Thorium phosphate, solubility

Thorium. Experimental and theoretical studies of thorium speciation, solubility, and sorption in low-ionic-strength waters are described by Langmuir and Herman (1980), Laflamme and Murray (1987), Osthols et ai (1994), Osthols (1995), and Quigley et al. (1996). Langmuir and Herman (1980) provide a critically evaluated thermodynamic database for natural waters at low temperature that is widely used. However, it does not contain information about important thorium carbonate complexes, and the stability of phosphate complexes may be overestimated (US EPA, 1999b). 

The principal source of thorium is monazite (p. 425), a phosphate of cerium and lanthanum with up to 15% of thoria. It is dissolved in concentrated sulphuric acid and the thorium phosphate precipitated with magnesium oxide. The washed phosphate heated with sodium carbonate gives crude thoria, ThOg, which is converted to the soluble oxalate and separated from the insoluble oxalates of cerium and lanthanum. After ignition to oxide the nitrate is made, purified by recrystallisation, and again calcined to thoria. 

Preparation and Characterization of Lanthanide and Actinide Solids. Crystalline / element phosphates were prepared as standards for comparison to the solids produced in the conversion of metal phytates to phosphates. The europium standard prepared was identified by X-ray powder diffiaction as hexagonal EuP04 H20 (JCPDS card number 20-1044), which was dehydrated at 204-234 °C and converted to monoclinic EUPO4 (with the monazite structure) at 500-600 °C. The standard uranyl phosphate solid prepared was the acid phosphate, U02HP04 2H20 (JCPDS card number 13-61). All attempts to prepare a crystalline thorium phosphate failed, though thorium solubility was low. In the latter case the solids were identified as amorphous Th(OH)4 with some minor crystalline inclusions of Th02. 

Based on preliminary leaching results for TPD (Dacheux et al., in press), normalized dissolution rates are of the order of 10 g/m d for neutral solutions. These leaching data are comparable to those for monazite and better than those for apatite. Thomas et al. (2000, 2001) have completed detailed leaching studies of Th-TPD and Th-U-TPD solid solutions as a function of surface area, flow rate, temperature and pH of the solution. For the Th-TPD, remarkably low leach rates of 10 g/m d were measured. Th-concentrations in solution were controlled by the formation of a thorium phosphate phase, identified by HRTEM, with a solubility <10 M in solutions in contact with the Th-TPD. With the substitution of uranium, the Th-U-TPD shows a slight increase in leach rate, lO " g/m d. The saturation concentrations in solution for U and Th were controlled by the formation of (U02)3(P04)2 5H20 and Th2(P04)2(HP04)H20, respectively. 

The authors have studied the dissolution of thorium phosphate diphosphate (TPD) with and without trivalent actinides they also studied a solid solution of Th(IV)/Pu(IV) phosphate diphosphate. The experiments consist of leaching studies where the rate of dissolution has been measured as a function of pH. This study does not provide any information on the solubility product of TPD. There is information on estimated equihb-rium constants for MP04(s) phases, where M = Am, Cm, Ce and Pr. These are secondary phases formed in the leach system. 

Thorium phosphate (or thorium oxide) is very soluble in concentrated phosphoric acid. Solutions containing up to 1100 g Th/liter with P04/Th... 

Oxo Ion Salts. Salts of 0x0 ions, eg, nitrate, sulfate, perchlorate, hydroxide, iodate, phosphate, and oxalate, are readily obtained from aqueous solution. Thorium nitrate is readily formed by dissolution of thorium hydroxide in nitric acid from which, depending on the pH of solution, crystalline Th(N02)4 5H20 [33088-17 ] or Th(N02)4 4H20 [33088-16-3] can be obtained (23). Thorium nitrate is very soluble in water and in a host of oxygen-containing organic solvents, including alcohols, ethers, esters, and ketones. Hydrated thorium sulfate, Th(S0 2 H20, where n = 9, 8, 6, or 4, is... 

On the basis of these facts, it was speculated that plutonium in its highest oxidation state is similar to uranium (VI) and in a lower state is similar to thorium (IV) and uranium (IV). It was reasoned that if plutonium existed normally as a stable plutonium (IV) ion, it would probably form insoluble compounds or stable complex ions analogous to those of similar ions, and that it would be desirable (as soon as sufficient plutonium became available) to determine the solubilities of such compounds as the fluoride, oxalate, phosphate, iodate, and peroxide. Such data were needed to confirm deductions based on the tracer experiments. 

The physical and chemical properties of elemental thorium and a few representative water soluble and insoluble thorium compounds are presented in Table 3-2. Water soluble thorium compounds include the chloride, fluoride, nitrate, and sulfate salts (Weast 1983). These compounds dissolve fairly readily in water. Soluble thorium compounds, as a class, have greater bioavailability than the insoluble thorium compounds. Water insoluble thorium compounds include the dioxide, carbonate, hydroxide, oxalate, and phosphate salts. Thorium carbonate is soluble in concentrated sodium carbonate (Weast 1983). Thorium metal and several of its compounds are commercially available. No general specifications for commercially prepared thorium metal or compounds have been established. Manufacturers prepare thorium products according to contractual specifications (Hedrick 1985). 

Thorium sulfate, being less soluble than rare earth metals sulfates, can be separated by fractional crystallization. Usually, solvent extraction methods are applied to obtain high purity thorium and for separation from rare earths. In many solvent extraction processes, an aqueous solution of tributyl phosphate is the extraction solvent of choice. 

Finely-ground monazite is treated with a 45% NaOH solution and heated at 138°C to open the ore. This converts thorium, uranium, and the rare earths to their water-insoluble oxides. The insoluble residues are filtered, dissolved in 37% HCl, and heated at 80°C. The oxides are converted into their soluble chlorides. The pH of the solution is adjusted to 5.8 with NaOH. Thorium and uranium are precipitated along with small quantities of rare earths. The precipitate is washed and dissolved in concentrated nitric acid. Thorium and uranium are separated from the rare earths by solvent extraction using an aqueous solution of tributyl phosphate. The two metals are separated from the organic phase by fractional crystallization or reduction. 

Simple thermodynamic calculations based on literature data (5-12) support the choice of phosphates as the optimum mineral phases for actinide immobilization. The calculations considered every relevant species reported (5-72) that contained protons, hydroxide, or the ligand in question for each metal ion. Where necessary, equilibrium constants were corrected to 0.1 M ionic strength using the Davies equation. As an example, the calculated solubility of europium, thorium, and uranium in various media at p[H] 7.0 (p[H] = - log of the hydrogen ion concentration), 0.001 M total ligand concentration, 0.1 M ionic strength, and 25 °C are shown in Table I. Within the constraints of the calculation, the solubility of thorium is limited by Th(OH)4, but the lowest europium and uranyl solubilities are observed for phosphates. 

Parallel experiments with uranyl-phytate mixtures produced a uranyl phosphate solid identified as (U02)3(P04)2 H20 by X-ray powder diffraction (2i), not U02HP04 nH20 as expected. Neither crystalline phosphates nor phytates, were observed in the thorium-phytate mixtures, although amorphous thorium phytates were likely present initially. Hydroxide or oxide species seem to control thorium solubility. 

We have shown that phytic acid readily hydrolyzes to produce phosphate with a projected lifetime of 100-150 years in the absence of microbiological effects, that actinide-phytate compounds are insoluble, and that europium and uranyl phytates are converted to phosphates within a month at 85 °C. Thorium solubility, on the other hand, is controlled by hydroxide or oxide species. Furthermore, the solubilities of radiotracer europium and uranyl are reduced by phosphate dosing of a simulated groundwater solution, even in the presence of citric acid. In the same systems, neptunium(V) solubility is only affected by 0.01 M phosphate at pH greater than 7. The results of these tracer-scale immobilization experiments indicate that phosphate mineral formation from representative deposits is under thermodynamic control. 

The Acid-Thorex process has been used in recent years to recover 233U from neutron irradiated thoria targets. (] M This process uses n-tributyl-phosphate (TBP) in normal paraffin hydrocarbon (NPH) as the extractant and the relative uranium and thorium solubilities in each phase are adjusted by control of the nitric acid concentration. The Acid-Thorex process is the primary candidate for use in proposed aqueous thorium fuel cycles. In this process, uranium is separated from thorium through exploitation of the difference in equilibrium distributions since no usable valence change is available to aid in this separation. 

Uranium, thorium and radium tend to fractionate because of chemical differences. Uranium tends to be mobile in oxidizing waters containing complexing bicarbonate, sulfate or phosphate anions in reducing environments the solubility of uranium is sharply decreased and precipitation occurs. Thorium is virtually immobile under almost all surface conditions. Radium is quite mobUe in high-Cl waters but in the presence of sulfate, radium is very insoluble. 

Thorium orthophosphate Th3(P04)4 is precipitated by phosphate ion from neutral or slightly acid solutions of thorium nitrate or sulfate. It is soluble in concentrated phosphoric or sulfuric acid, such as is present when monazite is dissolved in sulfuric add. 

This paper reports the solubilities of the thorium and uranyl phosphates otrly the Th(lV) studies will be discussed here. The authors have measured the solubility of two different Th(lV) phosphate sohds, Th3(P04)4(s) and Th(HP04)2(s) as a function of pH in nitric... 

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