New Clues to the Local Atomic Structure of Short-Range Ordered Ferric Arsenate from Extended X‑ray Absorption Fine Structure Spectroscopy

Short-range ordered ferric arsenate (FeAsO₄·<i>x</i>H₂O) is a secondary As precipitate frequently encountered in acid mine waste environments. Two distinct structural models have recently been proposed for this phase. The first model is based on the structure of scorodite (FeAsO₄·2H₂O) where isolated FeO₆ octahedra share corners with four adjacent arsenate (AsO₄) tetrahedra in a three-dimensional framework (framework model). The second model consists of single chains of corner-sharing FeO₆ octahedra being bridged by AsO₄ bound in a monodentate binuclear ²C complex (chain model). In order to rigorously test the accuracy of both structural models, we synthesized ferric arsenates and analyzed their local (<6 Å) structure by As and Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. We found that both As and Fe K-edge EXAFS spectra were most compatible with isolated FeO₆ octahedra being bridged by AsO₄ tetrahedra (<i>R</i>_Fe–As = 3.33 ± 0.01 Å). Our shell-fit results further indicated a lack of evidence for single corner-sharing FeO₆ linkages in ferric arsenate. Wavelet-transform analyses of the Fe K-edge EXAFS spectra of ferric arsenates complemented by shell fitting confirmed Fe atoms at an average distance of ∼5.3 Å, consistent with crystallographic data of scorodite and in disagreement with the chain model. A scorodite-type local structure of short-range ordered ferric arsenates provides a plausible explanation for their rapid transformation into scorodite in acid mining environments

Speciation of Zn in Blast Furnace Sludge from Former Sedimentation Ponds Using Synchrotron X-ray Diffraction, Fluorescence, and Absorption Spectroscopy

Blast furnace sludge (BFS), an industrial waste generated in pig iron production, typically contains high contents of iron and various trace metals of environmental concern, including Zn, Pb, and Cd. The chemical speciation of these metals in BPS is largely unknown. Here, we used a combination of synchrotron X-ray diffraction, micro-X-ray fluorescence, and X-ray absorption spectroscopy at the Zn K-edge for solid-phase Zn speciation in 12 BPS samples collected on a former BFS sedimentation pond site. Additionally, one fresh BPS was analyzed for comparison. We identified five major types of Zn species in the BFS, which occurred in variable amounts: (1) Zn in the octahedral sheets of phyllosilicates, (2) Zn sulfide minerals (ZnS, sphalerite, or wurtzite), (3) Zn in a KZn-ferrocyanide phase (K2Zn3[Fe-(CN)(6)](2)center dot 9H(2)O), (4) hydrozincite (Zn-5(OH)(6)(CO3)(2)), and (5) tetrahedrally coordinated adsorbed Zn. The minerals franklinite (ZnFe2O4) and smithsonite (ZnCO3) were not detected, and zincite (ZnO) was detected only in traces. The contents of ZnS were positively correlated with the total S contents of the BPS. Similarly, the abundance of the KZn-ferrocyanide phase was closely correlated with the total CN contents, with the stoichiometry suggesting this as cyanide phase. This study provides the first quantitative Zn speciation in BFS deposits, which is of great relevance environmental risk assessment, the development of new methods for recovering Zn and Fe from BPS, and potential applications of BFS as sorbent materials in wastewater treatment

Arsenic Species Formed from Arsenopyrite Weathering along a Contamination Gradient in Circumneutral River Floodplain Soils

Arsenic is a toxic trace element, which commonly occurs as contaminant in riverine floodplains and associated wetlands affected by mining and ore processing. In this study, we investigated the solid-phase speciation of As in river floodplain soils characterized by circumneutral pH (5.7–7.1) and As concentrations of up to 40.3 g/kg caused by former mining of arsenopyrite-rich ores. Soil samples collected in the floodplain of Ogosta River (Bulgaria) were size-fractionated and subsequently analyzed using a combination of X-ray fluorescence (XRF) spectrometry, powder X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and selective chemical extraction of poorly crystalline mineral phases. Arsenic and Fe were found to be spatially correlated and both elements were strongly enriched in the fine soil particle size fractions (<2 μm and 2–50 μm). Between 14 and 82% of the total As was citrate-ascorbate extractable. Molar As/Fe ratios were as high as 0.34 in the bulk soil extracts and increased up to 0.48 in extracts of the fine particle size fractions. Arsenic <i>K</i>-edge XAS spectra showed the predominance of As­(V) and were well fitted with a reference spectrum of As­(V) adsorbed to ferrihydrite. Whereas no As­(III) was detected, considerable amounts of As­(-I) were present and identified as arsenopyrite originating from the mining waste. Iron <i>K</i>-edge XAS revealed that in addition to As­(V) adsorbed to ferrihydrite, X-ray amorphous As­(V)-rich hydrous ferric oxides (“As-HFO”) with a reduced number of corner-sharing FeO₆ octahedra relative to ferrihydrite were the dominating secondary As species in the soils. The extremely high concentrations of As in the fine particle size fractions (up to 214 g/kg) and its association with poorly crystalline Fe­(III) oxyhydroxides and As-HFO phases suggest a high As mobilization potential under both oxic and anoxic conditions, as well as a high bioaccessibility of As upon ingestion, dermal contact, or inhalation by humans or animals

Bioaccessibility of Arsenic in Mining-Impacted Circumneutral River Floodplain Soils

Floodplain soils are frequently contaminated with metal­(loid)­s due to present or historic mining, but data on the bioaccessibility (BA) of contaminants in these periodically flooded soils are scarce. Therefore, we studied the speciation of As and Fe in eight As-contaminated circumneutral floodplain soils (≤21600 mg As/kg) and their size fractions using X-ray absorption spectroscopy (XAS) and examined the BA of As in the solids by in-vitro gastrointestinal (IVG) extractions. Arsenopyrite and As­(V)-adsorbed ferrihydrite were identified by XAS as the predominant As species. The latter was the major source for bioaccessible As, which accounted for 5–35% of the total As. The amount of bioaccessible As increased with decreasing particle size and was controlled by the slow dissolution kinetics of ferrihydrite in the gastric environment (pH 1.8). The relative BA of As (% of total) decreased with decreasing particle size only in a highly As-contaminated soil − which supported by Fe XAS − suggests the formation of As-rich hydrous ferric oxides in the gastric extracts. Multiple linear regression analyses identified Al, total As, C_org, and P as main predictors for the absolute BA of As (adjusted <i>R</i>² ≤ 0.977). Health risk assessments for residential adults showed that (i) nearly half of the bulk soils may cause adverse health effects and (ii) particles <5 μm pose the highest absolute health threat upon incidental soil ingestion. Owing to their low abundance, however, health risks were primarily associated with particles in the 5–50 and 100–200 μm size ranges. These particles are easily mobilized from riverbanks during flooding events and dispersed within the floodplain or transported downstream

Speciation of Zn in Blast Furnace Sludge from Former Sedimentation Ponds Using Synchrotron X‑ray Diffraction, Fluorescence, and Absorption Spectroscopy

Blast furnace sludge (BFS), an industrial waste generated in pig iron production, typically contains high contents of iron and various trace metals of environmental concern, including Zn, Pb, and Cd. The chemical speciation of these metals in BFS is largely unknown. Here, we used a combination of synchrotron X-ray diffraction, micro-X-ray fluorescence, and X-ray absorption spectroscopy at the Zn K-edge for solid-phase Zn speciation in 12 BFS samples collected on a former BFS sedimentation pond site. Additionally, one fresh BFS was analyzed for comparison. We identified five major types of Zn species in the BFS, which occurred in variable amounts: (1) Zn in the octahedral sheets of phyllosilicates, (2) Zn sulfide minerals (ZnS, sphalerite, or wurtzite), (3) Zn in a KZn–ferrocyanide phase (K₂Zn₃[Fe­(CN)₆]₂·9H₂O), (4) hydrozincite (Zn₅(OH)₆(CO₃)₂), and (5) tetrahedrally coordinated adsorbed Zn. The minerals franklinite (ZnFe₂O₄) and smithsonite (ZnCO₃) were not detected, and zincite (ZnO) was detected only in traces. The contents of ZnS were positively correlated with the total S contents of the BFS. Similarly, the abundance of the KZn–ferrocyanide phase was closely correlated with the total CN contents, with the stoichiometry suggesting this as the main cyanide phase. This study provides the first quantitative Zn speciation in BFS deposits, which is of great relevance for environmental risk assessment, the development of new methods for recovering Zn and Fe from BFS, and potential applications of BFS as sorbent materials in wastewater treatment

Arsenic species formed from arsenopyrite weathering along a contamination gradient in circumneutral river floodplain soils

Arsenic is a toxic trace element, which commonly occurs as contaminant in riverine floodplains and associated wetlands affected by mining and ore processing. In this study, we investigated the solid-phase speciation of As in river floodplain soils characterized by circumneutral pH (5.7–7.1) and As concentrations of up to 40.3 g/kg caused by former mining of arsenopyrite-rich ores. Soil samples collected in the floodplain of Ogosta River (Bulgaria) were size-fractionated and subsequently analyzed using a combination of X-ray fluorescence (XRF) spectrometry, powder X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and selective chemical extraction of poorly crystalline mineral phases. Arsenic and Fe were found to be spatially correlated and both elements were strongly enriched in the fine soil particle size fractions (<2 μm and 2–50 μm). Between 14 and 82% of the total As was citrate-ascorbate extractable. Molar As/Fe ratios were as high as 0.34 in the bulk soil extracts and increased up to 0.48 in extracts of the fine particle size fractions. Arsenic K-edge XAS spectra showed the predominance of As(V) and were well fitted with a reference spectrum of As(V) adsorbed to ferrihydrite. Whereas no As(III) was detected, considerable amounts of As(-I) were present and identified as arsenopyrite originating from the mining waste. Iron K-edge XAS revealed that in addition to As(V) adsorbed to ferrihydrite, X-ray amorphous As(V)-rich hydrous ferric oxides (“As-HFO”) with a reduced number of corner-sharing FeO6 octahedra relative to ferrihydrite were the dominating secondary As species in the soils. The extremely high concentrations of As in the fine particle size fractions (up to 214 g/kg) and its association with poorly crystalline Fe(III) oxyhydroxides and As-HFO phases suggest a high As mobilization potential under both oxic and anoxic conditions, as well as a high bioaccessibility of As upon ingestion, dermal contact, or inhalation by humans or animals