Persistent organic pollutants (POPs): state of the science

The environmental chemistry and ecotoxicology of persistent organic pollutants (POPs) are fascinating areas of scientific research. Our objective in this paper is to provide a brief, focussed overview of what constitutes a POP, highlight the harmful effects they may have on biota, make some comments on their environmental sources and analysis, their environmental trends and processes, their movement through foodchains and highlight some important regional-and global-scale environmental transport issues. Finally, we offer some personal thoughts on some current and future areas of scientific enquiry on POPs.     

Persistent organic pollutants (POPs) in populations of the clam Chione californiensis in coastal lagoons of the Gulf of California

This study examines the potential public health risk due to the massive use of organochlorine pesticides (OCs) in agriculture in the Gulf of California. Specimens of the clam Chione californiensis were collected from three coastal lagoons (Yavaros, Altata and Reforma). Sites were classified as polluted/nonpolluted based on the presence/absence of OCs as an indicator of the persistence of these pollutants; in polluted sites, the time elapsed since pesticide application (past or recent) was estimated. Screening values (SV) for protecting human health as per the U.S. Environmental Protection Agency (EPA) were used for risk assessment. OCs detected were ranked according to frequency of occurrence as follows: γ-chlordane (75%) > endrin (54%) > aldrin (48%) > heptachlor, and dichlorodiphenyl-trichloroethane (DDE) (37%) > β-heptachlor epoxide (30%) > lindane (α-BHC, δ-BHC) and endosulphan I (≤ 6%). Specifically, OCs detected at the highest concentration were heptachlor in Yavaros (0.0168 µgg^?1) and Altata (0.0046 µgg^?1), and aldrin in Reforma (0.0019 µgg^?1). β-Heptachlor epoxide in Altata and Reforma was the only OC with a concentration exceeding the EPA Screening Value. From our results and based on the monthly consumption limit set forth by EPA, the maximum safe consumption of clams to avoid a carcinogenic risk derived from β-heptachlor epoxide in the fishing villages of Yavaros and Altata is 4 servings per month (1 serving = 0.227 kg) by a 70-kg person. These findings suggest that concentrations of OCs and their isomers in C. californiensis populations reflect environmental persistence as well as recent inputs of OCs into coastal lagoons in the Gulf of California.     

Persistent organic pollutant in a fish community of a sub-alpine lake

This study investigated the presence of organochlorine pollutants in abiotic and biotic samples from Lake Como (Italy). DDTs and PCBs were found to be the major contaminants, ranging from 0.04 to 4.25 and from 0.25 to 40.8 μg/g lipid respectively. Evidence of biomagnification according to the trophic role of the investigated organisms was highlighted by means of Stable Isotope Analysis. A Trophic Magnification Factor (TMF) was calculated for the chemicals of interest and the applicability of the method for global use was confirmed. Statistically significant correlation has been found between the calculated trophic level and the concentrations of more lipophilic compounds, while for the less lipophilic (e.g., HCH, 3CBs) the relationship is no statistically significant and the TMF is close to 1.The role of the foraging area in affecting PCB and DDT concentrations within aquatic ecosystems has been highlighted by a Principal Component Analysis (PCA).     

Persistent organic pollutants (POPs) in antarctic fish: levels,patterns, changes

Organochlorine compounds were analysed in three fish species of different feeding types from the area of Elephant Island in the Antarctic. In 1996, hexachlorobenzene (HCB) (means: 15-20 ng/g lipid), p,p'-DDE (5-13 ng/g lipid) and mirex (1-7 ng/g lipid) predominated, while PCBs were minor components (PCB 153: 0.4-2 ng/g lipid). Concentration patterns were species-dependent: PCB 180, PCB 153, mirex, nonachlor III, trans-nonachlor and the toxaphene compound B8-1413 were highest in the bottom invertebrate feeder Gobionotothen gibberifrons and lowest in the krill feeder Champsocephalus gunnari. Levels of p,p'-DDE, PCB 138 and heptachloro-1'-methyl-1,2'-bipyrrole (Q1), a natural bioaccumulative product, were highest in the fish feeder Chaenocephalus aceratus, whereas HCB was present in about equal concentrations in all species. Most compounds were taken up preferentially via the benthic food chain, the chlorinated bipyrrole via the pelagic food chain and HCB from the water. In antarctic fish, biomagnification was generally more important than bioconcentration. Between 1987 and 1996, most persistent organic pollutant (POP) levels showed significant increases in the benthos feeder and the fish feeder, while they remained nearly constant or increased less in the krill feeder. Hence, the former species represent indicator species for changing POP levels in Antarctica. Ratios (1996/1987) of average concentrations in G. gibberifrons were: PCB 138 0.7, HCB 0.8, B8-1413 1.5, PCB 180 1.7, PCB 153 1.8, p,p'-DDE 2.0, nonachlor III 2.9, trans-nonachlor 3.3, mirex 6.7. By comparison with trends in the northern hemisphere it is concluded that global distribution of HCB is close to equilibrium. Changing levels of other POPs reflect global redistribution and increasing transfer to antarctic waters probably due to recent usage in the southern hemisphere and climate changes.     

Persistent organic pollutants in mangrove food webs in Singapore

In this study, persistent organic pollutants were quantified in sediments, subsurface seawater, sea-surface microlayer and twenty-four biota species collected at two separate mangrove habitats in Singapore. Data confirmed the ubiquity of POPs, including polybrominated diphenyl ethers (PBDEs), in the marine environment of Singapore. A biomagnification phenomenon was observed amongst the species collected and analysed from both mangrove sites studied. Thunder crabs and fish displayed the highest POP levels. Congener profiles of PBDEs varied amongst mangrove biota species and suggested different metabolic pathways exist for flame retardants. Similarly, crab species showed an ability to metabolize chlordane insecticide.     

Persistent organic pollutants (POPs) in Caspian seals of unusual mortality event during 2000 and 2001

Persistent organic pollutants including organochlorine pesticides, PCBs, and PCDDs/DFs were determined in the blubber of Caspian seals, which died during an outbreak of canine distemper virus in 2000 and 2001. DDTs were the predominant contaminants that ranged from 3.1 to 560 microg/g lipid. A negative correlation was observed between concentration of contaminants and blubber thickness. During spring, as the blubber layer becomes thin after breeding and moulting, seals may face higher risk due to the increased concentration of organochlorines in their bodies. TEQs in the blubber of Caspian seals (10-340 pg TEQ/g) were lower than those in seals from other locations, suggesting that toxic effects of these contaminants are a deal less in the present population and they are unlikely to be linked to mass mortality. The levels of PCBs and pesticides in Caspian seals, however, comparable to those in other aquatic mammals that have suffered from epizootics, might pose a risk of immunosuppression.     

Persistent organic pollutants in food items collected in Hong Kong

This study aims to investigate levels of POPs in meat, edible oils, nuts, milk and wine collected from Hong Kong. Naphthalene, pp-DDE, beta-, gamma-HCH and PBDE 47 were detected in most of the food items. Goose liver accumulated the highest PAHs (47.9 ng g⁻¹ wet wt), DDTs (25.6), HCHs (13.0), PCBs (4.17), PBDEs (468 pg g⁻¹ wet wt) among all the selected food. Meat and nut groups had significant (p < 0.01 or 0.05) correlations between lipid contents and concentrations of PAHs (meat: r = 0.878), HCHs (meat: r = 0.753), DDTs (meat: r = 0.937; nuts: r = 0.968) and PCBs (meat: r = 0.832; nut: r = 0.946). The concentrations of DDTs, HCHs and PCBs in vegetable oil were lower, but HCHs in fish oil were higher, when compared with other countries. The concentrations of PAHs, DDTs, PCBs and PBDEs in food tested in the present study were all below various safety guidelines.     

Persistent organic pollutants,heavy metals and parasites in the glaucous gull (Larus hyperboreus) on Spitsbergen

The prediction of a higher parasite infection as a consequence of an impaired immune system with increasing persistent organic pollution (POP) and heavy metal levels were investigated in adult glaucous gull (Larus hyperboreus) from Svalbard. The levels of chlorinated pesticides, polychlorinated biphenyls (PCBs), toxaphenes and polybrominated diphenyl ethers (PBDEs) were measured in liver. Cupper, cadmium, lead, mercury, selenium and zinc were measured in kidney samples. An elevated ratio of PCB-118 was found, suggesting that local contamination from the settlement was detectable in the glaucous gull. Eight cestodes, four nematodes, two acanthocephalan and three trematode helminth species were found in the intestine. A positive correlation was found between cestode intensities and selenium levels and between acanthocephalan intensities and mercury levels. No correlation was found between parasite intensities and POP concentrations. It is concluded that the contaminant levels found in glaucous gulls do not cause immune suppression severe enough to affect parasite intensity.     

Persistent organic pollutants (POPs) in human milk: A biomonitoring study in rural areas of Flanders (Belgium)

To collect information on the concentrations of persistent organic pollutants (POPs) in the rural areas in Flanders (Belgium), 84 breastfeeding mothers were recruited in rural communities in East and West Flanders and Flemish Brabant in 2009-2010. Polychlorinated biphenyl (PCB) congeners, organochlorine pesticides, brominated flame retardants, perfluorinated compounds, polychlorinated dibenzodioxines and dibenzofurans, and dioxin-like PCBs were measured in individual milk samples and in a pooled milk sample, while some additional pollutants were only measured in the pooled sample. For most pollutants, the concentrations in this study were lower or comparable to the concentrations measured in the pooled Belgian sample of the WHO human milk study of 2006, except for the pesticides dichlorodiphenyltrichloroethane DDT (+25% for ΣDDT and metabolites) and trans-nonachlor (+94%), and for the brominated flame retardant hexachlorocyclododecane HBCD (+153%). Perfluorinated compounds were for the first time determined in human milk samples from Belgium and the concentrations were comparable to those from other European countries. Also, interesting associations were found between the concentrations of POPs measured in human milk and personal characteristics as well as dietary habits of the study population. PFOS en PFOA concentrations were significantly higher in milk of primiparous participants compared to mothers who gave birth to their second child. Lower brominated PBDE congeners increased with increasing BMI of the mothers (p = 0.01 for BDE 47, p = 0.02 for BDE 99 and p = 0.02 for BDE 100). Participants consuming milk or dairy products daily had significant higher concentrations of ΣDDTs (p = 0.03) and oxychlordane (p = 0.047) in their human milk samples.     

Persistent organic pollutants in snow from European high mountain areas

Snow cores were collected in the catchment area of five remote mountain lakes in Europe. They were analysed for polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB), and organochlorine pesticides, namely DDTs, hexachlorobenzene (HCB) and hexachlorocyclohexanes (HCH). PAH are found in higher amounts in the Tatra and Caledonian mountains, PCB are higher in the Alps and HCH are highest in the Alps and Pyrenees. The qualitative PAH distributions are dominated by low molecular weight compounds, phenanthrene being the most abundant PAH in all but in one site. These compounds also occur predominantly in the gas phase in the atmosphere. Their high abundance in the snowpack witness the occurrence of effective transfer mechanisms from gas to snow flakes. In Starolesnianske (Tatra mountains), a higher contribution of high molecular weight compounds is found. This site exhibits the highest snow PAH and suspended particulate levels. Transformation of the concentration values of these compounds into annual deposition rates and correction for catchment/lake area indicates that in Scandinavia and the Alps a large proportion of PAH incorporation is mediated by snowfallout whereas in the Tatra mountains snow deposition only accounts for a small fraction of the compounds stored in the lake sediments. Among organochlorine compounds, only PCB and HCH have been found above method detection limit in most of the samples. The PCB congener distributions changes significantly between sites, although a predominance of the less chlorinated congeners have generally been observed.     

Persistent organic pollutants in human breast milk from Asian countries

In this paper, we concisely reviewed the contamination of persistent organic pollutants (POPs) such as polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), chlordane compounds (CHLs), hexachlorobenzene (HCB) in human breast milk collected from Asian countries such as Japan, China, Philippines, Vietnam, Cambodia, India, Malaysia, and Indonesia during 1999-2003. Dioxins, PCBs, CHLs in Japanese, and DDTs in Vietnamese, Chinese, Cambodian, Malaysian, and HCHs in Chinese, Indian, and HCB in Chinese breast milk were predominant. In India, levels of dioxins and related compounds (DRCs) in the mothers living around the open dumping site were notably higher than those from the reference site and other Asian developing countries, indicating that significant pollution sources of DRCs are present in the dumping site of India and the residents there have been exposed to relatively higher levels of these contaminants possibly via bovine milk.     

Persistent organic pollutants and sedimentary organic matter properties: a case study in the Kishon River, Israel

The Kishon River, the second largest coastal river in Israel, has been severely polluted for several decades. Sediments from upstream and downstream sites of the river were analyzed, lipid-extracted and evaluated for phenanthrene uptake. Total polycyclic aromatic hydrocarbon (PAH) concentration in downstream sediments was 299 microg kg(-1), consisting mostly of petrogenic-derived PAHs. Downstream sedimentary lipids were found to be dominated by fresh and decomposed petroleum-derived n-alkanes. The total PAH concentration in upstream sediments was 173 microg kg(-1), consisting mostly of pyrogenic-derived PAHs, whereas lipids from these sediments were mostly vegetation-derived. Spectroscopic data suggested an exceptionally high aromatic content in downstream humic acid, which originated from PAHs attached to its structure. Sorption data suggested that upstream sedimentary cuticle-derived lipids function as a sorption domain, while downstream sedimentary lipids, consisting of shorter-chain-length petroleum-derived alkanes, compete with phenanthrene for sorption sites.     

Linking molecular interactions to consequent effects of persistent organic pollutants (POPs) upon populations

There is great concern about the potential adverse effects of persistent organic pollutants (POPs) on wildlife. Threats come from toxic chemicals with long half lives in the environment that were released worldwide on a large scale in the past, at a time when little was known of their potential effects on the environment. Although the Stockholm Convention (2001) initially targeted 12 POP chemicals--organochlorinated compounds--for the reduction/elimination of releases, the problem can be extended to persistent toxic substances more generally. Therefore, identifying early biomarkers for possible toxic effects to populations in the long term is a challenge for ecotoxicologists. Regional decline in fish, bird and/or invertebrate populations resulting from exposure to POPs, such as DDT (dichlorodiphenyltrichloroethane), PCBs (polychlorinated biphenyls), PCDD (polychlorinated dibenzo-p-dioxins), and TBT (tributyltin) could be related to some biochemical, endocrine and physiological effects in individuals. Examples of known mechanisms of POP ecotoxicity will be illustrated in the first part. The next parts will be devoted to (i) data gaps and limitations to extrapolation from lower to higher levels of biological organization, (ii) confusing factors in field studies and the combined effects of persistent toxic pollutants and (iii) recommendations for the design and interpretation of experimental studies.     

Persistent organic pollutants in soil density fractions: distribution and sorption strength

The sorption strength of persistent organic pollutants in soils may vary among different soil organic matter (SOM) pools. We hypothesized that polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were unevenly distributed and had different soil organic carbon (SOC)-water partition coefficients (K(OC)) among soil density fractions. We determined the concentrations and K(OC) values of 20 PAHs and 12 PCBs in bulk samples and three density fractions (light, <2.0, medium, 2.0-2.4, and heavy, >2.4 g cm(-3)) of 11 urban topsoils (0-5 cm) from Bayreuth, Germany. The K(OC) values were determined using sequential extraction with methanol-water mixtures (35% and 65% methanol) at 60 degrees C. The sum of 20 PAH concentrations in bulk soil ranged 0.4-186 mg kg(-1), and that of 12 PCB concentrations 1.2-158 microg kg(-1). The concentrations of all PAHs and PCBs decreased in the order light>medium>heavy fraction. When normalized to the SOC concentrations, PAH concentrations were significantly higher in the heavy than in the other density fractions. The K(OC) values of the PAHs in density fractions were 3-20 times higher than those of the PCBs with similar octanol-water partition coefficients (K(OW)). The K(OC) values of individual PAHs and PCBs varied up to a factor of 1000 among the studied soils and density fractions. The K(OC) values of 5- and 6-ring PAHs tended to be highest in the heavy fraction, coinciding with their enrichment in this fraction. For the other PAHs and all PCBs, the K(OC) values did not differ among the density fractions. Thus, there is no relationship between sorption strength and distribution among density fractions, indicating that density fractionation is not a suitable tool to distinguish among differently reactive PAH and PCB pools in soils.     

Persistent organic pollutants in cork used for production of wine stoppers

Owing to the lipophilic character of some components of cork and the long periods in the open air (during growth and barks storage), there is a risk of the cork becoming environmentally polluted. Moreover, cork stoppers are in contact with wines for periods ranging from a few months to several years; so they must maintain high levels of hygiene. The present work aims to investigate the level of PCBs, organochlorine pesticides, and PAHs in cork from different countries, used for the manufacturing of one-piece wine stoppers. Samples of cork were analysed using a multi-residue method. PCBs were not detected in all the samples; only a few samples contained detectable amounts of DDE; phenanthrene and anthracene were found in all the samples and fluoranthene in fewer cases. It was not possible to find a significant correlation between POPs concentration and origin of cork. Globally, the detected amounts are consistent with values found in foods, so the investigated cork show a suitable hygienic quality.     

Persistent organic pollutants (POPs) in the conventional activated sludge treatment process: model predictions against experimental values

The FATE and treatibility estimator (FATE) model, developed by the United States Environmental Protection Agency was used for the prediction of the FATE of 26 persistent organic pollutants (POPs), i.e. 7 PCBs and 19 organochlorine compounds (OCs), during the conventional activated sludge treatment process applied in the waste water treatment plant (WWTP) of Thessaloniki, Greece. The removal rates predicted by the model for the primary and the secondary treatment stages were found to differ substantially from those experimentally measured. When the overall treatment was considered, the differences between measured and model predicted removals were within acceptable limits of confidence. Possible reasons that might cause deviations from experimental values were suggested to be the wastewater content in dissolved organic carbon (DOC), and/or the low concentrations of POPs in untreated wastewater.     

Persistent organic pollutants in moss as bioindicators of atmospheric pollution in Singapore

Moss samples were collected from the island of Singapore and analysed for a range of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs). Although all compounds analysed have been banned from use in Singapore, they were detected in all samples collected. Among the hexachlorocyclohexanes (HCH), beta-HCH was the most dominant isomer, while trans-chlorane was found to be the most dominant cyclodiene pesticide. High levels (79.12 ng g(-1)) of PCBs were detected in mosses collected from a nearby island due to active accumulation of pollutants associated with boat emissions. Significant spatial variations in the levels of organic pollutants in Singapore were largely absent, indicating that air masses moving over the island deposit OCPs and PCBs in a uniform pattern. A comparison of moss pollutant levels with available data from Czech Republic showed that dichlorodiphenyldichloroethylene (p,p'-DDE), dichlorodiphenyltrichloroethane (p,p'-DDT) and PCB levels in Singapore are the highest. The presence of these compounds suggests that they are still used in the region and are environmentally recalcitrant.     

Persistent organic pollutants in soils and sediments from James Ross Island, Antarctica

Soil and sediment samples from James Ross Island were analyzed for their PCB, OCP and PAH contents. Soil concentrations ranged between 0.51 and 1.82 ng g(-1) for seven indicator PCB congeners, between 0.49 and 1.34 ng g(-1) for HCH congeners, between 0.51 and 3.68 ng g(-1) for the sum of p,p'-DDT, DDE, and DDD, and between 34.9 and 171 ng g(-1) for the sum of 16 EPA PAHs. Sediment levels from 0.32 to 0.83 ng g(-1) were found for PCBs, from 0.14 to 0.76 ng g(-1) for HCHs, from 0.19 to 1.15 ng g(-1) for DDTs, and from 1.4 to 205 ng g(-1) for PAHs. A prevalence of low-mass PAHs, less chlorinated PCBs, and more volatile chemicals indicates that the long-range atmospheric transport from populated areas of Africa, South America, and Australia is the most probable contamination source for the solid matrices in James Ross Island.