Chunli Su

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.

Effects of anion competitive adsorption on arsenic enrichment in groundwater

Long-term intake of high arsenic groundwater has caused serious endemic disease on people in Datong Basin, northern China. The high arsenic groundwater has medium to high alkalinity with a mean pH value of 8.1; the water generally belongs to HCO3-Na type water and contains HPO4 2− in most samples. In this study, batch experiments and geochemical modeling were conducted to reveal the geochemical processes responsible for arsenic enrichment in the groundwater due to desorption, and to examine the effect of pH, phosphate, bicarbonate and silicate on this desorption in the studied groundwater system. The experimental pH ranging from 7.35 to 8.72 as observed in the high arsenic groundwater, was favorable for arsenic desorption from the aquifer sediments. Arsenic concentration in the aqueous phase significantly increased with the increase of added PO4 3− concentration. An elevated arsenic content of 13.6 μg/L was observed with the highest phosphate loading of 30 mg/L. Although bicarbonate addition caused less desorption of arsenic than phosphate on the mole basis, an elevated arsenic concentration of 56 μg/L in the batch solutions was observed when the added bicarbonate contents was up to 1500 mg/L. The contribution of silicate to arsenic desorption is lower than that of phosphate and bicarbonate.

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.

Monitoring and modeling the effects of groundwater flow on arsenic transport in Datong Basin

Although arsenic-contaminated groundwater in the Datong Basin has been studied for more than 10 years, little has been known about the complex patterns of solute transport in the aquifer systems. Field monitoring and transient 3D unsaturated groundwater flow modeling studies were carried out on the riparian zone of the Sanggan River at the Datong Basin, northern China, to better understand the effects of groundwater flow on As mobilization and transport. The results indicate that irrigation is the primary factor in determining the groundwater flow paths. Irrigation can not only increase groundwater level and reduce horizontal groundwater velocity and thereby accelerate vertical and horizontal groundwater exchange among sand, silt and clay formations, but also change the HS− concentration, redox conditions of the shallow groundwater. Results of net groundwater flux estimation suggest that vertical infiltration is likely the primary control of As transport in the vadose zone, while horizontal water exchange is dominant in controlling As migration within the sand aquifers. Recharge water, including irrigation return water and flushed saltwater, travels downward from the ground surface to the aquifer and then nearly horizontally across the sand aquifer. The maximum value of As enriched in the riparian zone is roughly estimated to be 1 706.2 mg·d−1 for a horizontal water exchange of 8.98 m3·d−1 close to the river and an As concentration of 190 μg·L−1

In-situ arsenic remediation by aquifer iron coating: Field trial in the Datong basin, China.

An aquifer Fe-coating technology was evaluated for in-situ As remediation. The groundwater in the aimed aquifer has low dissolved Fe(II) concentration and high As(III) concentration, which has a low affinity toward Fe-oxides/hydroxides. To overcome these challenges, dissolved Fe(II) (5.0 mM) and NaClO (2.6 mM) were injected into the studied aquifer to promote the formation of Fe oxides/hydroxides and to oxidize As(III) into As(V), thus removing aqueous As via adsorption and/or co-precipitation. During field experiment, As concentration in groundwater from the pumping well significantly decreased. Fe and As speciation calculations indicate that incorporation of negatively charged As(V) into goethite was the probable mechanism for As removal. Both chemical sequential extraction results and spectroscopic data also support that alternating injection of Fe(II) and NaClO can achieve aquifer Fe coating and immobilize As via adsorption onto Fe oxides/hydroxides. Geochemical modelling further confirms that although competition for sorption sites between As and other dissolved species is expected in the natural groundwater system, high surface area of the Fe oxides/hydroxides can provide sufficient sites for As retention. The ability to effectively decrease As concentration of in-situ aquifer Fe-coating technology indicates that this approach should have extensive applicability to similar high As groundwater occurred worldwide.