HIGHLIGHTS • Manganese and arsenic concentrations are elevated in Murshidabad groundwater. • Manganese release appears to be independent of dissolved organic matter quality. • Mineral precipitation and dissolution reactions impact fate of manganese. • Arsenic concentrations are related to dissolved organic matter quantity and quality. The prevalence of manganese (Mn) in Southeast Asian drinking water has recently become a topic of discussion, particularly when concurrent with elevated arsenic (As). Although Mn groundwater geochemistry has been studied, the link between dissolved organic matter (DOM) quality and Mn release is less understood. This work evaluates characteristics of DOM, redox chemistry, and the distribution of Mn within Murshidabad, West Bengal, India. Shallow aquifer samples were analyzed for cations, anions, dissolved organic carbon, and DOM properties using 3-dimensional fluorescence excitation emission matrices followed by parallel factor modeling analyses. Two biogeochemical regimes are apparent, separated geographically by the river Bhagirathi. East of the river, where E h and nitrate (NO − 3) values are low, humic-like DOM coexists with high dissolved Mn, As, and Fe. West of the river, lower dissolved As and Fe concentrations are coupled with more protein-like DOM and higher NO − 3 and E h values. Dissolved Mn concentrations are elevated in both regions. Based on the distribution of available electron acceptors, it is hypothesized that groundwater east of the Bhagirathi, which is more reducing and enriched in dissolved Fe and Mn but depleted in NO − 3 , is chemically dominated by Mn(IV)/Fe(III) reduction processes. West of the river where NO − 3 is abundant yet dissolved Fe is absent, NO − 3 and Mn(IV) likely buffer redox conditions such that E h values are not sufficiently reducing to release Fe into the dissolved phase. The co-occurrence of humic-like Vega et al. Biogeochemical Controls of Mn and As in Shallow Aquifers DOM with dissolved As, Fe, and Mn in the more reducing aquifers may reflect complex formation between humic DOM and metals, as well as electron shuttling processes involving humic DOM, which may enhance metal(loid) release. Saturation indices of rhodochrosite (MnCO 3) suggest that precipitation is thermodynamically favorable in a greater proportion of the more reducing sites, however humic DOM-Mn complexes may be inhibiting MnCO 3 precipitation. Where dissolved arsenic concentrations are low, it is postulated that Mn(IV) reduction is oxidizing As(III) to As(V), increasing the potential for re-adsorption of As(V) onto relatively stable, un-reduced or newly precipitated Fe-oxides. Manganese release appears to be independent of DOM quality, as it persists in both humic and protein-like DOM environments.