Complex patterns of catchment solute–discharge relationships for coastal plain rivers

Riverine solute versus discharge (C–Q) relationships provide information about the magnitude and dynamics of material fluxes from landscapes. We analysed long‐term patterns of C–Q relationships for 44 rivers in Florida across a suite of geogenic, nutrient, and organic solutes and investigated land cover, watershed size, and surficial geology as controls on these patterns. Solute concentrations generally exhibited far less variability than did discharge, with coherent solute‐specific behaviours repeated across watersheds. Geogenic solutes generally diluted with increasing discharge, whereas organic solutes generally enriched; patterns for nutrients were highly variable across watersheds, but on average exhibited chemostasis. Despite strong evidence of both geologic and land cover controls on solute flow‐weighted concentrations, these variables were poor predictors of C–Q slopes (β) or relative coefficients of variation (CV_C:CV_Q). CV_C:CV_Q generally increased with watershed size, and wetland area appeared to influence C–Q patterns for base cations and organic solutes. Perhaps most importantly, we observed significant slope breaks in C–Q association in approximately half of our observations, challenging the generality of using single power functions to describe catchment solute export patterns. For all solutes except phosphorus (P), C–Q slopes decreased above statistically identified breaks (slopes for P increased), with breaks consistently at or near median flow (i.e., 50% flow exceedance probability). This common pattern significantly impacts solute load estimates; failing to account for slope breaks overestimates nitrate and total organic carbon loads as much as 125% and underestimates P loads as much as 35%. In addition to challenging generic power‐law characterization of C–Q relationships for these coastal plain rivers, and exploring the load estimate consequences thereof, our study supports emerging insights about watershed hydrochemical behaviours across a wide array of solutes.     

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.     

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.     

Stream geochemical response to reductions in acid deposition in headwater streams: Chronic versus episodic acidification recovery

In the decades since dramatic reductions in acid emissions and subsequent deposition in North America and Europe, the vast majority of research on aquatic chemical recovery has focused on trends in acid–base concentrations during baseflow conditions. Missing from such assessments is consideration of higher flow periods, when flow paths and chemical concentrations change and episodic acidification may occur. Stream samples collected weekly and bi‐hourly during high‐flow storm events from 1992 to 2015 at three watersheds representing a gradient in response to acid deposition in the south‐eastern United States were used to evaluate temporal trends in acid anions, base cations, acid neutralizing capacity (ANC), and pH for each of five distinct flow exceedance regimes, as well as trends in concentration–discharge (C–Q) relationships. For the most well‐buffered watershed (mean ANC = 220 μeq L^?1), ANC and pH increased at a similar rate for baseflow and storm flow conditions. Decreases in sulfate controlled ANC trends at higher flows, whereas smaller sulfate decreases in combination with base cation increases resulted in similar ANC improvements for low‐flow periods. For the most acid sensitive watershed (mean ANC = 10 μeq L^?1), no trends in ANC or pH were observed for the lowest flows (>90% flow exceedance), whereas reductions in sulfate resulted in significant increases in ANC during higher flow conditions. At all sites, greater rates of sulfate decline during high‐flow, as compared with low‐flow, conditions are likely a result of a reduced capacity of near surface soils to adsorb and retain sulfur in these non‐glaciated watersheds. Overall, consistent increases in pH (~0.01–0.02 pH units year^?1) during higher flow conditions (<10% flow exceedance) in contrast to the variable trends observed during lower flows (>50% flow exceedance) illustrate that episodic acidification is recovering at an equal or greater rate than chronic acidification in these watersheds.     

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.     

Sources of uncertainty in estimating stream solute export from headwater catchments at three sites

Uncertainty in the estimation of hydrologic export of solutes has never been fully evaluated at the scale of a small‐watershed ecosystem. We used data from the Gomadansan Experimental Forest, Japan, Hubbard Brook Experimental Forest, USA, and Coweeta Hydrologic Laboratory, USA, to evaluate many sources of uncertainty, including the precision and accuracy of measurements, selection of models, and spatial and temporal variation. Uncertainty in the analysis of stream chemistry samples was generally small but could be large in relative terms for solutes near detection limits, as is common for ammonium and phosphate in forested catchments. Instantaneous flow deviated from the theoretical curve relating height to discharge by up to 10% at Hubbard Brook, but the resulting corrections to the theoretical curve generally amounted to <0.5% of annual flows. Calibrations were limited to low flows; uncertainties at high flows were not evaluated because of the difficulties in performing calibrations during events. However, high flows likely contribute more uncertainty to annual flows because of the greater volume of water that is exported during these events. Uncertainty in catchment area was as much as 5%, based on a comparison of digital elevation maps with ground surveys. Three different interpolation methods are used at the three sites to combine periodic chemistry samples with streamflow to calculate fluxes. The three methods differed by <5% in annual export calculations for calcium, but up to 12% for nitrate exports, when applied to a stream at Hubbard Brook for 1997–2008; nitrate has higher weekly variation at this site. Natural variation was larger than most other sources of uncertainty. Specifically, coefficients of variation across streams or across years, within site, for runoff and weighted annual concentrations of calcium, magnesium, potassium, sodium, sulphate, chloride, and silicate ranged from 5 to 50% and were even higher for nitrate. Uncertainty analysis can be used to guide efforts to improve confidence in estimated stream fluxes and also to optimize design of monitoring programmes. © 2014 The Authors. Hydrological Processes published John Wiley & Sons, Ltd.     

Land management impacts on runoff sources in small Amazon watersheds

Forest clearing and conversion to cattle pasture in the lowland Amazon region has been linked to soil compaction and increased soil water storage, which combine to diminish soil infiltration, enhance quick lateral flows and increase the stream flow response to precipitation. Quantifying the importance of quick surficial flow in response to this land use change requires identification of water sources within catchments that contribute to stream flow. Using an end member mixing analysis approach, potential contributing sources of stream flow were evaluated during an entire rainy season in a forest and a pasture watershed drained by ephemeral‐to‐intermittent streams in the south‐western Amazon. Water yield was 17% of precipitation in the pasture and 0·8% of precipitation in the forest. During the early rainy season, throughfall, groundwater, and soil water contributed 79%, 18%, and 3%, respectively, to total forest stream flow. Over the entire rainy season, throughfall, groundwater, and shallow soil water provided 57%, 24%, and 19%, respectively, of stream flow. In the pasture watershed, overland flow dominated stream flow both in the early (67%) and late (57%) rainy season, with a mean contribution of 60% overland flow, 35% groundwater, and 5% soil water. The uncertainty associated with those estimates was studied using a Monte Carlo approach. In addition to large changes in total surface flow, marked differences were found in the proportions of total stream flow in the second half of the rainy season between the forest and pasture watershed. These results suggest that (1) there is great potential for alteration of the hydrological budgets of larger watersheds as the proportion of deforested land in the Amazon increases, and (2) as more rainfall is diverted into fast flowpaths to streams in established pastures, the potential to deliver water with higher solute concentrations generated by erosion or by bypassing sites of solute removal increases. Copyright © 2007 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^?.     

Groundwater–surface water interactions in a lowland watershed: source contribution to stream flow

The lower coastal plain of the Southeast USA is undergoing rapid urbanisation as a result of population growth. Land use change has been shown to affect watershed hydrology by altering stream flow and, ultimately, impairing water quality and ecologic health. However, because few long‐term studies have focused on groundwater–surface water interactions in lowland watersheds, it is difficult to establish what the effect of development might be in the coastal plain region. The objective of this study was to use an innovative improvement to end‐member mixing analysis (EMMA) to identify time sequences of hydrologic processes affecting storm flow. Hydrologic and major ion chemical data from groundwater, soil water, precipitation and stream sites were collected over a 2‐year period at a watershed located in USDA Forest Service's Santee Experimental Forest near Charleston, South Carolina, USA. Stream flow was ephemeral and highly dependent on evapotranspiration rates and rainfall amount and intensity. Hydrograph separation for a series of storm events using EMMA allowed us to identify precipitation, riparian groundwater and streambed groundwater as main sources to stream flow, although source contribution varied as a function of antecedent soil moisture condition. Precipitation, as runoff, dominated stream flow during all storm events while riparian and streambed groundwater contributions varied and were mainly dependent on antecedent soil moisture condition. Sensitivity analyses examined the influence of 10% and 50% increases in analyte concentration on EMMA calculations and found that contribution estimates were very sensitive to changes in chemistry. This study has implications on the type of methodology used in traditional forms of EMMA research, particularly in the recognition and use of median end‐member water chemistry in hydrograph separation techniques. Potential effects of urban development on important hydrologic processes (groundwater recharge, interflow, runoff, etc.) that influence stream flow in these lowland watersheds were qualitatively examined. Copyright © 2011 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.     

Mercury transport in response to storm events from a northern forest landscape

Concentrations and fluxes of mercury (Hg) species in surface waters of forested watersheds are affected by hydrological events. The mechanisms of Hg transport during these events are poorly understood and yet may influence Hg bioavailability and exposure to aquatic biota. Three storm events with varying magnitude and intensity were investigated (June, September and November 2005) at a forested watershed in the Adirondack region of New York State, USA. Concentrations of Hg species increased during these events, both above and downstream of wetlands in the watershed. While Hg flux was higher from wetland drainage, the Hg flux from the upland site exhibited a greater relative increase to elevated runoff. Hg flux was controlled by discharge; however, Hg species concentrations were not well correlated with discharge, dissolved organic carbon (DOC), or total suspended solids (TSS) through the duration of events. A counter‐clockwise hysteresis response of DOC with increasing runoff contrasted with the clockwise response for total Hg, suggesting different contributions from source areas for these solutes. Correspondence with elevated total K and NO₃^? (α < 0·05) during the rising limb of the hydrograph suggests rapid delivery of throughfall Hg, potentially enhanced by hillslope hollows, to the stream channel. As the watershed saturated, stream Hg appears to be derived from the soil Hg pool. Results suggest that particulate Hg did not contribute substantially to total Hg flux during events (<25%). These results emphasize the role of watershed attributes and storm characteristics in Hg transport and bioavailability. Copyright © 2008 John Wiley & Sons, Ltd.     

Predicting high-frequency variation in stream solute concentrations with water quality sensors and machine learning

Stream solute monitoring has produced many insights into ecosystem and Earth system functions. Although new sensors have provided novel information about the fine-scale temporal variation of some stream water solutes, we lack adequate sensor technology to gain the same insights for many other solutes. We used two machine learning algorithms – Support Vector Machine and Random Forest – to predict concentrations at 15-min resolution for 10 solutes, of which eight lack specific sensors. The algorithms were trained with data from intensive stream sensing and manual stream sampling (weekly) for four full years in a hydrologic reference stream within the Hubbard Brook Experimental Forest in New Hampshire, USA. The Random Forest algorithm was slightly better at predicting solute concentrations than the Support Vector Machine algorithm (Nash-Sutcliffe efficiencies ranged from 0.35 to 0.78 for Random Forest compared to 0.29 to 0.79 for Support Vector Machine). Solute predictions were most sensitive to the removal of fluorescent dissolved organic matter, pH and specific conductance as independent variables for both algorithms, and least sensitive to dissolved oxygen and turbidity. The predicted concentrations of calcium and monomeric aluminium were used to estimate catchment solute yield, which changed most dramatically for aluminium because it concentrates with stream discharge. These results show great promise for using a combined approach of stream sensing and intensive stream discrete sampling to build information about the high-frequency variation of solutes for which an appropriate sensor or proxy is not available.     

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.     

Storm runoff and sediment losses from forest clearcutting and stand re‐establishment with best management practices in East Texas,USA

Nine small (2·5 ha) and four large (70–135 ha) watersheds were instrumented in 1999 to evaluate the effects of intensive silvicultural practices with best management practices (BMPs) on runoff and stream water quality in the Western Gulf Coastal Plain of East Texas, USA. Two treatments were implemented in 2002: a conventional treatment with clearcutting and herbicide site preparation, and an intensive treatment that added subsoiling, fertilization and a release herbicide application. Watershed effects were compared with results from a previously conducted study on the same watersheds in 1981, in which two combinations of harvesting and mechanical site preparation without BMPs were evaluated. Due to the reduction in evapotranspirational demand, total storm runoff increased on all six treated small watersheds following harvest by 0·94 to 13·73 cm in 2003. Runoff increases were not statistically significant on the treated large watersheds. Total first‐year sediment loss was significantly greater on two of the conventional and one of the intensive small watersheds. The greatest first‐year increase was 540·1 kg ha^?1, only one‐fifth of that observed on these watersheds from shearing and windrowing without BMPs in 1981. First‐year sediment loss was significantly greater on the intensive large watershed following harvest, but not on the conventional large watershed. These data suggest that BMPs are very effective in reducing potential water quality impacts from intensive silvicultural practices. Copyright © 2007 John Wiley & Sons, Ltd.     

Use of geochemical mass balance modelling to evaluate the role of weathering in determining stream chemistry in five mid-atlantic watersheds on different lithologies

The importance of mineral weathering was assessed and compared for five mid-Atlantic watersheds receiving similar atmospheric inputs but underlain by differing bedrock. Annual solute mass balances and volume-weighted mean solute concentrations were calculated for each watershed for each year of record. In addition, primary and secondary mineralogy were determined for each of the watersheds through analysis of soil samples and thin sections using petrographic, scanning electron microscope, electron microprobe and X-ray diffraction techniques. Mineralogical data were also compiled from the literature. These data were input to NETPATH, a geochemical program that calculates the masses of minerals that react with precipitation to produce stream water chemistry. The feasibilities of the weathering scenarios calculated by NETPATH were evaluated based on relative abundances and reactivities of minerals in the watershed. In watersheds underlain by reactive bedrocks, weathering reactions explained the stream base cation loading. In the acid-sensitive watersheds on unreactive bedrock, calculated weathering scenarios were not consistent with the abundance of reactive minerals in the underlying bedrock, and alternative sources of base cations are discussed. © 1997 John Wiley & Sons, Ltd.     

Hydrologic comparison between a forested and a wetland/lake dominated watershed using SWAT

The Soil and Water Assessment Tool (SWAT) is a physically‐based hydrologic model developed for agricultural watersheds, which has been infrequently validated for forested watersheds, particularly those with deep overwinter snow accumulation and abundant lakes and wetlands. The goal of this study was to determine the applicability of SWAT for modelling streamflow in two watersheds of the Ontonagon River basin of northern Michigan which differ in proportion of wetland and lake area. The forest‐dominated East Branch watershed contains 17% wetland and lake area, whereas the wetland/lake‐dominated Middle Branch watershed contains 26% wetland and lake area. The specific objectives were to: (1) calibrate and validate SWAT models for the East Branch and Middle Branch watersheds to simulate monthly stream flow, and (2) compare the effects of wetland and lake abundance on the magnitude and timing of streamflow. Model calibration and validation was satisfactory, as determined by deviation of discharge D and Nash and Sutcliffe coefficient values E that compared simulated monthly mean discharge versus measured monthly mean discharge. Streamflow simulation discrepancies occurred during summer and fall months and dry years. Several snow melting parameters were found to be critical for the SWAT simulation: TIMP (snow temperature lag factor) and SMFMX and SMFMN (melting factors). Snow melting parameters were not transferable between adjacent watersheds. Differences in seasonal pattern of long‐term monthly streamflow were found, with the forest‐dominated watershed having a higher peak flow during April but a lower flow during the remainder of the year in comparison to the wetland and lake‐dominated watershed. The results suggested that a greater proportion of wetland and lake area increases the capacity of a watershed to impound surface runoff and to delay storm and snow melting events. Representation of wetlands and lakes in a watershed model is required to simulate monthly stream flow in a wetland/lake‐dominated watershed. Copyright © 2007 John Wiley & Sons, Ltd.     

Effects of urbanization on streamflow in the Atlanta area (Georgia,USA): a comparative hydrological approach

For the period from 1958 to 1996, streamflow characteristics of a highly urbanized watershed were compared with less‐urbanized and non‐urbanized watersheds within a 20 000 km² region in the vicinity of Atlanta, Georgia: in the Piedmont and Blue Ridge physiographic provinces of the southeastern USA. Water levels in several wells completed in surficial and crystalline‐rock aquifers were also evaluated. Data were analysed for seven US Geological Survey (USGS) stream gauges, 17 National Weather Service rain gauges, and five USGS monitoring wells. Annual runoff coefficients (RCs; runoff as a fractional percentage of precipitation) for the urban stream (Peachtree Creek) were not significantly greater than for the less‐urbanized watersheds. The RCs for some streams were similar to others and the similar streams were grouped according to location. The RCs decreased from the higher elevation and higher relief watersheds to the lower elevation and lower relief watersheds: values were 0·54 for the two Blue Ridge streams, 0·37 for the four middle Piedmont streams (near Atlanta), and 0·28 for a southern Piedmont stream. For the 25 largest stormflows, the peak flows for Peachtree Creek were 30% to 100% greater than peak flows for the other streams. The storm recession period for the urban stream was 1–2 days less than that for the other streams and the recession was characterized by a 2‐day storm recession constant that was, on average, 40 to 100% greater, i.e. streamflow decreased more rapidly than for the other streams. Baseflow recession constants ranged from 35 to 40% lower for Peachtree Creek than for the other streams; this is attributed to lower evapotranspiration losses, which result in a smaller change in groundwater storage than in the less‐urbanized watersheds. Low flow of Peachtree Creek ranged from 25 to 35% less than the other streams, possibly the result of decreased infiltration caused by the more efficient routing of stormwater and the paving of groundwater recharge areas. The timing of daily or monthly groundwater‐level fluctuations was similar annually in each well, reflecting the seasonal recharge. Although water‐level monitoring only began in the 1980s for the two urban wells, water levels displayed a notable decline compared with non‐urban wells since then; this is attributed to decreased groundwater recharge in the urban watersheds due to increased imperviousness and related rapid storm runoff. Copyright © 2001 John Wiley & Sons, Ltd.     

Seasonal and event-scale variations in solute chemistry for four Sierra Nevada catchments

Hydrobiogeochemical processes controlling stream water chemistry were examined in four small (<5 km²) catchments having contrasting bedrock lithologies in the western Sierra Nevada foothills of California. The Mediterranean climate with its cool/wet and hot/dry cycle produces strong seasonal patterns in hydrological, biological and geochemical processes. Stream water solutes fall into three general groups according to seasonal fluctuation in concentration: strong, rainy season minimum–dry season maximum (Cl⁻, SO₄²⁻, base cations); weak, rainy season minimum–dry season maximum (Si); and rainy season maximum–dry season minimum (NO₃⁻ and K⁺). Solute dynamics in soil solutions and stream water suggest that mixing of drainage waters from bedrock and soil sources regulate stream water solute concentrations. Patterns are further altered by the leaching of solutes accumulated in the soil over the summer period of desiccation and the temporal discoupling of nutrient cycles that occurs due to differences in the timing between vegetation growth (late spring) and leaching (early winter). Solute concentrations are remarkably similar between watersheds with varying bedrock types, with the exception of nitrate, sulfate and bicarbonate. Three watersheds have nitrogen-bearing metasedimentary bedrock that contributes to elevated nitrate concentrations in stream waters. Watersheds whose bedrock includes mineralized veins of sulfide and carbonate minerals similarly have greater sulfate and bicarbonate concentrations in stream water. Hydrobiogeochemical processes are highly dynamic at the seasonal and storm-event temporal scales and spatially complex at the watershed scale making management of stream water chemical composition, such as nitrate concentrations, very challenging.     

Changes in dissolved organic matter (DOM) amount and composition along nested headwater stream locations during baseflow and stormflow

Amount and composition of dissolved organic matter (DOM) were evaluated for multiple, nested stream locations in a forested watershed to investigate the role of hydrologic flow paths, wetlands and drainage scale. Sampling was performed over a 4‐year period (2008–2011) for five locations with drainage areas of 0.62, 3.5, 4.5, 12 and 79 ha. Hydrologic flow paths were characterized using an end‐member mixing model. DOM composition was determined using a suite of spectrofluorometric indices and a site‐specific parallel factor analysis model. Dissolved organic carbon (DOC), humic‐like DOM and fluorescence index were most sensitive to changes with drainage scale, whereas dissolved organic nitrogen, specific UV absorbance, Sr and protein‐like DOM were least sensitive. DOM concentrations and humic‐like DOM constituents were highest during both baseflow and stormflow for a 3.5‐ha catchment with a wetland near the catchment outlet. Whereas storm‐event concentrations of DOC and humic DOM constituents declined, the mass exports of DOC increased with increasing catchment scale. A pronounced dilution in storm‐event DOC concentration was observed at peak stream discharge for the 12‐ha drainage location, which was not as apparent at the 79‐ha scale, suggesting key differences in supply and transport of DOM. Our observations indicate that hydrologic flow paths, especially during storms, and the location and extent of wetlands in the catchment are key determinants of DOM concentration and composition. This study furthers our understanding of changes in DOM with drainage scale and the controls on DOM in headwater, forested catchments. Copyright © 2014 John Wiley & Sons, Ltd.     

Evaluation of infiltration‐based stormwater management to restore hydrological processes in urban headwater streams

Urbanization threatens headwater stream ecosystems globally. Watershed restoration practices, such as infiltration‐based stormwater management, are implemented to mitigate the detrimental effects of urbanization on aquatic ecosystems. However, their effectiveness for restoring hydrologic processes and watershed storage remains poorly understood. Our study used a comparative hydrology approach to quantify the effects of urban watershed restoration on watershed hydrologic function in headwater streams within the Coastal Plain of Maryland, USA. We selected 11 headwater streams that spanned an urbanization–restoration gradient (4 forested, 4 urban‐degraded, and 3 urban‐degraded) to evaluate changes in watershed hydrologic function from both urbanization and watershed restoration. Discrete discharge and continuous, high‐frequency rainfall‐stage monitoring were conducted in each watershed. These datasets were used to develop 6 hydrologic metrics describing changes in watershed storage, flowpath connectivity, or the resultant stream flow regime. The hydrological effects of urbanization were clearly observed in all metrics, but only 1 of the 3 restored watersheds exhibited partially restored hydrologic function. At this site, a larger minimum runoff threshold was observed relative to the urban‐degraded watersheds, suggesting enhanced infiltration of stormwater runoff within the restoration structure. However, baseflow in the stream draining this watershed remained low compared to the forested reference streams, suggesting that enhanced infiltration of stormwater runoff did not recharge subsurface storage zones contributing to stream baseflow. The highly variable responses among the 3 restored watersheds were likely due to the spatial heterogeneity of urban development, including the level of impervious cover and extent of the storm sewer network. This study yielded important knowledge on how restoration strategies, such as infiltration‐based stormwater management, modulated—or failed to modulate—hydrological processes affected by urbanization, which will help improve the design of future urban watershed management strategies. More broadly, we highlighted a multimetric approach that can be used to monitor the restoration of headwater stream ecosystems in disturbed landscapes.