-layer model (DLM) was simulated using ferrihydrite and goethite as sorbents quantified from chemical extractions, calculated surface-site densities, published surface properties, and published laboratory-derived sorption constants for the sorbents. The model results are satisfactory for shallow wells (10.6. m below ground surface), where the redox condition is relatively oxic or mildly suboxic. However, for the deep alluvial aquifer (21-36.6. m below ground surface) where the redox condition is suboxic to anoxic, the model results are unsatisfactory. ?? 2011 Elsevier Ltd.

2. Plasma immersion ion implantation for surface treatment of complex branched structures

Kashin, Oleg A.; Lotkov, Alexander I.; Borisov, Dmitry P.; Slabodchikov, Vladimir A.; Kuznetsov, Vladimir M.; Kudryashov, Andrey N.; Krukovsky, Konstantin V.

2016-11-01

The paper presents experimental results demonstrating the capabilities of plasma immersion ion implantation of silicon (Si) for surface treatment of complex branched structures such are self-expanding intravascular nickel-titanium (NiTi) stents. Using NiTi stents of diameter 4 and 8 mm, it is shown that plasma immersion ion implantation can provide rather homogeneous doping of their outer and inner surfaces with Si atoms. Also presented are research data on the processes that determine the thickness, composition, and structure of surface layers subjected to this type of treatment.

3. Analytical estimation of solid angle subtended by complex well-resolved surfaces for infrared detection studies.

PubMed

Mahulikar, Shripad P; Potnuru, Santosh K; Kolhe, Pankaj S

2007-08-01

The solid angle (Omega) subtended by the hot power-plant surfaces of a typical fighter aircraft, on the detector of an infrared (IR) guided missile, is analytically obtained. The use of the parallel rays projection method simplifies the incorporation of the effect of the optical blocking by engine surfaces, on Omega-subtended. This methodology enables the evaluation of the relative contribution of the IR signature from well-resolved distributed sources, and is important for imaging infrared detection studies. The complex 3D surface of a rear fuselage is projected onto an equivalent planar area normal to the viewing aspect, which would give the same Omega-subtended.

4. Electromagnetic wave band structure due to surface plasmon resonances in a complex plasma

2016-07-01

The dielectric properties of complex plasma containing either metal or dielectric spherical inclusions (macroparticles, dust) are investigated. We focus on surface plasmon resonances on the macroparticle surfaces and their effect on electromagnetic wave propagation. It is demonstrated that the presence of surface plasmon oscillations can significantly modify plasma electromagnetic properties by resonances and cutoffs in the effective permittivity. This leads to related branches of electromagnetic waves and to the wave band gaps. The conditions necessary to observe the band-gap structure in laboratory dusty plasma and/or space (cosmic) dusty plasmas are discussed.

5. Application of surface complexation models to anion adsorption by natural materials

Technology Transfer Automated Retrieval System (TEKTRAN)

Various chemical models of ion adsorption will be presented and discussed. Chemical models, such as surface complexation models, provide a molecular description of anion adsorption reactions using an equilibrium approach. Two such models, the constant capacitance model and the triple layer model w...

6. Stable U(IV) complexes form at high-affinity mineral surface sites.

PubMed

Latta, Drew E; Mishra, Bhoopesh; Cook, Russell E; Kemner, Kenneth M; Boyanov, Maxim I

2014-01-01

Uranium (U) poses a significant contamination hazard to soils, sediments, and groundwater due to its extensive use for energy production. Despite advances in modeling the risks of this toxic and radioactive element, lack of information about the mechanisms controlling U transport hinders further improvements, particularly in reducing environments where U(IV) predominates. Here we establish that mineral surfaces can stabilize the majority of U as adsorbed U(IV) species following reduction of U(VI). Using X-ray absorption spectroscopy and electron imaging analysis, we find that at low surface loading, U(IV) forms inner-sphere complexes with two metal oxides, TiO2 (rutile) and Fe3O4 (magnetite) (at <1.3 U nm(-2) and <0.037 U nm(-2), respectively). The uraninite (UO2) form of U(IV) predominates only at higher surface loading. U(IV)-TiO2 complexes remain stable for at least 12 months, and U(IV)-Fe3O4 complexes remain stable for at least 4 months, under anoxic conditions. Adsorbed U(IV) results from U(VI) reduction by Fe(II) or by the reduced electron shuttle AH2QDS, suggesting that both abiotic and biotic reduction pathways can produce stable U(IV)-mineral complexes in the subsurface. The observed control of high-affinity mineral surface sites on U(IV) speciation helps explain the presence of nonuraninite U(IV) in sediments and has important implications for U transport modeling.

7. Adsorption of mercury on lignin: combined surface complexation modeling and X-ray absorption spectroscopy studies.

PubMed

Lv, Jitao; Luo, Lei; Zhang, Jing; Christie, Peter; Zhang, Shuzhen

2012-03-01

Adsorption of mercury (Hg) on lignin was studied at a range of pH values using a combination of batch adsorption experiments, a surface complexation model (SCM) and synchrotron X-ray absorption spectroscopy (XAS). Surface complexation modeling indicates that three types of acid sites on lignin surfaces, namely aliphatic carboxylic-, aromatic carboxylic- and phenolic-type surface groups, contributed to Hg(II) adsorption. The bond distance and coordination number of Hg(II) adsorption samples at pH 3.0, 4.0 and 5.5 were obtained from extended X-ray absorption fine structure (EXAFS) spectroscopy analysis. The results of SCM and XAS combined reveal that the predominant adsorption species of Hg(II) on lignin changes from HgCl(2)(0) to monodentate complex -C-O-HgCl and then bidentate complex -C-O-Hg-O-C- with increasing pH value from 2.0 to 6.0. The good agreement between SCM and XAS results provides new insight into understanding the mechanisms of Hg(II) adsorption on lignin.

8. SO2:H2O surface complex found at the vapor/water interface.

PubMed

Tarbuck, Teresa L; Richmond, Geraldine L

2005-12-07

A weakly bonded SO2:H2O surface complex is found at the vapor/water interface prior to the reaction and dissolution of SO2 into the aqueous phase. The results have important implications for understanding the formation of atmospheric aerosols and understanding the atmospheric sulfur cycle.

9. Interactive visual analysis of complex scientific data as families of data surfaces.

PubMed

Matković, Kresimir; Gracanin, Denis; Klarin, Borislav; Hauser, Helwig

2009-01-01

The widespread use of computational simulation in science and engineering provides challenging research opportunities. Multiple independent variables are considered and large and complex data are computed, especially in the case of multi-run simulation. Classical visualization techniques deal well with 2D or 3D data and also with time-dependent data. Additional independent dimensions, however, provide interesting new challenges. We present an advanced visual analysis approach that enables a thorough investigation of families of data surfaces, i.e., datasets, with respect to pairs of independent dimensions. While it is almost trivial to visualize one such data surface, the visual exploration and analysis of many such data surfaces is a grand challenge, stressing the users' perception and cognition. We propose an approach that integrates projections and aggregations of the data surfaces at different levels (one scalar aggregate per surface, a 1D profile per surface, or the surface as such). We demonstrate the necessity for a flexible visual analysis system that integrates many different (linked) views for making sense of this highly complex data. To demonstrate its usefulness, we exemplify our approach in the context of a meteorological multi-run simulation data case and in the context of the engineering domain, where our collaborators are working with the simulation of elastohydrodynamic (EHD) lubrication bearing in the automotive industry.

10. Formation, Migration, and Reactivity of Au CO Complexes on Gold Surfaces

DOE PAGES

Wang, Jun; McEntee, Monica; Tang, Wenjie; ...

2016-01-12

Here, we report experimental as well as theoretical evidence that suggests Au CO complex formation upon the exposure of CO to active sites (step edges and threading dislocations) on a Au(111) surface. Room-temperature scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy, transmission infrared spectroscopy, and density functional theory calculations point to Au CO complex formation and migration. Room-temperature STM of the Au(111) surface at CO pressures in the range from 10^ 8 to 10^ 4 Torr (dosage up to 10^6 langmuir) indicates Au atom extraction from dislocation sites of the herringbone reconstruction, mobile Au CO complex formation and diffusion, and Aumore » adatom cluster formation on both elbows and step edges on the Au surface. The formation and mobility of the Au CO complex result from the reduced Au Au bonding at elbows and step edges leading to stronger Au CO bonding and to the formation of a more positively charged CO (CO +) on Au. These studies indicate that the mobile Au CO complex is involved in the Au nanoparticle formation and reactivity, and that the positive charge on CO increases due to the stronger adsorption of CO at Au sites with lower coordination numbers.« less

11. Formation, Migration, and Reactivity of Au CO Complexes on Gold Surfaces

SciTech Connect

Wang, Jun; McEntee, Monica; Tang, Wenjie; Neurock, Matthew; Baddorf, Arthur P.; Maksymovych, Petro; Yates, Jr, John T.

2016-01-12

Here, we report experimental as well as theoretical evidence that suggests Au CO complex formation upon the exposure of CO to active sites (step edges and threading dislocations) on a Au(111) surface. Room-temperature scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy, transmission infrared spectroscopy, and density functional theory calculations point to Au CO complex formation and migration. Room-temperature STM of the Au(111) surface at CO pressures in the range from 10^ 8 to 10^ 4 Torr (dosage up to 10^6 langmuir) indicates Au atom extraction from dislocation sites of the herringbone reconstruction, mobile Au CO complex formation and diffusion, and Au adatom cluster formation on both elbows and step edges on the Au surface. The formation and mobility of the Au CO complex result from the reduced Au Au bonding at elbows and step edges leading to stronger Au CO bonding and to the formation of a more positively charged CO (CO +) on Au. These studies indicate that the mobile Au CO complex is involved in the Au nanoparticle formation and reactivity, and that the positive charge on CO increases due to the stronger adsorption of CO at Au sites with lower coordination numbers.

12. Environmental Applications of Geochemical Modeling

Zhu, Chen; Anderson, Greg

2002-05-01

This book discusses the application of geochemical models to environmental practice and studies, through the use of numerous case studies of real-world environmental problems, such as acid mine drainage, pit lake chemistry, nuclear waste disposal, and landfill leachates. In each example the authors clearly define the environmental threat in question; explain how geochemical modeling may help solve the problem posed; and advise the reader how to prepare input files for geochemical modeling codes and interpret the results in terms of meeting regulatory requirements.

13. Surface complexation of neptunium (V) onto whole cells and cell componets of Shewanella alga

SciTech Connect

Reed, Donald Timothy; Deo, Randhir P; Rittmann, Bruce E; Songkasiri, Warinthorn

2008-01-01

We systematically quantified surface complexation of neptunium(V) onto whole cells of Shewanella alga strain BrY and onto cell wall and extracellular polymeric substances (EPS) of S. alga. We first performed acid and base titrations and used the mathematical model FITEQL with constant-capacitance surface-complexation to determine the concentrations and deprotonation constants of specific surface functional groups. Deprotonation constants most likely corresponded to a carboxyl site associated with amino acids (pK{sub a} {approx} 2.4), a carboxyl group not associated with amino acids (pK{sub a} {approx} 5), a phosphoryl site (pK{sub a} {approx} 7.2), and an amine site (pK{sub a} > 10). We then carried out batch sorption experiments with Np(V) and each of the S. alga components at different pHs. Results show that solution pH influenced the speciation of Np(V) and each of the surface functional groups. We used the speciation sub-model of the biogeochemical model CCBATCH to compute the stability constants for Np(V) complexation to each surface functional group. The stability constants were similar for each functional group on S. alga bacterial whole cells, cell walls, and EPS, and they explain the complicated sorption patterns when they are combined with the aqueous-phase speciation of Np(V). For pH < 8, NpO{sub 2}{sup +} was the dominant form of Np(V), and its log K values for the low-pK{sub a} carboxyl, other carboxyl, and phosphoryl groups were 1.75, 1.75, and 2.5 to 3.1, respectively. For pH greater than 8, the key surface ligand was amine >XNH3+, which complexed with NpO{sub 2}(CO{sub 3}){sub 3}{sup 5-}. The log K for NpO{sub 2}(CO{sub 3}){sub 3}{sup 5-} complexed onto the amine groups was 3.1 to 3.6. All of the log K values are similar to those of Np(V) complexes with aqueous carboxyl and N-containing carboxyl ligands. These results point towards the important role of surface complexation in defining key actinide-microbiological interactions in the subsurface.

14. Modeling Low-temperature Geochemical Processes

Nordstrom, D. K.

2003-12-01

Geochemical modeling has become a popular and useful tool for a wide number of applications from research on the fundamental processes of water-rock interactions to regulatory requirements and decisions regarding permits for industrial and hazardous wastes. In low-temperature environments, generally thought of as those in the temperature range of 0-100 °C and close to atmospheric pressure (1 atm=1.01325 bar=101,325 Pa), complex hydrobiogeochemical reactions participate in an array of interconnected processes that affect us, and that, in turn, we affect. Understanding these complex processes often requires tools that are sufficiently sophisticated to portray multicomponent, multiphase chemical reactions yet transparent enough to reveal the main driving forces. Geochemical models are such tools. The major processes that they are required to model include mineral dissolution and precipitation; aqueous inorganic speciation and complexation; solute adsorption and desorption; ion exchange; oxidation-reduction; or redox; transformations; gas uptake or production; organic matter speciation and complexation; evaporation; dilution; water mixing; reaction during fluid flow; reaction involving biotic interactions; and photoreaction. These processes occur in rain, snow, fog, dry atmosphere, soils, bedrock weathering, streams, rivers, lakes, groundwaters, estuaries, brines, and diagenetic environments. Geochemical modeling attempts to understand the redistribution of elements and compounds, through anthropogenic and natural means, for a large range of scale from nanometer to global. "Aqueous geochemistry" and "environmental geochemistry" are often used interchangeably with "low-temperature geochemistry" to emphasize hydrologic or environmental objectives.Recognition of the strategy or philosophy behind the use of geochemical modeling is not often discussed or explicitly described. Plummer (1984, 1992) and Parkhurst and Plummer (1993) compare and contrast two approaches for

15. Geochemical characteristics of phosphorus in surface sediments of two major Chinese mariculture areas: the Laizhou Bay and the coastal waters of the Zhangzi Island.

PubMed

Zhuang, Wen; Gao, Xuelu; Zhang, Yong; Xing, Qianguo; Tosi, Luigi; Qin, Song

2014-06-15

Phosphorus (P) in surface sediments of the Laizhou Bay (LB) and the coastal waters around the Zhangzi Island (ZI) was analyzed. Six forms of P were separated - exchangeable or loosely sorbed P (Ads-P), aluminum-bound P (Al-P), iron-bound P (Fe-P), authigenic apatite plus CaCO3-bound P plus biogenic apatite (Ca-P), detrital apatite plus other inorganic P (De-P) and organic P (OP). The average contents of P in the LB were in the order: De-P>OP>Ca-P>Fe-P>Ads-P>Al-P; in the ZI, the corresponding order was De-P>OP>Fe-P>Ca-P>Ads-P>Al-P. Due to the high nutrient loadings from the surrounding rivers, TP contents in sediments of the LB were higher than in those of the ZI. The potential bio-available P (Ads-P and OP) accounted for 14.7% and 24.2% of TP in sediments of the LB and the ZI, respectively.

16. Archean crust-mantle geochemical differentiation

NASA Technical Reports Server (NTRS)

Tilton, G. R.

1983-01-01

Isotope measurements on carbonatite complexes and komatiites can provide information on the geochemical character and geochemical evolution of the mantle, including the sub-continental mantle. Measurements on young samples establish the validity of the method. These are based on Sr, Nd and Pb data from the Tertiary-Mesozoic Gorgona komatiite and Sr and Pb data from the Cretaceous Oka carbonatite complex. In both cases the data describe a LIL element-depleted source similar to that observed presently in MORB. Carbonatite data have been used to study the mantle beneath the Superior Province of the Canadian Shield one billion years (1 AE) ago. The framework for this investigation was established by Bell et al., who showed that large areas of the province appear to be underlain by LIL element-depleted mantle (Sr-85/Sr-86=0.7028) at 1 AE ago. Additionally Bell et al. found four complexes to have higher initial Sr ratios (Sr-87/Sr-86=0.7038), which they correlated with less depleted (bulk earth?) mantle sources, or possibly crustal contamination. Pb isotope relationships in four of the complexes have been studied by Bell et al.

17. Strong Coupling of Localized Surface Plasmons to Excitons in Light-Harvesting Complexes

PubMed Central

2016-01-01

Gold nanostructure arrays exhibit surface plasmon resonances that split after attaching light harvesting complexes 1 and 2 (LH1 and LH2) from purple bacteria. The splitting is attributed to strong coupling between the localized surface plasmon resonances and excitons in the light-harvesting complexes. Wild-type and mutant LH1 and LH2 from Rhodobacter sphaeroides containing different carotenoids yield different splitting energies, demonstrating that the coupling mechanism is sensitive to the electronic states in the light harvesting complexes. Plasmon–exciton coupling models reveal different coupling strengths depending on the molecular organization and the protein coverage, consistent with strong coupling. Strong coupling was also observed for self-assembling polypeptide maquettes that contain only chlorins. However, it is not observed for monolayers of bacteriochlorophyll, indicating that strong plasmon–exciton coupling is sensitive to the specific presentation of the pigment molecules. PMID:27689237

18. Origin of complex impact craters on native oxide coated silicon surfaces

Samela, Juha; Nordlund, Kai; Popok, Vladimir N.; Campbell, Eleanor E. B.

2008-02-01

Crater structures induced by impact of keV-energy Arn+ cluster ions on silicon surfaces are measured with atomic force microscopy. Complex crater structures consisting of a central hillock and outer rim are observed more often on targets covered with a native silicon oxide layer than on targets without the oxide layer. To explain the formation of these complex crater structures, classical molecular dynamics simulations of Ar cluster impacts on oxide coated silicon surfaces, as well as on bulk amorphous silica, amorphous Si, and crystalline Si substrates, are carried out. The diameter of the simulated hillock structures in the silicon oxide layer is in agreement with the experimental results, but the simulations cannot directly explain the height of hillocks and the outer rim structures when the oxide coated silicon substrate is free of defects. However, in simulations of 5keV /atom Ar12 cluster impacts, transient displacements of the amorphous silicon or silicon oxide substrate surfaces are induced in an approximately 50nm wide area surrounding the impact point. In silicon oxide, the transient displacements induce small topographical changes on the surface in the vicinity of the central hillock. The comparison of cluster stopping mechanisms in the various silicon oxide and silicon structures shows that the largest lateral momentum is induced in the silicon oxide layer during the impact; thus, the transient displacements on the surface are stronger than in the other substrates. This can be a reason for the higher frequency of occurrence of the complex craters on oxide coated silicon.

19. Cell-surface Attachment of Bacterial Multienzyme Complexes Involves Highly Dynamic Protein-Protein Anchors*

PubMed Central

Cameron, Kate; Najmudin, Shabir; Alves, Victor D.; Bayer, Edward A.; Smith, Steven P.; Bule, Pedro; Waller, Helen; Ferreira, Luís M. A.; Gilbert, Harry J.; Fontes, Carlos M. G. A.

2015-01-01

Protein-protein interactions play a pivotal role in the assembly of the cellulosome, one of nature's most intricate nanomachines dedicated to the depolymerization of complex carbohydrates. The integration of cellulosomal components usually occurs through the binding of type I dockerin modules located at the C terminus of the enzymes to cohesin modules located in the primary scaffoldin subunit. Cellulosomes are typically recruited to the cell surface via type II cohesin-dockerin interactions established between primary and cell-surface anchoring scaffoldin subunits. In contrast with type II interactions, type I dockerins usually display a dual binding mode that may allow increased conformational flexibility during cellulosome assembly. Acetivibrio cellulolyticus produces a highly complex cellulosome comprising an unusual adaptor scaffoldin, ScaB, which mediates the interaction between the primary scaffoldin, ScaA, through type II cohesin-dockerin interactions and the anchoring scaffoldin, ScaC, via type I cohesin-dockerin interactions. Here, we report the crystal structure of the type I ScaB dockerin in complex with a type I ScaC cohesin in two distinct orientations. The data show that the ScaB dockerin displays structural symmetry, reflected by the presence of two essentially identical binding surfaces. The complex interface is more extensive than those observed in other type I complexes, which results in an ultra-high affinity interaction (Ka ∼1012 m). A subset of ScaB dockerin residues was also identified as modulating the specificity of type I cohesin-dockerin interactions in A. cellulolyticus. This report reveals that recruitment of cellulosomes onto the cell surface may involve dockerins presenting a dual binding mode to incorporate additional flexibility into the quaternary structure of highly populated multienzyme complexes. PMID:25855788

20. A physically-based hybrid framework to estimate daily-mean surface fluxes over complex terrain

Huang, Hsin-Yuan; Hall, Alex

2016-06-01

In this study we developed and examined a hybrid modeling approach integrating physically-based equations and statistical downscaling to estimate fine-scale daily-mean surface turbulent fluxes (i.e., sensible and latent heat fluxes) for a region of southern California that is extensively covered by varied vegetation types over a complex terrain. The selection of model predictors is guided by physical parameterizations of surface flux used in land surface models and analysis showing net shortwave radiation that is a major source of variability in the surface energy budget. Through a structure of multivariable regression processes with an application of near-surface wind estimates from a previous study, we successfully reproduce dynamically-downscaled 3 km resolution surface flux data. The overall error in our estimates is less than 20 % for both sensible and latent heat fluxes, while slightly larger errors are seen in high-altitude regions. The major sources of error in estimates include the limited information provided in coarse reanalysis data, the accuracy of near-surface wind estimates, and an ignorance of the nonlinear diurnal cycle of surface fluxes when using daily-mean data. However, with reasonable and acceptable errors, this hybrid modeling approach provides promising, fine-scale products of surface fluxes that are much more accurate than reanalysis data, without performing intensive dynamical simulations.

1. Long-Lived, Sub-Surface Layers of Toxic Oil in the Deep-Sea: A Molecular Organic and Isotopic Geochemical Approach to Understanding their Nature, Molecular Distribution, Origin and Impact to the Northern Gulf of Mexico

Hollander, D. J.; Freeman, K. H.; Ellis, G.; Diefendorf, A. F.; Peebles, E. B.; Paul, J.

2010-12-01

Here we present the results from two research cruises to the Northern Gulf of Mexico (GoM) during May and August 2010, after the April 20th blowout of BP’s Deepwater Horizon (DWH) drilling rig. Not only was the DWH tragedy the largest oil spill to have ever occurred in the United States but it was also the first blowout of a deep-sea oil exploration well. The BP oil spill presents the scientific community with a critically important and unique opportunity: i) to characterize the occurrence, molecular distribution and abundance of the hydrocarbons in the sub-surface, ii) to identify the source of the oil in the environment and, iii) to study how the distribution and chemistry of the hydrocarbons change over time and space and whether the sub-surface hydrocarbons are toxic to marine plankton and bacteria. Using sonar, fluorometry and backscatter, we were able to trace the occurrence of layers of sub-surface oil. These oil layers were found suspended at depths of 400 m and 1000-1400 m in the form of small microdroplets that were not visible to the naked eye. Both the 400 and the 1000 m layers were traced for more than 20 miles in length and 4 miles in width. Molecular organic geochemical analyses determined that petroleum hydrocarbons were the dominant components of the 400 and 1000 m layers. Interesting, the distribution of compounds was extremely consistent among all the samples with n-alkanes ranging from C24 to C37 with a maximum at C28. The loss of the lower molecular weight components of the crude oil is attributed to biodegradation. This distribution of n-alkanes was the same regardless of whether the samples were from 400 or 1000 m, whether the sites were 25 or 45 miles from the DWH site or whether the samples were collected in May or August. These observations strongly suggest that the bacteria are not able to consume all of the oil, and that these higher molecular weight compounds may persist in the environment for extended lengths of time, at least months

2. Surface complexation of ferrous iron and carbonate on ferrihydrite and the mobilization of arsenic.

PubMed

Appelo, C A J; Van Der Weiden, M J J; Tournassat, C; Charlet, L

2002-07-15

Surface complexation models are commonly used to predict the mobility of trace metals in aquifers. For arsenic in groundwater, surface complexation models cannot be used because the database is incomplete. Both carbonate and ferrous iron are often present at a high concentration in groundwater and will influence the sorption of arsenic, but the surface complexation constants are absent in the database of Dzombak and Morel. This paper presents the surface complexation constants for carbonate and ferrous iron on ferrihydrite as derived for the double-layer model. For ferrous iron the constants were obtained from published data supplemented by new experiments to determine the sorption on the strong sites of ferrihydrite. For carbonate the constants were derived from experiments by Zachara et al., who employed relatively low concentrations of carbonate. The double-layer model, optimized for low concentrations, was tested against sorption experiments of carbonate on goethite at higher concentration by Villalobos and Leckie, and reasonable agreement was found. Sorption was also estimated using linear free energy relations (LFER), and results compared well with our derived constants. Model calculations confirm that sorption of particularly carbonate at common soil and groundwater concentrations reduces the sorption capacity of arsenic on ferrihydrite significantly. The displacing effect of carbonate on sorbed arsenate and arsenite has been overlooked in many studies. It may be an important cause for the high concentrations of arsenic in groundwater in Bangladesh. Sediments containing high amounts of sorbed arsenic are deposited in surface water with low carbonate concentrations. Subsequently the sediments become exposed to groundwater with a high dissolved carbonate content, and arsenic is mobilized by displacement from the sediment surface.

3. Baculovirus per os infectivity factors form a complex on the surface of occlusion-derived virus.

PubMed

Peng, Ke; van Oers, Monique M; Hu, Zhihong; van Lent, Jan W M; Vlak, Just M

2010-09-01

Five highly conserved per os infectivity factors, PIF1, PIF2, PIF3, PIF4, and P74, have been reported to be essential for oral infectivity of baculovirus occlusion-derived virus (ODV) in insect larvae. Three of these proteins, P74, PIF1, and PIF2, were thought to function in virus binding to insect midgut cells. In this paper evidence is provided that PIF1, PIF2, and PIF3 form a stable complex on the surface of ODV particles of the baculovirus Autographa californica multinucleocapsid nucleopolyhedrovirus (AcMNPV). The complex could withstand 2% SDS-5% beta-mercaptoethanol with heating at 50 degrees C for 5 min. The complex was not formed when any of the genes for PIF1, PIF2, or PIF3 was deleted, while reinsertion of these genes into AcMNPV restored the complex. Coimmunoprecipitation analysis independently confirmed the interactions of the three PIF proteins and revealed in addition that P74 is also associated with this complex. However, deletion of the p74 gene did not affect formation of the PIF1-PIF2-PIF3 complex. Electron microscopy analysis showed that PIF1 and PIF2 are localized on the surface of the ODV with a scattered distribution. This distribution did not change for PIF1 or PIF2 when the gene for PIF2 or PIF1 protein was deleted. We propose that PIF1, PIF2, PIF3, and P74 form an evolutionarily conserved complex on the ODV surface, which has an essential function in the initial stages of baculovirus oral infection.

4. Biomimetic environment to study E. coli complex I through surface-enhanced IR absorption spectroscopy.

PubMed

Kriegel, Sébastien; Uchida, Taro; Osawa, Masatoshi; Friedrich, Thorsten; Hellwig, Petra

2014-10-14

In this study complex I was immobilized in a biomimetic environment on a gold layer deposited on an ATR-crystal in order to functionally probe the enzyme against substrates and inhibitors via surface-enhanced IR absorption spectroscopy (SEIRAS) and cyclic voltammetry (CV). To achieve this immobilization, two methods based on the generation of a high affinity self-assembled monolayer (SAM) were probed. The first made use of the affinity of Ni-NTA toward a hexahistidine tag that was genetically engineered onto complex I and the second exploited the affinity of the enzyme toward its natural substrate NADH. Experiments were also performed with complex I reconstituted in lipids. Both approaches have been found to be successful, and electrochemically induced IR difference spectra of complex I were obtained.

5. Nonlinear optics and surface relief gratings in alkynyl-ruthenium complexes

Sahraoui, B.; Luc, J.; Meghea, A.; Czaplicki, R.; Fillaut, J.-L.; Migalska-Zalas, A.

2009-02-01

Generally, the organometallic complexes rich in carbon and containing π-conjugated chains are materials interesting for the study of electronic transfer processes. Currently, the ruthenium-acetylide organometallic complexes form part of the most studied organometallic compounds in nonlinear optics. In this work, we highlight the nonlinear optical properties and the photo-induced structure of new organometallic complexes containing a ruthenium-acetylide donor fragment able to compete with the strongest organic donors. We determine, using various experimental techniques (degenerate four-wave mixing, second and third harmonic generation), the influence of the functionalization of these molecular structures on the improvement of their second-and third-order nonlinear optical properties exploiting in particular the nature of the acceptor fragment and the π-conjugated transmitter. Also we present the dynamics of formation of photo-induced surface relief gratings using a transmission holographic technique and the atomic force microscopy on ruthenium-acetylide complexes containing an azobenzene fragment.

6. Reactive solute transport in streams: A surface complexation approach for trace metal sorption

USGS Publications Warehouse

Runkel, R.L.; Kimball, B.A.; McKnight, Diane M.; Bencala, K.E.

1999-01-01

A model for trace metals that considers in-stream transport, metal oxide precipitation-dissolution, and pH-dependent sorption is presented. Linkage between a surface complexation submodel and the stream transport equations provides a framework for modeling sorption onto static and/or dynamic surfaces. A static surface (e.g., an iron-oxide-coated streambed) is defined as a surface with a temporally constant solid concentration. Limited contact between solutes in the water column and the static surface is considered using a pseudokinetic approach. A dynamic surface (e.g., freshly precipitated metal oxides) has a temporally variable solid concentration and is in equilibrium with the water column. Transport and deposition of solute mass sorbed to the dynamic surface is represented in the stream transport equations that include precipitate settling. The model is applied to a pH-modification experiment in an acid mine drainage stream. Dissolved copper concentrations were depressed for a 3 hour period in response to the experimentally elevated pH. After passage of the pH front, copper was desorbed, and dissolved concentrations returned to ambient levels. Copper sorption is modeled by considering sorption to aged hydrous ferric oxide (HFO) on the streambed (static surface) and freshly precipitated HFO in the water column (dynamic surface). Comparison of parameter estimates with reported values suggests that naturally formed iron oxides may be more effective in removing trace metals than synthetic oxides used in laboratory studies. The model's ability to simulate pH, metal oxide precipitation-dissolution, and pH-dependent sorption provides a means of evaluating the complex interactions between trace metal chemistry and hydrologic transport at the field scale.

7. Surface complexation of carboxylate adheres Cryptosporidium parvum oocysts to the hematite-water interface

USGS Publications Warehouse

Gao, X.; Metge, D.W.; Ray, C.; Harvey, R.W.; Chorover, J.

2009-01-01

The interaction of viable Cryptosporidium parvum ??ocysts at the hematite (??-Fe2O3)-water interface was examined over a wide range in solution chemistry using in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. Spectra for hematite-sorbed ??ocysts showed distinctchangesin carboxylate group vibrations relative to spectra obtained in the absence of hematite, indicative of direct chemical bonding between carboxylate groups and Fe metal centers of the hematite surface. The data also indicate that complexation modes vary with solution chemistry. In NaCl solution, ??ocysts are bound to hematite via monodentate and binuclear bidentate complexes. The former predominates at low pH, whereas the latter becomes increasingly prevalent with increasing pH. In a CaCl2 solution, only binuclear bidentate complexes are observed. When solution pH is above the point of zero net proton charge (PZNPC) of hematite, ??ocyst surface carboxylate groups are bound to the mineral surface via outer-sphere complexes in both electrolyte solutions. ?? 2009 American Chemical Society.

8. ATR-FTIR spectroscopic characterization of coexisting carbonate surface complexes on hematite

USGS Publications Warehouse

Bargar, J.R.; Kubicki, J.D.; Reitmeyer, R.; Davis, J.A.

2005-01-01

The speciation of carbonate adsorbed to hematite in air-equilibrated aqueous solutions has been studied using ATR-FTIR spectroscopy. Samples were measured over a range of pH conditions, at 0.1 M NaCl and at low ionic strength, and in H2O and D2O solutions to permit a multispecies analysis of the data. Second-derivative analyses and fits to the spectra indicate the presence of two major and two minor surface-bound carbonate species. The two major complexes coexist at near-neutral pH and low ionic strength. One of these two complexes is relatively sensitive to ionic strength, being displaced at 0.1 M NaCl, whereas the other is not. Comparison of experimental to DFT/MO-calculated frequencies suggest these two major species to be (a) a monodentate binuclear inner-sphere carbonate surface complex, and (b) a fully or partially solvated carbonate (CO32-) species that is symmetry broken and appears to reside in the structured vicinal water layers at the hematite-water interface, retained by hydrogen bonding and/or other forces. Minor carbonate complexes include diffuse layer CO32- and an unidentified inner-sphere species. Both of the dominant species observed here are likely to be significant controls of the surface charge and sorptive properties of Fe-oxides. Copyright ?? 2005 Elsevier Ltd.

9. Complex dispersion relation of surface acoustic waves at a lossy metasurface

Schwan, Logan; Geslain, Alan; Romero-García, Vicente; Groby, Jean-Philippe

2017-01-01

The complex dispersion relation of surface acoustic waves (SAWs) at a lossy resonant metasurface is theoretically and experimentally reported. The metasurface consists of the periodic arrangement of borehole resonators in a rigid substrate. The theoretical model relies on a boundary layer approach that provides the effective metasurface admittance governing the complex dispersion relation in the presence of viscous and thermal losses. The model is experimentally validated by measurements in the semi-anechoic chamber. The complex SAW dispersion relation is experimentally retrieved from the analysis of the spatial Laplace transform of the pressure scanned along a line at the metasurface. The geometrical spreading of the energy from the speaker is accounted for, and both the real and imaginary parts of the SAW wavenumber are obtained. The results show that the strong reduction of the SAW group velocity occurs jointly with a drastic attenuation of the wave, leading to the confinement of the field close to the source and preventing the efficient propagation of such slow-sound surface modes. The method opens perspectives to theoretically predict and experimentally characterize both the dispersion and the attenuation of surface waves at structured surfaces.

10. Mixed DNA/Oligo(ethylene glycol) Functionalized Gold Surface Improve DNA Hybridization in Complex Media

SciTech Connect

Lee,C.; Gamble, L.; Grainger, D.; Castner, D.

2006-01-01

Reliable, direct 'sample-to-answer' capture of nucleic acid targets from complex media would greatly improve existing capabilities of DNA microarrays and biosensors. This goal has proven elusive for many current nucleic acid detection technologies attempting to produce assay results directly from complex real-world samples, including food, tissue, and environmental materials. In this study, we have investigated mixed self-assembled thiolated single-strand DNA (ssDNA) monolayers containing a short thiolated oligo(ethylene glycol) (OEG) surface diluent on gold surfaces to improve the specific capture of DNA targets from complex media. Both surface composition and orientation of these mixed DNA monolayers were characterized with x-ray photoelectron spectroscopy (XPS) and near-edge x-ray absorption fine structure (NEXAFS). XPS results from sequentially adsorbed ssDNA/OEG monolayers on gold indicate that thiolated OEG diluent molecules first incorporate into the thiolated ssDNA monolayer and, upon longer OEG exposures, competitively displace adsorbed ssDNA molecules from the gold surface. NEXAFS polarization dependence results (followed by monitoring the N 1s{yields}{pi}* transition) indicate that adsorbed thiolated ssDNA nucleotide base-ring structures in the mixed ssDNA monolayers are oriented more parallel to the gold surface compared to DNA bases in pure ssDNA monolayers. This supports ssDNA oligomer reorientation towards a more upright position upon OEG mixed adlayer incorporation. DNA target hybridization on mixed ssDNA probe/OEG monolayers was monitored by surface plasmon resonance (SPR). Improvements in specific target capture for these ssDNA probe surfaces due to incorporation of the OEG diluent were demonstrated using two model biosensing assays, DNA target capture from complete bovine serum and from salmon genomic DNA mixtures. SPR results demonstrate that OEG incorporation into the ssDNA adlayer improves surface resistance to both nonspecific DNA and protein

11. Evidence for Carbonate Surface Complexation during Forsterite Carbonation in Wet Supercritical Carbon Dioxide

SciTech Connect

Loring, John S.; Chen, Jeffrey; Benezeth Ep Gisquet, Pascale; Qafoku, Odeta; Ilton, Eugene S.; Washton, Nancy M.; Thompson, Christopher J.; Martin, Paul F.; McGrail, B. Peter; Rosso, Kevin M.; Felmy, Andrew R.; Schaef, Herbert T.

2015-07-14

Continental flood basalts are attractive formations for geologic sequestration of carbon dioxide because of their reactive divalent-cation containing silicates, such as forsterite (Mg2SiO4), suitable for long-term trapping of CO2 mineralized as metal carbonates. The goal of this study was to investigate at a molecular level the carbonation products formed during the reaction of forsterite with supercritical CO2 (scCO2) as a function of the concentration of H2O adsorbed to the forsterite surface. Experiments were performed at 50 °C and 90 bar using an in situ IR titration capability, and post-reaction samples were examined by ex situ techniques, including SEM, XPS, FIB-TEM, TGA-MS, and MAS-NMR. Carbonation products and reaction extents varied greatly with adsorbed H2O. We show for the first time evidence of Mg-carbonate surface complexation under wet scCO2 conditions. Carbonate is found to be coordinated to Mg at the forsterite surface in a predominately bidentate fashion at adsorbed H2O concentrations below 27 µmol/m2. Above this concentration and up to 76 µmol/m2, monodentate coordinated complexes become dominant. Beyond a threshold adsorbed H2O concentration of 76 µmol/m2, crystalline carbonates continuously precipitate as magnesite, and the particles that form are hundreds of times larger than the estimated thicknesses of the adsorbed water films of about 7 to 15 Å. At an applied level, these results suggest that mineral carbonation in scCO2 dominated fluids near the wellbore and adjacent to caprocks will be insignificant and limited to surface complexation, unless adsorbed H2O concentrations are high enough to promote crystalline carbonate formation. At a fundamental level, the surface complexes and their dependence on adsorbed H2O concentration give insights regarding forsterite dissolution processes and magnesite nucleation and growth.

12. Evidence for Carbonate Surface Complexation during Forsterite Carbonation in Wet Supercritical Carbon Dioxide

SciTech Connect

Loring, John S.; Chen, Jeffrey; Benezeth, Pascale; Qafoku, Odeta; Ilton, Eugene S.; Washton, Nancy M.; Thompson, Christopher J.; Martin, Paul F.; McGrail, B. Peter; Rosso, Kevin M.; Felmy, Andrew R.; Schaef, Herbert T.

2015-06-16

Continental flood basalts are attractive formations for geologic sequestration of carbon dioxide because of their reactive divalent-cation containing silicates, such as forsterite (Mg2SiO4), suitable for long-term trapping of CO2 mineralized as metal carbonates. The goal of this study was to investigate at a molecular level the carbonation products formed during the reaction of forsterite with supercritical CO2 (scCO2) as a function of the concentration of H2O adsorbed to the forsterite surface. Experiments were performed at 50 °C and 90 bar using an in situ IR titration capability, and post-reaction samples were examined by ex situ techniques, including SEM, XPS, FIB-TEM, TGA-MS, and MAS-NMR. Carbonation products and reaction extents varied greatly with adsorbed H2O. We show for the first time evidence of Mg-carbonate surface complexation under wet scCO2 conditions. Carbonate is found to be coordinated to Mg at the forsterite surface in a predominately bidentate fashion at adsorbed H2O concentrations below 27 µmol/m2. Above this concentration and up to 76 µmol/m2, monodentate coordinated complexes become dominant. Beyond a threshold adsorbed H2O concentration of 76 µmol/m2, crystalline carbonates continuously precipitate as magnesite, and the particles that form are hundreds of times larger than the estimated thicknesses of the adsorbed water films of about 7 to 15 Å. At an applied level, the implication of these results is that mineral trapping in scCO2 dominated fluids will be insignificant and limited to surface complexation unless adsorbed H2O concentrations are high enough to promote crystalline carbonate formation. At a fundamental level, the surface complexes and their dependence on adsorbed H2O concentration give insights regarding forsterite dissolution processes and magnesite nucleation and growth.

13. In vivo formation and binding of SeHg complexes to the erythrocyte surface.

PubMed

Cherdwongcharoensuk, Duangrudee; Oliveira, Maria João; Aguas, Artur Perez

2010-08-01

The in vivo dynamics of selenium (Se) and mercury (Hg) interaction was studied in mouse tissues using direct visualization of individual Se, Hg, and SeHg particles on the surface of circulating erythrocytes. This high-resolution detection of Se and Hg was obtained by scanning electron microscopy coupled to X-ray microanalysis. BALB/c mice were injected in the peritoneal cavity with Se and Hg salts, and the animals were sacrificed 3 min after the Hg injection. Only a minority (9%) of the metal dots seen on mouse liver erythrocytes were SeHg complexes when Se and Hg salts were mixed together before injection. In contrast, the majority (73%) of metal dots on liver erythrocytes were SeHg complexes if Se was injected at least 5 min before Hg injection. All metal dots on liver erythrocytes were of SeHg complexes if Se was injected 9 or 12 min before the Hg injection. We conclude that the formation of stable in vivo SeHg complexes requires preliminary interaction of Se with a putative serum factor before complexes between Se and Hg are formed and are bound to the erythrocyte cell surface.

14. Native Liquid Extraction Surface Analysis Mass Spectrometry: Analysis of Noncovalent Protein Complexes Directly from Dried Substrates

Martin, Nicholas J.; Griffiths, Rian L.; Edwards, Rebecca L.; Cooper, Helen J.

2015-08-01

Liquid extraction surface analysis (LESA) mass spectrometry is a promising tool for the analysis of intact proteins from biological substrates. Here, we demonstrate native LESA mass spectrometry of noncovalent protein complexes of myoglobin and hemoglobin from a range of surfaces. Holomyoglobin, in which apomyoglobin is noncovalently bound to the prosthetic heme group, was observed following LESA mass spectrometry of myoglobin dried onto glass and polyvinylidene fluoride surfaces. Tetrameric hemoglobin [(αβ)2 4H] was observed following LESA mass spectrometry of hemoglobin dried onto glass and polyvinylidene fluoride (PVDF) surfaces, and from dried blood spots (DBS) on filter paper. Heme-bound dimers and monomers were also observed. The `contact' LESA approach was particularly suitable for the analysis of hemoglobin tetramers from DBS.

15. Surface complexation modeling calculation of Pb(II) adsorption onto the calcined diatomite

Ma, Shu-Cui; Zhang, Ji-Lin; Sun, De-Hui; Liu, Gui-Xia

2015-12-01

Removal of noxious heavy metal ions (e.g. Pb(II)) by surface adsorption of minerals (e.g. diatomite) is an important means in the environmental aqueous pollution control. Thus, it is very essential to understand the surface adsorptive behavior and mechanism. In this work, the Pb(II) apparent surface complexation reaction equilibrium constants on the calcined diatomite and distributions of Pb(II) surface species were investigated through modeling calculations of Pb(II) based on diffuse double layer model (DLM) with three amphoteric sites. Batch experiments were used to study the adsorption of Pb(II) onto the calcined diatomite as a function of pH (3.0-7.0) and different ionic strengths (0.05 and 0.1 mol L-1 NaCl) under ambient atmosphere. Adsorption of Pb(II) can be well described by Freundlich isotherm models. The apparent surface complexation equilibrium constants (log K) were obtained by fitting the batch experimental data using the PEST 13.0 together with PHREEQC 3.1.2 codes and there is good agreement between measured and predicted data. Distribution of Pb(II) surface species on the diatomite calculated by PHREEQC 3.1.2 program indicates that the impurity cations (e.g. Al3+, Fe3+, etc.) in the diatomite play a leading role in the Pb(II) adsorption and dominant formation of complexes and additional electrostatic interaction are the main adsorption mechanism of Pb(II) on the diatomite under weak acidic conditions.

16. Modeling the surface tension of complex, reactive organic-inorganic mixtures

Schwier, A. N.; Viglione, G. A.; Li, Z.; McNeill, V. Faye

2013-11-01

Atmospheric aerosols can contain thousands of organic compounds which impact aerosol surface tension, affecting aerosol properties such as heterogeneous reactivity, ice nucleation, and cloud droplet formation. We present new experimental data for the surface tension of complex, reactive organic-inorganic aqueous mixtures mimicking tropospheric aerosols. Each solution contained 2-6 organic compounds, including methylglyoxal, glyoxal, formaldehyde, acetaldehyde, oxalic acid, succinic acid, leucine, alanine, glycine, and serine, with and without ammonium sulfate. We test two semi-empirical surface tension models and find that most reactive, complex, aqueous organic mixtures which do not contain salt are well described by a weighted Szyszkowski-Langmuir (S-L) model which was first presented by Henning et al. (2005). Two approaches for modeling the effects of salt were tested: (1) the Tuckermann approach (an extension of the Henning model with an additional explicit salt term), and (2) a new implicit method proposed here which employs experimental surface tension data obtained for each organic species in the presence of salt used with the Henning model. We recommend the use of method (2) for surface tension modeling of aerosol systems because the Henning model (using data obtained from organic-inorganic systems) and Tuckermann approach provide similar modeling results and goodness-of-fit (χ2) values, yet the Henning model is a simpler and more physical approach to modeling the effects of salt, requiring less empirically determined parameters.

17. Spectroscopic identification of binary and ternary surface complexes of Np(V) on gibbsite.

PubMed

Gückel, Katharina; Rossberg, André; Müller, Katharina; Brendler, Vinzenz; Bernhard, Gert; Foerstendorf, Harald

2013-12-17

For the first time, detailed molecular information on the Np(V) sorption species on amorphous Al(OH)3 and crystalline gibbsite was obtained by in situ time-resolved Attenuated Total Reflection Fourier-Transform Infrared (ATR FT-IR) and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. The results consistently demonstrate the formation of mononuclear inner sphere complexes of the NpO2(+) ion irrespective of the prevailing atmospheric condition. The impact of the presence of atmospheric equivalent added carbonate on the speciation in solution and on the surfaces becomes evident from vibrational data. While the 1:1 aqueous carbonato species (NpO2CO3(-)) was found to become predominant in the circumneutral pH range, it is most likely that this species is sorbed onto the gibbsite surface as a ternary inner sphere surface complex where the NpO2(+) moiety is directly coordinated to the functional groups of the gibbsite's surface. These findings are corroborated by results obtained from EXAFS spectroscopy providing further evidence for a bidentate coordination of the Np(V) ion on amorphous Al(OH)3. The identification of the Np(V) surface species on gibbsite constitutes a basic finding for a comprehensive description of the dissemination of neptunium in groundwater systems.

18. Spectroscopic study on uranyl carboxylate complexes formed at the surface layer of Sulfolobus acidocaldarius.

PubMed

Reitz, Thomas; Rossberg, Andre; Barkleit, Astrid; Steudtner, Robin; Selenska-Pobell, Sonja; Merroun, Mohamed L

2015-02-14

The complexation of U(vi) at the proteinaceous surface layer (S-layer) of the archaeal strain Sulfolobus acidocaldarius was investigated over a pH range from pH 1.5 to 6 at the molecular scale using time-resolved laser-induced fluorescence spectroscopy (TRLFS) and U L(III)-edge extended X-ray absorption fine structure (EXAFS). The S-layer, which represents the interface between the cell and its environment, is very stable against high temperatures, proteases, and detergents. This allowed the isolation and purification of S-layer ghosts (= empty cells) that maintain the size and shape of the cells. In contrast to many other microbial cell envelope compounds the studied S-layer is not phosphorylated, enabling the investigation of uranyl carboxylate complexes formed at microbial surfaces. The latter are usually masked by preferentially formed uranyl phosphate complexes. We demonstrated that at highly acidic conditions (pH 1.5 to 3) no uranium was bound by the S-layer. In contrast to that, at moderate acidic pH conditions (pH 4.5 and 6) a complexation of U(vi) at the S-layer via deprotonated carboxylic groups was stimulated. Titration studies revealed dissociation constants for the carboxylic groups of glutamic and aspartic acid residues of pK(a) = 4.78 and 6.31. The uranyl carboxylate complexes formed at the S-layer did not show luminescence properties at room temperature, but only under cryogenic conditions. The obtained luminescence maxima are similar to those of uranyl acetate. EXAFS spectroscopy demonstrated that U(vi) in these complexes is mainly coordinated to carboxylate groups in a bidentate binding mode. The elucidation of the molecular structure of these complexes was facilitated by the absence of phosphate groups in the studied S-layer protein.

19. Complex polymer brush gradients based on nanolithography and surface-initiated polymerization.

PubMed

Lin, Xiankun; He, Qiang; Li, Junbai

2012-05-07

Confined surface gradients consisting of polymer brushes have great potential in various applications such as microfluidic devices, sensors, and biophysical research. Among the available fabrication approaches, nanolithographies combined with self-assembled monolayers and surface-initiated polymerization have became powerful tools to engineer confined gradients or predefined complex gradients on the nanometre size. In this tutorial review, we mainly highlight the research progress of the fabrication of confined polymer brush gradients by using electron beam, laser, and probe-based nanolithographies and the physical base for these approaches. The application of these polymer brush gradients in biomedical research is also addressed.

20. Sub-monolayer film growth of a volatile lanthanide complex on metallic surfaces

PubMed Central

Chen, Jinjie; Edelmann, Kevin; Wulfhekel, Wulf

2015-01-01

Summary We deposited a volatile lanthanide complex, tris(2,2,6,6-tetramethyl-3,5-heptanedionato)terbium(III), onto metal surfaces of Cu(111), Ag(111) and Au(111) in vacuum and observed well-ordered sub-monolayer films with low temperature (5 K) scanning tunneling microscopy. The films show a distorted three-fold symmetry with a commensurate structure. Scanning tunneling spectroscopy reveals molecular orbitals delocalized on the ligands of the molecule. Our results imply that this complex can be transferred onto the metal substrates without molecular decomposition or contamination of the surface. This new rare-earth-based class of molecules broadens the choice of molecular magnets to study with scanning tunneling microscopy. PMID:26733215

1. Relationships involving metastable equilibrium solubility, surface complexes, and crystallite disorder with carbonated apatites.

PubMed

Zhuang, H; Baig, A A; Zhang, N; Chhettry, A; Higuchi, W I

2001-12-01

Previous studies have shown that the metastable equilibrium solubility (MES) behavior of carbonated apatites (CAPs) may be described by a surface complex with the hydroxyapatite (HAP) stoichiometry in the absence of solution fluoride and by that with the fluorapatite (FAP) stoichiometry when appreciable solution fluoride is present. Studies have also shown that the magnitude of the MES is directly related to the crystallinity of the CAP. The aim of the present investigation was to examine the relationship between the CAP MES determined in the presence of solution fluoride and CAP crystallinity and to examine the effect of the change in the stoichiometry of the surface complex (from that of HAP to that of FAP) upon the relationship of the CAP MES to crystallinity. CAP samples were prepared by methods based on the precipitation of CAP from calcium phosphate solutions and the hydrolysis of dicalcium phosphate dihydrate in bicarbonate solutions. From X-ray diffraction experiments, the crystallite microstrain, and the full width at half maximum (FWHM) of the 002 reflection were determined for the CAPs. From CAP MES experiments conducted in the presence of solu tion fluoride, linear plots of the mean MES (i.e., mean pK(FAP)) values vs the crystallinity parameter (i.e., microstrain and FWHM) were obtained that yielded slopes that were essentially the same as those obtained in the absence of solution fluoride (i.e., mean pK(HAP) values vs crystallinity). This parallel finding suggests that the CAP crystallite disorder affects the energetics of the two surface complexes essentially to the same extent and provides new insight into the nature of CAP surface complexes.

2. Potential energy surface and rovibrational energy levels of the H2-CS van der Waals complex.

PubMed

Denis-Alpizar, Otoniel; Stoecklin, Thierry; Halvick, Philippe; Dubernet, Marie-Lise; Marinakis, Sarantos

2012-12-21

Owing to its large dipole, astrophysicists use carbon monosulfide (CS) as a tracer of molecular gas in the interstellar medium, often in regions where H(2) is the most abundant collider. Predictions of the rovibrational energy levels of the weakly bound complex CS-H(2) (not yet observed) and also of rate coefficients for rotational transitions of CS in collision with H(2) should help to interpret the observed spectra. This paper deals with the first goal, i.e., the calculation of the rovibrational energy levels. A new four-dimensional intermolecular potential energy surface for the H(2)-CS complex is presented. Ab initio potential energy calculations were carried out at the coupled-cluster level with single and double excitations and a perturbative treatment of triple excitations, using a quadruple-zeta basis set and midbond functions. The potential energy surface was obtained by an analytic fit of the ab initio data. The equilibrium structure of the H(2)-CS complex is found to be linear with the carbon pointing toward H(2) at the intermolecular separation of 8.6 a(o). The corresponding well depth is -173 cm(-1). The potential was used to calculate the rovibrational energy levels of the para-H(2)-CS and ortho-H(2)-CS complexes. The present work provides the first theoretical predictions of these levels. The calculated dissociation energies are found to be 35.9 cm(-1) and 49.9 cm(-1), respectively, for the para and ortho complexes. The second virial coefficient for the H(2)-CS pair has also been calculated for a large range of temperature. These results could be used to assign future experimental spectra and to check the accuracy of the potential energy surface.

3. Surface complexation modeling of uranyl adsorption on corrensite from the Waste Isolation Pilot Plant Site

SciTech Connect

Park, Sang-Won; Leckie, J.O.; Siegel, M.D.

1995-09-01

4. Normal contour error measurement on-machine and compensation method for polishing complex surface by MRF

Chen, Hua; Chen, Jihong; Wang, Baorui; Zheng, Yongcheng

2016-10-01

The Magnetorheological finishing (MRF) process, based on the dwell time method with the constant normal spacing for flexible polishing, would bring out the normal contour error in the fine polishing complex surface such as aspheric surface. The normal contour error would change the ribbon's shape and removal characteristics of consistency for MRF. Based on continuously scanning the normal spacing between the workpiece and the finder by the laser range finder, the novel method was put forward to measure the normal contour errors while polishing complex surface on the machining track. The normal contour errors was measured dynamically, by which the workpiece's clamping precision, multi-axis machining NC program and the dynamic performance of the MRF machine were achieved for the verification and security check of the MRF process. The unit for measuring the normal contour errors of complex surface on-machine was designed. Based on the measurement unit's results as feedback to adjust the parameters of the feed forward control and the multi-axis machining, the optimized servo control method was presented to compensate the normal contour errors. The experiment for polishing 180mm × 180mm aspherical workpiece of fused silica by MRF was set up to validate the method. The results show that the normal contour error was controlled in less than 10um. And the PV value of the polished surface accuracy was improved from 0.95λ to 0.09λ under the conditions of the same process parameters. The technology in the paper has been being applied in the PKC600-Q1 MRF machine developed by the China Academe of Engineering Physics for engineering application since 2014. It is being used in the national huge optical engineering for processing the ultra-precision optical parts.

5. Enhancing the magnetic anisotropy of maghemite nanoparticles via the surface coordination of molecular complexes

PubMed Central

Prado, Yoann; Daffé, Niéli; Michel, Aude; Georgelin, Thomas; Yaacoub, Nader; Grenèche, Jean-Marc; Choueikani, Fadi; Otero, Edwige; Ohresser, Philippe; Arrio, Marie-Anne; Cartier-dit-Moulin, Christophe; Sainctavit, Philippe; Fleury, Benoit; Dupuis, Vincent; Lisnard, Laurent; Fresnais, Jérôme

2015-01-01

Superparamagnetic nanoparticles are promising objects for data storage or medical applications. In the smallest—and more attractive—systems, the properties are governed by the magnetic anisotropy. Here we report a molecule-based synthetic strategy to enhance this anisotropy in sub-10-nm nanoparticles. It consists of the fabrication of composite materials where anisotropic molecular complexes are coordinated to the surface of the nanoparticles. Reacting 5 nm γ-Fe2O3 nanoparticles with the [CoII(TPMA)Cl2] complex (TPMA: tris(2-pyridylmethyl)amine) leads to the desired composite materials and the characterization of the functionalized nanoparticles evidences the successful coordination—without nanoparticle aggregation and without complex dissociation—of the molecular complexes to the nanoparticles surface. Magnetic measurements indicate the significant enhancement of the anisotropy in the final objects. Indeed, the functionalized nanoparticles show a threefold increase of the blocking temperature and a coercive field increased by one order of magnitude. PMID:26634987

6. Chemical mechanism of surface-enhanced Raman scattering via charge transfer in fluorenone-Ag complex

Wang, Jing; Li, Yafei; Wu, Shiwei; Song, Peng; Xia, Lixin

2016-06-01

The intermolecular interaction between fluorenone (FN) and silver surfaces was investigated experimentally and theoretically. The structural, electronic and optical properties of the FN-Ag complex indicate that the carbonyl group O atom in FN molecules is the adsorbed position site to attach the silver substrate through the weak bond O…Ag. The analysis of vibrational modes and Raman activity of the largely enhanced Raman peaks using two FN-Ag4-x (x  =  l, s) complex models reveals that only the a1 vibrational modes with C 2v symmetry are selectively enhanced, from the point view of the change of dipole moment and polarizability induced by the interaction between FN and Ag4 substrate. Furthermore, the direct visualized evidence of the surface-enhanced Raman scattering (SERS) chemical enhancement mechanism for the FN-Ag complex is presented. The results reveal that only the intermolecular charge transfer with π-π transition characterization between FN and an Ag4 cluster facilitates the resonance Raman process and is directly responsible for chemical enhancement of Raman scattering of the FN-Ag complex.

7. Modules based on the geochemical model PHREEQC for use in scripting and programming languages

USGS Publications Warehouse

Charlton, Scott R.; Parkhurst, David L.

2011-01-01

The geochemical model PHREEQC is capable of simulating a wide range of equilibrium reactions between water and minerals, ion exchangers, surface complexes, solid solutions, and gases. It also has a general kinetic formulation that allows modeling of nonequilibrium mineral dissolution and precipitation, microbial reactions, decomposition of organic compounds, and other kinetic reactions. To facilitate use of these reaction capabilities in scripting languages and other models, PHREEQC has been implemented in modules that easily interface with other software. A Microsoft COM (component object model) has been implemented, which allows PHREEQC to be used by any software that can interface with a COM server—for example, Excel®, Visual Basic®, Python, or MATLAB". PHREEQC has been converted to a C++ class, which can be included in programs written in C++. The class also has been compiled in libraries for Linux and Windows that allow PHREEQC to be called from C++, C, and Fortran. A limited set of methods implements the full reaction capabilities of PHREEQC for each module. Input methods use strings or files to define reaction calculations in exactly the same formats used by PHREEQC. Output methods provide a table of user-selected model results, such as concentrations, activities, saturation indices, and densities. The PHREEQC module can add geochemical reaction capabilities to surface-water, groundwater, and watershed transport models. It is possible to store and manipulate solution compositions and reaction information for many cells within the module. In addition, the object-oriented nature of the PHREEQC modules simplifies implementation of parallel processing for reactive-transport models. The PHREEQC COM module may be used in scripting languages to fit parameters; to plot PHREEQC results for field, laboratory, or theoretical investigations; or to develop new models that include simple or complex geochemical calculations.

8. Modules based on the geochemical model PHREEQC for use in scripting and programming languages

USGS Publications Warehouse

Charlton, S.R.; Parkhurst, D.L.

2011-01-01

The geochemical model PHREEQC is capable of simulating a wide range of equilibrium reactions between water and minerals, ion exchangers, surface complexes, solid solutions, and gases. It also has a general kinetic formulation that allows modeling of nonequilibrium mineral dissolution and precipitation, microbial reactions, decomposition of organic compounds, and other kinetic reactions. To facilitate use of these reaction capabilities in scripting languages and other models, PHREEQC has been implemented in modules that easily interface with other software. A Microsoft COM (component object model) has been implemented, which allows PHREEQC to be used by any software that can interface with a COM server-for example, Excel??, Visual Basic??, Python, or MATLAB??. PHREEQC has been converted to a C++ class, which can be included in programs written in C++. The class also has been compiled in libraries for Linux and Windows that allow PHREEQC to be called from C++, C, and Fortran. A limited set of methods implements the full reaction capabilities of PHREEQC for each module. Input methods use strings or files to define reaction calculations in exactly the same formats used by PHREEQC. Output methods provide a table of user-selected model results, such as concentrations, activities, saturation indices, and densities. The PHREEQC module can add geochemical reaction capabilities to surface-water, groundwater, and watershed transport models. It is possible to store and manipulate solution compositions and reaction information for many cells within the module. In addition, the object-oriented nature of the PHREEQC modules simplifies implementation of parallel processing for reactive-transport models. The PHREEQC COM module may be used in scripting languages to fit parameters; to plot PHREEQC results for field, laboratory, or theoretical investigations; or to develop new models that include simple or complex geochemical calculations. ?? 2011.

9. Modules based on the geochemical model PHREEQC for use in scripting and programming languages

Charlton, Scott R.; Parkhurst, David L.

2011-10-01

The geochemical model PHREEQC is capable of simulating a wide range of equilibrium reactions between water and minerals, ion exchangers, surface complexes, solid solutions, and gases. It also has a general kinetic formulation that allows modeling of nonequilibrium mineral dissolution and precipitation, microbial reactions, decomposition of organic compounds, and other kinetic reactions. To facilitate use of these reaction capabilities in scripting languages and other models, PHREEQC has been implemented in modules that easily interface with other software. A Microsoft COM (component object model) has been implemented, which allows PHREEQC to be used by any software that can interface with a COM server—for example, Excel ®, Visual Basic ®, Python, or MATLAB ®. PHREEQC has been converted to a C++ class, which can be included in programs written in C++. The class also has been compiled in libraries for Linux and Windows that allow PHREEQC to be called from C++, C, and Fortran. A limited set of methods implements the full reaction capabilities of PHREEQC for each module. Input methods use strings or files to define reaction calculations in exactly the same formats used by PHREEQC. Output methods provide a table of user-selected model results, such as concentrations, activities, saturation indices, and densities. The PHREEQC module can add geochemical reaction capabilities to surface-water, groundwater, and watershed transport models. It is possible to store and manipulate solution compositions and reaction information for many cells within the module. In addition, the object-oriented nature of the PHREEQC modules simplifies implementation of parallel processing for reactive-transport models. The PHREEQC COM module may be used in scripting languages to fit parameters; to plot PHREEQC results for field, laboratory, or theoretical investigations; or to develop new models that include simple or complex geochemical calculations.

10. Preparing metal-complex surfaces based on self-assembled monolayers of thiols and disulfides on gold

Dolzhikova, V. D.; Bogdanova, Yu. G.; Majouga, A. G.; Beloglazkina, E. K.; Kudrinsky, A. A.

2017-02-01

The complexation of monolayers of sulfur-containing ligands self-assembled on surface of gold with Co(II) and Cu(II) ions is studied using quartz crystal microbalance (QCM) and wetting measurements. The optimum conditions for obtaining metal-complex surfaces and the compositions of the resulting monolayers are determined.

11. Nondispersive X-ray emission analysis for geochemical exploration

NASA Technical Reports Server (NTRS)

1969-01-01

Nondispersive X-ray emission technique uses lightweight, and rugged X-ray fluorescence units. The X-ray pulse-height spectra is excited by radioactive isotope sources. The technique is applicable for quantitative and qualitative analyses on complex chemical systems, and satisfies the goals for a lunar geochemical exploration device.

12. Organic geochemical constraints on paleoelevation

Polissar, P. J.; Rowley, D. B.; Currie, B. S.; Freeman, K. H.

2012-12-01

The elevation history of the land surface is an important factor in the interpretation of past tectonic, climate and ecological processes. However, quantitative estimates of paleoelevation are difficult to produce and new techniques are needed. Organic geochemical approaches to quantifying paleoelevations provide a new perspective on this difficult task. The hydrogen isotopic composition of organic biomarker molecules synthesized by plants and algae is systematically related to the water used for growth. Organic molecules in ancient sediments can provide values for the isotopic composition of this water and thus elevation, provided the relationship between elevation and isotopic values is known. Molecular hydrogen isotope ratios from Cenozoic lake sediments on the Tibetan Plateau demonstrate the utility of a biomarker approach. Terrestrial plant-wax D/H values on Neogene sediments from the Namling-Oiyug Basin provide new paleoelevation estimates that compare well with previous studies. Plant wax D/H ratios paired with lacustrine carbonate oxygen isotope values from the Lunpola and Hoh-Xil basins illustrate how paired isotope systems can unravel the isotopic composition of precipitation from evaporative enrichment of lake waters. A potentially fruitful avenue for future research is illustrated by D/H analyses on older sediments from the Namling-Oiyug Basin. These sediments—like many that could be useful for paleoaltimetry—have experienced significant burial and heating. As temperatures approach the oil window it becomes possible to exchange hydrogen in both the extractable organic molecules (bitumen) and the insoluble organic residue (kerogen). The extent to which this exchange alters the original isotopic composition will determine the usefulness of D/H analyses on thermally mature organic matter. The potential payoff and pitfalls of D/H analyses on heated sediments is illustrated with thermally immature and mature samples from the Namling-Oiyug Basin.

13. Synthesis in situ of gold nanoparticles by a dialkynyl Fischer carbene complex anchored to glass surfaces

Bertolino, María Candelaria; Granados, Alejandro Manuel

2016-10-01

In this work we present a detailed study of classic reactions such as "click reaction" and nucleophilic substitution reaction but on glass solid surface (slides). We used different reactive center of a dialkynylalcoxy Fischer carbene complex of tungsten(0) to be anchored to modified glass surface with amine, to obtain aminocarbene, and azide terminal groups. These cycloaddition reaction showed regioselectivity to internal triple bond of dialkynyl Fischer carbene complex without Cu(I) as catalyst. Anyway the carbene anchored was able to act as a reducing agent to produce in situ very stable gold nanoparticles fixed on surface. We showed the characterization of modified glasses by contact angle measurements and XPS. Synthesized nanoparticles were characterized by SEM, XPS, EDS and UV-vis. The modified glasses showed an important enhancement Raman-SERS. This simple, fast and robust method to create a polifunctional and hybrid surfaces can be valuable in a wide range of applications such as Raman-SERS substrates and other optical fields.

14. Formation and reactivity of surface-bound high oxidation state Ruthenium-oxo complexes.

SciTech Connect

Hornstein, B. J.; Dattelbaum, D. M.; Schoonover, J. R.; Meyer, T. J.

2004-01-01

Ruthenium polypyridyl oxalate complexes are precursors to high oxidation state species that can catalyze the oxidation of a variety of substrates. Covalent attachment of these reactive species to surfaces such at ZrO{sub 2} or TiO{sub 2} inhibit catalyst deactivation and provide supports from which to build electrocatalytic and photoelectrocatalytic devices. Unfortunately, few details of the effects of surface binding on reactivity are available in the literature. To this end, precursors such as, Ru(H{sub 2}O{sub 3}Ptpy)(C{sub 2}O{sub 4})(H{sub 2}O) and (C{sub 2}O{sub 4})(H{sub 2}O{sub 3}Ptpy)Ru-O-Ru(H{sub 2}O{sub 3}Ptpy)(C{sub 2}O{sub 4}) (tpy is terpyridine) have been synthesized and attached to TiO{sub 2}. Quantitative surface binding studies were carried out and acid catalyzed solvolysis was used to form the aqua species. The complexes were oxidized with Ce(IV) to their high-valent analogs and their reactivity toward selected substrates was tested. These studies not only provide information about the effects of surface binding on the reactivity of metal oxides but also have implications for the development of light-driven catalysts.

15. Double-Ended Surface Walking Method for Pathway Building and Transition State Location of Complex Reactions.

PubMed

Zhang, Xiao-Jie; Shang, Cheng; Liu, Zhi-Pan

2013-12-10

Toward the activity prediction with large-scale computations, here a double-ended surface walking (DESW) method is developed for connecting two minima on a potential energy surface (PES) and locating the associated transition state (TS) using only the first derivatives. The method operates two images starting from the initial and the final states, respectively, to walk in a stepwise manner toward each other. The surface walking involves repeated bias potential addition and local relaxation with the constrained Broyden dimer method to correct the walking direction. We apply the method to a model PES, a large set of gas phase Baker reactions, and complex surface catalytic reactions, which demonstrates that the DESW method can establish a low energy pathway linking two minima even without iterative optimization of the pathway, from which the TS can be located readily. By comparing the efficiency of the new method with the existing methods, we show that the DESW method is much less computationally demanding and is applicable for reactions with complex PESs. We hope that the DESW method may be integrated with the PES sampling methods for automated reaction prediction.

16. Downscaling surface wind predictions from numerical weather prediction models in complex terrain with WindNinja

Wagenbrenner, Natalie S.; Forthofer, Jason M.; Lamb, Brian K.; Shannon, Kyle S.; Butler, Bret W.

2016-04-01

Wind predictions in complex terrain are important for a number of applications. Dynamic downscaling of numerical weather prediction (NWP) model winds with a high-resolution wind model is one way to obtain a wind forecast that accounts for local terrain effects, such as wind speed-up over ridges, flow channeling in valleys, flow separation around terrain obstacles, and flows induced by local surface heating and cooling. In this paper we investigate the ability of a mass-consistent wind model for downscaling near-surface wind predictions from four NWP models in complex terrain. Model predictions are compared with surface observations from a tall, isolated mountain. Downscaling improved near-surface wind forecasts under high-wind (near-neutral atmospheric stability) conditions. Results were mixed during upslope and downslope (non-neutral atmospheric stability) flow periods, although wind direction predictions generally improved with downscaling. This work constitutes evaluation of a diagnostic wind model at unprecedented high spatial resolution in terrain with topographical ruggedness approaching that of typical landscapes in the western US susceptible to wildland fire.

17. Complex frequencies and field distributions of localized surface plasmon modes in graphene-coated subwavelength wires

Cuevas, Mauro; Riso, Máximo A.; Depine, Ricardo A.

2016-04-01

In this work we study the modal characteristics of localized surface plasmons in graphene-coated, circular cross-section wires. Localized surface plasmons are represented in terms of cylindrical multipole partial waves characterized by discrete, complex frequencies that depend on the size of the wire and can be dynamically tuned via a gate voltage. We consider both intrinsically nonplasmonic wires and intrinsically plasmonic wires. In the first case the localized surface plasmons are introduced by the graphene coating, whereas in the second case the localized eigenmodes of the graphene coating are expected to hybridize those already existing in the bare wire. We show that the approach presented here, valid for particle sizes where the retardation effects can be significant, is in good agreement with analytical expressions obtained in the limit when particle size is very small compared to the wavelength of the eigenmode and with results indirectly determined from scattering cross-section spectra.

18. Jahn-Teller effect for short-lived states: Study of the complex potential energy surfaces

Feuerbacher, Sven; Cederbaum, Lorenz S.

2004-07-01

The Jahn-Teller effect for bound electronic states has been investigated for many decades. In contrast, nothing is known regarding its occurrence for short-lived electronic states. Here we investigate the linear and the quadratic E⊗e Jahn-Teller effect for degenerate resonance states with special regard to the complex potential energy surfaces. We find many new phenomena for both the real and imaginary parts of the potential energy surfaces including additional minima and intersections. Possible simplifications of the equations describing the adiabatic potential energy surfaces are discussed. We also briefly investigate other Jahn-Teller effects in linear approximation. The theoretical concepts are exemplified by calculating ab initio data for the degenerate Π*-type resonance states of the tris(boramethyl)amin anion along two different doubly degenerate vibrational modes.

19. Ab initio potential energy and dipole moment surfaces of the F(-)(H2O) complex.

PubMed

Kamarchik, Eugene; Toffoli, Daniele; Christiansen, Ove; Bowman, Joel M

2014-02-05

We present full-dimensional, ab initio potential energy and dipole moment surfaces for the F(-)(H2O) complex. The potential surface is a permutationally invariant fit to 16,114 coupled-cluster single double (triple)/aVTZ energies, while the dipole surface is a covariant fit to 11,395 CCSD(T)/aVTZ dipole moments. Vibrational self-consistent field/vibrational configuration interaction (VSCF/VCI) calculations of energies and the IR-spectrum are presented both for F(-)(H2O) and for the deuterated analog, F(-)(D2O). A one-dimensional calculation of the splitting of the ground state, due to equivalent double-well global minima, is also reported.

20. MS for investigation of time-dependent protein adsorption on surfaces in complex biological samples

PubMed Central

Undin, Torgny; Lind, Sara Bergström; Dahlin, Andreas P

2015-01-01

Aim: This study aims at developing a nondestructive way for investigating protein adsorption on surfaces such as biomaterials using mass spectrometry. Methods: Ventricular cerebrospinal fluid in contact with poly carbonate membranes were used as adsorption templates and on-surface enzymatic digestion was applied to desorb proteins and cleave them into peptides. Mass spectrometric analysis provided both protein identification and determination of protein specific adsorption behavior. Results: In general, the adsorption increased with incubation time but also protein-specific time-resolved adsorption patterns from the complex protein solution were discovered. Conclusion: The method developed is a promising tool for the characterization of biofouling, which sometimes causes rejection and encapsulation of implants and can be used as complement to other surface analytical techniques. PMID:28031905

1. DIFFERENTIATION OF THE JUNCTIONAL COMPLEX OF SURFACE CELLS IN THE DEVELOPING FUNDULUS BLASTODERM

PubMed Central

Lentz, Thomas L.; Trinkaus, J. P.

1971-01-01

The structure of the junctional complex between surface cells was investigated in blastula, mid gastrula, late gastrula, and early embryo of the teleost fish Fundulus heteroclitus. In blastulae, the intercellular complex is simple and consists of an apical region where the adjacent membranes are closely apposed (40–60 A) and in places touch, an intermediate zone with a wider intercellular space (> 100 A), and incipient desmosomes. In gastrulae, there are frequent points of fusion of membranes along the apical zone of the complex. Dilatations and an increased number of desmosomes in different stages of development are found along the intermediate zone. In mid gastrula, a close or gap junction with an intercellular space of 20 A occurs below the level of the desmosomes. In late gastrula, the gap junction is reduced in extent and desmosomes are better developed. In the early embryo, the basic organization of the complex is the same, although the deeply situated close junctions are no longer apparent and desmosomes and their associated system of filaments are well developed. At this time, the junctional complex is comparable to that of many epithelia and consists of an apical zonula occludens, a short zonula adherens, and deeply situated maculae adherentes. PMID:5545331

2. Surface Induced Dissociation Yields Quaternary Substructure of Refractory Noncovalent Phosphorylase B and Glutamate Dehydrogenase Complexes

Ma, Xin; Zhou, Mowei; Wysocki, Vicki H.

2014-03-01

Ion mobility (IM) and tandem mass spectrometry (MS/MS) coupled with native MS are useful for studying noncovalent protein complexes. Collision induced dissociation (CID) is the most common MS/MS dissociation method. However, some protein complexes, including glycogen phosphorylase B kinase (PHB) and L-glutamate dehydrogenase (GDH) examined in this study, are resistant to dissociation by CID at the maximum collision energy available in the instrument. Surface induced dissociation (SID) was applied to dissociate the two refractory protein complexes. Different charge state precursor ions of the two complexes were examined by CID and SID. The PHB dimer was successfully dissociated to monomers and the GDH hexamer formed trimeric subcomplexes that are informative of its quaternary structure. The unfolding of the precursor and the percentages of the distinct products suggest that the dissociation pathways vary for different charge states. The precursors at lower charge states (+21 for PHB dimer and +27 for GDH hexamer) produce a higher percentage of folded fragments and dissociate more symmetrically than the precusors at higher charge states (+29 for PHB dimer and +39 for GDH hexamer). The precursors at lower charge state may be more native-like than the higher charge state because a higher percentage of folded fragments and a lower percentage of highly charged unfolded fragments are detected. The combination of SID and charge reduction is shown to be a powerful tool for quaternary structure analysis of refractory noncovalent protein complexes, as illustrated by the data for PHB dimer and GDH hexamer.

3. Biodiversity of benthic microbial communities in bioturbated coastal sediments is controlled by geochemical microniches.

PubMed

Bertics, Victoria J; Ziebis, Wiebke

2009-11-01

We used a combination of field and laboratory approaches to address how the bioturbation activity of two crustaceans, the ghost shrimp Neotrypaea californiensis and the fiddler crab Uca crenulata, affects the microbial diversity in the seabed of a coastal lagoon (Catalina Harbor, Santa Catalina Island, CA, USA). Detailed geochemical analyses, including oxygen microsensor measurements, were performed to characterize environmental parameters. We used a whole-assemblage fingerprinting approach (ARISA: amplified ribosomal intergenic spacer analysis) to compare bacterial diversity along geochemical gradients and in relation to subsurface microniches. The two crustaceans have different burrowing behaviors. The ghost shrimp maintains complex, deep-reaching burrows and permanently lives subterranean, supplying its burrow with oxygen-rich water. In contrast, the fiddler crab constructs simpler, J-shaped burrows, which it does not inhabit permanently and does not actively ventilate. Our goal was to address how varying environmental parameters affect benthic microbial communities. An important question in benthic microbial ecology has been whether burrows support similar or unique communities compared with the sediment surface. Our results showed that sediment surface microbial communities are distinct from subsurface assemblages and that different burrow types support diverse bacterial taxa. Statistical comparisons by canonical correspondence analysis indicated that the availability of oxidants (oxygen, nitrate, ferric iron) play a key role in determining the presence and abundance of different taxa. When geochemical parameters were alike, microbial communities associated with burrows showed significant similarity to sediment surface communities. Our study provides implications on the community structure of microbial communities in marine sediments and the factors controlling their distribution.

4. Was Mineral Surface Complexity and Toxicity an Impetus for Evolution of Microbial Extracellular Polymeric Substances?

Sahai, N.; Xu, J.; Zhu, C.; Campbell, J.; Hickey, W.; Zhang, N.

2011-12-01

Modern ecological niches are teeming with an astonishing diversity of microbial life closely associated with mineral surfaces, highlighting the remarkable success of microorganisms in conquering the challenges and capitalizing on the benefits presented by the mineral-water interface. Such community-living is enabled by an extracellular, polymeric, biofilm matrix developed at cell surfaces. Despite the energetic penalties, biofilm formation capability likely evolved on early Earth because of crucial cell survival functions, of which recognized roles include facilitating cell-attachment at mineral surfaces, intercellular signaling and lateral gene transfer, protection from dessication in tidal pools, and screening toxic UV light and toxic soluble metals. Cell-attachment to mineral surfaces was likely critical for cell survival and function, but the potential toxicity of mineral surfaces towards cells and the complexities of the mineral-water-cell interface in promoting biofilm formation, have not been fully appreciated. We examined the effects of nanoparticulate oxides (amorphous SiO2, anatase β-TiO2, and γ-Al2O3) on EPS- and biofilm-producing wild-type strains and their isogenic knock-out mutants which are defective in EPS-producing ability. In detail, we used Gram-negative wild-type Pseudomonas aeruginosa PAO1 and its EPS knock-out mutant Δ-psl, and the Gram-positive wild-type Bacillus subtilis NCIB3610 and its EPS-knock-out mutant yhxBΔ. We conducted bacterial growth experiments in the presence of each oxide in order to determine the viability of each cell type relative to oxide-free controls. The amount of EPS generated in the presence of oxides was also quantified and qualitatively analyzed by fluorescent stains. The results indicated a previously unrecognized role for microbial extracellular polymeric substances (EPS) in shielding both Gram-negative and Gram-positive cells against the toxic effects of mineral surfaces. This role is distinct from the

5. Seismic tomography in areas associated with complex near-surface structures

Al-Rufaii, Khalid

The energy demand of the world is increasing every day, forcing the oil industry to explore for oil hydrocarbon traps in locations where the problem complexity requires special imaging techniques. Dealing with complex near-surface structures is the most challenging problem for land seismic exploration. The seismic waves are often distorted and dispersed by extremely low and rapidly varying velocities, as well as poor or inconsistent coupling amongst shots and receivers. It is not uncommon when the near-surface problem degrades the surface reflection data to a useless level. To treat the problem, I employ a first-arrival seismic tomography to model the near-surface velocity structures. The removal of the induced near-surface distortions on seismic data is based on two principles: layer stripping and surface consistency. Though this approach has been taken by previous workers, our method has several unique features. First, the subsurface is parameterized by a grid of irregularly shaped blocks that mimic the topography and help to reduce the number of model variables. Second, a multi-scale inversion is employed that has been shown to give superior results than the conventional single-scale tomography. Third, the initial reference model is established based on the actual travel-time data, hence greatly reduces the concern for picking a wrong initial model. The accuracy of the first-arrival tomography is verified using various synthetic models simulating the complexity of real near-surface conditions. The method is applied to three field 2-D data sets in very different regions: a land data set from a mountainous thrust area in South America, a marine data set from the Gulf of Mexico, and a long-offset data set from the Tarim Basin in China. In addition, I attempt to implement reflection tomography as an alternative to conventional velocity analysis. Using reflection seismic tomography, we invert for velocity-depth models, which can be used for imaging or time processing

6. GEOCHEMICAL MODELING OF ARSENIC SPECIATION AND MOBILIZATION: IMPLICATIONS FOR BIOREMEDIATION

EPA Science Inventory

Geochemical modeling techniques were used to examine the biogeochemical linkages between Fe, S, and As in shallow alluvial aquifers. We modeled: 1) the adsorption and desorption of As on the surface of hydrous ferric oxides (HFO’s) in stream beds under aerobic conditions; 2) red...

7. Surface structure of the Ag-In-(rare earth) complex intermetallics

Hars, S. S.; Sharma, H. R.; Smerdon, J. A.; Yadav, T. P.; Al-Mahboob, A.; Ledieu, J.; Fournée, V.; Tamura, R.; McGrath, R.

2016-05-01

We present a study of the surface structure of the Ag-In-RE (RE: rare-earth elements Gd, Tb, and Yb) complex intermetallics using scanning tunneling microscopy and low-energy electron diffraction. The surface of the Ag-In-Yb approximant prepared by sputter-annealing methods under ultrahigh-vacuum conditions produces a flat (100) surface with no facets. However, the Ag-In-Gd and Ag-In-Tb 1/1 approximants, which have a surface miscut of about 12∘ relative to the (100) plane, develop surface facets along various crystallographic directions. The structure of each facet can be explained as a truncation of the rhombic triacontahedral clusters, i.e., the main building blocks of these systems. Despite their differences in atomic structure, symmetry, and density, the facets show common features. The facet planes are In rich. The analysis of the nearest-neighbor atom distances suggests that In atoms form bonds with the RE atoms, which we suggest is a key factor that stabilizes even low-density facet planes.

8. Surface modification of polydimethylsiloxane with a covalent antithrombin-heparin complex to prevent thrombosis.

PubMed

Leung, Jennifer M; Berry, Leslie R; Chan, Anthony K C; Brash, John L

2014-01-01

To prevent coagulation in contact with blood, polydimethylsiloxane (PDMS) was modified with an antithrombin-heparin (ATH) covalent complex using polyethylene glycol (PEG) as a linker/spacer. Using NHS chemistry, ATH was attached covalently to the distal chain end of the immobilized PEG linker. Surfaces were characterized by contact angle and X-ray photoelectron spectroscopy; attachment was confirmed by decrease in contact angles and an increase in nitrogen content as determined by X-ray photoelectron spectroscopy. Protein interactions in plasma were investigated using radiolabeled proteins added to plasma as tracers, and by immunoblotting of eluted proteins. Modification of PDMS with PEG alone was effective in reducing non-specific protein adsorption; attachment of ATH at the distal end of the PEG chains did not significantly affect protein resistance. It was shown that surfaces modified with ATH bound antithrombin selectively from plasma through the pentasaccharide sequence on the heparin moiety of ATH, indicating the ability of the ATH-modified surfaces to inhibit coagulation. Using thromboelastography, the effect of ATH modification on plasma coagulation was evaluated directly. It was found that initiation of coagulation was delayed and the time to clot was prolonged on PDMS modified with ATH/PEG compared to controls. For comparison, surfaces modified in a similar way with heparin were prepared and investigated using the same methods. The data suggest that the ATH-modified surfaces have superior anticoagulant properties compared to those modified with heparin.

9. Evidence for Carbonate Surface Complexation during Forsterite Carbonation in Wet Supercritical Carbon Dioxide.

PubMed

Loring, John S; Chen, Jeffrey; Bénézeth, Pascale; Qafoku, Odeta; Ilton, Eugene S; Washton, Nancy M; Thompson, Christopher J; Martin, Paul F; McGrail, B Peter; Rosso, Kevin M; Felmy, Andrew R; Schaef, Herbert T

2015-07-14

Continental flood basalts are attractive formations for geologic sequestration of carbon dioxide because of their reactive divalent-cation containing silicates, such as forsterite (Mg2SiO4), suitable for long-term trapping of CO2 mineralized as metal carbonates. The goal of this study was to investigate at a molecular level the carbonation products formed during the reaction of forsterite with supercritical CO2 (scCO2) as a function of the concentration of H2O adsorbed to the forsterite surface. Experiments were performed at 50 °C and 90 bar using an in situ IR titration capability, and postreaction samples were examined by ex situ techniques, including scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), focused ion beam transmission electron microscopy (FIB-TEM), thermal gravimetric analysis mass spectrometry (TGA-MS), and magic angle spinning nuclear magnetic resonance (MAS NMR). Carbonation products and reaction extents varied greatly with adsorbed H2O. We show for the first time evidence of Mg-carbonate surface complexation under wet scCO2 conditions. Carbonate is found to be coordinated to Mg at the forsterite surface in a predominately bidentate fashion at adsorbed H2O concentrations below 27 μmol/m(2). Above this concentration and up to 76 μmol/m(2), monodentate coordinated complexes become dominant. Beyond a threshold adsorbed H2O concentration of 76 μmol/m(2), crystalline carbonates continuously precipitate as magnesite, and the particles that form are hundreds of times larger than the estimated thicknesses of the adsorbed water films of about 7 to 15 Å. At an applied level, these results suggest that mineral carbonation in scCO2 dominated fluids near the wellbore and adjacent to caprocks will be insignificant and limited to surface complexation, unless adsorbed H2O concentrations are high enough to promote crystalline carbonate formation. At a fundamental level, the surface complexes and their dependence on adsorbed H2O

10. Robotic path planning for non-destructive testing of complex shaped surfaces

Mineo, Carmelo; Pierce, Stephen Gareth; Wright, Ben; Nicholson, Pascual Ian; Cooper, Ian

2015-03-01

The requirement to increase inspection speeds for non-destructive testing (NDT) of composite aerospace parts is common to many manufacturers. The prevalence of complex curved surfaces in the industry provides significant motivation for the use of 6 axis robots for deployment of NDT probes in these inspections. A new system for robot deployed ultrasonic inspection of composite aerospace components is presented. The key novelty of the approach is through the accommodation of flexible robotic trajectory planning, coordinated with the NDT data acquisition. Using a flexible approach in MATLAB, the authors have developed a high level custom toolbox that utilizes external control of an industrial 6 axis manipulator to achieve complex path planning and provide synchronization of the employed ultrasonic phase array inspection system. The developed software maintains a high level approach to the robot programming, in order to ease the programming complexity for an NDT inspection operator. Crucially the approach provides a pathway for a conditional programming approach and the capability for multiple robot control (a significant limitation in many current off-line programming applications). Ultrasonic and experimental data has been collected for the validation of the inspection technique. The path trajectory generation for a large, curved carbon-fiber-reinforced polymer (CFRP) aerofoil component has been proven and is presented. The path error relative to a raster-scan tool-path, suitable for ultrasonic phased array inspection, has been measured to be within + 2mm over the 1.6 m2 area of the component surface.

11. Rapid formation of cell-particle complexes via dielectrophoretic manipulation for the detection of surface antigens.

PubMed

Horii, Takuma; Yamamoto, Masashi; Yasukawa, Tomoyuki; Mizutani, Fumio

2014-11-15

A rapid and simple method for the fabrication of the island patterns with particles and cells was applied to detect the presence of specific antigens on the cell surface. An upper interdigitated microband array (IDA) electrode was mounted on a lower substrate with the same design to fabricate a microfluidic-channel device for dielectrophoretic manipulation. The electrode grid structure was fabricated by rotating the upper template IDA by 90° relative to the lower IDA. A suspension of anti-CD33 modified particles and HL-60 cells was introduced into the channel. An AC electrical signal (typically 20 V peak-to-peak, 100 kHz) was then applied to the bands of the upper and lower IDAs, resulting in the formation of island patterns at the intersections with low electric fields. Immunoreactions between the antibodies immobilized on the accumulated particles and the CD33 present on the surface of the cells led to the formation of complexes comprising corresponding antigen-antibody pairs. Non-specific pairs accumulated at the intersection, which did not form complexes, were then dispersed after removal of the applied field. The time required for the detection of the formation/dispersion of the complexes is as short as 6 min in the present procedure. Furthermore, this novel cell binding assay does not require pretreatment such as target labeling or washing of the unbound cells.

12. Spectroscopic evidence for ternary surface complexes in the lead(II)-malonic acid-hematite system

USGS Publications Warehouse

Lenhart, J.J.; Bargar, J.R.; Davis, J.A.

2001-01-01

Using extended X-ray absorption fine structure (EXAFS) and attenuated total reflectance Fourier-transform infrared (ATR-FTIR) measurements, we examined the sorption of Pb(II) to hematite in the presence of malonic acid. Pb LIII-edge EXAFS measurements performed in the presence of malonate indicate the presence of both Fe and C neighbors, suggesting that a major fraction of surface-bound malonate is bonded to adsorbed Pb(II). In the absence of Pb(II), ATR-FTIR measurements of sorbed malonate suggest the formation of more than one malonate surface complex. The dissimilarity of the IR spectrum of malonate sorbed on hematite to those for aqueous malonate suggest at least one of the sorbed malonate species is directly coordinated to surface Fe atoms in an inner-sphere mode. In the presence of Pb, little change is seen in the IR spectrum for sorbed malonate, indicating that geometry of malonate as it coordinates to sorbed Pb(II) adions is similar to the geometry of malonate as it coordinates to Fe in the hematite surface. Fits of the raw EXAFS spectra collected from pH 4 to pH 8 result in average Pb-C distances of 2.98 to 3.14 A??, suggesting the presence of both four- and six-membered Pb-malonate rings. The IR results are consistent with this interpretation. Thus, our results suggest that malonate binds to sorbed Pb(II) adions, forming ternary metal-bridging surface complexes. ?? 2001 Academic Press.

13. Computational analysis of contact forces influence on cold forming processes in the dies with complex surfaces

Dragnea, D.; Lixandru, P.; Chereches, T.; Velicu, St.

2016-08-01

Interaction forces between the workpiece and the die appear during the cold forming process of metals in dies. Surface forces of high-intensity influence the mesh structure and internal structure of the finished piece by mechanical action. Frictional forces hinder the flow of the material in contact with the die walls, especially on surfaces of complex shape. Under certain conditions, the material can adhere to the wall of the die, leading to the blocking of the cold forming process. In order to highlight the influence of contact forces on cold forming processes in dies with complex surfaces there were used numerical simulation methods with finite elements. Numerical simulations of the process of axial cold forming in the die were carried out for analysis data acquisition necessary, in order to achieve HTD pulleys, for an ordinary range of friction coefficients. The analysis was directed to the gearing area of the HTD pulleys (head, flank and base of the tooth). The analysis highlighted the negative effects of friction forces on the shape and quality of the products and the need to use quality lubricants. Also, using the cold forming process they can be achieved substantial savings by redistribution of the material without removing it.

14. An Evaluation of Fractal Surface Measurement Methods for Characterizing Landscape Complexity from Remote-Sensing Imagery

NASA Technical Reports Server (NTRS)

Lam, Nina Siu-Ngan; Qiu, Hong-Lie; Quattrochi, Dale A.; Emerson, Charles W.; Arnold, James E. (Technical Monitor)

2001-01-01

The rapid increase in digital data volumes from new and existing sensors necessitates the need for efficient analytical tools for extracting information. We developed an integrated software package called ICAMS (Image Characterization and Modeling System) to provide specialized spatial analytical functions for interpreting remote sensing data. This paper evaluates the three fractal dimension measurement methods: isarithm, variogram, and triangular prism, along with the spatial autocorrelation measurement methods Moran's I and Geary's C, that have been implemented in ICAMS. A modified triangular prism method was proposed and implemented. Results from analyzing 25 simulated surfaces having known fractal dimensions show that both the isarithm and triangular prism methods can accurately measure a range of fractal surfaces. The triangular prism method is most accurate at estimating the fractal dimension of higher spatial complexity, but it is sensitive to contrast stretching. The variogram method is a comparatively poor estimator for all of the surfaces, particularly those with higher fractal dimensions. Similar to the fractal techniques, the spatial autocorrelation techniques are found to be useful to measure complex images but not images with low dimensionality. These fractal measurement methods can be applied directly to unclassified images and could serve as a tool for change detection and data mining.

15. Surface Forces and Interaction Mechanisms of Emulsion Drops and Gas Bubbles in Complex Fluids.

PubMed

Xie, Lei; Shi, Chen; Cui, Xin; Zeng, Hongbo

2017-02-22

The interactions of emulsion drops and gas bubbles in complex fluids play important roles in a wide range of biological and technological applications, such as programmable drug and gene delivery, emulsion and foam formation, and froth flotation of mineral particles. In this feature article, we have reviewed our recent progress on the quantification of surface forces and interaction mechanisms of gas bubbles and emulsion drops in different material systems by using several complementary techniques, including the drop/bubble probe atomic force microscope (AFM), surface forces apparatus (SFA), and four-roll mill fluidic device. These material systems include the bubble-self-assembled monolayer (SAM), bubble-polymer, bubble-superhydrophobic surface, bubble-mineral, water-in-oil and oil-in-water emulsions with interface-active components in oil production, and oil/water wetting on polyelectrolyte surfaces. The bubble probe AFM combined with reflection interference contrast microscopy (RICM) was applied for the first time to simultaneously quantify the interaction forces and spatiotemporal evolution of a confined thin liquid film between gas bubbles and solid surfaces with varying hydrophobicity. The nanomechanical results have provided useful insights into the fundamental interaction mechanisms (e.g., hydrophobic interaction in aqueous media) at gas/water/solid interfaces, the stabilization/destabilization mechanisms of emulsion drops, and oil/water wetting mechanisms on solid surfaces. A long-range hydrophilic attraction was found between water and polyelectrolyte surfaces in oil, with the strongest attraction for polyzwitterions, contributing to their superior water wettability in oil and self-cleaning capability of oil contamination. Some remaining challenges and future research directions are discussed and provided.

16. MODELING MONOMETHYLMERCURY AND TRIBUTYLTIN SPECIATION WITH EPA'S GEOCHEMICAL SPECIATION MODEL MINTEQA2

EPA Science Inventory

Given the complexity of the various, simultaneous (and competing) equilibrium reactions governing the speciation of ionic species in aquatic systems, EPA has developed and distributed the geochemical speciation model MINTEQA2 (Brown and Allison, 1987, Allison et al., 1991; Hydrog...

17. Thermal, anisotropic microhardness and laser induced surface damage studies on certain metal complexes of thiourea

Dhanuskodi, S.; Sabari Girisun, T. C.

2011-09-01

Single crystals of thiourea metal complexes with selected group II metal ions, zinc and cadmium, have been grown by solvent evaporation technique and characterized by XRD studies. The thermal, mechanical and laser induced surface damage properties of thiourea and its metal complexes in (1 0 0) plane were studied. From the improved photopyroelectric technique the thermal properties of the metal complexes were evaluated. Due to larger heat capacity ZTS (382.4 J kg -1 K -1) has better thermal stability than BTCC (304.09 J kg -1 K -1), TTCS (293.5 J kg -1 K -1) and BTZC (255.24 J kg -1 K -1). Vickers hardness studies reveal that the materials have reverse indentation size effect and belong to soft material type. Elastic stiffness was found to be very large for ZTS (8.05) than TTCS (5.38), BTCC (1.57 GPa) and BTZC (0.76 GPa). Multi-shot laser damage studies reveal that ZTS (40 GW/cm 2) has higher laser damage threshold and the roles of the group II metal ions in improving the mechanical and thermal stability of the metal complexes are discussed.

18. The mineralogic evolution of the Martian surface through time: Implications from chemical reaction path modeling studies

NASA Technical Reports Server (NTRS)

Plumlee, G. S.; Ridley, W. I.; Debraal, J. D.; Reed, M. H.

1993-01-01

Chemical reaction path calculations were used to model the minerals that might have formed at or near the Martian surface as a result of volcano or meteorite impact driven hydrothermal systems; weathering at the Martian surface during an early warm, wet climate; and near-zero or sub-zero C brine-regolith reactions in the current cold climate. Although the chemical reaction path calculations carried out do not define the exact mineralogical evolution of the Martian surface over time, they do place valuable geochemical constraints on the types of minerals that formed from an aqueous phase under various surficial and geochemically complex conditions.

19. Surface induced dissociation: dissecting noncovalent protein complexes in the gas phase.

PubMed

Zhou, Mowei; Wysocki, Vicki H

2014-04-15

when the gas-phase proteins are activated by collision with a surface. Subcomplexes released after surface collision are consistent with the native quaternary structure of several protein systems studied, even for a large chaperone protein, GroEL, that approaches megadalton mass. The unique and meaningful data generated from surface induced dissociation (SID) have been attributed to the fast and energetic activation process upon collision with a massive target, the surface. In this Account, we summarize our SID studies of protein complexes, with emphasis on the more recent work on the combination of ion mobility (IM) with SID. IM has gained popularity over the years not only as a gas-phase separation technique but also as a technique with the ability to measure the size and shape of the proteins in the gas phase. Incorporation of IM before SID allows different conformations of a protein to be separated and examined individually by SID for structural details. When IM is after SID, the cross sections of the SID products can be measured, providing insight on the dissociation pathways, which may mimic disassembly pathways. Furthermore, the separation by IM greatly reduces the peak overlapping (same m/z) and coalescence (merging) of SID products, improving the resolving power of the method. While there are still many unanswered questions on the fundamental properties of gas-phase proteins and a need for further research, our work has shown that SID can be a complementary gas-phase tool providing useful information for studying quaternary structures of noncovalent protein complexes.

20. Magnetic anisotropy in surface-supported single-ion lanthanide complexes

Stoll, Paul; Bernien, Matthias; Rolf, Daniela; Nickel, Fabian; Xu, Qingyu; Hartmann, Claudia; Umbach, Tobias R.; Kopprasch, Jens; Ladenthin, Janina N.; Schierle, Enrico; Weschke, Eugen; Czekelius, Constantin; Kuch, Wolfgang; Franke, Katharina J.

2016-12-01

Single-ion lanthanide-organic complexes can provide stable magnetic moments with well-defined orientation for spintronic applications on the atomic level. Here, we show by a combined experimental approach of scanning tunneling microscopy and x-ray absorption spectroscopy that dysprosium-tris(1,1,1-trifluoro-4-(2-thienyl)-2,4-butanedionate) (Dy (tta) 3 ) complexes deposited on a Au(111) surface undergo a molecular distortion, resulting in distinct crystal field symmetry imposed on the Dy ion. This leads to an easy-axis magnetization direction in the ligand plane. Furthermore, we show that tunneling electrons hardly couple to the spin excitations, which we ascribe to the shielded nature of the 4 f electrons.

1. Potential Energy Surfaces and Charge Transfer of PAH-Sodium-PAH Complexes.

PubMed

Hjertenaes, Eirik; Andersson, Stefan; Koch, Henrik

2016-09-19

To further understanding of the role of sodium in carbon cathode degradation in Hall-Héroult cells, potential-energy surfaces and charge-transfer curves are presented for finite-size complexes of sodium intercalated between various polycyclic aromatic hydrocarbons. Calculations for lithium and potassium are included to highlight the disparate intercalation behaviour of the alkali metals in graphite intercalation compounds. Static energy barriers from DFT are used to compute macroscopic diffusion coefficients according to transition-state theory. Comparing the calculated diffusion coefficient to experimental values from the literature sheds light on the role of lattice diffusion of sodium-graphite intercalation compounds in sodium intrusion in graphitic carbon cathodes.

2. 5-level polysilicon surface micromachine technology: Application to complex mechanical systems

SciTech Connect

Rodgers, M.S.; Sniegowski, J.J.

1998-06-01

The authors recently reported on the development of a 5-level poly-ilicon surface micromachine fabrication process consisting of four levels of mechanical poly plus an electrical interconnect layer. They are now reporting on the first components designed for and fabricated in this process. These are demonstration systems, which definitively show that five levels of polysilicon provide greater performance, reliability, and significantly increased functionality. This new technology makes it possible to realize levels of system complexity that have so far only existed on paper, while simultaneously adding to the robustness of many of the individual subassemblies.

3. C-H and H-H Activation in Transition Metal Complexes and on Surfaces.

DTIC Science & Technology

1983-01-01

Jean-Yves Saillard and Roald Hoffmann Prepared for Publication in the Journal of the American Chemical Society. Depeartment of Chemistry DTIC...I ’TB METAL COMPLEXES AND ON SURFACES ’"flfl’t2 []J =: % if i I~t ion- Distrjlbution/ ,. "iity Codes " .and/or jean-Yves Saillard and Roald Hoffmann...Ni, using a method much better than ours, may be found in Wang , C. S.; Callasay, J. Phys. Rev. B 1977, 15, 298-306. There are some noticeable

4. Ultrasonic detection technology based on joint robot on composite component with complex surface

SciTech Connect

Hao, Juan; Xu, Chunguang; Zhang, Lan

2014-02-18

Some components have complex surface, such as the airplane wing and the shell of a pressure vessel etc. The quality of these components determines the reliability and safety of related equipment. Ultrasonic nondestructive detection is one of the main methods used for testing material defects at present. In order to improve the testing precision, the acoustic axis of the ultrasonic transducer should be consistent with the normal direction of the measured points. When we use joint robots, automatic ultrasonic scan along the component surface normal direction can be realized by motion trajectory planning and coordinate transformation etc. In order to express the defects accurately and truly, the robot position and the signal of the ultrasonic transducer should be synchronized.

5. Potential energy surface and bound states of the NH3-Ar and ND3-Ar complexes.

PubMed

Loreau, J; Liévin, J; Scribano, Y; van der Avoird, A

2014-12-14

A new, four-dimensional potential energy surface for the interaction of NH3 and ND3 with Ar is computed using the coupled-cluster method with single, double, and perturbative triple excitations and large basis sets. The umbrella motion of the ammonia molecule is explicitly taken into account. The bound states of both NH3-Ar and ND3-Ar are calculated on this potential for total angular momentum values from J = 0 to 10, with the inclusion of Coriolis interactions. The energies and splittings of the rovibrational levels are in excellent agreement with the extensive high-resolution spectroscopic data accumulated over the years in the infrared and microwave regions for both complexes, which demonstrates the quality of the potential energy surface.

6. Formal Killing fields for minimal Lagrangian surfaces in complex space forms

Wang, Joe S.

2017-04-01

The differential system for minimal Lagrangian surfaces in a 2C-dimensional, non-flat, complex space form is an elliptic integrable system defined on the Grassmann bundle of oriented Lagrangian 2-planes. This is a 6-symmetric space associated with the Lie group SL(3 , C) , and the minimal Lagrangian surfaces arise as the primitive maps. Utilizing this property, we derive the inductive differential algebraic formulas for a pair of the formal loop algebra sl(3 , C) [ [ λ ] ] -valued canonical formal Killing fields. For applications, (a) we give a complete classification of the (pseudo) Jacobi fields for the minimal Lagrangian system, (b) we obtain an infinite sequence of conservation laws from the components of the canonical formal Killing fields.

7. Surface-modified complex SU-8 microstructures for indirect optical manipulation of single cells

PubMed Central

Aekbote, Badri L.; Fekete, Tamás; Jacak, Jaroslaw; Vizsnyiczai, Gaszton; Ormos, Pál; Kelemen, Lóránd

2015-01-01

We introduce a method that combines two-photon polymerization (TPP) and surface functionalization to enable the indirect optical manipulation of live cells. TPP-made 3D microstructures were coated specifically with a multilayer of the protein streptavidin and non-specifically with IgG antibody using polyethylene glycol diamine as a linker molecule. Protein density on their surfaces was quantified for various coating methods. The streptavidin-coated structures were shown to attach to biotinated cells reproducibly. We performed basic indirect optical micromanipulation tasks with attached structure-cell couples using complex structures and a multi-focus optical trap. The use of such extended manipulators for indirect optical trapping ensures to keep a safe distance between the trapping beams and the sensitive cell and enables their 6 degrees of freedom actuation. PMID:26819816

8. HIFU scattering by the ribs: constrained optimisation with a complex surface impedance boundary condition

Gélat, P.; ter Haar, G.; Saffari, N.

2014-04-01

High intensity focused ultrasound (HIFU) enables highly localised, non-invasive tissue ablation and its efficacy has been demonstrated in the treatment of a range of cancers, including those of the kidney, prostate and breast. HIFU offers the ability to treat deep-seated tumours locally, and potentially bears fewer side effects than more established treatment modalities such as resection, chemotherapy and ionising radiation. There remains however a number of significant challenges which currently hinder its widespread clinical application. One of these challenges is the need to transmit sufficient energy through the ribcage to ablate tissue at the required foci whilst minimising the formation of side lobes and sparing healthy tissue. Ribs both absorb and reflect ultrasound strongly. This sometimes results in overheating of bone and overlying tissue during treatment, leading to skin burns. Successful treatment of a patient with tumours in the upper abdomen therefore requires a thorough understanding of the way acoustic and thermal energy is deposited. Previously, a boundary element (BE) approach based on a Generalised Minimal Residual (GMRES) implementation of the Burton-Miller formulation was developed to predict the field of a multi-element HIFU array scattered by human ribs, the topology of which was obtained from CT scan data [1]. Dissipative mechanisms inside the propagating medium have since been implemented, together with a complex surface impedance condition at the surface of the ribs. A reformulation of the boundary element equations as a constrained optimisation problem was carried out to determine the complex surface velocities of a multi-element HIFU array which generated the acoustic pressure field that best fitted a required acoustic pressure distribution in a least-squares sense. This was done whilst ensuring that an acoustic dose rate parameter at the surface of the ribs was kept below a specified threshold. The methodology was tested at an

9. Influence of tailored MLI for complex surface geometries on heat transfer

Neumann, H.; Mayrhofer, R.; Richter, T.

2015-12-01

Complex, non-developable surfaces require a tailored multi-layer insulation (MLI) for lowest heat load. The most experiments showing the heat transfer through MLI are performed under quasi-ideal conditions determining the principle insulation quality. But the surface to be insulated in real cryostats implies feed-throughs and other non-developable surface parts. The thermal performance of MLI is degraded significantly at cutting points. To investigate this degrading effect a LN2-filled cylinder with a diameter of 219 mm and a length of 1820 mm was insulated with MLI and the heat load was measured by means of calorimetry. In addition the heat load to an insulated cylinder with eighteen branches was measured. Both cylinders have the same surface of 1.37 m2 for a comparison of the results. This article describes the experiments with different ways of tailoring the MLI for the cylinder with branches and discusses their results. It was shown that the cutting points at the branches have a significant degrading influence on the thermal performance of MLI.

10. Lunar and Planetary Science XXXV: Weird Martian Minerals: Complex Mars Surface Processes

NASA Technical Reports Server (NTRS)

2004-01-01

The session "Complex Mars Surface" included the following reports:A Reappraisal of Adsorbed Superoxide Ion as the Cause Behind the Reactivity of the Martian Soils; Sub-Surface Deposits of Hydrous Silicates or Hydrated Magnesium Sulfates as Hydrogen Reservoirs near the Martian Equator: Plausible or Not?; Thermal and Evolved Gas Analysis of Smectites: The Search for Water on Mars; Aqueous Alteration Pathways for K, Th, and U on Mars; Temperature Dependence of the Moessbauer Fraction in Mars-Analog Minerals; Acid-Sulfate Vapor Reactions with Basaltic Tephra: An Analog for Martian Surface Processes; Iron Oxide Weathering in Sulfuric Acid: Implications for Mars; P/Fe as an Aquamarker for Mars; Stable Isotope Composition of Carbonates Formed in Low-Temperature Terrestrial Environments as Martian Analogs; Can the Phosphate Sorption and Occlusion Properties Help to Elucidate the Genesis of Specular Hematite on the Mars Surface?; Sulfate Salts, Regolith Interactions, and Water Storage in Equatorial Martian Regolith; Potential Pathways to Maghemite in Mars Soils: The Key Role of Phosphate; and Mineralogy, Abundance, and Hydration State of Sulfates and Chlorides at the Mars Pathfinder Landing Site.

11. Investigating the thermodynamic stability of Bacillus subtilis spore-uranium(VI) adsorption though surface complexation modeling

Harrold, Z.; Hertel, M.; Gorman-Lewis, D.

2012-12-01

12. PALADYN, a comprehensive land surface-vegetation-carbon cycle model of intermediate complexity

Willeit, Matteo; Ganopolski, Andrey

2016-04-01

PALADYN is presented, a new comprehensive and computationally efficient land surface-vegetation-carbon cycle model designed to be used in Earth system models of intermediate complexity for long-term simulations and paleoclimate studies. The model treats in a consistent manner the interaction between atmosphere, terrestrial vegetation and soil through the fluxes of energy, water and carbon. Energy, water and carbon are conserved. The model explicitly treats permafrost, both in physical processes and as important carbon pool. The model distinguishes 9 surface types of which 5 are different vegetation types, bare soil, land ice, lake and ocean shelf. Including the ocean shelf allows to treat continuous changes in sea level and shelf area associated with glacial cycles. Over each surface type the model solves the surface energy balance and computes the fluxes of sensible, latent and ground heat and upward shortwave and longwave radiation. It includes a single snow layer. The soil model distinguishes between three different macro surface types which have their own soil column: vegetation and bare soil, ice sheet and ocean shelf. The soil is vertically discretized into 5 layers where prognostic equations for temperature, water and carbon are consistently solved. Phase changes of water in the soil are explicitly considered. A surface hydrology module computes precipitation interception by vegetation, surface runoff and soil infiltration. The soil water equation is based on Darcy's law. Given soil water content, the wetland fraction is computed based on a topographic index. Photosynthesis is computed using a light use efficiency model. Carbon assimilation by vegetation is coupled to the transpiration of water through stomatal conductance. The model includes a dynamic vegetation module with 5 plant functional types competing for the gridcell share with their respective net primary productivity. Each macro surface type has its own carbon pools represented by a litter, a fast

13. Geochemical controls on groundwater chemistry in shales

SciTech Connect

Von Damm, K.L.

1989-01-01

The chemistry of groundwaters is one of the most important parameters in determining the mobility of species within a rock formation. A three pronged approach was used to determine the composition of, and geochemical controls, on groundwaters specifically within shale formations: (1) available data were collected from the literature, the US Geological Survey WATSTORE data base, and field sampling, (2) the geochemical modeling code EQ3/6 was used to simulate interaction of various shales and groundwaters, and (3) several types of shale were reacted with synthetic groundwaters in the laboratory. The comparison of model results to field and laboratory data provide a means of validating the models, as well as a means of deconvoluting complex field interactions. Results suggest that groundwaters in shales have a wide range in composition and are primarily of the Na-Cl-HCO/sub 3/- type. The constancy of the Na:Cl (molar) ratio at 1:1 and the Ca:Mg ratio from 3:1 to 1:1 suggests the importance of halite and carbonates in controlling groundwater compositions. In agreement with the reaction path modeling, most of the groundwaters are neutral to slightly alkaline at low temperatures. Model and experimental results suggest that reaction (1) at elevated temperatures, or (2) in the presence of oxygen will lead to more acidic conditions. Some acetate was found to be produced in the experiments; depending on the constraints applied, large amounts of acetate were produced in the model results. 13 refs., 1 tab.

14. Interaction between zinc and freshwater and marine diatom species: Surface complexation and Zn isotope fractionation

Gélabert, A.; Pokrovsky, O. S.; Viers, J.; Schott, J.; Boudou, A.; Feurtet-Mazel, A.

2006-02-01

This work is devoted to characterization of zinc interaction in aqueous solution with two marine planktonic ( Thalassiosira weissflogii = TW, Skeletonema costatum = SC) and two freshwater periphytic species ( Achnanthidium minutissimum = AMIN, Navicula minima = NMIN) by combining adsorption and electrophoretic measurements with surface complexation modeling and by assessing Zn isotopes fractionation during both long term uptake and short term adsorption on diatom cells and their frustules. Reversible adsorption experiments were performed at 25 and 5 °C as a function of exposure time (5 min to 140 h), pH (2 to 10), zinc concentration in solution (10 nM to 1 mM), ionic strength ( I = 0.001 to 1.0 M) and the presence of light. While the shape of pH-dependent adsorption edge is almost the same for all four species, the constant-pH adsorption isotherm and maximal Zn binding capacities differ by an order of magnitude. The extent of adsorption increases with temperature from 5 to 25 °C and does not depend on light intensity. Zinc adsorption decreases with increase of ionic strength suggesting competition with sodium for surface sites. Cell number-normalized concentrations of sorbed zinc on whole cells and their silica frustules demonstrated only weak contribution of the latter (10-20%) to overall zinc binding by diatom cell wall. Measurements of electrophoretic mobilities ( μ) revealed negative diatoms surface potential in the full range of zinc concentrations investigated (0.15-760 μmol/L), however, the absolute value of μ decreases at [Zn] > 15 μmol/L suggesting a change in surface speciation. These observations allowed us to construct a surface complexation model for Zn binding by diatom surfaces that postulates the constant capacitance of the electric double layer and considers Zn complexation with carboxylate and silanol groups. Thermodynamic and structural parameters of this model are based on previous acid-base titration and spectroscopic results and allow

15. The effect of sterilization on biological, organic geochemical and morphological information in natural samples

NASA Technical Reports Server (NTRS)

Hochstein, L. I.; Kvenvolden, K. A.; Philpott, D. E.

1974-01-01

The loss of biological, organic geochemical, and morphological science information that may occur should a Mars surface sample be sterilized prior to return to earth is examined. Results of experimental studies are summarized.

16. Geochemical characterisation of northern Norwegian fjords sediments: A source to sink study

Faust, Johan; Knies, Jochen; Scheiber, Thomas

2016-04-01

To provide a better understanding of the weathering, transportation and sedimentation processes in a complex fjord system forty-four surface sediment samples plus three sediment cores were recovered from the Vestfjord, Ofotfjord and Tysfjord in northern Norway. We analysed the elemental composition, Corg, bulk mineral composition, CaCO3, grain size and C, Nd, Sr and Hf isotopes. We found that the Vestfjord, Ofotfjord and Tysfjord can be characterised and separated by distinct geochemical signatures of the surface sediment samples e.g. in the distribution of REE and the relation between grain size and Ni, Fe and K. These variations are related to differences in the hinterland bedrock composition. The bedrock in the drainage area of these fjords consist mainly of para- and orthogneiss. Onshore soil and bedrock geochemistry data show that the orthogneiss can be distinguished from the paragneiss by the different content of Th, K, Mg, Ni and Fe. Moreover, a limestone formation rich in dolomite can be traced in the fjord system using the calcite/dolomite ratio. The investigation of the sediment cores shows that these parameters can be used as a geochemical fingerprint to trace the different rock types throughout the entire Holocene. This finding will also help to gain more knowledge about the timing of the past deglaciation and sea level variations in northern Norway.

17. Is formamide a geochemically plausible prebiotic solvent?

PubMed

Bada, Jeffrey L; Chalmers, John H; Cleaves, H James

2016-07-27

From a geochemical perspective, significant amounts of pure formamide (HCONH2) would have likely been rare on the early Earth. There may have been mixed formamide-water solutions, but even in the presence of catalyst, solutions with >20 weight% water in formamide would not have produced significant amounts of prebiotic compounds. It might be feasible to produce relatively pure formamide by a rare occurrence of freezing formamide/water mixtures at temperatures lower than formamide's freezing point (2.55 °C) but greater than the freezing point of water. Because of the high density of formamide ice it would have sunk and accumulated at the bottom of the solution. If the remaining water froze on the surface of this ice, and was then removed by a sublimation-ablation process, a small amount of pure formamide ice might have been produced. In addition a recent report suggested that ∼85 weight% formamide could be prepared by a geochemical type of fractional distillation process, offering another possible route for prebiotic formamide production.

18. Three-gradient regular solution model for simple liquids wetting complex surface topologies

PubMed Central

Akerboom, Sabine; Kamperman, Marleen

2016-01-01

Summary We use regular solution theory and implement a three-gradient model for a liquid/vapour system in contact with a complex surface topology to study the shape of a liquid drop in advancing and receding wetting scenarios. More specifically, we study droplets on an inverse opal: spherical cavities in a hexagonal pattern. In line with experimental data, we find that the surface may switch from hydrophilic (contact angle on a smooth surface θY < 90°) to hydrophobic (effective advancing contact angle θ > 90°). Both the Wenzel wetting state, that is cavities under the liquid are filled, as well as the Cassie–Baxter wetting state, that is air entrapment in the cavities under the liquid, were observed using our approach, without a discontinuity in the water front shape or in the water advancing contact angle θ. Therefore, air entrapment cannot be the main reason why the contact angle θ for an advancing water front varies. Rather, the contact line is pinned and curved due to the surface structures, inducing curvature perpendicular to the plane in which the contact angle θ is observed, and the contact line does not move in a continuous way, but via depinning transitions. The pinning is not limited to kinks in the surface with angles θkink smaller than the angle θY. Even for θkink > θY, contact line pinning is found. Therefore, the full 3D-structure of the inverse opal, rather than a simple parameter such as the wetting state or θkink, determines the final observed contact angle. PMID:27826512

19. Surface charge evolution of mineral-organic complexes during pedogenesis in Hawaiian basalt

2004-12-01

Changes in surface charge of soil particles that accompany mineral transformations during soil formation were measured for a humid tropical chronosequence in Hawaiian basalt ranging in lava flow age from 0.3 to 4100 kiloyears (ky). Parent mineralogy is dominated by glass, olivine, pyroxene, and feldspar, whereas poorly crystalline (PC) weathering products (allophane, microcrystalline gibbsite, ferrihydrite) accumulate in early to intermediate weathering stages (through 400 ky), and crystalline secondary minerals (kaolinite, gibbsite, goethite) are dominant in the oldest (1400 and 4100 ky) soils. Detailed characterization of the solid phase was accomplished with chemical extractions, X-ray diffraction analysis, and molecular spectroscopy (FTIR and 13C MAS NMR). Simultaneous proton titration and background ion adsorption measurements were made on LiCl saturated soils over a range in pH (2-9) and ionic strength (0.001 and 0.01 M LiCl). Dependence of variable surface charge on solution composition reflects the changing nature of mineral-organic interactions over the course of pedogenesis. Points of zero net proton charge (PZNPC) ranged from 3.4 to 6.2 and 2.0 to 5.8 at 0.001 and 0.01 M ionic strength ( I), respectively. Intermediate-aged soils containing the highest mass concentration of humified soil organic matter (SOM) and its complexes with PC minerals gave rise to the steepest charging curves (largest pH dependence) and highest PZNPC values. Surface charge properties of these soils most closely reflected their weakly acidic Al and Fe hydroxide constituents, which is consistent with metal hydroxide saturation of organic functional groups, rather than organic coating of mineral surfaces. Charging curves were less steep and PZNPC values were lower for the older soils, consistent with SOM coating of more crystalline goethite, kaolinite, and gibbsite surfaces in a soil system less impacted by labile Al and Fe.

20. Transmission X-ray scattering as a probe for complex liquid-surface structures

SciTech Connect

Fukuto, Masafumi; Yang, Lin; Nykypanchuk, Dmytro; Kuzmenko, Ivan

2016-01-28

The need for functional materials calls for increasing complexity in self-assembly systems. As a result, the ability to probe both local structure and heterogeneities, such as phase-coexistence and domain morphologies, has become increasingly important to controlling self-assembly processes, including those at liquid surfaces. The traditional X-ray scattering methods for liquid surfaces, such as specular reflectivity and grazing-incidence diffraction, are not well suited to spatially resolving lateral heterogeneities due to large illuminated footprint. A possible alternative approach is to use scanning transmission X-ray scattering to simultaneously probe local intermolecular structures and heterogeneous domain morphologies on liquid surfaces. To test the feasibility of this approach, transmission small- and wide-angle X-ray scattering (TSAXS/TWAXS) studies of Langmuir films formed on water meniscus against a vertically immersed hydrophilic Si substrate were recently carried out. First-order diffraction rings were observed in TSAXS patterns from a monolayer of hexagonally packed gold nanoparticles and in TWAXS patterns from a monolayer of fluorinated fatty acids, both as a Langmuir monolayer on water meniscus and as a Langmuir–Blodgett monolayer on the substrate. The patterns taken at multiple spots have been analyzed to extract the shape of the meniscus surface and the ordered-monolayer coverage as a function of spot position. These results, together with continual improvement in the brightness and spot size of X-ray beams available at synchrotron facilities, support the possibility of using scanning-probe TSAXS/TWAXS to characterize heterogeneous structures at liquid surfaces.

1. Transmission X-ray scattering as a probe for complex liquid-surface structures

DOE PAGES

Fukuto, Masafumi; Yang, Lin; Nykypanchuk, Dmytro; ...

2016-01-28

The need for functional materials calls for increasing complexity in self-assembly systems. As a result, the ability to probe both local structure and heterogeneities, such as phase-coexistence and domain morphologies, has become increasingly important to controlling self-assembly processes, including those at liquid surfaces. The traditional X-ray scattering methods for liquid surfaces, such as specular reflectivity and grazing-incidence diffraction, are not well suited to spatially resolving lateral heterogeneities due to large illuminated footprint. A possible alternative approach is to use scanning transmission X-ray scattering to simultaneously probe local intermolecular structures and heterogeneous domain morphologies on liquid surfaces. To test the feasibilitymore » of this approach, transmission small- and wide-angle X-ray scattering (TSAXS/TWAXS) studies of Langmuir films formed on water meniscus against a vertically immersed hydrophilic Si substrate were recently carried out. First-order diffraction rings were observed in TSAXS patterns from a monolayer of hexagonally packed gold nanoparticles and in TWAXS patterns from a monolayer of fluorinated fatty acids, both as a Langmuir monolayer on water meniscus and as a Langmuir–Blodgett monolayer on the substrate. The patterns taken at multiple spots have been analyzed to extract the shape of the meniscus surface and the ordered-monolayer coverage as a function of spot position. These results, together with continual improvement in the brightness and spot size of X-ray beams available at synchrotron facilities, support the possibility of using scanning-probe TSAXS/TWAXS to characterize heterogeneous structures at liquid surfaces.« less

2. Tetrathiafulvalene-Supported Triple-Decker Phthalocyaninato Dysprosium(III) Complex: Synthesis, Properties and Surface Assembly

PubMed Central

Gao, Feng; Zhang, Xue-Mei; Cui, Long; Deng, Ke; Zeng, Qing-Dao; Zuo, Jing-Lin

2014-01-01

Self-assembly of functional compounds into a prerequisite nanostructure with desirable dimension and morphology by controlling and optimizing intermolecular interaction attracts an extensive research interest for chemists and material scientist. In this work, a new triple-decker sandwich-type lanthanide complex with phthalocyanine and redox-active Schiff base ligand including tetrathiafulvalene (TTF) units has been synthesized, and characterized by single crystal X-ray diffraction analysis, absorption spectra, electrochemical and magnetic measurements. Interestingly, the non-centrosymmetric target complex displays a bias dependent selective adsorption on a solid surface, as observed by scanning tunneling microscopy (STM) at the single molecule level. Density function theory (DFT) calculations are utilized to reveal the formation mechanism of the molecular assemblies, and show that such electrical field dependent selective adsorption is regulated by the interaction between the external electric field and intrinsic molecular properties. Our results suggest that this type of multi-decker complex involving TTF units shows intriguing multifunctional properties from the viewpoint of structure, electric and magnetic behaviors, and fabrication through self-assembly. PMID:25088605

3. Excited state potential energy surfaces of bistridentate RuII complexes - A TD-DFT study

2012-10-01

Time-dependent density functional theory (TD-DFT) calculations have been used to investigate low-energy singlet and triplet excited state potential energy surfaces (PES) of two prototype RuII-bistridentate complexes: [RuII(tpy)2]2+ (tpy is 2,2':6',2''-terpyridine) and [RuII(dqp)2]2+ (dqp is 2,6-di(quinolin-8-yl)pyridine). Solvent effects were considered using a self-consistent reaction field scheme. The calculations provide information about the excited state manifold along pathways for activated decay of metal-to-ligand charge-transfer (MLCT) excited states via metal-centered (MC) states for the two complexes. Significant differences in the energy profiles of the investigated PESs are explained through characterization of the electronic properties of the involved states calculated by the TD-DFT calculations. Finally, implications of the computational results for the design of octahedral metal complexes utilizing ligand field splitting (LFS) strategies for efficient light-harvesting in photochemical applications such as artificial photosynthesis are discussed.

4. On the relationship between enamel band complexity and occlusal surface area in Equids (Mammalia, Perissodactyla)

PubMed Central

Davis, Edward Byrd

2016-01-01

Enamel patterns on the occlusal surfaces of equid teeth are asserted to have tribal-level differences. The most notable example compares the Equini and Hipparionini, where Equini have higher crowned teeth with less enamel-band complexity and less total occlusal enamel than Hipparionini. Whereas previous work has successfully quantified differences in enamel band shape by dividing the length of enamel band by the square root of the occlusal surface area (Occlusal Enamel Index, OEI), it was clear that OEI only partially removes the effect of body size. Because enamel band length scales allometrically, body size still has an influence on OEI, with larger individuals having relatively longer enamel bands than smaller individuals. Fractal dimensionality (D) can be scaled to any level, so we have used it to quantify occlusal enamel complexity in a way that allows us to get at an accurate representation of the relationship between complexity and body size. To test the hypothesis of tribal-level complexity differences between Equini and Hipparionini, we digitally traced a sample of 98 teeth, one tooth per individual; 31 Hipparionini and 67 Equini. We restricted our sampling to the P3-M2 to reduce the effect of tooth position. After calculating the D of these teeth with the fractal box method which uses the number of boxes of various sizes to calculate the D of a line, we performed a t-test on the individual values of D for each specimen, comparing the means between the two tribes, and a phylogenetically informed generalized least squares regression (PGLS) for each tribe with occlusal surface area as the independent variable and D as the dependent variable. The slopes of both PGLS analyses were compared using a t-test to determine if the same linear relationship existed between the two tribes. The t-test between tribes was significant (p < 0.0001), suggesting different D populations for each lineage. The PGLS for Hipparionini was a positive but not significant (p = 0

5. Shuffled complex evolution approach for effective and efficient surface wave analysis

Song, Xianhai; Tang, Li; Lv, Xiaochun; Fang, Hongping; Gu, Hanming

2012-05-01

Inversion of Rayleigh wave dispersion curves is challenging for most local-search methods due to its high nonlinearity and to its multimodality. In this paper, we proposed and tested a new Rayleigh wave dispersion curve inversion scheme called the shuffled complex evolution (SCE) approach, which is based on a synthesis of four global optimization strategies that have proved successful for global optimization: (a) combination of probabilistic and deterministic approaches; (b) the strategy of clustering; (c) systematic evolution of a complex of points spanning the space, in the direction of global improvement; and (d) competitive evolution. Incorporating these four global optimization strategies into the inverse procedure greatly enhances the performance of the SCE method because these steps not only can effectively locate the promising areas in the solution space for a global minimum but also avoid its wandering near the global minimum in the final stage of search. The proposed inverse procedure was applied to nonlinear inversion of fundamental-mode Rayleigh wave dispersion curves for near-surface shear (S)-wave velocity profiles. The calculation efficiency and stability of the inversion scheme are tested on four synthetic models and a real-world example from a waste disposal site in NE Italy. A comparative analysis with genetic algorithms (GA), marginal posterior probability density (MPPD) estimation, and simulated annealing (SA) is also made in the present study to further evaluate the performance of the proposed approach. Results from both synthetic and actual field data demonstrate that shuffled complex evolution algorithm promises to be robust, effective, and efficient for high-frequency surface wave analysis.

6. Interaction of ortho-Phospho-l-serine with Hydroxyapatite: Formation of a Surface Complex

PubMed

Misra

1997-10-01

ortho-Phospho-l-serine (H2Psi, where Psi represents the serinephosphato ion), a constituent of salivary proteins, seems to play an important role in the mineralization of teeth. To understand the basic mechanism of this interaction, the uptake of o-phospho-l-serine from relatively concentrated aqueous solutions (up to 100 mmol/L) onto synthetic hydroxyapatite was studied. Previous studies have shown that in the dilute concentration range (<12.5 mmol/L) the uptake followed a regular Langmuirian adsorption plot. At higher concentrations the uptake curve increased steeply, but no formation of a separate phase in the reacted apatite was discernible, either by optical or by scanning electron microscopy. The dissolution of apatite released phosphate and calcium ions into the solution in amounts linearly related to the uptake of serine with P/Psi = 1 and Ca/Psi = 2. The charge and mass balance of the reaction can be reconciled with the formation of the surface complex (shown within brackets):Ca10(OH)2(PO4)6 + 6H2Psi --> [Ca6(HPsi)2(HPO4)2(PO4)2] + 4Ca2+ + 2HPsi1- + 2Psi2- + 2H2PO1-4 + 2H2O.The formation of two other surface complexes is possible; however, the complex shown above probably disrupts the apatite lattice the least. Traces of CaPsi·H2O precipitate out from the filtrates of highly concentrated solutions after 6 days. Copyright 1997 Academic Press. Copyright 1997Academic Press

7. Comparison of in situ uranium KD values with a laboratory determined surface complexation model

USGS Publications Warehouse

Curtis, G.P.; Fox, P.; Kohler, M.; Davis, J.A.

2004-01-01

Reactive solute transport simulations in groundwater require a large number of parameters to describe hydrologic and chemical reaction processes. Appropriate methods for determining chemical reaction parameters required for reactive solute transport simulations are still under investigation. This work compares U(VI) distribution coefficients (i.e. KD values) measured under field conditions with KD values calculated from a surface complexation model developed in the laboratory. Field studies were conducted in an alluvial aquifer at a former U mill tailings site near the town of Naturita, CO, USA, by suspending approximately 10 g samples of Naturita aquifer background sediments (NABS) in 17-5.1-cm diameter wells for periods of 3 to 15 months. Adsorbed U(VI) on these samples was determined by extraction with a pH 9.45 NaHCO3/Na2CO3 solution. In wells where the chemical conditions in groundwater were nearly constant, adsorbed U concentrations for samples taken after 3 months of exposure to groundwater were indistinguishable from samples taken after 15 months. Measured in situ K D values calculated from the measurements of adsorbed and dissolved U(VI) ranged from 0.50 to 10.6 mL/g and the KD values decreased with increasing groundwater alkalinity, consistent with increased formation of soluble U(VI)-carbonate complexes at higher alkalinities. The in situ K D values were compared with KD values predicted from a surface complexation model (SCM) developed under laboratory conditions in a separate study. A good agreement between the predicted and measured in situ KD values was observed. The demonstration that the laboratory derived SCM can predict U(VI) adsorption in the field provides a critical independent test of a submodel used in a reactive transport model. ?? 2004 Elsevier Ltd. All rights reserved.

8. Geochemical Exploration Techniques Applicable in the Search for Copper Deposits

USGS Publications Warehouse

Chaffee, Maurice A.

1975-01-01

media. Samples of ice and snow have been used for limited geochemical surveys. Both geobotanical and biogeochemical surveys have been successful in locating copper deposits in many parts of the world. Micro-organisms, including bacteria and algae, are other unproved media that should be studied. Animals can be used in geochemical-prospecting programs. Dogs have been used quite successfully to sniff out hidden and exposed sulfide minerals. Tennite mounds are commonly composed of subsurface material, but have not as yet proved to be useful in locating buried mineral deposits. Animal tissue and waste products are essentially unproved but potentially valuable sampling media. Knowledge of the location of areas where trace-element-associated diseases in animals and man are endemic as well as a better understanding of these diseases, may aid in identifying regions that are enriched in or depleted of various elements, including copper. Results of analyses of gases in the atmosphere are proving valuable in mineral-exploration surveys. Studies involving metallic compounds exhaled by plants into the atmosphere, and of particulate matter suspended in the atmosphere are reviewed these methods may become important in the future. Remote-sensing techniques are useful for making indirect measurements of geochemical responses. Two techniques applicable to geochemical exploration are neutron-activation analysis and gamma-ray spectrometry. Aerial photography is especially useful in vegetation surveys. Radar imagery is an unproved but potentially valuable method for use in studies of vegetation in perpetually clouded regions. With the advent of modern computers, many new techniques, such as correlation analysis, regression analysis, discriminant analysis, factor analysis, cluster analysis, trend-surface analysis, and moving-average analysis can be applied to geochemical data sets. Selective use of these techniques can provide new insights into the interpretatio

9. Surface complexation of heavy metal cations on clay edges: insights from first principles molecular dynamics simulation of Ni(II)

Zhang, Chi; Liu, Xiandong; Lu, Xiancai; He, Mengjia; Jan Meijer, Evert; Wang, Rucheng

2017-04-01

Aiming at an atomistic mechanism of heavy metal cation complexing on clay surfaces, we carried out systematic first principles molecular dynamics (FPMD) simulations to investigate the structures, free energies and acidity constants of Ni(II) complexes formed on edge surfaces of 2:1 phyllosilicates. Three representative complexes were studied, including monodentate complex on the tbnd SiO site, bidentate complex on the tbnd Al(OH)2 site, and tetradentate complex on the octahedral vacancy where Ni(II) fits well into the lattice. The complexes structures were characterized in detail. Computed free energy values indicate that the tetradentate complex is significantly more stable than the other two. The calculated acidity constants indicate that the tetradentate complex can get deprotonated (pKa = 8.4) at the ambient conditions whereas the other two hardly deprotonate due to extremely high pKa values. By comparing with the 2 Site Protolysis Non Electrostatic Surface Complexation and Cation Exchange (2SPNE SC/CE) model, the vacant site has been assigned to the strong site and the other two to the weak site, respectively. Thus a link has been built between atomistic simulations and macroscopic experiments and it is deduced that this should also apply to other heavy metal cations based on additional simulations of Co(II) and Cu(II) and previous simulations of Fe(II) and Cd(II)). This study forms a physical basis for understanding the transport and fixation of heavy metal elements in many geologic environments.

10. A cell surface receptor complex for collagen type I recognizes the Arg- Gly-Asp sequence

PubMed Central

1987-01-01

To isolate collagen-binding cell surface proteins, detergent extracts of surface-iodinated MG-63 human osteosarcoma cells were chromatographed on affinity matrices of either type I collagen- Sepharose or Sepharose carrying a collagen-like triple-helical peptide. The peptide was designed to be triple helical and to contain the sequence Arg-Gly-Asp, which has been implicated as the cell attachment site of fibronectin, vitronectin, fibrinogen, and von Willebrand factor, and is also present in type I collagen. Three radioactive polypeptides having apparent molecular masses of 250 kD, 70 kD, and 30 kD were distinguishable in that they showed affinity toward the collagen and collagen-like peptide affinity columns, and could be specifically eluted from these columns with a solution of an Arg-Gly- Asp-containing peptide, Gly-Arg-Gly-Asp-Thr-Pro. These collagen-binding polypeptides associated with phosphatidylcholine liposomes, and the resulting liposomes bound specifically to type I collagen or the collagen-like peptide but not to fibronectin or vitronectin or heat- denatured collagen. The binding of these liposomes to type I collagen could be inhibited with the peptide Gly-Arg-Gly-Asp-Thr-Pro and with EDTA, but not with a variant peptide Gly-Arg-Gly-Glu-Ser-Pro. We conclude from these data that these three polypeptides are membrane molecules that behave as a cell surface receptor (or receptor complex) for type I collagen by interacting with it through the Arg-Gly-Asp tripeptide adhesion signal. The lack of binding to denatured collagen suggests that the conformation of the Arg-Gly-Asp sequence is important in the recognition of collagen by the receptor complex. PMID:3469204

11. Get a grip on chaos: Tailored measures for complex systems on surfaces

Firle, Sascha Oliver

Complex systems are ubiquitous in physics, biology and mathematics. This thesis is concerned with describing and understanding complex systems. Some new concepts about how large systems can be viewed in a lower dimensional framework are proposed. The systems presented are examples from ecology and chemistry. In both cases we have a large amount of interacting units that can be understood by The predator-prey system investigated consists of ground beetles, Pterostichus cuprens L. (Coleoptera: Carabidae), that feeds on bird-cherry oat aphids. The beetles' movement can consistently be described by a combined model of surface diffusion and biased random walk. This allows conclusions about how fast and in which fashion the beetle covers its habitat. Movement is dependent on aphid densities and predation, in turn modifies aphid distributions locally. The presented generalized functional response theory describes predation rates in the presence of spatial heterogeneity. A single measure for fragmentation captures all essential features of the prey aggregation and allows the estimation of outbreak densities and distributions. The chemical example is the catalytic oxidation of CO on a Pt(110) single crystal surface. Unstable periodic orbits reconstructed from experimental data are used to reveal the topology of the attractor, underlying the time series dynamics. The found braid supports an orbit which implies that the time series is chaotic. The system is simulated numerically by a set of partial differential equations for surface coverage in one space dimension. The bifurcation diagram of the corresponding traveling wave ODE reveals the homoclinic and heteroclinic orbits that organize the phase space and mediate the transition to chaos. Studies in the PDE- framework relate this to the stability and to the interaction of pulse-like solutions.

12. A Non-Electrostatic Surface Complexation Approach to Modeling Radionuclide Migration at the Nevada Test Site: I. Iron Oxides and Calcite

SciTech Connect

Zavarin, M; Bruton, C J

2004-12-17

13. Additive surface complexation modeling of uranium(VI) adsorption onto quartz-sand dominated sediments.

PubMed

Dong, Wenming; Wan, Jiamin

2014-06-17

Many aquifers contaminated by U(VI)-containing acidic plumes are composed predominantly of quartz-sand sediments. The F-Area of the Savannah River Site (SRS) in South Carolina (USA) is an example. To predict U(VI) mobility and natural attenuation, we conducted U(VI) adsorption experiments using the F-Area plume sediments and reference quartz, goethite, and kaolinite. The sediments are composed of ∼96% quartz-sand and 3-4% fine fractions of kaolinite and goethite. We developed a new humic acid adsorption method for determining the relative surface area abundances of goethite and kaolinite in the fine fractions. This method is expected to be applicable to many other binary mineral pairs, and allows successful application of the component additivity (CA) approach based surface complexation modeling (SCM) at the SRS F-Area and other similar aquifers. Our experimental results indicate that quartz has stronger U(VI) adsorption ability per unit surface area than goethite and kaolinite at pH ≤ 4.0. Our modeling results indicate that the binary (goethite/kaolinite) CA-SCM under-predicts U(VI) adsorption to the quartz-sand dominated sediments at pH ≤ 4.0. The new ternary (quartz/goethite/kaolinite) CA-SCM provides excellent predictions. The contributions of quartz-sand, kaolinite, and goethite to U(VI) adsorption and the potential influences of dissolved Al, Si, and Fe are also discussed.

14. Ab initio intermolecular potential energy surfaces for the Ar-NCCN van der Waals complexes

2014-11-01

The intermolecular potential energy surface of complex pairing argon with cyanogen molecule (NCCN) was calculated using the coupled cluster with single and double and perturbative triple excitations (CCSD(T)) with aug-cc-pvdz basis set extended with a set of mid-bond (3s3p2d1f1g) functions. The interaction energies were calculated by the supermolecular approach with the full counterpoise correction for the basis set superposition error. The calculated potential energies were fitted to an analytical expression. The calculated Ar-NCCN potential energy surface shows a global minimum at 3.35 Å, the distance between argon and centre of mass of cyanogen, for the T-shaped geometry and two local minimum at distance of 5.54 Å for the linear geometry on one side of cyanogen. Finally, the interaction second virial coefficients were calculated using the fitted potential energy surface and were compared with those obtained by the parameters of the Beattie-Bridgeman equation of states of pure argon and cyanogens fluids, approximately.

15. Complexity.

PubMed

Gómez-Hernández, J Jaime

2006-01-01

It is difficult to define complexity in modeling. Complexity is often associated with uncertainty since modeling uncertainty is an intrinsically difficult task. However, modeling uncertainty does not require, necessarily, complex models, in the sense of a model requiring an unmanageable number of degrees of freedom to characterize the aquifer. The relationship between complexity, uncertainty, heterogeneity, and stochastic modeling is not simple. Aquifer models should be able to quantify the uncertainty of their predictions, which can be done using stochastic models that produce heterogeneous realizations of aquifer parameters. This is the type of complexity addressed in this article.

16. Kinetic Fractionation Of Heavy Stable Isotopes At Earth Surface Temperatures: Complexity And Systematics

Johnson, T.

2003-04-01

Many applications of heavy stable isotopes are aimed at the oceans, ground water and surface water. In these environments, Cr, Fe, Cu, Zn, Se, and Mo isotope variations have been observed, and in most cases are generated by kinetic isotope effects (KIE's). Whereas equilibrium isotope effects are thermodynamic quantities that are insensitive to reaction mechanisms, KIE's depend strongly on reaction mechanisms and conditions. For example, the rates of reactions, the speciation of dissolved elements, and transient effects can all greatly affect the sizes of KIE's. Accurate interpretations of measured heavy stable isotope variations thus depend on sufficient understanding of variability in KIE's. Complexity in KIE's arises when they are induced by reactions consisting of multiple reaction steps arranged in series and possibly with branches. Paradoxically, a reaction can have a small KIE even though a single step within it has a large KIE. The key to understanding this, as explained in the carbon and sulfur isotope literature, is to consider the sizes and isotopic compositions of the intermediate species between steps. Intermediates consumed by relatively fast steps have low concentrations and short residence times, and tend to become strongly enriched in heavier isotopes. This reduces the size of the overall KIE. However, this situation takes some time to be established, and in the very early stages of reactions, "start-up effects" may be observed, with anomalously large KIE's. In the face of such complexity, laboratory and field experiments are both needed to develop understanding of KIE systematics. Simple laboratory experiments provide insight into the likely dependence of KIE's on reaction mechanisms and conditions. More complex laboratory experiments (e.g., sediment microcosms) can mimic natural conditions somewhat and provide estimates of naturally relevant KIE's. Finally, in-situ measurement of KIE's in natural settings are needed to determine naturally relevant

17. Microbiological and Geochemical Characterization of Fluvially Deposited Sulfidic Mine Tailings

PubMed Central

Wielinga, Bruce; Lucy, Juliette K.; Moore, Johnnie N.; Seastone, October F.; Gannon, James E.

1999-01-01

The fluvial deposition of mine tailings generated from historic mining operations near Butte, Montana, has resulted in substantial surface and shallow groundwater contamination along Silver Bow Creek. Biogeochemical processes in the sediment and underlying hyporheic zone were studied in an attempt to characterize interactions consequential to heavy-metal contamination of shallow groundwater. Sediment cores were extracted and fractionated based on sediment stratification. Subsamples of each fraction were assayed for culturable heterotrophic microbiota, specific microbial guilds involved in metal redox transformations, and both aqueous- and solid-phase geochemistry. Populations of cultivable Fe(III)-reducing bacteria were most prominent in the anoxic, circumneutral pH regions associated with a ferricrete layer or in an oxic zone high in organic carbon and soluble iron. Sulfur- and iron-oxidizing bacteria were distributed in discrete zones throughout the tailings and were often recovered from sections at and below the anoxic groundwater interface. Sulfate-reducing bacteria were also widely distributed in the cores and often occurred in zones overlapping iron and sulfur oxidizers. Sulfate-reducing bacteria were consistently recovered from oxic zones that contained high concentrations of metals in the oxidizable fraction. Altogether, these results suggest a highly varied and complex microbial ecology within a very heterogeneous geochemical environment. Such physical and biological heterogeneity has often been overlooked when remediation strategies for metal contaminated environments are formulated. PMID:10103249

18. Method and apparatus for enhanced sequencing of complex molecules using surface-induced dissociation in conjunction with mass spectrometric analysis

DOEpatents

Laskin, Julia [Richland, WA; Futrell, Jean H [Richland, WA

2008-04-29

The invention relates to a method and apparatus for enhanced sequencing of complex molecules using surface-induced dissociation (SID) in conjunction with mass spectrometric analysis. Results demonstrate formation of a wide distribution of structure-specific fragments having wide sequence coverage useful for sequencing and identifying the complex molecules.

19. Contaminant Organic Complexes: Their Structure and Energetics in Surface Decontamination Processes

SciTech Connect

Satish C. B. Myneni

2005-12-13

Siderophores are biological macromolecules (400-2000 Da) released by bacteria in iron limiting situations to sequester Fe from iron oxyhydroxides and silicates in the natural environment. These molecules contain hydroxamate and phenolate functional groups, and exhibit very high affinity for Fe{sup 3+}. While several studies were conducted to understand the behavior of siderophores and their application to the metal sequestration and mineral dissolution, only a few of them have examined the molecular structure of siderophores and their interactions with metals and mineral surfaces in aqueous solutions. Improved understanding of the chemical state of different functional moieties in siderophores can assist in the application of these biological molecules in actinide separation, sequestration and decontamination processes. The focus of our research group is to evaluate the (a) functional group chemistry of selected siderophores and their metal complexes in aqueous solutions, and (b) the nature of siderophore interactions at the mineral-water interfaces. We selected desferrioxamine B (desB), a hydroxamate siderophore, and its small structural analogue, acetohydroxamic acid (aHa), for this investigation. We examined the functional group chemistry of these molecules as a function of pH, and their complexation with aqueous and solid phase Fe(III). For solid phase Fe, we synthesized all naturally occurring Fe(III)-oxyhydroxides (goethite, lepidocrocite, akaganeite, feroxyhite) and hematite. We also synthesized Fe-oxides (goethite and hematite) of different sizes to evaluate the influence of particle size on mineral dissolution kinetics. We used a series of molecular techniques to explore the functional group chemistry of these molecules and their complexes. Infrared spectroscopy is used to specifically identify the variations in oxime group as a function of pH and Fe(III) complexation. Resonance Raman spectroscopy was used to evaluate the nature of hydroxamate binding in

20. Optimization of complex surface plasmon modulation using bi-material cantilever for the integration of the red, green, and blue complex modulation

Song, Eui-Young; Kim, Hwi; Lee, Byoungho

2015-10-01

A bi-material cantilever based surface plasmon modulation structure is proposed. It is shown that the mechanical actuation of bi-material cantilever by changing temperature can facilitate amplitude modulation. More specific, the issues of scaling-down and integration of the red, green, and blue are discussed. This work can be expanded to the complex modulation structure which is already demonstrated in our previous work. The optimization would be fit for the integration of the red, green, and blue complex modulation structures which can potentially lead to the development of full-color complex spatial light modulator.

1. Approaches to surface complexation modeling of Uranium(VI) adsorption on aquifer sediments

USGS Publications Warehouse

Davis, J.A.; Meece, D.E.; Kohler, M.; Curtis, G.P.

2004-01-01

Uranium(VI) adsorption onto aquifer sediments was studied in batch experiments as a function of pH and U(VI) and dissolved carbonate concentrations in artificial groundwater solutions. The sediments were collected from an alluvial aquifer at a location upgradient of contamination from a former uranium mill operation at Naturita, Colorado (USA). The ranges of aqueous chemical conditions used in the U(VI) adsorption experiments (pH 6.9 to 7.9; U(VI) concentration 2.5 ?? 10-8 to 1 ?? 10-5 M; partial pressure of carbon dioxide gas 0.05 to 6.8%) were based on the spatial variation in chemical conditions observed in 1999-2000 in the Naturita alluvial aquifer. The major minerals in the sediments were quartz, feldspars, and calcite, with minor amounts of magnetite and clay minerals. Quartz grains commonly exhibited coatings that were greater than 10 nm in thickness and composed of an illite-smectite clay with occluded ferrihydrite and goethite nanoparticles. Chemical extractions of quartz grains removed from the sediments were used to estimate the masses of iron and aluminum present in the coatings. Various surface complexation modeling approaches were compared in terms of the ability to describe the U(VI) experimental data and the data requirements for model application to the sediments. Published models for U(VI) adsorption on reference minerals were applied to predict U(VI) adsorption based on assumptions about the sediment surface composition and physical properties (e.g., surface area and electrical double layer). Predictions from these models were highly variable, with results overpredicting or underpredicting the experimental data, depending on the assumptions used to apply the model. Although the models for reference minerals are supported by detailed experimental studies (and in ideal cases, surface spectroscopy), the results suggest that errors are caused in applying the models directly to the sediments by uncertain knowledge of: 1) the proportion and types of

2. Contaminant-Organic Complexes, Their Structure and Energetics in Surface Decontamination Processes

SciTech Connect

Ainsworth, Calvin C.; Friedrich, Donald M.; Hay, Benjamin P.; Myneni, Satish C.B.; Traina, Samuel J.

1999-06-01

There are a wide variety of compounds that are naturally occurring biodegradable organic chelates (siderophores) that appear to be more effective at oxide dissolution and actinide complexation than EDTA or other organic acids now used in decontamination processes. These chelates bind hard acids [Fe(III) and actinides(IV)] with extraordinarily high affinities. For example, the binding constant for the siderophore enterobactin with iron is about 1050, and its binding constant for Pu(IV) is estimated to be as high. Hence, this project is investigating the efficacy of using siderophores (or siderophore-like chelates) as decontamination agents of metal surfaces. The specific goals of this project are as follows: 1. develop an understanding of the surface interaction between siderophores (and their functional moieties), iron, and actinide oxides; their surface chemical properties that foster their dissolution; and the conditions that maximize that dissolution 2. develop the computational tools necessary to predict the reactivity of different siderophore functional groups toward oxide dissolution and actinide(IV) solubilization 3. identify likely candidate chelates for use in decontamination processes. To meet these objectives, the project combines molecular spectroscopy and computational chemistry to provide basic information on the structure and bonding of siderophore functional groups to metal (iron and uranium) oxide specimens common to corrosion products and scales on carbon steel and stainless steel encountered in U.S. Department of Energy (DOE) facilities. The project explores fundamental scientific aspects of oxide mineral surface chemistry and dissolution related to chelate-induced solubilization. The spectroscopic and computational aspects of this project are complemented by macroscopic dissolution and solubilization studies of oxides and associated contaminants. From this combination of molecular, macroscopic, and computational studies, structure-function and

3. Exotic phenomena in 4f systems: From complex magnetism to surface conduction

Thomas, Sean Michael

For materials synthesized with f-electron elements, the interaction between f-electrons and conduction electrons often leads to interesting physics. As the temperature is lowered, the f-electrons can hybridize with the conduction electrons in a process known as the Kondo effect. In a Kondo lattice material, the screening may become coherent at the so-called coherence temperature T*. The resulting material is often metallic, containing heavy bands with effective masses many times larger than the free electron mass. In some cases, the development of coherence leads to a filled heavy-electron band where the chemical potential lies within the hybridization gap, resulting in insulating behavior. CeAgBi2 is an antiferromagnetic compound (TN = 6.4 K) belonging to the former (metallic) case. The close energy scales of the Kondo coherence, antiferromagnetism, and crystal field levels results in complex physical properties. Transport measurements reveal a coupling between the different magnetic phases and Hall resistivity. As the field is increased, the antiferromagnetic transition temperature is suppressed to zero Kelvin. Typically, this is expected to result in a quantum critical point. However, due to strange transport behavior in the paramagnetic regime, the usual signatures of quantum criticality are hidden. SmB6 is a Kondo insulator due to the fact that the hybridization results in the opening of a gap. However, as the temperature is further lowered, the resistance saturates. Originally believed to be due to in-gap conduction states in the bulk, the true reason for the resistance saturation is a robust conducting surface state. Several theories predict that the surface state is a result of SmB6 belonging to a class of materials known as topological insulators. However, direct imaging of the spin-momentum locking of the surface states indicative of a topological insulator has proved elusive. Through transport and magnetic measurements, indirect evidence of the nature of

4. A combined geochemical and hydrological approach for understanding macronutrient sources

Lapworth, Dan J.; Gooddy, Daren C.; Kent, Flo; Heaton, Tim H. E.; Cole, Steven J.; Allen, Debbie

2013-09-01

This study employed complementary geochemical techniques and distributed hydrological modelling to investigate multiple sources of catchment macronutrients and characterise their changes in contrasting storm and baseflow conditions. This approach was demonstrated for the Beult catchment in the county of Kent (England), a designated Site of Special Scientific Interest (SSSI) indentified as failing to meet water quality standards for key nutrients under the Water Framework Directive. Significant changes in nutrient stoichiometry and bioavailability are observed for surface waters under contrasting flow regimes. Soluble reactive phosphorus (SRP) concentrations are approximately twice as high during baseflow compared to high flow, while the inverse is true for particulate, colloidal and dissolved hydrolysable phosphorus, dissolved organic carbon and nitrate. Nitrogen (N):phosphorus (P) ratios are lower during baseflow for most surface waters impacted by diffuse sources of pollution. Fluorescence indices of dissolved organic matter (DOM) show that waste water inputs may be locally important sources of more complex low molecular weight DOM, particularly during baseflow. Nitrate N and O isotope signatures, combined with other dissolved chemical tracers, confirm the dominance of wastewater N inputs at sites downsteam of sewerage treatment works during baseflow, with a shift towards the soil N pool in surface waters across the catchment during high flow. Distributed hydrological modelling using the Grid-to-Grid model reveal areas with the greatest runoff also export higher N and P concentrations, and hence deliver a greater flux of macronutrients, while forested areas with low nutrient concentrations reduce runoff and nutrient fluxes. During periods of high runoff, nested sampling indicates that nutrient fluxes scale with catchment area. This combined approach enables a more thorough assessment of the macronutrient sources and dynamics, better informing management options

5. Geochemical cycles of atmospheric gases

NASA Technical Reports Server (NTRS)

Walker, J. C. G.; Drever, J. I.

1988-01-01

The processes that control the atmosphere and atmospheric changes are reviewed. The geochemical cycles of water vapor, nitrogen, carbon dioxide, oxygen, and minor atmospheric constituents are examined. Changes in atmospheric chemistry with time are discussed using evidence from the rock record and analysis of the present atmosphere. The role of biological evolution in the history of the atmosphere and projected changes in the future atmosphere are considered.

6. The geochemical record in rock glaciers

USGS Publications Warehouse

Steig, E.J.; Fitzpatrick, J.J.; Potter, N.; Clark, D.H.

1998-01-01

A 9.5 m ice core was extracted from beneath the surficial debris cover of a rock glacier at Galena Creek, northwestern Wyoming. The core contains clean, bubble-rich ice with silty debris layers spaced at roughly 20 cm intervals. The debris layers are similar in appearance to those in typical alpine glaciers, reflecting concentration of debris by melting at the surface during the summer ablation season. Profiles of stable isotope concentrations and electrical conductivity measurements provide independent evidence for melting in association with debris layers. These observations are consistent with a glacial origin for the ice, substantiating the glacigenic model for rock glacier formation. The deuterium excess profile in the ice indicates that the total depth of meltwater infiltration is less than the thickness of one annual layer, suggesting that isotope values and other geochemical signatures are preserved at annual resolution. This finding demonstrates the potential for obtaining useful paleoclimate information from rock glacier ice.

7. Sanitary study of surface water and of the beach of a water sports and leisure complex.

PubMed Central

Chabasse, D.; Laine, P.; Simitzis-Le-Flohic, A. M.; Martineau, B.; el Hourch, M.; Becaud, J. P.

1986-01-01

This report presents the parasitological, bacteriological, mycological and physicochemical data obtained from both surface water and beach sand of a lake used for water sports. These show that the lake is contaminated in both winter and spring by water which overflows from the River Maine, and is self-purified by a mechanism of 'lagunage'. In summer signs of pollution are at their lowest level although use of the complex is at its peak. Conversely, the amoebic flora, which is independent of the usual criteria of pollution, predominates in summer, and serves as a marker for the need for increased surveillance. The sand of the beaches does not appear to show any infectious hazard. Environmental pressure will doubtless change these data over a period of time, and it is planned to monitor this. PMID:3734425

8. To address surface reaction network complexity using scaling relations machine learning and DFT calculations.

PubMed

Ulissi, Zachary W; Medford, Andrew J; Bligaard, Thomas; Nørskov, Jens K

2017-03-06

Surface reaction networks involving hydrocarbons exhibit enormous complexity with thousands of species and reactions for all but the very simplest of chemistries. We present a framework for optimization under uncertainty for heterogeneous catalysis reaction networks using surrogate models that are trained on the fly. The surrogate model is constructed by teaching a Gaussian process adsorption energies based on group additivity fingerprints, combined with transition-state scaling relations and a simple classifier for determining the rate-limiting step. The surrogate model is iteratively used to predict the most important reaction step to be calculated explicitly with computationally demanding electronic structure theory. Applying these methods to the reaction of syngas on rhodium(111), we identify the most likely reaction mechanism. Propagating uncertainty throughout this process yields the likelihood that the final mechanism is complete given measurements on only a subset of the entire network and uncertainty in the underlying density functional theory calculations.

9. To address surface reaction network complexity using scaling relations machine learning and DFT calculations

PubMed Central

Ulissi, Zachary W.; Medford, Andrew J.; Bligaard, Thomas; Nørskov, Jens K.

2017-01-01

Surface reaction networks involving hydrocarbons exhibit enormous complexity with thousands of species and reactions for all but the very simplest of chemistries. We present a framework for optimization under uncertainty for heterogeneous catalysis reaction networks using surrogate models that are trained on the fly. The surrogate model is constructed by teaching a Gaussian process adsorption energies based on group additivity fingerprints, combined with transition-state scaling relations and a simple classifier for determining the rate-limiting step. The surrogate model is iteratively used to predict the most important reaction step to be calculated explicitly with computationally demanding electronic structure theory. Applying these methods to the reaction of syngas on rhodium(111), we identify the most likely reaction mechanism. Propagating uncertainty throughout this process yields the likelihood that the final mechanism is complete given measurements on only a subset of the entire network and uncertainty in the underlying density functional theory calculations. PMID:28262694

10. To address surface reaction network complexity using scaling relations machine learning and DFT calculations

Ulissi, Zachary W.; Medford, Andrew J.; Bligaard, Thomas; Nørskov, Jens K.

2017-03-01

Surface reaction networks involving hydrocarbons exhibit enormous complexity with thousands of species and reactions for all but the very simplest of chemistries. We present a framework for optimization under uncertainty for heterogeneous catalysis reaction networks using surrogate models that are trained on the fly. The surrogate model is constructed by teaching a Gaussian process adsorption energies based on group additivity fingerprints, combined with transition-state scaling relations and a simple classifier for determining the rate-limiting step. The surrogate model is iteratively used to predict the most important reaction step to be calculated explicitly with computationally demanding electronic structure theory. Applying these methods to the reaction of syngas on rhodium(111), we identify the most likely reaction mechanism. Propagating uncertainty throughout this process yields the likelihood that the final mechanism is complete given measurements on only a subset of the entire network and uncertainty in the underlying density functional theory calculations.

11. Using advanced surface complexation models for modelling soil chemistry under forests: Solling forest, Germany.

PubMed

Bonten, Luc T C; Groenenberg, Jan E; Meesenburg, Henning; de Vries, Wim

2011-10-01

Various dynamic soil chemistry models have been developed to gain insight into impacts of atmospheric deposition of sulphur, nitrogen and other elements on soil and soil solution chemistry. Sorption parameters for anions and cations are generally calibrated for each site, which hampers extrapolation in space and time. On the other hand, recently developed surface complexation models (SCMs) have been successful in predicting ion sorption for static systems using generic parameter sets. This study reports the inclusion of an assemblage of these SCMs in the dynamic soil chemistry model SMARTml and applies this model to a spruce forest site in Solling Germany. Parameters for SCMs were taken from generic datasets and not calibrated. Nevertheless, modelling results for major elements matched observations well. Further, trace metals were included in the model, also using the existing framework of SCMs. The model predicted sorption for most trace elements well.

12. 3D surface measurements with isogeometric stereocorrelation-Application to complex shapes

Dufour, John-Eric; Leclercq, Sylvain; Schneider, Julien; Roux, Stéphane; Hild, François

2016-12-01

The aim of the present study is to measure complex shapes of tested objects by using a priori information given by their CAD model via stereocorrelation. To follow a 3D object during its deformation and to determine 3D surface displacement fields, a first measurement of the object shape is necessary. It is achieved by updating the CAD reference via a global approach to stereocorrelation. Once the 3D shape has been determined, the next step is to measure 3D displacement fields during loading. The kinematics of the deformed shape is assumed to be written within the same isogeometric framework. Isogeometric stereocorrelation is applied to analyze a compression test on a ribbed cylinder in two different configurations of the stereo rig.

13. Validation of the WATEQ4 geochemical model for uranium

SciTech Connect

Krupka, K.M.; Jenne, E.A.; Deutsch, W.J.

1983-09-01

As part of the Geochemical Modeling and Nuclide/Rock/Groundwater Interactions Studies Program, a study was conducted to partially validate the WATEQ4 aqueous speciation-solubility geochemical model for uranium. The solubility controls determined with the WATEQ4 geochemical model were in excellent agreement with those laboratory studies in which the solids schoepite (UO/sub 2/(OH)/sub 2/ . H/sub 2/O), UO/sub 2/(OH)/sub 2/, and rutherfordine ((UO/sub 2/CO/sub 3/) were identified as actual solubility controls for uranium. The results of modeling solution analyses from laboratory studies of uranyl phosphate solids, however, identified possible errors in the characterization of solids in the original solubility experiments. As part of this study, significant deficiencies in the WATEQ4 thermodynamic data base for uranium solutes and solids were corrected. Revisions included recalculation of selected uranium reactions. Additionally, thermodynamic data for the hydroxyl complexes of U(VI), including anionic (VI) species, were evaluated (to the extent permitted by the available data). Vanadium reactions were also added to the thermodynamic data base because uranium-vanadium solids can exist in natural ground-water systems. This study is only a partial validation of the WATEQ4 geochemical model because the available laboratory solubility studies do not cover the range of solid phases, alkaline pH values, and concentrations of inorganic complexing ligands needed to evaluate the potential solubility of uranium in ground waters associated with various proposed nuclear waste repositories. Further validation of this or other geochemical models for uranium will require careful determinations of uraninite solubility over the pH range of 7 to 10 under highly reducing conditions and of uranyl hydroxide and phosphate solubilities over the pH range of 7 to 10 under oxygenated conditions.

14. Parameter sensitivity analysis for different complexity land surface models using multicriteria methods

Bastidas, L. A.; Hogue, T. S.; Sorooshian, S.; Gupta, H. V.; Shuttleworth, W. J.

2006-10-01

A multicriteria algorithm, the MultiObjective Generalized Sensitivity Analysis (MOGSA), was used to investigate the parameter sensitivity of five different land surface models with increasing levels of complexity in the physical representation of the vegetation (BUCKET, CHASM, BATS 1, Noah, and BATS 2) at five different sites representing crop land/pasture, grassland, rain forest, cropland, and semidesert areas. The methodology allows for the inclusion of parameter interaction and does not require assumptions of independence between parameters, while at the same time allowing for the ranking of several single-criterion and a global multicriteria sensitivity indices. The analysis required on the order of 50 thousand model runs. The results confirm that parameters with similar "physical meaning" across different model structures behave in different ways depending on the model and the locations. It is also shown that after a certain level an increase in model structure complexity does not necessarily lead to better parameter identifiability, i.e., higher sensitivity, and that a certain level of overparameterization is observed. For the case of the BATS 1 and BATS 2 models, with essentially the same model structure but a more sophisticated vegetation model, paradoxically, the effect on parameter sensitivity is mainly reflected in the sensitivity of the soil-related parameters.

15. Interfacial phenomena at a surface of individual and complex fumed nanooxides.

PubMed

Gun'ko, V M; Turov, V V; Zarko, V I; Goncharuk, O V; Pakhlov, E M; Skubiszewska-Zięba, J; Blitz, J P

2016-09-01

16. Petroleum-collecting and dispersing complexes based on oleic acid and nitrogenous compounds as surface-active agents for removing thin petroleum films from water surface.

PubMed

Asadov, Ziyafaddin H; Tantawy, Ahmed H; Zarbaliyeva, Ilhama A; Rahimov, Ravan A

2012-01-01

Petroleum-collecting and dispersing complexes were synthesized on the basis of oleic acid and nitrogen-containing compounds. Surface-active properties (interfacial tension) of the obtained complexes were investigated by stalagmometric method. Petroleum-collecting and dispersing properties of the oleic acid complexes in diluted (5% wt. water or alcoholic solution) and undiluted form have been studied in waters of varying salinity (distilled, fresh and sea waters). Some of physico-chemical indices of the prepared compounds such as solubility, acid and amine numbers as well as electrical conductivity have been determined. The ability of oleic acid complex with ethylenediamine as petro-collecting and dispersing agent towards different types of petroleum has been studied. The influence of thickness and "age" of the petroleum slick on collecting and dispersing capacity of this complex has been clarified. Surface properties studied included critical micelle concentration (CMC), maximum surface excess (Γ(max)), and minimum surface area (A(min)). Free energies of micellization (ΔG°(mic)) and adsorption (ΔG°(ads)) were calculated.

17. Geochemical modeling of cyanide in tailing dam gold processing plant

2009-09-01

This research is aimed at investigating possible neutralization of cyanide in tailing dam of Muteh gold processing plant in Isfahan, Iran at various conditions such as pH and temperature using USEPA Visual MINTEQ geochemical model simulation. The model is based on geochemical equilibrium which uses the simultaneous solution of the non-linear mass action expressions and linear mass balance relationships to formulate and solve the multiple-component chemical equilibrium problems. In this study the concentration of aqueous species in tailing dam as an aqueous, solid and gaseous were used as input in the model. Temperature and pH variation were simulated. The results of the model indicated that cyanide may be complexes in 10 < pH < 5. In other pH values complexation is not important. The results also indicated that cyanide reduction mechanism in acidic pH and temperature above 30°C is due to cyanide acid formation which is vaporized.

18. Predicting the infrared transition intensities in the Ar-HF complex: the key role of the dipole moment surface accuracy.

PubMed

Jankowski, Piotr; Ziółkowski, Marcin

2008-01-21

The method proposed earlier for the generation of the full-dimensional energy surface for van der Waals complexes [P. Jankowski, J. Chem. Phys. 121, 1655 (2004)] is used to obtain a fulldimensional dipole moment surface for the atom-diatom complex in calculations based on the coupled-cluster with single, double, and noniterative triple excitation approach and the aug-cc-pVQZ basis sets. This surface has been employed to calculate transition intensities of the infrared spectra of Ar-HF. Special attention has been paid to study the problem of relative intensities of the different bands which have not been properly predicted within the long-range models of the dipole moment [A. E. Thornley and J. M. Hutson, J. Chem. Phys. 101, 5578 (1994)]. The intensities calculated with the present dipole moment surface agree very well with the experimental data, which indicate that the short-range interactions significantly affect the dipole moment surface and the calculated intensities. To investigate the role of the accuracy of the dipole moment surface on infrared transition intensities in atom-diatom complexes, four models of increasing complexity are studied. Their performance is shown to strongly depend on the region of the interaction energy surface probed by the initial and final states of the individual transitions.

19. Contaminant-Organic Complexes, Their Structure and Energetics in Surface Decontamination Processes

SciTech Connect

Ainsworth, Calvin C.; Hay, Benjamin P.; Traina, Samuel J.; Myneni, Satish C. B.

2000-06-01

There are many compounds that are naturally occurring biodegradable organic chelates (siderophores) and appear to be more effective at oxide dissolution and actinide complexation than ethylenediaminetetraacetic acid (EDTA) or other organic acids currently used in decontamination processes. These chelates bind hard acids [Fe(III) and actinides(IV)] with extraordinarily high affinities. For example, the binding constant for the siderophore enterobactin with iron is about 1050, and its binding constant for Pu(IV) is estimated to be as high. Hence, this project is investigating the efficacy of using siderophores (or siderophore-like chelates) as decontamination agents of metal surfaces. The specific goals of this project are as follows: (1) To develop an understanding of the interactions between siderophores (and their functional moieties), Fe and actinide oxides, their surface chemical properties that foster their dissolution and the conditions that maximize that dissolution. (2) To develop the computational tools necessary to predict the reactivity of different siderophore functional groups toward oxide dissolution and actinide (IV) solubilization. (3) To identify likely candidate chelates for use in decontamination processes. To meet these objectives, the project combines x-ray absorption spectroscopy (XAS) and computational chemistry to provide basic information on the structure and bonding of siderophore functional groups to metal (Fe and U) oxide specimens common to corrosion products and scales on carbon steel and stainless steel encountered in DOE facilities. The project explores fundamental scientific aspects of oxide mineral surface chemistry and dissolution related to chelate-induced solubilization. The spectroscopic and computational aspects of this project are complemented by macroscopic dissolution and solubilization studies of oxides and associated contaminants. From this combination of molecular, macroscopic, and computational studies, structure

20. Recognition of geochemical anomalies using a deep autoencoder network

Xiong, Yihui; Zuo, Renguang

2016-01-01

In this paper, we train an autoencoder network to encode and reconstruct a geochemical sample population with unknown complex multivariate probability distributions. During the training, small probability samples contribute little to the autoencoder network. These samples can be recognized by the trained model as anomalous samples due to their comparatively higher reconstructed errors. The southwestern Fujian district (China) is chosen as a case study area. A variety of learning rates, iterations, and the size of each hidden layer are constructing and training the deep autoencoder networks on all the geochemical samples. The reconstruction error (or, anomaly score) of each training sample is used to recognize multivariate geochemical anomalies associated with Fe polymetallic mineralization. By comparing the results obtained with a continuous restricted Boltzmann machine, we conclude that the autoencoder network can be trained to recognize multivariate geochemical anomalies. Most of the known skarn-type Fe deposits are located in areas with high reconstruction errors or anomaly scores in the anomaly map, indicating that these anomalies may be related to Fe mineralization.

1. Geochemical Responses to Anthropogenic and Natural Influences in Ebinur Lake Sediments of Arid Northwest China

PubMed Central

Wu, Jinglu; Abuduwaili, Jilili; Liu, Wen

2016-01-01

Geochemical concentrations were extracted for a short sediment core from Ebinur Lake, located in arid northwest China, and mathematical methods were used to demonstrate the complex pattern of the geochemical anomalies resulting from the temporal changes in natural and anthropogenic forces on the lake sediments. The first element assemblage (C1) (aluminum, potassium, iron, magnesium, beryllium, etc.) was predominantly terrigenous; among the assemblage, total phosphorus and titanium were generally consistent with aluminum except with regards to their surface sequences, which inferred the differences of source regions for terrigenous detrital material led to this change around ca. 2000AD. The second assemblage (C2) (calcium and strontium) was found to have a negative relationship with aluminum through a cluster analysis. The third assemblage (C3) included sodium and magnesium, which were influenced by the underwater lake environment and deposited in the Ebinur depression. The concentration ratio of C1/(C1+C2) was used as an indicator for denudation amount of detrital materials, which was supported by the values of magnetic susceptibility. The enrichment factors for heavy metals suggested that the influence of human activities on heavy-metal enrichment in Ebinur Lake region was not severe over the past century. Prior to the 1960s, geochemical indicators suggested a stable lacustrine environment with higher water levels. Beginning in the 1960s, high agricultural water demand resulted in rapid declines in lake water level, with subsequent increases of lake water salinity, as evidenced by enhanced sodium concentration in lake core sediments. During this period, anthropogenic activity also enhanced the intensity of weathering and the denudation of the Ebinur watershed. PMID:27176765

2. PhreeqcRM: A reaction module for transport simulators based on the geochemical model PHREEQC

Parkhurst, David L.; Wissmeier, Laurin

2015-09-01

PhreeqcRM is a geochemical reaction module designed specifically to perform equilibrium and kinetic reaction calculations for reactive transport simulators that use an operator-splitting approach. The basic function of the reaction module is to take component concentrations from the model cells of the transport simulator, run geochemical reactions, and return updated component concentrations to the transport simulator. If multicomponent diffusion is modeled (e.g., Nernst-Planck equation), then aqueous species concentrations can be used instead of component concentrations. The reaction capabilities are a complete implementation of the reaction capabilities of PHREEQC. In each cell, the reaction module maintains the composition of all of the reactants, which may include minerals, exchangers, surface complexers, gas phases, solid solutions, and user-defined kinetic reactants. PhreeqcRM assigns initial and boundary conditions for model cells based on standard PHREEQC input definitions (files or strings) of chemical compositions of solutions and reactants. Additional PhreeqcRM capabilities include methods to eliminate reaction calculations for inactive parts of a model domain, transfer concentrations and other model properties, and retrieve selected results. The module demonstrates good scalability for parallel processing by using multiprocessing with MPI (message passing interface) on distributed memory systems, and limited scalability using multithreading with OpenMP on shared memory systems. PhreeqcRM is written in C++, but interfaces allow methods to be called from C or Fortran. By using the PhreeqcRM reaction module, an existing multicomponent transport simulator can be extended to simulate a wide range of geochemical reactions. Results of the implementation of PhreeqcRM as the reaction engine for transport simulators PHAST and FEFLOW are shown by using an analytical solution and the reactive transport benchmark of MoMaS.

3. Engineering yeast consortia for surface-display of complex cellulosome structures

SciTech Connect

Chen, Wilfred

2014-03-31

As our society marches toward a more technologically advanced future, energy and environmental sustainability are some of the most challenging problems we face today. Biomass is one of the most abundant renewable-feedstock for sustainable production of biofuels. However, the main technological obstacle to more widespread uses of this resource is the lack of low-cost technologies to overcome the recalcitrant nature of the cellulosic structure, especially the hydrolysis step on highly ordered celluloses. In this proposal, we successfully engineered several efficient and inexpensive whole-cell biocatalysts in an effort to produce economically compatible and sustainable biofuels, namely cellulosic ethanol. Our approach was to display of a highly efficient cellulolytic enzyme complex, named cellulosome, on the surface of a historical ethanol producer Saccharomyces cerevisiae for the simultaneous and synergistic saccharification and fermentation of cellulose to ethanol. We first demonstrated the feasibility of assembling a mini-cellulosome by incubating E. coli lysates expressing three different cellulases. Resting cells displaying mini-cellulosomes produced 4-fold more ethanol from phosphoric acid-swollen cellulose (PASC) than cultures with only added enzymes. The flexibility to assemble the mini-cellulosome structure was further demonstrated using a synthetic yeast consortium through intracellular complementation. Direct ethanol production from PASC was demonstrated with resting cell cultures. To create a microorganism suitable for a more cost-effective process, called consolidated bioprocessing (CBP), a synthetic consortium capable of displaying mini-cellulosomes on the cell surface via intercellular complementation was created. To further improve the efficiency, a new adaptive strategy of employing anchoring and adaptor scaffoldins to amplify the number of enzymatic subunits was developed, resulting in the creation of an artificial tetravalent cellulosome on the

4. An AP Endonuclease 1–DNA Polymerase β Complex: Theoretical Prediction of Interacting Surfaces

PubMed Central

Abyzov, Alexej; Uzun, Alper; Strauss, Phyllis R.; Ilyin, Valentin A.

2008-01-01

Abasic (AP) sites in DNA arise through both endogenous and exogenous mechanisms. Since AP sites can prevent replication and transcription, the cell contains systems for their identification and repair. AP endonuclease (APEX1) cleaves the phosphodiester backbone 5′ to the AP site. The cleavage, a key step in the base excision repair pathway, is followed by nucleotide insertion and removal of the downstream deoxyribose moiety, performed most often by DNA polymerase beta (pol-β). While yeast two-hybrid studies and electrophoretic mobility shift assays provide evidence for interaction of APEX1 and pol-β, the specifics remain obscure. We describe a theoretical study designed to predict detailed interacting surfaces between APEX1 and pol-β based on published co-crystal structures of each enzyme bound to DNA. Several potentially interacting complexes were identified by sliding the protein molecules along DNA: two with pol-β located downstream of APEX1 (3′ to the damaged site) and three with pol-β located upstream of APEX1 (5′ to the damaged site). Molecular dynamics (MD) simulations, ensuring geometrical complementarity of interfaces, enabled us to predict interacting residues and calculate binding energies, which in two cases were sufficient (∼−10.0 kcal/mol) to form a stable complex and in one case a weakly interacting complex. Analysis of interface behavior during MD simulation and visual inspection of interfaces allowed us to conclude that complexes with pol-β at the 3′-side of APEX1 are those most likely to occur in vivo. Additional multiple sequence analyses of APEX1 and pol-β in related organisms identified a set of correlated mutations of specific residues at the predicted interfaces. Based on these results, we propose that pol-β in the open or closed conformation interacts and makes a stable interface with APEX1 bound to a cleaved abasic site on the 3′ side. The method described here can be used for analysis in any DNA-metabolizing pathway

5. Precipitation of heavy metals from acid mine drainage and their geochemical modeling

Petrilakova, Aneta; Balintova, Magdalena; Holub, Marian

2014-06-01

Geochemical modeling plays an increasingly vital role in a number of areas of geoscience, ranging from groundwater and surface water hydrology to environmental preservation and remediation. Geochemical modeling is also used to model the interaction processes at the water - sediment interface in acid mine drainage (AMD). AMD contains high concentrations of sulfate and dissolved metals and it is a serious environmental problem in eastern Slovakia. The paper is focused on comparing the results of laboratory precipitation of metal ions from AMD (the Smolnik creek, Slovakia) with the results obtained by geochemical modeling software Visual Minteq 3.0.

6. Geochemical modelling of bentonite porewater in high-level waste repositories

Wersin, Paul

2003-03-01

The description of the geochemical properties of the bentonite backfill that serves as engineered barrier for nuclear repositories is a central issue for perfomance assessment since these play a large role in determining the fate of contaminants released from the waste. In this study the porewater chemistry of bentonite was assessed with a thermodynamic modelling approach that includes ion exchange, surface complexation and mineral equilibrium reactions. The focus was to identify the geochemical reactions controlling the major ion chemistry and acid-base properties and to explore parameter uncertainties specifically at high compaction degrees. First, the adequacy of the approach was tested with two distinct surface complexation models by describing recent experimental data performed at highly varying solid/liquid ratios and ionic strengths. The results indicate adequate prediction of the entire experimental data set. Second, the modelling was extended to repository conditions, taking as an example the current Swiss concept for high-level waste where the compacted bentonite backfill is surrounded by argillaceous rock. The main reactions controlling major ion chemistry were found to be calcite equilibrium and concurrent Na-Ca exchange reactions and de-protonation of functional surface groups. Third, a sensitivity analysis of the main model parameters was performed. The results thereof indicate a remarkable robustness of the model with regard to parameter uncertainties. The bentonite system is characterised by a large acid-base buffering capacity which leads to stable pH-conditions. The uncertainty in pH was found to be mainly induced by the pCO 2 of the surrounding host rock. The results of a simple diffusion-reaction model indicate only minor changes of porewater composition with time, which is primarily due to the geochemical similarities of the bentonite and the argillaceous host rock. Overall, the results show the usefulness of simple thermodynamic models to

7. Venus: Geochemical conclusions from the Magellan data

NASA Technical Reports Server (NTRS)

Wood, J. A.

1992-01-01

Though the Magellan mission was not designed to collect geochemical or petrological information, it has done so nonetheless. Since the time of the Pioneer Venus mission it has been known that high-altitude (greater than 2.5-5 km) mountainous areas on Venus exhibit anomalously low radiothermal emissivity (e less than 0.6). Magellan has greatly refined and extended these observations. The low emissivity requires surface material in the uplands to have a mineralogical composition that gives it a high bulk dielectric constant, greater than 20. The dielectric constant of dry terrestrial volcanic rocks seldom exceeds 7. The high-dielectric character of high-altitude surface material cannot be a primary property of the local volcanic rock, because there is no reason why rock having the required special mineralogy would erupt only at high altitudes. Therefore it is a secondary property; the primary Venus rock has reacted with the atmosphere to form a mineralogically different surface layer, and the secondary minerals formed are controlled by the ambient temperature, which decreases with altitude on Venus. A further investigation of venusian mineralogy is presented.

8. Antibody responses to the merozoite surface protein-1 complex in cerebral malaria patients in India

PubMed Central

Lucchi, Naomi W; Tongren, Jon Eric; Jain, Vidhan; Nagpal, Avinash C; Kauth, Christian W; Woehlbier, Ute; Bujard, Hermann; Dash, Aditya P; Singh, Neeru; Stiles, Jonathan K; Udhayakumar, Venkatachalam

2008-01-01

Background Plasmodium falciparum infection causes cerebral malaria (CM) in a subset of patients with anti-malarial treatment protecting only about 70% to 80% of patients. Why a subset of malaria patients develops CM complications, including neurological sequelae or death, is still not well understood. It is believed that host immune factors may modulate CM outcomes and there is substantial evidence that cellular immune factors, such as cytokines, play an important role in this process. In this study, the potential relationship between the antibody responses to the merozoite surface protein (MSP)-1 complex (which consists of four fragments namely: MSP-183, MSP-130, MSP-138 and MSP-142), MSP-636 and MSP-722 and CM was investigated. Methods Peripheral blood antibody responses to recombinant antigens of the two major allelic forms of MSP-1 complex, MSP-636 and MSP-722 were compared between healthy subjects, mild malaria patients (MM) and CM patients residing in a malaria endemic region of central India. Total IgG and IgG subclass antibody responses were determined using ELISA method. Results The prevalence and levels of IgG and its subclasses in the plasma varied for each antigen. In general, the prevalence of total IgG, IgG1 and IgG3 was higher in the MM patients and lower in CM patients compared to healthy controls. Significantly lower levels of total IgG antibodies to the MSP-1f38, IgG1 levels to MSP-1d83, MSP-119 and MSP-636 and IgG3 levels to MSP-1f42 and MSP-722 were observed in CM patients as compared to MM patients. Conclusion These results suggest that there may be some dysregulation in the generation of antibody responses to some MSP antigens in CM patients and it is worth investigating further whether perturbations of antibody responses in CM patients contribute to pathogenesis. PMID:18601721

9. Evaluation of one-dimensional potential energy surfaces for prediction of spectroscopic properties of hydrogen bonds in linear bonded complexes.

PubMed

2017-05-01

This work evaluated the reliability of the one-dimensional potential energy surface for calculating the spectroscopic properties (rovibrational constants and rotational line energies) of hydrogen bonds in linear bonded complexes by comparing theoretical results with the corresponding experimental results. For this purpose, two hydrogen bonded complexes were selected: the HCN···HCN homodimer and the HCN···HF heterodimer. The one-dimensional potential energy surfaces related to the hydrogen bonds in these complexes were calculated using different computational methods and basis sets. The calculated potential curve of each complex was fitted to an analytical one-dimensional potential function to obtain the potential parameters. The obtained analytical potential function of each complex was used in a two-particle Schrödinger equation to obtain the rovibrational energy levels of the hydrogen bond. Using the calculated rovibrational levels, the rovibrational spectra and constants of each complex were calculated and compared with experimental data available from the literature. Compared with experimental data, the calculated one-dimensional potential energy surface at the QCISD/aug-cc-pVDZ level of theory was found to predict the spectroscopic properties of hydrogen bonds better than the potential curves obtained using other computational methods, especially for the HCN···HCN homodimer complex. Generally, the results obtained for the HCN···HCN homodimer complex were closer to experimental data than those obtained for the HCN···HF heterodimer complex. The investigation performed in this work showed that the one-dimensional potential curve related to the hydrogen bond between two linear molecules can be used to predict the spectroscopic constants of hydrogen bonds. Graphical abstract Potential energy curves of HCN···HCN and HCN···HF complexes calculated at the different computational levels.

10. Interfacial electron transfer in TiO(2) surfaces sensitized with Ru(II)-polypyridine complexes.

PubMed

Jakubikova, Elena; Snoeberger, Robert C; Batista, Victor S; Martin, Richard L; Batista, Enrique R

2009-11-12

Studies of interfacial electron transfer (IET) in TiO(2) surfaces functionalized with (1) pyridine-4-phosphonic acid, (2) [Ru(tpy)(tpy(PO(3)H(2)))](2+), and (3) [Ru(tpy)(bpy)(H(2)O)-Ru(tpy)(tpy(PO(3)H(2)))](4+) (tpy = 2,2':6,2''-terpyridine; bpy = 2,2'-bipyridine) are reported. We characterize the electronic excitations, electron injection time scales, and interfacial electron transfer (IET) mechanisms through phosphonate anchoring groups. These are promising alternatives to the classic carboxylates of conventional dye-sensitized solar cells since they bind more strongly to TiO(2) surfaces and form stable covalent bonds that are unaffected by humidity. Density functional theory calculations and quantum dynamics simulations of IET indicate that electron injection in 1-TiO(2) can be up to 1 order of magnitude faster when 1 is attached to TiO(2) in a bidentate mode (tau approximately 60 fs) than when attached in a monodentate motif (tau approximately 460 fs). The IET time scale also depends strongly on the properties of the sensitizer as well as on the nature of the electronic excitation initially localized in the adsorbate molecule. We show that IET triggered by the visible light excitation of 2-TiO(2) takes 1-10 ps when 2 is attached in a bidentate mode, a time comparable to the lifetime of the excited electronic state. IET due to visible-light photoexcitation of 3-TiO(2) is slower, since the resulting electronic excitation remains localized in the tpy-tpy bridge that is weakly coupled to the electronic states of the conduction band of TiO(2). These results are particularly valuable to elucidate the possible origin of IET efficiency drops during photoconversion in solar cells based on Ru(II)-polypyridine complexes covalently attached to TiO(2) thin films with phosphonate linkers.

11. Effect of Grain Size on Uranium(VI) Surface Complexation Kinetics and Adsorption Additivity

SciTech Connect

Shang, Jianying; Liu, Chongxuan; Wang, Zheming; Zachara, John M.

2011-07-27

12. Interfacial Electron Transfer in TiO2 Surfaces Sensitized with Ru(II)-Polypyridine Complexes

Jakubikova, Elena; Snoeberger, Robert C., III; Batista, Victor S.; Martin, Richard L.; Batista, Enrique R.

2009-07-01

Studies of interfacial electron transfer (IET) in TiO2 surfaces functionalized with (1) pyridine-4-phosphonic acid, (2) [Ru(tpy)(tpy(PO3H2))]2+, and (3) [Ru(tpy)(bpy)(H2O)-Ru(tpy)(tpy(PO3H2))]4+ (tpy = 2,2':6,2''-terpyridine; bpy = 2,2'-bipyridine) are reported. We characterize the electronic excitations, electron injection time scales, and interfacial electron transfer (IET) mechanisms through phosphonate anchoring groups. These are promising alternatives to the classic carboxylates of conventional dye-sensitized solar cells since they bind more strongly to TiO2 surfaces and form stable covalent bonds that are unaffected by humidity. Density functional theory calculations and quantum dynamics simulations of IET indicate that electron injection in 1-TiO2 can be up to 1 order of magnitude faster when 1 is attached to TiO2 in a bidentate mode (τ ˜ 60 fs) than when attached in a monodentate motif (τ ˜ 460 fs). The IET time scale also depends strongly on the properties of the sensitizer as well as on the nature of the electronic excitation initially localized in the adsorbate molecule. We show that IET triggered by the visible light excitation of 2-TiO2 takes 1-10 ps when 2 is attached in a bidentate mode, a time comparable to the lifetime of the excited electronic state. IET due to visible-light photoexcitation of 3-TiO2 is slower, since the resulting electronic excitation remains localized in the tpy-tpy bridge that is weakly coupled to the electronic states of the conduction band of TiO2. These results are particularly valuable to elucidate the possible origin of IET efficiency drops during photoconversion in solar cells based on Ru(II)-polypyridine complexes covalently attached to TiO2 thin films with phosphonate linkers.

13. Robust affine-invariant feature points matching for 3D surface reconstruction of complex landslide scenes

Stumpf, André; Malet, Jean-Philippe; Allemand, Pascal; Skupinski, Grzegorz; Deseilligny, Marc-Pierrot

2013-04-01

Multi-view stereo surface reconstruction from dense terrestrial photographs is being increasingly applied for geoscience applications such as quantitative geomorphology, and a number of different software solution and processing streamlines have been suggested. For image matching, camera self-calibration and bundle block adjustment, most approaches make use of scale-invariant feature transform (SIFT) to identify homologous points in multiple images. SIFT-like point matching is robust to apparent translation, rotation, and scaling of objects in multiple viewing geometries but the number of correctly identified matching points typically declines drastically with increasing angles between the viewpoints. For the application of multi-view stereo of complex landslide scenes, the viewing geometry is often constrained by the local topography and barriers such as rocks and vegetation occluding the target. Under such conditions it is not uncommon to encounter view angle differences of > 30% that hinder the image matching and eventually prohibit the joint estimation of the camera parameters from all views. Recently an affine invariant extension of the SIFT detector (ASIFT) has been demonstrated to provide more robust matches when large view-angle differences become an issue. In this study the ASIFT detector was adopted to detect homologous points in terrestrial photographs preceding 3D reconstruction of different parts (main scarp, toe) of the Super-Sauze landslide (Southern French Alps). 3D surface models for different time periods and different parts of the landslide were derived using the multi-view stereo framework implemented in MicMac (©IGN). The obtained 3D models were compared with reconstructions using the traditional SIFT detectors as well as alternative structure-from-motion implementations. An estimate of the absolute accuracy of the photogrammetric models was obtained through co-registration and comparison with high-resolution terrestrial LiDAR scans.

14. Ligand effects on nitrate reduction by zero-valent iron: Role of surface complexation.

PubMed

Song, Xiaojie; Chen, Zhihao; Wang, Xiaomeng; Zhang, Shujuan

2017-05-01

Surface passivation is a key limiting factor in the application of zero-valent iron (ZVI) for water remediation. Addition of ligands is a useful approach to overcome this issue. In this work, a small amount of acetylacetone (AA) (0.5 mM) was found highly efficient to enhance the reduction of nitrate by ZVI at near neutral conditions (pH 6.0) with the formation of considerable black coating on ZVI. At an initial nitrate concentration of 20 mg N/L, the pseudo first-order reduction rate constant of nitrate in the ZVI-AA-NO3(-) system was 0.0991 h(-1), which was 52 times higher than that in the ZVI-NO3(-) system. Under otherwise identical conditions, the other five ligands, including EDTA, formate, acetate, oxalate, and phosphate, had negligible effects. Based on the pKa values of these ligands and the final species of iron, the ligand effects on nitrate reduction by ZVI were summarized from three aspects: (1) the ability to offer potentially dissociable protons from the ligands; (2) the complexation ability to eliminate iron (hydr)oxide precipitates from the surface of ZVI; and (3) the ability to lower down the redox potentials of iron species. The good performance of AA in these three aspects makes it advantage over the other ligands. A cycle test up to six runs demonstrates that AA could continuously take effect in the ZVI system. The results here point out the potential of AA as an effective ligand in ZVI system for enhanced contaminant transformation.

15. Precipitation and surface adsorption of metal complexes during electropolishing. Theory and characterization with X-ray nanotomography and surface tension isotherms.

PubMed

Nave, Maryana I; Chen-Wiegart, Yu-chen Karen; Wang, Jun; Kornev, Konstantin G

2015-09-21

Electropolishing of metals often leads to supersaturation conditions resulting in precipitation of complex compounds. The solubility diagrams and Gibbs adsorption isotherms of the electropolishing products are thus very important to understand the thermodynamic mechanism of precipitation of reaction products. Electropolishing of tungsten wires in aqueous solutions of potassium hydroxide is used as an example illustrating the different thermodynamic scenarios of electropolishing. Electropolishing products are able to form highly viscous films immiscible with the surrounding electrolyte or porous shells adhered to the wire surface. Using X-ray nanotomography, we discovered a gel-like phase formed at the tungsten surface during electropolishing. The results of these studies suggest that the electropolishing products can form a rich library of compounds. The surface tension of the electrolyte depends on the metal oxide ions and alkali-metal complexes.

16. Complex potential surface for the {sup 2}B{sub 1} metastable state of the water anion

SciTech Connect

Haxton, Daniel J.; Zhang, Zhiyong; McCurdy, C. William; Rescigno, Thomas N.

2004-04-23

The potential energy surface corresponding the complex resonance energy of the 2B1 Feshbach resonance state of the water anion is constructed in its full dimensionality. Complex Kohn variational scattering calculations are used to compute the resonance width, while large-scale Configuration Interaction calculations are used to compute the resonance energy. Near the equilibrium geometry, an accompanying ground state potential surface is constructed from Configuration Interaction calculations that treat correlation at a level similar to that used in the calculations on the anion.

17. Current trend in fabrication of complex morphologically tunable superhydrophobic nano scale surfaces

Abdulhussein, Ali T.; Kannarpady, Ganesh K.; Wright, Andrew B.; Ghosh, Anindya; Biris, Alexandru S.

2016-10-01

Superhydrophobic surfaces are found in nature and possess several fascinating properties, including the ability to self-clean. A typical superhydrophobic surface has micro/nanostructure roughness and low surface energy, which combine to give it its unusual anti-wetting properties. Because of their unique capabilities, these surfaces have interested scientists in research and industry fields for years. In recent decades, researchers have developed a number of synthetic methods for producing novel superhydrophobic surfaces that mimic natural surfaces. These synthetic surfaces have been widely applied on different types of substrates for potential widespread, practical applications. This review article focuses on these advances in fabricating manmade superhydrophobic surfaces.

18. Landscape and bio- geochemical strategy for monitoring transformation and reclamation of the soil mining sites

Korobova, Elena

2010-05-01

Sites of active or abandoned mining represent areas of considerable technogenic impact and need scientifically ground organization of their monitoring and reclamation. The strategy of monitoring and reclamation depends on the scale and character of the physical, chemical and biological consequences of the disturbances. The geochemical studies for monitoring and rehabilitation of the career-dump complexes should methodically account of formation of the particular new landforms and the changes in circulation of the remobilized elements of the soil cover. However, the general strategy should account of both the initial and transformed landscape geochemical structure of the area with due regard to the natural and new content of chemical elements in the environmental components. For example the tailings and waste rocks present new geochemical fields with specifically different concentration of chemical elements that cause formation of new geochemical barriers and landscapes. The way of colonization of the newly formed landscapes depends upon the new geochemical features of the technogenic environment and the adaptive ability of local and intrusive flora. The newly formed biogeochemical anomalies need organization of permanent monitoring not only within the anomaly itself but also of its impact zones. Spatial landscape geochemical monitoring combined with bio-geochemical criteria of threshold concentrations seems to be a helpful tool for decision making on reclamation and operation of the soil mining sites to provide a long-term ecologically sustainable development of the impact zone as a whole.

19. Risk evaluation of uranium mining: A geochemical inverse modelling approach

Rillard, J.; Zuddas, P.; Scislewski, A.

2011-12-01

It is well known that uranium extraction operations can increase risks linked to radiation exposure. The toxicity of uranium and associated heavy metals is the main environmental concern regarding exploitation and processing of U-ore. In areas where U mining is planned, a careful assessment of toxic and radioactive element concentrations is recommended before the start of mining activities. A background evaluation of harmful elements is important in order to prevent and/or quantify future water contamination resulting from possible migration of toxic metals coming from ore and waste water interaction. Controlled leaching experiments were carried out to investigate processes of ore and waste (leached ore) degradation, using samples from the uranium exploitation site located in Caetité-Bahia, Brazil. In experiments in which the reaction of waste with water was tested, we found that the water had low pH and high levels of sulphates and aluminium. On the other hand, in experiments in which ore was tested, the water had a chemical composition comparable to natural water found in the region of Caetité. On the basis of our experiments, we suggest that waste resulting from sulphuric acid treatment can induce acidification and salinization of surface and ground water. For this reason proper storage of waste is imperative. As a tool to evaluate the risks, a geochemical inverse modelling approach was developed to estimate the water-mineral interaction involving the presence of toxic elements. We used a method earlier described by Scislewski and Zuddas 2010 (Geochim. Cosmochim. Acta 74, 6996-7007) in which the reactive surface area of mineral dissolution can be estimated. We found that the reactive surface area of rock parent minerals is not constant during time but varies according to several orders of magnitude in only two months of interaction. We propose that parent mineral heterogeneity and particularly, neogenic phase formation may explain the observed variation of the

20. Effect of grain size on uranium(VI) surface complexation kinetics and adsorption additivity.

PubMed

Shang, Jianying; Liu, Chongxuan; Wang, Zheming; Zachara, John M

2011-07-15

1. Response surface optimization of bioremediation of Acid black 52 (Cr complex dye) using Aspergillus tamarii.

PubMed

Ghosh, Arpita; Dastidar, Manisha Ghosh; Sreekrishnan, T R

2017-02-01

Bioremediation of the Cr complex dye (Acid black 52) was performed in batch and continuous modes using growing Aspergillus tamarii. The removal of Cu which may be present as an impurity was 100% at 100 mg/L initial dye concentration. The removal of color and Cr decreased from 87% to 4% and from 92% to 8%, respectively, by increasing dye concentration from 100 to 5000 mg/L in batch mode. The removal of color and Cr increased from 27% to 67.8% and from 32% to 72%, respectively, with increasing hydraulic retention time from 28 to 220 h at 100 mg/L dye concentration in continuous mode. For optimization of color removal using response surface methodology (RSM) the ranges of parameters were kept at dye concentration: 200-500 mg/L; pH: 4-6 and time: 35-50 hours. Maximum color removal suggested by the model was 85.6809% at initial dye concentration 200 mg/L, pH 5.25 and time 50 h. The validation experiments in batch and continuous modes were conducted at the optimum conditions as suggested by the RSM model. The theoretical and experimental responses of color removal were in close agreement in batch mode. The scanning electron microscopy, energy dispersive X-ray analysis, transmission electron microscopy and gas chromatography-mass spectroscopy analyses indicated biosorption and biodegradation of dye.

2. Polyatomic ab Initio Complex Potential Energy Surfaces: Illustration of Ultracold Collisions.

PubMed

Bhattacharya, Debarati; Ben-Asher, Anael; Haritan, Idan; Pawlak, Mariusz; Landau, Arie; Moiseyev, Nimrod

2017-03-29

Resonances are metastable states that decay after a finite period of time. These states play a role in many physical processes. For example, in recent cold collision experiments, autoionization from a resonance state was observed. Complementing such observations with theory provides insight into the reaction dynamics under study. Theoretical investigation of autoionization processes is enabled via complex potential energy surfaces (CPESs), where the real and imaginary parts, respectively, provide the energy and decay rate of the system. Unfortunately, calculation of ab initio polyatomic CPESs are cumbersome; hence, they are not in abundance. Here, we present an ab initio polyatomic CPES utilizing a recently developed approach, which makes such calculations feasible. This CPES helps interpret the autoionization process observed in the He(2(3)S) + H2 collision. From the behavior of the calculated CPES we can conclusively determine the nature of the autoionization process. Moreover, this CPES was used to generate reaction rates for the collision of He with ortho- and para-H2. These reaction rates are obtained from first principles. The results show a remarkable agreement with the cold collision experimental measurements, which demonstrates the robustness of our method. Hereby, we provide a computational tool for designing and interpreting new types of experiments that involve resonance states, e.g., in nucleobase damages (DNA or RNA) or in interatomic (intermolecular) Coulombic decay.

3. Preliminary Ambient Seismic Noise Surface Wave Tomography of The Colima Volcanic Complex

Escudero, C. R.; Pacecho, H. P.

2013-05-01

The Colima Volcanic Complex (CVC) located in the western sector of the Trans Mexican Volcanic Belt is the most active Mexican volcano. The CVC is part of the active Colima Rift, a regional north south striking extensional structure. We use ambient seismic noise recorded by the Mapping the Riviera Subduction Zone (MARS) and the Colima Volcano Deep Seismic Experiment (CODEX) deployed in western Mexico. We compute the cross-correlations of vertical-component continuous records ambient noise data to extracted empirical Green' s functions. These functions provide detailed images of Rayleigh wave group velocity by measuring the Rayleigh wave group dispersion curves using the multiple-filter analysis method. We then pick the arrival times of these waves for a given period to estimated lateral variations in velocity for a given period using 2D tomography. To sampling different depths we perform the inversions for different periods that together provide information on velocity variations with depth. The study aim to better understand the geometry, and the seismic surface wave velocity structure of the CVC and relate it with the volcano structure, the geology setting of the region.

4. Detection of biomolecules in complex media using surface plasmon resonance sensors

Malone, Michael R.; Masson, Jean-Francois; Barhnart, Margaret; Beaudoin, Stephen; Booksh, Karl S.

2005-11-01

Detection of multiple biologically relevant molecules was accomplished at sub-ng/mL levels in highly fouling media using fiber- optic based surface plasmon resonance sensors. Myocardial infarction markers, myoglobin and cTnI, were quantified in full serum with limits of detection below 1 ng/mL. Biologically relevant levels are between 15-30 ng/mL and 1-5 ng/mL for myoglobin and cTnI respectively. Cytokines involved in chronic wound healing, Interleukin 1, Interleukin 6, and tumor necrosis factor α, were detected at around 1 ng/mL in cell culture media. Preliminary results in monitoring these cytokines in cell cultures expressing the cytokines were obtained. The protein diagnostic of spinal muscular atrophy, survival motor neuron protein, was quantified from cell lysate. To obtain such results in complex media, the sensor's stability to non-specific protein adsorption had to be optimized. A layer of the N-hydroxysuccinimide ester of 16-mercaptohexadecanoic acid is attached to the sensor. This layer optimizes the antibody attachment to the sensor while minimizing the non-specific signal from serum proteins.

5. Technical Report: Contaminant Organic Complexes: Their structure and energetics in surface decontamination

SciTech Connect

Samuel J. Traina; Shankar Sharma

2007-04-22

The Department of Energy has a goal of decontaminating an estimated 180,000 metric tons of metal wastes in various surplus facilities. Uranium (U) and other radioactive actinides and lanthanides are embedded within the mixed oxide structures of the passivity layers of corroded iron and steel. These toxic metals can be dissolved out of the surface layers by a naturally occurring bacterial siderophore called Desferrioxamine B (DFB). DFB is a trihydroxamate ligand with one amine (pK1 =10.89) and three hydroxamate groups (pK2 =9.70, pK3 =9.03, and pK4 =8.30), which chelates with metals through hydroxamate coordination. Complexation of DFB with U can be utilized in decontamination strategy of the passivity layers. Therefore, we have been studying reactions of uranyl U(VI) with zerovalent iron (Fe0) followed by dissolution by DFB. The objectives were to determine the structure and speciation of solution and solid phases of U and to assess the effectiveness of DFB in U dissolution.

6. Tracing origins of complex pharmaceutical preparations using surface desorption atmospheric pressure chemical ionization mass spectrometry.

PubMed

Zhang, Xinglei; Jia, Bin; Huang, Keke; Hu, Bin; Chen, Rong; Chen, Huanwen

2010-10-01

A novel strategy to trace the origins of commercial pharmaceutical products has been developed based on the direct chemical profiling of the pharmaceutical products by surface desorption atmospheric pressure chemical ionization mass spectrometry (DAPCI-MS). Besides the unambiguous identification of active drug components, various compounds present in the matrixes are simultaneously detected without sample pretreatment, providing valuable information for drug quality control and origin differentiation. Four sources of commercial amoxicillin products made by different manufacturers have been successfully differentiated. This strategy has been extended to secerning six sources of Liuwei Dihuang Teapills, which are herbal medicine preparations with extremely complex matrixes. The photolysis status of chemical drug products and the inferior natural herd medicine products prepared with different processes (e.g., extra heating) were also screened using the method reported here. The limit of detection achieved in the MS/MS experiments was estimated to be 1 ng/g for amoxicillin inside the capsule product. Our experimental data demonstrate that DAPCI-MS is a useful tool for rapid pharmaceutical analysis, showing promising perspectives for tracking the entire pharmaceutical supply chain to prevent counterfeit intrusions.

7. Complex Contact-Based Dynamics of Microsphere Monolayers Revealed by Resonant Attenuation of Surface Acoustic Waves

Hiraiwa, M.; Abi Ghanem, M.; Wallen, S. P.; Khanolkar, A.; Maznev, A. A.; Boechler, N.

2016-05-01

Contact-based vibrations play an essential role in the dynamics of granular materials. Significant insights into vibrational granular dynamics have previously been obtained with reduced-dimensional systems containing macroscale particles. We study contact-based vibrations of a two-dimensional monolayer of micron-sized spheres on a solid substrate that forms a microscale granular crystal. Measurements of the resonant attenuation of laser-generated surface acoustic waves reveal three collective vibrational modes that involve displacements and rotations of the microspheres, as well as interparticle and particle-substrate interactions. To identify the modes, we tune the interparticle stiffness, which shifts the frequency of the horizontal-rotational resonances while leaving the vertical resonance unaffected. From the measured contact resonance frequencies we determine both particle-substrate and interparticle contact stiffnesses and find that the former is an order of magnitude larger than the latter. This study paves the way for investigating complex contact-based dynamics of microscale granular crystals and yields a new approach to studying micro- to nanoscale contact mechanics in multiparticle networks.

8. Usp12 stabilizes the T-cell receptor complex at the cell surface during signaling

PubMed Central

Jahan, Akhee S.; Lestra, Maxime; Swee, Lee Kim; Fan, Ying; Lamers, Mart M.; Tafesse, Fikadu G.; Theile, Christopher S.; Spooner, Eric; Bruzzone, Roberto; Ploegh, Hidde L.; Sanyal, Sumana

2016-01-01

Posttranslational modifications are central to the spatial and temporal regulation of protein function. Among others, phosphorylation and ubiquitylation are known to regulate proximal T-cell receptor (TCR) signaling. Here we used a systematic and unbiased approach to uncover deubiquitylating enzymes (DUBs) that participate during TCR signaling in primary mouse T lymphocytes. Using a C-terminally modified vinyl methyl ester variant of ubiquitin (HA-Ub-VME), we captured DUBs that are differentially recruited to the cytosol on TCR activation. We identified ubiquitin-specific peptidase (Usp) 12 and Usp46, which had not been previously described in this pathway. Stimulation with anti-CD3 resulted in phosphorylation and time-dependent translocation of Usp12 from the nucleus to the cytosol. Usp12−/− Jurkat cells displayed defective NFκB, NFAT, and MAPK activities owing to attenuated surface expression of TCR, which were rescued on reconstitution of wild type Usp12. Proximity-based labeling with BirA-Usp12 revealed several TCR adaptor proteins acting as interactors in stimulated cells, of which LAT and Trat1 displayed reduced expression in Usp12−/− cells. We demonstrate that Usp12 deubiquitylates and prevents lysosomal degradation of LAT and Trat1 to maintain the proximal TCR complex for the duration of signaling. Our approach benefits from the use of activity-based probes in primary cells without any previous genome modification, and underscores the importance of ubiquitin-mediated regulation to refine signaling cascades. PMID:26811477

9. On the variability of the surface environment response to synoptic forcing over complex terrain: a multivariate data analysis approach

Halios, Christos H.; Helmis, Costas G.; Flocas, Helena A.; Nyeki, Stephan; Assimakopoulos, Dimosthenis N.

2012-11-01

Synoptic climatology relates the atmospheric circulation with the surface environment. The aim of this study is to examine the variability of the surface meteorological patterns, which are developing under different synoptic scale categories over a suburban area with complex topography. Multivariate Data Analysis techniques were performed to a data set with surface meteorological elements. Three principal components related to the thermodynamic status of the surface environment and the two components of the wind speed were found. The variability of the surface flows was related with atmospheric circulation categories by applying Correspondence Analysis. Similar surface thermodynamic fields develop under cyclonic categories, which are contrasted with the anti-cyclonic category. A strong, steady wind flow characterized by high shear values develops under the cyclonic Closed Low and the anticyclonic H-L categories, in contrast to the variable weak flow under the anticyclonic Open Anticyclone category.

10. TAPIR--Finnish national geochemical baseline database.

PubMed

Jarva, Jaana; Tarvainen, Timo; Reinikainen, Jussi; Eklund, Mikael

2010-09-15

In Finland, a Government Decree on the Assessment of Soil Contamination and Remediation Needs has generated a need for reliable and readily accessible data on geochemical baseline concentrations in Finnish soils. According to the Decree, baseline concentrations, referring both to the natural geological background concentrations and the diffuse anthropogenic input of substances, shall be taken into account in the soil contamination assessment process. This baseline information is provided in a national geochemical baseline database, TAPIR, that is publicly available via the Internet. Geochemical provinces with elevated baseline concentrations were delineated to provide regional geochemical baseline values. The nationwide geochemical datasets were used to divide Finland into geochemical provinces. Several metals (Co, Cr, Cu, Ni, V, and Zn) showed anomalous concentrations in seven regions that were defined as metal provinces. Arsenic did not follow a similar distribution to any other elements, and four arsenic provinces were separately determined. Nationwide geochemical datasets were not available for some other important elements such as Cd and Pb. Although these elements are included in the TAPIR system, their distribution does not necessarily follow the ones pre-defined for metal and arsenic provinces. Regional geochemical baseline values, presented as upper limit of geochemical variation within the region, can be used as trigger values to assess potential soil contamination. Baseline values have also been used to determine upper and lower guideline values that must be taken into account as a tool in basic risk assessment. If regional geochemical baseline values are available, the national guideline values prescribed in the Decree based on ecological risks can be modified accordingly. The national geochemical baseline database provides scientifically sound, easily accessible and generally accepted information on the baseline values, and it can be used in various

11. Modeling Np and Pu transport with a surface complexation model and spatially variant sorption capacities: Implications for reactive transport modeling and performance assessments of nuclear waste disposal sites

USGS Publications Warehouse

Glynn, P.D.

2003-01-01

One-dimensional (1D) geochemical transport modeling is used to demonstrate the effects of speciation and sorption reactions on the ground-water transport of Np and Pu, two redox-sensitive elements. Earlier 1D simulations (Reardon, 1981) considered the kinetically limited dissolution of calcite and its effect on ion-exchange reactions (involving 90Sr, Ca, Na, Mg and K), and documented the spatial variation of a 90Sr partition coefficient under both transient and steady-state chemical conditions. In contrast, the simulations presented here assume local equilibrium for all reactions, and consider sorption on constant potential, rather than constant charge, surfaces. Reardon's (1981) seminal findings on the spatial and temporal variability of partitioning (of 90Sr) are reexamined and found partially caused by his assumption of a kinetically limited reaction. In the present work, sorption is assumed the predominant retardation process controlling Pu and Np transport, and is simulated using a diffuse-double-layer-surface-complexation (DDLSC) model. Transport simulations consider the infiltration of Np- and Pu-contaminated waters into an initially uncontaminated environment, followed by the cleanup of the resultant contamination with uncontaminated water. Simulations are conducted using different spatial distributions of sorption capacities (with the same total potential sorption capacity, but with different variances and spatial correlation structures). Results obtained differ markedly from those that would be obtained in transport simulations using constant Kd, Langmuir or Freundlich sorption models. When possible, simulation results (breakthrough curves) are fitted to a constant K d advection-dispersion transport model and compared. Functional differences often are great enough that they prevent a meaningful fit of the simulation results with a constant K d (or even a Langmuir or Freundlich) model, even in the case of Np, a weakly sorbed radionuclide under the

12. From olivine nephelinite, basanite and basalt to peralkaline trachyphonolite and comendite in the Ankaratra volcanic complex, Madagascar: 40Ar/39Ar ages, phase compositions and bulk-rock geochemical and isotopic evolution

Cucciniello, Ciro; Melluso, Leone; le Roex, Anton P.; Jourdan, Fred; Morra, Vincenzo; de'Gennaro, Roberto; Grifa, Celestino

2017-03-01

The Ankaratra volcanic field covers an area of 3800 km2 in central Madagascar and comprises of lava flows, lava domes, scoria cones, tuff rings and maars emplaced at different ages (Miocene to Recent). The volcanic products include ultramafic-mafic (olivine-leucite nephelinite, basanite, alkali basalt, hawaiite and tholeiitic basalt), intermediate (mugearite and benmoreite) and felsic rocks (trachyphonolite, quartz trachyte and rhyolite), the latter often peralkaline. The 40Ar/39Ar determinations for mafic lavas yield ages of 17.45 ± 0.12 Ma, 16.63 ± 0.08 Ma and 8.62 ± 0.09 Ma, indicating a prolonged magmatic activity. The mineralogical and geochemical variations suggest that the magmatic evolution of the alkali basalt-hawaiite-mugearite-benmoreite-trachyte series can be accounted for by removal of olivine, feldspars, clinopyroxene, Fe-Ti oxides and accessory phases, producing residual trachytic and trachyphonolitic compositions mineralogically very similar to those of other volcanic areas and tectonic settings. The Ankaratra olivine leucite nephelinites, basanites and tholeiitic basalts do not seem to be associated with significant amounts of evolved comagmatic rocks. The 87Sr/86Sr (0.70504-0.71012), 143Nd/144Nd (0.51259-0.51244) and 206Pb/204Pb (17.705-18.563) isotopic ratios of trachytes and comendite are consistent with open-system processes. However, other trachyphonolites have 143Nd/144Nd (0.51280), 206Pb/204Pb (18.648), 207Pb/204Pb (15.582) and 208Pb/204Pb (38.795) similar to those of mafic rocks, suggesting differentiation processes without appreciable interaction with crustal materials. The Ankaratra volcanism is to be directly linked to a broadly E-W-trending intracontinental extension. A large-scale thermal anomaly, associated with an anomalously hot source region, is not required to explain the Cenozoic magmatism of Madagascar.

13. GeoComplexity and scale: surface processes and remote sensing of geosystems. GeoComplexity and scale: surface processes and remote sensing of geosystems

Muller, Jan-Peter

2015-04-01

Understanding the role of scaling in different planetary surface processes within our Solar System is one of the fundamental goals of planetary and solid earth scientific research. There has been a revolution in planetary surface observations over the past decade for the Earth, Mars and the Moon, especially in 3D imaging of surface shape (from the planetary scale down to resolutions of 75cm). I will examine three areas that I have been active in over the last 25 years giving examples of newly processed global datasets ripe for scaling analysis: topography, BRDF/albedo and imaging. For understanding scaling in terrestrial land surface topography we now have global 30m digital elevation models (DEMs) from different types of sensors (InSAR and stereo-optical) along with laser altimeter data to provide global reference models (to better than 1m in cross-over areas) and airborne laser altimeter data over small areas at resolutions better than 1m and height accuracies better than 10-15cm. We also have an increasing number of sub-surface observations from long wavelength SAR in arid regions, which will allow us to look at the true surface rather than the one buried by sand. We also still have a major limitation of these DEMs in that they represent an unknown observable surface with C-band InSAR DEMs representing being somewhere near the top of the canopy and X-band InSAR and stereo near the top of the canopy but only P-band representing the true understorey surface. I will present some of the recent highlights of topography on Mars including 3D modelling of surface shape from the ESA Mars Express HRSC (High Resolution Stereo Camera), see [1], [2] at 30-100m grid-spacing; and then co-registered to HRSC using a resolution cascade of 20m DTMs from NASA MRO stereo-CTX and 0.75m digital terrain models (as there is no land cover on Mars) DTMs from MRO stereo-HiRISE [3]. Comparable DTMs now exist for the Moon from 100m up to 1m. I will show examples of these DEM/DTM datasets

14. Geochemical Attributes and Gradients Within Geothermal Systems Define the Distribution of Specific Microbial Populations

Inskeep, W. P.; Macur, R. E.; Korf, S.; Taylor, W. P.; Ackerman, G.; Kozubal, M.; Nagy, A.

2006-12-01

Microorganisms in natural habitats interact with mineral surfaces in many different respects. For example, microorganisms are known to enhance the dissolution rates of some minerals via the production of organic acids and other exudates, but at the same time, may mineralize solid phases as a direct or indirect result of metabolic processes. It is also well-established that many microorganisms form biofilms on mineral surfaces, and may preferentially attach to surfaces rich in necessary nutrients or in elements used for energy conservation. In part due to the complexity of natural soil, water and sediments systems, it is generally difficult to ascertain mechanisms controlling the distribution of organisms on mineral surfaces and their role in mineral precipitation-dissolution reactions. Geothermal microbial communities are often less diverse than surface soils and sediments and offer opportunities for understanding relationships among specific microbial populations and geochemical processes that define the biogeochemical cycles of individual elements. We have investigated numerous acidic and near-neutral geothermal sites in Yellowstone National Park, and have performed a number of complimentary chemical and microbiological analyses to ascertain the role of microorganisms in S, Fe, As and Sb cycling in geothermal systems. Our results demonstrate the importance of microbiota in the formation of various Fe(III) oxide phases with variable anion chemistry, and the importance of chemolithotrophic metabolisms in Fe, S and As cycling. Where possible, these metabolisms are linked to specific microbial populations identified via molecular methods, and in some cases confirmed using isolation and characterization of individual organisms.

15. Re-Inversion of Surface Electrical Resistivity Tomography Data from the Hanford Site B-Complex

SciTech Connect

Johnson, Timothy C.; Wellman, Dawn M.

2013-05-01

This report documents the three-dimensional (3D) inversion results of surface electrical resistivity tomography (ERT) data collected over the Hanford Site B-Complex. The data were collected in order to image the subsurface distribution of electrically conductive vadose zone contamination resulting from both planned releases of contamination into subsurface infiltration galleries (cribs, trenches, and tile fields), as well as unplanned releases from the B, BX, and BY tank farms and/or associated facilities. Electrically conductive contaminants are those which increase the ionic strength of pore fluids compared to native conditions, which comprise most types of solutes released into the subsurface B-Complex. The ERT data were collected and originally inverted as described in detail in report RPP-34690 Rev 0., 2007, which readers should refer to for a detailed description of data collection and waste disposal history. Although the ERT imaging results presented in that report successfully delineated the footprint of vadose zone contamination in areas outside of the tank farms, imaging resolution was not optimized due to the inability of available inversion codes to optimally process the massive ERT data set collected at the site. Recognizing these limitations and the potential for enhanced ERT characterization and time-lapse imaging at contaminated sites, a joint effort was initiated in 2007 by the U.S. Department of Energy – Office of Science (DOE-SC), with later support by the Office of Environmental Management (DOE-EM), and the U.S. Department of Defense (DOD), to develop a high-performance distributed memory parallel 3D ERT inversion code capable of optimally processing large ERT data sets. The culmination of this effort was the development of E4D (Johnson et al., 2010,2012) In 2012, under the Deep Vadose Zone Applied Field Research Initiative (DVZ-AFRI), the U.S. Department of Energy – Richland Operations Office (DOE-RL) and CH2M Hill Plateau Remediation

16. Geochemical Signatures in Corals from Looe Key, Florida since 1870 A.D.

Smith, J. M.; Quinn, T. M.; Halley, R. B.

2004-12-01

Geochemical variations in modern and fossil coral skeletons (Sr/Ca, Mg/Ca, δ 18O, δ 13C) are increasingly being used to reconstruct climate variability in tropical ocean-atmosphere system on interannual to centennial timescales. Sub-annually resolved, centennial-length records of climate from the Atlantic that overlap with and extend beyond the instrumental record are sparse, yet required to assess interannual climate variations over decades to centuries. We address this data gap by presenting a %\\sim132 year time series of monthly geochemical variations in Montastraea annularis (complex) corals from Looe Key reef, Florida USA (24.5\\deg N, 81.4\\deg W). We first reconstructed estimates of hydrographic and temperature variability at Looe Key using temperature calibrations developed over the decade in which we have thermistor data. Calibration-verification exercises over this interval indicate differences in mean values of 0.6\\degC Sr/Ca-SST and 0.2\\degC \\delta\$18O-SST. Next we extended the calibration-verification intervals by comparing the coral geochemical variations with a SST record extracted from the HadISST 1.1 database using the appropriate 1° by 1° grid point for Looe Key. These longer-term verification exercises show a better agreement in estimation of the mean in δ 18O-SST (0.15° C) than Sr/Ca-SST (0.47° C). Comparisons of monthly Sr/Ca and δ 18O anomalies with monthly temperature anomalies over the entire record reveal weak relationships (r = -0.13, -0.10, respectively); however, there is a strong coupling between Sr/Ca and δ 18O anomalies (r = 0.51) that shares spectral power in the decadal band. The relationship between decadally smoothed geochemical values and the AMO is also weak (r = -0.13, 0.09; for Sr/Ca and δ 18O) despite a strong correlation between the AMO and SST from the Looe Key region (r = 0.72). The low correlation between SSTA/AMO and the coral proxies (Sr/Ca and δ 18O), despite the good fit between the coral proxies

17. Proceedings of the workshop on geochemical modeling

SciTech Connect

Not Available

1986-01-01

The following collection of papers was presented at a workshop on geochemical modeling that was sponsored by the Office of Civilian Radioactive Waste Management Program at the Lawrence Livermore National Laboratory (LLNL). The LLNL Waste Management Program sponsored this conference based on their belief that geochemical modeling is particularly important to the radioactive waste disposal project because of the need to predict the consequences of long-term water-rock interactions at the proposed repository site. The papers included in this volume represent a subset of the papers presented at the Fallen Leaf Lake Conference and cover a broad spectrum of detail and breadth in a subject that reflects the diverse research interests of the conference participants. These papers provide an insightful look into the current status of geochemical modeling and illustrate how various geochemical modeling codes have been applied to problems of geochemical interest. The emphasis of these papers includes traditional geochemical modeling studies of individual geochemical systems, the mathematical and theoretical development and refinement of new modeling capabilities, and enhancements of data bases on which the computations are based. The papers in this proceedings volume have been organized into the following four areas: Geochemical Model Development, Hydrothermal and Geothermal Systems, Sedimentary and Low Temperature Environments, and Data Base Development. The participants of this symposium and a complete list of the talks presented are listed in the appendices.

18. High-resolution and specific detection of bacteria on complex surfaces using nanoparticle probes and electron microscopy.

PubMed

Ye, Jun; Nielsen, Shaun; Joseph, Stephen; Thomas, Torsten

2015-01-01

The study of the interaction of bacteria with surfaces requires the detection of specific bacterial groups with high spatial resolution. Here, we describe a method to rapidly and efficiently add nanogold particles to oligonucleotide probes, which target bacterial ribosomal RNA. These nanogold-labeled probes are then used in an in situ hybridization procedure that ensures both cellular integrity and high specificity. Electron microscopy subsequently enables the visualization of specific cells with high local precision on complex surface structures. This method will contribute to an increased understanding of how bacteria interact with surface structures on a sub-micron scale.

19. High-Resolution and Specific Detection of Bacteria on Complex Surfaces Using Nanoparticle Probes and Electron Microscopy

PubMed Central

Ye, Jun; Nielsen, Shaun; Joseph, Stephen; Thomas, Torsten

2015-01-01

The study of the interaction of bacteria with surfaces requires the detection of specific bacterial groups with high spatial resolution. Here, we describe a method to rapidly and efficiently add nanogold particles to oligonucleotide probes, which target bacterial ribosomal RNA. These nanogold-labeled probes are then used in an in situ hybridization procedure that ensures both cellular integrity and high specificity. Electron microscopy subsequently enables the visualization of specific cells with high local precision on complex surface structures. This method will contribute to an increased understanding of how bacteria interact with surface structures on a sub-micron scale. PMID:26018431

20. Integrating seasonal optical and thermal infrared spectra to characterize urban impervious surfaces with extreme spectral complexity: a Shanghai case study

Wang, Wei; Yao, Xinfeng; Ji, Minhe

2016-01-01

Despite recent rapid advancement in remote sensing technology, accurate mapping of the urban landscape in China still faces a great challenge due to unusually high spectral complexity in many big cities. Much of this complication comes from severe spectral confusion of impervious surfaces with polluted water bodies and bright bare soils. This paper proposes a two-step land cover decomposition method, which combines optical and thermal spectra from different seasons to cope with the issue of urban spectral complexity. First, a linear spectral mixture analysis was employed to generate fraction images for three preliminary endmembers (high albedo, low albedo, and vegetation). Seasonal change analysis on land surface temperature induced from thermal infrared spectra and coarse component fractions obtained from the first step was then used to reduce the confusion between impervious surfaces and nonimpervious materials. This method was tested with two-date Landsat multispectral data in Shanghai, one of China's megacities. The results showed that the method was capable of consistently estimating impervious surfaces in highly complex urban environments with an accuracy of R2 greater than 0.70 and both root mean square error and mean average error less than 0.20 for all test sites. This strategy seemed very promising for landscape mapping of complex urban areas.

1. Using object-based analysis to derive surface complexity information for improved filtering of airborne laser scanning data

Yan, Menglong; Blaschke, Thomas; Tang, Hongzhao; Xiao, Chenchao; Sun, Xian; Zhang, Daobing; Fu, Kun

2017-03-01

Airborne laser scanning (ALS) is a technique used to obtain Digital Surface Models (DSM) and Digital Terrain Models (DTM) efficiently, and filtering is the key procedure used to derive DTM from point clouds. Generating seed points is an initial step for most filtering algorithms, whereas existing algorithms usually define a regular window size to generate seed points. This may lead to an inadequate density of seed points, and further introduce error type I, especially in steep terrain and forested areas. In this study, we propose the use of objectbased analysis to derive surface complexity information from ALS datasets, which can then be used to improve seed point generation.We assume that an area is complex if it is composed of many small objects, with no buildings within the area. Using these assumptions, we propose and implement a new segmentation algorithm based on a grid index, which we call the Edge and Slope Restricted Region Growing (ESRGG) algorithm. Surface complexity information is obtained by statistical analysis of the number of objects derived by segmentation in each area. Then, for complex areas, a smaller window size is defined to generate seed points. Experimental results show that the proposed algorithm could greatly improve the filtering results in complex areas, especially in steep terrain and forested areas.

2. Adsorption of a metalorganic complex at a metal surface: A density functional theory study vs. model description

SciTech Connect

Kostyrko, T. Ślusarski, T.

2015-01-21

A modification of the electronic and magnetic structure of a metalorganic complex by chemisorption at a metallic surface is addressed. The density functional theory (DFT) is applied to investigate a simplified form of a copper-dioxolene complex in a free state and connected to Au(111) surface with alkanethiol linkers. A systematic study of the dependence of the system electronic structure on the linker length is performed. It is found that the electronic structure of the complex is well preserved during the adsorption process. The magnetic moment of the Cu-dioxolene functional group is shown to be strictly correlated with the amount of the charge residing at the complex. On the basis of the DFT results, a model Hamiltonian of the adsorbed metalorganic system is proposed. The model is an extension of the Sandorfy's model of the alkanes and includes explicitly Coulomb interaction between electrons both within the alkane's backbone and the end group. We show that the latter feature is necessary to understand the evolution of the system's properties with the length of the linkers. The advantage of this approach is that it not only reproduces the main results of our DFT analysis but also provides a simple common basis to analyse a wide class of metal complexes bound to metal surfaces with alkanethiol linkers.

3. Influence of crystallite microstrain on surface complexes governing the metastable equilibrium solubility behavior of carbonated apatites.

PubMed

Papangkorn, Kongnara; Yan, Guang; Heslop, Dustin D; Moribe, Kunikazu; Baig, Arif A; Otsuka, Makoto; Higuchi, William I

2008-04-01

This study was on the influence of the mineral phase crystallite microstrain (CM) on the nature of the surface complex (SC) governing the metastable equilibrium solubility (MES) behavior of carbonated apatites (CAPs) in aqueous acidic media (0.10 M acetate buffers, with and without fluoride, 0.50 M ionic strength maintained with NaCl). The MES behavior of a set of four CAPs (synthesized at 85 degrees C by a precipitation method) of increasing CM and therefore of increasing MES (CAP4 > CAP3 > CAP2 > CAP1) was quantified. The following were the findings. For CAP1 and CAP2, the SCs deduced were Ca10(PO4)6(OH)2 and Ca10(PO4)6F2 for the nonfluoride and the fluoride cases, respectively. For CAP3 and CAP4, the SCs deduced were Ca9.5(PO4)6OH or Ca9.5(HPO4)(PO4)5(OH)2 and NaCa9.5(PO4)6F2 for the nonfluoride and the fluoride cases, respectively. These results together with that from an earlier limited study show that the Ca/P ratio of the SC decreases from 1.67 to 1.58 to 1.50 with increasing CM of the CAPs; this relationship inversely correlates with the chemistry of maturation of aqueously precipitated defective apatites. Also the SCs do not appear to exist as a continuous series and only a few SCs may account for the MES behavior over a wide range of CAP preparations.

4. Model complexity in carbon sequestration:A design of experiment and response surface uncertainty analysis

Zhang, Y.; Li, S.

2014-12-01

Geologic carbon sequestration (GCS) is proposed for the Nugget Sandstone in Moxa Arch, a regional saline aquifer with a large storage potential. For a proposed storage site, this study builds a suite of increasingly complex conceptual "geologic" model families, using subsets of the site characterization data: a homogeneous model family, a stationary petrophysical model family, a stationary facies model family with sub-facies petrophysical variability, and a non-stationary facies model family (with sub-facies variability) conditioned to soft data. These families, representing alternative conceptual site models built with increasing data, were simulated with the same CO2 injection test (50 years at 1/10 Mt per year), followed by 2950 years of monitoring. Using the Design of Experiment, an efficient sensitivity analysis (SA) is conducted for all families, systematically varying uncertain input parameters. Results are compared among the families to identify parameters that have 1st order impact on predicting the CO2 storage ratio (SR) at both end of injection and end of monitoring. At this site, geologic modeling factors do not significantly influence the short-term prediction of the storage ratio, although they become important over monitoring time, but only for those families where such factors are accounted for. Based on the SA, a response surface analysis is conducted to generate prediction envelopes of the storage ratio, which are compared among the families at both times. Results suggest a large uncertainty in the predicted storage ratio given the uncertainties in model parameters and modeling choices: SR varies from 5-60% (end of injection) to 18-100% (end of monitoring), although its variation among the model families is relatively minor. Moreover, long-term leakage risk is considered small at the proposed site. In the lowest-SR scenarios, all families predict gravity-stable supercritical CO2 migrating toward the bottom of the aquifer. In the highest

5. Molecular statics calculations of proton binding to goethite surfaces: A new approach to estimation of stability constants for multisite surface complexation models

Rustad, James R.; Felmy, Andrew R.; Hay, Benjamin P.

1996-05-01

A new approach to estimating stability constants for proton binding in multisite surface complexation models is presented. The method is based on molecular statics computation of energies for the formation of proton vacancies and interstitials in ideal periodic slabs representing the (100), (110), (010), (001), and (021) surfaces of goethite. Gas-phase energies of clusters representing the hydrolysis products of ferric iron are calculated using the same potential energy functions used for the surface. These energies are linearly related to the hydrolysis constants for ferric iron in aqueous solution. Stability constants for proton binding at goethite surfaces are estimated by assuming the same log K- Δ E relationship for goethite surface protonation reactions. These stability constants predict a pH of zero charge of 8.9, in adequate agreement with measurements on CO 2-free goethite. The estimated stability constants differ significantly from previous estimations based on Pauling bond strength. We find that nearly all the surface oxide ions are reactive; nineteen of the twenty-six surface sites investigated have log Kint between 7.7 and 9.4. This implies a site density between fifteen and sixteen reactive sites/nm for crystals dominated by (110) and (021) crystal faces.

6. Geochemical data synthesis and analysis

NASA Technical Reports Server (NTRS)

Philpotts, J. A.

1979-01-01

Data obtained at the Goddard Flight Center were collected for the purpose of completing analyses started at Goddard in order to maximize the scientific yield of the geochemistry program which was terminated in 1977. The major analytical task undertaken was to complete Gd analyses on a large number of samples already analyzed by mass spectrometry for other rare earth element abundances at Goddard. Gd values are important for pinning down the central part of the geochemically significant rare earth abundance pattern and are especially useful in the high precision definition of the utilitarian Eu anomaly. Isotope-dilution Gd abundances were obtained for 39 samples. The data are for 27 partition-coefficient samples, six Apollo 15 and 16 breccia samples, four terrestrial impactities, and associated rock standards.

7. Geochemical challenge to earthquake prediction.

PubMed

Wakita, H

1996-04-30

The current status of geochemical and groundwater observations for earthquake prediction in Japan is described. The development of the observations is discussed in relation to the progress of the earthquake prediction program in Japan. Three major findings obtained from our recent studies are outlined. (i) Long-term radon observation data over 18 years at the SKE (Suikoen) well indicate that the anomalous radon change before the 1978 Izu-Oshima-kinkai earthquake can with high probability be attributed to precursory changes. (ii) It is proposed that certain sensitive wells exist which have the potential to detect precursory changes. (iii) The appearance and nonappearance of coseismic radon drops at the KSM (Kashima) well reflect changes in the regional stress state of an observation area. In addition, some preliminary results of chemical changes of groundwater prior to the 1995 Kobe (Hyogo-ken nanbu) earthquake are presented.

8. Molecular and electronic structure of osmium complexes confined to Au(111) surfaces using a self-assembled molecular bridge

SciTech Connect

Llave, Ezequiel de la; Herrera, Santiago E.; Adam, Catherine; Méndez De Leo, Lucila P.; Calvo, Ernesto J.; Williams, Federico J.

2015-11-14

The molecular and electronic structure of Os(II) complexes covalently bonded to self-assembled monolayers (SAMs) on Au(111) surfaces was studied by means of polarization modulation infrared reflection absorption spectroscopy, photoelectron spectroscopies, scanning tunneling microscopy, scanning tunneling spectroscopy, and density functional theory calculations. Attachment of the Os complex to the SAM proceeds via an amide covalent bond with the SAM alkyl chain 40° tilted with respect to the surface normal and a total thickness of 26 Å. The highest occupied molecular orbital of the Os complex is mainly based on the Os(II) center located 2.2 eV below the Fermi edge and the LUMO molecular orbital is mainly based on the bipyridine ligands located 1.5 eV above the Fermi edge.

9. Probing complex reflection coefficients in one-dimensional surface plasmon polariton waveguides and cavities using STEM EELS.

PubMed

Schoen, David T; Atre, Ashwin C; García-Etxarri, Aitzol; Dionne, Jennifer A; Brongersma, Mark L

2015-01-14

The resonant properties of a plasmonic cavity are determined by the size of the cavity, the surface plasmon polariton (SPP) dispersion relationship, and the complex reflection coefficients of the cavity boundaries. In small wavelength-scale cavities, the phase propagation due to reflections from the cavity walls is of a similar magnitude to propagation due to traversing the cavity. Until now, this reflection phase has been inferred from measurements of the resonant frequencies of a cavity of known dispersion and length. In this work, we present a method for measuring the complex reflection coefficients of a truncation in a 1D surface plasmon waveguide using electron energy loss spectroscopy in the scanning transmission electron microscope (STEM EELS) and show that this insight can be used to engineer custom cavities with engineered reflecting boundaries, whose resonant wavelengths and internal mode density profiles can be analytically predicted given knowledge of the cavity dimensions and complex reflection coefficients of the boundaries.

10. Mechanism of Bacterial Cell-Surface Attachment Revealed by the Structure of Cellulosomal Type II Cohesin-dockerin Complex

SciTech Connect

Adams,J.; Pal, G.; Jia, Z.; Smith, S.

2006-01-01

Bacterial cell-surface attachment of macromolecular complexes maintains the microorganism in close proximity to extracellular substrates and allows for optimal uptake of hydrolytic byproducts. The cellulosome is a large multienzyme complex used by many anaerobic bacteria for the efficient degradation of plant cell-wall polysaccharides. The mechanism of cellulosome retention to the bacterial cell surface involves a calcium-mediated protein-protein interaction between the dockerin (Doc) module from the cellulosomal scaffold and a cohesin (Coh) module of cell-surface proteins located within the proteoglycan layer. Here, we report the structure of an ultra-high-affinity (K{sub a} = 1.44 x 10{sup 10} M{sup 1-}) complex between type II Doc, together with its neighboring X module from the cellulosome scaffold of Clostridium thermocellum, and a type II Coh module associated with the bacterial cell surface. Identification of X module-Doc and X module-Coh contacts reveal roles for the X module in Doc stability and enhanced Coh recognition. This extremely tight interaction involves one face of the Coh and both helices of the Doc and comprises significant hydrophobic character and a complementary extensive hydrogen-bond network. This structure represents a unique mechanism for cell-surface attachment in anaerobic bacteria and provides a rationale for discriminating between type I and type II Coh modules.

11. PHREEQC. Geochemical Speciation Mass Transfer

SciTech Connect

Parkhurst, D.L.

1995-01-01

PHREEQC is designed to model geochemical reactions. Based on an ion association aqueous model, PHREEQC can calculate pH, redox potential, and mass transfer as a function of reaction progress. It can be used to describe geochemical processes for both far-field and near-field performance assessment and to evaluate data acquisition needs and test data. It can also calculate the composition of solutions in equilibrium with multiple phases. The data base, including elements, aqueous species, and mineral phases, is independent of the program and is completely user-definable. PHREEQC requires thermodynamic data for each solid, gaseous, or dissolved chemical species being modeled. The two data bases, PREPHR and DEQPAK7, supplied with PHREEQC are for testing purposes only and should not be applied to real problems without first being carefully examined. The conceptual model embodied in PHREEQC is the ion-association model of Pearson and Noronha. In this model a set of mass action equations are established for each ion pair (and controlling solid phases when making mass transfer calculations) along with a set of mass balance equations for each element considered. These sets of equations are coupled using activity coefficient values for each aqueous species and solved using a continued fraction approach for the mass balances combined with a modified Newton-Raphson technique for all other equations. The activity coefficient expressions in PHREEQC include the extended Debye-Huckel, WATEQ Debye-Huckel, and Davies equations from the original United States Geological Survey version of the program. The auxiliary preprocessor program PHTL, which is derived from EQTL, converts EQ3/6 thermodynamic data to PHREEQC format so that the two programs can be compared. PHREEQC can be used to determine solubility limits on the radionuclides present in the waste form. These solubility constraints may be input to the WAPPA leach model.

12. Predictive Radiological Background Distributions from Geochemical Data

Haber, D.; Burnley, P. C.; Marsac, K.; Malchow, R.

2014-12-01

Gamma ray surveys are an important tool for both national security interests as well as industry in determininglocations of both anthropogenic radiological sources and natural occurrences of radiologic material. The purpose ofthis project is to predict the radiologic exposure rate of geologic materials by creating a model using publishedgeochemical data, geologic data, GIS software, and freely available remote sensing data sets. If K, U, and Thabundance values are known for a given geologic unit, the expected radiation exposure rate can be calculated. Oneof the primary challenges surrounding this project is that alluvial units are classified by age rather than rock type. Itis therefore important to determine sediment sources and estimate their relative contribution to alluvial units.ASTER data from the Terra satellite can differentiate between surface mineralogies and can aid us in calculating therelative percentage of sediment from each source and by extension the geochemical concentrations of challengingsurfaces such as alluvium. An additional problem is that U and Th do not directly contribute to the measuredradiation exposure rate. Instead, daughter isotopes of these radioelements emit detectable gamma rays and may nothave reached equilibrium in younger surfaces. U can take up to 1.5 Ma to come to equilibrium with its daughterisotopes while Th takes only about 40 years. Further modeling with software such as Monte Carlo N-ParticleTransport from Los Alamos National Laboratory, will help us correct for this disequilibrium in our models. Once the predicted exposure rate is calculated for a geologic unit, it can then be assigned to a geographic area basedon geologic and geomorphic trends. This prediction will be subtracted from data collected through aerial surveys,effectively ignoring geology, and allowing areas of interest to be narrowed down considerably. The study areasinclude the alluvium on the west shore of Lake Mohave and Government Wash north of Lake Mead

13. A surface site as polydentate ligand of a metal complex: Density functional studies of rhenium subcarbonyls supported on magnesium oxide

SciTech Connect

Hu, A.; Neyman, K.M.; Staufer, M.; Belling, T.; Gates, B.C.; Roesch, N.

1999-05-12

Notwithstanding the importance of supported organometallic species as industrial catalysts, most are nonuniform mixtures, with only a few being well-characterized at the atomic level. Rhenium subcarbonyls on MgO, in contrast, consist of nearly uniform surface species and are among the best-studied organometallic complexes on oxides. EXAFS and infrared spectra showed that decomposition of the precursors [HRe(CO){sub 5}], [H{sub 3}Re{sub 3}(CO){sub 12}], and [Re{sub 2}(CO){sub 10}] on MgO powder results in fragments, assigned as Re(CO){sub 3}{sup n+}, coordinated to surface ligands. The concept of a surface site as a polydentate ligand evokes the remarkable circumstance in which the adsorbate-substrate bonds are as strong as metal-ligand bonds in common transition metal complexes, as shown by the present investigation.

14. An original electrochemical method for assembling multilayers of terpyridine-based metallic complexes on a gold surface.

PubMed

Liatard, Sébastien; Chauvin, Jérôme; Balestro, Franck; Jouvenot, Damien; Loiseau, Frédérique; Deronzier, Alain

2012-07-24

A new method based on the electrochemical oxidation of thiols was used to easily generate multilayer assemblies of coordination complexes on a gold surface. For this purpose, two complexes bearing two anchoring groups for surface attachment have been prepared: [Ru(tpySH)(2)](2+) (1) and [Fe(tpySH)(2)](2+) (2) (tpySH = 4'-(2-(p-phenoxy)ethanethiol)-2,2':6',2″-terpyridine). Cyclic voltammetry of 1 in CH(3)CN exhibits two successive oxidation processes. The first is irreversible and attributed to the oxidation of the thiol substituents, whereas the second is reversible and corresponds to the 1 e(-) metal-centered oxidation. In the case of 2 both processes are superimposed. Monolayers of 1 or 2 have been formed on gold electrodes by spontaneous adsorption from micromolar solutions of the complexes in CH(3)CN. SAMs (self-assembled monolayers) exhibit redox behavior similar to the complexes in solution. The high surface coverage value obtained (Γ = 6 × 10(-10) and 4 × 10(-10) mol cm(-2) for 1 and 2, respectively) is consistent with a vertical orientation for the complexes; thus, one thiol is bound to the gold electrode, with the second unreacted thiol moiety exposed to the outer surface. Successive cyclic voltammetry induced a layer-by-layer nanostructural growth at the surface of the SAMs, and this is presumably due to the electrochemical formation of disulfide bonds, where the thiol moieties play a double role of both an anchoring group and an electroactive coupling agent. The conditions of the deposition are studied in detail. Modified electrodes containing both 1 and 2 alternatively can be easily prepared following this new approach. The film proved to be stable, displaying a similar current/voltage response for more than 10 repeating cycles in oxidation up to 0.97 V vs Ag/AgNO(3) (10(-2) M).

15. Optimal parameter and uncertainty estimation of a land surface model: Sensitivity to parameter ranges and model complexities

Xia, Youlong; Yang, Zong-Liang; Stoffa, Paul L.; Sen, Mrinal K.

2005-01-01

Most previous land-surface model calibration studies have defined global ranges for their parameters to search for optimal parameter sets. Little work has been conducted to study the impacts of realistic versus global ranges as well as model complexities on the calibration and uncertainty estimates. The primary purpose of this paper is to investigate these impacts by employing Bayesian Stochastic Inversion (BSI) to the Chameleon Surface Model (CHASM). The CHASM was designed to explore the general aspects of land-surface energy balance representation within a common modeling framework that can be run from a simple energy balance formulation to a complex mosaic type structure. The BSI is an uncertainty estimation technique based on Bayes theorem, importance sampling, and very fast simulated annealing. The model forcing data and surface flux data were collected at seven sites representing a wide range of climate and vegetation conditions. For each site, four experiments were performed with simple and complex CHASM formulations as well as realistic and global parameter ranges. Twenty eight experiments were conducted and 50 000 parameter sets were used for each run. The results show that the use of global and realistic ranges gives similar simulations for both modes for most sites, but the global ranges tend to produce some unreasonable optimal parameter values. Comparison of simple and complex modes shows that the simple mode has more parameters with unreasonable optimal values. Use of parameter ranges and model complexities have significant impacts on frequency distribution of parameters, marginal posterior probability density functions, and estimates of uncertainty of simulated sensible and latent heat fluxes. Comparison between model complexity and parameter ranges shows that the former has more significant impacts on parameter and uncertainty estimations.

16. Geochemical Fate and Transport of Sildenafil and Vardenafil

Richter, L.; Boudinot, G.; Vulava, V. M.; Cory, W. C.

2015-12-01

The geochemical fate of pharmaceuticals and their degradation products is a developing environmental field. The geologic, chemical, and biological fate of these pollutants has become very relevant with the increase in human population and the resulting increase in pollutant concentrations in the environment. In this study, we focus on sildenafil (SDF) and vardenafil (VDF), active compounds in Viagra and Levitra, respectively, two commonly used erectile dysfunction drugs. The main objective is to determine the sorption potential and transport behavior of these two compounds in natural soils. Both SDF and VDF are complex organic molecules with multiple amine functional groups in their structures. Two types of natural acidic soils (pH≈4.5), an organic-rich soil (7.6% OM) and clay-rich soil (5.1% clay) were used in this study to determine which soil components influence sorption behavior of both compounds. Sorption isotherms measured using batch reactors were nearly linear, but sorption was stronger in soil that contained higher clay content. Both compounds have multiple pKas due to the amine functional groups, the relevant pKas of SDF are 5.97 and 7.27, and those of VDF's are 4.72 and 6.21. These values indicate that these compounds likely behave as cations in soil suspensions and hence were strongly sorbed to negatively-charged clay minerals present in both soils. The clay composition in both soils is predominantly kaolinite with smaller amount of montmorillonite, both of which have a predominantly negative surface charge. Transport experiments using glass chromatography columns indicated that both compounds were more strongly retarded in the clay-rich soils. Breakthrough curves from the transport experiments were modeled using convection-dispersion transport equations. The organic matter in the soil seemed to play a less dominant role in the geochemistry in this study, but is likely to transform both compounds into derivative compounds as seen in other studies.

17. Geochemical Fate and Transport of Diphenhydramine and Cetirizine in Soil

Wireman, R.; Rutherford, C. J.; Vulava, V. M.; Cory, W. C.

2015-12-01

Pharmaceuticals compounds presence in natural soils and water around the world has become a growing concern. These compounds are being discharged into the environment through treated wastewater or municipal sludge applications. The main goal of this study is determine their geochemical fate in natural soils. In this study we investigated sorption and transport behavior of diphenhydramine (DPH) and cetirizine (CTZ) in natural soils. These two commonly-used antihistamines are complex aromatic hydrocarbons with polar functional groups. Two clean acidic soils (pH~4.5) were used for these studies - an A-horizon soil that had higher organic matter content (OM, 7.6%) and a B-horizon soil that had lower OM (1.6%), but higher clay content (5.1%). Sorption isotherms were measured using batch reactor experiments. Data indicated that sorption was nonlinear and that it was stronger in clay-rich soils. The pKa's of DPH and CTZ are 8.98 and 8.27 respectively, i.e., these compounds are predominantly in cationic form at soil pH. In these forms, they preferentially sorb to negatively charged mineral surfaces (e.g., clay) present in the soils. Soil clay mineral characterization indicated that kaolinite was the dominant clay mineral present along with small amount of montmorillonite. The nonlinear sorption isotherms were fitted with Freundlich model. Transport behavior of both compounds was measured using glass chromatography columns. As expected both DPH and CTZ were strongly retained in the clay-rich soil as compared with OM-rich soil. The asymmetrical shape of the breakthrough curves indicated that there were likely two separate sorption sites in the soil, each with different reaction rates with each compound. A two-region advection-dispersion transport code was used to model the transport breakthrough curves. There was no evidence of transformation or degradation of the compounds during our sorption and transport studies.

18. Boric acid adsorption on humic acids: Ab initio calculation of structures, stabilities, 11B NMR and 11B, 10B isotopic fractionations of surface complexes
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