Anthropogenic influences on dissolved organic matter transport in high arsenic groundwater: Insights from stable carbon isotope analysis and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry.

In East and Southeast Asia, the health of over 100 million people is threatened by the consumption of groundwater containing high concentrations of arsenic (>10 μg L), which is released from sediments through reductive dissolution of arsenic-bearing iron/manganese oxides. Dissolved organic matter (DOM) is known to play a crucial role in the process of arsenic mobilization in shallow aquifers, and its availability and reactivity are key factors controlling the variation of arsenic concentrations in groundwater. However, it is unclear how human activities influence the transport of DOM and how the transportation affects the DOM molecular properties in high arsenic groundwater. This study provides insights on the sources and molecular compositions of DOM in groundwater from the Jianghan Plain, central China, a newly discovered area with seasonal fluctuations in arsenic concentrations in shallow groundwater. Monitoring of water levels and stable carbon isotope compositions in groundwater from different depths and canal water over a year indicated that terrestrial DOM was the dominant source, accounting for 54.2%-85.5% of groundwater DOM. Electrospray ionization combined with ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry revealed that canal water infiltration transferred aliphatic, tannin-like and leached aromatic DOM from sediments into groundwater. Therefore, groundwater recharge through irrigation using canal water not only inputs terrestrial DOM, but also accelerates the release of sedimentary DOM. Furthermore, carboxylic-rich alicyclic molecule (CRAM)-like DOM that is derived from biomolecules has the highest proportion (60.1%-65.5%) among the identified DOM structures. And, it might be reused in biochemical processes during arsenic mobilization, suggesting a third source of groundwater DOM in addition to canal water and sediments. The findings in this study advance the understanding on transport processes and molecular properties of DOM in high arsenic groundwater under extensive anthropogenic influences.