Fluoride toxicity to aquatic organisms: a review

Published data on the toxicity of fluoride (F-) to algae, aquatic plants, invertebrates and fishes are reviewed. Aquatic organisms living in soft waters may be more adversely affected by fluoride pollution than those living in hard or seawaters because the bioavailability of fluoride ions is reduced with increasing water hardness. Fluoride can either inhibit or enhance the population growth of algae, depending upon fluoride concentration, exposure time and algal species. Aquatic plants seem to be effective in removing fluoride from contaminated water under laboratory and field conditions. In aquatic animals, fluoride tends to be accumulated in the exoskeleton of invertebrates and in the bone tissue of fishes. The toxic action of fluoride resides in the fact that fluoride ions act as enzymatic poisons, inhibiting enzyme activity and, ultimately, interrupting metabolic processes such as glycolysis and synthesis of proteins. Fluoride toxicity to aquatic invertebrates and fishes increases with increasing fluoride concentration, exposure time and water temperature, and decreases with increasing intraspecific body size and water content of calcium and chloride. Freshwater invertebrates and fishes, especially net-spinning caddisfly larvae and upstream-migrating adult salmons, appear to be more sensitive to fluoride toxicity than estuarine and marine animals. Because, in soft waters with low ionic content, a fluoride concentration as low as 0.5 mg F-/l can adversely affect invertebrates and fishes, safe levels below this fluoride/l concentration are recommended in order to protect freshwater animals from fluoride pollution.     

Statistical evaluation of chronic toxicity data on aquatic organisms for the hazard identification: the chemicals toxicity distribution approach

Presently, in the Globally Harmonised System of Classification and Labelling of Chemicals the classification of substances for long-term effects to aquatic life is based on acute toxicity in combination with degradation and/or bioaccumulation potential. Recently an OECD Working Group was created to develop the classification scheme to accommodate chronic toxicity data related to aquatic organisms for assigning a chronic hazard category. This study focuses on a new approach for setting chronic toxicity cut-off values based on Chemicals Toxicity Distributions (CTDs). A CTD is obtained through statistical fitting of the data used by regulatory bodies for setting hazard-based classifications. The CTDs were made using the lowest aquatic NOEC value of each chemical. A review of different toxicological sources reporting acute aquatic toxicities was carried out. Initially, the data were arranged according to the specific source and distributions for key taxonomic groups (i.e. fishes, crustaceans and algae) were evaluated separately. In most cases, no significant departures from normality were observed. Thereafter, a compiled database containing >900 values was developed and the CTDs were constructed for each taxonomic group. Significant deviation from normality (P < 0.05) was observed in the fishes and crustaceans' CTDs. However, this deviation was apparently produced by the presence of only seven values with NOECs <1 x 10(-5) mg l(-1), while high correlation between the data and the normal scores (r-values>or= 0.989) indicated that the data were samples from normal distributions. From these observations, potential cut-off values would allow quantitative estimations of the percentage of chemicals falling into each specific category. This approach results in a simple classification hazard scheme where most chemicals are covered in one of the categories, allowing a clear distribution of the chemicals among three categories for chronic toxicity.     

Studies on lethal concentrations and toxicity stress of some xenobiotics on aquatic organisms

Three widely used xenobiotics pentachlorophenol (PCP), 2,4-dichlorophenoxyacetic acid (2,4-D) and 2-chloro-2,6-diethyl-N-(butoxymethyl) acetanilide (Butachlor) are evaluated for acute toxicity and stress behavior on freshwater fish (Heteropneustes fossilis, Clarias batrachus, Channa punctatus) and mosquito larvae (Culex pipiens fatigans). The experiment was carried out by medium treatment using intermittent flow-through system. Median lethal concentrations (LC50) were calculated by probit analysis. The LC50 values and 95% confidence intervals showed variable range for tested chemicals. Mosquito larvae generally appeared resistant than fish, while H. fossilis was found to be most sensitive. Stress signs in the form of behavioral changes are also observed. Both types of organisms are recommended as good bioindicator for the risk assessment of aquatic environment due to chemicals tested.     

Modeling time-dependent toxicity to aquatic organisms from pulsed exposure of PAHs in urban road runoff

Understanding of the magnitude of urban runoff toxicity to aquatic organisms is important for effective management of runoff quality. In this paper, the aquatic toxicity of polycyclic aromatic hydrocarbons (PAHs) in urban road runoff was evaluated through a damage assessment model. Mortality probability of the organisms representative in aquatic environment was calculated using the monitored PAHs concentration in road runoff. The result showed that the toxicity of runoff in spring was higher than those in summer. Analysis of the time-dependent toxicity of series of runoff water samples illustrated that the toxicity of runoff water in the final phase of a runoff event may be as high as those in the initial phase. Therefore, the storm runoff treatment systems or strategies designed for capture and treatment of the initial portion of runoff may be inappropriate for control of runoff toxicity.     

In situ exposures using caged organisms: a multi-compartment approach to detect aquatic toxicity and bioaccumulation

An in situ toxicity and bioaccumulation assessment approach is described to assess stressor exposure and effects in surface waters (low and high flow), the sediment-water interface, surficial sediments and pore waters (including groundwater upwellings). This approach can be used for exposing species, representing major functional and taxonomic groups. Pimephales promelas, Daphnia magna, Ceriodaphnia dubia, Hyalella azteca, Hyalella sp., Chironomus tentans, Lumbriculus variegatus, Hydra attenuatta, Hexagenia sp. and Baetis tibialis were successfully used to measure effects on survival, growth, feeding, and/or uptake. Stressors identified included chemical toxicants, suspended solids, photo-induced toxicity, indigenous predators, and flow. Responses varied between laboratory and in situ exposures in many cases and were attributed to differing exposure dynamics and sample-processing artifacts. These in situ exposure approaches provide unique assessment information that is complementary to traditional laboratory-based toxicity and bioaccumulation testing and reduce the uncertainties of extrapolating from the laboratory to field responses.     

Toxicity of selected chlorobenzenes to aquatic organisms

Acute toxicity tests with six chlorobenzenes were performed on several aquatic organisms at different trophic levels. Fertility impairment on Daphnia and photosynthesis inhibition on Selenastrum were also carried on. Results are discussed together with physico-chemical properties of the molecules in order to identify structure-activity relationships and to predict environmental distribution. A hazard ranking procedure is also applied.     

Acute and chronic toxicity of organophosphate monocrotophos to Daphnia magna

The acute and chronic toxicity of monocrotophos (MCP), the binary joint toxicity of MCP and bifenthrin (BF), and sodium dodecyl benzene sulfonate (SDBS) to Daphnia magna (D. magna) was evaluated. The 24 h-median effective concentration (24 h-EC₅₀) and 48 h-median lethal concentration (48 h-LC₅₀) of MCP towards D. magna were 161 and 388 μ g/L, respectively. In addition, the lowest-observed effective concentration (LOEC) and non-observed effective concentration (NOEC) of MCP to D. magna were 10 and 5 μ g/L, respectively. Furthermore, the chronic value (ChV) of MCP against D. magna was 7 μ g/L and the acute chronic ratio (ACR) was 55. The number of offspring per female and the intrinsic rate of natural increase (r) were identified as the parameters that were most sensitive to MCP. In addition, toxic unit (TU) analysis was employed to evaluate the joint toxicities. The calculated TU_mix values of binary equitoxic mixtures of MCP + BF and MCP + SDBS were 1.47 and 1.63, respectively, which suggests that both equitoxic mixtures exert a limited antagonistic effect. The results of this study revealed that the toxic threshold of MCP towards D. magna is higher than its reported highest residue (4 μ g/L) in the ordinary aquatic environment, and that concurrent exposure to BF or SDBS may exert a slight antagonistic effect.     

Acute and chronic toxicity of veterinary antibiotics to Daphnia magna

The acute and chronic toxicity of nine antibiotics used both therapeutically and as growth promoters in intensive farming was investigated on the freshwater crustacean Daphnia magna. The effect of the antibiotics metronidazole (M), olaquindox (OL), oxolinic acid (OA), oxytetracycline (OTC), streptomycin (ST), sulfadiazine (SU), tetracycline (TC), tiamulin (TI) and tylosin (TY) was tested in accordance to the ISO (1989) and OECD (1996) standard procedures. The acute toxicities (48-h EC50 value, mg/l) in decreasing order were OA (4.6), TI (40), SU (221), ST (487), TY (680) and OTC (approximately 1000). NOECs were 340 mg/l for TC and 1000 mg/l for M and OL. Toxic effect on reproduction occurred generally at concentrations, which were one order of magnitude below the acute toxic levels. The chronic toxicity (EC50 values, mg/l) in the D. magna reproduction test in decreasing order were TI (5.4), SU (13.7), TC (44.8) and OTC (46.2). The NOECs (mg/l) obtained in the reproduction test with OA, ST, TY and M were 0.38 for OA, 32 for ST, 45 for TY and 250 for M. The observed toxicity of OA to D. magna indicates that this substance, which is a commonly used feed additive in fish farms, has a potential to cause adverse effects on the aquatic environment.     

Toxicity of ferric chloride sludge to aquatic organisms

Iron-rich sludge from a drinking water treatment plant (DWTP) was investigated regarding its toxicity to aquatic organisms and physical and chemical composition. In addition, the water quality of the receiving stream near the DWTP was evaluated. Experiments were carried out in August 1998, February 1999 and May 1999. Acute toxicity tests were carried out on a cladoceran (Daphnia similis), a midge (Chironomus xanthus) and a fish (Hyphessobrycon eques). Chronic tests were conducted only on D. similis. Acute sludge toxicity was not detected using any of the aquatic organisms, but chronic effects were observed upon the fecundity of D. similis. Although there were relatively few sample dates, the results suggested that the DWTP sludge had a negative effect on the receiving body as here was increased suspended matter, turbidity, conductivity, chemical oxygen demand (COD) and hardness in the water downstream of the DWTP effluent discharge. The ferric chloride sludge also exhibited high heavy metal concentrations revealing a further potential for pollution and harmful chronic effects on the aquatic biota when the sludge is disposed of without previous treatment.     

Combined effects of cadmium and composted manure to aquatic organisms

To evaluate the interactive toxicity of cadmium (Cd) and composted manure to aquatic organisms 96 h static bioassays were conducted in the laboratory with fry of common carp (Cyprinus carpio), copepod (Diaptomusforbesi) and oligochaete worm (Branchiura sowerbyi). Five concentrations of composted manure (0, 0.25, 0.5, 1.0 and 6.7 g/l) were prepared from the aquatic weed, Pistia stratiotes and each of them was combined with several concentrations of Cd to determine 96 h LC-50 values of Cd for the test organisms. Addition of composted manure, irrespective of concentration, significantly reduced the LC-50 value of Cd to the copepod and common carp fry while it increased the LC-50 value of Cd to the worm. Increased susceptibility of the worm to combined treatment of composted manure and small concentrations of Cd could be revealed only from the dose mortality curve. Results of acute toxicity bioassays were different from the results of bioassays conducted with small concentrations of Cd. Worms, exposed to 2.5 mg/l Cd, accumulated more Cd than did the carp fry and copepod. Accumulation of Cd by worms was increased by the addition of 6.7 g/l composted manure while it decreased in the carp fry and copepod. Food consumption rate of common carp fingerling was significantly reduced relative to the control by exposure to 2.5 mg/l Cd. No change in feeding rate was observed when Cd was combined with composted manure (6.7 g/l).     

Toxicity of fluoranthene and its biodegradation metabolites to aquatic organisms

The toxicity of nine stable products of the biodegradation of fluoranthene with the pure bacterial strain Pasteurella sp. IFA was studied. For their quantification, an improved analytical procedure with two-step liquid-liquid extraction, derivatisation and gas chromatographic-mass spectrometric detection was used. Growth inhibition and immobility tests for fluoranthene and its metabolites were carried out using algae (Scenedesmus subspicatus), bacteria (Pseudomonas putida) and crustaceans (Daphnia magna and Thamnocephalus platyurus). Tests using the alga S. subspicatus revealed that with the exception of 9-hydroxyfluorene, which was only four times less toxic than fluoranthene, all the other metabolites were 37 to approximately 3000 times less toxic than the parent material. P. putida cells were resistant to fluoranthene and its primary metabolites, but were inhibited by low molecular weight intermediates, especially benzoic acid. Fluoranthene was not toxic to T. Platyurus, but was toxic to D. magna. Its primary metabolites (including 9-fluorenone and 9-hydroxyfluorene) were toxic to D. magna, and a low molecular weight metabolite (2-carboxybenzaldehyde) was highly toxic to T. platyurus.     

A comparison of acute toxicity of biodiesel, biodiesel blends, and diesel on aquatic organisms

The increased demand of alternative energy sources has created interest in biodiesel and biodiesel blends; biodiesel is promoted as a diesel substitute that is safer, produces less harmful combustion emissions, and biodegrades more easily. Like diesel spills, biodiesel can have deleterious effects on the aquatic environments. The effect of neat biodiesel, biodiesel blends, and diesel on Oncorhynchus mykiss and Daphnia magna was evaluated using acute toxicity testing. Static nonrenewal bioassays of freshwater organisms containing B100, B50, B20, B5, and conventional diesel fuel were used to compare the acute effects of biodiesel to diesel. Mortality was the significant end point measured in this study; percent mortality and lethal concentration (LC50) at different exposure times were determined from the acute toxicity tests performed. Trials were considered valid if the controls exhibited > 90% survival. Based on percentage of mortality and LC50 values, a toxicity ranking of fuels was developed.     

Converging hazard assessment of gold nanoparticles to aquatic organisms

The gold nanoparticles (Au-NPs) are being increasingly used because of their huge diversity of applications, and consequently, elevated levels in the environment are expected. However, due to their physico-chemical properties and functionalization a high variety of Au-NPs can be found, and complete toxicological information for each type of Au-NPs still lacks, and even, the toxicological information for the same species is sometimes contradictory. Therefore, hazard assessment should be done case by case. Hence, the objective of this study was to obtain ecotoxicological information of the same Au-NPs in aquatic organisms and to find a rationale for Au-NPs toxicity. For such a purpose, bare and hyaluronic acid capped Au-NPs (12.5 nm) along with Au-NPs bulk material were tested on freshwater algae, Daphnia and zebrafish. Results showed that while gold nanoparticles were found to be harmless to the tested organisms, the soluble gold showed to be toxic to algae and Daphnia, with an LC₅₀ between 1 and 2 mg L⁻¹. Comparing our results with those gathered in the literature, it appears that a common hazard assessment of Au-NPs on the studied organisms can be elucidated.     

A model for non-specific toxicity with aquatic organisms over relatively long periods of exposure time

Experimental data have shown that the internal lethal concentrations of halobenzenes for aquatic organisms decreased with exposure time. In this paper, a model based on the concept of life expectancy reduction was developed to describe this relationship. The model was verified with experimental data for fish (Gambusia affinis) and juvenile crab (Porturius pelagicus(L)). It is proposed that long term non-specific toxicity can be measured as the reduction of the life expectancy of the exposed organism per unit internal concentration (or volume fraction) of the toxic compound. The model can be used to estimate internal lethal concentration at any given exposure period and vice versa. The model can also be used to estimate chronic values of the internal concentration, of the toxicants. It provides a useful tool for assessment of environmental risk of organic compounds in aquatic ecosystems.     

Waterborne and sediment toxicity of fluoxetine to select organisms

Ecological risk assessments of pharmaceuticals are currently difficult because little-to-no aquatic hazard and exposure information exists in the peer-reviewed literature for most therapeutics. Recently several studies have identified fluoxetine, a widely prescribed antidepressant, in municipal effluents. To evaluate the potential aquatic toxicity of fluoxetine, single species laboratory toxicity tests were performed to assess hazard to aquatic biota. Average LC(50) values for Ceriodaphnia dubia, Daphnia magna, and Pimephales promelas were 0.756 (234 microg/l), 2.65 (820 microg/l), and 2.28 microM (705 microg/l), respectively. Pseudokirchneriella subcapitata growth and C. dubia fecundity were decreased by 0.044 (14 microg/l) and 0.72 microM (223 microg/l) fluoxetine treatments, respectively. Oryias latipes survival was not affected by fluoxteine exposure up to a concentration of 28.9 microM (8.9 mg/l). An LC(50) of 15.2 mg/kg was estimated for Chironomus tentans. Hyalella azteca survival was not affected up to 43 mg/kg fluoxetine sediment exposure. Growth lowest observed effect concentrations for C. tentans and H. azteca were 1.3 and 5.6 mg/kg, respectively. Our findings indicate that lowest measured fluoxetine effect levels are an order of magnitude higher than highest reported municipal effluent concentrations.     

Acute toxicity and genotoxicity of aquatic hydrophobic pollutants sampled with semipermeable membrane devices

Triolein-filled semipermeable membrane devices (SPMDs) were deployed for 4 weeks in polluted water sources in Lithuania. The mixtures of pollutants sampled by the SPMDs were fractionated by size-exclusion chromatography (SEC). The fraction containing average molecular weight compounds such as polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides was screened by gas chromatography and mass spectrometry. The whole (non-fractionated) samples and their SEC fractions were tested in bioassays including Microtox, Mutatox, Daphnia pulex immobilization assay and the sister chromatid exchange (SCE) in human lymphocytes in vitro test. The Microtox test was most sensitive with the estimated EC(50) values in the range of milligrams or even micrograms per milliliter based on the amount of the SPMD triolein. Part of the observed toxicity was caused by elemental sulfur co-sampled by the SPMDs from sediments. The sum of toxicity equivalents of the SEC fractions was smaller than the relative toxicity of the whole samples indicating the presence of synergistic interactions in the complex mixtures of chemical pollutants. The toxic or genotoxic response induced by the chemical mixtures and their fractions was smaller in the D. pulex, Mutatox and SCE tests. In Mutatox, a positive response was only detected without the S9 metabolic activation which indicates the presence of mainly direct-acting mutagens in the samples. Interpretation of the Mutatox data was difficult due to the complexity of dose-response and time-response relationships. The study has demonstrated the potential as well as some limitations of SPMDs in the monitoring of biological effects of bioavailable organic pollutants in the aquatic environment.     

Acute toxicity of chlorophenols to earthworms using a simple paper contact method and comparison with toxicities to fresh water organisms

An acute toxicity test of chlorophenols on earthworms (Eisenia fetida) was performed using a simple paper contact method proposed by OECD testing guideline no. 207, that were applied as an earthworm toxicity test. The median lethal concentration, EC50, had significant correlation with logP(ow) (1-octanol/water partition coefficient) of the chemicals. The toxicity of chlorophenols on E. fetida was compared with toxicities for other species: an algae (Selenostrum capricornutum), a crustacean (Daphnia magna), and a fish (Oryzias latipes). It was found that the toxicity of chlorophenols was almost same for E. fetida and for fresh water organisms. These results suggest the possibility of drawing correlations between the effects of pollutants on living things in different environments, fresh water and soil.     

Relationship between toxicity of certain organic compounds and their concentrations in tissues of aquatic organisms: A perspective

This paper explores the relationship between the toxicity of certain organic pollutants and their tissue concentration and suggests that the latter may be a more accurate predictor of toxicity than exposure concentration.     

Acute and chronic ecotoxicity of carbaryl with a battery of aquatic bioassays

The ecotoxic effects of carbaryl (carbamate insecticide) were investigated with a battery of four aquatic bioassays. The nominal effective concentrations immobilizing 50% of Daphnia magna (EC50) after 24 and 48 h were 12.76 and 7.47 µg L^?1, respectively. After 21 days of exposure of D. magna, LOECs (lowest observed effect concentrations) for cumulative molts and the number of neonates per surviving adult were observed at carbaryl concentration of 0.4 µg L^?1. An increase of embryo deformities (curved or unextended shell spines) was observed at 1.8 and 3.7 µg L^?1, revealing that carbaryl could act as an endocrine disruptor in D. magna. Other bioassays of the tested battery were less sensitive: the IC50-72h and IC10-72h of the algae Pseudokirchneriella subcapitata were 5.96 and 2.87 mg L^?1, respectively. The LC50-6d of the ostracod Heterocypris incongruens was 4.84 mg L^?1. A growth inhibition of H. incongruens was registered after carbaryl exposure and the IC20-6d was 1.29 mg L^?1. Our results suggest that the daphnid test sensitivity was better than other used tests. Moreover, carbaryl has harmful and toxic effects on tested species because it acts at low concentrations on diverse life history traits of species and induce embryo deformities in crustaceans.