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.     

Seasonal and long-term temporal patterns in the chemistry of Adirondack lakes

There is considerable interest in the recovery of surface waters from acidification by acidic deposition. The Adirondack Long-Term Monitoring (ALTM) program was established in 1982 to evaluate changes in the chemistry of 17 Adirondack lakes. The ALTM lakes exhibited relatively uniform concentrations of SO₄ ^2?. Lake-to-lake variability in acid neutralizing capacity (ANC) was largely due to differences in the supply of basic cations (Ca²⁺, Mg²⁺, K⁺, Na⁺; C_B) to drainage waters. Lakes in the western and southern Adirondacks showed elevated concentrations of NO₃ ^?, while lakes in the central and eastern Adirondacks had lower NO₃ ^? concentrations during both peak and base flow periods. The ALTM lakes exhibited seasonal variations in ANC. Lake ANC was maximum during the late summer or autumn, and lowest during spring snowmelt. In general Adirondack lakes with ANC near 100 Μeq L^?1 during base flow periods may experience decreases in ANC to near or below 0 Μeq L^?1 during high flow periods. The ALTM lakes have exhibited long-term temporal trends in water chemistry. Most lakes have demonstrated declining SO₄ ^2?, consistent with decreases in SO₂ emissions and SO₄ ^2? in precipitation in the eastern U.S. Reductions in SO₄ ^2? have not coincided with a recovery in ANC. Rather, ANC values have declined in some ALTM lakes. This pattern is most likely due to increasing concentrations of NO₃ ^? that occurred in most of the ALTM drainage lakes.     

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.     

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.     

Recent trends in the acid-base status of surface waters in Maine,USA

Data from the EPA Long Term Monitoring Program lakes at the Tunk Mountain Watershed, Maine, indicate that decreases of ≤1 Μeq L^?1 yr^?1 in SO₄, and increases of ≤2 Μeq L^?1 yr^?1 in ANC occurred in the 1980s. The sum of base cations also increased. These changes in aquatic chemistry were coincident with decreased concentrations of all solutes in precipitation during the 1980s. Other data on lakes and streams in Maine collected between the 1930s and 1990 generally confirm these trends and further indicate that larger increases in ANC may have occurred in some lowland lakes since 1940. Paleolimnologic studies indicate that decreases of 0.1 to 0.5 pH units occurred in a few small mountain lakes during the past 20 to 70 yr. However, ongoing acidification of lakes is indicated based on available data. Only lakes that were already at least marginally acidic (pH ≤5.8, ANC approximately 0) appear to have acidified.     

Low cost limestone treatment of acid sensitive trout streams in the appalachian mountains of Virginia

The method of single point, single application liming has been studied as a means of mitigating anthropogenic acid in trout streams in Virginia. Three critically acid sensitive streams were dosed with a total of five applications of limestone sand and monitored before, during and after the treatments to assess changes in water chemistry and biota. Limestone treatments of 8 to 50 tons (particle sizes 150–1000 μm), with the amounts based on sulfate deposition loading and existent stream water chemistry, were used to restore ‘lost’ acid neutralizing capacity (ANC). Contact time between the limestone bed in the stream bottom and the water was the limiting factor affecting the degree of treatment with bed length primarily controlled by the gradient of the stream at the dosing site. A single site application was able to restore approximately 2/3 of the ANC. Exponential fits of limestone consumption data were used to predict that treaments of similar streams would last from two five years before reliming was necessary. Both total and monomeric aluminum levels were reduced up to 50%, and aquatic biota increased below the treatment sites. Post-liming average values for the three streams were pH 6.66, 82.7 μeq L^?1 ANC and 2.63 mg L^?1 Ca. The average ANC improvement suggests that some 88% of the native trout streams in Virginia, which average 29 μeq L^?1 ANC reduction from acid deposition, could be temporarily restored using single application liming.     

Temporal trends in low alkalinity lakes of the Upper Midwest (1983–1989)

The Upper Midwest contains a large concentration of low alkalinity lakes located across a west to east gradient of increasing deposition acidity. We present temporal trends in the chemistry of 28 lakes (4 in Minnesota, 13 in Wisconsin, and 11 in Michigan) representative of the acid-sensitive resource of the region. Lakes were sampled three times per year between 1983 and 1989. Temporal trends in SO₄ ^2? were all negative in direction, consistent with a regional decline in SO₂ emissions and atmospheric SO₄ ^2? deposition. However, these trends occurred predominantly in higher ANC (100 to 225 Μeq L^?1), non-seepage lakes and were associated with increases in ANC and pH in only one of the 8 lakes. ANC decreased in a second group of lakes, usually in concert with decreased [Ca²⁺+Mg²⁺], a response we associate with a severe drought. Disruptions in hydrologic flowpaths caused one lake to acidify rapidly after inputs of ANC-rich groundwater ceased and appeared to cause ANC and [Ca²⁺+Mg²⁺] declines in a second lake by reducing stream-water inflow. Our analysis was thus complicated by hydrochemical effects of climatic variability, which confounded trends related to acidic deposition. Periods longer than 6 yr are needed to transcend climatic signals and verify subtle trends related to atmospheric pollutants.     

Trends in the Chemistry of Acidified Bohemian Lakes from 1984 to 1995: I. Major Solutes

Temporal changes in major solute concentrations in six Czech Republic lakes were monitored during the period 1984–1995. Four chronically-acidic lakes had decreasing concentrations of strong-acid anions (C_SA = SO₄ ^2- + NO^{3 -} + Cl^-), at rates of 3.0 to 9.0 μeq L^-1 yr^-1. Decreases in SO₄ ^2-, NO₃ ^-, and Cl^- (at rates up to 5.1 μeq L^-1 yr^-1, 3.2 μeq L^-1 yr^-1, and 0.6 μeq L^-1 yr^-1, respectively) occurred. The response to the decrease in deposition of S was rapid and annual decline of SO₄ ^2- in lake water was directly proportional to SO₄ ^2- concentrations in the acidified lakes. Changes in NO₃ ^- concentrations were modified by biological consumption within the lakes. The decline in C^SA was accompanied in the four most acidic lakes by decreases in Al_T, increases in pH at rates of 0.011 to 0.016 pH yr^{- 1}, and decreases of Ca²⁺ and Mg²⁺ (but not Na⁺) in three lakes. The acid neutralizing capacity (ANC) increased significantly in all six lakes. Increases in base cation concentrations (CB = Ca²⁺ + Na⁺ + Mg²⁺ + K⁺) were the principal contributing factor to ANC increases in the two lakes with positive ANC, whereas decrease in C_SA was the major factor in ANC increases in the four chronically-acidic lakes. The continued chemical recovery of these lakes depends on the uncertain trends in N deposition, the cycling of N in the lakes and their catchments, and the magnitude of the future decrease in S deposition.     

Long-term trends in the chemistry of precipitation and lake water in the Adirondack Region of New York,USA

Long-term changes in the chemistry of precipitation (1978–94) and 16 lakes (1982–94) were investigated in the Adirondack region of New York, USA. Time-series analysis showed that concentrations of SO₄ ^2–, NO₃ ^–, NH₄ ⁺ and basic cations have decreased in precipitation, resulting in increases in pH. A relatively uniform rate of decline in SO₄ ^2– concentrations in lakes across the region (1.81±0.35 eq L^–1 yr^–1) suggests that this change was due to decreases in atmospheric deposition. The decrease in lake SO₄ ^2– was considerably less than the rate of decline anticipated from atmospheric deposition. This discrepancy may be due to release of previously deposited SO₄ ^2– from soil, thereby delaying the recovery of lake water acidity. Despite the marked declines in concentrations of SO₄ ^2– in Adirondack lakes, there has been no systematic increase in pH and ANC. The decline in SO₄ ^2– has corresponded with a near stoichiometric decrease in concentrations of basic cations in low ANC lakes. A pattern of increasing NO₃ ^– concentrations that was evident in lakes across the region during the 1980's has been followed by a period of lower concentrations. Currently there are no significant trends in NO₃ ^– concentrations in Adirondack lakes.     

Ion leaching from a sugar maple forest in response to acidic deposition and nitrification

Year-to-year variation in acidic deposition within a mature sugar maple-dominated forest and in leaching of ions from the associated podzolic soil were examined at the Turkey Lakes Watershed between 1981 and 1986. Below-canopy inputs to the soil of SO₄ ^2? and NO₃ ^? in throughfall averaged 640 and 295 eq. ha^?1 yr^?1; the corresponding ranges were 493–917 and 261–443 eq. ha^?1 yr^?1. The contribution of atmospheric deposition to SO₄ ^2? NO₃ ^? and Ca²⁺ leaching decreased over the six years. During the study period, the mean annual volume-weighted NO₃ ^? concentration decreased in throughfall and forest-floor percolate and increased in the mineral-soil solution collected below the effective rooting zone. A substantial shift in the balance between SO₄ ^2? and NO₃ ^?leaching from the mineral soil was observed; leaching of SO₄ ^2?decreased and NO₃ ^? leaching increased with time. Leaching of Ca²⁺ and Mg²⁺ from the soil was increased as a result of excess NO₃ ^? production in the soil. The calculated output of NO₃ ^? from the soil, which averaged 1505 eq. ha^?1 yr^?1, considerably exceeded the atmospheric deposition of NO₃ ^?, whereas SO₄ ^2? outputs were only moderately greater than inputs.     

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.     

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.     

Acid pulses from snowmelt at acidic cone pond,New Hampshire

A study was undertaken to examine whether ‘acid pulses’ from snowmelt created permanent changes in a pond's chemistry. Water samples were collected from clearwater acidic Cone Pond in the White Mountain National Forest, New Hampshire. The pond, inlet, and outlet were intensively sampled throughout winter and early spring 1983–84. Thaws brought more H⁺ into upper waters of the pond, but most was gone within a week. In contrast, SO₄ ^2? and Al showed dilution with increased streamflow into the pond, and NO₃ ^? was only detected in ice, slush, and surface waters. Bottom waters were anoxic throughout the winter and had pH 6.0 compared to 4.7 for most of the water column. Alkalinity at the bottom rose from 0 in November 1983 to 190 μeq L^?1 in April 1984. Between November and April the pond gained Al but lost SO₄ ^2? and H⁺. Most of the Al gain came after ice-out when loading through the inlet increased, but during the final snowmelt a temporary increase in Al concentration was also seen throughout the water column.     

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.     

Recovery of acidified catchments in the extremely polluted Krusne hory Mountains,Czech Republic

Runoff and atmospheric chemistry in the Krusne hory Mts. have changed significantly from 1978 to 1994. Forest die-back related deforestation resulted in decreased dry deposition of SO₂ and changes in streamwater chemical composition. Atmospheric sulphur (S) deposition decreased from extremely high values of 66.6 kg S ha^?1 year^?1, in the early 1980s to 35.5 kg S ha^?1 year^?1 in 1994. Decreasing S input is reflected in decrease of streamwater sulphate (SO₄ ^2?) concentrations, which decreased from 1560 μeq l^?1 to 1164 μeq l^?1. Runoff export of S was 53 kg S ha^?1 year^?1 in 1993, S is not retained in the catchments. Nitrogen (N) budget indicates accumulation in the catchment, which is attributed to forest regrowth.     

Effects of simulated throughfall pH and sulfate concentration on a deciduous forest soil

A model deciduous forest soil (Schaffenaker loamy sand) was treated for 8 mo in the greenhouse in 25 cm reconstructed columns with simulated throughfall at pH 6.0 or 4.0, and SO₄ ^2? levels of 12.8 or 24.8 mg L^?1. Red oak seedlings grown in the microcosms showed no growth or foliar element response to the treatments. Sulfate loading had a greater impact on soil and leachate chemistry than pH. Higher available soil P in the A, horizon was associated with the pH 6.0 and high SO₄ ^2?2 treatment combination. High SO₄ ^2? loading also reduced exchangeable K⁺ in the A_1?. Other soil horizons were unaffected by either treatment. Leachate chemistry was not significantly altered by througfall pH, but significantly greater export of Na⁺, Ca²⁺, Mg²⁺, Al³⁺, and NO₃ ^?, and lower SO₄ ^2? loss, occurred with low SO₄ ^? input. Comparatively half as much NO₃ ^? loss was associated with high SO₄ ^2? deposition. The high rate of NO₃ ^? leaching appeared responsible for greater equivalent mass loss of cations from the low SO₄ ^2? treatment. Leachate removal of SO₄ ^2? approximated input after 8 mo. The capacity of this soil to adsorb SO₄ ^2? appeared relatively limited in the absence of normal element cycling. The sulfate component of simulated deciduous forest throughfall was shown to have a potentially greater impact than pH on ion leaching from forest soil. Additional consideration of the role of SO^2? ₄ deposition, in the context of throughfall rather than incident precipitation, is warranted in studies of acidic deposition effects on internal forest soil processes.     

Source Identification of Rural Precipitation Chemistry in Japan

Precipitation chemistry was discussed from the viewpoint of potential sources for four rural sites where wet-only daily-basis measurement data sets were available during the period from April 1996 to March 1997 in Japan. Annual volume-weighted mean concentrations of nss-SO₄ ^2? and NO₃ ^? ranged from 18.0 to 34.6 µeq L^?1, and from 9.3 to 23.1 µeq L^?1, respectively. The degree of neutralization of input acidity in terms of the concentration ratio, [H⁺] / ([nss-SO₄ ^2?] + [NO₃ ^?]), ranged from 0.46 to 0.63. This suggests that about half of the input acidity due to H₂SO₄ and HNO₃ was neutralized by NH₄ ⁺ and nss-Ca²⁺ to produce the pH values of 4.46 to 4.82 for these sites. Maximum likelihood factor analysis was then performed on the logarithmically transformed daily wet deposition of major ions. Two factors successfully explained a total of about 80% of the variance in the data for each site. Interpreting varimax rotated factor loadings, we could identify two source types: (1) acid source with large loadings on ln(H⁺), ln(nss-SO₄ ^2?), ln(NO₃ ^?) and ln(NH₄ ⁺), (2) sea-salt source with large loadings on ln(Na⁺), ln(Cl^?), ln(Mg²⁺) and ln(K⁺). The rural wet deposition over Japan appears to have a similar structure in terms of the kinds of sources and their relative location.     

Climate confounds detection of chemical trends related to acid deposition in upper Midwest lakes in the USA

Between 1983–94, as acid deposition rates declined, SO₄ ^2? concentrations decreased in 18 of 28 lakes monitored by the upper Midwest LTM program. The expected recovery of ANC and pH was less common, however. Differences in climate may account for divergent trend patterns across the region. Only in Minnesota, where climatic shifts were less pronounced, did we observe a general pattern of increasing lake ANC and pH accompanying declines in SO₄ ^2?. In contrast, the widespread negative trends in lake SO₄ ^2? in the upper Michigan lakes were generally not associated with recovery of ANC and pH, but with decreases in Ca+Mg. These cation decreases may be linked to decreased groundwater inputs during the drier climatic conditions characterizing the study period and decreases in Ca+Mg in atmospheric deposition. In many of the Wisconsin lakes, an overall decline in SO₄ ^2? was precluded by SO₄ ^2? increases during a 4-year drought midway through the study period. During the drought, declining lake water level and volume caused evaporative concentration of solutes, and may have decreased the areal extent of sulfate reduction. Despite controls on sulfur emissions across the region, recovery of pH and ANC has been hindered by climatic shifts and concurrent decreases in atmospheric deposition of cations.     

Trends in Surface Water Acidification in Europe and North America (1989–1998)

During the last 20 years, emission reductions in Europe and North America have resulted in decreased atmospheric S-deposition of up to 50%, while N-deposition has stayed almost constant. Data from 98 ICP Waters sites were tested for trends in concentrations of major chemical components for the 10-year period 1989-1998 using the nonparametric seasonal Kendall test. The sites were grouped into regions and types for meta-analysis. All of the regions had highly significant downward trends in SO₄ ^2?* concentrations. Nitrate concentrations, on the other hand, show no regional patterns of change. Concentrations of base cations declined in most regions. All regions showed tendencies of increasing DOC. The low ANC sites showed the largest rates of recovery. Neither the high NO₃ ^? or low NO₃ ^? groups of sites exhibited significant trends in NO₃ ^? concentrations. Alpine (non-forested) sites show clear and consistent signals of recovery in ANC and pH, and appropriate (relative to SO₄ ^2?* trends) rates of base cation decline.     

Extreme acidification of a lake in southern Norway caused by weathering of sulphide-containing bedrock

In 1986 Lake Langedalstjenn in southern Norway was a weakly acidified lake with a pH of 5.2–5.6, and an average concentration of SO₄ of 330 μeq L^?1. The total Al concentration varied between 10 and 20 μeq L^?1 (expressed as Al³⁺). The lake supported populations of brown trout and perch and had supplied about 100 people with drinking water until the late 1980's. During 1986–1989, a dramatic change in the water chemistry occurred because of blasting of and weathering of sulphidic gneisses in the watershed. The oxidation of sulphide to sulphate (sulphuric acid) caused an increase in the SO₄ concentration of the draining stream of up to ≈ 4800 μeq L^?1. Weathering and/or cation exchange of Ca and Mg neutralized approximately 52% of the protons from the sulphuric acid production, while about 46% were consumed by mobilization of aluminium and iron. Nevertheless, about 2% of the hydrogen ions from the sulfuric acid were still present, which resulted in a stream pH of 4.0. In the lake, the pH was 4.4, and the concentrations of all major cations and anions were significantly lower than in the heavily affected stream. Mixing of the stream water with lake water, formation of aluminium-sulphate complexes and coprecipitation of Ca may explain the resulting concentrations of major ions in the lake.