ABSTRACT
Round robin studies have been used across fields of science for quality control testing and to investigate laboratory dependencies and cross-platform inconsistencies as well as to drive forward the improvement of understanding of experimental systems, systematic effects and theoretical limitations. Here, following the Q2XAFS Workshop and Satellite to IUCr Congress 2017 on `Data Acquisition, Treatment, Storage - quality assurance in XAFS spectroscopy', a mechanism is suggested for a suitable study across XAFS (X-ray absorption fine-structure) beamlines and facilities, to enable each beamline to cross-calibrate, provide representative test data, and to enable collaborative cross-facility activities to be more productive.
ABSTRACT
Diffusion is important in controlling local solute transport and reactions in unsaturated soils and geologic formations. Although it is commonly assumed that thinning of water films controls solute diffusion at low water contents, transport under these conditions is not well understood. We conducted experiments in quartz sands at low volumetric water contents (θ) to quantify ion diffusion within adsorbed films. At the lowest water contents, we employed fixed relative humidities to control water films at nm thicknesses. Diffusion profiles for Rb+ and Br- in unsaturated sand packs were measured with a synchrotron X-ray microprobe, and inverse modeling was used to determine effective diffusion coefficients, De, as low as â¼9 × 10-15 m2 s-1 at θ = 1.0 × 10-4 m3 m-3, where the film thickness = 0.9 nm. Given that the diffusion coefficients (Do) of Rb+ and Br- in bulk water (30 °C) are both â¼2.4 × 10-9 m2 s-1, we found the impedance factor f = De/(θDo) is equal to 0.03 ± 0.02 at this very low saturation, in agreement with the predicted influence of interface tortuosity (τa) for diffusion along grain surfaces. Thus, reduced cross-sectional area (θ) and tortuosity largely accounted for the more than 5 orders of magnitude decrease in De relative to Do as desaturation progressed down to nanoscale films.
Subject(s)
Water Movements , Water , Diffusion , Porosity , Silicon DioxideABSTRACT
X-ray microprobes (XRM) coupled with high-brightness synchrotron X-ray facilities are powerful tools for environmental biogeochemistry research. One such instrument, the XRM at the Geo Soil Enviro Center for Advanced Radiation Sources Sector 13 at the Advanced Photon Source (APS; Argonne National Laboratory, Lemont, IL) was recently improved as part of a canted undulator geometry upgrade of the insertion device port, effectively doubling the available undulator beam time and extending the operating energy of the branch supporting the XRM down to the sulfur K edge (2.3 keV). Capabilities include rapid, high-resolution, elemental imaging including fluorescence microtomography, microscale X-ray absorption fine structure spectroscopy including sulfur K edge capability, and microscale X-ray diffraction. These capabilities are advantageous for (i) two-dimensional elemental mapping of relatively large samples at high resolution, with the dwell times typically limited only by the count times needed to obtain usable counting statistics for low concentration elements, (ii) three-dimensional imaging of internal elemental distributions in fragile hydrated specimens, such as biological tissues, avoiding the need for physical slicing, (iii) spatially resolved speciation determinations of contaminants in environmental materials, and (iv) identification of contaminant host phases. In this paper, we describe the XRM instrumentation, techniques, applications demonstrating these capabilities, and prospects for further improvements associated with the proposed upgrade of the APS.
Subject(s)
Environmental Monitoring , Synchrotrons , Soil , X-Ray Absorption Spectroscopy , X-Ray DiffractionABSTRACT
Several studies have examined the effect of submergence on the mobility of metals present in mine waste materials. This study examines the effect of organic carbon (OC) and sulfur (S) additions and submergence time on redox-induced biogeochemical transformations of lead (Pb), zinc (Zn), and cadmium (Cd) present in mine waste materials collected from the Tri-State mining district located in southeastern Kansas, southwestern Missouri, and northeastern Oklahoma. A completely randomized design, with a two-way treatment structure, was used for conducting a series of column experiments. Two replicates were used for each treatment combination. Effluent samples were collected at several time points, and soil samples were collected at the end of each column experiment. Because these samples are highly heterogeneous, we used a variety of synchrotron-based techniques to identify Pb, Zn, and Cd speciation at both micro- and bulk-scale. Spectroscopic analysis results from the study revealed that the addition of OC, with and without S, promoted metal-sulfide formation, whereas metal carbonates dominated in the nonamended flooded materials and in mine waste materials only amended with S. Therefore, the synergistic effect of OC and S may be more promising for managing mine waste materials disposed of in flooded subsidence mine pits instead of individual S or OC treatments. The mechanistic understanding gained in this study is also relevant for remediation of waste materials using natural or constructed wetland systems.
Subject(s)
Cadmium/chemistry , Lead/chemistry , Soil Pollutants/chemistry , Zinc/chemistry , Environmental Monitoring , Kansas , Metals, Heavy , Mining , Missouri , Oklahoma , Oxidation-Reduction , Spectrum Analysis , Synchrotrons , X-RaysABSTRACT
Heating a mixture of uranyl(vi) nitrate and tantalum(v) oxide in the molar ratio of 2 : 3 to 1400 °C resulted in the formation of a new compound, UTa3O10. The honey colored to yellow brown crystals of UTa3O10 crystallize in an orthorhombic structure with the space group Fddd (no. 70), lattice parameters a = 7.3947(1), b = 12.7599(2), c = 15.8156(2) Å, and Z = 8. Vertex sharing [TaO6]7- octahedra of two crystallographically distinct Ta cations form a three dimensional tantalate framework. Within this framework, six membered rings of [TaO6]7- octahedra are formed within the (001) plane. The center of these rings is occupied by the uranyl cations [UO2]+, with an oxidation state of +5 for uranium. The pentavalence of U and Ta was confirmed by X-ray photoelectron spectroscopy and X-ray adsorption spectroscopy. The enthalpy of formation of UTa3O10 from Ta2O5, ß-U3O7, and U3O8 has been determined to be 13.1 ± 18.1 kJ mol-1 using high temperature oxide melt solution calorimetry with sodium molybdate as the solvent at 700 °C. The close to zero enthalpy of formation of UTa3O10 can be explained by closely balanced structural stabilizing and destabilizing factors, which may also apply to other UM3O10 compounds.
ABSTRACT
Although pentavalent uranium can exist in aqueous solution, its presence in the solid state is uncommon. Metal monouranates, MgUO4, CrUO4 and FeUO4 were synthesized for detailed structural and energetic investigations. Structural characteristics of these uranates used powder X-ray diffraction, synchrotron X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and (57)Fe-Mössbauer spectroscopy. Enthalpies of formation were measured by high temperature oxide melt solution calorimetry. Density functional theory (DFT) calculations provided both structural and energetic information. The measured structural and thermodynamic properties show good consistency with those predicted from DFT. The presence of U(5+) has been solidly confirmed in CrUO4 and FeUO4, which are thermodynamically stable compounds, and the origin and stability of U(5+) in the system was elaborated by DFT. The structural and thermodynamic behaviour of U(5+) elucidated in this work is relevant to fundamental actinide redox chemistry and to applications in the nuclear industry and radioactive waste disposal.
ABSTRACT
Terrestrial crops are directly exposed to silver nanoparticles (Ag-NPs) and their environmentally transformed analog silver sulfide nanoparticles (Ag2S-NPs) when wastewater treatment biosolids are applied as fertilizer to agricultural soils. This leads to a need to understand their bioavailability to plants. In the present study, the mechanisms of uptake and distribution of silver in alfalfa (Medicago sativa) were quantified and visualized upon hydroponic exposure to Ag-NPs, Ag2S-NPs, and AgNO3 at 3 mg total Ag/L. Total silver uptake was measured in dried roots and shoots, and the spatial distribution of elements was investigated using transmission electron microscopy (TEM) and synchrotron-based X-ray imaging techniques. Despite large differences in release of Ag(+) ions from the particles, Ag-NPs, Ag2S-NPs, and Ag(+) became associated with plant roots to a similar degree, and exhibited similarly limited (<1%) amounts of translocation of silver into the shoot system. X-ray fluorescence (XRF) mapping revealed differences in the distribution of Ag into roots for each treatment. Silver nanoparticles mainly accumulated in the (columella) border cells and elongation zone, whereas Ag(+) accumulated more uniformly throughout the root. In contrast, Ag2S-NPs remained largely adhered to the root exterior, and the presence of cytoplasmic nano-SixOy aggregates was observed. Exclusively in roots exposed to particulate silver, NPs smaller than the originally dosed NPs were identified by TEM in the cell walls. The apparent accumulation of Ag in the root apoplast determined by XRF, and the presence of small NPs in root cell walls suggests uptake of partially dissolved NPs and translocation along the apoplast.
Subject(s)
Environmental Pollutants/pharmacokinetics , Medicago sativa/drug effects , Metal Nanoparticles , Silver Compounds/pharmacokinetics , Silver/pharmacokinetics , Biological Availability , Biological Transport , Cytoplasm/drug effects , Cytoplasm/metabolism , Medicago sativa/metabolism , Metal Nanoparticles/chemistry , Microscopy, Electron, Transmission , Plant Roots/chemistry , Plant Roots/drug effects , Plant Roots/metabolism , Silver/analysis , Soil , Spectrometry, X-Ray Emission , Wastewater/chemistryABSTRACT
A penalized maximum-likelihood estimation is proposed to perform hyperspectral (spatio-spectral) image reconstruction for X-ray fluorescence tomography. The approach minimizes a Poisson-based negative log-likelihood of the observed photon counts, and uses a penalty term that has the effect of encouraging local continuity of model parameter estimates in both spatial and spectral dimensions simultaneously. The performance of the reconstruction method is demonstrated with experimental data acquired from a seed of arabidopsis thaliana collected at the 13-ID-E microprobe beamline at the Advanced Photon Source. The resulting element distribution estimates with the proposed approach show significantly better reconstruction quality than the conventional analytical inversion approaches, and allows for a high data compression factor which can reduce data acquisition times remarkably. In particular, this technique provides the capability to tomographically reconstruct full energy dispersive spectra without compromising reconstruction artifacts that impact the interpretation of results.
ABSTRACT
The garnet structure has been proposed as a potential crystalline nuclear waste form for accommodation of actinide elements, especially uranium (U). In this study, yttrium iron garnet (YIG) as a model garnet host was studied for the incorporation of U analogs, cerium (Ce) and thorium (Th), incorporated by a charge-coupled substitution with calcium (Ca) for yttrium (Y) in YIG, namely, 2Y(3+) = Ca(2+) + M(4+), where M(4+) = Ce(4+) or Th(4+). Single-phase garnets Y3-xCa0.5xM0.5xFe5O12 (x = 0.1-0.7) were synthesized by the citrate-nitrate combustion method. Ce was confirmed to be tetravalent by X-ray absorption spectroscopy and X-ray photoelectron spectroscopy. X-ray diffraction and (57)Fe-Mössbauer spectroscopy indicated that M(4+) and Ca(2+) cations are restricted to the c site, and the local environments of both the tetrahedral and the octahedral Fe(3+) are systematically affected by the extent of substitution. The charge-coupled substitution has advantages in incorporating Ce/Th and in stabilizing the substituted phases compared to a single substitution strategy. Enthalpies of formation of garnets were obtained by high temperature oxide melt solution calorimetry, and the enthalpies of substitution of Ce and Th were determined. The thermodynamic analysis demonstrates that the substituted garnets are entropically rather than energetically stabilized. This suggests that such garnets may form and persist in repositories at high temperature but might decompose near room temperature.
ABSTRACT
Biogeochemistry of uranium in wetlands plays important roles in U immobilization in storage ponds of U mining and processing facilities but has not been well understood. The objective of this work was to study molecular mechanisms responsible for high U retention by Savannah River Site (SRS) wetland sediments under varying redox and acidic (pH = 2.6-5.8) conditions using U L3-edge X-ray absorption spectroscopy. Uranium in the SRS wetland sediments existed primarily as U(VI) bonded as a bidentate to carboxylic sites (U-C bond distance at â¼2.88 Å), rather than phenolic or other sites of natural organic matter (NOM). In microcosms simulating the SRS wetland processes, U immobilization on roots was 2 orders of magnitude higher than on the adjacent brown or more distant white sands in which U was U(VI). Uranium on the roots were both U(IV) and U(VI), which were bonded as a bidentate to carbon, but the U(VI) may also form a U phosphate mineral. After 140 days of air exposure, all U(IV) was reoxidized to U(VI) but remained as a bidentate bonding to carbon. This study demonstrated NOM and plant roots can highly immobilize U(VI) in the SRS acidic sediments, which has significant implication for the long-term stewardship of U-contaminated wetlands.
Subject(s)
Plant Roots/chemistry , Uranium/chemistry , Wetlands , X-Ray Absorption Spectroscopy , Geologic Sediments/chemistry , Minerals/chemistry , Oxidation-Reduction , Rivers/chemistry , Water Pollutants, Radioactive/chemistryABSTRACT
The nonheterocystous cyanobacterium Trichodesmium fixes C and N concurrently during the light period in tropical and subtropical oceans. Synchrotron mapping of Fe, P and S in trichomes of Trichodesmium erythraeum Erhenberg IMS 101 (CCMP 1985) collected during exponential and senescent growth revealed that 16% of trichomes contained sections of up to 25 cells with ca. 2-fold elevated Fe and S but ca. 2-fold lowered P in comparison to neighboring trichome sections. The correlation between Fe and S in these trichomes was moderate to strongly positive (R > 0.35), while the correlation between Fe and P was moderate to strongly negative (R < 0.35). Higher Fe in theses trichome sections might indicate the presence of nitrogenase. Increase in S in conjunction with Fe is likely driven by other S-containing compounds in addition to Fe-S proteins. Furthermore, the concurrent increase in S and decrease in P in these Fe-rich trichome sections might indicate a switch from P- to S-containing compounds. Diurnal changes and growth phase-related differences in the correlation between Fe and P both point to Trichodesmium's ability to re-allocate elements depending on their physiological need. Concurrent P depletion and Fe and S enrichment in trichome sections is a strong indication that Trichodesmium is able to develop special trichome regions consisting of multiple cells with a unique chemical composition. Whether these cells are uniquely dedicated to N2-fixation (i.e., diazocytes) is an open question.
Subject(s)
Cyanobacteria/metabolism , Iron/analysis , Phosphorus/analysis , Sulfur/analysis , Cyanobacteria/chemistry , Cyanobacteria/growth & development , Cyanobacteria/ultrastructure , Iron/metabolism , Nitrogen Fixation , Phosphorus/metabolism , Sulfur/metabolismABSTRACT
Uranium speciation and retention mechanisms onto Savannah River Site (SRS) wetland sediments was studied using batch (ad)sorption experiments, sequential extraction, U L3-edge X-ray absorption near-edge structure (XANES) spectroscopy, fluorescence mapping and µ-XANES. Under oxidized conditions, U was highly retained by the SRS wetland sediments. In contrast to other similar but much lower natural organic matter (NOM) sediments, significant sorption of U onto the SRS sediments was observed at pH < 4 and pH > 8. Sequential extraction indicated that the U species were primarily associated with the acid soluble fraction (weak acetic acid extractable) and organic fraction (Na-pyrophosphate extractable). Uranium L3-edge XANES spectra of the U-bound sediments were nearly identical to that of uranyl acetate. Based on fluorescence mapping, U and Fe distributions in the sediment were poorly correlated, U was distributed throughout the sample and did not appear as isolated U mineral phases. The primary oxidation state of U in these oxidized sediments was U(VI), and there was little evidence that the high sorptive capacity of the sediments could be ascribed to abiotic or biotic reduction to the less soluble U(IV) species or to secondary mineral formation. Collectively, this study suggests that U may be strongly bound to wetland sediments, not only under reducing conditions by reductive precipitation, but also under oxidizing conditions through NOM-uranium bonding.
Subject(s)
Geologic Sediments/chemistry , Soil Pollutants, Radioactive/analysis , Uranium/analysis , Adsorption , Hazardous Waste Sites , Oxidation-Reduction , Radiation Monitoring , Radioactive Waste , Soil Pollutants, Radioactive/chemistry , South Carolina , Uranium/chemistry , WetlandsABSTRACT
The structural behavior of GeO2 glass has been investigated up to 64 GPa using results from x-ray absorption spectroscopy in a diamond anvil cell combined with previously reported density measurements. The difference between the nearest Ge-O distances of glassy and rutile-type GeO2 disappears at the Ge-O distance maximum at 20 GPa, indicating completion of the tetrahedral-octahedral transition in GeO2 glass. The mean-square displacement σ(2) of the Ge-O distance in the first Ge-O shell increases progressively to a maximum at 10 GPa, followed by a substantial reduction at higher pressures. The octahedral glass is, as expected, less dense and has a higher compressibility than the corresponding crystalline phase, but the differences in Ge-O distance and density between the glass and the crystals are gradually eliminated over the 20-40 GPa pressure range. Above 40 GPa, GeO2 forms a dense octahedral glass with a compressibility similar to that of the corresponding crystalline phase (α-PbO2 type). The EXAFS and XANES spectra show evidence for subtle changes in the dense glass continuing to occur at these high pressures. The Ge-O bond distance shows little change between 45-64 GPa, and this may reflect a balance between bond shortening and a gradual coordination number increase with compression. The density of the glass is similar to that of the α-PbO2-type phase, but the Ge-O distance is longer and is close to that in the higher-coordination pyrite-type phase which is stable above â¼60 GPa. The density data provide evidence for a possible discontinuity and change in compressibility at 40-45 GPa, but there are no major changes in the corresponding EXAFS spectra. A pyrite-type local structural model for the glass can provide a reasonable fitting to the XAFS spectra at 64 GPa.
ABSTRACT
The stabilization of Pb on additions of P to contaminated soils and mine spoil materials has been well documented. It is clear from the literature that different P sources result in different efficacies of Pb stabilization in the same contaminated material. We hypothesized that the differences in the efficacy of Pb stabilization in contaminated soils on fluid or granular P amendment addition is due to different P reaction processes in and around fertilizer granules and fluid droplets. We used a combination of several synchrotron-based techniques (i.e., spatially resolved micro-X-ray fluorescence, micro-X-ray absorption near-edge structure spectroscopy, and micro-X-ray diffraction) to speciate Pb at two incubation times in a smelter-contaminated soil on addition of several fluid and granular P amendments. The results indicated that the Pb phosphate mineral plumbogummite was an intermediate phase of pyromorphite formation. Additionally, all fluid and granular P sources were able to induce Pb phosphate formation, but fluid phosphoric acid (PA) was the most effective with time and distance from the treatment. Granular phosphate rock and triple super phosphate (TSP) amendments reacted to generate Pb phosphate minerals, with TSP being more effective at greater distances from the point of application. As a result, PA and TSP were the most effective P amendments at inducing Pb phosphate formation, but caution needs to be exercised when adding large amounts of soluble P to the environment.
ABSTRACT
The use of P to immobilize Pb in contaminated soils has been well documented. However, the influence of P on Zn speciation in soils has not been extensively examined, and these two metals often occur as co-contaminants. We hypothesized that additions of P to a Pb/Zn-contaminated soil would induce Zn phosphate mineral formation and fluid P sources would be more effective than granular P amendments. A combination of different synchrotron-based techniques, namely, spatially resolved micro-X-ray fluorescence (µ-XRF), micro-extended X-ray absorption fine structure spectroscopy (µ-EXAFS), and micro-X-ray diffraction (µ-XRD), were used to speciate Zn at two incubation times in the proximity of application points (0 to 4 mm) for fluid and granular P amendments in a Pb/Zn smelter-contaminated soil. Phosphate rock (PR), triple super phosphate (TSP), monoammonium phosphate (MAP), and fluid ammonium polyphosphate induced Zn phosphate formation. Ammonium polyphosphate was more effective at greater distances (up to 3.7 mm) from the point of P application. Phosphoric acid increased the presence of soluble Zn species because of increased acidity. Soluble Zn has implications with respect to Zn bioavailability, which may negatively impact vegetation and other sensitive organisms. Although additions of P immobilize Pb, this practice needs close monitoring due to potential increases in Zn solubility in a Pb/Zn smelter-contaminated soil.
Subject(s)
Industrial Waste/analysis , Lead/chemistry , Phosphates/chemistry , Soil Pollutants/chemistry , Zinc/chemistry , Environmental Monitoring , Extraction and Processing Industry , Soil/chemistry , X-Ray DiffractionABSTRACT
The safety of urban farming has been questioned due to the potential for contamination in urban soils. A laboratory incubation, a field trial, and a second laboratory incubation were conducted to test the ability of high-Fe biosolids-based composts to reduce the bioaccessibility of soil Pb and As in situ. Lead and As bioaccessibility were evaluated using an in vitro assay. Changes in Pb, As, and Fe speciation were determined on select samples after the second laboratory incubation using µ-X-ray fluorescence mapping followed by µ-X-ray absorption near-edge structure (XANES). A compost with Fe added to wastewater treatment residuals (Fe WTR compost) added to soils at 100 g kg decreased Pb bioaccessibility in both laboratory incubations. Mixed results were observed for As. Composts tested in the field trial (Fe added as Fe powder or FeCl) did not reduce bioaccessible Pb, and limited reductions were observed in bioaccessible As. These composts had no effect on Pb bioaccessibility during the second laboratory incubation. Bulk XANES showed association of Pb with sulfates and carbonates in the control soil. µ-XANES for three points in the Fe WTR amended soil showed Pb present as Fe-sorbed Pb (88 and 100% of two points) and pyromorphite (12 and 53% of two points). Bulk XANES of the Fe WTR compost showed 97% of total Fe present as Fe. The results of this study indicate that addition of high-Fe biosolids compost is an effective means to reduce Pb accessibility only for certain types of Fe-rich materials.
Subject(s)
Arsenic/chemistry , Iron/chemistry , Lead/chemistry , Sewage , Soil/chemistry , X-Ray Absorption SpectroscopyABSTRACT
The elemental composition of phytoplankton can depart from canonical Redfield values under conditions of nutrient limitation or production (e.g., N fixation). Similarly, the trace metal metallome of phytoplankton may be expected to vary as a function of both ambient nutrient concentrations and the biochemical processes of the cell. Diazotrophs such as the colonial cyanobacteria Trichodesmium are likely to have unique metal signatures due to their cell physiology. We present metal (Fe, V, Zn, Ni, Mo, Mn, Cu, Cd) quotas for Trichodesmium collected from the Sargasso Sea which highlight the unique metallome of this organism. The element concentrations of bulk colonies and trichomes sections were analyzed by ICP-MS and synchrotron x-ray fluorescence, respectively. The cells were characterized by low P contents but enrichment in V, Fe, Mo, Ni, and Zn in comparison to other phytoplankton. Vanadium was the most abundant metal in Trichodesmium, and the V quota was up to fourfold higher than the corresponding Fe quota. The stoichiometry of 600C:101N:1P (mol mol(-1)) reflects P-limiting conditions. Iron and V were enriched in contiguous cells of 10 and 50% of Trichodesmium trichomes, respectively. The distribution of Ni differed from other elements, with the highest concentration in the transverse walls between attached cells. We hypothesize that the enrichments of V, Fe, Mo, and Ni are linked to the biochemical requirements for N fixation either directly through enrichment in the N-fixing enzyme nitrogenase or indirectly by the expression of enzymes responsible for the removal of reactive oxygen species. Unintentional uptake of V via P pathways may also be occurring. Overall, the cellular content of trace metals and macronutrients differs significantly from the (extended) Redfield ratio. The Trichodesmium metallome is an example of how physiology and environmental conditions can cause significant deviations from the idealized stoichiometry.
ABSTRACT
Arsenic is naturally associated with gold mineralisation and elevated in some soils and mine waste around historical gold mining activity in Victoria, Australia. To explore uptake, arsenic concentrations in children's toenail clippings and household soils were measured, and the microdistribution and speciation of arsenic in situ in toenail clipping thin sections investigated using synchrotron-based X-ray microprobe techniques. The ability to differentiate exogenous arsenic was explored by investigating surface contamination on cleaned clippings using depth profiling, and direct diffusion of arsenic into incubated clippings. Total arsenic concentrations ranged from 0.15 to 2.1 microg/g (n=29) in clipping samples and from 3.3 to 130 microg/g (n=22) in household soils, with significant correlation between transformed arsenic concentrations (Pearson's r=0.42, P=0.023) when household soil was treated as independent. In clipping thin sections (n=2), X-ray fluorescence (XRF) mapping showed discrete layering of arsenic consistent with nail structure, and irregular arsenic incorporation along the nail growth axis. Arsenic concentrations were heterogeneous at 10x10 microm microprobe spot locations investigated (<0.1 to 13.3 microg/g). X-ray absorption near-edge structure (XANES) spectra suggested the presence of two distinct arsenic species: a lower oxidation state species, possibly with mixed sulphur and methyl coordination (denoted As(approximately III)(-S, -CH3)); and a higher oxidation state species (denoted As(approximately V)(-O)). Depth profiling suggested that surface contamination was unlikely (n=4), and XRF and XANES analyses of thin sections of clippings incubated in dry or wet mine waste, or untreated, suggested direct diffusion of arsenic occurred under moist conditions. These findings suggest that arsenic in soil contributes to some systemic absorption associated with periodic exposures among children resident in areas of historic gold mining activity in Victoria, Australia. Future studies are required to ascertain if adverse health effects are associated with current levels of arsenic uptake.
Subject(s)
Arsenic/metabolism , Environmental Exposure/analysis , Mining , Nails/metabolism , Soil Pollutants/metabolism , Toes , Adolescent , Arsenic/analysis , Arsenic/chemistry , Child , Child, Preschool , Environmental Monitoring , Female , Gold , Humans , Male , Soil/analysis , Soil Pollutants/analysis , Soil Pollutants/chemistryABSTRACT
We describe an approach for acquiring high quality x-ray absorption fine structure (XAFS) spectroscopy spectra with wide energy range at high pressure using diamond anvil cell (DAC). Overcoming the serious interference of diamond Bragg peaks is essential for combining XAFS and DAC techniques in high pressure research, yet an effective method to obtain accurate XAFS spectrum free from DAC induced glitches has been lacking. It was found that these glitches, whose energy positions are very sensitive to the relative orientation between DAC and incident x-ray beam, can be effectively eliminated using an iterative algorithm based on repeated measurements over a small angular range of DAC orientation, e.g., within +/-3 degrees relative to the x-ray beam direction. Demonstration XAFS spectra are reported for rutile-type GeO2 recorded by traditional ambient pressure and high pressure DAC methods, showing similar quality at 440 eV above the absorption edge. Accurate XAFS spectra of GeO2 glass were obtained at high pressure up to 53 GPa, providing important insight into the structural polymorphism of GeO2 glass at high pressure. This method is expected be applicable for in situ XAFS measurements using a diamond anvil cell up to ultrahigh pressures.
Subject(s)
Diamond , Pressure , Spectrum Analysis/instrumentation , X-Rays , Absorption , Algorithms , Germanium/chemistry , Glass/chemistry , Reproducibility of ResultsABSTRACT
Shooting ranges represent sites heavily polluted by Pb, Sb, Cu, Ni, and Zn, which are released during the weathering of bullets. The pristine bullets are made of a Pb-Sb core, Fe mantle, and minor amounts of Cu, Ni, and Zn in an interlayer between the core and mantle. At two selected sampling sites (Losone and Lucerne, both in Switzerland), corroding bullets were collected to determine the sinks of Sb within the weathering crust of the bullets. Bulk Sb concentrations in the crust were found to be as high as 1.3 wt.%. The oxalate-extractable fraction of Fe showed that the amorphous Fe oxides (e.g., ferrihydrite) prevail over goethite and lepidocrocite, which were identified by bulk X-ray diffraction experiments. Crystalline Pb phases are litharge (only found by X-ray diffraction) and cerussite, which result from weathering of the Pb core. No distinct Sb minerals were identified by X-ray diffraction. Investigations with electron microprobe (EMP) showed that Sb is mostly accumulated in those regions in the weathering crust where there is also a high concentration of Fe. In the weathering crust from Losone, such Fe-rich regions with Sb are represented by material that cements or rims silicate mineral grains. The cement was identified as lepidocrocite by micro-Raman analysis. At Lucerne, Sb is found in Fe-oxide aggregates, in sawdust particles where it may be bound to organic matter, or in aggregates enriched in Pb and depleted in Fe. Bulk EXAFS experiments suggested that the Fe oxides are the most important sink for Sb. Our modelling of Sb next-nearest neighbours suggests two types of inner-sphere complexes on the surfaces of Fe oxides. These are edge- and corner-sharing adsorption complexes. Hence, the predominant sink of Sb in the weathering crust of the bullets at the selected shooting ranges is Fe oxides, amorphous or crystalline.