Mineral phases which can be thought of as members of a metatorbernite–metazeunerite solid solution (Cu(UO2)2(PO4)2−x(AsO4)x.8H2O have been identified in radioactive samples from spoil heaps at the uranium mine site in South Terras, Cornwall (grid referenceSW935523). A complete solid solution (0 < x < 2) was synthesized by precipitation from solution using uranium (VI) nitrate and copper (II) chloride and phosphoric acid/arsenic acid in the appropriate molar proportions. Refined unit cell parameters determined by Pawley fitting of powder X-ray diffraction data showed a linear variation in theaunit cell parameter according to Vegard's Law, allowing the composition of the natural mineral phases found at South Terras to be determined from measurement of their unit cell parameters. High-resolution variable-temperature synchrotron powder X-ray diffraction studies were carried out at the Diamond Light Source on three members of this solid solution (x = 0, 1, 2) and showed different structural behaviour as a function of composition and temperature. Metatorbenite (x = 0) retains its tetragonal symmetry at low temperatures and dehydrates to an amorphous phase at 473 K, whereas metazeunrite (x = 2) transforms to an orthorhombic phase at low temperatures, regains its tetragonal symmetry on heating to 323 K and undergoes a further transition to an, as yet, unidentified phase at 473 K.This article is part of the theme issue ‘Fifty years of synchrotron science: achievements and opportunities’.

The influence of anthropogenic organic complexants (citrate, EDTA and DTPA from 0.005 to 0.1M) on the solubility of nickel(II), thorium(IV) and uranium (U(IV) and U(VI)) has been studied. Experiments were carried out in 95%-saturated Ca(OH)2 solutions, representing the high pH conditions anticipated in the near field of a cementitious intermediate level radioactive waste repository. Results showed that Ni(II) solubility increased by 2-4 orders of magnitude in the presence of EDTA and DTPA and from 3 to 4 orders of magnitude in the case of citrate. Citrate had the greatest effect on the solubility of Th(IV) and U(IV)/(VI). XRD and SEM analyses indicate that the precipitates are largely amorphous; only in the case of Ni(II), is there some evidence of incipient crystallinity, in the form of Ni(OH)2 (theophrastite). A study of the effect of calcium suggests that U(VI) and Ni(II) may form metal-citrate-OH complexes stabilised by Ca(2+). Thermodynamic modelling underestimates the concentrations in solution in the presence of the ligands for all the elements considered here. Further investigation of the behaviour of organic ligands under hyperalkaline conditions is important because of the use of the thermodynamic constants in preparing the safety case for the geological disposal of radioactive wastes.

White rice husk ash (WRHA) was obtained via thermal degradation of rice husks in air, which was used to remove Mn(II) ions from aqueous solutions. Thermodynamic and kinetic studies of adsorption were conducted under agitation at 288, 298 and 308 K and different solution concentrations. The obtained results showed that the removal of Mn(II) ions from aqueous solutions using WRHA is a chemisorption process, where the OH-groups of SiO2 take part, releasing H+ ions in the solution. The adsorption process was well described with the Langmuir isotherm. On its basis, the values of ΔG°, ΔH° and ΔS° for the adsorption of Mn(II) ions onto WRHA were calculated. Pseudo-first-order kinetic equation was found as the most appropriate kinetic model. The values of the rate constants of the sorption process at the studied temperatures were calculated, which were found to be equal to k288 = 8.75 × 10− 4 min− 1, k298 = 2.53 × 10− 3 min− 1 and k308 = 6.69 × 10− 3 min− 1. Using the Arrhenius equation, the values of the activation energy (EA = 75.02 kJ mol− 1) and the frequency factor (A = 3.55 × 1010 min− 1) were calculated. It was concluded that WRHA is an effective and very cheap adsorbent for removing Mn(II) ions from water solutions.

Superplasticisers improve the flow properties of fresh cement and offer undoubted benefits to the construction sector. There is concern in the nuclear industry, however, that the presence of a superplasticiser in grout or backfill cement may increase the solubility of radionuclides in the cementitious pore water and/or reduce their adsorption from solution. This paper describes the effect of a commercial, polycarboxylated, polyether comb type superplasticiser on the behaviour of selected metals in blended cements through a series of batch and monolith leach experiments. Results of batch experiments show that the presence of free superplasticiser in solution reduces uptake of nickel (63Ni) and europium (152Eu) by both blast-furnace-slag- and pulverised-fly-ash-modified ordinary Portland cement. Further, metal bound in the presence of free superplasticiser is readily remobilised on exposure to fresh cement solution. Conversely, metal uptake is almost complete and appears irreversible when exposed to hardened cements prepared with superplasticiser as part of the original mix. Monolithic slag cement samples prepared with superplasticiser suffer from bleed, with the surplus water containing a significant proportion of the metals added, including uranium and thorium. Digital autoradiography reveals heterogeneous distribution of radioactivity in the monoliths and demonstrates that the dissolved metals have not been effectively immobilised throughout the specimen. The mobility of thorium may indicate similar behaviour by other tetravalent actinide species, notably Pu(IV) and Np(IV).

The purpose of this study was to investigate the effects of competition between cobalt, europium and strontium for isosaccharinate, gluconate and picolinate. Systems where results indicated that competitive effects were significant have been identified. Thermodynamic calculations were performed for each system for comparison with the experimental results. Some exceptions may be due to precipitation of some species, or presence of species not in databases, or formation of mixed-metal complexes, or sorption to the solid phase(s). In some of the experiments, the complexity of the systems studied caused difficulty in identifying consistent trends. By concentrating on the results for simpler systems (i.e. for solubilities in the presence and absence of organic complexants and with just one competing metal ion), the evidence for competition effects has been investigated. Evidence for solubility enhancement due to organic ligands was apparent in the data for the systems Co with gluconate and Eu with isosaccharinate and gluconate. Of these above cases, the systems in which the effects of the competing ion are consistent with competition were limited to the cases of Eu with isosaccharinate and Sr as the competing ion, and Eu with gluconate and either Co or Sr as the competing ion.

The sorption behaviour of I-, Cs+, Ni2+, Eu3+, Th4+ and UO22+ on NRVB (Nirex reference vault backfill) a possible vault backfill, at pH 12.8 was studied. Sorption isotherms generated were compared to results obtained in the presence of cellulose degradation products (CDP). Whereas Cs was not affected by the presence of the organic compounds, a notable reduction in the sorption of Th and Eu to cement was observed. The results also indicated limited removal of Ni from solution (with or without an organic ligand) by sorption, the concentration in solution seemingly being determined solely by solubility processes. In the case of uranium, the presence of CDP increased the sorption to cement by almost one order of magnitude. Further studies into the uptake of CDP by cement are being undertaken to identify the mechanism(s) responsible.

Some recent developments made during the European Union 6th Framework Integrated Project FUNMIG in the understanding and prediction of behaviour in ternary systems of radionuclides, humic substances and mineral surfaces are described. These developments are placed in the context of the existing literature. The aim is to describe the current understanding of humic substance mediated radionuclide transport as it may be applied to calculations in support of Radiological Performance Assessment. Some improvements in experimental techniques that provide the raw data to calibrate metal ion binding models are explained. The various metal ion binding models that are available are described and contrasted, before the recent development of ternary system models, in particular the Ligand Charge Distribution model that can predict metal ion and humic substance behaviour in ternary systems. The kinetic effects in ternary systems are described along with the models that are used to describe them. Finally, the remaining challenges in making predictions of radionuclide transport for the Radiological Performance Assessment of radioactive waste repositories are discussed.

Safety assessments for radioactive waste disposal require estimations of the migration of radionuclides in soils. The influence of humic acid (HA) on the sorption of uranium in its +4 oxidation state to kaolin has been examined from pH 4 to 8, with HA concentrations of 15–200 ppm. In the absence of HA, 20–40% of the U(IV) was in solution, with more sorption occurring at higher pH. The presence of HA solubilised up to 90% of the uranium with higher solubilities at higher HA concentrations and higher pH values. Uranium sorption was mapped against HA sorption, and it was found that there was a lower level of U(IV) sorption than can be accounted for by just measuring HA sorption. However, this effect got less marked as the pH rose. Sensitivity analysis indicated that the fraction of surface-bound HA is the controlling parameter for modelling in these systems.

A new method is described for radiolabeling humic substances (HS) with iodine radioisotopes. The method radiolabels the electron-rich aromatic moieties of HS with the 3-[125I]iodobenzenediazonium ion via azocoupling. The method uses four steps: (i) 3-aminobenzenetrimethylstannane is synthesized and isolated by using a silica gel column, (ii) 3-[125I]iodoaniline is synthesized and isolated by HPLC, with radiochemical yields of up to 60%, (iii) 3-[125I]iodobenzenediazonium chloride is synthesized, and the reaction mixture from this step is used in step iv to radioiodinate HS with radiochemical yields of up to 95% (with reference to 3-[125I]iodoaniline). The advantage of this method is that it is selective radiolabeling, placing the radiolabel in a specific site (the 3-position of the phenyl ring) within HS molecules, which minimizes unwanted secondary chemical interactions. Investigations of the stability of the radiolabel and the effect of photoreductive dehalogenation showed that there was a negligible release of 125I. The production of radiolabeled HS using this method allows the sensitive detection of HS in laboratory and field studies. In addition, the method offers the possibility of using different iodine radioisotopes simultaneously in investigations using HS.

In the UK, tetraphenylphosphonium bromide (TPPB) has been used to remove technetium prior to disposal from some waste-streams by forming TPPBTc floc. If this floc were to be disposed of in a cementitious repository the TPPBTc would degrade by alkaline hydrolysis to triphenylphosphonium oxide, or by radiolysis to triphenylphosphine, releasing the Tc into solution. Its chemistry would be dominated by TcO4 in aerobic waters and sparingly soluble TcO2(s) in anaerobic. Repository heterogeneity could mean that both Tc(VII) and Tc(IV) are present simultaneously. If TcO4 migrates into reducing conditions, ligands in the waste may complex with Tc during reduction to form water-soluble complexes. Also possible, is increased Tc solubility when organic ligands react with TcO2(s). Comparisons of Tc solubilities at high pH starting from TcO2 and from TcO4 reduced in the presence of ligands were made. With EDTA and NTA no difference was observed, suggesting that Tc(IV)-ligand complexes were formed. For ISA and gluconic acid the Tc solubility starting from TcO4 was higher than in systems with TcO2 as the starting point. This suggests that the TcO4 was not reduced to TcO2, but an intermediate oxidation state complex was formed, e.g. Tc(V). The conditional stability constant for the Tc(IV)-gluconic acid complex has been determined to be log β = 26.6 ± 0.2.

Metal ions form strong complexes with humic substances. When the metal ion is first complexed by humic material, it is bound in an 'exchangeable' mode. The metal ion in this fraction is strongly bound, however, if the metal-humic complex encounters a stronger binding site on a surface, then the metal ion may dissociate from the humic substance and be immobilised. However, over time, exchangeably-bound metal may transfer to a 'non-exchangeable' mode. Transfer into this mode and dissociation from it are slow, regardless of the strength of the competing sink, and so immobilisation may be hindered. A series of coupled chemical transport calculations has been performed to investigate the likely effects of non-exchangeable binding upon the transport of metal ions in the environment. The calculations show that metal in the non-exchangeable mode will have a significantly higher mobility than that in the exchangeable mode. The critical factor is the ratio of the non-exchangeable first-order dissociation rate constant and the residence time in the groundwater column, metal ion mobility increasing with decreasing rate constant. A second series of calculations has investigated the effect of the sorption to surfaces of humic/metal complexes on the transport of the non-exchangeably bound metal. It was found that such sorption may reduce mobility, depending upon the humic fraction to which the metal ion is bound. For the more weakly sorbing humic fractions, under ambient conditions (humic concentration etc.) the non-exchangeable fraction may still transport significantly. However, for the more strongly sorbed fractions, the non-exchangeable fraction has little effect upon mobility. In addition to direct retardation, sorption also increases the residence time of the non-exchangeable fraction, giving more time for dissociation and immobilisation. The non-exchangeable dissociation reaction, and the sorption reaction have been classified in terms of two Damkohler numbers, which can be used to determine the importance of chemical kinetics during transport calculations. These numbers have been used to develop a set of rules that determine when full chemical kinetic calculations are required for a reliable prediction, and when equilibrium may be assumed, or when the reactions are sufficiently slow that they may be ignored completely.

Summary Technetium-99 is a β-emitting fission product of 238U. It is important when considering a safety case for nuclear waste disposal because of its high yield in radioactive waste and long half-life. The aqueous chemistry of Tc in a cementitious repository is likely to be dominated by Tc(VII), as TcO4 −, in aerobic areas and by Tc(IV), as TcO2 (am), in anaerobic. Some previous studies have shown an increase in Tc(IV) solubility with increasing pH above pH 9.5 whilst others have not observed this increase. This study found that the solubility of Tc(IV) remains independent of pH until around 13.5, when a small increase can be seen which continues to increase linearly with pH. Modelling suggests that this increase occurs as the species TcO(OH)3 − is formed. The formation constant was estimated with data from this study and was found to be logK 2=−21.6±0.3.

Aiming at an assessment of counteractive effects on colloid-borne migration of actinides in the event of release from an underground repository, competition by Fe(III) in respect of metal complexation by dissolved organic matter was investigated for the example of Eu(III) as an analogue of trivalent actinides. Complexation with different humic materials was examined in cation exchange experiments, using 59Fe and 152Eu as radioactive tracers for measurements in dilute systems as encountered in nature. Competitive effects proved to be significant when Fe is present at micromolar concentrations. Flocculation as a limiting process was attributed to charge compensation of humic colloids. Fe fractions bound to humic acids (HA) were higher than 90%, exceeding the capacity of binding sites at high Fe concentrations. It is thus concluded that the polynuclear structure of hydrolysed Fe(III) is maintained when bound to HA, which is also inferred from UV–Vis spectrometry. The competitive effect was found to be enhanced if Fe and HA were in contact before Eu was added. Depending on the time of Fe/HA pre-equilibration, Eu complexation decreased asymptotically over a time period of several weeks, the amount of bound Fe being unchanged. Time-dependent observations of UV–Vis spectra and pH values revealed that the ageing effect was due to a decline in Fe hydrolysis rather than structural changes within HA molecules. Fe polycations are slowly degraded in contact with humic colloids, and more binding sites are occupied as a consequence of dispersion. The extent of degradation as derived from pH shifts depended on the Fe/HA ratio.

Metal ions form strong complexes with humic substances. When the metal ion is first complexed by humic material, it is bound in an ‘exchangeable’ mode. The metal ion in this fraction is strongly bound, however, if the metal–humic complex encounters a stronger binding site on a surface, then the metal ion may dissociate from the humic substance and be immobilised. However, over time, exchangeably-bound metal may transfer to a ‘non-exchangeable’ mode. Transfer into this mode and dissociation from it are slow, regardless of the strength of the competing sink, and so immobilisation may be hindered. A series of coupled chemical transport calculations has been performed to investigate the likely effects of non-exchangeable binding upon the transport of metal ions in the environment. The calculations show that metal in the nonexchangeable mode will have a significantly higher mobility than that in the exchangeable mode. The critical factor is the ratio of the non-exchangeable first-order dissociation rate constant and the residence time in the groundwater column, metal ion mobility increasing with decreasing rate constant. A second series of calculations has investigated the effect of the sorption to surfaces of humic/metal complexes on the transport of the non-exchangeably bound metal. It was found that such sorption may reduce mobility, depending upon the humic fraction to which the metal ion is bound. For the more weakly sorbing humic fractions, under ambient conditions (humic concentration etc.) the non-exchangeable fraction may still transport significantly. However, for the more strongly sorbed fractions, the non-exchangeable fraction has little effect upon mobility. In addition to direct retardation, sorption also increases the residence time of the nonexchangeable fraction, giving more time for dissociation and immobilisation. The nonexchangeable dissociation reaction, and the sorption reaction have been classified in terms of two Damkohler numbers, which can be used to determine the importance of chemical kinetics during transport calculations. These numbers have been used to develop a set of rules that determine when full chemical kinetic calculations are required for a reliable prediction, and when equilibrium may be assumed, or when the reactions are sufficiently slow that they may be ignored completely.

Recently, tetraphenylphosphonium bromide (TPPB) has been used to remove technetium from some radioactive waste streams. However, before TPPB could be approved for use it was necessary to show that TPPB and its degradation products would not have a significant detrimental effect on post-closure performance of a radioactive waste repository. TPPB is known to be stable at neutral pH, however, under alkaline conditions it degrades by an alkaline hydrolysis mechanism to triphenylphosphonium oxide (TPPO). Degradation can also occur by radiolysis to produce triphenylphosphine (TPP). The kinetics of the alkaline hydrolysis degradation of TPPB is described and the solubility of europium, iodine, nickel, technetium(VII) and uranium(VI) in aqueous solutions of TPPB and its degradation products is reported. These results were used to support the use of TPPB in removing technetium from some waste streams.