气相色谱法直接进样测定环境空气中的卤代烃

用100mL玻璃注射器采集气样，直接进入气相色谱仪，卤代烃经HP—101毛细管柱分离、ECD测定。方法检出限为0.007mg／m^3-0．05mg／m^3，相对标准偏差为3．4％-7．6％，加标回收率为94％-106％。     

电催化产生 H2O2 和*OH 及去除废水中有机污染物的应用

采用自制的电催化装置研究了苯酚、苯胺和邻苯二甲酸二甲酯三种有机污染物的废水处理规律。证实了在电催化过程中活性物种Ｈ２Ｏ２和·ＯＨ的存在。实验结果表明，有机污染物去除效率的关键在于体系产生活性中间体的量。体系产生的Ｈ２Ｏ２量愈大，相应有机污染物去除效率愈高。体系产生的Ｈ２Ｏ２大于０．３ｍｇ／Ｌ时，有机物去除效率才会有明显的提高。     

Reaction mechanism and kinetics of Criegee intermediate and hydroperoxymethyl formate

The reaction mechanism and kinetics of the simplest Criegee intermediate CH₂OO reaction with hydroperoxymethyl formate (HPMF) was investigated at high-level quantum chemistry calculations. HPMF has two reactive functional groups, -C(O)OH and -OOH. The calculated results of thermodynamic data and rate constants indicated that the insertion reactions of CH₂OO with –OOH group of HPMF were more favorable than the reactions of CH₂OO with -C(O)OH group. The calculated overall rate constant was 2.33 × 10^?13 cm³/(molecule?sec) at 298 K and the rate constants decreased as the temperature increased from 200 to 480 K. In addition, we also proved the polymerization reaction mechanism between CH₂OO and -OOH of HPMF. This theoretical study interpreted the previous experimental results, and supplied the structures of the intermediate products that couldn't be detected during the experiment.     

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.     

丝孢酵母TX1及其固定化降解苯酚特性研究

为研究固定化技术在含酚废水治理中的应用,以聚乙烯醇(PVA)为载体将高效降酚菌株丝孢酵母TX1包埋处理得到胶珠颗粒,在分批培养反应器内分别研究游离体系和固定化体系中溶液p H值、培养温度和苯酚初始质量浓度对TX1降解苯酚效果的影响。结果表明,在游离细胞体系TX1对苯酚降解最佳培养条件为温度30℃,p H=7. 0;而固定化体系中的TX1对苯酚降解的最佳条件为温度30℃,p H=6. 5。在偏酸性条件下,游离细胞体系中TX1对苯酚降解效果比固定化体系差,在25～40℃时后者对苯酚的降解能保持50%以上,表明固定化技术有利于提高微生物的耐受温度。两个体系在降解苯酚过程中均受到底物抑制:在低质量浓度时(≤1 000 mg/L),游离细胞降解速率高于固定化细胞,但当苯酚质量浓度高达3 000 mg/L时,固定化体系中TX1对苯酚比降解速率为0. 088 h-1,远高于前者,表明固定化技术有利于实际高浓度废水的处理。此外,利用高效液相色谱和气相色谱-质谱检测苯酚降解中间产物,只在固定化体系中检测到中间产物为邻苯二酚和顺,顺-黏糠酸。该结果表明,降解过程中固定化体系发生的扩散阻力延迟了体系的降解反应,有利于发现中间体,使固定化技术有望成为新的检测中间体的方法。     

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.     

Analysis of anaerobic BTX biodegradation in a subarctic aquifer using isotopes and benzylsuccinates

In situ biodegradation of benzene, toluene, and xylenes in a petroleum hydrocarbon contaminated aquifer near Fairbanks, Alaska was assessed using carbon and hydrogen compound specific isotope analysis (CSIA) of benzene and toluene and analysis of signature metabolites for toluene (benzylsuccinate) and xylenes (methylbenzylsuccinates). Carbon and hydrogen isotope ratios of benzene were between -25.9 per thousand and -26.8 per thousand for delta13C and -119 per thousand and -136 per thousand for delta2H, suggesting that biodegradation of benzene is unlikely at this site. However, biodegradation of both xylenes and toluene were documented in this subarctic aquifer. Biodegradation of xylenes was indicated by the presence of methylbenzylsuccinates with concentrations of 17-50 microg/L in three wells. Anaerobic toluene biodegradation was also indicated by benzylsuccinate concentrations of 10-49 microg/L in the three wells with the highest toluene concentrations (1500-5000 microg/L toluene). Since benzylsuccinate typically accounts for a very small fraction of the toluene present in groundwater (generally <1 mol%), the signature metabolite approach works best at higher toluene concentrations when it is not constrained by detection limits. In wells with lower toluene concentrations (410-640 microg/L), carbon and hydrogen isotopic values were enriched by up to approximately 2 per thousand for delta13C and approximately 70 per thousand for delta2H. This evidence of isotopic fractionation verifies the effects of biodegradation in these low concentration wells where metabolites may already be below detection limits. The combined use of signature metabolite and CSIA data is particularly valuable given the challenge of verifying biodegradation in subarctic environments where degradation rates are typically much slower than in temperate environments.     

大孔树脂吸附法处理萘系染料中间体生产废水的进展

分析了萘系料中间体生产废水的水质特征,综述了国内曾经采用的处理工艺,重点介绍了大孔树会法在各种萘系染料中间体废水治理和资源化研究方面的进展和工业应用现状,并展望了其发展前景。     

A novel use of TiO2 fiber for photocatalytic ozonation of 2,4-dichlorophenoxyacetic acid in aqueous solution

More efficient oxidation methods are needed to degrade especially newly emerging recalcitrant organic contaminants at low concentrations in the water environment. Reduced photonic efficiency of immobilized TiO2 is a major challenge in TiO2-assisted advanced oxidation processes (AOP). Mineralization of 2,4-dichllorophenoxyacetic acid (2,4-D) in low aqueous solution by O3/UV/TiO2 using the world's first high-strength TiO2 fiber was investigated and compared with O3, UV/TiO2, and O3/TiO2 in laboratory batch ex...