湖泊沉积柱中的高溴联苯醚及其在环境中的降解

采用GC/MS方法分析了5个内陆湖泊(巢湖、滇池、红枫湖、青海湖和四海龙湾)钻孔沉积物中HB-PBDEs(高溴联苯醚,包括九溴和十溴的联苯醚)的垂直分布状况,并对它们的组成特征及其在环境中的降解进行了分析.结果显示,5个内陆湖泊表层沉积物中有机碳归一化后的w(ΣHB-PBDEs)为17.5～977.9 ng/g,其中滇池、红枫湖和巢湖HB-PBDEs的污染相对较为严重;与国内外其他研究相比,我国内陆湖泊沉积物中BDE-209的污染状况相对较轻.沉积物中HB-PBDEs的组成特征显示,BDE-209不但在大气传输过程中发生了明显降解,而且在进入湖泊沉积物后也发生了明显降解.由于BDE-209在不同环境介质中都可发生降解,并且降解产物为毒性更大的低溴代单体,因此进一步研究BDE-209在环境中的降解具有重要意义.      

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.     

垃圾焚烧发电厂周边土壤多溴联苯醚污染特征及来源解析

为了分析市政垃圾焚烧发电厂PBDEs(polybrominated diphenyl ethers,多溴联苯醚)排放对周边环境的影响,于2012年8—9月,在哈尔滨2座市政垃圾焚烧发电厂周边共采集20个表层(0~10 cm)土壤样品,分析土壤中PBDEs的污染特征及其来源. 结果表明:垃圾焚烧发电厂周边土壤中w(∑₁₂PBDEs)(12种PBDEs的质量分数之和)为5.32~169 ng/g(以干质量计,下同),平均值为62.9 ng/g;PBDEs的主要组分为BDE-209,w(BDE-209)为5.18~169 ng/g,占w(∑₁₂PBDEs)的95%以上;w(∑₁₂PBDEs)显著高于2006年哈尔滨市区污染土壤值,二者相差1~2个数量级. 由于垃圾处理年限和处理量差异较大,垃圾焚烧发电厂A周边土壤中w(PBDEs)显著高于垃圾焚烧发电厂B. 与国内其他用地类型污染土壤相比,垃圾焚烧发电厂周边土壤中PBDEs处于中度污染水平. 主成分分析结果显示,PBDEs主要来源于商用十溴联苯醚及其降解物和商用五溴联苯醚.      

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.     

三峡库区主要支流表层沉积物多溴联苯醚的分布特征

采用GC-MS(NCI)技术对三峡库区28个表层沉积物样品中的多溴联苯醚(PBDEs)进行分析,研究了其在三峡库区主要支流的污染现状与分布特征.实验发现三峡库区Σ26PBDEs和BDE209在沉积物中的检出含量分别为35.24 pg·g-1和11.92 pg·g-1,其中BDE28,47,77和99为Σ26PBDEs中最具支配地位的同族体.Σ26PBDEs和BDE209的最高检出含量在龙河河口采样点,分别为146.07 pg·g-1和502.63 pg·g-1.Σ26PBDEs和BDE209含量具有良好相关性,说明两者污染来源相同.实验结果与国内外水体沉积物中含量相比较,显示Σ26PBDEs和BDE209在三峡库区沉积物中含量处于较低污染水平,引起的潜在风险也相对较低.     

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.     

生产源区人血中多溴联苯醚水平与甲状腺激素相关性研究

采用气相色谱/负化学电离源-质谱法对莱州湾南岸地区十溴联苯醚生产源区36位居民血清中的5种多溴联苯醚浓度进行了检测,同时测定了样品中的甲状腺激素水平.血清中Σ5PBDEs（BDE-28、-47、-153、-183、-209）的质量浓度范围（以脂重计算,下同）为130.3～4 478.4 ng.g-1,平均值为529.9 ng.g-1.5种同族体中,BDE-209对Σ5PBDEs的平均贡献率达到了69.8%.在与甲状腺激素水平的相关性研究中,计算了两者的Spearman秩相关系数,结果显示BDE-28、-47、-153、-183与TSH水平呈高度负相关,BDE-183与fT4水平呈现显著性负相关,而BDE-28、-47与T3,BDE-28、-153、-183与fT3之间均呈现显著性正相关.本研究中,生产源区人体血清中PBDEs水平处于较高的暴露水平,主要同类物为BDE-209,人体对PBDEs的暴露会影响上述4种甲状腺激素的水平,PBDEs对人体的影响不容忽视,有关PBDEs暴露水平与甲状腺激素水平之间的相关性,应进一步深入研究.     

莱州湾地区土壤及底泥中多溴联苯醚水平及其分布

对莱州湾地区十溴联苯醚生产厂家附近土壤及底泥中的多溴联苯醚的含量进行了检测.所采集土壤和河流底泥样品中Σ8 PBDEs(BDE-28、-47、-100、-99、-154、-153、-183、-209) 的含量在58.2～7190.7 ng·g-1(干重)之间, 所有样品中,BDE-209 相对含量最高,其对Σ8PBDEs 的贡献为74.81% ～99.01 %.在8种PBDEs同族体的相关性研究中发现BDE-209与BDE-183、-154、-153、-100、-99呈现显著负相关,相关系数r为-0.842～-0.996(α=0.01).BDE-183、-154、-153、-100、-99之间呈显著正相关,相关系数r为0.805～0.994(α=0.01).产品十溴联苯醚在环境中的降解可能是测定样品中BDE-99、-100、-153、-154、-183的来源之一.     

杭州城区室内灰尘中多溴联苯醚的含量及人体暴露水平

为了评估杭州城区室内灰尘中多溴联苯醚(PBDEs)污染程度,2013年3~8月,在杭州城区随机采集19个办公室、家庭和学生宿舍的室内灰尘样品.用GC-ECD定量分析了样品中14种PBDEs同系物的含量水平、同系物分布和可能的影响因素,并估算了成年人和儿童通过灰尘摄入对PBDEs的暴露水平.结果表明,办公室Σ14PBDEs的平均值9.28×102ng·g-1,中值为1.03×103ng·g-1;家庭Σ14PBDEs的平均值7.83×102ng·g-1,中值为9.11×102ng·g-1;学生宿舍Σ14PBDEs的平均值4.07×102ng·g-1,中值为4.03×102ng·g-1,办公室的污染水平高于居住环境.BDE-209是贡献值最大的单体,其贡献值为75.48%,其次分别是BDE-190、BDE-154和BDE-71.成年人和儿童通过灰尘摄入的PBDEs暴露水平分别为13.12~32.63 ng·d-1和32.40~54.54 ng·d-1,灰尘中儿童的PBDEs人体暴露量高于成人的人体暴露量,主要是因为儿童灰尘摄入量要高于成人.分析得出,从室内灰尘摄入的PBDEs存在健康隐患,儿童潜在危害最大.     

废旧电器拆解区河流沉积物中多溴联苯醚(PBDEs)的污染特征与生态风险

在流经某废旧电器拆解区域的河段中采集沉积物样品,研究了该区域河流中多溴联苯醚(PBDEs)的污染特征和生态风险.结果表明,在所有沉积物样品中PBDEs含量在101~20400 ng·g-1之间,平均浓度为3700 ng·g-1,其中主要单体为BDE209,在23个样品中的平均比例达到94%以上;在河流中分布呈现出上游和下游低,中游高,而下游平均浓度比上游高的趋势,在拆解园区附近浓度达到最高;与其它地区相比,该地区PBDEs污染相对较为严重;废旧电器的拆解是该区域沉积物中PBDEs污染主要来源.经测算,当地近40年的拆解活动中共向该河流中排放了多溴联苯醚0.39 t,其中BDE209为0.36 t;采用危害商数法对沉积物中PBDEs进行了初步的生态风险评估,结果表明,该河流沉积物中OctaBDEs和DecaBDEs生态风险较低,而PentaBDEs则风险较高,可能对环境造成危害.     

Distribution of polybrominated diphenyl ethers and decabromodiphenylethane in surface sediments from Fuhe River and Baiyangdian Lake, North China

Nineteen surface sediment samples collected from Baiyangdian Lake and its inflowing river (Fuhe River) in North China were analyzed for polybrominated diphenyl ethers (PBDEs) and decabromodiphenylethane (DBDPE). The concentrations of PBDEs and DBDPE in sediments ranged from 5.5 to 300.7 ng/g dry weight (dw) and 1.1 to 68.2 ng/g dw, respectively. Their levels in sediments in Fuhe River were significantly higher than those in Baiyandian Lake. Compared to data from other regions, the PBDE levels in surface sediments from Baiyangdian Lake and Fuhe River were in the medium to lower range. Among the PBDE congeners, BDE209 was predominant, with contributions to the total PBDEs ranging from 79.4% to 97.3% in sediment samples. For the lowly brominated congeners (tri- to hepta-BDE), BDE47 and BDE99 were the most abundant, which contributed 52.1% and 44.1% to the sum of tri- to hepta-BDEs in the sediments from Baiyangdian Lake and Fuhe River, respectively. The compositional patterns of PBDEs in Baiyangdian Lake sediments indicated that technical deca-BDE mixture was the major pollutant sources with a minor contribution of penta-BDE mixture. The present study suggested that the importance of Fuhe River as a possibly potential sources of PBDEs contamination in Baiyangdian Lake.     

Advanced treatment of dyeing wastewater towards reuse by the combined Fenton oxidation and membrane bioreactor process

The performance of combined Fenton oxidation and membrane bioreactor (MBR) process for the advanced treatment of an effluent from an integrated dyeing wastewater treatment plant was evaluated. The experimental results revealed that under the optimum Fenton oxidation conditions (initial pH 5, H 2 O 2 dosage 17 mmol/L, and Fe 2+ 1.7 mmol/L) the average total organic carbon (TOC) and color removal ratios were 39.3% and 69.5% after 35 min of reaction, respectively. Results from Zahn-Wallens Test also represented that Fenton process was effective to enhance the biodegradability of the test wastewater. As for the further purification of MBR process, TOC removal capacity was examined at different hydraulic retention times (HRT) of 10, 18 and 25 hr. Under the optimum HRT of 18 hr, the average TOC concentration and color of the final MBR effluent were 16.8 mg/L and 2 dilution time, respectively. The sludge yield coefficient was 0.13 g MLSS/g TOC and TOC degradation rate was 0.078 kg TOC/(m 3 ·day). The final effluent of MBR can meet the reuse criteria of urban recycling water-water quality standard for miscellaneous water consumption GBT18920-2002.     

Contamination by persistent toxic substances in surface sediment of urban rivers in Chaohu City, China

The concentration and spatial distribution of persistent toxic substances (PTS) in the river sediment in Chaohu City, China were investigated. A total of nine surface sediments were collected and the selected PTS pollutants including six heavy metals and nineteen polybrominated diphenyl ethers (PBDEs) were analyzed. The mean heavy metal concentrations (in mg/kg, dry weight) ranged within 0.18-1.53 (Hg), 50.08-200.18 (Cu), 118.70-313.65 (Zn), 50.77-310.85 (Cr), 37.12-92.72 (Pb) and 13.29-197.24 (As), and Cu, Zn and As have been regarded as the main metal pollutants. The levels of PBDEs (1.2-12.1 ng/g) and BDE-209 (2.4-30.5 ng/g) were at the middle level of the global range. BDE-209 was the predominant congener (67.0%-85.7%), which agrees with the fact that technical deca-BDE mixtures are the dominant PBDE formulation in China. The relative high level of PTS pollutants in the western part of the city is probably owing to the intensive agricultural activities and lack of sewerage system there. The ecological risk assessment with the sediment quality guidelines (SOGs) indicates that the urban river sediments in the city have been heavily contaminated by heavy metals with probable ecotoxicological impacts on freshwater organisms and the main toxic pollutants are Hg and As. The results of current study imply that the city, and perhaps many other small cities in China as well, requires immediate pollution control measures with emphasis on not only conventional organic pollutants but also on PTS such as heavy metals and PBDEs.     

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.     

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.     

Accumulation of polybrominated diphenyl ethers in breast milk of women from an e-waste recycling center in China

Polybrominated diphenyl ethers(PBDEs) can be transferred to infants through the ingestion of breast milk, resulting in potential health risk. In this study, PBDEs, hydroxylated polybrominated diphenyl ethers(OH-PBDEs) and 2,2′,4,4′,5,6′-hexachlorobiphenyl(CB-153)in human milk from women living adjacent to e-waste recycling sites of Wenling,China, were investigated. The median level of PBDEs in samples from residents living in the e-waste recycling environment 20 years(R_20group, 19.5 ng/g lipid weight(lw))was significantly higher than that for residents living in Wenling 3 years(R_3group,3.88 ng/g lw)(p 0.05), likely ascribable to specific exposure to PBDEs from e-waste recycling activities. In the R_20 group, most congeners(except for BDE-209) were correlated with each other(p 0.05). Moreover, CB-153 showed significant association with most PBDE congeners, rather than BDE-209. The relationship indicated that most BDE congeners other than BDE-209 shared common sources and/or pathways with CB-153, e.g., dietary ingestion. The correlations between BDE-209 and other congeners were different in the two groups, likely suggesting their different exposure sources and/or pathways for PBDEs.Although estimated dietary intake of PBDEs for infants via breast milk was lower than the minimum value affecting human health, the PBDE exposure of infants should be of great concern because of their potential effect on the development of neonates over long-term exposure. OH-PBDEs were not detected in the collected samples, which is in accordance with reports in published literature, likely indicating that they were not apt to be accumulated in human milk.     

上海室内环境中多溴二苯醚的沉降通量与组成

对上海市主城区8个家庭和8个办公室的室内降尘于2008年7~8月间用洁净玻璃板进行了定量采集,使用气相色谱-质谱联用仪在负化学电离(NCI)和选择离子扫描(SIM)条件下对室内降尘中BDE-17,-28,-71,-47,-66,-77,-100,-99,-85,-118,-154,-153,-138,-183,-190和BDE-209共16种PBDEs同系物进行了分析,目的是了解上海市室内环境中多溴二苯醚的沉降通量、组成及其影响因素.结果表明,上海家庭和办公室中颗粒态PBDEs的沉降通量分别为(10.9±8.2)和(14.2±11.9)ng.(m2.d)-1,同系物组成以十溴二苯醚(BDE-209)为主,占总量的88.2%~99.2%.办公室环境中颗粒物沉降量较低[(3.1±2.0)mg.(m2.d)-1],但颗粒物中PBDEs含量[(3 361.6±1 987.4)ng.g-1]明显高于家庭环境[(1169.1±647.1)ng.g-1].上海室内降尘中PBDEs的含量与世界其他城市相比处于中等水平.PBDEs室内沉降通量与降尘通量、电器数量及使用时间相关,而与室内装修程度、家具数量的关系不明显.     

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.      

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.