生物净化挥发性有机化合物(VOCs)的研究进展

有机废气中大多含有低浓度的苯、甲苯、苯乙烯、多环芳烃等挥发性有机化合物(VOCs)。这类挥发性有机化合物会对人体健康和生态环境造成危害。治理VOCs污染是大气污染治理的重要部分。生物法处理有机废气具有运行费用低、没有二次污染等优点。常用的生物处理技术主要有生物过滤池、生物滴滤池和生物洗涤塔。20世纪80年代生物法在欧洲得到快速发展,我国于90年代以后也开始了生物处理VOCs废气的研究,并取得了一定的成就。     

Precursors and potential sources of ground-level ozone in suburban Shanghai

• Air masses from Zhejiang Province is the major source of O₃ in suburban Shanghai. • O₃ formation was in VOC-sensitive regime in rural Shanghai. • O₃ formation was most sensitive to propylene in rural Shanghai. A high level of ozone (O₃) is frequently observed in the suburbs of Shanghai, the reason for this high level remains unclear. To obtain a detailed insight on the high level of O₃ during summer in Shanghai, O₃ and its precursors were measured at a suburban site in Shanghai from July 1, 2016 to July 31, 2016. Using the Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model and concentration weighted trajectories (CWT), we found that Zhejiang province was the main potential source of O₃ in suburban Shanghai. When the sampling site was controlled by south-western winds exceeding 2 m/s, the O₃-rich air masses from upwind regions (such as Zhejiang province) could be transported to the suburban Shanghai. The propylene-equivalent concentration (PEC) and ozone formation potential (OFP) were further calculated for each VOC species, and the results suggested that propylene, (m+p)-xylene, and toluene played dominant roles in O₃ formation. The Ozone Isopleth Plotting Research (OZIPR) model was used to reveal the impact of O₃ precursors on O₃ formation, and 4 base-cases were selected to adjust the model simulation. An average disparity of 18.20% was achieved between the simulated and observed O₃ concentrations. The O₃ isopleth diagram illustrated that O₃ formation in July 2016 was in VOC-sensitive regime, although the VOC/NO_x ratio was greater than 20. By introducing sensitivity (S), a sensitivity analysis was performed for O₃ formation. We found that O₃ formation was sensitive to propylene, (m+p)-xylene, o-xylene and toluene. The results provide theoretical support for O₃ pollution treatment in Shanghai.     

Simulated reaction of formaldehyde and ambient atmospheric particulate matter using a chamber

The reaction of HCHO with Beijing winter's real ambient particulate matter(PM) inside a 3.3 m~3 Teflon Chamber was conducted in this study. NO_2, O_3 and H_2O gases were removed from the ambient aerosol before entering into the chamber. The decays of HCHO were monitored(acetylacetone spectrophotometry method) during the reactions at different PM number concentrations(N_a) and relative humidities(RHs), and the formed particulate formate was detected by IC and XPS techniques. The results showed that when RH was10%–15%, the decay rate of HCHO in the chamber was higher with the existence of PM from relatively clean days(with number concentration(N_a) 200,000 particle/L, 0.35–22.5 μm)compared to dirty days(N_a 200,000 particle/L, 0.35–22.5 μm). When RH increased to 30%–45%, PM can hardly have significant influences on the decay of HCHO. The formations of formate on the reacted PM were consistent with the HCHO decay rates at different ambient PM N_aand RH conditions. This is a first study related to the "real" ambient PM reacted with HCHO and suggested that in the clean and low RH days, PM could be an effective medium for the conversion of HCHO to formate.     

重庆市夏秋季VOCs对臭氧和二次有机气溶胶生成潜势的估算

为估算重庆市夏秋季VOCs（挥发性有机物）对O₃和SOA（二次有机气溶胶）的生成潜势,利用在线GC-MS/FID在2015年8月22日-9月23日对重庆市区点和郊区点VOCs开展了为期一个月的实时观测,获得市区点和郊区点$ \varphi $（TVOCs）（总挥发性有机物）分别为41.35×10-9和22.72×10-9,其中市区点以烷烃（35.2%）和烯炔烃（25.2%）为主,郊区点以含氧挥发性有机物（oxygenated volatile organic compounds,OVOCs）（30.6%）和烷烃（26.0%）为主.结合最大增量反应活性量化市区点和郊区点VOCs的OFPs（臭氧生成潜势）分别为149.11×10-9和71.09×10-9,市区点OFPs最大的是乙烯、丙烯、甲苯、C8和C9的芳香烃等,郊区点OFPs最大的VOCs是丙烯醛、异戊二烯和甲基乙烯基酮.结合气溶胶生成系数量化郊区点和市区点VOCs对SOA的生成贡献分别为0.36和1.26 μg/m3,相比国内其余城市VOCs的SOAP（二次有机气溶胶生成潜势）较小,主要以甲基环己烷、正壬烷、正葵烷和十一烷等高碳烷烃,以及甲苯、苯、二甲苯和乙苯等芳香烃的SOAP为主.研究显示,控制烯炔烃和芳香烃的浓度有助于控制重庆市O₃的生成,控制高碳烷烃和芳香烃则有助于控制重庆市SOA的生成.      

膜生物反应器处理甲苯性能及机制

采用膜生物反应器处理甲苯有机废气,研究了进气浓度、停留时间、循环液喷淋密度和pH值对甲苯去除率的影响.膜生物反应器能高效净化挥发性有机废气,甲苯去除率可达99%.适宜运行条件为:pH值为7.2、停留时间为6.4 s、循环液喷淋密度为2.5 m3.(m2.h)-1.采用GC-MS分析出口气样,研究结果表明乙醛酸(C2H2O3)和乙烯基甲酸(C3H4O2)为甲苯生物降解的中间产物.膜生物反应器处理甲苯机制为甲苯气体通过中空纤维膜传质到生物膜,被生物降解为乙醛酸和乙烯基甲酸,然后继续好氧降解为最终产物二氧化碳和水.     

我国VOCs的排放特征及控制对策研究

挥发性有机物(volatile organic compounds,VOCs)是一类具有刺激性、致畸、致癌、致突变作用、易燃易爆的有机物,对人体和生态系统健康有很大危害.本文从工业固定源、机动车尾气排放源和日常生活源等角度分析不同排放源的VOCs排放特征,绘制并分析了我国重点区域重点行业VOCs排放的空间分布格局,甄别出东部沿海地区VOCs 2010年总量和单位面积均高于中西部地区,且工业产生源有明显差异.进一步归类分析了欧美等发达国家针对VOCs排放控制的政策法规,对比分析我国目前治理VOCs的有关法规和标准,提出了现阶段我国VOCs管理存在的问题,并提出了相应的控制对策建议.     

挥发性有机污染物排放控制标准制订中的关键技术问题研究

研究分析了挥发性有机污染物排放标准制订中4个关键技术问题:污染因子选择、控制指标确定、限值的确定以及技术管理措施.结果表明,应根据毒性和光化学反应性选择污染因子;确定控制指标应既考虑有组织控制指标,又考虑无组织的控制指标;确定排放限值应明确是基于控制技术还是基于健康风险;同时制定技术管理措施以通过源头和过程控制挥发性有机污染物排放.     

杭州市典型企业废水中挥发性有机物排放特征及其评价

以10家杭州市典型企业进出口废水为调查对象,用顶空气相色谱质谱法测定77种挥发性有机物(VOCs),分析其排放特征,并对监测结果进行评价.结果表明,进口废水共定量检出22种VOCs,检出质量浓度范围为7~3.39×106μg·L-1;出口废水共定量检出14种VOCs,检出质量浓度范围为16~6.82×104μg·L-1.就行业而言,香精香料制造企业进出口废水VOCs检出的质量浓度最高.以《污水综合排放标准》(GB 8978-1996)三级排放标准为评价标准时,1号企业出口废水检出甲苯质量浓度为2.45×103μg·L-1,超过标准限值.以挥发性有机物的水介质排放环境目标值(DMEG WH)为标准时,3号企业出口废水检出的正丁醇、异丙醇、丙酮质量浓度均超过它们各自的水介质排放环境目标值.     

武汉市秸秆燃烧VOCs排放估算及管理对策

秸秆燃烧是我国人为源挥发性有机物(volatile organic compounds,VOCs)排放的重要来源之一,其排放对气候变化和人体健康都有很大影响.对该来源VOCs排放量的可靠估算是在区域或城市范围内进行排放效应分析和污染控制的重要前提.根据2005~2011年武汉市农作物的总产量,采用排放因子分析法估算了武汉市及主要6个农作物产区的秸秆燃烧VOCs的排放量,并分别计算其耕地排放强度(I c)和区域排放强度(I r).结果表明,武汉市2005~2011年年均秸秆燃烧VOCs排放量约为(3 163±139)t,I c和I r分别为(1.52±0.06)t·km-2和(0.37±0.02)t·km-2.粮食类和油料类农作物秸秆燃烧是主要的排放源,需优先控制7大类21种VOCs物质.武汉市分区VOCs排放量从大到小排序依次为黄陂区、新洲区、江夏区、蔡甸区、汉南区、东西湖区,前4个区的排放总量占到武汉市的近九成.江夏区、汉南区、黄陂区和新洲区应作为秸秆燃烧VOCs排放的优先控制区,尤其是能作为全国代表性的江夏区,应引起高度重视.在进行区域或城市范围的秸秆燃烧产生污染物质的生态风险评价时,该污染物的I c和I r都是需要考虑的重要基础数据.最后,提出大力发展农村秸秆资源综合循环经济利用是解决区域或城市范围内秸秆燃烧产生环境问题的可行之径.     

Characterization of typical taste and odor compounds formed by Microcystis aeruginosa

Production and characteristics of typical taste and odor (T&O) compounds by Microcystis aeruginosa were investigated. A few terpenoid chemicals, including 2-MIB, β-cyclocitral, and β-ionone, and a few sulfur compounds, such as dimethyl sulfide and dimethyl trisulfide, were detected. β-Cyclocitral and β-carotene concentrations were observed to be relevant to the growth phases of Microcystis. During the stable growth phase, 41-865 fg/cell of β-cyclocitral were found in the laboratory culture. β-Cyclocitral concentrations correlated closely with β-carotene concentrations, with the correlation coefficient R2 = 0.96, as it is formed from the cleavage reaction of β-carotene. For dead cell cases, a high concentration of dimethyl trisulfide was detected at 3.48-6.37 fg/cell. Four T&O compounds, including β-cyclocitral, β-ionone, heptanal and dimethyl trisulfide, were tested and found to be able to inhibit and damage Microcystis cells to varying degrees. Among these chemicals, β-cyclocitral has the strongest ability to quickly rupture cells.