多氯联苯醚类化合物污染研究进展

综述了当前国际上多氯联苯醚的研究现状,详细论述了环境中多氯联苯醚的来源、毒性效应、污染状况、迁移转化和生物富集规律以及多氯联苯醚形成机制.我国关于多氯联苯醚类污染物的研究相对滞后,当前开展适合我国国情的多氯联苯醚物质的环境水平、生态安全与毒理学研究十分必要.     

Desorption of sediment-associated polychlorinated dibenzo-p-dioxins, dibenzofurans, diphenyl ethers and hydroxydiphenyl ethers from contaminated sediment

The transport and bioavailability of sediment-associated contaminants are often controlled by the contaminants' desorbing behaviour. This study examines the desorption kinetics of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), diphenyl ethers (PCDEs) and hydroxydiphenyl ethers (HO-PCDEs) from the highly contaminated River Kymijoki sediment in Finland. The desorption kinetics data were generated using Tenax((R)) extraction, and a first-order three-compartment kinetic model was fitted to the data. The desorption data was compared to the previously published accumulation data from this same location to investigate the relationship between the rapidly desorbing fraction (F(r)) and biota-sediment accumulation factors (BSAFs) as well as semipermeable membrane device sediment accumulation factors (SSAFs). The PCDDs, PCDFs, PCDEs and HO-PCDEs were tightly attached to sediment particles and formed a large very slowly desorbing fraction (F(vs)). Rapidly desorbing fractions (F(r)) varied between 0.8% and 8% of total amount in sediment. The size of the desorbing fraction was congener-specific and F(r) decreased with the increasing lipophilicity of congeners. The size of the F(r) was unable to explain the small variation in the BSAFs of Lumbriculus variegatus but may help to explain the observed variation in the SSAFs. To our best knowledge, this study is the first effort to investigate the desorption of PCDDs, PCDFs, PCDEs and HO-PCDEs in field-contaminated sediments. The major finding that the very slow desorption of these chemicals will continue years, provides essential information for the modern risk assessment process.     

Polybrominated diphenyl ethers and polychlorinated biphenyls in cord blood from women in Poland

The purpose of this study was to assess human exposure in the prenatal period to selected PBDEs (BDE-47, BDE-99, BDE-153) and PCBs (CB-77, CB-101, CB-118, CB-126, CB-138, CB-153, CB-170, CB-180) basing on the analysis of these compounds in cord blood. The experimental material consisted of 89 cord blood samples taken from women resident in Warsaw and its vicinity. In over 90% of all tested samples the presence of congeners CB-153, CB-138, CB-180 and BDE-47 was identified. The least frequently found were CB-126 and BDE-153, which were present at relatively low concentration levels. Among all analysed PCBs, the highest average concentrations were found in the case of congeners CB-138 (11.8 ng/g of fat) and CB-153 (43.4 ng/g of fat), whereas the lowest was in the case of CB-170 (0.4 ng/g of fat) and CB-126 (0.1 ng/g of fat). In the case of PBDEs the greatest share in the total concentration was that of the congeners BDE-47 and BDE-99, whereas the smallest share was that of the higher brominated congener BDE-153. These results suggest that human exposure to the examined compounds begins already in the period of intrauterine life. The comparison of our own results with the findings of other authors indicates that the PCBs and PBDEs levels in cord blood of women living in Poland do not differ from the respective concentrations in cord blood of other female inhabitants of Europe.     

Distribution of polychlorinated biphenyls and polybrominated diphenyl ethers in birds of prey from Switzerland

Polychlorinated biphenyls (PCBs) and the structurally related polybrominated diphenyl ethers (PBDEs) have been associated with chronic neurotoxicity involving reduced motor activity and impaired attentiveness. Such neurobehavioral effects indicate that the central nervous system may represent an important target organ for the action of these persistent contaminants in wildlife. As a consequence, the brain of different terrestrial and aquatic birds collected in Switzerland was analysed for PCBs and PBDEs. In parallel, the same contaminants were examined in the accompanying adipose tissue. After clean-up by means of glass columns containing acidified silica, deactivated alumina and anhydrous sodium sulphate, the samples were analysed by high resolution gas chromatography/tandem mass spectrometry (HRGC-MS/MS). Median PCB concentrations in the brain (sum of PCB 28, PCB 52, PCB 101, PCB 118, PCB 138, PCB 153 and PCB 180) ranged between 13 ng g(-1) wet weight (ww) in blackbirds (Turdus merula) and 428 ng g(-1) ww in sparrow hawks (Accipiter nisus). Median PBDE concentrations in the brain (sum of BDE 28, BDE 47, BDE 99, BDE 100, BDE 153, BDE 154 and BDE 183) ranged from below the decision limit in buzzards (Buteo buteo) and blackbirds, to 14 ng g(-1) ww in sparrow hawks. After correction for the respective lipid content, higher PCB or PBDE concentrations in brain compared to adipose tissue, were found in three sparrow hawks, four buzzards and in all investigated blackbirds. These results suggest that a deficit in the neuroprotective function of the blood-brain barrier may cause unexpected levels of PCBs and PBDEs in the central nervous system.     

Polybrominated diphenyl ethers, polychlorinated naphthalenes and polycyclic musks in human fat from Italy: Comparison to polychlorinated biphenyls and organochlorine pesticides

Prior to this study, reports of occurrence of polycyclic musks and polychlorinated naphthalenes (PCNs) in human tissues from Italy were not available. In this study, concentrations of PCNs and polycyclic musks were determined in human adipose tissue from Italy collected during 2005-2006; for comparison, legacy organohalogen pollutants such as organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) were determined. ΣPCN concentrations ranged from 0.5 to 14 ng/g lipid wt (lw). Polycyclic musks such as HHCB and AHTN were found in 92% and 83% of the human samples, respectively. Concentrations of PBDEs in Italian adipose tissue ranged between 3.2 and 35.6 ng/g lw.     

Organochlorine pesticides, polychlorinated biphenyls and polybrominated diphenyl ethers in Singapore's coastal marine sediments

Persistent organic pollutants (POPs) are ubiquitous pollutants in the marine environment, particular in coastal areas affected by industry and shipping traffic. POPs are known for their recalcitrance and toxicity in the environment, and there is increasing concern over their global distribution and impact upon wildlife. Marine surface sediment samples taken within 6 km of the coastline of Singapore were analyzed to determine prevailing concentrations of organochlorine pesticides (OCPs), polychlorinated biphenyl (PCBs) and polybrominated diphenyl ethers (PBDEs). Total PCB concentrations varied widely from 1.4 to 329.6 ng/g (average 73.9 ng/g), where high concentrations were detected at sample locations closest to industrial areas with intensive shipping traffic. Total DDT concentrations ranged from 2.2 to 11.9 ng/g (average 6.7 ng/g) and were lower than the concentration range of 3.3-46.2 ng/g measured for total HCH (average 18.1 ng/g). Ratios of DDT/(DDE+DDD) in sediments do not indicate recent inputs of DDT into Singapore's marine environment, but high concentrations of alpha-HCH and gamma-HCH show evidence for the usage of HCHs in Southeast Asia. Peak concentrations of cis- and trans-Chlordane were 10 ng/g. Among the PBDE congeners BDE 47, 99, and 100 only BDE 47 could be detected at a range of 3.4-13.8 ng/g (average 6.2 ng/g). The levels of OCPs, PCBs and PBDEs were compared to available data for other countries in Asia, and indicated relatively moderate levels of contamination. Peak concentrations of PCBs, HCH isomers, Chlordane, Heptachlor, Heptachlor epoxide and Dieldrin have the potential to induce ecotoxicological impacts based on levels specified in the sediment quality standards of the USEPA and Canadian Council of Ministers of the Environment.     

Brominated-chlorinated diphenyl ethers formed by thermolysis of polybrominated diphenyl ethers at low temperatures

Polybrominated diphenyl ethers (PBDEs) are a group of brominated flame retardants (BFRs) used mainly as additives in different kinds of plastic material. Various PBDEs are found in all environmental compartments as well as in tissue and blood serum of animals and humans due to their persistence and tendency to bioaccumulate. Emission of PBDEs into the environment can occur during recycling of PBDE-containing plastic material or during their uncontrolled or insufficient combustion as e.g. in accidental fires or landfill fires. Under these circumstances, PBDEs can also function as precursor molecules for the formation of polybrominated dibenzodioxins (PBDDs) and dibenzofurans (PBDFs). In this study, we qualitatively investigated the reaction of two PBDE congeners, 2,2′,4,4′-tetrabromo diphenyl ether (BDE 47) and 2,2′,4,4′,5,5′-hexabromo diphenyl ether (BDE 153), as well as hexabromobenzene (HBB), a flame retardant used in the past, when exposed to temperatures between 250 °C and 500 °C. The formed reaction products were analysed by high resolution gas chromatography–low resolution mass spectrometry (HRGC-LRMS). Among others brominated–chlorinated diphenyl ethers were formed by chlorodebromination of the PBDEs. In addition, thermolysis of BDE 47 and BDE 153 in the presence of tetrachloromethane as model substance for an organic chlorine source was studied. Thermal treatment of HBB resulted in the formation of brominated–chlorinated benzenes.     

Polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in breast milk from the Pacific Northwest

Breast milk samples from 40 first-time mothers from the Pacific Northwest of the US and Canada were analyzed for polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs). Total PBDEs (summation operator PBDEs), calculated by summing values for the 12 PBDEs congeners analyzed, ranged from 6 to 321 ppb (lipid weight) (mean=96 ppb; median=50 ppb). In approximately 40% of the women (15/40), summation operator PBDEs>100 ppb lw in their milk, and four samples had levels >250 ppb lw. PBDE 47 was the dominant congener in most samples, whereas PBDE 153 was predominant in a few (3/40). summation operator PCBs were calculated by summing values for the 82 PCB congeners analyzed, and ranged from 49 to 415 ppb (lipid weight) (mean=147 ppb; median=126 ppb). approximately 30% of the mothers (13/40) have summation operator PBDEs> summation operator PCBs in their milk samples, and approximately 65% (25/40) have BDE 47>PCB 153 in breast milk samples, with BDE 47 averaging 3-fold greater levels than PCB 153. Clearly, the lower brominated PBDEs are surpassing PCBs as a major environmental concern in North America, and are likely affecting significant portions of the populations in these regions. PBDEs have become a major persistent organic pollutant. However, there are no positive correlations between levels of summation operator PBDEs and summation operator PCBs, or between levels of PBDE 47 and PCB 153, suggesting there may be some differences in exposure pathways for PBDEs and PCBs in humans.     

Polybrominated diphenyl ethers,polychlorinated dibenzo-dioxins,-furans,and-biphenyls in three species of antarctic penguins

Background, Aims and Scope Fish-eating seabirds are recognized to be at risk of accumulating toxic contaminants due to their high position in the trophic web and to their low ability to metabolize xenobiotic compounds. Penguins are widely distributed in Antarctica and represent an important fraction of the Antarctic biomass. They feed mainly on krill and, depending on krill availability, also on fish. It has been reported that predators may be a sink for volatile and toxic chemicals and this may pose a serious environmental problem. Polybrominated diphenyl ethers (PBDEs), polychlorinated dibenzo-dioxins (PCDDs),-furans (PCDFs), and-biphenyls (PCBs), including non-ortho congeners, hexachlorobenzene (HCB) and p,p′-DDE, were quantified in three species of Antarctic Pygoscelids in order to evaluate their accumulation patterns. The potential toxicity of twenty-two dioxin-like congeners was assessed and expressed as 2,3,7,8-tetraCDD equivalents (TEQs). Differences between males and females were investigated. Methods Blood samples of the Adélie penguin Pygoscelis adeliae, Chinstrap penguin Pygoscelis antarctica and Gentoo penguin Pygoscelis papua were collected at Admiralty Bay, King George Is (62°10′39″ S, 58°26′46″ W) in February 2004. Halogenated hydrocarbons were identified and quantified using gas chromatography coupled with gas chromatography mass spectrometry analyses. Results are expressed on a wet weight basis. Results and Discussion HCB, p,p′-DDE and ΣPCBs were higher in Adélie penguins (6.7±6.1, 8.2±3.3 and 9.8±3.8 ng/g, respectively) than in Chinstrap and Gentoo penguins, both of which showed values in the same order of magnitude, but approximately 40% lower than Adélie penguins. Hexa-CBs ranged 35–45% of the residue. Low-chlorinated PCBs (nos. 70+76+95+56+60+101) accounted for 40–60% in the three species. PCB101 made up 15% of the residue in Adélie penguins. PBDEs were 291±477, 107±104 and 116±108 pg/g in Adélie, Chinstrap and Gentoo penguins, respectively; the most abundant congeners were BDE47 in Adélie and Chinstrap penguins and BDE17 in Gentoo penguins. PCDDs were 22±32, 6.5±7.4 and 18±23 pg/g in Adélie, Chinstrap and Gentoo penguins, respectively. PCDFs were higher in Adélie penguins and lower in Chinstrap penguins. PCDDs/Fs and PBDEs were higher in males than in females of Gentoo and Chinstrap penguins; differences in concentrations were likely related to the partial detoxification that occurs in females during egg formation. Of the four non-ortho PCBs measured, PCB126 occurred at the highest concentrations and contributed the majority of the non-ortho PCB-TEQ in Gentoo and Chinstrap penguins. The highest TEQs were found in the Gentoo penguin and due mainly to PCDDs and non-ortho PCBs. Conclusions POP concentrations in penguins were lower than those found in seabird species from other areas of the world. Different chemical accumulation patterns were observed in relation to species and sex; the Adélie penguin showed the highest POP levels. Dissimilar ecological or metabolic features may be involved; the diverse timing of reproduction steps can be responsible for those differences; moreover, Adélie penguins feed on krill (a fatty resource) more abundantly than the other two species during the rearing period. Recommendation and Outlook The South Shetland Islands might be subjected to a higher chemical impact with respect to the rest of Antarctica, due to their being near South America. Because penguins are fish-eating birds showing low detoxifying capacities and key-species in Antarctic ecosystems, further studies on their xenobiotic metabolism should be carried out.     

Spatial trends of organochlorinated pesticides,polychlorinated biphenyls,and polybrominated diphenyl ethers in Atlantic Anguillid eels

The bioaccumulation of lipophilic contaminants such as polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), and polybrominated diphenyl ethers (PBDEs) can result in a reduction in fitness and spawner quality in eels and may be a factor in Anguillid sp. population declines. Contaminant concentrations in eels have been studied extensively in Europe, but data for American eels are severely lacking. Concentrations of PCBs, OCPs, and PBDEs were determined in American eel from eastern Canada and New York, USA, along with European eel from Belgium. Principal component analysis revealed that eels captured in the St. Lawrence estuary were a mixture of upstream migrants from the St. Lawrence River watershed, and fish captured in local tributaries. Contaminant concentrations were dependent on origin, related to the local environment, and were lower than historic values. In Canada, concentrations of OCPs and PCBs in eel tissues were below the Canadian human consumption guidelines for contaminants in fish, indicating that the current risk to consumers is low. However, concentrations of PCBs, total DDT, and mirex in eels from L. Ontario and the upper St. Lawrence R. were above Great Lakes guidelines for the protection of piscivorous predators. Concentrations of penta-BDE homologs exceeded the Canadian guideline for environmental quality in over half of the eels in this study, but concentrations of the other homolog groups were below the guideline.     

Biomagnification of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls in a highly contaminated freshwater food web from South China

To evaluate the biomagnification extent of polybrominated diphenyls ethers (PBDEs) and polychlorinated biphenyls (PCBs) in a highly contaminated freshwater food web from South China, trophic magnification factors (TMFs) for 18 PBDE congeners and 53 PCB congeners were calculated. The TMF values ranged 0.26-4.47 for PBDEs and 0.75-5.10 for PCBs. Forty-five of 53 PCBs and BDEs 47, 100 and 154 had TMFs greater than one, suggesting their biomagnification in the present food web. The TMFs for PBDEs were generally smaller than those for PCBs with the same degree of halogenation, indicating a lower biomagnification potential for PBDEs compared to PCBs. For PCBs, it followed a parabolic relationship between TMFs and log K_OW (octanol-water partition coefficient). However, this relationship was not significant for PBDEs, possibly due to the more complex behaviors of PBDEs in the food web (e.g., metabolism), compared to that of PCBs.     

Polybrominated diphenyl ethers (PBDEs) and indicator polychlorinated biphenyls (PCBs) in marine fish from four areas of China

The levels of polybrominated diphenyl ethers (PBDEs) and indicator polychlorinated biphenyls (PCBs) were determined in marine fish from four areas of China (South China Sea, Bohai Sea, East China Sea, and Yellow Sea) using GC/NCI-MS and GC/ITMS, respectively. Total concentrations of eight PBDEs (BDE-28, 47, 99, 100, 153, 154, 183 and 209) in all samples ranged from 0.3 ng g⁻¹ ww (wet weight) to 700 ng g⁻¹ ww, with median and mean values of 85 ng g⁻¹ ww and 200 ng g⁻¹ ww, respectively. BDE-209 and BDE-47 were the major congeners in all samples, contributing 54% and 19% to the total concentration, respectively. The sum of seven indicator PCB levels (CB-28, 52, 101, 118, 138, 153, and 180) ranged from 0.3 ng g⁻¹ ww to 3.1 μg g⁻¹ ww, with median and mean values of 6.4 ng g⁻¹ ww and 398 ng g⁻¹ ww, respectively. High contributions of CB-138 (32%) and CB-153 (25%) were found in all samples. In general, pollutants measured in this study were at high levels when compared with previous studies from other regions in the world. The relative abundance of BDE-209 may suggest that deca-BDE sources existed in studied area. And principal component analysis (PCA) showed that there were other PBDE sources in Yellow Sea. The pattern and PCA showed that PCB pollutions came from similar sources in the studied areas. In addition, concentrations of ∑₇PBDEs (u/209) were strongly correlated with those of ∑₇PCBs in all fish (r = 0.907, n = 44).     

GC-ECD和LC-MS/MS测定垃圾焚烧飞灰中氯苯和氯酚的方法

氯苯和氯酚是生活垃圾焚烧过程产生的重要污染物,目前对垃圾焚烧炉飞灰中氯苯和氯酚的研究较少。本文采用超声萃取法结合GC-ECD、LC-MS/MS,建立了飞灰等固体介质中的氯苯氯酚的定量检测方法,通过实验确定出较优的前处理条件,飞灰样品中滴加少量浓硫酸,以正己烷/丙酮（1：1）为萃取溶剂,40℃超声萃取20 min,萃取3次,然后液相萃取分离氯酚氯苯,分别净化,浓缩,最后进机检测,对三、四、五、六氯代苯和所有的氯酚均获得较好的回收率。应用建立的检测方法测试了3座正常运行过程中的生活垃圾焚烧炉飞灰的氯苯和氯酚含量,样品中一到四氯代氯酚的含量都在定量限以下,五氯酚含量范围为5~11 ng·g-1,三氯苯、四氯苯、五氯苯和六氯苯的含量在3~70 ng·g-1的范围。     

Concentrations of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in milk of women from Catalonia, Spain

In this study, the concentrations of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in milk from women living in the vicinity of a new hazardous waste incinerator (HWI) in Catalonia, Spain, were determined. The study was performed after 4 years of regular operations in the facility and the present PCB levels were compared with baseline concentrations obtained in a pre-operational program. PCBs and PBDEs levels were determined by HRGC/HRMS in 15 samples. In the present study planar PCBs ranged from 1.3 to 6.3 pg WHO-TEQ/g fat with a mean value of 3.8 pg WHO-TEQ/g fat. After adding dioxin-like mono-ortho-PCBs the total PCB-TEQ concentrations ranged from 3.8 to 13.3 pg WHO-TEQ/g fat (mean value: 8.7 pg WHO-TEQ/g fat). A comparison of the current data with those obtained in the baseline study showed significant decreases for both planar and total WHO-TEQ of PCBs: 47.9% and 44.6%, respectively. PCB concentrations in milk of women living in urban zones were higher than those living near industrial areas (10.1 and 7.4 pg WHO-TEQ/g fat, respectively). Mean PBDE concentrations were 2.2 and 2.5 ng/g fat for women living in urban and industrial zones, respectively. Dietary intake of PCBs and PBDEs for a standard adult woman samples were 898 and 843 ng/day for PCBs, and 72 and 63 ng/day for PBDEs, for residents in urban and industrials areas, respectively. This study suggests that dietary intake is more relevant for human exposure to PCBs and PBDEs than living near the HWI.     

Polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in human liver and adipose tissue samples from Belgium

Levels of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) were measured in paired human adipose tissue and liver samples (n=25) from Belgium. Average concentrations and standard deviation of sum PBDEs (congeners 28, 47, 99, 100, 153, 154 and 183) were 5.3+/-3.0 (range 1.4-13.2) and 3.6+/-2.1 (range 1.0-10.0)ngg(-1) lipid weight (lw) in adipose tissue and liver, respectively. These concentrations were similar to reported PBDE data from Belgium and were at the lower end of the concentration range reported elsewhere in the world. In both tissues under study, BDE 153 and BDE 47 were the most abundant PBDE congeners, contributing approximately 35% and 25% to the total PBDE content. Average concentrations and range of PCBs (sum of 23 congeners) were 490 (range 70-1130) and 380 (range 90-1140)ngg(-1)lw in adipose tissue and liver, respectively. No correlation between age and concentrations of PBDEs could be found (r=0.04), while PCB concentrations correlated significantly with age (r=0.62, p<0.01, for the sum PCBs; r=0.64, p<0.01 for PCB 153 alone). Factors, such as exposure pathways (food, dust and air), rates of bioaccumulation, metabolism and elimination, influence the concentrations of PBDEs differently than those of PCBs in humans.