污水及污泥中多溴联苯醚的研究进展

多溴联苯醚是一类溴代阻燃剂,包括三种主要的工业产品,五溴、八溴、十溴联苯醚.该物质曾广泛使用于电子、材料、家具等产品中.研究表明,在这些产品的生产、使用和处理过程中均会释放多溴联苯醚到周边环境中.多溴联苯醚具有持久性、可生物富集和长距离迁移,对人体和身体系统存在潜在危害,是一类新兴污染物.目前,这类物质中的部分化合物已...     

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。     

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.     

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。     

A/O工艺处理生活污水中PBDEs分布特征

文章对A/O法中的各工序污水以及污泥中PBDEs的含量以及分布状况作了比较系统的分析,采集了水体、污泥共56个样品,经过萃取、净化、浓缩之后利用GC/MS仪器进行分析测定。讨论了PRDEs的污染情况,并对PBDEs与水中常规参数作了初步分析。结果显示,在所采集的样品中均检出了PBDEs,经污水处理后PBDEs主要残留于...     

海洋生物样品中多溴联苯醚和多溴联苯的分析研究

将气相色谱-负离子化学源／质谱法(GC-NCI/MS)应用于分析海洋生物中五种多溴联苯醚(PBDEs)和五种多溴联苯(PBBs)残留.样品以正己烷／丙酮(1:l,v/v)作为提取剂,采用超声萃取法,提取液经酸性硅胶和中性硅胶层析柱净化和正己烷洗脱后,以PCB-103为内标物和GC-NCI/M的选择离子监测方式(SIM)...     

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.      

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∑<     

多溴联苯醚降解技术的研究进展

多溴联苯醚(PBDEs)是一类环境中广泛存在的全球性有机污染物。由于其环境持久性、毒性和潜在的生物蓄积性而备受关注,如何处理环境中的PBDEs已成为当前研究的热点问题之一。该文综述了国内外对PBDEs不同处理方法的最新研究进展,重点探讨了生物降解和光降解两大方面进展,并对目前存在问题及进一步的研究方向进行了展望。     

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.     

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.     

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.     

Concentrations and sources of an emerging pollutant, decabromodiphenylethane (DBDPE), in sewage sludge for land application

The presence of an emerging brominated flame retardant, decabromodiphenylethane (DBDPE), has been confirmed in Spanish sewage sludge. Thirty one samples from different urban wastewater treatment plants (WWTPs) were analyzed for this brominated flame retardant. DBDPE was positively identified and quantified in all samples at lower concentrations (47.0 ± 29.7 ng/g dry weight (dw); mean ± SD) than those obtained for decabromodiphenyl ether (BDE-209) (290 ± 236 ng/g dw; mean ± SD) in a previous study. Influence of the WWTP characteristics in the pollutant levels was evaluated. No significant correlations were obtained between DBDPE concentrations and the population or sewage sludge production rate associated with the plants, neither wastewater treatment method. Sources of DBDPE in the sludge were also evaluated. Data indicate a common origin for DBDPE and BDE-209, which may be related to leaching processes during the use and disposal of consumer products containing these chemicals. Nevertheless, DBDPE contents are not influenced by industrial activities, which suggests that the infusion of DBDPE commercial mixture is not a source of this chemical into the environment, and indicates that the use of DBDPE in the Spanish industry is still low compared to deca-BDE.     

珠江三角洲沉积物钻孔中多溴联苯醚的垂直变化规律研究

采用GC/MS分析方法测定了珠江三角洲水体5个钻孔(分别采自东江东莞段、珠江广州段、北江中段、西江入海口和顺德段)80个样品中10种多溴联苯醚(PBDEs,BDE209和∑9BDEs)的含量,对其沉积规律进行研究和探讨.∑9BDEs含量范围为1.54~94.8 ng·g-1,平均值为15.4 ng·g-1.BDE209含量范围为14.4~588 ng·g-1,平均值为136 ng·g-1,占总PBDEs含量的70%以上.钻孔中PBDEs含量从底部到表层呈现上升趋势,表明近年来珠江三角洲PBDEs环境排放仍在增加.5个钻孔中低溴代∑9BDEs从表层至底部逐渐增加,而高溴代∑9BDEs逐渐减少,意味着钻孔中可能存在脱溴降解行为.     

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.     

氮浓度对牟氏角毛藻富集2,2',4,4',5-五溴联苯醚的影响

以牟氏角毛藻为研究对象,采用半连续培养法,研究了不同氮浓度条件下牟氏角毛藻对2,2',4,4',5-五溴联苯醚富集.结果表明,牟氏角毛藻对多溴联苯醚的富集与氮营养条件有关,随着氮浓度的增加,富集量和富集因子均呈降低趋势.氮浓度为0,128,512μmol/L条件下,单位藻细胞的富集量分别为2.84,2.38,1.91ng/106 cells,单位体积藻液富集量分别为0.19,0.16,0.12ng/mL.富集因子的变化趋势相似,氮为0μmol/L时单位总脂富集因子(BCFlipid)为238.19×104 (ng/g)/(ng/mL),随着氮浓度的升高,BCFlipid明显降低.相关性分析表明,单位体积藻液富集量、单位藻细胞富集量和BCFlipid等均与氮浓度呈现显著的负相关关系(r>-0.8, P0.8, P<0.05).     

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.     

多溴联苯醚及其衍生物在土壤中的分布、转化和生物效应研究进展

多溴联苯醚（polybrominated diphenyl ethers,PBDEs）作为一种良好的溴系阻燃剂被大量地添加到工业产品中,随着产品的使用、回收和废弃处理会进入各种环境介质中,是一类分布十分广泛的持久性有机污染物.PBDEs的衍生物羟基化多溴联苯醚（hydroxylated polybrominated diphenyl ethers,OH-PBDEs）和甲氧基化多溴联苯醚（methoxylated polybrominated diphenyl ethers,MeO-PBDEs）,由于具有比母体化合物更大的毒性效应和更复杂的环境行为也受到人们广泛关注.通过对PBDEs及其衍生物在土壤中的分布特征、转化规律及生物效应研究的最新进展进行综述发现,PBDEs在土壤中的分布浓度随离工业区距离增加而减小,且大多数污染地区土壤中以高溴代PBDEs为主,偏远地区土壤中则以低溴代PBDEs为主.进入土壤的PBDEs在动物、植物体内及微生物作用下均可发生脱溴代谢转化产生低溴代PBDEs,也可发生羟基化生成OH-PBDEs和甲氧基化生成MeO-PBDEs,与此同时,OH-PBDEs和MeO-PBDEs之间也会发生相互转化.PBDEs及其衍生物作为一种环境内分泌的干扰物对大部分的植物、动物都有显著的毒性效应,对植物而言能够抑制植物种子萌发、幼苗生长、损伤细胞结构以及影响植物代谢活动等;对动物而言能够影响动物的内分泌功能、妨碍动物生殖系统的发育以及对神经系统产生毒性等.目前,关于PBDEs及其衍生物在土壤生态系统中环境化学行为和生态毒性的报道十分有限,探讨土壤中PBDEs的代谢转化过程和毒性效应可为全面深刻地认识PBDEs的环境行为和潜在生态风险提供科学参考.      

Role of sorbent surface functionalities and microporosity in 2,2’,4,4’-tetrabromodiphenyl ether sorption onto biochars

The study provides insight into the combined effect of sorbent surface functionalities and microporosity on2,2 ′,4,4 ′-tetrabromodiphenyl ether (BDE-47) sorption onto biochars. A series of biochars prepared underdifferent conditionswere used to test their sorption behaviorswith BDE-47. The extents of sorption behaviorswere parameterized in terms of the single-point adsorption equilibrium constant (Koc ) at three equilibrium concentration (C e ) levels (0.001Sw (solubility), 0.005Sw , and 0.05Sw )whichwasdetermined using the Freundlich model. To elucidate the concentration-dependentdominant mechanisms for BDE-47 sorption onto biochars, K ocwas correlatedwith four major parameters using multiple parameter linear analysis accompaniedwith significance testing. The results indicated that at low concentration (Ce = 0.001Sw ), the surface microporosity term,which represented a pore-filling mechanism, contributed significantly to this relationship,while as concentrationwas increased to higher levels, surface functionality related to surface adsorption began to take thedominant role,whichwas further confirmed by the results of Polanyi-based modeling. Given the above results, adual mode model based on Dubinin-Radushkevich andde Boer-Zwikker equationswas adopted to quantitatively assess the changes of significance of surface adsorption aswell as that of pore fillingwith sorption processdevelopment. In addition, UV spectra of four typical aromatic compoundswhich represented the key structural fragments of biochars before and after interactionswith BDE-47were analyzed todetermine the active functional groups and supply complementary evidence for thedominant interaction force for surface adsorption, based onwhich π-π electron-donor-acceptor interactionwas proposed to contribute greatly to surface adsorption.