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.     

Chemical and biological effects of acid, aluminium and lime additions to a Welsh Hill-stream

Chemical and biological responses to simultaneous additions of acid, aluminium and lime were investigated in contiguous 250m-reaches of a chronically acidic stream in Wales. Treatments were applied for 24 h, and from the upstream end were as follows: zone A-untreated, pH 5.0, 0.37 mg litre(-1) filterable Al; zone B-acidified to pH 4.5, 0.40 mg Al litre(-1) (47% of Al attributed to release from the stream bed due to acid additions); zone C-acidified to pH 4.5 and Al dosed to 0.67 mg litre(-1); zone D-dosed with limestone slurry, resulting in pH 7.2, 0.13 mg Al litre(-1). In all reaches, the chemistry of the interstitial water at depths of 0.15 and 0.3 m never fell below pH 5.5, with corresponding decreases in Al and increases in base cation concentrations. Brown trout, Salmo trutta, and crayfish, Austropotamobius pallipes, held in the stream showed decreases in plasma [Na(+)] and haemolymph [Na(+)], respectively, in all acidic zones (A, B, C): these responses were mitigated by liming (zone D). Thus both chronic and simulated episodic levels of pH and dissolved Al were sub-lethally toxic to test species of aquatic fauna. This experiment also demonstrates a stream bed source/sink of Al, and the availability of a possible refuge from acidic surface waters within the substratum.     

Mortality, growth, swimming activity and gill morphology of brook trout (Salvelinus fontinalis) and Atlantic salmon (Salmo salar) exposed to low pH with and without aluminum

Measurements were made of mortality, growth, swimming activity, and gill morphology of young-of-the-year brook trout (Salvelinus fontinalis) and Atlantic salmon (Salmo salar), exposed for 30 days to pH 5.6 +/- 0.5 (mean +/- 1 standard deviation) with and without addition of 107 +/- 57 microg liter(-1) exchangeable (labile monomeric) aluminum. The experiment was conducted in artificial stream channels adjacent to a natural stream and subject to daily and seasonal changes in temperature, light, and chemical conditions. There were no differences in survival or growth for brook trout in any treatment; Atlantic salmon survival and growth were significantly decreased in the acid + Al treatment. Scanning electron microscopy showed no damage to gills of either species in the acid treatments, but the acid + Al treatment caused slight swelling of brook trout gills near the filament tips and significant swelling and fusion of secondary lamellae of Atlantic salmon gills. The acid treatment increased swimming activity in brook trout, but both the acid and acid + Al treatments reduced activity in Atlantic salmon.     

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.     

Mitigation of low stream pH and its effects on salmonids

Crushed limestone (200 tonnes) was spread in bars on the bed of an acidic brook (mean pH 5.0) in Nova Scotia, Canada. A seasonally variable but significant increase in pH of running water resulted, and a longitudinal pH gradient over the limed section extended to the mouth of the brook. The effectiveness persisted after 3 years, during which pH downstream of the limestone increased an average of 0.4 pH units (range < 0.1-1.3 pH units) along with significantly increased Ca, Mg and acid neutralizing capacity. Total and exchangeable Al were not altered by the limestone and non-exchangeable forms dominated. The interstitial water was nearly neutral (mean pH 7.1) in limestone beds but it was acidic (mean pH 5.4) in gravel beds of the control section upstream. Spawning Atlantic salmon (Salmo salar) dug three times more redds in gravel of the limed section than in the control. Salmon fry survived and they were significantly more abundant in the limed section than in the control. The density of juvenile salmon increased over time, indicating a recovery of the population. The density of brook trout (Salvelinus fontinalis) also increased and trout fry were usually more abundant in the limed section than in the control. The observed benefits for salmonids suggest that small-scale application of limestone to stream beds and spawning sites can be used to mitigate the effects of low stream pH.     

Lethality of mexacarbate and of its formulation UCZF-19 to juvenile Atlantic salmon

Mexacarbate was less toxic to juvenile Atlantic salmon (Salmo salar) than its formulation, UCZF-19 (96-h LC50 - 19.5 and 3.4 mg/L, respectively). The increased lethality of the formulation is due to its volatile components (largely C3–C5 alkylbenzenes and naphthalene). The hazard indices of mexacarbate and UCZF-19 in forest spraying indicate low risk of direct mortality of juvenile Atlantic salmon.     

The influence of plantation forestry on the pH and aluminium concentration of upland welsh streams: a re-examination

Previous studies relating forest presence to stream acidity and aluminium concentration were based on small numbers of catchments, often precluding the elimination of confounding influences on stream chemistry, such as geology or soil type. Spatial patterns in aluminium and pH data from 113 Welsh catchments of contrasting land use were therefore analysed in three different ranges of acid sensitivity (< 10, 10-15, 15-25 mg CaCO(3) litre(-1) total hardness). In each range, pH declined and aluminium increased significantly with increasing percentage forest cover. There was no evidence that the relationships reflected a spurious effect of forest location. Where aluminium concentrations were elevated under forest in a sub-set of 13 streams, aluminium was present predominantly in the labile form, most toxic to fish. Regressions of pH and aluminium on percentage forest cover provide a useful method of assessing the amount of forest in Welsh catchments which might give rise to given chemical conditions (e.g. pH <6, Al > 80 microg litre(-1)), though some difficulties are likely in accurately specifying the conditions desirable for fish or other biota.     

Survival of brown trout during spring flood in DOC-rich streams in northern Sweden: the effect of present acid deposition and modelled pre-industrial water quality

Mortality and physiological responses in brown trout (Salmo trutta) were studied during spring snow melt in six streams in northern Sweden that differed in concentrations of dissolved organic carbon (DOC) and pH declines. Data from these streams were used to create an empirical model for predicting fish responses (mortality and physiological disturbances) in DOC-rich streams using readily accessible water chemistry parameters. The results suggest that fish in these systems can tolerate higher acidity and inorganic aluminium levels than fish in low DOC streams. But even with the relatively low contemporary deposition load, anthropogenic deposition can cause fish mortality in the most acid-sensitive surface waters in northern Sweden during spring flood. However, the results suggests that it is only in streams with high levels of organically complexed aluminium in combination with a natural pH decline to below 5.0 during the spring where current sulphur deposition can cause irreversible damage to brown trout in the region. This study support earlier studies suggesting that DOC has an ameliorating effect on physiological disturbances in humic waters but the study also shows that surviving fish recover physiologically when the water quality returns to less toxic conditions following a toxic high flow period. The physiological response under natural, pre-industrial conditions was also estimated.     

Abundance and population structure of perch (Perca fluviatilis L.) in some acidic Norwegian lakes

Abundance (catch per unit effort, n=3752) and population structure of perch Perca fluviatilis were studied in 30 acidic Norwegian lakes with relation to pH (4.3-5.9), calcium (0.41-2.44 mg litre(-1)), labile aluminium (24-255 microg litre(-1)) and total organic carbon (TOC, 1.7-13.8 mg C litre(-1)). Standard series of bottom gill-nets were used to sample fish populations. A multiple regression analysis showed that abundance was significantly correlated to TOC (P<0.05) and, to a smaller extent, to the Ca in lakes with concentrations between 0.41 and 1.70 mg litre(-1) (P=0.07). The lakes which were inhabited by pike were excluded from the analysis. Recruitment failure seems to be the main cause of reductions in perch numbers in the lakes studied. However, high mortality among adult individuals was also evident, and an episode of fish kill was observed in one of the lakes.     

Trout farm effluents: characterization and impact on the receiving streams

Effluents from three rainbow trout (Oncorhynchus mykiss) farms located in Northern Portugal were characterized and their impact on the receiving streams was evaluated. Mean fish productions in the studied fish farms were 15, 55 and 500 t of trout per year, respectively. The feeding water was abstracted from Fornelo, Inha and Coura Rivers, at flow rates ranging from 1.2 (15 t year(-1) fish farm) to 4.8 litre s(-1) per ton annual fish production (500 t year(-1) fish farm). As the water flows through the farms, net variations in the chemical characteristics were observed: a mean reduction in the dissolved oxygen (DO) concentration between 0.7 and 2.4 mg litre(-1); mean increases between 1.9 and 3.2 mg CaCO3 litre(-1) for total alkalinity, between 0.9 and 14 mg litre(-1) for BOD5, between 0.27 and 1.46 mg litre(-1) for ammonia nitrogen (NH4-N), between 0.060 and 0.579 mg litre(-1) for soluble phosphorus (PO4-P) and less than 16 mg litre(-1) for suspended solids; variations in the pH value and nitrate nitrogen concentration were not statistically significant (p<0.05). At the 500 t year(-1) fish farm it was also possible to detect net increases of total hardness (3.2 mg CaCO3 litre(-1)), electric conductivity (19 mS cm(-1)) and permanganate value (3.6 mgO2 litre(-1)). At the other farms net variations in these parameters were not significant. Net mass flow variations reported to the annual fish production are presented. The DO mass flow decreased, on average, between 255 and 549 g t(-1) of fish per day. The mean daily BOD5 increase ranged from 353 to 1510 g t(-1) of fish. The corresponding ranges for the other parameters were 105-157 g t(-1) for NH4-N, 24-62 g t(-1) for PO4-P, 348-1035 g CaCO3 t(-1) for total alkalinity and 224 x 10(6)-506 x 10(6) t(-1) for mesophilic bacteria. Daily net variations of suspended solids, total hardness, electric conductivity and permanganate value were below 1753 g t(-1), 342 g CaCO3 t(-1), 2081 mS cm t(-1) and 392 gO2 t(-1), respectively. Longitudinal concentration profiles for the most relevant parameters show the impact of the effluent discharges on the physico-chemical and bacteriological river water quality downstream from the trout farms. Analyzing the situations from a purely chemical point of view, the polluted stretches were 3, 5 and 12 km long downstream from the effluent discharges, respectively. The microbiological contamination extended over longer distances.     

Aluminium speciation in surface waters from a Welsh upland area

The complete aluminium speciation of surface waters from an acidified catchment, during dry weather and during storm episodes, is obtained. For the first time, estimates of adsorbed aluminium (Al(ad)) are reported together with other aluminium species. Al(ad) is calculated from the difference between monomeric aluminium content before and after separation of suspended solids by filtration (0.015 microm pore diameter). This fraction was very significant (Al(ad) >; 40 microg litre(-1)) for samples with high suspended solids content (ss >; 20 mg litre(-1)) collected during storm episodes. Plots of pAl(3+) versus pH for samples collected during dry weather are approximated by a straight line, close to the solubility line of synthetic gibbsite, and have a slope of 2.5, which suggests that these samples were saturated with respect to gibbsite. The cloud of pAl(3+) versus pH points for samples from storm episodes has a near zero slope, and shows a significant degree of undersaturation with respect to synthetic gibbsite. Various mechanisms of aluminium mobilisation are discussed.     

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.     

The impact of inorganic tin on the planktonic cyanobacterium Synechocystis aquatilis: the effect of pH and humic acid

The influence of inorganic tin compounds on the unicellular cyanobacterium Synechocystis aquatilis was studied, and its dependence on changing pH of the surrounding medium and the presence of humic acid. Both Sn(II) and Sn(IV), used as chlorides (at the concentrations 1-10 mg litre(-1)), inhibit the growth and chlorophyll a content of the cyanobacterium cultures, but only under alkaline conditions. Generally, the observed tin toxicity increased with increase of metal concentration, time of exposure and pH value of the medium (in the range 7-9.8). Sn(II) seems to be more toxic than Sn(IV). At the lowest studied metal concentration (1 mg litre(-1)), Sn(II) caused a 36 and 40% decrease in growth and chl a content, respectively, after 96 h exposure at pH 9.8, while Sn(IV) caused even a slight increase of both physiological parameters (hormetic effect). Similar increases in growth and chl a content were also observed at a high Sn (II) and Sn(IV) concentration (10 mg litre(-1)), but only in cultures exposed to metal at pH 7. At high pH (9.8), 10 mg litre(-1) of Sn(II) and Sn(IV) significantly suppressed both the growth of the cyanobacterium (by 54.2 and 26.1%, respectively) and the chl a content in cultures (by 58.2 and 24%, respectively). Humic acid reduced the toxicity of tin towards the cyanobacterium. The observed effects of pH and complexing ligand on the inorganic tin toxicity are discussed in the context of changing, chemical metal speciation and bioavailability.     

Marine and farmed fish on the Polish market: comparison of the nutritive value and human exposure to PCDD/Fs and other contaminants

Chemical analyses were performed in nine fish species that are popular on the Polish market. These included Baltic fish (cod, herring, salmon), fish farmed in Poland (carp, trout), marine fish imported from China (Alaska pollock, sole), and farmed fish imported from Vietnam and China (sutchi catfish, tilapia). The nutritional composition (amino acid, micro- and macronutrients, fat-soluble vitamins - A₁, D₃, E) and certain contaminants (organochlorine pesticides, OCPs; indicator polychlorinated biphenyl, PCB₆; polychlorinated dibenzo-paradioxins and polychlorinated dibenzofurans, PCDD/Fs; dioxin-like polychlorinated biphenyls, dl-PCBs; organotin compounds, OCTs; dyes, malachite green and crystal violet; veterinary drug residues, nitrofurans and chloramphenicol; toxic metals, Cd, Pb, Hg) in the muscle tissues of fish were determined. It was confirmed that the fish species analyzed were excellent sources of amino acids, and were rich in phosphorous and selenium. Baltic Sea fish (salmon, herring), fish farmed in Poland (carp and trout), and tilapia were also rich in vitamin D₃.Traces of OCP, PCB₆, OCT, dyes, veterinary drug residues, and heavy metals were detected in concentrations which do not pose a threat to consumers at the current rate of fish consumption in Poland. However, the problem might arise from the content of PCDD/Fs and dl-PCBs in fatty Baltic fish. The fish species analyzed, differed in their nutritional values and degrees of contamination. We suggest that for optimum health and safety, it is advisable that consumers include a variety of different fish species in their diets.     

Influence of some additives to aluminium species distribution in aluminium coagulants

Aluminium ions hydrolyse and polymerise into different species in water. Main aluminium species in aluminium coagulant solutions are monomeric Al species (Al1) and polymeric Al species Al13O4(OH)24(7+) (Al13). The aluminium species distribution in coagulant solutions can be influenced by many parameters. This paper studies influences of concentrations of total aluminium species (Al(t)) and other species--OH-, polysilicic acid and ferric species, which were added in aluminium coagulant solutions, on the aluminium species distribution through 27Al nuclear magnetic resonance (NMR) analysis. Results show that only Al1 and no Al13 exist in coagulant solutions at higher Al(t) concentrations (over 1 mol l(-1)), while both species exist at lower Al(t) concentrations (0.1 mol l(-1)). The increase of OH/Al value (molar ratio) increases the concentration of Al13 in coagulant solutions, while the addition of polysilicic acid and ferric species decreases the concentration of Al13.     

Effect of salinity on uptake of 14C-2,2′4,5,5′-pentachlorobiphenyl by juvenile Atlantic salmon

Uptake of ¹⁴C-2,2′,4,5,5′-pentachlorobiphenyl by appropiately adapted juvenile Atlantic salmon (Salmo salar) is more efficient from fresh water than from sea water. Concentrations of ¹⁴C-2,2′,4,5,5′-pentachlorobiphenyl in the whole body as well as in a number of organs and tissues were substantially higher in salmon exposed in fresh water.     

Trace metals in interstitial waters from sandstones: acidic inputs to shallow groundwaters

There is some evidence from southern Britain that shallow groundwaters in non-carbonate lithologies may be affected by acidic deposition. To investigate this, interstitial water profiles down to 12 m have been obtained from unsaturated sands or semi-consolidated sandstones from the Folkestone Beds (Lower Greensand) of Surrey and the Sherwood Sandstone of the West Midlands. The pH of the interstitial waters generally increased with depth and reflected an increase in the base saturation of the exchange complex. Beneath the highly acidic surface soil horizons (pH 3.0-3.5), interstitial waters with a pH of 4.0-4.5 were found down to depths of several metres. The pH progressively increased to around pH 5.5 because of base cation desorption and the weathering of silicate minerals. High concentrations of aluminium (10-20 mg litre(-1)) and other metals (Fe, Mn, Cu, Ni, Co, Zn, Be) were found in the interstitial water in the upper unsaturated zone. Most metal concentrations were strongly pH-dependent but also reflected the geochemical characteristics of the parent sands or sandstones. H+ and trace element concentrations were slightly higher beneath areas of afforestation than beneath heathland. The downward fluxes of solutes have been estimated using rainfall-derived chloride as a non-reactive solute. The profiles retain a record of 10-20 years input allowing the past inputs from SO4 and other species to be estimated using solute/chloride ratios. Cation exchange sites are probably depleted over a period of decades and there can be a significant decrease in the unsaturated zone pH as a result of increased or sustained acidic deposition. The shallow groundwater environment (0-15 m) in non-carbonate terrains is therefore a sensitive environment where high metal concentrations may be generated and may ultimately lead to water quality problems in shallow water supplies.     

Zinc toxicity in the fish Cnesterodon decemmaculatus in the Paraná River and Río de La Plata Estuary

Acute static tests were performed to assess Zn toxicity on adults of Cnesterodon decemmaculatus (not sexed), a neotropical fish of wide distribution in the Río de la Plata basin. Tests were carried out with ZnCl2 dissolved in natural waters from the Lower Paraná River, the Río de la Plata Estuary, reconstituted waters of similar composition, tap and distilled waters. Median lethal concentration at 24 h was positively correlated to conductivity and the concentrations of Ca2+, Mg2+, and HCO3- (r=0.99, 0.96, 0.97, 0.99, p<0.05, respectively), being higher at the Río de la Plata Estuary (61.2 mg l(-1)) than at the Lower Paraná River (35.3 mg l(-1)). Contaminant load in the natural waters tested was similar at both sites, being Zn concentration 40 and 44 microg l(-1), respectively. An assay with reconstituted water of similar alkalinity to the estuary showed a simultaneous decrease in HCO3- and dissolved Zn, while the Zn speciation, predicted with a computer program, suggested that Zn2+ precipitated as ZnCO3. The effect of Ca2+ on Zn toxicity is also discussed. Zn toxicity was higher in the Río de la Plata Estuary water than in synthetic water of similar ionic composition (24-h LC50 = 93.2 mg l(-1)), suggesting the synergistic effect of other toxic pollutants such as metals, present in the former which were absent in the later.     

Speciation of five arsenic species (arsenite, arsenate, MMAAV, DMAAV and AsBet) in different kind of water by HPLC-ICP-MS

A method using Ion Chromatography hyphenated to an Inductively Coupled Plasma-Mass Spectrometer has been developed to accurately determine arsenite (As(III)), arsenate (As(V)), mono-methylarsonic acid (MMAA(V)), dimethylarsinic acid (DMAA(V)) and arsenobetaine (AsBet) in different water matrices. The developed method showed a high sensitivity with detection limits for each arsenic species close to 0.4pg injected. Arsenite and arsenate were the major species found in surface and well waters, but AsBet and DMAA(V) were found in some surface waters, which has never been reported before, while in some natural mineral waters located in volcanic region, the arsenic content exceeded the maximal admissible arsenic content by European legislation standards and the predominant form was As(V).     

Toxicity test using medaka (Oryzias latipes) early fry and concentrated sample water as an index of aquatic habitat condition

The aim of the present study was to show a relationship between toxicity of 100-fold concentrated water and aquatic habitat conditions. Environmental waters are 100-fold concentrated with solid-phase extraction. Medaka early fry was exposed in these waters for 48 h. The number of death and disorder was counted at 1, 2, 3, 6, 12, 24, and 48 h; toxicity was expressed using inverse median effect time and median lethal time (ET (50)(-1), LT (50)(-1)). Average score per taxon (ASPT) for benthic animals and Index of Biotic Integrity (IBI) for fish were applied as indices of aquatic habitat conditions. The results of toxicity test were compared using ASPT and IBI. The different levels of toxicity were detected in the seawater of Japan. At the Husino River area, toxicity cannot be detected. In rivers, high toxicity appeared at urban districts without sewerage. By Spearman coefficient, the relationship between toxicity and high biochemical oxygen demand (BOD) were obtained. BOD household wastewater contains hydrophobic toxic matters; otherwise, seawater in industrial area does not show clear relationship between toxicity and chemical oxygen demand. Gas chromatography to mass spectrometry simultaneous analysis database may give an answer for the source of toxicity, but further test is required. Ratio of clear stream benthic animal sharply decreased over 0.25 of LT (50)(-1) or 0.5 of ET (50)(-1). Tolerant fish becomes dominant over 0.3 of LT (50)(-1) or 0.5-1.0 of ET (50)(-1). By Pearson product-moment correlation coefficient, correlation coefficient between toxicity and ASPT was obtained at -0.773 (ET (50)(-1)) and -0.742 (LT (50)(-1)) at 1 % level of significance with a high negative correlation. Toxicity (LT (50)(-1) ) has strong correlation with the ratio of tolerant species. By Pearson product-moment correlation coefficient, correlation coefficient between toxicity and IBI obtained were -0.155 (ET (50)(-1)) and -0.190 (LT (50)(-1)) at 1 % level of significance and has a low or no correlation between toxicity and IBI. Even with low toxic environmental waters, toxicity test using 100-fold concentrated and medaka early fly could detect acute toxicity. The detected toxicity seemed to limit the inhabiting aquatic species in the water body.