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Abstract Dissolved organic matter (DOM) impacts the structure and function of aquatic ecosystems. DOM absorbs light in the UV and visible (UV–Vis) wavelengths, thus impacting light attenuation. Because absorption by DOM depends on its composition, UV–Vis absorbance is used to constrain DOM composition, source, and amount. Ferric iron, Fe(III), also absorbs in the UV–Vis; when Fe(III) is present, DOM-attributed absorbance is overestimated. Here, we explore how differing behavior of DOM and Fe(III) at the catchment scale impacts UV–Vis absorbance and evaluate how system-specific variability impacts the effectiveness of existing Fe(III) correction factors in a temperate watershed. We sampled five sites in the Connecticut River mainstem bi-weekly for ~ 1.5 years, and seven sites in the Connecticut River watershed once during the summer 2019. We utilized size fractionation to isolate the impact of DOM and Fe(III) on absorbance and show that variable contributions of Fe(III) to absorbance at 254 nm (a 254 ) and 412 nm (a 412 ) by size fraction complicates correction for Fe(III). We demonstrate that the overestimation of DOM-attributed absorbance by Fe(III) is correlated to the Fe(III):dissolved organic carbon concentration ratio; thus, overestimation can be high even when Fe(III) is low. a 254 overestimation is highly variable even within a single system,more »but can be as high as 53%. Finally, we illustrate that UV-Vis overestimation might impart bias to seasonal, discharge, and land-use trends in DOM quality. Together, these findings argue that Fe(III) should be measured in tandem with UV–Vis absorbance for estimates of CDOM composition or amount.« less

The magnitude of stream and river carbon dioxide (CO 2 ) emission is affected by seasonal changes in watershed biogeochemistry and hydrology. Global estimates of this flux are, however, uncertain, relying on calculated values for CO 2 and lacking spatial accuracy or seasonal variations critical for understanding macroecosystem controls of the flux. Here, we compiled 5,910 direct measurements of fluvial CO 2 partial pressure and modeled them against watershed properties to resolve reach-scale monthly variations of the flux. The direct measurements were then combined with seasonally resolved gas transfer velocity and river surface area estimates from a recent global hydrography dataset to constrain the flux at the monthly scale. Globally, fluvial CO 2 emission varies between 112 and 209 Tg of carbon per month. The monthly flux varies much more in Arctic and northern temperate rivers than in tropical and southern temperate rivers (coefficient of variation: 46 to 95 vs. 6 to 12%). Annual fluvial CO 2 emission to terrestrial gross primary production (GPP) ratio is highly variable across regions, ranging from negligible (<0.2%) to 18%. Nonlinear regressions suggest a saturating increase in GPP and a nonsaturating, steeper increase in fluvial CO 2 emission with discharge across regions, which leadsmore »to higher percentages of GPP being shunted into rivers for evasion in wetter regions. This highlights the importance of hydrology, in particular water throughput, in routing terrestrial carbon to the atmosphere via the global drainage networks. Our results suggest the need to account for the differential hydrological responses of terrestrial–atmospheric vs. fluvial–atmospheric carbon exchanges in plumbing the terrestrial carbon budget.« less