The role of lithology,catchment size and the alluvial zone on the hydrogeochemistry of two intermittent Mediterranean streams

Hydrology and solute concentrations of two intermittent Mediterranean streams draining two nested catchments were compared. The two catchments were mainly underlain by granitic rocks and different types of sericitic schists. Only the lowland catchment had an alluvial zone and a well‐developed riparian forest. The rainfall–runoff relationship and the correlation between daily flow concentrations showed that hydrological behaviour was similar at both sites during most of the year. However, reverse fluxes were detected during the wetting and drying up periods only in the stream with an alluvial zone. The intermittence in stream flow also had effects on absolute solute concentrations, temporal solute dynamics and streamwater stoichiometry. Streamwater chemistry was not affected by drainage area, except for cations produced mainly by bedrock dissolution (i.e. calcium and magnesium) that increased with increasing catchment size. Differences in the relationship among cations and anions were detected between the two streams, which could be attributed to biogeochemical processes occurring in the alluvial zone. The multivariate model used in this study showed that stoichiometry was more useful than absolute concentrations when analyzing the influence of different lithologies on streamwater chemistry. Such differences were amplified in autumn, likely due to a low hydrological connectivity between the two nested catchments. Copyright © 2007 John Wiley & Sons, Ltd.     

Seasonal cycles of dissolved constituents in streamwater in two forested catchments in the mid-Atlantic region of the eastern USA

Streamwater discharge and chemistry of two small catchments on Catoctin Mountain in north-central Maryland have been monitored since 1982. Repetitive seasonal cycles in stream-water chemistry have been observed each year, along with seasonal cycles in the volume of stream discharge and in groundwater levels. The hypothesis that the observed streamwater chemical cycles are related to seasonal changes in the hydrological flow paths that contribute to streamflow is examined using a combination of data on groundwater levels, shallow and deep groundwater chemistry, streamwater discharge, streamwater chemistry, soil-water chemistry, and estimates of water residence times. The concentrations of constituents derived from rock weathering, particularly bicarbonate and silica, increase in streamwater during the summer when the water table is below the regolith-bedrock interface and stream discharge consists primarily of deep groundwater from the fractured-bedrock aquifer. Conversely, the concentrations in streamwater of atmospherically derived components, particularly sulfate, increase in winter when the water table is above the regolith-bedrock interface and stream discharge consists primarily of shallow groundwater from the regolith. Tritium and chlorofluorocarbon (CFC) measurements suggest that the groundwater in these systems is young, with a residence time of less than several years. The results of this study have implications for the design of large-scale water-quality monitoring programs.     

The seasonal variation of streamwater chemistry in three forested Mediterranean catchments

Streamwater chemistry is described for three streams draining undisturbed, evergreen broad-leaved forested catchments on phyllites in NE Spain: two streams with no or negligible flow in summer are located in the Prades massif, and one perennial stream is in the wetter Montseny mountains. Weekly data for a study period of 2–4 years are provided to (1) describe the seasonal variations in streamwater chemistry, (2) analyse the relationship between stream discharge and solute concentrations using a two-component mixing model and (3) search for patterns of temporal variation in stream solute concentrations after discounting the effects of discharge. At Prades, concentrations of all analysed ions, except NO⁻₃, showed marked seasonal variations in stream water, whereas at Montseny only ions related to mineral weathering (HCO⁻₃, Na⁺, Ca²⁺ and Mg²⁺) showed strong seasonality. Ion concentrations were more closely dependent on instantaneous discharge at Montseny than at Prades. The residuals of the relationship between solute concentrations and discharge retained a strong seasonality at Prades, but not at Montseny. These differences are related to the major hydrochemical processes that determine the streamwater chemistry at each site. The same processes are probably operative in the three catchments, but are of varying relative importance. At Montseny, the mixing of waters of different chemical composition seems to be the major process controlling streamwater chemistry, although the soilwater end-member composition predicted by the mixing model applied did not match the measured soilwater chemistry. In the drier Prades catchments, the two major hydrochemical processes determining the seasonal variation of streamwater chemistry are (1) the restart of flow after the summer drought, which flushes out the solutes accumulated during the dry period, and (2) the seasonal changes in groundwater chemistry that result from the interplay of water residence time, temperature and CO₂ partial pressure. In Mediterranean catchments with relatively high precipitation, such as Montseny, the seasonal variation in the streamwater chemistry is largely determined by the same processes as at humid-temperate sites, whereas in drier Mediterranean catchments, such as Prades, the major hydrochemical processes are clearly distinct.     

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.     

Relationship of topography to surface water chemistry with particular focus on nitrogen and organic carbon solutes within a forested watershed in Hokkaido,Japan

We studied the relationships between streamwater chemistry and the topography of subcatchments in the Dorokawa watershed in Hokkaido Island, northern Japan, to examine the use of topography as a predictor of streamwater chemistry in a watershed with relatively moderate terrain compared with other regions of Japan. Topographic characteristics of the Dorokawa watershed and its subcatchments were expressed as topographic index (TI) values, which ranged from 4·5 to 20·4 for individual grid cells (50 × 50 m²), but averaged from 6·4 to 7·4 for the 20 subcatchments. Streamwater samples for chemical analyses were collected four times between June and October 2002 from 20 locations in the watershed. The pH of water that passed through the watershed increased from ～5·0 to 7·0, with major increases in Na⁺ and Ca²⁺ and marked decreases in NO₃^? and SO . Distinctive spatial patterns were observed for dissolved organic carbon (DOC), dissolved organic nitrogen (DON), and NO₃^? concentrations of streamwater across the watershed. Statistical analyses indicated significant linear relationships between the average TI values of subcatchments and DOC, DON, and NO₃^? concentrations. Furthermore, the proportion of DOC in streamwaters in the wet season increased with TI values relative to other nitrogen species, whereas NO₃^? concentrations decreased with TI. The gradients of soil wetness and the presence of wetlands explained many of the observed spatial and temporal patterns of DOC, DON, and NO₃^? concentrations in the surface waters of the Dorokawa watershed. Our results suggest that the TI is especially useful for predicting the spatial distribution of DOC, DON and NO₃^? in the surface waters of Hokkaido, where topographical relief is moderate and wetlands more common than in other regions of Japan. Copyright © 2006 John Wiley & Sons, Ltd.     

Hydrochemical and sedimentary responses of paired High Arctic watersheds to unusual climate and permafrost disturbance,Cape Bounty,Melville Island,Canada

High Arctic river responses to changing hydroclimatic and landscape processes are poorly understood. In non‐glacierized basins, snowmelt and rainfall generate river discharge, which provides first order control over fluxes. Further factors include the seasonality of precipitation, seasonal active layer development, and permafrost disturbance. These controls were evaluated in terms of sedimentary and biogeochemical fluxes from paired catchments at Cape Bounty, Melville Island, Nunavut during 2006–2009. Results indicate that the source of runoff can be more important than the amount of runoff for sediment, solutes, and organic yields. Although the snowmelt period is typically the most important time for these yields, heavy late summer precipitation events can create disproportionately large yields. Rainfall increases yields because it hydrologically connects areas otherwise isolated. Inorganic solute yields from late summer rainfall are higher because the thick active layer maximizes hydrologic interactions with mineral soils and generates high solute concentrations. Results also indicate that while the catchments are broadly similar, subtle topographic differences result in important inter‐catchment differences in runoff and suspended and dissolved loads. The East watershed, which had less extensive permafrost disturbance, consistently had higher concentrations of dissolved solids. These higher dissolved fluxes cannot therefore be explained by thermokarst features, but rather by deeper active layer development, due to a greater proportion of south‐facing slopes. Although warm temperatures in 2007 led to extensive active layer disturbance in the West watershed, because the disturbances were largely hydrologically disconnected, the total disturbed area was small, and inter‐annual variability in discharge was high, there was no detectable response in dissolved loads to disturbances. Sediment availability increased after 2007, but yields have largely returned to pre‐disturbance levels. Results indicate that seasonality and frequency‐magnitude characteristics of projected increases in precipitation must be considered along with active layer changes to predict the fluvial sedimentary and biogeochemical response to regional climate change. Copyright © 2011 John Wiley & Sons, Ltd.     

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.     

Temporal and spatial variability of cation and silica export in an alpine watershed,Emerald Lake,California

A reaction set of possible mineral weathering reactions is proposed to explain observed cation and silica export for the Emerald Lake watershed, a small Sierra Nevada, California catchment. The reaction set was calculated through a stoichiometric mole‐balance method, using a multiyear record of stream flow and snowpack chemical analyses and site‐specific mineral compositions. Reaction‐set calculations were intended to explore how the processes controlling stream cation and silica export depend on differing bedrock mineralogy across the catchment as snowmelt and runoff patterns change over the year. Different regions within the watershed can be differentiated by lake inflow subdrainages, each exhibiting different stream‐flow chemistry and calculated weathering stoichiometry, indicating that different silica and cation generation processes are dominant in wet steep portions of the catchment. Short‐term differences in stream concentrations were assumed to reflect ion exchange equilibria and rapid biological processes, whereas long‐term persistent stream concentration differences in different areas of the catchment were assumed to reflect spatial variability in mineral weathering stoichiometry. Mineralogical analyses of rock samples from the watershed provided site‐specific chemical compositions of major mineral species for reaction calculations. Reaction sets were evaluated by linear regression of calculated versus observed differences between snowmelt and stream‐flow chemistry and by a combined measure. Initially, single weathering reactions were balanced and evaluated to determine the reactions that best explained observed stream chemical export. Next, reactions were combined, using mineral compositions from different rock types to estimate the dependence of ion fluxes on lithology. The seasonal variability of major solute calculated fluxes is low, approximately one order of magnitude, relative to the observed three orders of magnitude variability in basin discharge. Reaction sets using basin‐averaged lithology and Aplite lithologies gave superior explanations of stream chemical composition. Copyright © 2004 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.     

Evaluating the hydrological and hydrochemical responses of a High Arctic catchment during an exceptionally warm summer

The Arctic has experienced substantial warming during the past century with models projecting continued warming accompanied by increases in summer precipitation for most regions. A key impact of increasing air surface temperatures is the deepening of the active layer, which is expected to alter hydrological processes and pathways. The aim of this study was to determine how one of the warmest and wettest summers in the past decade at a High Arctic watershed impacted water infiltration and storage in deeply thawed soil and solute concentrations in stream runoff during the thaw period. In June and July 2012 at the Cape Bounty Watershed Observatory, we combined active layer measurements with major ion concentrations and stable isotopes in surface waters to characterize the movement of different runoff sources: snowmelt, rainfall, and soil water. Results indicate that deep ground thaw enhanced the storage of infiltrated water following rainfall. Soil water from infiltrated rainfall flowed through the thawed transient layer and upper permafrost, which likely solubilized ions previously stored at depth. Subsequent rainfall events acted as a hydrological flushing mechanism, mobilizing solutes from the subsurface to the surface. This solute flushing substantially increased ion concentrations in stream runoff throughout mid to late July. Results further suggest the importance of rainfall and soil water as sources of runoff in a High Arctic catchment during mid to late summer as infiltrated snowmelt is drained from soil following baseflow. Although there was some evaporation of surface water, our study indicates that flushing from solute stores in the transient layer was the primary driver of increased ion concentrations in stream runoff and not evaporative concentration of surface water. With warmer and wetter summers projected for the Arctic, ion concentrations in runoff (especially in the late thaw season), will likely increase due to the deep storage and subsurface flow of infiltrated water and subsequent flushing of previously frozen solutes to the surface.     

Nutrient concentration patterns in streams draining alpine and subalpine catchments, Fraser Experimental Forest, Colorado

Streamwater samples were collected during 1987–1988 from two adjacent gauged watersheds, the subalpine-alpine East St. Louis and the Fool Creek Alpine, in the Fraser Experimental Forest, Colorado. The study objective was to compare the relationships between streamwater discharge and ion concentration in alpine and alpine-subalpine watersheds at a site receiving low inputs of atmospheric contaminants. Streamwater discharge accounts for much of the variation in ion concentration. Trajectories of time, discharge, and ion concentration suggest that patterns of nutrient flux are controlled primarily by the magnitude of streamwater discharge, and seasonal differences in the relative contributions of snowmelt and soil water. In the subalpine catchment, increased streamwater discharge accounted for most of the decline in concentration of ions, with high concentrations in soil water relative to precipitation. This relationship was not seen in the alpine catchment, probably because of the influence of large diurnal variation in the ratio of snowmelt to soil water. In both catchments, ions with comparatively high concentrations in precipitation and the snowpack relative to soil water showed less concentration decline with increased streamwater discharge. The recurring nature of the trajectories, especially in the subalpine catchment, suggests that the time, discharge, and ion concentration patterns may represent a general characteristic in moderate-sized, undisturbed Rocky Mountain catchments which do not receive high inputs of airborne contaminants.     

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^?.     

On the biogeochemical response of a glacierized High Arctic watershed to climate change: revealing patterns,processes and heterogeneity among micro‐catchments

Our novel study examines landscape biogeochemical evolution following deglaciation and permafrost change in Svalbard by looking at the productivity of various micro‐catchments existing within one watershed. It also sheds light on how moraine, talus and soil environments contribute to solute export from the entire watershed into the downstream marine ecosystem. We find that solute dynamics in different micro‐catchments are sensitive to abiotic factors such as runoff volume, water temperature, geology, geomorphological controls upon hydrological flowpaths and landscape evolution following sea level and glacial changes. Biotic factors influence the anionic composition of runoff because of the importance of microbial SO₄^2? and NO₃^? production. The legacy of glaciation and its impact upon sea level changes is shown to influence local hydrochemistry, allowing Cl^? to be used as a tracer of thawing permafrost that has marine origins. However, we show that a ‘glacial signal’ dominates solute export from the watershed. Therefore, although climatically driven change in the proglacial area has an influence on local ecosystems, the biogeochemical response of the entire watershed is dominated by glacially derived products of rapid chemical weathering. Consequently, only the study of micro‐catchments existing within watersheds can uncover the landscape response to contemporary climate change. Copyright © 2014 John Wiley & Sons, Ltd.     

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.     

Effect of basin physical characteristics on solute fluxes in nine alpine/subalpine basins,Colorado, USA

Alpine/subalpine basins may exhibit substantial variability in solute fluxes despite many apparent similarities in basin characteristics. An evaluation of controls on spatial patterns in solute fluxes may allow development of predictive tools for assessing basin sensitivity to outside perturbations such as climate change or deposition of atmospheric pollutants. Relationships between basin physical characteristics, determined from geographical information system (GIS) tools, and solute fluxes and mineral weathering rates were explored for nine alpine/subalpine basins in Rocky Mountain National Park, Colorado, using correlation analyses for 1993 and 1994 data. Stream‐water nitrate fluxes were correlated positively with basin characteristics associated with the talus environment; i.e., the fractional amounts of steep slopes (≥ 30°), unvegetated terrain and young debris (primarily Holocene till) in the basins, and were correlated negatively with fractional amounts of subalpine meadow terrain. Correlations with nitrate indicate the importance of the talus environment in promoting nitrate flux and the mitigating effect of areas with established vegetation, such as subalpine meadows. Total mineral weathering rates for the basins ranged from about 300 to 600 mol ha^?1 year^?1. Oligoclase weathering accounted for 30 to 73% of the total mineral weathering flux, and was positively correlated with the amount of old debris (primarily Pleistocene glacial till) in the basins. Although calcite is found in trace amounts in bedrock, calcite weathering accounted for up to 44% of the total mineral weathering flux. Calcite was strongly correlated with steep slope, unvegetated terrain, and young debris—probably because physical weathering in steep‐gradient areas exposes fresh mineral surfaces that contain calcite for chemical weathering. Oligoclase and calcite weathering are the dominant sources of alkalinity in the basins. However, atmospherically deposited acids consume much of the alkalinity generated by weathering of calcite and other minerals in the talus environment. Published in 2001 by 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.     

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.     

Effects of compound-specific dilution on transient transport and solute breakthrough: A pore-scale analysis

This pore-scale modeling study in saturated porous media shows that compound-specific effects are important not only at steady-state and for the lateral displacement of solutes with different diffusivities but also for transient transport and solute breakthrough. We performed flow and transport simulations in two-dimensional pore-scale domains with different arrangement of the solid grains leading to distinct characteristics of flow variability and connectivity, representing mildly and highly heterogeneous porous media, respectively. The results obtained for a range of average velocities representative of groundwater flow (0.1–10 m/day), show significant effects of aqueous diffusion on solute breakthrough curves. However, the magnitude of such effects can be masked by the flux-averaging approach used to measure solute breakthrough and can hinder the correct interpretation of the true dilution of different solutes. We propose, as a metric of mixing, a transient flux-related dilution index that allows quantifying the evolution of solute dilution at a given position along the main flow direction. For the different solute transport scenarios we obtained dilution breakthrough curves that complement and add important information to traditional solute breakthrough curves. Such dilution breakthrough curves allow capturing the compound-specific mixing of the different solutes and provide useful insights on the interplay between advective and diffusive processes, mass transfer limitations, and incomplete mixing in the heterogeneous pore-scale domains. The quantification of dilution for conservative solutes is in good agreement with the outcomes of mixing-controlled reactive transport simulations, in which the mass and concentration breakthrough curves of the product of an instantaneous transformation of two initially segregated reactants were used as measures of reactive mixing.     

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.