Nitrate toxicity to aquatic animals: a review with new data for freshwater invertebrates

Published data on nitrate (NO3-) toxicity to freshwater and marine animals are reviewed. New data on nitrate toxicity to the freshwater invertebrates Eulimnogammarus toletanus, Echinogammarus echinosetosus and Hydropsyche exocellata are also presented. The main toxic action of nitrate is due to the conversion of oxygen-carrying pigments to forms that are incapable of carrying oxygen. Nitrate toxicity to aquatic animals increases with increasing nitrate concentrations and exposure times. In contrast, nitrate toxicity may decrease with increasing body size, water salinity, and environmental adaptation. Freshwater animals appear to be more sensitive to nitrate than marine animals. A nitrate concentration of 10 mg NO3-N/l (USA federal maximum level for drinking water) can adversely affect, at least during long-term exposures, freshwater invertebrates (E. toletanus, E. echinosetosus, Cheumatopsyche pettiti, Hydropsyche occidentalis), fishes (Oncorhynchus mykiss, Oncorhynchus tshawytscha, Salmo clarki), and amphibians (Pseudacris triseriata, Rana pipiens, Rana temporaria, Bufo bufo). Safe levels below this nitrate concentration are recommended to protect sensitive freshwater animals from nitrate pollution. Furthermore, a maximum level of 2 mg NO3-N/l would be appropriate for protecting the most sensitive freshwater species. In the case of marine animals, a maximum level of 20 mg NO3-N/l may in general be acceptable. However, early developmental stages of some marine invertebrates, that are well adapted to low nitrate concentrations, may be so susceptible to nitrate as sensitive freshwater invertebrates.     

The impact of an industrial effluent on the water quality,submersed macrophytes and benthic macroinvertebrates in a dammed river of Central Spain

This research was conducted in the middle Duratón River (Central Spain), in the vicinity of Burgomillodo Reservoir. An industrial effluent enters the river 300 m downstream from the dam. Fluoride and turbidity levels significantly increased downstream from the effluent, these levels being to some extent affected by differential water releases from the dam. The community of submersed macrophytes exhibited slighter responses and, accordingly, lower discriminatory power than the community of benthic macroinvertebrates, this indicating that metrics and indices based on macroinvertebrates may be more suitable for the biological monitoring of water pollution and habitat degradation in dammed rivers receiving industrial effluents. However, in relation to fluoride bioaccumulation at the organism level, macrophytes (Fontinalis antipyretica and Potamogeton pectinatus) were as suitable bioindicators of fluoride pollution as macroinvertebrates (Ancylus fluviatilis and Pacifastacus leniusculus). Fluoride bioaccumulation in both hard and soft tissues of these aquatic organisms could be used as suitable bioindicator of fluoride pollution (even lower than 1 mg F⁻ L⁻¹) in freshwater ecosystems. Echinogammarus calvus exhibited a great sensitivity to the toxicity of fluoride ions, with a 96 h LC₅₀ of 7.5 mg F⁻ L⁻¹ and an estimated safe concentration of 0.56 mg F⁻ L⁻¹. The great capacity of E. calvus to take up and retain fluoride during exposures to fluoride ions would be a major cause of its great sensitivity to fluoride toxicity. It is concluded that the observed fluoride pollution might be partly responsible for the absence of this native amphipod downstream from the industrial effluent.     

Sulphate toxicity to the aquatic moss, Fontinalis antipyretica

The aquatic moss, Fontinalis antipyretica was exposed to elevated sulphate concentrations for 21-days. Gametophores were sectioned to 2 cm lengths and exposed to sulphate concentrations up to 1500 mg/l, in waters of different water hardness. Significant reductions in shoot length, dry weight, and chlorophyll a and b concentrations (per gram dry weight) were observed in soft water (19 mg/l as CaCO3); however, effects were significantly reduced in waters of increasing hardness (up to 105 mg/l as CaCO3). The substantial reduction of sulphate toxicity in waters of increasing hardness suggests water chemistry plays a significant role in affecting sulphate toxicity and should be considered when setting sulphate discharge limits.     

Derivation of ambient water quality criteria for formaldehyde.

This paper describes the derivation of aquatic life water quality criteria for formaldehyde, developed in accordance with United States Environmental Protection Agency's (USEPA's) Guidelines for Deriving Numerical National Water Quality Criteria for the Protection of Aquatic Organisms and Their Uses. The initial step in deriving water quality criteria was to conduct an extensive literature search to assemble available acute and chronic toxicity data for formaldehyde. The literature search identified a large amount of information on acute toxicity of formaldehyde to fish and aquatic invertebrates. These acute data were evaluated with respect to data quality, and poor quality or uncertain data were excluded from the data base. The resulting data base met the USEPA requirements for criteria derivation by having data for at least one species in at least eight different taxonomic families. One shortcoming of the literature-derived data base, however, was that few studies involved analytical confirmation of nominal formaldehyde concentrations and reported toxicity endpoints. Also, there were relatively few data on chronic toxicity. The acute toxicity data set consisted of data for 12 species of fish, 3 species of amphibians, and 11 species of invertebrates. These data were sufficient, according to USEPA guidelines, to calculate a final acute value (FAV) of 9.15 mg/l, and an acute aquatic life water quality criterion (one-half the FAV) of 4.58 mg/l. A final acute-chronic ratio (ACR) was calculated using available chronic toxicity data and USEPA-recommended conservative default assumptions to account for missing data. Using the FAV and the final ACR (5.69), the final chronic aquatic life water quality criterion was determined to be 1.61 mg/l.     

Toxicity of methyl-tert-butyl ether to freshwater organisms

Increased input of the fuel oxygenate methyl-tert-butyl ether (MTBE) into aquatic systems has led to concerns about its effect(s) on aquatic life. As part of a study conducted by University of California scientists for the State of California, the Aquatic Toxicology Laboratory, UC Davis, reviewed existing literature on toxicity of MTBE to freshwater organisms, and new information was generated on chronic, developmental toxicity in fish, and potential toxicity of MTBE to California resident species. Depending on time of exposure and endpoint measured, MTBE is toxic to various aquatic organisms at concentrations of 57-> 1000 mg/l (invertebrates), and 388-2600 mg/l (vertebrates). Developmental effects in medaka (Oryzias latipes) were not observed at concentrations up to 480 mg/l, and all fish hatched and performed feeding and swimming in a normal manner. Bacterial assays proved most sensitive with toxicity to Salmonella typhimurium measured at 7.4 mg/l within 48 h. In microalgae, decreased growth was observed at 2400 and 4800 mg/l within 5 days. MTBE does not appear to bioaccumulate in fish and is rapidly excreted or metabolized. Collectively, the available data suggests that at environmental MTBE exposure levels found in surface waters (< 0.1 mg/l) this compound is likely not acutely toxic to aquatic life. However, more information is needed on chronic and sublethal effects before we can eliminate the possibility of risk to aquatic communities at currently detected concentrations.     

Do pharmaceuticals affect freshwater invertebrates? A study with the cnidarian Hydra vulgaris

Pharmaceuticals enter natural waters through sewage effluent and landfill leachates and present an unknown risk to aquatic species including freshwater invertebrates. In this study the acute and chronic toxicity of 10 drugs, commonly prescribed in the UK i.e. ibuprofen, paracetamol, acetylsalicylic acid, amoxicillin, bendroflumethiazide, furosemide, atenolol, diazepam, digoxin, amlodipine were assessed using the cnidarian Hydra vulgaris. In a 7 day exposure period there were no effects on survival at concentrations up to 1.0 mg l(-1) and after 17 days neither feeding nor bud formation were adversely affected. However the ability of dissected polyps to regenerate a hypostome, tentacles and foot was inhibited by diazepam, digoxin and amlodipine at 10 microg l(-1). It is suggested that other drugs targeted at mammalian receptor systems may also affect aquatic invertebrates although it is unlikely, at their low environmental concentrations, that those examined in this study actually present a risk.     

Possible alkylation of inorganic Hg(II) by photochemical processes in the environment

Contamination of surface waters by pesticides continues to be the focus of concern for water authorities due to the growing evidence of their deleterious effects on aquatic life. In this context, the present work investigates the occurrence of 16 selected pesticides belonging to the classes of triazines, phenylureas, organophosphates, chloroacetanilides and thiocarbamates in surface waters from the Llobregat River (NE Spain) and some of its tributaries (Anoia and Rubí) and assesses their potential impact on the aquatic organisms by applying a recently developed index, the Short-term Pesticide Risk Index for the Surface Water System (PRISW-1), which takes into account the pesticides concentrations and their overall toxicity against three aquatic organisms (algae, Daphnia, and fish). Chemical analysis, performed by means of a fully automated method based on isotope dilution on-line solid phase extraction-liquid chromatography-electrospray-tandem mass spectrometry (on-line SPE-LC-ESI-MS/MS), revealed diuron and diazinon as the most ubiquitous and abundant compounds with levels up to 818 and 132 ng L⁻¹, respectively. Total pesticide concentrations, which in only 1 out of 66 samples surpassed 500 ng L⁻¹, were higher in the tributaries than in the river but their contribution in terms of mass-loads to the overall pesticide pollution of the Llobregat River was relatively small. Contamination increased downstream of the river and was clearly influenced by rainfall and hence river flow. Application of the PRISW-1 index indicated that, although pesticides levels fulfilled the European Union Environmental Quality Standards (EQS) for surface waters, the existing pesticide contamination poses a low to high ecotoxicological risk for aquatic organisms, that algae and macro-invertebrates are at higher risk than fish, and that the organophosphates diazinon and malathion and the phenylurea diuron are the major contributors to the overall toxicity and therefore the most problematic compounds.     

Seasonal variation of sediment toxicity in the Rivers Dommel and Elbe

Contaminated sediment in the river basin has become a source of pollution with increasing importance to the aquatic ecosystem downstream. To monitor the temporal changes of the sediment bound contaminants in the River Elbe and the River Dommel monthly toxicity tests were applied to layered sediment and river water samples over the course of 10 months. There is an indication that contaminated sediments upstream adversely affected sediments downstream, but this process did not cause a continuous increase of sediment toxicity. A clear decrease of toxic effects in water and upper layer sediment was observed at the River Elbe station in spring related to high water discharge and algal blooms. The less obvious variation of sediment toxicity in the River Dommel could be explained by stable hydrological conditions. Future monitoring programmes should promote a more frequent and intensive sampling regime during these particular events for ecotoxicological evaluation.     

Fluoride in mandibles and antlers of roe and red deer from different areas of England and Scotland

Fluoride concentrations were measured in mandibles of 112 male roe deer (Capreolus capreolus) aged 1-6 years, from 5 localities in England and Scotland; also in bone from sections cut in series from orbit to antler-top of 10 other roe deer. Fluoride concentrations in mandibles were mostly within values expected from unpolluted areas, but approached those expected from moderately polluted areas at the upper end of their range, which extended from 43 to 901 microg g(-1). There were large variations in mandibular fluoride content between individual animals within each age group, and an upward trend of fluoride content with increasing age. There were also considerable differences in mandibular fluoride content between localities. No gradient in fluoride concentration was evident between the upper part of the skull and various points along the antler in 9 roe deer. A tenth animal showed an increase of 65% in fluoride concentration between the skull and the top of the antler, with exceptionally high values ranging from 1220 to 2010 micro g(-1). For 3 red deer (Cervus elaphus), no significant differences in fluoride concentrations were found between trabecular and cortical antler bone.     

A multispecies study to assess the toxic and genotoxic effect of pharmaceuticals: furosemide and its photoproduct

Pharmaceutical products for humans and animals, as well as their related metabolites end up in the aquatic environment after use. Recent investigations show that concentrations of pharmaceuticals are detectable in the order of ng/l-mug/l in municipal wastewater, groundwater and also drinking water. Little is known about the effects, and the hazard of long-term exposure to low concentrations of pharmaceuticals for non-target aquatic organisms. This study was designed to assess the ecotoxicity of furosemide, a potent diuretic agent, and its photoproduct in the aquatic environment. Bioassays were performed on bacteria, algae, rotifers and microcrustaceans to assess acute and chronic toxicity, while the SOS Chromotest and the Ames test were utilized to detect the genotoxic potential of the investigated compounds. A first approach to risk characterization was to calculate the environmental impact of furosemide by measured environmental concentration and predicted no effect concentration ratio (MEC/PNEC). To do so we used occurrence data reported in the literature and our toxicity results. The results showed that acute toxicity was in the order of mg/l for the crustaceans and absent for bacteria and rotifers. Chronic exposure to these compounds caused inhibition of growth population on the consumers, while the algae did not seem to be affected. A mutagenic potential was found for the photoproduct compared to the parental compound suggesting that byproducts ought to be considered in the environmental assessment of drugs. The risk calculated for furosemide suggested its harmlessness on the aquatic compartment.     

Status of industrial fluoride pollution and its diverse adverse health effects in man and domestic animals in India

Hydrofluorosis in humans and domestic animals is a worldwide health problem and caused by a prolonged period of fluoride exposure through drinking of fluoride contaminated water. But in recent years, due to rapid industrialization in India, diverse serious health problems among industrial workers and residents and domestic animals living in the industrial areas due to fluoride pollution are on the rise. A number of coal-burning and industrial activities such as power-generating stations, welding operations and the manufacturing or production of steel, iron, aluminum, zinc, phosphorus, chemical fertilizers, bricks, glass, plastic, cement, and hydrofluoric acid are generally discharging fluoride in both gaseous and particulate/dust forms into surrounding environments which create a industrial fluoride pollution and are an important cause of occupational exposure to fluoride in several countries including India. An industrial emitted fluoride contaminates not only surrounding soil, air, and water but also vegetation, crops and many other biotic communities on which man and animals are generally dependants for food. Long- time of inhalation or ingestion of industrial fluoride also causes serious health problems in the forms of industrial and neighborhood fluorosis. In India, whatever research works conducted so far on the chronic industrial fluoride intoxication or poisoning (industrial and neighborhood fluorosis) in man and various species of domestic animals due to a prolonged period of industrial fluoride exposure or pollution (contamination) are critically reviewed in the present communication. Simultaneously, we are also focused the various bio-indicators and bio-markers for chronic industrial fluoride intoxication or pollution.     

Biosorption of cadmium and copper contaminated water by Scenedesmus abundans

Experiments were conducted comparing the individual removals of cadmium and copper from water via biosorption using Scenedesmus abundans, a common green algae, to removal in a multi-component system to determine competitive effects, if any, between the metals. The goal was to characterize the biological treatment of water contaminated with heavy metals using live aquatic species. In addition, experiments were performed to measure cell viability as a function of metal concentration and also to compare metal removal using living species to that using nonliving ones. It was shown that, while both living and nonliving S. abundans removed cadmium and copper from water, living algae significantly outperformed nonliving algae. Further, in characterizing biosorption by three concentrations of live S. abundans, capacity curves were created comparing the metal biosorbed per mass algae to the initial metal concentration in solution. The algae concentration was not a factor in the biosorption of either metal individually, such that the capacity of the algae for the metal increased with decreasing algae concentration. At the lowest algae concentration considered, competitive effects were observed at copper and cadmium concentrations above 4 mg/l each. At the highest algae concentration considered, no competitive effects were observed in the range of cadmium and copper concentrations studied (1-7 mg/l). It was concluded that biological treatment of heavy metal contaminated water is possible and that at adequately high algae concentrations, multi-component metal systems can be remediated to the same level as individual metals.     

A comparative study of the toxicity of 1,1,2-trichloroethane,dieldrin, pentachlorophenol and 3,4 dichloroaniline for marine and fresh water organisms

The aquatic toxicity of 1,1,2-trichloroethane, dieldrin, pentachlorophenol and 3,4-dichloroaniline was determined for about 15 marine and fresh water animals and several unicellular algae. Acute, subchronic and chronic tests including reproduction studies, were carried out. The results are summarized in five tables.     

Biodegradation and removal of 3,4-dichloroaniline by Chlorella pyrenoidosa based on liquid chromatography-electrospray ionization-mass spectrometry

3,4-Dichloroaniline (3,4-DCA), widely used in the synthesis of dyes, textile and herbicides, is toxic to living organisms. The purpose of this study was to investigate the capability of green algae in degrading and removing 3,4-DCA in water. An environmentally ubiquitous green alga Chlorella pyrenoidosa was isolated from fresh aquatic environment. Then unicellular alga was incubated with 3,4-DCA at a concentration of 4.6 μg/?mL in water. The residual concentration of 3,4-DCA in the medium and the metabolites were analyzed. A removal percentage of 78.4 % was obtained over a 7-day period. Two major metabolites with less toxicity were identified as 3,4-dichloroformanilide and 3,4-dichloroacetanilide from the liquid chromatography-electrospray ionization-mass spectrometry analysis. The application of microalga C. pyrenoidosa may have potential for removing the environmental pollutant in aquatic environment.     

Uptake and depuration of anatoxin-a by the mussel Mytilus galloprovincialis (Lamarck, 1819) under laboratory conditions

Cyanobacterial blooms tend to be more common in warm and nutrient-enriched waters and are increasing in many aquatic water bodies due to eutrophication. The aim of this work is to study the accumulation and depuration of anatoxin-a by Mytilus galloprovincialis a widespread distributed mussel living in estuarine and coastal waters and recognized worldwide as a bioindicator (e.g. Mussel Watch programs). Research on the distribution and biological effects of anatoxin-a in M. galloprovincialis is important. Nevertheless, the risk of human intoxication due to the consumption of contaminated bivalves should also be considered. A toxic bloom was simulated in an aquarium with 5 x 10(5) cell ml(-1) of Anabaena sp. (ANA 37), an anatoxin-a producing strain. Mussels were exposed to Anabaena for 15 days and then 15 days of depuration followed. Three or more animals were sampled every 24h for total toxin quantification and distribution in soft tissues (edible parts). Water samples were also taken every 24h in order to calculate total dissolved and particulate anatoxin-a concentrations. Anatoxin-a was quantified by HPLC with fluorescence detection. No deaths occurred during accumulation and depuration periods. One day after the beginning of depuration, the toxin could not be detected in the animals. Anatoxin-a is distributed in the digestive tract, muscles and foot and is probably actively detoxified.     

Occurrence of aminopolycarboxylates in the aquatic environment of Germany

Aminopolycarboxylic acids, such as ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), 1,3-propylenediaminetetraacetic acid (1,3-PDTA), beta-alaninediacetic acid (beta-ADA), and methylglycinediacetic acid (MGDA), are used in large quantities in a broad range of industrial applications and domestic products in order to solubilize or inactivate various metal ions by complex formation. Due to the wide field of their application, their high polarity and partly low degradability, these substances reach the aquatic environment at considerable concentrations (in the microg/L-range) and have also been detected in drinking water. This review evaluates and summarizes the results of long-term research projects, monitoring programs, and published papers concerning the pollution of the aquatic environment by aminopolycarboxylates in Germany. Concentrations and loads of aminopolycarboxylates are presented for various types of water including industrial and domestic waste waters, surface waters (rivers and lakes), raw waters, and drinking waters.     

Derivation of site-specific surface water quality criteria for the protection of aquatic ecosystems near a Korean military training facility

This study suggested the first Korean site-specific ecological surface water quality criteria for the protection of ecosystems near an artillery range at a Korean military training facility. Surface water quality (SWQ) criteria in Korea address human health protection but do not encompass ecological criteria such as limits for metals and explosives. The first objective of this study was to derive site-specific SWQ criteria for the protection of aquatic ecosystems in Hantan River, Korea. The second objective was to establish discharge criteria for the artillery range to protect the aquatic ecosystems of Hantan River. In this study, we first identified aquatic organisms living in the Hantan River, including fishes, reptiles, invertebrates, phytoplankton, zooplankton, and amphibians. Second, we collected ecotoxicity data for these aquatic organisms and constructed an ecotoxicity database for Cd, Cu, Zn, TNT, and RDX. This study determined the ecological maximum permissible concentrations for metals and explosives based on the ecotoxicity database and suggested ecological surface water quality criteria for the Hantan River by considering analytical detection limits. Discharge limit criteria for the shooting range were determined based on the ecological surface water quality criteria suggested for Hantan River with further consideration of the dilution of the contaminants discharged into the river.     

The effect of acidification on the accumulation and toxicity of metals to freshwater invertebrates

This paper reviews the literature to determine if lowered water pH (a) affects metal bioaccumulation in freshwater invertebrates, (b) enhances the toxicity of a given metal, and (c) increases waterborne metal concentrations to levels toxic to invertebrates. The elements considered are mercury, lead, cadmium and aluminum. The available evidence suggests that of these elements only mercury is biomagnified in aquatic foodchains. The bioaccumulation of all these elements is influenced by water pH, but data concerning invertebrates is meagre for mercury and lead. The effect of pH on mercury and lead toxicity to invertebrates is unclear and may be largely species specific. Cadmium toxicity is reduced by lower pH, while aluminum toxicity to invertebrates is markedly higher due to changes in aluminum speciation at low pH.     

Ecological effects, transport, and fate of mercury: a general review

Mercury at low concentrations represents a major hazard to microorganisms. Inorganic mercury has been reported to produce harmful effects at 5 μg/l in a culture medium. Organomercury compounds can exert the same effect at concentrations 10 times lower than this. The organic forms of mercury are generally more toxic to aquatic organisms and birds than the inorganic forms. Aquatic plants are affected by mercury in water at concentrations of 1 mg/l for inorganic mercury and at much lower concentrations of organic mercury. Aquatic invertebrates widely vary in their susceptibility to mercury. In general, organisms in the larval stage are most sensitive. Methyl mercury in fish is caused by bacterial methylation of inorganic mercury, either in the environment or in bacteria associated with fish gills or gut. In aquatic matrices, mercury toxicity is affected by temperature, salinity, dissolved oxygen and water hardness. A wide variety of physiological, reproductive and biochemical abnormalities have been reported in fish exposed to sublethal concentrations of mercury. Birds fed inorganic mercury show a reduction in food intake and consequent poor growth. Other (more subtle) effects in avian receptors have been reported (i.e., increased enzyme production, decreased cardiovascular function, blood parameter changes, immune response, kidney function and structure, and behavioral changes). The form of retained mercury in birds is more variable and depends on species, target organ and geographical site. With few exceptions, terrestrial plants (woody plants in particular) are generally insensitive to the harmful effects of mercury compounds.