Fission solubilities

Uranium Purification. Subsequent uranium cycles provide additional separation from residual plutonium and fission products, particularly zirconium— niobium and mthenium (30). This is accompHshed by repeating the extraction/stripping cycle. Decontamination factors greater than 10 at losses of less than 0.1 wt % are routinely attainable. However, mthenium can exist in several valence states simultaneously and can form several nitrosyl—nitrate complexes, some for which are extracted readily by TBP. Under certain conditions, the nitrates of zirconium and niobium form soluble compounds or hydrous coUoids that compHcate the Hquid—Hquid extraction. SiUca-gel adsorption or one of the similar Hquid—soHd techniques may also be used to further purify the product streams. 

Control of the core is affected by movable control rods which contain neutron absorbers soluble neutron absorbers ia the coolant, called chemical shim fixed burnable neutron absorbers and the intrinsic feature of negative reactivity coefficients. Gross changes ia fission reaction rates, as well as start-up and shutdown of the fission reactions, are effected by the control rods. In a typical PWR, ca 90 control rods are used. These, iaserted from the top of the core, contain strong neutron absorbers such as boron, cadmium, or hafnium, and are made up of a cadmium—iadium—silver alloy, clad ia stainless steel. The movement of the control rods is governed remotely by an operator ia the control room. Safety circuitry automatically iaserts the rods ia the event of an abnormal power or reactivity transient. 

The primary issue is to prevent groundwater from becoming radioactively contaminated. Thus, the property of concern of the long-lived radioactive species is their solubility in water. The long-lived actinides such as plutonium are metallic and insoluble even if water were to penetrate into the repository. Certain fission-product isotopes such as iodine-129 and technicium-99 are soluble, however, and therefore represent the principal although very low level hazard. Studies of Yucca Mountain, Nevada, tentatively chosen as the site for the spent fuel and high level waste repository, are underway (44). 

Three classes of carbamoylmethylphosphoryl extractants were studied for their ability to extract selected tri-, tetra-, and hexavalent actinides from nitric acid. The three extractants are dihexyl-N,N-diethylcarbamoylmethylphosphonate (DHDECMP), hexyl hexyl-N,N-diethylcarbamoylmethylphosphinate (HHDECMP), and octyl(phenyl)-N,N-diisobutylcarbamoylmethylphos-phine oxide 0< >D[IB]CMP0. The above three extrac-trants were compared on the basis of nitric acid and extractant dependencies for Am(III), solubility of complexes on loading with Nd(III) and U(VI), and selectivity of actinide(III) over fission products. 

We have studied the extractant behavior of a series of compounds containing the carbamoylmethylphosphoryl (CMP) moiety in which the basicity of the phosphoryl group and the steric bulk of the substituent group are varied (10,LL). These studies have led to the development of extractants which have combinations of substituent groups that impart to the resultant molecule improved ability to extract Am(III) from nitric acid and to withstand hydrolytic degradation. At the same time good selectivity of actinides over most fission products and favorable solubility properties on actinide loading are maintained (11). 

Ethers are unaffected by sodium and by acetyl (or benzoyl) chloride. Both the purely aliphatic ethers e.g., di-n-butyl ether (C4H, )30 and the mixed aliphatic - aromatic ethers (e.g., anisole C3HSOCH3) are encountered in Solubility Group V the purely aromatic ethers e.g., diphenyl ether (C,Hj)20 are generally insoluble in concentrated sulphuric acid and are found in Solubility Group VI. The purely aliphatic ethers are very inert and their final identification may, of necessity, depend upon their physical properties (b.p., density and/or refractive index). Ethers do, however, suffer fission when heated with excess of 67 per cent, hydriodic acid, but the reaction is generally only of value for the characterisation of symmetrical ethers (R = R ) ... 

For the rapid determination of Tc in a mixture of uranium fission products. Love and Greendale have used the method of amalgam polarography. It consists in a selective reduction of technetium at a dropping mercury electrode at a potential of —1.55 V vs. SCE in a medium of 1 M sodium citrate and 0.1 M NaOH. Under these conditions, technetium is reduced to an oxidation state which is soluble in mercury. The amalgam is removed from the solution of fission fragments and the amount of Tc determined in nitric acid solution of the amalgam by a y count. For Tc the measurement accuracy is within 1 %, and the decontamination factor from other fission products 10 . 

Since the water movement will be very slow compared with the rate at which the wastes dissolve, we are concerned first and foremost with equilibrium solubility. Also, if only to relate behaviour on the geological time scale to that on the laboratory time scale, we will need to know about the mechanisms and kinetics of dissolution and leaching. The waste forms envisaged at present are glass blocks containing separated fission products and residual actinides fused into the glass and, alternatively, the uranium dioxide matrix of the used fuel containing unseparated fission products and plutonium. In the... 

Because of their similarity to the composition of human bile, which consists mainly of bile salts, phospholipids, and cholesterol, of interest for pharmaceutical studies are mainly binary bile salt micelles (BS/PL) (32,33). The function of the bile is to emulsify lipids in food and to dissolve the fission products of lipids as well as fat-soluble vitamins. The spontaneous formation of micelles is a necessary prerequisite to a contact of the lipophilic fission products with the intestinal wall. For affinity measurements, micellar sys-... 

The dissolution time for the unreprocessed fuel would be at least 1 million years due to the limited water supply, even if a rapid oxidation of uranium to the hexavalent state and a subse-guent formation of water soluble carbonate complexes are assumed (15). Since the conditions are reducing in the groundwater (see beTow) the dissolution time would probably be several orders of magnitude larger. The unsignificant dissolution of uranium and fission products observed in the Oklo-deposit (16) is an example of a similar extremely slow leaching process in the natural environment. 

The most important chemical parameter affecting the deposition and subsequent mobility of radioactive aerosols, such as the nuclides 90Sr and 137Cs examined in this study, is their solubility in rainwater. If these aerosols are dissolved in precipitation, the main factor in their transport is the movement of the rainwater, not the transport of insoluble aerosol particles. Huff and Kruger (2) examined the solubility products of strontium and chemically similar compounds which may carry trace amounts of 90Sr, and they estimated that strontium should be soluble in precipitation. Solubility tables also indicate that cesium compounds likely to exist in precipitation should be soluble. It was noted that the possibility did exist that some of the fission product "Sr and 137Cs might be bound within the structure of insoluble natural aerosols or nuclear weapon debris. 

Since the pioneering work of Siddall, /V./V-dialkyl amides have been evaluated extensively as alternative extractants to TBP (200, 201). The salient features of amides as extractants are (i) low volume of secondary waste generated (completely incinerable), (ii) innocuous nature of chemical and radiolytic degradation products (better decontamination from fission products andregeneration/clean up easier), (iii) low aqueous-phase solubility, (iv) final U and Pu products streams are free of P contamination, and (v) ease of synthesis. However, LOC values of U and Pu as well as viscosity are... 

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