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Photomineralization, the transformation of dissolved organic carbon (DOC) to CO 2 by sunlight, is an important source of CO 2 in arctic surface waters. However, quantifying the role of photomineralization in inland waters is limited by the understanding of hydrologic controls on this process. To bridge this gap, this study evaluates mixing limitations, i.e. , whether and by how much vertical mixing limits the depth-integrated photomineralization rate, in freshwater systems. We developed a conceptual model to qualitatively assess mixing limitations across the range of light attenuation and hydrologic conditions observed in freshwaters. For the common case of exponential light attenuation over depth, we developed a mathematical model to quantify mixing limitation, and used this model to assess a range of arctic freshwater systems. The results demonstrate that mixing limitations are important when there is significant light attenuation by suspended sediment (SS), which is the case in some arctic, boreal and temperate waters. Mixing limitation is pronounced when light attenuation over depth is strong and when the photomineralization rate at the water surface exceeds the vertical mixing rate. Arctic streams and rivers have strong vertical mixing relative to surface photomineralization, such that model results demonstrate no mixing limitation regardless of how much SS is present. Our analysis indicates that well-mixed assumptions used in prior work are valid in many, but not all, arctic surface waters. The effects of mixing limitations in reducing the photomineralization rate must be considered in arctic lakes with high SS concentrations. 

Abstract Assessments of riverine ecosystem health and water quality require knowledge of how headwater streams transport and transform nutrients. Estimates of nutrient demand at the watershed scale are commonly inferred from reach‐scale solute injections, which are typically reported as uptake velocities (v_f). Multiple interacting processes controlv_f, making it challenging to predict howv_fresponds to physical changes in the stream. In this study, we linkv_fto a continuous time random walk model to quantify howv_fis controlled by in‐stream (velocity, dispersion, and benthic reaction) and hyporheic processes (exchange rate, residence times, and hyporheic reaction). We fit the model to conservative (NaCl) and nitrate (NO₃⁻‐N) pulse tracer injections in unshaded replicate streams at the Notre Dame Linked Experimental Ecosystem Facility, which differed only in substrate size and distribution. Experiments were conducted over the first 25 days of biofilm colonization to examine how the interaction between substrate type and biofilm growth influenced modeled processes andv_f. Model fits of benthic reaction rates were ∼8× greater than hyporheic reaction rates for all experiments and did not vary with substrate type or over time. High benthic reactivity was associated with filamentous green algae coverage on the streambed, which dominated total algal biomass. Finally,v_fwas most sensitive to benthic reaction rate and stream velocity, and sensitivity varied with stream conditions due to its nonlinear dependence on all modeled processes. Together, these results demonstrate how reach‐scale nutrient demand reflects the relative contributions of biotic and abiotic processes in the benthic layer and the hyporheic zone.