Toxicity of acid aluminium-rich water to seven freshwater fish species: a comparative laboratory study

The present study focuses on the relative sensitivity among freshwater fish species to aqueous aluminium. Seven common Scandinavian fish species were exposed to acidic Al-rich water, acidic Al-poor water, and approximately neutral water as a control. The relative sensitivity among the species to an acute aluminium challenge was documented, and was in the following order: Atlantic salmon, Salmo salar, as the most sensitive; then roach, Rutilus rutilus; minnow, Phoxinus phoxinus; perch, Perca fluviatilis; grayling, Thymallus thymallus; brown trout, Salmo trutta; and Arctic char, Salvelinus alpinus. Substantial mortality was observed in all species when exposed to the Al-rich medium. Some mortality was also observed in minnow, roach, and brown trout exposed to the acidic Al-poor medium and the control medium. A high resistance to aluminium was observed in Arctic char, while perch was found to be more sensitive to aluminium than expected and, for the first time, a toxic response to aqueous aluminium in grayling was documented. Through controlled experimental studies, the results confirm that aluminium is an important factor in the toxicity of acidified waters to freshwater fish species.     

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.     

Toxicity of waters from two streams to early life stages of brown trout (Salmo trutta f. fario L.), tested under semi-field conditions.

The development of brown trout (Salmo trutta f. fario L.) in water of two differently polluted streams and in a control situation was monitored in order to get insights into the impact of anthropogenic chemical stressors on the reproductive success of this fish species indigenous to both streams. The test streams, situated in the south of Stuttgart, Germany, were the complexly polluted K?rsch stream and the less polluted Kr?henbach stream. Bypass systems connected to the streams and a laboratory control system were used for continuous exposure of early brown trout stages shortly after fertilisation up to the end of the embryonic development. Temperature and oxygen conditions were standardised in all test series in order to minimise unspecific effects. The examined endpoints were: (1) mortality, (2) developmental rate, (3) time course of hatching, (4) malformations, and (5) growth. A retarded development, reduced growth rates and higher mortality rates of K?rsch stream water exposed embryos indicated an embryotoxic potential for the more polluted stream. High infection-related mortality rates of embryos suggested the presence of confounding factors also in the less polluted Kr?henbach stream. In parallel to the exposure experiment, physicochemical and limnochemical parameters as well as concentrations of organic contaminants and heavy metals were monitored. Analytical data confirm the different degrees of pollution of both streams.     

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.     

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.     

The mixing zone between limed and acidic river waters: complex aluminium chemistry and extreme toxicity for salmonids

When liming running waters, dosers must compensate for different flow and water qualities and for the downstream inflow from acid tributaries which creates mixing zones. At a certain point in the mixing zone, a constant or fluctuating chemical disequilibrium will appear due to transformation processes. In laboratory assays, over-saturated solutions of aluminium with ongoing active precipitation of aluminium have been found to be especially toxic to fish. Recent experiments in a mixing zone in the limed River Audna, Norway, have confirmed this phenomenon. Atlantic salmon (Salmo salar L.) and sea trout (Salmo trutta L.) smolts were exposed to acid and limed waters and mixtures of the two waters downstream from the point of connection. In the acid tributary (mean values: pH=4.8, Ca=1.3 mg litre (-1)), Ali 236 microg litre(-1)=), LT5) was 22 and 40 h for Atlantic salmon and sea trout, respectively. In the mixing zone (pH=4.8-6.5, Ca=1.2-3.2 mg litre(-1), Ali=50-240 microg litre(-1)), LT50 was 7 h for both species, masking the normal species difference in tolerance. Osmoregulatory failure and rapid gill lesions occurred in the mixing zone as an effect of the transformation of Al into high molecular weight precipitating species. This is the first documentation of the existence of such highly toxic mixing zones in nature, and the results clearly show that the mixing zone is even more toxic to fish than acid aluminium-rich waters.     

Long-term increases in surface water dissolved organic carbon: observations, possible causes and environmental impacts

Dissolved organic carbon (DOC) concentrations in 22 UK upland waters have increased by an average of 91% during the last 15 years. Increases have also occurred elsewhere in the UK, northern Europe and North America. A range of potential drivers of these trends are considered, including temperature, rainfall, acid deposition, land-use, nitrogen and CO2 enrichment. From examination of recent environmental changes, spatial patterns in observed trends, and analysis of time series, it is suggested that DOC may be increasing in response to a combination of declining acid deposition and rising temperatures; however it is difficult to isolate mechanisms based on monitoring data alone. Long-term DOC increases may have wide-ranging impacts on freshwater biota, drinking water quality, coastal marine ecosystems and upland carbon balances. Full understanding of the significance of these increases requires further knowledge of the extent of natural long-term variability, and of the natural "reference" state of these systems.     

Acute and Chronic Toxicity of Chlorine Dioxide (ClO2) and Chlorite (ClO2ˉ) to Rainbow Trout (Oncorhynchus mykiss) (4 pp)

Goal, Scope and Background Chlorite (ClO2ˉ) is a primary decomposition product when chlorine dioxide (ClO2) is added during water treatment; therefore the toxic effects of both compounds on aquatic organisms are possible. Limited data are available concerning their toxicity to fish. The aim of this study was to investigate sensitivity of rainbow trout to acute and chronic toxicity of chlorine dioxide and chlorite, and to estimate the Maximum-Acceptable-Toxicant-Concentration (MATC) of those compounds in fish. Methods The acute and chronic toxicity of chlorine dioxide and chlorite to larval and adult rainbow trout was investigated in 96-hour to 20-day laboratory exposures evaluating the wide range spectrum of biological indices under semi-static conditions. Results and Discussion Median lethal concentration (96-hour LC50) values derived from the tests were: 2.2 mg/l for larvae; 8.3 mg/l for adult fish and 20-day LC50 for larvae was 1.6 mg/l of chlorine dioxide, respectively. Chlorite was found to be from 48 to 18 times less acutely toxic to larvae and adult fish, correspondingly. Both chemical compounds induced similar toxic effects in rainbow trout larvae during chronic tests (they affected cardio-respiratory and growth parameters), but chlorine dioxide had a higher toxic potency than chlorite. A significant decrease in the heart rate and respiration frequency of larvae was established. However, within an increase in exposure duration recovery of cardio-respiratory responses was seen to have occurred in larvae exposed to chlorite. Meanwhile, in larvae exposed to chlorine dioxide, a significant decrease in cardio-respiratory responses remained during all 20-day chronic bioassays. Chlorine dioxide also more strongly affected growth parameters of rainbow trout larvae at much lower test concentrations. Decreased rate of yolk-sack resorption occurred only in the tests with chlorine dioxide. Conclusions Maximum-Acceptable-Toxicant-Concentration (MATC) of 0.21 mg/l for chlorine dioxide and of 3.3 mg/l for chlorite to fish was derived from chronic tests based on the most sensitive parameter of rainbow trout larvae (growth rate). According to substance toxicity classification accepted for Lithuanian inland waters, chlorine dioxide and chlorite can be referred to substances of \moderate\ toxicity to fish. Recommendations and Outlook Due to its very reactive nature, chlorine dioxide is rapidly (in a few hours) reduced to chlorite, which is persistent also as a biocide but 16 times less toxic to fish, according to MATC. Therefore, it is much more likely that fish will be exposed to chlorite than to chlorine dioxide in natural waters. Presently accepted, the Maximum-Permitted-Concentration of total residual chlorine (TRC) in waste-water discharging into receiving waters is 0.6 mg/l. If this requirement will not be exceeded, it is unlikely that fish would be exposed to lethal or even to sublethal concentrations of chlorine dioxide or chlorite. Furthermore, chlorine dioxide does not generate toxic nitrogenous (chloramines) or carcinogenic organic residuals (trihalomethanes). All these properties make chlorine dioxide a more promising biocide than chlorine.     

The response of stream-dwelling fish to liming

The fish fauna in 22 limed and seven unlimed small streams was monitored using yearly electrofishing to assess the effects of liming on species occurrence and abundance. The liming techniques were divided into three main methods, lake liming, doser liming and wetland liming, to evaluate whether different strategies had different effects on the fish fauna. The predominant species at the investigated stations were salmonids, mainly brown trout (Salmo trutta) and Atlantic salmon (Salmo salar). Other species generally occurred in low numbers. The average number of fish species did not increase significantly after liming, which was probably due to recolonization difficulties caused by the frequent occurrence of migration obstacles in the streams. After liming the density of salmonids increased significantly, irrespective of the liming method. Other fish species showed no general increase, but in individual streams significant increases of European minnow (Phoxinus phoxinus) and bullhead (Cottus gobio) occurred. Some unlimed streams had acid spates with a pH below 6, which immediately lowered the numbers of salmonid parr. Other unlimed streams lost fish species progressively due to increasing acidification. pH, and probably increased levels of metals, were the major factors regulating the fish fauna. Few examples of biotic interactions were observed, but with an increase of Atlantic salmon parr after liming, brown trout abundances decreased in three streams.     

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.     

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.     

Effect of a heavy metal model mixture on biological parameters of rainbow trout <Emphasis Type="Italic">oncorhynchus mykiss</Emphasis>

The effects of a model mixture (HMMM) of seven heavy metals (Cu, Zn, Ni, Cr, Pb, Cd, Mn) on the rainbow trout Oncorhynchus mykiss at all stages of development (embryos, larvae, adults) were investigated based on the annual average concentrations of these metals in cooling waste waters discharging from Ignalina Nuclear Power Plant (Lithuania) into the Drūk?iai lake. According to mortality parameters, the most sensitive to HMMM were larvae, although no significant differences between the sensitivity of embryos and adult fish to HMMM were found. Maximal toxic effect of HMMM was observed during the hatching period. Long-term exposure to sublethal concentrations of HMMM affected embryo development, growth of larvae, their cardio-respiratory and behavioural responses, induced significant changes in morphological, morpho-physiological, physiological and haematological parameters of adult fish. Respiratory responses and growth parameters of fish were found to be the most sensitive to low concentrations of HMMM. Adult fish were capable of detecting and avoiding low, sublethal concentrations of HMMM. Heavy metals in a mixture at low concentrations were more toxic than single ones. According to the background of the damages induced by HMMM, after-effects in a fish organism, as well as in a whole population, can be predicted.     

The significance of water ionic strength on aluminium toxicity in brown trout (Salmo trutta L.)

The toxicity of aluminium to fish is related to interactions between aluminium and the gill surface. We investigated the possible effect of water ionic strength on this interaction. The mortality of brown trout (Salmo trutta L.) exposed to three different degrees of Al polymerisation was compared in water with increased ionic strength (mean 7.31 x 10(-4) M) after additions of the base cations Ca2+, Mg2+, Na+ or K+, and in water with no such addition (mean ionic strength 5.58 x 10(-4) M). Only a very slight ameliorating effect of increased ionic strength was observed, while the degree of Al polymerisation was of major importance in fish mortality. In addition, it was observed that smaller fish survived the Al exposures for a longer time than larger fish. We hypothesise that this is because larger fish are more susceptible to hypoxia than smaller fish.     

Aerobic dehalogenation potentials of four bacterial species isolated from soil and sewage sludge

In Polar regions subject to acid precipitation, the spring flood period is swift and can be divided into three phases. In phase one, dilution and anion substitution by SO4 controls episodic acidification. Phase two is characterized by interaction of snowmelt water with the catchment. A combination of several factors contributes to declines in pH and ANC. In forest and wetland ecosystems, organic acids greatly contribute to the pH depression in the streams. In the coastal tundra and forest-tundra zones, "salt-effect" acidification predominantes. The increase in toxic forms of trace (Ni, Cu) and rare (Fe, Al, Mn) elements during pH depressions may create stress conditions for the fauna of polar fresh waters during a flood period.     

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.     

Use of blood parameters in fish to assess acidic stress and chloride pollution in French running waters

The study investigated whether plasmatic parameters in fish such as Cl- content could serve as physiological indicators to evaluate water quality. The variations of plasma Cl- content in two fish species caught in a wide range of rivers representative of the hydrographic system of Lorraine (N-E France) were investigated. First, we studied autochthonous populations of chub (Leuciscus cephalus) which is a widespread species in the rivers of Lorraine. Organisms living in highly mineralised rivers (>1500 microScm(-1))--either naturally or due to salt mine contamination--showed plasma Cl- content significantly greater than organisms living in river with a lower mineralisation. Second, we investigated plasma Cl- content of brown trout (Salmo trutta fario) in poorly mineralised streams (<80 microS cm(-1)) with different degrees of acidification, both on autochthonous and transferred organisms. While indigenous trout maintained their Cl- content even in the acidic streams, transferred trout exhibited an important decrease of Cl- content after 48 h of exposure under acidic conditions.     

Recovery of Soil Water,Groundwater, and Streamwater From Acidification at the Swedish Integrated Monitoring Catchments

Recovery from anthropogenic acidification in streams and lakes is well documented across the northern hemisphere. In this study, we use 1996–2009 data from the four Swedish Integrated Monitoring catchments to evaluate how the declining sulfur deposition has affected sulfate, pH, acid neutralizing capacity, ionic strength, aluminum, and dissolved organic carbon in soil water, groundwater and runoff. Differences in recovery rates between catchments, between recharge and discharge areas and between soil water and groundwater are assessed. At the IM sites, atmospheric deposition is the main human impact. The chemical trends were weakly correlated to the sulfur deposition decline. Other factors, such as marine influence and catchment features, seem to be as important. Except for pH and DOC, soil water and groundwater showed similar trends. Discharge areas acted as buffers, dampening the trends in streamwater. Further monitoring and modeling of these hydraulically active sites should be encouraged.     

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.     

Physicochemical characterization of industrial effluents and their effect on fish survival.

Water samples taken from selected industrial drainages and receiving streams in and around Islamabad, Pakistan, during the summers of 1987 to 1990 showed disturbances in pH and low oxygen levels. Selected metals (Fe, Pb, Zn, Cd, Cu, Ni, Hg) were higher in all effluents than in receiving waters. Static bioassays of the undiluted industrial effluents from three sites caused 100% mortality in carp during the first 24 hrs. Fishes also suffered 30 to 60% mortality when exposed to other undiluted industrial effluents and some mortality when industrial effluents were diluted by 50%.     

Atmospheric deposition, retention, and stream export of dioxins and PCBs in a pristine boreal catchment

The mass-balance between diffuse atmospheric deposition of organic pollutants, amount of pollutants retained by the terrestrial environment, and levels of pollutants released to surface stream waters was studied in a pristine northern boreal catchment. This was done by comparing the input of atmospheric deposition of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) and PCBs with the amounts exported to surface waters. Two types of deposition samplers were used, equipped with a glass fibre thimble and an Amberlite sampler respectively. The measured fluxes showed clear seasonality, with most of the input and export occurring during winter and spring flood, respectively. The mass balance calculations indicates that the boreal landscape is an effective sink for PCDD/Fs and PCBs, as 96.0-99.9 % of received bulk deposition was retained, suggesting that organic pollutants will continue to impact stream water in the region for an extended period of time.