Impact of differential surface water mixing on seasonal arsenic mobilization in shallow aquifers of Nadia district; western Bengal Basin, India.

• The study provides a comprehensive effort of understanding the role of multiple factors driving seasonal As mobilization in shallow groundwater. • Increasing anoxia and dissolved As concentration is prominent in shallow GSA groundwater during dry pre-monsoon period than in post-monsoon time. • Magnitude of seasonal changes in groundwater As concentrations (Δ As = As PRM – As POM) vary over years due to variable hydrological conditions. • Variable rainfall, excess groundwater withdrawal, mixing, surface water infiltration, and local lithology are marked as probable seasonal redox drivers for As mobilization in shallow aquifer. • Excess withdrawal in pre-monsoon time acts as a conduit for organic-rich surface water infiltration or aquifer intercalated clay-pore water expulsion by compaction and mixing in the adjoining groundwater; promotes high As release. Arsenic (As) mobilization in groundwater is linked to the dissimilatory reductive dissolution of As(V) coated Fe(III)-oxy-hydroxides from the aquifer sediment coupled with the degradation of available dissolved organic carbon (DOC) due to the presence of anaerobic microbes under anoxic conditions. Understanding the seasonal pattern of As mobilization in the shallow groundwater of the Bengal Basin remains a challenging task due to the heterogeneous character of the shallow aquifers and the involvement of multiple factors. To resolve this issue, in the present study, we showcased a comprehensive effort to advance understanding of the seasonal As mobilization process in the shallow groundwater, utilizing multiple geochemical tracers (i.e., the abundance of dissolved total As, Fe, Mn, NO 3 –, SO 4 2-, DOC, Cl-, and δ18O, δ2H, δ13C-DOC isotopic tracers) between post-monsoon and pre-monsoon periods over multiple years from Nadia district, West Bengal, India. We quantified and explained the seasonal variation of dissolved total As concentrations in the groundwaters with the nature of the aquifer lithology (i.e., grey sand aquifer or 'GSA' and brown sand aquifer or 'BSA'). The present study reported elevated dissolved total As concentrations in the shallow groundwater samples during dry pre-monsoon ('PRM') periods compared to post-monsoon ('POM') time. However, the magnitude of such seasonal changes in groundwater As concentrations (denoted as Δ As = As PRM -As POM) varied between years depending on the extent of rainfall, surface water infiltration, mixing, and groundwater withdrawal. Our current findings are different from the past studies that reported elevated As concentrations in the shallow groundwater during the monsoon and post-monsoon periods compared to the dry pre-monsoon periods. However, the limitations of the past findings are that most of the previous studies were carried out between seasonal intervals over a single annual cycle without reinvestigating the seasonal trends over different years under variable hydrological conditions. We proposed that the excess groundwater withdrawal during the dry pre-monsoon period drive draw-down and, therefore, trigger infiltration of surface-derived deep pond water into the shallow aquifer. Such surface water infiltration introduces fresh labile organic matter into the shallow aquifer, promoting high As mobilization during the dry pre-monsoon period. A viable alternative approach of 'squeezing' of aquifer intercalated clay-peat sedimentary lenses and mixing of organic-rich pore water in the adjoining groundwater can also enhance high As mobilization during the dry time, as examined in this study. This process is triggered by the excessive groundwater withdrawal practices and drawdown encountered during dry time, driving the aquifer intercalated clay-pockets compaction. [ABSTRACT FROM AUTHOR]