水中有机物臭氧化去除反应机理

随着臭氧化在水处理技术中应用日益增多,研究臭氧化去除水中有机物的机理日显重要。本文在介绍了决定水中臭氧化反应速率的二种反应,即直接反应和间接反应的基础上,着重讨论了芳族化合物、烯烃化合物、环状烯烃化合物,苯酚、苯、苯胺、硝基芳烃、喹啉、二甲基4氯酚氧基醋酸、油酸、有机硫磷化合物,甲醇、甲醛、甲酸和马拉硫磷等与臭氧的反应机理。      

分离海洋不动杆菌及其对石油烃降解性能研究

石油降解菌在石油污染生物修复技术中起到非常重要的作用。本研究分别以渤海湾油污区采集的水样,油样,水油泥混合样为材料富集分离石油降解菌,对其进行生理生化及分子生物学鉴定,并采用GC-MS测定烷烃、环烃、芳香烃等石油烃组分的变化。其中3株菌具有较高石油烃降解能力,16SrRNA序列分析表明该3株菌均与不动杆菌属（Acinetobacter）有99%序列相似性,可初步鉴定为不动杆菌属（Acinetobacter）。3株菌的石油烃降解能力依次为Tust-DM21＞Tust-DC12＞Tust-DW04,对原油成分的降解效果依次为烷烃＞芳香烃＞环烃。其中菌株Tust-DM21为一株高效石油烃降解菌,28℃于富集培养基培养10 d后,对烷烃（C10~C30）的降解率可达98%,对芳香烃和环烃的降解率达88%。研究表明,Tust-DM21菌株对烷烃,环烃,芳香烃都有较强的降解能力,是一株具有较好开发前景的石油降解菌。     

Reactivity-based strategies for photochemical ozone control in Europe

A photochemical trajectory model has been used to assess reactivity-based VOC emission control strategies for Europe by implementing a detailed speciated VOC emission inventory and a highly explicit Master Chemical Mechanism. These reactivity-based strategies envisaged that the emissions of the xylenes, trimethylbenzenes and all aromatic species could be replaced or substituted by the emission of one of a potential range of 94 organic compounds, each present in current emissions. Depending on the reactivity of the substituted VOC species, ozone mixing ratios along an east–west air parcel trajectory travelling for 5 days across northwest Europe would increase or decrease relative to a base case without substitution. In all, eight alcohols, six esters, six ketones, three ethers and an alkane, a cycloalkane and a glycol ether have been identified that give greater ozone reductions when substituting for aromatic compounds than would be given by the corresponding mass-based control strategy. It is concluded that VOC substitution strategies for the stationary sources would offer significant ozone benefits compared with simple across-the-board mass emission reduction strategies of the kind proposed by the EU CAFÉ and UN ECE LRTAP convention processes.     

Release of volatile organic compounds during bio-drying of municipal solid waste

Three treatments were tested to investigate the release concentrations of volatile organic compounds (VOCs) during the bio-drying of municipal solid waste (MSW) by the aerobic and combined hydrolytic-aerobic processes. Results showed that VOCs were largely released in the first 4 days of bio-drying and the dominant components were: dimethyl disulfide, dimethyl sulfide, benzene, 2-butanone, limonene and methylene chloride. Thus, the combined hydrolytic-aerobic process was suggested for MSW bio-drying due to fewer aeration quantities in this phase when compared with the aerobic process, and the treatment strategies should base on the key properties of these prominent components. Malodorous sulfur compounds and terpenes were mainly released in the early phase of bio-drying, whereas, two peaks of release concentrations appeared for aromatics and ketones during bio-drying. Notably, for the combined hydrolytic-aerobic processes there were also high concentrations of released aromatics in the shift from hydrolytic to aerobic stages. High concentrations of released chlorinateds were observed in the later phase. For the VOCs produced during MSW bio-drying, i.e., malodorous sulfur compounds, terpenes and chlorinateds, their release concentrations were mainly determined by production rates; for the VOCs presented initially in MSW, such as aromatics, their transfer and transport in MSW mainly determined the release concentrations.     

深圳市工业区VOCs污染特征与臭氧生成敏感性

于2020年9~10月在深圳北部典型工业区开展在线观测以分析该地VOCs污染状况,并使用基于观测的模型(OBM)研究臭氧生成敏感性.观测期间VOCs的总浓度为48.5×10^-9,浓度水平上烷烃>含氧有机物(OVOCs)>卤代烃>芳香烃>烯烃>乙炔>乙腈.臭氧生成潜势(OFP)为320μg/m³,其中芳香烃、OVOCs以及烷烃贡献最大,这3类物种OFP贡献总和超过90%.乙烯与苯呈现“两峰一谷”的日变化特征,主要受到机动车排放的贡献.相对增量反应性(RIR)分析表明,削减人为源VOCs对控制当地臭氧生成最为有效,当中又应优先控制芳香烃;经典动力学曲线(EKMA)分析表明该片区臭氧生成处于过渡区,在开展VOCs区域联防联控的同时,需要在当地进行有力的NOx控制以强化该地区臭氧污染长期管控.     

废水生物脱氮过程中N2O排放数学模型研究进展

氧化亚氮(N₂O)的温室效应比CO₂强265倍,可从废水生物脱氮过程中产生并直接排放,如果不对其加以控制,会显著增加污水处理厂的碳足迹。N₂O排放的数学建模对于深入解析N₂O产生机制、量化N₂O排放、优化生物脱氮工艺和制定N₂O减排策略具有重要意义。结合当前国内外研究现状,阐述了废水生物脱氮过程中N₂O产生机制;归纳了基于不同机制建立的N₂O数学模型,包括氨氧化细菌(ammonia-oxidizing bacteria,AOB)经过羟胺氧化途径和AOB反硝化途径产生N₂O模型、异养反硝化途径产生N₂O模型以及耦合AOB和异养反硝化细菌产生N₂O模型;总结了新型生物脱氮系统N₂O模型,实际工程应用情况及校准N₂O数学模型中存在的问题;并对今后N₂O数学模型的研究方向进行了展望。     

Enhanced debromination of 4-bromophenol by the UV/sulfite process: Efficiency and mechanism

Halogenated aromatic compounds have attracted increasing concerns due to their toxicity and persistency in the environment, and dehalogenation is one of the promising treatment and detoxification methods. Herein, we systematically studied the debromination efficiency and mechanism of para-bromophenol(4-BP) by a recently developed UV/sulfite process. 4-BP underwent rapid degradation with the kinetics accelerated with the increasing sulfite concentration, pH(6.1–10) and temperature, whereas inhibited by dissolved oxygen and organic solvents. The apparent activation energy was estimated to be 27.8 kJ/mol. The degradation mechanism and pathways of 4-BP were explored by employing N_2O and nitrate as the electron scavengers and liquid chromatography/mass spectrometry to identify the intermediates. 4-BP degradation proceeded via at least two pathways including direct photolysis and hydrated electron-induced debromination. The contributions of both pathways were distinguished by quantifying the quantum yields of 4-BP via direct photolysis and hydrated electron production in the system. 4-BP could be readily completely debrominated with all the substituted Br released as Br-, and the degradation pathways were also proposed. This study would shed new light on the efficient dehalogenation of brominated aromatics by using the UV/sulfite process.     

取代芳香族化合物对4种水生生物的毒性研究

建立了105种取代芳香族化合物对4种水生生物(发光菌、四膜虫、大型蚤和斑马鱼)的毒性QSAR模型.取代芳香族化合物对生物体的毒性主要是由2个过程引起,化合物首先穿透细胞膜,然后与机体发生反应.讨论了生物种的种间和种内差别,这种差别可能与生物的脂肪含量有关.化合物分成了3类,非极性麻醉型化合物、极性麻醉型化合物和反应型化合物,极性麻醉型化合物比非极性麻醉型化合物毒性要高,反应型化合物毒性最高.     

g-C3N4-P25/光合细菌复合材料降解偶氮染料废水的机理

采用海藻酸钙将g-C3N4-P25和光合细菌进行共固定,合成了光催化-微生物复合材料,并进行了降解模拟偶氮染料废水的研究.结果表明,光催化-微生物复合材料的染料(活性艳红X-3B)脱色率和COD去除率分别为94%和84.7%,远远大于固定光催化剂与固定光合细菌.利用UV-Vis、FT-IR及GC-MS对反应残留物进行表征,根据结果可推测:由光催化产生的自由基和光合细菌共同破坏X-3B的偶氮结构,生成的苯胺类化合物经过一系列的水解、氧化还原作用生成多种具有苯环结构的化合物,然后自由基破坏苯环结构产生长链烷烃,减少芳香烃化合物的累积对光合细菌活性的影响.光合细菌及时利用光催化生成的长链烷烃,产生分子量较小的物质,最后矿化为CO2和H2O.     

铁内电解法处理硝基苯类废水的机理与展望

硝基苯类化合物是广泛应用的化工原料 ,目前它们已造成了严重的环境污染 ,并危及人体的健康。利用内电解法处理环境污染物的方法目前倍受青睐 ,本文介绍了内电解法处理硝基苯类废水的作用机理、硝基苯类化合物的转化途径 ,概述了内电解法去污的影响因素 ,探讨了其发展动向。     

微生物降解典型高分子量多环芳烃的研究进展

高分子量多环芳烃（high molecular weight polycyclic aromatic hydrocarbons,HMW-PAHs）属于持久性污染物,与低分子量多环芳烃（low molecular weight polycyclic aromatic hydrocarbons,LMW-PAHs）相比更难被降解.微生物修复是解决HMW-PAHs污染问题的有效手段.该文以2种典型HMW-PAHs——芘和苯并[a]芘为例,对影响其微生物降解效率的因素、提高降解率的强化手段和主要降解途径进行阐释,深入剖析微生物的降解调控机制,并对未来的研究和发展提出了展望,以期为微生物降解HMW-PAHs的相关研究提供参考.结果表明:①大多数微生物在中温、中性条件下对HMW-PAHs具有较好的降解性能,不同多环芳烃在降解过程中存在相互作用;②就HMW-PAHs的微生物强化降解手段而言,表面活性剂吐温80对降解的促进作用较为明显,生物炭是较为优良的固定化材料,在受体菌株中表达降解基因以构建基因工程菌是促进HMW-PAHs微生物降解的有效方式;③芘和苯并[a]芘主要通过K区氧化和LMW-PAHs途径降解;④由双加氧酶催化的羟基化是HMW-PAHs降解过程中的重要步骤;⑤多环芳烃的初始氧化过程也涉及细胞色素P450单加氧酶的活性.目前,基因工程菌的长效稳定性是限制相关技术广泛应用的瓶颈问题,未来需要综合多组学数据从基因、转录、蛋白和代谢水平对HMW-PAHs的微生物降解机制进行全面、深入地解析,为构建高效稳定的重组菌株提供理论支撑.      

原油中芳烃及其碳稳定同位素组成特征

芳烃作为原油的主要组分之一,蕴含丰富的地球化学信息,常用原油中芳烃的分布及其碳稳定同位素组成来评价原油的有机质来源和热成熟度等指标。为了补充油品化学指纹的基础鉴别指标和数据,找出适用于油样鉴别的芳烃地球化学指标以及碳稳定同位素组成,本文主要测定了来自不同地区七种原油芳香烃组分的相对含量以及碳稳定同位素组成,并计算分析了甲基萘比值（MNR）、二甲基萘比值（DNR）、三甲基萘比值（TNR）、甲基菲比值（MPR）、甲基菲指数（MPI1）和甲基菲分馏系数（MPDF）等常见的芳烃特征比值。从原油中芳烃组分相对含量分布来看,七种原油均显示出了各自的特点;从原油芳烃的特征比值来看,成熟度参数（MNR、TNR1、TNR2、MPR、MPI1、MPDF1和MPDF2）均反映出所有原油的高成熟度,其它芳烃参数如DNR1、DNR2和TNR4等比值反映原油的母质来源及生物降解等信息,由芳烃特征比值的单因素方差分析（ANOVA）结果可知,与成熟度参数MNR和MPI1相比,DNR1、DNR2和TNR4在不同原油间的差异更加明显;从原油芳烃碳稳定同位素组成来看,不同地区原油间差别较大,其中巴西原油最富集13C,阿曼原油和委内瑞拉原油最亏损13C,二甲基萘和菲的碳稳定同位素组成在不同油样间的差异最明显。将显著性差异大的芳烃参数与芳烃δ13C值联用,结果表明,该方法可以更加有效区分七种原油。最后使用主成分分析方法分析原油芳烃碳稳定同位素组成,七种原油显示出各自不同的碳稳定同位素组成特征和明显的区分效果,利用不同油样芳烃的碳稳定同位素组成差异可实现对油样来源的鉴别。     

优势菌种与三重环流三相流化床耦合处理油制气厂废水

从若干种菌源中分离出降解芳香烃类和长链烷烃类化合物的高效菌种 ,将此菌种与自行设计的新型结构内循环三相流化床相结合应用于处理油制气厂排出的难降解毒性有机废水 ,分别进行了废水处理动态试验及抗冲击负荷试验 ,讨论了气水比、pH与COD去除率的关系 ,分析了酚、氨氮及各类毒性有机物的生物降解情况 .结果表明 ,反应器容积负荷为 7 16kg(CODCr) (m3·d) ,CODCr平均去除率为 79 5 % ,芳烃类化合物的去除率为 79 8% ,酚类化合物的去除率达 94 8%以上 .反应器表现出优良的抗冲击能力与高效的处理能力     

Natural attenuation characteristics and comprehensive toxicity changes of C9 aromatics under simulated marine conditions

Microcosmic experiments were performed under a simulated marine environment to investigate the natural attenuation of C9 aromatics using nine components (propylbenzene, isopropylbenzene, 2-ethyltoluene, 3-ethyltoluene, 4-ethyltoluene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, and indene). This research aims to assess the contribution of biodegradation and abiotic activity to total attenuation of C9 aromatics and ascertain the changes in the comprehensive toxicity of seawater in the natural environment. The process of natural attenuation indicates the agreement with pseudo-first-order kinetics for all nine components in microcosmic experiments. The half-lives of the nine main compounds in C9 aromatics ranged between 0.34 day and 0.44 day under optimal conditions. The experiments showed that the natural attenuation of nine aromatic hydrocarbons mainly occurred via abiotic processes. Seawater samples significantly inhibited the luminescence of P. phosphoreum (the luminescence inhibition ratio reached 100%) at the beginning of the experiment. In addition, the toxicity declined slowly and continued for 25 days. The attenuation kinetics and changes in toxicity could be applied to explore the natural attenuation of C9 aromatics in the marine environment.     

土壤芘降解菌的分离及特性研究

本研究分离纯化出芘的高效降解菌株,并探讨了菌株在土壤环境中对芘降解情况,主要结论如下：通过富集培养的方法分离得到2株对芘具有较强降解能力的菌株：芽孢杆菌B6和假单孢菌B17。2菌株对除能有效降解利用芘外,还能有效利用苯、萘、菲、甲苯、苯酚、邻苯二酚和1一萘酚等多种芳香类化合物,具有一定的应用前景。     

Metabolism-independent chemotaxis of Pseudomonas sp. strain WBC-3 toward aromatic compounds

Pseudomonas sp. strain WBC-3 utilized methyl parathion or para-nitrophenol (PNP) as the sole source of carbon, nitrogen, and energy, and methyl parathion hydrolase had been previously characterized. Its chemotactic behaviors to aromatics were investigated. The results indicated that strain WBC-3 was attracted to multiple aromatic compounds, including metabolizable or transformable substrates PNP, 4-nitrocatechol, and hydroquinone. Disruption of PNP catabolic genes had no e?ect on its chemotactic behaviors w...     

难生化降解芳香化合物废水的电催化处理

经氟树脂改性的β-PbO₂电极作为新型阳极,对几种含典型难生化降解芳香化合物,苯胺、氯苯、对氯苯酚、对硝基酚的模拟废水进行了电催化降解.结果表明,在0.25A的电流下处理2h,目标有机物去除率达到75%～100%,COD去除率为20%～55%.处理效果:苯胺＞氯苯＞对氯苯酚＞对硝基酚.较高的电流和有机物初始浓度更有利于有机物的降解.检测到了降解的共同中间产物对苯醌、反丁烯二酸、草酸,提出了芳香有机物电催化降解反应的共同历程.     

2-硝基芴在大鼠肝匀浆S-9组分作用下的还原代谢

初步研究了在氮气保护无氧条件下,经Aroclor1254诱导的大鼠肝微粒体酶对2-硝基芴的还原代谢过程.对代谢体系及条件进行了选择用HPLC对代谢产物进行分离研究,经保留时间及紫外光谱核对显示2-硝基芴的主要还原代谢产物为2-氨基芴,除此之外还有三个量少的其代谢产物形成,因含量低而尚未进行结构鉴定.     

喹啉及其衍生物微生物降解研究进展

喹啉类氮杂环化合物在水、土壤环境中普遍存在，受其污染的水、土壤环境生物修复是目前环境治理领域的重要课题。介绍了近年来喹啉类氮杂环化合物微生物降解的国内外研究进展，主要包括可利用喹啉类氮杂环化合物作为碳源、氮源和能源的微生物资源、微生物降解的有氧代谢和无氧代谢两大途径，以及喹啉类化合物的降解动力学。在此基础上，提出了需要进一步研究的方向。     

西南典型区域夏季大气含氧挥发性有机化合物来源解析

含氧挥发性有机物（OVOCs）是大气光化学过程中的重要中间产物,是臭氧的重要来源之一.利用质子转移反应飞行时间质谱仪（PTR-TOF-MS）在成都平原对OVOCs进行观测,探讨其日变化特征、光化学反应活性、臭氧生成潜势和来源.结果表明,10个VOCs［乙醛、丙酮、异戊二烯、甲基乙基酮（methyl ethyl ketone,MEK）、甲基乙烯基甲酮（methyl vinyl ketone,MVK）、甲基丙烯醛（methacrolein,MACR）、苯、甲苯、苯乙烯、C8芳香烃和C9芳香烃］总浓度（体积分数）为（10.97±4.69）×10^-9,OVOCs为（8.54±3.44）×10^-9,芳香烃为（1.53±0.93）×10^-9,生物源VOCs为（0.90±0.32）×10^-9;光化学活性和臭氧生成潜势均排名前三的物种为：异戊二烯、乙醛和C8芳香烃;3个OVOCs物种（乙醛、丙酮和MEK）主要来源于本地生物源和人为二次源,且丙酮有较强的区域背景值,说明该地区的污染受到较为显著的区域传输的影响.本研究可加深对西南地区臭氧的区域形成机制的认识,为科学管控臭氧污染提供依据.