Abstract Rivers and streams act as globally significant sources of nitrous oxide (N2O) to the atmosphere, in part through denitrification reactions that will increase in response to ongoing anthropogenic nitrogen loading. While many factors that contribute to the release of N2O relative to inert dinitrogen (N2) are well described, the ability to predict N2O yields from streams remains a fundamental challenge. Here, I revisit results from the second Lotic Intersite Nitrogen eXperiments (LINX II) in the context of turbulent hyporheic exchange. Denitrification efficiency, or the fraction of nitrate delivered to the streambed by stream turbulence that is chemically reduced, emerges as the single best predictor of N2O yields and underpins the first statistically significant models of inter‐site N2O yields. This mechanistic connection is supported by reactive transport modeling of hyporheic zone denitrification representing advective flowpaths, flowpath mixing, and diffusion‐dominated anoxic microzones. Simulated N2O yields are inversely correlated with denitrification efficiency; however, advective models are unable to capture low LINX II N2O yields at low denitrification efficiencies. Hyporheic zone mixing exacerbates this inability to capture observed N2O yields via the promotion of N2O release from fast, oxic flowpaths. Instead, anoxic microzones are required to account for LINX II observations through consistently low N2O yields and the consumption of upstream‐produced N2O. Together, these results provide a framework for controls on stream N2O yields and suggest that stream corridor restoration designs aimed at increasing the capacity of hyporheic zones to remediate nitrate loading, as opposed to increasing hyporheic exchange, will also reduce proportional N2O emissions. 
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                            Seasonality Controls Biogeochemical Shifts in Oxygen, Carbon, and Nitrogen Along a 12‐m, 54 hr‐Long Hyporheic Flowpath
                        
                    
    
            Abstract Hyporheic exchange is critical to river corridor biogeochemistry, but decameter‐scale flowpaths (∼10‐m long) are understudied due to logistical challenges (e.g., sampling at depth, multi‐day transit times). Some studies suggest that decameter‐scale flowpaths should have initial hot spots followed by transport‐limited conditions, whereas others suggest steady reaction rates and secondary reactions that could make decameter‐scale flowpaths important and unique. We investigated biogeochemistry along a 12‐m hyporheic mesocosm that allowed for controlled testing of seasonal and spatial water quality changes along a flowpath with fixed geometry and constant flow rate. Water quality profiles of oxygen, carbon, and nitrogen were measured at 1‐m intervals along the mesocosm over multiple seasons. The first 6 m of the mesocosm were always oxic and a net nitrogen source to mobile porewater. In winter, oxic conditions persisted to 12 m, whereas the second half of the flowpath became anoxic and a net nitrogen sink in summer. No reactive hot spots were observed in the first meter of the mesocosm. Instead, most reactions were zeroth‐order over 12 m and 54 hr of transit time. Influent chemistry had less impact on hyporheic biogeochemistry than expected due to large amounts of in situ reactant sources compared to stream‐derived reactant sources. Sorbed or buried carbon likely fueled reactions with rates controlled by temperature and redox conditions. Each reactant showed different hyporheic Damköhler numbers, challenging the characterization of flowpaths being intrinsically reaction‐ or transport‐limited. Future research should explore the prevalence and biogeochemical contributions of decameter‐scale flowpaths in diverse field settings. 
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                            - PAR ID:
- 10593547
- Publisher / Repository:
- DOI PREFIX: 10.1029
- Date Published:
- Journal Name:
- Water Resources Research
- Volume:
- 61
- Issue:
- 5
- ISSN:
- 0043-1397
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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