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.     

Evidence for influence of mineral weathering on stream water sulphate in Vermont and New Hampshire (USA)

Mass balance studies in forested catchments in the northeastern USA show that S losses via streamwater SO₄^2? exceed measured atmospheric S inputs. Possible sources of the excess S loss include underestimated dry deposition, mineralization of organic S in soils, desorption of soil sulphate, oxidation of recently formed sulphides and mineral weathering. Evaluating the relative contribution of these sources and processes to SO₄^2? export is important to our understanding of S cycling as well as to policy makers in their evaluation of the efficacy of S emission controls. In order to evaluate the potential for mineral weathering contributions to SO₄^2? export, we measured concentration and isotopic composition (δ³⁴S and δ¹⁸O) of SO₄^2? in stream water, and concentration and δ³⁴S values of four S fractions in bedrock and soil parent material in catchments of varying geological composition. Geological substrates with low S concentrations were represented by catchments underlain by quartzite and granite, whereas geological substrates with high S concentrations were represented by catchments underlain by sulphidic slate, schist and metavolcanic rocks. Catchments with S‐poor bedrock had stream‐water SO₄^2? concentrations <100 µeq L^?1 and isotopic values consistent with those of atmospheric SO₄^2? that had been cycled through the organic soil pool. Catchments with S‐rich bedrock had stream‐water SO₄^2? concentrations ranging from 56 to 229 µeq L^?1. Isotopic values deviated from those of SO₄^2? in atmospheric deposition, clearly indicating a mineral weathering source in some cases, whereas in others spatial variability of mineral δ³⁴S values precluded the isotopic detection of a weathering contribution. These results, along with evidence suggesting formation of secondary sulphate minerals in bedrock weathering rinds, indicate that mineral weathering may be an important source of S in the surface waters of some forested catchments in the northeastern USA. Copyright © 2004 John Wiley & Sons, Ltd.     

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.     

淮北临涣矿采煤沉陷区不同水体水化学特征及其影响因素

为研究淮北临涣矿采煤沉陷区不同水体的补给水源及溶质来源,在现场调查的基础上,系统采集丰水期、平水期、枯水期沉陷区积水、地表河水和浅层地下水样进行测试分析,采用Piper三线图、Gibbs图和因子分析方法,对不同水体水化学特征及其影响因素进行讨论.结果表明:地表水水体总溶解性固体(TDS)质量浓度表现为枯水期丰水期平水期,浅层地下水表现为枯水期平水期丰水期,地表水TDS质量浓度明显高于浅层地下水.地表水中主要阴阳离子为Na~+、Cl~-和SO_4~(2-),水化学类型主要为SO_4~(2-)-Cl~--Na~+型;浅层地下水离子以HCO_3~-、Ca~(2+)和Mg~(2+)为主,表现为HCO_3~--Ca~(2+)-Mg~(2+)型.结合Gibbs图和因子分析可知,地表水受蒸发作用、地表径流以及采煤活动等因素影响,浅层地下水在一定程度上体现出大气降水和地表水补给的特点,受岩石风化作用影响较为明显.     

Isotope hydrology of a tropical coffee agroforestry watershed: Seasonal and event‐based analyses

Stable isotope variations are extremely useful for flow partitioning within the hydrologic cycle but remain poorly understood throughout the tropics, particularly in watersheds with rapidly infiltrating soils, such as Andisols in Central America. This study examines the fluctuations of stable isotope ratios (δ¹⁸O and δ²H) in the hydrologic components of a tropical coffee agroforestry watershed (~1 km²) with Andisol soils in Costa Rica. Samples were collected in precipitation, groundwater, springs, and stream water over 2 years. The local meteoric water line for the study site was δ²H = 8.5 δ¹⁸O + 18.02 (r² = 0.97, n = 198). The isotope ratios in precipitation exhibited an enriched trend during the dry season and a notable depletion at the beginning of the wet season. The δ¹⁸O compositions in groundwater (average = ?6.4‰, σ = 0.7) and stream water (average = ?6.7‰, σ = 0.6) were relatively stable over time, and both components exhibited more enriched values in 2013, which was the drier year. No strong correlation was observed between the isotope ratios and the precipitation amount at the event or daily time‐step, but a correlation was observed on a monthly scale. Stream water and base flow hydrograph separations based on isotope end‐member estimations showed that pre‐event water originating from base flow was prevalent. However, isotope data indicate that event water originating from springs appears to have been the primary driver of initial rises in stream flow and peak flows. These results indicate that isotope sampling improves the understanding of water balance components, even in a tropical humid location, where significant variations in rainfall challenge current modelling efforts. Further research using fine‐scale hydrometric and isotopic data would enhance understanding the processes driving spring flow generation in watersheds.     

太湖流域降雨和湖水酸根阴离子长期变化及其环境意义

为揭示太湖流域降雨和湖水酸根阴离子长期变化特征及环境意义,通过历史数据收集和采样分析,对太湖流域降雨和湖水中的SO₄^2-、NO₃^-变化特征和来源进行了研究.结果表明：自1990s以来太湖流域降雨中SO₄^2-呈显著下降趋势,年平均下降率为0.28 mg/（L·a）;NO₃^-浓度却呈显著上升趋势,年平均增长率为0.05 mg/（L·a）,降雨中氮污染呈现加重的趋势.与之相反,湖水中SO₄^2-呈显著上升趋势,年平均增长率为1.24 mg/（L·a）;NO₃^-浓度却呈显著下降趋势,年平均下降率为0.02 mg/（L·a）.30年以来,太湖水体SO₄^2-/NO₃^-比值不断升高,远高于降水SO₄^2-/NO₃^-比值.研究认为：流域SO₂排放引起的酸沉降是湖水SO₄^2-浓度增长的最重要原因,但氮氧化物排放并未引起湖水NO₃^-浓度升高,说明太湖流域对大气沉降的氮氧化物有滞留作用,而太湖水体是流域大气沉降硫酸盐的重要汇.综合治理太湖流域酸性物质排放对防止太湖水体酸化和治理富营养化都具有重要意义.     

Trace element and major ion concentrations and dynamics in glacier snow and melt: Eliot Glacier,Oregon Cascades

We present concentrations of environmentally available (unfiltered acidified 2% v/v HNO₃) As, Cu, Cd, Pb, V, Sr, and major ions including Ca²⁺, Cl^?, and SO₄^2? in a July 2005 and a March 2006 shallow snow profile from the lower Eliot Glacier, Mount Hood, Oregon, and its proglacial stream, Eliot Creek. Low enrichment factors (EF) with respect to crustal averages suggests that in fresh March 2006 snow environmentally available elements are derived primarily from lithogenic sources. Soluble salts occurred in lower and less variable concentrations in July 2005 snow than March 2006. Conversely, environmentally available trace elements occurred in greater and more variable concentrations in July 2005 than March 2006 snow. Unlike major solutes, particulate‐associated trace elements are not readily eluted during the melt season. Additionally, elevated surface concentrations suggest that they are likely added throughout the year via dry deposition. In a 1‐h stream sampling, ratios of dissolved (<0·45 µm) V:Cl^?, Sr:Cl^?, and Cu:Cl^? are enriched in the Eliot Stream with respect to their environmentally available trace element to Cl^? ratios in Eliot Glacier snow, suggesting chemical weathering additions in the stream waters. Dissolved Pb:Cl^? is depleted in the Eliot Stream with respect to the ratio of environmentally available Pb to Cl^? in snow, corresponding to greater adsorption onto particles at greater pH values. Copyright © 2009 John Wiley & Sons, Ltd.     

Snow and stream-water chemistry of the Ganga headwater basin,Garhwal Himalaya,India

Abstract

Studies of the chemical composition of snowpack and stream water were carried out in a catchment having an area of 53km² (31°03′-30°55′N and 78°40′-78°51′E) in the Garhwal Himalaya, India. The dominant ions in the snowpack and stream water were Ca²⁺, Na⁺, NO^? ₃, SO^2- ₄ and HCO^? ₃. Solute patterns in the snowpack show preferential elution. Investigation of the chemical composition of stream water shows that meltwater changes its composition substantially as it passes through soil pathways to the stream. The groundwater flushing perhaps controls the chemical composition of meltwater in the early spring. However, in the period from July to September, the stream water carries the chemical signature of monsoonal precipitation.     

The GEOMON network of Czech catchments provides long-term insights into altered forest biogeochemistry: From acid atmospheric deposition to climate change

In 1994, a network of small catchments (GEOMON) was established in the Czech Republic to determine input–output element fluxes in semi-natural forest ecosystems recovering from anthropogenic acidification. The network consists from 16 catchments and the primary observations of elements fluxes were complemented by monitoring of biomass stock, element pools in soil and vegetation, and the main water balance components. Over last three decades, reductions of SO₂, NO_x and NH₃ emissions were followed by sulphur (S) and nitrogen (N) deposition reductions of 75% and 30%, respectively. Steeper declines of strong acid anion concentrations compared to cations (Ca, Mg, Na, K, NH₄) in precipitation resulted in precipitation pH increase from 4.5 to 5.2 in bulk precipitation and from 4.0 to 5.1 in spruce throughfall. Stream chemistry responded to changes in deposition: S leaching declined. However at majority of catchments soils acted as a net source of S to runoff, delaying recovery. Stream pH increased at acidic streams (pH < 6) and aluminium concentration decreased. Stream nitrate (NO₃) concentration declined by 60%, considerably more than N deposition. Stream NO₃ concentration was tightly positively related to stream total dissolved nitrogen to total phosphorus (P) ratio, suggesting the role of P availability on N retention. Trends in dissolved organic carbon fluxes responded to both acidification recovery and to runoff temporal variation. An exceptional drought occurred between 2014 and 2019. Over this recent period, streamflow decreased by ≈ 40% on average compared to 1990s, due to the increases of soil evaporation and vegetation transpiration by ≈ 30% and declines in precipitation by ≈ 15% on average across the elevational gradient. Sharp decreases of stream runoff at catchments <650 m a.s.l. corresponded to areas of recent forest decline caused by bark beetle infestation on drought stressed spruce forests. Understanding of the interactions among legacies of acidification and eutrophication, drought effects on the water cycle and forest disturbance dynamics is requisite for effective management of forested ecosystems under anthropogenic influence.     

SULPHATE DYNAMICS IN RELATION TO GROUNDWATER–SURFACE WATER INTERACTIONS IN HEADWATER WETLANDS OF THE SOUTHERN CANADIAN SHIELD

The spatial and temporal distribution of sulphate (SO₄) concentrations in peat pore water and the outlet streams of two forested swamps was related to variations in the magnitude of upland runoff, wetland water levels and flow path. The swamps were located in headwater catchments with contrasting till depths typical of the southern Canadian Shield. Inputs of SO₄ from shallow hillslope tills and streams showed little seasonal variation in either source or concentration in both swamps. Sulphate dynamics at the outlet stream reflected hydrological and biogeochemical processes within the valley wetlands, which in turn were partly controlled by catchment hydrogeology. During high runoff, maximum water table elevations and peak surface flow in the swamps resulted in upland inputs largely bypassing anoxic peat. Consequently, SO₄ concentrations of 8–10 mg/l at the swamp outlets were similar to stream and groundwater inputs. During periods of low flow, concentrations of SO₄ at the swamp outlets declined to less than 3 mg/l. At this time lower water table elevations resulted in increased interaction of input water with anoxic peats, and therefore, SO₄ reduction. Contrasts in till depth and the nature of groundwater flow between catchments resulted in differences in SO₄ dynamics between years and swamps. In dry summers the absence of groundwater inputs to the swamp in the catchment with thin till resulted in a large water table drawdown and re-oxidation of accumulated S, which contributed to maximum SO₄ concentrations (up to 35 mg/l) during storm runoff. Continuous groundwater input to the swamp in the catchment with deeper till was critical to maintaining saturated surfaces and efficient SO₄ retention during both dry and wet summers. A conceptual model of wetland SO₄ retention and export, based on catchment hydrogeology, is developed to generalize the SO₄ dynamics of valley bottom wetlands at the landscape scale. © 1997 by John Wiley & Sons, Ltd.     

Sources and sinks of sea salt in a newfoundland blanket bog

Over an oceanic peatland, the concentration of Na in fog averaged 38.1 mgl^?1 compared with 1.8 mgl^?1 in rain, resulting in a significant flux of mineral elements to the surface. Between 16 May and 20 June 1990 the average mass flux of Na to the bog surface by fog, rain, and dry deposition was 21.9, 10.4 and 7.0 mg m^?2 d^?1. There was little long-term storage of Na within the peatland system, where Na losses measured in stream runoff averaged 34.8 mg m² d^?1, and deep groundwater losses 4 mg m^?2 d^?1. Calcium and Mg were preferentially retained in the organic soil, whereas K was relatively mobile. Potassium tended to become concentrated in the unsaturated zone. Stream runoff had a consistently higher pH than groundwater, corresponding to higher Ca and Mg concentrations, which may have been from mineral sources in the headwater ponds. Otherwise, the stream water chemistry was closely related to groundwater in the upper layers of the peat deposit.     

What can be deduced from chemical measurement in an open-field raingauge? An example in the Maures Massif,southeastern France

Abstract

The deposition of chemical elements in a catchment occurs through three different processes: wet, dry and cloud deposition. Total deposition cannot be inferred from measurements made with open-field raingauges, and still constitutes a challenge to scientific method. The chemical composition of samples from an open-field raingauge (bulk precipitation) was analysed over a period of several years in a small Mediterranean catchment in the Maures Massif, France. The input of chloride measured in this way was two times lower than the output, despite the fact that this element is reputed to be conservative, which means input and output should roughly balance. This implies that input has previously been underestimated. Analysis of the bulk precipitation data was carried out taking into account both the history of rain events and of sampling. This study allowed the relative parts of the different deposition processes to be quantified. Dry deposition can provide from 20% to more than 80% of the anthropogenic and terrigenic elements (Ca²⁺, Mg²⁺, K⁺, NO₃ ^?, SO₄ ^2-, SiO₂) to the rain samples. The occult deposition of marine elements on the catchment area (50% of total deposition) was found to be mostly due to cloud deposition during wet periods.     

Assessing the role of forests in mitigating eutrophication downstream of pasture during spring snowmelt

Little research has examined whether forests reduce stream water eutrophication in agricultural areas during spring snowmelt periods. This study evaluated the role of forests in ameliorating deteriorated stream water quality in agricultural areas, including pasture, during snowmelt periods. Temporal variation in stream water quality at a mixed land‐use basin (565 ha: pasture 13%, forestry 87%), northern Japan, was monitored for 7 years. Synoptic stream water sampling was also conducted at 16 sites across a wide range of forest and agricultural areas in a basin (18.3 km²) in spring, summer and fall. Atmospheric nitrogen (N) and phosphorus (P) deposition were measured for 4 years. The results showed that concentration pulses of nitrate, organic N and total P in stream water were observed when discharge increased during spring snowmelt. Their concentrations were high when silicate concentrations were low, suggesting surface water exported from pasture largely contributed to stream water pollution during snowmelt. Atmospheric N and P deposition (4.1 kg N ha^?1 y^?1; 0.09 kg P ha^?1 y^?1, respectively) was too low to affect the background concentrations of N and P in streams from forested areas. Reduction of eutrophication caused by nutrients from pasture was mainly due to dilution by water containing low concentrations of N and P exported from forested areas, whereas in‐stream reduction was not a dominant process. Results indicate that forests have a limited capacity to reduce the concentration pulses of N and P in stream water during snowmelt in this study basin. Copyright © 2014 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 .     

Downstream composition changes of acidic volcanic waters discharged into the Banyupahit stream, Ijen caldera, Indonesia

The crater lake of Kawah Ijen volcano contains extremely low pH (<0.4) waters with high SO₄ (70000 mg/kg), Cl (21000 mg/kg), F (1500 mg/kg), Al (5000 mg/kg), Fe (2000 mg/kg) and trace metal (Cu 0.5, Zn 4, Pb 3 mg/kg) contents. These brines seep outward through the western crater rim and reappear on the other side as streamlets, which form the headwaters of the Banyupahit stream. The Banyupahit first mixes with fresh rivers and thermal springs in the Ijen caldera and then irrigates a coastal agricultural plain which is 30 km from the summit crater.We discuss the downstream composition changes affecting the Banyupahit waters by using stable isotope, chemical and mineralogical data collected from sites along the stream length. The saturation of the stream waters with respect to minerals was evaluated with SOLVEQ and WATEQ4F and compared with the geochemical observations. An aluminous mineralogy (alunogen, pickeringite, tamarugite and kalinite) develops in the upper part of the Banyupahit due to concentration of the headwaters by evaporation. Downstream attenuation of dissolved element concentrations results principally from dilution and from mineral precipitation. The stream pH changes from 0 at the source to >4 close to the mouth. The δD and δ¹⁸O values and the relative SO₄–Cl–F contents of the Banyupahit waters indicate that the tributaries are mostly meteoric. Dissolved SO₄ in the acidic stream come only from the crater lake seepages and are not involved later in microbially mediated reactions, as shown by their δ³⁴S and δ¹⁸O values. Re-equilibration of the stream SO₄ oxygen-isotope composition with H₂O from tributaries does not occur.Calcium, SiO₂, Al, Fe, K and SO₄ behave non-conservatively in the stream waters. Gypsum, silica (amorphous or poorly ordered), a basic aluminum hydroxysulfate (basaluminite?), K-jarosite and amorphous ferric hydroxide may exert a solubility control on these elements along the entire stream length, or in certain stream sections, consistent with the thermochemical model results. Downstream concentration trends and mineral saturation levels suggest that precipitation of Sr-, Pb-rich barite and celestite consume Ba, Sr and Pb, whereas dissolved Cu, Pb and Zn may adsorb onto solid particles, especially after the junctions of the acidic stream with non-acidic rivers. We calculated that significant fluxes of SO₄, F, Cl, Al, SiO₂, Ti, Mn and Cu may reach the irrigation system, possibly causing serious environmental impacts such as soil acidification and induration.     

Factors controlling the acid‐neutralizing capacity of Japanese cedar forest watersheds in stands of various ages and topographic characteristics

Acid‐neutralizing capacity (ANC) is an important index for streamwater acidification caused by external factors (i.e. chronic acid deposition) and internal factors such as soil acidification due to nitrification. In this study, the influence of forest clear‐cutting and subsequent regrowth on internal acidification was investigated in central Japan, where stream pH (near 7·0) and ANC (above 0·1 meq L^?1) are high. pH, the concentrations of major cations (Na⁺, K⁺, Mg²⁺ and Ca²⁺), major anions (NO₃^?, Cl^? and SO₄^2?) and dissolved silica (Si), and ANC were measured in 33 watersheds of various stand ages, during 2002 to 2004. Only NO₃^? concentration decreased with stand age, whereas pH, ANC, and concentrations of the sum of base cations (BC) and Si were negatively correlated with the minimum elevation of the watershed. The correlation between the BC/Si ratio and minimum elevation suggested that factors contributing to acid neutralization changed at 1100 m above sea level. In watersheds at lower elevations (?1100 m), the relatively high contribution of soil water with longer soil contact times should result in higher ANC, and cation exchange reactions should be the dominant process for acid neutralization due to deposition of colluvial soils on the lower slope. In contrast, in higher‐elevation watersheds (≥1100 m), weathered residual soils are thin and the small contribution of deeper groundwater results in lower ANC. These results suggest that the local acid sensitivity is determined by the hydrological and geomorphologic factors generated by steep topography. Copyright © 2008 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^?.     

Temporal trends of bulk precipitation and stream water chemistry (1977–1997) in a small forested area,Krusné hory,northern Bohemia,Czech Republic

The Krusné hory (Erzgebirge or Ore Mountains) has been heavily affected by high atmospheric pollutant deposition caused by fossil fuel combustion in an adjacent Tertiary coal basin. Long‐term routine sampling of bulk precipitation (1977–1996) and stream water (1977–1998) in a forested area on the south‐eastern slope of the mountains were used to evaluate trends and patterns in solute concentration and flux with respect to controlling processes. From 1977 to 1996, the annual volume‐weighted Ca²⁺ and SOconcentrations decreased in bulk precipitation. However, after 1989, when a pronounced and continuous decrease occurred in coal production, annual volume‐weighted concentrations decreased for most solutes, except H⁺. The concentration decreases were marked, with 1996 levels at or below 50% of those in 1989. The lack of a trend in H⁺ is attributed to similar decreases in both acid anions and neutralizing base cations. Stream water concentrations of most solutes, i.e. H⁺, Ca²⁺, Mg²⁺, SONOwere highest at the onset of sampling in 1977, decreased markedly from 1977 to 1983 and decreased more gradually from 1983 to 1998. The spruce forest die‐back and removal reduced dry deposition of these solutes by reducing the filtering action, which was provided by the forest canopy. A notable decrease in stream water Ca²⁺ concentrations occurred after 1995 and may be due to the depletion of Ca²⁺, which was provided by catchment liming in 1986, 1988 and 1989. Solute flux trends in bulk atmospheric deposition and stream water generally were not significant and the lack of trend is attributed to the large interannual variability in precipitation quantity and runoff, respectively. All solutes except Na⁺ varied seasonally. The average seasonal concentrations varied between the solutes, but for most solutes were highest in winter and spring and lowest in summer, correlating with the seasonal trend in runoff. For Ca²⁺, Mg²⁺ and SOthe concentration minimum occurs in September and the maximum occurs in February or March, correlating with the seasonal baseflow. These solutes are primarily controlled by the contribution of soil water and groundwater to stream flow. During snowmelt, the meltwater generally causes concentrations to decrease as soil water and groundwater are diluted. For NO₃ , average minimum concentrations occur in August at the end of the growing season concurrent with the lowest stream flow, and the maximum occurs in February and March with high stream flow during snowmelt. Seasonal stream water NOconcentration variations are large compared with the long‐term decrease. Copyright © 1999 John Wiley & Sons, Ltd.     

Dissolved nitrous oxide (N2O) dynamics in agricultural field drains and headwater streams in an intensive arable catchment

Indirect nitrous oxide (N₂O) emissions produced by nitrogen (N) leaching into surface water and groundwater bodies are poorly understood in comparison to direct N₂O emissions from soils. In this study, dissolved N₂O concentrations were measured weekly in both lowland headwater streams and subsurface agricultural field drain discharges over a 2‐year period (2013–2015) in an intensive arable catchment, Norfolk, UK. All field drain and stream water samples were found to have dissolved N₂O concentrations higher than the water–air equilibrium concentration, illustrating that all sites were acting as a net source of N₂O emissions to the atmosphere. Soil texture was found to significantly influence field drain N₂O dynamics, with mean concentrations from drains in clay loam soils (5.3 μg N L^?1) being greater than drains in sandy loam soils (4.0 μg N L^?1). Soil texture also impacted upon the relationships between field drain N₂O concentrations and other water quality parameters (pH, flow rate, and nitrate (NO₃) and nitrite (NO₂) concentrations), highlighting possible differences in N₂O production mechanisms in different soil types. Catchment antecedent moisture conditions influenced the storm event mobilisation of N₂O in both field drains and streams, with the greatest concentration increases recorded during precipitation events preceded by prolonged wet conditions. N₂O concentrations also varied seasonally, with the lowest mean concentrations typically occurring during the summer months (JJA). Nitrogen fertiliser application rates and different soil inversion regimes were found to have no effect on dissolved N₂O concentrations, whereas higher N₂O concentrations recorded in field drains under a winter cover crop compared to fallow fields revealed cover crops are an ineffective greenhouse gas emission mitigation strategy. Overall, this study highlights the complex interactions governing the dynamics of dissolved N₂O concentrations in field drains and headwater streams in a lowland intensive agricultural catchment.     

亚热带地区典型水库流域氮、磷湿沉降及入湖贡献率估算

为了探究汤浦水库流域氮、磷湿沉降对水库水体营养的贡献率,本研究对2014 2015年的汤浦水库流域4个采样点的雨水及3条溪流进行样品收集,测定其中磷和不同形态氮的质量浓度,分析汤浦水库流域大气湿沉降中氮、磷营养盐的分布特征,并估算氮、磷营养盐湿沉降对汤浦水库入库负荷的贡献率.结果表明:湿沉降中总氮(TN)平均浓度为1.02±0.58 mg/L,氨氮、硝态氮和有机氮浓度占TN浓度的比例分别为60.65%、34.07%和5.28%;总磷(TP)平均浓度为0.033±0.028 mg/L.4个采样点湿沉降中氮、磷浓度均表现为冬春季(少雨季)高、夏秋季(多雨季)低.空间上,王化点位的各形态氮和总磷浓度显著高于其他3个采样点.TN和TP年均湿沉降通量约为18.15和0.62 kg/(hm~2·a),年均沉降总量为834.94和28.39 t;库区TN和TP水面湿沉降量为24.14和0.82 t,直接贡献率占河流输入的1.77%和3.07%.湿沉降来源的氮、磷营养盐随河流输入的间接贡献率为8.3%和4.6%.综上所述,氮、磷湿沉降是水库外源营养的重要输入部分,深入掌握其时空分布特征及入库贡献率是进一步加强流域管理和减轻水库外源营养输入的重要前提.