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Abstract: Assessing element speciation and solubility control mechanisms in multi-contaminated soils poses great challenges. In this study, we examined the speciation and mechanisms controlling the solubility of As and Zn in a soil historically contaminated with As, Cu, Cr, and Zn salts used for wood preservation. The leaching behavior of dissolved species, particles, and colloids was studied in an irrigation experiment with intact soil columns. Batch experiments were used to study the solubility of dissolved species as a function of pH (2–8). The speciation of As and Zn in bulk soil and leached particles was studied with microscale X-ray fluorescence (μ-XRF) and extended X-ray absorption fine structure (EXAFS) spectroscopy. Chemical speciation and solubility were evaluated by geochemical modelling. μ-XRF of bulk soil and particles showed that As and Zn were correlated in space. Bulk- and μ-EXAFS of As and Zn, in combination with calculated ion activity products of possible As-Zn minerals, suggested a koritnigite (ZnHAsO4·H2O) phase controlling the dissolved fraction of As(V) and Zn with an apparent log Ksp of −21.9 ± 0.46. This phase lowered the solubility of As by almost two orders of magnitude in soil at pH > 5, and could therefore be of great importance at other multi-contaminated sites.

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Abstract: The presence of uranium in groundwater at nuclear sites can be controlled by microbial processes. Here we describe the results from stimulating microbial reduction of U(VI) in sediment samples obtained from a nuclear-licensed site in the UK. A variety of different lithology sediments were selected to represent the heterogeneity of the subsurface at a site underlain by glacial outwash deposits and sandstone. The natural sediment microbial communities were stimulated via the addition of an acetate/lactate electron donor mix and were monitored for changes in geochemistry and molecular ecology. Most sediments facilitated the removal of 12 ppm U(VI) during the onset of Fe(III)-reducing conditions; this was reflected by an increase in the proportion of known Fe(III)- and U(VI)-reducing species. However U(VI) remained in solution in two sediments and Fe(III)-reducing conditions did not develop. Sequential extractions, addition of an Fe(III)-enrichment culture and most probable number enumerations revealed that a lack of bioavailable iron or low cell numbers of Fe(III)-reducing bacteria may be responsible. These results highlight the potential for stimulation of microbial U(VI)-reduction to be used as a bioremediation strategy at UK nuclear sites, and they emphasise the importance of both site-specific and borehole-specific investigations to be completed prior to implementation.

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Abstract: The interaction of groundwater with cement in a geological disposal facility (GDF) for intermediate level radioactive waste will produce a high pH leachate plume. Such a plume may alter the physical and chemical properties of the GDF host rock. However, the geochemical and mineralogical processes which may occur in such systems over timescales relevant for geological disposal remain unclear. This study has extended the timescale for laboratory experiments and shown that, after 15 years two distinct phases of reaction may occur during alteration of a dolomite-rich rock at high pH. In these experiments the dissolution of primary silicate minerals and the formation of secondary calcium silicate hydrate (C¨CS¨CH) phases containing varying amounts of aluminium and potassium (C¨C(A)¨C(K)¨CS¨CH) during the early stages of reaction (up to 15 months) have been superseded as the systems have evolved. After 15 years significant dedolomitisation (MgCa(CO3)2 + 2OH− ¡ú Mg(OH)2 + CaCO3 + CO32−(aq)) has led to the formation of magnesium silicates, such as saponite and talc, containing variable amounts of aluminium and potassium (Mg¨C(Al)¨C(K)¨Csilicates), and calcite at the expense of the early-formed C¨C(A)¨C(K)¨CS¨CH phases. This occured in high pH solutions representative of two different periods of cement leachate evolution with little difference in the alteration processes in either a KOH and NaOH or a Ca(OH)2 dominated solution but a greater extent of alteration in the higher pH KOH/NaOH leachate. The high pH alteration of the rock over 15 years also increased the rock¡¯s sorption capacity for U(VI). The results of this study provide a detailed insight into the longer term reactions occurring during the interaction of cement leachate and dolomite-rich rock in the geosphere. These processes have the potential to impact on radionuclide transport from a geodisposal facility and are therefore important in underpinning any safety case for geological disposal.

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Abstract: Caesium-137 (t1/2 = 30 years) is a common contaminant at nuclear legacy sites. Often the mobility of 137Cs in the environment is governed by its sorption to charged sites within the sediment. To this end it is important to understand the sorption behaviour of caesium across a wide range of environmental conditions. This work investigates the effect of varying solution composition (pH and competing ions) on the sorption of caesium to micaceous aquifer sediment across a large concentration range (1.0 × 10−11 – 1.0 × 10−1 mol L−1 Cs+). Experimental results show that Cs+ exhibits three distinct sorption behaviours at three different concentration ranges. At very low concentrations < 1.0 × 10−6 mol L−1 Cs+ sorption was unaffected by competition with Na+ or H+ but significantly reduced in high ionic strength K+ solution. Secondly between 1 × 10−6 and 1.0 × 10−3 mol L−1 Cs+ is strongly sorbed in a neutral pH, low ionic strength background but sorption is significantly reduced in solutions with either a high concentration of Na+ or K+ ions or low pH. At high concentrations > 1.0 × 10−3 mol L−1 Cs+ sorption is reduced in all systems due to saturation of the sediment’s sorption capacity. A multi-site cation exchange model was used to interpret the sorption behaviour. From this it was determined that at low concentrations Cs+ sorbs to the illite frayed edge sites only in competition with K+ ions. However, once the frayed edge sites are saturated the Cs+ sorbs to the Type II and Planar sites in competition with K+, Na+ and H+ ions. Therefore sorption of Cs+ at concentrations > 1.0 × 10−6 mol L−1 is significantly reduced in both high ionic strength and low pH solutions. This is a significant result with regard to predicting the migration of 137Cs+ in acidic or high ionic strength groundwaters.

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Abstract: At nuclear contaminated sites, microbially-mediated Fe(III) reduction under alkaline conditions opens up the potential for co-treatment of the groundwater contaminants 99Tc, though reduction to less mobile Tc(IV) phases, and 90Sr, through increased sorption and/or precipitation promoted at higher pH. In the experiments described here, microbial enrichment cultures derived from representative Sellafield sediments were used to probe the effect of microbially-mediated Fe(III) reduction on the mobility of 99Tc and Sr (as stable Sr2+ at elevated concentrations and 90Sr2+ at ultra-trace concentrations) under both neutral and alkaline conditions. The reduction of Fe(III) in enrichment culture experiments at an initial pH of 7 or 9 resulted in the precipitation of an Fe(II) bearing biomineral comprised of siderite and vivianite. Results showed that added at 1.6 × 10−6 M was removed (>80%) from solution concurrent with Fe(III) reduction at both pH 7 and pH 9. Furthermore, X-ray absorption spectroscopy of the reduced biominerals confirmed reduction of Tc(VII) to Tc(IV). To understand Sr behaviour in these systems, Sr2+ was added to enrichment cultures at ultra-trace concentrations (2.2 × 10−10 M (as 90Sr2+)) and at higher concentrations (1.15 × 10−3 M (as stable Sr2+)). In ultra-trace experiments at pH 7, microbially active systems showed enhanced removal of 90Sr compared to the sterile control. This was likely due to sorption of 90Sr2+ to the Fe(II)-bearing biominerals that formed in situ. By contrast, at pH 9, the sterile control showed comparable removal of 90Sr to the microbially active experiment even though the Fe-minerals formed were of very different character in the active (vivianite, siderite) versus sterile (an amorphous Fe(III)-phase) systems. Overall, 90Sr bioreduction experiments showed 60–70% removal of the added 90Sr across the different systems: this suggests that treatment strategies involving bioreduction and the promotion of Fe(III)-reducing conditions to scavenge Tc(IV) are not incompatible with treatment of groundwater 90Sr contamination. In systems with elevated Sr2+ concentrations and an initial pH of 7, microbially active systems showed <20% removal of added Sr2+ following Fe(III) reduction with little or no removal in sterile controls. At pH 9, significant Sr2+ was removed from solution in both sterile and microbially active experiments and was attributed to Sr-sorption to mineral phases both chemically precipitated in sterile controls, and biologically precipitated in the microbially active systems. These results confirm that in systems with an elevated natural or anthropogenic Sr2+ loading, bioreduction at modestly alkaline pH is compatible with co-treatment of both and 90Sr2+. These data are discussed in terms of aqueous geochemistry trends, X-ray diffraction and morphological data, and thermodynamic modelling. The results demonstrate the potential for removal of trace levels of 99Tc and 90Sr2+ from groundwaters during stimulated bioreduction and highlight that in the presence of stable Sr2+, optimal removal for technetium and strontium is likely to occur under mildly alkaline, reducing conditions.