Groundwater chemistry and redox processes: Depth dependent arsenic release mechanism

Patchy occurrences of elevated As are often encountered in groundwater from the shallow aquifers (<50 m) of the Bengal Delta Plain (BDP). A clear understanding of various biogeochemical processes, responsible for As mobilization, is very important to explain this patchy occurrence and thus to mitigate the problem. The present study deals with the periodical monitoring of groundwater quality of five nested piezometeric wells between December 2008 and July 2009 to investigate the temporal changes in groundwater chemistry vis-a-vis the prevalent redox processes in the aquifer. Geochemical modeling has been carried out to identify key phases present in groundwater. A correlation study among different aqueous redox parameters has also been performed to evaluate prevailing redox processes in the aquifer. The long term monitoring of hydrochemical parameters in the multilevel wells together with hydrogeochemical equilibrium modeling has shown more subtle differences in the geochemical environment of the aquifer, which control the occurrence of high dissolved As in BDP groundwater. The groundwater is generally of Ca–HCO3 type. The dissolved As concentration in groundwater exceeded both WHO and National drinking water standard (Bureau of Indian Standards; BIS, 10 μg L−1) throughout the sampling period. The speciation of As and Fe indicate persistent reducing conditions within the aquifer [As(III): 87–97% of AsT and Fe(II): 76–96% of FeT]. The concentration of major aqueous solutes is relatively high in the shallow aquifer (wells A and B) and gradually decreases with increasing depth in most cases. The calculation of SI indicates that groundwater in the shallow aquifer is also relatively more saturated with carbonate minerals. This suggests that carbonate mineral dissolution is possibly influencing the groundwater chemistry and thereby controlling the mobilization of As in the monitored shallow aquifer. Hydrogeochemical investigation further suggests that Fe and/or Mn oxyhydroxide reduction is the principal process of As release in groundwater from deeper screened piezometric wells. The positive correlations of U and V with As, Fe and Mn indicate redox processes responsible for mobilization of As in the deeper screened piezometric wells are possibly microbially mediated. Thus, the study advocates that mobilization of As is depth dependent and concentrations of As in groundwater depends on single/combined release mechanisms.