Behavior Of Persistent Organic Pollutants Research Articles

Potential implications of future climate and land‐cover changes for the fate and distribution of persistent organic pollutants in Europe

ABSTRACTAim Climate change is having far‐reaching effects on the global environment. Here, the ALARM (Assessing Large‐scale Risks for Biodiversity with Tested Methods, European Union 6th Framework Programme) climate change scenarios were used to assess changes to the fate of selected persistent organic pollutants (POPs). Scenarios detailing climate and land‐cover changes, such as precipitation, temperature and vegetation cover, were used as input in a European multi‐media chemical fate model to help understand their impact on the environmental fate and behaviour of POPs over the period 1990–2100 in Europe.Location Europe.Methods Chemicals chosen for study included four classical POPs (two polychlorinated biphenyl congeners and two polybrominated diphenyl ether congeners). Using 30‐year time steps, the model was run in steady‐state mode four times for each chemical and each ALARM scenario.Results PCB153 displayed the greatest changes, with a reduction in burden of up to 40% in some Mediterranean compartments (e.g. soil and fresh water) under the worst case climate change scenario. The overall continental persistence of PCB153 was reduced by 1.5 years (12%) due to increased volatilization and degradation in air from a drier and warmer south‐western Europe. This predicted loss resulted in a transfer and redeposition to the cooler and wetter north‐eastern Europe, and increased the burden of PCB153 to Arctic compartments by up to 22%. The remaining chemicals displayed less pronounced changes, particularly under more the sustainable scenarios.Main conclusions Overall, the model simulations suggest that the dominant driver behind differences seen between the present and climate‐changed future scenarios is temperature, resulting in a slight shift in chemical distribution from surface compartments to the air. This subsequently leads to a reduced continental persistence for PCBs and a north‐easterly migration due to prevailing meteorological conditions. As a result of these calculations, it is reasonable to conclude that chemicals with properties similar to PCBs may experience enhanced mobility due to climate change. However, the climate‐induced temperature changes were not large enough to significantly alter the distribution of brominated diphenyl ethers (BDEs), which are less volatile and have greater enthalpies of phase change.

A dynamic biophysical fugacity model of the movement of a persistent organic pollutant in Antarctic marine food webs

Environmental contextPersistent organic pollutants (POPs) are potentially toxic chemicals capable of long distance transport and are often found far from their source. Little is known of their behaviour in Antarctica, where the marine plankton food web is driven by strong seasonal variations in solar radiation. Here the first dynamic coupled ecosystem–fugacity model to describe how POPs distribute through the Antarctic environment is presented. The model is used to identify the important processes that govern the presence of hexachlorobenzene in Antarctic plankton. AbstractPolar regions can be repositories for many persistent organic pollutants (POPs). However, comparatively little is known of the movement and behaviour of POPs in Antarctic ecosystems. These systems are characterised by strong seasonal effects of light on plankton dynamics. This work describes a mass-conserving, fugacity-based dynamic model to describe the movement of POPs in the Antarctic physical and plankton systems. The model includes dynamic corrections for changes in the population volumes and the temperature dependence of the fugacity capacities, and was developed by coupling a dynamic Nutrient–Phytoplankton–Zooplankton–Detritus (NPZD) ecosystem model to fugacity models of the chemistry and biology of the Southern Ocean. The model is applied to the movement of hexachlorobenzene, a POP found in the Antarctic environment. The model predicts that the burden of HCB in the plankton varies with the seasonal cycle in Antarctic waters, and induces a seasonal variation in the biomagnification factor of zooplankton. This suggests that time series of POP concentrations in Antarctic biotic and abiotic systems should be measured over complete seasonal cycles. Furthermore, detritus is shown to be a key contributor to the movement of POPs in polar environments, linking physical and biological components of the model.

Introduction to Special Series: Science‐Based Guidance and Framework for the Evaluation and Identification of PBTs and POPs

There is a growing sense of urgency among scientists and environmental policy-makers concerning the need for improving the scientific foundation supporting international regulations for identifying and evaluating persistent, bioaccumulative, and toxic (PBT) substances and persistent organic pollutants (POPs) in the environment. The current national and international regulations define PBTs and POPs in terms of fairly strict criteria that are based on the state of the science in the late 1970s and early 1980s. Since then, an evolution in the state of the science has produced new insights into PBT substances and an array of new methods to identify PBT chemicals. The development of regulatory criteria has not kept up with the rapid development in environmental chemistry and toxicology, and as a result, scientists often find themselves in the situation where guidance on PBT and POPs criteria is limited and, in some respects, out of date. With this background, a Society of Environmental Toxicology and Chemistry (SETAC) Pellston Workshop brought together experts from academia, government, and industry to reach consensus on the significance of advancements in our understanding of the behavior and potential impact of POPs and PBTs in the environment, the current understanding of the state of the science, as well as recommendations for policy-makers to improve and coordinate national and international regulations on this issue. The workshop builds on the outcome of a previous Pellston workshop, held in 1998, which focused on the evaluation of persistence and long-range transport of organic chemicals in the environment, and is linked to other recent Pellston workshops, among them the Tissue Residue Approach for Toxicity Assessment workshop held in 2007. The results of this workshop are conveyed in a series of 9 articles, published in this issue of Integrated Environmental Assessment and Management, and describe the coordination of science, regulation, and management needed to more effectively achieve a common goal of managing chemicals on our planet.

Altitude dependence of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in surface soil from Tibetan Plateau, China

Remote mountain areas besides high latitude regions are beginning to receive increased attention in studying the transport and behavior of persistent organic pollutants (POPs). In the present work, surface soil samples were collected from the Tibetan Plateau, the highest plateau in the world which includes the northern slope of Mt. Qomolangma, to investigate the levels and trends of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) along the altitudinal gradient. The average PCB and PBDE concentrations were 185.6 ng kg −1 dry weight (dw) (range 47.1–422.6 ng kg −1 dw) and 11.1 ng kg −1 dw (range 4.3–34.9 ng kg −1 dw), respectively. Regression analysis between the log-transformed TOC-normalized concentrations and the altitudes of the sampling sites showed two opposite trends with regard to altitude dependence: negative relationship with altitude below about 4500 m followed by a positive altitude dependence above this point. Considering minimum anthropogenic activities and very sparse precipitation in the north of Himalayas, the trends above 4500 m imply that the significant altitude dependence of these two groups of POPs were irrespective of pollution sources, but could be predicted by the global distillation effect involving cold condensation in high altitude mountain areas. Increasing levels of heavier congeners were found in higher altitude sites, although the lighter congeners were the main contributors to the total amount, suggesting that less volatile congeners seem to become enriched easier than those more volatile at higher altitudes in this region.

Photochemical Degradation of PCBs in Snow

This work represents the first laboratory study known to the authors describing photochemical behavior of persistent organic pollutants in snow at environmentally relevant concentrations. The snow samples were prepared by shock freezing of the corresponding aqueous solutions in liquid nitrogen and were UV-irradiated in a photochemical cold chamber reactor at -25 degrees C, in which simultaneous monitoring of snow-air exchange processeswas also possible. The main photodegradation pathway of two model snow contaminants, PCB-7 and PCB-153 (c approximately 100 ng kg(-1)), was found to be reductive dehalogenation. Possible involvement of the water molecules of snow in this reaction has been excluded by performing the photolyses in D2O snow. Instead, trace amounts of volatile organic compounds have been proposed to be the major source of hydrogen atom in the reduction, and this hypothesis was confirmed by the experiments with deuterated organic cocontaminants, such as d6-ethanol or d8-tetrahydrofuran. It is argued that bimolecular photoreduction of PCBs was more efficient or feasible than any other phototransformations under the experimental conditions used, including the coupling reactions. The photodegradation of PCBs, however, competed with a desorption process responsible for the pollutant loss from the snow samples, especially in case of lower molecular-mass congeners. Organic compounds, apparently largely located or photoproduced on the surface of snow crystals, had a predisposition to be released to the air but, at the same time, to react with other species in the gas phase. It is concluded that physicochemical properties of the contaminants and trace co-contaminants, their location and local concentrations in the matrix, and the wavelength and intensity of radiation are the most important factors in the evaluation of organic contaminants' lifetime in snow. Based on the results, it has been estimated that the average lifetime of PCBs in surface snow, connected exclusively to the photoreductive dechlorination process, is 1-2 orders of magnitude longer than that in surface waters when subjected to the equivalent solar radiation. However, in case that the concentration of the hydrogen peroxide in natural snow is sufficient, the photoinduced oxidation process could succeed the photoreductive dechlorination and evaporative fluxes as the major sink.

What environmental fate processes have the strongest influence on a completely persistent organic chemical's accumulation in the Arctic?

Fate and transport models can be used to identify and classify chemicals that have the potential to undergo long-range transport and to accumulate in remote environments. For example, the Arctic contamination potential (ACP), calculated with the help of the zonally averaged global transport model Globo-POP, is a numerical indicator of an organic chemical's potential to be transported to polar latitudes and to accumulate in the Arctic ecosystem. It is important to evaluate how robust such model predictions are and in particular to appreciate to what extent they may depend on a specific choice of environmental model input parameters. Here, we employ a recently developed graphical method based on partitioning maps to comprehensively explore the sensitivity of ACP estimates to variations in environmental parameters. Specifically, the changes in the ACP of persistent organic contaminants to changes in each environmental input parameter are plotted as a function of the two-dimensional hypothetical “chemical space” defined by two of the three equilibrium partition coefficients between air, water and octanol. Based on the patterns obtained, this chemical space is then segmented into areas of similar parameter sensitivities and superimposed with areas of high default ACP and elevated environmental bioaccumulation potential within the Arctic. Sea ice cover, latitudinal temperature gradient, and macro-diffusive atmospheric transport coefficients, and to a lesser extent precipitation rate, display the largest influence on ACP-values for persistent organic contaminants, including those that may bioaccumulate within the polar marine ecosystems. These environmental characteristics are expected to be significantly impacted by global climate change processes, highlighting the need to explore more explicitly how climate change may affect the long-range transport and accumulation behavior of persistent organic pollutants.

Long-Term Fate of Polychlorinated Biphenyls and Polycyclic Aromatic Hydrocarbons in an Agricultural Soil

Laboratory studies are useful for understanding the behavior of persistent organic pollutants (POPs) in soil, although such investigations do not always relate directly to field conditions. Outdoor lysimeter studies may be used to overcome this problem. This work aimed to investigate the behavior of two polycyclic aromatic hydrocarbons (PAHs) (fluoranthene and benzo[a]pyrene) and two polychlorinated biphenyls (PCBs; congeners 28 and 52) in soil, using lysimeters established in 1990 atthe Agrosphere Institute (Forschungszentrum Julich GmbH, Germany). The two PAHs were in one lysimeter, and the PCBs were in a second lysimeter. Afurther aim of the study was to determine soil half-lives for each of the contaminants. The overall decline in PAH concentrations was considerably greater than forthe PCBs over the 152 month study. The PCBs exhibited greater chemical extractability than the PAHs and were demonstrated to have migrated through the soil column to a greater extent than the PAHs. Loss of PCBs from surface soil was not considered to have been congener specific for the two PCB congeners in this study. The two PAHs varied in their extents of total loss and movement through the soil column. Soil half-lives were determined as 10.9 y for [12C]PCB 28, 11.2 yr for [12C]PCB 52, 2.7 yr for benzoqpyrene, and 32 d (phase 1) to 38 yr (phase 2) for fluoranthene. These are shown to disagree with some previous estimates of POP half-lives in soil, suggesting that previous studies underestimated persistence by 10-fold or more.

Field Calibration of Rapidly Equilibrating Thin-Film Passive Air Samplers and Their Potential Application for Low-Volume Air Sampling Studies

This paper reports on a field calibration and ambient deployment study with rapidly equilibrating thin-film passive air samplers. POlymer-coated Glass (POG) samplers have a coating of ethylene vinyl acetate (EVA) less than 1 microm thick coated on to glass, which can be dissolved off after exposure and prepared for quantification of persistent organic pollutants (POPs) that have partitioned into the film during field exposure. In this study, POGs were exposed for up to 18 d, in a study to assess compound uptake rates and their time to approach equilibrium. Results confirmed theoretical predictions, with time to equilibrium varying between a few hours to ca. 20 d for PCB-18 and PCB-138, respectively. Performance reference compounds and contaminated POGs were used to investigate depuration kinetics, confirming that lighter congeners behave extremely dynamically with substantial losses from the films over periods of a few hours. Repeated deployments of the samplers for different3-d periods yielded detectable levels of a range of PCB congeners, which had partitioned from as little as approximately 2 to 10 m3 air. This highlights the potential utility of POGs for extremely sensitive and dynamic passive air sampling in the future to help improve understanding of sources, environmental fate, and behavior of POPs. Recommendations are made for future improvements/refinements in POG sampling and handling procedures.

Compositional and chiral profiles of weathered chlordane residues in soil

AbstractThe fate of chlordane and other persistent organic pollutants in the environment is of international concern. The behavior of persistent organic pollutants under both abiotic and biotic conditions must be determined for the comprehensive elucidation of their cycling through the biosphere. Standard analytical methods such as gas chromatography with electron capture detection are adequate for studies of cycling under abiotic conditions. Since two of the main components of technical chlordane, cis‐chlordane and trans‐chlordane, are optically active, chiral gas chromatography can be used to study the impact of biotic influences on chlordane's fate. We report here the use of chiral gas chromatography interfaced with ion trap mass spectrometry as part of an analytically rigorous method for the simultaneous determination of the compositional and chiral profiles of weathered soil residues of technical chlordane. Using the method described, several patterns in the long‐term weathering of technical chlordane in soil are observed.

Compositional and chiral profiles of weathered chlordane residues in soil.

The fate of chlordane and other persistent organic pollutants in the environment is of international concern. The behavior of persistent organic pollutants under both abiotic and biotic conditions must be determined for the comprehensive elucidation of their cycling through the biosphere. Standard analytical methods such as gas chromatography with electron capture detection are adequate for studies of cycling under abiotic conditions. Since two of the main components of technical chlordane, cis-chlordane and trans-chlordane, are optically active, chiral gas chromatography can be used to study the impact of biotic influences on chlordane's fate. We report here the use of chiral gas chromatography interfaced with ion trap mass spectrometry as part of an analytically rigorous method for the simultaneous determination of the compositional and chiral profiles of weathered soil residues of technical chlordane. Using the method described, several patterns in the long-term weathering of technical chlordane in soil are observed.

Introducing selective supercritical fluid extraction as a new tool for determining sorption/desorption behavior and bioavailability of persistent organic pollutants in sediment

This review article intends to introduce the possibility of utilizing selective supercritical fluid extraction (SFE) as a tool to study sorption/desorption processes and bioavailability of persistent organic pollutants (POP) in sediment. Sorption/desorption behavior and bioavailability studies of POPs is a large research area, but still many unsolved problems exists. Therefore novel approaches to investigate mechanistic behavior of POPs in sediments are needed. Present literature on SFE points to the fact that selective SFE measurements can improve our knowledge, and recent investigations have been performed that demonstrate this. Results obtained with selective SFE can be connected to desorption of POPs in sediments under natural conditions in aquatic ecosytems. The ultimate goal is to use selective SFE as a way to determine the bioavailable fraction present within a matrix. A few preliminary results are presented here which may serve as a starting point for future studies.

Leaching behavior of PCBs and PCDDs/DFs from some waste materials

Although it is well known that some waste materials and their incinerator residues contain persistent organic pollutants (POPs) such as PCBs and PCDDs/DFs, little attention has been paid to the leaching behavior of these chemicals because of their low solubility. Due to the coexistence of surfactants in wastes, however, leaching concentration of POPs may increase. Therefore, leaching tests with and without those substances were conducted in order to understand the influence of surfactant-like substances on POPs leaching. In those tests, linear alkylbenzene sulfonate (LAS) and humic acid were used as surfactant-like substances. Shredder residues from car/electrical goods recycling and fly ash from a municipal solid waste (MSW) incinerator were used in these leaching tests. Furthermore, an experiment was carried out to understand the influence of fine particles on the leaching concentration of POPs. The results indicate that surfactant-like substances increase the leaching concentration of POPs, and fine particles related closely to the transporting behavior of POPs.

Leaching behavior of persistent organic pollutants (POPs) in shredder residues

It is well known that some kinds of waste contain persistent organic pollutants (POPS) such as PCDD/DFs and PCBs. Leaching behaviors of these chemicals, however, have not been focused so much because of their low leachability. On the other hand, shredder residues originated from automobiles and electric appliances consist mainly of plastics, such as PVC, which contain additives including DEHP. In this study, contents analyses and leaching tests with and without surfactant-like substances for shredder residues were conducted. As a result, shredder residues from automobile and electric appliance contained PCBs in ppm level and a quantity of PCDD/DFs. Surfactant-like substances increase the leaching concentration of POPs. DEHP also leached out considerably even though using distilled water.