As-affected Aquifers Research Articles

Fermentation, methanotrophy and methanogenesis influence sedimentary Fe and As dynamics in As-affected aquifers in Vietnam.

High arsenic (As) concentrations in groundwater are a worldwide problem threatening the health of millions of people. Microbial processes are central in the (trans)formation of the As-bearing ferric and ferrous minerals, and thus regulate dissolved As levels in many aquifers. Mineralogy, microbiology and dissolved As levels can vary sharply within aquifers, making high-resolution measurements particularly valuable in understanding the linkages between them. We conducted a high spatial resolution geomicrobiological study in combination with analysis of sediment chemistry and mineralogy in an alluvial aquifer system affected by geogenic As in the Red River delta in Vietnam. Microbial community analysis revealed a dominance of fermenters, methanogens and methanotrophs whereas sediment mineralogy along a 46m deep core showed a diversity of Fe minerals including poorly crystalline Fe (II/III) and Fe(III) (oxyhydr)oxides such as goethite, hematite, and magnetite, but also the presence of Fe(II)-bearing carbonates and sulfides which likely formed as a result of microbially driven organic carbon (OC) degradation. A potential important role of methane (CH4) as electron donor for reductive Fe mineral (trans)formation was supported by the high abundance of Candidatus Methanoperedens, a known Fe(III)-reducing methanotroph. Overall, these results imply that OC turnover including fermentation, methanogenesis and CH4 oxidation are important mechanisms leading to Fe mineral (trans)formation, dissolution and precipitation, and thus indirectly affecting As mobility by changing the Fe-mineral inventory.

Arsenic immobilization by in-situ iron coating for managed aquifer rehabilitation

A long-lasting challenge in eliminating the worldwide impact of geogenic arsenic (As)-contaminated groundwater is the development of efficient, in-situ treatment technologies that are applicable in decentralized and rural areas. Here we present a managed aquifer rehabilitation (MAR) approach based on the in-situ creation of Fe-oxide scavengers for remediating As-contaminated groundwater. The Fe-oxide coatings on sediment surfaces were generated via periodic injection of Fe2+ and ClO− solutions into an As-affected sandy aquifer at the Datong Basin, northern China for 25 days. This treatment prompted the buildup of weakly alkaline/circumneutral and oxidizing conditions to enhance As(III) oxidation in the target aquifer. Dissolved As concentrations decreased from the initial average 78.0 to 9.8 μg/L over the 25-d amendment. Sediment imaging by scanning electron microscope-X-ray energy dispersive spectroscopy confirms the deposition of Fe-rich precipitates on sediment surfaces with the simultaneous retention of As, and high density electrical tomography suggests the occurrence of such a process throughout the target zone. Further X-ray diffraction analysis and sequential chemical extraction reveal that the neo-formed Fe minerals comprised both poorly crystalline (e.g., ferrihydrite) and better crystalline (e.g., goethite) Fe oxides. The process-based reactive-transport modeling for the variations of As species in the treated groundwater supports that the new Fe-oxide minerals, most probably goethite, acted as efficient removers of aqueous As. The low As level of ∼10 μg/L was maintained during the following 215-d monitoring, demonstrating the long effectiveness of the MAR approach. This study highlights the feasibility of As immobilization by manipulating in-situ Fe-oxide coating on sandy sediments at the pilot scale. The MAR technology may be applicable for As-affected aquifers with controlled oxidizing conditions in the Datong Basin and likely other high-As regions with similar hydrogeochemical settings.

Biogeochemical and reactive transport modeling of arsenic in groundwaters from the Mississippi River delta plain: An analog for the As-affected aquifers of South and Southeast Asia

Abstract Arsenic (As) concentrations and speciation were measured in groundwaters from the upper Chicot aquifer in southern Louisiana to: (1) ascertain the geochemical processes responsible for its mobilization into the groundwater; and (2) investigate the fate and transport of As in the aquifer following its mobilization into solution. Ancillary geochemical parameters, including dissolved iron (Fe) concentrations and speciation, major solutes, pH, and alkalinity were also quantified in the groundwaters, along with the mineralogy and geochemistry of the aquifer sediments. Arsenic concentrations as high as 644 nmol kg−1 (48.2 μg kg−1) were measured in the groundwaters, with the arsenite oxyanion (H3AsIIIO30) accounting for ca. 60%, on average, of the total dissolved As, and the remaining ca. 40% consisting of the arsenate oxyanion (i.e., H2AsVO42−). The groundwaters are Na – HCO3 type waters of slightly alkaline pH (8.09 ≤ pH ≤ 8.34), moderately high mineralization (7.3 mmol kg−1 ≤ I ≤ 13.7 mmol kg−1), and high Fe(II) concentrations (18 μmol kg−1 ≤ Fe(II) ≤ 47 μmol kg−1), and thus are compositionally similar to As-affected groundwaters from South and Southeast Asia (e.g., Bangladesh, West Bengal, India, and Vietnam). Groundwaters with the highest As concentrations also have the highest Fe(II) concentrations, which is consistent with reductive dissolution of Fe(III) oxides/oxyhydroxides releasing sorbed or co-precipitated As into the groundwaters. Biogeochemical reactive transport modeling that employs rates laws for microbial respiration indicates that dissimilatory reduction of Fe(III) oxides/oxyhydroxides coupled to organic matter oxidation can explain the high As concentrations along the mid-reaches of the studied flow path. Geochemical analysis of the aquifer sediments further demonstrates that the bulk of the environmentally mobile As in the aquifer is associated with Fe(III) oxides/oxyhydroxides and/or chemisorbed (i.e., inner-sphere surface complexed) onto aquifer mineral surfaces. Model calculations confirm that mobilization of 2–8% of this labile As could support the high As concentrations measured in these groundwaters. Reactive transport modeling coupled to the generalized double-layer surface complexation model predicts that As(III) could be transported ca. 10 km down gradient from the current location of the As “hot-spot” after 150 years, whereas As(V) is predicted to move between 2.4 km and 8.5 km depending on the composition of Fe(III) oxides/oxyhydroxides in the aquifer. Reactive transport modeling also illustrates how retardation and attenuation of As(III) and As(V) along flow paths in aquifer systems is strongly dependent on the type and content of Fe(III) oxides/oxyhydroxides present in the aquifer with higher contents of amorphous to poorly crystalline forms leading to greater retardation and attenuation of both As species. The data and modeling indicate that although As is readily mobilized by microbial reduction of Fe(III) oxides/oxyhydroxides, its tendency to form strong, inner sphere surface complexes on Fe(III) oxides/oxyhydroxides remaining in the aquifer will control the fate and transport of As once released into solution. We suggest that these observations may help explain the “patchy” spatial distributions of As concentrations commonly observed in As-affected aquifers, such as those of South and Southeast Asia.

Contrasting sorption behaviours affecting groundwater arsenic concentration in Kandal Province, Cambodia

Natural arsenic (As) contamination of groundwater which provides drinking water and/or irrigation supplies remains a major public health issue, particularly in South and Southeast Asia. A number of studies have evaluated various aspects of the biogeochemical controls on As mobilization in aquifers typical to this region, however many are predicated on the assumption that key biogeochemical processes may be deduced by sampled water chemistry. The validity of this assumption has not been clearly established even though the role of sorption/desorption of As and other heavy metals onto Fe/Mn (hydr)oxides is an important control in As mobilization. Here, selective chemical extractions of sand-rich and clay-rich sediments from an As-affected aquifer in Kandal Province, Cambodia, were undertaken to explore the potential role of partial re-equilibrium through sorption/desorption reactions of As and related solutes (Fe, Mn and P) between groundwater and the associated solid aquifer matrix. In general, groundwater As is strongly affected by both pH and Eh throughout the study area. However, contrasting sorption behaviour is observed in two distinct sand-dominated (T-Sand) and clay dominated (T-Clay) transects, and plausibly attributed to differing dominant lithologies, biogeochemical and/or hydrogeological conditions. Sorption/desorption processes appear to be re-setting groundwater As concentrations in both transects, but to varying extents and in different ways. In T-Sand, which is typically highly reducing, correlations suggest that dissolved As may be sequestered by sorption/re-adsorption to Fe-bearing mineral phases and/or sedimentary organic matter; in T-Clay Eh is a major control on As mobilization although binding/occlusion of Fe-bearing minerals to sedimentary organic matter may also occur. Multiple linear regression analysis was conducted with groups categorised by transect and by Eh, and the output correlations support the contrasting sorption behaviours encountered in this study area. Irrespective of transect, however, the key biogeochemical processes which initially control As mobilization in such aquifers, may be “masked” by the re-setting of As concentrations through in-aquifer sorption/desorption processes.

Vertical variability of arsenic concentrations under the control of iron-sulfur-arsenic interactions in reducing aquifer systems

High spatial variability of arsenic (As) concentration in geogenic As-contaminated groundwater has been commonly observed worldwide, but the underlying reasons remain not well understood. Selecting a sulfate-containing, As-affected aquifer at the Datong Basin, northern China as the study area and combining hydrogeochemical investigation and sediment extraction with reactive transport modeling, this work elucidated the roles of Fe-S-As interactions in regulating the vertical variation of As concentration in the groundwater. Dissolved As concentration varied between 0.05 and 18 μmol/L, but generally increased in the depth of 20–25 m and then decreased in 25–30 m. The high-As groundwater contained low Fe(II) (<0.007 mmol/L) and up to 15 μmol/L sulfide, in contrary to the S/SE Asian deltas/floodplains where high Fe(II) and As jointly occur in the groundwater devoid of sulfate reduction. The reductive dissolution of As-bearing Fe(III) oxides coupled to the degradation of organic matter with an estimated maximum rate of 0.22 mmol C/L/yr, mainly accounted for the depth-dependent increase of As concentration in the upper part of the shallow aquifer (<25 m deep). However, the decreasing reactivity of Fe(III) oxides together with the increase of pH over depth rendered the majority of electrons being transferred to sulfate reduction. The Fe(II) sulfides formed as a consequence not only helped to restrict the build-up of Fe(II) in the groundwater but also probably co-precipitated As to prompt As decrease in the depth of 25–30 m. Arsenite adsorbed on remaining Fe(III) oxides and newly-formed Fe(II) sulfides is another important pool of As in the aquifer, which varies in response to the extents of Fe(III)-oxide and sulfate reduction and consequently alters As distribution coefficient between the solid and the aqueous phases. This study highlights the importance of coupled geochemical cycling of Fe, S and As for As mobilization and reveals how it regulates As partitioning between groundwater and sediments.

Effect of microbially mediated iron mineral transformation on temporal variation of arsenic in the Pleistocene aquifers of the central Yangtze River basin

Significant seasonal variation of groundwater arsenic (As) concentrations in shallow aquifers of the Jianghan Plain, central Yangtze River Basin has been reported recently, but the underlying mechanisms remain not well understood. To elaborate biogeochemical processes responsible for the observed As concentration variation, 42-day incubation experiments were done using sediment samples collected respectively from the depth of 26, 36 and 60m of the As-affected aquifer which were labeled respectively as JH26, JH36, JH60. Where JH denotes Jianghan Plain, and the number indicates the depth of the sediment sample. The results indicated that As could be mobilized from the sediments of 26m and 36m depth under the stimulation of exogenous organic carbon, with the maximum As release amount of 1.60 and 1.03mgkg−1, respectively, while the sediments at 60m depth did not show As mobilization. The microbially mediated reductive dissolution of amorphous iron oxides and reduction of As(V) to As(III) could account for the observed As mobilization. The 16S rRNA high-throughput sequencing results indicated that the variation of microbial community correlated with the released As concentration (R=0.7, P<0.05) and the iron-reducing bacteria, including Pseudomonas, Clostridium and Geobacter, were the main drivers for the As mobilization from the sediments at 26m and 36m depth. The increase of arsC gene abundance (up to 1.4×105 copies g−1) during As release suggested that As reduction was mediated by the resistant reduction mechanism. By contrast, in the 60m sediments where the Fe and As release was absent, the iron-reducing bacteria accounted for a very minor proportion and sulfate-reducing bacteria were predominant in the microbial community. In addition, after 30days of incubation, the released As in the 26m sediments was immobilized via co-precipitation with or adsorption onto the Fe-sulfide mineral newly-formed by the bacterial sulfate reduction. These results are consistent with the results of our previous field monitoring, indicating that the bacterial sulfate reduction could lead to the temporal decrease in groundwater As concentrations. This study provides insights into the mechanism for As mobilization and seasonal As concentration variation in the Pleistocene aquifers from alluvial plains.

Role of colloidal particles for hydrogeochemistry in As-affected aquifers of the Hetao Basin, Inner Mongolia

High As groundwater was found in shallow aquifers of the Hetao Basin, Inner Mongolia, which has caused serious chronic arsenism. Groundwater particles are ubiquitous in natural aquifers, and significantly affect As mobilization and transportation. This study has investigated their effect on element hydrogeochemistry. Groundwater samples were filtered in the field through a progressively decreasing pore size (10, 5, 3, 1, 0.8, 0.45 μm). Unfiltered samples were also taken. Chemical analysis of 43 groundwater samples shows concentrations of most elements (Ba, Co, Mn, Mo, Ni, V, Sr, Mg, Ca, Na, K) in unfiltered samples are well correlated with those in <0.45 μm fraction, and the ratios between them are close to 1.00. Those elements are considered to be present in the form of true dissolved group and are not affected by the filtration. Although saturation indices for calcite and dolomite are greater than 0, they could possibly exist as small size colloids (<0.45 μm) in groundwater. Concentrations of Cd, Pb, Fe, and Al in <0.45 μm fraction are mostly less than those in unfiltered fraction, implying that large-size inorganic-rich (Al/Fe complexing) colloids could be possible carrier for Cd and Pb in the groundwaters. Arsenic, Cu, Zn and Cr are fallen into another group. These elements could mainly be associated with organic-complexing colloids with particle size less than 0.45 μm, although As could partially be carried by large-size colloids. In groundwaters saturated with respect to pyrite and siderite, a small proportion of As (about 15%) is associated with large-size Fe complexing particles (>0.45 μm). Larger amounts of As is trapped with small size organic colloids, which has been confirmed by the ultrafiltration. The study suggests that groundwater particles transported in the aquifers could affect element geochemistry, especially for As expected to be associated in small size complexes.