text:
The Richelieu of Wisconsin
W hen Crowley returned to Madison in the spring of 1932 his future looked as gloomy as the economy whose ascent and collapse it had so closely paralleled. But only briefly. By the summer, he was an important force in Wisconsin, chairing its Banking Review Board and and salvaging its banks; a year after he was nominally the governor's aide but effectively running the state; in another two years he was managing a major federal agency and advising the president of the United States; and these were only the earlier signs of what would be a new and remarkable career in both government and business. Crowley was lucky: his good friend Albert Schmedeman was elected governor in a nationwide Democratic sweep in November 1932. But he also seized a meager opportunity months before when he might have remained in Florida paralyzed with despair.
Crowley had strong reasons to take the chairmanship of Wisconsin's Banking Review Board: the post offered some protection for Bankshares; it maintained his mask of community service, and it might open a future beyond the confines of his General Paper Company. The job would require visiting almost every hamlet in the state, talking nightly to depositors, bankers, and community leaders. But he could help save the economy of rural and small town Wisconsin, at the same making contacts that, coupled with a deeply depressed economy and a divided Republican party, might elect Schmedeman governor that November.
The problem facing the Banking Review Board was fairly simple. Banks depended on loan payments or foreclosures and sales to meet the demands of depositors. With the price of farm products and of farms having fallen sharply since the previous July farmers could not meet their loan payments, foreclosures did not provide liquidity, and


text:
Theresa M. Ringle
Senior Attorney
Indianapolis, IN
Theresa M. Ringle is an attorney and a former practicing architect with over twenty years of combined experience. As an attorney, Ms. Ringle possesses substantial experience working on a variety of complex insurance, risk management and litigation matters (including jury trial and bench trial verdicts). Although primarily a litigator with a focus on construction law and insurance coverage matters, Ms. Ringle's experience has touched on a variety of areas ranging from failed business transactions and acquisitions, mortgage fraud, director/officer claims, shareholder/ownership disputes, environmental contamination claims, products liability matters, securities claims, employment discrimination claims, breach of warranty disputes, UCC related claims, and the defense administrative appeals involving special education disputes pending in district courts. Ms. Ringle is also listed on the roster of construction law arbitrators for the American Arbitration Association.
Ms. Ringle's construction law practice includes contract drafting and negotiation, litigation and general construction law counsel services for individuals serving as in-house or general counsel for various entities, as well services for contractors, designers, private owners, public entities, insurance carriers, bond companies, and other law firms. Ms. Ringle's practice also includes services related to green building, risk management, professional liability and commercial general liability insurance topics, as well as the prosecution and defense of professional errors and omissions claims involving architects, engineers or construction managers. Ms. Ringle also has experience with defective workmanship claims; concealed, differing site condition and extra work claims; delay and impact claims; surety bond disputes; payment claims; mold litigation; public bidding disputes; building code violations; contractor default issues; takeover agreement negotiations; development impact fee and plat approval matters; mechanic's liens; environmental contamination claims; breach of warranty and UCC claims and other construction, and real estate and other design related disputes.
Registered Architect in Indiana, 1996 (Certificate 9600159, presently inactive)
American Arbitration Association Arbitrator, 2007-Present
American Bar Association member, 2000-Present
Minority/Woman fellowship recipient, 2011
Forum on the Construction Industry, member, 2000-Present, Division 3 steering committee, 2012-Present
Construction Litigation Subcommittee on Design Professional Liability, co-chair, 2010-2012
ALFA International (Global Legal Network) Construction Practice Group, member, 2007-2009
American Institute of Architects, individual member, 1993-1997, allied member, 2010-2012
The Jefferson Society, Inc., organized to establish a forum for architect lawyers, member 2012-Present
Indiana State Bar Association & Indianapolis Bar Association, member 2000-Present
Diversity Task Force member, 2007-2010, Women and Law Division executive committee, 2010-2014
Bar Leader Series Class IV, 2008
Indianapolis Bar Association, member, 2000-Present
National Institute for Trial Advocacy, member, 2000-2009
Indianapolis Women in Architecture, co-chair, 1996
Indiana University Robert H. McKinney School of Law, J.D.
Ball State University College of Architecture, B. Arch. and B.S. Env. Design
Ms. Ringle is also a frequent author, speaker, or panel moderator on various construction and insurance coverage related issues including:
Green Building and the Construction Lawyer – Energy and Water Performance Chapter Co-Author (ABA Book – Oct. 2014)
Construction Subcontracting: A Comprehensive Practical and Legal Guide – Design Contracts and Design Issues Chapter Co-Author (ABA Book 2014)
- Who Holds the Bag? Risk and Liability in Design Firm Mergers and Acquisitions (Oct. 2013); ABA CLE Metcalf Construction v. U.S.: How the Duty of Independent Site Investigation Negated Owner's Duty to Pay (July 2013
The Increasing Trend of Specifications Leading to Risky Performance Guarantees (February 2013)
ABA CLE Construction Statutes of Limitation and Repose: Crumbling Under Legislation and Immunity (January 2013)
My Design-Build Concept is Creative! Can The Owner Direct The Successful Design-Build Team To Use It? (October 2012)
The Crumbling Statute of Repose? (June 2012)
Construction Law Viewpoint; Under Construction Vol. 14 No. 3: Minnesota Determines That Victim Compensation Fund Legislation May Be Used To Revive Claims Barred By The Statute Of Repose (Sept. 2012)
Legal Issues for Professional Engineers; the Law of Engineering Malpractice; Professional Liability Insurance for Engineers; Professional Conduct of Engineers (2011, 2012)
Fifty State Compendium of Construction Law Issues – Indiana Chapter (Chapter Co-Author, 2008, 2009)
- Green Building Construction: A Practical Guide to Transactional and Litigation Issues (Chapter Co-Author, 2014)
- Provided contract review and modification services for a designer that helped remove significant risks outside of the scope of typical professional liability coverage.
- Resolved complex insurance coverage dispute triggering the appointment of Cumis counsel in response to insurer's reservation of rights as to its indemnity obligations in the underlying litigation.
- Defended public entity in parallel proceeding pending in the federal district court and the Seventh Circuit Court of Appeals. Prepared al legal briefs that successfully prompted the plaintiff's global settlement of all litigation for 10% of the plaintiff's last demand at mediation.
- Represented regional design firm faced with potential negligence and malpractice claims and advised the client regarding interpretation of its professional malpractice and commercial general liability insurance policies. Legal advice enabled the client to amicably resolve potential claim issues prior to litigation and avoid potential liability for construction delays.
- Represented public entity in the prosecuting and successful settlement of claims against the project participants including claims that the HVAC system design failed to comply with the applicable standard of care.
- Represented national commercial real estate management company in litigation asserting third-party beneficiary breach of contract claims against a subcontractor for a defectively installed roof. Negotiated successful settlement after early disclosure of the client's expert witness report and prior to incurring costs to litigate.
- Represented multiple defendants in the United States Federal District Court and the Seventh Circuit Court of Appeals in a commercial dispute involving a credit default swap as part of a $120 million financing transaction.
- Defended a national engineering firm and one of its professional engineers in litigation asserting that personal injuries were caused by the defendants' negligent design and their failure to comply with the applicable standard of care. Litigation was resolved favorable to client.
- Represented private property owner with defective product and construction claims against the project's contractor and product manufacturer. Negotiated successful settlement including monetary payment and the replacement of the defectively manufactured product and construction prior to initiating formal litigation.
- Successfully defended taxpayer's preliminary injunction claims seeking to enjoin school corporation client's award of public works project to low bidder based on allegations that the project's plans and specifications unfairly prohibited competition and allegations that the low bid was unresponsive.
- Successfully defended client in United States Federal District Court in litigation seeking injunctive relief and damages. Injunctive relief was denied and the litigation was settled in the client's favor.
- Served as lead litigation counsel in a matter of upholding a favorable underlying administrative hearing decision appealed to the United States Federal District Court after a bench trial on plaintiff's additional evidence. Service as lead counsel continued in the Seventh Circuit Court of Appeals. The Seventh Circuit issued a ruling in the client's favor finding that the plaintiff's claims were rendered moot as a result of the plaintiff's actions pending appeal and the plaintiff's failure to properly plead her damages claim.

subset: commoncrawl


text:
Thomas Lottermoser
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Bean Soup
Bean Soup is as bare bones as you can get. Toss in some greens for a dose of folic acid and vitamin C.
Grilled Chicken with Feta and Red Pepper Sauce
Sweet pepper sauce is a perfect counterpoint for full-bodied feta in this herb-grilled chicken.
At the top of our list of recipes we like to make when the weather gets really hot is gazpacho. The cold soup, from the Andalusia region of southern Spain, is a wonderful midsummer treat.
Gingered Peach Crisp
Minced crystallized ginger elevates a simple summer crisp from "nice" to "spice."
Broiled Peach Halves with Vanilla and Black Peppercorns
Pepper-accented peaches can go either sweet or savory.
Huckleberry Pie
Huckleberries are smaller and sweeter than commercially-raised blueberries, but blueberries can easily substitute in this pie.


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2006 Mazda 3 • 136,000 miles
My car shudders at 45mph and then stops at 50mph, but only in the automatic transmission setting, not in the manual setting. It shakes around right hand turns above 20mph. The primary area of the shaking is the steering wheel. You can feel it in the floor boards nut not much. The tansmission fluid, oil, and coolant are new so are the spark plugs. The front tires are old and need replacing. The rear tires are new. The front right side suspension looks crudy, the left does not. The # 3 and 4 motor mounts look fine. The car when cold idles at 1,500 to 2,000 rpms. When warm it idles at 600. The a/c makes the revs go up and down and the car rattles. This is everything I can think of. Thank you for your help.
February 6, 2013.
February 6, 2013.
Check the CV shaft inner joints.
Have the throttle body and IAC cleaned. The idling speed is too low.
Have the throttle body and IAC cleaned. The idling speed is too low.
Feb 7, 2013.
Feb 7, 2013.
I purchased a new tire gauge and would like to determine the true pressure based on the reading, the outdoor temperature, and the number of miles traveled immediately before testing. ...
1 answer • 2008 Hyundai Elantra • 74,150 miles
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1 answer • 1998 Toyota Revo • 165,000 miles
I purchased a set of tires for my EXT and after installing them, I noticed the "Service Tire Monitor" appeared on the dash. The people did not know how to reset, pls advise how I may ...
2 answers • 2004 Cadillac Escalade Ext • 101,010 miles
2LT AWD...The original set of Goodyear Fortera tires lasted 46000 miles before cupping and becoming really loud. I switched to the Cooper CS4 Touring (60,000 mile tread life) from ...
3 answers • 2009 Chevrolet Traverse • 79,000 miles


text:
Festivals are a highlight of any Dollywood vacation. No matter what time of year you visit, the Pigeon Forge Theme Park has special shows, activities and entertainment planned to make your day at the park even more exciting. The featured festivals, along with the more than 40 rides and attractions, are part of the award-winning theme park located in the foothills of the Smoky Mountains.
Here's a quick guide to Dollywood Festivals in 2015:
Festival of Nations
March 21 – April 20
Celebrate music, dance, food and art from around the world during this captivating festival. New shows scheduled for this year include Rhythm of the Dance and Alash Ensemble.
BBQ & Bluegrass
May 23 – June 7
This free concert series has some of the biggest names in bluegrass music and some of the best BBQ in the country. Enjoy two of the best southern traditions at this Dollywood festival.
Great American Summer
June 13 – August 2
Nightly fireworks show and the Great American Country Show will celebrate summer during The Great American Summer Festival.
National Southern Gospel & Harvest Celebration
October 2 – October 31
Southern gospel music takes center stage while master craftsmen demonstrate their skills at the National Southern Gospel & Harvest Celebration.
Smoky Mountain Christmas
November 7 – January 2
This spectacular event features dazzling light displays, exciting live Christmas shows, Santa's Workshop, the Polar Express Experience and more.
Reserve a Dollywood vacation package today to experience all the 150-acre theme park has to offer. You can easily combine your day at the park with Splash Country, Dolly Parton's waterpark located next door. Both are two of the best ways to have family fun in the Smokies.
Ashley is Reserve Direct's travel expert, visiting Pigeon Forge to find the best travel tips, money-saving deals and insider information. With over 10 years of experience in first-hand-travel adventures, she shares her stories, advice, and current events to help you stay in the know.


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Download this free, 104-page Labeling Playbook jam-packed with strategies for success, best practices, and pitfalls to avoid.
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Sheboygan Falls High School student Amy Zhang's novel 'Failling into Place' is now available for pre-order.
- Filed Under
Sheboygan Falls High School student Amy Zhang and her publisher, Greenwillow Books of HarperCollins Publishers, has announced the title of her most recent novel, "Falling into Place." The book will be released Sept. 9 but is available now for pre-order.
According to the summary of Zhang's book: On the day Liz Emerson tries to die, they reviewed Newton's laws of motion in physics class. Then, after school, she put them into practice by running her Mercedes off the road. Amy Zhang's haunting and universal story will appeal to fans of Lauren Oliver, Gayle Forman, and Jay Asher, according to the publisher.
Zhang can be followed on Twitter at twitter.com/amyzwritesm, on Tumblr at amyzhangwrites.tumblr.com, on Facebook at facebook.com/pages/Amy-Zhang/592234500806772 and on her blog at astoryofadreamer.blogspot.com.


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Written on: 23/11/2012 by mirren09 (1 review written)
The range of choice is excellent, cheap prices, easy to order and very quick service. Good web page for browsing.
As rated by our community of reviewers
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" This is poo " Read More
" Giant Tower - Garden Jenga " Read More
Written by JulieNeimantas


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Software. Running. Bball. Inquisitive. Lazy. Liberal. I drive a prius. German Shepard with white coating.
Join OkCupid
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27 • Arlington, VA • Man
I'm looking for
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- Agnosticism and it's important
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Write a little about yourself. Just a paragraph will do.
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Help your potential matches find common interests.
The Idiot - Fyodor Dostoevsky, Malcolm Gladwell, David Copperfield, V for Vendetta, Big bang theory, Gone Girl
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Think outside the box. Sometimes the little things can say a lot.
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2) imagination
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4) empathy
5) love
6) water
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Global warming, lunch, or your next vacation… it's all fair game.
-words, i love words
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On a typical Friday night I am
Netflix and takeout, or getting your party on — how do you let loose?
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-learning how to tolerate my own/others emotions
-observing humanity
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you have a greater attention span than that of a baboon
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Or are we somehow suggesting that bank has any relation or comparison to the Federal Reserve Bank as we see it today?
Shortly after Hamilton proposed the creation of a National Bank for the U.S. a bill was introduced into Congress to accomplish Hamilton's proposal. There was major opposition to the bill on the grounds that creation of such a bank with a monopoly on issuing money was unconstitutional. The bill passed and was signed into law in 1791 but it provided only a twenty year charter for a Bank of the United States. The charter would need to be renewed in 1811.
The Bank of the United States solved many of the monetary problems that troubled the country before 1791. But the Bank of the United States was a private institution and foreign buyers purchased ownership shares of the bank until the 70 percent of the bank was owned by foreigners. This was worrisome to American politicians but this high share of foreign ownership was not unusual in the American financial system. Britain had been supplying capital to the U.S. economy for some time.
The First Bank acted as the federal government's fiscal agent, collecting tax revenues, securing the government's funds, making loans to the government, transferring government deposits through the bank's branch network, and paying the government's bills.15 The bank also managed the Treasury's interest payments to European investors in U.S. government securities.16 Besides its activities on behalf of the government, the Bank of the United States also accepted deposits from the public and made loans to private citizens and businesses.
James Madison, who represented Virginia in the House of Representatives, opposed the bank for similar reasons.8 In particular, he objected to the bank's proposed 20-year affront to states' rights and would make the states too subservient to the new federal government. Moreover, agreeing with Jefferson, many of the people who opposed the bank said that the Constitution did not grant the government the authority to establish banks. Still others thought that a national bank would have a monopoly on
government business, to the detriment of the state chartered banks.9


text:
Information technology is one of the corner stones of modern society. It is also a key driving force of the western economy, contributing substantially to economic growth by productivity gains and the creation of new products and services. All this was made possible by the uninterrupted exponential growth in computation, communication and storage capacity of the previous decades. Unfortunately, this now seems to have come to an end. Growth is predicted to slow down due to the fundamental laws of physics, and an increasing number of people are getting worried about the adverse effects of the progressively omnipresent use of information technology: loss of privacy, the impact on the job market, security and safety.
Devices will be more and more connected, entangled physically, cognitive and smart and requiring more and more computational, storage and communication resources. To ensure the further growth of information technology and to address these concerns, several key challenges need to be tackled.
Future computing systems will have to be more reliable - preferably secure, safe and dependable by design.
As the complexity of systems will further increase, we need HIGH PERFORMANCE AND EMBEDDED ARCHITECTURE AND COMPILATION.
Energy is currently the limiting factor of performance. We need solutions to dramatically increase the energy efficiency of information systems. The Internet of Things and cyber physical systems monitor and control the physical world and lead to an entanglement between the physical and virtual world. We need models and techniques for information systems to naturally interact, analyze and interpret the physical world.
Computing is used in all domains of human activity – and not just by computer scientists. We must develop better tools and models for non-computer scientists to design their own information systems and push for multidisciplinary approaches. Systems of those systems which are only locally optimized are not globally optimal. We need a more holistic approach to system design, taking into account functional and non-functional requirements.
In the next decade, several exponential growth laws will slow down. We must search for and industrially develop alternative technologies to continue the performance growth of information systems.
© 2004-2015 HiPEAC
The HiPEAC project has received funding from the European Union Seventh Framework Programme (FP7-ICT) under grant agreement number 287759.


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Registration takes less than 1 minute.
The four new Super Post-Panamax ship-to-shore cranes manufactured by Konecranes, which will operate at the Barbours Cut Container Terminal, will stand taller than any other marine cranes in North America.
Centiro has named a VP for global sales, while the Ports of Indiana Commission has added a new member.
Raymond P. Miles, who built up the containership operations of CP Ships during the late 1990s, died Nov. 6 at the age of 71 following a brief illness.


text:
Lesbian RomanceFavorites [+]
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Released: 08/2012
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A portion of couscous +
a portion of grilled halloumi +
a portion of Tesco stir fry vegetables, asparagus and mushrooms stir fried with soy sauce.
Season with lemon, black pepper and salt if you like.
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- LOVE life Mediterranean roasted halloumi with basil dressing (millasrecipes.wordpress.com)


text:
KPMG has been recognised for forward-thinking leadership and exceptional commitment to client support.
What start-ups need to consider? Where to get access to information? What events they can consider to attend?
The purpose of this publication is to assist you in understanding the financial statements of companies in the media sector that are prepared in accordance with IFRSs. The focus has been to provide an understanding of the approaches taken by media companies in dealing with some of the sector-specific accounting issues that they face; and to illustrate disclosures made by these companies in their consolidated financial statements that the ISG believes are useful in assessing the type of information being disclosed in practice, and the formats and methods of disclosure.
Each section is accompanied by survey results and a high-level summary focusing on media-specific issues. A summary of the main differences between US GAAP and IFRSs also is included.
This publication is based on a review of the consolidated financial statements of 28 media companies from 15 countries.
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KPMG Advisory (China) Limited, a wholly foreign owned enterprise in China and KPMG Huazhen LLP, a People's Republic of China partnership, are member firms of the KPMG network of independent member firms affiliated with KPMG International Cooperative ("KPMG International"), a Swiss entity. All rights reserved.
© 2015 KPMG, a Hong Kong partnership and a member firm of the KPMG network of independent member firms affiliated with KPMG International Cooperative ("KPMG International"), a Swiss entity. All rights reserved.
The KPMG name, logo and "cutting through complexity" are registered trademarks or trademarks of KPMG International.
KPMG International Cooperative ("KPMG International") is a Swiss entity. Member firms of the KPMG network of independent firms are affiliated with KPMG International. KPMG International provides no client services. No member firm has any authority to obligate or bind KPMG International or any other member firm vis-à-vis third parties, nor does KPMG International have any such authority to obligate or bind any member firm.


text:
S.815 - Employment Non-Discrimination Act of 2013113th Congress (2013-2014)
|Sen. Merkley, Jeff [D-OR] (Introduced 04/25/2013)
|Senate - Health, Education, Labor, and Pensions | House - Education and the Workforce; House Administration; Oversight and Government Reform; Judiciary
|Committee Reports:
|S. Rept. 113-105
|Latest Action:
|01/08/2014 Referred to the Subcommittee on the Constitution and Civil Justice. (All Actions)
|Major Recorded Votes:
|11/07/2013 : Passed Senate
|On 9/17/2014, a motion was filed to discharge the Committee on Rules from the consideration of H.Res.678 a resolution providing for consideration of S.815. A discharge petition requires 218 signatures for further action. (Discharge Petition No. 113-11: text with signatures.)
This bill has the status Passed Senate
Here are the steps for Status of Legislation:
- Introduced
- Passed Senate
Subject — Policy Area:
- Labor and Employment
- View subjects
Summary (3)
Text (4)
Actions (51)
Titles (5)
Amendments (12)
Cosponsors (56)
Committees (5)
Related Bills (3)
Amendments: S.815 — 113th Congress (2013-2014)All Bill Information (Except Text)
See amendments glossary definition
1-2 of 2
S.Amdt.2013 — 113th Congress (2013-2014)
Description: To strike the appropriate balance between protecting workers and protecting religious freedom. Sponsor: Sen. Toomey, Pat [R-PA] (Submitted 11/06/2013) (Proposed 11/06/2013) Cosponsors: 2 Latest Action: 11/07/13 Amendment SA 2013, under the order of 11/6/13, not having achieved 60 votes in the affirmative, was not agreed to in Senate by Yea-Nay Vote. 43 - 55. Record Vote Number: 230.
S.Amdt.2012 — 113th Congress (2013-2014)
Description: To promote fairness and equal opportunity in the workplace consistent with the fundamental right of religious freedom. Sponsor: Sen. Portman, Rob [R-OH] (Submitted 11/06/2013) (Proposed 11/06/2013) Cosponsors: 4 Latest Action: 11/06/13 Amendment SA 2012 agreed to in Senate by Voice Vote.


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Garland City, Ark.: Homicide suspect in custody
Man turned himself in, has been charged with second-degree murder
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A man officials had sought since a fatal shooting in Garland City, Ark., on Friday turned himself in Monday and has been charged with murder.
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Villa "mon Cheri" with 15% discount!
from £140 /night help Price for guests, Nights approx:
9 reviews
from £140 /night help Price for guests, Nights approx:
Estimated nightly price based on a weekly stay. Excludes fees (if applicable). Enter your dates to see the total cost.
Beautiful large 3 bed sea view villa..3 bathrooms..large plot.Very private garden…LRG pool...
Villa / 3 bedrooms / sleeps 7 Home 117070
Availability Your dates are available
Villa / 3 bedrooms / sleeps 7
|Key Info
WE GUARANTEE YOU WILL HAVE A GREAT STAY WITH Us !!!! FULLY MANAGED BY US...
.Great Family villa.....very private garden....peaceful surroundings....awesome views....convenient location...15 minutes drive from Paphos air port
BOOK this Stunning Luxurious large 3 bed villa!! we have set the highest standards with this villa ,and it is located in the heart of the elite Secret Valley Golf Course. A light & airy with a large 10m x 5m private pool & landscaped fenced garden with fan palms & car port. The villa enjoys day-long sun or if you prefer it cool, the shady terrace is the perfect place to relax or dine al fresco with pool and outstanding sea views.
.............The villa is home from home with quality furnishings throughout.......!!!!!!!!NEW FURNITURE 2012!!!!!!!
The swimming pool is kept to the highest standards always and is kept crystal clear,and the large garden has different fruit to eat throughout the year.
Large Master bedroom with en-suite has its own spacious balcony with spectacular all round sea views. Visitors enjoy the best of both worlds - a quiet rural location within easy reach of all amenities: 10 minutes from Paphos Airport, less than 20 minutes to Paphos Centre, 3 minutes from the golf course & 5 minutes from Aphrodite Hills. Traditional Cypriot villages with excellent restaurants are also nearby.
Note ....3rd bedroom has pull also out so can fit 1 more person if required....
We look after this villa personally as we only live a short distance away.We come and meet you and ensure you off a fab stay.
We guarantee satisfaction...And can send our owner comments...
Call now to get a great deal....no agents ....owner direct....
|Sleeps up to 7, 3 bedrooms
|3 bedrooms, 3 bathrooms of which 1 Family bathrooms, 1 En suites and 1 Shower rooms
|Nearest beach
|Aphodite rock 1 km
|Will consider
|Corporate bookings, House swap, Long term lets (over 1 month)
|Car advised
|Nearest Amenities
|2 km
|Nearest travel links
|Nearest airport: Pafos 10 km
|Family friendly
|Great for children of all ages
|No pets allowed, No smoking at this property
Features and Facilities
|Internet access, DVD player, Sea view
|Private outdoor pool (unheated)
|Central heating, Air conditioning, TV, CD player, Telephone, Pool or snooker table, Table tennis, Safe, Satellite TV, Wi-Fi available
|Kettle, Toaster, Iron, Hair dryer
|Clothes dryer, Dishwasher, Cooker, Microwave, Fridge, Freezer, Washing machine
|1 Sofa beds, Double beds (2), Single beds (3), Cots (1), Dining seats for 8, Lounge seats for 7
|Linen provided, High chair
|Private outdoor pool (unheated), Balcony or terrace, Private garden, BBQ, Bicycles available
|Secure parking, Suitable for people with restricted mobility, Not suitable for wheelchair users
|Further details indoors
Call NOW .......08001700582....08001700582......or 0035796339688...0035799105621...
Our Family owned villa is perfectly located in secrete valley,It has a large plot,quality furniture,large pool,ample lounging and out door eating areas with new Ratan furniture new 2012 and comfortable sofa new 2012.It has modern TV play station games and a selection of DVD.You can NOW NEW FOR 2012--2013...also hire a pool table,table tennis,table football.It is looked after personally by us so we guarantee you have a great stay,,,Most off our guests are now are friends and book teat after year,,We can provide ref anytime also look at our comments on our site. BOOK OUR VILLA AND ENSURE A PEACEFUL STAY!! 0035796339688 CALL Paul or Cheryl 0035799105621.
|Further details outdoors
The Property boasts lush spacious gardens with plenty of area for activities and space to lounge around the pool.
Plenty of area for kids to play the plot is around 800 SQ meters.It has a large carport for you car,Fruit garden,Large green area to lay,sit and play games on.The garden is secure and private with large bushes all round.
If your a golfer it is only minutes away from the local course and a few more minutes to Aphrodite and Elea golf course pool table..table tennis...table football... WIIFI AVAILABLE
Secrete Vally new championship golf course is now open...WE CAN HELP WITH DISCOUNTS ON GOLF COURSES....
|Further details
We are proud of our villa and enjoy making clients happy,We are at hand and can answer any questions you may have before you book.We supply a free welcome pack and have a full list of great places to eat and travel around.
WE are hands on and our goal is your perfect holiday,,,check our comments out...We ensure our customers are happy!!!!!
Call us and we can help with any questions you may have...
Call to book or email .....08001700582....
The Paphos District
Located in the prestigious Secret Valley just 10 minutes from Paphos Airport and the lovely Cypriot village & beach of Pissouri, Secret valley Villa is also only a couple of minutes from the golf course and 5 minutes from Aphrodite Hills Resort and Golf Club & Aphrodites' Rock. Less than 20 minutes away is the lively tourist town of Paphos with its restaurants, shopping centres and nightlife as well as historical attractions. For a true Cypriot experience, enjoy the excellent local food and wines served in friendly tavernas in nearby traditional villages like Kouklia and Pissouri. Whether it's golfing, water sports, sightseeing, sunbathing, shopping, walking, touring, eating and drinking or just relaxing in privacy by the pool, this villa has something to offer everybody.
Ha Potami Phase B
Secret Valley is a 15 minute drive out of Paphos next to Aphrodite Hills. It is conveniently situated near enough to the airport without it being imposing and is within a ten minute drive of some lovely traditional Greek tavernas. It is 2 minutes drive to the NEW Championship Secret Valley Golf club, 5 minutes from Aphrodite Hills Golf, Hotel and Leisure complex, 10 minutes to Elea golf course...20 minutes from Tsada Golf club Locally, you can explore Aphrodite's Rock, the Tomb of the Kings, beaches, water-sports, the water-park and enjoy the lively atmosphere of Paphos, 15 minutes drive away, with its harbour, restaurants, bars and nightclubs. Alternatively, savour the excellent food and wines in the quieter tavernas in nearby Pissouri and Kouklia with their gentle and friendly character. For the more adventurous why not try skiing in the Troodos mountains 75 minutes away or, take a day trip to Beirut or an inexpensive 2-day round cruise to Egypt to see the Pyra
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11 Nov 2014
"Very peaceful."
The Villa is in a nice location for peace and quiet and is a nice size both inside and out. Nice sized pool.. The Villa is starting to show its age but remains comfortable and was very clean both times we have used it..
Thank you for your review which is very important to us so that we can continue improving our villa and what we provide for our guests. Since your holiday in October the villa has been repainted inside and out and a new mattress is on order for the bed in the master room. Work is always done during the Winter months as the villa is fully booked throughout the rest of the year. We are really pleased to hear that you again enjoyed the villa and your holiday and look forward to your return in 2015 :)
14 Jan 2014
"Nice and comfortable house for family holiday in quiet place for good rentle price."
You will need a car to go somewhere from the villa. The owners are very good people! Grate hospitality!
7 Sep 2013
"Beautiful Villa"
What a lovely and relaxing holiday. The villa was perfect, great location, clean, comfy and perfect for children. The pool was excellent, well maintained and we couldn't keep the kids out of it. The owner Cheryl is such a lovely lady and friendly, we only met her once but it felt like we had known her for a long time. I would suggest hiring a car when you book a stay at this villa to visit places like Coral Bay and a drive to Troodos is a must, we saw these amazing mountain views and also went horse riding in Troodos which i really enjoyed. We will definitely be booking our next holiday and looking forward to another stay at this beautiful villa. Thank you Cheryl
15 Jan 2013
"Very relaxing"
Beautiful clean house with a to-die-for pool. The views are fantastic and you get a great sunset from the balcony. Two minutes from Secret valley Golf course and 10 from Aphrodite Hills GC Although a little far away from it all, it was just what the doctor ordered.."Peace & quiet" Only a 10 minute car journey to the lovely Pissouri village or Mandria for fish & Chips. Teena and I loved our stay and we will be back
25 Nov 2012
"Perfect villa in a perfect location for a relaxing, peaceful break!"
For those looking for a quiet relaxing holiday in beautiful surroundings you couldn't ask for more! You will need a car due to its slightly remote location but that's why we chose it & weren't disappointed! Excellent service from Paul & Cheryl & we are already planning our 2013 visit!
31 Oct 2012
"Cracking Cyprus"
Our holiday in this property was just what we wanted, an excellent, clean house with a large clean pool. There is plenty of room to either join in with the family fun or sit in a corner with a good book. The house is on an estate, but you rarely see or hear any neighbours. The shops are not too far away. The Cypriots are very friendly, speak good English and are very helpful. Cyprus is beautiful and exploring is easy - they drive on the same side of the road as the UK, We have stayed at this house twice, once in 2010 and once in 2011 - it is definitely a holiday home you would return to.
12 Oct 2012
"Stunning Villa and peaceful location"
This is now the 3rd year in a row that we have stayed in this villa in Secret Vally. It is a real home from home, beautifully decorated, maintained to a high standard and equipped with everything you need for a perfect holiday. The garden is beautiful and well established with trees, flowers and fruit trees. The private pool is a good size and a great way to enjoy the hot days. Secret Valley is very peaceful with access to all amenities just a short drive away. Located approximately 20 minutes drive from the lovely village of Pissouri where you will find a great beach (which never gets too busy) and full selection of restaurants offering both International and local cuisine. We have come to know the owners of this property very well during the past few years and they are close at hand should you have any problems or require any local information. I highly recommend this property to make your holiday in Cyprus a truly wonderful one!
This advert is created and maintained by the advertiser; we can only publish adverts in good faith as we don't own, manage or inspect any of the properties. We advise you to familiarise yourself with our terms of use.
You're booking with
Paul / Cheryl Hann (Property Manager PAUL HANN RENTYOURCYPRUSPROPERTYS LTD)
- 6 Years listed
65% Response rate
Calendar last updated:12 Oct 2015
Based in
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- English
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The Past Perfect Collection - Top Quality Antique Colonial Furniture
An unrivalled choice of antique furniture spanning the British, Dutch and Portuguese era in India. Imagine the romance of colonial European style courting Indian craftsmanship! Add that special character to your home. 896, Dunearn Rd, Sime Darby Centre.


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Preston — It was a pyrotechnics display impressive enough to rival a Hollywood action flick and rattle a few windows at the former Norwich Hospital property.
FBI bomb technicians on Wednesday used everything from household chemicals to full sticks of dynamite to demonstrate an array of explosions — creating a wall of fire, sending a burning tire 100 feet into the air and rattling observers with a concussive impact.
They even blew up a Perdue oven roaster chicken to demonstrate the impact of an explosion on the human body.
The demonstration was day three of a five-day post-blast bomb school hosted by the FBI's New Haven division and Connecticut State Police Emergency Services Unit.
More than 60 local, state and federal law enforcement personnel, including a Norwich police officer, are learning to investigate crime scenes through the recovery and reconstruction of bomb components, crime scene analysis, interviews and other techniques, said FBI Special Agent Sam DiPasquale, a bomb technician coordinator.
"There's a big difference between talking about it in a classroom and actually seeing and hearing it," DiPasquale said.
Course participants on Wednesday picked through the debris left by the explosions and later this week were expected to develop probable cause for an arrest after visiting one of five different rooms in one of the sprawling buildings on site. Bombs were detonated inside the rooms, creating a post-blast scene ready for investigation.
"It's the real deal," DiPasquale said. "Investigation should lead to an arrest and prosecution."
FBI Special Agent Tim Petrousky, a bomb technician and instructor from Baltimore, narrated the day's demonstration. He showed how, with the right mixture, commonly available items such as brake fluid, anti-freeze or ammonia could be used to make an improvised incendiary device.
Preston Fire Marshal Thomas Casey, who completed the course five years ago, said the skills necessary to identify bomb components, or recognize when a certain chemical was used, are unfortunately needed "in the world we live in today."
Norwich Police Officer Robert Smith, a member of the city's arson task force, said the training will be useful in future investigations — especially the ability to identify certain bomb-making materials or chemicals used to start a fire.
"It's absolutely valuable, probably one of the best instructional classes I've been to in a long time," Smith said.
With the April bombing in Boston still fresh on their minds, members of the Hartford Marathon Foundation took the opportunity to watch the explosions and planned to pass along information to members of their security team.
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Bono, Clooney, Kardashian part of all-star campaign for AIDS
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A Cure For Cat Allergies?
by Chris Malone
posted Jul 29 2013 5:27AM
Take a look at this study that has identified how cat dander triggers allergic reactions, and the discovery could lead to new treatments for people with pet allergies.
Read the story here.
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UNIVERSITY PARK — SMU finally has depth on defense, having stocked the program with faster and more athletic prospects.
The Mustangs can only hope their young players develop as quickly as they run. Deadline for realizing potential is Aug. 31, when SMU opens against reigning Big 12 champion Baylor.
The Mustangs, prone to injuries and big plays last year, are confident their numbers equal strength.
"All in all, the young guys have done a good job of coming together, hustling and playing hard," coach June Jones said. "But they are going to have to grow up in a hurry."
With SMU's offense in transition from the departure of quarterback Garrett Gilbert, the need for help from the defense is dire.
Sophomore quarterback Neal Burcham may develop into a top-ranked passer. But it's a tad unrealistic to think he's going to win a shootout over one of the nation's most prolific offenses. Or against their other nonconference opponents, North Texas, Texas A&M and TCU.
The Mustangs ranked 114th nationally in pass defense (271.8 ypg) and 100th in points allowed (33.3) last season.
They surrendered at least 41 points five times, including 52 to Rutgers and 49 to Temple. And they ranked 101st with a minus-7 turnover ratio.
But young players pressed into duty last year should benefit from experience.
"We've had problems keeping our corners healthy but up front we're three or four deep with pretty good football players there," defensive coordinator Tom Mason said. "It really helps a lot."
The Mustangs are so deep in the front seven that Beau Barnes has gone from starting defensive end last season to backup outside linebacker midway through training camp.
Junior Zach Wood and highly touted sophomore Zelt Minor will probably be the starting ends with Mason Gentry, Elie Nabushosi and Cameron Smith also competing for time.
Senior Darrian Wright and junior Andrew McCleneghen appear to be Nos. 1 and 2 at nose tackle.
Competition at the four linebacker positions has been intense with the addition of Cameron Nwosu, a former starter at Rice, and junior college transfer Caleb Tuiasosopo joining the mix.
Likely starters would be Stephon Sanders, who posted 86 tackles, 13.5 for loss in 2013, on the strong side (backed by Derek Longoria), Nick Horton (backed by Nwosu and John Bordano) and Jonathan Yenga (backed by Tuiasosopo and Jackson Mitchell) starting in the middle and Robert Seals in front of Barnes on the weak side.
Mason has all sorts of looks he can experiment with. Outside linebackers Sanders and Horton are also getting looks on the inside.
"That will change even as we go through camp," Mason said. "We have a pretty good nucleus of experienced linebackers and we are so much faster than we've ever been."
One of the tightest camp battles is between free safeties Shakiel Randolph and Hayden Greenbauer, sidelined last year by a knee injury. At strong safety, Darrion Richardson is trying to hold off A.J. Justice.
Injuries, though, continue to haunt the cornerbacks. Projected starter J.R. Richardson has had one practice. Recovering from complications with sickle cell, he is awaiting medical clearance. His status remains uncertain.
Sophomore Horace Richardson, the starter at right cornerback, has missed several practices with an undisclosed injury. Behind him is redshirt freshman Jesse Montgomery.
Ajee Montes and Trey Washington are competing on the left side where Richardson would be.
Considering that all the corners are sophomores, lack of experience is a concern.
"I feel like we'll be in nickel a lot and the dime package more because we're so deep at safety," Horace Richardson said. "We've got a lot of good talent on the corners but they just have to get the system down."
SMU's defense showed improvement down the stretch last year. With experience and key personnel additions, the Mustangs may turn the close losses of 2013 — seven losses by 10 or fewer points — into wins.
"It's just a whole different world when you've got bodies in there that can play," Mason said.
In the Know...
Coach: June Jones
Record: Seventh year at SMU, 36-41 overall
Returning starters: Five offense, six defense
Can new QB learn fast? After tailoring the offense for senior Garrett Gilbert, who ranked second nationally in total offense, the Mustangs must tweak the playbook again for sophomore Neal Burcham. Transfer Matt Davis has mobility but lacks Burcham's knowledge of the run and shoot.
Will special teams improve? A major weakness last year, except for kicker Chase Holder, this unit reboots with a new kicker (Cody Rademacher), punter (Jackson Koonce) and punt returner (Ryheem Malone), and freshman Darius Durall will probably join Deion Sanders Jr. on kickoff returns.
Will Mustangs survive rough beginnings? Breaking in young players at key positions will be complicated by a tough non-conference schedule. Big losses can rattle confidence, but strong opposition can hasten growth. Minimizing injuries and accentuating positives will be essential to survival.
Will program continue to progress? June Jones has led the Ponies to four bowls in the last five seasons, and his contract was renewed after last season. But in turning the program around, he has raised expectations.
Stumbling block: For a young team it's hard to envision a worse opener than Baylor — reigning Big 12 champs, Heisman Trophy candidate at quarterback who has five of his top six targets returning, a Sunday night game on the banks of the Brazos in new McLane Stadium.
Aug. 31
at Baylor
Sept. 6
at North Texas
Sept. 20
Texas A&M
Sept. 27
Oct. 4
at East Carolina
Oct. 18
Oct. 25
Nov. 8
at Tulsa
Nov. 15
Nov. 22
at UCF
Nov. 28
Dec. 6
at Connecticut
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Publications (112)521.48 Total impact
Article: Synthesis of the Stable Ordered Conjugated Polymer Poly(dibromodiacetylene) from an Explosive Monomer[Show abstract] [Hide abstract]
ABSTRACT: Dibromobutadiyne is an extremely unstable compound that explodes at room temperature, even under inert atmosphere. This instability has limited the studies of dibromobutadiyne almost entirely to spectroscopic characterization. Here we report an approach to control the reactivity of dibromobutadiyne, via topochemical reaction in cocrystals, leading to the ordered polymer poly(dibromodiacetylene), PBDA. At low temperatures (-15 to -18 °C), dibromobutadiyne can form cocrystals with oxalamide host molecules containing either pyridyl or nitrile side groups, in which halogen bonds align the dibromobutadiyne monomers for topochemical polymerization. The cocrystals with the bis(nitrile) oxalamide host undergo complete ordered polymerization to PBDA, demonstrated by solid-state MAS-NMR, Raman, and optical absorption spectroscopy. Once formed, the polymer can be separated from the host; unlike the monomer, PBDA is stable at room temperature.Angewandte Chemie International Edition 10/2015; DOI:10.1002/anie.201504713 · 11.26 Impact Factor
Article: Maskelynite Formation via Solid-State Transformation: Evidence of Infrared and X-Ray Anisotropy[Show abstract] [Hide abstract]
ABSTRACT: We present the results of a combined study of shocked labradorite from the Lonar Crater, India, using optical microscopy, micro-Raman spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, high-energy X-ray total scattering experiments, and micro-Fourier transform infrared (micro-FTIR) spectroscopy. We show that maskelynite of shock class 2 is structurally more similar to fused glass than to crystalline plagioclase. However, there are slight but significant differences – preservation of original pre-impact igneous zoning, anisotropy at infrared wavelengths, X-ray anisotropy, and preservation of some intermediate range order – which are all consistent with a solid-state transformation from plagioclase to maskelynite.The Journal of Geophysical Research Planets 02/2015; 120(3). DOI:10.1002/2014JE004764 · 3.44 Impact Factor
Article: A 31P NMR and TG/DSC-FTIR investigation of the influence of initial pH on phosphorus recovery as struvite[Show abstract] [Hide abstract]
ABSTRACT: Phosphorus can be reclaimed from nutrient-rich sources as the mineral struvite (MgNH4PO4·6H2O) for reuse as fertilizer. This study determines the impact of initial pH (pHi) from 8 to 11 on the fraction of precipitated struvite from a MgCl2–(NH4)2HPO4–NaCl–H2O system. The rate of P removal from solution increases with pHi and maximizes at pHi 10. Scanning electron microscopy (SEM) of recovered precipitates shows changes in morphology and decreasing particle size with increasing pHi. 31P nuclear magnetic resonance spectroscopy (NMR) confirms that struvite constitutes 96–99% of the phosphate at pHi 8–10, with newberyite (MgHPO4·3H2O) as a minor crystalline phase. At pHi 11, 60% of the solid is struvite, with 22% of the phosphate contained in an amorphous phase and 18% as sodium phosphate. Thermogravimetric analysis (TG) reveals a correlation in the mass loss from the solids with the percentage of struvite detected. Coupling Fourier transform infrared spectroscopy (FT-IR) with TG indicates that the molar concentration of evolved H2O(g) and NH3(g) is influenced by the adsorption of NH4+(aq) at pHi 8–10 and by the low percentage of struvite at pHi 11. Overall, results indicate that both the amount of P recovered and the fraction of struvite are optimized at pHi 10. These findings can be used as a starting point in the selection of a suitable pHi for struvite recovery from nutrient-rich wastes.ACS Sustainable Chemistry & Engineering 04/2014; 2(4):816–822. DOI:10.1021/sc4004746 · 4.64 Impact Factor
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ABSTRACT: Amorphous calcium carbonate (ACC) is a common transient precursor to biogenic crystalline calcium carbonate, but factors controlling the amorphous to crystalline transformation remain unclear. We present a structural analysis and comparison of hydrated and partially dehydrated, synthetic ACC samples. Thermogravimetric analysis showed total H2O losses of 46% with heating to 115 °C and 75% for heating to 150 °C. The 1H NMR spectra of hydrous ACC, obtained both directly and indirectly, via 13C-detection, contain signals from four principal hydrogen environments: translationally rigid structural H2O, a restrictedly mobile H2O environment, fluidlike mobile H2O that is decoupled from rigid H and C, and hydroxyl. The retention of some restrictedly mobile H2O and lack of change in X-ray total scattering and absorption spectroscopy data for dehydrated ACC suggest that thermal dehydration does not significantly disrupt the calcium-rich ACC framework. NMR results and thermal analyses of samples dehydrated isothermally for extended periods indicate that the H2O loss mechanism is kinetically hindered and occurs in three stages: simultaneous loss of fluidlike mobile, restrictedly mobile, and rigid H2O → loss of restrictedly mobile and rigid H2O → loss of hydroxyl and trapped rigid and mobile components that cannot be removed without transformation to crystalline calcium carbonate.Crystal Growth & Design 02/2014; 14(3):938–951. DOI:10.1021/cg401073n · 4.89 Impact Factor
Dataset: Supporting Information 03282013
Dataset: es400874s si 001
Article: Solid-State NMR Spectroscopic Study of Phosphate Sorption Mechanisms on Aluminum (Hydr)oxides[Show abstract] [Hide abstract]
ABSTRACT: Sorption reactions occurring at mineral/water interfaces are of fundamental importance in controlling the sequestration and bioavailability of nutrients and pollutants in aqueous environments. To advance the understanding of sorption reactions, development of new methodology is required. In this study, we applied novel 31P solid-state nuclear magnetic resonance (NMR) spectroscopy to investigate the mechanism of phosphate sorption on Al hydroxides at different environmental conditions, including pH (4 - 10), concentration (0.1 - 10 mM), ionic strength (0.001 M - 0.5 M) and reaction time (15 min - 22 d). Under these conditions, the NMR results suggest formation of bidentate binuclear inner-sphere surface complexes was the dominant mechanism. However, it was found that surface wetting caused a small difference. A small amount (<3%) of monodentate mononuclear inner-sphere surface complexes was observed in addition to the majority of bidentate binuclear surface complexes on a wet paste sample prepared at pH 5, which was analyzed in situ using a double resonance NMR technique, namely 31P{27Al} rotational echo adiabatic passage double resonance (REAPDOR). Additionally, we found that adsorbents can substantially impact phosphate sorption not only on the macroscopic sorption capacity but also on their 31P NMR spectra. Very similar NMR peaks were observed for phosphate sorbed to gibbsite and bayerite, whereas the spectra for phosphate adsorbed to boehmite, corundum and γ-alumina were significantly different. All of these measurements reveal that NMR spectroscopy is a useful analytical tool for studying phosphorus chemistry at environmental interfaces.Environmental Science & Technology 07/2013; 47(15). DOI:10.1021/es400874s · 5.33 Impact Factor
Article: Characterization of Structure in Biogenic Amorphous Calcium Carbonate: Pair Distribution Function and Nuclear Magnetic Resonance Studies of Lobster Gastrolith[Show abstract] [Hide abstract]
ABSTRACT: Total X-ray scattering and pair distribution function analysis are combined with nuclear magnetic resonance spectroscopy to identify key differences in structural properties between biogenic and synthetic samples of amorphous calcium carbonate (ACC). Biogenic samples studied are gastroliths taken from the American lobster and are composed of hydrated ACC containing minor impurities. X-ray pair distribution functions reveal that the short- and medium-range structure found in synthetic ACC also occurs in gastrolith ACC, notably with atomic pair correlations extending up to 10 Å. The 13C NMR spectra of gastrolith ACC show a distribution of carbonate environments as seen in synthetic hydrated ACC. However, 1H NMR spectroscopy reveals that a mobile H2O component and hydroxyl groups found in synthetic hydrated ACC are absent in the gastrolith ACC. This difference may arise from differences in local conditions of ACC formation. The 31P NMR results indicate that inorganic phosphate is the principal form of the minor phosphorus. Gastrolith that was allowed to age shows the presence of calcite and vaterite, as well as residual ACC. 31P NMR also reveals trace amounts of monetite (CaHPO4) in aged samples, raising the possibility that fresh gastrolith ACC may contain a minor component of amorphous calcium phosphate. The findings suggest that important differences in the hydrous components between synthetic and biogenic hydrated ACC influence stability of the amorphous phase and its transformation to crystalline forms, thereby extending the foundation for advanced materials applications in engineered systems.Crystal Growth & Design 06/2013; 13(5). DOI:10.1021/cg301653s · 4.89 Impact Factor
Article: Inhibition mechanisms of Zn precipitation on aluminum oxide by glyphosate: A 31P NMR and Zn EXAFS study[Show abstract] [Hide abstract]
ABSTRACT: In this research, we investigated the effects of glyphosate (GPS) on Zn sorption/precipitation on γ-alumina using a batch technique, Zn K-edge EXAFS, and 31P NMR spectroscopy. The EXAFS analysis revealed that, in the absence of GPS, Zn adsorbed on the aluminum oxide surface mainly as bidentate mononuclear surface complexes at pH 5.5, whereas Zn-Al layered double hydroxides (LDH) precipitates formed at pH 8.0. In the presence of GPS, the EXAFS spectra of Zn sorption samples at pH 5.5 and 8.0 were very similar, both of which demonstrated that Zn did not directly bind to the mineral surface but bonded with the carboxyl group of GPS. Formation of γ-alumina-GPS-Zn ternary surface complexes were further suggested by 31P solid state NMR data which indicated the GPS binds to γ-alumina via phosphonate group, bridging the mineral surface and Zn. Additionally, we showed the sequence of additional GPS and Zn can influence the sorption mechanism. At pH 8, Zn-Al LDH precipitates formed if Zn was added first and no precipitates formed if GPS was added first or simultaneously with Zn. In contrast, at pH 5.5, only γ-alumina-GPS-Zn ternary surface complexes formed regardless of whether GPS or Zn was added first or both were added simultaneously.Environmental Science & Technology 04/2013; 47(9). DOI:10.1021/es305120x · 5.33 Impact Factor
Article: Molecular level investigations of phosphate sorption on corundum (α-Al2O3) by 31P solid state NMR, ATR-FTIR and quantum chemical calculation[Show abstract] [Hide abstract]
ABSTRACT: Phosphate sorption at the corundum (α-Al2O3)/water interface was investigated as a function of phosphate concentration (0.1–1 mM) and pH (3–11) by 31P solid state NMR spectroscopy, ATR-FTIR, and quantum chemical calculation. The 31P NMR spectra indicate that under these experimental conditions phosphate adsorbs onto corundum mainly as inner-sphere complexes that yield a peak at δP = −2.8 ppm with full width at half maximum (FWHM) of 9.2 ppm, with a small amount aluminum phosphate surface precipitates as suggested by an NMR signal observed from δP = −12 to −20 ppm. We employed 31P{27Al} rotational echo adiabatic passage double resonance (REAPDOR) to further analyze the phosphate adsorption samples prepared at pH 5 and 9 in order to determine the phosphate/Al coordination. To aid interpretation of the NMR data, a series of bidentate and monodentate structural models of phosphate adsorbed on corundum (0 0 1) and (0 1 2) surfaces were calculated using density function theory (DFT). By comparing the experimental REAPDOR curves and those simulated from these models, we can assign the dominant peaks to bidentate binuclear surface complexes. Formation of bidentate binuclear surface complexes is supported by the ATR/FTIR spectra combined with DFT calculation, which further suggests a mixture of non-protonated bidentate and mono-protonated bidentate surface complexes on the corundum surface at pH 5. At pH 9, both NMR and ATR/FTIR indicate the formation of bidentate surface complexes on corundum surface.Geochimica et Cosmochimica Acta 04/2013; 107:252–266. DOI:10.1016/j.gca.2013.01.007 · 4.33 Impact Factor
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ABSTRACT: Variations in speleothem P concentration show cyclic patterns that have important implications for high resolution palaeoclimate and palaeoenvironmental reconstructions. However, little is known about the speciation of P in calcite speleothems. Here we employ solid-state 31P and 1H magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopic techniques as a non-destructive method for analyzing the distribution of P in speleothems. The 31P MAS NMR results show three peaks indicating the presence of three primary types of phosphate species in samples from the Grotta di Ernesto (northeastern Italy): a broad peak at a chemical shift δP-31 = 3.1 to 3.7 ppm from individual phosphate ions incorporated within calcite, a narrow set of peaks near δP-31 = − 0.9 ppm from crystalline monetite and a narrow peak at δP-31 = 2.9 ppm from an unidentified crystalline phosphate phase. Essentially identical results were obtained for a synthetic calcite/phosphate coprecipitate. Spectra collected for a sample from Grotte de Clamouse (southern France) show only a broad peak near 3.5 ppm suggesting a possible limit for phosphate incorporation into the calcite structure. These data suggest that P in this system can interact to form calcium phosphate surface precipitates during infiltration events and are subsequently enclosed during calcite growth.Earth and Planetary Science Letters 01/2013; 254:313-322. DOI:10.1016/j.epsl.2006.11.040 · 4.73 Impact Factor
Article: Solid-State NMR Spectroscopic Study of Phosphate Sorption Mechanisms on Aluminum (Hydr)oxides[Show abstract] [Hide abstract]
ABSTRACT: Sorption reactions occurring at mineral/water interfaces are of fundamental importance in controlling the sequestration and bioavailability of nutrients and pollutants in aqueous environments. To advance the understanding of sorption reactions, development of new methodology is required. In this study, we applied novel 31 P solid-state nuclear magnetic resonance (NMR) spectroscopy to investigate the mechanism of phosphate sorption on aluminum hydroxides under different environ-mental conditions, including pH (4−10), concentration (0.1−10 mM), ionic strength (0.001−0.5 M), and reaction time (15 min−22 days). Under these conditions, the NMR results suggest formation of bidentate binuclear inner-sphere surface complexes was the dominant mechanism. However, it was found that surface wetting caused a small difference. A small amount (<3%) of monodentate mononuclear inner-sphere surface complexes was observed in addition to the majority of bidentate binuclear surface complexes on a wet paste sample prepared at pH 5, which was analyzed in situ by a double-resonance NMR technique, namely, 31 P{ 27 Al} rotational echo adiabatic passage double resonance (REAPDOR). Additionally, we found that adsorbents can substantially impact phosphate sorption not only on the macroscopic sorption capacity but also on their 31 P NMR spectra. Very similar NMR peaks were observed for phosphate sorbed to gibbsite and bayerite, whereas the spectra for phosphate adsorbed to boehmite, corundum, and γ-alumina were significantly different. All of these measurements reveal that NMR spectroscopy is a useful analytical tool for studying phosphorus chemistry at environmental interfaces. ■ INTRODUCTION Phosphate is widely recognized as an essential nutrient for plants and crops and has received extensive attention. However, in the past several decades, overfertilization has caused excessive phosphate mobility from agricultural soils to water bodies, and an adverse consequence is the acceleration of lake and coastal eutrophication. 1 To effectively mitigate phosphate as a non-point-source agricultural pollutant, a good under-standing of phosphate interactions with soil minerals is necessary. In soils, phosphate anions can strongly sorb on metal (hydr)oxides, and the sorption behavior depends on the phosphate concentration, pH, ionic strength, and presence of competing ions (i.e., CO 3 2− , SO 4 2− , etc.). 2 In general, phosphate sorption mechanisms involve formation of inner-sphere surface complexes and surface precipitation. 2 In the surface complexation process, phosphate can either replace two adjacent surface hydroxyl groups (e.g., MeOH) to form bidentate binuclear bonding [(MeO) 2 −PO 2 ] or replace one to form monodentate mononuclear bonding [(MeO)−PO 3 ] (Scheme 1). Surface precipitation occurs when adsorbed phosphate ions interact with the metal ions dissolved from adsorbents 2,3 and form a new solid phase (i.e., surface precipitates). However, many details with respect to the twoEnvironmental Science and Technology 01/2013; 47:8308-8315. · 5.33 Impact Factor
Article: Formation of Crystalline Zn–Al Layered Double Hydroxide Precipitates on γ-Alumina: The Role of Mineral Dissolution[Show abstract] [Hide abstract]
ABSTRACT: To better understand the sequestration of toxic metals such as nickel (Ni), zinc (Zn), and cobalt (Co) as layered double hydroxide (LDH) phases in soils, we systematically examined the presence of Al and the role of mineral dissolution during Zn sorption/precipitation on γ-Al(2)O(3) (γ-alumina) at pH 7.5 using extended X-ray absorption fine structure spectroscopy (EXAFS), high-resolution transmission electron microscopy (HR-TEM), synchrotron-radiation powder X-ray diffraction (SR-XRD), and (27)Al solid-state NMR. The EXAFS analysis indicates the formation of Zn-Al LDH precipitates at Zn concentration ≥0.4 mM, and both HR-TEM and SR-XRD reveal that these precipitates are crystalline. These precipitates yield a small shoulder at δ(Al-27) = +12.5 ppm in the (27)Al solid-state NMR spectra, consistent with the mixed octahedral Al/Zn chemical environment in typical Zn-Al LDHs. The NMR analysis provides direct evidence for the existence of Al in the precipitates and the migration from the dissolution of γ-alumina substrate. To further address this issue, we compared the Zn sorption mechanism on a series of Al (hydr)oxides with similar chemical composition but differing dissolubility using EXAFS and TEM. These results suggest that, under the same experimental conditions, Zn-Al LDH precipitates formed on γ-alumina and corundum but not on less soluble minerals such as bayerite, boehmite, and gibbsite, which point outs that substrate mineral surface dissolution plays an important role in the formation of Zn-Al LDH precipitates.Environmental Science & Technology 10/2012; 46(21). DOI:10.1021/es3018094 · 5.33 Impact Factor
Article: Anion Exchange Materials: Selectivity, Kinetics, and Efficiency of Reversible Anion Exchange with TcO4− in a Supertetrahedral Cationic Framework (Adv. Funct. Mater. 11/2012)[Show abstract] [Hide abstract]
ABSTRACT: [ThB5O6(OH)6][BO(OH)2]·2.5H2O (Notre Dame Thorium Borate-1, NDTB-1) is an inorganic supertetrahedral cationic framework material that is derived from boric acid flux reactions. NDTB-1 exhibits facile single crystal to single crystal anion exchange with a variety of common anions such as Cl−, Br−, NO3−, IO3−, ClO4−, MnO4−, and CrO42−. More importantly, NDTB-1 is selective for the removal of TcO4− from nuclear waste streams even though there are large excesses of competing anions such as Cl−, NO3−, and NO2−. Competing anion exchange experiments and magic-angle spinning (MAS)-NMR spectroscopy of anion-exchanged NDTB-1 demonstrate that this unprecedented selectivity originates from the ability of NDTB-1 to trap TcO4− within cavities, whereas others remain mobile within channels in the material. The exchange kinetics of TcO4− in NDTB-1 are second-order with the rate constant k2 of 0.059 s−1 M−1. The anion exchange capacity of NDTB-1 for TcO4− is 162.2 mg g−1 (0.5421 mol mol−1) with a maximum distribution coefficient Kd of 1.0534 × 104 mL g−1. Finally, it is demonstrated that the exchange for TcO4− in NDTB-1 is reversible. TcO4− trapped in NDTB-1 can be exchanged out using higher-charged anions with a similar size such as PO43− and SeO42−, and therefore the material can be easily recycled and reused.Advanced Functional Materials 06/2012; 22(11):2241-2250. DOI:10.1002/adfm.201103081 · 11.81 Impact Factor
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ABSTRACT: The interaction of calcium with phosphate at mineral/water interfaces is of importance for understanding both P sequestration and phosphate mineral formation. We investigated the effect of dissolved calcium on phosphate uptake by boehmite in batch sorption studies as a function of pH. Examination of the solids by 31P NMR spectroscopy and powder X-ray diffraction (XRD) shows evidence for formation of hydroxylapatite from pH 7 to pH 9, which is supported by correlation of Ca and P on particle surfaces at pH 9 observed by scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM/EDX) analysis. At pH 6, two major 31P NMR peaks are observed at δP–31 = 0 and −6 ppm, indicating the presence of bidentate binuclear complexes with surface Al atoms, similar to those found in the absence of dissolved Ca. At higher pH, an additional 31P peak at δP–31 = 2.65 ppm is observed, consistent with hydroxylapatite (Hap). The NMR data indicate that after 30 days most of the phosphate (75%) remained as adsorption complexes at pH 7, but that Hap accounts for most of the phosphate at higher pH, although surface complexes were still evident in CP/MAS NMR spectra. The identification of crystalline Hap is further supported by 31P{1H} heteronuclear correlation (HetCor) experiments in which the 2.65 ppm 31P peak correlates to a narrow 1H peak at δH–1 = 0.2 ppm that is diagnostic of the hydroxyl groups of Hap. In powder X-ray diffraction patterns, two small peaks are observed at slow scan rates that match the major reflections of Hap. Nonetheless, Hap crystals could not be identified in SEM images suggesting small particle size, in agreement with broad XRD peaks. At short reaction times only adsorbed phosphate is observed at pH 7, whereas Hap forms within 15 min at pH 9. These results indicate that the crystallization rate of Hap is enhanced by the boehmite surface, although the detailed mechanisms could not be discerned from these data.Geochimica et Cosmochimica Acta 05/2012; 85:289–301. DOI:10.1016/j.gca.2012.02.021 · 4.33 Impact Factor
Article: The Effect of Dissolved Humic Acids on Aluminosilicate Formation and Associated Carbon Sequestration[Show abstract] [Hide abstract]
ABSTRACT: Allophane and imogolite neogenesis in soils may occur in the presence of organic matter. To understand this process under conditions relevant to soils, the influence of dissolved organic carbon (DOC) as humic acid (HA), on aluminosilicate formation was studied at 25 C ∘ , pH 6, and low-DOC concentrations. For solutions with initial Al/Si ratios of 1–2.1, and 0–6 mg/L DOC, precipitates recovered after 20 h had Al/Si ratios of 2.2–2.7. The formation of allophane, imogolite-like material, and aluminosilicate gel was confirmed by XRD, FTIR, and NMR. The effect of DOC was to produce a small, but systematic increase in imogolite-like Si in the precipitate, and a decrease in the formation of aluminosilicate gel. Results suggest that the presence of DOC as HA slows the otherwise rapid polymerization of Al and Si at low temperature, and may also promote the formation of imogolite. The high C content of these precipitates indicates that this process may facilitate the sequestration of organic matter, slowing C cycling in soils.Applied and Environmental Soil Science 01/2012; 2012(1). DOI:10.1155/2012/430354
Article: Differential Pair Distribution Function Study of the Structure of Arsenate Adsorbed on Nanocrystalline γ-Alumina[Show abstract] [Hide abstract]
ABSTRACT: Structural information is important for understanding surface adsorption mechanisms of contaminants on metal (hydr)oxides. In this work, a novel technique was employed to study the interfacial structure of arsenate oxyanions adsorbed on γ-alumina nanoparticles, namely, differential pair distribution function (d-PDF) analysis of synchrotron X-ray total scattering. The d-PDF is the difference of properly normalized PDFs obtained for samples with and without arsenate adsorbed, otherwise identically prepared. The real space pattern contains information on atomic pair correlations between adsorbed arsenate and the atoms on γ-alumina surface (Al, O, etc.). PDF results on the arsenate adsorption sample on γ-alumina prepared at 1 mM As concentration and pH 5 revealed two peaks at 1.66 Å and 3.09 Å, corresponding to As-O and As-Al atomic pair correlations. This observation is consistent with those measured by extended X-ray absorption fine structure (EXAFS) spectroscopy, which suggests a first shell of As-O at 1.69 ± 0.01 Å with a coordination number of ~4 and a second shell of As-Al at ~3.13 ± 0.04 Å with a coordination number of ~2. These results are in agreement with a bidentate binuclear coordination environment to the octahedral Al of γ-alumina as predicted by density functional theory (DFT) calculation.Environmental Science & Technology 11/2011; 45(22):9687-92. DOI:10.1021/es200750b · 5.33 Impact Factor
Article: Phosphate defects and apatite inclusions in coral skeletalaragonite revealed by solid-state NMR spectroscopy[Show abstract] [Hide abstract]
ABSTRACT: Recent development of paleo-nutrient proxies based on the phosphorus/calcium (P/Ca) ratio in tropical- and deep-water corals (also known as cold-water corals) require an understanding of the processes by which P is incorporated into the coral skeletal aragonite. Here, we apply single- and double-resonance solid-state nuclear magnetic resonance (NMR) spectroscopy to determine the speciation of P in coral aragonite. The results show that the majority of P occurs as phosphate defects in the aragonite structure, but in many samples a significant fraction of the P occurs also in crystalline hydroxylapatite inclusions. Quantification of the amount of hydroxylapatite indicates that its presence is not related simply to external environmental factors and that it can occur at varying abundances in different parts of the same corallite. Since there is currently no model available to describe the relationship between dissolved inorganic phosphate and its incorporation as apatite inclusions into carbonates, careful screening of samples which contain only phosphate in the aragonite structure or selective microsampling could improve proxy development.Geochimica et Cosmochimica Acta 10/2011; 75(23):7446-7457. DOI:10.1016/j.gca.2011.10.002 · 4.33 Impact Factor
Article: Phosphate uptake by TiO2: Batch studies and NMR spectroscopic evidence for multisite adsorption[Show abstract] [Hide abstract]
ABSTRACT: Systematic studies, combining batch experiments with NMR spectroscopic methods, are carried out for phosphate sorption on titanium dioxide (TiO(2)). It is found that phosphate sorption on TiO(2) decreases with increasing pH, whereas the phosphate uptake by TiO(2) increases with increasing ionic strength of the solution. In I ≤ 0.1 M, the sorption sharply increases and reaches a near maximum and then followed by little changes showing Langmuir-type behavior, whereas in I = 0.7 M, non-Langmuirian uptake becomes evident as equilibrium phosphate concentrations increase in solution. The sorption of phosphate on TiO(2) is rapid and mostly irreversible at pH 4.5 and 7.0. At pH 9.0, however, the phosphate sorption is initially reversible and followed by resorption of phosphate on TiO(2) at the system re-equilibration. (31)P{(1)H} cross-polarization and magic angle spinning (CP/MAS) NMR spectra contain at least four main peaks which appear similar in position and width under all adsorption conditions, but vary in intensity with surface loading. The spectral characteristics of these peaks, including cross-polarization dynamics and chemical shift anisotropy obtained from spinning sideband analysis, suggest that they arise from distinct inner-sphere adsorption complexes, most of which are protonated. These results indicate that uptake of phosphate by TiO(2) occurs by formation of several types of surface complexes.Journal of Colloid and Interface Science 08/2011; 364(2):455-61. DOI:10.1016/j.jcis.2011.07.088 · 3.37 Impact Factor
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