Applied Geochemistry (v.27, #11)

High arsenic water has been a global focus of both scientists and water supply managers because of its serious adverse impact on human health and wide distribution in the world. Processes of redox, sorption, precipitation, and dissolution release arsenic in both natural systems and in environments intensely modified by human activities. In natural systems, groundwater arsenic is controlled by lithologic geochemistry, sedimentation conditions, hydrogeologic setting and groundwater chemistry. However, in the intensely human-affected systems (such as mining and tilling areas), arsenic mobilization is dependent on the composition of the primary materials, treatment methods, storage design, and local climate. Well-designed experimental systems aid in characterizing sorption, precipitation, and redox processes associated with arsenic dynamics during water-rock interaction. Continued investigations of field sites will further refine understanding of the processes favoring arsenic mobility in the range of natural and man-made systems. The combination of field and experimental studies will lead to better understanding of arsenic cycling in all systems and sustainable management of water resources in arsenic-affected areas.

► We identified elevated groundwater As and U concentrations around San Luis Potosí. ► Incompatibility of As and U leads to common enrichment in late volcanic products. ► Volcanic glass dissolution is the main trace element release mechanism. ► Contributions from basin filling sediments modify As/U signatures. ► Similarities and differences to a comparable climatogeological area were detected.Uranium and As in deep groundwater of the volcano-sedimentary Villa de Reyes Graben around the city of San Luis Potosí in semi-arid North-Central Mexico (mean U: 7.6 μg L−1, max. 138 μg L−1; mean As: 11.4 μg L−1, max. 25.8 μg L−1) partly exhibit concentrations in excess of the WHO guideline values and thus endanger the quality of the most important drinking water source. To unravel the mechanisms for their enrichment in groundwater, the potential trace element sources, volcanic rocks and basin fill sediments, were characterized. A total of 131 solid and liquid samples were analyzed for major and trace element composition. The As/U hydrogeochemical signatures, their behavior during rock alteration and evidence from other major and trace element distributions, especially rare earth elements, strongly argue for dissolution of acid volcanic glass to be the dominating process of U and As release into groundwater. This natural baseline quality representing water–acid volcanic rock interaction is modified by additional trace element (preferentially As) mobilization from the sedimentary basin fill, representing a secondary source, in the course of decarbonatization of playa lake sediments and desorption from Fe-(hydr)oxide coated clastic material. The common behavior of both elements during magmatic differentiation and growing drift apart in sedimentary environments are important findings of this work. Comparison with recent findings in a similar environment suggests a common primary trace element source identification but significant differences in the evolution of As and U distribution. Geological and climatic similarity to numerous volcano-sedimentary basins makes the findings useful for water management purposes and transferable to other semi-arid regions facing challenges of geogenically impacted drinking water quality.

► Arsenic mobilization in groundwater is addressed in a freshening groundwater system. ► Positive relationship of As with Na/(Ca + Mg) indicates release in freshening water. ► As mobility enhanced by basic and reducing groundwater. ► Possible release mechanisms are redox promoted dissolution of oxides or sulfides.Arsenic release to groundwater and conditions favoring As mobility are investigated in a system of aquifers formed within unconsolidated Quaternary sediments. The studied groundwater system is comprised of unconfined aquifers formed in glaciofluvial sediments with Ca–Mg–HCO3 groundwater, and confined aquifers formed within glaciomarine sediments with high As (above 10 μg/L) Na–HCO3 or Na–Cl groundwater. A positive relationship of As concentrations with the Na/(Ca + Mg) ratio of groundwater indicates that As release occurs in glaciomarine sediments concurrent to cation exchange reactions related to groundwater freshening. Arsenic is mobile in confined aquifers as a result of groundwater basic pH which prevents arsenate from adsorbing to mineral surfaces, and reducing conditions that favor speciation to arsenite. Selected extractions applied to sediment core samples indicate that As occurs in sediments predominantly in sulfide minerals and in Mn oxides and/or Fe oxyhydroxides. General positive relationships between As and the reduced species Fe2+, NH3 and dissolved S2− suggest that As release occurs at increasingly reducing conditions. Despite likely As release via Fe oxyhydroxide reductive dissolution, Fe remains at relatively low concentrations in groundwater (up to 0.37 mg/L) as a result of possible Fe adsorption and Fe reprecipitation as carbonate minerals favored by basic pH and high alkalinity. The presence of S2− in some samples, a negative relationship between δ34S of SO4 and SO 4 2 - concentrations, and a positive relationship between δ34S and δ18O of SO4 indicate that groundwater in confined aquifers is undergoing bacterial SO4 reduction.

► Groundwater As and F concentration show a large spatial variation. ► Within depths <30 m, As concentrations increase with increasing depth. ► Fluoride concentrations do not show a consistent trend with depth. ► Desorption, evaporation and precipitation are controlling F concentration. ► Reducing environment is the major factor controlling As mobilization.Twenty-nine wells were selected for groundwater sampling in the town of Shahai, in the Hetao basin, Inner Mongolia. Four multilevel samplers were installed for monitoring groundwater chemistry at depths of 2.5–20 m. Results show that groundwater As exhibits a large spatial variation, ranging between 0.96 and 720 μg/L, with 71% of samples exceeding the WHO drinking water guideline value (10 μg/L). Fluoride concentrations range between 0.30 and 2.57 mg/L. There is no significant correlation between As and F concentrations. Greater As concentrations were found with increasing well depth. However, F concentrations do not show a consistent trend with depth. Groundwater with relatively low Eh has high As concentrations, indicating that the reducing environment is the major factor controlling As mobilization. Low As concentrations (<10 μg/L) are found in groundwater at depths less than 10 m. High groundwater As concentration is associated with aquifers that have thick overlying clay layers. The clay layers, mainly occurring at depths <10 m, have low permeability and high organic C content. These strata restrict diffusion of atmospheric O2 into the aquifers, and lead to reducing conditions that favor As release. Sediment composition is an additional factor in determining dissolved As concentrations. In aquifers composed of yellowish-brown fine sands at depths around 10 m, groundwater generally has low As concentrations which is attributed to the high As adsorption capacity of the yellow–brown Fe oxyhydroxide coatings. Fluoride concentration is positively correlated with pH and negatively correlated with Ca2+ concentration. All groundwater samples are over-saturated with respect to calcite and under-saturated with respect to fluorite. Dissolution and precipitation of Ca minerals (such as fluorite and calcite), and F adsorption–desorption are likely controlling the concentration of F in groundwater.

Conversion, sorption, and transport of arsenic species in geological media by Q.H. Hu; G.X. Sun; X.B. Gao; Y.G. Zhu (2197-2203).
► LC-ICP-MS employed to study arsenic speciation. ► Integrated batch and column approaches used to study coupled processes. ► Sorption of As(V) onto geological media generally much larger than that of As(III). ► Inter-conversion of As(III) and As(V) found in geological media.This work addresses the inter-conversion and sorption of inorganic As species in representative geological media. Through the sensitive quantification of As(III) and As(V) with liquid chromatography–inductively coupled plasma-mass spectrometry, and through integrated batch and column approaches, it is shown that natural media can either reduce or oxidize As species. Oxidation of As(III) to As(V) is shown in the Hanford sediment, while reduction of As(V) to As(III) is shown for the surface soil of Savannah River Site. Overall, the sorption distribution coefficient of As(V) onto geological media is much larger than that of As(III), and a reduction of the more sorptive As(V) to As(III) will lead to groundwater enrichment with As. Coupled with the different sorption behavior of As(III) and As(V), the inter-conversion of these species will strongly affect the geochemical cycling of redox-sensitive As in the subsurface.

Display Omitted► Aqueous As in soils surrounding a smelting plant decreased through a natural attenuation process. ► As in water extracts from soils matched thermodynamic equilibrium modeling results. ► Modeling indicates that lead arsenates of low-solubility control As mobility. ► Sequential chemical extractions are consistent with the solubility behavior of lead arsenates. ► Microscopic evidence of lead arsenates was obtained by HRTEM–EDS.Accurate identification of individual As species in contaminated environments is critical because the toxicology, mobility and adsorptive properties of this element may vary substantially with its chemical forms and oxidation states. The goal of this work was to relate the geochemical behavior of As in soils contaminated by a lead smelter in Mexico, with its chemical speciation, and to achieve direct identification of low-solubility poorly-crystalline metal arsenates. Arsenic was identified as the most mobile trace element in the wastes from the smelting plant. Arsenic solubility in soils was significantly lower than its solubility in wastes, showing natural attenuation of this element. Its solubility in soil was quantitatively described in selected samples through thermodynamic equilibrium modeling. The results indicated that As solubility is controlled by solid Pb and Cu arsenate formation. The behaviors of the sequential chemical extractions were consistent with the presence of the predicted arsenates. Microscopic evidence of the formation of solid metal arsenates were obtained in fine soil fractions of selected samples with high As contents, by using the following complementary techniques: X-ray diffraction, scanning electron microscopy and transmission electron microscopy, both coupled with energy dispersive X-ray spectroscopy, and the latter with a high angle annular dark field detector. All results supported the formation of low-solubility Pb arsenates as controlling As mobility in the samples studied, in which As(V) adsorption to Fe (hydr)oxides was not the dominant process of natural attenuation.

► We conducted laboratory experiments to examine chlorine-promoted sulfide oxidation. ► Chlorine increases oxidation of sulfides, releasing As. ► Chlorine increases ferrous iron oxidation, resulting in iron oxide formation to which As sorbs. ► Iron oxides can be sinks for As but can also release As if biogeochemical conditions change. ► Results have implications for aquifer storage and recovery in sulfide-bearing aquifers.Elevated As concentrations have been measured in wells in the St. Peter Sandstone aquifer of eastern Wisconsin, USA. The primary source is As-bearing sulfide minerals (pyrite and marcasite) within the aquifer. There is concern that well disinfection by chlorination may facilitate As release to groundwater by increasing the rate and extent of sulfide oxidation. The objective of this study was to examine the abiotic processes that mobilize As from the aquifer solids during controlled exposure to chlorinated solutions. Thin sections made from sulfidic aquifer material were characterized by quantitative electron probe micro-analysis before and after 24 h exposure to solutions of different Cl2 concentrations. Batch experiments using crushed aquifer solids were also conducted to examine changes in solution chemistry over 24 h. Results of the combined experiments indicate that Cl2 addition affects As release and uptake in two ways. First, Cl2 increases oxidation of sulfide minerals, releasing more As from the mineral structure. Chlorine addition also increases the rate of Fe(II) oxidation and subsequent hydrous ferric oxide (HFO) precipitation, allowing for increased uptake of As onto the mineral surface. Although HFOs can act as sinks for As, they can release As if biogeochemical conditions (e.g. redox, pH) change. These results have implications not only for disinfection of drinking water wells in the study area, but also suggest that introduction of oxidants may adversely affect water quality during aquifer storage and recovery programs in aquifers containing As-bearing minerals.

Geochemical processes and mobilization of toxic metals and metalloids in an As-rich base metal waste pile in Zimapán, Central Mexico by M.A. Armienta; G. Villaseñor; O. Cruz; N. Ceniceros; A. Aguayo; O. Morton (2225-2237).
► Mobilization of As, Sb and metals was studied in As-rich tailing profiles. ► Soluble Fe, Cu, Zn, As, Pb, Ni higher in low-pH, and Sb, Tl in near-neutral samples. ► Calcite decreases mobilization of As and most metals but increases Sb release. ► Mobility decreased as: Tl > Cd, Zn, Cu, Sb, Ni, As > Pb, Fe, Cr, but low Tl contents.The geochemistry and mineralogy of samples collected along depth profiles from an As-rich tailing deposit with abundant calcite was studied to determine the processes that influence the mobility of Fe, Zn, Cu, Ni, Cd, As, Sb, Cr and Tl. In spite of their near neutral pH, almost all of them are acid potential generators. Total concentrations decreased as: Fe > As > Zn > Pb > Cu > Sb > Cd > Cr > Ni > Tl. Soluble contents were lower and followed a slightly different order. Mobility decreased as: Tl > Cd, Zn, Cu, Sb, Ni, As > Fe, Pb > Cr. Higher soluble concentrations of Fe, Cu, Zn, As, Pb, and Ni were found in low-pH samples and of Sb and Tl in near-neutral samples. Sulfide oxidation processes are developing in the tailing’s dam. These processes do not have a trend with depth but occur mainly in acid layers. Near neutral layers formed by primary sulfides and calcite probably correspond to wastes produced from the processing of ore coming mainly from pods within the skarn, and acid layers with abundant secondary minerals from material mined from chimneys and mantos. The presence of calcite influences speciation, neutralizes acid mine drainage (AMD), and decreases the mobility of most toxic metals and metalloids (TMMs). However, a hard-pan layer was not observed in the studied profiles. Retention of TMM within tailings probably occurs through the formation of low solubility metal carbonates and from elevation of pH that promotes Fe hydroxides precipitation that may retain As, Sb and metals. Calcite occurrence promotes As, Cd, Cu, Fe, Zn, Pb, Cd and Cr retention, does not play a role on Tl and Ni mobilization, and increases Sb release.

► We studied As species in mine wastes using various mineralogical and chemical methods. ► Weathering of tailings led to the change of primary As associations with metals. ► The As concentrations in pore waters are instable during the process of storage.Interest in the redistribution of As-bearing species during long-term storage of hydrometallurgical tailings is motivated partly by the need to prevent As from being released into the environment. The speciation of As in mine wastes from the Tuva Cobalt Plant (Khovu-Aksy mine site, Tuva Republic, Russia) has been studied using mineralogical techniques, and chemical analyses of solids (tailings, soils, vegetation) and solutions (recovered pore waters, leach solutions). Ore at the plant was processed by hot autoclave leaching with an ammoniacal carbonate solution followed by treatment with CO2(gas) and caustic magnesite, MgO. Pronounced differences in element concentrations were measured in the five separate tailings ponds and one trench that were filled sequentially during operation of the plant. The concentration of each element was relatively uniform within each pond but the correlations among solid-phase Co, Ni, Zn and Cu gradually decrease from the most recent to oldest ponds as does the correlation between solid-phase As, Ag, Cd and Pb. In the oldest ponds, significant correlations are present between solid-phase Fe–As, Fe–Sb and Fe–Zn. High carbonate content in the ores and leaching reagents control the pH of the pore waters (pH = 7.27–9.10) where the major cation is Ca2+, followed by NH 4 + and Mg2+. Concentrations of As in pore solutions reach up to 140 mg L−1, and average 15 mg L−1. The high pore-water As concentrations are a consequence of instability of the processing residues, which include Mg(NH4)AsO4nH2O and Mg3(AsO4)2nH2O. The concentrations of Zn, Cu and As in pore waters increase from the youngest pond to the oldest storage impoundment (trench), which is evidence of the increase in element mobility with time. In contrast to the metals, As is preferentially sorbed to Fe oxides formed in the tailings. Aerosol transport of dust from the dry ponds has produced anomalies of As and metals in the surrounding area with As in the most polluted soils reaching up to 540 ppm. Moreover, vegetation growing on the surface of the disposal ponds absorbs solutes from the soil.

Display Omitted► Modeling describes competition between precipitation and adsorption in clean systems. ► Relatively simple lab experiments can reproduce the two main As(V) geochemical processes. ► Adsorption is only dominant at very low As/Fe molar ratios. ► Lead arsenate precipitation is dominant in most conditions. ► In soils contaminated with mine-related wastes predominance of precipitation is predicted.Soil contamination with As and potentially harmful metals is a widespread problem around the world especially from mining and metallurgical wastes, which release substantial amounts of these elements to the environment in potentially mobile species. Recently, it has been found that in various Mexican soils contaminated with these types of wastes, arsenate is not in the form of sorbed species on Fe oxides present in the soils, as generally reported in the literature, but in the form of very insoluble compounds such as Pb, Cu and Ca arsenates. Here a thermodynamic model is applied and validated with the results from wet chemical experiments to determine the fundamental geochemical conditions governing the mobility of As in the presence of Pb. For this purpose, a relatively simple but fundamental system of goethite (α-FeOOH)/As(V)/Pb(II)/carbonate was defined as a function of the As(V)/Fe(III) ratio, in a pH range of 5–10. The speciation model included the simultaneous inclusion of triple layer surface complexation and arsenate precipitation equilibria. The model predicts that from very low total As(V)/Fe(III) molar ratios (0.012 at pH 7) the precipitation mechanism significantly influences the attenuation of As(V), and rapidly becomes the dominant process over the adsorption mechanism. Model results identify the quantitative conditions of predominance for each mechanism and describe the transition conditions in which relatively large fractions of adsorbed, precipitated and dissolved As(V) species prevail. Experimental measurements at selected As(V)/Fe(III) ratios and pH confirmed the predictions and validated the coupled thermodynamic model utilized.

Arsenic mobility in two mine tailings drainage systems and its removal from solution by natural geochemical barriers by Nataliya V. Yurkevich; Olga P. Saeva; Nadezhda A. Pal’chik (2260-2270).
► Near neutral natural water mobilize As from the sulfide-bearing mill wastes. ► As contents in affected rivers are 2–3 orders higher than background level. ► The limestone and clay barriers immobilize As in acid oxidized conditions. ► The gypsum and Fe(III) hydroxides decrease the efficiency of barriers. ► Arsenides as an alternative barrier lowered As mobility in the reduced conditions.Sulfide-mineral-bearing mill wastes are sources of high concentrations of acid, soluble metals, and As. These are serious problems for ore mining areas such as the Kemerovo and Cheljabinsk regions in Russia. This study evaluated the distribution of the mill wastes, the mobility of As from the wastes, and the potential of natural materials to attenuate As dispersion in the broader environment. Arsenic contents in wastes of the Belovo Zn-processing (Kemerovo) and the Karabash Cu-smelting plants (Cheljabinsk) are 2–3 orders of magnitude higher than the content of continental crust. Main mineral forms of As in these wastes are arsenopyrite (FeAsS) and scorodite (FeAsO4·2H2O). High dissolved As concentrations are found in water draining the wastes and in rivers adjacent to the mill sites. The water concentrations commonly exceed drinking water standards. High As concentrations in bottom sediments of the affected rivers extend a 100 m downstream of the waste drainage input. These sediments are also a source of river water contamination. Experiments were conducted to evaluate the ability of natural water to mobilize As from the wastes. The Belovo tailings released 86% of their contained As to the infiltrating water, whereas the less reactive Karabash tailings released only 22% of total As. The experimental leachates were used as influent to columns that tested the ability of limestone and natural clay to reduce the concentration of dissolved As and associated metals. Some dissolved As was precipitated with Fe, Pb and Sb initially in the limestone column. The decrease in dissolved As is consistent with the accumulation of As in yellow ferriferous sediments in the Belovo settling pond. In the pond and wetland sediments, As mobility is also decreased by the formation of sulfides and arsenides. Cubanite (CuFe2S3), klaprothite (Cu3BiS3), rammelsbergite (NiAs2), maucherite (Ni11As8), semseyite (Cu9Sb8S21), and skutterudite (CoAs3) were found in the chemically reducing lower sediments of the Belovo settling pond.