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The insecticide and current use pesticide chlorpyrifos (CLP) is transported via global distillation to the Arctic where it may pose a threat to this ecosystem. CLP is readily detected in Arctic environmental compartments, but current research has not studied its partitioning between water and dissolved organic matter (DOM) nor the role of photochemistry in CLP's fate in aquatic systems. Here, the partition coefficients of CLP were quantified with various types of DOM isolated from the Arctic and an International Humic Substances Society (IHSS) reference material Suwannee River natural organic matter (SRNOM). While CLP readily partitions to DOM, CLP exhibits a significantly higher binding constant with Arctic lacustrine DOM relative to fluvial DOM or SRNOM. The experimental partitioning coefficients (KDOC) were compared to a calculated value estimated using poly parameter linear free energy relationship (pp-LFER) and was found to be in good agreement with SRNOM, but none of the Arctic DOMs. We found that Arctic KDOC values decrease with increasing SUVA254, but no correlations were observed for the other DOM compositional parameters. DOM also mediates the photodegradation of CLP, with stark differences in photo-kinetics using Arctic DOM isolated over time and space. This work highlights the chemo-diversity of Arctic DOM relative to IHSS reference materials and highlights the need for in-depth characterization of DOM that transcends the current paradigm based upon terrestrial and microbial precursors. 

Retention of carbon (C), either by physical mechanisms or microbial uptake, is a key driver of the transformation and storage of C and nutrients within ecosystems. Both the molecular composition and nutrient content of organic matter influence the rate at which it is retained in streams, but the relative influence of these characteristics remains unclear. We estimated the effects of nutrient content and molecular composition of dissolved organic C (DOC) on uptake in boreal streams by measuring rates of C retention, in situ, following introduction of leachates derived from alder, poplar, and spruce trees subject to long-term fertilization with nitrogen (N) or phosphorus (P). Leachate C:N varied approximately twofold, and C:P varied nearly 20-fold across species and nutrient treatments. Uptake of DOC was greatest for leachates derived from trees that had been fertilized with P, a finding consistent with P-limitation of uptake and/or preferential sorption of P-containing molecules. Optical measures indicated that leachates derived from the three tree species varied in molecular composition, but uptake of DOC did not differ across species, suggesting weak constraints on retention imposed by molecular composition relative to nutrient limitation. Observed coupling between P and C cycles highlights the potential for increased P availability to enhance DOC retention in headwater streams.