Source, attenuation and potential mobility of arsenic at New Britannia Mine, Snow Lake, Manitoba

This study was to investigate the source, mobility and attenuation of As at the New Britannia Mine, Snow Lake, Manitoba. One major source of As contamination was determined to be an arsenopyrite residue stockpile (ARS) containing refractory Au in a waste rock impoundment. It appears that As is still moving through glacial clay at the base of the ARS into a confined aquifer even though the pile was capped in the year 2000. Arsenic is also being mobilized from a deposit of tailings, which formed following spills by previous owners, Nor Acme. Arsenic from the tailings is being mobilized by oxidation of arsenopyrite and reduction of arsenate to the more mobile arsenite by arsenate-reducing bacteria. This contamination is affecting a shallow unconfined aquifer and surface water flowing from the tailings through wetlands towards Snow Lake. Arsenic is being attenuated by adsorption to hydrated ferric oxides (HFO) in the tailings, wetland soils and aquatic plants. Although As in surface water, soils and plants along the flow path from the mine to Snow Lake are above Canadian drinking water guidelines, efficient natural attenuation by HFO in soils and plants of the wetlands have limited the concentration in Snow Lake to below drinking water standards.     

Geochemical distribution of arsenic in waters,sediments and weathered gold mineralized rocks from Iron Quadrangle,Brazil

The Iron Quadrangle has been the scenery of the most important gold production in Brazil. It is estimated that during the three centuries of gold mining in the Iron Quadrangle, at least 390,000 t of arsenic was discharged into the drainage system. This study presents geochemical data for the three river basins in the region, with focus on surface water and stream sediment monitoring. Samples of primary and oxidized sulfide ores as well as of tailings and groundwater from the major gold mines were also studied. The highest As concentrations in water and stream sediments occur in the vicinity of mining areas. In surface water, up to 300 g As/l were found whereas the As contents in stream sediments were in the range of 20 to 4,000 mg/kg. The As³⁺/As⁵⁺ concentration ratios obtained for some water samples range from 1.10^у to 4.10^ф. The As mobility associated with ore-deposit weathering could be traced in some closed gold mines by observation of in-situ pyrite and arsenopyrite oxidation, precipitation of scorodite and gippsite, As adsorption onto goethite, and final liberation of As into underground and surface waters. This process is likely to produce large volumes of mine effluents containing total As and trivalent As up to 1,960 and 60 g/l, respectively. River sediments and tailings pile samples were submitted to a leaching procedure showing maximal arsenic release from 1 to 4% of the original total As in the samples. There are potential risks for As hazards in some areas induced by, for instance, the dispersion of old tailings by flooding, occupation of poisoned soils for settlements, and occasional consumption of contaminated surface and groundwater.     

Consolidation and incipient oxidation of alkaline arsenopyrite-bearing mine tailings,Macraes Mine,New Zealand

Fine grained (ca. 15 μm), arsenopyrite-bearing mine tailings have been exposed to drying and oxidation for 4 a pending relocation. The tailings are still partly covered by a pond of decanted pore waters. The water table in drying tailings has lowered by 1–3 m and desiccation cracks up to 2 cm wide have formed on the 1 m scale, extending through the unsaturated zone. Tailings in the unsaturated zone have similar pore water contents to saturated tailings: typically 16–32 wt% water. Saturated tailings retain alkaline pH (ca. 10) from the mine cyanidation plant, but pH lowers progressively towards ca. 7 near the surface, or near desiccation cracks, in the unsaturated zone. The redox state of the tailings changes in parallel with pH, with an empirical relationship: Eh(mV)=−55 pH+290. Water in the remnant decant pond reflects this relationship also. Unsaturated tailings have variable but low permeabilities, typically 10⁻³ to 10⁻⁴ m/day, and more permeable horizons have allowed incursion of oxygenated air and/or rain water from desiccation cracks. Sulphide grains in all tailings examined are unaltered. Sulphides and solutions in the tailings are out of thermodynamic equilibrium predicted from the redox–pH conditions, due to kinetic constraints. Incursion of rain water locally facilitates deposition from pore waters of insoluble Fe oxide and arsenate minerals, thus fixing As in the dry unsaturated tailings.     

腾冲热泉中砷的甲基化和巯基化过程

为了研究热泉中砷的形态及其分布、转化规律,针对云南腾冲热泉各种砷形态进行了IC-ICP-MS测试和水文地球化学分析.在91处热泉中检出了11种砷形态,包括(亚)砷酸盐、无机硫代砷和甲基(硫代)砷.其中(亚)砷酸盐含量>无机硫代砷含量>甲基砷含量.热泉中无机硫代砷含量及其巯基化程度与硫/砷比正相关.甲基砷含量低是富硫化物...     

Arsenic speciation in Mono Lake, California: Response to seasonal stratification and anoxia

Mono Lake is a closed-basin, alkaline, hypersaline lake located at the western edge of the Great Basin in eastern California. We studied the distribution of arsenic (As) species in the water column of Mono Lake between February and November, 2002. This period captured the seasonal progression from winter mixing, through summer thermal stratification, to autumn overturn. Arsenic speciation was determined by ion chromatography-inductively coupled-plasma-mass spectrometry of samples preserved in the field by flash-freezing in liquid nitrogen. We found that arsenic speciation was dominated (>90%) by arsenate when oxygen was detectable. Once levels fell below 6 μmol/L O₂, arsenic speciation shifted to dominance by reduced species. Arsenate and arsenite co-occurred in a transition zone immediately below the base of the oxycline and low but significant concentrations of arsenate were occasionally detected in sulfidic hypolimnion samples. Thio-arsenic species were the dominant form of As found in sulfidic waters. Maxima of thio-arsenic species with stoichiometries consistent with mono-, di- and trithio-arsenic occurred in succession as sulfide concentration increased. A compound with a stoichiometry consistent with trithio-arsenic was the dominant As species (∼50% of total As) in high sulfide (2 mmol/L) bottom water. Lower concentrations of total As in bottom water relative to surface water suggest precipitation of As/S mineral phases in response to sulfide accumulation during prolonged anoxia.     

高温富硫化物热泉中硫代砷化物存在形态的地球化学模拟:以云南腾冲热海水热区为例

天然水环境中地质成因砷的存在是世界范围内对人类威胁极大的环境问题之一.在高温富硫化物地热水中,硫代砷化物是砷的主要存在形态之一.在国内尚无硫代砷化物定量检测方法的背景下,以云南腾冲地热带的热海水热区为典型研究区,基于不同类型硫代砷化物的最新化学热力学数据wateq4f.dat,利用水文地球化学模拟软件PHREEQC开展了不同类型热泉中砷的存在形态的地球化学模拟.结果表明,热海热泉中砷的主要形态是硫代砷酸盐,砷酸盐和亚砷酸盐次之,硫代亚砷酸盐则含量极低;在各类硫代砷酸盐中,按平均百分含量降序依次为:一硫代砷酸盐→三硫代砷酸盐→四硫代砷酸盐→二硫代砷酸盐.pH、Eh和总硫化物含量是热泉中砷的形态分布的控制性因素.在酸性条件下,砷以硫代砷酸盐和亚砷酸盐为主要存在形式;而在中性/偏碱性条件下,砷的形态则以硫代砷酸盐为主,砷酸盐次之.偏还原环境和高硫化物含量是硫代砷化物、特别是三硫代砷酸盐和四硫代砷酸盐稳定存在的有利条件.      

Speciation and behavior of arsenic in evaporation basins,California, USA

Disposal of saline subsurface drainage waters from croplands into evaporation basins (or ponds) in the San Joaquin Valley of California causes excessive accumulation of salts and elevated concentrations of arsenic (As), a potentially high risk element with little information about its fate, in the agricultural evaporation ponds. We examined dissolved As concentration, speciation, and distribution in waters as well as As fractionation in sediments in the 10-cell South Evaporation Basin for better understanding of processes and conditions affecting As transformations and fate in a specific drainage disposal facility. The increase of total dissolved As concentrations were observed with higher Cl⁻ and electric conductivity along flow path indicating that evaporation was an important factor regulating total dissolved As concentration. The increases of reduced As species such as arsenite [As(III)] and organic As (monomethylarsonic acid and dimethylarsinic acid) were found towards the terminal flow pathway. However, arsenate [As(V)], the oxidized species remained greater than 67% of total dissolved As in all cell waters. Sequential extractions of sediments indicated that reducing conditions may influence As behavior in sediments to be more soluble and exchangeable. Arsenic association with oxides was appreciable only under oxidizing condition. Carbonate minerals played an important role in immobilizing As into the sediments under alkaline condition and a broad range of redox conditions. However, these sink mechanisms did not significantly reduce As concentrations in the cell waters. The reducing condition facilitated by high concentration of organic matter might be a major factor for the increase in As mobility.     

Effect of arsenic concentration on microbial iron reduction and arsenic speciation in an iron-rich freshwater sediment

Depth profiles in the sediment porewaters of the Chattahoochee River (Georgia, USA) show that iron oxides scavenge arsenate in the water column and settle to the sediment-water interface (SWI) where they are reduced by iron-reducing bacteria. During their reduction, these particles seem to release arsenic to the porewaters in the form of arsenate only. Sediment slurry incubations were conducted to determine the effect of low concentrations of arsenic (?10 μM) on biogeochemical processes in these sediments. Experiments confirm that any arsenate (As(V)) added to these sediments is immediately adsorbed in oxic conditions and released in anoxic conditions during the microbial reduction of authigenic iron oxides. Incubations in the presence of ?1 μM As(V) reveal that arsenate is released but not concomitantly reduced during this process. Simultaneously, microbial iron reduction is enhanced significantly, spurring the simultaneous release of arsenate into porewaters and secondary formation of crystalline iron oxides. Above 1 μM As(V), however, the microbial reductive dissolution of iron oxides appears inhibited by arsenate, and arsenite is produced in excess in the porewaters. These incubations show that even low inputs of arsenic to riverine sediments may affect microbial processes, the stability of iron oxides and, indirectly, the cycling of arsenic. Possible mechanisms for such effects on iron reduction are proposed.     

Groundwater arsenic in the Verde Valley in central Arizona,USA

Forty-one water samples were collected and analyzed from throughout the Verde Valley watershed to identify the source of As in well water used for domestic and agricultural purposes. Each water sample was analyzed for anions, cations and trace chemical constituents by atomic absorption spectroscopy, anion chromatography and traditional wet chemical procedures. Arsenic concentrations ranged from 10 to 210 μg/l, with the highest values observed for water pooled on tailings from an abandoned Cu mine. Geostatistical analysis of the data revealed the primary source of As to be groundwater in contact with the Supai and Verde formations, as opposed to runoff from the abandoned mine tailings. Montezuma Well, a collapsed travertine spring, contained the highest levels of naturally occurring As (> 100 μg/l). Arsenic in Montezuma Well water was shown to be 100% arsenate. X-ray absorbance near edge spectra (XANES) of Potomogeton illinoiensis, an endemic plant species of Montezuma Well, demonstrate that As is absorbed as arsenate, reduced to arsenite in the plant and retained as an organic glutathione complex. XANES spectra of Montezuma Well sediments show 4 forms of As present: arsenate (∼54%), As(III)-glutathione complex (∼32%) and an As-organic complex (∼14%) containing dimethylarsinic acid and arsenobetaine. This is the first report of As(III)-glutathione in sediments.     

Mineralogy and trace element relative solubility patterns of shallow marine sediments affected by submarine tailings disposal and artisanal gold mining,Buyat-Ratototok district,North Sulawesi,Indonesia

Shallow marine sediments of the Buyat-Ratototok district of North Sulawesi, Indonesia, are affected by submarine disposal of industrial gold mine tailings and small-scale gold mining using mercury amalgamation. Industrial mine tailings contained 590–660 ppm arsenic, 490–580 ppm antimony, and 0.8–5.8 ppm mercury. Electron microprobe survey found both colloidal iron–arsenic-phases without sulphur and arsenian pyrite in tailings and sites to which tailings had dispersed, but only arsenopyrite in sediments affected by artisanal mining. Antimony in tailings was present as antimony oxides, colloidal iron–antimony phases, colloidal iron–antimony phases, and stibnite in sediments affected by both types of mining. A sequential extraction found that 2% of arsenic held in tailings and tailings-contaminated sediments was exchangeable, 20–30% was labile, including weakly adsorbed, carbonate- and arsenate bound, 20–30% was metastable, probably incorporated into iron or manganese oxyhydroxides, or strongly adsorbed to silicate minerals, and 40–48% was relatively insoluble, probably incorporated into sulphides or silicates. Arsenic in sediments affected by artisanal gold mining was 75–95% relatively insoluble. Antimony in all sediments was >90% relatively insoluble. Relative solubility patterns of most other metals did not differ between industrial tailings-affected, artisanal-mining affected areas, and fluvial sediments. Results suggest that submarine tailings disposal is not suitable for refractory Carlin-like gold deposits because ore processing converts arsenic to forms unstable in anoxic marine sediments. Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

西藏搭格架高温热泉中砷的地球化学异常及其存在形态

西藏搭格架高温热泉是我国大陆少有的大型间歇性喷泉,砷元素作为对人类威胁极大的环境问题普遍存在于热泉之中,搭格架高温热泉中砷元素质量浓度最高已达到了9.75 mg/L,其对地表水和浅层地下水的污染不容忽视。硫代砷是富含硫化物热泉中砷的存在形态之一,鉴于国内相关研究较少,本文对西藏搭格架地热区的热泉样品进行了水化学分析,并利用水文地球化学模拟软件PHREEQC开展了对热泉中砷元素存在形态的地球化学模拟。结果表明：西藏搭格架热泉中砷元素的存在形态有亚砷酸盐、砷酸盐和硫代砷,其中亚砷酸盐与砷酸盐是砷的主要存在形态,且在pH影响下两者之间存在相互转化关系;各种硫代砷按质量浓度由高至低依次为一硫代砷酸盐、三硫代砷酸盐、二硫代砷酸盐、一硫代亚砷酸盐、四硫代砷酸盐;硫代砷形态占总砷浓度比例主要受热泉中硫化物质量浓度、Eh（氧化还原电位）和pH等因素的控制,在硫化物质量浓度总体偏低的情况下,硫化物质量浓度的上升可促进其他形态的砷向硫代砷形态转化,强还原性环境有利于硫代砷形态的存在;此外,在中性环境下,硫代砷占总砷浓度比例随pH上升亦有上升趋势。     

Predicting arsenic concentrations in the porewaters of buried uranium mill tailings

The proposed JEB Tailings Management Facility (TMF) to be emplaced below the groundwater table in northern Saskatchewan, Canada, will contain uranium mill tailings from McClean Lake, Midwest and Cigar Lake ore bodies, which are high in arsenic (up to 10%) and nickel (up to 5%). A serious concern is the possibility that high arsenic and nickel concentrations may be released from the buried tailings, contaminating adjacent groundwaters and a nearby lake. Laboratory tests and geochemical modeling were performed to examine ways to reduce the arsenic and nickel concentrations in TMF porewaters so as to minimize such contamination from tailings buried for 50 years and longer. The tests were designed to mimic conditions in the mill neutralization circuit (3 hr tests at 25°C), and in the TMF after burial (5–49 day aging tests). The aging tests were run at, 50, 25 and 4°C (the temperature in the TMF). In order to optimize the removal of arsenic by adsorption and precipitation, ferric sulfate was added to tailings raffinates¹ having Fe/As ratios of less that 3–5. The acid raffinates were then neutralized by addition of slaked lime to nominal pH values of 7, 8, or 9.Analysis and modeling of the test results showed that with slaked lime addition to acid tailings raffinates, relatively amorphous scorodite (ferric arsenate) precipitates near pH 1, and is the dominant form of arsenate in slake limed tailings solids except those high in Ni and As and low in Fe, in which cabrerite-annabergite (Ni, Mg, Fe(II) arsenate) may also precipitate near pH 5–6. In addition to the arsenate precipitates, smaller amounts of arsenate are also adsorbed onto tailings solids.The aging tests showed that after burial of the tailings, arsenic concentrations may increase with time from the breakdown of the arsenate phases (chiefly scorodite). However, the tests indicate that the rate of change decreases and approaches zero after 72 hrs at 25°C, and may equal zero at all times in the TMF at 4°C. Consistent with a kinetic model that describes the rate of breakdown of scorodite to form hydrous ferric oxide, the rate of release of dissolved arsenate to tailings porewaters from slake limed tailings: (1) is proportional to pH above pH 6–7; (2) decreases exponentially as the total molar Fe/As ratio of tailings raffinates is increased from 1/1 to greater than 5/1; and (3) is proportional to temperature with an average Arrhenius activation energy of 13.4 ± 4.2 kcal/mol.Study results suggest that if ferric sulfate and slaked lime are added in the tailings neutralization circuit to give a raffinate Fe/As molar ratio of at least 3–5 and a nominal (initial) pH of 8 (final pH of 7–8), arsenic and nickel concentrations of 2 mg/L or less, are probable in porewaters of individual tailings in the TMF for 50 to 10,000 yrs after tailings disposal. However, the tailings will be mixed in the TMF, which will contain about 35% tailings with Fe/As = 3.0, and 65% tailings with Fe/As = 5.0–7.7. Thus, it seems likely that average arsenic pore water concentrations in the TMF may not exceed 1 mg/L.     

Effects of pH on arsenic mineralogy and stability in Poldice Valley,Cornwall, United Kingdom

Many abandoned mine sites in Cornwall, UK, are characterised by elevated concentrations of arsenic (As), which can cause contamination of surrounding soil and water resources. These sites have important historical value that requires access to be maintained, despite exposure of humans to toxins that may lead to health issues including hyperpigmentation keratosis (including skin cancers) and liver fibrosis. The abandoned mine tailings at Wheal Maid has been assessed for As-bearing mineralogy and stability taking into account the public footpaths made by the local council to areas of potential contamination.To assess the potential risk associated with these mine sites, the As concentration in waters along the tailings dam and Carnon River have been measured and range up to 3.6 ppm, which is 2 orders of magnitude above the WHO guideline value of 0.01 ppm for drinking water. Samples of water, rocks and soils from the mine tailings ponds and the Carnon River were analysed using Inductively Coupled Plasma – Optical Emission Spectrometry (ICP-OES) and Inductively Coupled Plasma – Mass Spectrometry (ICP-MS) to determine the concentration of individual elements in each sample followed by mineral identification using X-Ray Diffraction (XRD). Mineralogical evaluation indicated that the majority of mine tailings consist of clay-rich rocks, with few associated As-bearing minerals. Scorodite (FeAsO₄·2H₂O) is observed in the mine tailings pond and appears critical to the As distribution and storage in this surface environment. Using the analysed water chemistry, a modified version of PHREEQC is used to calculate the saturation index of scorodite as a function of pH conditions. The strong variation of the solubility of this mineral with pH and oxidation state highlights potential risks for using scorodite for As fixation and storage.     

Arsenic contamination in surface drainage and groundwater in part of the southeast Asian tin belt,Nakhon Si Thammarat Province,southern Thailand

The occurrence of human health problems resulting from arsenic contamination of domestic water supplies in Ron Phibun District, Nakhon Si Thammarat Province, southern Thailand was first recognized in 1987. The area has an extensive history of bedrock and alluvial mining, the waste from which is typically rich in arsenopyrite and related alteration products. In 1994 a collaborative study was instigated involving Thai and British government authorities to establish the distribution and geochemical form of As in surface drainage and aquifer systems in the affected area, the probable sources of As contamination, and the potential for problem alleviation. Hydrochemical analyses of surface- and groundwaters have confirmed the presence of dissolved As at concentrations exceeding WHO potable water guidelines by up to a factor of 500. Contamination of the shallow alluvial aquifer system is systematically more severe than the underlying carbonate-hosted aquifer. Deep boreholes may therefore provide the best available potable water source for the local population. The presence of up to 39% of total As as arsenite (H₃AsO₃) within the carbonate aquifer may, however, constitute a hidden toxicological risk, not evident in the shallow groundwater (in which arsenate species account for > 95% of total As). Mineralogical investigations of As-rich tailings and flotation wastes were undertaken to evaluate their likely impact on water quality. The results indicate that although some flotation wastes contain up to 30% As, the rate of leaching is extremely low. Consequently the As loading of drainage emanating from such waste is below the subregional average. Analyses of the silty alluvium that covers much of the central sector of the study area have highlighted As concentrations of up to 5000 mg kg^–1, probably carried by disseminated arsenopyrite. Following sulfide dissolution, the mobility of As in this material may be high (with resultant contamination of shallow groundwater) due to the low Fe content of the soil. On the basis of the data acquired, a range of pollution mitigation schemes are currently under investigation including Fe supplementation of alluvium and microbial degradation of disseminated arsenopyrite.     

土壤中不同形态砷的分析方法

选取磷酸作为提取剂,比较了超声和水浴两种方法辅助提取土壤中不同形态的砷,离子色谱一氢化物发生原子荧光光谱联用法(IC-HGAFS)测定砷的4种形态,即As(Ⅲ)、As(Ⅴ)、MMA (甲基胂酸)和DMA(二甲基胂酸)。从测定结果可以看出,水浴的提取效果明显高于超声的提取效果。土壤中砷以无机态为主,而无机态砷又以As(Ⅴ)为主,没有检测到有机砷。测定土壤中各种形态砷的加标回收率为72.0%～105.4%,相对标准偏差(RSD,n=5)为2.61%～8.19%。     

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

Remediation 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.     

Sorption and desorption of arsenate and arsenite on calcite

The adsorption and desorption of arsenate (As(V)) and arsenite (As(III)) on calcite was investigated in a series of batch experiments in calcite-equilibrated solutions. The solutions covered a broad range of pH, alkalinity, calcium concentration and ionic strength. The initial arsenic concentrations were kept low (<33 μM) to avoid surface precipitation. The results show that little or no arsenite sorbs on calcite within 24 h at an initial As concentration of 0.67 μM. In contrast, arsenate sorbs readily and quickly on calcite. Likewise, desorption of arsenate from calcite is fast and complete within hours, indicating that arsenate is not readily incorporated into the calcite crystal lattice. The degree of arsenate sorption depends on the solution chemistry. Sorption increases with decreasing alkalinity, indicating a competition for sorption sites between arsenate and (bi)carbonate. pH also affects the sorption behavior, likely in response to changes in arsenate speciation or protonation/deprotonation of the adsorbing arsenate ion. Finally, sorption is influenced by the ionic strength, possibly due to electrostatic effects. The sorption of arsenate on calcite was modeled successfully using a surface complexation model comprising strong and weak sites. In the model, the adsorbing arsenate species were and . The model was able to correctly predict the adsorption of arsenate in the wide range of calcite-equilibrated solutions used in the batch experiments and to describe the non-linear shape of the sorption isotherms. Extrapolation of the experimental results to calcite bearing aquifers suggests a large variability in the mobility of arsenic. Under reduced conditions, arsenite, which does not sorb on calcite, will dominate and, hence, As will be highly mobile. In contrast, when conditions are oxidizing, arsenate is the predominant species and, because arsenate adsorbs strongly on calcite, As mobility will be significantly retarded. The estimated retardation factors for arsenate in carbonate aquifers range from 25 to 200.     

The behavior of arsenic and antimony at Pezinok mining site,southwestern part of the Slovak Republic

Arsenic and antimony contamination is found at the Pezinok mining site in the southwest of the Slovak Republic. Investigation of this site included sampling and analysis of water, mineralogical analyses, sequential extraction, in addition to flow and geochemical modeling. The highest dissolved arsenic concentrations correspond to mine tailings (up to 90,000 μg/L) and the arsenic is present predominately as As(V). The primary source of the arsenic is the dissolution of arsenopyrite. Concentration of antimony reaches 7,500 μg/L and its primary source is the dissolution of stibnite. Pore water in mine tailings is well-buffered by the dissolution of carbonates (pH values between 6.6 and 7.0) and arsenopyrite grains are surrounded by reaction rims composed of ferric iron minerals. Based on sequential extraction results, most solid phase arsenic is in the reducible fraction (i.e. ferric oxyhydroxides), sulfidic fraction, and residual fraction. Distribution of antimony in the solid phase is similar, but contents are lower. The principal attenuation mechanism for As(V) is adsorption to ferric oxide and hydroxides, but the adsorption seems to be limited by the competition with Sb(V) produced by the oxidation of stibnite for adsorption sites. Water in mine tailings is at equilibrium with gypsum and calcite, but far from equilibrium with any arsenic and antimony minerals. The concentrations of arsenic and antimony in the surrounding aquifer are much lower, with maximum values of 215 and 426 μg/L, respectively. Arsenic and antimony are transported by ground water flow towards the Blatina Creek, but their loading from ground water to the creek is much lower compared with the input from the mine adits. In the Blatina Creek, arsenic and antimony are attenuated by dilution and by adsorption on ferric iron minerals in stream sediments with resulting respective concentrations of 93 and 45 μg/L at the site boundary south of mine tailing ponds.     

Effect of silicic acid on arsenate and arsenite retention mechanisms on 6-L ferrihydrite: A spectroscopic and batch adsorption approach

The competitive adsorption of arsenate and arsenite with silicic acid at the ferrihydrite–water interface was investigated over a wide pH range using batch sorption experiments, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) modeling. Batch sorption results indicate that the adsorption of arsenate and arsenite on the 6-L ferrihydrite surface exhibits a strong pH-dependence, and the effect of pH on arsenic sorption differs between arsenate and arsenite. Arsenate adsorption decreases consistently with increasing pH; whereas arsenite adsorption initially increases with pH to a sorption maximum at pH 7–9, where after sorption decreases with further increases in pH. Results indicate that competitive adsorption between silicic acid and arsenate is negligible under the experimental conditions; whereas strong competitive adsorption was observed between silicic acid and arsenite, particularly at low and high pH. In situ, flow-through ATR-FTIR data reveal that in the absence of silicic acid, arsenate forms inner-sphere, binuclear bidentate, complexes at the ferrihydrite surface across the entire pH range. Silicic acid also forms inner-sphere complexes at ferrihydrite surfaces throughout the entire pH range probed by this study (pH 2.8–9.0). The ATR-FTIR data also reveal that silicic acid undergoes polymerization at the ferrihydrite surface under the environmentally-relevant concentrations studied (e.g., 1.0 mM). According to ATR-FTIR data, arsenate complexation mode was not affected by the presence of silicic acid. EXAFS analyses and DFT modeling confirmed that arsenate tetrahedra were bonded to Fe metal centers via binuclear bidentate complexation with average As(V)-Fe bond distance of 3.27 Å. The EXAFS data indicate that arsenite forms both mononuclear bidentate and binuclear bidentate complexes with 6-L ferrihydrite as indicated by two As(III)–Fe bond distances of ∼2.92–2.94 and 3.41–3.44 Å, respectively. The As–Fe bond distances in both arsenate and arsenite EXAFS spectra remained unchanged in the presence of Si, suggesting that whereas Si diminishes arsenite adsorption preferentially, it has a negligible effect on As–Fe bonding mechanisms.     

Arsenic attenuation in tailings at a former Cu–W–As mine,SW Finland

Nearly half a century after mine closure, release of As from the Ylöjärvi Cu–W–As mine tailings in groundwater and surface water run-off was observed. Investigations by scanning electron microscopy (SEM), electron microprobe analysis (EMPA), synchrotron-based micro-X-ray diffraction (μ-XRD), micro-X-ray absorption near edge structure (μ-XANES) and micro-extended X-ray absorption fine structure (μ-EXAFS) spectroscopy, and a sequential extraction procedure were performed to assess As attenuation mechanisms in the vadose zone of this tailings deposit. Results of SEM, EMPA, and sequential extractions indicated that the precipitation of As bearing Fe(III) (oxy)hydroxides (up to 18.4 wt.% As₂O₅) and Fe(III) arsenates were important secondary controls on As mobility. The μ-XRD, μ-XANES and μ-EXAFS analyses suggested that these phases correspond to poorly crystalline and disordered As-bearing precipitates, including arsenical ferrihydrite, scorodite, kaňkite, and hydrous ferric arsenate (HFA). The pH within 200 cm of the tailings surface averaged 5.7, conditions which favor the precipitation of ferrihydrite. Poorly crystalline Fe(III) arsenates are potentially unstable over time, and their transformation to ferrihydrite, which contributes to As uptake, has potential to increase the As adsorption capacity of the tailings. Arsenic mobility in tailings pore water at the Ylöjärvi mine will depend on continued arsenopyrite oxidation, dissolution or transformation of secondary Fe(III) arsenates, and the As adsorption capacity of Fe(III) (oxy)hydroxides within this tailings deposit.