山东地区三类典型制药企业的VOCs源成分谱及排放特征研究

制药行业因在提取等过程中使用有机溶剂排放大量挥发性有机物（VOCs）而备受关注.本研究在山东省选择化学合成、生物发酵、中药共三家制药企业开展了107种VOCs组分的监测和分析,并建立制药企业的VOCs源成分谱.研究结果表明：化学合成类和生物发酵类制药企业排放总质量浓度均超过20 mg/m³,中药制药企业的样品的平均质量浓度相对较小,为902.66 μg/m³.本研究所分析的107种组分中,以含氧挥发性有机物（OVOCs）为主,三家企业均超过75%,其中,化学合成制药类卤代烃物种的占比较高.企业类型、生产环节、收集排放措施等是影响VOCs成分的重要因素.     

山东地区典型金属罐喷涂企业VOCs排放特征研究

了解涂装行业挥发性有机物（VOCs）的排放特征是制定山东地区臭氧（O₃）和PM_2.5防控策略的重要环节.本研究在山东地区测定了两家典型食品金属包装企业喷涂过程中VOCs的排放组成,企业产品以饮料罐和罐头为主.结果表明：两家企业排放的总VOCs质量浓度水平相当,质量浓度变化范围在50~1 500 μg/m³;但两家企业喷涂过程中VOCs的排放组成具有一定的差异,以生产铝罐和马口铁罐为主的企业中的含氧挥发性有机物（OVOCs）含量最多,占比89.71%（质量分数,下同）;而生产铝罐的企业芳香烃（56.15%）是首要的排放种类,其次是OVOCs （32.32%）.通过分析两家企业内外喷涂工艺的VOCs源成分谱,发现同一企业不同工艺之间有一定差异,多种罐生产企业的内、外喷涂中乙醇占比最高,分别为94.28%、84.46%;单铝罐生产企业的内喷涂2-丁酮（24.33%）是重要组分,外喷涂中甲苯（36.40%）含量较高.     

泰州市大气挥发性有机物化学组分特征、活性及来源解析

挥发性有机物（VOCs）是臭氧和大气颗粒物的重要前体物,本研究利用在线气相色谱-质谱仪（Online-GC-MS）于2018年5—6月对江苏省泰州市大气中98种VOCs进行监测,依据监测结果对泰州市大气VOCs的组成特征、日变化趋势进行分析,对醛酮类VOCs数据进行参数化拟合探究其一次二次贡献,并采用正矩阵因子分解模型（PMF）对VOCs数据进行来源分析,用最大增量反应活性（MIR）计算臭氧生成潜势（OFP）.研究结果表明：泰州市大气VOCs中烷烃占比最高,其次为醛酮;烷烃、烯烃、卤代烃和芳香烃浓度日变化趋势明显,特征相近;参数化方法表明醛类物质主要来自于二次生成,而酮类物质主要来自一次排放;PMF模型结果表明泰州市VOCs的主要贡献源分别为机动车排放、油气溶剂挥发、生物质燃烧、其他工业和天然源;OFP的主要贡献物种为烯烃类,占比34.18%.研究结果表明,控制工业排放和溶剂使用是泰州市大气污染物控制的重点.     

德州市冬季大气挥发性有机物污染特征及其对臭氧和二次有机气溶胶生成的贡献

利用气相色谱-质谱仪/火焰离子检测器（Online-GC-MS/FID）对2017年冬季山东德州大气中99种挥发性有机物（VOCs）进行连续测量,研究了VOCs浓度和组分特征、日变化趋势、来源及其对臭氧（O₃）、二次有机气溶胶（SOA）生成的贡献.结果表明,德州大气VOCs平均体积分数为（47.74±33.11）×10^-9,烷烃占比最大,为40.66%.总VOCs及其组分表现出早晚体积分数高、中午体积分数低的日变化规律.德州大气中丙烷、丙烯、苯及甲苯和二氯甲烷分别受到液化石油气挥发、生物质燃烧、机动车排放和溶剂使用等人为源的影响.反向轨迹模型分析发现,北方内陆气团对德州VOCs体积分数具有一定贡献.烷烃、烯烃、芳香烃的臭氧生成潜势分别为（34.87±33.60）、（120.48±118.76）和（59.77±94.14）μg/m³,乙烯、丙烯、甲苯和间/对二甲苯的贡献较大.芳香烃氧化主导了SOA生成,其贡献率为93.7%,甲苯、间/对二甲苯、苯对SOA生成的贡献最大.为解决大气复合污染问题、实现臭氧和PM_2.5协同控制,德州应重点控制甲苯、间/对二甲苯等芳香烃的排放.     

2017年8—9月湖州市臭氧污染特征及其生成机制研究

近年来近地面臭氧问题日益凸显,成为影响空气质量持续改善的瓶颈.本研究基于2017年8—9月在湖州市城区开展的为期1个月的臭氧及其前体物挥发性有机物（VOCs）和氮氧化物（NO_x）在线观测数据,分析了臭氧及其前体物污染特征,利用正矩阵因子分析（PMF）解析了VOCs来源,并采用基于观测的模型（OBM）对臭氧生成机制进行研究.研究结果表明：1）观测期间湖州市VOCs平均体积分数为（24.78±9.10）×10^-9,其中占比最高的组成为烷烃、含氧VOCs （OVOCs）和卤代烃;2）在臭氧非超标时段,湖州市臭氧生成处于VOCs控制区,而在臭氧重污染期间湖州市处于以VOCs控制为主的过渡区;3）在臭氧超标时段,对臭氧生成潜势（OFP）贡献最大的是芳香烃（39.6%）,其次是烯烃（21.5%）和OVOCs （19.4%）,排名前三的关键组分为甲苯、乙烯和间/对二甲苯;4）源解析结果显示观测期间湖州市VOCs的主要来源是溶剂使用（27.0%）、交通排放（22.7%）、背景+传输（19.3%）、工业排放（16.9%）、汽油挥发（7.7%）和植物排放（6.4%）,重污染过程期间对OFP贡献最大的两类源是交通排放源和溶剂使用源,贡献百分比分别为35.1%和30.5%.因此,对交通排放和溶剂使用方面进行控制管理对湖州市大气臭氧污染防控有重要意义.     

江苏省城区VOCs污染特征及其关键活性物种识别

利用2019年8月13日—9月30日江苏省13个设区市离线监测的VOCs数据,对江苏省城区VOCs污染特征及其关键活性组分进行分析研究.结果表明,江苏省逐日VOCs的体积分数范围为8.83×10^-9~45.11×10^-9,表现为烷烃 > 芳香烃 > 烯烃 > 炔烃.江苏省13个设区市VOCs的体积分数为7.85×10^-9~30.52×10^-9,徐州市VOCs最高,这与徐州市监测点位置分布及其工业结构相关.全省13个设区市臭氧浓度处于优、良、轻度污染和中度污染时,VOCs总体积分数分别为14.96×10^-9、17.96×10^-9、25.85×10^-9和25.11×10^-9,臭氧浓度处于污染状态时的VOCs高于优、良状态,且炔烃占比随着臭氧污染程度的加重呈升高趋势,表明现阶段臭氧生成与人类活动关系密切.通过加权的方式筛选出间/对二甲苯、乙烯、甲苯、丙烯、异戊二烯、邻二甲苯等物种,它们是目前对江苏省城区影响程度较大且影响范围较广的关键活性物种.     

武汉市居民区大气VOCs的污染特征和来源解析

于2016年7月-2017年6月在武汉市典型居民区对大气中101种挥发性有机物（VOCs）进行了监测,以便研究武汉市典型居民区周边VOCs的组成特征和变化规律,并探讨了其主要来源.结果表明,武汉市空气中VOCs的体积分数为（46.24±24.57）×10^-9,表现为烷烃>含氧有机物>烯烃>卤代烃>芳香烃.受交通排放影响烷烃的比例上午高于下午,1月机动车尾气为武汉市主要的VOCs排放源,夏季含氧类化合物浓度高于冬季,可能更多地受本地喷涂等溶剂使用行业和光化学反应生成的影响,5-9月表现出明显的生物源排放特征.利用正交矩阵因子分析（PMF）得到武汉市居民区大气VOCs主要有6个来源,分别为燃烧源、机动车尾气、工业排放、溶剂使用、汽油挥发和植物排放.其中,燃烧源、机动车尾气贡献比例最高,是该区域VOCs控制的重要排放源.     

不同类型草地挥发性有机物排放特征的研究

2003年9月,对内蒙古草原不同类型草地挥发性有机物(VOC)的排放、太阳辐射、气象参数等进行观测,结果表明,固定和新的羊草样地、封育样地、不同程度放牧样地异戊二烯、α蒎烯、β蒎烯、柠檬烯、蒈烯的排放均有明显的日变化规律,并与可见光辐射以及温度有较好的一致性.羊草样地、封育样地、过度放牧、适度放牧样地异戊二烯排放的最大值分别为139.5、25.9、132.3、107.1(单位:μg·m-2·h-1,以碳计).多数情况下,异戊二烯排放通量的测定结果为羊草样地高于封育样地、过度放牧样地高于适度放牧样地.不同程度放牧样地α蒎烯、β蒎烯、柠檬烯、蒈烯等的排放具有明显差别,一般是过度放牧草地高于适度放牧草地.剪草增大了绝大部分VOC组分的排放、以及过度和适度放牧草地VOC的排放,剪草可以造成过度和适度放牧草地异戊二烯排放在中午前后的增加.剪草后,过度放牧草地异戊二烯、α蒎烯、β蒎烯、柠檬烯、蒈烯等的排放通量均远大于适度放牧草地的相应值.土壤异戊二烯、α蒎烯、β蒎烯等的排放很小,分别占相近可见光辐射和温度条件下固定羊草样地排放的0.2%、0、3.0%.     

高温热浪下江苏省典型臭氧污染过程的特征及成因分析

基于环境空气质量监测数据,本文分析了2022年6月14—18日高温热浪期间江苏省臭氧污染过程的时空变化特征,并结合天气形势、WRF-CMAQ模拟和典型城市大气超级站挥发性有机物(VOCs)在线监测数据进行了成因分析。结果表明：高温热浪期间,江苏省13个地级城市臭氧污染超标率达96.9%,中度污染超标率为27.6%,臭氧日最大8 h(MDA8 O₃)峰值质量浓度高达260.0μg·m^-3。南通市、无锡市、苏州市3个典型城市臭氧质量浓度的日变化特征显示,07—13时臭氧质量浓度增长率在27.9%～46.7%,多个时段净增量超过40.0μg·m^-3。利用WRF-CMAQ模型对污染过程进行了数值模拟、过程分析和溯源分析。结果显示,典型城市白天小时平均光化学贡献在24.5～33.0μg·m^-3之间,稳定高值的光化学贡献,叠加持续稳定或突发的传输贡献,导致此次高温热浪下臭氧质量浓度爆发式升高,出现峰值污染。在偏南风的影响下,省外污染源来自浙江省贡献最高,在13.9%～33.8%,其中无锡市和苏州市受浙江省外源影...     

基于旋翼无人机观测的雾天和霾天VOCs垂直分布特征研究

为研究雾和霾天气下VOCs时空变化特征,于2020年11月19日—2021年1月15日在江苏省东海国家气象观测站进行为期58 d的外场观测试验。利用自主研发的多旋翼无人机捕获2次辐射雾和2次霾天气过程,获得气温、气压、相对湿度、风向、风速、VOCs、O₃等7种要素100多条垂直廓线。结果表明：时间上,霾过程夜间VOCs体积浓度(0.225～0.253 ppm(parts per million, 1 ppm=10^-6))明显高于白天(0.191～0.205 ppm),雾形成前体积浓度(0.121～0.239 ppm)显著高于雾过程(0.056～0.209 ppm)。雾过程中VOCs体积浓度与雾强度变化相反,雾层高度与VOCs体积浓度剧烈变化高度一致,雾层(<200 m)中VOCs体积浓度(0.172～0.178 ppm)明显减小,显著低于雾形成前(0.195～0.240 ppm),雾层以上浓度变化大,雾结束后1 h内保持雾过程中分布特点。雾对逆温层中的水溶性污染物有清除作用,VOCs体积浓度和O₃质量浓度均下降。     

Assessment of ambient volatile organic compounds (VOCs) near major roads in urban Nanjing, China

Volatile organic compounds (VOCs) are a major component of atmospheric pollutants in Nanjing, a large city in the east of China. Accordingly, 12-h diurnal monitoring for ten consecutive days was performed adjacent to major roads in five districts, ca.1.5 m above ground level, in April, July and October 2006, and January 2007. The most numerous species of VOCs (benzene, toluene, ethylbenzene, m/p-xylene, o-xylene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, tetrachloromethane, trichloroethane and tetrachloroethane) were selected as the target pollutants for this field study of atmospheric distribution. The eleven VOCs were mostly found in gas phase due to their high vapor pressures. Gas-phase concentrations ranged between 0.6 and 67.9 μg m^− 3. Simultaneously, the levels of those VOCs measured near major roads were associated slightly with their regional background level. For all these areas, as expected, the high traffic area was the highest in terms of concentration. A positive correlation was also found between the VOC levels and traffic density. Our studies also provided VOC distribution, and vertical/horizontal profiles. The results show that traffic-related exposure to VOCs in major road microenvironments is higher than elsewhere and poses a potential threat to pedestrians, commuters, and traffic-exposed workers.     

Establishment and Evaluation of a Method for Analyzing Atmospheric Volatile Organic Compounds

An automated cumulative sampling system and a method that combines a two-step cryo-concentrated system and gas chromatography/mass spectrometry （CCS-GC/MS） are introduced. The method is evaluated by a set of special experiments and the results are presented. The lowest measurement detection limit was expanded from 10^-6 nmol mol^-1 to 10^-12 nmol mol^-1 by using CCS-GC/MS instead of the simpler method of gas chromatography/mass spectrometry （GC/MS）, with the average responsible factor of 39 object compounds being 2.9 × 10^-12. When the volume of air sample reached 1000 cm^3, the lowest detection limit reached up to 7 × 10^-12-40 × 10^-12 nmol mol^-1. The CCS-GC/MS method can potentially identify all objective chemical species in an atmospheric sample, with an average 2.5 s bias error of retention time for 39 gas chromatography （GC） peaks. Within the range 0-400×10^-9 nmol mol^-1, the concentration of 39 kinds of objective compounds can be individually calculated very accurately by a standard curve [average r^2 （coefficient of determination） value of above 0.99]. The recovery efficiency was 88%-111%, with an average of 100.8% ±5.6%. The bias error of precision was 2%-14%, with an average of 6.6%.     

Characterization and source apportionment of volatile organic compounds in urban and suburban Tianjin,China

Tianjin is the third largest megacity and the fastest growth area in China, and consequently faces the problems of surface ozone and haze episodes. This study measures and characterizes volatile organic compounds(VOCs), which are ozone precursors, to identify their possible sources and evaluate their contribution to ozone formation in urban and suburban Tianjin,China during the Ha Chi(Haze in China) summer campaign in 2009. A total of 107 species of ambient VOCs were detected,and the average concentrations of VOCs at urban and suburban sites were 92 and 174 ppbv, respectively. Of those, 51 species of VOCs were extracted to analyze the possible VOC sources using positive matrix factorization. The identified sources of VOCs were significantly related to vehicular activities, which specifically contributed 60% to urban and 42% to suburban VOCs loadings in Tianjin. Industrial emission was the second most prominent source of ambient VOCs in both urban and suburban areas, although the contribution of industry in the suburban area(36%) was much higher than that at the urban area(16%). We conclude that controlling vehicle emissions should be a top priority for VOC reduction, and that fast industrialization and urbanization causes air pollution to be more complex due to the combined emission of VOCs from industry and daily life, especially in suburban areas.     

Exchange of Short-Chain Oxygenated Volatile Organic Compounds (VOCs) between Plants and the Atmosphere: A Compilation of Field and Laboratory Studies

Field and laboratory investigations of the exchange of the short-chain organic acids – formic acid and acetic acid – as well as their homologous aldehydes are discussed. Both acids are substantially released from several plant species. Emission measurements under field conditions are compiled to give an overview of three years of measurements. Emission rates from several tree species were found in the range between zero and 60 nmoles m^–2 min^–1 for acetic acid and between zero and 90 nmoles m^–2 min^–1 for formic acid though also a deposition has been observed to orange trees. Investigations under laboratory conditions showed an order of magnitude lower emission rates with significant differences under light and dark conditions, and a deposition was observed under certain conditions. Hence, low emission rates or even a bi-directional exchange, emission as well as deposition have to be taken into account. Further differences between field and laboratory studies are discussed considering age of trees, stress effects and a potential production of acids by photochemical conversion of precursors inside enclosures during sampling. Field data on the exchange of form- and acetaldehyde show a complex behavior. We found emission as well as uptake. The bi-directional exchange is significantly triggered by the ambient mixing ratios of both aldehyde species and exhibits a compensation point. Further studies are needed for generalization of the exchange of these and potentially also for other compounds.