Exposure of ruminants to persistent organic pollutants and potential of decontamination

Human activities are emitting persistent organic pollutants (POPs) to the environment. These compounds have raised concerns about the risk of transfer through the food chain via animal products. They are characterized by a strong persistence in environmental matrices and a lipophilicity which may lead to their accumulation in fat tissues. In EU Regulations (no. 1881/2006, 1259/2011), maximum acceptable levels for polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans (PCDD/Fs), and dioxin-like or nondioxin-like polychlorinated biphenyls (PCBs) in food of animal origin have been set. Transfer rates from contaminated fodder to milk have been established: for PCBs, the rate of transfer varies from 5 to 90 % and for PCDD/Fs from 1 to 40 %. The differential transfer of the compounds towards milk is related to the hydrophobicity of the pollutants and to their metabolic susceptibility. According to numerous authors, soil is the major reservoir for POPs, and its involuntary ingestion by farm animals reared outdoors may be the main cause of animal product contamination (meat, milk, or eggs). Recent studies seem to indicate that soil is a real risk matrix in terms of transfer of pollutants to the food chain. A POP crisis management is extremely difficult, since it impacts many farmers located in the contaminated area. The question arising is to know if livestock contaminated by POPs may be decontaminated and further used for their initial purpose. Recent data demonstrate that the decontamination process appear feasible and depends on initial level of contamination or the physiological status of the animals.     

Global-scale environmental transport of persistent organic pollutants

In order to realistically simulate both chemistry and transport of atmospheric organic pollutants, it is indispensable that the applied models explicitly include coupling between different components of the global environment such as atmosphere, hydrosphere, cryosphere and soil system. A model with such properties is presented.

The atmospheric part of the model is based on the equations in a general contravariant form which permits easy changes of the coordinate system by redefining the metric tensor of a specifically employed coordinate system. Considering a need to include explicitly the terrain effects, the terrain following spherical coordinate system is chosen from among many possible coordinate systems. This particular system is a combination of the Gal-Chen coordinates, commonly employed in mesoscale meteorological models, and the spherical coordinates, typical for global atmospheric models.

In addition to atmospheric transport, the model also simulates the exchange between air and different types of underlying surfaces such as water, soil, snow, and ice. This approach permits a realistic representation of absorption and delayed re-emission of pollutants from the surface to the atmosphere and, consequently, allows to capture hysteresis-like effects of the exchange between the atmosphere and the other components of the system. In this model, the most comprehensive numerical representation of the exchange is that for soil. In particular, the model includes a realistic soil module which simulates both diffusion and convection of a tracer driven by evaporation from the soil, precipitation, and gravity.

The model is applied to a long-term simulation of the transport of pesticides (hexachlorocyclohexanes in particular). Emission fluxes from the soil are rigorously computed on the basis of the realistic data of the agricultural application. All four modelled systems, i.e. atmosphere, soil, hydrosphere and cryosphere, are driven by objectively analysed meteorological data supplemented, when necessary, by climatological information. Therefore, the verification against the observed data is possible. The comparison of the model results and the observations taken at remote stations in the Arctic indicates that the presented global modelling system is able to capture both trends and short-term components in the observed time series of the concentrations, and therefore, provides a useful tool for the evaluation of the source–receptor relationships.     

The legacy of persistent organic pollutants in Azerbaijan: an assessment of past use and current contamination

Azerbaijan has a history of production and heavy use of organochlorine pesticides (OCPs) with use focused in the main agricultural lowland region centred on the Kur River. Using a number of data sources, including archived reports from several government ministries, we attempt to construct production and use inventories for dichlorodiphenyltrichloroethane (DDT) and HCHs and compare these to scientific estimates of production and use of these chemicals in the 1960s to the 1980s. Notable discrepancies are evident particularly for DDT, with Azeri government records indicating much higher use (147-fold) than that estimated by the international scientific community. Soil and river sediment data from the 1980s and 2000s are also presented. While it is recognised that analytical uncertainties remain high for these older data (generated by GC–ECD), there is some evidence to show a decline in concentrations for some OCPs over this period. Extremely high concentrations of OCPs are evident for soils sampled in the vicinity of obsolete pesticide storage sites (found in numerous locations around the agricultural lowlands) and these levels may pose a health risk to wildlife and humans. River sediment data indicate high levels of both OCPs and polychlorinated biphenyls (PCBs), particularly downstream of the confluence of the two main rivers, the Kur and Araz. Particle-bound annual fluxes from the Kur River into the Caspian Sea are estimated for PCBs and OCPs and these are likely to influence levels observed in local coastal sediments, with agreement between river sediment data generated in the early 2000s and coastal marine sediment data generated from separate studies. We recommend that monitoring efforts should focus on soils in agricultural areas and around pesticide storage and production facilities as these soils will continue to provide a source of POPs to the regional environment.     

持久性有机污染物分析和处理技术研究进展

阐述了持久性有机污染物 (POPs)的特性、POPs对人体健康和生态环境的危害及其判定基准 ,综述了其分析和研究方法及治理技术 ,归纳了POPs的研究内容。     

The use of clays to sequestrate organic pollutants. Leaching experiments

Leaching experiments are performed from clay-pollutant systems in order to evaluate the capability of clays to sequestrate organic pollutants from wastewaters. Reference kaolinite KGa-1b, montmorrillonite SWy-2 and reference soil BCR^®-700 are the sorbent materials. 2,4,6-trichloroaniline (2,4,6-TCA) and 4-chlorophenol (4-CP) are the typical pollutants, sorbed at amounts of 10.0 mg g⁻¹ and 5.8 mg g⁻¹ on SWy-2 and 7.3 mg g⁻¹ and 2.2 mg g⁻¹ on KGa-1b, respectively.The leaching agents are ultrapure water and model solutions of acid rain and surface waters that simulate meteoric leaching. 1.0 mM HNO₃, 1.0 mM H₂SO₄ solutions and a methanol/water 50/50 (v/v) mixture simulate leaching agents of industrial source.The results are compared and the preferential capability of the clays to sequestrate the more lipophilic 2,4,6-TCA is evidenced.The bond interactions are discussed and explained through preferential adsorption reactions. For montmorrillonite also a simultaneous intercalation in the phyllosilicate interlayer is proposed.     

On enumeration of congeners of common persistent organic pollutants

Congeners are molecules based on the same carbon skeleton but different by the number of substituents and/or a substitution pattern. Various Persistent Organic Pollutants (POPs) exist in the environment as families of halogen substituted congeners and/or their hydroxyl and methoxy substituted derivatives. Numbers of possible congeners resulting from substitution of a parent POP molecule with only one type of chemical group are generally available. At the same time, numbers of mixed-substituent congeners have not been counted and presented yet, although there is an increasing interest in such as is the increasing number of research articles presenting results on already identified Cl−/Br−mixed type congeners and/or their HO-/CH₃O-mixed metabolites. We have enumerated and counted possible mixed-substituent congeners of common POPs. This article presents the obtained numbers for congener families of benzene, naphthalene, biphenyl, diphenyl ether, dibenzo-p-dioxin, dibenzofuran, anthracene, pyrene and others and obtained by substitution of up to five chemical group types.     

The global re-cycling of persistent organic pollutants is strongly retarded by soils

'Persistent organic pollutants' (POPs) are semi-volatile, mobile in the environment and bioaccumulate. Their toxicity and propensity for long-range atmospheric transport (LRAT) has led to international bans/restrictions on their use/release. LRAT of POPs may occur by a 'single hop' or repeated temperature-driven air-surface exchange. It has been hypothesised that this will result in global fractionation and distillation-with condensation and accumulation in polar regions. Polychlorinated biphenyls (PCBs)--industrial chemicals banned/restricted in the 1970s--provide a classic illustration of POP behaviour. A latitudinally-segmented global PCB inventory has been produced, which shows that approximately 86% of the 1.3 x 10(6) tonnes produced was used in the temperate industrial zone of the northern hemisphere. A global survey of background surface soils gives evidence for 'fractionation' of PCBs. More significantly, however, very little of the total inventory has 'made the journey' via primary emission and/or air-surface exchange and LRAT out of the heavily populated source regions, in the 70 years since PCBs were first produced. Soils generally occlude PCBs, especially soils with dynamic turnover of C/bioturbation/burial mechanisms. This limits the fraction of PCBs available for repeated air-soil exchange. The forested soils of the northern hemisphere, and other C-rich soils, appear to be playing an important role in 'protecting' the Arctic from the advective supply of POPs. Whilst investigations on POPs in remote environments are important, it is imperative that researchers also seek to better understand their release from sources, persistence in source regions, and the significant loss mechanisms/global sinks of these compounds, if they wish to predict future trends.     

Perfluorinated chemicals in relation to other persistent organic pollutants in human blood

In order to evaluate blood levels of some perfluorinated chemicals (PFCs) and compare them to current levels of classical persistent organic pollutants (POPs) whole blood samples from Sweden were analyzed with respect to 12 PFCs, 37 polychlorinated biphenyls (PCBs), p,p'-dichlorodiphenyl-dichloroethylene (DDE), hexachlorobenzene (HCB), six chlordanes and three polybrominated diphenyl ethers (PBDEs). The median concentration, on whole blood basis, of the sum of PFCs was 20-50 times higher compared to the sum of PCBs and p,p'-DDE, 300-450 times higher than HCB, sum of chlordanes and sum of PBDEs. Estimations of the total body amount of PFCs and lipophilic POPs point at similar body burdens. While levels of for example PCBs and PBDEs are normalized to the lipid content of blood, there is no such general procedure for PFCs in blood. The distributions of a number of perfluorinated compounds between whole blood and plasma were therefore studied. Plasma concentrations were higher than whole blood concentrations for four perfluoroalkylated acids with plasma/whole blood ratios between 1.1 and 1.4, whereas the ratio for perflurooctanesulfonamide (PFOSA) was considerably lower (0.2). This suggests that the comparison of levels of PFCs determined in plasma with levels determined in whole blood should be made with caution. We also conclude that Swedish residents are exposed to a large number of PFCs to the same extent as in USA, Japan, Colombia and the few other countries from which data is available today.     

The emissions of heavy metals and persistent organic pollutants from modern coal-fired power stations

Extensive research for establishing the emissions of heavy metals from coal-fired power stations is performed in the Netherlands for the past 25 years. In the Netherlands coal is fired from all over the world. This means that the emissions are established for coal of various origins. In the eighties, the emissions of installations equipped with ESPs (electrostatic precipitators) were measured. In the nineties, the influence of wet FGD (flue gas desulphurisation) on the emissions was studied. The effect of co-combustion of biomass and other secondary fuels is the main item for the last 10 years.Fifty-five elements were measured in the solid state and eight elements in the gaseous phase. It appeared that at low particulate concentration the influence of calcium containing evaporated water droplets downstream the wet FGD on the emissions of heavy metals is bigger than the composition of the coal. Also it appeared that at modern coal-fired power stations the emissions are hardly influenced by co-combustion of biomass. All the results are used for modelling, resulting in the KEMA TRACE MODEL^®, by which the emissions can be predicted. The established emission factors are for most elements in good agreement with literature values for comparable modern installations.Persistence organic pollutants (POPs) that were detected in the flue gases of coal-fired power stations are polycyclic aromatic hydrocarbons (PAH) and dioxins/furans. Measurements during full coal-firing and during co-firing of biomass have indicated that these emissions are negligible.     

Assessment of the Mediterranean sediments contamination by persistent organic pollutants

A compilation of information about levels of selected persistent organic pollutants, namely polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroetane and its degradation products (DDTs) and hexachlorobenzene (HCB), in Mediterranean sediments, including data published from 1971 to 2005, has been conducted in order to assess their main drivers and pressures in the environment. The application of mapping tools (GIS) and statistical instruments enabled the assessment of geographical and temporal trends. Chemical contamination mainly originates from land-based sources, and decreases significantly when moving off-shore. Contamination hot spots are generally located along the Northern coastline. The data for open sea sediments enabled the establishment of background levels of contamination for the region. A decreasing temporal trend in concentrations was found, more evident in the case of DDTs probably due to a more efficient regulation of this chemical. Finally, some gaps in reliable data were also identified which were related to the lack of information in the southern and eastern parts of the Mediterranean as well as the variety of analytical methodologies used.     

Assessment of the detection abilities of monitoring networks for passive tracers at local and regional scales

We propose a method to evaluate the detection abilities of networks used for protection purposes. Such networks are designed for the detection of nuclear, biological or gaseous emissions, without constraint on the source location. Their assigned goal is to have the best chance to detect a threatening emission located anywhere in the vicinity of a domain to protect. Two sensors siting applications are addressed: sensors placed in the surroundings of a facility to protect, or sensors carried by people scattered within a small area. A network protection ability is related both to its detection scope, and to its response time. To assess the performance of such networks, two statistical indicators are therefore designed: the detection probability, computed on a large number of possible source locations, and the saturation time, which is the time when the maximum detection probability has been reached.Simulations are then carried out with the Polyphemus air quality modeling system for many emission scenarios, including 961 possible source locations, various emitted species, and a few representative meteorological situations. This allows to assess the performance of single sensors as well as full networks, and their sensitivity to parameters like meteorological conditions and source characteristics. The emitted quantity and meteorological dispersion are found to be important parameters, whereas the species type does not significantly influence the results. Two network design methods are considered: (1) networks composed of a given number of the “best” sensors according to an indicator, and (2) sensors placed in circles around the protected domain. The networks built with respect to the detection probability show good results with a limited number of sensors, while the saturation time is not reliable enough to build networks. The networks based on circles also show a good performance in the studied cases, provided there is a sufficient number of sensors.     

The effect of export to the deep sea on the long-range transport potential of persistent organic pollutants

BACKGROUND: Export to the deep sea has been found to be a relevant pathway for highly hydrophobic chemicals. The objective of this study is to investigate the influence of this process on the potential for long-range transport (LRT) of such chemicals. METHODS: The spatial range as a measure of potential for LRT is calculated for seven PCB congeners with the multimedia fate and transport model ChemRange. Spatial ranges for cases with and without deep sea export are compared. RESULTS AND DISCUSSION: Export to the deep sea leads to increased transfer from the air to the surface ocean and, thereby, to lower spatial ranges for PCB congeners whose net deposition rate constant is similar to or greater than the atmospheric degradation rate constant. This is fulfilled for the PCB congeners 101, 153, 180, and 194. The spatial ranges of the congeners 8, 28, and 52, in contrast, are not affected by deep sea export. With export to the deep sea included in the model, the spatial ranges of the heavier congener are similar to those of the lighter ones, while the intermediate congeners 101 and 153 have the highest potential for long-range transport. CONCLUSIONS: Transfer to the deep ocean affects the mass balance and the potential for LRT of highly hydrophobic chemicals and should be included in multimedia fate models containing a compartment for ocean water.     

The effect of export to the deep sea on the long-range transport potential of persistent organic pollutants

Background  

Export to the deep sea has been found to be a relevant pathway for highly hydrophobic chemicals. The objective of this study is to investigate the influence of this process on the potential for long-range transport (LRT) of such chemicals.     

Approaches to assess the oral bioaccessibility of persistent organic pollutants: a critical review

Oral bioaccessibility, also known as in vitro gastrointestinal extraction or the physiologically based extraction test (PBET), is an important tool when assessing the risk to humans from persistent organic pollutants (POPs) (and metals). The approach seeks to mimic the processes of human food digestion and thereby assess the bioavailability of POPs (and metals) from materials consumed either accidentally or intentionally in the diet. In vitro conditions are created to simulate various actions in the stomach and intestines (although some methods also include the mouth compartment). This paper reviews the current status of oral bioaccessibility with respect to the release of POPs from soil and related samples of environmental importance. Particular emphasis is placed on the parameters that influence gastrointestinal extraction including gastric and intestinal pH, enzymes, bile salts, food constituents and residence time. In addition, important developments in the use of in vitro gastrointestinal extraction are highlighted. These developments include the use of epithelial Caco-2 cells to mimic the intestinal cell lining, the potential for biotransformation of POPs into estrogenic metabolites as a result of colon microbiota, and the use of in vivo studies to validate existing approaches.     

Sensitivity of biogenic secondary organic aerosols to future climate change at regional scales: An online coupled simulation

Biogenic emissions and secondary organic aerosols (SOA) are strongly dependent on climatic conditions. To understand the SOA levels and their sensitivity to future climate change in the United States (U.S.), we present a modeling work with the consideration of SOA formation from the oxidation of biogenic emissions with atmospheric oxidants (e.g., OH, O₃, and NO₃). The model simulation for the present-day climate is evaluated against satellite and ground-based aerosol measurements. Although the model underestimates aerosol concentrations over the northwestern U.S. due to the lack of fire emissions in the model simulations, overall, the SOA results agree well with previous studies. Comparing with the available measurements of organic carbon (OC) concentrations, we found that the amount of SOA in OC is significant, with the ratio ranging from 0.1 to 0.5/0.6. The enhanced modeling system driven by global climate model output was also applied for two three-year one-month simulations (July, 2001–2003 and 2051–2053) to examine the sensitivity of SOA to future climate change. Under the future two emissions scenarios (A1B and A2), future temperature changes are predicted to increase everywhere in the U.S., but with different degrees of increase in different regions. As a result of climate change in the future, biogenic emissions are predicted to increase everywhere, with the largest increase (～20%) found in the southeastern and northwestern U.S. under the A1B scenario. Changes in SOA are not identical with those in biogenic emissions. Under the A1B scenario, the biggest increase in SOA is found over Texas, with isoprene emissions being the major contributor to SOA formation. The range of change varies from 5% over the southeast region to 26% over Texas. The changes in either biogenic emissions or SOA under the two climate scenarios are different due to the differences in climatic conditions. Our results also suggest that future SOA concentrations are also influenced by several other factors such as the partitioning coefficients, the atmospheric oxidative capability, primary organic carbon aerosols and anthropogenic emissions.     

Molecular perspectives and recent advances in microbial remediation of persistent organic pollutants

Nutrition and pollution stress stimulate genetic adaptation in microorganisms and assist in evolution of diverse metabolic pathways for their survival on several complex organic compounds. Persistent organic pollutants (POPs) are highly lipophilic in nature and cause adverse effects to the environment and human health by biomagnification through the food chain. Diverse microorganisms, harboring numerous plasmids and catabolic genes, acclimatize to these environmentally unfavorable conditions by gene duplication, mutational drift, hypermutation, and recombination. Genetic aspects of some major POP catabolic genes such as biphenyl dioxygenase (bph), DDT 2,3-dioxygenase, and angular dioxygenase assist in degradation of biphenyl, organochlorine pesticides, and dioxins/furans, respectively. Microbial metagenome constitutes the largest genetic reservoir with miscellaneous enzymatic activities implicated in degradation. To tap the metabolic potential of microorganisms, recent techniques like sequence and function-based screening and substrate-induced gene expression are proficient in tracing out novel catabolic genes from the entire metagenome for utilization in enhanced biodegradation. The major endeavor of today’s scientific world is to characterize the exact genetic mechanisms of microbes for bioremediation of these toxic compounds by excavating into the uncultured plethora. This review entails the effect of POPs on the environment and involvement of microbial catabolic genes for their removal with the advanced techniques of bioremediation.     

Elimination of persistent organic pollutants from fish oil with solid adsorbents

Fish oils are one of the main sources of ω-3 fatty acids in animal and human diet. However, they can contain high concentrations of persistent organic pollutants due to their lipophilic properties. The aim of this study is the reduction of persistent organic pollutants in fish oil using silicon-based and carbon-based solid adsorbents. A wide screening study with different commercially available adsorbents was carried out, in order to determine their capacity of pollutant removal from fish oil. Moreover, adsorption conditions were evaluated and optimized with using an experimental design and adjustment of the experimental results to response surfaces, obtaining removals rates of more than 99% of PCDD/Fs, 81% of dioxin-like PCBs, 70% of HCB, 41% of DDTs, 16% of marker PCBs and 10% of PBDEs. Finally, fish oil fatty acids were analyzed before and after the treatment with solid adsorbents, confirming that it did not affect its nutritive properties.     

EU-wide survey of polar organic persistent pollutants in European river waters

This study provides the first EU-wide reconnaissance of the occurrence of polar organic persistent pollutants in European river waters. More than 100 individual water samples from over 100 European rivers from 27 European Countries were analysed for 35 selected compounds, comprising pharmaceuticals, pesticides, PFOS, PFOA, benzotriazoles, hormones, and endocrine disrupters. Around 40 laboratories participated in this sampling exercise. The most frequently and at the highest concentration levels detected compounds were benzotriazole, caffeine, carbamazepine, tolyltriazole, and nonylphenoxy acetic acid (NPE₁C). Only about 10% of the river water samples analysed could be classified as “very clean” in terms of chemical pollution. The rivers responsible for the major aqueous emissions of PFOS and PFOA from the European Continent could be identified. For the target compounds chosen, we are proposing “indicative warning levels” in surface waters, which are (for most compounds) close to the 90th percentile of all water samples analysed.