Oxidative transformation of polybrominated diphenyl ether congeners (PBDEs) and of hydroxylated PBDEs (OH-PBDEs)

BACKGROUND, AIM, AND SCOPE: The historical and widespread use of polybrominated diphenyl ethers (PBDEs) as flame retardants in consumer products worldwide has caused PBDEs to now be regarded as pervasive environmental contaminants. Most recently, hydroxylated PBDEs (OH-PBDEs) and methoxylated PBDEs (MeO-PBDEs) have emerged as environmentally relevant due to reports of their natural production and metabolism. An important parameter for assessing the environmental impact of a chemical substance is persistence. By formulating the concept that persistence is the result of the substance's physicochemical properties and chemical reactivity, Green and Bergman have proposed a new methodology to determine the inherent persistence of a chemical. If persistence could be predicted by straightforward methods, substances with this quality could be screened out before large-scale production/manufacturing begins. To provide data to implement this concept, we have developed new methodologies to study chemical transformations through photolysis; hydrolysis, substitution, and elimination; and via oxidation. This study has focused on adapting an oxidative reaction method to be applicable to non-water soluble organic pollutants. MATERIALS AND METHODS: PBDEs and one MeO-PBDE were dissolved in tetrahydrofuran/methanol and then diluted in alkaline water. The OH-PBDEs were dissolved in alkaline water prior to reaction. The oxidation degradation reaction was performed at 50 degrees C using potassium permanganate as described elsewhere. The pH was maintained at 7.6 with disodium hydrogen phosphate and barium hydrogen phosphate, the latter also serving as a trapping agent for manganate ions. The oxidation reactions were monitored by high-performance liquid chromatography and reaction rates were calculated. RESULTS: The OH-PBDEs have very fast oxidative transformation rates compared to the PBDEs. The reaction rates seem to be primarily dependent on substitution pattern of the pi-electron-donating bromine substituents and of bromine content. There are indications that further reactions of OH-PBDEs, e.g., methylation to the MeO-PBDEs, decrease the oxidation rates, and thereby generate more persistent substances. DISCUSSION: The resistance of PBDEs to oxidation, a major degradation pathway in air, should be further investigated, since these compounds do undergo long range transport. With slight modifications, the original method has been adapted to include a larger variety of chemical substances, and preliminary data are now available on the oxidative transformation rates for PBDEs and of OH-PBDEs. CONCLUSIONS: The original oxidation degradation method can now include non-water soluble compounds. This modification, using low concentrations of test chemicals, allows us to measure oxidative transformation rates, for some of the lower brominated DEs, data that can be used to assess their persistence in future model calculations. Oxidative transformation rates for PBDEs are slow compared to those for the OH-PBDEs. This suggests that OH-PBDEs, when released into the environment, undergo faster oxidative metabolism and excretion than the PBDEs. RECOMMENDATIONS AND PERSPECTIVES: To evaluate the modified method, more degradation reactions with non-water soluble compounds should be investigated. Recent studies show that OH-PBDEs are present in rats and in humans and, because of their activity as endocrine disruptors, determining their subsequent environmental fate is of importance. The resistance of PBDEs to oxidative degradation should be acknowledged as of possible future concern. Several other compound classes (such as polychlorinated biphenyls (PCBs), hydroxylated polychlorinated biphenyls (OH-PCBs), and pharmaceuticals) need to be subjected to this screening method to increase the database of transformation rates that can be used with this model.     

新制和老化微塑料对多溴联苯醚的吸附

以2,2′,4,4′-四溴联苯醚(BDE-47)为多溴联苯醚(PBDEs)代表化合物,研究了新制和紫外光照射老化的聚乙烯(PE)和聚苯乙烯(PS)微塑料对BDE-47的吸附动力学和等温吸附,分析了盐度和溶解性有机质等环境因素对其吸附的影响,采用扫描电镜、 X射线衍线和全反射红外光谱对新制和老化微塑料进行了表征,探讨了新制和老化微塑料对PBDEs的吸附机制.结果表明,新制与老化PE的主要吸附模式为表面吸附和外液膜扩散,新制与老化PS主要受表面吸附影响.Freudlich模型的拟合度最好,表明微塑料对于BDE-47的吸附均表现为多相多层的不均匀吸附过程.BDE-47在新制PE、老化PE、新制PS和老化PS上的平衡吸附量分别为3.72、 3.76、 6.04和3.46 ng·g~(-1).老化PE与新制PE相比,其平衡吸附量没有变化;但老化PS与新制PS相比,平衡吸附量降低了42.38%.外液膜扩散的分配作用是影响PE吸附的主要机制.与新制PS相比,结晶度和表面含氧官能团的增加,导致老化PS平衡吸附量降低.盐度对BDE-47在新制和老化微塑料上的吸附影响不大,但溶解性有机质的存在会降低新制和老化微塑料对BDE-47的吸附.     

电子废弃物拆解厂排放多溴联苯醚和重金属的吸入性健康风险评估

以江苏某典型正规电子废弃物拆解厂为研究对象,在实测排放源数据的基础上,采用Calpuff大气扩散模式模拟其排放的多溴联苯醚(PBDEs)和重金属Pb、Cd大气浓度的区域与局部空间分布,进而对所排放PBDEs、Pb和Cd导致的健康风险进行评估.研究结果表明:在气象条件最为不利的情景下,污染物在东北、西南方向污染物扩散行为显著.PBDEs、Pb和Cd在区域空间范围的大气浓度最大值分别为3×10~(-6)、8.6×10~(-5)和3.6×10~(-6)μg·m~(-3),而局部范围的浓度则会高出一个数量级;其中BDE-209对于PBDEs的大气浓度贡献可达77%.在局部范围内,以HQ表达的PBDEs和Pb健康风险数值均在10~(-3)以下,非致癌健康风险极低;BDE-209和Cd的终生致癌风险最大值为1.10×10~(-12)与6.32×10~(-7),致癌风险可以忽略.该评估表明,正规操作的电子废弃物拆解厂的大气污染物不会对公共健康造成不可控风险.     

氮磷浓度对东海原甲藻优势种群吸附BDE28和BDE47的影响

以东海原甲藻为优势种群的浮游微藻作为研究对象,在不同氮浓度(0、128、512μmol·L-1)和磷浓度(0、8、32μmol·L-1)下培养,研究了氮、磷浓度对东海原甲藻优势种群生化组成和吸附2,4,4’-三溴联苯醚(BDE28)和2,2’,4,4’-四溴联苯醚(BDE47)的影响,分析了东海原甲藻优势种群对BDE28和BDE47的吸附量与生化组成的相关性.结果表明,氮浓度为0μmol·L-1时,单位细胞对BDE28和BDE47的吸附量分别为2.2 ng·(106cells)-1和2.9 ng·(106cells)-1,是氮为128μmol·L-1和512μmol·L-1浓度的1.3～1.9倍.不同氮浓度之间单位体积藻液吸附量和对BDE28和BDE47的吸附百分数均没有显著差异,单位体积藻液吸附量范围为0.160～0.184 ng·mL-1,吸附百分数为80.2%～92.1%.磷浓度为0μmol·L-1时,单位细胞BDE28和BDE47的吸附量分别为7.6 ng·(106cells)-1和8.4 ng·(106cells)-1,是磷为8μmol·L-1、32μmol·L-1浓度时的5.4～6倍,单位体积藻液吸附量和吸附百分数在不同磷浓度间未出现显著差异,单位体积藻液的吸附量为0.167～0.194 ng·mL-1,吸附百分数为80.2%～93.2%.相关性分析表明,氮浓度与单位细胞BDE28和BDE47的吸附量呈负相关,磷浓度与单位体积吸附量和吸附百分数呈正相关;同时,吸附量与总脂呈正相关关系.氮、磷浓度导致东海原甲藻优势种群细胞的生化组成发生变化,进一步引起对BDE28和BDE47吸附的变化.     

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.     

台州电子垃圾拆解区水和沉积物中多溴联苯醚污染特征与生态风险

以台州某电子垃圾拆解工业园为圆心,在半径为16 km的范围内,由近及远设计了C(3 km)、S(5~10 km)和R(10~16km)三圈共30个采样点,研究了该区域水及沉积物中多溴联苯醚(PBDEs)的污染特征与生态风险.结果表明,水中PBDEs含量为9.4~57.2 ng·L~(-1),平均值为25.9 ng·L~(-1);沉积物中PBDEs含量为3.7~38 775 ng·g~(-1),平均值为2 779 ng·g~(-1);BDE-209均为主要成分.水及沉积物中PBDEs含量的空间分布态势均为:C圈S圈R圈,沉积物中PBDEs含量和离工业园区中心的距离呈极显著负相关(P0.01).与国内外其它地区相比,该调查区PBDEs污染较为严重,电子垃圾拆解是PBDEs污染的主要来源.经推算,该区域近40年的拆卸活动向该地输入的PBDEs总量达30.7 t,其中BDE-209为28.9 t.采用商值法对PBDEs进行初步的生态风险评估表明,拆解核心区(半径为1.5 km)沉积物中五溴联苯醚(Penta-BDEs)的污染程度已达高风险等级,对该地区的生态安全和人群健康可能造成严重影响.     

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.     

Development of indirect competitive fluorescence immunoassay for 2,2′,4,4′-tetrabromodiphenyl ether using DNA/dye conjugate as antibody multiple labels

An indirect competitive fluorescence immunoassay using a DNA/dye conjugate as antibody multiple labels was developed on 96-well plates for the identification and quantification of 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47) in aqueous samples. A hapten, 2,4,2′-tribromodiphenyl ether-4′-aldehyde, was synthesized, and was conjugated to bovine serum albumin to form a coating antigen. Specific recognition of the antigen by anti-PBDE antiserum was confirmed by a surface plasmon resonance measurement. In the immunoassay, the coating antigen was adsorbed on a 96-well plate first, and a sample, antiserum and biotinylated goat anti-rabbit secondary antibody were then added and reacted sequentially. A biotinylated, double-stranded DNA with 219 base pairs was attached to the secondary antibody by using streptavidin as a molecular bridge. In situ multiple labeling of the antibody was accomplished after addition of a DNA-binding fluorescent dye, SYBR Green I. The working range of the immunoassay for the BDE-47 standard was 3.1-390 μg/L, with an IC₅₀ value of 15.6 μg/L. The calculated LOD of the immunoassay is 0.73 μg/L. The immunoassay demonstrated relatively high selectivity for BDE-47, showing very low cross-reactivity (< 3%) with BDE-15, BDE-153 and BDE-209. With a spiked river water sample containing 50 μup g/L BDE-47, quantification by the immunoassay was 41.9 μg/L, which compared well with the standard GC-ECD method (45.7 μg/L). The developed immunoassay provides a rapid screening tool for polybrominated diphenyl ethers in environmental samples.     

办公室内颗粒物载带溴系阻燃剂的人体呼吸暴露

通过对封闭房间、通风房间和室外环境中大气颗粒物分级采样,分析了大气颗粒相上溴系阻燃剂(BFRs)的负荷水平,并对目标污染物在颗粒相的粒径分布特征及其控制因素进行研究.以此为基础,采用人体呼吸暴露数值模型,估算了大气颗粒相载带BFRs在人体呼吸道各部位的暴露量.研究表明,在室内外大气颗粒相样品中,多溴联苯醚(PBDEs)以BDE-209为主,而六溴环十二烷(HBCDs)则以α-HBCD为主;整体上,室内大气颗粒物中BFRs高于室外的相应浓度,其浓度水平与电子垃圾处理厂周边大气颗粒相目标物浓度近似,高于中国其它地区室内外大气颗粒相载带BFRs浓度.粒径分布分析结果显示,PBDEs在封闭房间中主要分布在0.4~0.7μm和5.8~9.0μm的粒径上,呈现双峰形式,而在通风和室外环境中则主要分布在4.7~10.0μm的大颗粒上;HBCDs则主要分布在大颗粒上.呼吸暴露估算结果表明,在封闭状态下的办公室内,呼吸道各部位经由呼吸摄入的总PBDEs和HBCDs暴露量分别为22.56~1 503 pg·(h·kg)-1和0.09~9.25 pg·(h·kg)-1;而在自然通风状态下的办公室内,上述暴露量则分别为13.89~601.1 pg·(h·kg)-1和0.07~1.75 pg·(h·kg)-1.显然,自然通风有利于室内污染物向室外扩散,从而减小了室内呼吸暴露风险.通过比较,可以看出呼吸摄入BFRs暴露量小于灰尘摄入的暴露量,呼吸不是BFRs室内人体暴露的主要途径.     

废弃日用品塑料中多溴联苯醚浸出特征及地下水健康风险

选择典型废弃日用品塑料,对特征处置场景下其PBDEs的浸出特征及健康风险进行了评价.结果表明,日用品塑料在硫酸/硝酸、醋酸和腐殖酸溶液中达到溶出平衡时,∑21PBDEs释放量分别为20.00、63.65、125.60μg·kg-1,均以BDE209为主.进入生活垃圾填埋场的释放量高于堆存和简易填埋过程,在最不利条件下距填埋场下游500 m处地下水中PBDEs最大浓度为39.67μg·L-1,居民饮用地下水产生的非致癌风险指数为2.11×10-1,其中十溴代物(BDE209)的非致癌风险指数为1.85×10-1,均小于美国标准中非致癌的可接受风险水平(1.0),表明废旧日用品塑料可进入生活垃圾填埋场处置.