Artificial acidification of a non-acidic and an acidic headwater stream in Maine, USA

Two headwater streams with low DOC and different pHs (4.5-4.8 and 5-6.5) were acidified with H2SO4 to pH 4.1 and 4.5, respectively, for 24-h periods. Neutralization of the added acid occurred by protonation of ANC (HCO3-dominated in the higher pH stream), desorption of Ca (< 15 microeq litre(-1)) and Mg (<6 microeq litre(-1)), and desorption and dissolution of AL (<250 microg litre(-1)) from the stream bed. The concentrations of dissolved organic carbon (DOC) remained constant within the experimental reaches. The concentrations of Na, K an H4SiO4 also remained constant, indicating no detectable increase in the rate of chemical weathering in the stream bed. After acid addition was stopped, concentrations of Ca, Mg and Al decreased to below background, indicating reversible ion exchange as the principal mechanism for the mobility of Ca and Mg and to a lesser extent for Al. Repeated acidifications indicated that significant regeneration of cations on the exchange surfaces of the stream substrate occurs rapidly.     

Persistent episodic acidification of streams linked to acid rain effects on soil

Episodic acidification of streams, identified in the late 1980s as one of the most significant environmental problems caused by acidic deposition, had not been evaluated since the early 1990s despite decreasing levels of acidic deposition over the past decade. This analysis indicates that episodic acidification of streams in upland regions in the northeastern United States persists, and is likely to be much more widespread than chronic acidification. Depletion of exchangeable Ca in the mineral soil has decreased the neutralization capacity of soils and increased the role of the surface organic horizon in the neutralization of acidic soil water during episodes. Increased accumulation of N and S in the forest floor from decades of acidic deposition will delay the recovery of soil base status, and therefore, the elimination of acidic episodes, which is anticipated from decreasing emissions.     

Water chemistry and fish community responses to episodic stream acidification in Pennsylvania, USA

Five streams were studied on the Northern Appalachian Plateau of Pennsylvania from October 1988 through June 1989 to determine chemical changes that occur during episodic storm run-off and the responses of fish to these events. These second-order streams flowed through undisturbed, wooded, sandstone bedrock catchments with surface areas ranging from 500 to 1000 hectares. Median pH of precipitations was about 4.2, and among streams it ranged from 5.0 to 6.2. During storm events, pH declined by as much as 1.2 units and peak concentrations of total monomeric Al ranged from < 0.01 to 0.75 mg litre(-1). Organically bound A1 was generally a minor component of total monomeric A1. Wild brook trout (Salvelinus fontinalis) were found in all streams, although only a remnant population existed in the most acidic stream. Sculpins (Cottus bairdi or C. cognatus) were collected only in the two streams with the least severe episodes. Mortality of brook trout and sculpins in in situ bioassays ranged from 0 to about 80% among streams during acidic episodes and was positively related to concentrations of total dissolved Al. Radio-tagged brook trout moved downstream during episodes when Al reached toxic concentrations. Some displaced trout were found near groundwater seeps, where pH was higher and dissolved Al was lower than in the main channel.     

Assessment of sediment contamination in Casco Bay, Maine, USA

The current status of contaminant concentrations in Casco Bay, decadal trends of these contaminants and changes in their geographical distribution are assessed using sediment samples collected approximately 10 years apart. In general, regulated contaminants appeared to be decreasing in concentration. Total PAH and dioxins/furans concentrations did not significantly change over this period. Total organochlorine pesticides, 4,4-DDE, 4,4-DDD, total DDT, PCB, tributyltin and total butyltin decreased in concentration. Trace element concentrations in sediments decreased at the majority of the sampling sites for chromium, nickel, and selenium while arsenic, cadmium, copper, lead, mercury, silver, and zinc remained relatively constant. None of the contaminants measured has increased by more than a factor of 2. Selected sites located in the Inner Bay, where concentrations are higher and new inputs were more likely, showed increased concentrations of contaminants. Most contaminants were not found at concentrations expected to adversely affect sediment biota based on ERL/ERM guidelines.     

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.     

Comparison of episodic acidification in Canada, Europe and the United States

Episodic acidification is practically a ubiquitous process in streams and drainage lakes in Canada, Europe and the United States. Depressions of pH are often smaller in systems with low pre-episode pH levels. Studies on European surface waters have reported episodes most frequently with minimum pH levels below 4.5. In Canada and the United States, studies have also reported a number of systems that have had minimum pH levels below 4.5. In all areas, change in water flowpath during hydrological events is a major determinant of episode characteristics. Episodic acidification is also controlled by a combination of other natural and anthropogenic factors. Base cation decreases are an important contributor to episodes in circumneutral streams and lakes. Sulphate pulses are generally important contributors to episodic acidification in Europe and Canada. Nitrate pulses are generally more important to episodic acidification in the Northeast United States. Increases in organic acids contribute to episodes in some streams in all areas. The sea-salt effect is important in near-coastal streams and lakes. In Canada, Europe and the United States, acidic deposition has increased the severity (minimum pH reached) of episodes in some streams and lakes.     

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.     

Modelling episodic acidification of surface waters: the state of science

Field studies of chemical changes in surface waters associated with rainfall and snowmelt events have provided evidence of episodic acidification of lakes and streams in Europe and North America. Modelling these chemical changes is particularly challenging because of the variability associated with hydrological transport and chemical transformation processes in catchments. This paper provides a review of mathematical models that have been applied to the problem of episodic acidification. Several empirical approaches, including regression models, mixing models and time series models, support a strong hydrological interpretation of episodic acidification. Regional application of several models has suggested that acidic episodes (in which the acid neutralizing capacity becomes negative) are relatively common in surface waters in several regions of the US that receive acid deposition. Results from physically based models have suggested a lack of understanding of hydrological flowpaths, hydraulic residence times and biogeochemical reactions, particularly those involving aluminum. The ability to better predict episodic chemical responses of surface waters is thus dependent upon elucidation of these and other physical and chemical processes.     

Source areas contributing to the episodic acidification of a forested headwater stream

A study was initiated on the Leading Ridge Experimental Watersheds in central Pennsylvania to investigate the extent to which episodic depressions of streamwater pH result from direct channel interception of acidified rainwaters and from rapid subsurface stormflow. During a 4.78-cm rainfall event on June 6, 1986, stream pH declined from 5.93 to 5.46. Analysis of the storm hydrograph indicated that direct channel interception accounted for only 2.8% of the total stormflow volume but contributed 40% of the total increase in the concentration of H⁺. At peak flow, channel interception accounted for 5.7% of the stormflow volume and 72% of H⁺. Large increases in the height of the saturated soil zone and coinciding increases in H⁺ concentrations in soilwater were measured at a number of soilwater observation wells. These fluctuations occurred almost simultaneously with measured fluctuations in both streamflow and streamwater H⁺ concentrations, indicating direct interactions between saturated soilwater and the storm discharge. These results indicate that cathcments in which soil macropores permit rapid subsurface flow could be especially susceptible to stream acidification.     

Complex biological responses to the experimental acidification of Little Rock Lake, Wisconsin, USA

Acidification can affect aquatic organisms directly through hydrogen ion toxicity, and indirectly through disrupted food web dynamics and altered abiotic conditions. Field populations from selected taxa were studied during the Little Rock Lake whole-basin acidification experiment to illustrate patterns whose timing suggests direct (i.e. immediate) or indirect (i.e. delayed or non-uniform) responses to pH change. As the treatment basin was acidified to pH 5.6, 5.2 and 4.7, immediate changes consistent with a direct pH response were observed for species representing several trophic levels. For other taxa (e.g. littoral invertebrates associated with filamentous algal mats, several species of pelagic zooplankton), indirect mechanisms induced by food web changes were more likely explanations for abundance patterns. The results presented here suggest that the responses of aquatic ecosystems to acidification involve a complex interplay between direct pH effects and subsequent indirect interactions.     

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.     

Effects of hydromorphology and riparian vegetation on the sediment quality of agricultural low-order streams: consequences for stream restoration

Intensive agricultural land use imposes multiple pressures on streams. More specifically, the loading of streams with nutrient-enriched soil from surrounding crop fields may deteriorate the sediment quality. The current study aimed to find out whether stream restoration may be an effective tool to improve the sediment quality of agricultural headwater streams. We compared nine stream reaches representing different morphological types (forested meandering reaches vs. deforested channelized reaches) regarding sediment structure, sedimentary nutrient and organic matter concentrations, and benthic microbial respiration. Main differences among reach types were found in grain sizes. Meandering reaches featured larger mean grain sizes (50–70 μm) and a thicker oxygenated surface layer (8 cm) than channelized reaches (40 μm, 5 cm). Total phosphorous amounted for up to 1,500 μg?g^?1 DW at retentive channelized reaches and 850–1,050 μg?g^?1 DW at the others. While N-NH₄ accumulated in the sediments (60–180 μg?g^?1 DW), N-NO₃ concentrations were generally low (2–5 μg?g^?1 DW). Benthic respiration was high at all sites (10–20 g O₂ m^?2?day^?1). Our study shows that both hydromorphology and bank vegetation may influence the sediment quality of agricultural streams, though effects are often small and spatially restricted. To increase the efficiency of stream restoration in agricultural landscapes, nutrient and sediment delivery to stream channels need to be minimized by mitigating soil erosion in the catchment.     

Changes in trace metal concentrations in lake water and biota during experimental acidification of Little Rock Lake, Wisconsin, USA

Little Rock Lake, a small (18 ha), low-alkalinity (25 microeq litre(-1), pH 6.1) seepage lake in northern Wisconsin, was divided into two basins by a flexible, inert barrier and, beginning in spring 1985, the north basin was acidified in three 2-year steps to pH 5.6, 5.1 and 4.7. The annual average pH of the reference basin remained near 6.1. As part of a comprehensive programme to determine the chemical and biological responses to acidification, minor metals (Al, Fe, Mn) and trace metals (Cd, Cu, Pb, Zn) in lake water (0.4 microm pore filtered samples), periphyton, zooplankton, and yellow perch (Perca flavescens) were measured. At pH 5.6, dissolved Mn and Fe increased in the acidified basin. At pH 5.1 and 4.7, dissolved Al, Fe, Mn, Cd and Zn were elevated in the acidified basin. At pH 4.7, dissolved Pb in the acidified basin became elevated over reference basin levels. Dissolved Cu remained similar in both basins down to pH 4.7. Cd burdens in periphyton collected on artificial substrates were lower in the treatment basin at pH 5.1 (1.8 microg g(-1) dry wt.) than in the reference basin at pH 6.1 (7.5 microg g(-1) dry wt.), but Al and Fe burdens in periphyton were similar in both basins. Likewise, Cd levels in muscle tissue of perch from the treatment basin at pH 4.7 were lower (26 ng g(-1) dry wt.) than in the reference basin at pH 6.1 (36 ng g(-1) dry wt.); Al and Fe burdens were similar in perch muscle tissue from both basins. Levels of Cd and Fe in zooplankton from the acidified basin at pH 4.7 were approximately equal to 2x higher than in animals from the reference basin. In both basins of the lake, Al and Cd levels in lake biota decreased with increasing trophic level, demonstrating that food chain biomagnification does not occur for these metals.     

Influence of fipronil compounds and rice-cultivation land-use intensity on macroinvertebrate communities in streams of southwestern Louisiana, USA

Laboratory tests of fipronil and its degradation products have revealed acute lethal toxicity at very low concentrations (LC50) of <0.5 microg/L to selected aquatic macroinvertebrates. In streams draining basins with intensive rice cultivation in southwestern Louisiana, USA, concentrations of fipronil compounds were an order of magnitude larger than the LC50. The abundance (rho=-0.64; p=0.015) and taxa richness (r2=0.515, p<0.005) of macroinvertebrate communities declined significantly with increases in concentrations of fipronil compounds and rice-cultivation land-use intensity. Macroinvertebrate community tolerance scores increased linearly (r2=0.442, p<0.005) with increases in the percentage of rice cultivation in the basins, indicating increasingly degraded stream conditions. Similarly, macroinvertebrate community-tolerance scores increased rapidly as fipronil concentrations approached about 1 microg/L. Pesticide toxicity index determinations indicated that aquatic macroinvertebrates respond to a gradient of fipronil compounds in water although stream size and habitat cannot be ruled out as contributing influences.     

The impact of episodic coal mine drainage pollution on benthic macroinvertebrates in streams in the Anthracite region of Pennsylvania

Episodic coal mine drainage, caused by fluctuations in mine discharges relative to stream flow, has devastating effects on aquatic macroinvertebrate communities. Seven stream reaches in the Anthracite region of Pennsylvania were identified as chronically, episodically or not impaired by mine drainage, and sampled seasonally for 1 year to determine the effect of episodic mine drainage on macroinvertebrates. Specific conductance fluctuated seasonally in episodic sites; it was lower in winter when discharge increased and higher in summer when discharges decreased and mine drainage made up a larger proportion of stream flow. Although we hypothesized that episodic streams would have higher macroinvertebrate richness than chronic streams, comparisons showed no differences in richness between treatments. Episodic pollution may result from undersized or poorly maintained passive treatment systems; therefore, intensive macroinvertebrate monitoring may be needed to identify streams being affected by episodic mine drainage because macroinvertebrate richness may be sensitive to water quality fluctuations.     

Semipermeable membrane device (SPMD) for monitoring PCDD and PCDF levels from a paper mill effluent in the Androscoggin River, Maine, USA

Paper mill effluents may contain polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) that are normally generated due to chlorinated bleaching of pulp and paper. We used the semipermeable membrane device (SPMD) to monitor PCDD/F levels upstream and downstream of a paper mill on the Androscoggin River, in Jay (ME). Following the 36 day deployment, SPMD dialysis and cleanup, the samples were analyzed by HRGC/HRMS. Total concentrations of PCDD/Fs in SPMDs (sum of all tetra-through octachlorinated congeners) ranged from 4.71 pg g(-1) to 26.26 pg g(-1). Five out of the targeted 17 toxic congeners were detected, including: 2,3,7,8-TCDF; 1,2,3,7,8-PeCDF; 2,3,4,7,8-PeCDF; 1,2,3,4,6,7,8-HpCDD and OCDD. Permeability reference compounds (PRCs) were used for in situ calibration of the SPMD sampling rate (Rs). In all sites, water concentrations were the highest for OCDD (0.081-0.103 pg l(-1)), and the lowest for 1,2,3,7,8-PeCDF (0.005-0.009 pg l(-1)). There was not a consistent pattern of upstream-downstream gradient in the PCDD/F levels. This suggested that processes other than the mill in Jay (multiple sources, river dynamics) governed the flux of PCDD/Fs in the sampling locations. The SPMD results were validated by comparison to other studies on the Androscoggin River and elsewhere, confirming the potential of the device as a useful monitoring technique for PCDD/Fs in large river systems.     

Leaf litter processing and invertebrate assemblages along a pollution gradient in a Maine (USA) headwater stream

During the autumn of 1997 and 1998, leaf litter processing rates and leaf pack invertebrate assemblages were examined at eight stations along a pollution gradient in Goosefare Brook, a first-order coastal plain stream in southern Maine (USA). There was no significant effect on litter softening rate in 1997, and only the most polluted station showed a decrease in 1998. However, litter loss rates showed decreases in both years. The structure of invertebrate assemblages changed in response to the stresses, showing a decline in EPT richness and an increase in the proportion of collecting taxa. However, total shredder biomass was only weakly affected. Shredder biomass at all stations was dominated by Tipula, and biomass of other shredder taxa showed a serial replacement along the gradient of stress related to their pollution tolerance. Rather than the expected relationship with shredder biomass, litter processing rates were directly related to water and sediment quality. Goosefare Brook demonstrates how variable pollution tolerance of community members enables stress resistance and a consequent preservation of ecosystem function.     

Use of historical assessment for evaluation of process-based model projections of future environmental change: Lake acidification in the Adirondack mountains, New York, USA

Because of the considerable uncertainties associated with modeling complex ecosystem processes, it is essential that every effort be made to test model performance prior to relying on model projections for assessment of future surface water chemical response to environmental perturbation. Unfortunately, long-term chemical data with which to validate model performance are seldom available. The authors present here an evaluation of historical acidification of lake waters in the northeastern United States, and compare historical changes in a set of lakes to hindcasts from the same watershed model (MAGIC) used to estimate future changes in response to acidic deposition. The historical analyses and comparisons with MAGIC model hindcasts and forecasts of acid-base response demonstrate that the acidic and low-ANC lakes in this region are responsive to strong acid inputs. However, the model estimates suggest lakewater chemistry is more responsive to atmospheric inputs of sulfur than do the estimates based on paleolimnological historical analyses. A 'weight-of-evidence approach' that incorporates all available sources of information regarding acid-base response provides a more reasonable estimate of future change than an approach based on model projections alone. The results of these analyses have important implications for predicting future surface water chemical change in response to acidic deposition, establishing critical loads of atmospheric pollutants, and other environmental assessment activities where natural variation often exceeds the trends under investigation (high noise-to-signal ratio). Under these conditions, it is particularly important to evaluate future model projections in light of historical trends data.     

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.     

A review of the likely causal pathways relating the reduced density of breeding dippers Cinclus cinclus to the acidification of upland streams

Previous work has shown that the breeding density of a bird characteristic of upland streams, the dipper Cinclus cinclus, is markedly reduced at low pH in both Wales and Scotland. Populations also declined when streams became more acidic. Evidence of causal explanation for these relationships is that: (1) Food quantity is reduced in acidic streams, and important prey, including those rich in calcium, are scarce; (2) Blood chemistry in pre-breeding birds differs between acid and circumneutral streams, with plasma calcium reduced in those breeding at low pH. Skeletal sources of calcium are probably limited; (3) The time spent foraging by pre-breeding birds on acidic streams is markedly increased, even though overall energy costs on acidic and circumneutral streams are similar. Body condition is inferior to birds on circumneutral streams; (4) Egg laying is significantly delayed on acidic streams irrespective of an effect on laying of altitude, and clutch and brood sizes are significantly reduced; (5) Eggs are lighter and shells thinner at low pH; (6) Chick growth is reduced at low pH; (7) Contamination by heavy metals and persistent organochlorines is low in the populations on acidic streams and cannot explain the impaired breeding performance. None of these features can exclude the possibilities that acidic streams either hold populations of poor quality birds, which show the above features, or that acidity affects the breeding ecology of all dippers that attempt to breed at low pH. The qualitative outcome of these two alternatives is identical.