Mengyu Duan

Geochemistry of redox-sensitive elements and sulfur isotopes in the high arsenic groundwater system of Datong Basin, China

High arsenic groundwater in the Quaternary aquifers of Datong Basin, northern China contain As up to 1820 microg/L and the high concentration plume is located in the slow flowing central parts of the basin. In this study we used hydrochemical data and sulfur isotope ratios of sulfate to better understand the conditions that are likely to control arsenic mobilization. Groundwater and spring samples were collected along two flow paths from the west and east margins of the basin and a third set along the basin flow path. Arsenic concentrations range from 68 to 670 microg/L in the basin and from 3.1 to 44 microg/L in the western and eastern margins. The margins have relatively oxidized waters with low contents of arsenic, relatively high proportions of As(V) among As species, and high contents of sulfate and uranium. By contrast, the central parts of the basin are reducing with high contents of arsenic in groundwater, commonly with high proportions of As(III) among As species, and low contents of sulfate and uranium. No statistical correlations were observed between arsenic and Eh, sulfate, Fe, Mn, Mo and U. While the mobility of sulfate, uranium and molybdenum is possibly controlled by the change in redox conditions as the groundwater flows towards central parts of the basin, the reducing conditions alone cannot account for the occurrence of high arsenic groundwater in the basin but it does explain the characteristics of arsenic speciation. With one exception, all the groundwaters with As(III) as the major As species have low Eh and those with As(V) have high Eh. Reductive dissolution of Fe-oxyhydroxides or reduction of As(V) are consistent with the observations, however no increase in dissolved Fe concentration was noted. Furthermore, water from the well with the highest arsenic was relatively oxidizing and contained mostly As(V). From previous work Fe-oxyhydroxides are speculated to exist as coatings rather than primary minerals. The wide range of delta(34)S([SO4]) values (from -2.5 to +36.1 per thousand) in the basin relative to the margins (from +8 per thousand to +15 per thousand) indicate that sulfur is undergoing redox cycling. The highly enriched values point to sulfate reduction that was probably mediated by bacteria. The presence of monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) is also evidence of microbial reactions. The depleted signatures indicate that some oxidation of depleted sulfide occurred in the basin. It must be noted that the samples with depleted sulfur isotope values have very low sulfate concentrations and therefore even a small amount of sulfide oxidation will bias the ratio. No significant correlation was observed between delta(34)S([SO4]) values and total arsenic contents when all the samples were considered. However, the wells in the central basin do appear to become enriched in delta(34)S([SO4]) as arsenic concentration increases. Although there is evidence for sulfate reduction, it is clear that sulfate reduction does not co-precipitate or sequester arsenic. The one sample with high arsenic that is oxidizing cannot be explained by oxidation of pyrite and is likely an indication that there are multiple redox zones that control arsenic speciation but not necessarily its mobilization and contradict the possibility that Fe-oxyhydroxides sorb appreciable amounts of arsenic in this study area. It is evident that this basin like other two young sedimentary basins (Huhhot and Hetao in Inner Mongolia) of northern China with high arsenic groundwater is transporting arsenic at a very slow rate. The data are consistent with the possibility that the traditional models of arsenic mobilization, namely reductive dissolution of Fe-oxyhydroxides, reduction of As(V) to more mobile As(III), and bacteria mediated reactions, are active to varying degrees. It is also likely that different processes control arsenic mobilization at different locations of the basin and more detailed studies along major flow paths upgradient of the high arsenic aquifers will shed more light on the mechanisms.

Mobilization of arsenic in aquifers from the Datong Basin, China: Evidence from geochemical and iron isotopic data

Iron isotope compositions of various Fe pools in aquifer sediments were measured at a known As-contaminated site in the Datong Basin, China. The δ(56)Fe values of HCl-extracted poor-crystalline Fe(III) range widely from -0.41‰ to 0.36‰. We interpret the low Fe(II)/Fe(Extractable) ratios (<50%) and the negative correlation between Fe(II)/Fe(Extractable) and δ(56)Fe values in HCl-extracted poor-crystalline Fe to be best explained by redox cycling of Fe induced by microbial Fe(III) reduction. However, the high Fe(II)/Fe(Extractable) ratios (~/>70%) and positive correlation between Fe(II)/Fe(Extractable) and δ(56)Fe values for HCl-extracted poor-crystalline Fe indicates production of sulfides (FeSs). The δ(56)Fe values of crystalline Fe(III) extracted by reductant appears to be comparatively small varying from -0.01‰ to 0.24‰, which is consistent with the δ(56)Fe values for ferric oxides/hydroxides having undergone microbial Fe(III) reduction. The Fe isotope composition of various Fe pools shows the transformation between crystalline Fe(III) and poor-crystalline crystalline Fe(III) and the secondary Fe(II) phases has already occurred or is occurring in aquifer sediments. More importantly, there is a significant difference in the As concentrations in crystalline Fe(III) oxides/hydroxides and HCl-extracted Fe phases. The concentrations of As range from 1.6 to 29.9 mg kg(-1) and from 0.6 to 3.0 mg kg(-1), for crystalline Fe(III) and HCl-extracted Fe phases respectively. Accordingly, the transformation of Fe minerals induced by microbial Fe(III) reduction can contribute to the mobilization of As. This study is the first to examine the Fe isotope compositions in high As aquifer sediments; the results show that the Fe isotope would be an important tool in demonstrating the enrichment of As in groundwater.

In situ treatment of arsenic contaminated groundwater by aquifer iron coating: Experimental Study

In situ arsenic removal from groundwater by an aquifer iron coating method has great potential to be a cost effective and simple groundwater remediation technology, especially in rural and remote areas where groundwater is used as the main water source for drinking. The in situ arsenic removal technology was first optimized by simulating arsenic removal in various quartz sand columns under anoxic conditions. The effectiveness was then evaluated in an actual high-arsenic groundwater environment. The arsenic removal mechanism by the coated iron oxide/hydroxide was investigated under different conditions using scanning electron microscopy (SEM)/X-ray absorption spectroscopy, electron probe microanalysis, and Fourier transformation infrared spectroscopy. Aquifer iron coating method was developed via a 4-step alternating injection of oxidant, iron salt and oxygen-free water. A continuous injection of 5.0 mmol/L FeSO4 and 2.5 mmol/L NaClO for 96 h can form a uniform goethite coating on the surface of quartz sand without causing clogging. At a flow rate of 7.2 mL/min of the injection reagents, arsenic (as Na2HAsO4) and tracer fluorescein sodium to pass through the iron-coated quartz sand column were approximately at 126 and 7 column pore volumes, respectively. The retardation factor of arsenic was 23.0, and the adsorption capacity was 0.11 mol As per mol Fe. In situ arsenic removal from groundwater in an aquifer was achieved by simultaneous injections of As(V) and Fe(II) reagents. Arsenic fixation resulted from a process of adsorption/co-precipitation with fine goethite particles by way of bidentate binuclear complexes. Therefore, the study results indicate that the high arsenic removal efficiency of the in situ aquifer iron coating technology likely resulted from the expanded specific surface area of the small goethite particles, which enhanced arsenic sorption capability and/or from co-precipitation of arsenic on the surface of goethite particles.

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

Abstract 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.