table of contents for review purposes only) 1. Introduction 2. Materials and methods 2.1. Study area and sampling 2.2. Chemical analysis 2.3. Geochemical modeling 2.4. Spatial analysis of watershed characteristics 2.5. Solute source determination 2.6. Chemical flux calculations 2.7. Compilation of global river Cr concentrations and discharge 3. Results 3.

Groundwater resources in California represent a confluence of high-risk factors for hexavalent chromium contamination as a result of industrial activities, natural geology, and, potentially, land use. Here, we examine state-wide links in California between groundwater Cr(VI) concentrations and chemicals that provide signatures for source attribution. In environmental monitoring wells, Cr(VI) had the highest co-occurrence and also clustered with 1,4-dioxane and several chlorinated hydrocarbons indicative of the metal plating industry. Additionally, hotspots of Cr(VI) co-occurring with bromoform result from volatile organic compound remediation using in situ chemical oxidation that inadvertently oxidizes naturally occurring Cr(III). In groundwater supply wells, which are typically free of industrial inputs, Cr(VI) correlates with dichlorodiphenyldichloroethylene (DDE), vanadium, and ammonia and clusters with nitrate and dissolved oxygen, suggesting potential links between agricultural activities and Cr(VI). Specific controls on Cr(VI) vary substantially by region: from the metal plating industry around Los Angeles and the San Francisco Bay areas to natural redox conditions along flow paths in the Mojave Desert and to correlations with agricultural practices in the Central Valley of California. While industrial uses of Cr lead to the most acute cases of groundwater Cr(VI) contamination, oxidation of naturally occurring Cr affects a larger area, more wells, and a greater number of people throughout California.

Hexavalent chromium (Cr(VI)) is generated in serpentine soils and exported to surface and groundwaters at levels above health-based drinking water standards. Although Cr(VI) concentrations are elevated in serpentine soil pore water, few studies have reported field evidence documenting Cr(VI) production rates and fluxes that govern Cr(VI) transport from soil to water sources. We report Cr speciation (i) in four serpentine soil depth profiles derived from the California Coast Range serpentinite belt and (ii) in local surface waters. Within soils, we detected Cr(VI) in the same horizons where Cr(III)-minerals are colocated with biogenic Mn(III/IV)-oxides, suggesting Cr(VI) generation through oxidation by Mn-oxides. Water-extractable Cr(VI) concentrations increase with depth constituting a 7.8 to 12 kg/km reservoir of Cr(VI) in soil. Here, Cr(VI) is produced at a rate of 0.3 to 4.8 kg Cr(VI)/km/yr and subsequently flushed from soil during water infiltration, exporting 0.01 to 3.9 kg Cr(VI)/km/yr at concentrations ranging from 25 to 172 μg/L. Although soil-derived Cr(VI) is leached from soil at concentrations exceeding 10 μg/L, due to reduction and dilution during transport to streams, Cr(VI) levels measured in local surface waters largely remain below California's drinking water limit.

Around 50% of humankind relies on groundwater as a source of drinking water. Here we investigate the age, geochemistry, and microbiology of 138 groundwater samples from 95 monitoring wells (<250 m depth) located in 14 aquifers in Canada. The geochemistry and microbiology show consistent trends suggesting large-scale aerobic and anaerobic hydrogen, methane, nitrogen, and sulfur cycling carried out by diverse microbial communities. Older groundwaters, especially in aquifers with organic carbon-rich strata, contain on average more cells (up to 1.4 × 107 mL−1) than younger groundwaters, challenging current estimates of subsurface cell abundances. We observe substantial concentrations of dissolved oxygen (0.52 ± 0.12 mg L−1 [mean ± SE]; n = 57) in older groundwaters that seem to support aerobic metabolisms in subsurface ecosystems at an unprecedented scale. Metagenomics, oxygen isotope analyses and mixing models indicate that dark oxygen is produced in situ via microbial dismutation. We show that ancient groundwaters sustain productive communities and highlight an overlooked oxygen source in present and past subsurface ecosystems of Earth.

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Groundwater ecosystems are globally widespread yet still poorly understood. We investigated the age, aqueous geochemistry, and microbiology of 138 groundwater samples from 87 monitoring wells (<250m depth) located in 14 aquifers in the Canadian Prairie. Geochemistry and microbial ecology were tightly linked revealing large-scale aerobic and anaerobic hydrogen, methane, nitrogen, and sulfur cycling carried out by diverse microbial communities. Older groundwaters contained on average more cells (up to 1.4×107/mL) than younger groundwaters. Organic carbon-rich strata featured some of the highest abundances, challenging current estimates of global groundwater population sizes. Substantial concentrations of dissolved oxygen (n=57; 0.52±0.12 mg/L [mean ± SE]; 0.39 mg/L [median]) in older groundwaters could support aerobic lifestyles in subsurface ecosystems at an unprecedented scale. Metagenomics, oxygen isotope analyses and mixing models indicated that microbial ″dark oxygen″ contributed to the dissolved oxygen pool in subsurface ecosystems commonly assumed to be anoxic.

Groundwater is a vital resource for human welfare. However, due to various factors, groundwater pollution is one of the main environmental concerns. Yet, it is challenging to simulate groundwater quality dynamics due to the insufficient representation of nutrient percolation processes in the soil and Water Assessment Tool model. The objectives of this study were extending the SWAT module to predict groundwater quality. The results proved a linear relationship between observed and calculated groundwater quality with coefficient of determination (R2), Nash–Sutcliffe efficiency (NSE), percent bias (PBIAS) values in the satisfied ranges. While the values of R2, NSE and PBIAS were 0.69, 0.65, and 2.68 during nitrate calibration, they were 0.85, 0.85 and 5.44, respectively during nitrate validation. Whereas the values of R2, NSE and PBIAS were 0.59, 0.37, and − 2.21 during total dissolved solid (TDS) calibration and they were 0.81, 0.80, 7.5 during the validation. The results showed that the nitrate and TDS concentrations in groundwater might change with varying surface water quality. This indicated the requirement for designing adaptive management scenarios. Hence, the extended SWAT model could be a powerful tool for future regional to global scale modelling of nutrient loads and effective surface and groundwater management.

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