Mid-term trends in acid precipitation,streamwater chemistry and element budgets in the strengbach catchment (Vosges Mountains,France)

In the Vosges Mountains (NE of France), integrated plot-catchment studies have been carried out since 1985 in the Strengbach basin to study the influence of acid atmospheric inputs on surface water quality and element budgets. In this paper, available mid-term time series (1985–1991) have been considered to detect obvious trends, if any, in surface water chemistry and element budgets. Air quality data showed a slight decline for SO₂, whereas NO₂ slightly increased over the period, but these trends are not very significant. This is in agreement with increased N concentration (mainly as NH ₄ ⁺ ) and with the stability of SO ₄ ^2? in open field precipitation. Because of a significant decrease in rainfall amount over the period, only inputs of NH ₄ ⁺ increased significantly whereas H⁺ and SO ₄ ²⁺ inputs declined. In spring and streamwaters, pH and dissolved Si concentration increased mainly as a result of a reduced flow. Na⁺, K⁺, Cl^? and HCO-3~^? concentrations remained stable whereas Ca²⁺, Mg²⁺ and SO ₄ ²⁺ concentrations declined significantly. Only NO ₃ ^? concentration increased significantly in springwaters. The catchment budgets revealed significant losses of base cations, Si and SO ₄ ^2? . These losses decreased over the period. Nitrogen was retained in the ecosystem. However, a longer record is needed to determine whether or not changes in surface water chemistry have resulted from short-term flow reductions or long-term changes in input-output ion budgets. This is specially true with N because the decline in SO ₄ ^2? output was accompanied by N accumulation.     

Changes in the concentrations and speciation of aluminum in response to an experimental addition of ammonium sulfate to the bear Brook Watershed,Maine, USA

An understanding of the biogeochemistry of aluminum (Al) in acid-sensitive terrestrial and aquatic ecosystems is critical to assessments of the effects of acidic deposition. Bear Brook Watershed, Maine, USA includes paired watersheds, East Bear and West Bear. Starting in November 1989, experimental additions of ammonium sulfate ((NH₄)₂SO₄; 900 mol/ha-yr) have been made to West Bear Brook Watershed. Chemical analysis of soil and stream waters were conducted to evaluate the speciation of Al prior to (1987–89) and following (1989–92) the experimental treatments. Before the treatments, soilwater Al occurred largely as inorganic monomeric Al (Ali). Concentrations of organic monomeric Al (Alo), Ali and dissolved organic C (DOC) were high in soil solutions draining the E horizon, and decreased in the lower mineral soilwater (Bs horizon) and streamwater. Streamwater concentrations of monomeric Al (Alm) were largely in the form of Alo. After the (NH₄)₂SO₄ treatments were initiated in the West Bear Brook Watershed, concentrations of Alm increased in soilwater and streamwater, largely as Ali. These increases in Al accompanied decreases in pH and increases in concentrations of SO₄ ^2? and NO₃ ^? in drainage waters. Increases in stream concentrations of Al were particularly evident during high flow events. This pattern, coupled with the increases in concentrations of Ali in upper soilwaters in response to the (NH₄)₂SO₄ addition, suggests that episodic increases in Ali were due to inputs of water entering the stream from shallow hydrologic flowpaths.     

Examination of the Dissolved Inorganic Nitrogen Budget in Three Experimental Microbasins with Contrasting Land Cover—A Mass Balance Approach

A long-term hydrological and water chemistry research was conducted in three experimental microbasins differing in land cover: (1) a purely agricultural fertilized microbasin, (2) a forested microbasin dominated by Carpinus betulus (European hornbeam), and (3) a forested microbasin dominated by Picea abies (L.) (Norway spruce). The dissolved inorganic nitrogen (DIN: NH ₄ ⁺ , NO ₂ ^? , NO ₃ ^? ) budget was examined for a period of 3 years (1991–1993). Mean annual loads of DIN along with sulfate SO ₄ ^2? and base cations Ca²⁺, Mg²⁺, Na⁺, K⁺, and HCO ₃ ^? were calculated from ion concentrations measured in stream water, open-area rainfall, throughfall (under tree canopy), and streamwater at the outlets from the microbasins. Comparison of the net imported/exported loads showed that the amount of NO ₃ ^? leached from the agricultural microbasin is ～3.7 times higher (43.57 kg ha^?1?a^?1) than that from the spruce dominated microbasin (11.86 kg ha^?1?a^?1), which is a markedly higher export of NO ₃ ^? compared to the hornbeam dominated site. Our analyses showed that land cover (tree species) and land use practices (fertilization in agriculture) may actively affect the retention and export of nutrients from the microbasins, and have a pronounce impact on the quality of streamwater. Sulfate export exceeded atmospheric rainfall inputs (measured as wet deposition) in all three microbasins, suggesting an additional dry depositions of SO ₄ ^2? and geologic weathering.     

Trends in surface water acidification at ecological monitoring sites in southeastern Canada (1981–1993)

Atmospheric deposition and surface water chemistry have been monitored intensively at 5 geologically “sensitive” sites in southeastern Canada. The sites receive differing acid inputs that span the entire range found in Canada. Surface water data collected at 9 stations from 1981 to 1993 for SO ₄ ^2? , NO ₃ ^? , Alkalinity, DOC, pH, Ca²⁺ and Mg²⁺ have been analyzed to detect monotonic trends. Similarities between the temporal patterns and trends for SO ₄ ^2? in deposition and surface water suggest that they are strongly linked at our sites. Our 13-year datasets showed significant negative SO ₄ ^2? trends at the 3 Ontario sites and a positive trend in Nova Scotia. A climatically-induced SO ₄ ^2? increase in northwestern Ontario has been reversed. Mobilization and export of adsorbed SO ₄ ^2? and/or reoxidized S from the basins of central Ontario sites is delaying their recovery. Two of our 9 stations (in Quebec and central Ontario) are continuing to acidify. The 2 Nova Scotia stations have the highest DOC levels and both exhibit a decreasing trend. Ionic compensation for declining SO ₄ ^2? varies from station to station, sometimes involving an Alk increase, sometimes a base cation decrease, and sometimes more complex combinations. Additional factors (e.g. climatic variation) also influence variable trends, and data records longer than those presently available will be needed to unequivocally verify acidification recovery.     

Soil Solution Chemical Response to Two Decades of Experimental Acidification at the Bear Brook Watershed in Maine

We examined long-term changes in soil solution chemistry associated with experimental, whole watershed-acidification at the Bear Brook Watershed in Maine (BBWM). At BBWM, the West Bear (WB) watershed has been treated with bimonthly additions of ((NH₄)₂ SO₄) since 1989. The adjacent East Bear (EB) watershed serves as a biogeochemical reference. Soil solution chemistry in the EB watershed was relatively stable from 1989?C2007, with the exception of declining SO₄?CS concentrations associated with a progressive decline in SO₄?CS deposition during this period. Soil solution chemistry in WB reflected a progressive change in acid-neutralization mechanisms from base cation buffering to Al buffering associated with treatment during this period. Total dissolved Al concentrations progressively increased over time and were ~4× higher in 2007 than in 1989. Treatment of WB was also associated with long-term increases in soil solution H⁺, SO₄?CS, and NO₃?CN, whereas soil solution dissolved organic carbon (DOC) was unresponsive to treatment. For solutes such as Ca, H⁺, and SO₄?CS, changes in stream chemistry were generally parallel to changes in soil solution chemistry, indicating a close coupling of terrestrial and aquatic processes that regulate the chemistry of solutions in this first-order stream watershed. For other solutes such as Al and DOC, solute concentrations were higher in soil solutions compared with streams, suggesting that sorption and transformation processes along hydrologic flow-paths were important in regulating the chemistry of solutions and the transport of these solutes.     

Effects of Land Use on Hydrochemistry and Contamination of Karst Groundwater from Nandong Underground River System, China

The Nandong Underground River System (NURS) is located in Southeast Yunnan Province, China. Groundwater in NURS plays a critical role in socio-economical development of the region. However, with the rapid increase of population in recent years, groundwater quality has degraded greatly. In this study, the analysis of 36 groundwater samples collected from springs in both rain and dry seasons shows significant spatial disparities and slight seasonal variations of major element concentrations in the groundwater. In addition, results from factor analysis indicate that NO ₃ ^? , Cl^?, SO ₄ ^2? , Na⁺, K⁺, and EC in the groundwater are mainly from the sources related to human activities while Ca²⁺, Mg²⁺, HCO ₃ ^? , and pH are primarily controlled by water–rock interactions in karst system with Ca²⁺ and HCO ₃ ^? somewhat from anthropogenic inputs. With the increased anthropogenic contaminations, the groundwater chemistry changes widely from Ca-HCO₃ or Ca (Mg)-HCO₃ type to Ca-Cl (+NO₃) or Ca (Mg)-Cl (+NO₃), and Ca-Cl (+NO₃+SO₄) or Ca (Mg)-Cl (+NO₃+SO₄) type. Concentrations of NO ₃ ^? , Cl^?, SO ₄ ^2? , Na⁺, and K⁺ generally show an indistinct grouping with respect to land use types, with very high concentrations observed in the groundwater from residential and agricultural areas. This suggests that those ions are mainly derived from sewage effluents and fertilizers. No specific land use control on the Mg²⁺ ion distribution is observed, suggesting Mg²⁺ is originated from natural dissolution of carbonate rocks. The distribution of Ca²⁺ and HCO ₃ ^? does not show any distinct land use control either, except for the samples from residential zones, suggesting the Ca²⁺ and HCO ₃ ^- mainly come from both natural dissolution of carbonate rocks and sewage effluents.     

Sulfur and oxygen isotope ratios in sulfate during an acidification reversal study at Lake Gårdsjön,Western Sweden

The reversibility of acidification is being investigated in a full scale catchment manipulation experiment at Lake Gårdsjön on the Swedish west coast using isotopes as environmental tracers. A 6300 m² roof over the catchment enables researchers to control depositional variables. Stable S isotope values were determined in bulk deposition, throughfall, runoff, groundwater and soil-extracted water during one year prior to and two years of experimental control. Data collected prior to experimental control suggest that the inorganic SO ₄ ^2? pool within the catchment has a homogeneousδ ³⁴S value of about+5.5‰. Sprinkling of water spiked with small amounts of sea-water derived SO ₄ ^2? started in April 1991. Theδ ³⁴S value of this SO ₄ ^2? is around+19.5‰. Since April 1991, the SO ₄ ^2? concentration in runoff has decreased by some 30%, however, theδ ³⁴S value have increased by only 0.5‰. This suggests mixing of sprinkling water S with a large reservoir of S in the catchment. Oxygen isotopes in SO ₄ ^2? suggest that less than one third of the SO ₄ ^2? in runoff is secondary SO ₄ ^2? formed within the soil profile. This is, however, no evidence for net mineralization of S. The SO ₄ ^2? in runoff in the roofed catchment is a mixture of SO ₄ ^2? previously adsorbed in the soil, mineralized organic S and SO ₄ ^2? from the sprinkler water. Calculations based on isotope data indicate that the turnover time of S within the catchment is on the order of decades. Since SO ₄ ^2? facilitates base cation flow, the acidification reversal will take a much longer time than concentration decreases of SO ₄ ^2? would suggest.     

The geographical distribution and temporal variations of acidic deposition in Eastern North America

Data from two national precipitation chemistry monitoring networks, and several regional air and precipitation chemistry networks are used to describe some broad-scale features of acidic deposition in eastern North America. In northeastern North America, the coefficient of variation is shown to increase from 10–16% for annual averages to nearly 100% for daily values. There is a strong annual cycle in H⁺, SO _inf4 ^sup= and NH _inf4 ^sup+ deposition and some of the other ions although these cycles are not all in phase. The wet NO _inf3 ^sup? deposition contributes relatively more than SO _inf4 ^sup= to the acidity of snow as compared to rain. Wet deposition is highly “episodic” with about 50% to 70% of the total annual deposition of SO _inf4 ^sup= and NO _inf3 ^sup? accumulating in the highest 20% of the days. Estimates made in various ways indicate that, over eastern North America as a whole, dry deposition is approximately equal to wet for both SO _inf4 ^sup= and NO _inf3 ^sup? . Dry may exceed wet in the high emissions zone but drops to about 20% of the total deposition in more remote areas. Deposition via fog or low cloud impaction is an important input to high elevation forests, but more data are required to quantify the magnitude and regional extent of this.     

Biogeochemistry of two Appalachian deciduous forest sites in relation to episodic stream acidification

Bulk precipitation, throughfall, and soil water chemistry were studied from November 1983 to November 1984 at two ridge-top Appalachian deciduous forest sites to isolate causes of differing episodic stream acidification. The Fork Mountain site in West Virginia, which exhibited little episodic stream acidification, had lower deposition of H⁺ and SO _inf4 ^sup2? and greater reductions of H⁺ in the water circulating through the forest canopy, forest floor, and mineral soil than the Peavine Hill site in Pennsylvania. Greater neutralization at Fork Mountain was linked to higher Ca and Mg carbonate contents in the sandstone and shale soil parent materials. Fork Mountain had greater amounts of exchangeable bases in the organic and mineral soil horizons. Neither site appeared to be accumulating SO _inf4 ^sup2? in the soil, with Peavine Hill losing 56% more than was received in bulk deposition. Anions in soil leachate at Fork Mountain were largely balanced by Ca²⁺ and Mg²⁺, while at the Peavine Hill site A1" was the dominant cation. Results suggest that the typically-low carbonate content of sandstone and shale soil parent materials commonly found in Appalachian forests may be a key parameter controlling soil and stream acidification. Data for the one-year period also suggest bulk deposition of H⁺ was 63% greater at Peavine Hill than Fork Mountain.     

Stream chemistry impacts of conifer harvesting in welsh catchments

Hydrochemical data have been collected for between 6 and 9 years from forest harvesting experiments in small catchments (>10 ha) at Plynlimon and Beddgelert, Wales, UK. Felling resulted in rapid increases in NO ₃ ^? and K⁺ concentrations at both sites. A maximum of 3.2 mg N L^?1 was observed at Plynlimon about one year after the start of felling. Concentrations declined to control stream values (0.5 mg N L^?1) after 5 years. At Beddgelert, NO ₃ ^? concentrations in the manipulated catchments remained above those in the unfelled control catchment for three years, before declining below control values. The NO ₃ ^? pulse was related to increased rates of mineralization and nitrification in the soil after felling. The initial increase in K⁺ concentration after felling at Plynlimon was followed by a slow decline, but concentrations were still above those in the control stream after 5 years. From 4 to 8 years after felling at Beddgelert, K⁺ concentrations fell below and then generally remained lower than control values. The NO ₃ ^? pulse after felling at Plynlimon sustained inorganic anion concentrations above those in the control stream for the first 18 months after felling. As the NO ₃ ^? pulse declined, inorganic anion concentrations decreased to below those in the control stream about 4 years after felling. At Beddgelert, the smaller increase in NO ₃ ^? concentrations had less of an effect on inorganic anion concentrations which decreased after felling relative to values in the control stream. The increase in NO ₃ ^? was associated with temporary streamwater acidification in the felled catchments due to the increased rates of nitrification and nitrate leaching. At Plynlimon, streamwater filterable Al concentrations declined after felling, but controls on Al behaviour are complex and not explained by simple equilibrium relationships with Al(OH)₃ or by variations in inorganic anion concentrations. At Beddgelert, felling had no effect on stream water filterable Al concentrations. Felling at Plynlimon led to a large reduction in streamwater Cl^?, Na⁺ and SO ₄ ^2? concentrations. At Beddgelert reductions in SO ₄ ^2? and ‘sea salt’ ion concentrations were less clear, reflecting the smaller proportions of the catchments which were harvested. Felling had no deleterious effects on water quality, apart from a temporary slight further decline in stream pH at Beddgelert. Increases in NO ₃ ^? concentrations were short-lived and concentrations were well below drinking water standards. Filterable Al concentrations were already higher than statutory standards, but were not increased or decreased through felling.     

Mesoscale spatial variability of sulfate in air and rainwater at St. Louis

Sulfate concentrations in rainwater and in air measured on four summer days at St. Louis were highly variable, both spatially or temporally. Maximum/minimum ratios of aerosol SO _inf4 ^sup? varied by up to a factor of 9, and those in rainwater by a factor of 3 on the average. Generally, SO _inf4 ^sup? concentration patterns in air and rainwater were similar, and consistent with wind direction and the location of sources. Direct relationships between SO _inf4 ^sup? in air and in water were evident on two of the individual days, but not for all days together. The non-uniformity of the SO _inf4 ^sup? pattern plus consideration of possible sources of SO _inf4 ^sup? suggests that nucleation of SO _inf4 ^sup? particles must be a major cause of S scavenging, with some possible influence from sub-cloud impaction.     

Simulating acidification and recovery processes in experimental catchments with the ILWAS model

The Integrated Lake Watershed Acidification Study (ILWAS) model was used to simulate soil discharge chemistry at two neighboring experimental catchments. One catchment underwent deacidification because of the artificial application of deacidified precipitation whereas the other catchment received unaltered acidic precipitation. Simulated results reproduce the observed seasonal dynamics in the concentrations of base cations, NO ₃ ^? , Al, and H₄SiO ₄ ⁰ in soil discharges for both catchments. Simulated results also indicate that the export flux of base cations was decreased by 30% at the deacidification catchment in response to the decrease in acid deposition. However, simulated SO ₄ ^2? concentrations show decreases that are about 40% more rapid than were observed. Simulated organic acid concentrations were also substantially lower than those observed at the deacidification catchment, indicating that organic matter decomposition processes were not correctly simulated. Acid-base budgets for both 5 and 50-yr simulations indicate that acid displacement by base cations through ion exchange is the principal process delaying recovery of runoff alkalinity, whereas SO ₄ ^2? desorption has a minor role. Silicate weathering is the dominant acid-consuming process at both catchments. Criteria proposed here for assessing forecast reliability include reproducing seasonal dynamics in discharge chemistry, providing numerically accurate chemical concentrations when compared to monitoring data, and correctly predicting deacidification rate and extent. The ILWAS model generally meets these criteria, indicating that the model can produce a reliable forecast of the effects of acid deposition on the acid-base chemistry of surface waters given sufficient temporal data for confident optimization of the calibrated variables in the model.     

Mercury antagonists: Effects of sodium chloride and sulfur group (VIa) compounds on excystment of the brine shrimp artemia

Brine shrimp excystment, although highly resistant, is severely inhibited by mmolar mercuric chloride. The presence of 100 mmolar NaCl largely prevents the toxic response. The chloride effect can be explained if the toxic Hg species, neutral HgCl₂, is converted into HgCl _inf3 ^sup2? and HgCl _inf4 ^sup2? since charged species not likely to penetrate cyst walls. Other Hg antagonists include SO _in3 ^su2? , SeO _inf3 ^sup2? , TeO _inf3 ^sup2? and TeO _inf4 ^sup2? , but not SO _inf4 ^sup2? and SeO _inf4 ^sup2? . The activity of both Te species can be explained by ready reduction of Te(VI) to Te(IV). Significant anti-mercurial effects were seen in mmolar thiols, ethionine and organoselenium compounds. Thiamine and methionine were both active Hg antagonists at 10 to 30 mmolar levels. The activities of S, Se and Cl^? compounds show that both geochemical and physiological modes of defense against and adaptation to high Hg levels exist.     

Biotic and abiotic processes controlling water chemistry during snowmelt at rabbit ears pass,Rocky Mountains,Colorado, U.S.A.

The chemical composition of snowmelt, groundwater, and streamwater was monitored during the spring of 1991 and 1992 in a 200-ha subalpine catchment on the western flank of the Rocky Mountains near Steamboat Springs, Colorado. Most of the snowmelt occurred during a one-month period annually that began in mid-May 1991 and mid-April 1992. The average water quality characteristics of individual sampling sites (meltwater, streamwater, and groundwater) were similar in 1991 and 1992. The major ions in meltwater were differentially eluted from the snowpack, and meltwater was dominated by Ca²⁺, SO ₄ ^2? , and NO ₃ ^? . Groundwater and streamwater were dominated by weathering products, including Ca²⁺, HCO ₃ ^? (measured as alkalinity), and SiO₂, and their concentrations decreased as snowmelt progressed. One well had extremely high NO ₃ ^? . concentrations, which were balanced by Ca²⁺ concentrations. For this well, hydrogen ion was hypothesized to be generated from nitrification in overlying soils, and subsequently exchanged with other cations, particularly Ca²⁺. Solute concentrations in streamwater also decreased as snowmelt progressed. Variations in groundwater levels and solute concentrations indicate that most of the meltwater traveled through the surficial materials. A mass balance for 1992 indicated that the watershed retained H⁺, NH ₄ ⁺ , NO ₃ ^? , SO ₄ ^2? and Cl^? and was the primary source of base cations and other weathering products. Proportionally more SO ₄ ^2? was deposited with the unusually high summer rainfall in 1992 compared to that released from snowmelt, whereas NO ₃ ^? was higher in snowmelt and Cl^? was the same. The sum of snowmelt and rainfall could account for greater than 90% of the H⁺ and NH ₄ ⁺ retained by the watershed and greater than 50% of the NO ₃ ^? .     

Inorganic and organic sulfur profiles in nine Sphagnum peat bogs in the United States and Czechoslovakia

Depth profiles of total S, organic S, soluble SO ₄ ^2? -S, FeS, and FeS₂ were characterized for Sphagnum-derived peat cores collected from 9 sites. Marcell S-2 Bog (MN), Tamarack Swamp (PA), Cranesville Swamp (MD/WV), and Big Run Bog (WV) receive water from precipitation and upland runoff; atmospheric S deposition is 13, 47, 54, and 114 mmol m^?2, yr^?1, respectively. McDonald's Branch Swamp (NJ) is predominantly groundwater fed. Tub Run Bog (WV) and Allegheny Mining Bog (MD) receive augmented SO ₄ ^2? inputs through acid coal mine drainage. Jezerní slat' and Bo?í Dar Bog in Czechoslovakia receive atmospheric S inputs of 33 and 243 mmol m^?2 yr^?1, respectively. In the peat from all sites except Allegheny Mining Bog, where the substantially augmented SO ₄ ^2? input was reflected in an unusually high dissolved SO ₄ ^2? pool in the surface peat, organic S (probably mostly carbon bonded S) was the dominant S fraction; FeS₂ was generally the dominant inorganic S fraction. Subsurface peaks in total S, organic S and FeS₂-S in peat from the runoff water fed sites were interpreted as indicative of depth-dependent patterns in S reduction/oxidation and in S immobilization/mineralization. Unless SO ₄ ^2? inputs to a site are tremendously augmented (e.g., Allegheny Mining Bog), the rapid turnover of the dissolved SO ₄ ^2? pool combined with the relative stability of the other inorganic and organic S pools, apparently functions as an effective buffer against site differences in S inputs, leading to a general similarity in vertical S profiles in the peat deposits.     

Intercomparison of snow Sampling and Analysis Within the Alpine-Wide Snowpack Investigation (SNOSP)

In order to investigate the seasonal and geographical distribution of snow concentrations anddeposition fluxes of environmentally relevant ionic species in the Alps, the international programSNOSP was initiated. In the framework of this program, intercomparisons of snow samplingtechniques and analytical methods to determine the ionic species C1^-, NO ₃ ^- ,SO ₄ ^2- , K⁺, Na⁺, NH4 ⁺, Mg²⁺, and Ca²⁺, as well as the pH and the specificconductivity were performed. The concentrations of these species in the snow samples collectedin the SNOSP program varied by orders of magnitude with, e.g., concentrations of NO ₃ ^- , SO ₄ ^2- , and NH4 ⁺ ranging from 0.2-60, 0.2-90, and 0.1-60 µeq L^-1,respectively. The intercomparisons revealed a reasonable agreement of the determinations of thespecies Cl^-, NO ₃ ^- , SO ₄ ^2- , Na⁺, and NH4 ⁺ in snow. Results were less satisfactory for K⁺, Mg²⁺, Ca²⁺,and H⁺, mainly due to the very low concentrations. In conclusion, recommendations areformulated for the reliable derivation of chemical inventories from snow packs.     

Nutrient Fluxes in Planted Norway Spruce Stands of Different Age in Southern Poland

The fluxes of N–NO ₃ ^? , N–NH ₄ ⁺ , S–SO ₄ ^2? , Na⁺, K⁺, Ca²⁺ and Mg²⁺ from bulk precipitation to throughfall, stemflow and soil water surface flows were studied during 1999–2003 in planted Norway spruce forest stands of different ages (11, 24, 91 and 116 years in 1999). Also, runoff from the corresponding Potok Dupniański Catchment in the Silesian Beskid Mts was studied. N deposition was above the critical load for coniferous trees. The interception increased with stand age as well as leaf area index and so did the leaching from the canopy of almost all the analysed elements, but especially S–SO ₄ ^2? , H⁺ and K⁺. The nutrient fluxes varied with age of the spruce stands. Throughfall showed a high amount of S and of the strong acids (S–SO ₄ ^2? and N–NO ₃ ^? ) deposited to the soil, especially in older spruce age classes. Decomposition of organic matter caused a rise in water acidity and an increase in the concentrations of all the analysed ions; the leaching of minerals, however, was low (under 1%). The horizontal soil water flow showed an increase in the amount of water and amount of ions and contributed to a further decrease of pH at the soil depth of 20 cm. Element concentrations and their amounts increased with water penetrating vertically and horizontally on the slopes. Considerable amounts of ions, especially S and alkaline cations, were carried beyond the reach of the root system and then left the catchment. In the long term, these mineral losses will adversely affect health and growth of the spruce stands, and the increased acidity with stand age will presumably have negative effects on the runoff water ecosystem.     

Episodic acidification of a coastal plain stream in Virginia

This study investigates the episodic acidification of Reedy Creek, a wetland-influenced coastal plain stream near Richmond, Virginia. Primary objectives of the study were to quantify the episodic variability of acid-base chemistry in Reedy Creek, to examine the seasonal variability in episodic response and to explain the hydrological and geochemical factors that contribute to episodic acidification. Chemical response was similar in each of the seven storms examined, however, the ranges in concentrations observed were commonly greater in summer/fall storms than in winter/spring storms. An increase in SO _inf4 ^sup2? concentration with discharge was observed during all storms and peak concentration occurred at or near peak flow. Small increases in Mg²⁺, Ca²⁺, K⁺ concentrations and dissolved organic carbon (DOC) were observed during most storms. At the same time, ANC, Na⁺ and Cl^? concentrations usually decreased with increasing discharge. In summer/fall storms, the absolute increase in SO _inf4 ^sup2? concentration was one-third to 15 times the increase observed in winter/spring storms; the decrease in ANC during summer/fall storms was usually within the range of the decrease observed in winter/spring storms. In contrast, the decrease in Na⁺ and Cl^? concentrations during winter/spring storms was much greater than that observed during summer/fall storms. Data show that while base flow anion deficit was higher in summer/fall than in winter/spring, anion deficit decreased during most summer/fall storms. In contrast, base flow anion deficit was lower in spring and winter, but increased during winter/spring storms. Increased SO _inf4 ^sup2? concentration was the main cause of episodic acidification during storms at Reedy Creek, but increased anion deficit indicates organic acids may contribute to episodic acidification during winter/spring storms. Changes in SO _inf4 ^sup2? concentration coincident with the hydrograph rise indicate quick routing of water through the watershed. Saturation overland flow appears to be the likely mechanism by which solutes are transported to the stream during storm flow.     

Deposition of air pollutants in a wind-exposed forest edge

The atmospheric deposition of air pollutants at a forest edge was studied by means of monitoring canopy throughfall at the edge and at five different parallel lines in the forest behind the edge. The investigation was carried out at a pine forest on the Swedish west coast. Throughfall and bulk deposition samples were analyzed for volume, SO ₄ ^2? , NO ₃ ^? , Cl^?, NH ₄ ⁺ , Na⁺, K⁺, Mg²⁺, Ca²⁺, and for pH. The results show that the throughfall flow at the edge was increased substantially for most ions. The ratios in throughfall flows between the edge and the line 50 m into the forest were for SO ₄ ^2? , 1.5, NO ₃ ^? 2.9, NH ₄ ⁺ 2.7, and Na⁺ 3.1. Since this effect is not only valid for forest edges but also for hillsides, hilltops, and edges between stands of different age, etc., there might be substantial areas which get much larger total deposition than the normally considered closed forest.     

Chemical deposition to a high elevation red spruce forest

A preliminary analysis of O₃, SO₂, SO _inf4 ^sup2? , and total NO _inf3 ^sup? deposition to the red spruce forest on the summit of Whitetop Mountain, Virginia, illustrates uncertainties in analysis methodologies, establishes the relative importance of three deposition pathways, and suggests areas for further research. Results are presented here for an analysis of the dry, wet (precipitation), and cloud water deposition pathways for the four chemical species during a 26-day period in April and May 1986. Dry and cloud water depositions are estimated using available models along with air and cloud water chemistry measurements made at the summit. For water soluble species, depositions by precipitation and cloud interception are found to be comparable in magnitude, while dry deposition appears to be about an order of magnitude less. High levels of atmospheric O₃ lead to a large estimate of 03 deposition (on a mass flux basis) when compared to the estimated deposition of gaseous SO₂. This is in spite of the fact that computed SO₂ dry deposition velocities exceed those for O₃. Model uncertainties are large for both dry deposition velocity and cloud water flux computations, and some bias in computations probably exists because of the application of the models to a complex terrain situation. Field evaluation of the cloud water deposition model is of greatest priority because of the apparent relative importance of that deposition pathway.