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.     

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.     

Evidence of sulphur and nitrogen deposition signals at the United Kingdom Acid Waters Monitoring Network sites

Some recent studies of trends in sulphate in surface waters have alluded to possible lag effects imposed by catchment soils, resulting in discrepancies between trends in deposition and run-off. To assess the extent of these possible effects in the UK, sulphate concentration data from the United Kingdom Acid Waters Monitoring Network (AWMN) sites are compared with estimates of sulphur deposition at each site. From these data, input-output budgets are computed at an annual time scale. The estimated budgets suggest a close association between catchment sulphur inputs and outputs at an annual scale, with well-balanced annual budgets at most sites, indicative of only minor lag effects. A similar analysis of the AWMN site nitrogen budget shows little evidence of an association between nitrogen inputs and outputs at this time scale.     

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.     

Acid rain and nitrogen deposition in a sub-tropical watershed (Piracicaba): ecosystem consequences

High levels of wet N and acidic deposition were measured in southeast Brazil. In this study we addressed the sensitivity of water bodies and soils to acidification and N deposition in the Piracicaba River basin (12,400 km2). Average acid neutralization capacity (ANC) at 23 river sampling sites varied from 350 to 1800 microeq l(-1). Therefore, rivers and streams in the Piracicaba basin are well buffered, if the lower limit of 200 microeq l(-1) is assumed as an indication of poorly buffered waters. ANC is increased by untreated wastewaters discarded into rivers and streams of the region. Average NO3 concentrations varied from 20 to 70 microeq l(-1). At the most polluted river sites, NO3 concentration is not highest, however, probably due to NO3 reduction and denitrification. Most of the nitrogen in streams is also provided by wastewaters and not by wet deposition. The majority of the soils in the basin, however, are acidic with a low base cation content and high aluminum concentration. Therefore, soils in this basin are poorly buffered and, in areas of forest over sandy soils, acidification may be a problem.     

Afforestation, seasalt episodes and acidification--a paired catchment study in western Norway

As acid deposition has declined during the past 15-20 years in western Norway, afforestation and episodic seasalt deposition have become factors of increasing importance in explaining the mobilization of toxic aluminum (Aln+) to rivers and lakes. We conducted a paired catchment at four sites in western Norway across a gradient in acid deposition to evaluate the importance of afforestation and seasalt episodes. Streamwater was sampled intensively before, during and after seasalt episodes over a three-year period. A seasalt episode in January 2003 caused considerable impact on the streamwater chemistry. pH dropped and concentrations of Aln+ increased due to cation exchange of Na+ ions for H+ and Aln+ in the soil. The response was larger in streams draining the catchments which receive high acid deposition and in those afforested with spruce as compared with adjacent catchments in native birch. The results indicate that acid pulses induced by episodic inputs of seasalts are exacerbated by land use change from native birch to planted spruce.     

The influence of organic acids in relation to acid deposition in controlling the acidity of soil and stream waters on a seasonal basis

Much uncertainty still exists regarding the relative importance of organic acids in relation to acid deposition in controlling the acidity of soil and surface waters. This paper contributes to this debate by presenting analysis of seasonal variations in atmospheric deposition, soil solution and stream water chemistry for two UK headwater catchments with contrasting soils. Acid neutralising capacity (ANC), dissolved organic carbon (DOC) concentrations and the Na:Cl ratio of soil and stream waters displayed strong seasonal patterns with little seasonal variation observed in soil water pH. These patterns, plus the strong relationships between ANC, Cl and DOC, suggest that cation exchange and seasonal changes in the production of DOC and seasalt deposition are driving a shift in the proportion of acidity attributable to strong acid anions, from atmospheric deposition, during winter to predominantly organic acids in summer.     

Scale-dependence of land use effects on water quality of streams in agricultural catchments

The influence of land use on water quality in streams is scale-dependent and varies in time and space. In this study, land cover patterns and stocking rates were used as measures of agricultural development in two pasture and one native grassland catchment in New Zealand and were related to water quality in streams of various orders. The amount of pasture per subcatchment correlated well to total nitrogen and nitrate in one catchment and turbidity and total phosphorous in the other catchment. Stocking rates were only correlated to total phosphorous in one pasture catchment but showed stronger correlations to ammonium, total phosphorous and total nitrogen in the other pasture catchment. Winter and spring floods were significant sources of nutrients and faecal coliforms from one of the pasture catchments into a wetland complex. Nutrient and faecal coliform concentrations were better predicted by pastural land cover in fourth-order than in second-order streams. This suggests that upstream land use is more influential in larger streams, while local land use and other factors may be more important in smaller streams. These temporal and spatial scale effects indicate that water-monitoring schemes need to be scale-sensitive.     

Metals in bulk deposition and surface waters at two upland locations in northern England

Concentrations of aluminium and minor metals (Mn, Ni, Cu, Zn, Sr, Cd, Ba, Pb) were measured in precipitation and surface water at two upland locations (Upper Duddon Valley, UDV; Great Dun Fell, GDF) in northern England for 1 year commencing April 1998. At both locations, the loads in bulk precipitation were at the lower ends of ranges reported for other rural and remote sites, for the period 1985-1995. The deposited metals were mostly in the dissolved form, and their concentrations tended to be greatest when rainfall volumes were low. The concentrations of Cu, Zn and Pb in deposition were correlated (r2 > or = 0.40) with concentrations of non-marine sulphate. Three streams, ranging in mean pH from 5.07 to 7.07, and with mean concentrations of dissolved organic carbon (DOC) < 1 mg l(-1). were monitored at UDV, and two pools (mean pH 4.89 and 6.83, mean DOC 22 and 15 mg l(-1)) at GDF. Aluminium and the minor metals were mainly in the dissolved form, and in the following ranges (means of 49-51 samples. microg l(-1)): Al 36-530. Mn 4.4-36, Ni 0.26-2.8, Cu 0.25-1.7, Zn 2.1-30, Cd 0.03-0.16, Ba 1.9-140, Pb 0.10-4.5. Concentrations were generally higher at GDF. Differences in metal concentrations between the two locations and between waters at each location, and temporal variations in individual waters, can be explained qualitatively in terms of sorption to solid-phase soil organic matter and mineral surfaces, complexation and transport by DOC, and chemical weathering. The UDV catchments are sinks for Pb and sources of Al, Mn, Sr, Cd and Ba. The GDF catchments are sources of Al, Mn, Ni, Zn, Sr, Cd and Ba. Other metals measured at the two locations are approximately in balance. Comparison of metal:silicon ratios in the surface waters with values for silicate rocks indicates enrichment of Ni and Cu, and substantial enrichment of Zn, Cd and Pb. These enrichments, together with high metal deposition in the past, make it likely that concentrations of the metals in the surface waters are governed by release from catchment pools of atmospherically-deposited metal. The catchments appear to be responding on a time scale of decades, possibly centuries, to changes in metal deposition. For the more acid waters at UDV, the calculated free-ion concentrations of Al are similar to published LC50 values for acute toxicity towards fish. The free-ion concentrations of Ni, Cu, Zn and Cd in all the surface waters are one-to-four orders of magnitude lower than reported LC50 values for fish.     

Recovery from acidification in central Europe--observed and predicted changes of soil and streamwater chemistry in the Lysina catchment,Czech Republic

The geochemical model MAGIC was applied to estimate streamwater and soil chemistry between 1851 and 2030 at the Lysina catchment, an acid-sensitive granitic catchment covered by planted Norway spruce monoculture in the western Czech Republic. The total deposition of sulfur to the catchment was 164 meq m(-2) in 1991, but had declined to 52 meq m(-2) by 2000. Although SO2 emissions in the region declined by 90% compared to the 1980s, acidification recovery was small within the period 1990-2000. Stream pH increased only slightly (from 3.92 to 4.07), although SO4 concentration declined sharply from 568 microeq l(-1) (1990) to 232 microeq l(-1) (2000). Organic acids played an important role in streamwater buffering. According to the MAGIC prediction using deposition measured in 1999-2000, streamwater pH will increase to 4.3 and soil base saturation will increase to 6.2% by 2030 (from 5.7% in 2002). Pre-industrial pH was estimated to be 5.5 and soil base saturation 24.7%. The loss of base cations (Ca, Mg, Na, K) was caused predominantly by atmospheric acidity, but intensive forestry was responsible for approximately one third of the net base cation loss via accumulation in harvested biomass. Severely damaged sites, under continued pressure from forestry, will not return to a good environmental status in the near future (if ever) when the acid deposition input is only partially reduced.     

Evaluating common drivers for color,iron and organic carbon in Swedish watercourses

The recent browning (increase in color) of surface waters across much of the northern hemisphere has important implications for light climate, ecosystem functioning, and drinking water treatability. Using log-linear regressions and long-term (6–21 years) data from 112 Swedish watercourses, we identified temporal and spatial patterns in browning-related parameters [iron, absorbance, and total organic carbon (TOC)]. Flow variability and lakes in the catchment were major influences on all parameters. Co-variation between seasonal, discharge-related, and trend effects on iron, TOC, and absorbance were dependent on pH, landscape position, catchment size, latitude, and dominant land cover. Large agriculture-dominated catchments had significantly larger trends in iron, TOC, and water color than small forest catchments. Our results suggest that while similarities exist, no single mechanism can explain the observed browning but show that multiple mechanisms related to land cover, climate, and acidification history are responsible for the ongoing browning of surface waters.     

Dissolved phosphorus transport from soil to surface water in catchments with different land use

Diffuse phosphorus (P) export from agricultural land to surface waters is a significant environmental problem. It is critical to determine the natural background P losses from diffuse sources, but their identification and quantification is difficult. In this study, three headwater catchments with differing land use (arable, pasture and forest) were monitored for 3 years to quantify exports of dissolved (<0.45 µm) reactive P and total dissolved P. Mean total P exports from the arable catchment ranged between 0.08 and 0.28 kg ha^?1 year^?1. Compared with the reference condition (forest), arable land and pasture exported up to 11-fold more dissolved P. The contribution of dissolved (<0.45 µm) unreactive P was low to negligible in every catchment. Agricultural practices can exert large pressures on surface waters that are controlled by hydrological factors. Adapting policy to cope with these factors is needed for lowering these pressures in the future.     

Seasonal variability of total and easily leachable element contents in topsoils (0-5 cm) from eight catchments in the European Arctic (Finland, Norway and Russia)

Frozen topsoil samples (0-5 cm) were collected during March/April 1994 in eight Arctic catchments in northern Europe (4 in Russia, 3 in Finland, 1 in Norway) at varying distances and wind directions from the emissions of the Russian nickel ore mining, roasting and smelting industry on the Kola Peninsula. Between 14 and 25 sites were sampled in catchment basins ranging in size from 12 to 35 km(2). Sampling was repeated in spring immediately after the snow melted, in summer and in autumn to study seasonal variability and the fate of elements when the snow melts. The <2 mm fraction of air-dried topsoils was analysed for total (aqua regia extraction) and easily leachable (in 1 m ammonium acetate, buffered at pH 4.5) element concentrations using ICP-AES and GFAAS for up to 35 elements. Results for selected elements are presented here. Soil organic matter can be shown to be the controlling factor determining element contents and fate. In catchments close to the Russian nickel industry, the topsoils have low carbon and nitrogen contents. Using both extraction methods most elements reach maximum concentrations in winter; lowest concentrations are observed in midsummer. Soil organic matter and elements associated with it are thus leached out of the soils together with soluble elements when the snow melts. This process continues in summer. Elements will enrich surface waters, the lower layers of podzol profiles, or reach the groundwater. The use of the two extractions described provides a simple method to study the mobilities and pathways of elements in the topsoils during the arctic year. Using the proportions of easily leachable to total concentration, a good estimation of the status of the topsoil in the study area can be given.     

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.     

A classification of acidified catchments in Britain

To compare catchments of possible acidified waters in Britain an extensive database was compiled for nearly 600 catchments of lakes and streams for which chemical data were available. Information on the database included map-derived data, pollutant deposition estimates and hydrological characteristics. To stratify the catchment database a randomly selected subset of 328 catchments was used to derive eight classes of catchments using the classification program TWINSPAN. Several classifications were generated by this method using an increasing number of catchment parameters. TWINSPAN classes were defined on the basis of some catchment parameters (indicators) but were shown to be associated with other variables. A general linear model (GLM) analysis of the available chemical data was used to test the different classifications. A TWINSPAN classification which excluded soil and geology characteristics gave the best GLM model because soil and geology types were poorly correlated with other catchment parameters. However, because of the recognized importance of soils and geology in acidification processes, these parameters were introduced into the GLM model as separate GLM classes. The resulting three-class model (TWINSPAN class, soil type, geology type) proved superior to both the one-class model and to two-class models which included either soil or geology. It was demonstrated that the TWINSPAN classes were associated with particular geographical areas and particular monitoring programmes. The TWINSPAN classification was used to evaluate a set of catchments selected as long-term monitoring sites for Britain. In general, the set covered a wide range of catchment types as defined by the classification. It was possible to identify minor shortfalls in classes of catchment selected and suggest possible additions to the sampling programme. Whilst the classification procedure has been applied to possible acidified waters, the method is of general relevance to all catchments and waters of more diverse nature.     

Long-term change in the suitability of welsh streams for dippers Cinclus cinclus as a result of acidification and recovery: a modelling study

Using a recognized and widely used hydrochemical model, MAGIC, long-term changes in acidity were simulated at 104 sites in the acid sensitive region of upland Wales. Conditions were modelled in the future (2010) under different reductions in sulphate deposition from 0 to 90% of 1984 values. Chemical output from the model was used to simulate change in the chemical suitability of streams for a species of river bird, the Dipper Cinclus cinclus, known to be affected by acidification According to simulations, only reductions in sulphate deposition by over 50% of 1984 levels prevented decline in the number of streams chemically suitable for Dippers. Greater reductions in deposition in the model permitted some recovery except where conifer forestry occupied acid sensitive catchments. There are several uncertainties with the models in their present form.     

Storage and distribution of trace metals and spheroidal carbonaceous particles (SCPs) from atmospheric deposition in the catchment peats of Lochnagar, Scotland.

Lochnagar is a remote mountain lake to the south-east of the Cairngorm region in Scotland. Its catchment receives anthropogenic trace metals solely from atmospheric deposition. Ten peat cores were taken from the catchment and analysis confirmed that they have been contaminated by trace metals. The peats have an high affinity for trace metals and this results in metal accumulation in the surface peat layers. The formation of trace metal sulphides may also reduce remobilisation. In this way, trace metals derived from atmospheric deposition have been scavenged and accumulated. In contaminated peat layers, 77.4% Hg, 89.6% Pb, 93.4% Cu, 72.4% Zn and 86.5% Cd of the total stored are from anthropogenic sources. The accumulated trace metals in the peats can potentially influence the lake system through erosion. Spheroidal carbonaceous particle (SCP) profiles were used to date the peat cores. By referring to the SCP profiles in the peats and comparing these with the trace metal profiles in the lake sediments, the mobility of trace metals in the catchment peats is confirmed.     

Predicting stream-water quality using catchment and soil chemical characteristics

The distribution and chemistry of soils in 10 upland catchments in NE Scotland have been used to develop a means of predicting minimum, maximum and mean concentrations of calcium and hydrogen ions in streams. The approach is based on the control of stream-water chemistry by soil chemical properties. Stream-water chemistry was monitored over a two-year period. Each catchment was surveyed and soils sampled to characterize the chemistry of the main soil units. Stream-water chemical parameters are related to the chemical characteristics of the upper and lower soil horizons in the catchments. The contribution of each soil unit is assessed using randomly generated flow paths. Soil chemistry is weighted according to the distribution of soils in the immediate vicinity of the stream. In this paper the approach is largely confined to the prediction of minimum, maximum and mean concentrations of calcium ions in stream waters. In the longer term, the approach may have the potential to predict what effects changes in soil chemistry and management practice (drainage, ploughing) will have on water quality in upland catchments.     

The MAGIC simulation of surface water acidification at, and first year results from, the Bear Brook Watershed Manipulation, Maine, USA

The catchments of East and West Bear Brooks, Maine, USA, have been hydrologically and chemically monitored for 3.5 years. Stream chemistries and hydrographs are similar. These clear water streams are low in ANC (0-70 microeq litre(-1)), with variations caused by changing concentrations of base cations, SO4, NO3 and Cl. The latter range between 90-120, 0-40 and 65-75 microeq litre(-1), respectively. The West Bear catchment is being treated with six applications per year of dry (NH4)2SO4 at 1800 eq ha(-1) year(-1). After one year of treatment, the response of the stream chemistry and the response modelled by MAGIC are similar. Retentions of NH4 and SO4 are nearly 100% and greater than 80%, respectively. The additional flux of SO4 is compensated principally by an increased Ca concentration. Episodes of high discharge in the treated catchment are now characterized by lower ANC and pH, and higher Al than prior to the manipulation. Concentrations of NO3 have increased about 10 microeq litre(-1) during the dormant season, presumably due to additional nitrification of N from NH4. Discharge-chemistry relationships indicate that changes in stream chemistry, except for NO3, are dominated by ion exchange reactions in the upper part of the soil profile.     

Riparian Zone Influence on Stream Water Dissolved Organic Carbon Concentrations at the Swedish Integrated Monitoring Sites

Short-term variability in stream water dissolved organic carbon (DOC) concentrations is controlled by hydrology, climate and atmospheric deposition. Using the Riparian flow-concentration Integration Model (RIM), we evaluated factors controlling stream water DOC in the Swedish Integrated Monitoring (IM) catchments by separating out hydrological effects on stream DOC dynamics. Model residuals were correlated with climate and deposition-related drivers. DOC was most strongly correlated to water flow in the northern catchment (Gammtratten). The southern Aneboda and Kindla catchments had pronounced seasonal DOC signals, which correlated weakly to flow. DOC concentrations at Gårdsjön increased, potentially in response to declining acid deposition. Soil temperature correlated strongly with model residuals at all sites. Incorporating soil temperature in RIM improved model performance substantially (20–62% lower median absolute error). According to the simulations, the RIM conceptualization of riparian processes explains between 36% (Kindla) and 61% (Aneboda) of the DOC dynamics at the IM sites.