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Abstract Sunlight can oxidize dissolved organic carbon (DOC) to dissolved inorganic carbon (DIC) in freshwaters. The importance of complete photooxidation, or photomineralization, as a sink for DOC remains unclear in temperate rivers, as most estimates are restricted to lakes, high latitude rivers, and coastal river plumes. In this study, we construct a model representing over 75,000 river reaches in the Connecticut River Watershed (CRW), USA, to calculate spectrally resolved photomineralization. We test the hypothesis that photomineralization is a negligible DOC sink across all reaches and flow conditions relative to DOC fluxes. Our model quantifies reaction rates and transport drivers within the river reaches for the ranges of flow conditions, incoming solar irradiance, and canopy cover shading observed throughout the year. Our model predicts average daily areal photomineralization rates ranging from 1.16 mg‐C m−2 day−1in low flow river reaches in the winter, to 18.33 mg‐C m−2 day−1in high flow river reaches during the summer. Even for high photomineralization fluxes, corresponding photomineralization uptake velocities are typically at least an order of magnitude smaller than those reported for other instream processes. We calculate DOC elimination by photomineralization relative to DOC fluxes through individual stream reaches as well as the entire riverine portion of the CRW. We find that relative photomineralization fluxes are highest in summer drought conditions in low order streams. In median flows and mean light intensities, for an average watershed travel distance, 3%–5% of the DOC fluxes are eliminated, indicating that photomineralization is a minor DOC sink in temperate rivers.
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Global Controls on DOC Reaction Versus Export in Watersheds: A Damköhler Number Analysis
Abstract The relative capacity for watersheds to eliminate or export reactive constituents has important implications on aquatic ecosystem ecology and biogeochemistry. Removal efficiency depends on factors that affect either the reactivity or advection of a constituent within river networks. Here, we characterized Damköhler number (Da) for dissolved organic carbon (DOC) uptake in global river networks. Da equals the advection to reaction timescale ratio and thus provides a unitless indicator for DOC reaction intensity during transport within river networks. We aim to demonstrate the spatial and temporal patterns and interplays among factors that determine DOC uptake across global river networks. We show that watershed size imposes a primary control on river network DOC uptake due to a three orders of magnitude difference in water residence time (WRT) between the smallest and largest river networks. DOC uptake capacity in tropical river networks is 2–6 times that in temperate and the Arctic river networks, coinciding with larger DOC removals in warm than in cold watersheds. River damming has a profound impact on DOC uptake due to significantly extended WRTs, particularly in temperate watersheds where most constructed dams are situated. Global warming is projected to increase river network DOC uptake by ca. 19% until year 2100 under the RCP4.5 scenario.
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- Award ID(s):
- 1840243
- PAR ID:
- 10375319
- Publisher / Repository:
- DOI PREFIX: 10.1029
- Date Published:
- Journal Name:
- Global Biogeochemical Cycles
- Volume:
- 36
- Issue:
- 4
- ISSN:
- 0886-6236
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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