Polybrominated diphenyl ether levels in wild and farmed Chilean salmon and preliminary flow data for commercial transport

This pilot study documented the occurrence and levels of brominated flame retardants in the tissues of farmed and wild salmon in southern Chile. Samples of Coho salmon and rainbow trout were obtained from fish farms, rivers and lakes in the Patagonia in Aysen Region, Chile. The samples were analyzed by Gas Chromatography Negative Chemical Ionization Mass Spectrometry for the different polybrominated diphenyl ether (PBDE) congeners. Contaminants were observed in all the samples, and the congeners BDE 17, 28, 47 and 66 were observed in all both farmed and wild samples. The concentrations were higher in the farmed Coho salmon, presenting significant differences with wild salmon. The levels reached 182 pg/g wet weight (ww) vs. 120 ww. In the case of the rainbow trout, the concentrations were lower, although the congener profile was quite similar. The levels reached an average of 100 pg/g ww in the farmed fish versus 110 pg/g ww in wild fish, and no significant difference was observed between the species. In both species, the congener with the highest concentration was BDE 47. Based on this information, the BDE flow was estimated for commerce, which is a form of pollutant transport not usually considered in POP pollution studies. A preliminary estimation indicated that the quantity of PBDEs mobilized by commerce was in the order of kg, and in the case of Chile might reach almost 1 kg.     

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.     

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.     

渤海湾天津近岸典型海域PBDEs污染状况及分布规律研究

本文利用气相色谱质谱联用法开展了天津近岸典型海域水体、沉积物和生物体等不同介质中PBDEs含量分析,给出了天津近岸典型海域不同介质中PBDEs的污染状况以及各种同系物的分布情况,初步探讨了天津近岸海域新兴持久污染物PBDEs污染状况及污染风险。结果显示,（1）水体中PBDEs的含量相对较高,为（43.8~93.3）ng/L,平均含量为59.4 ng/L,沉积物中PBDEs的含量为（15.9~37.9）×10-9（干重）,平均含量为22.8×10-9（干重）,而生物体内的PBDEs含量为（6.19~34.8）×10-9（干重）,平均含量为19.4×10-9（干重）。（2）三种海洋生物中海洋贝类对PBDEs具有最强的富集能力而海洋鱼类最弱。生物样品中监测到低溴代同系物为主要组分,而环境介质中以高溴代（主要为BDE-209）为主。（3）与我国其他地区相比,海水中PBDE的浓度较珠江入海口稍高,沉积物和生物体中浓度处于同一水平。海水样品中BDE-209占主要成分,而沉积物和生物体内低溴代联苯醚占主要成分。天津离岸海域PBDEs污染状况究竟如何以及类似持久性污染物的污染状况以及可能对人类造成的危害程度等研究都有待于进一步加强。     

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.     

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．     

Polybrominated diphenyl ethers in soil from three typical industrial areas in Beijing, China

Areas containing industrial facilities belonging to three different typical industries that may cause pollution by polybrominated diphenyl ethers （PBDEs） in Beijing, China were investigated. Specifically, the areas contained a solid waste incineration plant, a chemical factory, and a heat and power plant. Investigation of the pollution status of PBDEs in the surface soil from areas around these industries revealed the highest concentration of 42 PBDE congeners （118 ng/g, dry mass） at the solid waste incineration plant. In the other two plants, the highest concentrations were both 26 ng/g （dry mass）. Among the PBDE homologues, the PBDE contamination at all sites showed similar congener compositions, with BDE 209 being the dominant congener. Our findings established the first contamination status of three typical industrial areas in Beijing. Furthermore, the total concentrations of 42 PBDE congeners tended to decrease as the distance from the investigated plants increased. Overall, these plants were identified as potential pollution sources of PBDEs in Beijing. Moreover, Pearson correlation analysis revealed that the major PBDE source in Beijing may be associated with the technical deca-BDE and penta-BDE mixture. Based on the data obtained in this preliminary investigation, further study of the potential of these sources to emit PBDEs in Beijing is warranted.     

电子废弃物处理地室内外灰尘中多溴联苯醚的污染及其人群暴露水平

2006年10月和2007年10月,在广东省清远市一个典型电子废弃物处理地采集了24个室内和15个室外灰尘样品,分析了其中的17种多溴联苯醚(PBDEs).结果显示,PBDEs在所有灰尘样品中均有检出,室内灰尘中PBDEs含量为230～157 500ng.g-1,平均9 400 ng.g-1;室外灰尘中PBDEs含量为212～25 880 ng.g-1,平均3 311 ng.g-1.与世界其他地区灰尘中PBDEs的含量相比,本研究地区灰尘中PBDEs的含量处在较高水平.BDE209是灰尘中最重要的同族体;与工业品中PBDEs的组成对比显示,灰尘中相对高丰度的八至九溴同族体可能来自BDE209的降解.婴幼儿、儿童和成人通过灰尘对PBDEs的平均日暴露量分别为470、329和188 ng.d-1,婴幼儿和儿童的最高日暴露量(31 500和19 700 ng.d-1)分别是成人的4和2.5倍.灰尘可能是当地人群(特别是婴幼儿和儿童)暴露PBDEs的重要途径.     

A review of polybrominated diphenyl ethers and alternative brominated flame retardants in wildlife from China: Levels, trends, and bioaccumulation characteristics

Accelerated industrialization and urbanization, and unregulated disposal of waste of electric and electronic equipment (e-waste) in China have caused environmental pollution of brominated flame retardants (BFRs). This review summarized the levels, trends, and bioaccumulation characteristics of polybrominated diphenyl ethers (PBDEs) and other potential alternative BFRs including hexabromocyclododecanes (HBCDs), 1,2-bis(2,4,6-dibromophenoxy) ethane (BTBPE) and decabromodiphenylethane (DBDPE) in wildlife from China. PBDE levels in wildlife from China were generally higher than those from other parts in Asia, and were comparable to those from Europe but were lower than those from North America. However, wildlife from the e-waste recycling sites in South China and East China contained much higher PBDEs compared to other reports around the world, suggesting the heavy contamination of PBDEs in these regions. The alternative BFRs were also detected in wildlife, revealing that the animals are exposed to these chemicals, in addition to PBDEs. Temporal trends indicated by levels in marine mammals from South China suggested that PBDE levels increased from the beginning of 1990s to 2000s, but decreased from the middle of 2000s, followed by relatively steady levels. In contrast, HBCDs were found to be continuously increasing from 1997 to 2007, indicating the increasing usage of HBCDs in China in recent years. Compared to PBDE profiles found in other parts, aquatic species and birds from China contained relatively higher contributions of BDE-28 and 209, respectively, suggesting the possible different usage pattern of PBDEs. Future works including keeping monitoring at a reasonable scale and frequency to make sure levels near urban centers indicative of population do not increase are needed. Additionally, focus effort on e-waste recycling regions to look for impacts and to determine if regulation/controls are resulting in lower environmental contamination, and incorporation of sentinel species in monitoring efforts are recommended.     

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∑<     

典型电子垃圾拆解区大气中多溴联苯醚的污染

分别在典型电子垃圾拆解区(E)和其上风向参考点(S)采集了大气颗粒相和气相样品.以研究该区域大气中PBDEs的浓度水平、污染特征和气/固分布特点.分析过程中运用气相色谱.质谱联用仪,负化学离子源(GC-NCI-MS)检测了11种PBDEs结果表明,电子垃圾拆解造成r比较严蘑的PBDEs污染,三溴-十溴联苯醚的浓度范围为51.1～2 685 pg.m-3,(平均值830Pg.m-3),而对照区由于制衣行业的影响也造成了一定程度的PBDEs污染,三溴～十溴联苯醚的浓度范围为1.00-98.9Pg.m-3(平均值28.7 Pg.m-3).在气/固分布的研究中发现,不同的PBDEs在气相和颗粒相的分布比例相差很大,从低溴至高溴PBDEs在气相中的比例呈降低趋势,而在颗粒相中的比例呈上升趋势.电子垃圾拆解区以五溴.联苯醚污染为主,占∑11PBDEs总量的54.3%;而十溴-联苯醚污染次之,占∑11PBDEs总最的23.8%,该污染特征进一步证实了该地区电子垃圾的来源,不仅来自亚洲国家,而且还来自欧美等国家.     

长江中游沉积物中多溴联苯醚的污染特征及风险评价

多溴联苯醚(PBDEs)具有高毒性和生物累积性,进入水体后易与有机质相结合,成为PBDEs污染物的重要归宿,对人类健康和水生生态系统造成潜在的危险.为揭示多溴联苯醚(PBDEs)在长江中游流域的污染现状,通过采集该地区流域内13个表层沉积物样品,采用高分辨气相色谱/高分辨质谱法(HRGC/HRMS)对沉积物中9种PBDEs同类物进行分析.结果表明该地区沉积物中9种PBDEs的含量范围(干重)约为46.1~326 pg·g~(-1),而BDE-99是其中最主要的贡献单体,平均贡献率约为51.6%;其次是BDE-47,约为19.6%.与国内外其他海域的研究相比,长江中游沉积物中PBDEs残留量处于较低水平.通过测定沉积物中总有机碳(TOC),研究结果发现PBDEs含量与TOC无明显的正相关关系.结合商值法对PBDEs的健康风险进行初步评估,结果表明,本研究中PBDEs对人体产生的健康风险较小.     

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.     

Uptake, translocation, and debromination of polybrominated diphenyl ethers in maize

Uptake, translocation and debromination of three polybrominated diphenyl ethers (PBDEs), BDE-28, -47 and -99, in maize were studied in a hydroponic experiment. Roots took up most of the PBDEs in the culture solutions and more highly brominated PBDEs had a stronger uptake capability. PBDEs were detected in the stems and leaves of maize after exposure but rarely detected in the blank control plants. Furthermore, PBDE concentrations decreased from roots to stems and then to leaves, and a very clear decreasing gradient was found in segments upwards along the stem. These altogether provide substantiating evidence for the acropetal translocation of PBDEs in maize. More highly brominated PBDEs were translocated with more difficulty. Radial translocation of PBDEs from nodes to sheath inside maize was also observed. Both acropetal and radial translocations were enhanced at higher transpiration rates, suggesting that PBDE transport was probably driven by the transpiration stream. Debromination of PBDEs occurred in all parts of the maize, and debromination patterns of different parent PBDEs and in different parts of a plant were similar but with some differences. This study for the first time provides direct evidence for the acropetal translocation of PBDEs within plants, elucidates the process of PBDE transport and clarifies the debromination products of PBDEs in maize.     

纳米零价铁降解水中多溴联苯醚(PBDEs)及降解途径研究

纳米零价铁(nZVI)法是多溴联苯醚(polybrominated biphenyl ethers,PBDEs)脱溴的有效方法.其反应动力学与途径对阐明PBDEs降解机制具有重要意义.本研究采用液相还原法制备的nZVI,在含有表面活性剂聚乙二醇辛基苯基醚(Triton X-100)的条件下,46 h内完全降解商用八溴联苯醚(octa-BDE)混合物中高溴代物质(7~9个溴代的同系物),其降解过程符合类一级反应动力学(pseudo-first-order)方程,平均降解速率常数(k)为0.106 h-1.本研究利用数量结构保留关系(quantatitivestructure retention relationship,QSRR)模型建立了在缺乏全系标准样品的情况下PBDEs降解产物的有效分析方法.通过混标中39种PBDEs各标准物在气相色谱中的保留时间,再以BDE47和BDE183的平均保留时间归一化后得到每种标准物的相对保留时间(relative retention time,RRT),再将数据库中的相对保留时间指数(relative retention time index,RRTI)与实验测得的相对保留时间拟合,得到QSRR模型.利用该模型对octa-BDE降解产物进行定性分析,推导得出nZVI对octa-BDE的还原降解途径.结果表明,nZVI对PBDEs的逐级脱溴过程中,间位的溴原子最容易被取代.     

婴儿脐带血和母亲血中多溴联苯醚的研究

为研究环境污染物多溴联苯醚(PBDEs)在人体的含量,采集了21对婴儿脐带和母亲静脉血样,用气相色谱和质谱法进行测定.结果表明,在所检测的7个PBDEs同系物(BDE-28,-47,-99,-100,-153,-154和-183)中,BDE-47和BDE-153为最主要的同系物.总PBDEs的含量分布于1.5~17ng/g;略高于挪威报道的含量水平,但低于瑞典和德国,远低于美国所报道的水平.      

海河流域14条河流表层沉积物中多溴联苯醚的分布特征

海河流域是我国受人类活动扰动强度最大的地区,为了解多溴联苯醚（PBDEs）在该流域的污染现状与分布特征,通过采集14条主要河流的48个表层沉积物样品,采用高分辨的GC-MS/MS技术对干燥后的沉积物中27种PBDEs进行分析.结果发现沉积物中PBDEs的平均含量范围为0.06～2.10 ng·g^-1;其中徒骇河沉积物...     

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.      

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.