二噁英、多氯联苯和氯丙醇的痕量与超痕量检测技术研究

为建立食品中二噁英、多氯联苯和氯丙醇的检测技术并达到国际水平，将稳定性同位素稀释质谱技术应用到中国食品安全和环境分析领域，针对不同目标化合物分别建立了高分辩磁质谱、四极杆低分辩质谱和离子阱串联质谱的标准化检测技术，特别是采用双同位素稀释同时测定4种氯丙醇的技术。通过对EPA1613A／1668A、FDA4084和EPSI／RM／31、AOAC2000．01等国际先进方法用食品（鱼、鱼油、鹿肉、奶粉和猪油）和环境样品（飞灰、土壤和底泥）开展对比筛选和一系列实验室闻协同性验证，确立了二噁英和多氯联苯的稳定性同位素稀释质谱检测方法，建立了用双稳定性同位素进行酱油中单氯取代和双氯取代氯丙醇同时测定的方法，提出了符合国际规范的技术方案，作为国家标准方法待颁布。利用该检测技术在中国首次开展鱼贝类和土壤中污染的二噁英和多氯联苯同系物类型特征指纹库研究和酱油中氯丙醇的大规模调查，获得了中国人群膳食二噁英毒性当量和氯丙醇摄入状况的暴露数据，不仅证明所建立的方法实用、可行，也为我国履行承诺摸清了家底，提供了依据。     

PCB pollution behaviour in the River Seine

The contamination of the River Seine (France) and its main tributaries (Yonne, Marne, Oise) have been studied, under different hydrological conditions, at the end of spring before the low watermark and at the beginning of autumn after the first swelling of flow.The sector under study consists of the Seine basin, centered on the Paris area; the variability of PCB concentration in water, apart from flow dependence, shows that important lateral discharges are involved. The pollution level is particularly noticeable at Paris and downstream from Paris and the median concentration in sediments reaches 3800 ng l⁻¹ (ppb). Data on particulate organic carbon and various grain size fractions show the PCB to be preferentially adsorbed on organic-rich sedimentary particles.Partition coefficients between particulate matter and liquid phase have been computed and show that the liquid phase has the main role in micropollutant transport.     

Development and application of a simplified clean-up procedure for the determination of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in horse fat by gas chromatography-tandem mass spectrometry (GC-MS/MS)

A simplified clean-up procedure was developed in combination with gas chromatography-tandem mass spectrometry (GC-MS/MS) for the determination of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in adipose tissue. Clean-up was performed by the successive application of a Mega Bond Elut® silica column and a Bond Elut® PCB column. Validation of the method was conducted according to European Union Commission Decision 2002/657/EC. In order to evaluate the applicability of the method, 44 horse fat samples were analysed. The total PCB concentration (sum of PCBs 28, 52, 101, 118, 138, 153 and 180) ranged from 5.35 to 140 ng g^-1 lipid weight. The total PBDE concentration (sum of BDEs 28, 47, 99, 100, 153, 154 and 183) ranged from below the decision limit to 6.34 ng g^-1 lipid weight.     

Applications of sample preparation techniques in the analysis of pesticides and PCBs in food

Pesticides and polychlorinated biphenyls (PCBs) are found in various parts of the environment in quite small concentrations, but they accumulate and thus become a threat to human health and life. A review is focused on the application of some popular techniques for sample preparation in analysis of these compounds in food. Even with the emergence of advanced techniques of final analysis, complex matrices, such as food, require extensive sample extraction and purification. Traditional sample preparation techniques are time consuming and require large amount of solvents, which are expensive, generate considerable waste, contaminate the sample and can enrich it for analytes. There have been many sample preparation techniques proposed to meet the requirements connected with the multiplicity of food. Optimal sample preparation can reduce analysis time, sources of error, enhance sensitivity and enable unequivocal identification and quantification. Sample extraction and purification techniques are discussed and their most recent applications in food analysis are provided. This review pointed out that sample preparation is the critical step.     

Contaminant blubber burdens in Atlantic bottlenose dolphins (Tursiops truncatus) from two southeastern US estuarine areas: Concentrations and patterns of PCBs, pesticides, PBDEs, PFCs, and PAHs

Polychlorinated biphenyls (PCBs), chlorinated pesticides (i.e., dichlorodiphenyltrichloroethane (DDT) and its metabolites, chlordanes (CHLs), dieldrin, hexachlorobenzene (HCB), and mirex), polybrominated diphenyl ethers (PBDEs), perfluorinated chemicals (PFCs), and polyaromatic hydrocarbons (PAHs) were measured in blubber biopsy samples collected from 139 wild bottlenose dolphins (Tursiops truncatus) during 2003-2005 in Charleston (CHS), SC and the Indian River Lagoon (IRL), FL. Dolphins accumulated a similar suite of contaminants with ∑ PCB dominating (CHS 64%, IRL 72%), followed by ∑ DDT (CHS 20%, IRL 17%), ∑ CHLs (CHS 7%; IRL 7%), ∑ PBDE (CHS 4%, IRL 2%), PAH at 2%, and dieldrin, PFCs and mirex each 1% or less. Together ∑ PCB and ∑ DDT concentrations contributed ∼ 87% of the total POCs measured in blubber of adult males. ∑ PCBs in adult male dolphins exceed the established PCB threshold of 17 mg/kg by a 5-fold order of magnitude with a 15-fold increase for many animals; 88% of the dolphins exceed this threshold. For male dolphins, CHS (93,980 ng/g lipid) had a higher ∑ PCBs geomean compared to the IRL (79,752 ng/g lipid) although not statistically different. In adult males, the PBDE geometric mean concentration was significantly higher in CHS (5920 ng/g lipid) than the IRL (1487 ng/g). Blubber ∑ PFCs concentrations were significantly higher in CHS dolphins. In addition to differences in concentration of PCB congeners, ∑ PBDE, TEQ, ∑ CHLs, mirex, dieldrin, and the ratios ∑ DDE/∑DDT and trans-nonachlor/cis-nonachlor were the most informative for discriminating contaminant loads in these two dolphin populations. Collectively, the current ∑ PCB, ∑ DDT, and ∑ PBDEs blubber concentrations found in CHS dolphins are among the highest reported values in marine mammals. Both dolphin populations, particularly those in CHS, carry a suite of organic chemicals at or above the level where adverse effects have been reported in wildlife, humans, and laboratory animals warranting further examination of the potential adverse effects of these exposures.     

A comparison of PCB bioaccumulation factors between an arctic and a temperate marine food web

To test how environmental conditions in the Arctic and the resulting ecological adaptations affect accumulation of persistent organic pollutants (POPs) in the marine food web, bioaccumulation of four polychlorinated biphenyls (PCBs) in an arctic (Barents Sea 77 °N-82 °N) and a temperate marine (Baltic Sea 54 °N-62 °N) food web were compared. Three different trophic levels were studied (zooplankton, fish, and seal), representing the span from first-level consumer to top predator. Previously published high-quality data on PCB water concentrations in the two areas were used for calculation of bioaccumulation factors (BAF). BAF was calculated as the ratio of the PCB concentration in the organism ([PCB]_org; pg/kg lipid) to the dissolved water concentration (C_w; pg/L). The BAF_Arctic:BAF_Temperate ratios were above 1 for all four PCB congeners in zooplankton (6.4-13.8) and planktivorous fish (2.9-5.0)), whereas the ratios were below 1 in seal. The mean ratio between arctic and temperate BAFs for all trophic levels and congeners (BAF_Arcti:BAF_Temperate) was 4.8. When the data were corrected for the seawater temperature difference between the two ecosystems, the ratio was 2.0. We conclude that bioaccumulation differences caused by ecological or physiological adaptations of organisms between the two ecosystems were well within a water concentration variability of 50%. Further, our data support the hypothesis that lower seawater temperature lead to a thermodynamically favoured passive partitioning to organic matrices and thus elevated ambient BAFs in the Arctic compared to the Baltic Sea. This would imply that bioaccumulation in the Arctic may be described in the same way as bioaccumulation in temperate regions, e.g. by the use of mechanistic models parameterised for the Arctic.     

Concentrations and determinants of organochlorine levels among pregnant women in Eastern Spain

Persistent organic pollutants (POPs) comprise a large variety of toxic substances with ample distribution. While exposure to these toxins occurs mainly through diet, maternal POP levels may be influenced by certain sociodemographic, environmental, or lifestyle factors. This is important given that these substances may have adverse effects on fetal development. The aim of this study is to examine the sociodemographic, environmental, lifestyle, and dietary determinants of the levels of hexachlorobenzene (HCB), b-hexachlorocyclohexane (b-HCH), 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane (4,4′-DDT), 1,1-dichloro-2,2-bis(4-chlorophenyl)ethylene (4,4′-DDE), and polychlorinated biphenyls (PCB congeners 118, 138, 153, 180) measured in the blood of pregnant women participating in a mother-child cohort study conducted in Valencia (Spain).The study population consisted of 541 pregnant women who formed part of the INMA (Childhood and the Environment) cohort (2004-2006). POP levels were determined in blood taken during the 12th week of pregnancy with the aid of gas chromatography with electron capture detection. Sociodemographic, environmental, and dietary information was obtained from a questionnaire. Multivariate Tobit regression models were constructed in order to assess the association between POP levels and selected covariates.The results showed that all the women had detectable levels of at least one of these compounds while in 43% of the subjects, all eight compounds were detected. The compounds found in the greatest number of women were 4,4′-DDE (100%) and PCBs 153 and 180 (95%). The most important determinants of high POP levels were the mother's age, country of origin, increased body mass index, and number of weeks of breastfeeding after previous pregnancies. With regard to diet, 4,4′-DDT and 4,4′-DDE levels increased with the intake of meat, fruit, and cereal. PCB 153 levels increased with the intake of seafood. The levels of HCB, b-HCH, 4,4′-DDT, and 4,4′-DDE observed in this study were slightly higher than in other studies, whereas the PCB levels were similar.     

Development of a strain for efficient degradation of polychlorinated biphenyls by patchwork assembly of degradation pathways

Rhodococcus jostii RHA1 accumulates chlorobenzoates (CBA) during the degradation of polychlorinated biphenyls (PCBs). CBA degradation is considered one of the rate-limiting steps in the complete degradation of PCBs. To reduce the accumulation of CBAs, the upper pathway enzyme genes for PCB degradation of RHA1 were introduced into a CBA-degrading bacterium, Burkholderia sp. NK8. The resulting recombinant strain exhibited no biphenyl 2,3-dioxygenase (BphA) activity encoded by bphAaAbAcAd genes, which encode the large and small subunits of the terminal oxygenase component and the ferredoxin and reductase subunits responsible for electron transfer from NADH to the large subunit. The remaining enzyme genes involved in the transformation of biphenyl to benzoate, bphB2C1D1, which encode dehydrogenase, ring-cleavage dioxygenase and hydrolase, conferred activities to NK8. To obtain the BphA activity of RHA1 in NK8, sets of BphA genes were constructed by combining the bphAaAbAcAd genes of RHA1 and bphA3A4 of Pseudomonas pseudoalcaligenes KF707, encoding the ferredoxin and reductase subunits. Hybrid derivatives of BphA containing the KF707 bphA3 conferred BphA activity to NK8, and a derivative containing the RHA1 bphAaAb and KF707 bphA3A4 genes exhibited the highest BphA activity. A plasmid containing the RHA1 bphAaAb and KF707 bphA3A4 genes plus the RHA1 bphB2C1D1 genes was constructed and introduced into NK8. The resulting recombinant strain efficiently degraded 2-, 3- and 4-chlorobiphenyls with an apparent reduction in CBA accumulation in comparison to the recombinant mutant strain, which had an insertion in the cbeA gene to inactivate CBA dioxygenase.     

Mercury,selenium, PCBs and fatty acids in fresh and canned fish available on the Slovenian market

In order to contribute to the general understanding of the risks and benefits of consuming fish and fish products, total mercury (THg), monomethylmercury (MeHg), polychlorinated biphenyls (PCBs), selenium (Se), n-3 and n-6 fatty acids were determined in fresh and canned fish on the Slovenian market. Furthermore, the mercury exposure of pregnant women in Slovenia was assessed by determining total mercury (THg) in hair, and through fresh and canned fish consumption obtained by a food frequency questionnaire. Based on the frequency of fish consumption and levels of MeHg, THg and PCBs determined in the present study, it can be concluded that fish available on the Slovenian market do not represent a health risk. It was also confirmed that fish are important sources of selenium and n-3 fatty acids.