Genotoxicity effects on Geophagus brasiliensis fish exposed to Doce River water after the environmental disaster in the city of Mariana, MG, Brazil / Efeitos da genotoxicidade em peixes da espécie Geophagus brasiliensis expostos a água do Rio Doce após o desastre ambiental na cidade de Marina, MG, Brasil

Abstract The Doce River basin has suffered the largest environmental accident ever occurred in Brazil with the influx of tailings from Fundão and Santarém, belonging to Samarco mining company, due to the disaster in Mariana. A spill between 50 and 60 million m3 of tailings was estimated by the company. According to Samarco, the wastewater was composed mainly of clay, silt and heavy metals like iron, copper and manganese. Thereby, the objective of the present study was evaluated the genotoxic damage in juvenile of Geophagus brasiliensis (Quoy e Gaimard, 1824) exposed to Doce river water before (DRWBA - Doce River water before acident) and after (DRWAA - Doce River water after acident) the influx of tailings from the Germano and Santarém Dam disasters in Mariana, MG, Brazil. For this, 24 individuals of the species G. brasiliensis (obtained on IFES/ALEGRE fish culture) were submitted to a bioassay with three treatments and eight replicates. The treatments were: 1) Control water (water from the urban water supply system, filtered with a 0.45 µm membrane), 2) DRBA and 3) DRAA. After 96 h, these fishes were anesthetized to remove blood for evaluation of genotoxic damage (micronucleus and comet). For the bioassay, a total of 80 L of The Doce River water were collected before the influx of tailings and after the influx and then submitted to metal quantification analysis. Fish exposed to DRWBA and DRWAA treatments showed a significant increase in both the number of erythrocyte micronuclei and the DNA damage index in relation to the control fish; however, they did not present any differences between the two treatments. The results demonstrate that the DRWBA treatment was already genotoxic for the fish, mainly due to dissolved Cu concentrations in the water. The DRWAA treatment probably presented genotoxicity due to the increase in the dissolved fraction and synergistic effects of several metals found in the tailings of the Mariana accident.

Resumo A bacia do Rio Doce sofreu o maior acidente ambiental com o influxo de rejeitos de Fundão e Santarém, pertencentes à empresa de mineração Samarco, devido ao desastre em Mariana. Um derramamento entre 50 e 60 milhões de m3 de rejeitos foi estimado pela empresa. De acordo com a Samarco, o rejeito despejado era composto principalmente de argila, silte e alguns metais pesados como ferro, cobre e manganês. Com isso, o presente estudo teve como objetivo avaliar os danos genotóxicos em juvenis de Geophagus brasilienses expostos a água do rio Doce antes (DRWAA - água do Rio Doce antes do acidente) e depois (DRWBA- água do Rio Doce depois do acidente) da chegada dos rejeitos do rompimento das barragens de Germano e Santarém em Mariana, MG, Brasil. Para isso, 24 indivíduos da espécie G. brasilienses (obtidos na piscicultura do IFES/ALEGRE) foram submetidos a um bioensaio com três tratamentos e oito réplicas. Os tratamentos eram: 1) Controle (com água do abastecimento urbano, filtrada com filtro analítico de 0,45 µm); 2) DRWBA e 3) DRWAA. Após um período de 96 h, esses peixes foram anestesiados para retirada de sangue para avaliação dos danos genotóxicos (micronúcleo e cometa). Para a realização do bioensaio, um total de 80 L de água do Rio Doce foram coletados antes da chegada dos rejeitos e outros 80 L foram coletados depois da chegada dos rejeitos e ambas foram submetidas a análises de quantificação de metal. Os peixes expostos ao DRWBA e ao DRWAA apresentaram um aumento significativo na quantidade de micronúcleos eritrocitários e no índice de danos do DNA em relação aos peixes controle, no entanto não apresentaram diferenças entre si. Os resultados obtidos demonstram que a DRWBA já era genotóxica para os peixes, principalmente, em função das concentrações de Cu dissolvido na água. A DRWAA apresentou genotixicidade, provavelmente, em função do aumento da fração dissolvida e do efeito sinérgico de diversos metais presentes nos rejeitos do acidente de Mariana.

Target site model: Predicting mode of action and aquatic organism acute toxicity using Abraham parameters and feature-weighted k-nearest neighbors classification.

A database of 1480 chemicals with 47 associated modes of action compiled from the literature encompasses a wide range of chemical classes (alkanes, polycyclic aromatic hydrocarbons, pesticides, and polar compounds) and includes toxicity data for 79 different aquatic genera. The data were split into a calibration group and a validation group (80/20) to apply k-nearest neighbors (k-NN) methodology to predict the toxic mode of action for the compound. Other approaches were tested (support vector machines and linear discriminant analysis) as well as variations in the k-NN technique (distance weighting, feature weighting). Best-prediction results were found with k = 3, in a voting platform with optimized feature weighting. Using the predicted mode of action, the appropriate polyparameter target site model for that mode of action is applied to calculate the 50% lethal concentration (LC50). Predicted LC50s for the validation database resulted in a root-mean squared error (RMSE) of 0.752. This can be compared to an RMSE of 0.655 for the same validation set using the reference mode of action labels. The complete database resulted in an RMSE of 0.793 for reference mode of action labels. This confirms that the classification model has sufficient accuracy for predicting the mode of action and for determining toxicity using the target site model. Environ Toxicol Chem 2019;38:375-386. © 2018 SETAC.

Simultaneous in-vial acetylation solid-phase microextraction followed by gas chromatography tandem mass spectrometry for the analysis of multiclass organic UV filters in water.

UV filters are a class of emerging contaminants that are widely used in personal care products (PCPs) and that can be detected at low concentrations in the aquatic environment (ngL-1). Sensitive modern analytical methods are then mandatory to accurately analyze them. A methodology based on solid-phase-microextraction (SPME), considered as a 'Green Chemistry' technique, followed by gas chromatography-tandem mass spectrometry (GC-MS/MS) has been developed for the simultaneous analysis of 14 UV filters of different chemical nature in environmental and recreational waters. In-vial low-cost derivatization was carried out to improve chromatographic performance of phenolic compounds. The extraction parameters (fiber coating, extraction mode, and salt addition) were optimized by means of experimental designs in order to achieve reliable conditions. Finally, the SPME-GC-MS/MS method was validated in terms of linearity, accuracy and precision with LODs in the low ngL-1 level. Its application to the analysis of 28 different samples including sea, river, spa, swimming pool, and aquapark waters, enabled the detection of 11 target UV filters at concentration levels up to 540µgL-1, highlighting the presence of OCR in all analyzed samples and of 2EHMC (proposed to be considered as priority pollutant) in 79% of them.

Concentration, composition, bioavailability, and N-nitrosodimethylamine formation potential of particulate and dissolved organic nitrogen in wastewater effluents: A comparative study.

Wastewater-derived organic nitrogen (org-N) can act as both nutrients and carcinogenic nitrogenous disinfection byproduct precursors. In this study, the concentration, composition, bioavailability, and N-nitrosodimethylamine (NDMA) formation potential of particulate organic nitrogen (PON) from three different municipal wastewater treatment plants were characterized and compared with that of effluent dissolved organic nitrogen (DON). The average effluent PON and DON concentrations ranged from 0.09 to 0.55mgN/L and from 0.91 to 1.88mgN/L, respectively. According to principal component analysis, org-N composition and characterization differed in PON and DON samples (n=20). Compared with DON, PON tended to be enriched in protein and nucleic acids, and showed a more proteinaceous character. Composition of org-N functional groups estimated from the X-ray photoelectron spectroscopy N 1s spectra indicate no significant differences in the molecular weight distribution of the protein-like materials between PON and DON. Moreover, PON exhibited a significantly higher bioavailability (61.0±13.3%) compared to DON (38.5±12.4%, p˂0.05, t-test) and a significantly higher NDMA yields (791.4±404.0ng/mg-N) compared to DON (374.8±62.5ng/mg-N, p˂0.05, t-test). Accordingly, PON contributed to approximately 12.3-41.7% of the total bioavailable org-N and 22.0-38.4% of the total NDMA precursors in wastewater effluents. Thus, the potential adverse effects of PON on wastewater discharge and reuse applications should not be overlooked, even though it only accounted for 7.4-26.8% of the total effluent org-N.

A meta-analysis synthesizing the effects of pesticides on swim speed and activity of aquatic vertebrates.

Pesticide contaminants are ubiquitous in aquatic environments and pose a threat to biodiversity. Pesticides also have diverse mechanisms of action that make it difficult to identify impacts on exposed wildlife. Behavioral measures represent an important link between physiological and ecological processes, and are often used to generalize sub-lethal effects of pesticide exposure. In order to bridge the toxicological and behavioral literature, and identify chemical classes that denote the largest threat, we conducted a meta-analysis summarizing the effects of pesticides on swim speed and activity of aquatic vertebrates. We found that exposure to environmentally relevant concentrations of pesticides reduced the swim speed of exposed amphibians and fish by 35%, and reduced overall activity by 72%. There were also differences in the magnitude of this effect across chemical classes, which likely reflect underlying physiological processes. Pyrethroids, carbamates, and organophosphates all produced a large decrease in swim speed, where as phosphonoglycines and triazines showed no overall effect. Pyrethroids, carbamates, organophosphates, organochlorines, and organotins also produced a large decrease in activity, while phosphonoglycines had no overall effect, and triazines had the opposite effect of increasing activity. Our results indicate that even sub-lethal concentrations of pesticides have a strong effect on critical behaviors of aquatic vertebrates, which can affect fitness and alter species interactions. We expect our synthesis can be used to identify chemical classes producing the largest sub-lethal effects for further research and management.

Transformation/dissolution characteristics of a nickel matte and nickel concentrates for acute and chronic hazard classification.

For the purposes of aquatic hazard classification under the United Nations Globally Harmonized System of Classification (UNGHS), we have examined the transformation/dissolution (T/D) characteristics of a Ni matte and 4 Ni concentrates at pH 6 using the United Nations (UN) Transformation/Dissolution Protocol (T/DP) for metals and sparingly soluble metal compounds. Among the analytes Ni, Co, and Cu, Ni was released into the T/D solutions in the highest concentrations and was thus the main driver in establishing the hazard classification. We applied an extrapolation-scaling approach to obtain concentrations of total dissolved Ni at low loadings of 0.1 and 0.01 mg/L for derivation of chronic classification outcomes in the European Union (EU) classification, labeling, and packaging (CLP) scheme. The T/D data would classify the Ni matte as Acute 2-Chronic 2 under the Globally Harmonized System (GHS) scheme, and Chronic 1 under the EU CLP. Three of the 4 Ni concentrates would classify as GHS Acute 2-Chronic 2 and EU CLP Chronic 2, whereas the 4th would classify as GHS Acute 3-Chronic 3 and EU CLP Chronic 3. In applying the critical surface area (CSA) approach to the Ni concentrates, acute and chronic hazard classification outcomes were the same as those derived from direct application of the T/D data to the GHS and EU schemes. Such agreement provided confidence that the CSA approach could yield scientifically defensible acute and chronic hazard classification outcomes.

Prioritising anticancer drugs for environmental monitoring and risk assessment purposes.

Anticancer drugs routinely used in chemotherapy enter wastewater through the excretion of the non-metabolised drug following administration to patients. This study considers the consumption and subsequent behaviour and occurrence of these chemicals in aquatic systems, with the aim of prioritising a selection of these drugs which are likely to persist in the environment and hence be considered for environmental screening programmes. Accurate consumption data were compiled from a hospital survey in NW England and combined with urinary excretion rates derived from clinical studies. Physical-chemical property data were compiled along with likely chemical fate and persistence during and after wastewater treatment. A shortlist of 15 chemicals (from 65) was prioritised based on their consumption, persistency and likelihood of occurrence in surface waters and supported by observational studies where possible. The ecological impact of these 'prioritised' chemicals is uncertain as the measured concentrations in surface waters generally fall below standard toxicity thresholds. Nonetheless, this prioritised sub-list should prove useful for developing environmental screening programmes.

Speciation analysis of mercury in water samples by dispersive liquid-liquid microextraction coupled to capillary electrophoresis.

In this study, a method of pretreatment and speciation analysis of mercury by dispersive liquid-liquid microextraction along with CE was developed. The method was based on the fact that mercury species including methylmercury (MeHg), ethylmercury (EtHg), phenylmercury (PhHg), and Hg(II) were complexed with 1-(2-pyridylazo)-2-naphthol to form hydrophobic chelates and l-cysteine could displace 1-(2-pyridylazo)-2-naphthol to form hydrophilic chelates with the four mercury species. Factors affecting complex formation and extraction efficiency, such as pH value, type, and volume of extractive solvent and disperser solvent, concentration of the chelating agent, ultrasonic time, and buffer solution were investigated. Under the optimal conditions, the enrichment factors were 102, 118, 547, and 46, and the LODs were 1.79, 1.62, 0.23, and 1.50 µg/L for MeHg, EtHg, PhHg, and Hg(II), respectively. Method precisions (RSD, n = 5) were in the range of 0.29-0.54% for migration time, and 3.08-7.80% for peak area. Satisfactory recoveries ranging from 82.38 to 98.76% were obtained with seawater, lake, and tap water samples spiked at three concentration levels, respectively, with RSD (n = 5) of 1.98-7.18%. This method was demonstrated to be simple, convenient, rapid, cost-effective, and environmentally benign, and could be used as an ideal alternative to existing methods for analyzing trace residues of mercury species in water samples.

Binary classification of a large collection of environmental chemicals from estrogen receptor assays by quantitative structure-activity relationship and machine learning methods.

There are thousands of environmental chemicals subject to regulatory decisions for endocrine disrupting potential. The ToxCast and Tox21 programs have tested ∼8200 chemicals in a broad screening panel of in vitro high-throughput screening (HTS) assays for estrogen receptor (ER) agonist and antagonist activity. The present work uses this large data set to develop in silico quantitative structure-activity relationship (QSAR) models using machine learning (ML) methods and a novel approach to manage the imbalanced data distribution. Training compounds from the ToxCast project were categorized as active or inactive (binding or nonbinding) classes based on a composite ER Interaction Score derived from a collection of 13 ER in vitro assays. A total of 1537 chemicals from ToxCast were used to derive and optimize the binary classification models while 5073 additional chemicals from the Tox21 project, evaluated in 2 of the 13 in vitro assays, were used to externally validate the model performance. In order to handle the imbalanced distribution of active and inactive chemicals, we developed a cluster-selection strategy to minimize information loss and increase predictive performance and compared this strategy to three currently popular techniques: cost-sensitive learning, oversampling of the minority class, and undersampling of the majority class. QSAR classification models were built to relate the molecular structures of chemicals to their ER activities using linear discriminant analysis (LDA), classification and regression trees (CART), and support vector machines (SVM) with 51 molecular descriptors from QikProp and 4328 bits of structural fingerprints as explanatory variables. A random forest (RF) feature selection method was employed to extract the structural features most relevant to the ER activity. The best model was obtained using SVM in combination with a subset of descriptors identified from a large set via the RF algorithm, which recognized the active and inactive compounds at the accuracies of 76.1% and 82.8% with a total accuracy of 81.6% on the internal test set and 70.8% on the external test set. These results demonstrate that a combination of high-quality experimental data and ML methods can lead to robust models that achieve excellent predictive accuracy, which are potentially useful for facilitating the virtual screening of chemicals for environmental risk assessment.

[Classification of substances to predict the order of magnitude of their safe water levels in terms of carcinogenic effect].

A classification has been developed to predict the safe water levels of chemical compounds in terms of their carcinogenic effect, by using as the base the LTD@10 value that is a lower 95% confidence limits for the lowest dose that statistically significantly causes a 10% increase in the incidence of cancer in laboratory animals continuously receiving a daily dose of the compound throughout their life, which is given in the CPDB internet resource, and the carcinogenicity classification adopted by the International Agency or Research on Cancer Based on an analysis ofthe maximum allowable concentration (MAC) of the standardized water substances in terms of their carcinogenic effect, the authors determined MA4 C ranges corresponding to different classes in accordance with the proposed classification. They predicted the orders of magnitude of MAC of the standardized water substances without taking into account their carcinogenic effect and those of four substances unstandardized in Russia.

Preliminary risk assessment of trace metal pollution in surface water from Yangtze River in Nanjing Section, China.

In order to investigate the contamination levels of trace metals, surface water samples were collected from six regions along Yangtze River in Nanjing Section. The concentrations of trace metals (As, B, Ba, Be, Cd, Cr, Cu, Fe, Pb, Li, Mn, Mo, Ni, Sb, Se, Sn, Sr, V and Zn) were determined using inductively coupled plasma-atomic emission spectrometry (ICP-AES). Total concentrations of the metals in the water samples ranged from 825.1 to 950.4 microg/L. The result was compared with international water quality guidelines. Seven metals levels were above the permissible limit as prescribed by guidelines. A preliminary risk assessment was then carried out to determine the human health risk via calculating Hazard Quotient and carcinogenic risk of the metals. Hazard Quotients of all metals were lower than unity, except As. The carcinogenic risk of As and Cd was higher than 10(-6), suggesting that those two metals have potential adverse effects on local residents.

The assessment of genotoxic effects of wastewater from a fertilizer factory.

In this study we investigated cytotoxic, mutagenic and genotoxic effects of different concentrations of wastewater from the phosphoric gypsum depot near the factory for fertilizing agents 'INA Petrokemija' (Kutina, Croatia). The Ames test was performed on Salmonella typhimurium TA98 and TA100 strains, in the presence of S9 mix, glutathione and buffer, respectively. Cytotoxicity was studied on human laryngeal carcinoma cells (HEp2) and human cervical cells (HeLa). The level of lipid peroxidation in these two cell lines was evaluated in parallel. To establish the levels of primary DNA damage, the alkaline comet assay was performed on treated human peripheral blood leukocytes. No mutagenic effects of phosphoric gypsum on Salmonella typhimurium strains in the presence of S9 mix, GSH or PBS were observed. However, strong cytotoxic effect was observed on both human cell lines when they were treated with different concentrations of wastewater. Lipid peroxidation was induced and increased by prolonged time of incubation, highlighting that the damage was not repaired, but increased with the time of incubation. The results of the alkaline comet assay indicate significant DNA damaging potential of wastewater for human leukocytes. Since phosphoric gypsum transport water in its present composition and acidity is highly toxic and acts as prooxidant, causing free radicals formation and DNA damage, urgent neutralization/purification of the wastewater to a level acceptable for disposal into the environment is mandatory.

Speciation of arsenic in exfoliated urinary bladder epithelial cells from individuals exposed to arsenic in drinking water.

BACKGROUND: The concentration of arsenic in urine has been used as a marker of exposure to inorganic As (iAs). Relative proportions of urinary metabolites of iAs have been identified as potential biomarkers of susceptibility to iAs toxicity. However, the adverse effects of iAs exposure are ultimately determined by the concentrations of iAs metabolites in target tissues. OBJECTIVE: In this study we examined the feasibility of analyzing As species in cells that originate in the urinary bladder, a target organ for As-induced cancer in humans. METHODS: Exfoliated bladder epithelial cells (BECs) were collected from urine of 21 residents of Zimapan, Mexico, who were exposed to iAs in drinking water. We determined concentrations of iAs, methyl-As (MAs), and dimethyl-As (DMAs) in urine using conventional hydride generation-cryotrapping-atomic absorption spectrometry (HG-CT-AAS). We used an optimized HG-CT-AAS technique with detection limits of 12-17 pg As for analysis of As species in BECs. RESULTS: All urine samples and 20 of 21 BEC samples contained detectable concentrations of iAs, MAs, and DMAs. Sums of concentrations of these As species in BECs ranged from 0.18 to 11.4 ng As/mg protein and in urine from 4.8 to 1,947 ng As/mL. We found no correlations between the concentrations or ratios of As species in BECs and in urine. CONCLUSION: These results suggest that urinary levels of iAs metabolites do not necessarily reflect levels of these metabolites in the bladder epithelium. Thus, analysis of As species in BECs may provide a more effective tool for risk assessment of bladder cancer and other urothelial diseases associated with exposures to iAs.

Comparison of a score-based approach with risk-based ranking of in-use agricultural pesticides in Canada to aquatic receptors.

The purpose of this paper is to present a new risk-based approach developed by Environment Canada for ranking pesticides and their potential risk to aquatic life. These rankings are compared to those generated using a more traditional score-based approach. Two hundred and twelve active ingredients registered in Canada for use in agricultural field crops were included in this assessment. For each major aquatic taxon assessed (fish, insects, crustaceans, algae, and macrophytes), risk was calculated by dividing the 96-h estimated environmental concentration (modeled using parameters such as the application rate and method as well as physicochemical properties) by HC5 values (obtained through calculations of species sensitivity distribution-based toxicity endpoints). The traditional approach assigned scores based on toxicity endpoints in standard test species as well as physicochemical properties associated with the potential for aquatic contamination. A number of similarities were observed between the rankings but also notable differences. Only 22 active ingredients were common to the top 50 ranking positions from both approaches. The main reasons that accounted for the discrepancies between both rankings were the choice of toxicity endpoints, whether based on single or multiple species; the taxonomic breadth of retained data; the use of scores versus risk quotients; and the choices made in situations where multiple data points were available. We conclude that a risk-based approach that considers a broad representation of species toxicity data and estimates of runoff and drift concentration in receiving aquatic systems (even from generic application scenarios) is a more realistic representation of potential toxicological effects and a superior method of ranking products for the risk they pose to the aquatic environment.

Quantification of human pharmaceuticals in water samples by high performance liquid chromatography-tandem mass spectrometry.

An improved analytical method for determination of human pharmaceuticals in natural and wastewaters with ng L(-1) sensitivity is presented. The method is applicable to pharmaceuticals from a wide range of therapeutic classes including antibiotics, analgesics, anti-inflammatories and anti-cancer compounds. Pharmaceuticals were extracted from waters using solid-phase extraction, and after concentration, analysed by high performance liquid chromatography with tandem mass spectrometric detection (HPLC-MS/MS). Identification of each compound was secured using retention time and by the selected reaction monitoring of two transitions, one of which was additionally used for quantification. Limits of detection ranged from 0.03 to 0.96 ng L(-1) and were up to two orders of magnitude lower than those of previously published methods. The method was validated using spiked samples prepared from tap, river and sea water as well as wastewater effluents, collected from the North of Scotland. Analysis of wastewater effluents revealed the presence of mefenamic acid, ibuprofen, erythromycin, diclofenac and trimethoprim. None of the selected pharmaceuticals were detected in river, tap or sea water samples.

Poly(methyltetradecylsiloxane) immobilized onto silica for extraction of multiclass pesticides from surface waters.

A new material based on poly(methyltetradecylsiloxane) (PMTDS) thermally immobilized onto a silica support has been tested as a sorbent for the solid-phase extraction (SPE) from water of several pesticides used in soybean cultivation. The SPE methodology was developed and validated for six of these pesticides (imazethapyr, imazaquin, metsulfuron-methyl, bentazone, chlorimuron-ethyl and tebuconazole) according to the International Conference on Harmonization directives and the results were compared with those obtained with a commercial C18 SPE cartridge. The PMTDS-based sorbent gives results similar to the commercial sorbent with recoveries and precisions in agreement with directives for residue analysis. The quantification limits, after concentration, of all the pesticides evaluated were 1.0 microg L(-1), below the levels imposed by the principal regulatory agencies. The PMTDS-based sorbent preparation is fast, easy and reproducible and the cartridges are less expensive than similar commercial SPE materials.

Description of industrial pollution in Spain.

BACKGROUND: Toxic substances released into the environment (to both air and water) by many types of industries might be related with the occurrence of some malignant tumours and other diseases. The publication of the EPER (European Pollutant Emission Register) Spanish data allows to investigate the presence of geographical mortality patterns related to industrial pollution. The aim of this paper is to describe industrial air and water pollution in Spain in 2001, broken down by activity group and specific pollutant, and to plot maps depicting emissions of carcinogenic substances. METHODS: All information on industrial pollution discharge in 2001 was drawn from EPER-Spain public records provided by the European Commission server. We described the distribution of the number of industries and amounts discharged for each pollutant, as well as emission by pollutant group and the industrial activities associated with each pollutant. Maps of Spain were drawn up, with UTM coordinates being used to plot pollutant foci, and circles with an area proportional to the emission to depict pollution emission values. RESULTS: The EPER-Spain contained information on 1,437 industrial installations. The industrial plants that discharge pollutant substances into air and water above the pollutant-specific EPER threshold were mainly situated in the Autonomous Regions of Aragon, Andalusia and Catalonia and in Catalonia, the Basque Country and Andalusia respectively. Pollution released in 2001 into air approached 158 million Mt. Emissions into water were over 8 million Mt. CONCLUSION: A few single industrial plants are responsible for the highest percentage of emissions, thus rendering monitoring of their possible health impact on the surrounding population that much simpler. Among European countries Spain is the leading polluter in almost one third of all EPER-registered pollutant substances released into the air and ranks among the top three leading polluters in two-thirds of all such substances. Information obtained through publication of EPER data means that the possible consequences of reported pollutant foci on the health of neighbouring populations can now be studied.

Discriminating toxicant classes by mode of action. 1. (Eco)toxicity profiles.

BACKGROUND AND SCOPE: Predictive toxicology, particularly quantitative structure-activity relationships (QSARs), require classification of chemicals by mode of action (MOA). MOA is, however, not a constant property of a compound but it varies between species and may change with concentration and duration of exposure. A battery of MOA-specific in-vitro and low-complexity assays, featuring biomolecular targets for major classes of environmental pollutants, provides characteristic responses for (1.) classification of chemicals by MOA, (2.) identification of (eco)toxicity profiles of chemicals, (3.) identification of chemicals with specific MOAs, (4.) indication of most sensitive species, (5.) identification of chemicals that are outliers in QSARs and (6.) selection of appropriate QSARs for predictions. METHODS: Chemicals covering nine distinct modes of toxic action (non-polar non-specific toxicants (n=14), polar non-specific toxicants (n=18), uncouplers of oxidative phosphorylation (n=25), inhibitors of photosynthesis (n=15), inhibitors of acetylcholinesterase (n=14), inhibitors of respiration (n=3), thiol-alkylating agents (n=9), reactives (irritants) (n=8), estrogen receptor agonists (n=9)) were tested for cytotoxicity in the neutralred assay, oxygen consumption in isolated mitochondria, oxygen production in algae, inhibition of AChE, reaction with GSH and activity in the yeast estrogen receptor assay. Data on in-vivo aquatic toxicity (LC50, EC50) towards fish, daphnids, algae and bacteria were collected from the literature for reasons of comparison and reference scaling. RESULTS AND DISCUSSION: In the MOA-specific in-vitro test battery, most test chemicals are specifically active at low concentrations, though multiple effects do occur. Graphical and statistical evaluation of the individual classes versus MOA 1 (non-polar non-specific toxicants) identifies interactions related to predominant MOA. Discriminant analyses (DA) on subsets of the data revealed correct classifications between 70% (in-vivo data) and >90% (in-vitro data). Functional similarity of chemical substances is defined in terms of their (eco)toxicity profiles. Within each MOA class, the compounds share some properties related to the rate-limiting interactions, e.g., steric fit to the target site and/or reactivity with target biomolecules, revealing a specific pattern (fingerprint) of characteristic effects. CONCLUSION: The successful discrimination of toxicant classes by MOA is based on comprehensive characterization of test chemicals' properties related to interactions with target sites. The suite of aquatic in-vivo tests using fish, daphnids, algae and bacteria covers most acute effects, whilst long-term (latent) impacts are generally neglected. With the MOA-specific in-vitro test battery such distinctions are futile, because it focuses on isolated targets, i.e. it indicates the possible targets of a chemical regardless of the timescale of effects. The data analysis indicates that the in-vitro battery covers most effects in vivo and moreover provides additional aspects of the compounds' MOA. RECOMMENDATION AND PERSPECTIVE: Translating in-vitro effects to in-vivo toxicity requires combining physiological and chemical knowledge about underlying processes. Comparison of the specific in-vitro effects of a compound with the respective sensitivities of aquatic organisms indicates particularly sensitive species. Classifications of toxicants by MOA based on physicochemical descriptors provides insight to interactions and directs to mechanistic QSARs.

Characterization and source of oil contamination on the beaches and seabird corpses, Sable Island, Nova Scotia, 1996-2005.

During April 1996-May 2005, 2343 oiled seabird corpses were recorded in beach surveys conducted on Sable Island, Nova Scotia. One hundred eighty-three samples of oil were collected from the beaches and from the feathers of bird corpses. Gas chromatographic (GC/FID) analysis was used to identify generic oil type and likely marine source. During this period, at least 74 marine oil discharge events were probably responsible for beached pelagic tar and contamination of seabird corpses found on Sable Island, of which 77.0% were crude oils, 14.9% were fuel oils, and 8.1% were bilge oil mixtures. While fuel and bilge oils may be discharged by all vessel and platform types, crude oil discharges are associated with tanker operations. This study demonstrates that oiling of the sea from tankers remains a serious wildlife issue in the Northwest Atlantic.

Fully automated multianalyte determination of different classes of pesticides, at picogram per litre levels in water, by on-line solid-phase extraction-liquid chromatography-electrospray-tandem mass spectrometry.

This paper reports the development of a fully automated method for the multianalyte determination of twenty pesticides belonging to different classes (triazines, phenylureas, organophosphates, anilines, acidic, propanil, and molinate) in natural and treated waters. The method, based on on-line solid-phase extraction-liquid chromatography-electrospray-tandem mass spectrometry, is highly sensitive (limits of detection between 0.004 and 2.8 ng L(-1)), precise (relative standard deviations between 2.0 and 12.1%), reliable (two selected reaction-monitoring transitions are monitored per compound), rapid (45 min per sample), and simple. The application of this method to the monitoring of the target compounds in a waterworks revealed the presence of the pesticides investigated at concentrations up to 516 and 82 ng L(-1) (total pesticide concentration) in river water and ground water, respectively, used as sources, and their gradual removal through the purification process.