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.     

活性炭纤维吸附模拟废气中的乙醇和乙醚

采用动态吸附法研究了5种活性炭纤维（ACF）对乙醇、乙醚及模拟混合废气中的乙醇和乙醚的吸附性能。实验结果表明：当ACF-1,ACF-2,ACF-3,ACF-4分别吸附乙醇和乙醚时,在室温、乙醇质量浓度12.0 mg/L、乙醚质量浓度13.0 mg/L的条件下,4种ACF对乙醇的穿透吸附量和饱和吸附量分别为60~70 mg/g和339~409 mg/g,对乙醚的穿透吸附量和饱和吸附量分别为50~65 mg/g和301~344 mg/g;在室温、模拟混合废气中乙醇和乙醚的质量浓度均为11.6 mg/L、吸附时间120 min的条件下,具有较大的比表面积和微孔体积的ACF-5对乙醇的吸附量为205 mg/g,对乙醚的吸附量为223 mg/g;在脱附真空度-0.95 Pa、脱附时间20 min的条件下,经17 次使用的ACF-5对模拟混合废气中乙醇和乙醚的穿透吸附量均为87 mg/g,穿透时间均为12 min。     

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。     

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.     

生物滴滤塔净化甲基叔丁基醚废气的研究

应用生物滴滤塔处理甲基叔丁基醚废气,研究其挂膜启动及稳定运行阶段的降解性能,并考察了稳定期该系统的生物群落结构.结果表明,生物滴滤塔在停留时间为60 s,进气质量浓度为100 mg·m~(-3)的条件下,运行23 d后完成挂膜,填料上的生物量明显增加,去除率可维持在70%以上.反应器稳定运行时,去除负荷可达13.47 g·(m3·h)~(-1),矿化率可达68%;用Haldane模型拟合生物滴滤塔中去除负荷的变化趋势,获得理论ECmax为21.03 g·(m3·h)~(-1),KS为0.16 g·m~(-3),KI为0.99g·m~(-3).运用高通量测序技术分析生物膜中的微生物群落结构,发现其中优势菌属为Methylibium sp.和Blastocatella sp.,分别占11.33%和9.95%.     

基于毒理基因组学的PBDE-209和镉联合毒性效应研究

多污染物引发的联合毒性是环境污染物风险评价中的重要问题之一,然而此类研究相对不足.多溴联苯醚和重金属镉可在多种环境介质中共存,虽对其各自单独暴露所产生的毒性已有相对明确的认识,但对二者联合毒性效应及其分子机制的探索仍十分有限.生物信息学的发展为污染物的健康效应研究提供了一种新的思路.为此,本研究基于比较毒理基因组学数据库(CTD)分析了十溴联苯醚和镉在单独或共同暴露下所影响的基因和相关疾病,推测两种污染物对胎儿红系造血过程产生的潜在影响,并进一步整合外源红系细胞基因表达数据库中的基因芯片确证二者共同影响的基因集合.同时,通过对这些基因集合进行生物学过程和信号通路富集分析,筛选出潜在的靶基因JAK3和AKT2,并在无显著细胞毒性的暴露条件下,通过体外细胞实验验证了十溴联苯醚和镉对这两个靶基因表达的干扰.本研究结果可为预防多溴联苯醚和重金属的联合暴露风险提供一定的科学依据,同时,CTD数据库和外源特定疾病发生发展相关基因表达数据库联合使用,并结合传统毒理学研究手段的评价模式,可为污染物的共同暴露与特定疾病的相关性及分子机理的探索在研究思路和技术手段上提供参考.     

八氯二丙醚的研究现状与展望

八氯二丙醚是一种农药增效剂,多用于农药喷雾剂、蚊香等。八氯二丙醚在环境中滞留时间长,属于类持久性有机污染物,可能具有致畸、致癌、致突变作用。近10年来国内外学者对环境中的八氯二丙醚进行了比较多的调查和研究。首先对八氯二丙醚的性质、应用情况进行了阐述,然后分析八氯二丙醚的研究现状及可能来源,最后对未来八氯二丙醚的研究的重点和发展趋势进行了展望。文献分析表明：（1）目前国内外的研究集中报道八氯二丙醚在环境中的含量（如农药、蚊香、茶叶、大米、蔬菜、水果等）,缺乏八氯二丙醚的环境行为及其在环境中的迁移、转化及降解机理的研究,更缺乏农产品中八氯二丙醚残留的快速检测研究。（2）报道八氯二丙醚对动物及昆虫的毒性及毒理学试验、杀虫活性研究,缺乏八氯二丙醚对人体暴露风险的研究。     

甲基叔丁基醚在地下水系统中的自然衰减

地下水中的甲基叔丁基醚（MTBE）自然衰减是生物与非生物过程综合作用的结果。在厌氧条件下,MTBE的同位素方面的证据表明：挥发、吸附和稀释等非生物过程中MTBE自然衰减的主要作用。在实际工作中,应结合当地水文地质条件,从主要环境因子来分析MTBE的自然衰减,从而判定MTBE自然衰减的速率和程度。在进行地下水中MTBE自然衰减研究时,应加强对于能反映MTBE自然衰减的＂印迹＂的研究。对这些＂印迹＂的确定将为野外监测MTBE的自然衰减提供理论上的依据。     

利用黄磷尾气生产二甲醚的初步研究

生产lt黄磷要排放250Nm^3-3000Nm^3尾气，经过尾气净化和精制、甲醇合成和甲醇催化脱水等工艺，可利用黄磷尾气制取二甲醚。以年产5千t的黄磷厂为例，每年可减少1280万Nm^3尾气排放，从而减少3．63t硫、3．47t磷和0．14t氟排入空中，同时可生产二甲醚3500t、甲醇500t。本方法技术上可行，经济效益良好，环境效益显著。