In this work, we report a route to enhance the reactivity and longevity of biogenic magnetite in Cr(VI) remediation under continuous-flow conditions by combining functionalization of the biomagnetite surface with a precious metal catalyst, nanoscale palladium, and exposure to formate. Column influent conditions were varied to simulate oxic, anoxic, and nitrate cocontaminated environments. The addition of sodium formate as an electron donor for Pd-functionalized magnetite increased capacity and longevity allowing 80% removal of Cr(VI) after 300 h in anoxic conditions, whereas complete breakthrough occurred after 60 h in anoxic nonformate and nonfunctionalized systems. Removal of Cr(VI) was optimized under anoxic conditions, and the presence of oxidizing agents results in a modest loss in reductive capacity. Examination of reacted Pd-functionalized magnetite reveals close association of Fe with Cr, suggesting that Pd-coupled oxidation of formate serves to regenerate the reactive surface. XMCD studies revealed that Cr(III) is partially substituted for Fe in the magnetite structure, which serves to immobilize Cr. No evidence for a mechanistic interference by nitrate cocontamination was observed, suggesting that this novel system could provide robust, effective and sustained reduction of contaminants, even in the presence of common oxidizing cocontaminants, outperforming the reductive capacity of nonfunctionalized biogenic magnetite.

Detailed mineralogical analysis of soils from the UK's historical uranium mine, South Terras, was performed to elucidate the mechanisms of uranium degradation and migration in the 86 years since abandonment. Soils were sampled from the surface (0-2 cm) and near-surface (25 cm) in two distinct areas of ore processing activities. Bulk soil analysis revealed the presence of high concentrations of uranium (<1690 p.p.m.), arsenic (1830 p.p.m.) and beryllium (~250 p.p.m.), suggesting pedogenic weathering of the country rock and ore extraction processes to be the mechanisms of uranium ore degradation. Micro-focus XRF analysis indicated the association of uranium with arsenic, phosphate and copper; µ-XRD data confirmed the presence of the uranylarsenate minerals metazeunerite (Cu(UO 2 ) 2 (AsO 4 ) 2 ·8H 2 O) and metatorbernite (Cu(UO 2 ) 2 (PO 4 ) 2 ·8H 2 O) to be ubiquitous. Our data are consistent with the solid solution of these two uranyl-mica minerals, not previously observed at uranium-contaminated sites. Crystallites of uranyl-mica minerals were observed to coat particles of jarosite and muscovite, suggesting that the mobility of uranium from degraded ores is attenuated by co-precipitation with arsenic and phosphate, which was not previously considered at this site.

Use of depleted uranium (DU) munitions has resulted in contamination of the near-surface environment with penetrator residues. Uncertainty in the long-term environmental fate of particles produced by impact of DU penetrators with hard targets is a specific concern. In this study DU particles produced in this way and exposed to the surface terrestrial environment for longer than 30 years at a U.K. firing range were characterized using synchrotron X-ray chemical imaging. Two sites were sampled: a surface soil and a disposal area for DU-contaminated wood, and the U speciation was different between the two areas. Surface soil particles showed little extent of alteration, with U speciated as oxides U3O7 and U3O8. Uranium oxidation state and crystalline phase mapping revealed these oxides occur as separate particles, reflecting heterogeneous formation conditions. Particles recovered from the disposal area were substantially weathered, and U(VI) phosphate phases such as meta-ankoleite (K(UO2)(PO4) · 3H2O) were dominant. Chemical imaging revealed domains of contrasting U oxidation state linked to the presence of both U3O7 and meta-ankoleite, indicating growth of a particle alteration layer. This study demonstrates that substantial alteration of DU residues can occur, which directly influences the health and environmental hazards posed by this contamination.

Contamination of soils with depleted uranium (DU) from munitions firing occurs in conflict zones and at test firing sites. This study reports the development of a chemical extraction methodology for remediation of soils contaminated with particulate DU. Uranium phases in soils from two sites at a UK firing range, MOD Eskmeals, were characterised by electron microscopy and sequential extraction. Uranium rich particles with characteristic spherical morphologies were observed in soils, consistent with other instances of DU munitions contamination. Batch extraction efficiencies for aqueous ammonium bicarbonate (42-50% total DU extracted), citric acid (30-42% total DU) and sulphuric acid (13-19% total DU) were evaluated. Characterisation of residues from bicarbonate-treated soils by synchrotron microfocus X-ray diffraction and X-ray absorption spectroscopy revealed partially leached U(IV)-oxide particles and some secondary uranyl-carbonate phases. Based on these data, a multi-stage extraction scheme was developed utilising leaching in ammonium bicarbonate followed by citric acid to dissolve secondary carbonate species. Site specific U extraction was improved to 68-87% total U by the application of this methodology, potentially providing a route to efficient DU decontamination using low cost, environmentally compatible reagents.