Sources of acidity in lakes and streams of the United States

Acidic (acid neutralizing capacity [ANC] < or = 0) surface waters in the United States sampled in the National Surface Water Survey (NSWS) were classified into three groups according to their probable sources of acidity: (1) organic-dominated waters (organic anions > SO4*; (2) watershed sulphate-dominated waters (watershed sulphate sources > deposition sulphate sources); and (3) deposition-dominated waters (anion chemistry dominated by inputs of sulphate and nitrate derived from deposition). The classification approach is highly robust; therefore, it is a useful tool in segregating surface waters into chemical categories. An estimated 75% (881) of acidic lakes and 47% (2190) of acidic streams are dominated by acid anions from deposition and are probably acidic due to acidic deposition. In about a quarter of the acidic lakes and streams, organic acids were the dominant source of acidity. In the remaining 26% of the acidic streams, watershed sources of sulphate, mainly from acid mine drainage, were the dominant source of acidity.     

Restoring acidified streams in upland Wales: a modelling comparison of the chemical and biological effects of liming and reduced sulphate deposition

Increasing emphasis is being placed on the restoration of surface waters which have been affected by acidification. Amongst the possible strategies are management of the causes, by reducing acidic deposition, and management of the symptoms, by treating affected areas with basic material such as limestone. In few cases have there been comparisons of the likely effect of these two strategies on surface water chemistry and ecology, although there is widespread belief that the two are similar in outcome. At present, only a modelling approach permits such a comparison. This paper describes chemical and biological responses of three Welsh streams whose catchments were limed experimentally in 1987-1988 as part of the Llyn Brianne project. Actual changes are compared with simulated changes which occur following reduced acid deposition according to the hydrochemical model, MAGIC (Model of Acidification of Groundwaters in Catchments). The results indicate that liming and 90% reduction in sulphate deposition reduce concentrations of toxic aluminium to similar levels. However, calcium concentrations and pH were increased by liming to values which were high by comparison with conditions simulated at low acid deposition, either in the past or future. Trout density increased in two of the streams following liming to levels similar to those simulated under low acid deposition. By contrast, the aquatic invertebrate fauna changed after liming so that streams acquired species typical of higher calcium concentrations than those simulated under low acid deposition. Species characteristic of 'soft water' communities were apparently lost, although more data are required to separate treatment effects from random change in the longer term. The 'soft water' community also declined in the model as a result of acidification, indicating that both liming and acid deposition resulted in a different faunal community from that prior to acidification. The results support those who conclude that liming is suitable for the restoration or protection of a fishery, but indicate that there may be other ramifications, for example to conservation, which must be considered when liming is implemented. However, the simulation of biological conditions under low acid deposition involves extrapolation from the initial data base. Further data are now required to assess empirically the likely biological character of British streams which have low base cation concentrations unaffected by acid deposition.     

Critical loads and steady-state chemistry for streams in the state of Maryland

The critical loads to streams, steady-state stream chemistry and catchment chemical weathering rate in 73 catchments has been determined in the state of Maryland, USA. It was calculated with the PROFILE model from chemical limits for biological indicators, soil mineralogy, soil texture, annual average temperature, average soil moisture, net long-term uptake of base cations and nitrogen to the vegetation, annual precipitation and runoff and deposition of sulphur and nitrogen precursors of acid deposition. The results show a full range of critical loads from very low values in the sensitive catchments of western Maryland and the Coastal Plain on the Chesapeake Bay, to insensitive catchments in the Fredrick Valley and Ridge and the Piedmont plain. The critical loads will be used as an input to an integrated regional assessment of the quantitative sensitivity of streams to acid rain, and the assessment of regional stream alkalinity response to different abatement strategies. The mapping of steady-state stream chemistry indicates that streams in Maryland are still acidfying under the present deposition load. Land-use seems to play an important role in maintaining neutral pH in many of the streams of Maryland.     

Modelling acidification at Beacon Hill-a low rainfall, high pollutant deposition site in Central England

The model MAGIC (Model of Acidification of Groundwater In Catchments) has been applied to the Beacon Hill site, near Loughborough in Central England. This site is heavily impacted by wet and dry deposition of oxides of sulphur and nitrogen. The high acid inputs have caused soil acidification and acid stream waters. Long term simulations suggest that there has been a major decline in alkalinity and pH over the past 50 years. Despite recent reductions in deposition levels, soils and streams are predicted to continue to acidify in the future. For this heavily impacted site, deposition must be reduced by 80-90% to reverse the acidification trend and allow recovery of soil and stream waters.     

Recovery from acidification in Swedish forest streams

Sulphur deposition in Sweden has decreased to less than half of the levels recorded in 1970 and now signs of recovery from acidification of surface waters are beginning to appear. We investigated time trends of water chemistry between 1985 and 1998 in 13 streams draining small forested catchments with generally shallow acid sensitive soils. At nine of the catchments, bulk deposition was monitored as well. Sulphate concentrations decreased in both stream water and deposition, although with somewhat smaller trends in stream water compared with deposition. The magnitude of the trends in sulphate increased from north to south, following a gradient of increasing industrial influence. Five sites in the southern half of the country showed weak signs of recovery from acidification in terms of increasing concentrations of acid neutralising capacity and decreasing concentrations of hydrogen ions, corresponding to annual increases of 0.01 pH units. Changes in stream discharge and concentrations of marine salts and organic acids could not explain the observed decrease in acidity and the results were interpreted as recovery from anthropogenic acidification. For the northern half of Sweden, any changes in water chemistry could be attributed to natural variation in climate and marine influence, and the effect of anthropogenic acidification was negligible.     

Changes in the atmospheric deposition of acidifying compounds in the UK between 1986 and 2001

Emissions of a precursor of acidity in precipitation, sulphur dioxide (SO2), declined in the UK and the EU (15) by 71% and 72%, respectively, between 1986 and 2001, while nitrous oxide emissions declined by about 40%. Acidity in UK precipitation and the deposition of sulphate in precipitation halved during this period, but reductions were larger in the English Midlands than at the west coast and in high rainfall areas (>2000 mm). There is evidence that the smaller reductions in sulphur deposition in the west and south are due in part to shipping sources of SO2. Reductions in sulphur dry deposition (74%) are larger than in wet deposition (45%), due to changes in the canopy resistance to dry deposition. For reduced nitrogen, there has been a small (10%) reduction in emissions and deposition, while for oxidized nitrogen, a substantial reduction in emissions (40%) occurred but wet deposition of nitrate changed by less than 10%.     

Reversal of acidification in tributaries of the River Duddon (English Lake District) between 1970 and 1998

Long-term changes in stream water chemistry in the upper Duddon catchment (southwest Lake District, UK) were investigated. Ten streams were sampled and analysed weekly during 1998, and the results compared with data for the early 1970s and 1986. The waters exhibited a range of pH, average values for 1998 being 5.04-7.04. For all the streams, the average pH in 1998 was greater than that during 1971-73. Statistical analysis was carried out, using the 1970s data to estimate the magnitude of inter-annual variation, and taking discharge into account on the basis of antecedent rainfall. The results showed that for two of the streams the pH increase was significant at the 2.5% level, while for a further three it was significant at the 10% level. Comparison of the 1998 concentrations of nitrate and non-marine sulphate with data obtained for five streams in 1973-74 showed that average nitrate concentration had increased from 11 to 20 microeq dm(-3) while that of non-marine sulphate had decreased from 94 to 50 microeq dm(-3). For four of the streams, comparisons were also made between the 1998 data and those for 1986. In three cases, pH in 1998 was generally higher, and Al generally lower, than the values for 1986, but in the fourth case little difference was evident. The present results support observations for five nearby standing waters, strengthening the evidence for a general reversal of acidification in the southwest part of Lake District, due to a decline in the deposition of pollutant sulphur.     

Acid rain and acidification in China: the importance of base cation deposition

Acid deposition has been recognized as a serious environmental problem in China. Most acid deposition studies have focused on sulfur deposition and the pH of precipitation. However, as high concentration of alkaline dust is an important feature of the atmosphere in large parts of China, base cation deposition must be taken into account when discussing possible effects on soils and vegetation from acid deposition. We estimate the deposition of sulfur as well as calcium, i.e. the dominating anion and cation, on a regional scale in China using data both from measurements and modeling. The ratio of sulfur/calcium in deposition is then used as an indicator for identifying areas where deposition acidity exceeds alkalinity, and where soils may be at risk to acidification. The dynamic soil acidification model MAGIC is applied with data from two sites receiving high deposition loads in southwest China. The model predictions indicate that considerable soil acidification has been going on for the last decades due to acid deposition inputs. Effects on the spatial distribution of acidic deposition in China, using different future deposition scenarios, are illustrated. As the size of the anthropogenic fraction of the base cation deposition is unknown, different possible future trends in calcium deposition were used. Soil response, according to the model, using different combinations of sulfur and calcium deposition scenarios is shown. Applying the most strict measures to reduce sulfur emission will almost eliminate the acid deposition problem; however, such a scenario is not economically feasible in the short term. A strict, but possibly realistic, future scenario for sulfur may be enough to keep the situation at the present level, assuming only moderate reductions in calcium deposition. With large decreases in base cation deposition, increased soil acidification can be expected even with considerable sulfur emission reductions.     

Trends in surface water chemistry of acidified UK freshwaters, 1988-2002

Analysis of water chemistry data from 15 years of monitoring at 22 acid-sensitive lakes and streams in the UK reveals coherent national chemical trends indicative of recovery from acidification. Excess sulphate and base cations exhibit significant decline, often accompanied by an increase in an alkalinity-based determination of acid neutralising capacity (AB-ANC) and, at fewer sites, a decline in hydrogen and labile aluminium. Acid neutralising capacity determined by "charge-balance" (CB-ANC) exhibits few trends, possibly due to compound errors associated with its determination. Trend slopes in excess sulphate correlate with those for base cations, hydrogen ion and AB-ANC, with between-site variability linked to catchment hydrology, sea-salt inputs and forestry. Nitrate concentrations have not changed significantly but show high sensitivity to varying climate. Trends in AB-ANC are influenced by significant increases in dissolved organic carbon, the cause of which it is vital to establish before trends in the former can definitively be attributed to decreasing acidic deposition.     

Acid-sensitive waters of the English Lake District: a steady-state model of streamwater chemistry in the upper Duddon catchment

Data on deposition and streamwater chemistry, obtained for the upper catchment of the River Duddon in the 1970s and 1980s, are reviewed. These data, together with soil chemical data, are used to deduce key processes in the deposition-catchment interaction, the analysis being based on current concepts of acidification. The processes are incorporated into a steady-state model that allows streamwater compositions to be calculated. The large baseflow pH range (5-7) of Duddon streams is accounted for in the model by a range of base cation weathering rates. Other processes invoked are evapotranspiration, the uptake of nitrogen by plants, dissolution of Al(OH)(3) in the mineral soil, precipitation of Al(OH)(3) in the baserock zone and in streamwater, Al(3+) hydrolysis, and reactions of the carbonate system. Both cation exchange and sulphate adsorption are ignored, because they are assumed to influence rates-of-change between steady states, but not steady-state water compositions per se. The model can be used to estimate variations in streamwater composition with flow. Model calculations suggest that a 50% decrease in depositional acidifying components (sulphur oxides and NH(4)(+)) would result in increases of up to 1 pH unit in streamwaters with present-day baseflow pH values of 5 or less. It appears that water quality in the upper Duddon is currently more sensitive to inputs of NH(4)(+) than of H(2)SO(4). To improve the reliability of model predictions, more information is required on (a) the pH dependence of base cation weathering, (b) transformations involving nitrogen, (c) aluminium chemistry and (d) partial pressures of CO(2) in soil and baserock.     

Will reduced sulphur emissions under the Second Sulphur Protocol lead to recovery of acid sensitive sites in UK?

A conceptual model of the combined effects of acid deposition and land-use, Model of Acidification of Groundwater In Catchments (MAGIC), was applied to 21 upland sites in the UK Acid Waters Monitoring Network (AWMN) to assess the likely future recovery in response to the latest international agreements controlling anthropogenic sulphur emissions throughout Europe. Future estimates of sulphur deposition were generated by the Hull Acid Rain Model (HARM), based on the agreed reductions outlined in the Second Sulphur Protocol. The results indicate only a limited degree of recovery in surface-water chemistry at all sites over the next 50 years; moreover, a continuing decline in soil base status is predicted to occur at 70% of sites, resulting in longer term reacidification of surface-water at 38% of sites. However, compared with a 'business as usual' scenario the recovery is pronounced, although acidified sites will require further reductions in acidic deposition if recovery to pre-industrial chemical conditions are to be achieved. Furthermore, land-use scenarios at afforested sites suggest that replanting of felled forest will lead to a further increase in acidification. This strengthens the argument that plantation forestry should be avoided in areas considered geologically sensitive to acidic deposition.     

The United Kingdom Acid Waters Monitoring Network: a review of the first 15 years and introduction to the special issue

The United Kingdom Acid Waters Monitoring Network (AWMN) was established in 1988 to determine the ecological impact of acidic emissions control policy on acid-sensitive lakes and streams. AWMN data have been used to explore a range of causal linkages necessary to connect changes in emissions to chemical and, ultimately, biological recovery. Regional scale reductions in sulphur (S) deposition have been found to have had an immediate influence on surface water chemistry, including increases in acid neutralising capacity, pH and alkalinity and declines in aluminium toxicity. These in turn can be linked to changes in the aquatic biota which are consistent with "recovery" responses. A continuation of the current programme is essential in order to better understand apparent non-linearity between nitrogen (N) in deposition and runoff, the substantial rise in organic acid concentrations, and the likely impacts of forecast climate change and other potential constraints on further biological improvement.     

Sensitivity of modelled sulphate and nitrate aerosol to cloud,pH and ammonia emissions

A Lagrangian dispersion model has been used to predict daily sulphate aerosol in 2006 at five UK rural measurement sites and hourly nitrate aerosol in April 2003 at Harwell (UK). The sensitivity of aqueous phase sulphate production to the meteorological input has been investigated. Large differences were found between cloud fraction and cloud liquid water output from the regional and mesoscale Met Office Unified Model. The impact on the sulphate aerosol was relatively small, with the mesoscale meteorology giving better results.Sulphate aerosol production in the aqueous phase was found to be very sensitive to modelled cloud pH. As the cloud becomes acidic sulphate production is greatly limited, conversely if the cloud is basic large amounts of sulphate aerosol are produced. A fixed model pH of 5.8 was found to produce better results than allowing the model to calculate pH which resulted in large over-predictions of measured sulphate aerosol in some episodes.Nitrate aerosol was not sensitive to cloud variables or pH, but showed a slight increase with 30% more ammonia emissions, and a slight decrease with 30% less ammonia.Sulphate production in model runs with fixed pH was not sensitive to changing ammonia emissions, however the sulphate production with modelled pH was very sensitive to plus or minus 30% ammonia. This work suggests that good modelling of ammonia is essential to correct estimation of aqueous phase sulphate aerosol if cloud pH is modelled. It is concluded that modelling to estimate the effect of reduced ammonia emission scenarios on future ambient aerosol levels should also take into account the neutralising effect of ammonia in cloud and hence the effect on aqueous phase production of sulphate.     

Modelling the long-term soil response to atmospheric deposition at intensively monitored forest plots in Europe

The dynamic soil chemistry model SMART was applied to 121 intensive forest monitoring plots (mainly located in western and northern Europe) for which both element input (deposition) and element concentrations in the soil solution were available. After calibration of poorly known parameters, the model accurately simulated soil solution concentrations for most plots as indicated by goodness-of-fit measures, although some of the intra-annual variation especially in nitrate and aluminium concentrations could not be reproduced. Model evaluations of two emission-deposition scenarios (current legislation and maximum feasible reductions) for the period 1970-2030 show a strong reduction in sulphate concentrations between 1980 and 2000 in the soil due to the high reductions in sulphur emissions. However, current legislation hardly reduces future nitrogen concentrations, whereas maximum feasible reductions reduces them by more than half. Maximum feasible reductions are also more effective in increasing pH and reducing aluminium concentrations, mostly below ‘critical’ values.     

The impact of acidification on macroinvertebrate assemblages in welsh streams: towards an empirical model

The acidification of surface waters has profound ecological consequences. There is a need to predict the effects of possible future patterns of acid deposition on the biological components of fresh waters. This paper describes a model of the relationships between water chemistry and macroinvertebrate assemblages in eighteen streams in the upper Tywi whose catchments are subject to different land uses. Using established statistical techniques on data sets derived from riffle and margin samples taken in spring and summer, the macroinvertebrate assemblages were classified into three groups, which corresponded with streams draining conifer afforested catchments, acidic moorland streams and circumneutral moorland streams. Following principal components analysis to select key environmental variables, the application of multiple discriminant analysis generated two discriminant functions which were related most strongly to mean filterable aluminium concentration and mean total hardness, respectively. The discriminant functions were used to assign site-group membership with 100% success in the case of the spring data set with combined habitats. In addition, multiple regression of the primary ordination axis of each data set on mean aluminium concentration and mean hardness or pH, produced equations which explained 62.0%-87.2% of the variance. We conclude that the methods used here provide an effective analytical and potentially predictive tool for use in the understanding and management of the impact of acidification on freshwater ecosystems.     

Dynamic modelling of recovery from acidification of lakes in Killarney Park,Ontario, Canada

During much of the 1900s, the lakes in Killarney Provincial Park have been exposed to high levels of acid deposition due to sulfur emissions from the nearby metal smelters in Sudbury. The sulfur emissions from this large point source have decreased to about 10% of what they were in the 1960s. Lake water quality in Killarney Park has greatly changed in response to reduced emissions, with noticeable declines in sulfate, aluminum and calcium concentrations. Here we apply the dynamic acidification model MAGIC to 3 lakes in Killarney Park. The lakes, which have different buffering capacities and response times, were selected to represent fast, intermediate and slow recovery from acidification. The model was calibrated to match observed data for the lakes and 4 different forecast scenarios for future sulfur deposition reductions were applied. The results indicate that there is still a large potential for improvement in the water quality in Killarney. The recovery time for the different lakes varies greatly. For the lake having the slowest response time several decades are needed for the chemistry to stabilize after implementation of deposition reductions.     

Nitrogen deposition threatens species richness of grasslands across Europe

Evidence from an international survey in the Atlantic biogeographic region of Europe indicates that chronic nitrogen deposition is reducing plant species richness in acid grasslands. Across the deposition gradient in this region (2-44 kg N ha⁻¹ yr⁻¹) species richness showed a curvilinear response, with greatest reductions in species richness when deposition increased from low levels. This has important implications for conservation policies, suggesting that to protect the most sensitive grasslands resources should be focussed where deposition is currently low. Soil pH is also an important driver of species richness indicating that the acidifying effect of nitrogen deposition may be contributing to species richness reductions. The results of this survey suggest that the impacts of nitrogen deposition can be observed over a large geographical range.     

Surface water acidification in the South Pennines II. Temporal trends

Data for eight reservoirs in the South Pennines covering the period 1980-98, and for 1988-98 at the River Etherow Acid Waters Monitoring Network site, have been analysed for temporal trends using the Seasonal Kendall test. Rising trends in pH were identified at seven of the eight reservoirs, generally accompanied by declining aluminium levels. Nitrate concentrations have, however, increased sharply at the two reservoirs for which adequate data were available. Data for a wider range of determinands at the Etherow suggest that pH increases in the region can be attributed to declining sulphate concentrations, as a result of reductions in sulphur deposition. Nitrate concentrations have again increased at this site. Results are significant in a national context in that pH recovery, although widely believed to have taken place in the UK since the 1970s, has rarely been shown to have occurred. For the South Pennine region, which has been severely acidified by historically high acid deposition levels, there have clearly been improvements over the last 18 years, although many surface waters remain acidic. Observed trends for nitrate suggest that some of the pH recovery resulting from reduced sulphur deposition may have been offset by nitrogen saturation in the region, due in part to continued high levels of nitrogen deposition.     

Modeling recovery of Swedish ecosystems from acidification

Dynamic models complement existing time series of observations and static critical load calculations by simulating past and future development of chemistry in forest and lake ecosystems. They are used for dynamic assessment of the acidification and to produce target load functions, that describe what combinations of nitrogen and sulfur emission reductions are needed to achieve a chemical or biological criterion in a given target year. The Swedish approach has been to apply the dynamic acidification models MAGIC, to 133 lakes unaffected by agriculture and SAFE, to 645 productive forest sites. While the long-term goal is to protect 95% of the area, implementation of the Gothenburg protocol will protect approximately 75% of forest soils in the long term. After 2030, recovery will be very slow and involve only a limited geographical area. If there had been no emission reductions after 1980, 87% of the forest area would have unwanted soil status in the long term. In 1990, approximately 17% of all Swedish lakes unaffected by agriculture received an acidifying deposition above critical load. This fraction will decrease to 10% in 2010 after implementation of the Gothenburg protocol. The acidified lakes of Sweden will recover faster than the soils. According to the MAGIC model the median pre-industrial ANC of 107 microeq L(-1) in acid sensitive lakes decreased to about 60 microeq L(-1) at the peak of the acidification (1975-1990) and increases to 80 microeq L(-1) by 2010. Further increases were small, only 2 microeq L(-1) between 2010 and 2040. Protecting 95% of the lakes will require further emission reductions below the Gothenburg protocol levels. More than 7000 lakes are limed regularly in Sweden and it is unlikely that this practice can be discontinued in the near future without adverse effects on lake chemistry and biology.     

Anthropogenic sulphate aerosol from India: estimates of burden and direct radiative forcing

A one-box chemical-meteorological model had been formulated to make preliminary estimates of sulphate aerosol formation and direct radiative forcing over India. Anthropogenic SO₂ emissions from India, from industrial fuel use and biomass burning, were estimated at 2.0 Tg S yr^-1 for 1990 in the range of previous estimates of 1.54 and 2.55 Tg S yr ^-1 for 1987. Meteorological parameters for 1990 from 18 Indian Meteorological Department stations were used to estimate spatial average sulphate burdens through formation from SO₂ reactions in gas and aqueous phase and removal by dry and wet deposition. The hydrogen peroxide reaction was found dominating for undepleted oxidant-rich conditions. Monthly mean sulphate burdens ranged from 2–10 mg m^-2 with a seasonal variation of winter–spring highs and summer lows in agreement with previous GCM studies. The sulphate burdens are dominated by sulphate removal rates by wet deposition, which are high in the monsoon period from June–November. Monthly mean direct radiative forcing from sulphate aerosols is high (−3.5 and −2.3 W m^-2) in December and January, is moderate (−1.3 to −1.5 W m^-2) during February to April and November and low (−0.4 to −0.6 W m^-2) during May to October also in general agreement with previous GCM estimates. This model, in reasonable agreement with detailed GCM results, gives us a simple tool to make preliminary estimates of sulphate burdens and direct radiative forcing.