Abstract. Endmember mixing analysis (EMMA) is often used by hydrogeochemists to interpret the sources of stream solutes, but variations in stream concentrations and discharges remain difficult to explain. We discovered that machine learning can be used to highlight patterns in stream chemistry that reveal information about sources of solutes and subsurface groundwater flowpaths. The investigation has implications, in turn, for the balance of CO2 in the atmosphere. For example, CO2-driven weathering of silicate minerals removes carbon from the atmosphere over ∼106-year timescales. Weathering of another common mineral, pyrite, releases sulfuric acid that in turn causes dissolution of carbonates. In that process, however, CO2 is released instead of sequestered from the atmosphere. Thus, understanding long-term global CO2 sequestration by weathering requires quantification of CO2- versus H2SO4-driven reactions. Most researchers estimate such weathering fluxes from stream chemistry, but interpreting the reactant minerals and acids dissolved in streams has been fraught with difficulty. We apply a machine-learning technique to EMMA in three watersheds to determine the extent of mineral dissolution by each acid, without pre-defining the endmembers. The results show that the watersheds continuously or intermittently sequester CO2, but the extent of CO2 drawdown is diminished in areas heavily affected by acid rain. Prior to applying the new algorithm, CO2 drawdown was overestimated. The new technique, which elucidates the importance of different subsurface flowpaths and long-timescale changes in the watersheds, should have utility as a new EMMA for investigating water resources worldwide.

Earth’s climate may be stabilized over millennia by solubilization of atmospheric carbon dioxide (CO 2 ) as minerals weather, but the temperature sensitivity of this thermostat is poorly understood. We discovered that the temperature dependence of weathering expressed as an activation energy increases from laboratory to watershed as transport, clay precipitation, disaggregation, and fracturing increasingly couple to dissolution. A simple upscaling to the global system indicates that the temperature dependence decreases to ~22 kilojoules per mole because (i) the lack of runoff limits weathering and retains base metal cations on half the land surface and (ii) other landscapes are regolith-shielded and show little weathering response to temperature. By comparing weathering from laboratory to globe, we reconcile some aspects of kinetic and thermodynamic controls on CO 2 drawdown by natural or enhanced weathering.

Reservoirs along rivers have the potential to act as nutrient sinks (e.g., denitrification and sedimentation) or sources (e.g., decomposition and redox changes), potentially reducing or enhancing nutrient loads downstream. This study investigated the spatial and temporal variability of water and lakebed sediment chemistry for an agricultural reservoir, Carlyle Lake (Illinois, U.S.), to assess the role of sediments as nutrient sinks or sources. Samples were collected across the reservoir over a 2‐year period. We measured N‐ and P‐species in water at the sediment‐water interface, in sediment porewaters, and loosely bound to sediment exchange sites. Total N, total P, total C, organic matter, Fe, Mn, and grain size were measured in bulk sediments. We observed a strong gradient in sedimentary total N, total P, total C, organic matter, and metals along the reservoir, with the lowest concentrations at the river mouth and the highest concentrations near the dam. Additionally, we did a long‐term nutrient mass balance using historical water quality data for streams entering and exiting the reservoir and the reservoir itself. Mass balance calculations showed that Carlyle Lake, on average, removed 2,738 Mg N/year and released 121 Mg P/year over the multidecadal observation period. While N was consistently removed from the system over time, P was initially stored in, but later released from, the reservoir. The subsequent release of legacy P from the reservoir led to higher outgoing, compared with incoming, P loads. Thus, reservoirs in intensively managed landscapes can act as sinks for N but sources for P over decadal timescales.

No abstract