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This study focuses on characterizing the contributions of key terrestrial pathways that deliver dissolved organic carbon (DOC) to streams during hydrological events and on elucidating factors governing variation in water and DOC fluxes from these pathways. We made high‐frequency measurements of discharge, specific conductance (SC), and fluorescent dissolved organic matter (FDOM) during 221 events recorded over 2 years within four Vermont (USA) watersheds that range in area from 0.4 to 139 km2. Using the SC measurements, together with statistical information on discharge, we separated the event hydrographs into contributions from three terrestrial pathways, which we refer to as riparian quickflow, subsurface quickflow, and slow‐flow groundwater. The pathway discharges were used as input to a mixing model that closely approximated sub‐hourly streamwater DOC concentrations as measured with the FDOM sensors. Subsurface quickflow, comprised of pre‐event water, was the leading contributor to streamwater DOC fluxes, while riparian quickflow, comprised of event water, was the second‐leading contributor to streamwater DOC fluxes, despite comprising the smallest proportion of streamflow yield among the three end‐member pathways. Fixed‐effects regression analysis revealed that the relationship between DOC fluxes from the end‐member pathways and event magnitude was consistent across the four watersheds. This analysis also showed that DOC fluxes from the quickflow pathways increased significantly with temperature and varied inversely, but weakly, with catchment antecedent wetness. We believe that our approach, which leverages in‐stream sensors that enable high‐frequency measurements over extended periods, may be applicable for evaluating controls on DOC export from other watersheds within and beyond our study region. Key Points: Calculations of a mixing model reproduce sub‐hourly observations of streamwater dissolved organic carbon (DOC) concentrations in four watershedsStreamwater specific conductance can be used to quantify discharge from terrestrial flowpaths and constrain the DOC mixing modelDOC fluxes from principal flow paths vary discernibly with event magnitude, temperature, and antecedent wetness [ABSTRACT FROM AUTHOR]

Colloid-facilitated transport of contaminants in the vadose zone has important implications to groundwater quality, and has received considerable attention. Natural organic matter (NOM) is ubiquitous in subsurface environments, and its influence on mineral colloids and solute transport has been well documented. However, research on the influence of NOM on colloid-facilitated transport is limited. The objective of this paper is to elucidate the effects of NOM on colloid-facilitated transport of a radioactive contaminant (Cs-137) within partially-saturated sediments. Measurements made with re-packed columns reveal that Cs-137 mobility was low when mineral colloids were absent and was unaffected by the presence of NOM. The addition of mineral colloids to influent increased Cs-137 mobility, and effluent Cs-137 was dominated by the colloid-associated form. When NOM was added to systems that contained mineral colloids and Cs-137, the mobility of Cs-137 further increased. A mathematical model simulating colloid-facilitated transport showed that NOM increases Cs-137 transport by increasing colloid mobility and reducing the rate of Cs-137 adsorption to the porous medium. [ABSTRACT FROM AUTHOR]

Stream water concentrations of dissolved organic matter (DOM) exhibit large temporal variations during precipitation on forested, headwater catchments. We present a modeling framework appropriate for describing streamflow and event-driven export of DOM from small, forested watersheds. Our model links parametrically simple formulations for rainfall-runoff generation and soil water carbon dynamics. The rainfall-runoff formulation is developed by modifying the catchment model of Kirchner (2009) to account for hysteresis in the relationship between stream discharge and catchment water storage. Time series computations of catchment water storage are used by the soil carbon model to approximate the effects of leaching, adsorption, and mineralization on soil water DOM concentrations and the export of DOM from the terrestrial reservoir to the stream. Our findings show that this model is capable of reproducing hourly variations of stream discharge (ranging from 0.01 to 0.38 mm h-1) and stream water DOM concentrations (ranging from 1.8 to 14 mg C L-1) measured in a forested headwater stream in north central Massachusetts. Our analysis highlights the strong linkage between soil carbon dynamics and hydrological processes that govern catchment water storage and flow paths connecting the terrestrial system to the stream. [ABSTRACT FROM AUTHOR]

We performed a meta-data analysis to investigate the importance of event based fluxes to DOC export from forested watersheds. A total of 30 small eastern United States forested watersheds with no wetland component, with a total of 5,176 DOC and accompanying discharge measurements were used in this analysis. There is a clear increase in DOC concentration during hydrologic events (storms and snow melt) that follows a power relationship. We estimate that 86% of DOC is exported during events. The majority (70%) of this event based DOC flux occurs during the rising hydrograph and during large events. Events with a discharge greater than 1.38 cm day make up only 4.8% of the annual hydrograph, yet are responsible for 57% of annual DOC flux. The relationship between event discharge and both DOC concentration and flux is also regulated by temperature and antecedent conditions, with a larger response in both fluxes and concentrations to events during warmer periods and periods where the preceding discharge was low. The temperature relationship also shows seasonality indicating a potential link to the size or reactivity of watershed OM pools. The 86% of DOC lost during events represents a conservative estimate of the amount of allochthonous forested DOC transported laterally to streams. Future research on watershed cycling of DOC should take into account the importance of events in regulating the transport of DOC to downstream ecosystems, determine the relative importance of abiotic versus biotic processes for the temperature regulation of event-associated DOC fluxes, and elucidate the interactions between processes that respond to climate on event versus longer time scales. [ABSTRACT FROM AUTHOR]