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.     

A preliminary assessment of nitrogen-based fresh water acidification in southeastern Canada

Sulphate deposition is the primary cause of acidification in northeastern North America, and new SO₂ emission control is being implemented. However, continuation of existing levels of N deposition may undermine the environmental benefits derived from SO₂ control. This likelihood has been assessed for Canadian lakes. Maximum N deposition (～13 kg N ha^?1 yr^?1) occurs in south-central Ontario and southwestern Quebec. Regional median NO ₃ ^? levels are generally low (<5 μeq L^?1) suggesting that on average, N-based acidification is minor compared to the S-based component. However, examination of the seasonal NO ₃ ^? pattern at 5 intensively monitored basins reveals that 2 of them (in Ontario and Quebec) have incipient N saturation. A regional status for nitrogen-based acidification was qualitatively assessed by classifying survey data to identify cases of NO ₃ ^? leaching. Many lakes throughout southeastern Canada exhibit some leaching, particularly those in south-central Ontario and southwestern Quebec. While the evidence for a deposition-acidification link appears strong, sources of N other than the atmosphere should be considered for certain anomalous cases.     

Airborne transport of sulphur: Impacts on chemical composition of rivers on north shore of the St. Lawrence River (Québec)

The St. Lawrence North Shore region (Québec) is subject to acid precipitation entailing sulphate deposition (17 to 22 kg SO₄ ^2? ha^?1 yr^?1) which poses a threat to sensitive aquatic ecosystems. Physicochemical surveys conducted in 1982–1983 revealed the extreme sensitivity of the region owing to weak mineralization of the waters (mean alkalinity of 55 μeq L^?1 and conductivity of 17 μS cm^?1). Calculation of the annual loads of S discharged from 21 rivers throughout the region shows atmospheric deposition as the principal source of sulphate. A decreasing west-east gradient in the concentration is interpreted in terms of the impact of long-range airborne transport, although certain local sources of S emission are not to be overlooked. Analysis of the seasonal variation in the sulphate load balance, conducted in a small drainage basin (40 km²), revealed that the sulphate anion plays a part in lowering the water pH in spring. The spring pH depression is apparently intensified by an additional input of sulphate stemming from the release of this element subsequent to accumulation in the drainage basin during summer and fall. Organic acids play a measurable role in the chemical equilibrium of surface waters in the region, particularly in the eastern sector where there is less S fallout. Low pH levels in this sector (5.5 to 6.0) point to some degree of organic acidification.     

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.     

Can Phosphate Help Acidified Lakes to Recover?

Experimental addition of phosphate to enclosures in an acidified lake in Southern Norway was performed to study the effect on nitrate, pH and labile aluminium along a gradient of phosphate from 4–19 µg P L^?1. Nitrate decreased from 180 µg L^?1 to below detection limit after three weeks at P-concentrations > 17 µg L^?1, due to phytoplankton uptake. pH increased from 4.9 to 5.2, corresponding to a 50% decrease of H⁺-equivalents from 12 to 6 µg P L^?1 due to algal uptake of H⁺-ions when assimilating NO₃ ^?-ions. Due to the increased pH and probably also precipitation with phosphate, concentrations of labile aluminium decreased from 150 to 100 µg L^?1 within the P-interval 4–19 µg L^?1. Algal biomass increased from 0.5 to 6 µg chlorophyll a L^?1 along the same P-gradient. The results suggest that moderate P-addition (< 15 µg P L^?1 to avoid eutrophication problems) can improve water quality in moderately acidified lakes, and also increase nitrate retention in strongly acidified lakes. In humic lakes, the treatment will be less efficient due to light limitation of primary production and the presence of organic acids.     

Application of henriksen's ‘acidification indicator’ and ‘predictor nomograph’ to two adirondack lakes

During the period 1977–1980 we studied the effects of highly acidic precipitation (mean pH 4.1 to 4.2) on the chemistry of three Adirondack lakes: Woods Lake, Panther Lake, and Sagamore Lake. Two of these lakes (Woods and Panther) are enough like those lakes of southern Sweden and Norway studied by Henriksen that they should constitute a valid test of his ‘acidification indicator’ and ‘predictor homograph’. In our comparison we used data from weekly samples taken near the surface of the lakes during unstratified summer and fall conditions over a 3 yr period. The acidification indicator and predictor nomograph were developed using data from lake samples taken under similar conditions in Scandinavia. Our principal finding is that with regard to the empirical line of the acidification indicator (that Henriksen found separated data from lakes receiving precipitation greater or less than pH 4.6) and with the precipitation pH axis of the predictor nomograph, these two methods of evaluation are not directly applicable ‘as is’ to our lakes. The reason for this is that the chemistry of precipitation in the Adirondacks is significantly different from (and for) which the acidification indicator and predictor nomograph were developed. In the Adirondacks, acids other than H₂SO₄ play a much greater role in the overall acidity of the precipitation. This causes relationships between precipitation pH and lake chemistry in the two regions to be different.     

Acidification by nitric acid — Future considerations

HNO₃ is more efficient in acidifying lakes than has been generally believed. This is because as nitrate loading to lakes increases, the efficiency of in-lake nitrate removal decreases markedly. Efficiencies decrease because algal N requirements are exceeded and because denitrification, which becomes an important removal process, is not as efficient as algal removal. Thus, nitrate and the accompanying H⁺ accumulate and HNO₃ becomes an important factor in acidification. Data from an experimentally acidified system suggest that midsummer surface-water nitrate concentrations in excess of only 1 µmol L^?1 indicate that algal requirements have been exceeded. While 1 µmol L^?1 NO₃ ^? is not a significant quantity in terms of affecting the acidity of the water, it is useful as an indicator to identify lakes where algal requirements have been exceeded and where further increases in HNO₃ loading could lead to lake acidification.     

Recovery Pattern from Acidification of Headwater Lakes in Finland

Acid sensitive headwater lakes (n=163) throughout Finland have been monitored during autumn overturn between 1987–1998. Statistically significant decline in sulphate concentration is detected in 60 to 80 percent of the lakes, depending on the region. Median slope estimates are from ?1.1 µeq L^?1 in North Finland to ?3.3 µeq L^?1 in South Finland. The base cation (BC) concentrations are still declining especially in southern Finland (slope ?2.5 µeq L^?1), where every second lake exhibits a significant downward trend. The BC slope is steeper for lakes with less peatlands, more exposed bedrock, longer retention time and southerly location, but these factors are inter correlated. Gran alkalinity slope medians for the three regions range from 1.4 to 1.8 µeq L^?1 yr^?1. No significant negative alkalinity trends were detected. The similarity in the slopes of SO₄, BC and alkalinity in this data compared to seasonal sampling data from Nordic Countries can be regarded as indirect evidence that autumnal sampling is representative for long term monitoring for these ions. There are no indications of increased organic carbon in lakes, as found in some recent trend analyses of similar regional data sets. Although the processes behind the positive development in these lakes have to be revealed with site- specific intensive studies, this data suggests, that the initial recovery from lake acidification in Finland is a regional phenomenon.     

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.     

Low Success Rate in Re-Establishing European Perch in Some Highly Acidified Lakes in Southernmost Norway

In order to test whether major reductions in acid inputs had improved water quality sufficiently for fish populations to recover, we stocked wild European perch (Perca fluviatilis) in three highly acidified lakes that had previously supported this species, and in one limed lake. The fish, which were introduced from a local lake (donor lake), generally ranged from 12 to 16 cm in total length, and were stocked at densities of 117–177 fish ha^?1. The untreated lakes were highly acid, with minimum pH values and maximum inorganic aluminium concentrations (Al_i) during the spring of 4.6–4.7 and 118–151 µg L^?1 respectively. In the limed lake, the corresponding values for pH and Al_i ranged between 5.8 and 6.6 and 5 and 19 µg L^?1 respectively. Gill-netting in two subsequent years after the introduction yielded only a few recruits (0+) and one adult in one of the three acidified lakes in one year only. However, stocked perch reproduced successfully in both years in the limed lake. There was a significant linear relationship between the catches (CPUE) of juvenile perch (age 0+) in the different lakes in the autumn and the water quality in May (time of hatching), both in terms of Al_i (r ²=0.934, P<0.05) and pH (r ²=0.939, P<0.05). Our data suggest unsuccessful recruitment in waters of pH <5.1 and Al_i>60 µg L^?1.     

Regional chemical characteristics of lakes in North America: Part I — Eastern Canada

Data defining the major ion chemistry of lakes located in eastern Canada have been compiled for the purpose of evaluating the current status of surface water quality in relation to acidic deposition. A companion paper for lakes in the eastern United States (i.e. Part II, Linthurst et al., 1986) has been prepared also. Data sources in Canada included the National Inventory Survey, the Ontario Lake Sensitivity data set, and the National Aquatic Data base which provided an overall data base of approximately 5700 lakes. Only recently collected data (largely 1980 or later) were used in the analysis. Frequency distribution statistics were obtained for pH, acid neutralizing capacity (ANC), SO₄ and organic anion (A^?) concentrations. Acidic and low ANC waters in eastern Canada occur in a pattern explained by a combination of biogeochemical factors and atmospheric deposition. Nova Scotia contained the highest proportion of acidic and ultralow ANC lakes of any region surveyed in eastern North America; since this region receives approximately 20 kg.ha^?1.yr^?1 wet SO₄ deposition, the proposed target loading may be too high to protect the highly sensitive waters of Maritime Canada. Compared to the rest of eastern Canada, lakes in Ontario have relatively high ANCs due to the influence of CaCO₃ contained in the glacial till of the area. Variation in the SO₄ concentration of lakes approximately follows expected gradients in wet SO₄ deposition. Naturally occurring organic acids do not play a dominating role in the acidification of eastern Canadian lakes.     

Response of lake trout (Salvelinus namaycush) and brook trout (S. fontinalis) to surface water acidification in Ontario

Netting surveys of lakes varying in pH (4.4–7.1) showed that lake trout (Salvelinus namaycush) populations fail to recruit at pH <5.5 and are lost from lakes with pH<5.2. Brook trout (S. fontinalis) were extirpated in lakes with pH <5.0. In regional chemical surveys of Ontario lakes, it was found that 2% of sampled brook trout lakes and 2.5% of lake trout lakes were acidified (alkalinity <0 uEq L^?1). Threshold pH levels determined from fisheries assessments were used to estimate that 1% of lake trout and brook trout populations have been lost due to acidification.     

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?.     

Biology and chemistry of three Pennsylvania lakes: Responses to acid precipitation

The biology and chemistry of three northeastern Pennsylvania lakes was studied from summer 1981 through summer 1983 to evaluate lakes with different sensitivities to acidification. At the acidified lake (total alkalinity ≤ 0.0 μeq L^?1) there were fewer phytoplankton and zooplankton species than at the moderately sensitive lakes. The most numerous plankton species in all three lakes are reportedly acid tolerant. Among the benthic macro- invertebrates (BMI) there were more acid tolerant Chironomidae at the acidified lake, but more acid intolerant Ephemeroptera and Mollusca and a higher wet weight at the least sensitive lake. There were no differences among the lakes' BMI mean total numbers or mean number of taxa. The fish community at the acidified lake was dominated by stunted Lepomis gibbosus, but L. machrochirous were most abundant in the other lakes. Principal component analysis suggested a shift in all three lakes over the sampling period toward combined lower pH, alkalinity, specific conductance, Ca and Mg and higher Al and Mn. Such chemical changes have been associated with acidification. The rate and extent of acidification appeared to be controlled by geological and hydrological characteristics of the drainage basins.     

Response to a smelter closure in Cascade mountain lakes

A statistically significant decrease in sulfate was observed in high elevation Cascade lakes during 1983 through 1988. The total decrease averaged 2.2 μeq L^?1 in two slow-flush lakes and 4.2 μeq L^?1 in three fast-flush lakes for 1983–1985 vs 1986–1988, respectively. Coincident with these changes in sulfate concentrations were a sharp decrease of SO₂ emissions from the ASARCO smelter (100 km SE of the lakes), from 87 to 70 kt yr^?1 during 1983–1984 to 12 in 1985, the year of its closure, and a gradual change in SO₂ emissions from Mt. St. Helens, from 39 to 27 during 1983–1984 to 5 in 1988. The sharpest decreases occurred in non-marine sulfate in fast-flush lakes from 1984 to 1985 (about 2 μeq L^?1) and in slow-flush lakes from 1985 to 1986 (1 μeq L^?1, which point to the ASARCO closure as the sole cause. However, some of the more gradual decline in non-marine sulfate observed during 1983 through the 1988 sampling periods may have been due to a slow washout of sulfate enriched ash from the 1980 Mt. St. Helens' eruption. Sulfate concentrations in precipitation also declined significantly by about 2 μeq L^?1, but changes in volume-weighted sulfate content were not significant. Lake alkalinity did not show a consistent increase in response to decreased sulfate. This was probably due to either watershed neutralization of acidic deposition or the greater variability in alkalinity measurements caused by small changes in acidic deposition making it difficult to detect changes.     

Total cadmium concentrations in the water and littoral sediments of Central Ontario Lakes

Lakes within 20 km of Sudbury, Ontario, have significantly higher Cd concentrations in surface waters (geometric mean 122 ng L^?1; n = 7) than lakes elsewhere in central Ontario (10.8 ng L^?1; n = 57). Cadmium concentrations in water from lakes beyond the Sudbury halo were negatively correlated (r = 0.797; p < 0.001) with pH. A weak correlation between fluoride and Cd concentrations leads to speculation that some Cd may be mobilized from watersheds with Al. Cadmium concentrations in littoral sediments are not elevated near Sudbury. The geometric mean Cd concentration of littoral sediments in central Ontario lakes is 0.08 mg Cd kg^?1 dry mass (n = 75). Cadmium concentrations in littoral sediments are strongly correlated with sediment loss on ignition (r = 0.860; p < 0.001). After correction for differences in organic content, littoral sediments are less enriched with Cd than profundal sediments, as reported in the literature. The difference between littoral and profundal sediments, and the sensitivity of Cd concentrations in water to pH, may be due to the importance of Cd binding by Fe/Mn hydrous oxides in the profundal zone, while organic matter binds Cd in the littoral zone. The lack of sensitivity of Cd concentrations in littoral sediments to acidification may be due to the incorporation of much of the Cd in those sediments into organic particulates.     

Acidic precipitation: Considerations for an air quality standard

Acidic precipitation, wet or frozen precipitation with a H⁺ concentration greater than 2.5 μeq l^?1, is a significant air pollution problem in the United States. The chief anions accounting for the H⁺ in rainfall are nitrate and sulfate. Agricultural systems may derive greater net nutritional benefits from increasing inputs of acidic rain than do forest systems when soils alone are considered. Agricultural soils may benefit because of the high N and S requirements of agricultural plants. Detrimental effects to forest soils may result if atmospheric H⁺ inputs significantly add to or exceed H⁺ production by soils. Acidification of fresh waters of southern Scandinavia, southwestern Scotland, southeastern Canada, and northeastern United States is caused by acid deposition. Areas of these regions in which this acidification occurs have in common, highly acidic precipitation with volume weighted mean annual H⁺ concentrations of 25 μeq l^?1 or higher and slow weathering of granitic or precambrian bedrock with thin soils deficient in minerals which would provide buffer capacity. Biological effects of acidification of fresh waters are detectable below pH 6.0. As lake and stream pH levels decrease below pH 6.0, many species of plants, invertebrates, and vertebrates are progressively eliminated. Generally, fisheries are severely impacted below pH 5.0 and are completely destroyed below pH 4.8. At the present time studies documenting effects of acidic precipitation on terrestrial vegetation are insufficient to establish an air quality standard. It must be demonstrated that current levels of precipitation acidity alone significantly injure terrestrial vegetation. For aquatic ecosystems, current research indicates that establishing a maximum permissible value for the volume weighted annual H⁺ concentration of precipitation at 25 μeq l^?1 may protect the most sensitive areas from permanent lake acidification. Such a standard would probably protect other systems as well.     

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.     

Fish species distribution and water chemistry in Nova Scotia lakes

During the summers of 1981-1984, 19,714 fish (23 species) were netted in 234 Nova Scotian lakes. Surface and mid-depth water samples were also analyzed for major ions, metals, and DOC. Lakewater pH varied from 4.4 to 7.7, including eight lakes which produced no fish in standard 23-hr net sets. Fish data were partitioned into 6 pH groupings for analysis. Stepwise multiple regressions of fish species vs. H+, S0₄,A1, Fe, and Mn showed little predictive power. Productive lakes ranged up to 530 μg L^?1 Al, 1680 pg L^?1 Fe, and 836 μg L^?1 Mn. Apart from pH, fish distribution and abundance showed no significant relationships with water chemistry data. We note, however, that the more acidic lakes had fewer species of fish.