Levels and bioaccumulation of organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDEs) in fishes from the Pearl River estuary and Daya Bay, South China

Fifty fish samples were collected from the Pearl River estuary (PRE) and Daya Bay, South China and were analyzed for DDTs, HCHs, chlordanes and polybrominated biphenyl ethers (PBDEs). Except the high concentrations of DDT observed in fishes, the concentrations of HCHs, chlordanes and PBDEs were low when compared to other regions. BDE-47 was the predominant PBDE congener and the BDE-209 concentrations were relatively low, despite its high concentration in surface sediments. The absence of significant increase of DDT, HCH, chlordane and PBDE concentrations towards higher delta15N values, as well as the lack of a significant correlation (p<0.1) between log concentrations (lipid normalized) and delta15N, may indicate a weak biomagnification of these chemicals in the food webs. Good agreement was observed between their concentrations and lipid contents of the organisms. Bioconcentration was suggested to be responsible for the accumulation of OCPs and PBDEs in the lower trophic organisms in the studied subtropical waters.     

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).     

多溴联苯醚与四溴双酚A的生物代谢研究进展

分析了生物体内多溴联苯醚（PBDEs）和四溴双酚A（TBBPA）的来源和分布,综述了PBDEs和TBBPA在生物体内发生还原代谢和氧化代谢的研究进展,从体内原位代谢和体外模拟代谢2个方面探讨了PBDEs和TBBPA的生物代谢机制、代谢途径及代谢中可能涉及的代谢酶,指出今后应进一步深入开展PBDEs和TBBPA的生物积累和代谢产物的定量分析的研究。     

基于间接竞争抑制ELISA的2,2',4,4'-四溴联苯醚检测方法

针对现有的检测多溴联苯醚（PBDEs）方法中存在的样品处理繁复、样品检测耗时以及费用昂贵等不足,开展了针对此类物质中代表性化合物2,2',4,4'-四溴联苯醚（BDE-47）的间接竞争抑制酶联免疫吸附法（ELISA）的检测分析研究,并与气相色谱-质谱检测法、酶联免疫吸附分析试剂盒检测法进行对比分析。研究表明：间接竞争抑制ELISA法测定BDE-47的IC50值为0.11 mg·L-1,定量限为0.04 mg·L-1,检出范围为0.01~0.50 mg·L-1。该方法在满足复杂基质中微量目标物检测灵敏度及重现性要求下,具有检测更快捷、更经济实用的特点,宜适用于大批量此类环境样品的初期筛查。     

Detection of a Toxic Product Released by a Polyurethane-Containing Film Using a Composting Test Method Based on a Mineral Bed

The degradation of a film containing a 4,4diphenyl methane diisocyanate (MDI) poly(€-caprolactone)-based polyurethane was followed in a test system based on a mineral solid bed designed to facilitate analysis of break-down products released under composting conditions. The use of a mineral solid bed can help extraction and analytical procedures which could be hindered by the heterogeneous nature of compost. The fermentation conditions are typical of the composting environment and generate a powerfully degradative environment. The film fully disintegrated within 30 days of treatment. Analysis on the mineral bed extracts showed that: (i) about 40% of the initial polyurethane was still present in the bed extracts; (ii) this residue was strongly degraded in the poly(€-caprolactone) part, while the urethane part was almost completely recovered (from 80 to 95%, according to the measurement method); (iii) 4,4 diamino diphenyl methane (MDA), a very dangerous product of MDI, was released during biodegradation. The results indicate that a mineral bed can be employed to study degradation and metabolites formation in solid phase fermentation and that the MDI-based polyurethanes are not susceptible of a full degradation during composting and maintain the potential of a slow release of MDA into the environment after soil application.     

Brominated flame retardants and polychlorinated biphenyls in fish from the river Scheldt, Belgium

Levels of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), and polychlorinated biphenyls (PCBs) were measured in several fish species originating from the river Scheldt (Belgium). Five sampling locations were chosen in a highly industrialized area along the river, while two ponds in the vicinity of the river served as reference sites. The present study is a follow-up of a survey performed in 2000 which reported extremely high levels of PBDEs and HBCDs in eel (Anguilla anguilla) collected from the same region (Oudenaarde, Flanders). The sum of tri- to hepta-BDE congeners (2270+/-2260 ng/g lipid weight (lw), range 660-11500 ng/g lw) and total HBCDs (4500+/-3000 ng/g lw, range 390-12100 ng/g lw) were one order of magnitude higher than levels usually reported from freshwater systems, indicating the presence of point sources. In most samples, levels of total HBCDs were higher than those of PBDEs, probably due to the high density of factories using HBCD as an additive brominated flame retardant (BFR). The high values of HBCDs were confirmed by both gas- and liquid-chromatography-mass spectrometry. Although BFR levels were between the highest ever reported in freshwater ecosystems, PCBs could be detected at even higher concentrations (16000+/-14300 ng/g lw, range 3900-66600 ng/g lw), being among the highest levels recorded in Belgium. The inter-sampling site variation of PBDEs, HBCDs and PCBs was comparable. All locations presented similar PBDE congener profiles, with BDE 47 being the dominant congener, followed by BDE 100, BDE 99 and BDE 49, probably originating from the former use of the penta-BDE technical mixture. In order to estimate the impact of these point sources on human exposure, we further focussed on eels which showed a considerable decrease in the PBDE and HBCD levels between 2000 and 2006. Due to the wide span in concentrations between the different sampling locations, a variable contribution to the total human exposure through local eel consumption was estimated. The calculated daily intake ranged from 3 ng to 330 ng PBDEs/day for normal eel consumers, but was as high as 9800 ng PBDEs/day for anglers, which may be considered at risk.     

多溴联苯醚与雌激素受体作用的CoMFA／CoMSIA研究

以多溴联苯醚类化合物的ER亲合力为生物活性指标，运用基于配体结构信息的CoMFA／CoMSIA方法，模拟该类化合物与雌激素受体的结合作用机制，结果表明，这些结构类似化合物中存在的不同受体作用模式，需要结合基于受体功能区结构的QSAR方法进一步探讨。     

乙醇/PODE/柴油燃料及喷油参数对柴油机燃烧和排放影响

在一台六缸四冲程高压共轨柴油机上开展了乙醇/聚甲氧基二甲醚（PODE）/柴油混合燃料对内燃机燃烧和排放影响的试验研究.结果表明,在转速为1137 r·min^-1,转矩为735 N·m的工况条件下,随着掺混PODE和乙醇比例的增大,双峰放热越来越明显,扩散燃烧速率增大,有效燃油消耗率增大,有效热效率降低,但降低幅度小于1%,其中,DPE5（PODE体积分数为20%,乙醇体积分数为5%）的有效热效率与D100（纯柴油）基本相当.提前主喷时刻、增大喷油压力均使有效热效率增大,CO和碳烟排放降低,NO_x排放增大,而对降低HC排放的影响较小.相比D100,混合燃料可降低CO、HC、碳烟排放,在低喷油压力和较晚主喷时刻下,对碳烟的减排效果更为显著,最大降幅分别为85.5%（主喷时刻-1℃ A ATDC、喷油压力900 bar）和82.9%（主喷时刻-3℃ A ATDC、喷油压力600 bar）,但不同混合燃料间的排放差异较小.综上所述,重型柴油机使用乙醇/PODE/柴油混合燃料可在热效率相当的前提下对排放有较大改善.     

电脑散热风扇灰尘中多溴二苯醚的污染特征和环境健康风险评价

以多溴二苯醚（PBDEs）为阻燃剂的电器的使用是室内灰尘中PBDEs的一个重要来源,其中,电脑是人们日常使用时间较长的电子设备之一.采集了主要电脑厂商过去十年间生产的笔记本和台式机内置散热风扇处的灰尘,研究了灰尘中PBDEs的含量、组成、来源及人体暴露量,并评价了其环境健康风险.结果表明,各主流品牌电脑均有部分样品∑PBDEs含量较高,显示其可能都曾使用PBDEs作为阻燃剂.组成上,笔记本和台式机均以BDE-209为主（笔记本：89.4%,台式机：93.3%）.53%的笔记本（19/36）和台式机（10/19）灰尘中∑PBDEs与室内降尘对照样的比值>1.其中,8台笔记本和2台台式机的比值>10（77±99和53±61）,表明部分电脑的组件中添加了PBDEs,其运行使用是室内环境中PBDEs的来源之一.人体通过灰尘摄入途径暴露于电脑释放源∑PBDEs的非致癌风险（HI）和BDE-209的致癌风险（CR）均比呼吸暴露途径高1~2个数量级,显示灰尘摄入在人体对电脑等室内PBDEs释放源的暴露中扮演主要角色.各暴露途径的暴露量均低于RfD,HI > 1和CR > 10^-6（可接受致癌风险的上限）的超标概率均小于0.000%,显示人体通过灰尘摄入和呼吸途径暴露于电脑释放源PBDEs的环境健康风险低,但由于人体对PBDEs暴露途径的多样性,其叠加后的暴露量和健康风险仍需进一步研究评估.BDE-209是我国人体经灰尘摄入和呼吸途径暴露于电脑释放源PBDEs的首要同系物.主要低溴BDE的暴露风险随溴代数降低而增加,BDE-209漫长复杂的自然降解所产生低溴BDE的环境健康风险值得继续关注.