recent lake acidification and recovery trends in southern quebec,canada

A total of 51 lakes in southern Quebec, Canada, were sampled between 1985 and 1993 to study changes in water chemistry following reductions in SO₂ emissions (main precursor of acid precipitation). Time series analysis of precipitation chemistry revealed significant reductions in concentrations and deposition of SO₄ ^2- from 1981 to 1992 in southern Quebec as well as reductions in concentrations and deposition of base cations (Ca²⁺, Mg²⁺), NO₃ ^- and H⁺ in the western section of the study area. Reductions in atmospheric inputs of SO₄ ^2- have resulted in decreased lakewater SO₄ ^2- concentrations in the majority of the lakes in our study, although only a small fraction (9 of 37 lakes used in the temporal analysis) have improved significantly in terms of acidity status (pH, acid neutralizing capacity – ANC). The main response of the lakes to decreased SO₄ ^2- is a decrease in base cations (Ca²⁺+Mg²⁺), which was observed in 17 of 37 lakes. Seventeen lakes also showed significant increases in dissolved organic carbon (DOC) over the period of study. The resulting increases in organic acidity as well as the decrease in base cations could both play a role in delaying the recovery of our lakes.     

Experimental acidification of alpine catchments at Sogndal,Norway: Results after 8 years

Manipulations with whole catchments were initiated in Norway in 1983 (RAIN project Reversing Acidification In Norway) to obtain direct experimental evidence relating to the reversibility of soil and water acidification, rate of change, and the relative roles of sulfur and nitrogen. We present here results for soil and runoff chemistry during 8 years of acid addition at Sogndal, a pristine acid-sensitive site in central Norway characterized by gneissic bedrock, thin and patchy soils, and alpine vegetation. Catchment SOG2 receives 100 meq m^?2 yr^?1 H₂SO₄, catchment SOG4 receives a 1∶1 mixture of H₂SO₄ and HNO₃, while catchments SOG1 and SOG3 serve as untreated controls. Acid is applied to the snowpack in April and in 5 portions of 11 mm of pH 3.2 acidified lakewater during the snowfree period. The 8-years of acid addition have caused major changes in runoff chemistry. Concentrations of sulfate and base cations have increased while acid neutralizing capacity (ANC) has decreased. Henriksen's F-factor (change in concentration of non-marine Ca+Mg divided by change in concentration of non-marine SO₄) is about 0.35, but is expected to decrease as soil acidification proceeds. Runoff is acidic, aluminum-rich, and toxic to fish and other aquatic organisms. Repeated soil sampling indicates no dramatic trends related to treatment. Year-to-year variations are large, and mask changes expected. The input-output budgets indicate that over the 8-yr period Ca has been depleted by about 5% of the total soil pool of exchangeable Ca. The observed trends are consistent with response predicted by MAGIC, a process-oriented model of soil and water acidification. The gradual increase in nitrate flux from catchment SOG4 may be the first indication of ‘nitrogen saturation’ induced simply by increasing nitrogen deposition.     

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.     

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.     

Aluminium Mobility at an Acid Sensitive Site with High S-Deposition

Soil water at an acid-sensitive forested catchment in southwestern Poland has been studied for four years. Median base saturation (BS) is only 5% in the podzol B-horizons. Very low pH values in the soil water from the O-horizons (10- and 90 percentiles pH 3.5 and 4.3) increased to a typical median pH in the B-horizons of 4.4, mainly by release of inorganic labile aluminium (Al_i). Median concentrations in the B horizons were 3.4mg Al_i L^?1. Al-soil/soilwater interactions were studied over a large span of sulphate concentrations resulting from both a generally decreasing S-deposition during the last decades and an increase in precipitation during the study period. These changes led sulphate to leach from the mineral soil. Aluminium mobilisation is better described by jurbanite- than by gibbsite solubility. For the soils with aluminium saturation (AlS) >90%, there is a tendency that the concentration of Al³⁺ decreases less than divalent base cations with a decrease in SO₄ ^2? concentration. This causes the critical load molar ratio (R_CL={Al³⁺}/{Ca²⁺+Mg²⁺}) to increase with a decrease in the sulphate concentration in soil water, which is not in agreement with a simple cation-exchange model.     

Acidification in Norway — Status and trends

Surface and ground water monitoring in Norway is designed to give a regional coverage with most of the stations in areas with acidification and some stations in unpolluted areas that give background values. Surface water (weekly sampling) and precipitation (daily measurement) are monitored at 6 calibrated catchments, 5 located in southern Norway and 1 in northernmost Norway close to the Russian border. Ground water (weekly sampling) is monitored in 4 reservoirs in Southern Norway. 73 lakes located all over Norway are surveyed each fall. Nineteen rivers in western and southern Norway are monitored by monthly sampling. All sites are considered sensitive to acidification and are chosen to minimise the effects of anthropogenic catchment based impacts. Results from the monitoring over the period 1980–1994 show that there is a reduction of sulphate of about 25–35% in surface waters which is related to a 30–45% reduction in sulphate concentration in precipitation. An improvement in water quality as measured as increase in ANC has only been apparent since 1990. Due to heavy seasalt episodes in the most coastal catchments like Birkenes and the rivers in western Norway, there has been no improvement of ANC since 1980. Deposition of nitrogen has not changed over the last 10 years, and there is no change in the levels of nitrate in the monitored surface waters.     

Regional monitoring of lake acidification in Finland

The primary objective of this monitoring is to detect long-term Long-Range Transboundary Air Pollution (LRTAP) induced changes in the water quality of small lakes, throughout Finland, with low conductivity. The monitored lakes (n=171, sampled every autumn since 1990 and in 1987) have a smaller watershed (usually headwater or seepage lakes), a larger lake/catchment ratio, and lower base cation concentrations, alkalinity and pH than Finnish lakes on average. The monitoring network provides background data for air pollution dose/response studies, critical load calculations and for the modelling of acidification scenarios. The declining sulphate deposition seems to be reflected in small headwater lakes all over southern and central Finland as a lowering of the sulphate concentration in the waters. Nitrate concentrations in these lakes have been typically low in the autumn. The base cation concentration is not generally declining, as it is in deposition in many areas. The sulphate concentration in lakes has declined more than base cations. Hydrologically, the recent years have been quite variable because of varying annual precipitation. The variation in alkalinity and pH in typical Finnish lakes is dependent on the content of humic material derived from catchments. The monitoring period is too short to reveal consistent trends in major ion chemistry. However, signs of improvement in recent years can be seen; in comparing 1993 to 1987, years with similar organic acidity and base cations, it seems that the sulphate decline in lakes monitored is compensated by a significant rise in both alkalinity and pH.     

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.     

Trends in Sulfate,Base Cations and H+ Concentrations in Bulk Precipitation and Throughfall at Integrated Monitoring Sites in Finland 1989-1995

Temporal trends in sulfate, base cation (Ca2+ + Mg2+ + K+), and H+ ion concentrations in bulk precipitation and throughfall samples collected over a seven year period (1989-95) in four forested catchments in Finland are presented. The catchments are in remote locations and span the boreal zone (61-69 °N). The stands represent old, undisturbed forests, and are composed of varying proportions of Scots pine, Norway spruce and deciduous species (mainly Betula spp.). Monthly SO₄ ^2- and H+ ion concentrations in bulk precipitation averaged over the study period and catchments were: 18.7 µmol L^-1 and 32.3 µmol L^-1. The corresponding values for throughfall were: 37.4 µmol L^-1 and 32.4 µmol L^-1. Sulfate and H+ ion concentrations in bulk precipitation and throughfall both showed negative linear trends, which were significant (p < 0.05) for the three southernmost catchments. Concentrations and trend slope decreased northwards (e.g., bulk precipitation SO₄ ^2- slope estimates: ^-1.6 to ^-1.0 µmol L^-1 yr^-1). The decline was greater for throughfall than for bulk precipitation, indicating a proportionally greater reduction in dry deposition than wet. The sum of base cation concentrations averaged 12.1 µmol(+) L^-1 in bulk precipitation and 83.1 µmol(+) L^-1 in throughfall. There were no significant trends in the sum of base cations (p > 0.05). It is concluded that the reported reduction in S emissions over the study period has resulted in a significant reduction in the acidity and SO₄ ^2- concentration of bulk precipitation, and this reduction has has been reflected in throughfall concentrations. The greatest reduction has taken place in the southern part of the country.     

Interrelationships between mercury levels in yearling yellow perch,fish condition and water quality

Yearling yellow perch were collected from sixteen Muskoka-Haliburton lakes to determine interrelationships between water quality, Hg residues in fish and fish condition. The lakes studied were Precambrian shield lakes with a pH range of 5.6 to 7.3 and total inflection point alkalinities of 0.4 to 16.0 mg L^?1. Mercury residues in yellow perch ranged from 31 to 233 ng g^?1 and were inversely correlated (p < 0.001; r = 0.84) with lakewater pH. Stepwise linear regression analyses selected lakewater pH as the only significant parameter associated with Hg accumulations. Alkalinities, sulphate, Ca and dissolved organic carbon (DOC) were not selected as significant. Likewise, lakewater pH and Hg residues in yellow perch were inversely (p < 0.001) correlated with fish condition. Lakewater pH, accounted for 74% and Hg in fish a further 11% of the variability in fish condition. Terrestrial drainage size/lake volume ratios were also correlated (p < 0.05; r = 0.78) with Hg accumulations in perch from a subset of nine headwater lakes. No temporal trends in Hg residues were evident in yellow perch over a 9 yr interval (1978–1987).     

The Effect of Changes in European Anthropogenic Emissions on the Concentrations of Sulphur and Nitrogen Components in Air and Precipitation in Lithuania

Sulphur (S) and nitrogen (N) components are of great concern because acidification and eutrophication still remain an important environmental issue in many regions of the world. Continuous monitoring (1981–1999) of S and N components both in air and precipitation in Lithuania (LT) has allowed us to evaluate the regional and temporal variations in relation to the pollutant emission changes. Despite of inter-site variability in concentration of pollutants within the regional scale, data showed a marked decrease in S concentrations both in air and precipitation over the Lithuania as a whole. Non-seasalt sulphate (nssSO₄ ^2?) concentrations in precipitation and air decreased from 2.06 to 0.52 mgS/l and from 3.97 to 1.07 µgS/m³, respectively. The number of acidic (pH<5) precipitation did not exceed 50 % during 1995–1999. The observed trends for S species are consistent with those for sulphur dioxide (SO₂) emission in Europe and Lithuania. Although nitrogen dioxide (NO₂) concentration in air decreased by 17 %, significant changes in nitrate (NO₃ ^?) concentrations neither in precipitation nor in air have been observed. Three-day backward air isobaric trajectories were used for the identification of the source region of air pollutants     

Trends in Water Chemistry of Acidified Bohemian Lakes from 1984 to 1995: II. Trace Elements and Aluminum

The concentrations of Al, Be, Cd, Cu, F, Fe, Mn, Pb, and Zn were monitored in five glacial lakes and one man-made lake in the southwestern part of the Czech Republic. The lakes had median pHs of 4.4 to 6.5 during 1984 to 1995. Decreases in the concentrations of Mn and Pb occurred in five acidified lakes. The concentrations of Al_T, Be, Cd, and F decreased in the four chronically acidified lakes, Zn decreased in two lakes. Concentrations of Cu and Fe remained unchanged. The decreases in Be, Mn, and Zn concentrations were proportional to the decrease in C_SA (C_SA = SO₄ ^2- + NO₃ ^-+ Cl^-); decreases in Al_T, Cd, and Pb concentrations were proportionately higher, while F was lower. The greater decrease in the Pb concentrations (61 to 79%, at a rate up to 0.15 μg L^-1yr^-1) was caused by pronounced decreases in deposition of Pb derived from mobile sources. The decrease of Al_T concentrations was dominated by a decrease in Al³⁺, whose concentration decreased by 51 to 86%. The concentrations of complexes Al(OH)²⁺, Al(OH)₂ ⁺, AlF²⁺, and AlH₃SiO₄ ²⁺ also decreased. The decrease in the concentrations of inorganic forms of Al (Al_i) compensated 65% of the decrease in C_SA. The Cd concentrations were highly variable in the years 1986 to 1988 because of variable amounts of accumulation on particles.     

Estimation of background sulphate concentrations in natural surface waters in Sweden

In order to measure the extent of acidification the background, ‘preindustrial’ conditions must be known. An equation for the estimation of background concentrations of sulphate in surface water in Norway was proposed by Henriksen. When applied on data from the Swedish lake survey in 1990 it was found that the calculated background concentrations exceeded those measured for about one-third of the lakes. The proposed revision is based on a background concentration in precipitation and an estimated contribution from weathering, the latter associated with base cations. Three different approaches were tested to establish the contribution from weathering; geochemical ratios or groundwater chemistry data as a basis, and historical data on denudification. The weathering calculated from groundwater chemistry data seems to give the best estimate of the background sulphate concentration in surface water. Organic matter as source or sink of sulphur is discussed and considered negligible.     

Sulphate in Sudbury, Ontario, Canada, Lakes: Recent Trends and Status

Sulphur emissions from the Sudbury, Ontario, metal smelting industry have affected thousands of lakes in Ontario, Canada. Reductions in these emissions during the 1970's resulted in reduced lakewater SO₄ concentrations and other water quality changes in the 1970's and 1980's. Further declines in lakewater SO₄ concentrations have accompanied additional recent S emission reductions achieved by 1994. Recent (1997) SO₄ concentrations are still related to distance from the Sudbury smelters. A strong inverse relationship with distance is evident to about 45 km, and is most pronounced in lakes within about 20 km. In lakes beyond 45 km, dissolved organic carbon (DOC), which was correlated with hydrological response time and total phosphorus concentrations, was the best correlate with recent SO₄ concentrations, indicating that some slowly-flushing, oligotrophic lakes still exhibit a "Sudbury" effect. Most lakes beyond 45 km, however, showed SO₄ declines and recent SO₄ concentrations comparable to lakes around Dorset, ～200 km from Sudbury, suggesting that these lakes are now most affected by the long-range atmospheric transport of S.     

Reduced Acid Deposition Leads to a New Start for Brown Trout (<Emphasis Type="Italic">Salmo trutta</Emphasis>) in an Acidified Lake in Southern Norway

Acid deposition has led to acidification and loss of fish populations in thousands of lakes and streams in Norway. Since the peak in the late 1970s, acid deposition has been greatly reduced and acidified surface waters have shown chemical recovery. Biological recovery, in particular fish populations, however, has lagged behind. Long-term monitoring of water chemistry and fish populations in Lake Langtjern, south-eastern Norway, shows that around 2008, chemical recovery had progressed to the point at which natural reproduction of brown trout (Salmo trutta) reoccurred. The stocked brown trout reproduced in the period 2008–2014, probably for the first time since the 1960s, but reproduction and/or early life stage survival was very low. The results indicate that chemical thresholds for reproduction in this lake are approximately pH?=?5.1, Al_i?=?26 μg l^?1, ANC?=?47 μeq l^?1, and ANC_oaa?=?10 μeq l^?1 as annual mean values. These thresholds agree largely with the few other cases of documented recovery of brown trout in sites in Norway, Sweden, and the UK. Occurrence and duration of acidic episodes have decreased considerably since the 1980s but still occur and probably limit reproduction success.     

Factors influencing fluoride concentrations in Norwegian lakes

The sources and mechanisms regulating fluoride (F) in Norwegian lake waters are studied using data from regional surveys of precipitation chemistry, lake water chemistry and bedrock geology. Fluoride concentrations in Norwegian lakes range from < 5 to 560 μg L^?1. Fluoride content in the bedrock is the most important factor controlling F levels in lake waters, as shown by significant differences in median value of F concentrations between lakes situated in different geological provinces. There are also weak but significant correlations between F in the lakes and components typical for weathering such as non-marine Ca, Mg, Na and K. The regional picture of F concentration in lake water shows elevated F concentrations in the acidified areas in southern and southeastern Norway compared to other regions of the country with comparable geology. There is a weak but significant correlation between F and SO₄, a typical indicator of acidification in surface water. Mass balance calculations in three catchments show that F is retained in soils in pristine areas, while F output exceeds precipitation input in acidified areas. This both demonstrates the strong retention capacity for F in soils and indicates that anthropogenic F added through polluted rain is a minor source of F in surface waters. Fluoride is mobilized in acidifies areas, probably due to complexation with Al.     

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.     

Sulphur and nitrogen deposition in Norway,status and trends

The total deposition of sulphur (S) and nitrogen (N) components in Norway during the period 1988–1992 has been estimated on the basis of measurement data of air- and precipitation chemistry from the national monitoring network. There are large regional variations in depositions with highest values in the southwestern part of Norway. Time series analysis of annual mean concentrations of sulphur dioxide (SO₂) and sulphate (SO₄ ^––) in air, non marine SO₄ ^––, nitrate (NO₃ ^–) and ammonium (NH₄ ⁺) in precipitation, shows a significant reduction in the S concentrations both in air and precipitation. In precipitation the concentrations are reduced by 30–45 percent in Southern Norway and 45–55 percent in Central and Northern Norway. Even larger reductions are observed in air concentrations with 50–65 percent reduction in Southern Norway and 65–88 percent reduction further north. For N components there are generally no significant trends in concentration levels nor in precipitation or air. The observed trends are comparable with reported trends in emission.     

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.     

RAIN project: Role of organic acids in moderating ph change following reduction in acid deposition

The RAIN project (Reversing Acidification In Norway) entails catchment-scale experimental manipulations to investigate the effect on water and soil chemistry of drastic changes in precipitation chemistry. At Risdalsheia in southernmost Norway wet deposition of acid is excluded from a 860-m² headwater catchment by means of a roof and “clean” precipitation is added beneath. Four years of acid exclusion (through June 1988) have resulted in lower concentrations of the strong acid anions NO₃ (from 35 to 7 ueq L^-1) and SO₄ (from 110 to 53 ueq L^-1) in runoff. The decline in strong acid anion concentrations has been compensated partially by a decrease in concentrations of base cations (55%) and partially by an increase in alkalinity (45%). pH has increased only slightly from 4.0 to 4.1. Organic acids have become increasingly important for the pH of runoff. Runoff from the shallow organic soils contains 10 to 20 mg C L^-1 total organic carbon (TOC). The concentration of organic anions (estimated from the ionic balance) has increased from about 22 ueq L^-1 in 1984 to 49 ueq L^-1 in 1987. This increase is due to increased dissociation of organic acids and not to change in TOC concentrations. The organic C in these acid samples apparently has a maximum charge density of about 4.5 ueq mg C^-1 and pK of about 4.