Sources of stream sulphate in headwater catchments in Otter Creek Wilderness,West Virginia,USA

Upland forested catchments in the Appalachian Plateau region receive among the greatest rates of atmospheric sulphur (S) deposition in the eastern USA, although coal mines and S‐bearing minerals in bedrock may also contribute to stream acidity in this region. Watershed mass balance and stable S isotopic values (δ³⁴S) of sulphate (SO₄^2?) were used to assess the contributions to stream SO₄^2? from atmospheric and lithogenic sources at Yellow Creek (YC), a headwater catchment on the Appalachian Plateau in West Virginia. Oxygen isotopic values (δ¹⁸O) of water were used to study catchment hydrology. Stream output of SO₄^2? was c. 60% of atmospheric S deposition during a relatively dry year, whereas atmospheric S input was nearly balanced by stream output during a year with above normal amounts of precipitation. The temporal patterns and values of δ³⁴S were similar between bulk precipitation and stream water at two upper elevation sites. At the lowest elevation site, stream δ³⁴S values were similar to bulk precipitation values during the dormant season but were slightly lower than precipitation during the low‐flow summer, probably as the result of a greater proportion of stream water being derived from deep hydrological flowpaths that have contacted S‐bearing minerals with low δ³⁴S values in coal seams. Stream δ³⁴S values at YC were significantly higher than at Coal Run, a catchment containing abandoned coal prospects and having a greater amount of S‐bearing minerals than YC. Results suggested that lithogenic S is a relatively minor source and that atmospheric deposition is the principal source of stream SO₄^2?, and thus stream acidity, at YC. Copyright © 2001 John Wiley & Sons, Ltd.     

Evaluating sulfur dynamics during storm events for three watersheds in the northeastern USA: a combined hydrological,chemical and isotopic approach

Concerns related to climate change have resulted in an increasing interest in the importance of hydrological events such as droughts in affecting biogeochemical responses of watersheds. The effects of an unusually dry summer in 2002 had a marked impact on the biogeochemistry of three watersheds in the north‐eastern USA. Chemical, isotopic and hydrological responses with particular emphasis on S dynamics were evaluated for Archer Creek (New York), Sleepers River (Vermont) and Cone Pond (New Hampshire) watersheds. From 1 August to 14 September 2002, all three watersheds had very low precipitation (48 to 69 mm) resulting in either very low or no discharge (mean 0·015, 0·15 and 0·000 mm day^?1 for Archer Creek, Sleepers River and Cone Pond, respectively). From 15 September to 31 October 2002, there was a substantial increase in precipitation totals (212, 246 and 198 mm, respectively) with increased discharge. Archer Creek was characterized by a large range of SO₄^2? concentrations (152 to 389 µeq L^?1, mean = 273 µeq L^?1) and also exhibited the greatest range in δ³⁴S values of SO₄^2? (?1·4 to 8·8 ‰ ). Sleepers River's SO₄^2? concentrations ranged from 136 to 243 µeq L^?1 (mean = 167 µeq L^?1) and δ³⁴S values of SO₄^2? ranged from 4·0 to 9·0 ‰ . Cone Pond's SO₄^2? concentrations (126–187 µeq L^?1, mean = 154 µeq L^?1) and δ³⁴S values (2·4 to 4·3 ‰ ) had the smallest ranges of the three watersheds. The range and mean of δ¹⁸O‐SO₄^2? values for Archer Creek and Cone Pond were similar (3·0 to 8·9 ‰ , mean = 4·5 ‰ ; 3·9 to 6·3 ‰ , mean = 4·9 ‰ ; respectively) while δ¹⁸O‐SO₄^2? values for Sleepers River covered a larger range with a lower mean (1·2 to 10·0 ‰ , mean = 2·5). The difference in Sleepers River chemical and isotopic responses was attributed to weathering reactions contributing SO₄^2?. For Archer Creek wetland areas containing previously reduced S compounds that were reoxidized to SO₄^2? probably provided a substantial source of S. Cone Pond had limited internal S sources and less chemical or isotopic response to storms. Differences among the three watersheds in S biogeochemical responses during these storm events were attributed to differences in S mineral weathering contributions, hydrological pathways and landscape features. Further evaluations of differences and similarities in biogeochemical and hydrological responses among watersheds are needed to predict the impacts of climate change. Copyright © 2008 John Wiley & Sons, Ltd.     

Carbon isotope fractionation of dissolved inorganic carbon (DIC) due to outgassing of carbon dioxide from a headwater stream

The stable isotopic composition of dissolved inorganic carbon (δ¹³C‐DIC) was investigated as a potential tracer of streamflow generation processes at the Sleepers River Research Watershed, Vermont, USA. Downstream sampling showed δ¹³C‐DIC increased between 3–5‰ from the stream source to the outlet weir approximately 0·5 km downstream, concomitant with increasing pH and decreasing PCO₂. An increase in δ¹³C‐DIC of 2·4 ± 0·1‰ per log unit decrease of excess PCO₂ (stream PCO₂ normalized to atmospheric PCO₂) was observed from downstream transect data collected during snowmelt. Isotopic fractionation of DIC due to CO₂ outgassing rather than exchange with atmospheric CO₂ may be the primary cause of increased δ¹³C‐DIC values downstream when PCO₂ of surface freshwater exceeds twice the atmospheric CO₂ concentration. Although CO₂ outgassing caused a general increase in stream δ¹³C‐DIC values, points of localized groundwater seepage into the stream were identified by decreases in δ¹³C‐DIC and increases in DIC concentration of the stream water superimposed upon the general downstream trend. In addition, comparison between snowmelt, early spring and summer seasons showed that DIC is flushed from shallow groundwater flowpaths during snowmelt and is replaced by a greater proportion of DIC derived from soil CO₂ during the early spring growing season. Thus, in spite of effects from CO₂ outgassing, δ¹³C of DIC can be a useful indicator of groundwater additions to headwater streams and a tracer of carbon dynamics in catchments. Copyright © 2007 John Wiley & Sons, Ltd.     

δ53Cr values of catchment runoff exhibit seasonality regardless of bedrock Cr concentrations: Role of periodically changing chromium export fluxes

One pre-requisite for the construction of a global chromium isotope mass balance is detailed understanding of Cr isotope systematics in the critical zone where redox-processes can modify the isotope signature of geogenic Cr input into the hydrosphere. A Cr isotope inventory of bedrock, soil, and runoff was performed in a Central European headwater catchment underlain by amphibolite, situated in the vicinity of two previously studied catchments underlain by different bedrock types (serpentinite and leucogranite). Fresh bedrock in the amphibolite catchment NAZ contained ~300 mg/kg Cr, serpentinite at PLB contained ~800 mg/kg Cr, and leucogranite at LYS contained ~2 mg/kg Cr. Monthly hydrochemical monitoring at all three sites revealed higher Cr(VI) export fluxes in winter than in summer. NAZ was characterized by a distinct seasonality in the δ⁵³Cr values, with minima during winter/spring snowmelts (−0.35‰) and maxima during dry summers (0.40‰). Similar seasonality in δ⁵³Cr values had been reported from PLB and LYS. Bedrock at all three sites had similar Cr isotope composition close to −0.10‰, a value indistinguishable from the δ⁵³Cr value of bulk silicate Earth (BSE). Positive mean δ⁵³Cr value of NAZ runoff indicated Cr-isotope fractionations during weathering of geogenic Cr(III), combined with adsorption of the resulting Cr(VI) on soil particles during pedogenesis. However, the mass-weighted mean δ⁵³Cr of NAZ runoff was lower (−0.08‰), indistinguishable from the Cr isotope signature of bedrock. The same pattern of lower mass-weighted mean δ⁵³Cr values of runoff, compared to arithmetic mean δ⁵³Cr values of runoff, were observed also at PLB and LYS. We suggest that elevated Cr runoff fluxes in winter remove some of the residual isotopically light Cr that accumulated in the soil during summer. Seasonality in runoff δ⁵³Cr values appears to be a relatively widespread phenomenon, de-coupled from Cr availability for chemical weathering.     

Acidification recovery in a changing climate: Observations from thirty-five years of stream chemistry monitoring in forested headwater catchments at the Turkey Lakes watershed,Ontario

Long-term ecosystem studies are valuable for understanding integrated ecosystem response to global changes in atmospheric deposition and climate. We examined trends for a 35-year period (1982/83–2017/18) in concentrations of a range of solutes in precipitation and stream water from nine headwater catchments spanning elevation and surficial geology gradients at the Turkey Lakes watershed (TLW) in northeastern Ontario, Canada. Average annual water year (WY, October to September) concentrations in precipitation significantly declined over the period for sulphate (SO₄²⁻), nitrate (NO₃⁻) and chloride (Cl⁻), while calcium (Ca²⁺) and potassium (K⁺) concentrations increased, resulting in a significant pH increase from 4.2 to 5.7. Trends in stream chemistry through time are generally consistent with expectations associated with acidification recovery. Concentration of many stream water solutes (SO₄²⁻, Cl⁻, calcium [Ca²⁺], magnesium [Mg²⁺] and NH₄⁺ generally decreased, while others (silica [SiO₂] and dissolved organic carbon [DOC]) generally increased. Increases were also observed for alkalinity (six of nine catchments), acid neutralizing capacity ([ANC]; six of nine catchments) and pH (eight of nine catchments), while conductivity declined (six of nine catchments). Variability in trends among catchments are associated with differences in surficial geology and wetland cover. While absolute solute concentrations were generally lower at bedrock dominated high-elevation catchments compared to till dominated lower elevation catchments, the rate of change of concentration was often greater for high elevation catchments. This study confirms continued, but non-linear stream chemistry recovery from acidification, particularly at the less buffered high and moderate elevation sites. The heterogeneity of responses among catchments highlights our incomplete understanding of the relative importance of different mechanisms influencing stream chemistry and the consequences for downstream ecosystems.     

Tracking denudation and sediment production and transport with cosmogenic 10Be in arid,high-altitude Himalayan half-grabens,Zanskar, northern India

Understanding the extent to which local factors, including bedrock and structure, govern catchment denudation in mountainous environments as opposed to broader climate or tectonic patterns provides insight into how landscapes evolve as sediment is generated and transported through them, and whether they have approached steady-state equilibrium. We measured beryllium-10 (¹⁰Be) concentrations in 21 sediment samples from glaciated footwall and hanging wall catchments, including a set of nested catchments, and 12 bedrock samples in the Puga and Tso Morari half-grabens located in the high-elevation, arid Zanskar region of northern India. In the Puga half-graben where catchments are underlain by quartzo-feldspathic gneissic bedrock, bedrock along catchment divides is eroding very slowly, about 5 m/Ma, due to extreme aridity and ¹⁰Be concentrations in catchment sediments are the highest (~60–90 × 10⁵ atoms/g SiO₂) as colluvium accumulates on hillslopes, decoupled from their ephemeral streams. At Puga, ¹⁰Be concentrations and the average erosion rates of a set of six nested catchments demonstrate that catchment denudation is transport-limited as sediment stagnates on lower slopes before reaching the catchment outlet. In the Tso Morari half-graben, gneissic bedrock is also eroding very slowly but ¹⁰Be concentrations in sediments in catchments underlain by low grade meta-sedimentary rocks, are significantly lower (~10–35 × 10⁵ atoms/g SiO₂). In these arid, high-elevation environments, ¹⁰Be concentrations in catchment sediments have more to do with bedrock weathering and transport times than steady-state denudation rates. © 2020 John Wiley & Sons, Ltd.     

Isotopic and hydrochemistry spatial variation of sulfate for groundwater characterization in karstic aquifers

The Sierra Gorda aquifer is one of the most extensive of southern Spain. The main groundwater discharge is produced at its northern boundary through several high‐flow springs. In this study, stable isotopes of dissolved sulfate (δ³⁴S and δ¹⁸O) and groundwater chemistry were used to determine the origin of the sulfate and to characterize the groundwater flow. We sampled the main springs, as well as other minor outlets related to perched water tables, in order to determine the different sources of SO₄^2? (e.g., dissolution of evaporites and atmospheric deposition). The substantial difference in the amount of dissolved SO₄^2? between the springs located in its northwestern part (≈25 mg/L) and those elsewhere in the northern part (≈60 mg/L) suggests zones with separate groundwater flow systems. A third group of springs, far from the northeastern boundary of the permeable outcrops, shows higher SO₄^2? content than the rest (≈125 mg/L). The isotopic range of sulfate (?0.3‰ to 14.82‰ V‐CTD) points to several sources, including dissolution of Triassic or Miocene evaporites, atmospheric deposition, and decomposition of organic material in the soil. Among these, the dissolution of Triassic gypsum—which overlies the saturated zone as a consequence of the folds and faults that deform the aquifer—is the main source of SO₄^2? (range from 12.79‰ to 14.82‰ V‐CTD). This range is typical for Triassic gypsum. The higher karstification in the western sector, together with important differences in the saturated thickness between the western and eastern sectors, would also be due to the tectonic structure and could explain the difference in SO₄^2? contents in the water. This singular arrangement may cause a higher residence time of groundwater in the eastern sector; thus, a higher contact time with Triassic evaporitic rocks is inferred. Accordingly, the stable isotopes of SO₄^2? are found to be a valuable tool for identifying areas with different flow systems in the saturated zone of karstic aquifers, as well as for evaluating aspects such as the degree of karstification .     

Dissolved major ions,Sr and 87Sr/86Sr of coastal lakes from Larsemann hills,East Antarctica: Solute sources and chemical weathering in a polar environment

Dissolved major ions, Sr concentrations and ⁸⁷Sr/⁸⁶Sr ratios of 10 coastal lakes from the Larsemann Hills, East Antarctica have been studied to constrain their solute sources, transport and glacial weathering patterns in their catchments. In absence of perennial river/streams, lakes serve as only reliable archive to study land surface processes in these low-temperature regions. The lake water chemistry is mostly Na-Cl type and it does not show any significant depth variations. Sr isotope compositions of these lakes vary from 0.7110 to 0.7211 with an average value of 0.7145, which is higher than modern seawater value. In addition to oceanic sources, major ions and Sr isotopic data show appreciable amount of solute supply from chemical weathering of silicate rocks in lake catchments and dissolution of Ca-Mg rich salts produced during the freezing of seawaters. The role of sulphide oxidation and carbonate weathering are found to be minimal on lake hydro-chemistry in this part of Antarctica. Inverse model calculations using this chemical dataset provide first-order estimates of dissolved cations and Sr; they are mostly derived from oceanic (seawater + snow) sources (cations approximately 76%) and (Sr approximately 92%) with minimal supplies from weathering of silicates (cations approximately 15%); (Sr approximately 2%) and Ca-rich minerals (cations approximately 9%); (Sr approximately 7%). The silicate weathering rate and its corresponding atmospheric CO₂ consumption rate estimates for Scandrett lake catchment (3.6 ± 0.3 tons/km²/year and 0.5 × 10⁵ moles/km²/year), are lower than that of reported values for the average global river basins (5.4 tons/km²/year and 0.9 × 10⁵ tons/km²/year) respectively. The present study provides a comprehensive report of chemical weathering intensity and its role in atmospheric CO₂ consumption in low-temperature pristine environment of Antarctica. These estimates underscore the importance of Antarctica weathering on atmospheric CO₂ budget, particularly during the past warmer periods when the large area was exposed and available for intense chemical weathering.     

Contrasting carbon export dynamics of human impacted and pristine tropical catchments in response to a short‐lived discharge event

Utilising newly available instrumentation, the carbon balance in two small tropical catchments was measured during two discharge events at high temporal resolution. Catchments share similar climatic conditions, but differ in land use with one draining a pristine rainforest catchment, the other a fully cleared and cultivated catchment. The necessity of high resolution sampling in small catchments was illustrated in each catchment, where significant chemical changes occurred in the space of a few hours or less. Dissolved and particulate carbon transport dominated carbon export from the rainforest catchment during high flow, but was surpassed by degassing of CO₂ less than 4 h after the discharge peak. In contrast, particulate organic carbon dominated export from the cleared catchment, in all flow conditions with CO₂ evasion accounting for 5–23% of total carbon flux. Stable isotopes of dissolved inorganic carbon (DIC) in the ephemeral rainforest catchment decreased quickly from ~1.5 ‰ to ~ ?16 ‰ in 5 h from the flood beginning. A two‐point mixing model revealed that in the initial pulse, over 90% of the DIC was of rainwater origin, decreasing to below 30% in low flow. In the cultivated catchment, δ¹³C_DIC values varied significantly less (?11.0 to ?12.2 ‰) but revealed a complex interaction between surface runoff and groundwater sources, with groundwater DIC becoming proportionally more important in high flow, due to activation of macropores downstream. This work adds to an increasing body of work that recognises the importance of rapid, short‐lived hydrological events in low‐order catchments to global carbon dynamics. Copyright © 2013 John Wiley & Sons, Ltd.     

Origin and chemical and isotopic evolution of dissolved inorganic carbon (DIC) in groundwater of the Okavango Delta,Botswana

The origin and the chemical and isotopic evolution of dissolved inorganic carbon (DIC) in groundwater of the Okavango Delta in semi-arid Botswana were investigated using DIC and major ion concentrations and stable oxygen, hydrogen and carbon isotopes (δD, δ¹⁸O and δ¹³C_DIC). The δD and δ¹⁸O indicated that groundwater was recharged by evaporated river water and unevaporated rain. The river water and shallow (<10 m) groundwater are Ca–Na–HCO₃ type and the deep (≥10 m) groundwater is Na–K–HCO₃ to HCO₃–Cl–SO₄ to Cl–SO₄–HCO₃. Compared to river water, the mean DIC concentrations were 2 times higher in shallow groundwater, 7 times higher in deep groundwater and 24 times higher in island groundwater. The δ¹³C_DIC indicate that DIC production in groundwater is from organic matter oxidation and in island groundwater from organic matter oxidation and dissolution of sodium carbonate salts. The ionic and isotopic evolution of the groundwater relative to evaporated river water indicates two independent pools of DIC.     

Chemistry of streams draining grassland and forest catchments at Plynlimon,mid-Wales

Abstract

The chemistry of streamwater, bulk precipitation, throughfall and soil waters has been studied for three years in two plantation forest and two moorland catchments in mid-Wales. Na and CI are the major ions in streamwater reflecting the maritime influence on atmospheric inputs. In all streams, baseflow is characterised by high pH waters enriched in Ca, Mg, Si and HCO³. Differences in baseflow chemistry between streams reflect the varying extent of calcite and base metal sulphide mineralization within the catchments. Except for K, mean stream solute concentrations are higher in the unmineralized and mineralized forest catchments compared with their respective grassland counterparts. In the forest streams, storm flow concentrations of H⁺ are approximately 1.5 times and Al four times higher than in the moorland streams. Annual catchment losses of Na, Cl, SO⁴, NO³, Al and Si are greatest in the forest streams. In both grassland and forest systems, variations in stream chemistry be explained by mixing waters from different parts of the catchment, although NO³ concentrations may additionally be controlled by N transformations occurring between soils and streams. Differences in stream chemistry and solute budgets between forest and moorland catchments are related to greater atmospheric scavenging by the trees and changes in catchment hydrology consequent on afforestation. Mineral veins within the catchment bedrock can significantly modify the stream chemical response to afforestation.     

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.     

Time-series of δ26Mg values in a headwater catchment reveal decreasing magnesium isotope variability from precipitation to runoff

Data on temporal variability in Mg isotope ratios of atmospheric deposition and runoff are critical for decreasing the uncertainty associated with construction of isotope mass balances in headwater catchments, and statistical evaluation of isotope differences among Mg pools and fluxes. Such evaluations, in turn, are needed to distinguish between biotic and abiotic contributions to Mg²⁺ in catchment runoff. We report the first annual time-series of δ²⁶Mg values simultaneously determined for rainfall, canopy throughfall, soil water and runoff. The studied 55-ha catchment, situated in western Czech Republic, is underlain by Mg-rich amphibolite and covered by mature spruce stands. Between 1970 and 1996, the site received extremely high amounts of acid deposition and fly ash form nearby coal-burning power plants. The δ²⁶Mg values of open-area precipitation (median of −0.79‰) at our study site were statistically indistinguishable from the δ²⁶Mg values of throughfall (−0.73‰), but significantly different from the δ²⁶Mg values of soil water (−0.55‰) and runoff (−0.55‰). The range of δ²⁶Mg values during the observation period decreased in the order: open-area precipitation (0.57‰) > throughfall (0.27‰) > runoff (0.21‰) > soil water (0.16‰). The decreasing variability in δ²⁶Mg values of Mg²⁺ from precipitation to soil water and runoff reflected an increasing homogenization of atmospheric Mg in the catchment and its mixing with geogenic Mg. In addition to atmospheric Mg, runoff also contained Mg mobilized from the three major solid Mg pools, bedrock (δ²⁶Mg of −0.32‰), soil (−0.28‰), and vegetation (−0.31‰). The drought of summer 2019 did not affect the nearly constant δ²⁶Mg value of runoff. Collectively, our data show that within-catchment processes buffer the Mg isotope variability of the atmospheric input.     

Isotopic composition of precipitation in a topographically steep,seasonally snow‐dominated watershed and implications of variations from the global meteoric water line

The local meteoric water line (LMWL), the functional relationship between locally measured values of δ¹⁸O and δ²H in precipitation, represents the isotopic composition of water entering hydrologic systems. The degree to which the LMWL departs from the global meteoric water line (GMWL), moreover, can reveal important information about meteoric sources of water (e.g. oceanic or terrestrial) and atmospheric conditions during transport. Here we characterize the isotopic composition of precipitation within an experimental watershed in the Western US that is subject to large topographic and seasonal gradients in precipitation. Interpreting the hydrometeorologic and spatial controls on precipitation, we constructed a seasonally weighted LMWL for southwestern Idaho that is expressed by the equation δ²H = 7.40 × δ¹⁸O ? 2.17. A seasonally weighted LMWL that is based on weighting isotopic concentrations by climatic precipitation volumes is novel, and we argue better represents the significant seasonality of precipitation in the region. The developed LMWL is considerably influenced by the semiarid climate experienced in southwest Idaho, yielding a slope and y‐intercept lower than the GMWL (δ²H = 8 × δ¹⁸O + 10). Moderate to strong correlations exist between the isotopic composition of precipitation from individual events and surface meteorologic variables, specifically surface air temperature, relative humidity, and precipitation amount. A strong negative correlation exists between the annual average isotopic composition of precipitation and elevation at individual collection sites, with a lapse rate of ?0.22‰/100 m. Copyright © 2016 John Wiley & Sons, Ltd.     

Mass‐balance modeling of mineral weathering rates and CO2 consumption in the forested,metabasaltic Hauver Branch watershed,Catoctin Mountain,Maryland, USA

Mineral weathering rates and a forest macronutrient uptake stoichiometry were determined for the forested, metabasaltic Hauver Branch watershed in north‐central Maryland, USA. Previous studies of Hauver Branch have had an insufficient number of analytes to permit determination of rates of all the minerals involved in chemical weathering, including biomass. More equations in the mass‐balance matrix were added using existing mineralogic information. The stoichiometry of a deciduous biomass term was determined using multi‐year weekly to biweekly stream‐water chemistry for a nearby watershed, which drains relatively unreactive quartzite bedrock. At Hauver Branch, calcite hosts ~38 mol% of the calcium ion (Ca²⁺) contained in weathering minerals, but its weathering provides ~90% of the stream water Ca²⁺. This occurs in a landscape with a regolith residence time of more than several Ka (kiloannum). Previous studies indicate that such old regolith does not typically contain dissolving calcite that affects stream Ca²⁺/Na⁺ ratios. The relatively high calcite dissolution rate likely reflects dissolution of calcite in fractures of the deep critical zone. Of the carbon dioxide (CO₂) consumed by mineral weathering, calcite is responsible for approximately 27%, with the silicate weathering consumption rate far exceeding that of the global average. The chemical weathering of mafic terrains in decaying orogens thus may be capable of influencing global geochemical cycles, and therefore, climate, on geological timescales. Based on carbon‐balance calculations, atmospheric‐derived sulfuric acid is responsible for approximately 22% of the mineral weathering occurring in the watershed. Our results suggest that rising air temperatures, driven by global warming and resulting in higher precipitation, will cause the rate of chemical weathering in the Hauver Branch watershed to increase until a threshold temperature is reached. Beyond the threshold temperature, increased recharge would produce a shallower groundwater table and reduced chemical weathering rates. Copyright © 2013 John Wiley & Sons, Ltd.     

Linking transit times to catchment sensitivity to atmospheric deposition of acidity and nitrogen in mountains of the western United States

Transit times are hypothesized to influence catchment sensitivity to atmospheric deposition of acidity and nitrogen (N) because they help determine the amount of time available for infiltrating precipitation to interact with catchment soil and biota. Transit time metrics, including fraction of young water (F_yw) and mean transit time (MTT), were calculated for 11 headwater catchments in mountains of the western United States based on differences in the amplitude of the seasonal signal of δ¹⁸O in streamflow and precipitation. Results were statistically compared with catchment characteristics to elucidate controlling mechanisms. Transit times also were compared with stream solute concentrations to test the hypothesis that transit times are a primary influence on weathering rates and biological assimilation of atmospherically deposited N. Results indicate that transit times in the study catchments are strongly related to soil, vegetation, and topographic characteristics, with barren terrain (bare rock and talus) and steep slopes linked to high F_yw and short MTT, whereas forest soil (hydrogroup B) was linked to low F_yw and greater MTT. Concentrations of silicate weathering products (Na⁺ and Si) were negatively related to F_yw and barren terrain, and positively related to MTT and forest soil, supporting the concept that weathering fluxes and buffering capacity tend to be low in alpine areas due to short transit times. Nitrate concentrations were positively related to N deposition, catchment slope, and barren terrain, and negatively related to forest, indicating that hydrologic and/or biogeochemical processes associated with steep slopes limit uptake of atmospherically deposited N by biota. Interannual and seasonal variability in transit times and source water contributions in the study catchments was substantial, reflecting the influence of strong temporal variations in snowmelt inputs in high‐elevation catchments of the western United States. Results from this study confirm that short transit times in these areas are a key reason they are highly sensitive to atmospheric pollution and climate change.     

Use of stable water isotopes to identify hydrological processes of meteoric water in montane catchments

This study analyzes the stable isotopic compositions of hydrogen and oxygen (δ²H, δ¹⁸O) in montane meteoric waters including precipitation and stream water of central Taiwan to identify hydrological processes in montane catchments. Results of precipitation demonstrate that monsoon and altitude effects are two principal processes affecting δ and deuterium excess (d^E) values of inland precipitation in central Taiwan. Furthermore, slope and intercept values of summer and winter local meteoric water line are modified by secondary evaporation effects such as moisture recycling and raindrop evaporation. Additionally, stream water's results indicate that differences in δ values among stream waters reflect isotopic altitude effect whereby lower values are more evident in stream water originating from high‐elevation catchments than low‐elevation catchments. Comparison of the isotopic results between precipitation and stream water indicates that summer precipitation containing recycled moisture is the most important water source for the studied stream waters and indicates that catchment effect and base flow contribution are the two major hydrological processes affecting mountain stream hydrology. The hydrological processes identified by the isotopic study re‐stress the important role of forests in mountain hydrology. Copyright © 2015 John Wiley & Sons, Ltd.     

Factors controlling the major ion chemistry of streams in the blue ridge and valley and ridge physiographic provinces of Virginia and Maryland

The factors controlling the chemistry of 69 low-order streams in the Blue Ridge and Valley and Ridge physiographic provinces of Virginia and Maryland were studied over a 13-month period. Principal component analysis was used to examine regional patterns in stream chemistry and to examine the degree to which the chemistry of low-order streams is controlled by the bedrock upon which they flow. Streams clustered into regionally isolated groups, strongly related to bedrock type, with SO^2?₄ and HCO^?₃ the chemical variables of most importance. Sulphate concentrations appear to be strongly controlled by climate and hydrology, and sorption in the soils within the watershed. Much of the atmospherically derived SO^2?₄ accumulates in watersheds during the growing season and is later flushed out. Weathering reactions were found to be particularly important in the production of HCO^?₃, accounting for 91 per cent on an annual basis, and export of divalent cations from these watersheds, accounting for 48–50 per cent on an annual basis. About half of non-anthropogenic Na⁺ was derived from weathering of silicates, whereas nearly all K⁺ was identified with leaching by SO^2?₄. Water chemistry was strongly related to the rock type in the watershed and the weatherability of the component minerals. Rock type is not a randomly distributed function; instead, it is controlled by geologic factors that result in clusters of similar rock types in a given region. When planning large synoptic studies, it is extremely important to consider that a sampling scheme based on random sampling of a non-randomly distributed function May, not provide the most accurate representation of the variables of interest. Instead, a hierarchical sampling scheme May, be indicated. Our results also suggest that, although one sample in time May, be sufficient to characterize the primary geochemical factors controlling stream chemistry throughout the year, it May, not be sufficient to detect subtle, flow-related alterations in chemistry.     

Continuous monitoring of stream δ18O and δ2H and stormflow hydrograph separation using laser spectrometry in an agricultural catchment

A portable Wavelength Scanned‐Cavity Ring‐Down Spectrometer (Picarro L2120) fitted with a diffusion sampler (DS‐CRDS) was used for the first time to continuously measure δ¹⁸O and δ²H of stream water. The experiment took place during a storm event in a wet tropical agricultural catchment in north‐eastern Australia. At a temporal resolution of one minute, the DS‐CRDS measured 2160 δ¹⁸O and δ²H values continuously over a period of 36 h with a precision of ±0.08 and 0.5‰ for δ¹⁸O and δ²H, respectively. Four main advantages in using high temporal resolution stream δ¹⁸O and δ²H data during a storm event are highlighted from this study. First, they enabled us to separate components of the hydrograph, which was not possible using high temporal resolution electrical conductivity data that represented changes in solute transfers during the storm event rather than physical hydrological processes. The results from the hydrograph separation confirm fast groundwater contribution to the stream, with the first 5 h of increases in stream discharge comprising over 70% pre‐event water. Second, the high temporal resolution stream δ¹⁸O and δ²H data allowed us to detect a short‐lived reversal in stream isotopic values (δ¹⁸O increase by 0.4‰ over 9 min), which was observed immediately after the heavy rainfall period. Third, δ¹⁸O values were used to calculate a time lag of 20 min between the physical and chemical stream responses during the storm event. Finally, the hydrograph separation highlights the role of event waters in the runoff transfers of herbicides and nutrients from this heavily cultivated catchment to the Great Barrier Reef. Copyright © 2015 John Wiley & Sons, Ltd.     

Sulfur and carbon isotopic systematics of Guadalupian‐Lopingian (Permian) mid‐Panthalassa: δ34S and δ13C profiles in accreted paleo‐atoll carbonates in Japan

Immediately before the extinction of the end‐Guadalupian (Middle Permian; ca 260 Ma), a significant change to the global carbon cycle occurred in the superocean Panthalassa, as indicated by a prominent positive δ¹³C excursion called the Kamura event. However, the causes of this event and its connection to the major extinction of marine invertebrates remain unclear. To understand the mutual relationships between these changes, we analyzed the sulfur isotope ratio of the carbonate‐associated sulfate (CAS) and HCl‐insoluble residue, as well as the carbon isotope ratio of bulk organic matter, for the Middle‐Upper Permian carbonates of an accreted mid‐oceanic paleo‐atoll complex from Japan, where the Kamura event was first documented. We detected the following unique aspects of the stable carbon and sulfur isotope records. First, the extremely high δ¹³C values of carbonate (δ¹³C_carb) over +5 ‰ during the Capitanian (late Guadalupian) were associated with large isotopic differences between carbonate and organic matter (Δ¹³C = δ¹³C_carb ? δ¹³C_org). We infer that the Capitanian Kamura event reflected an unusually large amount of dissolved organic matter in the expanded oxygen minimum zone at mid‐depth. Second, the δ³⁴S values of CAS (δ³⁴S_CAS) were inversely correlated with the δ¹³C_carb values during the Capitanian to early Wuchiapingian (early Late Permian) interval. The Capitanian trend may have appeared under increased oceanic sulfate conditions, which were accelerated by intense volcanic outgassing. Bacterial sulfate reduction with increased sulfate concentrations in seawater may have stimulated the production of pyrite that may have incorporated iron in pre‐existing iron hydroxide/oxide. This stimulated phosphorus release, which enhanced organic matter production and resulted in high δ¹³C_carb. Low δ³⁴S_CAS values under high sulfate concentrations were maintained and the continuous supply of sulfate cannot by explained only by the volcanic eruption of the Emeishan Trap, which has been proposed as a cause of the extinction. The Wuchiapingian δ³⁴S_CAS–δ¹³C_carb correlation, likely related to low sulfate concentration, may have been caused by the removal of oceanic sulfate through the massive evaporite deposition.