Xianjun Xie

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.

Direct determination of trace cadmium in environmental samples by dynamic reaction cell inductively coupled plasma mass spectrometry.

Cadmium is subject to significant Zr and Mo based oxide/hydroxide interferences in ICP-MS analysis of environmental samples. In this work, a dynamic reaction cell (DRC) technology was used to eliminate these metal oxide/hydroxide interferences. The potentially interfering ions (94)Zr(16)OH(+), (94)Mo(16)OH(+) and (95)Mo(16)O(+) on (111)Cd(+) were oxidized to higher oxides (94)ZrO(2)H(+)/(94)ZrO(3)H(+), (94)MoO(2)H(+)/(94)MoO(3)H(+), and (95)MoO(2)(+)/(95)MoO(3)(+) by O(2) as the reaction gas in DRC. Under the optimized O(2) flow rate (2.0 mLmin(-1)) and DRC rejection parameter q (Rpq, 0.75), the background signal was reduced by up to 100-fold at m/z 111 and the limit of quantitation (LOQ, 10σ) of 0.1 ngg(-1) was obtained. The proposed method was applied to direct analysis of trace Cd in a series of soil and sediment standard reference materials and the satisfactory results showed that it has great potential for the direct determination of trace or ultra-trace levels of cadmium in environmental samples.

Occurrence, behavior and distribution of high levels of uranium in shallow groundwater at Datong basin, northern China.

Geochemical investigations of uranium (U) occurrence in the environments were conducted at Datong basin of northern China. The results suggest that U contents were generally <1mg/kg for the igneous and metamorphic rocks, typically 2-5mg/kg for the Carboniferous and Permian sedimentary rocks and around 3mg/kg for sediments and topsoil, respectively. U in the Quaternary aquifer sediments may be primarily associated with carnotite from the Carboniferous and Permian coal-bearing clastic rocks around the basin. Shallow groundwater had U concentrations of <0.02-288 μg/L (average 24 μg/L), with 24% of the investigated boreholes above the WHO provisional guideline of 30 μg/L for U in drinking water. Average U concentration for surface water was 5.8 μg/L. In oxidizing waters, uranyl (UO2(2+)) species is dominant and strongly adsorbed onto iron (hydro)xides, while it would be preferentially complexed with carbonate in the alkaline groundwater, forming highly soluble uranyl-carbonate complexes at Datong. Under reducing conditions, uranous (U(IV)) species is ready to precipitate or bind to organic matter, therefore having a low mobility. At the study area, high U groundwater (>30 μg/L) occurs at the alluvial plains due to intermediate redox and enhanced alkaline conditions. The abnormally high levels of U in groundwater (>100 μg/L) are locally found at the west alluvial plains. By contrast, U co-precipitation with secondary carbonate minerals like Ca2UO2(CO3)3 in the dominant Ca-Mg-Na-HCO3 type groundwater may prevail at the east alluvial plains. Besides, bedrocks such as Carboniferous and Permian sedimentary rocks, especially the coal-bearing strata which have higher U contents at the west mountain areas may also account for the abnormally high levels of U in groundwater.

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.

Iodine mobilization in groundwater system at Datong basin, China: Evidence from hydrochemistry and fluorescence characteristics

Characterizing the speciation of iodine in groundwater is essential for understanding its hydrogeochemical behavior in aquifer systems. To quantify the variations in iodine speciation and assess factors controlling the distribution and transformation of iodine, 82 groundwater samples and 1 rain water were collected from the Datong basin, northern China in this study. Factor analysis (FA) and excitation emission matrix with parallel factor analysis (EEM-PARAFAC) were used to clarify the potential relationships among iodine species and other hydrochemical parameters. The iodine concentrations of groundwater range from 6.23 to 1380 μg L(-1) with 47% of samples exceeding its drinking water level of 150 μg L(-1) as recommended by the Chinese government. 57% of samples have ratios of iodate to total iodine greater than 60%, while iodide as the major species in 22% of the samples. Significant amounts of organic iodine with concentrations higher than 100 μg L(-1) were observed in 9 groundwater samples. Redox conditions of groundwater system strongly affect iodine concentration and speciation of inorganic iodine in groundwater, and extremely reducing condition restricts the iodine release from sediments into groundwater. The results of FA show that iodine mobilization in groundwater is related to the nature of dissolved organic matter. EEM-PARAFAC model demonstrates the dominance of terrestrial DOM sources and the presence of microbial activities in groundwater system of the Datong basin. It is proposed that degradation of organic matter and reductive dissolution of iron oxyhydroxides are major hydrogeochemical processes responsible for the mobilization of iodine release and the genesis of organic iodine.

Cl/Br ratios and chlorine isotope evidences for groundwater salinization and its impact on groundwater arsenic, fluoride and iodine enrichment in the Datong basin, China.

In order to identify the salinization processes and its impact on arsenic, fluoride and iodine enrichment in groundwater, hydrogeochemical and environmental isotope studies have been conducted on groundwater from the Datong basin, China. The total dissolved solid (TDS) concentrations in groundwater ranged from 451 to 8250 mg/L, and 41% of all samples were identified as moderately saline groundwater with TDS of 3000-10,000 mg/L. The results of groundwater Cl concentrations, Cl/Br molar ratio and Cl isotope composition suggest that three processes including water-rock interaction, surface saline soil flushing, and evapotranspiration result in the groundwater salinization in the study area. The relatively higher Cl/Br molar ratio in groundwater from multiple screening wells indicates the contribution of halite dissolution from saline soil flushed by vertical infiltration to the groundwater salinization. However, the results of groundwater Cl/Br molar ratio model indicate that the effect of saline soil flushing practice is limited to account for the observed salinity variation in groundwater. The plots of groundwater Cl vs. Cl/Br molar ratio, and Cl vs δ(37)Cl perform the dominant effects of evapotranspiration on groundwater salinization. Inverse geochemical modeling results show that evapotranspiration may cause approximately 66% loss of shallow groundwater to account for the observed hydrochemical pattern. Due to the redox condition fluctuation induced by irrigation activities and evapotranspiration, groundwater salinization processes have negative effects on groundwater arsenic enrichment. For groundwater iodine and fluoride enrichment, evapotranspiration partly accounts for their elevation in slightly saline water. However, too strong evapotranspiration would restrict groundwater fluoride concentration due to the limitation of fluorite solubility.

Basement and alluvial aquifers of Malawi: An overview of groundwater quality and policies

This paper highlights the quality of groundwater in basement and alluvial aquifers of Malawi through literature assessment. Groundwater in these aquifers serves about 60% of Malawian population. Alluvial aquifers yield high groundwater in excess of 10 L/s and more mineralized than basement aquifers. The values from literature are presented as ranges. The geochemical quality of both aquifer types are classified as good. However, in some cases values higher than maximum permissible limits (MPL) are worrisomely apparent. Significant levels for some elements have been demonstrated. Although groundwater policies and instruments are available, more groundwater research, monitoring, data archiving is needed.

Hydrogeochemistry of co-occurring geogenic arsenic, fluoride and iodine in groundwater at Datong Basin, northern China.

Abnormal levels of co-occurring arsenic (As), fluorine (F) and iodine (I) in groundwater at Datong Basin, northern China are geochemically unique. Hydrochemical, (18)O and (2)H characteristics of groundwater were analyzed to elucidate their mobilization processes. Aqueous As, F and I ranged from 5.6 to 2680 μg/L, 0.40 to 3.32 mg/L and 10.1 to 186 μg/L, respectively. High As, F and I groundwater was characterized by moderately alkaline, high HCO3(-), Fe(II), HS(-) and DOC concentrations with H3AsO3, F(-) and I(-) as the dominant species. The plots of δ(18)O values and Cl/Br ratios versus Cl(-) concentration demonstrate build-up of more oxidizing conditions and precipitation of carbonate minerals induced by vertical recharge and intensive evaporation facilitate As retention to Fe (hydr) oxides, but enhance F and I mobilization from host minerals. Under reducing conditions, As and I can be simultaneously released via reductive dissolution of Fe (hydr) oxides and reduction of As(V) and I(V) while F migration may be retarded due to effects of dissolution-precipitation equilibria between carbonate minerals and fluorite. With the prevalence of sulfate-reducing condition and lowering of HCO3(-) concentration, As and I may be sequestered by Fe(II) sulfides and F is retained to fluorite and on clay mineral surfaces.

Arsenic Resistance and Bioaccumulation of an Indigenous Bacterium Isolated from Aquifer Sediments of Datong Basin, Northern China

To obtain bacteria with arsenic accumulation potential that can be used to remove arsenic from contaminated waters, experiments were made to investigate the tolerance and accumulation to arsenic of an indigenous bacterium XZM002 isolated from aquifer sediments of Datong Basin, northern China. The results showed that strain XZM002 belongs to the genus Bacillus and has evolved defense mechanisms to reduce arsenic injury: the change of cellular shape from initial rod to oval and then to round with increment of arsenic toxicity. The effect of arsenate or arsenite on the bacterial growth was also investigated. Results showed that growth of the strain was inhibited under As(III) and high concentration As(V) (over 1200 μg l−1) conditions in the first 2 days and promoted under low concentration As(V) (under 400 μg l−1) condition. Its arsenic bioaccumulation potential was surveyed by monitoring the concentration changes of total arsenic and arsenic speciation in the medium and in the cytoplasm, and those of total arsenic on the membrane. Methylated arsenic species were not detected throughout the experiment. The results indicated that 11.5% of arsenic was removed from liquid medium into the bacterial cells and 9.22% of As(V) in the medium was transformed gradually to As(III) during 4 d of incubation. Approximately 80% of the total accumulated arsenic was adsorbed onto the membrane instead of into cytoplasm; and the arsenic accumulation almost approached saturation after incubation for 72 h.

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.