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.      

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.     

典型废旧塑料处置地土壤中多溴联苯醚污染特征

选择我国北方典型废旧塑料处置地为研究区域,对土壤中21种PBDEs(多溴联苯醚)的含量、同系物组成和分布特征进行了研究. 结果表明,该区域土壤中w(∑PBDEs)为1.25~3673.41ng/g,平均值为749.29ng/g,其中w(BDE209)占w(∑PBDEs)的92%以上. 整体上,处置作坊内土壤中w(∑PBDEs)明显高于作坊间道路土壤和处置地周边土壤. 塑料中添加的十溴联苯醚工业品是该区域土壤中PBDEs的主要来源. 该区域土壤PBDEs污染水平与我国电子废物集中处置场地相当,高出我国一般城市及工业城市土壤1~3个数量级,是我国另一类PBDEs高污染区,其环境风险性应引起足够的重视.      

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.     

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.     

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.     

有机氯农药和多溴联苯醚在白洋淀鸭子组织中分布特征研究

利用气相色谱-质谱(GC/MS)方法定量分析了白洋淀鸭子肌肉、肝脏、脑组织中HCHs、DDTs和PBDEs的分布特征.结果表明,3种组织中HCHs和DDTs的含量范围分别为0.9～5.0 ng/g(以湿重计,下同)和0.3～2.8 ng/g,而PBDEs的含量范围是0.03～0.65 ng/g.统计分析鸭子不同组织中持久性卤代烃的含量差异,结果显示,DDTs和PBDEs的含量水平有较大差异(p0.05);而HCHs在3种组织中的含量差异不明显(p0.05).肝脏中DDTs和PBDEs的平均含量较高,分别为2.3和0.37 ng/g.在HCHs和DDTs同系物(代谢物)组成中,β-HCH在肝脏和脑组织中占主要地位,p,p′-DDE是DDTs的主要代谢产物;在PBDEs同系物中,BDE47和BDE99是鸭子组织中主要的组成部分.鸭子不同组织中HCHs、DDTs和PBDEs的组成模式反映了白洋淀仍然受到历史残留的有机氯农药污染;同时,来自白洋淀上游的工业污染很可能输入新型持久性有机污染物(PBDEs).     

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...     

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.      

Polybrominated diphenyl ethers in atmosphere and soil of a production area in China: Levels and partitioning

Polybrominated diphenyl ethers (PBDEs) were measured in atmosphere and soil samples taken in winter and summer at a PBDE production area of Laizhou Bay in China. The concentrations of P11PBDE were 0.017–1.17 ng/m3 in gaseous phase, 0.5–161.1 ng/m3 in particulate phase, and 73–2629 ng/g dry weight in soil samples. The PBDE congener pattern in the gaseous phase di ered from that in the particulate phase, and the PBDE congener pattern in the particulate phase was similar with that in soil. This demonstrated that there was little di erence with atmospheric particle-soil transfer e ciency among PBDE congeners. In addition, there were seasonal variations in percentages on particle for lower brominated congeners. The BDE-28 was mostly in the gaseous phase in summer (88.3%), whereas the average proportion of BDE-28 in gaseous phase in winter was 38.9%. Higher brominated congeners (i.e., BDE-206, BDE- 207, BDE-208, and BDE-209) were bound to the atmospheric particulate phase, and their potentials for long-range migration were mainly a ected by the environmental behavior of atmospheric particles. Results indicated that PBDE congeners in summer were closer to gas-particle partition equilibrium than in winter. Temperature should be considered the main factor causing nonequilibrium in winter.     

珠江三角洲及南海北部海域表层沉积物中多溴联苯醚的分布特征

自珠江三角洲和南海北部海域采集了66个表层沉积物样品,以研究该区域中PBDEs的含量、分布、来源和在环境中的迁移.研究结果表明,东江和珠江是PBDEs的高污染区,含量为12.7～7361ng·g-1,其中BDE209平均含量为1199ng·g-1,是目前世界上已报道沉积物中含量最高的区域之一.在几乎所有被分析的样品中BDE209都是最主要的同系物.东江和珠江的PBDEs主要来自东莞和广州的本地排放,而西江的PBDEs主要通过大气的传播输入.另一个高污染区澳门水域被验证是珠江三角洲水体环境中有机污染物的“汇”.     

北京冬季大气中多溴联苯醚的污染水平和分布特征

2010年11月至2011年2月利用聚氨酯泡沫(PUF)大气被动采样技术采集了北京市海淀、朝阳、丰台、石景山、昌平、大兴、通州等区域的大气样品,采用高分辨气相色谱/高分辨质谱联用法(HRGC/HRMS)分析了其中13种多溴联苯醚(PBDEs)同族体的污染浓度和分布特征.结果表明,北京大气中PBDEs总含量(Σ13PBDEs)为0.97~41.1pg/m3,平均值为7.85pg/m3.在区域分布规律方面呈现东南地区的采样点污染物浓度明显高于西北地区,工业地区和人口密集的商业地区明显高于郊区和背景对照区的分布特征.     

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。     

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.     

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.     

日用塑料制品中PBDEs的污染特征及其人体健康暴露风险

采用气相色谱/质谱联用仪和健康风险评价模型,研究了北京居民日常接触的典型日用塑料制品中PBDEs(多溴二苯醚)的赋存特征及其人体健康暴露风险. 结果表明:①塑料盆、垃圾桶、塑料垫、塑料板凳、拖把、热水壶壳、给水管、采暖管、排水管、拖鞋、收纳箱、文件框等12种日用塑料制品中w(∑₂₁PBDEs)为0.45~21.30 mg/kg,平均值为5.98 mg/kg. ②日用塑料制品中十溴二苯醚是主要的PBDEs同系物,w(十溴二苯醚)平均占w(∑₂₁PBDEs)的82.51%; 九溴二苯醚是次要PBDEs同系物,平均占9.76%;三溴~六溴二苯醚质量分数较低,平均占1.77%,日用塑料制品生产过程中添加含十溴二苯醚的废弃阻燃塑料是引起PBDEs污染的主要原因. ③成人通过呼吸吸入、皮肤接触和手-口3种途径摄入的PBDEs暴露量分别为295.77、44.29、0.00 pg/(kg·d),儿童通过3种途径的PBDEs暴露量分别为769.55、40.83、1.91 pg/(kg·d)表明呼吸吸入是主要暴露途径. ④日用塑料制品中PBDEs对成人和儿童的释放暴露非致癌危害熵分别为2.28×10-4和5.46×10-4,低于美国标准中可接受风险熵(1.0),表明日用塑料制品中PBDEs对人体的健康风险影响很小.      

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.     

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.     

工业园及电子垃圾区大气中的溴代阻燃剂(BFRs)

对广州市主要的工业园以及清远电子垃圾回收拆解园周边空气中溴代阻燃剂（BFRs）进行了分析.结果表明,两地区大气中均以多溴联苯醚（PBDEs）和十溴二苯乙烷（DBDPE）为主（城市地区占比分别为30.0%和68.0%,电子垃圾区分别为74.5%和22.8%）,其中PBDEs在城市地区和电子垃圾区的浓度中值分别为184和411pg/m³;DBDPE则分别为414和193pg/m³.在城市地区,PBDEs的浓度高值多出现在与机械、电子、装饰材料和汽车制造业有关的工业园,新型阻燃剂DBDPE高浓度则多在与机械和电子产品制造业相关的大气中,而1,2-二（2,4,6-三溴苯氧基）乙烷（BTBPE）可能受当地面源污染影响较大.城市地区低分子量的PBDEs的组成波动较大,与五溴联苯醚的禁用（直接排放减少）和来源复杂有关;而电子垃圾区低分子量PBDEs组成稳定,气-固相分配更接近平衡,说明来源较为单一.通过模型估算,城市地区的21个工业园每年约向空气中释放48.0kg的BDE209与163kg的DBDPE,4个电子垃圾拆解园每年约释放31.8kg的PBDEs与12.0kg的DBDPE.