Crystalline and glassy phases in the ‘leucite’ systems (K,Rb,Cs)Fe3+Si2O6 and (K,Rb,Cs)2(Mg,Mn,Fe,Co,Ni,Cu,Zn)2+–Si5O12 have been studied using K-edge X-ray Absorption Spectroscopy (XAS) for 3d transition elements and Mg. Crystalline samples of known structure are used as model compounds for deducing the local structures of the equivalent glasses. ‘Ideal’ tetrahedral framework X2+–O distances are: Mn2+–O 2.02, Fe2+–O 1.98; Co2+–O 1.96, Ni2+–O 1.95, Cu2+–O 1.92, Zn2+–O 1.93 and Mg2+–O 1.93Å. The quenched glasses have Extended X-ray Absorption Fine Structure (EXAFS) first-shell distances and coordination numbers consistent with Mg and 3d elements occurring in tetrahedral coordination in most cases. The X-ray Absorption Near Edge Structure (XANES) spectra of the glasses are basically the same as those for the crystalline samples showing that they have similar medium range order, consistent with most of the Mg and 3d elements acting as network formers along with the associated alkalis as X2Y2+O2 complexes. Anhydrous glasses in the system CaO–MgO–Al2O3–SiO2 together with a basalt glass from Hawaii show examples of Mg in octahedral- (2.07Å, basalt), tetrahedral- (~1.87Å, siliceous glass) and 5-coordinated (2.01–2.04Å) sites. Although most Earth scientists assume that Mg and Fe2+ act as network modifiers in natural magmas, ultra-potassic, peralkaline compositions ((Na+K)/(Al+Fe3+)>1) could have had some Fe2+ and Mg complexes with alkalis in the melt network as K2(Mg,Fe2+)O2 and the implications of this to melt density and viscosity are considered.

Woodlice efficiently sequester copper (Cu) in ‘cuprosomes' within hepatopancreatic ‘S' cells. Binuclear ‘B’ cells in the hepatopancreas form iron (Fe) deposits; these cells apparently undergo an apocrine secretory diurnal cycle linked to nocturnal feeding. Synchrotron-based µ-focus X-ray spectroscopy undertaken on thin sections was used to characterize the ligands binding Cu and Fe in S and B cells of Oniscus asellus (Isopoda). Main findings were: (i) morphometry confirmed a diurnal B-cell apocrine cycle; (ii) X-ray fluorescence (XRF) mapping indicated that Cu was co-distributed with sulfur (mainly in S cells), and Fe was co-distributed with phosphate (mainly in B cells); (iii) XRF mapping revealed an intimate morphological relationship between the basal regions of adjacent S and B cells; (iv) molecular modelling and Fourier transform analyses indicated that Cu in the reduced Cu+ state is mainly coordinated to thiol-rich ligands (Cu–S bond length 2.3 Å) in both cell types, while Fe in the oxidized Fe3+ state is predominantly oxygen coordinated (estimated Fe–O bond length of approx. 2 Å), with an outer shell of Fe scatterers at approximately 3.05 Å; and (v) no significant differences occur in Cu or Fe speciation at key nodes in the apocrine cycle. Findings imply that S and B cells form integrated unit-pairs; a functional role for secretions from these cellular units in the digestion of recalcitrant dietary components is hypothesized.

A Serratia sp. bacterium manufactures amorphous calcium phosphate nanominerals (BHAP); this material has shown increased sorption capacity for divalent radionuclide capture. When heat-treated (≥450 °C) the cell biomass is removed and the biominerals are transformed to hydroxyapatite (HAP). Using a multimethod approach, we have elucidated both the site preferences and stability of analogue radionuclide incorporation for Sr, Co, Eu, and U. Strontium incorporates within the bulk amorphous inorganic phase of BHAP; however, once temperature modified to crystalline HAP, bonding was consistent with Sr substitution at the Ca(1) and/or Ca(2) sites. Cobalt incorporation occurs within the bulk inorganic amorphous phase of BHAP and within the amorphous grain boundaries of HAP. Europium (an analogue for trivalent actinides) substituted at the Ca(2) and/or the Ca(3) position of tricalcium phosphate, a known component of HAP grain boundaries. Uranium was surface complexed with no secondary minerals detected. With multiple sites for targeted radionuclide incorporation, high loadings, and good stability against remobilization, BHAP is shown to be a potential material for the remediation of aqueous radionuclide in groundwater.

SummarySelenium (Se) is an essential trace element for animals and displays a narrow range between dietary deficiency and toxicity. The toxicity of Se depends on its bioavailability, which is directly related to its oxidation states, of which four occur in the environment (SeVI, SeIV, Se0 and SeII−). Microbial communities drive the cycling of Se between these oxidation states. In order to investigate the effect of microbial activity on Se cycling in the environment, a field site in County Meath, Ireland, was identified with anomalously large concentrations of Se as a result of weathering of black shales within the Lucan formation, leading to cases of Se toxicity in farm animals. Soil cores were extracted from the site for Se speciation and microbial community analysis prior to microcosm experiments to assess Se stability and microbial Se transformations. Selenium was present as a recalcitrant, reduced organic phase that was strongly coordinated with carbon, concordant with suggested hypotheses of Se phyto‐concentration within a clay‐lined, postglacial marshland. Selenium was not mobilized in microcosm experiments, and supplementation with SeVI resulted in rapid reduction and removal from solution as Se0. Additional electron donors did not affect Se stability or removal from solution, although nitrate did hinder SeVI reduction. Terminal restriction fragment length polymorphism analysis indicated a significant shift in microbial community after amendment with SeVI. This work extends the current knowledge of Se cycling in the environment, and provides information on the bioavailability of Se in the soil, which determines Se content of foodstuffs.

Using synchrotron- and electron microscope-based X-ray microanalyses, the distribution and speciation of Zn and Pb were examined in situ in two earthworm species (Dendrodrilus rubidus and Lumbricus rubellus) living in heavily-polluted soils. Main findings: (i) Zn spectra in ingested soil and in tissues more closely resembled Zn-3(PO4)(2) than ZnS; (ii) Zn speciation in tissues gave a best fit for Zn to the inner shell of 4 oxygens at 1.94 angstrom (or nitrogens at 1.96 angstrom); (iii) the best fit for Pb in tissue was with a shell of oxygens at 2.18 angstrom and a shell of sulphurs at 2.67 angstrom; (iv) a component of the Zn and much of the Pb detectable in gut contents was co-distributed with S; (v) Zn and Pb display 'soft' acid affinities in soil, but 'hard' acid affinities in tissue. This is the first metal characterisation study conducted on an invertebrate quench-frozen in the field. (C) 2012 Elsevier Ltd. All rights reserved.

Abstract Combined microfocus XAS and XRD analysis of α-particle radiation damage haloes around thorium-containing monazite in Fe-rich biotite reveals changes in both short- and long-range order. The total α-particles flux derived from the Th and U in the monazite over 1.8 Ga was 0.022 α particles per atomic component of the monazite and this caused increasing amounts of structural damage as the monazite emitter is approached. Short-range order disruption revealed by Fe K-edge EXAFS is manifest by a high variability in Fe-Fe bond lengths and a marked decrease in coordination number. XANES examination of the Fe K-edge shows a decrease in energy of the main absorption by up to 1 eV, revealing reduction of the Fe3+ components of the biotite by interaction with the 42He2+, the result of low and thermal energy electrons produced by the cascade of electron collisions. Changes in d spacings in the XRD patterns reveal the development of polycrystallinity and new domains of damaged biotite structure with evidence of displaced atoms due to ionization interactions and nuclear collisions. The damage in biotite is considered to have been facilitated by destruction of OH groups by radiolysis and the development of Frenkel pairs causing an increase in the trioctahedral layer distances and contraction within the trioctahedral layers. The large amount of radiation damage close to the monazite can be explained by examining the electronic stopping flux.

Luminescent quantum dots were synthesized using bacterially derived selenide (SeII−) as the precursor. Biogenic SeII− was produced by the reduction of SeIV by Veillonella atypica and compared directly against borohydride-reduced SeIV for the production of glutathione-stabilized CdSe and β-mercaptoethanol-stabilized ZnSe nanoparticles by aqueous synthesis. Biological SeII− formed smaller, narrower size distributed QDs under the same conditions. The growth kinetics of biologically sourced CdSe phases were slower. The proteins isolated from filter sterilized biogenic SeII− included a methylmalonyl-CoA decarboxylase previously characterized in the closely related Veillonella parvula. XAS analysis of the glutathione-capped CdSe at the S K-edge suggested that sulfur from the glutathione was structurally incorporated within the CdSe. A novel synchrotron based XAS technique was also developed to follow the nucleation of biological and inorganic selenide phases, and showed that biogenic SeII− is more stable and more resistant to beam-induced oxidative damage than its inorganic counterpart. The bacterial production of quantum dot precursors offers an alternative, ‘green’ synthesis technique that negates the requirement of expensive, toxic chemicals and suggests a possible link to the exploitation of selenium contaminated waste streams.

Understanding the relationships between accumulated metal speciation in cells and tissues of ecologically significant taxa such as earthworms will improve risk assessments. Synchrotron-based μ-focus X-ray spectroscopy was used to detect, localize, and determine ligand-speciation of Zn and Pb in thin sections of two epigeic earthworm species collected from a Pb/Zn-mine soil. The findings indicated that Zn and Pb partition predominantly as typical hard acids (i.e., strong affinities for O-donors) within liverlike chloragocytes. Moreover, Zn speciation was very similar in the chloragog and intestinal epithelia but differed subtly in the kidneylike nephridial tubules; neither Zn nor Pb was detectable in the ventral nerve cord. High resolution X-ray mapping of high pressure-frozen, ultrathin, freeze-substituted sections in a transmission electron microscope (TEM), combined with conventional TEM structural analysis, identified a new cell type packed with highly organized rough endoplasmic reticulum and containing deposits of Cd (codistributed with S); there was no evidence that these cells are major depositories of Zn or Pb. These data may be used in a systems biology approach to assist in the interpretation of metal-evoked perturbations in whole-worm transcriptome and metabolome profiles.

Potassium-rich mafic dykes and lavas from the Highwood Mountains Igneous Province, USA were studied by electron-microprobe and bulk-rock analysis. For the mafic phonolites, compositional trends for olivine and augite phenocrysts and groundmass biotite, alkali feldspar and titanomagnetites are presented and substitution mechanisms discussed. Phenocrysts of biotite and augite in the minettes are also characterized, together with groundmass alkali feldspar and titanomagnetite. The alkali feldspars and biotites are commonly enriched in Ba. Olivine, clinopyroxene and biotite phenocrysts are generally quite magnesium-rich, which is consistent with the primitive natures of the least evolved rocks.Bulk-rock major-element compositions are combined with modal and microprobe data for the principal phenocrysts to calculate model residual liquid compositions for mafic phonolites, minettes and a syenitic rock. On the basis of phase-equilibria, it is suggested that the main controls of differentiation are polybaric involving crystallization during transport of primary magmas from the mantle for the minettes, and low-pressure differentiation for the mafic phonolites. Whereas magma mixing might have contributed to petrogenesis, many of the disequilibrium features exhibited by clinopyroxene and biotite phenocrysts can also be attributed to pre-existing phenocrysts undergoing decompression melting during magma uprise from its mantle source, followed by rapid crystal growth and episodic volatile loss in sub-volcanic magma chambers.

The chemical composition oft he natural arsenate-apatite mineral johnbaumite [nominally Ca-10(AsO4)(6)(OH)(2)] and its alteration product hedyphane [Ca4Pb6(AsO4)(6)Cl-2] have been determined by electron microprobe analysis and the structures of johnbaumite and synthetic Sr-, Ba- and Pb-arsenate apatites have been studied by As K-edge X-ray absorption spectroscopy and synchrotron X-ray powder diffraction. All samples belong to the holosymmetric apatite space group P6(3)/m with As5+ substituted for P5+ in the tetrahedral structural site. Johnbaumite contains small amounts of F and Pb (similar to 0.9 and similar to 4.4 wt.% respectively) and hedyphane has the ideal composition (formula given above); the compositions of these coexisting phases define the two limbs of a solvus occurring between Ca- and Pb-arsenate apatite end members. The unit-cell parameters and cation-oxygen bond lengths for the arsenate apatites studied are discussed alongside published data for end-member Ca-, Sr-, Ba- and Pb-phosphate apatite analogues with (OH), F, Cl or Br as the anions at the centres of the channels in the apatite structure. This discussion rationalizes the relationships between the two structural sites A(1) and A(2) occupied by divalent cations in terms of the size of the A-O polyhedra and the distortion of the A(1)-O polyhedron as measured by the metaprism twist angle [O(1)-A(1)-O(2) projected onto (001)].

Spectroscopic study of the local chemical environment during biotransformation of uranium M. AL-BOKARI*, J.R. LLOYD, J.M. CHARNOCK AND F.R. LIVENS Institute of Atomic Energy Resarch, King Abdulaziz City for Science and Technology, 6086, Riyadh 11442, Saudi Arabia (*correspondence: mbokari@kacst.edu.sa) Williamson Research Centre for Molecular Environmental Science, and School of Earth, Atmospheric and Environmental Sciences, The University of Manchester, M13 9PL, UK Centre for Radiochemistry Research, The University of Manchester, M13 9PL, UK

Previous studies provided no unequivocal evidence demonstrating that field populations of Lumbricus rubellus Hoffmeister (1843), exhibit genetically inherited resistance to As-toxicity. In this study F1, F2 and F3 generation offspring derived from adults inhabiting As-contaminated field soil were resistant when exposed to 2000 mg kg(-1) sodium arsenate. The offspring of uncontaminated adults were not As-resistant. Cocoon viability was 80% for F1 and 82% for F2 offspring from As-contaminated adults and 59% in the F1 control population. High energy synchrotron analysis was used to determine whether ligand complexation of As differed in samples of: resistant mine-site adults, the resistant F1 and F2 offspring of the mine-site earthworms exposed to the LC(25) sodium arsenate (700 mg kg(-1)) of the F1 parental generation; and adult L. rubellus from an uncontaminated site exposed to LC(25) concentrations of sodium arsenate (50 mg kg(-1)). XANES and EXAFS indicated that As was present as a sulfur-coordinated species.

Arsenic (As) is mobilized from delta and floodplain aquifer sediments throughout S.E. Asia via reductive dissolution of As bound to iron (Fe) oxyhydroxides. The reductive driving force is organic carbon, but its source and constitution is uncertain. Here batch incubation experiments were conducted to investigate the role of organic matter (OM) carbon:nitrogen (C:N) ratio on the mobilization of arsenic, Fe and N from As dosed, Fe oxyhydroxide coated sands. As mobilization into pore waters from the sand was strongly regulated by the C:N ratio of the OM, and also the concentration of OM present. The lower the C:N, the more As released. Fe and ammonium release were similarly dependent on the quality and quantity of OM, but Fe mobilization was more rapid and ammonium release slower than As suggesting that the mobilization of these 3 moieties although interdependent, were not directly linked. It was concluded that low C:N ratios for OM responsible for reducing aquifers were As in groundwater is observed were likely.

Abstract Technetium is a radioactive contaminant found in groundwaters at sites where nuclear wastes have been processed or stored. The redox chemistry of technetium is a major control on its environmental mobility. Under oxic conditions, technetium exists as the pertechnetate ion, Tc(VII)O4−, which is poorly sorbed by minerals across a wide range of environmentally relevant pH values. Under reducing conditions pertechnetate is converted to lower valency species, of which Tc(IV) tends to predominate. Typically, the Tc(IV) oxidation state readily precipitates as insoluble hydrous Tc(IV) oxides or, at low concentrations, is removed from solution by association with mineral surfaces. Here, we present novel X-ray absorption spectroscopy (XAS) data examining Tc associations with reduced Dounreay soils. In reduced unamended microcosms and in microcosms where we added the co-contaminants ethylenediaminetetraacetic acid (EDTA) or bicarbonate to investigate their effect on Tc biogeochemistry, Tc was removed from solution on exposure to the reduced sediments and was present on solids as hydrous Tc(IV)O2-like phases. Furthermore, to investigate the long term stability and remobilization of solid phase associated Tc in reduced soils, we reoxidized reduced, Tc(IV)-labeled soils, in the presence of air and nitrate. The extent of remobilization of Tc to solution was dependent on the oxidant used. After reoxidation with air for 60 d, (42±6)% of the initial soil bound Tc was resolubilized. In the presence of 25 or 100 mmol L−1 nitrate as an oxidant, negligible microcosm reoxidation or remobilization of Tc to solution occurred. XAS analysis of soils treated with the two oxidants showed that in both systems, the remaining soil associated Tc was present as hydrous TcO2-like phases. The recalcitrance of Tc remobilization under reoxidizing conditions has implications for the fate of Tc in contaminated environments.

Handley, K. M. Boothman, C. McBeth, J. M. Charnock, J. M. Wincott, P. L. Vaughan, D. J. Polya, D. A. Lloyd, J. R. 0 OXFORD 12 Suppl. 1 321JU

Arsenic is known to accumulate with iron plaque on macrophyte roots. Three to four years after the Aznalcóllar mine spill (Spain), residual arsenic contamination left in seasonal wetland habitats has been identified in this form by scanning electron microscopy. Total digestion has determined arsenic concentrations in thoroughly washed ‘root+plaque’ material in excess of 1000mg kg−1, and further analysis using X-ray absorption spectroscopy suggests arsenic exists as both arsenate and arsenite. Certain herbivorous species feed on rhizomes and bulbs of macrophytes in a wide range of global environments, and the ecotoxicological impact of consuming arsenic rich iron plaque associated with such food items remains to be quantified. Here, greylag geese which feed on Scirpus maritimus rhizome and bulb material in areas affected by the Aznalcóllar spill are shown to have elevated levels of arsenic in their feces, which may originate from arsenic rich iron plaque.

The biogeochemical activities of free-living and symbiotic fungi must be acknowledged in attempts to understand uranium cycling and dispersal in the environment. Although the near-surface geochemistry of uranium is very complex and a wide variety of mineral phases is known, uranium trioxide (UO3) and triuranium octaoxide (U3O8) can be used as well characterized models in the study of biotransformations. We have used a complex methodological approach involving advanced solid state speciation and scanning electron microscopy to study the ability of saprotrophic, ericoid and ectomycorrhizal fungi to transform these model oxides. This study has revealed that fungi exhibit a high uranium oxide tolerance, and possess the ability to solubilize UO3 and U3O8 and to accumulate uranium within the mycelium to over 80 mg (g dry weight)(-1) biomass. X-ray absorption spectroscopy of uranium speciation within the biomass showed that in most of the fungi the uranyl ion was coordinated to phosphate ligands, but in ectomycorrhizal fungi mixed phosphate/carboxylate coordination was observed. Abundant uranium precipitates associated with phosphorus were found in the mycelium and encrusted the hyphae. Some of the fungi caused the biomineralization of well-crystallized uranyl phosphate minerals of the meta-autunite group. This is the first experimental evidence for fungal transformations of uranium solids and the production of secondary mycogenic uranium minerals.