【作者】 胡余明；

【导师】 姚守拙； 陈波；

【作者基本信息】 湖南师范大学 ， 分析化学， 2013， 博士

【摘要】 持久性有机污染物(POPs)是人工合成的一类具有高毒性、持久性、生物蓄积性的化合物,能通过大气进行长距离迁移、沉积,会对环境和人类健康产生有害效应。人类主要通过呼吸、皮肤、膳食摄入暴露于POPs。膳食是POPs暴露的主要途径,而鱼类摄入又是人类膳食中POPs主要的暴露来源。洞庭湖是我国第二大淡水湖,为长江流域重要的鱼类及水生生物栖息地,鱼类的年产量大3.79万吨。本研究分别于洞庭湖蓄水季和枯水季,抽取13种鱼样,对鱼中二噁英(PCDD/Fs)、多氯联苯(PCBs)、多溴联苯醚(PBDEs)的含量进行了研究,结果如下。1.洞庭湖蓄水季和枯水季鱼中PCDD/Fs的平均浓度分别为29.993和1.017pg/g ww,范围分别在5.787-198.36和0.368-3.276pg/g ww。 DL-PCBs的平均浓度分别为87.837和58.285pg/g ww,范围11.536-411.018和7.676-238.181pg/g ww。鱼中总PCDD/Fs+PCBs的毒性当量均值分别为0.842和0.314WHO-TEQ/g ww,范围分别在0.110-5.619和0.081-1.095pg WHO-TEQ/g ww。鱼中PCDD/Fs同系物浓度中OCDD、2378-TCDF为主。DL-PCBs同系物浓度中PCB118浓度最高。蓄水季12378-PeCDD毒性当量占总的PCDD/Fs毒性当量百分比最大。枯水季23478-PeCDF毒性当量占总的PCDD/Fs毒性当量百分比最大。蓄水季枯水季都以PCB126毒性当量占总的DL-PCBs毒性当量百分比最大。鱼中PCDD/Fs的浓度,蓄水季显著高于枯水季。而DL-PCBs的浓度在枯水季和蓄水季并无差别。洞庭湖流域五氯酚钠的使用可能是影响鱼中PCDD/Fs浓度的重要因素。洞庭湖13种鱼中蓄水季鳤鱼中PCDD/Fs的毒性当量最大,超过了欧盟允许最大值。2.蓄水季和枯水季13种鱼中7种指示性PCBs的浓度均数为421.7和294.4pg/g ww,范围为46.7-2209.2和35.5-1270.6pg/gww。蓄水季和枯水季指示性PCBs的浓度都以长吻鮠和黄颡鱼中最高。鱼中指示性PCBs同系物以PCB28和PCB153为主。蓄水季、枯水季鱼中指示性PCBs的浓度并无差别。鱼类的食性可能会影响指示性PCBs在鱼体内的含量,肉食性鱼类指示性PCBs的含量远高于草食性鱼类。鱼类中指示性PCBs的含量与脂肪率呈正相关。鱼中指示性PCBs含量远远小于我国《食品污染限量》。与我国其它地区相比,本研究鱼中指示性PCBs的含量与我国淡水鱼相当,比我国海水鱼污染较轻。与欧美等发达工业化国家相比,洞庭湖流域鱼中指示性PCBs的污染较轻。3.蓄水季和枯水季PBDEs的浓度均数分别为143.8和128.7pg/g ww,范围为21.3～488.0和19.6～419.6pg/g ww。蓄水季和枯水季PBDEs的浓度都以长吻鮠和黄颡鱼中最高。蓄水季鱼中PBDEs同系物以BDE-47为主,枯水季部分鱼中BDE183为主,BDE-47的百分含量也很高。蓄水季、枯水季鱼中PBDEs的浓度并无差别。鱼的生活习性可能会影响鱼中PBDEs的含量,底栖性鱼类PBDEs的含量高。鱼的脂肪率与鱼中PBDEs的含量呈正相关。鱼中指示性PCBs含量也与鱼中PBDEs的含量呈正相关。鱼中PBDEs的含量,国内外其它地区相比,处于一个很低的水平。4.评估洞庭湖流域居民通过鱼类PCDD/Fs、PCBs、PBDEs的膳食暴露量。发现鱼类PCDD/Fs、DL-PCBs的膳食暴露量低于JECFA制定的暂定每月耐受摄入量(PTMI)70pgWHO TEQ/kg bw和EUSCF制定的暂定每周耐受摄入量(TWI)14pg WHO TEQ/kg bw。但如果城市居民长期食用鳍鱼,可能产生健康风险。蓄水季鱼类指示性PCBs、PBDEs的暴露水平要高于枯水季,城市居民通过鱼类摄入指示性PCBs、PBDEs的水平要高于农村居民。与亚洲其它地区相比,洞庭湖流域鱼类PCDD/Fs、DL-PCBs的暴露处于一个相对较低的水平,但与欧洲发达国家相比鱼类PCDD/Fs、DL-PCBs的暴露要稍高。更多还原

【Abstract】 Persistent organic pollutants (POPs)are a class of synthetic compounds, have highly toxic, persistent, bioaccumulative, can migrate long distances by the atmosphere, at last deposited in the environment, which may have a harmful effect to human health. Spiratory, skin, dietary intake are the main ways of humans’POPs exposure. Dietary exposure of POPs is the most important way of human exposure, while fish intake of POPs is a major source of exposure in human diet. Dongting Lake is the second largest freshwater lake of China and an important fish and aquatic habitat of the Yangtze River, which the annual production of fish is37,900tons. In this study, the level of dioxins (PCDD/Fs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) were analyzed in13kinds offish of the Dongting Lake’s water season and dry season. The results are as follows.1.In Dongting Lake water season and the dry season, The average concentration of PCDD/Fs were29.993and1.017pg/g ww, the range were5.787-198.36and0.368-3.276pg/g ww in fish respectively. The average concentration of DL-PCBs was87.837and58.285pg/g ww, the range were11.536-411.018and7.676-238.181pg/g ww, respectively. The mean of total TEQ of PCDD/Fs+DL-PCBs in fish were0.842and0.314WHO-TEQ/g ww, the range were0.110-5.619and0.081-1.095pg WHO-TEQ/g ww, respectively. The main of PCDD/Fs congeners were OCDD,2378-TCDF in fish. The highest concentration of DL-PCBs congeners was PCB118in Fish.12378-PeCD and23478-PeCDF have the largest percentage of total PCDD/Fs TEQ in water and dry season, respectively. PCB126has the largest percentage of total DL-PCBs TEQ was in both water and dry season. The concentration of PCDD/Fs in water season was significantly higher than the dry season, but the concentration of DL-PCBs was no different in the dry and the water season. The use of sodium pentachlorophenol in Dongting Lake maybe an important factor to affect PCDD/Fs concentration of fish.In Dongting Lake, PCDD/Fs TEQ of Guan fish was largest in13kinds offish, which is above the EU maximum limilit.2.1n Dongting Lake water season and the dry season, the average concentration of Indicative PCBs were421.7and294.4pg/g ww, the range were46.7-2209.2and35.5-1270.6pg/g ww, respectively. The concentration of indicative PCBs in the long snout catfish and catfish were very high in water and dry season. The main of indicative PCBs congeners were PCB28and PCB153. The concentration of indicative PCBs in fish is no different in Water and dry season. Feeding habits of fish may affect the content of indicative PCBs in fish, the level of indicative PCBs in carnivorous fish higher than herbivorous fish. The concentration of Indicative PCBs in fish was positively correlated with fat content of fish. The level of indicative PCBs in fish is far less than China’s "food contamination limited11. Compared with other areas of China, the content of indicative PCBs in fish is equal to freshwater fish, but lower than marine fish of our country and Europe and other developed industrialized countries.3.In Dongting Lake water season and the dry season, the average concentration of PBDEs were43.8and128.7pg/g ww, the range were21.3-488.0and19.6-419.6pg/g ww, respectively. The concentration of PBDEs in the long snout catfish and catfish were very high in water and dry season. The most main of PBDEs congeners were BDE-47in water season, and in dry season the most main was BDE-183, next was BDE-47.The concentration of PBDEs in fish was no different in Water and dry season. The habits offish may affect the content of PBDEs in fish, fish was positively correlated with fat content of fish, and the concentration of indicative PCBs in fish was positively correlated with PBDEs in fish. Levels of PBDEs in fish, compared to other regions at home and abroad, at a very low level.4.Assessing residents PCDD/Fs, PCBs, PBDEs dietary exposure by intake fish, we found PCDD/Fs, DL-PCBs dietary exposure by intake fish below the JECFA established provisional tolerable intake per month (PTMI)70pgWHO TEQ/kg bw and EUSCF developed tentative weekly tolerable intake (TWI)14pg WHO TEQ/kg bw. However, if urban residents intake Mateo Fish for a long time, may have health risks. Indicative PCBs, PBDEs exposure levels in water season were higher than the dry season, and the city residents’indicative PCBs, PBDEs exposure levels by fish were higher than rural residents. Compared with other parts of Asia, PCDD/Fs, DL-PCBs exposure by fish at a relatively low level, but compared with developed countries in Europe, PCDD/Fs, DL-PCBs exposure to slightly higher.更多还原