Abstract:Concentration-discharge relationships have been widely used as clues to the hydrochemical processes that control runoff chemistry. Here we examine concentration-discharge relationships for solutes produced primarily by mineral weathering in 59 geochemically diverse US catchments. We show that these catchments exhibit nearly chemostatic behaviour; their stream concentrations of weathering products such as Ca, Mg, Na, and Si typically vary by factors of only 3 to 20 while discharge varies by several orders of magnitude. Similar patterns are observed at the inter-annual time scale. This behaviour implies that solute concentrations in stream water are not determined by simple dilution of a fixed solute flux by a variable flux of water, and that rates of solute production and/or mobilization must be nearly proportional to water fluxes, both on storm and inter-annual timescales. We compared these catchments' concentration-discharge relationships to the predictions of several simple hydrological and geochemical models. Most of these models can be forced to approximately fit the observed concentration-discharge relationships, but often only by assuming unrealistic or internally inconsistent parameter values. We propose a new model that also fits the data and may be more robust. We suggest possible tests of the new model for future studies. The relative stability of concentration under widely varying discharge may help make aquatic environments habitable. It also implies that fluxes of weathering solutes in streams, and thus fluxes of alkalinity to the oceans, are determined primarily by water fluxes. Thus, hydrology may be a major driver of the ocean-alkalinity feedback regulating climate change.

Trends in the timing of snowmelt and associated runoff in Colorado were evaluated for the 1978-2007 water years using the regional Kendall test (RKT) on daily snow-water equivalent (SWE) data from snowpack telemetry (SNOTEL) sites and daily streamflow data from headwater streams. The RKT is a robust, nonparametric test that provides an increased power of trend detection by grouping data from multiple sites within a given geographic region. The RKT analyses indicated strong, pervasive trends in snowmelt and streamflow timing, which have shifted toward earlier in the year by a median of 2-3 weeks over the 29-yr study period. In contrast, relatively few statistically significant trends were detected using simple linear regression. RKT analyses also indicated that November-May air temperatures increased by a median of 0.98C decade 21 , while 1 April SWE and maximum SWE declined by a median of 4.1 and 3.6 cm decade 21 , respectively. Multiple linear regression models were created, using monthly air temperatures, snowfall, latitude, and elevation as explanatory variables to identify major controlling factors on snowmelt timing. The models accounted for 45% of the variance in snowmelt onset, and 78% of the variance in the snowmelt center of mass (when half the snowpack had melted). Variations in springtime air temperature and SWE explained most of the interannual variability in snowmelt timing. Regression coefficients for air temperature were negative, indicating that warm temperatures promote early melt. Regression coefficients for SWE, latitude, and elevation were positive, indicating that abundant snowfall tends to delay snowmelt, and snowmelt tends to occur later at northern latitudes and high elevations. Results from this study indicate that even the mountains of Colorado, with their high elevations and cold snowpacks, are experiencing substantial shifts in the timing of snowmelt and snowmelt runoff toward earlier in the year.

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.