Effect of grain size variation on strontium sorption to heterogeneous aquifer sediments.

Strontium-90 (90Sr) is a major contaminant at nuclear legacy sites. The mobility of 90Sr is primarily governed by sorption reactions with sediments controlled by high surface area phases such as clay and iron oxides. Sr2+ adsorption was investigated in heterogeneous unconsolidated aquifer sediments, analogous to those underlying the UK Sellafield nuclear site, with grainsizes ranging from gravels to clays. Batch sorption tests showed that a linear Kd adsorption model was applicable to all grainsize fractions up to equilibrium [Sr] of 0.28 mmol L-1. Sr2+ sorption values (Kd; Langmuir qmax) correlated well with bulk sediment properties such as cation exchange capacity and surface area. Electron microscopy showed that heterogeneous sediments contained porous sandstone clasts with clay minerals (i.e. chlorite) providing an additional adsorption capacity. Therefore, gravel corrections that assumed that the > 2 mm fractions are inert were not appropriate and underestimated Kd(bulk) adsorption coefficients. However, Kd (<2 mm) values measured from sieved sediment fractions, were effectively adjusted to within error of Kd (bulk) using a surface area dependant gravel correction based on particle size distribution data. Amphoteric pH dependent Sr2+ sorption behaviour observed in batch experiments was consistent with cation exchange modelling between pH 2-7 derived from the measured cation exchange capacities. Above pH 7 model fits were improved by invoking a coupled cation exchange/surface complexation which allowed for addition sorption to iron oxide phases. The overall trends in Sr2+ sorption (at pH 6.5-7) produced by increasing solution ionic strength was also reproduced in cation exchange models. Overall, the results showed that Sr2+ sorption to heterogeneous sediment units could be estimated from Kd (<2 mm) data using appropriate gravel corrections, and effectively modelled using coupled cation exchange and surface complexation processes.

Behaviour of carbon-14 containing low molecular weight organic compounds in contaminated groundwater under aerobic conditions.

Short chain carbon-14 (14C) containing organic compounds can be formed by abiotic oxidation of carbides and impurities within nuclear fuel cladding. During fuel reprocessing and subsequent waste storage there is potential for these organic compounds to enter shallow subsurface environments due to accidental discharges. Currently there is little data on the persistence of these compounds in such environments. Four 14C-labelled compounds (acetate; formate; formaldehyde and methanol) were added to aerobic microcosm experiments that contained glacial outwash sediments and groundwater simulant representative of the Sellafield nuclear reprocessing site, UK. Two concentrations of each electron donor were used, low concentration (10-5 M) to replicate predicted concentrations from an accidental release and high concentration (10-2 M) to study the impact of the individual electron donor on the indigenous microbial community in the sediment. In the low concentration system only ∼5% of initial 14C remained in solution at the end of experiments in contact with atmosphere (250-350 h). The production of 14CO2(g) (measured after 48 h) suggests microbially mediated breakdown is the primary removal mechanism for these organic compounds, although methanol loss may have been partially by volatilisation. Highest retention of 14C by the solid fractions was found in the acetate experiment, with 12% being associated with the inorganic fraction, suggesting modest precipitation as solid carbonate. In the high concentration systems only ∼5% of initial 14C remains in solution at the end of the experiments for acetate, formate and methanol. In the formaldehyde experiment only limited loss from solution was observed (76% remained in solution). The microbial populations of unaltered sediment and those in the low concentration experiments were broadly similar, with highly diverse bacterial phyla present. Under high concentrations of the organic compounds the abundance of common operational taxonomic units was reduced by 66% and the community structure was dominated by Proteobacteria (particularly Betaproteobacteria) signifying a shift in community structure in response to the electron donor available. The results of this study suggest that many bacterial phyla that are ubiquitous in near surface soils are able to utilise a range of 14C-containing low molecular weight organic substances very rapidly, and thus such substances are unlikely to persist in aerobic shallow subsurface environments.

Coprecipitation of (14)C and Sr with carbonate precipitates: The importance of reaction kinetics and recrystallization pathways.

This study investigated the simultaneous removal of Sr(2+) and (14)CO3(2-) from pH>12 Ca(OH)2 solution by the precipitation of calcium carbonate. Initial Ca(2+):CO3(2-) ratios ranged from 10:1 to 10:100 (mM:mM). Maximum removal of (14)C and Sr(2+) both occurred in the system containing 10mM Ca(2+) and 1mM CO3(2-) (99.7% and 98.6% removal respectively). A kinetic model is provided that describes (14)C and Sr removal in terms of mineral dissolution and precipitation reactions. The removal of (14)C was achieved during the depletion of the initial TIC in solution, and was subsequently significantly affected by recrystallization of the calcite precipitate from an elongate to isotropic morphology. This liberated >46% of the (14)C back to solution. Sr(2+) removal occurred as Ca(2+) became depleted in solution and was not significantly affected by the recrystallization process. The proposed reaction could form the basis for low cost remediation scheme for (90)Sr and (14)C in radioactively contaminated waters (<$0.25 reagent cost per m(3) treated).