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River organic matter transformations impact the cycling of energy, carbon, and nutrients. The delivery of distinct dissolved organic matter (DOM) sources can alter aquatic DOM cycling and associated biogeochemical processes. Yet DOM source and reactivity are not well‐defined for many river systems, including in western Canada. Here, we explore DOM cycling in the mainstem of the Oldman River (stream order 6–7), a heavily regulated river network in southern Alberta (Canada). We compared seasonal river DOM content, composition, and bioavailability with nine endmember leachates from the river valley using optical properties and incubations to estimate biodegradable dissolved organic carbon (BDOC). River DOM composition was most similar to terrestrial soil leachates, followed by autochthonous DOM leachates. River DOM bioavailability was low (BDOC = 0%–16.6%, mean of 7.1%). Endmember leachate bioavailability increased from soils (BDOC = 23.9%–53.7%), to autochthonous sources (fish excretion, macrophytes, biofilm; BDOC = 49.9%–80.0%), to terrestrial vegetation (leaves, shrubs, grass; BDOC >  80%), scaling positively with protein‐like DOM content and amount of leachable dissolved organic carbon (DOC), and negatively with aromaticity. Seasonally, DOC concentrations changed little despite >15‐fold increases in discharge during spring. River DOM composition shifted modestly toward soil‐like endmembers in spring and more bioavailable autochthonous end members in autumn and winter. Low DOM bioavailability in the river mainstem and low DOC yields shown in previous work point to limited internal processing of DOM and limited bioavailable DOM delivery to downstream habitats, possibly due to upstream flow regulation. Our observations provide important insights into the functioning of western Canadian aquatic networks. 

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, 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.