Polybrominated diphenyl ethers (PBDEs) and alternative brominated flame retardants in air and seawater of the European Arctic

The spatial distribution of polybrominated diphenyl ethers (PBDEs) and several alternative non-PBDE, non-regulated brominated flame retardants (BFRs) in air and seawater and the air-seawater exchange was investigated in East Greenland Sea using high-volume air and water samples. Total PBDE concentrations (Ó₁₀PBDEs) ranged from 0.09 to 1.8 pg m⁻³ in the atmosphere and from 0.03 to 0.64 pg L⁻¹ in seawater. Two alternative BFRs, Hexabromobenzene (HBB) and 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE), showed similar concentrations and spatial trends as PBDEs. The air-seawater gas exchange was dominated by deposition with fluxes up to −492 and −1044 pg m⁻² day⁻¹ for BDE-47 and DPTE, respectively. This study shows the first occurrence of HBB, DPTE and other alternative flame retardants (e.g., pentabromotoluene (PBT)) in the Arctic atmosphere and seawater indicating that they have a similar long-range atmospheric transport potential (LRAT) as the banned PBDEs.     

地下水浅埋区某加油站特征污染物空间分布简

加油站渗漏污染地下水已经是一个世界性的问题。由于浅埋区加油站储罐与地下水密切接触,更加剧储罐的腐蚀。为揭示加油站渗漏的典型污染物石油烃（TPH）、苯系物（BTEX）、萘和甲基叔丁基醚（MTBE）在该水文地质条件下的迁移变化,在浅埋区某加油站开展了平、枯、丰水期的地下水监测工作。在水平分布上,TPH、BTEX、萘基本相似,均在加油岛附近形成高浓度区,而MTBE则更易随地下水流动而迁移,呈现出不同的污染晕。在垂直分布上,地下水的水位变动是污染物浓度分布的主要影响因素。     

新型冠醚交联壳聚糖的吸附性能

合成３,５－二叔丁基－二苯并１４－冠－４双氯代乙酸酯冠醚,然后使之与壳聚糖发生反应制备成壳聚糖－３,５－二叔丁基－二苯并１４－冠－４双乙酸酯冠醚,经元素分析,ＦＴ－ＩＲ红外光谱分析和Ｘ－射线粉末衍射分析表征了结构。     

甲基叔丁基醚(MTBE)在不同粘性土壤中的吸附特性

土壤对有机物的吸附是污染土壤及地下水原位修复技术中的重要参数.通过静态间歇吸附实验研究了甲基叔丁基醚(MTBE)在不同粘性土壤中的吸附特性.结果表明,MTBE在粘性土壤中的吸附行为均可用线性方程很好描述,粘粒是土壤对MTBE吸附的主要影响因素,吸附常数与土壤粘粒含量呈y=4.382×10-3x-0.817 ×10-3直线关系.对不同温度下的吸附数据分析发现,粘性土壤对MTBE的平衡吸附量随温度的升高而降低,由吸附热力学推导可得等量吸附焓变△H与平衡吸附量无关,且△H＜0,表明该吸附为故热过程.     

Ah Receptor Agonists in UV-exposed Toluene Solutions of Decabromodiphenyl Ether (decaBDE) and in Soils Contaminated with Polybrominated Diphenyl Ethers (PBDEs) (9 pp)

Goal, Scope and Background The use of polybrominated diphenyl ethers (PBDEs) as flame retardants increases the risk for emissions of other brominated compounds, such as polybrominated dibenzodioxins (PBDDs) and dibenzofurans (PBDFs). The large homology in structure of PBDD/Fs and mechanism of toxic action, i.e. the capacity to activate the Ah receptor (AhR) pathway, compared to their well-studied chlorinated analogues, justifies a raised concern to study the environmental levels and fate of these compounds. Decabromodiphenyl ether (decaBDE) is the most widely used PBDE today. Studies on photolytic debromination of decaBDE in organic solvents have shown debromination of decaBDE, as well as formation of PBDFs. However, little is known about the transformation mechanisms and there are only scarce data on photoproducts and PBDE transformation in environmentally relevant matrices. In this study, mechanism-specific dioxin bioassays were used to study photolytic formation of AhR agonists in toluene solutions of decaBDE. In addition, the influence of irradiation time and UV-light wavelength on the formation was studied. PBDE congener patterns and presence of PBDD/Fs were analysed. Further, AhR agonists were analysed in agricultural soils contaminated with PBDEs. Soils were also exposed to UV-light to study changes in AhR agonist levels. Methods Toluene solutions of decaBDE were irradiated using three different spectra of UV-light, simulating UV-A (320-400 nm), UV-AB (280-400 nm), and UV-ABC (250-400 nm). Additionally, decaBDE solutions were exposed to narrow wavelength intervals (10 nm bandwidth) with the central wavelengths 280, 290, 300, 310, 320, 330, 340, 350, 360 nm. AhR agonists in decaBDE solutions were analysed with two different bioassays, the chick embryo liver-cell assay for dioxins (Celcad) and the dioxin responsive, chemically activated luciferase expression assay (DR-Calux). Also, the decaBDE solutions were analysed with LRGC-LRMS to obtain PBDE congener patterns for breakdown of decaBDE, and with HRGC-HRMS, for presence of PBDD/Fs. Four soils were exposed to UV-AB light, under both dry and moist conditions. Levels of AhR agonists in soil extract fractions, before and after UV-exposure, were analysed with the DR-Calux. Results and Discussion Significant levels of photoproducts able to activate the AhR pathway, up to 31 ng bio-TEQ/ml, were formed in UV-exposed decaBDE solutions. The transformation yield of decaBDE into AhR agonists was estimated to be at the 0.1%-level, on a molar basis. The net formation was highly dependent on wavelength, with the sample irradiated at 330 nm showing the highest level of dioxin-like activity. No activity was detected in controls. PBDE analysis confirmed decaBDE degradation and a clear time-dependent pattern for debromination of PBDE congeners. AhR agonist effect in the recalcitrant fractions of the soils corresponded to the levels of chemically derived TEQs, based only on chlorinated dioxin-like compounds in an earlier study. It was concluded that no significant levels of other AhR agonists, e.g. PBDFs, were accumulated in the soil. UV-light caused changes in AhR-mediated activity in the more polar and less persistent fractions of the soils, but it is not known which compounds are responsible for this. Recommendations and Perspective . The laboratory experiments in this study show that high levels of AhR agonists can be formed as photoproducts of decaBDE and it is important to elucidate if and under which conditions this might occur in nature. However, soil analysis indicates that photoproducts of PBDE do not contribute to the accumulated levels of persistent dioxin-like compounds in agricultural soil. Still, more data is needed to fully estimate the environmental importance of PBDE photolysis and occurrence of its photoproducts in other environmental compartments. Analysis with dioxin bioassays enabled us to gather information about photoproducts formed from decaBDE even though the exact identities of these compounds were not known. Conclusion Bioassays are valuable for studying environmental transformation processes like this, where chemical analysis and subsequent toxicological evaluation requires available standard compounds and information on toxicological potency. The use of bioassays allows a rapid evaluation of toxicological relevance.     

Tri-decabrominated diphenyl ethers and hexabromocyclododecane in indoor air and dust from Stockholm microenvironments 2: indoor sources and human exposure

Data on polybrominated diphenyl ether (PBDE) and hexabromocyclododecane (HBCD) concentrations from Stockholm, Sweden, indoor microenvironments were combined with information from detailed questionnaires regarding the sampling location characteristics, including furnishing and equipment present. These were used to elucidate relationships between possible flame-retarded sources and the contaminant concentrations found in air and dust. Median concentration ranges of ΣPenta-, ΣOcta-, ΣDecaBDE and HBCD from all microenvironments were 19-570, 1.7-280, 29-3200 and < 1.6-2 pg/m³ in air and 22-240, 6.1-80, 330-1400 and 45-340 ng/g in dust, respectively. Significant correlations were found between concentrations of some PBDEs and HBCD in air and/or dust and the presence of electronic/electrical devices, foam furniture, PUF mattresses and synthetic bed pillows in, as well as floor area and construction year of the microenvironment. Car interiors were a source to indoor air in dealership halls. Using median and maximum concentrations of ΣPenta-, ΣOcta-, ΣDecaBDE and HBCD in air and dust, adult and toddler (12-24 months) intakes from inhalation and dust ingestion were estimated. Toddlers had higher estimated intakes of ΣPenta-, ΣDecaBDE and HBCD (7.8, 43, 7.6 ng/d, respectively) from dust ingestion than adults (5.8, 38, 6.0 ng/d, respectively). Air inhalation in offices was also an important exposure pathway for ΣPenta-, ΣOcta- and ΣDecaBDE in adults. For ΣPentaBDE and HBCD, air inhalation and dust ingestion play minor roles when compared to previously published Swedish dietary intakes (median exposures). However, in worst case scenarios using maximum concentrations, dust ingestion may represent 77 and 95% of toddler intake for ΣPentaBDE and HBCD, respectively.     

脂肪醇醚羧酸盐的合成

介绍了脂肪聚氧乙烯醚（０～１５）羧酸盐的合成和性能。通过正交确定了较佳的合成工艺条件，并对其进行红外光谱的实验测试。     

2,2',4,4'-四溴联苯醚高效好氧降解菌的鉴定及其降解路径

2,2',4,4'-四溴联苯醚(BDE-47)是环境和生物体中普遍检出且生物毒性较大的一种多溴联苯醚同系物.本研究从广东省贵屿镇电子垃圾拆解厂周边采集的农田土壤中分离出一株BDE-47的高效好氧降解菌GYP1,考察了其对BDE-47的降解性能、降解路径及不同的环境因素对菌株降解BDE-47的影响.根据菌株形态特征、16S r DNA基因序列及系统发育树分析,将该菌鉴定为伯克霍尔德菌(Burkholderia cepacia).结果表明,菌株GYP1在好氧条件下能够利用BDE-47为唯一碳源生长,在BDE-47初始质量浓度为1 mg·L~(-1)、温度为30℃、摇床转速为150r·min~(-1)的条件下避光培养4 d,该菌株对BDE-47的降解率可达到82.4%.菌株GYP1在15~35℃和p H=4.0~7.0的环境条件范围内对BDE-47均能保持良好的降解性能,但外加蔗糖、酵母粉、联苯醚等碳源会明显抑制其对BDE-47的降解.在菌株GYP1对BDE-47的降解过程中检测到6-OH-BDE-47、5-OH-BDE-47、4'-OH-BDE-17、2'-OH-BDE-3这4种羟基多溴联苯醚及2,4-二溴苯酚,证明菌株GYP1对BDE-47的好氧降解机理主要是羟基化过程.     

水体中悬浮颗粒物对十溴二苯醚的吸附/解吸特性研究

采用室内试验法,以沉积颗粒物和浮游植物颗粒(铜绿微囊藻和普通小球藻)作为水体中悬浮颗粒物(SPM),研究了SPM对十溴二苯醚(BDE-209)的吸附/解吸特性.结果表明,沉积颗粒物和浮游植物颗粒对BDE-209的吸附分别在1.5h和0.5h内达到最大,在3h内可以充分达到平衡;沉积颗粒物和浮游植物颗粒对BDE-209的吸附能力存在差异,这与颗粒物中有机质的浓度和类型有关;在实验浓度范围内,BDE-209在SPM上的吸附可用Freundlich等温吸附方程较好地拟合;解吸过程表现出一定的迟滞性,且沉积颗粒物比浮游植物颗粒物具有更明显的迟滞性;pH中性、温度20～30℃的水体有利于SPM对BDE-209的吸附.     

2,2’,4,4’-四溴联苯醚对大型溞的毒性效应

以实验室培养的大型溞为受试生物,进行了2,2’,4,4’-四溴联苯醚(BDE-47)对大型溞的48h急性毒性实验和21d慢性毒性实验,并研究了暴露在不同质量浓度和处理时间的BDE-47中,大型溞的抗氧化酶系中的超氧化物歧化酶(SOD)和谷胱甘肽硫转移酶(GST)的酶活性变化。结果表明,BDE-47对大型溞的48h的半致死浓度为1.04mg·L-1,属于高毒物质;在BDE-47慢性毒性实验低浓度处理组中,大型溞的体长及繁殖能力受到了抑制,而高浓度处理组中大型溞的体长及繁殖能力上升,其中第一次产仔数和产卵总数是表征BDE-47慢性毒性的最灵敏参数。随着BDE-47浓度的增加,大型溞SOD和GST活性均呈现出低浓度诱导高浓度抑制的现象。SOD和GST均表现出一定的敏感性,但相对SOD,GST对BDE-47暴露更为敏感。