Debrominated and methoxylated polybrominated diphenyl ether metabolites in rainbow trout (Oncorhynchus mykiss) after exposure to decabromodiphenyl ether

Decabromodiphenyl ether (BDE209) is the primary component in a commonly used flame retardant. Previous studies had proved that BDE209 itself was not toxic, while its metabolites including debrominated diphenyl ethers (De-BDEs) and methoxylated brominated diphenyl ethers (MeO-BDEs) posed a potential threat to organisms. Many studies had indicated that BDE209 could metabolize quickly in mammals, but lacking in the basic data about the metabolism of BDE209 in fish. In the present study, two replicate treatment groups of rainbow trout (Oncorhynchus mykiss) were exposed to BDE209 via a single intraperitoneal injection approximately 100 and 500 ng/g, respectively. Muscle, liver and blood samples were collected to analyze the specific metabolites on day 1 and day 28 post injection. The highest concentration of BDE209 was detected in muscle tissues, from 796.1 ng/g wet weight (day 1) to 687.1 ng/g wet weight (day 28) in high dose group, suggesting that BDE209 could accumulate slightly in muscle tissues. However, BDE209 was not detected in the blood for all treatments. Most congeners of De-BDEs were found in muscle and liver tissues, with the highest concentration in the liver. The main De-BDEs were nona-, octa-, hepta- and penta-De-BDEs. A total of seven MeO-BDE metabolites were observed among di erent fish tissues. Blood had the highest contribution of the MeO-BDE metabolites. Each MeO-BDE congener increased over the 28 days. These results in contrast to other studies suggested possible species-specific di erences in metabolic abilities.     

中国东北主要河流沉积物中多溴二苯醚的含量状况及生态风险分析

为揭示多溴二苯醚(PBDEs)在东北主要河流流域内的污染现状,通过采集该地区流域内表层沉积物样品,采用GC-NCIMS技术对沉积物中41种PBDEs同类物进行分析.结果发现沉积物中BDE209含量低于检出限,其它40种PBDEs同类物总含量(不包含BDE209)范围(干重)为0.91~17.67 ng·g-1.其中第二松花江吉林市上游和下游沉积物样品中PBDEs的检出含量最高,分别为15.86 ng·g-1、17.67 ng·g-1,以BDE207和BDE47为主,分别占PBDEs总量的86.5%和76.6%;其它河流沉积物中各同族体含量差异并不明显.实验结果与国内外最近的文献报道值相比较,再结合生态风险分析显示,东北主要河流沉积物中PBDEs的含量处于低污染水平,目前不存在生态风险.     

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.     

Levels and distribution of brominated flame retardants in the soil of Harbin in China

This study reports the presence of brominated flame retardants in the topsoil in and around Harbin, a city in northeastern China. Samples of soil were collected from 17 locations in 2006, and the levels of 9 polybrominated diphenylethers (PBDEs 17, 28, 47, 66, 99, 100, 153, 154, and 183) ranged from 2.45 to 55.9 pg/g dry weight (dw) with a mean of 26.3 pg/g dw. These levels are very low comparing with those for some cities in Europe and USA. BDE 209 and hexabromocyclododecane were the two dominant congeners, with mean concentrations of 520 pg/g dw and 1750 pg/g dw, respectively. The concentrations of the total nine PBDE congeners clearly decreased from urban areas to background, but the compositions of individual congeners di ered. Proportions of heavier congeners decreased while those of lighter congeners increased, along urban-rural-background transect, providing evidence for an urban fractionation e ect. Correlation analysis indicated similar sources for PBDEs, hexabromocyclododecane, and 1,2-bis(2,4,6-tribromophenoxy)-ethane from urban areas but pentabromoethylbenzene was probably present due to long-range atmospheric transport. Principal component analysis was used to determine the characteristics of the relationships among these brominated flame retardants in the field.     

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.     

GC/MS法测定生物样品中多溴联苯醚类化合物

本研究建立了多溴联苯醚（PBDEs）生物样品分析方法,获得了优化的前处理条件、气相色谱和质谱检测条件.对定性定量方法及实验条件必须满足的要求进行了评价.通过质量控制（quality control, QC）对整个方法进行了验证.结果证明,本研究所建立的分析方法满足生物样品PBDEs测定的要求,回收率在50.5%～112.3%之间,回收率相对标准偏差在5.3%～9.9%之间,方法检测限在7.1～161.8 pg/g之间.在建立的方法基础上,测定了部分养殖和野生鱼类样品,测得的野生鳜鱼和鲫鱼以及2个养殖鲈鱼样品的结果分别为1.53、1.11、5.31和6.15 ng/g(干重),其中主要的同族体为BDE47.     

Occurrence of polybrominated diphenyl ethers in fish and shellfish downstream from electronic-waste recycling plants

We measured 39 polybrominated diphenyl ethers (PBDEs) in the muscle tissue of three species of fish (Sciaenops ocellatus, Sparus macrocephalus, and Lateolabrax japonicus) and four species of shellfish (Tegillarca granosa, Cyclina sinensis, Sinonovacula constricta, and Ostrea cucullata) that were collected downstream of electronic-waste recycling plants in Taizhou, China. A total of 24 PBDE congeners (PBDE24) in the samples were detected. The PPBDE24 (total PBDE) ranged from 545.4 to 1688.7 ng/kg ww (wet weight). The mean PPBDE24 concentration was 1382.6 ng/kg ww in fish and 858.1 ng/kg ww in shellfish. The lower brominated congeners were detected at relatively high concentrations in all species. The penta-products, produced from e-waste, were found at relatively low levels. A principal component analysis suggested a significant correlation among di-, tri-, tetra-, and hepta-BDEs for the three species of fish. Similarly, we found a significant correlation between mono- and tri-BDEs in the shellfish. Our results suggested that the processes of PBDE metabolism and elimination were similar in both fish and shellfish. In addition, the primary source of PBDEs appeared to be from the debromination of high brominated PBDEs.     

多溴联苯醚在电子废弃物拆卸地沉积物中的垂直分布

采用气相色谱质谱联用仪对采自清远电子废弃物拆卸地水库钻孔沉积物中的多溴联苯(polybrominated diphenyl ethers,PBDEs)进行了分析,调查其在沉积物中的垂直分布.结果表明,PBDEs在所有的样品中均检出,含量为0.43～141 ng/g,平均为9.26 ng/g.PBDEs在下层(16 cm以下)沉积物中含量较低、变化很小(0.43～2.30 ng/g),但在上层沉积物中含量明显增加(2.90～141 ng/g),反映了当地电子废弃物拆卸活动的影响;3种工业源的PBDEs,即五溴、八溴和十溴PBDEs,表现出相似的垂向分布趋势,说明其来源的一致性.其中,十溴PBDEs是最主要的PBDEs,平均占所有PBDEs的79.6%,其次是五溴PBDEs(14.7%),而八溴PBDEs所占比例最低(5.69%).3种PBDEs的组成模式显示,它们与相应的工业品PBDEs组成都有一定差异,可能因其降解行为不同所致.一些PBDE的同族体组成在沉积钻孔的垂直变化也进一步说明高溴代PBDE在沉积物的埋藏期间可能发生了降解,虽然还需要进一步研究证实.     

多溴联苯醚在桂花鱼体内的分布

使用 GC-MS-NCI检测方法对持久性有机污染物多溴联苯醚(PBDEs)的同系物BDE28,47,66,85,99,100,138,153,154,183,209 在桂花鱼体内的含量及分布进行了研究．结果表明,Σ₁₀ PBDEs（不包括BDE209）在肾脏中含量最高,肌肉中含量最低,其干重平均值分别为5.71 ng·g^-1 和0.95 ng·g^-1．Σ₁₀ PBDEs在肾脏、鱼鳔、肝脏、鱼鳃、生殖腺、鱼皮、肠胃和肌肉中的干重含量分别为3.04～12.8、0.81～6.90、1.28～8.87、0.09～6.36、1.05～5.73、0.022～5.06、0.69～5.98和0.14～2.61 ng·g^-1．Σ₁₀ PBDEs在各组织和器官的含量顺序为: 肾脏、鱼鳔、肝脏> 鱼鳃、生殖腺> 肠胃、肌肉、鱼皮．桂花鱼体所含低溴取代 PBDEs 以 BDE47 为主要同系物,所占丰度为35.7%～65.6%．十溴取代物 BDE209 在所有样品中检出率为 45.2%,其中在肾脏和生殖腺中含量较高．研究表明,PBDEs 由摄食、呼吸2种主要途径进入桂花鱼体内,易富集在肝脏、鱼鳔、鱼鳃等脂肪含量较高的组织和器官中．     

废弃电容器封存点及旧工业场地多氯联苯的污染特征

研究了四川资阳机车厂废弃电力电容器封存点与旧工业场地土壤与降尘中28种多氯联苯（PCBs）的污染水平与组成特征.电容器封存山洞未封闭洞口处土壤中PCBs含量最高,28种PCBs的总含量（ΣPCBs）达227 502 ng.g-1,铸铁车间窗台降尘中也有高残留的PCBs,ΣPCBs在10μg.g-1以上,封存点和铸铁车间样品中PCBs单体含量之间均存在显著的正相关关系（P〈0.01）.高污染样品中PCBs的同族体分布均以四氯代PCBs为最高,其次为三氯代PCBs和五氯代PCBs.与封存点土壤相比,铸铁车间样品中高氯代PCBs的贡献更大.12种类二英PCBs的毒性当量（TEQ）介于75.43～24 027 pg.g-1之间,远大于电子垃圾拆解区土壤,但普遍都以PCB126的毒性当量贡献占绝对优势.     

Ecotoxicological effects of mixed pollutants resulted from e-wastes recycling and bioaccumulation of polybrominated diphenyl ethers in Chinese loach （Misgurnus anguiUicaudatus）

To understand potential ecotoxicological e ects of electrical and electronic equipment waste (e-waste) recycling and polybrominated diphenyl ethers (PBDEs) bioaccumulation in loaches, a semi-field experiment using Chinese loach (Misgurnus anguillicaudatus) as experimental fish was performed. Larval loaches were kept in net-cage for three months in an e-wastes recycling site and a reference site in Southeastern China. There was significant di erence of the survival rate between the loaches from the e-wastes recycling site (27%, 19/70) and from reference site (70%, 49/70). Histopathological responses were also found in all the livers examined in loaches from the e-wastes recycling site. These results showed that mixed pollutants resulted from e-wastes recycling led to ecotoxicological e ects on loaches. The bioaccumulation of polybrominated diphenyl ethers (PBDEs), the main pollutants in e-waste, in loaches was also studied, the mean concentration of total PBDEs in sediment was 6726.17 ng/g wet weight and in water samples was 4.08 ng/L (dissolved phase). BDE 209 was the dominant congener in sediment and with relatively high concentration in water. Relatively low concentration of BDE 209 (less than 0.01% of total PBDEs) and high concentration of BDE47 (up to 39.34% of total PBDEs) were detected in loaches.     

珠江河口水生生物中多溴联苯醚的分布

对珠江河口生物样品中多溴联苯醚(PBDEs)的含量进行了检测.所采集的鱼类(鱼、大黄鱼、银鲳、舌鳎、龙头鱼),虾类(刀额新对虾、近缘新对虾)及虾蛄类生物样品肌肉组织中10种PBDEs(BDE28,47,66,100,99,85,154,153,138,183)的含量分别为37.8～407.1 ng·g^-1(脂肪归一化浓度)、49.0～239.1 ng·g^-1和142～444.5 ng·g^-1.所有样品中,BDE47相对含量最高,其相对于∑<     

Occurrence and bioaccumulation of polybrominated diphenyl ethers in sediments and paddy ecosystems of Liaohe River Basin, northeast China

Concentrations of 16 polybrominated diphenyl ether(PBDE) congeners were measured in river sediments, paddy soils and three species of paddy-field organisms(crab, loach and carp) collected from the Liaohe River Basin, northeastern China. The total contents of PBDEs(∑_(16)PBDEs) in sediments and paddy soils were in the ranges of 273.4–3246.3 pg/g dry weight(dw), and 192.1–1783.8 pg/g dw, respectively. BDE 209 was the dominant congener both in sediments and paddy soils. The concentrations of ∑_(16)PBDEs in sediments were significantly higher than those in the adjacent paddy soils, indicating a potential transport of PBDEs from river to paddy ecosystems via river water irrigation. The biota–soil accumulation factor(BSAF) was calculated as the ratio between the lipid-normalized concentration in paddyfield organisms and the total organic carbon-normalized concentration in paddy soil. The average BSAF values of ∑15PBDEs followed the sequence of crab(3.6) loach(3.3) carp(2.1). BDE 154 had the highest BSAF value, and a parabolic trend between BSAF values of individual PBDE congeners and their log KOWvalues was observed. In view of the fact that crab had the larger BSAF value and higher lipid content, the ecological risk and health risk for crab cultivation in paddy fields should be of particular concern.     

济南市夏季环境空气中PBDEs的浓度分布及潜在风险分析

为准确评估济南市夏季环境空气中PBDEs（多溴联苯醚）的污染情况,利用气相色谱-负化学离子源-质谱（GC-NCI-MS）方法,对采集到的大气颗粒物滤膜和气相样品进行了分析,得到不同粒径颗粒相和气相PBDEs在济南市夏季环境空气中的质量浓度.结果表明:观测期间,济南市环境空气中TSP（总悬浮颗粒物）、PM₁₀和PM_2.5中的ρ（PBDEs）分别为（224.1±14.0）（156.5±43.7）（110.2±27.4）pg/m3,质量浓度较高的3种PBDEs单体分别为BDE209、BDE99、BDE183;气相中ρ（PBDEs）为（54.8±13.2）pg/m3,其中,质量浓度较高的单体分别为BDE209、BDE47、BDE99.通过主因子分析发现,不同粒径颗粒物上吸附的PBDEs特征单体不同,TSP中以五溴联苯醚为主,PM₁₀中以八溴联苯醚和五溴联苯醚为主,PM_2.5中则以五溴联苯醚、八溴联苯醚、十溴联苯醚为主.通过将2种模型的预测值和实测值进行比较发现,稳衡态模型比K_OA（辛醇-空气分配系数）模型更好地模拟了PBDEs的气-粒分配情况.在稳衡态模型下,PBDEs在气-粒分配中接近于平衡状态.高溴代PBDEs主要分布于颗粒相中,而低溴代PBDEs的真实情况不同于理论预测结果,BDE99及BDE47在颗粒相的分配比高于50%,说明济南市低溴代PBDEs也容易吸附在颗粒相中.根据计算的PBDEs呼吸暴露水平可知,PM_2.5上PBDEs呼吸暴露量占TSP呼吸暴露量的49.1%,儿童约是成人的1.5倍.济南市普通儿童和成人对BDE99最高总摄入量分别为234.78和169.57 pg/（kg·d）,均低于BDE99最大允许摄入量260 pg/（kg·d）.根据US EPA（美国环境保护局）发布的PBDEs健康风险评价方法（EPA/540/R/070/002）,利用国内外相关参数分别计算空气吸入致癌风险指数发现,济南市夏季环境空气中PBDEs的致癌风险处于较低水平.研究显示,济南市夏季环境空气中不同粒径颗粒物PBDEs的质量浓度处于较低污染水平,其产生的潜在健康风险也较低.      

Levels and distributions of polychlorinated biphenyls in sewage sludge of urban wastewater treatment plants

Concentrations of polychlorinated biphenyls (PCBs) have been measured in sewage sludge samples from 8 urban wastewater treatment plants in Beijing, China. The PCB congeners were analyzed by isotope dilution high resolution gas chromatography/high resolution mass spectrometry method. The concentration of PCBs ranged from 65.6 to 157 ng/g dry weight (dw), with a mean value of 101 ng/g dw. The dioxin-like PCB WHO-TEQs (World Health Organization-Toxic Equivalents) of the sludge were lower than 1 pg /g dw. Conse...     

洞庭湖不同营养级鱼组织中PCBs的分布特征

采用稳定同位素分析技术和气相色谱-高分辨质谱联用技术,测定了洞庭湖6种鱼组织的稳定氮同位素丰度值（δ¹⁵N值）和多氯联苯（PCBs）的含量,研究了鱼组织中PCBs分布特征及其与营养级的相关性.结果表明,∑PCBs₁₁₅的浓度范围为0.04~9.77ng/g湿重,在鲤鱼性腺组织中最高.毒性当量为：0.0003~2.39pg/g湿重,在鳡鱼脂肪组织中最高.洞庭湖鱼中PCBs的含量处于较低水平.PCB28,52,95,99,101,105,110,118,138,153,155和209在所有组织中检出.Co-PCBs,Ind-PCBs和PCB209具有组织分布特异性.不同计量方式下,鱼组织中PCBs与δ¹⁵N值具有相关性的同类物不同.     

北京市部分地区土壤中二英类物质污染水平初探

采集北京市部分非污染区土壤样品16个,对样品中二(口恶)英类物质分布形态和浓度水平进行初步探讨.结果表明:空地土壤中的二(口恶)英类物质质量分数为0.229 1～3.332 pg/g(全文均指pg(I-TEQ)/g),平均值为1.478 pg/g,与美国农村背景值相当;林地质量分数为0.769 1～2.760 pg/g,平均值为1.329 pg/g;耕地质量分数为2.278～7.307 pg/g,平均值为4.462 pg/g.与国外数据对比可以看出:空地和林地土壤样品与欧洲国家的浓度水平相当,耕地土壤则高于欧洲国家,但比日本低很多.总之,耕地土壤样品中二(口恶)英类物质的质量分数较高,空地次之,林地土壤质量分数最小.对于形态分布而言,受某种主要因素影响的土壤中二(口恶)英类物质形态分布相似,受综合因素影响的土壤与大气中的二(口恶)英类物质形态分布类似.另外讨论了浓度异常采样点可能的污染来源.      

Ecotoxicological effects of mixed pollutants resulted from e-wastes recycling and bioaccumulation of polybrominated diphenyl ethers in Chinese loach (Misgurnus anguillicaudatus)

To understand potential ecotoxicological effects of electrical and electronic equipment waste (e-waste) recycling and polybrominated diphenyl ethers (PBDEs) bioaccumulation in loaches, a semi-field experiment using Chinese loach (Misgurnus anguillicaudatus) as experimental fish was performed. Larval loaches were kept into net-cage for three months in an e-wastes recycling site and a reference site in Southeastern China. There was significant difference of the survival rate between the loaches from the e-wastes recycling site (27%, 19/70) and from reference site (70%, 49/70). Histopathological responses were also found in all the livers examined in loaches from the e-wastes recycling site. These results showed that mixed pollutants resulted from e-wastes recycling led to ecotoxicological effects on loaches. The bioaccumulation of polybrominated diphenyl ethers (PBDEs), the main pollutants in e-waste, in loaches was also studied in this e-wastes recycling site, the mean concentrations of total PBDEs in sediment was 6726.17 ng/g wet weight and in water samples was 4.08 ng/L (dissolved phase). BDE209 was the dominant congener in sediment and with relatively high concentration in water. Relatively low concentration of BDE209 (less than 0.01% of total PBDEs) and high concentration of BDE47 (up to 39.34% of total PBDEs) were detected in loaches.     

Characterization, treatment and releases of PBDEs and PAHs in a typical municipal sewage treatment plant situated beside an urban river, East China

Characterization, treatment and releases of eight polybrominated diphenyl ethers (PBDEs) congeners and sixteen polycyclic aromatic hydrocarbons (PAHs) in wastewater were evaluated along the treatment processes of a typical secondary treatment municipal sewage treatment plant (STP) (in Hefei City) situated the beside Nanfei River, East China. The findings showed that the average concentrations of the total PBDEs in raw wastewater and treated effluent were 188.578 and 36.884 ng/L respectively. Brominated diphenyl ether (BDE) 209 congener, the predominant PBDE in the STP and Nanfei River, could be related to the discharge of car-industry-derived wastes. For PAHs, the average concentrations in raw wastewater and treated effluent were 5758.8 and 2240.4 ng/L respectively, with naphthalene, benzo[a]pyrene and indeno[1,2,3-c,d]pyrene being detected at the highest concentrations. PAHs mainly originate from the combustion of biomass/coal and petroleum. The STP reduced about 80% of the PBDEs and 61% of the PAHs, which were eliminated mainly by sedimentation processes. The removal rates of PBDEs/PAHs increased with the increase of their solid-water partitioning coefficients. Accordingly, the STP's effluent, containing some PBDE congeners (e.g., BDE 47, 99 and 209, etc.) and low-molecular-weight PAHs, could be an important contributor of these contaminants' input to Nanfei River. It resulted in a significant increase of PBDE/PAH concentrations and PAH toxicological risk in the river water downstream. About 4.040 kg/yr of PBDEs and 245.324 kg/yr of PAHs could be released into the Nanfei River. The current conventional wastewater treatment processes should be improved to remove the relatively low-molecular-weight PBDEs/PAHs more effectively.