Role of precipitation chemistry versus other watershed properties in Wisconsin lake acidification

Data for over 100 watershed properties, including aspects of topography, hydrology, geology, soils, vegetation, lake morphometry and input precipitation chemistry, have been developed since 1980 for 316 watersheds in northern Wisconsin. The hypothesis being evaluated for this lake population is that the observed water chemistry, can be accounted for as a function of antecedent water and chemical inputs, after considering exchange processes in the lake and watershed and the lake/groundwater interactions. The variables found by regression analysis to explain observed variability in color, sulfate, and acid neutralizing capacity (ANC) levels in Wisconsin lakes are: for color, vegetative characteristics, mean depth, and water renewal times; for sulfate, precipitation concentration of sulfur, evaporative concentration, and lake water renewal time; ANC appears to be controlled by the size of the watershed, lake depth or water renewal time, and the intensity of anthropogenic inputs and cultural developments in the watershed. These results differ from previous studies in Wisconsin and nearby areas of Michigan and Minnesota by indicating that in some lakes acidity may not be in equilibrium with current precipitation chemistry.     

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.     

Effects of lake liming on phytoplankton production in acidic Adirondack lakes

Phytoplankton community characteristics were monitored prior to and following CaCO₃ addition to two small, highly acidic lakes (Cranberry Pond and Woods Lake) and one larger, less acidic lake (L. Simon Pond). Data were also collected from a control site (Dart's Lake) exhibiting chemical characteristics similar to the pretreatment conditions observed at the experimental sites. In the two small, most acidic lakes, base addition was associated with higher chlorophyll levels during the first summer following treatment. Woods Lake was maintained at a circumneutral pH for 3 yr and exhibited increased phytoplankton abundance throughout the posttreatment period. In contrast, Cranberry Pond reacidified within 1 yr following based addition. Reacidification was accomplished by a decrease in lake chlorophyll levels to pre-treatment levels. At the larger, less acidic lake (L. Simon Pond), liming was associated with lower chlorophyll levels during the first summer after treatment. Reductions in chlorophyll levels at L. Simon Pond reflect the absence of the spring phytoplankton peak and a decrease in phytoplankton growth below the depth of the thermocline. At Cranberry Pond, annual differences in phytoplankton production did not correspond to changes in lake acidity and phytoplankton abundance. Productivity in Woods Lake exhibited an increasing trend during the 3 yr following treatment. Interpretation of treatment effects on productivity was confounded by high between-year variability at the control site.     

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.     

Biogeochemistry of a forested watershed in the central Adirondack Mountains: Temporal changes and mass balances

Information on atmospheric inputs, water chemistry and hydrology were combined to evaluate elemental mass balances and assess temporal changes in elemental transport from 1983 through 1992 for the Arbutus Lake watershed. This watershed is located within a northern hardwood ecosystem at the Huntington Forest within the central Adirondack Mountains of New York (USA). Changes in water chemistry, including increasing NO₃ ^? concentrations (1.1 μmol _c , L^?1 yr-1), have been detected during this study period. Starting in 1991 hydrological flow has been measured from Arbutus Lake and these measurements were compared with predicted flow using the BROOK2 hydrological simulation model. The model adequately (r²=0.79) simulated flow from this catchment and was used to estimate drainage for earlier periods when direct hydrological measurements were not available. Modeled drainage water losses coupled with estimates of wet and dry atmospheric deposition were used to calculate solute budgets. Export of SO₄ ^2? (831 mol _c ha^?1 yr^?1) from the greater Arbutus Lake watershed exceeded estimates of atmospheric deposition in an adjacent hardwood stand suggesting an additional source of S. These large drainage losses of SO₄ ^2? also contributed to the drainage fluxes of basic cations (Ca²⁺, Mg²⁺, K⁺ and Na⁺). Most of the atmospheric inputs of inorganic N were retained (average of 74% of wet precipitation and 85% total deposition) in the watershed. There were differences among years (56 to 228 mol ha^?1 yr^?1) in drainage water losses of N with greatest losses occurring during a warm, wet period (1989–1991).     

Acid deposition and lake chemistry in southwest China

A water quality survey has been performed on selected lakes and streams in southwest China. The purpose of the study was to measure the concentrations of acidic deposition and surface water chemistry in a region of severe air pollution, forest decline, and relatively sensitive geology to acidic deposition. We show that, although there are some high elevation lakes of low acid neutralizing capacity (ANC<150μeq L^?1, acidification of lakes has not occurred in southwest China due to production of base cations in soil and dry deposition of dust that serves to neutralize acidic deposition. Water chemistry is buffered by high base cation concentrations (Ca²⁺, Mg²⁺, Na⁺, and K⁺ greater than 300μeq L^?1, and pH values are always greater than 6.5.     

Environmental chemistry of copper in torch lake,Michigan

A study of Keweenaw Peninsula and adjacent Lake Superior waters was undertaken to evaluate the significance of Cu tailings deposits as a potential source of Cu and the controlling Cu concentrations in these waters. Metal concentrations were determined by atomic absorption techniques. Copper concentrations, especially in areas affected by discharge of large quantities of Cu mine tailings for over 100 yr, were relatively high. Concentrations of apparently dissolved Cu of up to 100 μg 1^?1 were found in Torch Lake in the summer of 1972. These high Cu levels may be partially explained by industrial spills of copper wastes that occurred around that time. However, relatively high concentrations appeared to persist in Torch Lake waters throughout the annual cycle. The vast quantities of crushed Cu-bearing ore that comprise the bottom sediments and line the shores show a Cu content ranging from 1300 to 3800 mg 1^?1. These materials act as a reservoir of Cu providing a continual supply of Cu to these waters. Laboratory leaching studies of these materials demonstrate that they can release potentially significant amounts of Cu when suspended in lake water. Although the Cu levels found in Torch Lake exceed US EPA-recommended maximum allowable levels for these waters, there are reports of substantial fish and algal populations. Equilibrium calculations indicate the predominance of various soluble Cu species in the following order of abundance: Cu(OH)⁺ > Cu⁺⁺ > CuCO₃. However, Cu in these waters may not be controlled by solubility relationships of Cu compounds but rather by sorption onto surfaces of Fe and Mg hydrous oxides resulting in the occurrence of Cu in relatively non-toxic forms. Any additional mining or reclamation operations pose a potential hazard to aquatic ecosystems because of the wide-spread Cu contamination that already exists in the waters of this area.     

The role of dissolved organic carbon in the chemistry and bioavailability of mercury in remote Adirondack lakes

A number of recent studies have documented elevated concentrations of mercury (Hg) in fish caught in remote lakes and a pattern of increased concentrations of Hg in fish tissue with decreasing water column pH. Because of the potential linkage between fish Hg and surface water acidification, factors regulating water column concentrations and bioavailability of Hg were investigated in Adirondack lakes through a field study and application of the Mercury Cycling Model (MCM). Concentrations of total Hg and total MeHg were highly variable, with concentrations of total MeHg about 10% of total Hg in lakes which did not show anoxic conditions. In lakes exhibiting anoxic conditions in the hypolimnion during summer stratification, concentrations of total MeHg were elevated. Concentrations of total Hg and total MeHg increased with decreasing pH in remote Adirondack lakes. However, more importantly, concentrations of total Hg and total MeHg increased with increasing concentrations of dissolved organic carbon (DOC) and percent near-shore wetlands in the drainage basin. Mercury concentrations in muscle tissue of yellow perch from Adirondack lakes were elevated above the U.S. FDA action level (1 μg/g Hg) in 7% of the fish sampled or in one or more individual fish from 9 of the 16 lakes sampled. Fish Hg concentrations generally increased with increasing fish length, weight and age. Patterns of increasing Hg concentration with age likely reflect shifts in prey of yellow perch and the bioconcentration of Hg along the food chain. For age 3 to 5 perch, concentrations of Hg increased with increasing concentrations of DOC and percent near-shore wetlands in the drainage basin. However, for a lake with very high DOC concentrations, fish concentrations of Hg declined. Calculations with the MCM also show that concentrations of Hg species increase with increasing DOC due to complexation reactions. Increases in DOC result in increasing concentrations of Hg in biota but decreases in the bioconcentration factor of Hg in fish tissue. This research suggests that DOC is important in the transport of Hg to lake systems. High concentrations of DOC may complex MeHg, diminishing its bioavailability. At high concentrations of monomeric Al, the complexation of MeHg with DOC apparently decreases, enhancing the bioavailability of MeHg.     

Headwater lake chemistry during the spring freshet in North-Central Ontario

From data on 30 headwater lakes in north-central Ontario we found that, during the spring snow melt of 1981, all lakes underwent serious declines in alkalinity. Generally, SO₄ ^2?, alkalinity, Ca⁺ and Mg²⁺ concentrations were reduced by runoff and rain then recovered to intermediate levels after the major inputs declined. As expected, a range in responses was evident with lower alkalinity systems showing the greatest changes. The observed changes, however, were consistent with acid loading having depleted alkalinity. In calculating an input-output budget for each lake, we found that changes in Cl^?, Na⁺, and K⁺ were consistent with atmospheric inputs being the major source as the difference between the expected input and the actual contribution from rain and snow had a mean near zero. There appears to be a significant, ? 45%, watershed source of sulphate that we hypothesize is from dry deposition occurring prior to snowfall and is eluted with the melting process. With refinements to a mass balance approach explaining the watershed source of SO₄ ^2? and Al, we feel it is possible to predict springtime lake changes given a few chemical and simple morphometric variables.     

Sulphur deposition and changes in Swedish lake chemistry 1988–1993

Acidification of surface waters in northern Europe due to anthropogenic sulphur (S) deposition has led to new emission restrictions based on Critical Loads (CL). There is likely to be considerable interest in documenting the effect resulting S deposition changes have on surface water quality. This paper will focus on how the chemistry of 134 reference lakes in Sweden has changed between 1988 and 1993 in response to a decline in S deposition. Only 10% of the reference lakes had significant declines in sulphate during the 5 year study period. A similar number of lakes had an increase in the acid neutralizing capacity (ANC), but few of those with an increase in ANC were also lakes with significant sulphate decreases. Since there is good evidence that S deposition decreases will eventually result in ANC increases, a five year period is probably too short for evaluating the S protocol in terms of changes in lake chemistry. It takes a number of years to equilibriate to new deposition levels, and weather patterns may also obscure longer term trends.     

An evaluation of New York state lake liming data and the application of models from Scandinavian lakes to Adirondack lakes

Limestone dissolution efficiencies and reacidification rates observed in ten small Adirondack Mountain lakes, treated in 1983 to 1984 as part of the Extensive Liming Study (ELS), were compared with Scandinavian model predictions of dissolution (Sverdrup and Bjerle, 1983), and reacidification (Wright, 1985). The standard deviation of predicted initial dissolution was 15.4% of the observed fraction of limestone dissolved. Model predictions of dissolution for the Scandinavian lakes were similarly within 8 to 14% of observed values. Further analysis of the ELS data indicated that of the dissolution model parameters, dose rate alone was the best predictor of initial dissolution efficiency. Dissolution rates declined exponentially with time to undetectable levels within 2 to 3 yr following treatment. Total limestone dissolution efficiencies were in the range of 17 to 59% for the ELS lakes, which are comparable to levels observed in Scandinavian treatments with similar limestone materials (26 to 64%). Analysis of data from other Adirondack lakes limed by private groups and the New York State Department of Environmental Conservation for fisheries management programs, yielded similar estimates of dissolution efficiency for calcite based materials (average 36%). However, some of these lakes which were treated with slaked lime [Ca(OH)₂], exhibited initial dissolution efficiencies approaching 100%. The simple two box dilution model of reacidification, satisfactorily predicted Ca loss rates in the ELS lakes, indicating the importance of hydrology (water retention time) as a factor controlling reacidification rates in these small, limed lakes. For the ELS lakes, the ratio of watershed area/lake volume satisfactorily predicted Ca loss rates (R² = 0.96) and this simplified empirical model was applied to other Adirondack lakes where inadequate water chemistry and hydrologic data were available to utilize the dilution model. Limed Adirondack lakes with mean water retention times less than 4 mo reacidified within 1 yr after treatment. Given the preponderance of acidified lakes in the Adirondack region with retention times less than this threshold value of 4 mo (approximately 80% of lakes <10 ha surface area), simple whole lake liming practices would not be adequate for maintaining water quality suitable for the support of viable fish populations in these lakes.     

Anthropogenic trace elements and polycyclic aromatic hydrocarbon levels in sediment cores from two lakes in the Adirondack acid lake region

Sediment cores were taken from the remote Sagamore and Woods Lakes in New York State's Adirondack acid lake region and analyzed for 3 to 7 ring polycyclic aromatic hydrocarbons (PAHs) and Ag, Al, As, Be, Cd, Cr, Cu, Hg, Ni, Ph, Se, Sn, TI, V, and Zn. With the exception of perylene, all of the parental PAHs, e.g. those without sidechains, and several of the metals, Pb, As, and Cd, were found to be significantly increased in the sediments of both lakes compared to their natural integrated deposits (ng cm^?2) and their background concentrations (μg g^?1 or ng g^?1 dry wt). Although the concentrations were generally much higher in Woods Lake, the total anthropogenic integrated depositions were about the same in both lakes for most of the metals and the 3 to 4 ring PAHs. The prime source of most of the 3 to 7 ring PAHs and trace elements measured is ascribed to anthropogenic combustion. Anthropogenically derived materials decreased in concentration with depth to baseline levels in sediment layers estimated by¹³⁷Cs analyses to be ～30 yr old, while biogenic or crustal derived species remained constant or fluctuated with core depth.     

Testing,improvement, and confirmation of a watershed model of acid-base chemistry

Strategies to control the emission of atmospheric pollutants such as sulfur and nitrogen, are generally based in large part on projections using models that simulate the influence of sulfur and/or nitrogen deposition on the acid-base chemistry of surface waters. One of the principal models used throughout Europe and North America for such assessment is the Model of Acidification of Groundwater in Catchments (MAGIC). All watershed models are simplified representations of reality, and as such require careful testing to establish their veracity prior to use for making policy projections. This is particularly true where the use of these model projections has the potential for serious environmental or economic consequences. During the past five years, we have tested the MAGIC model in a large variety of settings and under quite varying environmental conditions. This work has included comparing model hindcast simulations with diatom-inferences of historical acidification, sensitivity analyses to examine the response of the model to alternative assumptions and formulations, and detailed testing of model forecasts by comparing simulated chemistry with the results of catchment-scale and plot-scale experimental acidification and deacidification. Our analyses have elucidated a number of potentially-important deficiencies in model structure and method of application. These have resulted in changes to the model and its calibration procedures. Our work has included in-depth evaluation of issues related to regional aggregation of soils data, background sulfur deposition, natural organic acidity, and aluminum mobilization. The result has been an improved and more thoroughly-tested version of MAGIC. The process we have followed to improve and confirm the MAGIC model has been iterative and time consuming. It required the availability of large volumes of data from experimental manipulation and paleolimnological studies. We believe that such model testing and confirmation efforts should be a critical prerequisite for regional or national assessment activities that are based largely on the results of environmental models.     

Aerosol and precipitation chemistry relationships at big bend national park

Aerosol chemistry, precipitation and visibility parameters are currently being measured at Big Bend National Park in Texas. This is part of a large-scale air resource evaluation program which the National Park Service is sponsoring in several southwestern national parks and monuments to determine the potential impact of local and distant pollutant sources on the environmental quality within these areas. Analysis of aerosol samples collected at six sites in the Southwest indicates that soil-derived components, organic materials and the acid-base ions of sulfate, nitrate, and ammonium are the major constituents of suspended airborne particulate matter in the remote areas of the arid region. Comparison of particulate matter chemistry and precipitation chemistry data at Big Bend National Park shows consistent features which indicate that the airborne alkaline soil material and NH₃ largely neutralize the atmospheric acidic species of H₂SO₄ and HNO₃. Given the similarity of the particulate matter composition and loading at the other monitoring sites, it is suggested that the trace chemical composition of precipitation will be similar in many remote regions of the Southwest.     

Gårdsjön Project: lake acidification,chemistry in catchment runoff,lake liming and microcatchment manipulations

The Gårdsjön Project is an ecosystem approach in studying acid deposition and its effects on terrestrial parts and lakes within a catchment. The study is an attempt to quantify the processes causing the acidification as well as an analyses of the chemical and biological conditions before liming of the lake and manipulations in microcatchments. This paper gives a brief overview of some studies already performed and recently started experiments within the project, such as lake liming, lime application on land, forest fertilization, clearcutting and applications of acid and neutral sulphate on land.     

Chemistry differences in two streams entering an acidic lake in the Adirondack Mountains,New York (U.S.A.)

Solution chemistry was measured in two major inlets, lake water column, lake outlet, and soils of the South Lake watershed in the Adirondack Mountains, New York. The east inlet had greater concentrations of H⁺, sulfate-S, and Al and smaller concentrations of base cations and silica than the west inlet (70, 116, 25, 90, 64 and 4, 99, 8, 228, 148 μeq L^?1 of H⁺ and sulfate-S, μmol L^?1 Al, μeq L^?1 total base cations and μmol L^?1 silica in east and west inlets, respectively). Concentrations of base cations in C horizon soil solutions (157 μeq L^?1 total base cations) were smaller and greater than west and east inlets, respectively. This suggests that water flowing into the west inlet contacted deeper mineral layers, whereas water reaching the east inlet did not. Lake and lake outlet concentrations were also intermediate between the two inlets, and the lake was acidic (pH 4.9 to 5.1) with relatively high total monomeric Al concentrations (8 to 9 μmol Al L^?1). The east inlet also had greater DOC concentrations than the west (0.38 and 0.24 μmol C L^?1, respectively), again indicating that soil solutions entering the east inlet passed through the forest floor but had more limited contact with deeper mineral layers in comparison with the west inlet. Differences between the streams are hypothesized to be related to contact of percolating solutions with mineral soil horizons and underlying glacial till, which provides neutralization of acidic solutions and releases base cations. This work indicates that processes controlling surface water acidification can be spatially quite variable over a small watershed.     

Denitrification characteristics of pond sediments in a Chinese agricultural watershed

Ponds are widely distributed in rice-based agricultural watersheds, particularly in southern China, and may play an important role in nitrate (     ) removal. However, the denitrification rate of pond sediment, measured using the acetylene (C₂H₂) inhibition technique, indicated that the amount of nitrogen removed by denitrification accounted for <1% of the total nitrogen applied. The present study was undertaken to determine the effects of sediment depth and temperature on denitrification of pond sediment using the C₂H₂ inhibition technique. The highest denitrification potential was found in the upper 5 cm of sediment, but this only accounted for approximately 34% of the total denitrification of the upper 0–30 cm of sediment, suggesting that sediment denitrification potential would be underestimated if only the upper 5 cm of sediment was measured. The denitrification potential was low and showed a weak response over a temperature range of 6–18°C, whereas denitrification increased significantly from 18 to 30°C, indicating that denitrification may play an important role in the removal of     in warm seasons. A comparison of the     disappearance and C₂H₂ inhibition methods showed that they were significantly ( P  < 0.01) and positively correlated. However, the C₂H₂ inhibition method gave only approximately 25% of the values determined by the     disappearance method.     

太湖流域麦田土壤氮素流失过程的模拟研究

应用田间模拟降雨,研究了太湖流域稻麦轮作方式下,不同雨强和施氮水平对农田氮素径流流失的影响。结果显示,随施氮量增加,农田径流液中氮素的平均浓度和氮素径流累积流失量提高,两者间呈显著正相关。降雨量相同的条件下,低雨强农田产生径流时间较长,而高雨强引起的农田径流量较高;低雨强引起的农田氮素径流累积流失量较高,高雨强引起的农田氮素径流累积流失量较低,这种现象在中、高施氮水平条件下更为明显。试验还表明,在降雨量相同的条件下,降雨持续时间长的小雨引起的农田氮素径流流失量要超过降雨持续时间短的大雨。     

Trends in small lake water chemistry near Sudbury,Canada, 1983–1991

While many studies have documented improvements in chemical conditions of large lakes near Sudbury, Canada in response to reduced smelter emissions, few have examined changes in water chemistry of small lakes. We studied trends in water chemistry of 97 small (<10 ha), shallow (<15 m) lakes northeast of Sudbury that are important habitat for breeding waterfowl. Currently, many small lakes near Sudbury are acidified, with little acid-neutralizing capacity and with relatively high concentrations of Al, Mn, and Ni. We also present evidence of short-term improvements in pH and SO₄ levels, but demonstrate that, over a nine year period, there has been no consistent, long-term trend of chemical recovery. Chemical conditions in these lakes varied considerably between 1983 and 1991, and responded quickly to changes in precipitation levels. However, the present condition of most lakes suggests that further reductions in emissions will be required to improve these habitats for breeding waterfowl.