植物挥发性有机物的分析方法

为了分析植物排放到大气中的挥发性有机物，在2000年1-6月期间，与美国国家大气研究中心（NCAR）的科学家共同发展和研究了一套自动的气相色谱系统和分析方法。该系统引入一个小型冰箱以除去空气样品进样时的水分，得到了对挥发性有机物样品进行分析时比较好的准确度。在5℃以及稳定的进样速率的条件下，可以得到比较好的除水效果。对NCAR附近的大气进行了采样，并利用此系统做了分析。本简单介绍此自动系统以及样品分析结果。实验结果表明，此套系统具有良好的重复性和稳定性，主要的挥发性有机物的成分如异戊二烯和单萜烯等具有明显的日变化。     

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%.     

珠三角关键大气挥发性有机物的模拟精度评估

大气挥发性有机物（VOCs）是导致臭氧污染的关键前体物,是城市空气质量建模不可或缺的重要组成部分,但由于其非常复杂的构成和来源以及监测数据缺乏,目前对其模拟精度的了解仍非常有限。本文利用嵌套网格空气质量模式预报系统（NAQPMS）对珠江三角洲（简称珠三角）地区2017年9月21日至11月20日的VOCs开展了模拟试验,并利用光化学监测网8个地面站点的VOCs浓度监测数据,对模式模拟的关键VOCs组分进行了精度评估。结果发现,模式对强活性的甲苯、乙烯和二甲苯具有较高的模拟精度,模拟浓度偏差百分比为0.4%～26.6%,模拟能较好再现其日均浓度变化趋势和日变化的双峰特征。但是模式对化学反应活性强且与植物排放密切相关的异戊二烯具有很大的模拟偏差,偏差比近100%,无法再现其白天浓度高、夜间浓度低的观测日变化特征。通过分析发现,现有模拟系统主要考虑人为污染物排放而未考虑生物源排放,可能是导致这一模拟偏差的关键原因。同时,评估结果也表明模式在VOCs空间分布模拟上仍面临很大的不确定性。本文结果揭示了珠三角VOCs模拟面临的关键不确定性,表明融合VOCs观测数据来揭示并减小VOCs模拟的不确定性具有非常迫切的需求。     

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.     

餐饮源挥发性有机物(VOCs)排放特征及对臭氧生成的影响

餐饮排放是城市地区挥发性有机物（VOCs）重要的无组织来源,由于其排放特征复杂,是大气环境研究和管理的薄弱环节.本研究采用了现场和实验模拟两种采样方式,利用2,4-二硝基苯肼（DNPH）采样柱和不锈钢罐分别采集羰基化合物和全空气样品,然后利用高效液相色谱（HPLC）和气相色谱-质谱联用仪（GC-MS/FID）对116种组分进行定性定量分析.在此基础上,分析了餐饮源VOCs的排放特征及其影响因素.总体来看,含氧有机物（OVOCs）和烷烃是VOCs浓度的主要贡献者,但不同餐饮源的源谱特征差异较大.另外,通过比较发现食用油的种类、油的使用次数、加热方式、烹饪方式和调味料等因素会对餐饮源VOCs排放特征造成显著影响.进一步分析了不同菜系所排放VOCs的臭氧生成潜势（OFP）,关键组分主要是甲醛、乙醛、丁烯醛、乙烯和丙烯等.本研究成果能够补充我国餐饮源VOCs控制所需的基础数据.     

森林排放非甲烷碳氢化合物的初步研究

1995年6月至1996年4月,在广东肇庆鼎湖山自然保护区每两周采样一次,利用0.8 L不锈钢采样钢瓶采样和气相色谱法分析、研究森林排放的非甲烷碳氢化合物的浓度。结果表明,森林排放的异戊二烯有明显的季节变化,其浓度与温度有明显的正相关关系。     

基于CMAQ-MCM模型的长三角地区夏季臭氧和大气氧化性影响的研究

传统的空气质量模型多使用简化的光化学反应机制来模拟大气污染物的形成.这些机制主要基于烟雾箱实验拟合的反应速率和产物来模拟二次产物（如臭氧（O₃））前体物的氧化反应,具有一定的不确定性,导致模拟结果产生偏差.针对该问题,本研究将详细的大气化学机理（MCMv3.3.1）与美国国家环境保护局研制的第三代空气质量预报和评估系统CMAQ相结合（CMAQ-MCM）,模拟研究长三角地区2015年8月27—9月5日臭氧高发时段的空气质量.CMAQ-MCM模型可以较好地模拟长三角地区6个代表城市O₃和其前体物随时间的变化趋势.对模拟的O₃日最大8 h平均浓度的统计分析表明,徐州表现最好（标准平均误差=-0.15,标准平均偏差=0.23）.在长三角地区,居民源对挥发性有机物（VOCs）的贡献最大,占39.08%,其次是交通运输（33.25%）和工业（25.56%）.能源对总VOCs的贡献最小,约为2.11%.对活性氧化氮（NO_y）的分析表明,其主要组分是NO_x（80%）,其次是硝酸（HNO₃）（<10%）.O₃的空间分布与NO_y和NO_x非常相似.HCHO等其他氧化产物的分布与NO_x相似,这很可能是由于在高NO_x条件下VOCs氧化产生的产物.甲基乙烯基酮（MVK）和甲基丙烯醛（MACR）的空间分布与自然源VOCs （BVOCs）非常相似,表明长三角地区MVK和MACR主要由BVOCs氧化生成.长三角地区受到人为源和自然源排放相互作用的影响.     

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.     

Volatile Organic Compounds in the Po Basin. Part B: Biogenic VOCs

Measurements of volatile organic compounds (VOCs) were performed in the Po Basin, northern Italy in early summer 1998, summer 2002, and autumn 2003. During the three campaigns, trace gases and meteorological parameters were measured at a semi-rural station, around 35 km north of the city center of Milan. Bimodal diurnal cycles of isoprene with highest concentrations in the morning and evening were found and could be explained by the interaction of emissions, chemical reactions, and vertical mixing. The diurnal cycle could be qualitatively reproduced by a three-dimensional Eulerian model. The nighttime decay of isoprene could be attributed mostly to reactions with NO₃, while the decay of the isoprene oxidation products could not be explained with the considered chemical reactions. Methanol reached very high mixing ratios, up to 150 ppb. High concentrations with considerable variability occurred during nights with high relative humidities and low wind speeds. The origin of these nighttime methanol concentrations is most likely local and biogenic but the specific source could not be identified.     

Emission of Biogenic Volatile Organic Compounds: An Overview of Field, Laboratory and Modelling Studies Performed during the `Tropospheric Research Program' (TFS) 1997–2000

The present paper summarises results on the emission of biogenicvolatile organic compounds (BVOC) achieved within the frame of thenational `German Tropospheric Research Programme' (TFS) between 1997 and2000. Field measurements were carried out at the meteorologicalmonitoring station `Hartheimer Wald' located in the vicinity of Freiburg(upper Rhine valley), Germany, within a pine plantation dominated byScots pine (Pinus sylvestris L.). The measured BVOC emissionrates were used to determine the daily and seasonal variation of BVOCemission and its dependence on important meteorological and plantphysiological parameters. In parallel, laboratory experiments usingyoung trees of pine (P. sylvestris), poplar (Populustremula ×P. alba) and pedunculate oak (Quercusrobur L.) were performed, and the influence of abiotic (e.g.,light, temperature, seasonality, flooding) factors on the biosynthesisand emission of BVOC was quantified. Based on these data, emissionalgorithms were evaluated and a process-oriented numerical model for thesimulation of the isoprene emission by plants was developed. Inaddition, newly calculated land use and tree species distributions wereused for the calculation of an actual BVOC emission inventory ofGermany.     

Biogenic Volatile Organic Compounds (VOC): An Overview on Emission, Physiology and Ecology

This overview compiles the actual knowledge of the biogenic emissions of some volatile organic compounds (VOCs), i.e., isoprene, terpenes, alkanes, alkenes, alcohols, esters, carbonyls, and acids. We discuss VOC biosynthesis, emission inventories, relations between emission and plant physiology as well as temperature and radiation, and ecophysiological functions. For isoprene and monoterpenes, an extended summary of standard emission factors, with data related to the plant genus and species, is included. The data compilation shows that we have quite a substantial knowledge of the emission of isoprene and monoterpenes, including emission rates, emission regulation, and biosynthesis. The situation is worse in the case of numerous other compounds (other VOCs or OVOCs) being emitted by the biosphere. This is reflected in the insufficient knowledge of emission rates and biological functions. Except for the terpenoids, only a limited number of studies of OVOCs are available; data are summarized for alkanes, alkenes, carbonyls, alcohols, acids, and esters. In addition to closing these gaps of knowledge, one of the major objectives for future VOC research is improving our knowledge of the fate of organic carbon in the atmosphere, ending up in oxidation products and/or as aerosol particles.     

A Database for Volatile Organic Compounds

The database for volatile organic compounds (VOC data base) was created with the aim of providing an overview of tropospheric hydrocarbon measurements. The data base contains 202 substances, for which atmospheric and useful kinetic data such as rate coefficients, photolysis frequencies, mixing ratios, emission data and ozone formation potentials are compiled from available literature. The database file can be downloaded without charge from http://www.physchem.uni-wuppertal.de/voc-database. Registered users will be informed about the appearance of updates.     

Anthropogenic Effects on Biogenic Secondary Organic Aerosol Formation

Anthropogenic emissions alter biogenic secondary organic aerosol(SOA) formation from naturally emitted volatile organic compounds(BVOCs). We review the major laboratory and field findings with regard to effects of anthropogenic pollutants(NOx, anthropogenic aerosols, SO_2, NH_3) on biogenic SOA formation. NOx participate in BVOC oxidation through changing the radical chemistry and oxidation capacity, leading to a complex SOA composition and yield sensitivity towards NOx level for different or even specific hydrocarbon precursors. Anthropogenic aerosols act as an important intermedium for gas–particle partitioning and particle-phase reactions, processes of which are influenced by the particle phase state, acidity, water content and thus associated with biogenic SOA mass accumulation. SO_2 modifies biogenic SOA formation mainly through sulfuric acid formation and accompanies new particle formation and acid-catalyzed heterogeneous reactions. Some new SO_2-involved mechanisms for organosulfate formation have also been proposed.NH_3/amines, as the most prevalent base species in the atmosphere, influence biogenic SOA composition and modify the optical properties of SOA. The response of SOA formation behavior to these anthropogenic pollutants varies among different BVOCs precursors. Investigations on anthropogenic–biogenic interactions in some areas of China that are simultaneously influenced by anthropogenic and biogenic emissions are summarized. Based on this review, some recommendations are made for a more accurate assessment of controllable biogenic SOA formation and its contribution to the total SOA budget. This study also highlights the importance of controlling anthropogenic pollutant emissions with effective pollutant mitigation policies to reduce regional and global biogenic SOA formation.     

Air-Sea Exchange of Volatile Organic Compounds: A New Model with Microlayer Effects

The authors propose a new “three-layer” conceptual model for the air-sea exchange of organic gases, which includes a dynamic surface microlayer with photochemical and biological processes. A parameterization of this three-layer model is presented, which was used to calculate the air-sea fluxes of acetone over the Pacific Ocean. The air-sea fluxes of acetone calculated by the three-layer model are in the same direction but possess half the magnitude of the fluxes calculated by the traditional two-layer model in the absence of photochemical and biological processes. However, photochemical and biological processes impacting acetone in the microlayer can greatly vary the calculated fluxes in the three-layer model, even reversing their direction under favorable conditions. Our model may help explain the discrepancies between measured and calculated acetone fluxes in previous studies. More measurements are needed to validate our conceptual model and provide constraints on the model parameters.     

Vertical Evolution of Boundary Layer Volatile Organic Compounds in Summer over the North China Plain and the Differences with Winter

The vertical observation of volatile organic compounds(VOCs) is an important means to clarify the mechanisms of ozone formation. To explore the vertical evolution of VOCs in summer, a field campaign using a tethered balloon during summer photochemical pollution was conducted in Shijiazhuang from 8 June to 3 July 2019. A total of 192 samples were collected, 23 vertical profiles were obtained, and the concentrations of 87 VOCs were measured. The range of the total VOC concentration was 41–48 ppbv below 600 m. It then slightly increased above 600 m, and rose to 58 ± 52 ppbv at 1000 m.The proportion of alkanes increased with height, while the proportions of alkenes, halohydrocarbons and acetylene decreased. The proportion of aromatics remained almost unchanged. A comparison with the results of a winter field campaign during 8–16 January 2019 showed that the concentrations of all VOCs in winter except for halohydrocarbons were more than twice those in summer. Alkanes accounted for the same proportion in winter and summer. Alkenes,aromatics, and acetylene accounted for higher proportions in winter, while halohydrocarbons accounted for a higher proportion in summer. There were five VOC sources in the vertical direction. The proportions of gasoline vehicular emissions + industrial sources and coal burning were higher in winter. The proportions of biogenic sources + long-range transport, solvent usage, and diesel vehicular emissions were higher in summer. From the surface to 1000 m, the proportion of gasoline vehicular emissions + industrial sources gradually increased.     

Emissions of Volatile Organic Compounds from Sunflower and Beech: Dependence on Temperature and Light Intensity

Emissions of volatile organic compounds (VOCs) from sunflower (Helianthus annuus L. cv. giganteus) were measured in a continuously stirred tank reactor. The compounds predominantly emitted from sunflower were: isoprene, the monoterpenes -pinene, -pinene, sabinene, 3-carene and limonene, an oxygenated terpene, not positively identified so far and the sesquiterpene -caryophyllene. Emission rates ranged from 0.8 x 10^–16 to 4.3 x 10 ^–15 mol cm^–2 s^–1 at a temperature of 25°C and at a light intensity of 820 µEm^–2 s^–1. A dependence of the emission rates on temperature as well as on light intensity was observed. The emission rates of -pinene, sabinene and thujene from beech (Fagus sylvatica L.) were also affected by temperature as well as by light intensity. Our results suggest that an emission algorithm for all compounds emitted from sunflower and beech has to consider temperature and light intensity simultaneously. The observations strongly indicate that the emissions of VOCs from sunflower and beech are in part closely coupled to the rate of biosynthesis and in part originate from diffusion out of pools. The emission rates can be described by an algorithm that combines the model given by Tingey and coworkers with the algorithm given by Guenther and coworkers after slight modification.     

Vertical Profiles of Volatile Organic Compounds in Suburban Shanghai

As Volatile Organic Compounds(VOCs) are one of the precursors of ozone, their distribution and variable concentrations are highly related to local ozone pollution control. In this study, we obtained vertical profiles of VOCs in Shanghai's Jinshan district on 8 September and 9 September in 2016 to investigate their distribution and impact on local atmospheric oxidation in the near surface layer. Vertical samples were collected from heights between 50 m and 400 m by summa canisters using an unmanned aerial vehicle(UAV). Concentrations of VOCs(VOCs refers to the 52 species measured in this study) varied minimally below 200 m, and decreased by 21.2% from 100 m to 400 m. The concentrations of VOCs above 200 m decreased significantly in comparison to those below 200 m. The proportions of alkanes and aromatics increased from 55.2% and 30.5% to 57.3% and 33.0%, respectively. Additionally, the proportion of alkenes decreased from 13.2% to 8.4%. Toluene and m/p-xylene were the key species in the formation of SOA and ozone. Principal component analysis(PCA) revealed that the VOCs measured in this study mainly originated from industrial emissions.