Holocene estuarine sediments as a source of arsenic in Pleistocene groundwater in suburbs of Hanoi,Vietnam

Groundwater pollution by arsenic is a major health threat in suburban areas of Hanoi, Vietnam. The present study evaluates the effect of the sedimentary environments of the Pleistocene and Holocene deposits, and the recharge systems, on the groundwater arsenic pollution in Hanoi suburbs distant from the Red River. At two study sites (Linh Dam and Tai Mo communes), undisturbed soil cores identified a Pleistocene confined aquifer (PCA) and Holocene unconfined aquifer (HUA) as major aquifers, and Holocene estuarine and deltaic sediments as an aquitard layer between the two aquifers. The Holocene estuarine sediments (approximately 25–40 m depth, 9.6–4.8 cal ka BP) contained notably high concentrations of arsenic and organic matter, both likely to have been accumulated by mangroves during the Holocene sea-level highstand. The pore waters in these particular sediments exhibited elevated levels of arsenic and dissolved organic carbon. Arsenic in groundwater was higher in the PCA (25–94 μg/L) than in the HUA (5.2–42 μg/L), in both the monitoring wells and neighboring household tubewells. Elevated arsenic concentration in the PCA groundwater was likely due to vertical infiltration through the arsenic-rich and organic-matter-rich overlying Holocene estuarine sediments, caused by massive groundwater abstraction from the PCA. Countermeasures to prevent arsenic pollution of the PCA groundwater may include seeking alternative water resources, reducing water consumption, and/or appropriate choice of aquifers for groundwater supply.     

Arsenic in groundwater of the Red River floodplain, Vietnam: Controlling geochemical processes and reactive transport modeling

The mobilization of arsenic (As) to the groundwater was studied in a shallow Holocene aquifer on the Red River flood plain near Hanoi, Vietnam. The groundwater chemistry was investigated in a transect of 100 piezometers. Results show an anoxic aquifer featuring organic carbon decomposition with redox zonation dominated by the reduction of Fe-oxides and methanogenesis. Enhanced P_CO2 pressure causes carbonate dissolution to take place but mainly in the soil and unsaturated zone. The concentration of As increases over depth to a concentration of up to 550 μg/L. Most As is present as As(III) but some As(V) is always found. Arsenic correlates well with NH₄, relating its release to organic matter decomposition and the source of As appears to be the Fe-oxides being reduced. Part of the produced Fe(II) is apparently reprecipitated as siderite containing less As. Results from sediment extraction indicate most As to be related to the Fe-oxide fractions. The measured amount of sorbed As is low. In agreement, speciation calculations for a Fe-oxide surface suggest As(III) to constitute only 3% of the surface sites while the remainder is occupied by carbonate and silica species. The evolution in water chemistry over depth is homogeneous and a reactive transport model was constructed to quantify the geochemical processes along the vertical groundwater flow component. A redox zonation model was constructed using the partial equilibrium approach with organic carbon degradation in the sediment as the only rate controlling parameter. Apart from the upper meter a constant degradation rate of 0.15 C mmol/L/yr could explain the redox zonation throughout the aquifer. Modeling also indicates that the Fe-oxide being reduced is of a stable type like goethite or hematite. Arsenic is contained in the Fe-oxides and is first released during their dissolution. Our model further suggests that part of the released As is adsorbed on the surface of the remaining Fe-oxides and in this way may be retarded.     

Source and distribution of naturally occurring arsenic in groundwater from Alberta’s Southern Oil Sands Regions

Arsenic (As) concentrations as high as 179 μg/L have been observed in shallow groundwater in the Alberta’s Southern Oil Sand Regions. The geology of this area of Alberta includes a thick cover (up to 200 m) of unconsolidated glacial deposits, with a number of regional interglacial sand and gravel aquifers, underlain by marine shale. Arsenic concentrations observed in 216 unconsolidated sediment samples ranged from 1 and 17 ppm. A survey of over 800 water wells sampled for As in the area found that 50% of the wells contained As concentrations exceeding drinking water guidelines of 10 μg/L. Higher As concentrations in groundwater were associated with reducing conditions. Measurements of As speciation from 175 groundwater samples indicate that As(III) was the dominant species in 74% of the wells. Speciation model calculations showed that the majority of groundwater samples were undersaturated with respect to ferrihydrite, suggesting that reductive dissolution of Fe-oxyhydroxides may be the source of some As in groundwater. Detailed mineralogical characterization of sediment samples collected from two formations revealed the presence of fresh framboidal pyrite in the deeper unoxidized sediments. Electron microprobe analysis employing wavelength dispersive spectrometry indicated that the framboidal pyrite had variable As content with an average As concentration of 530 ppm, reaching up to 1840 ppm. In contrast, the oxidized sediments did not contain framboidal pyrite, but exhibited spheroidal Fe-oxyhydroxide grains with elevated As concentrations. The habit and composition suggest that these Fe-oxyhydroxide grains in the oxidized sediment were an alteration product of former framboidal pyrite grains. X-ray absorption near edge spectroscopy (XANES) indicated that the oxidized sediments are dominated by As(V) species having spectral features similar to those of goethite or ferrihydrite with adsorbed As, suggesting that Fe-oxyhydroxides are the dominant As carriers. XANES spectra collected on unoxidized sediment samples, in contrast, indicated the presence of a reduced As species (As(−I)) characteristic of arsenopyrite and arsenian pyrite. The results of the mineralogical analyses indicate that the oxidation of framboidal pyrite during weathering may be the source of As released to shallow aquifers in this region.     

Distinguishing potential sources of arsenic released to groundwater around a fault zone containing a mine site

Arsenic (As) contamination in groundwater in mineralized areas typically results from the oxidation of As-rich sulfide minerals in aquifers, from hydrothermal alteration of geothermal systems, or as a result of anthropogenic influences such as mining activity. The primary goal of this study was to determine the spatial and temporal variance in As concentrations in shallow groundwater in a mineralized area and to identify the main As source controlling the concentration patterns. To this end, a combination of a geostatistical technique for space–time modeling of As concentrations and a numerical simulation, which models the transport of As in groundwater, is implemented. A study site in North Sulawesi, Sulawesi Island, Indonesia was selected as it was suitable for investigating the importance of fault lines and metal mining on As contamination. Initially, stable isotope analysis was used to ascertain the groundwater source and the mixing mechanism of the shallow and deep groundwater. Geostatistical modeling revealed consistent general patterns of As concentrations during the past 10 years, with high concentrations found along a NW–SE axis. By matching the geostatistical results with the distributions of As concentrations obtained through transport modeling, the deep-seated hydrothermal system along the fault zone was found to be the major As source. Wastewater from the mine was also observed to be a local As source. Another important influence on the As concentration pattern was a river, which acted as a boundary to separate the groundwater systems into two regions.     

Preliminary trace element analysis of arsenic in Nepalese groundwater may pinpoint its origin

Arsenic contamination of groundwater used as drinking water in South Asia poses a serious health threat to the inhabitants living on alluvial plains of the Himalayan foreland of countries like Bangladesh, India, Nepal and Myanmar. Although the geological and geochemical conditions favoring the release of the highly poisonous contaminant from the sediments hosting the groundwater are meanwhile quite well understood, there is still a significant debate about the origin of arsenic. The sediments forming a huge proportion of the Terai (lowlands of Nepal) aquifers are derived from two main sources, (i) sediments deposited by large rivers that erode the upper Himalayan crystalline rocks and (ii) weathered meta-sediments carried by smaller rivers originating in the Siwalik foothills adjacent to the Terai. In this article a so far underestimated source of As is discussed: the peraluminous leucogranites found ubiquitously in the Nepal Himalaya. The relationship between the trace elements analyzed in the groundwater in the Terai and trace elements found in such felsic rocks reflect the origin of the arsenic in the high Himalayas of Nepal. In addition to the high concentration of As, a striking feature is the presence of the lithophile trace elements like Li, B, P, Mn, Br, Sr and U in the groundwater. The mentioned elements point to a felsic initial source like metapelites or leucogranites—all rocks showing a high abundance of especially B, P and As as well as Cd and Pb.     

Naturally occurring arsenic in groundwater and identification of the geochemical sources in the Duero Cenozoic Basin, Spain

Arsenic concentrations surpassing potability limit of 10 μg/L in the groundwater supplies of an extensive area in the Duero Cenozoic Basin (central Spain) have been detected and the main sources of arsenic identified. Arsenic in 514 samples of groundwater, having mean values of 40.8 μg/L, is natural in origin. Geochemical analysis of 553 rock samples, assaying arsenic mean values of 23 mg/kg, was performed. Spatial coincidence between the arsenic anomaly in groundwater and the arsenic lithogeochemical distribution recorded in the Middle Miocene clayey organic-rich Zaratan facies illustrates that the rocks of this unit are the main source of arsenic in groundwater. The ferricretes associated to the Late Cretaceous–Middle Miocene siliciclastics also constitute a potential arsenic source. Mineralogical study has identified the presence of arsenic in iron oxides, authigenic pyrite, manganese oxides, inherited titanium–iron oxides, phyllosilicates and organomineral compounds. Arsenic mobilization to groundwater corresponds to arsenic desorption from iron and manganese oxides and from organic matter.     

Arsenic distribution and source in groundwater of Yangtze River Delta economic region,China

This thesis focuses Arsenic(As) distribution and occurrence in groundwater of Yangtze River Delta economic region, East China. 2019 groundwater samples were collected to analyze 26 chemical compositions, including As. The Principal Component Analysis(PCA) was used to find out As source in groundwater. The results show that average As concentration in groundwater of this study is 9.33 μg/l, and maximum As concentration is up to 510 μg/l. The variation coefficient is 314.34%. High arsenic phreatic water(10 μg/l) distributes along the Yangtze River and its estuary. Weak hydrodynamic conditions, wide p H value variation range and deteriorating environment are dominating factors, especially in Yangtze River Delta. The PCA suggests that arsenic in phreatic water is mainly of natural origin. Part of arsenic may directly originate from sediment organics and be related to organics decomposition.     

Groundwater recharge in suburban areas of Hanoi,Vietnam: effect of decreasing surface-water bodies and land-use change

Over-exploited groundwater is expected to remain the predominant source of domestic water in suburban areas of Hanoi, Vietnam. In order to evaluate the effect on groundwater recharge, of decreasing surface-water bodies and land-use change caused by urbanization, the relevant groundwater systems and recharge pathways must be characterized in detail. To this end, water levels and water quality were monitored for 3 years regarding groundwater and adjacent surface-water bodies, at two typical suburban sites in Hanoi. Stable isotope (δ¹⁸O, δD of water) analysis and hydrochemical analysis showed that the water from both aquifers and aquitards, including the groundwater obtained from both the monitoring wells and the neighboring household tubewells, was largely derived from evaporation-affected surface-water bodies (e.g., ponds, irrigated farmlands) rather than from rivers. The water-level monitoring results suggested distinct local-scale flow systems for both a Holocene unconfined aquifer (HUA) and Pleistocene confined aquifer (PCA). That is, in the case of the HUA, lateral recharge through the aquifer from neighboring ponds and/or irrigated farmlands appeared to be dominant, rather than recharge by vertical rainwater infiltration. In the case of the PCA, recharge by the above-lying HUA, through areas where the aquitard separating the two aquifers was relatively thin or nonexistent, was suggested. As the decrease in the local surface-water bodies will likely reduce the groundwater recharge, maintaining and enhancing this recharge (through preservation of the surface-water bodies) is considered as essential for the sustainable use of groundwater in the area.

     

Arsenic toxicity of groundwater in parts of the Bengal basin in India and Bangladesh: the role of Quaternary stratigraphy and Holocene sea-level fluctuation

 Arsenic toxicity in groundwater in the Ganges delta and some low-lying areas in the Bengal basin is confined to middle Holocene sediments. Dissected terraces and highlands of Pleistocene and early Holocene deposits are free of such problems. Arsenic-rich pyrite or other arsenic minerals are rare or absent in the affected sediments. Arsenic appears to occur adsorbed on iron hydroxide-coated sand grains and clay minerals and is transported in soluble form and co-precipitated with, or is scavenged by, Fe(III) and Mn(IV) in the sediments. It became preferentially entrapped in fine-grained and organic-rich sediments during mid-Holocene sea-level rises in deltaic and some low-lying areas of the Bengal basin. It was liberated subsequently under reducing conditions and mediated further by microbial action. Intensive extraction of groundwater for irrigation and application of phosphate fertilizer possibly triggered the recent release of arsenic to groundwater. This practice has induced groundwater flow, mobilizing phosphate derived from fertilizer, as well as from decayed organic matter, which has promoted the growth of sediment biota and aided the further release of arsenic. However, the environment is not sufficiently reducing to mobilize iron and arsenic in groundwater in the Ganges floodplains upstream of Rajmahal. Thus, arsenic toxicity in the groundwater of the Bengal basin is caused by its natural setting, but also appears to be triggered by recent anthropogenic activities. Received: 23 August 1999 · Accepted: 16 November 1999     

Arsenic Levels in Groundwater from Quaternary Alluvium in the Ganga Plain and the Bengal Basin, Indian Subcontinent: Insights into Influence of Stratigraphy

Late Quaternary stratigraphy and sedimentation in the Ganga Alluvial Plain and the Bengal Basin have influenced arsenic contamination of groundwater. Arsenic contaminated aquifers are pervasive within lowland organic rich, clayey deltaic sediments in the Bengal Basin and locally within similar facies in narrow, entrenched river valleys within the Ganga Alluvial Plain. These were mainly deposited during early-mid Holocene sea level rise. Arsenic was transported from disseminated sources as adsorbed on dispersed phases of hydrated-iron-oxide. These were preferentially entrapped as sediment coatings on organic-rich, fine-grained deltaic and floodplain sediments. Arsenic was released later to groundwater mainly by reductive dissolution of hydrated-iron-oxide and corresponding oxidation of sediment organic matter. Strong reducing nature of groundwater in the Bengal Basin and parts of affected middle Ganga floodplains is indicated by high concentration of dissolved iron (maximum 9-35 mg/l). Groundwater being virtually stagnant under these settings, released arsenic accumulates and contaminates groundwater. The upland terraces in the Bengal Basin and in the Central Ganga Alluvial Plain, made up of the Pleistocene sediments are free of arsenic contamination in groundwater. These sediments are weakly oxidised in nature and associated groundwater is mildly reducing in general with low concentration of iron (<1 mg/l), and thus incapable to release arsenic. These sediments are also flushed free of arsenic, released if any, by groundwater flow due to high hydraulic head, because of their initial low-stand setting and later upland terraced position.     

Arsenic-rich groundwater in an urban area experiencing drought and increasing population density,Perth, Australia

Groundwater in the Gwelup groundwater management area in Perth, Western Australia has been enriched in As due to the exposure of pyritic sediments caused by reduced rainfall, increased groundwater abstraction for irrigation and water supply, and prolonged dewatering carried out during urban construction activities. Groundwater near the watertable in a 25–60 m thick unconfined sandy aquifer has become acidic and has affected shallow wells used for garden irrigation. Arsenic concentrations up to 7000 μg/L were measured in shallow groundwater, triggering concerns about possible health effects if residents were to use water from household wells as a drinking water source. Deep production wells used for public water supply are not affected by acidity, but trends of progressively increasing concentrations of Fe, SO₄ and Ca over a 30-a period indicate that pyrite oxidation products extend to the base of the unconfined aquifer. Falling Eh values are triggering the release of As from the reduction of Fe(III) oxyhydroxide minerals near the base of the unconfined aquifer, increasing the risk that groundwater used as a drinking water source will also become contaminated with high concentrations of As.     

Mobilization of natural arsenic in groundwater: targeting low arsenic aquifers in high arsenic occurrence areas

研究表明饮用水中微小数量的砷会对人类健康产生不利影响.世界上居住在贫穷地区的人数超过了100万,目前他们正直接饮用来自含水层中砷离子含量(>10μg/L)非安全标准的地下水.砷有时称为毒中之王,在水环境中常常以五价氧化物形式出现.自2000年以来,许多国家开始执行更为严格的10μg/L(WHO认可的居民安全饮水标准)饮用水标准,可以确定地说,在世界范围内的饮用水中检测到砷的情况越来越多.亚洲地区砷中毒的人数比世界其他地区总和还多.最受影响的地区位于南亚和东南亚富砷带,环绕恒河一雅鲁藏布江-梅克纳河三角洲及恒河平原上游的冲洪积扇含水层、红河三角洲、湄公河和伊洛瓦底江;在中国境内包括内蒙黄河冲积盆地,山西大同盆地、新疆准噶尔盆地,其中的地下水富含砷和氟化物而引发砷中毒和氟中毒.尽管还未完全掌握其中的水文地质及生物地球化学作用的详细过程,但对大多数沉积介质含水层,在还原条件下砷离子容易从沉积介质转移到地下水中.孟加拉研究实例表明地质时期尺度的冲刷降低了沉积介质中的As和有机物含量从而形成低砷地下水.这一认识为孟加拉国的降砷策略提供了科学指导,是未来水文学,矿物学,地质学和生物地球化学方面很有意义的研究方向,并有利于地砷病区低砷地下水的可持续利用.     

Soil geochemistry and groundwater contamination in an arsenic-affected area of the Datong Basin,China

This study describes the geochemistry of the topsoils from an arsenic (As)-affected area of the Datong Basin and identifies the possible sources and the enrichment mechanisms of As in groundwater. A total of 122 soil samples were collected from the study area. Analytical results indicate that soil As is higher than the average value of the Shanxi province topsoils. Fertilizer application and weathering of the bedrock both contributed to the presence of elements, including As, in the soil of the area. Furthermore, these elements may be strongly bound to Fe and Mn oxides/hydroxides. In addition, the depletion of K indicates that this element is readily leached into the groundwater rather than being retained in the soils. A groundwater area with high As levels corresponding spatially to soil samples with no As accumulation clearly shows the effects of irrigation or salt flushing on the soil compositions. Arsenic can be mobilized under reducing condition due to organic matter input or changes in redox conditions induced by irrigation or salt flushing and can be transported with vertically recharged water into shallow, unconfined aquifers, thus elevating the As concentration in groundwater.     

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.     

Arsenic solubilization and redistribution under anoxic conditions in three aquifer sediments from a basin-fill aquifer in Northern Utah: The role of natural organic carbon and carbonate minerals

The basin-fill aquifers of the Western U.S. contain elevated concentrations of arsenic in the groundwater due to ancient volcanic deposits that host arsenic minerals. Microcosms were constructed using two oxidized sediments and, by contrast, a reduced sediment collected from a shallow basin-fill aquifer in the Cache Valley Basin, Northern Utah to evaluate the fate of geologic arsenic under anoxic conditions. Sequential extractions indicated the primary arsenic host mineral was amorphous iron oxides, but 13%–17% of the total arsenic was associated with carbonate minerals. Arsenic was solubilized from the sediments when incubated with groundwater in the presence of native organic carbon. Arsenic solubilization occurred prior to iron reduction rather than the commonly observed co-reactivity. Arsenic(V) associated with carbonate minerals was the main source of arsenic released to solution and redistributed onto less soluble minerals, including FeS and siderite as defined by chemical extraction. Arsenic reduction occurred only in the site-oxidized sediments. The addition of a carbon and energy source, glucose, resulted in enhanced arsenic solubilization, which was coupled with iron reduction from the site-oxidized sediments. Adding glucose promoted iron reduction that masked the role of carbonate minerals in arsenic solubilization and retention as observed with incubation with groundwater only.     

Arsenic-enriched aquifers: Occurrences and mobilization of arsenic in groundwater of Ganges Delta Plain, Barasat, West Bengal, India

Hydrogeochemical characteristics and elemental features of groundwater and core sediments have been studied to better understand the sources and mobilization process responsible for As-enrichment in part of the Gangetic plain (Barasat, West Bengal, India). Analysis of water samples from shallow tubewells (depth 24.3–48.5 m) and piezometer wells (depth 12.2–79.2 m) demonstrate that the groundwater is mostly the Ca-HCO₃ type and anoxic in nature (mean Eh_SHE = 34 mV). Arsenic concentrations ranged from <10–538 μg/L, with high concentrations only present in the shallow to medium depth (30–50 m) of the aquifer along with high Fe (0.07–9.8 mg/L) and relatively low Mn (0.15–3.38 mg/L) as also evidenced in core sediments. Most groundwater samples contained both As(III) and As(V) species in which the concentration of As(III) was generally higher than that of As(V), exhibiting the reducing condition. Results show lower concentrations of NO₃, SO₄ and NO₂ along with higher values of DOC and HCO₃, indicating the reducing nature of the aquifer with abundant organic matter that can promote the release of As from sediments into groundwater. Positive correlations of As with Fe and DOC were also observed. The presence of DOC may actively drive the redox processes. This study revealed that reduction processes of FeOOH was the dominant mechanism for the release of As into the groundwater in this part of the Ganges Delta plain.     

Speciation and natural attenuation of arsenic and iron in a tidally influenced shallow aquifer

The mobility of subsurface arsenic is controlled by sorption, precipitation, and dissolution processes that are tied directly to coupled redox reactions with more abundant, but spatially and temporally variable, iron and sulfur species. Adjacent to the site of a former pesticide manufacturing facility near San Francisco Bay (California, USA), soil and groundwater arsenic concentrations are elevated in sediments near the prior source, but decrease to background levels downgradient where shallow groundwater mixes with infiltrating tidal waters at the plume periphery, which has not migrated appreciably in over two decades of monitoring. We used synchrotron X-ray absorption spectroscopy, together with supporting characterizations and sequential chemical extractions, to directly determine the oxidation state of arsenic and iron as a function of depth in sediments from cores recovered from the unsaturated and saturated zones of a shallow aquifer (to 3.5 m below the surface). Arsenic oxidation state and local bonding in sediments, as As-sulfide, As(III)-oxide, or As(V)-oxide, were related to lithologic redox horizons and depth to groundwater. Based on arsenic and iron speciation, three subsurface zones were identified: (i) a shallow reduced zone in which sulfide phases were found in either the arsenic spectra (realgar-like or orpiment-like local structure), the iron spectra (presence of pyrite), or both, with and without As(III) or As(V) coordinated by oxygen; (ii) a middle transitional zone with mixed arsenic oxidation states (As(III)–O and As(V)–O) but no evidence for sulfide phases in either the arsenic or iron spectra; and (iii) a lower oxidized zone in the saturated freshwater aquifer in which sediments contained only oxidized As(V) and Fe(III) in labile (non-detrital) phases. The zone of transition between the presence and absence of sulfide phases corresponded to the approximate seasonal fluctuation in water level associated with shallow groundwater in the sand-dominated, lower oxic zone. Total sediment arsenic concentrations showed a minimum in the transition zone and an increase in the oxic zone, particularly in core samples nearest the former source. Equilibrium and reaction progress modeling of aqueous-sediment reactions in response to decreasing oxidation potential were used to illustrate the dynamics of arsenic uptake and release in the shallow subsurface. Arsenic attenuation was controlled by two mechanisms, precipitation as sulfide phases under sulfate-reducing conditions in the unsaturated zone, and adsorption of oxidized arsenic to iron hydroxide phases under oxidizing conditions in saturated groundwaters. This study demonstrates that both realgar-type and orpiment-type phases can form in sulfate-reducing sediments at ambient temperatures, with realgar predicted as the thermodynamically stable phase in the presence of pyrite and As(III) under more reduced conditions than orpiment. Field and modeling results indicate that the potential for release of arsenite to solution is maximized in the transition between sulfate-reduced and iron-oxidized conditions when concentrations of labile iron are low relative to arsenic, pH-controlled arsenic sorption is the primary attenuation mechanism, and mixed Fe(II,III)-oxide phases do not form and generate new sorption sites.