Intrinsic chemiluminescence production from the degradation of haloaromatic pollutants during environmentally-friendly advanced oxidation processes: Mechanism, structure–activity relationship and potential applications

The ubiquitous distribution of halogenated aromatic compounds(XAr) coupled with their carcinogenicity has raised public concerns on their potential risks to both human health and the ecosystem. Recently, advanced oxidation processes(AOPs) have been considered as an"environmentally-friendly" technology for the remediation and destruction of such recalcitrant and highly toxic XAr. During our study on the mechanism of metal-independent production of hydroxyl radicals(UOH) by halogenated quinones and H_2O_2, we found, unexpectedly, that an unprecedented UOH-dependent two-step intrinsic chemiluminescene(CL) can be produced by H_2O_2 and tetrachloro-p-benzoquinone, the major carcinogenic metabolite of the widely used wood preservative pentachlorophenol. Further investigations showed that, in all UOH-generating systems, CL can also be produced not only by pentachlorophenol and all other halogenated phenols, but also by all XAr tested. A systematic structure–activity relationship study for all 19 chlorophenolic congeners showed that the CL increased with an increasing number of Cl-substitution in general. More importantly, a relatively good correlation was observed between the formation of quinoid/semiquinone radical intermediates and CL generation. Based on these results, we propose that UOH-dependent formation of quinoid intermediates and electronically excited carbonyl species is responsible for this unusual CL production; and a rapid, sensitive,simple, and effective CL method was developed not only to detect and quantify trace amount of XAr, but also to provide useful information for predicting the toxicity or monitoring real-time degradation kinetics of XAr. These findings may have broad chemical, environmental and biological implications for future studies on halogenated aromatic persistent organic pollutants.     

Conventional and emerging halogenated flame retardants (HFRs) in sediment of Yangtze River Delta (YRD) region,East China

The occurrence and distribution of polybrominated diphenyl ethers (PBDEs) and eleven non-PBDE halogenated flame retardants (HFRs) were investigated through the collection of marine and river sediment from Yangtze River Delta (YRD), East China. Among them, PBDEs, decabromodiphenyl ethane (DBDPE) and 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH) were the three predominant HFRs with the highest detection frequencies in the sediment. Significant correlation between PBDEs and DBDPE indicated that they may have the similar emission sources. The production and use of DBDPE is growing rapidly and comparable concentrations between PBDEs and DBDPE in YRD sediment may suggest that DBDPE will likely become one of the major HFRs emerging in the environment in China. Of the seven detected non-PBDE HFRs, this is the first time that TBECH was reported in the Chinese environment and its predominance and prevalence in the YRD may imply its extensive use in these areas.     

卤代烃污染物的电化学氧化还原降解技术研究进展

开发新型的、无害化降解卤代烃污染物的处理方法已成为环境科学研究的难点和热点.有关卤代烃污染物的电化学氧化还原处理方法也逐渐引起了国际上的重视.在论述了电化学氧化和电化学还原两种方法处理卤代烃污染物的技术原理基础上,对电化学处理卤代烃污染物的研究现状进行了综述,着重介绍了目前应用该技术处理一些卤代烃污染物的电流效率以及电极研究的进展.探讨了电化学氧化还原降解技术在这一领域应用的可行性.     

QSAR models for predicting the toxicity of halogenated phenols to Tetrahymena

Halogenated phenols are industrial pollutants which may cause serious damage to the environment. In this work, a two-dimensional (2D) and two three-dimensional (3D) quantitative structure–activity relationship models for the toxicity prediction of halogenated phenols in Tetrahymena were developed. The structural factors that mainly influence toxicity were explored, agreeing with previously reported data. The results obtained with the 3D model were in agreement with those obtained with the 2D model. According to our findings, several new molecules with different predicted activities were designed.     

热脱附-气相色谱法测定环境空气中芳烃和卤代烃

建立了热脱附-气相色谱法测定环境空气中9种芳烃和卤代烃方法。阐述了样品管制备、采样袋预处理、现场采样和实验富集等过程。采用保留时间定性、外标法定量。进行了自动热脱附仪的吸附和解吸效率的试验,各组分的吸附效率均在97%以上,解吸效率达98 9%。最低检出质量浓度氯乙烯为0 0003mg/m3、1,2-二氯乙烷和1,2-二氯丙烷为0 0002mg/m3、苯、甲苯、乙苯、对二甲苯、苯乙烯和邻二甲苯均为0 0001mg/m3。试图以不更换TenaxTA吸附剂标准冷阱来测定齐鲁石化环境空气中特征污染物乙烯,由于冷阱对乙烯的二级吸附未能很好地解决,试验效果不理想,有待进一步研究。     

应用分子拓扑理论预测卤代芳烃的正辛醇/水分配系数

以分子拓扑理论为基础，提出了一个新的拓扑指数Ｙ，并用Ｙ研究了部分卤代芳烃的正辛醇／水分配系数ＫＯＷ。研究表明，Ｙ与卤代芳烃的正辛醇／水分配系数ＫＯＷ的ｌｏｇＫＯＷ呈良好的线性关系，并给出了相关方程。新方法计算方便、精确度高、物理意义明确     

西南某化工园区周边区域环境空气中苯系物和卤代烃的污染特征及健康风险研究

于2020年8月和11月,在中国西南某化工园区周边6个采样点采集环境空气样品,对5种典型苯系物(苯、甲苯、乙苯、邻二甲苯、间/对二甲苯)和7种典型卤代烃(三氯甲烷、三氯乙烯、四氯化碳、四氯乙烯、三溴甲烷、一溴二氯甲烷和二溴一氯甲烷)进行研究,明确了区域典型苯系物和卤代烃(BSHs)的污染特征,并评估其对人体的健康风险。结果表明:化工园区周边环境空气中苯系物检出率均 60%,卤代烃中除三溴甲烷、一溴二氯甲烷和二溴一氯甲烷外,检出率均 50%。苯系物和卤代烃的平均质量浓度分别为4.14～11.19μg/m~3和0.30～10.86μg/m~3。BSHs的浓度夏季低于冬季,这可能与人为的季节性燃烧源有关。苯、四氯化碳和四氯乙烯超过国际WELL建筑标准v2,全年超标率分别为3.33%,8.33%和11.67%。BSHs的非致癌和致癌风险均为成人儿童,成人和儿童的非致癌总风险分别为1.87×10~(-2)和1.26×10~(-2),处于可接受水平;成人和儿童的致癌风险分别为1.76×10~(-3)和1.19×10~(-3),处于不可接受水平。     

The origin of stable halogenated compounds in volcanic gases

BACKGROUND: Halogenated compounds in the atmosphere are of great environmental concern due to their demonstrated negative effect on atmospheric chemistry and climate. Detailed knowledge of the emission budgets of halogenated compounds has to be gained to understand better their specific impact on ozone chemistry and the climate. Such data are also highly relevant to guide policy decisions in connexion with international agreements about protection of the ozone layer. In selected cases, the relevance of specific emission sources for certain compounds were unclear. In this study we present new and comprehensive evidence regarding the existence and relevance of a volcanic contribution of chlorofluorocarbons (CFCs), hydrofluorocarbons (HFCs), hydrochlorofluorocarbons (HCFCs), halons (bromine containing halo(hydro)carbons), and fully fluorinated compounds (e.g. CF4 and SF6) to the atmospheric budget. METHODS: In order to obtain new evidence of a volcanic origin of these compounds, we collected repeatedly, during four field campaigns covering a period of two years, gases from fumaroles discharging over a wide range of temperatures at the Nicaraguan subduction zone volcanoes Momotombo, Cerro Negro and Mombacho, and analysed them with very sensitive GC/MS systems. RESULTS AND DISCUSSION: In most fumarolic samples certain CFCs, HFCs, HCFCs, halons, and the fully fluorinated compounds CF4 and SF6 were present above detection limits. However, these compounds occur in the fumarole gases in relative proportions characteristic for ambient air. CONCLUSION: This atmospheric fingerprint can be explained by variable amounts of air entering the porous volcanic edifices and successively being incorporated into the fumarolic gas discharges. Recommendation and Outlook. Our results suggest that the investigated volcanoes do not constitute a significant natural source for CFCs, HFCs, HCFCs, halons, CF4, SF6 and NF3.     

吹扫捕集- GC/MS法测定水中卤代烃的质量控制指标研究

采用吹扫捕集-气相色谱/质谱联用法,通过实际样品测试及全国多家实验室测定数据统计两种方法,针对水中三氯甲烷、四氯化碳、溴仿、二氯甲烷、1,2-二氯乙烷、1,1-二氯乙烯、三氯乙烯、四氯乙烯等8种卤代烃的平行样测定相对偏差、空白加标回收率及实际样品加标回收率等3个指标,研究了每种卤代烃的质控指标评价标准,提出其平行样测定...