Ecotoxicological and chemical evaluation of phenolic compounds in industrial effluents

The aim of this paper was to evaluate the ecotoxicological response of industrial effluents containing phenolic compounds. All complex effluents collected from a chemical plant and then after both a chemical–physical and biological treatment were characterised with chemical analysis, biodegradability tests and four ecotoxicological tests (Daphnia magna, Artemia salina, Brachionus plicatilis and Vibrio fisheri with Microtox^®). The evaluation of the chemical and ecotoxicological data was useful for predicting the effect of the raw effluent on the treatment plant and the impact of the final treated effluent on the receiving water. Besides the toxicity of the effluent from the chemical plants, the acute toxicity of its main components was also determined. The results of the tests and toxicity data from literature were transformed in Toxic Units (TUs). Effluent toxicity was under- or over-estimated by calculating the sum of the TUs of the individual components, depending on which toxicity data and test organisms were used.     

Effects of pharmaceuticals on Daphnia survival, growth, and reproduction

Pharmaceuticals have been globally detected in surface waters, and the ecological impacts of these biologically-active, ubiquitous chemicals are largely unknown. To evaluate the aquatic toxicity of individual pharmaceuticals and mixtures, we performed single species laboratory toxicity tests with Daphnia magna, a common freshwater zooplankton. We conducted acute (6-day) and chronic (30-day) exposure pharmaceutical bioassays and evaluated survivorship and morphology of adults and neonates, adult length, resting egg production, brood size (fecundity), and the proportion of male broods produced (sex ratio). In general, exposure to a single pharmaceutical in the 1-100 microg/l range yielded no apparent effects on the normal life processes of Daphnia. However, chronic fluoxetine exposure (36 microg/l) significantly increased Daphnia fecundity, and acute clofibric acid exposure (10 microg/l) significantly increased sex ratio. A mixture of fluoxetine (36 microg/l) and clofibric acid (100 microg/l) caused significant mortality; the same fluoxetine concentration mixed with 10 microg/l clofibric acid resulted in significant deformities, including malformed carapaces and swimming setae. Mixtures of three to five antibiotics (total antibiotic concentration 30-500 microg/l) elicited changes in Daphnia sex ratio. We conclude: (1) individual and mixtures of pharmaceuticals affect normal development and reproduction of Daphnia magna, (2) aquatic toxicity of pharmaceutical mixtures can be unpredictable and complex compared to individual pharmaceutical effects, and (3) timing and duration of pharmaceutical exposure influence aquatic toxicity.     

Characterizing the toxicity of pulsed selenium exposure to Daphnia magna

The acute toxicity of selenium (Se) to aquatic biota has been studied extensively for decades. However, most studies have used a constant concentration aqueous exposure of Se to an invertebrate species. Since constant concentration exposure of toxicants to invertebrates is unusual in the environment, episodic exposure or pulsed exposures may represent true risk to aquatic biota more accurately. This research was designed to characterize the toxicity effects of pulsed Se exposure to Daphnia magna. Selenium exposure was varied during a 21-d chronic toxicity test to examine the effects of exposure concentration, duration, and recovery on survival, growth, and reproduction of D. magna. While D. magna did not die during exposures, latent mortality was observed. Latent mortality increased with exposure concentration and duration. Hence, standard toxicity test using continuous exposures would underestimate Se toxicity. Risk assessment method using results of continuous exposure would underestimate risk of Se to biota. For double-pulse exposures, cumulative mortality on day 21 was higher when time interval between pulses was shorter. With the same total exposure time, continuous exposure caused higher toxicity than did pulsed exposures due to recovery and tolerance development in D. magna after earlier pulses. Growth and reproduction of surviving D. magna were not affected by pulsed Se exposure due to recovery of D. magna after removal of the pulses. Based on these results, risk assessment for Se should take latent effects and the effect of recovery in to account.     

Acute toxicity of leachates of tire wear material to Daphnia magna--variability and toxic components

Large amounts of tire rubber are deposited along the roads due to tread wear. Several compounds may leach from the rubber and cause toxicity to aquatic organisms. To investigate the toxic effects of tire wear material from different tires, rubber was abraded from the treads of twenty-five tires. Leachates were prepared by allowing the rubber to equilibrate with dilution water at 44 degrees C for 72 h. Then the rubber was filtered from the leachates, and test organisms (Daphnia magna) were added. Forty-eight hour EC50s ranged from 0.5 to >10.0 g l(-1). The toxicity identification evaluation (TIE) indicated that non-polar organic compounds caused most of the toxicity. UV exposure of the filtered tire leachates caused no significant increase in toxicity. However, when tested as unfiltered leachates (the rubber was not filtered from the leachates before addition of D. magna) photo-enhanced toxicity was considerable for some tires, which means that test procedures are important when testing tire leachates for aquatic (photo) toxicity. The acute toxicity of tire wear for Daphnia magna was found to be <40 times a predicted environmental concentration based on reports on the concentration of a tire component found in environmental samples, which emphasizes the need for a more extensive risk assessment of tire wear for the environment.     

Biodegradation in laboratory activated sludge plants and aquatic toxicity of herbicides

The biodegradation and the aquatic toxicity of four herbicides (isoproturon, terbuthylazine, mecoprop, metamitron) were investigated. Laboratory activated sludge plants were used for biodegradation experiments. The biodegradation of mecoprop reached nearly 100%, the other herbicides were not eliminated by biodegradation. The acute Daphnia magna 24-h assay, the algal 72-h inhibition test, and the recently developed lemna growth inhibition 7-d test were applied to evaluate the biological effects of herbicides as original substances. EC 50 and EC 10 values were determined. Algal and lemna test show that isoproturon and terbuthylazine are both much more toxic than mecoprop and metamitron. Daphnids are generally less sensitive against herbicides than plants. Biodegradation and toxicity test were coupled for mecoprop to assess biological long-term effects of possible biodegradation products of this herbicide. The effluents of the laboratory activated sludge units were used in toxicity tests (Daphnia magna 21-d reproduction test, lemna growth inhibition 7-d test). No inhibiting effect on the tested organisms was observed.     

Lactate dehydrogenase activity as an effect criterion in toxicity tests with Daphnia magna straus.

Activity of lactate dehydrogenase (LDH) was used as an effect criterion in toxicity tests with Daphnia magna. In the first part of the work, the conditions for the use of LDH activity in toxicity tests with juveniles and adults of D. magna, were optimized. The influence of parameters such as the number of animals per sample, nutritional status, age and the presence of eggs in the brood chamber were investigated. In the second part of the study, both in vivo and in vitro tests based on the alteration of LDH activity of D. magna were developed and tested using zinc chloride as test substance. The results obtained indicate that LDH activity of D. magna may be used as an indicative parameter in aquatic toxicity tests.     

Acute toxicity of triphenyltin hydroxide to three cladoceran species

The toxicity of an organotin pesticide, triphenyltin hydroxide, was assessed with several freshwater cladoceran species. Daphnia pulex, Daphnia magna, and Ceriodaphnia dubia were exposed for 48 h to triphenyltin hydroxide in static acute toxicity tests. Values of the 48-h trimmed Spearman-Karber EC(50)s for the three species were found to be 14.5, 16.5, and 11.3 microg litre(-1), respectively. Analysis of variance performed on EC(50) values of replicates revealed no significant differences between the three species. Methods were employed which decrease animal handling stress and increase the accuracy and precision of the concentrations.     

Reverse osmosis sampling does not affect the protective effect of dissolved organic matter on copper and zinc toxicity to freshwater organisms

Dissolved organic matter (DOM) plays a significant role in protecting freshwater organisms against metal toxicity. To study this, reverse osmosis (RO) has been widely used as a highly efficient method for rapid collection of large quantities of DOM from natural surface waters. The objective of this study was to examine the potential impact of the RO isolation technique on the protective effects of DOM on the toxicity of copper and zinc to the cladoceran Daphnia magna and the green alga Pseudokirchneriella subcapitata. DOM was concentrated from a natural surface water using RO and at the same time a natural (unconcentrated) surface water was taken. The concentrated DOM was rediluted to the level of the natural water to obtain the so-called reconstituted water. Chemical analyses and toxicity tests were performed with both the natural surface water and the reconstituted water. First, most chemical parameters were not significantly changed by the RO sampling. For both copper and zinc, no significant differences were observed in 48 h-EC50s for D. magna and in 72 h-EC50s for P. subcapitata between the reconstituted water and the natural water. Hence, it may be concluded that reverse osmosis does not significantly affect the protective effect of natural DOM against copper and zinc toxicity.     

Chronic toxicity of diclofenac,carbamazepine and their mixture to Daphnia magna: a comparative two-generational study

Environmental Science and Pollution Research - The chronic toxicity of diclofenac (DCF) and carbamazepine (CBZ) as separate substances and in conjunction with their mixture on Daphnia magna was...     

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.     

Evaluation of genotoxicity and toxicity of water and sediment samples from a Brazilian stream influenced by tannery industries

This paper reports results of genotoxicity and toxicity studies of water and sediment samples collected from the Estancia Velha stream of southern Brazil, a stream transporting both domestic sewage and effluents from regional factories working in the leather industry. Three sites were selected: in the stream headwaters (Site 1), located downstream of an urban area (Site 2), and near the basin outfall (Site 3). Results obtained with Allium cepa showed no evidence of chromosomal mutation, either in water or in sediment, during winter or summer seasons, but samples collected below Site 1 showed high toxicity. Physical and chemical analyses showed high concentrations of pollutants at these sites. Ecotoxicity tests with Daphnia magna and Ceriodaphnia dubia measured toxicity in water from Sites 2 and 3 in summer 2004. A toxic effect on Hyalella azteca was only found in sediment from Site 3 during winter 2003 and summer 2004. The results suggest that the synergy among different compounds in domestic and industrial sewage discharges can make it difficult to maintain system stability.     

Aquatic toxicity of cartap and cypermethrin to different life stages of Daphnia magna and Oryzias latipes

Cartap and cypermethrin, which are among the most widely used pesticides in many countries, are considered safe because of their low mammalian toxicity and their low persistence in the environment. However, recent findings of endocrine-disrupting effects and developmental neurotoxicity have raised concerns about the potential ecological impacts of these pesticides. We evaluated the aquatic toxicity of cartap [S,S'-(2-dimethylaminotrimethylene) bis(thiocarbamate), unspecified hydrochloride] and cypermethrin [(RS)-alpha-cyano-3-phenoxybenzyl-(1RS,3RS,1RS,3SR)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane carboxylate], both individually and combined, on different life stages of the freshwater cladoceran Daphnia magna and a freshwater teleost, Japanese medaka (Oryzias latipes). The 96-hr Daphnia median effective concentrations (EC50s) for cartap and cypermethrin were 91.0 microg/L and 0.00061 microg/L, respectively. Rapid recovery of Daphnia was observed after short-term pulsed exposure to cartap and cypermethrin; there were no adverse effects on reproduction or survival 20 d after a 24 hr exposure to cartap up to 1240 microg/L and cypermethrin up to 1.9 microg/L. Chronic continuous exposure (for 21 d) of 7-d-old Daphnia to cypermethrin significantly reduced the intrinsic population growth rate in a concentration-dependent manner. However, because the intrinsic population growth rates were all above zero, populations did not decrease even at the highest experimental concentration of 200 ng/L. Exposure of Daphnia neonates (< 24 hr old) to cypermethrin for 21 d caused significant, sub-lethal reproduction-related problems, such as increased time to first brood, reduced brood size, and reduced total brood number, at 0.0002, 0.002, and 0.2 ng/L cypermethrin, but the intrinsic population growth rate was not significantly affected. Oryzias latipes was relatively more resistant to both pesticides. In particular, embryos appeared to be more resistant than juveniles or adults, which may be partly due to the protective role of the chorion. The incidence of larval fish deformity was significantly higher after a 96 hr exposure to as low as 250 microg/L of cartap or 40 microg/L of cypermethrin. The mixture of both compounds showed no synergistic toxicity. The extremely high acute-to-chronic ratio suggests that the standard acute lethal toxicity assessment might not reflect the true environmental hazards of these frequently used pesticides. Ecological hazard assessments of long-term low dose or pulsed exposures to cartap and cypermethrin may reveal more realistic consequences of these compounds in surface water.     

Comparative acute toxicity of organic pollutants and reference values for crustaceans. I. Branchiopoda, Copepoda and Ostracoda

The acute toxicity of 468 organic pollutants to planktonic crustaceans (Branchiopoda, Copepoda and Ostracoda) from pre-existing data was compared by means of statistical analysis and relative tolerance indices (Trel). A surrogate species commonly used in toxicity bioassays (Daphnia magna) showed toxicity levels--within one order of magnitude--similar to all other Cladocera species, at least for 82% of the chemicals studied. All neurotoxic insecticides except neonicotinoids, PCBs, organometallic compounds and PAHs are the most toxic substances to these organisms. Sensitivity levels among taxa were compared for individual chemicals as well as groups of chemicals with similar characteristics. Whilst there are marked differences in sensitivity among taxa and particular groups of chemicals, no consistent trends were found for freshwater and saltwater species in relation to the latter groups. No correlation between LC50 and size of these organisms was found other than by chance, making extrapolations based on allometric equations impossible.     

Sediment toxicity and stormwater runoff in a contaminated receiving system: consideration of different bioassays in the laboratory and field.

Several field and laboratory assays were employed below an urban storm sewer outfall to define the relationship between stormwater runoff and contaminant effects. Specifically, two bioassays that measure feeding rate as a toxicological endpoint were employed in the field and in the laboratory, along with bioassays measuring survival and growth of test organisms. In 7 to 10 d in situ exposures, amphipod leaf disc processing, growth and survival were monitored. Different exposure scenarios were investigated by varying the mesh size (74 microns or 250 microns mesh) and method of deployment (water column, sediment surface, or containing sediment) of in situ exposure chambers. Hyalella azteca, Daphnia magna, and Pimephales promelas survival were monitored in 48 h in situ exposures. Feeding inhibition was investigated via enzyme inhibition of H. azteca and D. magna and via leaf disc processing measurements of the detritivore H. azteca. Additionally, we investigated the extent of phototoxicity at this site via field exposures in sun and shade and laboratory exposures with and without UV light. The measurement of detritivore leaf disc processing, and thus its usefulness as an endpoint, was hindered by individual variability in the amount of leaf consumed and by leaf weight gain during the summer field exposures. For D. magna, enzyme inhibition measured in a laboratory exposure did not reveal the toxicity observed in field exposures. For H. azteca, enzyme inhibition measured in the laboratory indicated toxicity similar to that observed in short term chronic in situ exposures. Enzyme inhibition also did not detect differences in toxicity due to variations in flow conditions. There were no statistically significant effects of any exposure on P. promelas survival or H. azteca growth, and there were no statistically significant effects due to mesh size or sun exposure. Survival of H. azteca was the most sensitive and the least variable endpoint. Effects on survival were noted in the same treatments over short-term chronic exposures in the laboratory and in situ. Significant differences in survival were noted due to the method of deployment under low flow conditions. In situ chambers containing sediment resulted in greater mortality in the 10 d low flow in situ experiments. Under high flow conditions, significant reductions in survival and leaf disc processing were noted under all methods of deployment at the two impacted sites over a 7 d exposure. Also under high flow conditions, significantly greater mortality of H. azteca was reported at the downstream field site when sediment was included in the chamber at deployment. These results suggest that significant toxicity at this site is due to accumulation of contaminants in the sediment and the mobilization of these contaminants during a storm event. In situ exposures detected toxicity not observed in laboratory exposures. These results suggest that a combination of laboratory and field bioassays is most useful in defining field effects.     

Effect of food level on the acute and chronic responses of daphnids to lindane

The toxic effects of lindane on the zooplankton communities may be strongly related to the population fitness, which is highly dependent on food availability. In order to test this hypothesis, acute (immobilisation) and chronic (life-history) responses of Daphnia longispina and Daphnia magna, reared at different food levels (low, normal, and high), were assessed in laboratorial exposures to several concentrations of lindane. A bifactorial design was employed (food level versus lindane concentration) for both species. Results showed that lindane was toxic to both D. magna and D. longispina, within a similar range. However, lindane toxicity to daphnids was dependent on food level, suggesting that the latter is an important factor to take into account when assessing the toxic effects of lindane on zooplankton communities.     

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 identification and reduction of wastewaters from a pigment manufacturing factory

In this study, major toxicants in pigment wastewaters (i.e. raw wastewater and effluent) were determined by toxicity identification evaluations (TIEs), and changes in their toxicities due to combined gamma-ray (gamma-ray) and ozone treatments were evaluated. From TIE results using Daphnia magna, Cr(VI) and o-toluidine were identified as major toxicants in the raw wastewater with concentrations of 2.47 and 25.3mg l(-1), respectively. This was confirmed by subsequent spiking and mass balance approaches. For effluent, TIE results suggested that organic anions were likely responsible for the observed toxicities. Toxicity reduction tests showed that gamma-rays with ozone treatment after coagulation was more efficient in reducing toxicities in the raw wastewater (3.9-2.0 TU) than gamma-ray treatment alone (3.9-3.1 TU). For pigment effluent, gamma-ray/O3 treatment resulted in a complete removal of the acute toxicity.     

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.     

Influences of macroalga-derived dissolved organic carbon on the aquatic toxicity of copper and cadmium

In this study, the effect of dissolved organic carbon (DOC) derived from macroalga (Sargassum) on the acute toxicity of copper (Cu) and cadmium (Cd) to a freshwater cladoceran (Daphnia magna) was investigated. Potassium-loaded macroalga was incubated with ultrapure water to extract macroalgal DOC, which was then spiked with the constituents of the Elendt M7 hard water media. The 48 h median lethal concentration of Cu increased linearly with DOC levels but that of Cd was relatively independent of DOC levels (0-44 mg l(-1)). The independence of Cd toxicity on DOC level might be due to the competitive effect of high calcium concentrations in the media with Cd for the binding sites of DOC. The decreased Cu toxicity was a result of reduced Cu uptake as evidenced in a separate accumulation test. Also, the capability of the macroalgal DOC on reducing Cu toxicity was found to be comparable to DOC tested in other studies. Therefore, the present study suggested that the biosorption treatment process using macroalgae should consider the effect of DOC release from the biomass as a step of modifying the metal toxicity as well as influencing metal biosorption capacity.