持久性有机污染物的环境分布与生物危害

介绍了国内外持久性有机物的研究进展,分析了中国典型地区中的持久性有机污染物的分布情况,其中淮河中下游的PAHs含量较高,而大连湾检测出的DDTs和PCBs含量均高于其他地区。持久性有机污染物可以在动植物体内不断富集,据分析,有机污染物在鱼类的富集因子可高达1124．1,持久性有机污染物通过食物链的富集逐级放大,对全球生态构成潜在巨大的威胁。近年来,由于持久性有机污染物的影响,在世界各地出现了动物的死亡、甚至灭绝的现象,而且有机污染物在人体内的蓄积,会对人体产生极大的的影响。最后,就当前存在的问题,提出了对策与建议,指出了该领域的发展方向。     

National PCDD/PCDF release inventories under the Stockholm Convention on Persistent Organic Pollutants

National inventories to estimate releases of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans have been undertaken since the mid 1980s. These inventories were scattered and hard to compare since there was no harmonized method available. With the conclusion of the Stockholm Convention on Persistent Organic Pollutants and its entry into force, Parties to the Convention at the global level, have to establish PCDD/PCDF release inventories and report these results. UNEP Chemicals has developed a methodology that allows developing and developed countries to make estimates of PCDD/PCDF releases into the environment along all vectors. Presently, there are 23 national release inventories available that have been made with this methodology, the Toolkit. Among the most important sources, open fires in agriculture/forests as well as open burning of wastes have been identified as the major sources of PCDD/PCDF. The results from these inventories may serve as the starting point for interventions to reduce or eliminate sources of PCDD/PCDF by application of best available techniques and best environmental practices. The Toolkit will be updated as needs arise.     

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 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 gull eggs of two species (Larus michahellis and Larus audouinii) from the Ebro delta Natural Park

The aim of this study was to determine the impact of priority and emerging Persistent Organic Pollutants (POPs) in gull eggs from two species, the scavenger Larus michahellis and the protected species, Larus audouinii. These two species share habitat in the Natural Park of the Ebro delta (Catalonia, Spain). Compounds studied are included or under consideration in the Stockholm Convention and comprise polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), organochlorinated compounds (OCs), perfluorinated compounds (PFCs) and short chain chlorinated paraffins (SCCPs). Four methods based in selective extraction and gas or liquid chromatography coupled to mass spectrometry were used and quality parameters are provided. OC pesticides and marker PCBs were the most abundant chemical families detected in eggs from the two species, followed by PFCs, PBDEs (especially BDE 209) and SCCPs. Dioxin-like PCBs and PCDD/Fs were also detected in all samples. The overall widespread presence of POPs is discussed in terms of feeding habits, bird ecology and anthropogenic pressures in the protected Ebro delta breeding area.     

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 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.     

Background levels of Persistent Organic Pollutants in humans from Taiwan: Perfluorooctane sulfonate and perfluorooctanoic acid

Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) have recently received attention due to their widespread contamination of the environment. PFOS and PFOA are stable in the environment and resistant to metabolism, hydrolysis, photolysis and biodegradation. PFOS and PFOA have been found in human blood and tissue samples from both occupationally exposed workers and the general worldwide population. This study aimed to determine the background levels of PFOS and PFOA in the Taiwanese population, investigate related factors, and compare exposure in Taiwan to that in other countries. The concentration of PFOS in the 59 serum samples collected from the general population in Taiwan ranged from 3.45 to 25.65 ng mL⁻¹ (median: 8.52), and the concentration of PFOA ranged from 1.55 to 7.69 ng mL⁻¹ (median: 3.22). There was a significant positive correlation (r = 0.51; p < 0.0001) between PFOS and PFOA concentrations. Males had higher concentrations of PFOA and PFOS than females. PFOS levels in serum increased with age. This study is the first investigation to reveal the PFOS and PFOA levels of serum samples in the general population of Taiwan. The levels of PFOS and PFOA in Taiwanese serum samples were comparable with those from other countries (PFOS: 5.0–35 ng mL⁻¹, PFOA: 1.5–10 ng mL⁻¹).     

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 (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.     

Changes in Chlorinated Organic Pollutants and Heavy Metal Content of Sediments during Pyrolysis (7 pp)

Background There has been an increasing concern about the treatment and disposal of contaminated sediment from dredged river, harbor or estuary due to the accumulated toxic organics such as dioxins and inorganics particularly heavy metals like Cr, Pb, Zn, Cu, Hg and Cd. However, considering the huge amount of materials and financial costs involved, any candidate technology must ultimately result to reusable residual by-products. This can only be made possible if the toxic pollutants are removed or stabilized in the raw sediment and then fed back into the materials cycle. Currently, we are developing a pyrolysis process for the commercial-scale cleanup of dioxins and heavy metal-contaminated river sediment to yield reusable char for various economical applications. In this connection, this paper describes our preliminary investigation into the extent of dioxins and heavy metal volatilization from actual contaminated sediment. The stabilization of certain metallic species particularly Cr ions was studied. Methods Laboratory scale pyrolysis experiments were conducted using a special horizontal lab-scale pyrolyzer. Sediment samples from Shanghai Suzhou Creek and Tagonoura Harbor were pyrolyzed in the reactor under nitrogen gas at 800°C and different retention times of 30, 60 and 90 min. A constant heating rate of 10°C min-1 was employed. The pyrolysis gas was first allowed to pass through a cold trap to condense the tar. Uncondensed gases were then channeled through a column containing an adsorbent (XAD-2 Resin) for dioxins. Heavy metal concentrations in the initial and final sediment residues were analyzed by ICP (Nippon Jarrel-Ash) following their acid and alkali (for Cr6+) digestion. Dioxins content of the pyrolysis char, tar, and exhaust gases in the dioxin adsorbent were also determined. For comparative purpose, thermal treatment under air flow was conducted. Results The data for the removal of heavy metals from Suzhou Creek sediment showed very significant reductions in Pb, Zn and Cr6+ content of the sediment at this condition. Percentage removals were 42.4%, 60.8% and 42.2%, respectively. The disappearance of Cr6+ was due to reduction reactions rather than volatilization since the total Cr content remained almost unchanged. Other heavy metals such as Cu, Fe and Ni showed very minimal reductions. Nonetheless, Toxicity Characteristics Leaching Procedure (TCLP) tests confirmed that these residual heavy metals were rather stable in the pyrolysis char. Reduction of toxic Cr6+ at 42.2% has also been achieved by pyrolysis (with N2) as opposed to the more than 580 % increase in Cr6+ observed during thermal oxidation (with air). Discussion Pyrolysis also remove toxic organics particularly dioxins from the sediment. For the total dioxins, removal percentage of 99.9999% was achieved even at the lowest retention time of 30 min. Almost all polychlorinated dibenzo-p-dioxine (PCDDs) and polychlorinated dibenzo-furans (PCDFs) were removed at any retention time. The TEQs detected from the solid residues were mainly contributed by dioxin-like PCBs, yet these were present in relatively trace quantities. At the shortest retention time of 30 min, only 0.000085 pg-TEQ g-1 of polychlorinated biphenyls (PCBs) was detected in the pyrolysis char. Furthermore, the residual PCBs have very low toxicity ratings and none of the highly toxic PCBs, which were initially present in the sediment such as 3,3',4,4',5-PeCB and 3,3',4,4'5,5'-HxCB, were detected in the char. Results further confirmed that most of the dioxins that were removed were transferred to the gas phase so that volatilization may be considered as the main mechanism for their removal. Conclusion Some heavy metals particularly Pb and Zn can be volatilized under N2 pyrolysis at 800oC. Pyrolysis also prevented the formation of more toxic Cr6+ ions and at the same time resulted to its reduction by around 42.2% contrast to the 580% increase during thermal oxidation. PCDDs and PCDFs have been removed and were not formed in the solid products over the retention time range of 30-90 min at 800°C. Dioxin-like PCBs mostly remained and a retention time of 30 min was found sufficient for its maximum removal. Recommendations and Perspective . With the above results, a temperature of 800oC at a retention time of 30 min is sufficient for the removal of total dioxins and some heavy metals by volatilization. It is however necessary to destroy the dioxins as well as recover heavy metals in the gas phase. Stability of remaining heavy metals in the char also needs to be confirmed by leaching tests. These are the major concerns, which we are currently evaluating to establish the feasibility of our proposed large scale pyrolysis system for sediment treatment.     

饮用水源水、出厂水有机污染物GC/MS分析

于1998年对成都市饮用水源水、出厂水的有机污染物进行了GC／MS分析,该市饮用水和出厂水均存在有机物污染,且含有优先控制污染物;污染来源主要为生活污水。枯水期有机物检出率高于丰水期。     

Endocrine effects of sublethal exposure to persistent organic pollutants (POPs) on silver carp (Hypophthalmichthys molitrix)

Silver carp (Hypophthalmichthys molitrix) samples were collected from five selected sites that represent diverse levels of downgraded persistent organic pollutants (POPs) contamination in Ya-Er Lake in October 1999. Hepatic ethoxyresorufin-O-deethylase (EROD) and UDP glucuronosyltransferase (UDPGT) activities, hepatosomatic index (HSI), hepatic retinoids, serum thyroid hormones were measured. It was found that hepatic retinol and serum free 3,5,3'- tetraiodothyronine (FT3) significantly increased (P < 0.01) when both hepatic EROD and UDPGT activities significantly declined (P < 0.01) from pond 1 to 5 with decrease in the degree of pollution. This significant negative correlation (P < 0.01) suggests that the persistent organochlorinated contaminants could induce hepatic EROD and UDPGT activities, alter retinoid and thyroid hormone homeostasis, and finally lead to the reduction of retinol and FT3, the two biologically active forms of retinoids and thyroid hormone in silver carp of Ya-Er Lake.