RESUMEN
Background: Due to their high biodiversity, small water bodies play an important role for freshwater ecosystems. Nonetheless, systematic pesticide monitoring in small creeks with a catchment <30 km2 is rarely conducted. Methods: In this study, event-driven water samples were taken from May until November 2017 and March until July 2018 after 20 rain events at three sampling sites with catchment areas of <27 km2 in the Wetterau, a region with intensive agriculture in Southern Hesse, Germany. Additionally, enriched extracts of the native water samples from the campaign in 2018 were used for the Microtox assay to determine baseline toxicity to invertebrates over time and sum of toxic units (STU) were calculated to compare the potential toxicity of the samples. Results: Overall, 37 pesticides and 17 transformation products were found, whereby the herbicide metamitron (79 µg/L) showed the highest concentration. Regularly, pesticide concentrations peaked at the time of the highest water level within each sampling event. Within each sampling event maximum pesticide concentration was mostly reached in water samples taken during the first two hours. The sum of the time-weighted mean concentration values of all pesticides was between 2.0 µg/L and 7.2 µg/L, whereby the measured concentrations exceeded their regulatory acceptable concentration (RAC) at 55% of all sampling events for at least one pesticide. The mean EC50 values varied between 28.6 ± 13.1 to 41.3 ± 12.1 REF (relative enrichment factor). The results indicated that several samples caused baseline toxicity, whereby the highest activity was measured at the time of highest water levels and pesticides concentrations, and then steadily decreased in parallel with the water level. Median STUs of invertebrates ranged from -2.10 to -3.91, of algae/aquatic plants from -0.79 to -1.84 and of fish from -2.47 to -4.24. For one of the three sampling sites, a significant linear correlation between baseline toxicity and STUinvertebratewas found (r2 = 0.48). Conclusion: The results of the present study suggest that (1) current pesticide monitoring programs underestimate risks posed by the exposure to pesticides for aquatic organisms and (2) pre-authorization regulatory risk assessment schemes are insufficient to protect aquatic environments.
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Plaguicidas , Contaminantes Químicos del Agua , Animales , Plaguicidas/toxicidad , Ecosistema , Contaminantes Químicos del Agua/toxicidad , Monitoreo del Ambiente/métodos , Agricultura , Invertebrados , Alemania , AguaRESUMEN
The pollution state in the German Bight was investigated by determination of pollutant concentrations of sediment samples using equilibrium passive sampling. Polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAH) were determined in the pore water of North Sea sediment. The freely dissolved pore water concentration (Cfree) was measured applying Solid Phase Microextraction (SPME) by using PDMS-coated glass fibers. The obtained results show that the North Sea contamination level with the investigated pollutants is relatively low. However, the stations close to the sediment-dumping site were higher contaminated. A macrofauna analysis showed that bioturbation activities were mostly present in the upper sediment layers, but a direct bioturbation influence on the sediment concentration distribution could not be shown. Overall, the contamination load was below baseline toxicity, but considering that several other priority pollutants will also make a contribution to the baseline toxicity, it can be counted as relatively high.
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Contaminantes Ambientales , Bifenilos Policlorados , Hidrocarburos Policíclicos Aromáticos , Contaminantes Químicos del Agua , Sedimentos Geológicos/química , Contaminantes Químicos del Agua/análisis , Mar del Norte , Efectos Antropogénicos , Monitoreo del Ambiente/métodos , Agua/análisis , Bifenilos Policlorados/análisis , Contaminantes Ambientales/análisis , Compuestos Orgánicos/análisis , Hidrocarburos Policíclicos Aromáticos/análisisRESUMEN
This study describes the chemical composition and in vitro toxicity of the organic fraction of fine particulate matter (PM2.5) at an urban background site, which receives emissions either from Frankfurt international airport or the city centre, respectively. We analysed the chemical composition of filter extracts (PM2.5) using ultrahigh-performance liquid chromatography coupled to a high-resolution mass spectrometer, followed by a non-target analysis. In parallel, we applied the bulk of the filter extracts to a Microtox and acetylcholinesterase-inhibition assay for in vitro toxicity testing. We find that both the chemical composition and toxicity depend on the prevailing wind directions, and the airport operating condition, respectively. The occurrence of the airport marker compounds tricresyl phosphate and pentaerythritol esters depends on the time of the day, reflecting the night flight ban as well as an airport strike event during November 2019. We compared the organic aerosol composition and toxicity from the airport wind-sector against the city centre wind-sector. We find that urban background aerosol shows a higher baseline toxicity and acetylcholinesterase inhibition compared to rural PM2.5 that is advected over the airport. Our results indicate that the concentration and individual composition of PM2.5 influence the toxicity. Suspected drivers of the acetylcholinesterase inhibition are i.e. organophosphorus esters like triphenyl phosphate and cresyldiphenyl phosphate, and the non-ionic surfactant 4-tert-octylphenol ethoxylate. However, further research is necessary to unambiguously identify harmful organic air pollutants and their sources and quantify concentration levels at which adverse effects in humans and the environment can occur.
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Acetilcolinesterasa , Contaminantes Atmosféricos , Aerosoles/análisis , Contaminantes Atmosféricos/análisis , Contaminantes Atmosféricos/toxicidad , Monitoreo del Ambiente/métodos , Humanos , Material Particulado/análisis , Material Particulado/toxicidadRESUMEN
Protonophoric uncoupling of phosphorylation is an important factor when assessing chemicals for their toxicity, and has recently moved into focus in pharmaceutical research with respect to the treatment of diseases such as cancer, diabetes, or obesity. Reliably identifying uncoupling activity is thus a valuable goal. To that end, we screened more than 6000 anionic compounds for in vitro uncoupling activity, using a biophysical model based on ab initio COSMO-RS input parameters with the molecular structure as the only external input. We combined these results with a model for baseline toxicity (narcosis). Our model identified more than 1250 possible uncouplers in the screening dataset, and identified possible new uncoupler classes such as thiophosphoric acids. When tested against 423 known uncouplers and 612 known inactive compounds in the dataset, the model reached a sensitivity of 83% and a specificity of 96%. In a direct comparison, it showed a similar specificity than the structural alert profiler Mitotox (97%), but much higher sensitivity than Mitotox (47%). The biophysical model thus allows for a more accurate screening for uncoupling activity than existing structural alert profilers. We propose to use our model as a complementary tool to screen large datasets for protonophoric uncoupling activity in drug development and toxicity assessment.
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Fosforilación Oxidativa , Estructura Molecular , DesacopladoresRESUMEN
A large number of toxicity studies report abnormalities in early life-stage (ELS) fish that are described here as a sublethal toxicity syndrome (TxSnFELS) and generally include a reduced heart rate, edemas (yolk sac and cardiac), and a variety of morphological abnormalities. The TxSnFELS is very common and not diagnostic for any chemical or class of chemicals. This sublethal toxicity syndrome is mostly observed at high exposure concentrations and appears to be a baseline, non-specific toxicity response; however, it can also occur at low doses by specific action. Toxicity metrics for this syndrome generally occur at concentrations just below those causing mortality and have been reported for a large number of diverse chemicals. Predictions based on tissue concentrations or quantitative-structure activity relationship (QSAR) models support the designation of baseline toxicity for many of the tested chemicals, which is confirmed by observed values. Given the sheer number of disparate chemicals causing the TxSnFELS and correlation with QSAR derived partitioning; the only logical conclusion for these high-dose responses is baseline toxicity by nonspecific action and not a lock and key type receptor response. It is important to recognize that many chemicals can act both as baseline toxicants and specific acting toxicants likely via receptor interaction and it is not possible to predict those threshold doses from baseline toxicity. We should search out these specific low-dose responses for ecological risk assessment and not rely on high-concentration toxicity responses to guide environmental protection. The goal for toxicity assessment should not be to characterize toxic responses at baseline toxicity concentrations, but to evaluate chemicals for their most toxic potential. Additional aspects of this review evaluated the fish ELS teratogenic responses in relation to mammalian oral LD50s and explored potential key events responsible for baseline toxicity.
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Contaminantes Químicos del Agua , Animales , Peces , Sustancias Peligrosas , Dosificación Letal Mediana , Relación Estructura-Actividad Cuantitativa , Contaminantes Químicos del Agua/toxicidadRESUMEN
The assessment of the actual impact of discharged wastewater on the whole ecosystem and, in turn, on human health requires the execution of bioassays. In effect, based on the chemical characterization alone, the synergistic/antagonistic effect of mixtures of pollutants is hardly estimable. The aim of this work was to evaluate the applicability of a battery of bioassays and to suggest a smart procedure for results representation. Two real wastewater treatment plants were submitted to analytical campaigns. Several baseline toxicity assays were conducted, together with tests for the determination of endocrine activity, genetic toxicity and carcinogenicity of wastewater. A "traffic light" model was adopted for an easy-to-understand visualization of the results. Although the legal prescriptions of chemical parameters are fully complied with, bioassays show that a certain biological activity still residues in the treated effluents. Moreover, influent and effluent responses are not always appreciably different. Some tests employing human cells were revealed to be only partially adequate for environmental applications. An interesting and helpful development of the present approach would consist in the estimation of biological equivalents of toxicity, as shown for the estrogenic compound 17-ß-estradiol.
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Aguas Residuales , Contaminantes Químicos del Agua , Bioensayo , Ecosistema , Monitoreo del Ambiente , Estrógenos/análisis , Humanos , Eliminación de Residuos Líquidos , Contaminantes Químicos del Agua/análisis , Contaminantes Químicos del Agua/toxicidadRESUMEN
Nonpolar narcosis, also known as baseline toxicity, has been described as the minimal toxicity that an organic chemical may elicit based on its lipophilicity. Although lethal effects of narcosis-inducing chemicals (NICs) have been thoroughly investigated, knowledge of sublethal effects is still very limited. We investigated the effects of 3 well-known NICs (phenanthrene, 1,3,5-trichlorobenzene, and pentachlorobenzene) on a variety of organismal endpoints (malformations, swim bladder inflation, respiration, heart rate, swimming activity, and turning angles), which can be plausibly linked to narcosis in zebrafish embryos. Baseline toxicity recorded as mortality is typically observed in similar exposure ranges in a wide variety of species including fish, corresponding to a chemical activity range between 0.01 and 0.1. In the present study, we found that sublethal effects occurred at concentrations approximately 5 times below lethal concentrations. Altered swimming activity and impaired swim bladder inflation were the most sensitive endpoints occurring at exposure levels below the generally accepted threshold for baseline toxicity for 2 out of 3 compounds. Overall, most effective exposure levels across the sublethal endpoints and compounds did fall within the range typically associated with baseline toxicity, and deviations were generally limited to a factor 10. Although there could be benefit in adding sublethal endpoints to toxicity tests, such as the fish embryo acute toxicity (FET) test, based on the present sublethal endpoints and available evidence from our and other studies, the underestimation of toxicity as a result of the sole assessment of mortality as an endpoint in an FET test may be limited for narcosis. Environ Toxicol Chem 2021;40:2802-2812. © 2021 SETAC.
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Estupor , Contaminantes Químicos del Agua , Animales , Embrión no Mamífero , Pruebas de Toxicidad Aguda , Contaminantes Químicos del Agua/toxicidad , Pez CebraRESUMEN
Plastics can release numerous chemicals and thereby, contribute to the chemical pollution in aquatic systems. To which extent environmental degradation processes influence the release of plastic chemicals, is currently unknown and subject of research. We therefore evaluated aqueous leachates of 12 differently formulated plastics (e.g., pre-production, post-industrial and recycled pellets as well as final products) using in vitro bioassays and chemical analysis via LC-HRMS nontarget approach. We weathered these plastics by UV irradiation (UV-C and UV-A/B) under laboratory conditions in dryness and a subsequent leaching period in ultrapure water ('atmospheric' weathering) or directly in water ('aquatic' weathering, UV-A/Baq). A dark control (DC) without UV light served as a reference treatment. Some plastics triggered several toxicological endpoints (low-density polyethylene recyclate (LDPE-R), starch blend (SB), bio-based polybutylene succinate (Bio-PBS) and polyvinyl chloride (PVC)), whereas others caused little to no effects (polyethylene terephthalate (PET), polystyrene (PS), polypropylene (PP) and LDPE). UV irradiation enhanced the plastics' toxicity, even for samples initially evaluated as toxicologically inconspicuous. The plastic samples caused oxidative stress (85%), baseline toxicity (42%), antiestrogenicity (40%) and antiandrogenicity (27%). Positive findings were measured after UV-C (63%) and UV-A/Baq (50%) treatments, followed by UV-A/B (48%) and DC (33%). Overall, we detected between 42 (DC) and 2896 (UV-A/Baq) chemical compounds. Our study demonstrates that differently formulated plastics leach toxic chemicals. UV exacerbates the plastics' toxicity by either generating active compounds and/or by facilitating their release. UV light even leads to the release of bioactive compounds from plastics of low chemical complexity. To prevent the exposure to plastic-associated chemicals, the application of chemicals could be reduced to a minimum, while on a regulatory level the evaluation of plastic eluates could be another focal point next to singular compounds.
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Plásticos , Rayos Ultravioleta , Polietileno , Polipropilenos , PoliestirenosRESUMEN
BACKGROUND: Ozone gas is commercially used for deodorization and microbial control. Its efficacy against stored product insect pests is well documented. In the midst of the common bed bug (Cimex lectularius L.) outbreak, claims were made that ozone gas was effective for their control. This study was conducted to determine baseline ozone concentrations and exposure times required for the control of an insecticide-susceptible C. lectularius strain under laboratory conditions. Dichlorvos (DDVP), an organophosphate class fumigant insecticide was used as a positive control. RESULTS: Nymphs and adults were more susceptible to ozone than eggs. Complete (100%) nymph and adult mortality was achieved at an ozone concentration (C) of 1500 ppm and exposure time (T) of 180 min, or concentration × time product (CT) of 270 000 ppm-min, whereas eggs required an eightfold higher CT (2 040 000 ppm-min). DDVP vapor was 2070-, 2542- and 450-fold more potent than ozone, against nymphs, adults and eggs, respectively. CONCLUSIONS: Baseline ozone toxicity data provide insights on the practicality of using this gas for the management of common bed bugs. High ozone CT products required for C. lectularius control, particularly eggs, suggest that its use for treating infested human dwellings is not feasible due to logistic, safety and monetary concerns. © 2020 Society of Chemical Industry.
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Chinches , Insecticidas , Ozono , Animales , Humanos , Insecticidas/farmacología , Laboratorios , Ninfa , Ozono/farmacologíaRESUMEN
In the current study, improved exposure control and measurements were applied for the aquatic toxicity testing of a highly hydrophobic organic compound. The aim was to reliably determine the ecotoxicity of the model compound dodecylbenzene (DDB, Log KOW = 8.65) by applying passive dosing for aquatic toxicity testing exactly at the solubility limit. Methodologically, silicone O-rings were saturated by immersion in pure liquid DDB (i.e., "loading by swelling") and then used as passive dosing donors. Daphnia immobilization and fish embryo toxicity tests were successfully conducted and provide, together with recently reported algal growth inhibition data, a full base-set of ecotoxicological data according to REACH. All tests were conducted in closed test systems to avoid evaporative losses, and exposure concentrations were measured throughout test durations. The Daphnia test was optimized by placing the O-rings in cages to prevent direct contact between daphnids and the passive dosing donor. Toxicologically, Daphnia magna immobilization was 19.3 ± 8% (mean ± 95% CI; 6 tests) within 72 h, whereas Danio rerio fish embryos did not show any significant lethal or sublethal toxic responses within 96 h. Growth rate inhibition for the algae Raphidocelis subcapitata was previously reported to be 13 ± 5% in a first and 8 ± 3% in a repeated test. These results for aquatic organisms, spanning three trophic levels, demonstrate toxicity of a highly hydrophobic compound and suggest that improvements of the current ecotoxicological standard tests are needed for these "difficult-to-test" chemicals. Furthermore, the obtained toxicity results significantly question the existence of a generic Log KOW cut-off in baseline toxicity.
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Derivados del Benceno/toxicidad , Contaminantes Químicos del Agua/toxicidad , Animales , Organismos Acuáticos , Daphnia , Ecotoxicología , Interacciones Hidrofóbicas e Hidrofílicas , Alimentos Marinos , Solubilidad , Pruebas de Toxicidad/métodos , Contaminantes Químicos del Agua/química , Pez CebraRESUMEN
Species may vary markedly in terms of their sensitivity to toxicants, and such variation can be described through the species sensitivity distribution (SSD) approach. Using SSD cumulative functions, it is possible to calculate the hazardous concentration for 5% of the species (HC5), namely the contaminant concentration at which 5% of species will be affected. HC5 is often utilised to derive the predicted no-effect concentration, or the concentration at which a chemical will likely have no toxic effects on the different species present in an ecosystem. However, the lack of sufficient ecotoxicological data frequently obstructs the derivation of SSD curves and consequently the HC5. In the last 30 years, quantitative structure-activity relationship (QSAR) models have been widely used to predict the toxicity of chemicals to single species. The aim of this study was to evaluate the possibility of extending the applicability domain of these models from single species to the community level by predicting the HC5 values for aquatic communities and bypassing the need to derive SSD curves. This approach's practical advantage is that it would allow information on the toxicity of contaminants to be obtained on a hierarchical scale (aquatic community), which is ecologically more relevant than on the scale of single species, without the need for a robust toxicity data set. In the first part of the study, two simple QSAR models were developed for narcotic and polar narcotic compounds. Then, the QSAR model developed for narcotic compounds was utilised to define the baseline toxicity for aquatic communities and to calculate the toxicity ratios for various specifically acting compounds (insecticides and herbicides).
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Insecticidas/toxicidad , Narcóticos/toxicidad , Contaminantes Químicos del Agua/toxicidad , Animales , Organismos Acuáticos/efectos de los fármacos , Ecotoxicología , Herbicidas/toxicidad , Relación Estructura-Actividad Cuantitativa , Contaminantes Químicos del Agua/químicaRESUMEN
Ionizable organic chemicals (IOCs) such as organic acids and bases are an important substance class requiring aquatic hazard evaluation. Although the aquatic toxicity of IOCs is highly dependent on the water pH, many toxicity studies in the literature cannot be interpreted because pH was not reported or not kept constant during the experiment, calling for an adaptation and improvement of testing guidelines. The modulating influence of pH on toxicity is mainly caused by pH-dependent uptake and bioaccumulation of IOCs, which can be described by ion-trapping and toxicokinetic models. The internal effect concentrations of IOCs were found to be independent of the external pH because of organisms' and cells' ability to maintain a stable internal pH milieu. If the external pH is close to the internal pH, existing quantitative structure-activity relationships (QSARs) for neutral organics can be adapted by substituting the octanol-water partition coefficient by the ionization-corrected liposome-water distribution ratio as the hydrophobicity descriptor, demonstrated by modification of the target lipid model. Charged, zwitterionic and neutral species of an IOC can all contribute to observed toxicity, either through concentration-additive mixture effects or by interaction of different species, as is the case for uncoupling of mitochondrial respiration. For specifically acting IOCs, we recommend a 2-step screening procedure with ion-trapping/QSAR models used to predict the baseline toxicity, followed by adjustment using the toxic ratio derived from in vitro systems. Receptor- or plasma-binding models also show promise for elucidating IOC toxicity. The present review is intended to help demystify the ecotoxicity of IOCs and provide recommendations for their hazard and risk assessment. Environ Toxicol Chem 2020;39:269-286. © 2019 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC.
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Organismos Acuáticos/efectos de los fármacos , Ecotoxicología/métodos , Sustancias Peligrosas/toxicidad , Modelos Teóricos , Compuestos Orgánicos/toxicidad , Contaminantes Químicos del Agua/toxicidad , Animales , Relación Dosis-Respuesta a Droga , Sustancias Peligrosas/química , Concentración de Iones de Hidrógeno , Interacciones Hidrofóbicas e Hidrofílicas , Compuestos Orgánicos/química , Relación Estructura-Actividad Cuantitativa , Agua/química , Contaminantes Químicos del Agua/químicaRESUMEN
The freely dissolved concentration (Cfree) was measured for PAHs and PCBs in sediments of the German Bight and Wadden Sea. Ex-situ Solid Phase Microextraction (SPME) was applied using Polydimethlysiloxane (PDMS) coated glass fibers followed by automated thermal desorption and GC-MS analysis. This study provides the first dataset on the spatial distribution of Cfree for PAHs and PCBs in the German Bight and the Wadden Sea. We found elevated PCB concentrations in the Wadden Sea and especially in the Weser estuary. Sandy North Sea sediments were rather less contaminated, except for some former dumping sites. The sorption strength of PAHs was generally stronger, while PCBs in the Wadden Sea sediments were only weakly bound. This SPME method is a rapid and sensitive tool to study Cfree of hydrophobic organic chemicals to improve todays sediment risk assessment.
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Sedimentos Geológicos/química , Bifenilos Policlorados/análisis , Hidrocarburos Policíclicos Aromáticos/análisis , Contaminantes Químicos del Agua/análisis , Contaminación Química del Agua/análisis , Monitoreo del Ambiente , Mar del Norte , Agua de Mar , Microextracción en Fase SólidaRESUMEN
The fish embryo toxicity (FET) test with the zebrafish Danio rerio is widely used to assess the acute toxicity of chemicals thereby serving as animal alternative to the acute fish toxicity test. The minimal toxicity of neutral chemicals in the FET can be predicted with a previously published Quantitative Structure-Activity Relationship (QSAR) based on the liposome-water partition coefficient Klipw. Such a QSAR may serve to plan toxicity testing and to evaluate whether an observed effect is caused by a specific mode of action (MoA). The applicability domain of this QSAR was extended to ionizable organic chemicals (IOC) without any modification of slope and intercept simply by replacing the Klipw with the speciation-corrected liposome-water distribution ratio (Dlipw(pH)) as descriptor for the uptake into the embryo. FET LC50 values of IOCs were extracted from an existing FET database and published literature. IOCs were selected that are present concomitantly as neutral and charged, species, i.e., acids with an acidity constant pKa <10 and bases with pKa>5. IOCs were grouped according to their putative MoA of acute aquatic toxicity. The toxic ratios (TR) in the FET were derived by of the experimental FET-LC50 in comparison with the baseline toxicity QSAR. Baseline toxicants were confirmed to align well with the FET baseline toxicity QSAR (TR < 10). Chemicals identified to act as specific or reactive chemicals with the toxic ratio analysis in the FET test (TR > 10) were generally consistent with MoA classification for acute fish toxicity with a few exceptions that were suspected to have had issues with the stability of the pH during testing. One critical aspect for the effect analysis of ionizable chemicals is the pH, since the difference between pH and pKa determines the speciation and thereby the Dlipw(pH).
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Embrión no Mamífero/efectos de los fármacos , Compuestos Orgánicos/química , Compuestos Orgánicos/toxicidad , Relación Estructura-Actividad Cuantitativa , Pruebas de Toxicidad Aguda , Pez Cebra/embriología , Animales , Concentración 50 Inhibidora , Iones , Contaminantes Químicos del Agua/toxicidadRESUMEN
Chemical activity quantifies the energetic level of an organic compound relative to its pure liquid [0-1], and several studies have reported that baseline toxicity generally requires chemical activities of 0.01-0.1. The first aim was to challenge this chemical activity range for baseline toxicity. Algal growth inhibition data (median effective concentrations, EC50) were compiled from two recent studies and included 108 compounds categorised as non-polar (mode of toxic action, MOA1) and polar (MOA2) narcotics. These data were linked to chemical activity by (1) plotting them relative to a regression for (subcooled) liquid solubility (SL), which served as visual reference for chemical activity of unity and (2) determining EC50/SL ratios that essentially equal median effective chemical activity (Ea50). Growth inhibition required chemical activity >0.01 for MOA1 and >0.001 for MOA2 compounds. The second aim was to identify compounds exerting excess toxicity, i.e., when growth inhibition occurred at chemical activity <0.001. From a recent review with 2323 data entries, 315 EC50 values passed our selection criteria. 280 of these EC50 values were within or near the baseline toxicity range (Ea50>0.001), and 25 compounds were found to exert excess toxicity (Ea50<0.001). Of these compounds, 16 are pesticides or precursors. Methodologically, this study includes two methods for translating EC50 values into the chemical activity framework, each having advantages and limitations. Scientifically, this study confirms that baseline toxicity generally requires chemical activities of 0.01-0.1 and extends the application of the chemical activity approach beyond baseline toxicity, by demonstrating its utility to identify compounds that exert excess toxicity.
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Chlorophyta/crecimiento & desarrollo , Compuestos Orgánicos/toxicidad , Pruebas de Toxicidad/métodos , Contaminantes Químicos del Agua/toxicidad , Chlorophyta/efectos de los fármacos , Narcóticos/toxicidad , Plaguicidas/toxicidadRESUMEN
Fish early life stage (ELS) tests (Organisation for Economic Co-operation and Development test guideline 210) are widely conducted to estimate chronic fish toxicity. In these tests, fish are exposed from the embryonic to the juvenile life stages. To analyze whether certain modes of action are related to high toxic ratios (i.e., ratios between baseline toxicity and experimental effect) and/or acute-to-chronic ratios (ACRs) in the fish ELS test, effect concentrations (ECs) for 183 compounds were extracted from the US Environmental Protection Agency's ecotoxicity database. Analysis of ECs of narcotic compounds indicated that baseline toxicity could be observed in the fish ELS test at similar concentrations as in the acute fish toxicity test. All nonnarcotic modes of action were associated with higher toxic ratios, with median values ranging from 4 to 9.3 × 104 (uncoupling < reactivity < neuromuscular toxicity < methemoglobin formation < endocrine disruption < extracellular matrix formation inhibition). Four modes of action were also found to be associated with high ACRs: 1) lysyl oxidase inhibition leading to notochord distortion, 2) putative methemoglobin formation or hemolytic anemia, 3) endocrine disruption, and 4) compounds with neuromuscular toxicity. For the prediction of ECs in the fish ELS test with alternative test systems, endpoints targeted to the modes of action of compounds with enhanced toxic ratios or ACRs could be used to trigger fish ELS tests or even replace these tests. Environ Toxicol Chem 2018;37:955-969. © 2018 SETAC.
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Peces/crecimiento & desarrollo , Pruebas de Toxicidad Aguda , Pruebas de Toxicidad Crónica , Animales , Disruptores Endocrinos/toxicidad , Interacciones Hidrofóbicas e Hidrofílicas , Contaminantes Químicos del Agua/toxicidadRESUMEN
Sediment cores and bottom water samples from across the Baltic Sea region were analyzed for freely dissolved concentrations (Cfree), total sediment concentrations (CT) and the dissolved aqueous fraction in water of seven indicator PCBs. Ex-situ equilibrium sampling of sediment samples was conducted with polydimethylsiloxane (PDMS) coated glass fibers that were analyzed by automated thermal desorption GC-MS, which yielded PCB concentrations in the fiber coating (CPDMS). Measurements of CPDMS and CT were then applied to determine (i) spatially resolved freely dissolved PCB concentrations; (ii) baseline toxicity potential based on chemical activities (a); (iii) site specific mixture compositions; (iv) diffusion gradients at the sediment water interface and within the sediment cores; and (vi) site specific distribution ratios (KD). The contamination levels were low in the Gulf of Finland and moderate to elevated in the Baltic Proper, with the highest levels observed in the western Baltic Sea. The SPME method has been demonstrated to be an appropriate and sensitive tool for area surveys presenting new opportunities to study the in-situ distribution and thermodynamics of hydrophobic organic chemicals at trace levels in marine environments.
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Monitoreo del Ambiente/métodos , Bifenilos Policlorados/análisis , Agua de Mar/química , Contaminantes Químicos del Agua/análisis , Contaminación Ambiental/análisis , Finlandia , Cromatografía de Gases y Espectrometría de Masas , Sedimentos Geológicos/química , Compuestos Orgánicos/análisisRESUMEN
Charged organic chemicals are a prevailing challenge for toxicity modelling. In this contribution we strive to recapitulate the lessons learned from the well-known modelling of narcosis (or baseline toxicity) of neutral chemicals and apply the concept to charged chemicals. First we reevaluate the organism- and chemical independent critical membrane concentration causing 50% mortality,.cmemtox, based on a critical revision of a previously published toxicity dataset for neutral chemicals. In accordance to values reported in the literature we find a mean value for cmemtox of roughly 100 mmol/kg (membrane lipid) for a broad variety of 42 aquatic organisms (333 different chemicals), albeit with a considerable scatter. Then we apply this concept to permanently charged ionic liquids (ILs). Using COSMOmic, a quantum mechanically based mechanistic model that makes use of the COSMO-RS theory, we predict membrane-water partition coefficients (Kmem/w) of the anionic and cationic IL components. Doing so, cmemtox(total) for permanently charged ILs can be estimated assuming independent, concentration additive contributions of the cationic and its respective anionic species. The resulting values for some of the toxicity data for ionic liquids are consistent with the expected range for baseline toxicity for neutral chemicals while other values are consistently greater or smaller. Based on the calculation of toxic ratios we identify ILs that exert a specific mode of toxic action. Limitations of the modelling approach especially but not exclusively due to the use of nominal concentrations instead of freely-dissolved concentrations in the published literature are critically discussed.
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Organismos Acuáticos/efectos de los fármacos , Líquidos Iónicos/toxicidad , Membranas Artificiales , Modelos Teóricos , Organismos Acuáticos/citología , Líquidos Iónicos/química , Compuestos Orgánicos/química , Teoría Cuántica , Agua/químicaRESUMEN
Crude oil and refined petroleum products contain many polycyclic and heterocyclic aromatic hydrocarbons, in particular, alkylated PAHs. Although alkylated PAHs are found in significantly higher quantities than their corresponding unsubstituted PAHs, the most studies on the physico-chemical properties and toxicities of these compounds have been conducted on unsubstituted PAHs. In this study, we measured crucial physico-chemical properties (i.e., water solubility, partition coefficients between polydimethylsiloxane and water (KPDMSw), and partition coefficient between liposomes and water (Klipw)) of selected alkylated PAHs, and evaluated their toxicity using the luminescence inhibition of Aliivibrio fischeri and growth inhibition of Raphidocelis subcapitata. In general, the logarithms of these properties for alkylated PAHs showed good linear correlations with log Kow, as did those for unsubstituted PAHs. Changes in molecular symmetry on the introduction of alkyl groups on aromatic ring structure significantly altered water solubility. The inhibition of bacterial luminescence and algal growth by alkylated PAHs can be explained well by the baseline toxicity hypothesis, and good linear relationships between log Kow or log Klipw and log (1/EC50) were found.
Asunto(s)
Hidrocarburos Policíclicos Aromáticos/química , Hidrocarburos Policíclicos Aromáticos/toxicidad , Contaminantes Químicos del Agua/química , Contaminantes Químicos del Agua/toxicidad , Aliivibrio fischeri/efectos de los fármacos , Chlorophyta/efectos de los fármacos , Petróleo , SolubilidadRESUMEN
Three water contaminants were selected to be tested in the zebrafish embryo toxicity test (DarT) in order to investigate the sensitivity of the zebrafish embryo toxicity test with respect to mixture effect detection. The concentration-response curves for the observed effects lethality and hypo-pigmentation were calculated after an exposure of the embryos for 96 h with a fungicide (carbendazim), a plasticizer or propellent precursor (2,4-DNT: 2,4- dinitrotoluene) and an aromatic compound (AαC: 2-amino-9H-pyrido[2,3-b]indol), respectively. Follow-up mixture tests were based on the calculated LC50 or EC50 of the single compounds and combined effects were predicted according to the mixture concepts of concentration addition (CA) and independent action (IA). The order of toxicity for the single substances was carbendazim (LC50 = 1.25 µM) < AαC (LC50 = 8.16 µM) < 2,4-DNT (LC50 = 177.05 µM). For AαC and 2,4 DNT hypo-pigmentation was observed in addition (AαC EC50 = 1.81 µM; 2,4-DNT EC50 = 8.81 µM). Two binary and one ternary mixture were studied on lethality and one on hypo-pigmentation: 2,4-DNT/AαC (LC50 = 119.21 µM, EC50 = 5.37 µM), carbendazim/AαC (LC50 = 4.49 µM) and AαC/Carbendazim/2,4 DNT (LC50 = 108.62 µM). Results showed that the effects were in agreement with the CA model when substances were tested in mixtures. Therefore, in a reasonable worst case scenario substance combination effects in fish embryos were at maximum only prone to overestimation when using CA as the mixture concept.