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.     

Chemical characteristics and temporal trends in eight streams of the Catskill Mountains,New York

Discharge to concentration relationships for eight streams studied by the U.S. Geological Survey (USGS) as part of the U.S. Environmental Protection Agency's (U.S. EPA) Long-Term Monitoring Project (1983–89) indicate acidification of some streams by H₂SO₄ and HNO₃ in atmospheric deposition and by organic acids in soils. Concentrations of major ions in precipitation were similar to those reported at other sites in the northeastern United States. Average concentrations of SO₄ ^2? and NO₃ ^? were similar among streams, but base cation concentrations differed widely, and these differences paralleled the differences in acid neutralizing capacity (ANC). Baseflow ANC is not a reliable predictor of stream acidity at high flow; some streams with high baseflow ANC (>150 Μeq L^?1) declined to near zero ANC at high flow, and one stream with low baseflow ANC (<50 Μeq L^?1) did not approach zero ANC as flow increased. Episodic decreases in ANC and pH during peak flows were associated with increased concentrations of NO₃ ^? and dissolved organic carbon (DOC). Aluminum concentrations exceeding 300 Μg L^?1 were observed during peak flows in headwater streams of the Neversink River and Rondout Creek. Seasonal Kendall Tau tests for temporal trends indicate that SO₄ ^2? concentrations in streamwater generally decreased and NO₃ ^? concentrations increased during the period 1983–1989. Combined acid anion concentrations (SO₄ ^2? + NO₃ ^?) were generally unchanged throughout the period of record, indicating both that the status of these streams with respect to acidic deposition is unchanged, and that NO₃ ^? is gradually replacing SO₄ ^2? as the dominant acid anion in the Catskill streams.     

Sources of sulphate and acidity in wetlands and lakes in Nova Scotia

There is a declining gradient of wet SO₄ deposition from south to north in Nova Scotia with the highest values being in the south, along with a localized increase around the Halifax metropolitan area, due to local SO₄ emission. Edaphic conditions such as drainage from soils containing gypsum or drainage on disturbed rocks containing pyrite, provide additional SO₄ to surface waters.Acidity is usually absent in the former (pH > 7.0) and very high in the latter (as low as pH 3.6). By contrast peaty, organic drainages release water low in SO₄ during the growing season but they release high amounts of organic anions (A?), consequently, these waters maintain decreased pH values, usually < 4.5. A study of over 80 wetlands and lakes during the ice free period in Nova Scotia showed that sea salt corrected SO₄ concentrations range from 45 ueq L^?1 in the south end of the province, ～30 ueq L^?1 in the Kejimkujik area and < 17 ueq L^?1 in the northern areas with values > 85 ueq L^?1 in the Halifax area, reflecting the atmospheric deposition pattern of SO₄ The SO₄ concentrations may be > 2000 ueq L^?1 in drainages containing gypsum, > 700 ueq L^?1 in drainages over pyrite bearing socks but < 20 ueq/L^?1 in streams draining bogs. The SO₄ concentrations change considerably during the non-growing season when the ground is saturated with water or frozen, and the runoff is high (snow and rain often alternate in winter). Under such conditions SO₄ concentration drops in the two former cases and increases in bog drainages, accompanied with a considerable drop in (A?) concentrations. Care should be taken when interpreting SO₄ concentrations in surface waters in Nova Scotia with respect to atmospheric SO₄ deposition.     

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.     

Snowmelt in a boreal forest site: an integrated model of meltwater quality (SNOQUALI)

An integrated model (SNOQUALI) for the simulation of meltwater quality has been developed for a boreal forest site (Lake Laflamme, Québec). The model consists of a physical module and a chemical module; it has been validated for H⁺, NO₃ and SO₄ ^2? concentrations in discharge from the snowcover during the spring melt of 1984. Good agreement of simulated ion concentrations with those measured in the field were obtained for the strong acid anions NO₃ ^? and SO₄ ^2?. Greater deviations of simulated concentrations from observed concentrations were recorded in the case of H+. These are attributed to ion exchange reactions between the ion and the organic debris which is deposited continously onto the snowcover from the forest canopy during the winter season.     

Biomass and compositional changes in the periphytic community of an artificial stream in response to lowered pH

Two artificial streams simulating low-order, softwater streams of the Upper Peninsula of Michigan were employed to examine the effects of lowered pH on periphytic algae. The control stream contained water with a circumneutral pH whereas the pH of the water in the acidified stream was decreased to pH 4 with H₂SO₄. Chlorophyll a concentrations and cell densities in the periphytic algal communities were used to measure differences in biomass accumulations between the 2 streams over a 42-d, spring colonization period. Relative abundances of algal genera and Stander's similarity index (SIMI) were used to examine compositional differences between the control and acidified periphytic algal communities. These algal communities exhibited pronounced differences in their total biomasses and compositions indicating periphytic algal communities inhabiting low-order, softwater streams, such as those of the Upper Peninsula of Michigan, are vulnerable to acidic deposition. Decreased biomass accumulation under acidified conditions was believed to result primarily from decreased nutrient availability, and possibly secondarily from elevated aluminum and/or iron concentrations. The shift in community compositions was interpreted to be a more direct response to the lowered pH as acidophils and acid tolerant genera became favored, and thus more abundant.     

Seasonal variations of water chemistry in oligotrophic streams and rivers in Kejimkujik National Park,Nova Scotia

The seasonal patterns of flow and the concentrations of color, Mg, Ca, H⁺, Na, Cl, organic anions, SO₄, and Gran alkalinity are examined for five streams or rivers in Kejimkujik National Park (Lower Mersey River, Atkins Brook, Grafton Brook, Pebbleloggitch Brook, and Beaverskin Brook). These range in organic color and acidity from very darkwater Atkins Brook (average 191 Hazen units, pH 4.2) to clearwater Beaverskin Brook (5 Hazen units, pH 5.5). In general, most dissolved substances are present in a relatively large concentration during the high-flow period of winter-spring (most notably color, Mg, H⁺, Ca, Na, organic anions, and SO₄). In contrast, Gran alkalinity generally occurs in its highest concentration during the lowflow period. These observations suggest that during the high-flow period, substances are “flushed” from the terrestrial watersheds of these rivers and streams.     

凉水国家级自然保护区溪流水化学特征分析

 采用集水区对比分析方法,探讨凉水国家级自然保护区不同森林类型对溪流水化学特征的影响。结果表明:保护区内各集水区溪流水均呈弱酸性至中性;主要离子中阳离子均以Ca2+的质量浓度最高,Na+次之,阴离子均以HCO3-的质量浓度最高,SO2-4次之;不同集水区溪流水中TP月平均质量浓度为0.031～0.077mg/L,TN为0.682～0.942 mg/L,NO-3-N的质量浓度高于NH+4-N;Fe的月平均质量浓度为0.030～0.037mg/L,Mn为0.010～0.012 mg/L。溪流水化学季节变化规律表现为:除HCO-3、SO2-4、Ca2+、Fe和Mn外,其他元素在融雪（4、5月）含量均较高;大多数元素在雨季的质量浓度比9月份低,而TN、TP、Fe、Mn表现为9月份的质量浓度低于雨季。保护区内原始阔叶红松林集水区溪流水质为最优,其他研究集水区溪流中的溶解物质含量增高,但除TP和SO2-4（p<0.05）外,差异性均不显著。说明凉水国家级自然保护区内虽进行过森林采伐和人工造林等人为干扰,但对于溪流水质并没有显著影响。     

Acid-base chemistry of high-elevation streams in the great smoky mountains

Longitudinal and temporal variations in water chemistry were measured in several low-order, high-elevation streams in the Great Smoky Mountains to evaluate the processes responsible for the acid-base chemistry. The streams ranged in average base flow ANC from ?30 to 28 μeq L^?1 and in pH from 4.54 to 6.40. Low-ANC streams had lower base cation concentrations and higher acid anion concentrations than did the high-ANC streams. NO₃ ^? and SO₄ ^2? were the dominant acid anions. NO₃ ^? was derived from a combination of high leaching of nitrogen from old-growth forests and from high rates of atmospheric deposition. Streamwater SO₄ ^2? was attributed to atmospheric deposition and an internal bedrock source of sulfur (pyrite). Although dissolved Al concentrations increased with decreasing pH in the study streams, the concentrations of inorganic monomeric Al did not follow the pattern expected from equilibrium with aluminum trihydroxide or aluminum silicate phases. During storm events, pH and ANC declined by as much as 0.5 units and 15 μeq L^?1, respectively, at the downstream sites. The causes of the episodic acidification were increases in SO₄ ^2? and DOC.     

Aluminum speciation in running waters on the Canadian pre-Cambrian Shield: Kinetic aspects

To evaluate the extent to which chemical disequilibrium may exist in stream waters following naturally occurring short-term pH changes, surface water samples were collected from two streams in the Lake Laflamme watershed north of Quebec City, placed in large polyethylene containers and stirred continuously at the in situ temperature; changes in Al speciation were followed with time for up to 24 hr. The original samples were collected during the spring snow-melt period and during summer low flows. In this latter case, a pH depression was induced by artificial acidification (H₂SO₄; pH 4) and changes in Al speciation with time were followed in both the acidified and the unacidified samples. Aluminum speciation as operationally defined did respond to artificial acidification (pH lowered; non-exchangeable and non-extractable Al decreased), and these pH-induced changes occurred rapidly (< 4 hr). During storage of natural water samples at in situ T for up to 24 hr, little change in Al speciation was noted, even in the case of samples collected during spring snow-melt; no clear cases of chemical disequilibrium existed among the studied samples. The distribution of Al among its various physico-chemical forms thus appears to be established within the stream itself; at a given stream sampling point the speciation of A1 will not necessarily reflect its geochemical origins, but rather the prevailing in situ conditions (e.g. pH, ligand concentrations).     

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.     

Sulfate adsorption by variable charge soils: Effect of low-molecular-weight organic acids

Sulfate (SO₄ ^2–) movement and transport in soils has received considerable attention in recent years. In most soils, SO₄ ^2– coexists with a variety of natural organic compounds, especially organic acids. Studies were conducted to assess the effect of low-molecular-weight organic acids (eight aliphatic and five aromatic acids) on SO₄ ^2– adsorption by variable charge soils from Chile and Costa Rica. The effects of type of organic acid, pH, type of soil, and organic acid concentration were investigated. In one experiment, a 1.0 g soil sample was equilibrated with 25 ml 0, 0.5, 1.0, 2.0, 4.0, or 6.0 mM K₂SO₄ in 1 mM NaCl in the presence or absence of 5 mM citric acid. In the second set of experiments, the adsorption of 2 mM SO₄ ^2– in soils at pH 4 or pH 5 in the presence or absence of one of 13 organic acids at a concentration of 2 mM or 5 mM was studied. Results showed that citric acid significantly decreased SO₄ ^2– adsorption by the two soils. Sulfate adsorption decreased with increasing pH of the equilibrium solution. Aliphatic acids, with the exception of cis-aconitic acid, decreased the amount of SO₄ ^2– adsorbed by the two soils, with oxalic, tartaric, and citric acid showing the greatest effect. The differences in pH values of the equilibrium solutions in the presence and absence of organic acids were significantly, but negatively, correlated with the amount of SO₄ ^2– adsorbed, suggesting chemisorption of SO₄ ^2– and the release of hydroxide ions. The ionization fraction values of the organic acids at the equilibrium pH were correlated with the amounts of SO₄ ^2– adsorbed, suggesting that the protonation of surface hydroxyl groups of the mineral phase increased as the strength of the ionization of the acid increased, thus creating more positively charged surfaces. Received: 12 February 1997     

Long-Term Annual and Seasonal Patterns of Acidic Deposition and Stream Water Quality in a Great Smoky Mountains High-Elevation Watershed

The recovery potential of stream acidification from years of acidic deposition is dependent on biogeochemical processes and varies among different acid-sensitive regions. Studies that investigate long-term trends and seasonal variability of stream chemistry in the context of atmospheric deposition and watershed setting provide crucial assessments on governing biogeochemical processes. In this study, water chemistries were investigated in Noland Divide watershed (NDW), a high-elevation watershed in the Great Smoky Mountains National Park (GRSM) of the southern Appalachian region. Monitoring data from 1991 to 2007 for deposition and stream water chemistries were statistically analyzed for long-term trends and seasonal patterns by using Seasonal Kendall Tau tests. Precipitation declined over this study period, where throughfall (TF) declined significantly by 5.76?cm?year^?1. Precipitation patterns play a key role in the fate and transport of acid pollutants. On a monthly volume-weighted basis, pH of TF and wet deposition, and stream water did not significantly change over time remaining around 4.3, 4.7, and 5.8, respectively. Per NDW area, TF SO₄ ^2- flux declined 356.16?eq?year^?1 and SO₄ ^2- concentrations did not change significantly over time. Stream SO₄ ^2- remained about 30???eq L^?1 exhibiting no long-term trends or seasonal patterns. SO₄ ^2- retention was generally greater during drier months. TF monthly volume-weighted NH₄ ⁺ and NO₃ ^- concentrations significantly increased by 0.80???eq L^?1?year^?1 and 1.24???eq L^?1?year^?1, respectively. TF NH₄ ⁺ fluxes increased by 95.76?eq?year^?1. Most of NH₄ ⁺ was retained in the watershed, and NO₃ ^- retention was much lower than NH₄ ⁺. Stream monthly volume-weighted NO₃ ^- concentrations and fluxes significantly declined by 0.56???eq L^?1?year^?1 and 139.56?eq?year^?1, respectively. Overall, in NDW, inorganic nitrogen was exported before 1999 and retained since then, presumably from forest regrowth after Frazer fir die-off in the 1970s from balsam wooly adelgid infestation. Stream export of NO₃ ^- was greater during winter than summer months. During the period from 1999 to 2007, stream base cations did not exhibit significant changes, apparently regulated by soil supply. Statistical models predicting stream pH, ANC, SO₄ ^2-, and NO₃ ^- concentrations were largely correlated with stream discharge and number of dry days between precipitation events and SO₄ ^2- deposition. Dependent on precipitation, governing biogeochemical processes in NDW appear to be SO₄ ^2- adsorption, nitrification, and NO₃ ^- forest uptake. This study provided essential information to aid the GRSM management for developing predictive models of the future water quality and potential impacts from climate change.     

The effects of drying and re-wetting and increased temperature on sulphate release from upland and wetland material

In central Ontario, elevated SO₄ concentrations and export have been measured in both upland and wetland-draining catchments following summer droughts, although the source of excess SO₄ is unclear. The objective of this study was to determine the effects of drying and re-wetting and temperature, respectively, on the release of SO₄ from the primary S pools in wetlands (Sphagnum and peat) and uplands (forest floor and mineral soil), using material collected from the PC1 catchment in Haliburton County, and from catchment S50 in the Turkey Lakes Watershed. Peat exhibited the most marked response to drying of the four materials considered, and within 24 h of re-wetting dried peat from both catchments released 3-4 times more SO₄ (50-67 mg kg⁻¹ S-SO₄) than continuously moist peat (16 mg kg⁻¹ S-SO₄), although temperature had only a marginal effect on SO₄ concentrations. There was no immediate response of Sphagnum to either drying or temperature, although S-SO₄ concentrations in Sphagnum tended to increase over the 30-day (d) incubation. There was a small but immediate increase in S-SO₄ concentrations in forest floor material (LFH) from both catchments within the first 24 h of incubation, which was greatest in treatments that were dried and/or incubated at a higher temperature. In contrast, neither temperature nor drying appeared to affect SO₄ release from mineral soil collected from either site. Results of laboratory incubations suggest that increases in SO₄ concentration that have been reported in wetland-draining streams immediately following summer dry periods may be quantitatively explained by drying and re-wetting of peat rather than increased mineralization in Sphagnum. Similarly, the higher SO₄ concentrations that have been measured in upland streams following summer droughts may in part be due to enhanced SO₄ release from the forest floor following drying and re-wetting. In contrast, while the mineral soil constitutes a large pool of total S, it does not appear to be responsive to changes in moisture or temperature in the short-term (<30 d) and therefore likely does not contribute to reported climate-related temporal variations in stream SO₄.     

Trends and patterns in lake acidification in the State of Vermont: Evidence from the Long-Term Monitoring Project

Twenty-four low acid neutralizing capacity (ANC) lakes in Vermont have been monitored since 1980 to characterize their chemical variability, and to determine if they exhibit temporal trends in acid/base chemistry. Many of the lakes exhibit significant decreasing trends in SO₄ ^2? and base cation (C_B) concentrations, but few exhibit significant changes in pH or ANC. An examination of all trend results (significant and insignificant) suggests a tendency for ANC and pH values in these lakes to be increasing, but either the changes are too small, or the number of observations too small, for these trends to be significant. Data from these lakes suggest that the primary responses of surface waters in this region to declining rates of SO₄ ^2? deposition are decreases in SO₄ ^2? concentrations and rates of cation leaching from watershed soils. Decreasing rates of c_b deposition may combine with lower rates of cation leaching to produce declines in c_B that are very similar to measured declines in SO₄ ^2? concentration. Vermont lakes exhibit their lowest ANC values in spring, attributable, for the most part, to dilution of c_B concentrations during spring snow melt. Concentrations of SO₄ ^2? are also more dilute in the spring, but c_B decreases are greater, and the net effect is a lowering of ANC. One quarter of the Vermont lakes monitored exhibit strong seasonality in NO₃ ^? concentrations, with peak concentrations near 70 Μeq L^?1. In these lakes, spring increases in NO₃ ^? concentrations are more important than C_B dilution in producing minimal spring ANC values.     

Studies of Soils, Soil Water and Stream Water at a Small Catchment near Guiyang, China

Acid deposition is considered to be a major environmental problem in China, but information about effects on soils and waters is scarce. To contribute to increased knowledge about the problem a small catchment (about 7 ha) in the outskirts of Guiyang, the provincial capital of Guizhou in south-western China, was instrumented for collection of precipitation, throughfall, soil water and stream water. In addition soil samples have been collected and analyzed for key properties. Median pH in the precipitation is 4.40 (quartiles: 4.19 and 4.77) and the median sulfate concentration 228 µeq/L (quartiles: 147 and 334 µeq/L). The dry deposition of both SO₂ and alkaline dust is considerable. The sum of wet deposition of sulfate and dry deposition of SO₂ has been estimated to about 8.5 gSm^-2yr^-1. The total S-deposition may be somewhat higher due to dry deposition of sulfate and occult deposition. In soil water, SO₄ ^2- is the major anion, generally ranging from 300 to 2500 µeq/L in the different plots. Calcium is an important cation, but there is also a considerable contribution of aluminum from the soil. In some of the plots the concentrations of inorganic monomeric aluminum (Ali) are typically between 200 and 400 µm. Potential harmful levels of aluminum and/or high Ali/(Ca²⁺ + Mg²⁺) molar ratios occur in the catchment, but damages to vegetation have not yet been reported. In most cases exchangeable aluminum accounts for between 75 and 95% of the total effective cation exchange capacity (CEC_E) in the mineral soils. The aluminum chemistry cannot easily be explained by conventional models as the Gaines-Thomas ion-exchange equation or equilibrium with an Al(OH)₃ mineral phase. The stream water is generally less acidic and has considerably lower concentrations of aluminum than the soil water, even though quite acid events have been observed (pH < 4.4). The median pH values are 4.9 and 5.0 in the two first order streams and 6.3 in the dam at the lower boarder of the catchment.     

Ion elution and release sequence from deep snowpacks in the central Sierra Nevada,California

Elution of Cl^?, SO₄ ^2?, NO₃ ^?, and H⁺ often occurred in that order at a site in the central Sierra Nevada, California, that receives an annual average of 1000 cm of snowfall which is low in acidic components. During eight winter periods of above-base level snowpack outflow, and one spring melt period, on the average 25% of the ions were discharged at the following percentages of outflow volumes: Cl^? at 11%, NO₃ ^? at 13%, SO₄ ^2? at 18%, and H⁺ at 20%. Seven of eight winter outflows were associated with low ionic strength rainfall onto the snowpack. Mean solute concentrations during the first 25% and first 50% of the total outflow were significantly greater than during the last 75% and last 50% of the total outflow for Cl^?, NO₃ ^?, and SO₄ ^2?, but not for H⁺. Maximum solute concentrations were up to 2.9 times the overall event volume-weighted mean concentrations for Cl^?, 3.7 times for NO₃ ^?, 3.0 times for SO₄ ^2?, and 2.9 times for H⁺.     

The effects of acid nitrogen and acid sulphur deposition on CH4 oxidation in a forest soil: a laboratory study

Sieved soil and soil core experiments were performed to determine the potential sensitivity of forest soil CH₄ oxidation to oxidised N, reduced N and oxidised S atmospheric deposition. Ammonium sulphate was used to simulate reduced N deposition, HNO₃ oxidised N deposition and H₂SO₄ oxidised S deposition. The effects of NH₄⁺, NO₃⁻, SO₄²⁻ and H⁺ on soil CH₄ flux were shown to be governed by the associated counter-anion or cation of the investigated ions. Ammonium sulphate, at concentrations greater than those that would be experienced in polluted throughfall, showed a low potential to cause inhibition of CH₄ oxidation. In contrast, HNO₃ strongly inhibited net CH₄ oxidation in sieved soils and also in soil cores. In addition, soil CO₂ production was inhibited and the organic and mineral soil horizons acidified in HNO₃ treated soil cores. This suggested that the HNO₃ effect on CH₄ flux might be indirectly mediated through aluminium toxicity. Sulphuric acid only inhibited CH₄ oxidation when added at pH 1. At concentrations more representative of heavily polluted throughfall, H₂SO₄ had no effect on soil CH₄ flux or CO₂ production from soil cores, even after 210 days of repeated addition. In contrast to HNO₃ additions, acidification of the soil was not marked and was only significant for the mineral soil. The findings suggest that the response of forest soil CH₄ oxidation to atmospheric acid deposition is strongly dependent on the form of acid deposition.     

A Comparison of Methods for Deriving Solute Flux Rates Using Long-Term Data from Streams in the Mirror Lake Watershed

Calculation of chemical flux rates for streams requires integration of continuous measurements of discharge with discrete measurements of solute concentrations. We compared two commonly used methods for interpolating chemistry data (time-averaging and flow-weighting) to determine whether discrepancies between the two methods were large relative to other sources of error in estimating flux rates. Flux rates of dissolved Si and SO₄ ^2- were calculated from 10 years of data (1981^-1990) for the NW inlet and outlet of Mirror Lake and for a 40-day period (March 22 to April 30, 1993) during which we augmented our routine (weekly) chemical monitoring with collection of daily samples. The time-averaging method yielded higher estimates of solute flux during high-flow periods if no chemistry samples were collected correponding to peak discharge. Concentration-discharge relationships should be used to interpolate stream chemistry during changing flow conditions if chemical changes are large. Caution should be used in choosing the appropriate time-scale over which data are pooled to derive the concentration-discharge regressions because the model parameters (slope and intercept) were found to be sensitive to seasonal and inter-annual variation. Both methods approximated solute flux to within 2^-10% for a range of solutes that were monitored during the intensive sampling period. Our results suggest that errors arising from interpolation of stream chemistry data are small compared with other sources of error in developing watershed mass balances.