Concentration–discharge relationships describe solute and sediment mobilization,reaction, and transport at event and longer timescales

Concentration–discharge (C‐Q) relationships reflect material sources, storage, reaction, proximity, and transport in catchments. Differences in hydrologic pathways and connectivity influence observed C‐Q patterns at the catchment outlet. We examined solute and sediment C‐Q relationships at event and interannual timescales in a small mid‐Atlantic (USA) catchment. We found systematic differences in the C‐Q behaviour of geogenic/exogenous solutes (e.g., calcium and nitrate), biologically associated solutes (e.g., dissolved organic carbon), and particulate materials (e.g., total suspended solids). Negative log(C)–log(Q) regression slopes, indicating dilution, were common for geogenic solutes whereas positive slopes, indicating concentration increase, were common for biologically associated solutes. Biologically associated solutes often exhibited counterclockwise hysteresis during events whereas geogenic solutes exhibited clockwise hysteresis. Across event and interannual timescales, solute C‐Q patterns are linked to the spatial distribution of hydrologic sources and the timing and sequence of hydro‐biogeochemical source contributions to the stream. Groundwater is the primary source of stormflow during the earliest and latest stages of events, whereas precipitation and soil water become increasingly connected to the stream near peakflow. This sequence and timing of flowpath connectivity results in dilution and clockwise hysteresis for geogenic/exogenous solutes and concentration increase and counterclockwise hysteresis for biologically associated solutes. Particulate materials demonstrated positive C‐Q slopes over the long‐term and clockwise hysteresis during individual events. Drivers of particulate and solute C‐Q relationships differ, based on longitudinal and lateral expansion of active channels and changing shear stresses with increasing flows. Although important distinctions exist between the drivers of solute and sediment C‐Q relationships, overall solute and sediment C‐Q patterns at event and interannual timescales reflect consistent catchment hydro‐biogeochemical processes.     

Seasonal dynamics and exports of elements from a first‐order stream to a large inland lake in Michigan

Headwater streams are critical components of drainage systems, directly connecting terrestrial and downstream aquatic ecosystems. The amount of water in a stream can alter hydrologic connectivity between the stream and surrounding landscape and is ultimately an important driver of what constituents headwater streams transport. There is a shortage of studies that explore concentration–discharge (C‐Q) relationships in headwater systems, especially forested watersheds, where the hydrological and ecological processes that control the processing and export of solutes can be directly investigated. We sought to identify the temporal dynamics and spatial patterns of stream chemistry at three points along a forested headwater stream in Northern Michigan and utilize C‐Q relationships to explore transport dynamics and potential sources of solutes in the stream. Along the stream, surface flow was seasonal in the main stem, and perennial flow was spatially discontinuous for all but the lowest reaches. Spring snowmelt was the dominant hydrological event in the year with peak flows an order of magnitude larger at the mouth and upper reaches than annual mean discharge. All three C‐Q shapes (positive, negative, and flat) were observed at all locations along the stream, with a higher proportion of the analytes showing significant relationships at the mouth than at the mid or upper flumes. At the mouth, positive (flushing) C‐Q shapes were observed for dissolved organic carbon and total suspended solids, whereas negative (dilution) C‐Q shapes were observed for most cations (Na⁺, Mg²⁺, Ca²⁺) and biologically cycled anions (NO₃^?, PO₄^3?, SO₄^2?). Most analytes displayed significant C‐Q relationships at the mouth, indicating that discharge is a significant driving factor controlling stream chemistry. However, the importance of discharge appeared to decrease moving upstream to the headwaters where more localized or temporally dynamic factors may become more important controls on stream solute patterns.     

Land cover effects on runoff patterns in eastern Piedmont (USA) watersheds

Physiography and land cover determine the hydrologic response of watersheds to climatic events. However, vast differences in climate regimes and variation of landscape attributes among watersheds (including size) have prevented the establishment of general relationships between land cover and runoff patterns across broad scales. This paper addresses these difficulties by using power spectral analysis to characterize area‐normalized runoff patterns and then compare these patterns with landscape features among watersheds within the same physiographic region. We assembled long‐term precipitation and runoff data for 87 watersheds (first to seventh order) within the eastern Piedmont (USA) that contained a wide variety of land cover types, collected environmental data for each watershed, and compared the datasets using a variety of statistical measures. The effect of land cover on runoff patterns was confirmed. Urban‐dominated watersheds were flashier and had less hydrologic memory compared with forest‐dominated watersheds, whereas watersheds with high wetland coverage had greater hydrologic memory. We also detected a 10–15% urban threshold above which urban coverage became the dominant control on runoff patterns. When spectral properties of runoff were compared across stream orders, a threshold after the third order was detected at which watershed processes became dominant over precipitation regime in determining runoff patterns. Finally, we present a matrix that characterizes the hydrologic signatures of rivers based on precipitation versus landscape effects and low‐frequency versus high‐frequency events. The concepts and methods presented can be generally applied to all river systems to characterize multiscale patterns of watershed runoff. Copyright © 2013 John Wiley & Sons, Ltd.     

Watershed structural influences on the distributions of stream network water and solute travel times under baseflow conditions

Watershed structure influences the timing, magnitude, and spatial location of water and solute entry to stream networks. In turn, stream reach transport velocities and stream network geometry (travel distances) further influence the timing of export from watersheds. Here, we examine how watershed and stream network organization can affect travel times of water from delivery to the stream network to arrival at the watershed outlet. We analysed watershed structure and network geometry and quantified the relationship between stream discharge and solute velocity across six study watersheds (11.4 to 62.8 km²) located in the Sawtooth Mountains of central Idaho, USA. Based on these analyses, we developed stream network travel time functions for each watershed. We found that watershed structure, stream network geometry, and the variable magnitude of inputs across the network can have a pronounced affect on water travel distances and velocities within a stream network. Accordingly, a sample taken at the watershed outlet is composed of water and solutes sourced from across the watershed that experienced a range of travel times in the stream network. We suggest that understanding and quantifying stream network travel time distributions are valuable for deconvolving signals observed at watershed outlets into their spatial and temporal sources, and separating terrestrial and in‐channel hydrological, biogeochemical, and ecological influences on in‐stream observations. Copyright © 2016 John Wiley & Sons, Ltd.     

The impact of storm events on solute exports from a glaciated forested watershed in western New York,USA

This study analysed the importance of precipitation events from May 2003 to April 2004 on surface water chemistry and solute export from a 696 ha glaciated forested watershed in western New York State, USA. The specific objectives of the study were to determine: (a) the temporal patterns of solutes within individual storm events; (b) the impact of precipitation events on seasonal and annual export budgets; and (c) how solute concentrations and loads varied for precipitation events among seasons as functions of storm intensity and antecedent moisture conditions. Analysis of solute trajectories showed that NH₄⁺, total Al and dissolved organic nitrogen (DON) peaked on the hydrograph rising limb, whereas dissolved organic carbon (DOC) concentrations peaked following the discharge peak. Sulphate and base‐cations displayed a dilution pattern with a minimum around peak discharge. End‐member mixing analysis showed that throughfall contributions were highest on the rising limb, whereas valley‐bottom riparian waters peaked following the discharge peak. The trajectories of NO₃^? concentrations varied with season, indicating the influence of biotic processes on the generation, and hence flux, of this solute. Storm events had the greatest impact on the annual budgets for NH₄⁺, K⁺, total dissolved Al, DON and DOC. Storm events during summer had the greatest impact on seasonal solute budgets. Summer events had the highest hourly discharges and high concentrations of solutes. However, NO₃^? and DOC exports during a spring snowmelt event were considerably more than those observed for large events during other periods of the year. Comparisons among storms showed that season, precipitation amount, and antecedent moisture conditions affected solute concentrations and loads. Concentrations of solutes were elevated for storms that occurred after dry antecedent conditions. Seven of the largest storms accounted for only 15% of the annual discharge, but were responsible for 34%, 19%, 64%, 13%, 39% and 24% of the annual exports of NH₄⁺, K⁺, Al, NO₃^?, DON and DOC respectively. These results suggest that the intense and infrequent storms predicted for future climate‐change scenarios will likely increase the exports of solutes like DOC, DON, NH₄⁺, Al and K⁺ from watersheds. Copyright © 2006 John Wiley & Sons, Ltd.     

The role of the hyporheic zone across stream networks

Many hyporheic papers state that the hyporheic zone is a critical component of stream ecosystems, and many of these papers focus on the biogeochemical effects of the hyporheic zone on stream solute loads. However, efforts to show such relationships have proven elusive, prompting several questions: Are the effects of the hyporheic zone on stream ecosystems so highly variable in place and time (or among streams) that a consistent relationship should not be expected? Or, is the hyporheic zone less important in stream ecosystems than is commonly expected? These questions were examined using data from existing groundwater modelling studies of hyporheic exchange flow at five sites in a fifth‐order, mountainous stream network. The size of exchange flows, relative to stream discharge (Q_HEF:Q), was large only in very small streams at low discharge (area ≈ 100 ha; Q < 10 l/s). At higher flows (flow exceedance probability > 0·7) and in all larger streams, Q_HEF:Q was small. These data show that biogeochemical processes in the hyporheic zone of small streams can substantially influence the stream's solute load, but these processes become hydrologically constrained at high discharge or in larger streams and rivers. The hyporheic zone may influence stream ecosystems in many ways, however, not just through biogeochemical processes that alter stream solute loads. For example, the hyporheic zone represents a unique habitat for some organisms, with patterns and amounts of upwelling and downwelling water determining the underlying physiochemical environment of the hyporheic zone. Similarly, hyporheic exchange creates distinct patches of downwelling and upwelling. Upwelling environments are of special interest, because upwelling water has the potential to be thermally or chemically distinct from stream water. Consequently, micro‐environmental patches created by hyporheic exchange flows are likely to be important to biological and ecosystem processes, even if their impact on stream solute loads is small. Published in 2011 by John Wiley & Sons, Ltd.     

Variable nitrate concentration–discharge relationships in a forested watershed

The relationship between solute concentrations and discharge can inform an integrated understanding of hydrological and biogeochemical processes at watershed scales. Recent work from multiple catchments has shown that there is typically little variation in concentration relative to large variations in discharge. This pattern has been described as chemostatic behavior. Pond Branch, a forested headwater catchment in Maryland, has been monitored for stream nitrate (NO₃^?) concentrations at weekly intervals for 14 years. In the growing season and autumn of 2011 a high‐frequency optical NO₃^? sensor was used to supplement the long‐term weekly data. In this watershed, long‐term weekly data show that NO₃^? concentrations decrease with increasing discharge whereas 6 months of 15‐minute sensor observed concentrations reveal a more chemostatic behavior. High‐frequency NO₃^? concentrations from the sensor collected during different storm events reveal variable concentration–discharge patterns highlighting the importance of high resolution data and ecohydrological drivers in controlling solute export for biologically reactive solutes such as NO₃^?.     

Phosphorus export dynamics and hydrobiogeochemical controls across gradients of scale,topography and human impact

Concentration‐discharge (c‐Q) plots are routinely used as an integrated signal of watershed response to infer solute sources and travel pathways. However, the interpretation of c‐Q data can be difficult unless these data are fitted using statistical models. Such models are frequently applied for geogenic solutes, but it is unclear to what extent they might aid in the investigation of nutrient export patterns, particularly for total dissolved phosphorus (TDP) which is a critical driver of downstream eutrophication problems. The goal of the present study was therefore to statistically model c‐Q relations (where c is TDP concentrations) in a set of contrasting watersheds in the Northern Great Plains—ranging in size from 0.2 to 1000+ km²—to assess the controls of landscape properties on TDP transport dynamics. Six statistical models were fitted to c‐Q data, notably (a) one linear model, (b) one model assuming that c‐Q relations are driven by the mixing of end‐member waters from different landscape locations (i.e., hydrograph separation), (c) one model relying on a biogeochemical stationarity hypothesis (i.e., power law), (d) one model hypothesizing that c‐Q relations change as a function of the solute subsurface contact time (i.e., hyperbolic model), and (e) two models assuming that solute fluxes are mostly dependent on reaction rates (i.e., chemical models). Model performance ranged from mediocre (R² < 0.2) to very good (R² > 0.9), but the hydrograph separation model seemed most universal. No watershed was found to exhibit chemostatic behaviour, but many showed signs of dilution or enrichment behaviour. A tendency toward a multi‐model fit and better model performance was observed for watersheds with moderate slope and higher effective drainage area. The relatively poor model performance obtained outside these conditions illustrates the likely importance of controls on TDP concentrations in the region that are independent of flow dynamics.     

The influence of fire and permafrost on sub‐arctic stream chemistry during storms

Permafrost and fire are important regulators of hydrochemistry and landscape structure in the discontinuous permafrost region of interior Alaska. We examined the influence of permafrost and a prescribed burn on concentrations of dissolved organic carbon (DOC), dissolved organic nitrogen (DON) and other solutes ( , Ca²⁺, K⁺, Mg²⁺, Na⁺) in streams of an experimentally burned watershed and two reference watersheds with varying extents of permafrost in the Caribou–Poker Creeks Research Watershed in interior Alaska. The low‐permafrost watershed has limited permafrost (3%), the high‐permafrost watershed has extensive permafrost (53%), and the burn watershed has intermediate permafrost coverage (18%). A three end‐member mixing model revealed fundamental hydrologic and chemical differences between watersheds due to the presence of permafrost. Stormflow in the low‐permafrost watershed was dominated by precipitation and overland flow, whereas the high‐permafrost watershed was dominated by flow through the active layer. In all watersheds, organic and groundwater flow paths controlled stream chemistry: DOC and DON increased with discharge (organic source) and base cations and (from weathering processes) decreased. Thawing of the active layer increased soil water storage in the high‐permafrost watershed from July to September, and attenuated the hydrologic response and solute flux to the stream. The FROSTFIRE prescribed burn, initiated on 8 July 1999, elevated nitrate concentrations for a short period after the first post‐fire storm on 25 July, but there was no increase after a second storm in September. During the July storm, nitrate export lagged behind the storm discharge peak, indicating a flushing of soluble nitrate that likely originated from burned soils. Copyright © 2006 John Wiley & Sons, Ltd.     

Seasonal controls on stream chemical export across diverse coastal watersheds in the USA

The current study focuses on understanding key factors controlling geochemical export in eight diverse coastal watersheds at seasonal and annual time scales. Geochemical, atmospheric and hydrologic data across a range of hydro‐climatic regimes and varying land uses were investigated and relationships analysed. A hyperbolic dilution model was fitted for each watershed system to evaluate discharge–concentration relationships. Nitrate concentration effects were observed in watersheds exposed to high atmospheric deposition rates as well as agricultural watersheds, whereas urban watersheds showed nitrate dilution effects. Dilution patterns were observed for calcium, magnesium and sulfate for almost all watersheds. Seasonal loads for almost all constituents were noted to be mainly driven by hydrologic seasonality, but are also dependent on inputs (atmospheric deposition and land use sources). Understanding the primary controls on hydro‐chemical interactions is critical for developing and refining predictive water quality models, especially in coastal watersheds where sensitive downstream ecosystems act as receiving waters for upstream pollutant loads. Copyright © 2012 John Wiley & Sons, Ltd.     

Estimating stream solute loads from fixed frequency sampling regimes: the importance of considering multiple solutes and seasonal fluxes in the design of long‐term stream monitoring networks

Reduced sampling frequency is known to increase the error associated with estimates of stream solute load. However, the extent to which the magnitude of error differs among commonly measured solutes and across seasons is unclear. In this study, a high sampling frequency data set from two forested streams (one upland‐draining and one wetland‐draining stream) in south‐central Ontario was systematically sub‐sampled to simulate weekly, fortnightly and monthly fixed frequency sampling regimes for 12 stream solutes. We found that solutes which had a higher degree of temporal variation in concentration (i.e. higher %RSD) had poorer precision (C_v) in estimates of annual load relative to solutes with a lower %RSD. In addition, the magnitude and direction of bias varied considerably among solutes and were related to differences in spring concentration‐discharge relationships (m_{[spring Q vs C]}) among the 12 solutes. Solutes which decreased in concentration with increases in spring flow (i.e. m_{[spring Q vs C]} <0) exhibited positive bias in annual load while solutes which increased in concentration with increases in spring flow (i.e. m_{[spring Q vs C]} >0) were negatively biased. In terms of differences between seasonal and annual load errors, precision was generally lower for estimates of seasonal load relative to annual load while bias varied in both magnitude and direction among seasons. When the root mean square error (RMSE) of load estimates was compared to a threshold of acceptable error (<15%), the proportion of solutes attaining acceptable levels of uncertainty ranged from 11/12 for annual load estimates at a weekly sampling frequency to only 4/12 at a monthly frequency when both annual and seasonal loads were considered. Our results demonstrate that commonly measured solutes do not behave uniformly in response to changes in sampling frequency and that estimates of seasonal loads are often less accurate than estimates of annual load. These findings provide important insights into the design of stream monitoring programs and the evaluation of existing long‐term data sets. Copyright © 2015 John Wiley & Sons, Ltd.     

Factors controlling nitrogen and dissolved organic carbon exports across timescales in two watersheds with different land uses

Investigating factors controlling the temporal patterns of nitrogen (N) and dissolved organic carbon (DOC) exports on the basis of a comparative study of different land uses is beneficial for managing water resources, especially in agricultural watersheds. We focused our research on an agricultural watershed (AW) and a forested watershed (FW) located in the Shibetsu watershed of eastern Hokkaido, Japan, to investigate the temporal patterns of N and DOC exports and factors controlling those patterns at different timescales (inter‐annual, seasonal, and hydrological event scales). Results showed that the annual patterns of N and DOC exports significantly varied over time and were probably controlled by climate. Higher discharge volumes in 2003, a wet year, showed higher N and DOC loadings in both watersheds. However, this process was also regulated by land use associated with N inputs. Higher concentrations and loadings were shown in the agricultural watershed. At the seasonal scale, N and DOC exports in the AW and the FW were more likely controlled by sources associated with land use. The Total N (TN) and Nitrate‐N (NO₃^?‐N) had higher concentrations during snowmelt season in the AW, which may be attributed to manure application in late autumn or early winter in the agricultural watershed. Concentrations of TN, NO₃^?‐N, dissolved organic nitrogen (DON), and DOC showed higher values during the summer rainy season in the FW, related to higher litter decomposition during summer and autumn and the fertilizer application in the agricultural area during summer. Higher DOC concentrations and loadings were observed during the rainy season in the AW, which is probably attributed to higher DOC production related to temperature and microbial activity during summer and autumn in grasslands. Correlations between discharge and concentrations differed during different periods or in different watersheds, suggesting that weather discharge can adequately represent the fact that N export depends on N concentrations, discharge level, and other factors. The differing correlations between N/DOC concentrations and the Si concentration indicated that the N/DOC exports might occur along different flow paths during different periods. During baseflow, the high NO₃^?‐N exports were probably derived from deep groundwater and might have percolated from uplands during hydrological events. During hydrological events, NO₃^?‐N exports may occur along near‐surface flow paths and in deep groundwater, whereas DOC exports could be related to near‐surface flow paths. At the event scale, the relationships between discharge and concentrations of N and DOC were regulated by antecedent soil moisture (shallow groundwater condition) in each watershed. These results indicated that factors controlling N and DOC exports varied at different timescales in the Shibetsu area and that better management of manure application during winter in agricultural lands is urgently needed to control water pollution in streams. Copyright © 2013 John Wiley & Sons, Ltd.     

Concentration–discharge relationships reflect chemostatic characteristics of US catchments

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. Copyright © 2009 John Wiley & Sons, Ltd.     

Assessment of suspended sediment transport in four alpine watersheds (France): influence of the climatic regime

High‐frequency water discharge and suspended sediment concentration (SSC) databases were collected for 3 years on four contrasted watersheds: the Asse and the Bléone (two Mediterranean rainfall regime watersheds) and the Romanche and the Ferrand (two rainfall–snowmelt regime watersheds). SSCs were calculated from turbidity recordings (1‐h time step), converted into SSC values. The rating curve was calculated by means of simultaneous SSC measurement taken by water sampling and turbidity recording. Violent storms during springtime and autumn were responsible for suspended sediment transport on the Asse and the Bléone rivers. On the Ferrand and the Romanche, a large share of suspended sediment transport was also caused by local storms, but 30% of annual fluxes results from snowmelt or icemelt which occurred from April to October. On each watershed, SSC up to 50 g l^?1 were observed. Annual specific fluxes ranged from 450 to 800 t km^?2 year^?1 and 40–80% of annual suspended sediment fluxes occurred within 2% of the time. These general indicators clearly demonstrate the intensity of suspended sediment transport on these types of watersheds. Suspended sediment fluxes proved to be highly variable at the annual scale (inter‐annual variability of specific fluxes) as well as at the event scale (through a hysteresis loop in the SSC/Q relationship) on these watersheds. In both cases, water discharge and precipitations were the main processes involved in suspended sediment production and transport. The temporal and spatial variability of hydro‐meteorological processes on the watershed provides a better understanding of suspended sediment dynamics. Copyright © 2009 John Wiley & Sons, Ltd.     

Catchment chemostasis revisited: Water quality responds differently to variations in weather and climate

Solute concentrations in streamflow typically vary systematically with stream discharge, and the resulting concentration–discharge relationships are important signatures of catchment biogeochemical processes. Solutes derived from mineral weathering often exhibit decreasing concentrations with increasing flows, suggesting dilution of a kinetically limited weathering flux by a variable flux of water. However, previous work showed that concentration–discharge relationships of weathering‐derived solutes in 59 headwater catchments were much weaker than this simple dilution model would predict. Instead, catchments behaved as chemostats, with rates of solute production and/or mobilization that were nearly proportional to water fluxes, on both event and interannual timescales. Here, we re‐examine these findings using data for a wider range of solutes from 2,186 catchments, ranging from ~10 to >1,000,000 km² in drainage area and spanning a wide range of lithologic and climatic settings. Concentration–discharge relationships among this much larger set of larger catchments are broadly consistent with the previously described chemostatic behaviour, at least on event and interannual timescales for weathering‐derived solutes. Among these same catchments, however, site‐to‐site variations in mean concentrations of weathering‐derived solutes exhibit strong negative correlations with long‐term average precipitation and discharge, reflecting strong climatic control on long‐term leaching of the critical zone. We use multiple regression of site characteristics including discharge to identify potential controls on long‐term mean concentrations and find that lithologic and land cover controls are significant predictors for many analytes. The picture that emerges is one in which, on event and interannual timescales, weathering‐derived stream solute concentrations are chemostatically buffered by groundwater storage and fast chemical reactions, but each catchment's chemostatic “set point” reflects site‐to‐site differences in climatically driven evolution of the critical zone. In contrast to these weathering products, some nutrients and particulates are often near‐chemostatic across all timescales, and their long‐term mean concentrations correlate more strongly with land use than climatic characteristics.     

Comparison of methods for calculating annual solute exports from six forested appalachian watersheds

Six methods were compared for calculating annual stream exports of sulfate, nitrate, calcium, magnesium and aluminum from six small Appalachian watersheds. Approximately 250–400 stream samples and concurrent stream flow measurements were collected during baseflows and storm flows for the 1989 water year at five Pennsylvania watersheds and during the 1989–1992 water years at a West Virginia watershed. Continuous stream flow records were also collected at each watershed. Solute exports were calculated from the complete data set using six different scenarios ranging from instantaneous monthly measurements of stream chemistry and stream flow, to intensive monitoring of storm flow events and multiple regression equations. The results for five of the methods were compared with the regression method because statistically significant models were developed and the regression equations allowed for prediction of solute concentrations during unsampled storm flows. Results indicated that continuous stream flow measurement was critical to producing exports within 10% of regression estimates. For solutes whose concentrations were not correlated strongly with stream flow, weekly grab samples combined with continuous records of stream flow were sufficient to produce export estimates within 10% of the regression method. For solutes whose concentrations were correlated strongly with stream flow, more intensive sampling during storm flows or the use of multiple regression equations were the most appropriate methods, especially for watersheds where stream flows changed most quickly. Concentration–stream flow relationships, stream hydrological response, available resources and required level of accuracy of chemical budgets should be considered when choosing a method for calculating solute exports. © 1997 John Wiley & Sons, Ltd.     

The effect of El Niño Southern Oscillation cycles on the decadal scale suspended sediment behavior of a coastal dry‐summer subtropical catchment

Rivers display temporal dependence in suspended sediment–water discharge relationships. Although most work has focused on multi‐decadal trends, river sediment behavior often displays sub‐decadal scale fluctuations that have received little attention. The objectives of this study were to identify inter‐annual to decadal scale fluctuations in the suspended sediment–discharge relationship of a dry‐summer subtropical river, infer the mechanisms behind these fluctuations, and examine the role of El Niño Southern Oscillation climate cycles. The Salinas River (California) is a moderate sized (11 000 km²), coastal dry‐summer subtropical catchment with a mean discharge (Q_mean) of 11.6 m³ s^?1. This watershed is located at the northern most extent of the Pacific coastal North America region that experiences increased storm frequency during El Niño years. Event to inter‐annual scale suspended sediment behavior in this system was known to be influenced by antecedent hydrologic conditions, whereby previous hydrologic activity regulates the suspended sediment concentration–water discharge relationship. Fine and sand suspended sediment in the lower Salinas River exhibited persistent, decadal scale periods of positive and negative discharge corrected concentrations. The decadal scale variability in suspended sediment behavior was influenced by inter‐annual to decadal scale fluctuations in hydrologic characteristics, including: elapsed time since small (~0.1 × Q_mean), and moderate (~10 × Q_mean) threshold discharge values, the number of preceding days that low/no flow occurred, and annual water yield. El Niño climatic activity was found to have little effect on decadal‐scale fluctuations in the fine suspended sediment–discharge relationship due to low or no effect on the frequency of moderate to low discharge magnitudes, annual precipitation, and water yield. However, sand concentrations generally increased in El Niño years due to the increased frequency of moderate to high magnitude discharge events, which generally increase sand supply. Copyright © 2014 John Wiley & Sons, Ltd.     

Controls on surface water chemistry in two lake‐watersheds in the Adirondack region of New York: differences in nitrogen solute sources and sinks

The southwestern Adirondack region of New York receives among the highest rates of atmospheric nitrogen (N) deposition in the USA. Atmospheric N deposition to sensitive ecosystems, like the Adirondacks, may increase the acidification of soils through losses of exchangeable nutrient cations, and the acidification of surface waters associated with enhanced mobility of nitrate (NO₃^?). However, watershed attributes, including surficial terrestrial characteristics, in‐lake processing, and geological settings, have been found to complicate the relationships between atmospheric N deposition and N drainage losses. We studied two lake‐watersheds in the southwestern Adirondacks, Grass Pond and Constable Pond, which are located in close proximity (～26 km) and receive similarly high N deposition, but have contrasting watershed attributes (e.g. wetland area, geological settings). Since the difference in the influence of N deposition was minimal, we were able to examine both within‐ and between‐watershed influences of land cover, the contribution of glacial till groundwater inputs, and in‐lake processes on surface water chemistry with particular emphasis on N solutes and dissolved organic carbon (DOC). Monthly samples at seven inlets and one outlet of each lake were collected from May to October in 1999 and 2000. The concentrations of NO₃^? were high at the Grass Pond inlets, especially at two inlets, and NO₃^? was the major N solute at the Grass Pond inlets. The concentrations of likely weathering products (i.e. dissolved Si, Ca²⁺, Mg²⁺, Na⁺) as well as acid neutralizing capacity and pH values, were also particularly high at those two Grass Pond inlets, suggesting a large contribution of groundwater inputs. Dissolved organic N (DON) was the major N solute at the Constable Pond inlets. The higher concentrations of DON and DOC at the Constable Pond inlets were attributed to a large wetland area in the watershed. The DOC/DON ratios were also higher at the Constable Pond inlets, possibly due to a larger proportion of coniferous forest area. Although DON and DOC were strongly related, the stronger relationship of the proportion of wetland area with DOC suggests that additional factors regulate DON. The aggregated representation of watershed physical features (i.e. elevation, watershed area, mean topographic index, hypsometric‐analysis index) was not clearly related to the lake N and DOC chemistry. Despite distinctive differences in inlet N chemistry, NO₃^? and DON concentrations at the outlets of the two lakes were similar. The lower DOC/DON ratios at the lake outlets and at the inlets having upstream ponds suggest the importance of N processing and organic N sources within the lakes. Although an inverse relationship between NO₃^? and DOC/DON has been suggested to be indicative of a N deposition gradient, the existence of this relationship for sites that receive similar atmospheric N deposition suggest that the relationship between NO₃^? and the DOC/DON ratio is derived from environmental and physical factors. Our results suggest that, despite similar wet N deposition at the two watershed sites, N solutes entering lakes were strongly affected by hydrology associated with groundwater contribution and the presence of wetlands, whereas N solutes leaving lakes were strongly influenced by in‐lake processing. Copyright © 2006 John Wiley & Sons, Ltd.     

Run‐off processes from mountains to foothills: The role of soil stratigraphy and structure in influencing run‐off characteristics across high to low relief landscapes

The critical zone features that control run‐off generation, specifically at the regional watershed scale, are not well understood. Here, we addressed this knowledge gap by quantitatively and conceptually linking regional watershed‐scale run‐off regimes with critical zone structure and climate gradients across two physiographic provinces in the Southeastern United States. We characterized long‐term (~20 years) discharge and precipitation regimes for 73 watersheds with United States Geological Survey in‐stream gaging stations across the Appalachian Mountain and Piedmont physiographic provinces of North Carolina. Watersheds included in this analysis had <10% developed land and ranged in size from 14.1–4,390 km². Thirty‐four watersheds were located in the Piedmont physiographic province, which is typically classified as a low relief landscape with deep, highly weathered soils and regolith. Thirty‐nine watersheds were located in the Appalachian Mountain physiographic province, which is typically classified as a steeper landscape with highly weathered, but shallower soils and regolith. From the United States Geological Survey daily mean run‐off time series, we calculated annual and seasonal baseflow indices (BFI), minimum, mean, and maximum daily run‐off, and Pearson's correlation coefficients between precipitation and baseflow. Our results showed that Appalachian Mountain watersheds systematically had higher minimum daily flows and BFI values. Piedmont watersheds displayed much larger deviations from mean annual BFI in response to year‐to‐year variability in precipitation. A series of linear regression models between 21 landscape metrics and annual BFIs showed non‐linear and complex terrestrial–hydrological relationships across the two provinces. From these results, we discuss how distinct features of critical zone architecture, with specific focus on soil depth and stratigraphy, may be dominating the regulation of hydrological processes and run‐off regimes across these provinces.     

Elevation‐dependent responses of streamflow to climate warming

Warming will affect snowline elevation, potentially altering the timing and magnitude of streamflow from mountain landscapes. Presently, the assessment of potential elevation‐dependent responses is difficult because many gauged watersheds integrate drainage areas that are both snow and rain dominated. To predict the impact of snowline rise on streamflow, we mapped the current snowline (1980 m) for the Salmon River watershed (Idaho, USA) and projected its elevation after 3 °C warming (2440 m). This increase results in a 40% reduction in snow‐covered area during winter months. We expand this analysis by collecting streamflow records from a new, elevation‐stratified gauging network of watersheds contained within high (2250–3800 m), mid (1500–2250 m) and low (300–1500 m) elevations that isolate snow, mixed and rain‐dominated precipitation regimes. Results indicate that lags between percentiles of precipitation and streamflow are much shorter in low elevations than in mid‐ and high‐elevation watersheds. Low elevation annual percentiles (Q₂₅ and Q₇₅) of streamflow occur 30–50 days earlier than in higher elevation watersheds. Extreme events in low elevations are dominated by low‐ and no‐flow events whereas mid‐ and high‐elevation extreme events are primarily large magnitude floods. Only mid‐ and high‐elevation watersheds are strongly cross correlated with catchment‐wide flow of the Salmon River, suggesting that changes in contributions from low‐elevation catchments may be poorly represented using mainstem gauges. As snowline rises, mid‐elevation watersheds will likely exhibit behaviours currently observed only at lower elevations. Streamflow monitoring networks designed for operational decision making or change detection may require modification to capture elevation‐dependent responses of streamflow to warming. Copyright © 2014 John Wiley & Sons, Ltd.