The evolution of mass balance models of persistent organic pollutant fate in the environment

Current approaches to modelling the fate of persistent organic pollutants (POPs) in the environment have evolved in response to four dominant characteristics of these substances; namely: (1) the presence of POPs in virtually all environmental phases and the ease with which they move from one to the other requires multi-compartmental modelling. Describing transport across phase boundaries becomes as, or even more, important as quantifying transport within the phases; (2) POPs may persist in the environment for many decades. For chemicals that 'have time', concepts such as equilibrium partitioning and steady-state become more important than for short-lived substances whose fate is more controlled by the rates of transformation; (3) measuring POPs is difficult and expensive and observed concentrations of POPs are not available in high spatial or temporal resolution. Consequently, high resolution tends not to be a high priority in POP models; and (4) detrimental effects of POPs often manifest themselves in top predators, which has led to a focus on modelling biotic uptake and transfer within food chains. The task of building a POPs model is viewed as combining the four 'building blocks' of partitioning, transport, transformation and source data with the help of the law of the conservation of mass. Process models, evaluative models, models of real local, regional and global fate, as well as biological uptake models are presented and references to numerous examples are provided. An attempt is made to forecast future directions in the field of POPs modelling. It is expected that modelling techniques that do not rely on quantitative emission estimates as well as approaches that take into account spatial, temporal and climatic variability as well as parameter uncertainty will increase in importance. Finally, the relationship between modelling POPs and models of other pollutant issues is addressed, as are potential interactions between POPs and pollutant issues such as eutrophication, acidification and global climate change.     

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.     

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.     

Respiratory uptake kinetics of neutral hydrophobic organic chemicals in a marine benthic fish, Pseudopleuronectes yokohamae

We investigated the respiratory uptake kinetics of polychlorinated biphenyls (PCBs), organohalogen pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs), and 2,2′,4,4′-tetrabrominated diphenyl ether (BDE #47) in a marine benthic fish, Pseudopleuronectes yokohamae. The respiratory uptake efficiencies (E_W) of the chemicals, of which there have been no reports for the majority of persistent organic pollutants (POPs), were obtained by measuring the respiratory uptake rate constants (k₁) and the oxygen consumption rates of fish. Fish were exposed to water in which these chemicals were dissolved at environmentally relevant concentrations for 28 d, followed by 168 d of depuration in clean seawater. The k₁ and E_W values for 99 compounds were obtained, and they ranged from 2000 to 42 000 L kg-lipid⁻¹ d⁻¹ and from 0.060 to 1.3, respectively. The E_W values of the chemicals, except for PAHs, tended to increase with increasing values of the log octanol–water partition coefficients (K_OW) of the chemicals up to a log K_OW of 5. For log K_OW in the range 3–5, the E_W values in this study were much lower than those in a published study (about one-third). As a result of analysis by a two-phase resistance model, the resistance of transport rates to the lipid phase in this study was lower than was the case in the published study. These findings indicate that the E_W predicted by the published study for log K_OW in the range 3–5 may differ among fish species and water temperature, and further study is needed.     

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 (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.     

PAFC对水体中持久性有机污染物PFOA的混凝效果

针对含全氟辛酸(PFOA)的工业废水及应对PFOA的污染突发事件,采用PAFC及其复配粘土矿物凹凸棒和沸石进行混凝实验,并对几个影响因素进行了考察。结果表明,在PAFC的最佳投加量10 mg/L时,PFOA和浊度的去除率分别达到70.25%和99.42%,PAFC混凝处理PFOA的效果优于PAC;pH值对PAFC去除PFOA有一定的影响,当pH大于6时有利于PFOA的去除;PFOA和浊度的去除率随原始浊度的增加而增加;活性炭、盐酸改性凹凸棒、盐酸改性沸石、CT-MAB改性的沸石复配PAFC均可提高PFOA的去除率;改性处理后的沸石应用于PFOA的处理中,有望降低处理成本。     

Persistent organic pollutants (PCB, DDT, HCH, HCB & BDE) in eels (Anguilla anguilla) in Scotland: Current levels and temporal trends

Eels are an ideal biomonitor for persistent organic pollutants (POPs) because of their high lipid content, longevity and tendency to remain within a defined range during their freshwater life phase. This study investigated concentrations of POPs in eels (Anguilla anguilla) from 30 sites across Scotland, including polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (BDEs), DDT (and metabolites), hexachlorocyclohexanes (α, β, γ-HCH), hexachlorobenzene (HCB), hexachlorobutadiene (HCBD) and pentachlorobenzene. Despite its EU-wide ban ∼30 years ago, DDT and its derivatives were detected in almost all samples. PCB 153 and 138 were the most widely detected PCB congeners, while BDE 47 was the dominant BDE. Pentachlorobenzene was not detected, while HCBD was detected once only. α-HCH, β-HCH and HCB concentrations were very low (generally <3 μg/kg or below detection). When compared with 1986 and 1995 data, the results revealed considerable decreases in p,p′-DDE concentrations. More drastic reductions were evident for γ-HCH, reflecting the tightening restrictions on pesticide use imposed over the previous decades.     

Relationships between organic matter, black carbon and persistent organic pollutants in European background soils: Implications for sources and environmental fate

Black carbon (BC) and total organic carbon (TOC) contents of UK and Norwegian background soils were determined and their relationships with persistent organic pollutants (HCB, PAHs, PCBs, co-planar PCBs, PBDEs and PCDD/Fs) investigated by correlation and regression analyses, to assess their roles in influencing compound partitioning/retention in soils. The 52 soils used were high in TOC (range 54-460 mg/g (mean 256)), while BC only constituted 0.24-1.8% (0.88%) of the TOC. TOC was strongly correlated (p < 0.001) with HCB, PCBs, co-PCBs and PBDEs, but less so with PCDD/Fs (p < 0.05) and PAHs. TOC explained variability in soil content, as follows: HCB, 80%; PCBs, 44%; co-PCBs, 40%; PBDEs, 27%. BC also gave statistically significant correlations with PBDEs (p < 0.001), co-PCBs (p < 0.01) and PCBs, HCB, PCDD/F (p < 0.05); TOC and BC were correlated with each other (p < 0.01). Inferences are made about possible combustion-derived sources, atmospheric transport and air-surface exchange processes for these compounds.     

Congener-specific accumulation and trophic transfer of polychlorinated biphenyls in spider crab food webs revealed by stable isotope analysis

Polychlorobiphenyls (PCB) and stable isotopes (delta15N and delta13C) were analyzed in the spider crab (Maja brachydactyla) food web from the Iroise Sea (Western Brittany) and the Seine Bay (Eastern English Channel). PCB concentrations were all significantly higher in organisms from the Seine Bay than those from the Iroise Sea. PCB patterns were strongly related to the feeding mode of the species, and increased influence of higher chlorinated congeners was highlighted with trophic position of the organisms. PCB concentrations (lipid normalized) were significantly related to the isotopically derived trophic level (TL) in spider crab food webs. The highest trophic magnification factors (TMFs) were calculated for the congeners with 2,4,5-substitution, and were lower in the Seine Bay compared to the Iroise Sea. The confrontation of PCB and TL data also revealed biotransformation capacity of decapod crustaceans for specific congeners based on structure-activity relations.     

Levels of persistent organic pollutant and their predictors among young adults

Exposure to persistent organic pollutants (POPs), such as polychlorinated biphenyls (PCBs), dichlorodiphenyldichloroethane (p,p′-DDE), and hexachlorobenzene (HCB) continues to be of concern due to their ubiquitous distribution and high persistence. Current toxicant body burden is still a primary concern within the Akwesasne Mohawk Nation since other studies conducted within the community have shown relationships between these POPs and endocrine disruption.In this article we describe the levels of these toxicants in young adults of the Akwesasne Mohawk Nation between the ages of 17 and 21 years of age (mean age 18.1 years), and investigate potential influences of their current body burden. Seventeen congeners in fourteen chromatographic peaks were detected in 50% or more of the individuals sampled (geometric mean [GM] of the sum of these congeners = 0.43 ppb). Congeners 118, 138[+163 + 164] and 153 had the highest rate of detection (?98%) within the Akwesasne young adults. Of the other organochlorines, HCB (GM = 0.04 ppb) and p,p′-DDE (GM = 0.38 ppb) were found in 100% and 99% of the sample respectively.Significantly higher levels of PCBs were found among individuals who were breastfed as infants, were first born, or had consumed local fish within the past year. When compared to levels of p,p′-DDE, HCB, and 13 specific congeners reported by the CDC for youth between the ages of 12 and 19 years, the geometric means of several congeners (CBs 99, 105, 110, and 118) among the Akwesasne were higher than the reported CDC 90th percentile. In contrast, levels of CB 28 in Akwesasne young adults were ∼50% or less than those of the CDC cohort. p,p′-DDE and HCB levels were generally higher in the CDC cohort (GM of 0.516 and 0.065 ppb, respectively for Mohawks vs. 2.51 and 0.123, respectively, for CDC). Concentrations of non-persistent PCBs among this sample of Akwesasne young adults were higher than those reported by the CDC suggesting continued exposure, but lower than those associated with severe contamination.Additional research into the concentration trends of individual PCB congeners within Akwesasne youth and young adults is warranted to further improve our insight into the determinants and influences of organochlorine concentrations within members of the Akwesasne community.     

Effects of environmental exposure and diet on levels of persistent organic pollutants (POPs) in eggs of a top predator in the North Atlantic in 1980 and 2008

Concentrations of POPs in Great skua eggs from Shetland are among the highest in North Atlantic seabirds, with up to 11,600 μg/kg (ww) DDE and up to 17,900 μg/kg ww ∑PCB. Concentrations of legacy POPs were significantly lower in 2008 than 1980. Decreases were greatest for least persistent compounds. Median ∑PBDEs increased from 99 μg/kg ww in 1980 to 173 μg/kg ww in 2008. There were changes in Great skua breeding season diet, with more adult Herring and Mackerel and less Sandeel. These changes increase exposure to POPs, since Herring and Mackerel accumulate more POPs than Sandeels. In both years, eggs with higher δ¹⁵N had higher POP concentrations. In 1980, birds feeding more on demersal discard fish from trawl fisheries and less on Sandeels, had higher POP levels in eggs. In 2008, individuals feeding more on Herring and Mackerel, and less on discards, had higher POP levels in eggs.     

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.     

Scaling up a treatment to simultaneously remove persistent organic pollutants and heavy metals from contaminated soils

Soil washing is a treatment process that can be used to remediate both organic and inorganic pollutants from contaminated soils, sludges, and sediments. A soil washing procedure was evaluated utilizing about 100 g samples of soil that had been field-contaminated with arsenic, chromium, copper, pentachlorophenol (PCP), polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). The highest level of mobilization/detoxification was achieved in three soil washes with a mixture of 0.1M [S,S]-ethyelnediaminedisuccinate ([S,S]-EDDS) and 2% Brij 98 at pH 9 with 20 min of ultrasonication treatment at room temperature. This combination mobilized 70% of arsenic, 75% of chromium, 80% of copper, 90% of PCP, and 79% of PCDDs and PCDFs, so that the decontaminated soil met the maximum acceptable concentrations of the generic C-level criteria regulated by the Ministère du Développement Durable, de l’Environnement et des Parcs for the Province of Québec, Canada.The organic pollutants were back-extracted from the aqueous suspension with hexane. Heavy metals were virtually completely precipitated from the aqueous washing suspension with Mg⁰ particles at room temperature. The PCP was detoxified by catalytic hydrodechlorination with a stream of 5% (v/v) H₂-supercritical CO₂ that transported the organosoluble fraction through a reaction chamber containing 2% Pd/γ-Al₂O₃.In toto, this soil washing procedure demonstrates that persistent organic pollutants and selected heavy metals can be co-extracted efficiently from a field-contaminated soil with three successive washes with the same soil washing solution containing [S,S]-EDDS and a non-ionic surfactant (Brij 98) in admixture. An industrial-scale ex situ soil washing procedure with a combination of a non-ionic surfactant and a complexing reagent seems to be a plausible remediation technique for this former wooden utility pole storage facility.     

Levels and temporal trends (1983-2003) of persistent organic pollutants (POPs) and mercury (Hg) in seabird eggs from Northern Norway

The main objective of this study was to investigate possible temporal trends of persistent organic pollutants (POPs) and mercury in eggs of herring gulls (Larus argentatus), black-legged kittiwakes (Rissa tridactyla), common guillemots (Uria aalge) and Atlantic puffins (Fratercula arctica) in Northern Norway. Eggs were collected in 1983, 1993 and 2003. Egg concentrations of POPs (PCB congeners IUPAC numbers: CB-28, 74, 66, 101, 99, 110, 149, 118, 153, 105, 141, 138, 187, 128, 156, 157, 180, 170, 194, 206, HCB, alpha-HCH, beta-HCH, gamma-HCH, oxychlordane, trans-chlordane, cis-chlordane, trans-nonachlor, cis-nonachlor, p,p'-DDE, o,p'-DDD, p,p'-DDD, o,p'-DDT and p,p'-DDT) and mercury were quantified. Generally, POP levels decreased between 1983 and 2003 in all species. No significant temporal trend in mercury levels was found between 1983 and 2003.     

The effects of tertiary treated municipal wastewater on fish communities of a small river tributary in Southern Ontario, Canada

Fish community changes associated with a tertiary treated municipal wastewater effluent outfall in the Speed River, Ontario, Canada, were evaluated at nine sites over two seasons (2008) using standardized electrofishing. Habitat evaluations were conducted to ensure that the riffle sites selected were physically similar. The fish community was dominated by several species of darters that differed in their response to the effluent outfall. There was a significant decrease in Greenside Darter (Etheostoma blennioides) but an increase in Rainbow Darter (E. caeruleum) abundance directly downstream of the outfall. Stable isotope signatures (δ¹³C and δ¹⁵N), which indicate shifts in energy utilization and flow, increased in Rainbow Darter downstream, but showed no change in Greenside Darter. Rainbow Darter may be exploiting a food source that is not as available at upstream sites giving them a competitive advantage over the Greenside Darter immediately downstream of the outfall.     

Soil burdens of persistent organic pollutants - Their levels, fate and risk. Part I. Variation of concentration ranges according to different soil uses and locations

Detailed soil screening data from the Czech Republic as a typical Central European country are presented here. Determination of a wide selection of organic and inorganic pollutants as well as an assessment of specific soil parameters allowed us to study the soil contamination in relation to the land use and soil properties. While HCHs and HCB were found at highest levels in arable soils, the higher concentrations of PCDDs/Fs, PCBs, PAHs and DDTs were observed in high altitude forest soils. Concentrations of these compounds strongly correlated with the soil organic carbon content. Several possible reasons have been suggested for the observed higher concentrations in mountain forest soils but the impact of each of these influencing factors remains to be identified. An inventory of the soil contamination is needed as a first step in our effort to estimate an extent to which the secondary sources contribute to the enhanced atmospheric levels of POPs.     

Correlates of mercury in fish from lakes near Clyde Forks, Ontario, Canada

Subsurface soils near Clyde Forks, Ontario, Canada, can have naturally high concentrations of mercury (Hg) from local geological sources. To investigate Hg in local aquatic food webs, Hg was measured in fish dorsal muscle (mainly yellow perch [YP] and pumpkinseed sunfish [PS]) and surface sediments from 10 regional lakes. Water chemistry, along with fork length, weight, and stable isotopes (delta15N, delta13C, delta34S) in fish were also measured. No lake sediments had elevated (>0.3microg/g dw) Hg, and average Hg concentrations in fish were not sufficiently high (<1microg/g dw) to be of concern for fish-eating wildlife. Variance in fish Hg was best explained by dietary carbon source (delta13C), and certain lake variables (e.g., pH for YP). PS with more pelagic feeding habits had higher delta34S and Hg than those with more littoral feeding habits. Potential biological linkages between fish Hg and delta34S, a parameter that may be related to the lake sulphate-reducing bacteria activity, requires further investigation.     

Effects of hydrodynamics on the distribution of trace persistent organic pollutants and macrobenthic communities in Bohai Bay

In recent years, the rapid economic development along Bohai Bay, has brought out continuous increasing of the pollution loads in the Bohai Sea, especially by the large coastal reclamation project, Tianjin Binhai New Area. In the period of 2007-2009, we collected the sediments of the main rivers, estuaries, intertidal zone, and near-shore area of Bohai Bay, and Macrobenthos associated with the marine sediments to assess the influence of hydrodynamics in the coastal environment on the pattern of trace contaminants and the macrobenthic community. Based on data derived from these samples, the levels of polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) in sediments followed the order PAHs > OCPs > PCBs > PBDEs. The higher concentrations of PCBs, OCPs, PAHs and PBDEs were found in the estuarine and near-shore environment of the Dagu Drainage River. The spatial distribution of OCPs was different to that of PCBs due to the direction of the velocity field of Bohai Bay in its old and new topography, and the higher water-solubility of OCPs than that of PCBs. The results of the Pearson correlation and the PCA indicate that the medium diameter (MD) of sediments was the predominant factor influencing the distribution of PCBs and OCPs, most sampling sites were characterized mainly by TOC of sediments and biomass of macrobenthos. The results indicate that the distribution of trace contaminants and macrobenthic community in Bohai Bay are mainly affected by the hydrodynamic conditions.     

Assessing seasonal and spatial trends of persistent organic pollutants (POPs) in Indian agricultural regions using PUF disk passive air samplers

The first survey of persistent organic pollutant (POP) concentrations in air across several Indian agricultural regions was conducted in 2006-2007. Passive samplers comprising polyurethane foam (PUF) disks were deployed on a quarterly basis at seven stations in agricultural regions, one urban site and one background site. The project was conducted as a sub-project of the Global Atmospheric Passive Sampling (GAPS) Network. In addition to revealing new information on air concentrations of several organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs), the study has demonstrated the feasibility of conducting regional-scale monitoring for POPs in India using PUF disk samplers. The following analytes were detected with relatively high concentrations in air (mean for 2006 and 2007, pg/m³): α- and γ-hexachlorocyclohexane (HCH) (292 and 812, respectively); endosulfan I and II (2770 and 902, respectively); p,p′-DDE and p,p′-DDT (247 and 931, respectively); and for the sum of 48 PCBs, 12,100 (including a site with extremely high air concentrations in 2007) and 972 (when excluding data for this site).