Abstract

In this study, the sources and the cycling of Ba have been evaluated in the Ganga (Hooghly) River estuary using the composition of the suspended sediments and the water samples collected during six seasons of contrasting water discharge over two years (2012 and 2013). In addition, the data on the samples of groundwater from areas adjacent to the estuary, and the industrial effluent water and urban wastewater draining into the estuary are presented. Selective extraction experiments were also performed on the suspended particulate matter of two seasons to assess the distribution of exchangeable concentrations of major ions and Ba. In the mixing zone, the variation patterns of the dissolved Ba concentrations show mid-salinity maxima and are similar to the patterns of variation of the particulate Mg/Al and Mg/Fe, suggesting that the production of dissolved Ba is linked to the adsorption of major ions on to the clay minerals and Fe–Mn oxyhydroxides in the particulate matter. The inference of coupled adsorption–desorption processes is supported by the observations that the particulate Ba/Mg and Ba/K ratios exhibit significant to strong negative correlations with the concentrations of Al, Fe and Mn. The observations of mid-salinity maxima for the concentrations of exchangeable Mg and K, and of the exchangeable Ba concentrations that decrease with salinity provide strong evidence that the solute-particle interactions is the major driver in regulating the dissolved Ba distributions in the estuary. The estimates of the quantity of desorbed Ba based on three different approaches suggest that desorption is sufficient to account for the calculated excess Ba (Baxs) concentrations. The contribution of Ba to the dissolved load via dissolution of the particulate carbonate phases is minor, up to 3% of the maximum Baxs concentrations. The estimates of anthropogenic contributions are insignificant, and account for ⩽2% of maximum Baxs in the estuary. Groundwater contributions are less significant and account for up to 5% of the annual Ba flux from the Hooghly estuary.The estimates of Ba flux show that annually (1.5–1.9)×107moles of Ba is transported by the Hooghly River. About (3.6–4.3)×107moles of Ba is generated annually in the estuary through desorption. Added together, the desorbed and riverine Ba fluxes generate a total Ba flux of (5.1–6.2)×107moles per year. Thus, the solute-particle interactions enhance the riverine Ba flux by >300%. A compilation of the available data shows that the enhancement of the riverine Ba flux and the fractions of desorbed Ba flux scale with (particulate matter flux/water flux) ratio in several estuaries of the world, suggesting that the process of solute-particle interactions is a major driver for the estuarine production of Ba on a global scale. Among the rivers considered in this study, the estuaries of the Hooghly River and the Ganges–Brahmaputra rivers, characterized by very high (sediment flux/water flux) ratio, depict the highest increase in the riverine Ba flux. This unique feature of the Ganga River system is inferred to be resulting from the collective impact of the tectonic activity and the monsoonal rainfall in the catchment areas.

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