Perfluorooctane sulfonate （PFOS） and related fluorochemicals in chicken egg in China

The ubiquitous occurrence of perfluorinated compounds （PFCs） in environmental samples has drawn much attention. Recent human exposure studies found relatively high perfluorooctane sulfonate （PFOS） concentrations in blood samples from several cities in China when compared with other countries. The objectives of the present study were： （1） to measure PFC concentrations and compositions in chicken egg samples from local markets in China; and （2） to conduct a preliminary human health risk assessment of egg consumption. Eight pooled egg samples from eight locations were analyzed for 11 PFCs. The results showed that close to 100% of the PFOS in the egg was distributed in egg yolk and PFOS was not detected in egg white （〈0.08 ng/g wet weight, w/w）. Of the perfluoroalkylsulfonates, only PFOS was detected in all egg samples, while of the perfluoroalkylcarboxylates, perfluoroundecanoic acid （PFUnDA） was detected in all samples, followed by perfluorooctanoate （PFOA） （75% occurrence） and perfluorodecanoic acid （PFDA） （50% occurrence）. PFOS concentrations in egg ranged from 45.0 to 86.9 ng/g w/w. The results suggested that current concentrations of PFOS in domestic chicken eggs are unlikely to cause immediate harm to Chinese populations.     

Perfluorooctane sulfonate and perfluorooctanoic acid in the fingernails of urban and rural children

Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) are two typical perfluorinated compounds (PFCs), found in a wide range of environmental media and organisms, including humans. Human biomonitoring studies of body fluids have revealed that in many areas of the world the general population has been exposed to background levels of PFOS and PFOA. Fingernail has been suggested as a promising biopsy material for assessment of PFCs environmental exposure. In the present study, PFOS and PFOA were quantified using high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) in fingernails of urban and rural children (N=93) aged 6–12 years. A questionnaire was conducted to determine factors that could influence the PFOS and PFOA levels in the children. The levels of PFOS in urban children were significantly higher (geometric mean (GM)=328 ng/g) than those in rural children (GM=27 ng/g). In contrast, PFOA levels were significantly lower in the urban children compared with the rural children. Significant positive correlation (R=0.53, P<0.05 for urban areas; R=0.71; P<0.001 for rural areas) between the PFOS and PFOA concentrations indicated they had similar sources. The PFOS and PFOA levels were higher in fingernail samples from children aged <9 years than in children aged ⩾9 years. In addition, females had higher PFOA levels than males, in both regions. Other factors that significantly influenced PFOS and PFOA levels were dietary habits and socio-economic background. The results of this study indicate fingernails are a suitable material for biomonitoring of PFCs environmental exposure. However, the levels determined in the fingernail samples need to be first evaluated with regard to the levels determined in other samples, such as human serum.     

多溴联苯醚在我国生物体中的污染现状

多溴联苯醚(PBDEs)作为一种新型的持久性有机污染物,对生物体存在甲状腺毒性、神经系统毒性、生殖发育毒性和潜在的致癌性等。通过文献资料查阅等方法,归纳总结了PBDEs在我国生物体及人体中的污染现状,提出今后对PBDEs污染研究需加强的方面:建立一套适合我国国情的PBDEs分析检测方法;增加内陆生物体中的PBDEs研究;增加PBDEs在生物体不同组织中的残留水平和分布特征的研究;加大生物体中PBDEs源解析研究等。     

多溴联苯醚的环境行为及其生态毒理效应

多溴联苯醚(PBDEs)是一类环境中广泛存在的全球性有机污染物。近年来由于其持久性、毒性和潜在的生物蓄积性而备受关注;且在环境中的浓度快速增长,对人体健康造成的危害日益引起各国科学家的关注;已成为当前环境科学的一大热点。对最近几年来环境中PBDEs研究的进展进行综述,对多溴联苯醚的理化性质、环境暴露及途径、环境中的降解和生物代谢、生物富集与放大以及生态毒理效应方面的研究进行了总结,对目前存在问题及进一步的研究方向进行了讨论和展望。     

Contamination trends of polybrominated diphenyl ethers, organochlorine pesticides and heavy metals in sediments from Dagu Drainage River estuary, Tianjin

Concentrations of polybrominated diphenyl ethers （PBDEs）, organochlorine pesticides （OCPs） and heavy metals in two sediment cores, taken from the Dagu Drainage River, were determined. The contamination trends of these three kinds of compounds were obtained. The results showed that concentrations of PBDEs increased in recent years; there were new contamination sources for OCPs in this area; contamination levels of heavy metals had no significant change in the last several years. Comparing the results of these two cores, erosion and dilution of seawater had different effects on the transportation of these compounds.     

环境污染物PFOS可致人脑微血管内皮细胞骨架蛋白改变

目的:探讨全氟辛烷磺酰基化合物(PFOS)引起的人脑微血管内皮细胞(HBMEC)骨架蛋白(F-actin)排列变化.方法:培养正常的人脑毛细血管内皮细胞,不同浓度PFOS作用30分钟,利用免疫荧光染色的方法检测细胞骨架蛋白F-actin的变化.结果:PFOS可使细胞骨架蛋白F-actin发生重排,这与PFOS的浓度有关.     

汉江水体和沉积物中全氟化合物的风险评估

采集汉江旱季和雨季的水样和沉积物,应用超高效液相色谱–三重四级杆质谱,对其中的11种全氟化合物(PFCs)进行检测,研究该区域全氟化合物的污染状况。结果表明,11种全氟化合物都有不同程度的检出,旱季和雨季水样中∑PFCs浓度分别为0.3~23.04和0.16~19.68 ng/L,沉积物中∑PFCs浓度分别为0~55.1和0.99~85.07 ng/g。水样总浓度的最高值出现在汉江汇入长江处的武汉,且武汉采样点的全氟辛酸(PFOA)浓度最高,旱、雨季分别达到22.52和12.52 ng/L。沉积物中总浓度最高值出现在陶岔,且以全氟庚酸(PFHp A)和全氟己酸(PFHx A)为主,沉积物中组分组成的季节差异不大。采用实际检测到的水样中PFOA、全氟辛烷磺酸盐(PFOS)、全氟壬酸(PFNA)、PFHx A和全氟葵酸(PFDA)的浓度以及沉积物中PFOA和PFOS的浓度,运用熵值法,对汉江流域进行全氟化合物污染的风险评估,结果表明,水体和沉积物中的浓度均未达到对生态环境具有风险的水平。     

溴代阻燃剂

溴代阻燃剂是添加型阻燃剂的一种,其种类繁多,是目前世界上产量最大、阻燃效率最高、应用最广泛的有机阻燃剂之一。溴代阻燃剂在国际上的生产与使用可以追溯到上世纪七十年代,目前在生产的溴代阻燃剂大约有70多种,其中最为重要的是多溴代二苯醚类(PBDEs)、四溴双酚A(TBBPA)以及六溴环十二烷(HBCD)等。前两者的产量可占溴代阻燃剂总产量的50%左右。近年来,随着全世界环境安全观念意识的增强,部分传统的溴代阻燃剂如十溴二苯醚因为受到环境安全要求的压力已被限制使用,这就迫使研究人员及相关企业寻找溴代阻燃剂的代用品,因而促进了许多新型环保型阻燃剂的问世。多溴代二苯醚类等传统溴代阻燃剂市场的萎缩,为溴化环氧树脂、十溴二苯乙烷以及溴化聚苯乙烯等环境友好型溴代阻燃剂产品提供了更为广阔的市场空间。     

Effects of substituent position on the interactions between PBDEs/PCBs and DOM

Dissolved organic matters (DOM) have important influence on the environmental behavior and fate of organic pollutants, therefore rationalization of interaction mechanisms between pollutants and DOM has become a hot topic in the field of environmental studies. In this paper, polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs), widely detected pollutants, were chosen as target compounds. The effects of substituent position on the interaction between PBDEs/PCBs and DOM were explored. Equilibrium dialysis technique combined with quantum chemistry and molecular docking calculations were employed to reveal the interaction mechanism from the view of charge distribution and molecular conformation. It is shown that non-ortho-substituted isomers have larger volumes and stronger hydrophobicity than those of ortho-substituted, therefore non-ortho-substituted isomers bind more favorably with DOM by hydrophobic partition. By calculating the atomic charge distribution of target chemicals and Leonardite humic acid (LHA) molecular model, π-πinteractions between the aromatic rings of target chemicals with LHA are proposed and further proved in molecular docking calculations. There were 10, 8, 6 docking conformations demonstrating π-πinteraction with LHA for CB-77, BDE-77 and BDE-47, respectively, but none was found for CB-47. By comparing the change of dihedral angle of the aromatic rings and energy barrier, non-ortho-substituted PBDEs/PCBs have larger dihedral angle adjustment space and flexibility, which results in stronger interaction and binding capability with DOM than ortho-substituted isomers. This paper shed some lights on the effect of substituent position on the environmental behaviors of PBDEs and PCBs.     

微塑料和全氟辛烷磺酸类物质共暴露对翡翠贻贝滤食率和抗氧化系统的影响

为了探索微塑料和全氟辛烷磺酸类物质(PFOS)在海洋生物体内的复合污染毒性机制, 以翡翠贻贝为研究对象, 在聚苯乙烯微塑料(0.2 μm) 4.55×10⁸个/L以及PFOS浓度为10, 100和1000 μg/L的条件下, 研究PFOS或微塑料单独暴露以及二者复合暴露对翡翠贻贝滤食率、活性氧水平(ROS)、丙二醛(MDA)含量、超氧化物歧化酶(SOD)活性、过氧化氢酶(CAT)活性、谷胱甘肽巯基转移酶(GST)活性和谷胱甘肽还原酶(GR)活性的影响。结果表明, 与溶剂对照组相比, 暴露于微塑料和PFOS后翡翠贻贝的滤食率均没有显著变化。在翡翠贻贝的鳃、内脏团和性腺中, 微塑料或PFOS的胁迫都会引起酶响应的显著变化。与PFOS单独暴露组相比, 微塑料和 1000 μg/L PFOS共同暴露时, ROS水平在鳃和性腺中显著提升, 在内脏团中显著下降; MDA含量在鳃和内脏团中显著提升, 在性腺中显著下降; GST和GR活性在鳃中显著下降, 在性腺中显著提高。研究结果说明微塑料会改变翡翠贻贝对PFOS的氧化应激响应。     

Distribution and partition of polybrominated diphenyl ethers （PBDEs） in water of the Zhujiang River Estuary

The spatial, temporal, and vertical distributions of polybrominated diphenyl ethers （PBDEs） in water columns from the Zhujiang River Estuary were examined, and the partition behavior of PBDEs between particle and dissolved phases was investigated in the present study. The results show that the distributions of PBDEs concentrations in the water varied with the sampling seasons. The PBDEs concentrations in water samples were lower in May 2005, when the brackish water was dominant in the estuary, than in October 2005, when fresh water from river runoff dominated the estuary. The spatial distribution of PBDEs in October 2005 indicated that the river runoff was the major mode to input PBDEs to the estuary, and the concentration of PBDEs in water might be dissolved organic carbon （DOC） dependence. The spatial and vertical distributions of PBDEs in May 2005 were relatively homogeneous, and SPM was the major factor on controlling the levels of PBDEs in this sampling time. Both DOC and POC could play certain roles in determining the distribution and partition of PBDEs between particle and dissolved phases, but their effects varied with the water properties.     

环境资本与人力资本的纳什均衡动态机制

在纳入人力资本因素所建立的两种资本(物质资本和人力资本)的内生经济增长模型基础上,将环境的外部有效性引入模型,考察利用划分有限边界情况下,同一代人产生的环境矛盾和各代人之间产生的环境矛盾对人力资本形成产生的影响.采用一个世代交叠模型研究环境和人力资本的纳什动态机制,推出了均衡的一般形式及简化形式,并考察了均衡路径的特征及经济含义.结果表明,自由放任的经济是否停滞、增长或衰退,取决于环境资本和人力资本学习回报的情况,经济的最初状态,以及环境产品和消费品的价格.     

深圳市表层土壤中PBDEs空间分布特征及蓄积量估算

为了解深圳30年快速城市化过程引发的土壤有机污染现状, 同时调查城市化过程有机污染历史累积情况,在深圳市收集了 110 个表层土壤样品, 分析了深圳市土壤多溴联苯醚(PBDEs) 的空间分布特征, 并对其表层土壤PBDEs 蓄积总量进行 了估算。结果表明,深圳市土壤 中6 12 PBDEs 及 BDE209 的含量水平范围分别为 1.1 ～ 85.8 ng/g (dw) 和1. 2 ～1931ng/g(dw)。PBDEs 总含量在不同土地利用功能分区上表现为工业用地 > 居住用地> 商业用地 > 城市公园> 郊野公园的分布规律。深圳市土壤中PBDEs 含量整体表现出从西部的南山区和宝安区向东南方向的龙岗区和盐田区递减的趋势, 且 PBDEs 含量水平与各行政区的城市化水平呈显著的指数函数关系( r = 0. 98, p < 0. 01) , 表明城市化水平是影响深圳市土壤 PBDEs 污染程度的主要因素。采用基于行政区单元和基于土地利用类型两种估算方法对深圳市表层土壤 PBDEs 蓄积量进行估算的差异较大, 研究认为基于土地利用类型所估算出的数值更为准确, 以此估算出深圳市表层土壤中6 12 PBDEs 和 BDE209 蓄积量分别为1.51t和15.9t。     

贵州红枫湖表层沉积物中多溴联苯醚的分布研究

分别自贵州红枫湖7个采样点采集2个水文期的表层沉积物样品,以研究贵州红枫湖中PBDEs的含量、分布特征及来源。研究结果表明,贵州红枫湖中∑PBDEs为ND-9.04 ng/g(dw),与已有的文献报道相比,贵州红枫湖中PBDEs的污染还处于一个较低的水平。在所有被分析的样品中,BDE47为最主要的同系物,大气沉降是红枫湖中PBDEs的主要来源。     

全氟辛磺酸对于爪蟾的甲状腺激素干扰效应

运用两栖类变态实验(AMA)研究了全氟辛磺酸(PFOS)对于非洲爪蟾(Xenopus laevis)蝌蚪的生长、变态和甲状腺组织结构的影响.结果显示,与对照组相比,7d后,10,50和250μg.L-1PFOS暴露组蝌蚪的后肢长分别减小了17%,11%和18%,蝌蚪的发育延缓了1~2个阶段;19d后,10,50和250μg.L-1PFOS组蝌蚪的体重分别增加了17%,10%和20%,体长分别增加了5%,4%和6%,而10μg.L-1和250μg.L-1PFOS组蝌蚪的后肢长分别减小了12%和13%;暴露组甲状腺组织结构出现滤泡数目减少、上皮细胞增生、胶质减少甚至滤泡溶通等现象.结论是,在本实验浓度下,PFOS对于非洲爪蟾的蝌蚪生长有促进作用,对于变态发育过程却有抑制作用.参照AMA的方法,可以判断PFOS为抗甲状腺激素干扰物.     

PFOS暴露对秀丽线虫寿长的影响及其与IIS相关基因的关联

以秀丽隐杆线虫(C.elegans)为模型,本文研究了全氟辛烷磺酸(PFOS)对机体寿长的影响及初步机理.结果显示0.2~200μmol/L的PFOS暴露50 h导致野生型秀丽线虫寿长呈剂量依赖性缩短.在4类转基因线虫上,观察到Insulin/IGF-l.1信号通路(IIS)相关的daf-16、daf-2和age-1基因突变或敲除能影响线虫的寿长.进一步观察PFOS暴露导致4类转基因线虫的寿长变化率,并与野生型线虫比较.在CF1139和CF1580突变种上daf-16或daf-2的突变均未改变PFOS的缩短寿长效应.而在CF1295和TJ1052转基因型上发现daf-16b的基因敲除或age-1基因突变阻断PFOS的减寿效应.结果表明PFOS慢性暴露能加速动物衰老,缩短寿长.PFOS作用与IIS信号通路关系密切,daf-16b和age-1基因在其中起重要作用.     

贵屿表层土壤中多溴联苯醚的水平与儿童健康风险

在广东省贵屿镇采集了12个地点的表层土壤样品, 测定了其中14种多溴联苯醚(polybrominated diphenyl ethers, PBDEs)同系物的含量. 结果表明: 该地区已受到了PBDEs 的污染, PBDEs 浓度在76.5～13 354.0 ng/g干重之间, 远高于国内外其他地区. BDE209 为最主要的同系物, 其次为BDE47, BDE99 和BDE183, 说明该地区污染主要源于十溴工业品, 其次为五溴和八溴工业品. 通过总日摄入量和日吸收量来评估儿童通过土壤暴露PBDEs 的量, 并采用非致癌危险商数(hazard quotient, HQ)对其带来的风险进行评估. 结果表明: 通过皮肤接触和口服暴露的PBDEs 的平均日摄入量分别为31.1～5 430.0 和7.7～1 335.0 ng,皮肤接触摄入是其暴露人体的主要途径; 若考虑到吸收率, 则平均日摄入量降到0.3～54.3 和1.3～184.0 ng, 口服摄入是其主要暴露途径. 在两种情况下, HQ 值均小于1, 表明土壤中的PBDEs 并不会给当地儿童带来显著的非致癌健康风险.     

环境污染物PFOS可引起大鼠海马干细胞的增殖

目的:观察全氟辛烷磺酰基化合物(PFOS)大鼠海马干细胞增殖情况.方法:利用大鼠腹腔内连续注射不同剂量的PFOS 14天,建立动物模型.以Brdu作标记物,利用免疫组织化学染色的方法检测不同剂量PFOS作用下大鼠海马干细胞增殖情况.结果:以Brdu作标记物,高剂量PFOS作用下大鼠海马内可检测到大量阳性细胞存在,对照组和低剂量PFOS作用下无此阳性结果产生.结论:推测PFOS可引起大鼠海马干细胞的增殖.     

Persistent organic pollutants PCNs and PBDEs in sediments from coastal waters of Qingdao,Shandong Peninsula

Thirty-one congeners of polychlorinated naphthalenes (PCNs) and 21 congeners of polybrominated diphenylethers(PBDEs)in surface sediments at 5 stations and one mussel sample from Qingdao coastal waters were analyzed. The maximum contents occur at the station near the Haibo River mouth. The total PCNs contents are in the range of 212-1209 pg/g dw, dominated by tri-Cl CN. The total PBDEs contents are in the range of 117-5510 pg/g dw,dominated by tri- to hexa-BrBDEs. The local sources of PCNs are likely from combustion processes such as incinerations and coal burnings. The sources of PBDEs are molecular diffusion from the materials containing them. Except for the area near the river mouth where is affected by the sewage sludges, an important source of PCNs and PBDEs in this area is believed to be the atmospheric deposition. Mussels enrich PCNs and PBDEs relative to the sediments. The total TEQs of PCNs in mussels are lower than the total TEQs of PCBs.     

河蚬(Corbicula fluminea)对氧化石墨烯和全氟辛烷磺酸类物质(PFOS)联合胁迫的生理生化响应

为了探索碳纳米材料氧化石墨烯(GO)和全氟辛烷磺酸类物质(PFOS)在淡水底栖贝类体内的联合毒性效应, 以河蚬为研究对象, 考察 1 mg/L GO和500 ng/L PFOS单独及联合暴露28天后对河蚬体长、体重、滤食率、活性氧水平、抗氧化系统酶活性和丙二醛含量的影响, 并采用优化的综合生物标志物响应指数(EIBR)进行整体评估。结果表明, 暴露结束后, 河蚬的体长和体重没有明显的变化。与空白对照组和溶剂对照组相比, GO和PFOS的单独暴露组及联合暴露组的滤食率均显著下降。在河蚬的鳃和内脏团中, GO和PFOS的胁迫都会引起抗氧化系统酶活性响应的显著变化, 且两器官中变化趋势一致。EIBR结果表明, 鳃和内脏团中联合暴露组的毒性比 PFOS或GO单独暴露组的毒性更强。