Study on acute toxicity and structure-activity relationship of zebrafish (Danio rerio) exposed to naphthoquinones

In this paper, we evaluated the acute toxicity of five naphthoquinone compounds, expressed as median lethal concentration at 96 h (LC₅₀) using zebrafish as a model. The five compounds were classified as harmful or very toxic. The Gaussian method was used to calculate the quantitative-chemical parameters of each compound. Based on the structure-activity relationship analysis, the interaction between the naphthoquinones and the target is likely mediated by 1-carbonyl and the hydrophobic fraction substituted in α -position of naphthoquinone via hydrogen bonding and hydrophobic interactions. Our results provide a foundation for evaluating the aquatic ecological risk and the mode of action of naphthoquinones in the environment.     

Classification of chemicals according to mechanism of aquatic toxicity: an evaluation of the implementation of the Verhaar scheme in Toxtree

A number of mechanisms have been identified that can lead to (acute) aquatic toxicity. The assignment of compounds to a particular mechanism of action is important in the development and utilisation of (quantitative) structure-activity relationships ((Q)SARs) for ecotoxicity. Assignment to a mechanism can be difficult; however in 1992 Verhaar et al. published a series of structural rules which aimed to classify compounds according to mechanism of action. Recent interest has seen the Verhaar rules coded into freely available software such as Toxtree available from the European Chemicals Bureau. To date, a complete critical evaluation of these rules has been lacking. Therefore, the aim of this study was to evaluate the Toxtree implementation of the Verhaar rules using two well characterised aquatic toxicity datasets (Pimephales promelas and Tetrahymena pyriformis phenol databases) for which mechanisms of toxic action are well established. The present study highlights rule, and possible coding, errors that may lead to misclassifications. Improvements to both the rules and prediction architecture are suggested. In particular further rules to improve predictions for polar narcosis (class 2) are suggested.     

A multiple testing approach for hazard evaluation of complex mixtures in the aquatic environment: the use of diesel oil as a model

Traditional single species toxicity tests and multiple component laboratory-scaled microcosm assays were combined to assess the toxicological hazard of diesel oil, a model complex mixture, to a model aquatic environment. The immediate impact of diesel oil dosed on a freshwater community was studied in a model pond microcosm over 14 days: a 7-day dosage and a 7-day recovery period. A multicomponent laboratory microcosm was designed to monitor the biological effects of diesel oil (1.0 mg litre(-1)) on four components: water, sediment (soil + microbiota), plants (aquatic macrophytes and algae), and animals (zooplanktonic and zoobenthic invertebrates). To determine the sensitivity of each part of the community to diesel oil contamination and how this model community recovered when the oil dissipated, limnological, toxicological, and microbiological variables were considered. Our model revealed these significant occurrences during the spill period: first, a community production and respiration perturbation, characterized in the water column by a decrease in dissolved oxygen and redox potential and a concomitant increase in alkalinity and conductivity; second, marked changes in microbiota of sediments that included bacterial heterotrophic dominance and a high heterotrophic index (0.6), increased bacterial productivity, and the marked increases in numbers of saprophytic bacteria (10 x) and bacterial oil degraders (1000 x); and third, column water acutely toxic (100% mortality) to two model taxa: Selenastrum capricornutum and Daphnia magna. Following the simulated clean-up procedure to remove the oil slick, the recovery period of this freshwater microcosm was characterized by a return to control values. This experimental design emphasized monitoring toxicological responses in aquatic microcosm; hence, we proposed the term 'toxicosm' to describe this approach to aquatic toxicological hazard evaluation. The toxicosm as a valuable toxicological tool for screening aquatic contaminants was demonstrated using diesel oil as a model complex mixture.     

Nitrate causes deleterious effects on the behaviour and reproduction of the aquatic snail Potamopyrgus antipodarum (Hydrobiidae, Mollusca)

Nitrate (NO₃ ^?) is present in aquatic ecosystems as a natural component of the nitrogen cycle. However, in the last decades, several human activities are the causes of the rising amounts of organic matter and inorganic nitrogen nutrients in aquatic ecosystems, causing notable increase of nitrate above background natural levels. In spite of the toxicity of nitrate to aquatic animals, there are relatively few studies on the chronic toxicity of this compound to invertebrates. The aim of our study is to assess the effect of chronic (35 days) exposure to nitrate on the behaviour (velocity of movement) and reproduction (number of newborns) of the aquatic snail Potamopyrgus antipodarum. Four actual concentrations of nitrate were used (21.4, 44.9, 81.8 and 156.1 mg?N-NO₃ ^?/L). In each treatment, 12 animals were individually monitored for velocity (weekly) and newborn production (every 3–4 days). Velocity was recorded using quantitative video monitoring. Our results showed that nitrate did not cause mortality, but it reduced the velocity of movement (at 44.9, 81.8 and 156.1 mg?N-NO₃ ^?/L) and number of live newborns (in all tested concentrations). Reproductive impairment was caused at realistic nitrate concentrations which is relevant to the risk assessment of this compound. Our study contributes to the knowledge of the chronic effects of nitrate on the behaviour and reproduction of an aquatic snail.     

Effects of a major municipal effluent on the St. Lawrence River: A case study

The St. Lawrence River (SLR) is the second largest waterway in North America. The discharge of the City of Montreal wastewater treatment plant (WWTP) represents the largest volume of treated wastewaters being released into the river. It also ranks as the largest sewage treatment plant of its kind in North America. Over the last decade, intensive multidisciplinary research has focused on assessing the impacts of Montreal wastewater effluents on the SLR. We describe the major findings of these investigations, including the determination of the fate of contaminants, bioaccumulation in fish and invertebrates, ecotoxicological measurements of aquatic animal health, evaluation of endocrine disruption, parasitism in fish, and combined effects of multiple stressors on the SLR. Impacts of the effluents from the WWTP on aquatic organisms from the SLR are both toxicological and ecological, demonstrating the need for an integrated view of the impacts of municipal effluents on aquatic ecosystems.     

水生植物应用于富营养化控制的研究趋向

阐述了水生植物在治理富营养化水体中的作用机理和研究现状,指出了水生植物治理富营养化水体存在的问题,展望了水生植物在治理富营养化水体方面的发展方向。     

Biodegradability of antineoplastic compounds in screening tests: influence of glucosidation and of stereochemistry

Some pharmaceuticals such as antineoplastics are carcinogenic, mutagenic, teratogenic and fetotoxic. Antineoplastics and their metabolites are excreted by patients into waste water. In laboratory testing the frequently used isomeric anti-tumour agents cyclophosphamide (CP) and ifosfamide (IF) were shown to be not biodegradable. They are not eliminated in municipal sewage treatment plants and therefore detected in their effluents. Structural related compounds are beta-D-glucosylisophosphoramidmustard (beta-D-Glc-IPM; INN = glufosfamide) and beta-L-glucosylisophosphoramidmustard (beta-L-Glc-IPM). beta-L-Glc-IPM has no antineoplastic effects whereas beta-D-Glc-IPM is active against tumours. In contrast to IF and CP and almost all other investigated antineoplastics beta-D-Glc-IPM is inherently biodegradable. Improved biodegradability of beta-D-Glc-IPM compared to IF shows that reducing the impact of pharmaceuticals on the aquatic environment is feasible by changing the chemical structure of a given compound exerting a similar mode of action and therapeutic activity. Stereochemistry may be crucial for pharmaceutical activity of the compounds as well as for its biodegradability in the environment.     

Leaching of azoxystrobin and its degradation product R234886 from Danish agricultural field sites

The objective was to estimate leaching of the fungicide azoxystrobin (methyl (αE)-2-[[6-(2-cyanophenoxy)-4-pyrimidinyl]oxy]-α-(methoxymethylene)benzene-acetate) and one of its primary degradation products R234886 ([(E)-2-(2-[6-cyanophenoxy)-pyrimidin-4-yloxyl]-phenyl-3-methoxyacrylic acid], major fraction) at four agricultural research fields (one sandy and three loamy) in Denmark. Water was sampled from tile drains, suction cups and groundwater wells for a minimum period of two years after application of azoxystrobin. Neither azoxystrobin nor R234886 were detected at the sandy site, but did leach through loamy soils. While azoxystrobin was generally only detected during the first couple of months following application, R234886 leached for a longer period of time and at higher concentrations (up to 2.1 μg L⁻¹). Azoxystrobin is classified as very toxic to aquatic organisms and R234886 as very harmful. Our study shows that azoxystrobin and R234886 can leach through loamy soils for a long period of time following application of the pesticide and thereby pose a potential threat to vulnerable aquatic environments and drinking water resources. We thus recommend the inclusion of azoxystrobin and R234886 in pesticide monitoring programmes and further investigation of their long-term ecotoxicological effects.     

Effects assessment: boron compounds in the aquatic environment

In previous studies, boron compounds were considered to be of comparatively low toxicity in the aquatic environment, with predicted no effect concentration (PNEC) values ranging around 1 mg B/L (expressed as boron equivalent). In the present study, we describe an evaluation of toxicity data for boron available for the aquatic environment by different methods.For substances with rich datasets, it is often possible to perform a species sensitivity distribution (SSD). The typical outcome of an SSD is the Hazardous Concentration 5% (HC₅), the concentration at which 95% of all species are protected with a probability of 95%. The data set currently available on the toxic effects of boron compounds to aquatic organisms is comprehensive, but a careful evaluation of these data revealed that chronic data for aquatic insects and plants are missing. In the present study both the standard assessment factor approach as well as the SSD approach were applied. The standard approach led to a PNEC of 0.18 mg B/L (equivalent to 1.03 mg boric acid/L), while the SSD approach resulted in a PNEC of 0.34 mg B/L (equivalent to 1.94 mg boric acid/L). These evaluations indicate that boron compounds could be hazardous to aquatic organisms at concentrations close to the natural environmental background in some European regions. This suggests a possible high sensitivity of some ecosystems for anthropogenic input of boron compounds. Another concern is that the anthropogenic input of boron could lead to toxic effects in organisms adapted to low boron concentration.     

水环境数学模型的研究进展

在作者多年研究工作和查阅大量文献资料的基础上,本文综述了环境数学模型国内外的研究现状、发展历史及未来趋势。重点介绍了这方面研究的最新进展。该文还介绍了本领域所涉及的理论和实际应用问题,提出了今后值得进行研究的若干前沿课题,给出了60余篇关于水环境数学模型研究的主要参考文献目录。     

AMEG: the new SETAC advisory group on aquatic macrophyte ecotoxicology

Introduction and background

Primary producers play critical structural and functional roles in aquatic ecosystems; therefore, it is imperative that the potential risks of toxicants to aquatic plants are adequately assessed in the risk assessment of chemicals. The standard required macrophyte test species is the floating (non-sediment-rooted) duckweed Lemna spp. This macrophyte species might not be representative of all floating, rooted, emergent, and submerged macrophyte species because of differences in the duration and mode of exposure; sensitivity to the specific toxic mode of action of the chemical; and species-specific traits (e.g., duckweed's very short generation time).

Discussion and perspectives

These topics were addressed during the workshop entitled “Aquatic Macrophyte Risk Assessment for Pesticides” (AMRAP) where a risk assessment scheme for aquatic macrophytes was proposed. Four working groups evolved from this workshop and were charged with the task of developing Tier 1 and higher-tier aquatic macrophyte risk assessment procedures. Subsequently, a SETAC Advisory Group, the Macrophyte Ecotoxicology Group (AMEG) was formed as an umbrella organization for various macrophyte working groups. The purpose of AMEG is to provide scientifically based guidance in all aspects of aquatic macrophyte testing in the laboratory and field, including prospective as well as retrospective risk assessments for chemicals. As AMEG expands, it will begin to address new topics including bioremediation and sustainable management of aquatic macrophytes in the context of ecosystem services.     

Evaluation of surface water quality using an ecotoxicological approach: a case study of the Alqueva Reservoir (Portugal)

Background, aim, and scope  

Freshwater reservoirs can be impacted by several hazardous substances through inputs from agricultural activity, sewage discharges, and groundwater leaching and runoff. The water quality assessment is very important for implementation of the monitoring and remediation programs to minimize the risk promoted by hazardous substances in aquatic ecosystems. Evaluation of the degree of contamination of aquatic environments must not take in account only its chemical characterization but it must be complemented with biological assays, which determine potential toxic effects and allows an integrated evaluation of its effects in populations and aquatic ecosystem communities. The application of this type of strategy has clear advantages allowing a general evaluation of the effects from all the water components, including those due to unknown substances and synergic, antagonistic, or additive effects. There are only a few studies that reported ecotoxicological acute end points, for the assessment of surface water quality, and the relationship among toxicity results and the anthropogenic pollution sources and the seasonal period. The aim of this study was to assess the ecotoxicological characterization of the surface water from Alqueva reservoir (South of Portugal) and to evaluate the influence of anthropogenic sources of pollution and their seasonal variation in its toxicity. The construction of Alqueva reservoir was recently finished (2002) and, to our knowledge, an ecotoxicological assessment of its surface water has not been performed. Because of that, no information is available on the possible impact of pollutants on the biota. The surface water toxicity was assessed using acute and chronic bioassays. The results are to be used for developing a monitoring program, including biological methods.     

Biodegradability and transformation of human pharmaceutical active ingredients in environmentally relevant test systems

Human pharmaceutical active ingredients that are orally or parenterally administered may be metabolised in the body and after excretion may be further transformed in the receiving environmental compartments. The optimal outcome from an environmental point of view—complete mineralisation—is rarely observed. Small molecule pharmaceuticals are commonly not readily biodegradable according to Organisation for Economic Cooperation and Development (OECD) 301 tests. However, primary transformation is often observed. To gain information on the transformation of active ingredients in the environment, long-term studies like transformation in aquatic water/sediment systems according to OECD guideline 308 are required for the environmental risk assessment for human active pharmaceutical ingredients. Studies received until mid 2010 as part of the dossiers for marketing authorisation applications were evaluated concerning transformation products. The evaluation revealed that in 70 % of the studies, at least one transformation product (TP) is formed above 10 % of the originally applied dose, but in only 26 % of the studies are all TP identified. The evaluation also revealed that some TP of pharmaceutical active ingredients show a considerably longer DT₅₀ compared to the parent compound. An example is the TP (val)sartan acid that is formed from an antihypertensive compound.     

有毒物质对水生态系统效应研究的进展

本文总结了近年来有毒物质对水生态系统的生态效应研究现状及发展趋势,提出了今后测定有毒物质生态效应应该注意的问题。     

Organochlorine contaminants in cormorant, darter, egret, and ibis eggs from South Africa

During the last 15 years, no research has been published on the levels of pesticides in bird eggs from South Africa, despite the high levels found previously. We analysed eggs from African darter, cattle egret, reed cormorant, African sacred ibis, as well as single eggs from some other species, and found HCB, DDTs, HCHs, chlordanes and PCBs at detectable levels. The presence of mirex in all species was unexpected, since this compound was never registered in South Africa. It also seemed as if terrestrial feeding birds had higher DDE:PCB ratios when compared with aquatic feeding birds. Except for chlordane, the African darter eggs had the highest levels of all other compounds (mean 370 and 300 ng g(-1) ww Sigma pesticides and Sigma PCBs, respectively). Multivariate analysis clearly distinguished the aquatic and terrestrially feeding birds on pollution profile. The African darter (aquatic feeding) and the cattle egret (terrestrial feeding) would be good indicator candidates. Eggshell thinning was detected in the African darter, and was associated with most of the compounds, including DDE and PCBs. We raise a concern that generally longer living birds in warmer climates, laying fewer eggs per clutch, might be at increased risk when compared with trophically similar birds exposed to equivalent levels of pollution in colder climates. Given the scarcity of water and the high biodiversity in Southern Africa, climate change will exert strong pressure, and any additional anthropogenic contamination at levels that can cause subtle behavioural, developmental and reproductive changes, can have serious effects.     

DNA and chromosomal damage induced in fish (Anguilla anguilla L.) by aminomethylphosphonic acid (AMPA)—the major environmental breakdown product of glyphosate

The assessment of the direct impact of breakdown products of pesticide components on aquatic wildlife is ecotoxicologically relevant, but frequently disregarded. In this context, the evaluation of the genotoxic hazard posed by aminomethylphosphonic acid (AMPA—the major natural degradation product of glyphosate) to fish emerges as a critical but unexplored issue. Hence, the main goal of the present research was to assess the AMPA genotoxic potential to fish following short-term exposures (1 and 3 days) to environmentally realistic concentrations (11.8 and 23.6 μg L^?1), using the comet and erythrocytic nuclear abnormalities (ENA) assays, as reflecting different levels of damage, i.e. DNA and chromosomal damage, respectively. Overall, the present findings pointed out the genotoxic hazard of AMPA to fish and, subsequently, the importance of including it in future studies concerning the risk assessment of glyphosate-based herbicides in the water systems.     

Development of aquatic life criteria in China: viewpoint on the challenge

While more developed countries have a well-established systems to develop water quality criteria (WQC), little research has been done on the adequacy of the current WQC to protect endemic species of China. In order to maintain the health of aquatic ecosystems in China, a series of projects to establish national WQC based on regional characteristics has recently been initiated. However, the establishment of a completely novel methodology would be costly and time consuming. Also, due to the similarities in physiologies and natural histories of classes of aquatic organisms, there is no reason to believe that WQC would not be sufficient to protect unique species in China. This review was undertaken to identify key outstanding issues regarding establishment of aquatic life criteria (ALC) to be applied in China, including prioritization of chemicals, test species, mode of action, field/semi-field data, and methods of aggregating the information and calculating the ALC. This was used to identify the principle issues that need to be addressed in order to better understand the methods for development of criteria for the protection of aquatic life and provide a reference to China and other developing countries committed to the establishment of their own WQC system.     

Toxic Effects of Crude Oil Combined with Oil Cleaner Simple Green on Yolk-sac Larvae and Adult Rainbow Trout Oncorhynchus mykiss (4 pp)

Background, Goal and Scope Cleaner CRYSTAL Simple Green (SG) was used for the cleanup of the oil spill in the Baltic Sea near Lithuania in 2001. No scientific data are available on the effects and consequences of its application for local aquatic life. The aim of this study was to determine and compare sublethal effects of a) solution SG; b) crude oil alone; c) SG in combination with oil on rainbow trout Oncorhynchus mykiss at different stages of its development in laboratory conditions.Methods Laboratory studies were performed on adult rainbow trout (4-day duration) and on yolk-sac larvae (25-day duration) evaluating their biological parameters. Concentrations of water-soluble and thin-dispersed fractions of petroleum hydrocarbons were measured using gas chromatography.Results and Discussion SG solution (0.5 mg/l) did not affect the survival of larvae and adult fish, and no significant changes were determined in respiratory parameters of the exposed larvae and adult fish. The most expressed alterations were found in morphological parameters (a decrease in the average body mass) of larvae and in haematological indices (a decrease in the leukocyte count) of adult fish at the end of the tests. Crude oil (1610 mg/l) did not affect the survival of adult fish during the 4-day exposure. An increase in larvae mortality rate (~ 36%) was recorded at the end of the tests. A significant decrease in the average body mass and heart rate of larvae as well as in gill ventilation frequency of larvae and adult fish were determined. SG combined with oil induced an increase in larval mortality  46% of individuals died at the end of the tests. No mortality was recorded in adult fish. The average body mass and heart rate of larvae were significantly decreased. Marked changes were also found in respiratory parameters (gill ventilation frequency of larvae and adult fish significantly decreased, while “coughing” rate increased). A 1-day, 2-day exposure of fish to SG combined with oil induced a significant decrease in the leukocyte count of adult fish, which was also determined at the end of the tests. The augmentation of adverse impact could be explained by the data obtained from our studies. When SG was added into dilution water with crude oil the concentration of petroleum hydrocarbons in the mixture increased 3 ~ 4.5 times after 24 h and 96 h, respectively. Conclusions The comparative study of the effects of crude oil alone, SG and SG combined with oil showed that their toxic effects on fish differed. Oil combined with SG was found to be more toxic to fish (larvae and adults) than SG alone and oil alone. Fish at early stages of development (yolk-sac larvae) were more sensitive to the effects of the compounds studied than adults.Recommendations and Outlook To diminish the negative impact of oil spill cleanup using chemicals on aquatic ecosystems, it is recommended to carry out more comprehensive studies of their effects and after-effects in laboratory conditions using a wide scale of local aquatic organisms. The selected species of the most sensitive aquatic organisms should include those which are unable to escape the impact of combined action of oil and cleaners. Special attention should be directed to the research of effects of these pollutants on studied organisms at their most sensitive stages of life (reproduction, hatching, early stages of development), as after-effects of exposure to pollutants may be observed in future generations.