Arsenic enriched groundwater discharge to a tropical ocean: Understanding controls and processes.

The role of submarine groundwater discharge (SGD) in transporting terrestrial-sourced arsenic (As) to the global oceans is not well documented. In the present study, executed on a coast adjoining the extensive groundwater As-contaminated Ganges river delta, we hypothesize that As-enriched groundwater discharges to the adjoining Bay of Bengal (BoB) through SGD flow paths. We conducted high-resolution, field-based investigations and thermodynamic modeling to understand the SGD-sourced As discharge and geochemical cycling of As and other redox-sensitive solutes along the discharge path under varying redox conditions and water sediment interactions. The As distribution and other solutes were measured in a series of multi-depth observation wells and sediment cores, extending from the high tide line (HTL) to 100 m toward the sea, for pre- and post-monsoon seasons. Results reveal the presence of a plume carrying up to 30 µg/L dissolved load of As toward the sea. Arsenic is associated with a plume of Fe and exhibits similar shore-perpendicular variability. Arsenic distribution and transport is controlled by the Fe-Mn redox cycle and influenced by terrestrial groundwater discharge. Field-observations and geochemical modeling demonstrate that Fe-hydroxide precipitates in the subterranean estuary and acts as an interim sink for As , which is eventually mobilized on alteration of geochemical conditions with the season. Fluctuating plume size can be attributed to seasonal variation in fresh groundwater input to the site. Estimates indicate up to 55mg/m2/d As is released to BoB from the site. Based on physicochemical observations this study demonstrates the yet to be studied SGD derived As cycles and the role of SGD dynamics in controlling the fate of redox-sensitive contaminants and their discharge into global oceans.

Arsenic fate in upper Indus river basin (UIRB) aquifers: Controls of hydrochemical processes, provenances and water-aquifer matrix interaction.

Major river basins of the Himalayas contain a significant amount of arsenic (As) in the geological matrix, which tends to contaminate the groundwater at a local and regional scale. Although As enrichment in Quaternary deposits has been linked to primary provenances (Himalayan orogeny), limited studies have reported As enrichment in bedrock aquifers. In the present study, the hard rock and groundwater samples were collected across the upper Indus river basin (UIRB), Ladakh to assess the hydrogeochemical processes and environments responsible for As mobilization and release. The higher As concentrations were found in Khardung volcanics followed by Ophiolitic melange, Dras volcanics, Nindam sandstone, and Nindam Shale. The variability in As concentration among different rock samples is largely governed by the presence of felsic minerals and the type of magmatic setting. The groundwater is less mineralized, with moderate electrical conductivity (EC), and weakly acidic to alkaline in nature. The results indicated that mineral weathering, dissolution, and active cation exchange reactions have a strong influence on the major ion chemistry of the groundwater. Redox-sensitive processes are influencing the As mobilization and release under reducing environmental conditions. As in groundwater poses a serious threat to human health hence awareness is urgent towards achieving sustainable As mitigation globally. The study provided a significant dataset to better understand the processes and environmental conditions responsible for hydrogeochemical evolution, sources of solutes, and As mobilization and release in groundwater which will help in sustainable water resource management policies and ecosystem restoration across the Himalayas.

Contrasting controls on hydrogeochemistry of arsenic-enriched groundwater in the homologous tectonic settings of Andean and Himalayan basin aquifers, Latin America and South Asia.

High groundwater arsenic (As) across the globe has been one of the most well researched environmental concerns during the last two decades. Consequently, a large scientific knowledge-base has been developed on As distributions from local to global scales. However, differences in bulk sediment As concentrations cannot account for the As concentration variability in groundwater. Instead, in general, only aquifers in sedimentary basins adjacent to mountain chains (orogenic foreland basins) along continental convergent tectonic margins are found to be As-enriched. We illustrate this association by integrating observations from long-term studies of two of the largest orogenic systems (i.e., As sources) and the aquifers in their associated foreland basins (As sinks), which are located in opposite hemispheres and experience distinct differences in climate and land-use patterns. The Andean orogenic system of South America (AB), an active continental margin, is in principle a modern analogue of the Himalayan orogenic system associated with the Indus-Ganges-Brahmaputra river systems in South Asia (HB). In general, the differences in hydrogeochemistry between AB and HB groundwaters are conspicuous. Major-solute composition of the arid, oxic AB groundwater exhibits a mixed-ion hydrochemical facies dominated by Na-Ca-Cl-SO4-HCO3. Molar calculations and thermodynamic modeling show that although groundwater of AB is influenced by cation exchange, its hydrochemical evolution is predominated by feldspar dissolution and relationships with secondary clays. In contrast, humid, strongly reducing groundwater of HB is dominated by Ca-HCO3 facies, suggestive of calcite dissolution, along with some weathering of silicates (monosiallitization). This work demonstrates that although hydrogeochemical evolutionary trends may vary with local climate and lithology, the fundamental similarities in global tectonic settings can still lead to the elevated concentrations of groundwater As.

Plate tectonics influence on geogenic arsenic cycling: From primary sources to global groundwater enrichment.

More than 100 million people around the world are endangered by geogenic arsenic (As) in groundwater, residing in sedimentary aquifers. However, not all sedimentary aquifers are groundwater As enriched, and the ultimate source of As in enriched aquifer sediments is yet-unknown, globally. A reconnaissance of the major aquifers suggests that major As enriched aquifers are predictably systematic on a global scale, existing in sedimentary foreland basins in the vicinity of modern or ancient orogenic systems. In conformity with the Principle of Uniformitarianism, we demonstrate that the groundwater As comes from magmatic arcs (primary source) in present (e.g. Andes) or ancient (e.g. Himalaya) continental convergent margins of some of the most prominent orogenic systems across the globe, and ends up in sediments (secondary source) in adjoining foreland or related basins that eventually act as aquifers. These arc magmas scavenge As while rising through the deep continental crust. Erosion of such orogens ultimately increases the bulk As content in sediments of adjoining basins, leading to groundwater As enrichment in downstream aquifers. Such As-polluted aquifers are eventually extensively used for groundwater exploitation, for drinking and other human purposes. Surface geological and biogeochemical processes, like redox reactions, are conducive to such groundwater As enrichment. We suggest this model by integrating our study of long-time observations in Himalayan and Andean basin aquifers, and generalizing 63 major aquifers across the globe, to demonstrate the source-to-sink transport of As, thereby delineating it's geogenic cycling in the subsurface. This work outlines the specifics of the mechanisms that would drive the processes of groundwater As enrichment across spatio-temporal scales, i.e. tectonic-scale taking place over millions of years on continental-scale and groundwater pollution taking place at human time-scales on village to household scale. Thus, in this work, we demonstrate a direct evidence of connectivity between global geological processes and individual human health.