Organic vs. minerogenic acidity in headwater streams in Finland

This study provides an assessment of the transport of organic carbon and organic acids from typical Finnish forested catchments since the 1960's. The 21 study catchments (0.69–56 km²) are located over Finland excluding the northernmost regions. The mean annual total organic carbon (TOC) load from the catchments ranges from 2 600 to 8 800 kg/km²/a. Using a total acidity of 9.7 eq/mg DOC this would represent organic acid load of about 25–85 keq/km²/a which is higher than the mean annual deposition of strong acids in the highest deposition areas in southern Finland. The study demonstrates that organic acids dominate stream water acidity over large regions in Finland. In southern Finland minerogenic acidity is, however, more important. Organic acids exceeded mineral acids not only in autumn but also during spring snowmelt in 18 catchments. Moreover, the lowest pH values (25th percentile) were dominated by organic acids in 20 catchments. In most catchments TOC better explained pH than non-marine sulphate. In stepwise multiple regression base cations and TOC explained 67–83 % of the variation in pH for catchments divided into six groups according to season, deposition and peatland percentage; non-marine sulphate had minor contribution.     

Organic versus anthropogenic acidity in tributaries of the kejimkujik watersheds in Western Nova Scotia

Dilute waters (Ca = 0.3 to 0.8 mg L^?1) respond by depressed pH levels throughout the year to existing atmospheric wet deposition of sulphate (20 kg ha^?1yr^?1).This occurs in southwest Nova Scotia particularly during the cold, wet season when runoff is high. Colored waters of similar Ca levels receiving runoff from peaty catchments exhibit pH values one unit lower (4.7 to 4.1) than those of catchments of similar Ca levels but free from peat deposits (pH > 5.3). In colored streams sulphate and organic anions show opposing cyclic patterns while the negative gran alkalinity is the near mirror image of sulphate. Sulphate anion peaks during the high spring discharge when the organic anion concentration is lowest. Sulphate suddenly drops during the summer months during periods of high evapotranspiration, low water table and runoff, when the concentration of organic anions is highest. Both Al and Fe follow cyclic patterns similar to that of the organic anions while H⁺ reflects that of the sulphate anion. Hydrogen ion concentration is always higher than that of sulphate in very colored waters, particularly during the summer months when organic anion concentrations are very high. Analysis of data in the tributaries in the Kejimkujik watersheds indicates that while considerable organic acidity is present in colored waters, anthropogenic sulphate further increases the free acidity of these waters, particularly at times of high discharge.     

Peatland Interstitial Water Chemistry in Relation to that of Surface Pools along a Peatland Mineral Gradient

The elemental (including silica (Si), calcium (Ca), magnesium (Mg), manganese (Mn) and iron (Fe)) and nutrient composition of peatland surface pools and concentrations of Ca, Mg, Mn, and Fein peat interstitial waters and surface peat concentrations of oxides of Mn and Fe were determined for 15 peatlands sampled along a mineral gradient. Surface pool concentrations of Si wereca. ten fold less in surface pools of mineral-poor peatlands thanin the mineral rich, supporting the use of this element as an indicator of minerotrophic influence in peatlands. Principle component analysis of surface pool water chemistry parametersdifferentiated mineral-poor and moderately-poor peatlands frommineral-rich peatlands based on the concentrations of Ca, Mgand alkalinity of pools. Several lines of evidence indicated that peatland interstitial waters were important contributors to peatland alkalinity and included; (1) maximum interstitial water concentrations of Ca and Mg correlating with overlying surface pool alkalinity, (2) a negative correlation between interstitial water Ca:Mg ratios and surface pool concentrationsof Si and (3) Ca:Mg ratios of moderately-poor to mineral-poorpeatland interstitial waters approaching the Ca:Mg ratio of rainwater rather than those of bedrock. Interstitial water concentrations of dissolved Mn and Fe correlated with amountsof reducible Fe and Mn (oxides of Fe and Mn) recovered from thepeat/water interface indicating that groundwater inputs areimportant sources of these two elements to fens. As a consequence, for peatlands that are not truly ombrotrophic,groundwater inputs of Mn and Fe may interfere with interpretingpeat metal profiles thought to be due to anthropogenic inputs alone.     

Regional Patterns of Streamwater Acidity and Catchment Afforestation in Galloway,SW Scotland

This paper investigates the regional relationships between highflow water chemistry and conifer forest cover in 95 streamsspread over an area of approximately 2000 km² in Galloway,south-west Scotland, paying particular attention to the use ofdetailed catchment area data. Catchment forest data areextracted from a 30 m resolution tree height map derived fromsatellite imagery; geology data from a digital geology map; andaltitude and slope data from a 50 m resolution Digital TerrainModel (DTM). The results show that over the entire region pHlevels are lower with increasing catchment afforestation whilstaluminium concentrations are higher. Concentrations of sulphate arealso higher with increasing afforestation, which suggests thatconifers play a primary role in increasing the acidity levels ofstreams by exacerbating aerial acid deposition in the entireregion.     

Effects of sulfate deposition on pore water dissolved organic carbon,nutrients, and microbial enzyme activities in a northern peatland

Export of dissolved organic carbon from lakes and streams has increased throughout Europe and North America over the past several decades. One possible cause is altered deposition chemistry; specifically, decreasing sulfate inputs leading to changes in ionic strength and dissolved organic carbon solubility. To further investigate the relationship between deposition chemistry and dissolved organic carbon export in peatlands, a field experiment was conducted to compare the pore water chemistry and peat microbial enzyme activity of mesocosms receiving sulfate amendments to mesocosms receiving no additions. To consider how peatlands respond during recovery from increased inputs of sulfate, samples were also analyzed from an area of the same peatland that was previously amended with sulfate. Current additions of sulfate decreased dissolved organic carbon concentration and increased dissolved organic carbon aromaticity. Total dissolved phosphorus decreased in response to current sulfate amendments but was elevated in the area of the peatland recovering from sulfate amendment. The total dissolved phosphorus increase, which was reflected in microbial enzyme activity, may have shifted the system from P limitation to N limitation. This shift could have important consequences for ecosystem processes related to plant and microbial communities. It also suggests that the recovery from previous sulfate amendments may take longer than may be expected.     

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.     

Aluminium chemistry in two contrasted acid forest soils and headwater streams impacted by acid deposition,Vosges mountains,N.E. France

Al chemistry was studied in two acidic watersheds, one with a podzol, the other with an acid brown soil, in the Vosges mountains (N.E. France), by analysing both leaching and centrifugation soil solutions and spring waters over 3 yr. In the podzol, Al was mobilized in the eluvial horizons under the predominant influence of organic acidity, then leached down the profile as organic and F-bound Al. Strong undersaturation with respect to proto-imogolite and imogolite showed that the proto-imogolite theory of podzolization could not apply. Al was transferred from the soil to spring water mostly as Al³⁺ and Al-F. Al³⁺, as well as additional minor species (AlOH²⁺, AlSO₄ ⁺), originated from the redissolution of the top of the spodic horizons under the influence of both soil solution acidity and the occurrence of mobile anions derived from atmospheric deposition. Conversely, in the acid brown soil, Al mobilization was regulated by nitrate and occurred mainly as Al³⁺. Most of Al was retained in the deep soil and only traces of monomeric Al reached spring water. In the podzol eluvial horizons, soil solutions were undersaturated with respect to all relevant mineral phases and their chemical composition agree with the concept of a mobilization of Al from the solid soil organic Al and a control of Al³⁺ activity by complexation reaction with the solid and soluble soil organic matter and F. In the acid brown soil, soil solutions were found to be in equilibrium with natural alunite, and the formation of this mineral, if confirmed, would account for the occurrence of 'open' vermiculites instead of the expected hydroxy-Al interlayered vermiculites. Al solubility control in surface water of both watersheds remains unclear. The Al-F species in both watersheds and the likely control of Al solubility by alunite in the acid brown soil emphasize the influence of acid deposition on Al chemistry in acid watersheds.     

Predicted changes in streamwater chemistry following reduced/increased sulphur deposition using the “Birkenes model”

A sensitivity analysis of some important parameters in a mathematical model previously found to reproduce major short-term variations in water chemistry in some streams, has been carried out. The results are also relevant in a discussion of possible changes in stream acidity for changes in S deposition. In the simulations sulphate concentrations in streamwater were doubled or halved compared to present day values. Assuming no change in the lime potential of the soil, the peak acidity during snowmelt changed with up to 0.9 pH units; shifts from 0.4 to 0.5 units occurred in many cases. By simultaneously changing the sulphate stream concentration and the lime potential with 0.2 units shifts of about 1 pH unit were obtained in the simulations for some acidity peaks.     

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.     

Relationships between afforestation,water chemistry and fish stocks in an upland catchment in south west Scotland

The soils and waters in the Galloway hills of south-west Scotland have undergone considerable acidification during the present century. The aims of this study were to examine the extent to which afforestation can influence water chemistry, and the occurrence of fish stocks within an individual catchment in this area. Studies were carried out at 45 sites in the Bladnoch catchment during 1994. River water samples were collected at all sites and determinations made of pH, total organic carbon, calcium and monomeric aluminium concentrations. In order to quantify the size and abundance of fish populations, electrofishing was carried out at 21 of the sites. Estimates of afforestation were made by a combination of field surveys and the use of 1∶:10 000 scale ordnance survey maps. The presence of coniferous trees had a substantial affect on water chemistry. In areas where the whole catchment was afforested, the water pH was 0.7 units lower than in unafforested areas (p<0.001). Afforestation was also correlated with low concentrations of calcium, and increases in the concentrations of monomeric aluminium and total organic carbon. There was a clear relationship between fish populations and water chemistry. Numbers of trout were positively correlated with pH (r ²=0.69; p<0.001), and with concentrations of calcium (r ²=0.55; p<0.001). The study has shown that salmonid fish populations are sensitive to acidity and the associated changes in river water chemistry; these problems were exacerbated by afforestation.     

Finnish lake survey: the role of organic and anthropogenic acidity

A lake survey consisting of 987 randomly selected lakes was conducted in Finland in autumn 1987. The survey covered the whole country, and the water quality of the lakes can be considered as representative of the approximately 56 000 lakes larger than 0.01 km² in Finland. The median TOC concentration is 12 mg L^-1 and the median pH 6.3. The proportion of lakes with TOC concentrations > 5 mg L^-1 in the whole country is 91 %. Organic anion is the main anion in the full data set (median 89 μeq L^-1). The high organic matter concentrations in Finnish lakes are associated with catchment areas containing large proportions of peatlands and acid organic soils under coniferous forest. The survey demonstrated that organic matter strongly affects the acidity of lakes in Finland. The decreasing effect of organic matter on the pH values was demonstrated by both regression analysis and ion balances. At current deposition levels of ^*SO₄ the pH of humic lakes in Finland is determined to a greater extent by high TOC concentrations than by ^*SO₄ in most areas. In lakes with pH values lower than 5.5 the average organic anion contribution is 56 % and non-marine sulfate contribution 39 %. However, in the southern parts of the country, where the acidic deposition is highest, the minerogenic acidity commonly exceeds the catchment derived organic acidity.     

The effect of peatland drainage and rewetting (ditch blocking) on extracellular enzyme activities and water chemistry

Extensive areas of European peatlands have been drained by digging ditches in an attempt to improve the land, resulting in increased carbon dioxide fluxes to the atmosphere and enhanced fluvial dissolved organic carbon (DOC) concentrations. Numerous peatland restoration projects have been initiated which aim to raise water tables by ditch blocking, thus reversing drainage‐induced carbon losses. It has been suggested that extracellular hydrolase and phenol oxidase enzymes are partly responsible for controlling peatland carbon dynamics and that these enzymes are affected by environmental change. The aim of this study was to investigate how drainage and ditch blocking affect enzyme activities and water chemistry in a Welsh blanket bog, and to study the relationship between enzyme activity and water chemistry. A comparison of a drained and undrained site showed that the drained site had higher phenol oxidase and hydrolase activities, and lower concentrations of phenolic compounds which inhibit hydrolase enzymes. Ditch blocking had little impact upon enzyme activities; although hydrolase activities were lowered 4–9 months after restoration, the only significant difference was for arylsulphatase. Finally, we noted a negative correlation between β‐glucosidase activity and DOC concentrations, and a positive correlation between arylsulphatase activity and sulphate concentration. Phenol oxidase activity was negatively correlated with DOC concentrations in pore water, but for ditch water phenol oxidase correlated negatively with the ratio of phenolics to DOC. Our results imply that drainage could exacerbate gaseous and fluvial carbon losses and that peatland restoration may not reverse the effects, at least in the short term.     

The role of sea-salts in enhancing and mitigating surface water acidity

Enhancement of the acidity of fresh waters due to sea-salt “episodes” has been reported in western regions of Scotland, Ireland and Norway and eastern regions of Canada and the United States of America. In all cases these short-term pH depressions have been ascribed to cation-exchange processes in catchment soils whereby sodium ions displace acidic cations (H⁺, Al³⁺) resulting in a lowering of the Na/Cl ratio in run-off water. Studies of sea-salt episodes in different catchment types of similar sensitivity in Scotland show significant variations in chemical responses, especially in terms of acidification status. Catchments with high background salt content, in a low sulphur deposition area, show only a small increase in acidity with negligible aluminium release and most of the sodium retention matched by Ca and Mg release. Catchments in intermediate deposition areas, with low background salt levels, exhibit smaller sodium retention with increased leaching of acidity and labile aluminium. High non-marine S deposition sites, with intermediate background salt levels, reveal high levels of acidity and aluminium leaching associated with some calcium leaching and evidence of Mg retention. Mitigation of acidification occurs at sites with high background sea-salt levels (eg north west Scotland) where acidic deposition is selectively retained in catchment soils. Non-marine sulphate values in run-off are therefore much lower (often producing negative values) than those predicted from current S deposition values. Consequently such sites are presently producing false exceedances of freshwater Critical Loads when current S deposition values are used. Future reductions in S deposition will probably affect the adsorption characteristics at these sites with consequent effects on sulphate leaching.     

Aluminium chemistry and acidification processes in a shallow podzol on the Swedish westcoast

Processes pertinent to soil acidification with special emphasis on the solution chemistry of A1, were studied in three adjacent small catchments on the Swedish westcoast, with mixed coniferous forest and shallow podzols (average soil depth 50 cm). Soil solution from different depths, groundwater and stream-water were sampled. Separation of organic and inorganic Al species was done with an ion exchange technique. The concentration of organic A1 species was linearly correlated with the concentration of dissolved organic C (r,², varied from 0.38 to 0.69 with p, < 0.001). In the A horizon 83 to 97 % of the dissolved A1 consisted of organic species. The average concentration of total A1 varied from 3.3 to 9.8 μmole 1^?1, in soil leachates collected below the A₀, horizon, and from 29.3 to 47.0 pmole 1^?1, in leachates collected below the A₂, horizon. The organic Al species decreased in importance with increasing soil depth. Leachates collected below the B horizon had average total A1 concentrations ranging from 95.3 to 115 pmole 1^?1, with a contribution of organic species varying between 8 and 20% of the total concentration. Activity calculations indicated an equilibrium with A1(OH)SO₄, (pK _S = 17.23) in the lower part of the B horizon, while groundwater together with some of the leachates from the upper B horizon showed a better fit with A1₁₄(OH)₁₀SO₄ (pK₁ = 117.51). Streamwater was obviously influenced by the soil organic matter in the outflow areas in terms of A1- organic matter complexes and protolysis of dissolved organic acids. There was a net outflow of Al and sulphate from the lower part of the B horizon compared to input in throughfall precipitation. The relative concentration increase varied from 64.4 to 78.0 (A1) and from 1.52 to 1.92 (sulphate). The relative increase due to evapotranspiration was estimated to be 1.4. The corresponding concentration factors for Mg and Ca were from 2.06 to 2.38, and from 0.81 to 1.07, respectively, indicating a very low Ca weathering. Data were compared with other studies, both recent and older ones. The possible influence from present-day levels of H⁺ and sulphurous compounds in the atmospheric deposition is evaluated.     

Chemical and Biochemical Characteristics of Alpine Soils in the Tatra Mountains and their Correlation with Lake Water Quality

Soils and lakes were sampled in fifteen catchments in the alpinezone of the Tatra Mountains (Slovak-Polish border) to evaluate the dependence of lake water chemistry on soil properties. The amount of soil in alpine meadows varied from 38 to 255 kg m^-2 (dry weight soil <2 mm; average of 121 kg m^-2). The average cation exchange capacity (CEC) was 12 eq m^-2, average base saturation was 12%, and average ${\text{pH}}_{{\text{CaCl}}_{\text{2}} } $ was 4.0. Moraine areas had, on average, 13 kg m^-2 of <2 mm soil in small deposits between stones. Their chemical properties were similar to mineral horizons of alpine soils but had higher concentrations of P forms. Soil composition was spatially uniform, having coefficientsof variation of all parameters between 5 and 115%, and did not exhibit significant differences between the catchments or along the elevation gradient. Variation in pools of soil constituents was ～2-fold higher. Soil organic matter concentration was theparameter that most strongly and positively correlated with N, P, S, CEC, exchangeable base cations, exchangeable acidity, and all biochemical parameters (C, N, and P in microbial biomass and C and N mineralisation rates). Lake water concentrations of organic C, N, and total P were positively correlated (P < 0.01) with the pool of soil organic matter in the catchments, while NO₃ ^- concentrations were negatively correlated (P < 0.001). No correlations were found between C, N, and P concentrations in lakes and soil chemistry, indicating the dominant role of soil quantity over quality for surface water composition in the Tatra lakes. Relatively high concentrations of Ca²⁺, Na⁺, SO₄ ^2-, reactive Si, and acid neutralising capacity in some lakes were not explained by soil characteristics, and were more probably related to bedrock composition and structure.     

Hydrochemical processes at a pristine site in nord-trøndelag,mid-Norway

A detailed study of hydrochemical processes associated with vegetation and soils was undertaken at a pristine site in mid-Norway. Inputs to the site during snow-free periods showed a marked seasonality with excess sulphate concentrations in rainfall only during the summer months. However, this represented a small fraction of total annual loading and there was a dominant influence of sea salt deposition. Site vegetation modified the chemistry of water reaching the soil surface, and this also showed a marked seasonal response. The pristine nature of this site results in the soils retaining acid-soluble components which may have been eluted from impacted sites. In the soils, the extractable aluminium remains largely (70%) in the organic bound forms. The contribution of different sources of water in affecting streamwater output quality at this site are discussed.     

Effects of acid deposition on acidity and exchangeable cations in podzols of the Kola Peninsula

Response of soil and soil water of podzols in the Kola Peninsula to acid deposition was estimated under both field and laboratory conditions. A significant increasing trend of exchangeable acidity in organic (O) horizons and exchangeable Al in podzolic (E) horizons of podzols with distance from the nickel smelter was observed. The simulated rain at pH 4.5 did not alter chemical properties of soils and soil solutions. As much as 95–99% of the applied H⁺ ions were retained by soils and appeared in the percolates after a treatment period that depended on acid load and soil thickness. Ca and Mg in soil solutions were highly sensitive to acid loading. Simulated acid rain enhanced the leaching of exchangeable base cations out of root zone. Acid inputs resulted in decreased pH, amount of exchangeable base cations and base saturation, in elevated exchangeable acidity and it's Al fraction in soil solid phase. The most significant changes occurred in O and E horizons. Substantial amounts of both Ca and Mg can be lost from the root zone of podzols in the north-western Kola, subjected to acid deposition, thus leading to forest productivity damage.     

Natural and anthropogenic acidity sources for Finnish Lakes

The headwater lakes in peat-rich areas in Finland commonly have high organic matter concentrations and are surrounded by soils and bedrock poor in bases. As a result the organic acid load on the watercourses is generally high. The significance of the organic vs anthropogenic acidity in 78 moderately acid lakes (pH range 4.3 to 7.1, TOC range 0.6 to 33.9 mg L^?1) was evaluated in areas receiving different levels of acid deposition. The lakes were sampled during autumn overturn, and their water quality (mean TOC = 10.9 mg L^?1, mean pH = 5.9) represents rather well the average water quality in small lakes in Finland. According to the correlation and regression analyses, TOC is a better predictor of pH than non-marine sulfate. Base cation concentrations are important in determining the sensitivity of the lakes to organic and anthropogenic acidity. The highest minerogenic acid contribution is found in high-deposition areas, while the percent organic acid contribution is greater in low deposition areas although TOC levels are comparable in both areas. It would appear that the pH of humic lakes is determined to a greater extent by individual watershed characteristics than by their geographical location at the present atmospheric loadings received in Finland.     

Factors affecting snowmelt streamwater chemistry in the black forest (West Germany)

Site conditions such as parent material, soils, but also vegetation cover and elevation explain the varying snowmelt streamwater chemistry in the Black Forest. The results are derived from multiple statistical analysis of a regional survey of 104 small mountain streams in the first phase of snowmelt in spring 1984. Cluster analysis classifies the snowmelt streams into three groups which are clearly linked to bedrock geology. Factor analysis finds podsolization, weathering and mineralization processes in the soils of the catchments to have most impact even under snowmelt conditions. There is no evidence that acidic atmospheric deposition directly affects the acidity of the investigated streams. However, the deposition rates are low compared to certain other regions in Central Europe. In areas with podsolic soils the organic soil layer plays a key role in the acidity and mobilization of Al and heavy metals. This is shown in the high correlations between pH, DOC, UV-extinction, color and metal concentrations. Because the concentrations of DOC are low (<10 mg.L^?1) and an anion deficit cannot be found, it is assumed that water acidity is not caused by dissolved humic acids, but by cations exchanged in the organic layer of acidic soils. Streamwater chemistry in areas with brown earth soil types is mainly affected by leaching of basic cations in the mineral soil horizons and mineral weathering.     

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.