固相萃取技术在水体有机物分析中的应用

本文简述了固相萃取技术（ＳＰＥ）的原理、方法及特点,阐述了ＳＰＥ和气相色谱（ＧＣ）在线与离线两种联用技术应用于水样中有机化合物的分析,并着重介绍了ＳＰＥＧＣ应用于分析水环境中痕量多氯有机化合物,包括多氯联苯化合物（ＰＣＢｓ）和有机氯农药（ＯＣＰｓ）的方法进展情况     

白洋淀几种不同食性鱼类对六六六、DDT的富集

对白洋淀几种不同食性鱼体内六六六和ＤＤＴ残留量分析表明，草食性鱼体内农药残留量最少，六六六含量为５９．３μｇ／ｋｇ，ＤＤＴ含量为２９．６μｇ／ｋｇ；其次是杂食性鱼类，六六六含量为９０．４μｇ／ｋｇ，ＤＤＴ含量为１０８．５μｇ／ｋｇ；肉食性鱼体内农药残留量最高，六六六含量为１１０．７μｇ／ｋｇ，ＤＤＴ含量为１２４．４μｇ／ｋｇ。鱼体对ＤＤＴ的浓缩因子为３１１～１２４４，明显高于六六六的１７７～３６８。鱼体内ＢＨＣ４种异构体的残留顺序为δ＞α＞γ＞β，与其在水体中的比例α＞γ＞δ＞β略有不同。鱼体内ＤＤＴ主要以代谢物ｐ，ｐ＇－ＤＤＥ的形式存在，但个别样品中少量的ｐ，ｐ＇－ＤＤＤ及ｏ，ｐ＇－ＤＤＴ的检出，表明白洋淀水生生态系统最近受到ＤＤＴ的轻度污染。本项研果与１９７５～１９７７年检测结果进行比较；白洋淀鱼体内六六六残留量显著下降，下降率为１５．８％～７９．２％；ＤＤＴ残留量却明显增加（草食性鱼类除外），增加率约为４７．８％～９７．８％。     

农药微生物降解的研究现状与发展策略

本文在农药降解菌的富集分离及农药微生物降解的途径，特别在微生物产生的农药降解酶和农药微生物降解基因操作方面对农药微生物降解的研究现状作了简要综述，提出了农药微生物降解的研究趋势。联系地址：中国科学院广州地球化学研究所，广州五山，５１０６４０津、环草隆、三氯醋酸、氯苯胺灵等。芽孢杆菌属（Ｂａｃｉｌｌｕｓ）：ＤＤＴ、ｒ－ＢＨＣ、艾氏剂、狄氏剂、异狄氏剂、七氯、苯硫磷、对硫磷、甲基对硫磷、杀螟松、毒杀芬、茅草枯、三氯醋酸、利谷隆、灭草隆、毒旁定。节细菌属（Ａｒｔｈｒｏｂａｃｔｅｒ）：ＤＤＴ、艾氏剂、异狄氏剂、七氯、草多索、马拉硫磷、二嗪农、２，４－Ｄ、２甲４氯、茅草枯、三氯醋酸、毒莠定、西玛津、味哺丹［８］。棒状杆菌属（Ｃｏｒｙｎｂｏａｃｔｅｒｉｕｍ）：ＤＤＴ、２，４－Ｄ、２甲４氯、茅草枯、二硝甲酚、百草枯、草枯醚。无色杆菌属（Ａｃｈｒｏｍｏｂａｃｔｅｒ）：ＤＤＴ、西维因、２，４－Ｄ、２甲４氯、２，４，５－Ｔ、氯苯胺灵。土壤杆菌属（Ａｇｒｏｂａｃｔｅｒｉｕｍ）：ＤＤＴ、氯苯胺灵、茅草枯、三氯醋酸、毒莠定。黄杆菌属（Ｆｌａｖｏｂａｃｔｅｒｉｕｍ）：对硫磷、甲基对硫磷、马拉硫磷、二嗪农、毒死蜱、２，４－Ｄ、２甲４氯、     

流化床垃圾焚烧炉产生的有毒二噁英同类物分布研究

测定了流化床垃圾焚烧炉焚烧产生的飞灰、烟尘和烟气中的2，3，7，8位氯取代二噁英同类物的含量及其毒性当量。结果表明，产生的二噁英主要存在于飞灰中，烟气中的含量很少。飞灰中二噁英总浓度和毒性当量分别为8.44ng／g和0．80ng／g，经过布袋除尘器后的烟尘和烟气中二噁英的浓度之和与毒性当量之和分别为0．34ng／m^3和0．02ng／m^3，而布袋除尘器前的烟尘和烟气中二噁英的浓度之和与毒性当量之和分别为40．78ng／m^3和3．0ng／m^3。飞灰和烟尘中2，3，7，8位氯取代二噁英同类物的分布相似，但是与烟气中2，3，7，8位氯取代二噁英同类物的分布差别较大。通过了解有毒二噁英同类物的分布，可以进一步优化流化床垃圾焚烧炉的焚烧条件，降低二噁英的排放量，减少垃圾焚烧对环境的污染。     

PCB and dioxin-like PCB in indoor air of public buildings contaminated with different PCB sources--deriving toxicity equivalent concentrations from standard PCB congeners

Data on dioxin-like PCB in indoor air of buildings with PCB-containing materials and on possible correlation between toxicity equivalent concentrations (TEQ) and levels of non-dioxin-like standard PCB is sparse. As part of a larger survey on indoor-air contamination with PCB, the connection between the concentration of standard PCB congeners and the dioxin-like toxicity expressed as TEQ was investigated. Indoor air samples (n=8) were collected in four public buildings with known PCB sources and total PCB levels in the range from 715 to 2250 ng/m3 and analyzed for the six non-dioxin-like standard PCB (congeners 28, 52, 101, 138, 153, 180), the twelve dioxin-like PCB congeners according to WHO and the 17 2,3,7,8-substituted PCDD/PCDF congeners. In three buildings where PCB were used as flame retardant coatings of acoustic ceiling tiles, PCB 101 had the maximum level among the six standard PCB, while in the building with permanent elastic sealants as PCB source, congeners 28 and 52 dominated the pattern by far. In the case of permanent elastic sealants as PCB source (n=3) a total PCB concentration of 1000 ng/m3 corresponded to a total TEQ level of 0.3-0.6 pg/m3. In contrast, in rooms with acoustic ceiling tiles as PCB source, 1.8-4.7 pg TEQ/m3 per 1000 ng total PCB/m3 were found. Linear regression analysis between PCB and TEQ indicated that PCB 118 might be used to calculate the total TEQ of dioxin-like PCB and PCDD/PCDF. By means of such a correlation it is possible to estimate TEQ by extrapolation from the results of less sophisticated analytical methods. It is tentatively recommended to use PCB 118 for screening purposes or re-evaluation of standard PCB indoor-air measurements. If only the six non-dioxin-like PCB standard congeners are available, a regression algorithm using the sum of PCB 101, 138, 153 and 180 might be used instead.     

Congener profiles of PCBs and PCDD/Fs in Yucheng victims fifteen years after exposure to toxic rice-bran oils and their implications for epidemiologic studies

In 1978-1979, a mass poisoning occurred in central Taiwan from rice-bran oil contaminated by heat-degraded PCBs was later called the Yucheng (oil disease in Chinese). Only a few studies have so far investigated the levels of specific polychlorinated biphenyl (PCB) or polychlorinated dibenzodioxin/furan (PCDD/F) congeners in the Yucheng victims. This study aimed to investigate the serum residual levels of thirty-three PCBs and seventeen 2,3,7,8-substituted PCDD/F congeners in the Yucheng victims 15 years after the exposure. Forty-one blood samples were collected from individual Yucheng victims in 1994-1995. The mean levels of total 33 PCBs and 17 PCDD/Fs were 2468 ng/g lipid (13.3 ng/g sample) and 6550 pg/g lipid (30.9 pg/g sample) respectively. The higher levels were found in PCBs #99, #138, #153, #156, #170, #179, and #180 among 33 PCB congeners, while 2,3,4,7,8-PeCDF, 1,2,3,4,7,8-HxCDF, and OCDD had the higher concentrations among 17 PCDD/F congeners. The total TEQ was contributed in decreasing order by 10 PCDFs (44%), three non-ortho-PCBs (24%), six mono-ortho-PCBs (20%), and seven PCDDs (12%). The mean total PCB levels and TEQ value of the 17 PCDD/Fs in the Yucheng victims 15 years after the toxic exposure were still 9 and 46 times higher than those in the general population in Taiwan. Principle component analysis (PCA) indicated that seven PCB congeners, PCBs #99, #138, #153, #156, #170, #179, and #180, accounted for 73% of the total variances in PCBs. On the other hand, six PCDD/F congeners, 2,3,4,7,8-PeCDF, 1,2,3,4,7,8-HxCDF, 1,2,3,6,7,8-HxCDF, 1,2,3,6,7,8-HxCDD, 1,2,3,4,6,7,8-HpCDF, and OCDD, accounted for 97% of the total variances in PCDD/Fs. In addition, PCA revealed that at least three characteristic patterns of congener profiles for PCBs were observed among the Yucheng victims. Similar trend was also observed for PCDD/Fs. These patterns may reflect distinctive exposure scenarios and/or different metabolizing capabilities among the Yucheng victims. We suggest that these patterns, in contrast to total PCB and PCDD/F levels, may be valuable for the future epidemiologic studies when linking exposure with specific health effect.     

Congener profiles of PCB and a proposed new set of indicator congeners

In this study, a new method for calculating total PCB and toxic equivalents (TEQ) of coplanar PCB (Co-PCB) was proposed, called the 'PCB dual method'. This method analysed various kinds of technical PCB, samples contaminated by technical PCB and byproduct PCB. In the PCB dual method, a data set of 15 indicator congeners was utilized for the calculations, having IUPAC nos. #3, #8, #28, #52, #77, #101, #105, #118, #126, #138, #153, #180, #194, #206 and #209. The 15 congener set was chosen from the major congeners, determined by HRGC/HRMS analysis, in 18 technical PCB, Kanechlor, Aroclor, Clophen and Chlorofen, and 20 other samples, such as indoor air, flue gases, emission gases, municipal solid waste (MSW), ash and sealant. To obtain total PCB and TEQ of Co-PCB, the intermediate sum for the concentration of the 15 congeners was multiplied by each multiplication factor. As a result, we obtained the average factor used to calculate total PCB in technical PCB and other samples. For technical PCB, the factor was 3.01, while for indoor air samples, flue and emission gases, MSW, ash and sealants, the factors were 3.92, 4.16, 3.68, 4.52 and 4.77, respectively. Moreover, the factor used to calculate the TEQ of Co-PCB in Kanechlor and other source samples were also obtained. The factors for Kanechlor, indoor air samples and emission gases from a cement plant were in the order of 10(-5), while the factor for flue gases in a MSW incinerator was in the order of 10(-3). These data were valuable for the rough estimation of the TEQ of Co-PCB without separation from other PCB before individual measurements.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans from food salt samples processed by heat treatment in Korea

Eight samples of processed food salt collected from five plants in Korea were analyzed for 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) using liquid-liquid extraction, clean-up procedures, and high resolution gas chromatography-high resolution mass spectrometry. The study included the analyses of two kinds of salt product sample: bamboo-salt and parched salt. The levels of toxic PCDD/Fs found in the salt product samples were extremely low: the results revealed TEQ levels ranging between the sub pg TEQ/g and sub fg TEQ/g. The differences in the TEQ values of toxic PCDD/F were observed between the salt product samples, which were treated with different frequency of baking using four different fuels (firewood, pine wood, pine resin, and indirect heating by gas) at temperatures from 300 to 2000 degrees C. In bamboo-salt samples, the concentrations and TEQ values of toxic PCDD/Fs ranged between 0.57-66 pg/g and 5.7x10(-5)-0.64 pg TEQ/g, respectively. PCDD/Fs levels in bamboo-salts baked by firewood were found to be higher than those baked by pinewood or pine resin. In parched salt samples, the concentrations and TEQ values of toxic PCDD/Fs ranged between 0.97-3.7 pg/g and 0.0097-0.017 pg TEQ/g, respectively. The data was discussed regarding the concentration and the distribution pattern of congeners.     

Detailed study on the levels of polychlorinated dibenzo-p-dioxins,polychlorinated dibenzofurans and polychlorinated biphenyls in Yusho rice oil

One bottle of Yusho rice oil was obtained from a Yusho family in 1998. The levels of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in the causal oil were investigated with two different approaches and the individual concentrations of all the 17 2,3,7,8-substituted PCDD/F and 14 coplanar PCB (Co-PCB) congeners were elucidated for the first time. The concentrations of PCDDs and PCDFs were found to be 0.60 and 8.8 ppm, respectively. For PCBs, more than 130 PCB peaks were observed and a total concentration of 850 ppm including 170 ppm of Co-PCBs was obtained. The toxic equivalents (TEQs) of PCDDs, PCDFs, and Co-PCBs were calculated to be 17, 470, and 120 ppb, respectively. The relative contribution of these classes to the total TEQ in Yusho oil is 3%, 77%, and 20%, respectively, indicating that PCDFs play a major role in the toxicity of Yusho oil. Furthermore, it was confirmed that 2,3,4,7,8-penta-CDF contributes 58% to the total TEQ, supporting the view that this compound is the principal causal agent in Yusho poisoning. It is noteworthy that the most toxic 2,3,7,8-tetra-CDD was newly discovered, although it contributes only 0.1% to the total TEQ. Based on our data, the smallest TEQ intake during the latent period was estimated to be 0.067 mg for Yusho patients. This value is about 60% of that previously reported, suggesting a lower minimum threshold level for the development of the toxic symptoms of Yusho.     

Levels and congener profiles of PCBs and PCDD/Fs in blue shark (Prionace glauca) liver from the South-Eastern Mediterranean Sea (Italy)

Liver of blue shark (Prionace glauca) specimens from the South-Eastern Mediterranean Sea were analyzed for the presence of polychlorinated biphenyls (PCBs), including coplanar congeners, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). PCBs were the dominant chemicals, followed by PCDFs and PCDDs. The pattern of PCB congener concentrations in the hepatic tissue was dominated by higher chlorinated compounds. The specific profile of toxic PCDD/F congeners was characterized mainly by 2,3,7,8-TCDF and 2,3,7,8-TCDD, followed by 1,2,3,6,7,8-HxCDD and 2,3,4,6,7,8-HxCDF. The total 2,3,7,8-TCDD toxic equivalent (TEQs) was 149 pg g⁻¹ lipid wt. The profile of TEQ shows that PCDDs present the greatest risk to this species contributing to total toxicity with a percentage approximately of 60%, while the contribution of PCDFs and DL-PCBs is almost the same being 22.4% and 21.6%, respectively. Further investigations are urgently needed to characterize the PCDD/Fs contamination levels not only in elasmobranch fish but in all Mediterranean marine biota.     

Evaluation of toxicity and sex-related variation of PCB levels in Mediterranean striped dolphins affected by an epizootic

Individual PCB congener concentrations, including non-ortho chloro substituted, were determined in 30 striped dolphins (Stenella coeruleoalba) affected by the 1990–1992 Mediterranean epizootic to investigate their toxic potential. PCB congener concentrations in these dolphins were among the highest ever found in comparable studies on marine mammals. Concentrations in males and females were significantly different because of pollutant transfer to offspring by females. Thus, PCB concentrations and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) toxic equivalents (TEO) in males were approximately double those in females. Non-ortho, mono-ortho and di-ortho coplanar congeners accounted for approximately one third of the overall toxicity assessed through toxic equivalent factors (TEFs), as defined by Ahlborg et al. (1994). Di-ortho congener 170 and non- ortho congener 126 were the major contributors to TEQ (33% and 30% respectively).     

Bioaccumulation profiles of polychlorinated biphenyls including coplanar congeners and possible toxicological implications in Baikal seal (Phoca sibirica)

Isomer specific concentrations of individual polychlorinated biphenyls (PCBs) including toxic non-ortho (IUPAC 77, 126, 169), mono-ortho (105, 118, 156) and di-ortho (137, 138, 153, 180) coplanar congeners were determined in the blubber of 40 Baikal seals (Phoca sibirica) and as their fish diet collected from Lake Baikal, Siberia. Residue levels of total PCBs in Baikal seals were noticeably high and comparable to those reported for seals from the North Sea, suggesting the recent usage of this compound in the watershed of Lake Baikal. Non-, mono-, and di-ortho coplanar congeners were also detected in Baikal seals and fish. An approach to estimate bioaccumulation profiles of PCB congeners revealed that the non-ortho PCBs, IUPAC 77, 126 and 169 seemed to be less persistent than other congeners. Furthermore, selective biotransformation of PCB congeners having either meta-para vicinal H atoms or both adjacent chlorinated meta-para and ortho-meta positions has been suggested. Comparison of 2,3,7,8-TCDD toxic equivalents (TEQ) of non-, mono- and di-ortho coplanar congeners in Baikal seals with those for other marine mammals suggested higher enrichment of mono-ortho congeners, particularly IUPAC 105 and 118, which contributed significantly to the total TEQs in Baikal seals. Results imply that the TCDD-like toxicity is relatively serious in Baikal seals, because of the enrichment of these toxic PCB congeners in tissues.     

Congener specific accumulation and toxic assessment of polychlorinated biphenyls in common cormorants, Phalacrocorax carbo, from Lake Biwa, Japan

Isomer-specific accumulation of polychlorinated biphenyls (PCBs) including di-, mono- and non-ortho congeners and hepatic P-450 activities were determined in adult common cormorants from Lake Biwa, Japan. The mean total PCB levels in male and female birds were 7.2 +/- 6.1 and 2.1 +/- 0.74 microg g(-1) wet wt, respectively, in the liver. The highly biomagnified congeners were IUPAC 126, 153, 169, 180 and 194, whereas a higher degree of biotransformation could be observed in both meta-para chlorine unsubstituted congeners in the cormorant liver. The estimated metabolic index also showed that common cormorants had higher PB-type enzyme activities than some avian and marine mammals but poor MC-type enzyme activities. The concentrations of non-ortho coplanar congeners were in the order of IUPAC 126 > IUPAC 169 > IUPAC 77 with mean values 6.1 +/- 5.9, 1.3 +/- 1.4 and 0.43 +/- 0.26 ng g(-1) wet wt, respectively. The calculated mean 2,3,7,8-TCDD toxic equivalent (TEQ) concentration in cormorants was 1.8 +/- 1.7 ng g(-1) wet wt and was dominated by IUPAC 118, followed by IUPAC 126. A significant increase of ethoxyresorufin-O-deethylase (EROD) and pentoxyresorufin-O-deethylase (PROD) activities was observed with estimated TEQ of PCBs in the cormorants, suggesting that the current contamination level is sufficient for altering their biochemical responses.