Temporal variability of groundwater chemistry in shallow and deep aquifers of Araihazar, Bangladesh.

Samples were collected every 2-4 weeks from a set of 37 monitoring wells over a period of 2-3 years in Araihazar, Bangladesh, to evaluate the temporal variability of groundwater composition for As and other constituents. The monitoring wells are grouped in 6 nests and span the 5-91 m depth range. Concentrations of As, Ca, Fe, K, Mg, Mn, Na, P, and S were measured by high-resolution ICPMS with a precision of 5% or better; concentrations of Cl were measured by ion chromatography. In shallow wells <30 m deep, As and P concentrations generally varied by <30%, whereas concentrations of the major ions (Na, K, Mg, Ca and Cl) and the redox-sensitive elements (Fe, Mn, and S) varied over time by up to +/-90%. In wells tapping the deeper aquifers >30 m often below clay layers concentrations of groundwater As were much lower and varied by <10%. The concentrations of major cations also varied by <10% in these deep aquifers. In contrast, the concentration of redox-sensitive constituents Fe, S, and Mn in deep aquifers varied by up to 97% over time. Thus, strong decoupling between variations in As and Fe concentrations is evident in groundwaters from shallow and deep aquifers. Comparison of the time series data with groundwater ages determined by (3)H/(3)He and (14)C dating shows that large seasonal or inter-annual variations in major cation and chloride concentrations are restricted to shallow aquifers and groundwater recharged <5 years ago. There is no corresponding change in As concentrations despite having significant variations of redox sensitive constituents in these very young waters. This is attributed to chemical buffering due to rapid equilibrium between solute and solid As. At two sites where the As content of groundwater in existing shallow wells averages 102 microg/L (range: <5 to 648 microg/L; n=118) and 272 microg/L (range: 10 to 485 microg/L; n=65), respectively, a systematic long-term decline in As concentrations lends support to the notion that flushing may slowly deplete an aquifer of As. Shallow aquifer water with >5 years (3)H/(3)He age show a constant As:P molar ratio of 9.6 over time, suggesting common mechanisms of mobilization.

Impact of irrigating rice paddies with groundwater containing arsenic in Bangladesh.

Soil and soil-water As profiles were obtained from 4 rice paddies in Bangladesh during the wet growing season (May-November), when surface water with little arsenic is used for irrigation, or during the dry season (January-May), when groundwater elevated in arsenic is used instead. In the upper 5 cm of paddy soil, accumulation of 13+/-12 mg/kg acid-leachable As (n=11) was observed in soil from 3 sites irrigated with groundwater containing 80-180 microg/L As, whereas only 3+/-2 mg/kg acid-leachable As (n=8) was measured at a control site. Dissolved As concentrations averaged 370+/-340 microg/L (n=7) in the upper 5 cm of the soil at the 3 sites irrigated with groundwater containing 80-180 microg/L As, contrasting with soil water As concentrations of only 18+/-7 microg/L (n=4) over the same depth interval at the control site. Despite the accumulation of As in soil and in soil water attributable to irrigation with groundwater containing elevated As levels, there is no evidence of a proportional transfer to rice grains collected from the same sites. Digestion and analysis of individual grains of boro winter rice from the 2 sites irrigated with groundwater containing 150 and 180 microg/L As yielded concentrations of 0.28+/-0.13 mg/kg (n=12) and 0.44+/-0.25 mg/kg (n=12), respectively. The As content of winter rice from the control site was not significantly different though less variable (0.30+/-0.07; n=12). The observations suggest that exposure of the Bangladesh population to As contained in rice is less of an immediate concern than the continued use of groundwater containing elevated As levels for drinking or cooking, or other potential consequences of As accumulation in soil and soil-water.