Uranyl carbonates

Owing to the stability of the uranyl carbonate complex, uranium is universally present in seawater at an average concentration of ca. 3.2/rgL with a daughter/parent activity ratio U) of 1.14. " In particulate matter and bottom sediments that are roughly 1 x 10 " years old, the ratio should approach unity (secular equilibrium). The principal source of dissolved uranium to the ocean is from physicochemical weathering on the continents and subsequent transport by rivers. Potentially significant oceanic U sinks include anoxic basins, organic rich sediments, phosphorites and oceanic basalts, metalliferous sediments, carbonate sediments, and saltwater marshes. " ... 

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].

AUC [Ammonium uranyl carbonate] A process for converting uranium hexafluoride into uranium dioxide for use as a nuclear reactor fuel. The hexafluoride vapor, together with carbon dioxide and ammonia, are passed into aqueous ammonium carbonate at 70°C, precipitating ammonium uranyl carbonate ... 

Goishi and Libby have investigated the extraction of pertechnetate from alkali solutions with pyridine. Later work showed that a better extraction is obtained using a mixture of sodium hydroxide and sodium carbonate as the aqueous phase. Since the uranyl carbonate complex is not extracted into pyridine, this system may be used for the separation of technetium from uranium. Distribution coefficients of fission products in pyridine are given in Table 4. Substituted pyridine such as 2,4-dimethylpyridine or 4-(5-nonyl)pyridine ) are useful for separating technetium from solutions containing appreciable amounts of aluminum nitrate. 

At the prevailing pH in the Namibian groundwaters, the predicted solubility of carnotite is low and close to saturation. From one hole in the Tubas deposit, carnotite saturation is close to 0 and predicted to be over saturated around the water-table zone and in the near-surface upper 2m of the gypcrete. Where Eh is positive carnotite is predicted to be nearsaturation. This indicates that carnotite accumulation at or above the regional water-table can occur by upward diffusion of uranyl carbonate species with possible precipitation due to nucleation on clay minerals or gypsum, as evidenced in the Tubas River. 

Owing to the stability of the uranyl carbonate complex, uranium is universally present in seawater at an average concentration of ca. 3.2/rgL with a daughter/parent activity ratio of 1.14. " In particulate matter and... 

This paper is devoted to the sorption of uranyl, which exhibits a complex aqueous and surface chemistry. We review briefly the sorption behaviour of An in the environment, and illustrate the variety of environmental processes using published data of uranyl sorption in the Ban-gombe natural reactor zone. After summarizing the general findings of the mechanisms of An sorption, we then focus particularly on the current knowledge of the mechanisms of uranyl sorption. A major area of research is the influence of the aqueous uranyl speciation on the uranyl surface species. Spectroscopic data of U(VI) sorbed onto silica and alumina minerals are examined and used to discuss the role of aqueous uranyl polynuclear species, U02(0H)2 colloids and uranyl-carbonate complexes. The influence of the mineral surface properties on the mechanisms of sorption is also discussed. 

Investigations of uranyl carbonate complexes on an amorphous Al phase using EXAFS... 

Procedure. The solid used is a Merck alumina gel. The product is predominantly amorphous but its X-ray diffraction pattern exhibits small peaks characteristics of gibbsite. Its surface charge determined by counter-ions adsorption is reported in Fig. 4. Batch experiments were performed using 5 g/L solid contacted with ltr4 m uranyl carbonated solutions at pH 7... 

For the treatment of camotite several methods are available. The method recommended by the United States Bureau of Mines2 is as follows The ore is leached with concentrated nitric acid at 100° C., neutralised with caustic soda, and barium chloride and sulphuric acid added to the solution to precipitate the radium as barium-radium sulphate. The precipitate settles in three or four days, after which time the clear liquid is decanted into tanks and is treated with excess of boiling sodium carbonate solution in order to precipitate any iron, aluminium and chromium present. The solution now contains sodium uranyl carbonate and sodium vanadate. It is nearly neutralised with nitric acid, and caustic soda is added in sufficient quantity to precipitate the uranium as sodium uranate. After filtering, the remaining solution is neutralised with nitric acid and ferrous sulphate added, whereupon iron vanadate is thrown down. By this method it is claimed that 90 per cent, of the radium, all the uranium, and 50 per cent, of the vanadium in the camotite are recovered. 

In the alkaline process, uranyl carbonate is eluted from the resin by concentrated (approximately 1 M) solutions of chloride, carbonate or bicarbonate, and is recovered from the eluate by treatment with an acid to destroy the carbonate complex, followed by precipitation of the diuranate, e.g. 

Weak-base resins have been tested from time to time but have not found wide acceptance in the uranium industry, The main reason for this is that the major advantage of weak- over strong-base resins, viz. elution by neutralization, cannot be utilized in uranium processing since it is not possible for the weak-base resin to be converted to the free-base form without diuranate precipitating within the pores of the resin (unless a complexing agent such as carbonate is added to the eluate). In the presence of carbonate, uranium remains in solution as the uranyl carbonate anion, even in very alkaline solution, so is readily eluted from a weak-base resin in the free-base form. This eluate would then be treated as depicted in equations (105) and (106) for the recovery of uranium. Alternatively, weak-base resins can be eluted by ion-exchange mass action. 

Table 3 Stability Constants for Uranyl Carbonate and Hydroxocarbonate Complexes36...

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