Abstract:A better understanding is needed of how hydrological and biogeochemical processes control dissolved organic carbon (DOC) concentrations and dissolved organic matter (DOM) composition from headwaters downstream to large rivers. We examined a large DOM dataset from the National Water Information System of the US Geological Survey, which represents approximately 100 000 measurements of DOC concentration and DOM composition at many sites along rivers across the United States. Application of quantile regression revealed a tendency towards downstream spatial and temporal homogenization of DOC concentrations and a shift from dominance of aromatic DOM in headwaters to more aliphatic DOM downstream. The DOC concentration-discharge (C-Q) relationships at each site revealed a downstream tendency towards a slope of zero. We propose that despite complexities in river networks that have driven many revisions to the River Continuum Concept, rivers show a tendency towards chemostasis (C-Q slope of zero) because of a downstream shift from a dominance of hydrologic drivers that connect terrestrial DOM sources to streams in the headwaters towards a dominance of instream and near-stream biogeochemical processes that result in preferential losses of aromatic DOM and preferential gains of aliphatic DOM.

Climate warming is projected to affect forest water yields but the effects are expected to vary. We investigated how forest type and age affect water yield resilience to climate warming. To answer this question, we examined the variability in historical water yields at long-term experimental catchments across Canada and the United States over 5-year cool and warm periods. Using the theoretical framework of the Budyko curve, we calculated the effects of climate warming on the annual partitioning of precipitation (P) into evapotranspiration (ET) and water yield. Deviation (d) was defined as a catchment's change in actual ET divided by P [AET/P; evaporative index (EI)] coincident with a shift from a cool to a warm period – a positive d indicates an upward shift in EI and smaller than expected water yields, and a negative d indicates a downward shift in EI and larger than expected water yields. Elasticity was defined as the ratio of interannual variation in potential ET divided by P (PET/P; dryness index) to interannual variation in the EI – high elasticity indicates low d despite large range in drying index (i.e., resilient water yields), low elasticity indicates high d despite small range in drying index (i.e., nonresilient water yields). Although the data needed to fully evaluate ecosystems based on these metrics are limited, we were able to identify some characteristics of response among forest types. Alpine sites showed the greatest sensitivity to climate warming with any warming leading to increased water yields. Conifer forests included catchments with lowest elasticity and stable to larger water yields. Deciduous forests included catchments with intermediate elasticity and stable to smaller water yields. Mixed coniferous/deciduous forests included catchments with highest elasticity and stable water yields. Forest type appeared to influence the resilience of catchment water yields to climate warming, with conifer and deciduous catchments more susceptible to climate warming than the more diverse mixed forest catchments.

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We combine experimental and modeling results from a headwater catchment at the Hubbard Brook Experimental Forest (HBEF), New Hampshire, USA, to explore the link between stream solute dynamics and water age. A theoretical framework based on water age dynamics, which represents a general basis for characterizing solute transport at the catchment scale, is here applied to conservative and weatheringderived solutes. Based on the available information about the hydrology of the site, an integrated transport model was developed and used to compute hydrochemical fluxes. The model was designed to reproduce the deuterium content of streamflow and allowed for the estimate of catchment water storage and dynamic travel time distributions (TTDs). The innovative contribution of this paper is the simulation of dissolved silicon and sodium concentration in streamflow, achieved by implementing first-order chemical kinetics based explicitly on dynamic TTD, thus upscaling local geochemical processes to catchment scale. Our results highlight the key role of water stored within the subsoil glacial material in both the short-term and long-term solute circulation. The travel time analysis provided an estimate of streamflow age distributions and their evolution in time related to catchment wetness conditions. The use of age information to reproduce a 14 year data set of silicon and sodium stream concentration shows that, at catchment scales, the dynamics of such geogenic solutes are mostly controlled by hydrologic drivers, which determine the contact times between the water and mineral interfaces. Justifications and limitations toward a general theory of reactive solute circulation at catchment scales are discussed. IntroductionUnderstanding streamflow sources and their impact on river hydrochemistry is a common problem in hydrology with direct implications for the protection and management of water resources worldwide. Highly monitored watersheds hosting multidisciplinary experimental activities provide unique opportunities to investigate catchment functioning from different perspectives [Burt, 1994;Lindenmayer et al., 2012]. The availability of extensive data sets encompassing water quantity and quality, possibly over long periods and at high frequency, is considered a necessary requirement for proper process representation [McDonnell and Beven, 2014]. These data sets may also trigger feedbacks with hydrologic modeling, in a setting where models can be guided by and critically compared to existing measurements to provide quantitative information on catchment functioning. Typical data sets include stream discharge and solute concentration, which are integrated measures of the heterogeneous contributions to runoff from spatially distinct sources across the catchment [e.g. Likens, 2013]. Such integrated measurements go along with catchment-scale modeling approaches because they integrate spatial heterogeneity and allow parsimonious model development.The study of water age dynamics plays an important role in deciphering the proc...