成渝经济区河流表层沉积物中多溴联苯醚的分布特征

在成渝经济区内采集了19个表层沉积物样品,采用GC/MS方法对其中的PBDEs(Polybrominated Diphenyl Ethers,多溴联苯醚)进行了检测. 结果表明,沉积物中w(ΣPBDEs)(ΣPBDEs包括BDE-1,BDE-15,BDE-17,BDE-28,BDE-47,BDE-66,BDE-71,BDE-85,BDE-99,BDE-100,BDE-126,BDE-138,BDE-153,BDE-154,BDE-166,BDE-181,BDE-183和BDE-190)为0.20～6.45 ng/g,w(BDE-209)为0.44～6.29 ng/g. 与其他地区相比,成渝经济区内PBDEs的污染水平相对较低, 大部分样品中的PBDEs以BDE-209为主,说明成渝经济区河流沉积物中的PBDEs主要来自十溴联苯醚; 但PBDEs的组成特征显示,彭山岷江大桥沉积物中的PBDEs主要来自五溴联苯醚,而官渡沉积物中的PBDEs主要来自八溴联苯醚. 此外,一些以往工作较少关注的PBDEs单体,如BDE-1,BDE-15,BDE-181和BDE-190等,不但在沉积物中的检出率较高(均高于70%),而且有的含量也相对较高.      

中国8个城市大气多溴联苯醚的污染特征及人体暴露水平

利用大流量采样器采集了我国东西部地区8个城市的大气气相和颗粒相样品,分析了样品中8种多溴联苯醚.结果表明,气相中以BDE-28(三溴组分)浓度最高[(6.25±4.95)pg·m~(-3)]不同于以往研究中BDE-99和-47为气相中优势同系物单体;颗粒相中则以BDE-209浓度最高[(25.4±124)pg·m~(-3)].北京和广州这两个大型城市的大气PBDEs浓度较高,尤其是广州的颗粒相BDE-209浓度,比其他城市的浓度高两个数量级.与早期的观测结果相比,我国城市大气PBDEs浓度呈普遍的下降趋势.同时,对比发现气相浓度下降较慢,颗粒相浓度下降较快,结合相关性分析结果,这一现象可能与工业五溴和八溴联苯醚的停产禁用高溴组分的光降解及城市大气颗粒物浓度的降低有关.城市婴幼儿的吸入暴露量约为成人的2~3倍,反映出城市大气PBDEs对城镇居民尤其是婴幼儿的潜在健康危害仍不容忽略.     

武汉市大气中多溴联苯醚的分布特征研究

为了评估武汉大气中多溴联苯醚(PBDEs)的污染程度,2015年4月-2016年11月,利用大流量空气采样器采集背景点位、武汉市市内交通枢纽区、工业区、居民区及某排放源周边点位的气相和颗粒相大气样品,利用高分辨气相色谱/高分辨质谱仪对PBDEs进行分析。9种PBDEs的总浓度(气相+颗粒相)范围为5.99~45.4 pg/m~3,平均值为14.5 pg/m~3。各采样点周围大气中低溴代联苯醚浓度在气相中占比相对较高,高溴代联苯醚则主要分布在颗粒相中。大气中PBDEs浓度与PM_(10)及PM_(2.5)浓度有显著的正相关性,与SO_2、NO_2、O_3、CO等指标相关性不明显,说明PBDEs更多的吸附在颗粒相中进行传输。主成分分析发现,武汉市市区大气中PBDEs来源主要是商业用工业八溴联苯醚和工业五溴联苯醚。儿童对∑PBDEs的暴露量平均值为5.38 pg/(kg·d),是成人的2倍多,PBDEs对儿童造成的危害更大。     

典型电器工业区河涌沉积物中的多溴联苯醚空间和垂直分布

对珠江三角洲佛山市顺德区容桂镇电器工业区河涌沉积物多溴联苯醚(PBDEs)的含量进行了空间和垂直分布研究.选择该镇中心城区内河涌作为研究河道,根据河涌水流情况选取8个采样点采集沉积物样品.所有样品中均检出PBDEs.各监测点的PBDEs总含量变化范围为62～349 ng.g-1(平均为178 ng.g-1),各采样点的浓度差异较大.其中,十溴联苯醚含量为56～337 ng.g-1(平均为171 ng.g-1),占PBDEs总含量的90%～99%(平均95%).所检测到的部分同系物(如BDE-196、197和203)可能是BDE-209的降解产物.PBDEs的垂直分布模式显示,0～10 cm层面样品的PBDEs浓度为147 ng.g-1,30～40 cm层面样品的PBDEs浓度为260 ng.g-1,PBDEs在沉积物中的丰度随垂直深度的增加而增加.12种同系物在采自各个深度层样品中的比例基本相同,由十溴工业品来源的BDE-209、208、207和206占总PBDEs的94%,而五溴和八溴所占比例较低.由此可见,该地区普遍存在PBDEs污染,其中十溴联苯醚是最主要污染物,这可能与十溴工业品是电器工业主要使用的阻燃材料相关.     

珠江口钻孔沉积物中多溴联苯醚的沉积记录

对采自珠江口的3个钻孔沉积物中的多溴联苯醚(PBDEs)进行了分析,结果表明,PBDEs在所有的样品中均检出.3个沉积物钻孔中∑PBDEs(不包括BDE209)的含量(以干重计)为0.01～6.99ng/g(平均1.50ng/g),BDE209的含量为0.10～61.50ng/g(平均7.82ng/g).PBDEs在钻孔中的垂直分布显示,从20世纪90年代开始,珠江三角洲部分地区五溴联苯醚阻燃剂的使用已减少,但主要区域低溴代联苯醚的排放仍然存在.受珠江三角洲电子产业飞速发展的影响,珠江口沉积物钻孔中BDE209的含量及通量从1990年以后快速增加.不同钻孔沉积物中PBDEs的组成模式反映了PBDEs的不同来源及输入途径.钻孔#1和钻孔#2主要受流经工业发达地区河流输出PBDEs的影响,钻孔#3主要受经过大气长距离迁移后经河流输出的PBDEs的影响.     

广州市室内尘土中多溴联苯醚的分布特点及来源

随机采集了广州市46个家庭和12个办公室内尘土样品,同时采集了17个室外尘土样品、2个电视机和2个电脑尘土样品并分析了室内尘土中多溴联苯醚(PBDEs)的含量、单体分布及来源.结果表明,家庭尘土中∑10PBDEs(BDE28,47,66,85,99,100,153,154,183,209之和)的含量为 564.3~9654ng/g,中值和均值分别为 2686,3407ng/g;办公室尘土中∑10PBDEs 的含量为 1737~4408ng/g,中值和均值分别为3133,3179ng/g.室内尘土中PBDEs的最主要单体为BDE209,分别占家庭尘土和办公室尘土∑10PBDEs的97.4%和99.0%.BDE47、99和183在室内尘土中含量也较高.大多数室内尘土中∑10PBDEs的含量高于室外,说明室内可能有重要的PBDEs释放源.室内尘土中PBDEs的主要工业品来源为十溴联苯醚,五溴联苯醚次之,八溴联苯醚较少.     

经口摄入土壤多溴联苯醚生物可给性变化及影响因素的体外消化模拟

误食土壤是污染物(如多溴联苯醚)人体(主要是儿童)暴露的重要途径,人体消化道内污染物吸收的生物可给性是针对此种暴露方式进行定量风险评估的有效途径之一.本研究采用体外消化实验模拟3种不同有机碳含量的天然土壤中典型多溴联苯醚(BDE-28、BDE-47、BDE-99和BDE-153)在胃和小肠消化液中的释放,验证部分消化释放的多溴联苯醚因消化残留固相表面的再吸附造成低估实际生物可给性,并通过不同水土比的拟合计算予以校正.结果表明,校正后的消化率普遍高于校正前;就不同土样而言,BDE-28、BDE-47、BDE-99和BDE-153在不同初始暴露浓度条件下平均提升比例范围分别为14.3%~42.3%、11.1%~32.1%、4.9%~12.3%和0.0%~7.7%.因此,未经校正的消化率会显著低估PBDEs消化道内的生物可给性,尤其是低溴代组分及PBDEs初始浓度较高或高TOC含量的土样.校正后BDE-28、BDE-47、BDE-99和BDE-153的消化率分别维持在21.9%~54.7%、18.8%~43.1%、13.4%~27.2%和9.3%~19.9%.此外,PBDEs的消化率与其辛醇-水分配系数的对数lg KOW呈显著负相关;而与土壤TOC含量及PBDEs初始暴露浓度的相关性并不显著,尤其是高溴代组分.     

胶州湾养殖区贝类生物体中多溴联苯醚的分布特征

对胶州湾养殖区贝类中的多溴联苯醚(PBDEs)的含量进行检测。结果表明,所采集的菲律宾蛤仔、长牡蛎和栉孔扇贝生物样品中9种PBDEs(BDE-15、BDE-28、BDE-47、BDE-75、BDE-99、BDE-100、BDE-138、BDE-153、BDE-154)的含量分别为(422.2～512.6)×10-12(干重)、(957.0～1102.7)×10-12(干重)和979.5×10-12(干重),其中位于海泊河口处的贝类生物体中的含量最高。所有样品中,BDE-47相对含量最高,其相对于∑9PBDEs的贡献率为38.8%～41.8%。贝类样品的9种PBDEs含量及组成的差别可能与它们对PBDEs的吸收和代谢能力的差异有关。胶州湾养殖区贝类生物体中BDE-47和BDE-99的含量远小于香港、美洲和欧洲等工业发达地区,和亚洲发达国家韩国等处于同一数量级,但相比于2002年青岛近岸紫贻贝中的含量有一定程度的增加,表明近年来青岛沿海地区PBDEs污染加重,这一点必须引起足够的重视。     

广州市夏季大气中多氯联苯和多溴联苯醚的含量及组成对比

用GC-ITD-MS和GC-NCI-MS分别测定了广州市区4个代表性的地点大气中多氯联苯(PCBs)和多溴联苯醚(PBDEs)的含量.∑64PCBs的含量范围为307.2～2720.8 pg·m-3,含量处于世界中等水平;除工业区两侧的黄浦和天河2个采样点外,市区∑10PBDEs和BDE-209的含量范围分别为41.5～256.8 pg·m-3和116.3～888.7 pg·m-3,∑10PBDEs的含量和世界其它地方相当,而BDE-209的含量高于其它地区.PCBs中主要以三、四和五氯代PCBs为主,它们的含量占∑64PCBs的80%以上,同系物分布与国外不同,原因可能是我国曾生产和使用不同的工业产品.PBDEs中以四、五和十溴BDEs为主,其含量占∑11 PBDEs的80%以上,BDE-209、BDE-47和BDE-99是主要成分,表明污染主要来自于五溴和十溴联苯醚工业品4个采样点∑10PBDEs和∑64PCBs含量的分布表明这两类污染物有不同的排放源,PCBs主要来自于老城区,而PBDEs主要来自于新工业区.     

行政办公室内PBDEs污染特征及人体暴露量

为研究普通行政办公场所内多溴联苯醚(PBDEs)的污染现状、同类物分布特征及办公人群吸入暴露量,于2013年3月~8月期间在杭州市行政办公场所采集20个空气样品,用GC-ECD分析样品中14种PBDEs同类物.结果发现:杭州市办公场所空气中PBDEs总平均浓度达9.57×102pg/m3,与欧洲国家相比处于较高污染水平,其中BDE-209是主要污染成分,占总含量的57.4%,说明杭州市办公场所PBDEs的主要工业品来源是十溴联苯醚.与家庭住宅空气样品对照发现,办公场所PBDEs平均浓度是家庭住宅的1.26倍,并且这一浓度差异主要体现在BDE-209单体上.办公场所各采样点同类物气固相对百分含量在50.0%左右,说明空气中PBDEs一半以气态形式存在,一半则吸附在空气颗粒物中,这可能是PBDEs气固分配还未平衡所致.此外,杭州市普通行政办公人群BDE-99的总摄入量为2.03′102pg/(kg×d),比国际标准BDE-99每日允许摄入量低21.7%.     

Polybrominated diphenyl ethers in chicken tissues and eggs from an electronic waste recycling area in southeast China

The levels and distributions of polybrominated diphenyl ethers (PBDEs) in chicken tissues from an electronic waste (e-waste) recycling area in southeast China were investigated. Human dietary intake by local residents via chicken muscle and eggs was estimated. The mean PBDEs concentrations in tissues ranged from 15.2 to 3138.1 ng/g lipid weight (lw) and in egg the concentration was 563.5 ng/g lw. The results showed that the level of total PBDEs (PPBDEs) in the chicken tissue was 2–3 orders of magnitude higher than those reported in the literature. The large di erence of PPBDEs concentrations between tissues confirmed that the distribution of PBDEs in tissues depend on tissue-specificity rather than the “lipid-compartment”. BDE-209 was the predominant congener (82.5%– 94.7% of PPBDEs) in all chicken tissues except in brain (34.7% of PPBDEs), which indicated that deca-BDE (the major commercial PBDE formulation comprising 65%–70% of total production) was major pollution source in this area and could be bioaccumulated in terrestrial animals. The dietary PBDEs intake of the local residents from chicken muscle and egg, assuming only local bred chickens and eggs were consumed, ranged from 2.2 to 22.5 ng/(day kg body weight (bw)) with a mean value of 13.5 ng/(day kg bw), which was one order of magnitude higher than the value reported in previous studies for consumption of all foodstu s.     

Effects of two polybrominated diphenyl ethers (BDE-47, BDE-209) on the swimming behavior, population growth and reproduction of the rotifer Brachionus plicatilis

Polybrominated diphenyl ethers (PBDEs) are new kinds of persistent organic pollutants (POPs) and their potential threats to the equilibrium and sustainability of marine ecosystems have raised worldwide concerns. Here, two kinds of PBDEs, tetra-BDE (BDE-47) and deca-BDE (BDE-209) were applied, and their toxic effects on the swimming behavior, population growth and reproduction of Brachionus plicatilis were investigated. The results showed that: (1) The actual concentrations of BDE-47 and -209 in the seawater phase measured by GC-MS (Gas Chromatography-Mass Spectrometer) were much lower than their nominal concentrations. (2) In accordance with the 24-hr acute tests, BDE-209 did not show any obvious swimming inhibition to rotifers, but a good correlation did exist between the swimming inhibition rate and BDE-47 concentration suggesting that BDE-47 ismore toxic than BDE-209. (3) Both BDE-47 and -209 had a significant influence on the population growth and reproduction parameters of B. plicatilis including the population growth rate, the ratio of ovigerous females/non-ovigerous females (OF/NOF), the ratio of mictic females/amictic females (MF/AF), resting egg production and the mictic rate, which indicate that these parameters in B. plicatilis population were suitable for monitoring and assessing PBDEs. Our results suggest that BDE-47 and -209 are not acute lethal toxicants and may pose a low risk to marine rotifers at environmental concentrations for short-term exposure. They also accumulate differently into rotifers. Further research data are needed to understand the mechanisms responsible for the effects caused by PBDEs and to assess their risks accurately.     

Effects of two polybrominated diphenyl ethers (BDE-47, BDE-209) on the swimming behavior,population growth and reproduction of the rotifer Brachionus plicatilis

Polybrominated diphenyl ethers (PBDEs) are new kinds of persistent organic pollutants (POPs) and their potential threats to the equilibrium and sustainability of marine ecosystems have raised worldwide concerns. Here, two kinds of PBDEs, tetra-BDE (BDE-47) and deca-BDE (BDE-209) were applied, and their toxic effects on the swimming behavior, population growth and reproduction of Brachionus plicatilis were investigated. The results showed that: (1) The actual concentrations of BDE-47 and -209 in the seawater phase measured by GC–MS (Gas Chromatography−Mass Spectrometer) were much lower than their nominal concentrations. (2) In accordance with the 24-hr acute tests, BDE-209 did not show any obvious swimming inhibition to rotifers, but a good correlation did exist between the swimming inhibition rate and BDE-47 concentration suggesting that BDE-47 is more toxic than BDE-209. (3) Both BDE-47 and -209 had a significant influence on the population growth and reproduction parameters of B. plicatilis including the population growth rate, the ratio of ovigerous females/non-ovigerous females (OF/NOF), the ratio of mictic females/amictic females (MF/AF), resting egg production and the mictic rate, which indicate that these parameters in B. plicatilis population were suitable for monitoring and assessing PBDEs. Our results suggest that BDE-47 and -209 are not acute lethal toxicants and may pose a low risk to marine rotifers at environmental concentrations for short-term exposure. They also accumulate differently into rotifers. Further research data are needed to understand the mechanisms responsible for the effects caused by PBDEs and to assess their risks accurately.     

东海沉积物中多溴联苯醚的分布特征研究

采集分析了中国东海28个表层沉积物和7个柱状沉积物.结果表明,东海表层沉积物中除BDE-209外∑PBDEs的浓度范围为0.20~2.09ng/g dw,BDE-209的浓度范围为0.57~2.87ng/g dw,在总PBDEs中所占浓度百分比为57.9%~76.7%;接下来分别是BDE-99和BDE-47,所占比例分别为11.7%~21.5%和7.1%~17.4%.表层沉积物中PBDEs分布呈现出(离海岸线)由近及远浓度越来越低的趋势,由北到南浓度上升的趋势.东海柱状沉积物中PBDEs浓度随着深度加深呈现出先上升后下降的趋势,很好的反映出了PBDEs在中国大陆的使用历史和现状.表层沉积物TOC含量在0.54%~0.88%之间,柱状沉积物TOC的含量在0.62%~0.88%之间,而且不管是表层沉积物(R²=0.723,P < 0.01)还是柱状沉积物(R²=0.595, P < 0.01),PBDEs浓度和TOC含量之间有较强的线性关系,表明沉积物中TOC含量是影响PBDEs分布的一个重要因素.     

昆明市大气总悬浮颗粒物和PM2.5上多溴联苯醚的分布特征和潜在风险

为探究PBDEs（多溴联苯醚）在昆明大气中的环境行为,于2014年3月对昆明8个采样点大气TSP（总悬浮颗粒物）和PM_2.5样本进行了收集并利用GC-MS技术对其上附着的PBDEs的13种同系物进行了测定,进而对TSP和PM_2.5上PBDEs的分布特征和潜在风险进行了分析.结果表明:附着在TSP上的∑PBDE浓度（多溴联苯醚的总质量浓度）的范围为21.10~175.00 pg/m3.而附着在PM_2.5上的∑PBDE浓度范围为17.50~149.00 pg/m3,约占TSP中∑PBDE浓度的35.31%~85.14%,并且高溴化的同系物（BDE-138~BDE-209）比低溴化的同系物（BDE-17~BDE-99）更容易附着在PM_2.5上,约占∑PBDE浓度的8.50%~61.60%.对大气颗粒物中PBDEs的潜在影响和空气吸入暴露剂量评估结果表明,成人和儿童对PBDEs的DED_air（呼吸日暴露量）分别在5.28~43.75和6.90~57.23 pg/（kg·d）之间,TDI（每日总摄入量）分别在114.78~951.09和150.00~1 244.13 pg/（kg·d）之间,远低于最低无害水平[1 mg/（kg·d）].BDE-99的TDI分别为11.09~72.39和14.35~94.57 pg/（kg·d）,均低于最低摄入水平[260 pg/（kg·d）].研究显示,昆明市大气TSP和PM_2.5上的PBDEs对人体不存在健康风险.      

上海市典型家庭室内空气中PCBs与PBDEs初步研究

于2008年12月─2009年3月用PUF被动采样器采集了上海市6个典型家庭室内的空气样本,利用GC-EI-MS和GC-NCI-MS法分别测定了样本中14种多氯联苯(PCBs)和7种多溴联苯醚(PBDEs)的质量浓度,采用GC-ECD法测定了ρ(BDE-209). 结果表明:ρ(PCBs)为313.84 ～ 753.79 pg/m3,平均值为442.09 pg/m3;ρ(PBDEs)为0.62 ～83.35 pg/m3,平均值为21.83 pg/m3;ρ(BDE-209)为114.9～ 221.19 pg/m3,平均值为185.58 pg/m3. 与文献报道相比,上海市家庭室内空气中ρ(PCBs)处于中等水平,ρ(PBDEs)略低,但ρ(BDE-209)明显高于其他地区. 儿童和成人对PCBs的日均暴露量达到1 980和4 772 pg/d,对PBDEs的日均暴露量达到930和2 241 pg/d. PCBs和PBDEs能够引起人体生物毒性效应,因此,作为在室内空气中普遍存在的有机污染物,其持续低剂量的暴露应引起重视.      

二溴联苯醚对纤细裸藻的生态遗传毒性效应

通过检测纤细裸藻生长、抗氧化酶活性和单细胞凝胶电泳(彗星试验)研究了4,4’-二溴联苯醚(BDE-15)对纤细裸藻(Euglena gracilis)的生态遗传毒性效应.结果表明,低浓度BDE-15(3×10-6mg/L)对纤细裸藻的生长无显著影响,高浓度时(3mg/L)具有明显的抑制作用,相比空白抑制率达69.70%;叶绿素a和类胡萝卜素含量在高浓度BDE-15作用下显著上升;谷胱甘肽(GSH)和细胞总蛋白含量则随BDE-15浓度增加明显下降;抗氧化酶系统中超氧化物歧化酶(SOD)活性随BDE-15浓度升高显著下降,具明显的剂量-效应关系,过氧化物酶(POD)活性随BDE-15浓度增加呈上升趋势,最高浓度组(3mg/L)比空白对照提高93.45%,显示BDE-15胁迫可诱导抗氧化酶活性;彗星试验结果显示纤细裸藻细胞DNA损伤程度随BDE-15浓度增加而加重,表明高浓度BDE-15具有潜在致突变性.     

Polybrominated diphenyl ether (PBDE) in blood from children (age 9–12) in Taizhou, China

Polybrominated diphenyl ethers (PBDEs) as ubiquitous persistent organic pollutants have attracted much attention in recent years. Exposure to PBDEs could induce a high health risk for children. The aim of this study was to investigate the PBDEs exposure of children (9–12 years) from Taizhou, China. Fifty-eight blood samples were collected in one school in a mountainous area in Taizhou. The concentrations of Σ9PBDEs (sum of BDE-28, -47, -99, -100, -153, -154, -183, -197 and -209) ranged from 2.66 to 33.9 ng/g lipid wet (lw) with a median of 7.22 ng/g lw. These concentrations were lower than those of children in USA, but close to European and Asian general population levels. The results showed that children in Taizhou countryside were at a low level of PBDEs exposure. The predominant congener was BDE-209, followed by BDE-28, -47, -197 and -153. High abundance of BDE-209 was consistent with the pollution background of PBDEs in China characterized by high brominated congeners as main pollutants.     

苏州工业园区室内外颗粒物中多溴联苯醚污染特征及人体暴露水平

利用大流量主动采样技术在苏州市工业园区工厂车间、办公室、住宅区和风景区,采集PM₁₀样品,GC-MS测定PM₁₀中8种PBDEs的含量.室内PM₁₀中PBDEs总浓度范围为9.22~64.15 pg·m^-3（均值为20.93 pg·m^-3）,室外样品中PBDEs总浓度范围为1.06~8.44 pg·m^-3（均值为5.11 pg·m^-3）,室内含量显著高于室外含量.PM₁₀中∑₈PBDEs平均浓度从高到低顺序依次为工业车间、办公室、住宅区和室外大气,与其他地区室内外颗粒物含量相比,苏州室内外大气颗粒物中PBDEs都处于较低水平.室内外大气中BDE-209是最主要化合物（平均占总PBDEs的63%）,其次为BDE-99和BDE-47.车间员工、办公室员工和儿童的PBDEs日呼吸摄入剂量分别为3.75、2.78和2.60 pg·（kg·d）^-1,这表明苏州居民呼吸暴露PBDEs的潜在健康危害并不明显.