Changes in water quality in the Laflamme Lake Watershed Area,Canada

The Laflamme Lake Watershed Area is located in a sensitive region on the Canadian Shield and is subjected to wet atmospheric loading between 17 and 25 kg ha^?1 yr^?1. From 1981 to 1988, the level and fluctuations of the atmospheric deposition of acidifying substances has led to various responses in the water chemistry of headwater lakes in the area. The general trend in atmospheric inputs is a gradual increase of acidifying substances from 1981 to 1985 followed by a 2 yr decrease then a return to previous values. In the two lakes with almost no alkalinity acidification has occured throughout the 1983 to 1988 period. In the four lakes with slightly higher alkalinity values, a reversal in acidification is seen when atmospheric loading decreased in 1986. Along with the interannual trends, seasonal variability to acidification occurs with sensitivity of surface waters being highest during spring melt. Sensitivity to acidification can also be altered by watershed processes and in the Laflamme Lake Watershed, soil processes are effective in altering the acidity of precipitation before it reached the lake. In this watershed, wet atmospheric inputs of H⁺ and NO₃ ^? are larger than surface water outputs while the reverse occurs for Ca²⁺, Mg²⁺, Na⁺, K⁺, Cl^? and SO₄ ^2?.     

Empirical models for lake acidification in the upper Great Lakes Region

A large data base on inland lakes in the Upper Great Lakes Region (UGLR) was used to evaluate assumptions and relationships of empirical acidification models. Improved methods to calculate background alkalinity and background SO₄ ^2? are reported; SO₄ ^2? enrichment factors indicate that terrestrial SO₄ ^2? sources and watershed or lake sinks must be considered for site-specific background SO₄ ^2? estimates. Significant relationships were found between lake acidification estimated as change in SO₄ ^2? and precipitation acidity but not between changes in lake alkalinity and precipitation acidity in this lightly impacted region.     

Influence of atmospheric deposition on lake mass balances in the Turkey Lakes Watershed,Central Ontario

Ion mass budgets were measured for 2 water yr (June–May, 1981–83) for a high and a ).ow elevation lake and their associated catchments. The lakes are located in the Turkey Lakes Watershed (TLW) in central Ontario, Canada, which is an undeveloped basin located on the Canadian Shield, 50 km north of Sault Ste. Marie. The ionic budgets of the lakes show that atmospheric deposition directly to the lakes' surfaces is the principal input pathway for H⁺ and NH₄, whereas basic cations, SO₄, NO₃, and probably alkalinity are supplied primarily by inflow from the surrounding terrestrial basin and/or upstream lake. The lakes strongly retain H⁺ (i.e. output ? input), weakly retain the N species, and are in balance (i.e. output = input) for other ions except Ca and alkalinity which show an excess output compared to measured + estimated inputs. We hypothesize that an input of groundwater and/or seepage accounts for most of the Ca and alkalinity imbalance although the existence of within-lake alkalinity generation is probable also.     

Alkalinity production in epilimnetic sediments: Acidic and non-acidic lakes

Interstitial water profiles in epilimnetic sediments of lakes with varying water column alkalinities were collected to assess the origin and importance of sedimentary alkalinity in freshwater lakes. Release of Ca²⁺ and NH₄ ⁺, and consumption of SO₄ ^? are the most important contributors to alkalinity production m sediments of non-acidic lakes. In acidic lakes, Fe²⁺ and Mn²⁺ replace Ca²⁺ as the dominant cation contributors to alkalinity production. The sedimentary alkalinity flux is an important component of the acid neutralizing capacity of freshwater lakes. However, the presence of large alkalinity gradients in sediment porewaters does not necessarily indicate a large source of alkalinity for the lake, as a significant portion of the alkalinity iu associated with the formation of Fe²⁺, Mn²⁺ and NH₄ ⁺ Oxidation of Fe²⁺ and Mn²⁺ at the anoxic-oxic interface and biological removal of NH₄ ⁺ in the overlying water column results in consumption of the co-diffusing alkalinity.     

The use of calibrated lakes and watersheds for estimating atmospheric deposition near a large point source

We have measured the input and output rates of substances to and from both lakes and watersheds in the Sudbury and Muskoka-Haliburton areas of Ontario. At the former location, we have conducted mass balance studies on 5 lakes and their watersheds for 2½ yrs. At the latter site, we have measured mass balances for 6 lakes and about 30 individual watersheds for the past 5 yrs. Substances studied included SO₄ ^2?, NO₃ ^?, NH₄ ⁺, H⁺, major cations (Ca²⁺, Mg²⁺, Na⁺, K⁺) and HCO₃ ^?. During the course of the investigation at Sudbury we have made several observations that indicate that the inputs of some substances, specifically SO₄ ^2? or SO₄ ^2?-precursors and strong acids, to lakes and watersheds are underestimated when measured as bulk deposition (i.e. by collection in a continuously open container): (a) The output of SO₄ ^2? from the calibrated watersheds was substantially greater than the input measured as bulk deposition. (b) The SO₄ ^2? concentrations of the lakes could not be explained on the basis of the measured inputs. An additional input directly to the lake surface was needed to obtain a mass balance. (c) The net input of acids measured as bulk deposition to the watersheds was much less than the acid consumed, which was estimated by the net output of Ca²⁺, Mg²⁺, Na⁺, K⁺, Al³⁺, and the net retention of NO₃ ^?. (d) The major cation content of the study lakes could be explained on the basis of weathering reactions in the lakes' watersheds only if the input of strong acid had been underestimated. When these observations were quantified, they indicated a major portion of the total input of SO₄ ^2?-precursors and of strong acid was not included in our bulk deposition measurements. Deposition of SO₂ is the most likely explanation for these observations.     

Episodic acidification during snowmelt of high elevation lakes in the Sierra Nevada mountains of California

Atmospheric loads to dilute lakes in the Sierra Nevada mountains of California are very low, and fall almost entirely as snow. When acidic anions preferentially elute from melting snow, these low loads may nontheless be enough to acidify low ANC lakes. Two of the ten lakes included in the Sierra Episodes Study are discussed here: High Lake, the only lake in the study to become acidic during snowmelt; and Treasure Lake, typical of the remainder of the lakes. All lakes exhibited increases in NO₃ ^? concentrations during early snowmelt; these were accompanied by increases in base cations, primarily Ca²⁺. In the first few days of snowmelt, NO₃ ^? concentrations at High Lake increased more rapidly than concentrations of base cations, resulting in ANC values below zero. Export of both NO₃ ^? and SO₄ ^2? from the watersheds exceeded the inputs from the snowpack, suggesting that other sources (e.g., watershed minerals, stored inputs from the previous summer, transformations of other inputs) of these anions are important.     

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.     

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.     

In-lake alkalinity generation by sulfate reduction: A paleolimnological assessment

The generation of alkalinity by SO₄ reduction and net storage of reduced S in lake sediments has been estimated from an analysis of sediment cores from 16 lakes in ME, VT, NY, MI, MN, and WY. The cores have been dated by ²¹⁰Pb. The rate of pre-1850 (background) storage of S in lake sediments suggests that alkalinity contribution to lake water from this process ranged from 0.2 to 9.3 geq L^?1, with an average of 4 geq L^?1, Background values are similar for all lakes and remain low in the WY lakes up to the present. Maximum alkalinity contributions recorded in sediment, from upper mid-west and eastern lakes, dated between 1850 and 1985 are between 0.4 and 33 geq L^?1, with a lake mean maximum of 9.9 geq L^?1, Significant increases in recent S storage only occur in eastern lakes. Average values for net S accumulation in the sediment of most lakes for post-1850 sediment are typically less than half of maximum values.     

Watershed vs in-lake alkalinity generation: A comparison of rates using input-output studies

As a means of assessing the relative contributions of watershed (terrestrial) and in-lake processes to overall lake/watershed alkalinity budgets, alkalinity production rates for watersheds and low alkalinity lakes were compiled from the literature and compared. Based on net alkalinity production data, derived using wet or bulk deposition data, mean and median alkalinity production for 20 watersheds in North America and Europe were 89 and 69 meq m^?2 yr^?1 (range 20 to 235 meq m^?2 yr^?1). For a subset of 10 watersheds with dry deposition data, terrestrial alkalinity production neutralized an additional 35 meq m^?2 yr^?1 of acidic deposition. For 11 lakes, mean and median in-lake alkalinity generation were 99 and 88 meq m^?2 yr^?1 (range 22 to 240 meq m^?2 yr^?1). Analysis of data indicates that for the low alkalinity systems described here, areal alkalinity production rates for watersheds and lakes are approximately equal. This relationship suggests that watershed area to lake area ratio can be used as a convenient estimator of the relative importance of watershed and in-lake sources of alkalinity for drainage lake systems. For precipitation-dominated seepage lakes and other systems where hydrology limits soil-water contact, hydrologic flow paths and residence times can be of overriding importance in determining alkalinity sources. For regions dominated by drainage lakes with high watershed area to lake area ratios (such as the Northeastern U.S.), however, alkalinity budgets are dominated by watershed processes. Omission of in-lake alkalinity consideration for most lakes in such regions would have little impact on computed alkalinity budgets or on predicted response to changes in acidic deposition loadings.     

Pathways of chemical recovery in acidified,metal-contaminated lakes near Sudbury,Ontario, Canada

This paper describes the recovery pathways of two lakes situated near the Coniston nickel-copper smelter. These lakes were exposed to very intense airborne pollution, including SO₂, H₂SO₄, Ni and Cu, during the 60 year operation of the smelter. After the closure of the Coniston smelter in 1972 and the subsequent improvement in air quality, the water quality in both lakes began to improve. Despite their proximity and exposure to similar inputs, the lakes differed both in the rate and magnitude of recovery. This study demonstrates the capacity of lakes to recover from chemical stresses over a very short period. Changes in Cu and Ni concentration could be predicted, while changes in pH, measured as H⁺, could not. The reasons for this discrepancy as well as the processes and lake parameters that control chemical recovery are discussed.     

The significance of in-lake production of alkalinity

Alkalinity production in terrestrial and aquatic ecosystems of Canada, the U.S.A., Norway and Sweden is calculated from either strong acid titrations or budgets for base cations and strong acid anions, using mass-balance budgets. Where alkalinity budgets for lakes and their catchments are calculated in acid-vulnerable geological settings, in-lake processes often contribute more to lake alkalinity than yield from terrestrial catchments. Nitrate and sulfate removal, and Ca exchange with sediments are the predominant alkalinity generating mechanisms in lakes. Nitrate and sulfte removal rates increase as the concentrations of NO^? ₃ and SO₄ ^2? in lake water increase, so that in-lake acid neutralizing capacity increases as acid deposition increases. Both processes occur in sediments overlain by oxic waters, at rates which seem to be controlled primarily by diffusion.     

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).     

Patterns of water chemistry among twenty-seven oligotrophic lakes in Kejimkujik National Park,Nova Scotia

A cluster analysis was used to apportion 27 oligotrophic lakes in southwestern Nova Scotia into five multivariate groups on the basis of patterns of covariation of 11 chemical variables (Cl, SO₄, Gran alkalinity, organic anions, Ca, Mg, K, Na, H⁺, and color). These groups are described in terms of the average values of the chemical variables. The relationships among the groups were investigated by an ordination by detrended correspondence analysis. The first, and by far the strongest axis of the ordination separated lakes with relatively large concentrations of alkalinity, from strongly colored lakes with large concentrations of H⁺ and organic anions. Axis 2 separated acidic lakes, from lakes with large concentrations of Ca and alkalinity.     

Seasonal,annual and long-term variability in the water chemistry of a remote high mountain lake: Acid rain versus natural changes

Seasonal fluctuations as well as long-term trends in water chemistry were studied in Schwarzsee ob Sölden (Tyrol, Austria), an oligotrophic softwater lake situated at 2796 m a.s.l. The catchement is composed of granite, plagioclase and micaschists containing considerable amounts of sulphur, with little soil cover. The lake is ice covered for about nine months, during this time the deepest layers (>16m) become anoxic. During summer overturn, alkalinity (ALK) is lowest (?8 μeq l^?1) in the whole water column, whereas pH reaches its minimum (4.88) at the surface during snowmelt. A decrease of pH from 5.8 to 5.4 during winter is caused by CO₂ oversaturation, but deep water ALK increases to up to 130 μeq l^?1 due to in-lake ALK generation by reductive processes and base cation (BC) release. The seasonal pattern of ALK in SOS is driven by in-lake processes in winter, the snowmelting in spring and watershed processes and precipitation during summer. Since 1989 summer sulfate concentrations in SOS, originating mainly from the catchment, show a tendency to increase presumably caused by enhanced weathering. In contrast, SO₄ ^2? concentrations in other high mountain lakes which are dominated by atmospheric depositions show a decreasing trend. SOS is a good example for the complexity of interactions between catchment and in-lake processes which act at different time scales and depend on climate changes and atmospheric inputs.     

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.     

Element Budgets in a Forested Watershed in Southern China: Estimation of a Proton Budget

We evaluated the element budgets in a forested watershed in Jiulianshan, southern China. The element input in bulk precipitation was characterized by high depositions of H⁺, NH₄ ⁺, Ca²⁺, and SO₄ ^2?, i.e., 400, 351, 299, and 876 eq/ha/yr, respectively. The outputs of H⁺, NH₄ ⁺, and SO₄ ^2? from the watershed were very low, while those of Ca²⁺ and Mg²⁺ were high, 712 and 960 eq/ha/yr, respectively. The element budgets suggested that i) the net retentions of H⁺, NH₄ ⁺, and SO₄ ^2? in this watershed were high, and ii) the net release of Mg²⁺ from this watershed was high mainly due to weathering. The net release of Ca²⁺ was not so high because of the high atmospheric deposition, while atmospheric deposition of Mg²⁺ was not so high (130 eq/ha/yr). Decrease of acid neutralizing capacity in the soil, i.e., net soil acidification, was caused mainly by the net release of Mg²⁺. Moreover, the net retention of SO₄ ^2? also contributed to soil acidification.     

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.     

Relations between lake acidification and sulfate deposition in Northern Minnesota,Wisconsin, and Michigan

From a level of 1 kg ha^?1yr^?1 in north central Minnesota, emission-related wet SO₄ deposition increases across northern Wisconsin and northern Michigan to about 18 kg ha^?1yr^?1 in south central Michigan. Samples taken from 82 clearwater (low color) lakes across this region in the summer of 1984 showed a pattern of acidification in proportion to deposition. We found a linear increase in the difference between alkalinity and Ca+Mg and in lake SO₄ concentration with increasing deposition. We developed a simple equation to predict the emission-related SO₄ deposition levels that will cause the alkalinity of sensitive clear-water lakes to go to zero.