RESUMO
Shipping activities are increasing with sea ice receding in the Arctic, leading to higher risks of accidents and oil spills. Because Arctic toxicity data are limited, oil spill risk assessments for the Arctic are challenging to conduct. In the present study, we tested if acute oil toxicity metrics obtained at temperate conditions reflect those at Arctic conditions. The effects of temperature (4 °C, 12 °C, and 20 °C) on the median lethal concentration (LC50) and the critical body residue (CBR) of the temperate invertebrate Gammarus locusta exposed to water accommodated fractions of a fuel oil were determined. Both toxicity metrics decreased with increasing temperature. In addition, data for the temperate G. locusta were compared to data obtained for Arctic Gammarus species at 4 °C. The LC50 for the Arctic Gammarus sp. was a factor of 3 higher than that for the temperate G. locusta at 4 °C, but its CBR was similar, although both the exposure time and concentration were extended to reach lethality. Probably, this was a result of the larger size and higher weight and total lipid content of Arctic gammarids compared to the temperate gammarids. Taken together, the present data support the use of temperate acute oil toxicity data as a basis for assessing risks in the Arctic region, provided that the effects of temperature on oil fate and functional traits (e.g., body size and lipid content) of test species are considered. As such, using the CBR as a toxicity metric is beneficial because it is independent of functional traits, despite its temperature dependency. To the best of our knowledge, the present study is the first to report CBRs for oil. Environ Toxicol Chem 2024;43:1627-1637. © 2024 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.
Assuntos
Anfípodes , Poluição por Petróleo , Temperatura , Poluentes Químicos da Água , Animais , Regiões Árticas , Anfípodes/efeitos dos fármacos , Poluentes Químicos da Água/toxicidade , Petróleo/toxicidade , Dose Letal MedianaRESUMO
Sediments are an integral component of aquatic systems, linking multiple water uses, functions, and services. Contamination of sediments by chemicals is a worldwide problem, with many jurisdictions trying to prevent future pollution (prospective) and manage existing contamination (retrospective). The present review assesses the implementation of sediment toxicity testing in environmental regulations globally. Currently, the incorporation of sediment toxicity testing in regulations is most common in the European Union (EU), North America, and Australasian regions, with some expansion in Asia and non-EU Europe. Employing sediment toxicity testing in prospective assessments (i.e., before chemicals are allowed on the market) is most advanced and harmonized with pesticides. In the retrospective assessment of environmental risks (i.e., chemicals already contaminating sediments), regulatory sediment toxicity testing practices are applied inconsistently on the global scale. International harmonization of sediment toxicity tests is considered an asset and has been successful through the widespread adoption and deployment of Organisation for Economic Co-operation and Development guidelines. On the other hand, retrospective sediment assessments benefit from incorporating regional species and protocols. Currently used toxicity testing species are diverse, with temperate species being applied most often, whereas test protocols are insufficiently flexible to appropriately address the range of environmental contaminants, including nanomaterials, highly hydrophobic contaminants, and ionized chemicals. The ever-increasing and -changing pressures placed on aquatic resources are a challenge for protection and management efforts, calling for continuous sediment toxicity test method improvement to insure effective use in regulatory frameworks. Future developments should focus on including more subtle and specific toxicity endpoints (e.g., incorporating bioavailability-based in vitro tests) and genomic techniques, extending sediment toxicity testing from single to multispecies approaches, and providing a better link with ecological protection goals. Environ Toxicol Chem 2024;43:1697-1716. © 2024 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.
Assuntos
Sedimentos Geológicos , Testes de Toxicidade , Poluentes Químicos da Água , Sedimentos Geológicos/química , Poluentes Químicos da Água/toxicidade , Poluentes Químicos da Água/análise , Monitoramento Ambiental/métodos , Política Ambiental , AnimaisRESUMO
Per- and polyfluoroalkyl substances (PFAS) are persistent, bioaccumulative, and toxic synthetic chemicals of concern, which have been detected in nearly all environmental compartments. The present study provides a data analysis on PFAS concentrations in the Dutch inland and coastal national waters and fish sampled from 2008 to 2022 and 2015 to 2022, respectively. Although the fish database is relatively small, the water database is unique because of its temporal dimension. It appears that PFAS are omnipresent in Dutch water and fish, with relatively small spatial differences in absolute and relative concentrations (fingerprints) and few obvious temporal trends. Only perfluorooctanoic acid and perfluorooctanesulfonic acid (PFOS) aqueous concentrations in the rivers Rhine and Scheldt have substantially decreased since 2012. Still, PFOS concentrations exceed the European water quality standards at all and fish standards at many locations. Masses of PFAS entering the country and the North Sea are roughly 3.5 tonnes/year. Generally, the data suggest that most PFAS enter the Dutch aquatic environment predominantly through diffuse sources, yet several major point sources of specific PFAS were identified using fingerprints and monthly concentration profiles as identification tools. Finally, combining concentrations in fish and water, 265 bioaccumulation factors were derived, showing no statistically significant differences between freshwater and marine fish. Overall, the analysis provides new insights into PFAS bioaccumulation and spatiotemporal trends, mass discharges, and sources in The Netherlands. Environ Toxicol Chem 2024;43:965-975. © 2024 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.
Assuntos
Monitoramento Ambiental , Peixes , Fluorocarbonos , Poluentes Químicos da Água , Países Baixos , Poluentes Químicos da Água/metabolismo , Poluentes Químicos da Água/análise , Fluorocarbonos/metabolismo , Fluorocarbonos/análise , Peixes/metabolismo , Animais , Ácidos Alcanossulfônicos/análise , Ácidos Alcanossulfônicos/metabolismo , Bioacumulação , Rios/química , Caprilatos/metabolismoRESUMO
Sediment toxicity tests have applications in ecological risk and chemical safety assessments. Despite the many years of experience in testing and the availability of standard protocols, sediment toxicity testing remains challenging with very hydrophobic organic chemicals (VHOCs; i.e., chemicals with a log octanol/water partition coefficient of more than 6). The challenges primarily relate to the chemicals' low aqueous solubilities and slow kinetics, due to which several experimental artifacts may occur. To investigate the potential artifacts, experiments were performed, focusing on spiking and equilibrating (aging) sediments, as well as exposure quantification with passive sampling. The results demonstrated that generally applied, Organisation for Economic Co-operation and Development-recommended spiking (coating) methods may lead to significant chemical losses and the formation of nondissolved, nonbioavailable VHOCs. Direct spiking appeared to be the most optimal, provided that intensive mixing was applied simultaneously. Passive dosing was tested as a novel way of spiking liquid VHOCs, but the approach proved unsuccessful. Intensive postspiking mixing during sediment equilibration for 1 to 2 weeks was shown to be essential for producing a homogeneous system, minimizing the presence of nondissolved chemical (crystals or nonaqueous phase liquids; NAPLs), and creating a stable toxicological response in subsequent toxicity tests. Finally, exposure quantification of VHOCs in sediments through passive sampling was found to be feasible with different polymers, although prolonged equilibration times may be required, and determining sampler/water partition coefficients can be extremely challenging. The results of additional experiments, focusing on toxicity test exposure duration, concentrations above which NAPLs will occur, and ways to distinguish actual toxicity from false-positive results, are presented in Part 2 of this publication series. Environ Toxicol Chem 2024;43:1717-1727. © 2024 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.
Assuntos
Sedimentos Geológicos , Interações Hidrofóbicas e Hidrofílicas , Testes de Toxicidade , Poluentes Químicos da Água , Sedimentos Geológicos/química , Poluentes Químicos da Água/toxicidade , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/química , Compostos Orgânicos/toxicidade , Compostos Orgânicos/química , AnimaisRESUMO
Sediment toxicity testing with very hydrophobic organic chemicals (VHOCs) is challenging because of the chemicals' low aqueous solubilities and slow kinetics. The present study presents the results of experiments investigating whether the standard exposure duration of 28 days with benthic invertebrates is sufficient for VHOCs; above which concentrations in sediment VHOCs are present as "free phase," that is, crystals or non-aqueous-phase liquids (NAPLs); and whether it is possible to discriminate between actual VHOC toxicity and physical effects caused by NAPLs through fouling of the test organisms. The results suggest that the standard sediment toxicity test duration is sufficient for obtaining steady-state VHOC concentrations in Hyalella azteca and Lumbriculus variegatus, provided that spiking and equilibration are performed properly (i.e., no free phase present). Under these conditions, transient (days 3-20) peak-shaped toxicokinetics were observed, with steady-state concentrations reached at approximately 28 days. The concentration above which NAPLs are present, the so-called critical separate phase concentration (CSPC), was determined for several VHOCs by modeling and two experimental methods. Modeling resulted in unrealistic and variable data and therefore should be applied with caution. Experimentally determining CSPCs was successful and yielded values of approximately 1000 (400-2000) mg/kg dry weight, depending on the chemical. Finally, it was demonstrated that distinguishing actual toxicity from physical effects is possible by applying a well-considered test setup, combining toxicity tests with multiple invertebrates (including Lumbriculus, which serves as a negative control for fouling); a broad test concentration range, preferably up to at least 30 000 mg/kg; and passive sampling to localize the CSPC. Applying this setup, false-positive effects due to fouling, as well as false-negative results due to testing at too low concentrations (trying to stay below the CSPC), can be avoided. Environ Toxicol Chem 2024;43:1728-1739. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.
Assuntos
Anfípodes , Sedimentos Geológicos , Interações Hidrofóbicas e Hidrofílicas , Oligoquetos , Compostos Orgânicos , Testes de Toxicidade , Poluentes Químicos da Água , Sedimentos Geológicos/química , Animais , Oligoquetos/efeitos dos fármacos , Anfípodes/efeitos dos fármacos , Compostos Orgânicos/toxicidade , Poluentes Químicos da Água/toxicidadeRESUMO
Since recognizing the importance of bioavailability for understanding the toxicity of chemicals in sediments, mechanistic modeling has advanced over the last 40 years by building better tools for estimating exposure and making predictions of probable adverse effects. Our review provides an up-to-date survey of the status of mechanistic modeling in contaminated sediment toxicity assessments. Relative to exposure, advances have been most substantial for non-ionic organic contaminants (NOCs) and divalent cationic metals, with several equilibrium partitioning-based (Eq-P) models having been developed. This has included the use of Abraham equations to estimate partition coefficients for environmental media. As a result of the complexity of their partitioning behavior, progress has been less substantial for ionic/polar organic contaminants. When the EqP-based estimates of exposure and bioavailability are combined with water-only effects measurements, predictions of sediment toxicity can be successfully made for NOCs and selected metals. Both species sensitivity distributions and toxicokinetic and toxicodynamic models are increasingly being applied to better predict contaminated sediment toxicity. Furthermore, for some classes of contaminants, such as polycyclic aromatic hydrocarbons, adverse effects can be modeled as mixtures, making the models useful in real-world applications, where contaminants seldomly occur individually. Despite the impressive advances in the development and application of mechanistic models to predict sediment toxicity, several critical research needs remain to be addressed. These needs and others represent the next frontier in the continuing development and application of mechanistic models for informing environmental scientists, managers, and decisions makers of the risks associated with contaminated sediments. Environ Toxicol Chem 2023;00:1-17. © 2023 SETAC. This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.
RESUMO
For most passive sampling applications, the availability of accurate passive sampler-water partition coefficients (Kp-w ) is of key importance. Unfortunately, a huge variability exists in literature Kp-w values, in particular for hydrophobic chemicals such as polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). This variability is a major source of concern in the passive sampling community, which would benefit from high-quality Kp-w data. Hence, in the present study "best available" PAH and PCB Kp-w values are proposed for the two most often applied passive sampling materials, that is, low-density polyethylene and polydimethylsiloxane (PDMS), based on (1) a critical assessment of existing literature data, and (2) new Kp-w determinations for polyethylene and PDMS, with both polymers coming in six different versions (suppliers, thicknesses). The experimental results indicated that Kp-w values for PDMS are independent of the source, thus allowing straightforward standardization. In contrast, Kp-w values for polyethylene from different sources differed by up to 30%. Defining best available Kp-w values for this polymer therefore may require standardization of the polymer source. Application of the proposed best available Kp-w values will substantially improve the accuracy of freely dissolved concentration results by users and the potential for comparisons across laboratories. Environ Toxicol Chem 2022;41:1370-1380. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.
Assuntos
Bifenilos Policlorados , Hidrocarbonetos Policíclicos Aromáticos , Poluentes Químicos da Água , Dimetilpolisiloxanos/química , Monitoramento Ambiental/métodos , Bifenilos Policlorados/análise , Hidrocarbonetos Policíclicos Aromáticos/análise , Polietileno/química , Polímeros/química , Água/química , Poluentes Químicos da Água/análiseRESUMO
The freely dissolved concentration (Cfree) of hydrophobic organic chemicals (HOCs) in pore water is an important parameter in the risk assessment and management of contaminated sediments and soils. It can be determined most conveniently through ex situ passive sampling, i.e., in the laboratory. For this purpose, samples are taken from the field and transported to the laboratory, where they are stored and possibly manipulated by sieving, freezing, drying and/or grinding. Although the objective of ex situ passive sampling often is to determine a Cfree that reflects the metric under in situ conditions, hardly any information is available on possible effects of sample manipulation. Hence, the present study investigated the impact of freezing, freeze-drying, and grinding on Cfree of HOCs in field sediments, as determined with solid phase microextraction (SPME). Freezing increased the Cfree of 3- and 4-ring polycyclic aromatic hydrocarbons (PAHs) with up to a factor of 4, whereas for 5- and 6-ring PAHs hardly any effects were observed. Generally, additional freeze-drying did not further increase Cfree, but subsequently grinding the samples (further) increased Cfree of all PAHs with up to a factor of 4, leading to an overall maximum observed increase in Cfree of a factor of 16. Probably, these effects are caused by a structural change in the sorption matrix, enhancing PAH availability. The results indicate that freezing, freeze-drying, and grinding prior to ex situ Cfree determinations should be avoided, as these treatments may considerably increase the Cfree of HOCs, leading to an overestimation of risks.
Assuntos
Hidrocarbonetos Policíclicos Aromáticos , Poluentes Químicos da Água , Monitoramento Ambiental , Sedimentos Geológicos , Compostos Orgânicos , Hidrocarbonetos Policíclicos Aromáticos/análise , Poluentes Químicos da Água/análiseRESUMO
The freely dissolved concentration (Cfree) of hydrophobic organic chemicals in sediments and soils is considered the driver behind chemical bioavailability and, ultimately, toxic effects in benthic organisms. Therefore, quantifying Cfree, although challenging, is critical when assessing risks of contamination in field and spiked sediments and soils (e.g., when judging remediation necessity or interpreting results of toxicity assays performed for chemical safety assessments). Here, we provide a state-of-the-art passive sampling protocol for determining Cfree in sediment and soil samples. It represents an international consensus procedure, developed during a recent interlaboratory comparison study. The protocol describes the selection and preconditioning of the passive sampling polymer, critical incubation system component dimensions, equilibration and equilibrium condition confirmation, quantitative sampler extraction, quality assurance/control issues and final calculations of Cfree. The full procedure requires several weeks (depending on the sampler used) because of prolonged equilibration times. However, hands-on time, excluding chemical analysis, is approximately 3 d for a set of about 15 replicated samples.
Assuntos
Sedimentos Geológicos/análise , Poluentes do Solo/análise , Solo/química , Microextração em Fase Sólida/métodos , Poluição Ambiental , Interações Hidrofóbicas e HidrofílicasRESUMO
This work presents the results of an international interlaboratory comparison on ex situ passive sampling in sediments. The main objectives were to map the state of the science in passively sampling sediments, identify sources of variability, provide recommendations and practical guidance for standardized passive sampling, and advance the use of passive sampling in regulatory decision making by increasing confidence in the use of the technique. The study was performed by a consortium of 11 laboratories and included experiments with 14 passive sampling formats on 3 sediments for 25 target chemicals (PAHs and PCBs). The resulting overall interlaboratory variability was large (a factor of â¼10), but standardization of methods halved this variability. The remaining variability was primarily due to factors not related to passive sampling itself, i.e., sediment heterogeneity and analytical chemistry. Excluding the latter source of variability, by performing all analyses in one laboratory, showed that passive sampling results can have a high precision and a very low intermethod variability (Assuntos
Sedimentos Geológicos
, Poluentes Químicos da Água
, Monitoramento Ambiental
, Compostos Orgânicos
, Medição de Risco
RESUMO
Greater knowledge of biotransformation rates for ionizable organic compounds (IOCs) in fish is required to properly assess the bioaccumulation potential of many environmentally relevant contaminants. In this study, we measured in vitro hepatic clearance rates for 50 IOCs using a pooled batch of liver S9 fractions isolated from rainbow trout (Oncorhynchus mykiss). The IOCs included four types of strongly ionized acids (carboxylates, phenolates, sulfonates, and sulfates), three types of strongly ionized bases (primary, secondary, tertiary amines), and a pair of quaternary ammonium compounds (QACs). Included in this test set were several surfactants and a series of beta-blockers. For linear alkyl chain IOC analogues, biotransformation enzymes appeared to act directly on the charged terminal group, with the highest clearance rates for tertiary amines and sulfates and no clearance of QACs. Clearance rates for C12-IOCs were higher than those for C8-IOC analogues. Several analogue series with multiple alkyl chains, branched alkyl chains, aromatic rings, and nonaromatic rings were evaluated. The likelihood of multiple reaction pathways made it difficult to relate all differences in clearance to specific molecular features the tested IOCs. Future analysis of primary metabolites in the S9 assay is recommended to further elucidate biotransformation pathways for IOCs in fish.
Assuntos
Fígado/metabolismo , Oncorhynchus mykiss/metabolismo , Animais , Biotransformação , Extratos Hepáticos/metabolismo , Compostos Orgânicos/químicaRESUMO
Stringent and periodic iteration of regulations related to the monitoring of chemical releases from the offshore oil and gas industry requires the use of ever changing, rapidly developing and technologically advancing techniques. Passive samplers play an important role in water column monitoring of produced water (PW) discharge to seawater under Norwegian regulation, where they are used to; i) measure aqueous concentrations of pollutants, ii) quantify the exposure of caged organisms and investigate PW dispersal, and iii) validate dispersal models. This article summarises current Norwegian water column monitoring practice and identifies research and methodological gaps for the use of passive samplers in monitoring. The main gaps are; i) the range of passive samplers used should be extended, ii) differences observed in absolute concentrations accumulated by passive samplers and organisms should be understood, and iii) the link between PW discharge concentrations and observed acute and sub-lethal ecotoxicological end points in organisms should be investigated.
Assuntos
Ecotoxicologia/métodos , Monitoramento Ambiental/métodos , Indústria de Petróleo e Gás , Águas Residuárias , Animais , Aquicultura , Bivalves , Meio Ambiente , Monitoramento Ambiental/legislação & jurisprudência , Modelos Teóricos , Noruega , Água do Mar/química , Eliminação de Resíduos Líquidos/métodos , Águas Residuárias/análise , Águas Residuárias/química , Poluentes Químicos da Água/análiseRESUMO
In a previous study, we found a dose-dependent synergistic effect in recombinant yeast stably transfected with the human androgen receptor (AR), in response to co-exposure to testosterone and a commercially-available lubricant (engine) oil for cars. As there is relatively little knowledge on synergistic toxic effects and causative compounds, particularly for the androgenic system, the objective of the present study was to investigate this oil in more detail. The oil was fractionated into SARA fractions (so-called 'saturates', 'aromatics', 'resins', and 'asphaltenes') by open column chromatography. Surprisingly, when exposing the recombinant AR yeast to testosterone in combination with the separate SARA fractions, the synergistic effect could not be reproduced fully. After pooling the fractions again however, the full synergism returned. From subsequent exposures to combinations of two or three SARA fractions, it appeared that both the 'saturates' and the 'resins' fraction were required for obtaining the synergistic response with testosterone. This clearly demonstrates a synergistic effect related to the androgenic system caused by the joint action of at least three chemically-distinct compounds, or groups of compounds (i.e. testosterone, 'resins' and 'saturates'). Although detailed chemical analyses could not reveal the identity of the causative compounds and the in vivo relevance of the present results remains unclear, the results do add to the growing body of evidence on the potentially extremely complex character of mixture effects.
Assuntos
Androgênios/toxicidade , Petróleo/toxicidade , Receptores Androgênicos/genética , Testosterona/toxicidade , Androgênios/análise , Fracionamento Químico , Sinergismo Farmacológico , Regulação da Expressão Gênica/efeitos dos fármacos , Proteínas de Fluorescência Verde/genética , Humanos , Petróleo/análise , Testosterona/análise , Leveduras/genéticaRESUMO
Octanol-water partition coefficients (KOW ) are widely used in fate and effects modeling of chemicals. Still, high-quality experimental KOW data are scarce, in particular for very hydrophobic chemicals. This hampers reliable assessments of several fate and effect parameters and the development and validation of new models. One reason for the limited availability of experimental values may relate to the challenging nature of KOW measurements. In the present study, KOW values for 13 polycyclic aromatic hydrocarbons were determined with the gold standard "slow-stirring" method (log KOW 4.6-7.2). These values were then used as reference data for the development of an alternative method for measuring KOW . This approach combined slow stirring and equilibrium sampling of the extremely low aqueous concentrations with polydimethylsiloxane-coated solid-phase microextraction fibers, applying experimentally determined fiber-water partition coefficients. It resulted in KOW values matching the slow-stirring data very well. Therefore, the method was subsequently applied to a series of 17 moderately to extremely hydrophobic petrochemical compounds. The obtained KOW values spanned almost 6 orders of magnitude, with the highest value measuring 10(10.6) . The present study demonstrates that the hydrophobicity domain within which experimental KOW measurements are possible can be extended with the help of solid-phase microextraction and that experimentally determined KOW values can exceed the proposed upper limit of 10(9) . Environ Toxicol Chem 2016;35:1371-1377. © 2015 SETAC.
Assuntos
Modelos Químicos , Octanóis/química , Hidrocarbonetos Policíclicos Aromáticos/química , Água/química , Dimetilpolisiloxanos/química , Interações Hidrofóbicas e Hidrofílicas , Microextração em Fase SólidaRESUMO
Nowadays, passive sampling is a widely applied technique to determine freely dissolved aqueous concentrations of hydrophobic organic chemicals (HOCs), such as polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). Crucial to the measurements are sampler-water partition coefficients, which are generally determined in the laboratory under "standard conditions" (in freshwater at 20 °C). Theoretically, however, the coefficients are dependent on environmental conditions, such as temperature and salinity. Yet, there are insufficient experimental data in the scientific literature to prove this for different polymers. Several polymers are already being applied during field monitoring, however, and neglecting any effects may lead to imprecise results. In the present study, we therefore quantified the effects of temperature and salinity on the sampler-water partition coefficients of PAHs and PCBs for silicone rubber, a material used in Dutch passive sampling monitoring campaigns. The results demonstrated a chemical-specific and hydrophobicity-dependent temperature effect, being independent of salinity, and a chemical- and temperature-independent salinity effect. Based on the obtained data, location-specific silicone rubber-water partition coefficients (Ksr-w; adjusted for temperature and salinity) can be calculated. The impact of applying such location-specific values was demonstrated using the Dutch passive sampling field monitoring database, covering ten years of PAH and PCB data for several locations. Adjusting the Ksr-w values resulted in aqueous concentrations that were lowered by a factor of 1.6 on average. The reduction was rather constant because of the manner of sampling (under nonequilibrium conditions and using performance reference compounds) and calculating. When sampling under equilibrium conditions in seawater at temperatures at about freezing, and/or applying different calculation approaches, the adjustment effect can potentially increase up to a factor of about 5-6 for the more hydrophobic PAHs and PCBs. Although this study exclusively focused on silicone rubber, qualitatively the results will also apply to other passive sampling materials.
Assuntos
Monitoramento Ambiental/instrumentação , Monitoramento Ambiental/métodos , Interações Hidrofóbicas e Hidrofílicas , Compostos Orgânicos/análise , Salinidade , Elastômeros de Silicone/análise , Temperatura , Bifenilos Policlorados/análise , Hidrocarbonetos Policíclicos Aromáticos/análise , Padrões de Referência , Fatores de TempoRESUMO
Ecotoxicological effect data are generally expressed as effective concentrations in the external exposure medium and do thus not account for differences in chemical uptake, bioavailability, and metabolism, which can introduce substantial data variation. The Critical Body Residue (CBR) concept provides clear advantages, because it links effects directly to the internal exposure. Using CBRs instead of external concentrations should therefore reduce variability. For compounds that act via narcosis even a constant CBR has been proposed. Despite the expected uniformity, CBR values for these compounds still show large variability, possibly due to biased and inconsistent experimental testing. In the present study we tested whether variation in CBR data can be substantially reduced when using an improved experimental design and avoiding confounding factors. The aim was to develop and apply a well-defined test protocol for accurately and precisely measuring CBR data, involving improved (passive) dosing, sampling, and processing of organisms. The chemicals 1,2,4-trichlorobenzene, 1,2,3,4-tetrachlorobenzene, 2,3,4-trichloroaniline, 2,3,5,6-tetrachloroaniline, 4-chloro-3-methylphenol, pentylbenzene, pyrene, and bromophos-methyl were tested on Lumbriculus variegatus (California blackworm), Hyalella azteca (scud), and Poecilia reticulata (guppy), which yielded a high-quality database of 348 individual CBR values. Medians of CBR values ranged from 2.1 to 16.1 mmol/kg wet weight (ww) within all combinations of chemicals and species, except for the insecticide bromophos-methyl, for which the median was 1.3 mmol/kg ww. The new database thus covers about one log unit, which is considerably less than in existing databases. Medians differed maximally by a factor of 8.4 between the 7 chemicals but within one species, and by a factor of 2.6 between the three species but for individual chemicals. Accounting for the chemicals' internal distribution to different partitioning domains and relating effects to estimated concentrations in the target compartment (i.e., membrane lipids) was expected to but did not decrease the overall variability, likely because the surrogate partition coefficients for membrane lipid, storage lipid, protein, and carbohydrate that were used as input parameters did not sufficiently represent the actual partitioning processes. The results of this study demonstrate that a well-designed test setup can produce CBR data that are highly uniform beyond chemical and biological diversity.
Assuntos
Anfípodes/metabolismo , Poluentes Ambientais/farmacocinética , Oligoquetos/metabolismo , Poecilia/metabolismo , Compostos de Anilina/farmacocinética , Animais , Clorobenzenos/farmacocinética , Cresóis/farmacocinética , Relação Dose-Resposta a Droga , Feminino , Masculino , Organotiofosfatos/farmacocinética , Pirenos/farmacocinética , Projetos de Pesquisa , Medição de RiscoRESUMO
SOLUTIONS (2013 to 2018) is a European Union Seventh Framework Programme Project (EU-FP7). The project aims to deliver a conceptual framework to support the evidence-based development of environmental policies with regard to water quality. SOLUTIONS will develop the tools for the identification, prioritisation and assessment of those water contaminants that may pose a risk to ecosystems and human health. To this end, a new generation of chemical and effect-based monitoring tools is developed and integrated with a full set of exposure, effect and risk assessment models. SOLUTIONS attempts to address legacy, present and future contamination by integrating monitoring and modelling based approaches with scenarios on future developments in society, economy and technology and thus in contamination. The project follows a solutions-oriented approach by addressing major problems of water and chemicals management and by assessing abatement options. SOLUTIONS takes advantage of the access to the infrastructure necessary to investigate the large basins of the Danube and Rhine as well as relevant Mediterranean basins as case studies, and puts major efforts on stakeholder dialogue and support. Particularly, the EU Water Framework Directive (WFD) Common Implementation Strategy (CIS) working groups, International River Commissions, and water works associations are directly supported with consistent guidance for the early detection, identification, prioritisation, and abatement of chemicals in the water cycle. SOLUTIONS will give a specific emphasis on concepts and tools for the impact and risk assessment of complex mixtures of emerging pollutants, their metabolites and transformation products. Analytical and effect-based screening tools will be applied together with ecological assessment tools for the identification of toxicants and their impacts. The SOLUTIONS approach is expected to provide transparent and evidence-based candidates or River Basin Specific Pollutants in the case study basins and to assist future review of priority pollutants under the WFD as well as potential abatement options.
Assuntos
Conservação dos Recursos Naturais/métodos , Poluentes Químicos da Água/análise , Poluição Química da Água/prevenção & controle , Recursos Hídricos/estatística & dados numéricos , Ecossistema , Monitoramento Ambiental , Política Ambiental , União Europeia , Substâncias Perigosas/análise , Medição de Risco , Poluição Química da Água/estatística & dados numéricosRESUMO
Whereas octanol, triacylglycerides, and liposomes have all been proposed as surrogates for measuring the affinity of hydrophobic organic contaminants to human lipids, no comparative evaluation of their suitability exists. Here we conducted batch sorption experiments with polyoxymethylene passive samplers to determine the partition coefficients at 37 °C of 18 polychlorinated biphenyls (PCBs) from water into (i) triolein (Ktriolein/water), (ii) eight types of liposomes (Kliposome/water), (iii) human abdominal fat tissues (KAFT/water) from seven individuals, and (iv) human MCF-7 cells cultured in vitro (Kcell/water). Differences between KAFT/water among individuals and between Kliposome/water among liposome types were very small and not correlated to structural attributes of the PCBs. Similarly, the length and degree of saturation of the phospholipid carbon chains, the headgroup, and the composition of the liposome did not affect the partitioning of PCBs into the studied liposomes. Whereas Kliposome/water values were similar to literature values of Koctanol/water adjusted to 37 °C, they both were lower than KAFT/water and Kcell/water by a factor of 3 on average. Partitioning of PCBs into triolein on the other hand closely mimicked that into human lipids, for which triolein is thus a better surrogate than either octanol or liposomes. Previously published polyparameter linear free energy relationships for partitioning from water into storage lipids and liposomes predicted the measured partition coefficients with a root-mean-square error of less than 0.15 log units, if the chosen equations and solute descriptors do not allow chlorine substitution in the ortho-position to influence the prediction. By guiding the selection of (i) a surrogate for the experimental determination and (ii) a method for the prediction of partitioning into human lipids, this study contributes to a better assessment of hydrophobic organic contaminant bioaccumulation in humans.
Assuntos
Tecido Adiposo/metabolismo , Lipossomos/metabolismo , Octanóis/metabolismo , Bifenilos Policlorados/metabolismo , Trioleína/metabolismo , Adulto , Idoso , Cloro/metabolismo , Feminino , Humanos , Interações Hidrofóbicas e Hidrofílicas , Lipídeos , Lipossomos/química , Células MCF-7 , Pessoa de Meia-Idade , Octanóis/química , Bifenilos Policlorados/química , Termodinâmica , Trioleína/química , Água/químicaRESUMO
This article provides practical guidance on the use of passive sampling methods (PSMs) that target the freely dissolved concentration (Cfree ) for improved exposure assessment of hydrophobic organic chemicals in sediments. Primary considerations for selecting a PSM for a specific application include clear delineation of measurement goals for Cfree , whether laboratory-based "ex situ" and/or field-based "in situ" application is desired, and ultimately which PSM is best-suited to fulfill the measurement objectives. Guidelines for proper calibration and validation of PSMs, including use of provisional values for polymer-water partition coefficients, determination of equilibrium status, and confirmation of nondepletive measurement conditions are defined. A hypothetical example is described to illustrate how the measurement of Cfree afforded by PSMs reduces uncertainty in assessing narcotic toxicity for sediments contaminated with polycyclic aromatic hydrocarbons. The article concludes with a discussion of future research that will improve the quality and robustness of Cfree measurements using PSMs, providing a sound scientific basis to support risk assessment and contaminated sediment management decisions.