Ferric Arsenate Research Articles

Mineralogical Controls on the Bioaccessibility of Arsenic in Fe(III)-As(V) Coprecipitates.

X-ray amorphous Fe(III)-As(V) coprecipitates are common initial products of oxidative As- and Fe-bearing sulfide weathering, and often control As solubility in mine wastes or mining-impacted soils. The formation conditions of these solids may exert a major control on their mineralogical composition and, hence, As release in the gastric tract of humans after incidental ingestion of As-contaminated soil. Here, we synthesized a set of 35 Fe(III)-As(V) coprecipitates as a function of pH (1.5-8) and initial molar Fe/As ratio (0.8-8.0). The solids were characterized by synchrotron X-ray diffraction, FT-IR spectroscopy, and electrophoretic mobility measurements, and their As bioaccessibility (BAAs) was evaluated using the gastric-phase Solubility/Bioavailability Research Consortium in vitro assay (SBRC-G). The coprecipitates contained 1.01-4.51 mol kg-1 As (molar Fe/Assolid: 1.00-8.29) and comprised varying proportions of X-ray amorphous hydrous ferric arsenates (HFAam) and As(V)-adsorbed ferrihydrite. HFAam was detected up to pH 6 and its fraction decreased with increasing pH and molar Fe/As ratio. Bioaccessible As ranged from 2.9 to 7.3% of total As (x̅ = 4.8%). The BAAs of coprecipitates formed at pH ≤ 4 was highest at formation pH 3 and 4 and controlled by the intrinsically high solubility of the HFAam component, possibly enhanced by sorbed sulfate. In contrast, the BAAs of coprecipitates dominated by As(V)-adsorbed ferrihydrite was much lower and controlled by As readsorption and/or surface precipitation in the gastric fluid. Bioaccessible As increased up to 95% with increasing liquid-to-solid ratio, indicating an enhanced solubility of these solids due to interactions between Fe and the glycine buffer. We conclude (i) that natural Fe(III)-As(V) coprecipitates exhibit a particularly high solubility in the human gastric tract when formed at pH ∼ 3-4 in the presence of sulfate, and (ii) that the in vitro bioaccessibility of As in Fe(III)-As(V) coprecipitates as assessed by tbe SBRC-G assay depends critically on their solid-phase concentration in As-contaminated soil and mine-waste materials.

Arsenic Speciation of Contaminated Soils / Solid Wastes and Relative Oral Bioavailability in Swine and Mice.

Arsenic (As) is one of the most widespread, toxic elements in the environment and human activities have resulted in a large number of contaminated areas. However abundant, the potential of As toxicity from exposure to contaminated soils is limited to the fraction that will dissolve in the gastrointestinal system and be absorbed into systemic circulation or bioavailable species. In part, the release of As from contaminated soil to gastrointestinal fluid depends on the form of solid phase As also termed “As speciation.” In this study, 27 As-contaminated soils and solid wastes were analyzed using X-ray absorption spectroscopy (XAS) and results were compared to in vivo bioavailability values determined using the adult mouse and juvenile swine bioassays. Arsenic bioavailability was lowest for soils that contained large amounts of arsenopyrite and highest for materials that contained large amounts of ferric arsenates. Soil and solid waste type and properties rather than the contamination source had the greatest influence on As speciation. Principal component analysis determined that As(V) adsorbed and ferric arsenates were the dominant species that control As speciation in the selected materials. Multiple linear regression (MLR) was used to determine the ability of As speciation to predict bioavailability. Arsenic speciation was predictive of 27% and 16% of RBA As determined using the juvenile swine and adult mouse models, respectively. Arsenic speciation can provide a conservative estimate of RBA As using MLR for the juvenile swine and adult mouse bioassays at 55% and 53%, respectively.

Synergistic arsenic(v) and lead(ii) retention on synthetic jarosite. I. Simultaneous structural incorporation behaviour and mechanism.

Jarosite [KFe3(SO4)2(OH)6] minerals are effective scavengers of potentially toxic elements (PTEs) and are abundant, for example, in acid rock/mine drainage scenarios. The retention process is highly relevant for environmental attenuation of heavy metals and metalloids since these are usually highly soluble and thus mobile under acidic conditions. We investigated both macroscopically and at the molecular scale the extent and the effects of concomitant incorporation of As(v) and Pb(ii) into synthetic jarosite at different As/Pb starting molar ratios, using XRD-Rietveld, SEM, ATR-FTIR spectroscopy and wet chemistry. The amount of arsenate substituted in the jarosite structure was larger when Pb(ii) was also incorporated, the former filling up to approximately 33% of the tetrahedral sites normally occupied by SO42-, as compared to 21% when Pb(ii) was absent. Similarly, the amount of Pb(ii) incorporated in the structure was larger when As(v) was also taken up. The jarosite unit cell volume increased as higher amounts of As(v) incorporated into its structure, but simultaneous Pb(ii) incorporation seemed to limit this increase due to its smaller size as compared to K+. The extent to which As and Pb can accommodate in the jarosite structure was found to be limited by concentration maxima under the imposed synthesis conditions. At As/Pb ratios up to 1, Pb-As-jarosites were the only crystalline products. Above this ratio, a mixture of Pb-As-jarosite, anglesite (PbSO4) and poorly-crystalline ferric arsenate (AFA) phases was observed. At the highest As/Pb ratio investigated of 1.80 Pb-As-jarosite was no longer formed. Infrared spectroscopy analysis was applied for the first time here to substituted jarosites with both cations and anions, showing spectral changes in the solids as the As/Pb ratio increased: a characteristic As-O doublet at ∼810 and ∼855 cm-1 was observed upon Pb incorporation, showing an indirect effect of Pb(ii) on the As-O bonds in the jarosite structure. Thus, structural incorporation of Pb plays a pivotal role in the unit cell environment of jarosite to balance the distortion caused by AsO4-for-SO4 substitution. The retention processes found in this work have important environmental implications and impacts: through the synergistic incorporation encountered, remediation enhancement of cationic pollutants such as Pb(ii) is possible in a concomitant fashion with As(v) attenuation in acidic mining and metallurgical environments.

Rethinking anaerobic As(III) oxidation in filters: Effect of indigenous nitrate respirers

Microorganisms play a key role in the redox transformation of arsenic (As) in aquifers. In this study, the impact of indigenous bacteria, especially the prevailing nitrate respirers, on arsenite (As(III)) oxidation was explored during groundwater filtration using granular TiO2 and subsequent spent TiO2 anaerobic landfill. X-ray absorption near edge structure spectroscopy analysis showed As(III) oxidation (46% in 10 days) in the presence of nitrate in the simulated anaerobic landfills. Meanwhile, iron (Fe) species on the spent TiO2 were dominated by amorphous ferric arsenate, ferrihydrite and goethite. The Fe phase showed no change during the anaerobic landfill incubation. Batch incubation experiments implied that the indigenous bacteria completely oxidized As(III) to arsenate (As(V)) in 10 days using nitrate as the terminal electron acceptor under anaerobic conditions. The bacterial community analysis indicated that various kinds of microbial species exist in groundwater matrix. Phylogenetic tree analysis revealed that Proteobacteria was the dominant phylum, with Hydrogenophaga (34%), Limnohabitans (16%), and Simplicispira (7%) as the major bacterial genera. The nitrate respirers especially from the Hydrogenophaga genus anaerobically oxidized As(III) using nitrate as an electron acceptor instead of oxygen. Our study implied that microbes can facilitate the groundwater As oxidation using nitrate on the adsorptive media.

Characterising microbial reduction of arsenate sorbed to ferrihydrite and its concurrence with iron reduction

A series of model anoxic incubations were performed to understand the concurrence between arsenate and ferrihydrite reduction by Shewanella putrefaciens strain CN-32 at different concentrations of arsenate, ferrihydrite and lactate, and with given ΔGrxn for arsenate and ferrihydrite reduction in non-growth conditions. The reduction kinetics of arsenate sorbed to ferrihydrite is predominately controlled by the availability of dissolved arsenate, which is measured by the integral of dissolved arsenate concentrations against incubation time and shown to correlate with the first order rate constants. High lactate concentrations slightly slowed down the rate of arsenate reduction due to the competition with arsenate for microbial contact. Under all experimental conditions, simultaneous arsenate and ferrihydrite reduction occurred following addition of S. putrefaciens inoculums and suggested no apparent competition between these two enzymatic reductions. Ferrous ions released from iron reduction might retard microbial arsenate reduction at high arsenate and ferrihydrite concentrations due to formation of ferrous arsenate. At high arsenate to ferrihydrite ratios, reductive dissolution of ferrihydrite shifted arsenate from sorption to dissolution and hence accelerated arsenate reduction. The interaction between microbial arsenate and ferrihydrite reduction did not correlate with ΔGrxn, but instead was governed by other factors such as geochemical and microbial parameters.

Effect of iron reduction by enolic hydroxyl groups on the stability of scorodite in hydrometallurgical industries and arsenic mobilization.

Scorodite (FeAsO4·2H2O) is an important arsenic-bearing solid waste in hydrometallurgical industries, but its stability in reducing environments is not well understood. This study investigated the effect of Fe(III) reduction by enolic hydroxyl groups on the stability of scorodite and arsenic mobilization at various pH values and ascorbic acid/scorodite molar ratios (AH2/Sc). The results showed that 47-89% Fe(III) reduction by ascorbic acid caused approximately 10-69% (~37-260mgL-1) arsenic release and 4.5-63% (~13-176mgL-1) Fe(II) release at pH 5-8. The releases of arsenic and Fe(II) increased with increasing AH2/Sc, whereas they decreased as pH increased. The results of the solid characterization and chemical analysis indicated that the mixture of poorly crystalline parasymplesite and probably amorphous FeHAsO4⋅xH2O was the new arsenic sink. The high solubility of this ferrous arsenate with the Fe(II)/As(V) molar ratio >1 was deemed to be a major contributor to the relatively high arsenic release. This work differed from our previous finding that almost all arsenic was retained in the solid phase after similar Fe(III) reduction in scorodite with hydroquinone. Phenolic hydroxyl groups complexed with aqueous Fe(II), unlike enolic hydroxyl groups, was possibly the dominant reason for the formation of different secondary minerals, which strongly influenced arsenic redistribution between aqueous and solid phases.

Microbiological As(III) Oxidation and Immobilization as Scorodite at Moderate Temperatures

The potential utility of mesophilic/moderately thermophilic acidophiles was investigated for immobilization of arsenic (As) as scorodite (FeAsO4·2H2O) at moderate temperatures (35–45 °C). Here, the acid-tolerant mesophile Thiomonas cuprina Hö5 and acidophilic moderately thermophile Acidimicrobium ferrooxidans ICP were selected as As (III)- and Fe (II)- oxidizers, respectively. Due to a difference in their optimal growth pHs, a 2-step reaction consisting of the 1st As (III) oxidation step followed by the Fe (II) oxidation + precipitation step was studied. In our previous study, the optimal [Fe (II)]ini/[As (III)]ini molar ratio for bioscorodite formation at 70 °C was shown to be around 1.4. However, setting the same molar ratio at moderate temperatures (35-45 °C) resulted in formation of unstable amorphous ferric arsenate. Lowering the ratio to ≤ 1.0 led to precipitation of crystalline bioscorodite with > 90% As (III) removal at 45 °C.

Mechanism of Silver-Catalyzed Bioleaching of Enargite Concentrate

Silver-catalyzed bioleaching of enargite concentrate with three bacteria (Acidimicrobium ferrooxidans ICP, Sulfobacillus sibiricus N1, Acidithiobacillus caldus KU) and one archaeon (Ferroplasma acidiphilum Y) was conducted in order to elucidate the catalytic mechanism of silver sulfide in enargite bioleaching. Whereas Cu recovery remained relatively low (43%) and Fe dissolved completely without silver sulfide, Cu recovery was greatly enhanced (96%) and Fe dissolution was suppressed (29%) in the presence of 0.04% silver sulfide. In the latter case, 52% of the solubilized As was re-immobilized, in contrast to only 14% As re-immobilization in the former. The silver-catalyzed bioleaching (at 0.04% silver sulfide) proceeded at low redox potentials within the optimal range, which likely promoted enargite dissolution via formation of intermediate Cu2S. XAFS analysis revealed that As was mainly immobilized as As (V), which was in agreement with the EPMA results detecting ferric arsenate passivation on some enargite grains. Furthermore, formation of trisilver arsenic sulfide (Ag3AsS4) was detected by XRD and EPMA, covering the surface of enargite particles. An intermediate layer, consisting of (Cu,Ag)3AsS4, was also observed between the enargite grain and trisilver arsenic sulfide layer, implying that Cu in enargite may be gradually substituted by solubilized Ag. The overall mechanism of silver-catalyzed bioleaching of enargite concentrate will be proposed.

Investigating arsenic speciation in the JEB Tailings Management Facility at McClean Lake, Saskatchewan using X-ray absorption spectroscopy

AREVA Resources Canada operates the McClean Lake Operation (MLO), a uranium mine and processing facility located in northern Saskatchewan. Uranium-containing ores processed at the MLO contain high concentrations of arsenic that is oxidized to soluble arsenite and arsenate species when leaching and recovering uranium. To reduce the environmental impact of AREVA's mining operations, AREVA has developed a tailings preparation process designed to trap arsenic in a mineral form before the tailings are permanently deposited in the JEB Tailings Management Facility (TMF). Scorodite (FeAsO4·2H2O) is predicted to be the primary arsenic species produced from the tailings preparation process. However, scorodite has never been observed in aged tailings samples. Confirming the presence of scorodite in the tailings is important in verifying that the tailings preparation process at the MLO can isolate high concentrations of arsenic from the environment in the form of stable minerals. Herein, X-ray Absorption Near-Edge Structure (XANES) spectroscopy was used to investigate arsenic speciation in a series of samples collected from the JEB TMF in 2013. Arsenic K-edge XANES analysis confirmed that most (86wt%) of the arsenic content in the tailings samples consisted of iron-containing arsenates. Of these, crystalline scorodite was the most abundant arsenate species followed by poorly crystalline arsenates in the form of poorly crystalline ferric arsenate (FeAsO4·xH2O) and arsenate adsorbed on ferrihydrite (AsO4–FeOOH). Arsenite adsorbed on ferrihydrite (AsO3–FeOOH), and gersdorffite (NiAsS) were also identified as minor arsenic species in the tailings samples. The abundance and distribution of scorodite in the TMF suggests that it is the major arsenic species produced in the tailings preparation process.

Biological attenuation of arsenic and iron in a continuous flow bioreactor treating acid mine drainage (AMD)

Passive water treatments based on biological attenuation can be effective for arsenic-rich acid mine drainage (AMD). However, the key factors driving the biological processes involved in this attenuation are not well-known. Here, the efficiency of arsenic (As) removal was investigated in a bench-scale continuous flow channel bioreactor treating As-rich AMD (∼30–40 mg L−1). In this bioreactor, As removal proceeds via the formation of biogenic precipitates consisting of iron- and arsenic-rich mineral phases encrusting a microbial biofilm. Ferrous iron (Fe(II)) oxidation and iron (Fe) and arsenic removal rates were monitored at two different water heights (4 and 25 mm) and with/without forced aeration. A maximum of 80% As removal was achieved within 500 min at the lowest water height. This operating condition promoted intense Fe(II) microbial oxidation and subsequent precipitation of As-bearing schwertmannite and amorphous ferric arsenate. Higher water height slowed down Fe(II) oxidation, Fe precipitation and As removal, in relation with limited oxygen transfer through the water column. The lower oxygen transfer at higher water height could be partly counteracted by aeration. The presence of an iridescent floating film that developed at the water surface was found to limit oxygen transfer to the water column and delayed Fe(II) oxidation, but did not affect As removal. The bacterial community structure in the biogenic precipitates in the bottom of the bioreactor differed from that of the inlet water and was influenced to some extent by water height and aeration. Although potential for microbial mediated As oxidation was revealed by the detection of aioA genes, removal of Fe and As was mainly attributable to microbial Fe oxidation activity. Increasing the proportion of dissolved As(V) in the inlet water improved As removal and favoured the formation of amorphous ferric arsenate over As-sorbed schwertmannite. This study proved the ability of this bioreactor-system to treat extreme As concentrations and may serve in the design of future in-situ bioremediation system able to treat As-rich AMD.

Comparison of contrasting gold mine processing residues in a temperate rain forest, New Zealand

Processing residues high in metallic elements are the legacy of historic gold processing sites, concentrating naturally occurring metalloids in the ore (As, Sb) as well as chemicals and metals added during processing to recover the gold (Zn, Pb, Hg). This study uses electron microscopy to investigate the link between variations in processing residue mineralogy and the processing technique used to extract the gold. Semi-cemented amorphous ferric arsenate and As-bearing iron oxyhydroxides attenuating As, Zn and Pb are the products of the simplest processing technique of crushing, sulphide concentration and gold recovery through Hg-amalgamation. Zinc, Pb and Ca added during cyanidation form Zn-rich carbonate and Zn oxide mineralogy. Ore roasting concentrates As to elevated levels (>35 wt%) as well as concentrating Sb from the ore, and Hg from the amalgamation process. Roasting rapidly oxidises sulphide concentrates producing toxic and highly mobile arsenolite (As2O3 (As3+)). Roaster tailings processed by all of these techniques, crushing, roasting and cyanidation, are largely comprised of As-hematite and quartz.Mine residue weathering causes localised acidification and leaching of metallic elements, along with the high rainfall on these site remobilising elements. Lime added during processing and the carbonate-host rock neutralises this acidification. The formation of secondary Fe3+ oxyhydroxide minerals formed during residue weathering and oxidisation sequesters As, Zn and Pb. Redox conditions and the pH of a site will control the stability of these secondary minerals. The toxicity of a site/processing residue can be correlated to the processing technique used, with characterisation of processing residue mineralogy having important implications for site remediation and management.

Oxidative dissolution of amorphous FeS and speciation of secondary Fe minerals: Effects of pH and As(III) concentration

Oxidative dissolution of Fe sulfides is an important geochemical process mediating As mobility in aqueous environments. However, little is known regarding the presence of As(III) on the oxidative dissolution rate of FeS and on speciation of secondary Fe minerals under pH-neutral and alkaline conditions. In this study, oxidative dissolution of FeS under different concentrations of As(III) and pHs were carried out. The enhanced dissolution rates of Fe(II) from FeS with increasing As(III) concentrations (≤4.7mM) indicate that strong interactions between As(III) and S(−II) in FeS enhance the dissolution rates of structural Fe(II), whereas such an enhancement cannot be observed in the As(III)-FeS system under anoxic conditions at pHs7.0 and 9.0, suggesting the importance of dissolved oxygen in the enhanced dissolution of FeS by As(III). On the other hand, >98.5% of 6.7 and 4.7mM As(III) can be immobilized by 2gL−1 FeS within 1.5h at pHs7.0 and 9.0, respectively, demonstrating the high efficiency of amorphous FeS in the immobilization of concentrated As(III) under oxic conditions. XPS analysis further reveals that, irrespective of pH and initial As(III) concentrations, >60% As(III) was oxidized to As(V) before it was immobilization in secondary Fe minerals, and no As-S compound could be observed after 48h of oxidation. As(III) also influences speciation of secondary Fe minerals during oxidative dissolution of FeS. Analyses of XRD, FTIR, Raman, SEM and TEM demonstrate that the plate lepidocrocite is the primary oxidation product in the absence of As(III), but shows degenerations with increasing As(III) concentrations, and completely changes to ferric arsenate in the presence of 6.7mM As(III), revealing the inhibition of As(III) and/or As(V) on the development of lepidocrocite at pHs7.0 and 9.0. This also suggests that, apart from adsorption, coprecipitation of ferric arsenate is another important pathway to immobilize concentrated As(III) during oxidative dissolution of FeS.

Study on Removing As(III) by Oxidation and Precipitation from Acid-leaching Solution of Pyrite Cinder

Arsenic removal from acid-leaching solution of pyrite cinder which contains a lot of As3+, and some of Fe3+, Fe2+, Cu2+ through an oxidation and precipitation processed by ferric ions has been studied in this work. In order to reuse the acid solution and recycle the cooper in the following process, ICP-MAS was employed to determine the content of As, Fe, Cu of acid-leaching solution and the solution after precipitation. Experiments used hydrogen peroxide as pre-oxidant, which was performed under different temperature, reaction time and at various pH levels. The formation process of insoluble ferric arsenate was analyzed by thermodynamic The results showed that the maximum extractions of arsenic and iron in leaching solution reached 99.89% and 99.77% respectively, and the maximum loss rate of copper was 3.35% when the end point pH value is 3 and reaction lasts for 10min at room temperature. Copper and arsenic in the leaching solution are respectively turned into copper sulfate solution and ferric arsenate slag to separate copper and arsenic.

Coordination of arsenic and nickel to aluminum and magnesium phases in uranium mill raffinate precipitates

The Key Lake U mill uses a stepwise neutralization process (pH 4.0, 6.5, 9.5, and 10.5) to treat raffinate (acidic, metal-rich wastewater) prior to safely releasing effluent to the environment. This process generates a complex mixture of precipitates that are deposited to a tailings facility. In this study, the coordination environments of As and Ni with respect to Al-Mg phases precipitated in the presence and absence of Fe in mill-generated and synthetic precipitates were defined using bulk X-ray absorption spectroscopy complemented with bulk X-ray diffraction. In low pH (pH 4.0–4.6) samples, As(V) precipitates as ferric arsenate and adsorbs to AlOHSO4 (an amorphous hydrobasaluminite-like phase) and ferrihydrite via bidentate-binuclear complexes. Nickel(II) predominantly adsorbs to amorphous Al(OH)3 via edge-sharing bidentate-mononuclear complexes. In high pH (pH 9.5–9.9) samples, As(V) adsorbs to amorphous Al(OH)3, ferrihydrite, and MgAlFe-hydrotalcite (bidentate complex). Nickel(II) octahedra adsorb to amorphous Al(OH)3 and likely form a Ni-Al layered double hydroxide (LDH) surface precipitate on MgAlFe-hydrotalcite via Al dissolution-precipitation. In the final solids (blended low and high pH precipitates) discharged at ∼ pH 10.5, As(V) adsorbs to amorphous Al(OH)3, ferrihydrite, and MgAlFe-hydrotalcite. Nickel(II) adsorbs to amorphous Al(OH)3 and forms Ni-Al LDH surface precipitates on hydrotalcite. This study demonstrates that neutralization of chemically complex wastewater precipitates multiple phases capable of controlling dissolved As and Ni concentrations. Knowledge gained from this study will aid investigations in understanding the long-term fate of these potential contaminants in the environment and can be applied to other industries and environmental systems with similar conditions.

New Insight into the Local Structure of Hydrous Ferric Arsenate Using Full-Potential Multiple Scattering Analysis, Density Functional Theory Calculations, and Vibrational Spectroscopy.

Hydrous ferric arsenate (HFA) is an important arsenic-bearing precipitate in the mining-impacted environment and hydrometallurgical tailings. However, there is no agreement on its local atomic structure. The local structure of HFA was reprobed by employing a full-potential multiple scattering (FPMS) analysis, density functional theory (DFT) calculations, and vibrational spectroscopy. The FPMS simulations indicated that the coordination number of the As-Fe, Fe-As, or both in HFA was approximately two. The DFT calculations constructed a structure of HFA with the formula of Fe(HAsO4)x(H2AsO4)1-x(OH)y·zH2O. The presence of protonated arsenate in HFA was also evidenced by vibrational spectroscopy. The As and Fe K-edge X-ray absorption near-edge structure spectra of HFA were accurately reproduced by FPMS simulations using the chain structure, which was also a reasonable model for extended X-Ray absorption fine structure fitting. The FPMS refinements indicated that the interatomic Fe-Fe distance was approximately 5.2 Å, consistent with that obtained by Mikutta et al. (Environ. Sci. Technol. 2013, 47 (7), 3122-3131) using wavelet analysis. All of the results suggested that HFA was more likely to occur as a chain with AsO4 tetrahedra and FeO6 octahedra connecting alternately in an isolated bidentate-type fashion. This finding is of significance for understanding the fate of arsenic and the formation of ferric arsenate minerals in an acidic environment.

Mobility of arsenic and environmentally significant elements in mine tailings following liming

ABSTRACTRemediation of a legacy tin-tailings site in northeast Tasmania, Australia was carried out by statutory authorities. This study evaluated the fate of As and other deleterious trace metals Cd, Cu, Fe and Zn (among others) following the application of lime and fertiliser. Arsenic concentrations in the tailings ranged from 86 mg/kg to 0.26 wt%. Surface application of lime resulted in a 100-fold reduction in dissolved As concentrations in on-site surface waters; from an average of 196 µg/L prior to lime addition, to between 2.0 and 7.4 µg/L post-amendment. The concentration of other deleterious elements, however, varied between dry and wet cycles. The concentrations of Cd, Cu and Zn in surface waters were high and similar to pre-remediation levels during dry conditions (0.4, 13.5 and 6.1 mg/L, respectively), and only below freshwater ecosystem protection values during wet conditions. Bioaccumulation of Cd was observed in the naturally occurring coloniser, Juncus pallidus, with 4–5 times more Cd in the above-ground biomass relative to the tailings. Ferric arsenate (scorodite) was the dominant source of As identified in the tailings mineralogy. Hydrous ferric oxides and Fe-bearing cassiterite were also identified as hosting As. The pH increase in the surface lime-amended tailings was inferred to result in precipitation of observed hydrous ferric oxides, hematite and goethite, providing high-surface area for adsorption of arsenate onto positively charged surfaces. Jarosite was observed in both the surface lime-amended and subsurface non-amended tailings and suggests a continued supply of acidity to the pore waters despite the application of lime. Leaching experiments showed that As was more mobile in the lime-dosed tailings than in subsurface non-amended tailings, likely owing to desorption in alkaline pH conditions. By contrast, the mobility of Cd, Cu and Zn in the surface lime-amended tailings was reduced by at least two orders of magnitude compared with subsurface non-amended tailings. Evaluation of the applied rehabilitation strategy highlights the limits of a single chemical remediation approach to a polymetallic (including metalloids) waste with complex mineralogy and large seasonal fluctuations. Rehabilitation of metalliferous mine sites requires a complete understanding of all environmentally significant elements and their pathways into local receptors.

Sequestration of As and Mo in uranium mill precipitates (pH 1.5–9.2): An XAS study

As- and Mo- bearing secondary mineral phases formed during the neutralization of uranium mill wastes require characterization. Previous studies indicate that arsenate and molybdate adsorbed to ferrihydrite are the dominant controls in the tailings materials. A lab-scale plant was employed to characterize secondary precipitates from a variety of ore blends. Through total elemental analysis of precipitates and As and Mo K-edge X-ray absorption spectroscopy, different ratios of contributing phases were determined for each pH stage (4.2, 6.5, and 9.2) of the neutralization process. Overall, arsenate adsorbed to ferrihydrite was the dominant As mineral phase regardless of pH or sample blend (53–77%), with fractional contribution from ferric arsenates, and adsorption to aluminum phases. Molybdate adsorbed to ferrihydrite was the dominant Mo mineral phase, with fractional contribution decreasing with increasing pH (100–69%). The characterization of these phases in the secondary precipitates provides further understanding of the contributing mineral species in tailing facilities.

Mobility and attenuation of arsenic in sulfide-rich mining wastes from the Czech Republic

The mineralogical composition of mining wastes deposited in countless dumps around the world is the key factor that controls retention and release of pollutants. Here we report a multi-method data set combining mineralogical (X-ray diffraction, electron microprobe and Raman microspectrometry) and geochemical (sequential extraction and pore water analysis) methods to resolve As mobility in two 50-years-old mining waste dumps. Originally, all of the As in the mining wastes selected for the study was present as arsenopyrite and with time it has been replaced by secondary As phases. At Jedová jáma mining area, the most of As precipitated as X-ray amorphous ferric arsenate (HFA). Arsenic is also accumulated in the scorodite and Fe (hydr)oxide (with up to 3.2wt.% As2O5) that is particularly represented by hematite. Mining wastes at Dlouhá Ves contain only trace amount of scorodite. Arsenic is primarily bound to Pb-jarosite and Fe (hydr)oxides (especially goethite) with up to 1.6 and 1.8wt.% As2O5, respectively. The pore water collected after rainfall events indicated high concentrations of As (~4600μg·L−1) at Jedová jáma, whereas aqueous As at Dlouhá Ves was negligible (up to 1.5μg·L−1). Highly mobile As at Jedová jáma is attributed to the dissolution of HFA and simultaneous precipitation of Fe (hydr)oxides under mildly acidic conditions (pH~4.4); immobile As at Dlouhá Ves is due to the efficient adsorption on the Fe (hydr)oxides and hydroxosulfates under acidic pH of ~2.8. Taken together, As mobility in the ferric arsenates-containing mining wastes may significantly vary. These wastes must be kept under acidic conditions or with high aqueous Fe(III) concentrations to prevent the release of As from incongruent dissolution of ferric arsenates.

As(III) removal and speciation of Fe (Oxyhydr)oxides during simultaneous oxidation of As(III) and Fe(II)

Abiotic oxidation of Fe(II) is an important pathway in the formation of Fe (oxyhydr)oxides. However, how can As(III) affect the oxidation rate of Fe(II) and the speciation of Fe (oxyhydr)oxides, and what's the extent of the newly formed Fe (oxyhydr)oxides on the removal of aqueous arsenic are still poorly understood. Oxidation of Fe(II) under neutral pH conditions was therefore investigated under different molar ratios of As:Fe. Our results suggest that co-existence of aqueous As(III) significantly slows down the oxidation rate of Fe(II). Speciation of Fe (oxyhydr)oxides is dependent on pH and As:Fe ratios. At pH 6.0, formation of lepidocrocite and goethite is apparently inhibited at low As:Fe ratios, and ferric arsenate is favored at high As:Fe ratios. At pH 7.0, lepidocrocite gradually degenerates with the increasing As:Fe ratios. At pH 8.0, arsenite significantly inhibits the development of magnetite and favors a formation of lepidocrocite. XPS analysis further reveals that more than half of As(III) is oxidized to As(V) at pH 6.0 and 7.0, whereas at pH 8.0, the rapid oxidation of Fe(II) as well as the rapid formation of Fe (oxyhydr)oxides facilitate a rapid removal of dissolved As(III) before its further oxidation to As(V).

Relationship of arsenic speciation and bioavailability in mine wastes for human health risk assessment

Environmental context X-ray absorption near-edge spectroscopy (XANES) was applied to give arsenic chemical forms directly in the solid phase of mine wastes from two mine sites, including fluvial dispersion. The arsenic speciation data explained the variation of in vitro bioaccessibility and in vivo bioavailability (rat uptake) data of the mine wastes. The As speciation from XANES fitting supported the hypothesis that when soil intake is adjusted for bioaccessibility, the potential health risk estimate to local residents is significantly lower. Abstract X-ray absorption near-edge spectroscopy (XANES) was used for arsenic speciation in mine processing and waste samples from two mines in northern Australia. XANES fitting of model compound spectra to samples was used, in combination with in vitro bioaccessibility data for the pure compounds, to predict bioaccessibility of each mine waste sample (Pearson’s correlation R2=0.756, n=51). The XANES fitting data for a smaller set of the samples (n=12) were compared with in vivo bioavailability and in vitro bioaccessibility data. The bioavailability of arsenic (As) in the mine wastes, which is dependent, at least in part, on its oxidation state, was found to be <14% (0.9–13.5%) for arsenite (AsIII) and <17% (3.5–16.4) for arsenate (AsV). Arsenic bioaccessibility in the mine wastes ranged from 8–36% in the stomach to 1–16% in the intestinal phase, indicating that a small portion of the total As concentration in the mine waste was available for absorption. A significant correlation showed that bioaccessibility can be used as a predictor of bioavailability. The XANES results support that bioavailability and bioaccessibility results were very similar and show a strong association with the presence of ferric arsenate and As sulfides. It can be concluded that, when soil intake is adjusted for bioaccessibility, the potential health risk estimate to local residents exposed to the mine waste was significantly lower than that estimated based on a 100% bioavailability often employed for the risk assessment.