content of actinium in most natural objects corresponds to the isotopic equilibrium of parent isotope 235U, and it is not affected by the weak Ac migration. Protactinium is more abundant (10−12%) in the Earth's crust than actinium. It was discovered in the uranium ore in 1913 by Fajans and Göhring. As actinium, the distribution of protactinium follows that of 235U. The half-life of the longest-lived isotope of neptunium, 237Np, is negligible compared to the age of the Earth. Thus neptunium is present in nature in negligible amounts produced as intermediate decay products of other isotopes. Traces of plutonium in uranium minerals were first found in 1942, and the more systematic results on 239Pu are summarized in the table (no other plutonium isotopes could be detected in those samples). The upper limit of abundance of the longest-living isotope of plutonium, 244Pu, is 3%. Plutonium could not be detected in samples of lunar soil. Owing to its scarcity in nature, most plutonium is produced synthetically. Extraction Owing to the low abundance of actinides, their extraction is a complex, multistep process. Fluorides of actinides are usually used because they are insoluble in water and can be easily separated with redox reactions. Fluorides are reduced with calcium, magnesium or barium: Among the actinides, thorium and uranium are the easiest to isolate. Thorium is extracted mostly from monazite: thorium pyrophosphate (ThP2O7) is reacted with nitric acid, and the produced thorium nitrate treated with tributyl phosphate. Rare-earth impurities are separated by increasing the pH in sulfate solution. In another extraction method, monazite is decomposed with a 45% aqueous solution of sodium hydroxide at 140 °C. Mixed metal hydroxides are extracted first, filtered at 80 °C, washed with water and dissolved with concentrated hydrochloric acid. Next, the acidic solution is neutralized with hydroxides to pH = 5.8 that results in precipitation of thorium hydroxide (Th(OH)4) contaminated with ~3% of rare-earth hydroxides; the rest of rare-earth hydroxides remains in solution. Thorium hydroxide is dissolved in an inorganic acid and then purified from the rare earth elements. An efficient method is the dissolution of thorium hydroxide in nitric acid, because the resulting solution can be purified by extraction with organic solvents: Th(OH)4 + 4 HNO3 → Th(NO3)4 + 4 H2O Metallic thorium is separated from the anhydrous oxide, chloride or fluoride by reacting it with calcium in an inert atmosphere: ThO2 + 2 Ca → 2 CaO + Th