Surface chemistry of disordered mackinawite (FeS)

Disordered mackinawite, FeS, is the first formed iron sulfide in ambient sulfidic environments and has a highly reactive surface. In this study, the solubility and surface chemistry of FeS is described. Its solubility in the neutral pH range can be described by K_s^app = {Fe²⁺} · {H₂S(aq)} · {H⁺}⁻² = 10^+4.87±0.27. Acid-base titrations show that the point of zero charge (PZC) of disordered mackinawite lies at pH ∼7.5. The hydrated disordered mackinawite surface can be best described by strongly acidic mono-coordinated and weakly acidic tricoordinated sulfurs. The mono-coordinated sulfur site determines the acid-base properties at pH < PZC and has a concentration of 1.2 × 10⁻³ mol/g FeS. At higher pH, the tricoordinated sulfur, which has a concentration of 1.2 × 10⁻³ mol/g FeS, determines surface charge changes. Total site density is 4 sites nm⁻². The acid-base titration data are used to develop a surface complexation model for the surface chemistry of FeS.     

The dry oxidation of tetragonal FeS1- x mackinawite

The gradual oxidation of dry mackinawite (tetragonal FeS_{1? x} ) has been studied using X-ray diffraction (XRD), transmission electron microscopy (TEM), transmission Mössbauer spectroscopy (TMS) and X-ray photoelectron spectroscopy (XPS). The initial material and samples exposed to the air (5?min to 6?months) have been analysed. Diffraction patterns showed the slow disappearance of mackinawite with time with concomitant appearance of greigite (Fe₃S₄) and elemental sulphur (S(0)) as well as iron (oxyhydr)oxides, i.e. magnetite (Fe₃O₄) and probably goethite (α-FeOOH). After 6 months' air exposure, mackinawite and also greigite were entirely converted into elemental sulphur and iron (oxyhydr)oxide(s), indicating that greigite was an intermediate reaction product. Mössbauer spectra of samples oxidized in air appeared rather complex for interpreting what was easily conceivable in view of the association of several phases, as revealed by the diffraction patterns. The low-temperature Mössbauer spectrum obtained after 6?months air exposure was attributed to magnetite, although a mixture of magnetite and goethite was not completely excluded. XPS iron and oxygen data confirmed the formation of Fe(III) (oxyhydr)oxides at the surface after an induction period. Sulphur spectra demonstrated various oxidation states from S(-II) (monosulphide) to S(VI) (sulphate) for the longest experiments. Mackinawite in these experiments reacted mainly with adsorbed O₂ to form elemental sulphur and magnetite. Additionally, sufficient sulphur was generated to react stoichiometrically with mackinawite to produce greigite. Finally, greigite, in the longest experiments, was transformed into elemental sulphur and magnetite.     

Arsenic mobility in the ambient sulfidic environment: Sorption of arsenic(V) and arsenic(III) onto disordered mackinawite

Arsenate, As(V), sorption onto synthetic iron(II) monosulfide, disordered mackinawite (FeS), is fast. As(V) sorption decreases above the point of zero surface charge of FeS and follows the pH-dependent concentration of positively charged surface species. No redox reaction is observed between the As(V) ions and the mineral surface over the time span of the experiments. This observation shows that As(V) dominantly forms an outer-sphere complex at the surface of mackinawite. Arsenite, As(III), sorption is not strongly pH-dependent and can be expressed by a Freundlich isotherm. Sorption is fast, although slower than that of As(V). As(III) also forms an outer-sphere complex at the surface of mackinawite. In agreement with previous spectroscopic studies, complexation at low As(V) and As(III) concentration occurs preferentially at the mono-coordinated sulfide edge sites. The K_d (L g⁻¹) values obtained from linear fits to the isotherm data are ∼9 for As(V) and ∼2 for As(III). Stronger sorption of As(V) than As(III), and thus a higher As(III) mobility, may be reflected in natural anoxic sulfidic waters when disordered mackinawite controls arsenic mobility.     

Lepidocrocite-catalyzed Mn(II) oxygenation by air and its effect on the oxidation and mobilization of As(III)

Manganese (oxy)hydroxides (MnO_X) play important roles in the oxidation and mobilization of toxic As(III) in natural environments. Abiotic oxidation of Mn(II) to MnO_X in the presence of Fe minerals has been proved to be an important pathway in the formation of Mn(III, IV) (oxy)hydroxides. However, interactions between Mn(II) and As(III) in the presence of Fe minerals are still poorly understood. In this study, abiotic oxidation of Mn(II) on lepidocrocite, and its effect on the oxidation and mobilization of As(III) were investigated. The results show that MnO_X species are detected on lepidocrocite and their contents increase with increasing pH values ranging from 7.5 to 8.4. After 10 days, an MnOx component, groutite (α-MnOOH) was found on lepidocrocite. During the simultaneous oxidation of Mn(II) and As(III), and the As(III) pre-adsorbed processes, the presence and oxidation of Mn(II) significantly promotes the removal of soluble As(III). In addition, MnOx formed on lepidocrocite also contributes to the oxidation of soluble and adsorbed As(III) to As(V), the latter being subsequently released into solution. In the process where Mn(II) is pre-adsorbed on lepidocrocite, less As(III) is removed, given that the active sites occupied by MnOx inhibit the adsorption of As(III). In all experiments, the removal percentages of As(III) and the release of As(V) are correlated positively with pH values and initial concentrations of Mn(II), although they are not apparent in the Mn(II) pre-adsorbed system.     

Metamorphic decarbonation in the Neoproterozoic and its environmental implication

Metamorphic decarbonation reactions and volcanic degassing lead to significant influx of CO₂, a major greenhouse gas, into the ocean-atmosphere system from the solid Earth. Here we present quantitative estimates on CO₂ derived through metamorphic degassing during ultrahigh-temperature (UHT) metamorphism in the Neoproterozoic through the mineralogical and geological analyses of the UHT decarbonation. Our computations show that an extra flux of CO₂ was added to the atmosphere through a Himalayan scale UHT metamorphism to the extent of 6 × 10¹⁶ to 3.0 × 10¹⁸ mol/my, for a duration of 10 my. A calculation of the impact of the extra CO₂ influx to the global mean temperature in the context of carbon cycle and greenhouse effect of CO₂ shows that at the peak influx stage, the steady state temperature would be raised by 4 °C from 15 °C and by 13 °C from 4 °C. Our results have important bearing in evaluating the mechanism of melting and the duration of the Snowball Earth. Our estimate of the maximum degassing rate during UHT metamorphism suggests that the duration of the Marinoan snowball Earth was probably shorter, and the recovery from an ice-covered Earth to ocean-covered Earth was faster than previous estimates.     

栖霞组沉积地球化学特征及其环境意义

沉积环境的古氧相特征是沉积环境和古海洋特征恢复的重要内容。岩石地球化学特征是判断其形成环境氧化还原条件的重要手段之一。本文以来宾地区铁桥面为重点．通过对栖霞组灰岩的地球化学分析，结合沉积学、古生态学特征．认为栖霞组沉积于贫氧的沉{只背景．是在海水深度和海域的局限程度等沉积条件发生周期性变化的情况下形成的。古氧相地球化学指标V(V十Ni)、Cc/La、U／Th值都适用于该组以钙质沉积为主的沉积物。黄铁矿矿化程度(DOP值)变。化较大．眨映该区多变的古氧相特征。     

Hydrogeochemical characteristics and its role in controlling arsenic mobilization in a shallow aquifer

The relevance of groundwater hydrogeochemistry to explain the occurrence and distribution of arsenic in groundwater is of great interest. The insightful discussions on the control of shallow groundwater (< 50 m) hydrogeochemistry in arsenic mobilization are known to be a viable tool to explain the arsenic menace in shallow groundwater. The present investigation emphasizes the hydrogeochemical driver and/or control over the reductive dissolution of Fe-bearing host minerals and thereby releasing arsenic into the shallow groundwater of the study area. The study suggests that hydrogeochemical evolution is mainly governed by carbonate minerals dissolution, silicate weathering, and competitive ion-exchange processes in the shallow aquifers (< 50 m). The present study also indicates the prevalence of carbonate minerals dissolution over silicate weathering. The emergence of Cl⁻ concentration in the shallow groundwater founds the possibilities of anthropogenic inputs into the shallow aquifers (< 50 m). The reducing environment in shallow aquifers (< 50 m) of the study area is evident in the reductive dissolution of Fe- bearing shallow aquifer minerals which absorb arsenic in the solid phase and mobilize arsenic onto shallow groundwater. The study opted for many statistical approaches to delineate the correlation among major and minor ionic constituents of the groundwater which are very helpful to understand the comprehensive mechanism of arsenic mobilization into shallow groundwater.

     

Kinetics of sorption and abiotic oxidation of arsenic(III) by aquifer materials

The fate of arsenic in groundwater depends largely on its interaction with mineral surfaces. We investigated the kinetics of As(III) oxidation by aquifer materials collected from the USGS research site at Cape Cod, MA, USA, by conducting laboratory experiments. Five different solid samples with similar specific surface areas (0.6-0.9 m² g⁻¹) and reductively extractable iron contents (18-26 μmol m⁻²), but with varying total manganese contents (0.5-3.5 μmol m⁻²) were used. Both dissolved and adsorbed As(III) and As(V) concentrations were measured with time up to 250 h. The As(III) removal rate from solution increased with increasing solid manganese content, suggesting that manganese oxide is responsible for the oxidation of As(III). Under all conditions, dissolved As(V) concentrations were very low. A quantitative model was developed to simulate the extent and kinetics of arsenic transformation by aquifer materials. The model included: (1) reversible rate-limited adsorption of As(III) onto both oxidative and non-oxidative (adsorptive) sites, (2) irreversible rate-limited oxidation of As(III), and (3) equilibrium adsorption of As(V) onto adsorptive sites. Rate constants for these processes, as well as the total oxidative site densities were used as the fitting parameters. The total adsorptive site densities were estimated based on the measured specific surface area of each material. The best fit was provided by considering one fast and one slow site for each adsorptive and oxidative site. The fitting parameters were obtained using the kinetic data for the most reactive aquifer material at different initial As(III) concentrations. Using the same parameters to simulate As(III) and As(V) surface reactions, the model predictions were compared to observations for aquifer materials with different manganese contents. The model simulated the experimental data very well for all materials at all initial As(III) concentrations. The As(V) production rate was related to the concentrations of the free oxidative surface sites and dissolved As(III), as with apparent second-order rate constants of and for the fast and the slow oxidative sites, respectively. The As(III) removal rate decreased approximately by half for a pH increase from 4 to 7. The pH dependence was explained using the acid-base behavior of the surface oxidative sites by considering a surface pK_a = 6.2 (I = 0). In the presence of excess surface adsorptive and oxidative sites, phosphate diminished the rate of As(III) removal and As(V) production only slightly due to its interaction with the oxidative sites. The observed As(III) oxidation rate here is consistent with previous observations of As(III) oxidation over short transport distances during field-scale transport experiments. The model developed here may be incorporated into groundwater transport models to predict arsenic speciation and transport in chemically heterogeneous systems.     

长江三角洲东部沉积物粒度特征及其环境意义

本文从沉积物粒度特征讨论不同时期的古地理环境,探讨第四纪时期新构造运动、古气候及海平面等因素控制对沉积环境的控制,建立长江三角洲东部的第四纪沉积环境演化模式.     

The geochemical study of fluvio-lacustrine aquifers in the Kathmandu Basin (Nepal) and the implications for the mobilization of arsenic

The geochemical analyses of fluvial-lacustrine aquifer sediments of the Kathmandu Valley have been made as a step in assessing the environment for the mobilization of arsenic in groundwater. Elements measured by X-ray fluorescence (XRF) include 4 major oxides (Fe₂O₃, TiO₂, CaO, P₂O₅) and 14 trace elements (As, Pb, Zn, Cu, Ni, Cr, V, Sr, Y, Nb, Zr, Th, Sc and TS). Elution tests of 15 selected core samples were also carried out to determine the potential leaching of arsenic from the sediments. The XRF results show that average bulk concentrations of the major oxides and trace elements are similar to modern unconsolidated sediments and average upper continental crust. However, the abundance of elements varies with grain size, with higher concentrations in finer-size grades. Variations in elemental abundances within the basin are strongly controlled by sediment facies. The elution tests show that greater amounts of arsenic are generally eluted from the fine sediments, although the rates are variable. The results overall suggest that As concentrations in the bulk sediments are not a controlling factor for elevated As in the Kathmandu Basin groundwater, and the roles of other factors such as redox conditions and organic matter contents are likely to be more significant.     

Microbial reduction of ferrous arsenate: Biogeochemical implications for arsenic mobilization

In reduced aqueous environments, the presence of As in solution is a function of both biotic and abiotic mechanisms. Recent studies have demonstrated a significant release of As(III) through the microbial reduction of dissolved and mineral-bound As(V), which raises health concerns when the greater comparative mobility and toxicity of As(III) is considered. These release mechanisms do not operate in isolation but occur in concert with a number of removal processes, including secondary mineralization and sorption to other natural substrates. Thermodynamic and applied experimental studies have shown that ferrous arsenates, such as symplesite [Fe(II)₃(As(V)O₄)₂·8H₂O], may provide a significant sink for Fe(II) and As(V). In this study, the stability of a representative ferrous arsenate phase in the presence of the arsenate-reducing bacterium Shewanella sp. strain ANA-3 is examined. The reduction of ferrous arsenate by ANA-3 results in the release of aqueous As(III) and, subsequently, the progressive nucleation of a biogenic ferrous arsenite phase proximal to the microbial cells. The valence states of secondary solid-phase products were verified using X-ray absorption spectroscopy (XAS). Electron microscopy reveals that nucleation occurs on cellular exudates which may imply a role of extracellular reduction through c-type cytochromes as investigated in recent literature. These observations provide new insights into the reduction mechanisms of ANA-3 and the biogeochemical cycling of As(III) in natural systems.     

Arsenic attenuation in geothermal streamwater coupled with biogenic arsenic(III) oxidation

In the present study, we investigated As behavior in a high-As hot spring (Sambe hot spring, Shimane, Japan) by coupling direct chemical speciation by synchrotron-based XAFS and HPLC–ICP-MS with microbial As-redox transformation gene analysis. The concentration of soluble As in the spring streamwater decreased immediately along the flow in correlation with Fe behavior, indicating that As in the streamwater was naturally attenuated in the streamwater. Iron XAFS analysis suggested deposition of Fe(III) oxyhydroxides along the flow. Thus, considering the strong affinity of As to Fe oxyhydroxides, the observed attenuation in As was possibly caused by sorption (or incorporation) of As on Fe(III) oxyhydroxides. Both dissolved As(III) and As(V) were present in the aqueous phase, and As(III) was rapidly oxidized to As(V) (<30 s) along the flow. The oxidation kinetics indicated the occurrence of biotic As(III) oxidation, because obtained As(III) oxidation rate (6.7–7.8 μM min⁻¹) was much faster than the reported abiotic oxidation rates. Furthermore, the bacterial arsenite oxidase gene (aioA) was detected in DNA extracted from all samples (average of 2.0 × 10⁵ copies dry g⁻¹), which also supported potential attributes of biological As(III) oxidation in situ. In solid phase samples from sampling points analyzed by XAFS, most of the As existed as oxidized pentavalent form, As(V). This result indicated that this form was preferentially partitioned to the solid phase because of the much higher affinity of As(V) than of As(III) to Fe(III) oxyhydroxides. Considering the kinetic and microbiological findings, it is indicated that biotic process was predominantly responsible for As(III) oxidation at the present site, and this biotic As(III) oxidation to As(V) controlled the observed attenuation of As, because oxidized As(V) was removed from the aqueous phase by Fe(III) oxyhydroxides more efficiently.     

Vertical geochemical variations and arsenic mobilization in the shallow alluvial aquifers of the Chapai-Nawabganj District, northwestern Bangladesh: implication of siderite precipitation

Core sediments from three disturbed boreholes (JOR, GHAT, and RAJ) and two undisturbed boreholes (DW1 and DW2) were collected in the study area of the Chapai-Nawabganj district of northwestern Bangladesh for geochemical analyses. In the study area, groundwater samples from fourteen As-contained private wells and five nested piezometers at both the DW1 and DW2 boreholes were also collected and analyzed. The groundwater arsenic concentrations in the uppermost aquifer (10–40 m of depth) range from 3 to 315 μg/L (mean 47.73 ± 73.41 μg/L), while the arsenic content in sediments range from 2 to 14 mg/kg (mean 4.36 ± 3.34 mg/kg). An environmental scanning electron microscope (ESEM) with an energy dispersive X-ray spectrometer was used to investigate the presence of major and trace elements in the sediments. Groundwaters in the study area are generally the Ca–HCO₃ type with high concentrations of As, but low levels of Fe, Mn, NO₃ ^? and SO ₄ ^?2 . The concentrations of As, Fe, Mn decrease with depth in the groundwater, showing vertical geochemical variations in the study area. Statistical analysis clearly shows that As is closely associated with Fe and Mn in the sediments of the JOR core (r = 0.87, p < 0.05 for Fe and r = 0.78, p < 0.05 for Mn) and GHAT core (r = 0.95, p < 0.05 for Fe and r = 0.93, p < 0.05 for Mn), while As is not correlated with Fe and Mn in groundwater. The comparatively low Fe and Mn concentrations in some groundwater and the ESEM image revealed that siderite precipitated as a secondary mineral on the surface of the sediment particles. The correlations along with results of sequential extraction experiments indicated that reductive dissolution of FeOOH and MnOOH represents a mechanism for releasing arsenic into the groundwater.     

Permanganate oxidation of arsenic(III): Reaction stoichiometry and the characterization of solid product

Permanganate (MnO₄⁻) has widely been used as an effective oxidant for drinking water treatment systems, as well as for in situ treatment of groundwater impacted by various organic contaminants. The reaction stoichiometry of As(III) oxidation by permanganate has been assumed to be 1.5, based on the formation of solid product, which is putatively considered to be MnO₂(s). This study determined the stoichiometric ratio (SR) of the oxidation reaction with varying doses of As(III) (3-300 μM) and MnO₄⁻ (0.5 or 300 μM) under circumneutral pH conditions (pH 4.5-7.5). We also characterized the solid product that was recovered ∼1 min after the oxidation of 2.16 mM As(III) by 0.97 mM MnO₄⁻ at pH 6.9 and examined the feasibility of secondary heterogeneous As(III) oxidation by the solid product. When permanganate was in excess of As(III), the SR of As(III) to Mn(VII) was 2.07 ± 0.07, regardless of the solution pH; however, it increased to 2.49 ± 0.09 when As(III) was in excess. The solid product was analogous to vernadite, a poorly crystalline manganese oxide based on XRD analysis. The average valence of structural Mn in the solid product corresponded to +III according to the splitting interval of the Mn3s peaks (5.5 eV), determined using X-ray photoelectron spectroscopy (XPS). The relative proportions of the structural Mn(IV):Mn(III):Mn(II) were quantified as 19:62:19 by fitting the Mn2p_3/2 spectrum of the solid with the five multiplet binding energy spectra for each Mn valence. Additionally, the O1s spectrum of the solid was comparable to that of Mn-oxide but not of Mn-hydroxide. These results suggest that the solid product resembled a poorly crystalline hydrous Mn-oxide such as (Mn^II_0.19Mn^III_0.62Mn^IV_0.19)₂O₃·nH₂O, in which Mn(II) and Mn(IV) were presumably produced from the disproportionation of aqueous phase Mn(III). Thermodynamic calculations also show that the formation of Mn(III) oxide is more favorable than that of Mn(IV) oxide from As(III) oxidation by permanganate under circumneutral pH conditions. Arsenic(III), when it remained in the solution after all of the permanganate was consumed, was effectively oxidized by the solid product. This secondary heterogeneous As(III) oxidation consisted of three steps: sorption to and oxidation on the solid surface and desorption of As(V) into solution, with the first step being the rate-limiting process as observed in As(III) oxidation by various Mn (oxyhydr)oxides reported elsewhere. We also discussed a potential reaction pathway of the permanganate oxidation of As(III).     

生物纳米FeS强化灰岩去除酸矿废水中砷的研究

通过两种还原型微生物铁还原菌JF-5和硫酸盐还原菌SRB对模拟酸矿废水中Fe~(3+)和SO~(2-)_4的还原作用合成纳米FeS,并将该生物纳米FeS包覆在灰岩表面,以提高灰岩可渗透反应墙(PRBs)对酸矿废水中砷的去除能力。通过批吸附实验研究As(Ⅴ)的静态吸附机理,柱实验研究As(Ⅴ)在包覆灰岩柱中的动态吸附和迁移,结果表明,包覆层生物FeS粒径为纳米级,并呈现一定晶形,能有效提高灰岩表面的比表面积和对As(Ⅴ)的吸附能力,红外光谱分析表明化学吸附为主要吸附机制;生物纳米FeS包覆灰岩静态吸附实验最大吸附量为187.46μg/g,达到纯灰岩吸附量(6.64μg/g)的30倍;JF-5和SRB形成的生物包覆吸附性质优于SRB和Fe(Ⅱ),二者对As(Ⅴ)的吸附能力都远大于纯灰岩对As(Ⅴ)的滞留能力。     

Geochemical processes controlling arsenic mobility in groundwater: A case study of arsenic mobilization and natural attenuation

The behavior of As in the subsurface environment was examined along a transect of groundwater monitoring wells at a Superfund site, where enhanced reductive dechlorination (ERD) is being used for the remediation of groundwater contaminated with chlorinated solvents. The transect was installed parallel to the groundwater flow direction through the treatment area. The ERD technology involves the injection of organic C (OC) to stimulate in situ microbial dechlorination processes. A secondary effect of the ERD treatment at this site, however, is the mobilization of As, as well as Fe and Mn. The concentrations of these elements are low in groundwater collected upgradient of the ERD treatment area, indicating that, in the absence of the injected OC, the As that occurs naturally in the sediment is relatively immobile. Batch experiments conducted using sediments from the site inoculated with an Fe(III)- and As(V)-reducing bacterium and amended with lactate resulted in mobilization of As, Fe and Mn, suggesting that As mobilization in the field is due to microbial processes.     

生物合成FeS及其稳定性柱迁移研究

金属纳米硫化亚铁(FeS)在重/类金属修复上具有广阔的应用前景。使用嗜酸性铁还原菌(JF-5)和硫酸盐还原菌(SRB)合成生物纳米FeS,探讨其自然沉降规律,并使用羧甲基纤维素钠(CMC)作为稳定剂,探讨CMC-FeS在石英砂柱中的迁移特性。结果表明,SRB和JF-5菌液在一定比例下混合即能生成纳米FeS,且当混合菌液中n(Fe)/n(S)=0.2时FeS生成量最多,颗粒物浓度达2 400 mg/L;FeS的自然沉降速率在0.1%CMC溶液中得到有效减缓。对流扩散模型能很好地描述CMC-FeS悬浮颗粒在石英砂柱中的迁移行为,相比于纯水-FeS体系(R²=0.20),其模型相关性最高达0.85;在90、180和360 mL/h这3种输入流速下,中等流速180 mL/h能够获得最佳渗透性,其渗透系数平均值为243.97 cm/h。实验结果表明,CMC-FeS的稳定性和迁移性较纯水-FeS均得到加强,可为土壤污染修复提供理论参考。     

Chemical and structural characterization of As immobilization by nanoparticles of mackinawite (FeSm)

The mobility and availability of arsenite, As(III), in anoxic environments is largely controlled by adsorption onto iron sulfides and/or precipitation of arsenic in solid phases. The interaction of As(III) with synthetic mackinawite (FeS_m) in pH 5 and 9 suspensions was investigated using high-angle annular dark field (HAADF) scanning transmission electron microscopy (STEM), STEM elemental mapping, high resolution TEM, and X-ray photoelectron spectroscopy (XPS). At pH 5, arsenic sulfide phases precipitate among the FeS_m particles as discrete particles that are an amorphous hydrous phase of arsenic sulfide. The oxidation state of As in the surface layers of the arsenic sulfide precipitates is ‘realgar-like’ based on XPS results showing that > 75% of the As 3d peak area is due to As with oxidation states between 0 and 2+. Discrete, arsenic sulfide precipitates are absent at pH 9, but elemental mapping in STEM-EDX mode shows that arsenic is uniformly distributed on the FeS_m, suggesting that uptake is caused by the sorption of As(III) oxyanions and/or the precipitation of highly dispersed arsenic sulfides on FeS_m. XPS also revealed that the FeS_m that equilibrated without As(III) has a more oxidized surface composition than the sample at pH 9, as indicated by the higher concentration of O ( three times greater than that at pH 9) and the larger fraction of Fe(III) species making up the total Fe (2p_3/2) peak. These findings provide a better understanding of redox processes and phase transitions upon As(III) adsorption on iron sulfide substrates.     

Arsenite sorption on troilite (FeS) and pyrite (FeS2)

Arsenic is a toxic metalloid whose mobility and availability are largely controlled by sorption on sulfide minerals in anoxic environments. Accordingly, we investigated reactions of As(III) with iron sulfide (FeS) and pyrite (FeS₂) as a function of total arsenic concentration, suspension density, sulfide concentration, pH, and ionic strength. Arsenite partitioned strongly on both FeS and FeS₂ under a range of conditions and conformed to a Langmuir isotherm at low surface coverages; a calculated site density of near 2.6 and 3.7 sites/nm² for FeS and FeS₂, respectively, was obtained. Arsenite sorbed most strongly at elevated pH (>5 to 6). Although solution data suggested the formation of surface precipitates only at elevated solution concentrations, surface precipitates were identified using X-ray absorption spectroscopy (XAS) at all coverages. Sorbed As was coordinated to both sulfur [d(As-S) = 2.35 Å] and iron [d(As-Fe) = 2.40 Å], characteristic of As coordination in arsenopyrite (FeAsS). The absorption edge of sorbed As was also shifted relative to arsenite and orpiment (As₂S₃), revealing As(III) reduction and a complete change in As local structure. Arsenic reduction was accompanied by oxidation of both surface S and Fe(II); the FeAsS-like surface precipitate was also susceptible to oxidation, possibly influencing the stability of As sorbed to sulfide minerals in the environment. Sulfide additions inhibit sorption despite the formation of a sulfide phase, suggesting that precipitation of arsenic sulfide is not occurring. Surface precipitation of As on FeS and FeS₂ supports the observed correlation of arsenic and pyrite and other iron sulfides in anoxic sediments.     

Geochemical and hydrologic controls on the mobilization of arsenic derived from herbicide application

The fate and transport of As was examined at an industrial site where soil- and groundwater contamination are derived from the application of As₂O₃ as a herbicide. Application of arsenical herbicides was discontinued in the 1970s and soils in the source area were partially excavated in 2003. Arsenic contamination (up to 280 mg/kg) remains in the source area soils and a plume of As-contaminated groundwater persists in the surficial aquifer downgradient of the source area with maximum observed As concentrations of 1200 μg/L near the source area. The spatial extent of As contamination as defined by the 10 μg/L contour appears to have remained relatively stable over the period 1996–2006; the boundary of the 1000 μg/L contour has retreated over the same time period indicating a decrease in total As mass in the surficial groundwater.In column experiments conducted with source area soil, the As concentrations in the column effluent were comparable to those observed in groundwater near the source area. A substantial fraction of the As could be leached from the source area soil with ammonium sulfate and ammonium phosphate. Exhaustive extraction with background groundwater removed most of the total As. These results indicate that As in the source area soils is geochemically labile. Source area soils are low in extractable Fe, Mn and Al, and characterization by X-ray absorption spectroscopy and electron microscopy indicated that As is present primarily as arsenate sorbed to (alumino)silicate minerals. Batch sorption experiments showed much less sorption on surficial aquifer sediments than on sediments from the Jackson Bluff Formation (JBF), a presumed confining layer. This limited capacity of the surficial aquifer sediments for As sorption is consistent with the similar As contents observed for these sediments within and upgradient of the As plume. The apparent stability of the As plume cannot be explained by sequestration of As within the surficial aquifer. Sorption to JBF sediments may contribute to As sequestration, but As enrichment in JBF sediments within the plume (i.e., as compared with JBF sediments upgradient) was not observed. These results indicate that neither the persistence of As in the source area soils or the apparent stability of the plume of As-contaminated groundwater at this site can be explained by geochemical controls on As mobility. The absence of demonstrable geochemical bases for such observations suggests that possible hydrologic controls should be further investigated at this site.