Uraninites

L. radius, ray) Radium was discovered in 1898 by Mme. Curie in the pitchblende or uraninite of North Bohemia, where it occurs. There is about 1 g of radium in 7 tons of pitchblende. The element was isolated in 1911 by Mme. Curie and Debierne by the electrolysis of a solution of pure radium chloride, employing a mercury cathode on distillation in an atmosphere of hydrogen this amalgam yielded the pure metal. 

Uranium, not as rare as once thought, is now considered to be more plentiful than mercury, antimony, silver, or cadmium, and is about as abundant as molybdenum or arsenic. It occurs in numerous minerals such as pitchblende, uraninite, carnotite, autunite, uranophane, and tobernite. It is also found in phosphate rock, lignite, monazite sands, and can be recovered commercially from these sources. 

Geochemical Nature and Types of Deposits. The cmst of the earth contains approximately 2—3 ppm uranium. AlkaHc igneous rock tends to be more uraniferous than basic and ferromagnesian igneous rocks (10). Elemental uranium oxidizes readily. The solubiHty and distribution of uranium in rocks and ore deposits depend primarily on valence state. The hexavalent uranium ion is highly soluble, the tetravalent ion relatively insoluble. Uraninite, the most common mineral in uranium deposits, contains the tetravalent ion (II). 

Uranium dioxide [1344-57-6], UO2, is found ki nature as the mineral pitchblende and as a component ki uraninite. The crystalline soHd melts at 2878°C and is paramagnetic with a room temperature magnetic moment of 3.2 )Xg. The density has been found to range from 10.79 to 10.95 g/cm, lower values are... 

Uranium, too, is widely distributed and, since it probably crystallized late in the formation of igneous rocks, tends to be scattered in the faults of older rocks. Some concentration by leaching and subsequent re-precipitation has produced a large number of oxide minerals of which the most important are pitchblende or uraninite, U3O8, and camotite, K2(U02)2(V04)2.3H20. However, even these are usually dispersed so that typical ores contain only about 0.1% U, and many of the more readily exploited deposits are nearing exhaustion. The principal sources are Canada, Africa and countries of the former USSR. 

Figure 4. Solubility of uraninite as a function of Eh and PCO2 at pH = 8 and 25°C. The increase of uraninite solubility at high Pco2 results from the formation of uranyl carbonate complexes. [Used with permission of Elsevier Science, from Langmuir (1978) Geochim Cosmochim Acta, Vol. 42, Fig. 15, p. 561].

Oxides and hydroxides Cuprite, uraninite, baddeleyite, corundum, haematite, rutile, cassiterite, brucite, diaspore, goethite, limonite... 

Bound in minerals such as uraninite, pitchblende, coffinite, etc. fixed as a replacement ion for Y, Ce, Zr, Th, Ca, and Ba in other, particularly accessory minerals and adsorbed as ion on clay minerals, hydrous iron oxides, etc. 

Primary (predominantly tetravalent uranium) Uraninite Ideally U02... 

The separation of impurities such as calcium, barium and radium can be effected by the precipitation of their sulfates. In the case of sulfuric acid leaching of uraninite ore, the leach liquor contains radium which is removed if barium chloride is added since barium sulfate acts as a carrier for radium sulfate. 

The incorporation of anions, as for example, S04 , CO2-, etc., makes leaching possible through the formation of stable uranyl (VI) oxyanions. In sulfate leaching, an observation of the potential-pH diagram for the uranium system reveals that uranium species in solution may be in the form of cations U02+, neutral species U02(S04)2 or anions U02(S04)4-. The oxidation of uraninite, U02, in acid solutions, transforming U(IV) to U(VI), yields soluble uranyl sulfate through the reaction as shown below ... 

Alkaline leaching is carried out by using sodium carbonate solution. In this case any U(IV) present in the ore must also be oxidized to U(VI). The uranium species soluble in carbonate leach solutions in the uranyl tricarbonate ion. The formation of this ion by solubilization of a hexavalent uranium mineral such as camotite, or a tetravalent uranium mineral such as uraninite, may be represented by the following reactions ... 

As shown by Grandstaff (1976) the cations, thorium, lead and the rare earths, associated with uraninite retard the dissolution of UO2 significantly. 

Fayek M, Kyser TK (2000) Low temperature oxygen isotopic fractionation in the uraninite-UOj-COj-HjO system. Geochim Cosmochim Acta 64 2185-2197... 

Abstract uranium isotopes fractionate as a result of nuclear volume effects such that ratios vary as a funotion of uranium oxidation state, being highest in reduced species such as U"" in uraninite. The values of uranium minerals from volcanic-, metasomatic-, unconformity-,... 

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