基于铁塔观测的深圳大气VOCs垂直分布特征

2018年8～9月,利用深圳市铁塔的11个垂直梯度平台进行了9轮挥发性有机物(VOCs)不锈钢罐采样,并应用气相色谱质谱联用仪(GC/MS)对103种VOCs组分进行定量分析,研究不同垂直高度上VOCs组分特征及对近地面臭氧(O₃)生成的影响.结果表明,从地面到345m高空VOCs总体污染水平相近,在垂直梯度上变化不大;但烯烃浓度随高度上升呈现下降趋势,主要受地面天然源排放的异戊二烯主导.结合典型物种及物种对的分析发现,日间的二次生成、工业排放和光化学反应消耗是影响垂直梯度上VOCs浓度变化的主要原因.应用混合层梯度方法对VOCs通量进行计算发现,烷烃(28%)和芳香烃(23%)的通量贡献最多;二氯甲烷(1.93±0.29)mg/(m²·h)、甲苯(1.86±0.39)mg/(m²·h)具有较高的垂直通量值.结合二氧化氮(NO₂)和O₃垂直廓线的关系分析得出,总挥发性有机物(TVOCs)/NO₂在300m以上高空达到峰值,更加有利于O₃     

Characterization, reactivity, source apportionment, and potential source areas of ambient volatile organic compounds in a typical tropical city

Based on one-year observation, the concentration, sources, and potential source areas of volatile organic compounds (VOCs) were comprehensively analyzed to investigate the pollution characteristics of ambient VOCs in Haikou, China. The results showed that the annual average concentration of total VOCs (TVOCs) was 11.4 ppbV, and the composition was dominated by alkanes (8.2 ppbV, 71.4%) and alkenes (1.3 ppbV, 20.5%). The diurnal variation in the concentration of dominant VOC species showed a distinct bimodal distribution with peaks in the morning and evening. The greatest contribution to ozone formation potential (OFP) was made by alkenes (51.6%), followed by alkanes (27.2%). The concentrations of VOCs and nitrogen dioxide (NO₂) in spring and summer were low, and it was difficult to generate high ozone (O₃) concentrations through photochemical reactions. The significant increase in O₃ concentrations in autumn and winter was mainly related to the transmission of pollutants from the northeast. Traffic sources (40.1%), industrial sources (19.4%), combustion sources (18.6%), solvent usage sources (15.5%) and plant sources (6.4%) were identified as major sources of VOCs through the positive matrix factorization (PMF) model. The southeastern coastal areas of China were identified as major potential source areas of VOCs through the potential source contribution function (PSCF) and concentration-weighted trajectory (CWT) models. Overall, the concentration of ambient VOCs in Haikou was strongly influenced by traffic sources and long-distance transport, and the control of VOCs emitted from vehicles should be strengthened to reduce the active species of ambient VOCs in Haikou, thereby reducing the generation of O₃.     

Review of the influencing factors of secondary organic aerosol formation and aging mechanism based on photochemical smog chamber simulation methods

The formation and aging mechanism of secondary organic aerosol (SOA) and its influencing factors have attracted increasing attention in recent years because of their effects on climate change, atmospheric quality and human health. However, there are still large errors between air quality model simulation results and field observations. The currently undetected components during the formation and aging of SOA due to the limitation of current monitoring techniques and the interactions among multiple SOA formation influencing factors might be the main reasons for the differences. In this paper, we present a detailed review of the complex dynamic physical and chemical processes and the corresponding influencing factors involved in SOA formation and aging. And all these results were mainly based the studies of photochemical smog chamber simulation. Although the properties of precursor volatile organic compounds (VOCs), oxidants (such as OH radicals), and atmospheric environmental factors (such as NO_x, SO₂, NH₃, light intensity, temperature, humidity and seed aerosols) jointly influence the products and yield of SOA, the nucleation and vapor pressure of these products were found to be the most fundamental aspects when interpreting the dynamics of the SOA formation and aging process. The development of techniques for measuring intermediate species in SOA generation processes and the study of SOA generation and aging mechanism in complex systems should be important topics of future SOA research.     

京津冀地区典型印刷企业VOCs排放特征及臭氧生成潜势分析

本研究在京津冀地区选取23家典型印刷企业进行调研,并对其中具备采样条件的企业通过气袋采样-GC-MSD/FID采集及分析系统,获得48组分析结果,定量分析了京津冀地区印刷企业VOCs的排放特征,并估算其臭氧生成潜势.结果表明,各企业排气筒有组织排放的VOCs(以非甲烷总烃表征)浓度差异很大,包装印刷企业VOCs排放浓度范围为29. 9～755. 0 mg·m~(-3),出版物印刷企业VOCs排放浓度范围为3. 3～99. 0 mg·m~(-3);各企业车间印刷工位中,包装印刷企业VOCs排放浓度在129. 7～958. 4 mg·m~(-3)之间,出版物印刷企业VOCs排放浓度范围为19. 1～113. 7 mg·m~(-3);包装印刷企业排放的VOCs浓度普遍高于出版物印刷企业,这与其使用溶剂型油墨有关. VOCs组分构成方面,包装印刷和出版物印刷企业印刷工位排放的VOCs中,含氧VOCs均为首要VOCs种类,占比在32. 6%～99. 4%之间,其次是烷烃.臭氧生成潜势方面,印刷企业臭氧生成潜势(OFP值)平均值为505. 5 mg·m~(-3),其中包装印刷企业为564. 1 mg·m~(-3),出版物印刷企业为52. 9 mg·m~(-3);臭氧生成系数(SR值)平均值为1. 24 g·g-1,其中包装印刷企业为1. 70 g·g-1、出版物印刷企业为0. 89 g·g-1.从OFP值和SR值可以看出,包装印刷企业应作为未来京津冀地区印刷行业VOCs管控的重点.     

建筑胶黏剂使用VOCs排放系数与排放清单

建筑装饰是我国VOCs重要人为排放源之一,关于建筑胶黏剂VOCs排放相关研究极少.本文以建筑胶黏剂为研究对象,通过实测获取各类建筑胶黏剂VOCs含量水平和排放系数,采用排放系数法,自上而下建立了我国2013~2017年建筑胶黏剂VOCs排放清单.结果表明,建筑胶黏剂使用VOCs综合排放系数为97 kg·t^-1,其中溶剂型、水基型和本体型建筑胶黏剂的VOCs排放系数分别为543、45和63 kg·t^-1;2013~2017年我国建筑胶黏剂使用VOCs排放量分别为16.5、18.1、18.8、20.1和21.9万t.水基型、本体型和溶剂型建筑胶黏剂的VOCs排放量贡献分别为25.5%、23.6%和50.9%;2017年山东、江苏、浙江、四川、广东、河南、云南和福建等8省贡献较大,排放量合计为12.0万t,占全国建筑胶黏剂VOCs排放量的约55%.     

Sorption mechanism of naphthalene by diesel soot: Insight from displacement with phenanthrene/p-nitrophenol

The nonlinear sorption of hydrophobic organic contaminants (HOCs) could be changed to linear sorption by the suppression of coexisting solutes in natural system, resulting in the enhancement of mobility, bioavailability and risks of HOCs in the environment. In previous study, inspired from the competitive adsorption on activated carbon (AC), the displaceable fraction of HOCs sorption to soot by competitor was attributed to the adsorption on elemental carbon fraction of soot (EC-Soot), while the linear and nondisplaceable fraction was attributed to the partition in authigenic organic matter of soot (OM-Soot). In this study, however, we observed that the linear and nondisplaceable fraction of HOC (naphthalene) to a diesel soot (D-Soot) by competitor (phenanthrene or p-nitrophenol) should be attributed to not only the linear partition in OM-Soot, but also the residual linear adsorption on EC-Soot. We also observed that the competition on the surface of soot dominated by external surface was different from that of AC dominated by micropore surface, i.e., complete displacement of HOCs by p-nitrophenol could occur for the micropore surface of AC, but not for the external surface of soot. These observations were obtained through the separation of EC-Soot and OM-Soot from D-Soot with organic-solvent extraction and the sorption comparisons of D-Soot with an AC (ACF300) and a multiwalled carbon nanotube (MWCNT30). The obtained results would give new insights to the sorption mechanisms of HOCs by soot and help to assess their environmental risks.     

中国室内挥发性有机物污染特征

近年来室内空气污染问题频发,已引起全社会的广泛关注.挥发性有机物(volatile organic compounds,VOCs)是室内空气的主要污染物之一,其成分复杂,来源广泛,严重威胁人体健康.本文综述了中国近十年来室内VOCs在来源、浓度水平、影响因素及健康评价方面的研究进展.研究表明,室内建筑装修材料、人类活动及室外污染等来源都会影响VOCs的室内浓度;中国住宅内甲醛、苯等VOCs污染普遍存在,家具市场是甲醛污染最高的公共场所;VOCs浓度受到温湿度、通风和装修时间等因素影响;中国室内部分VOCs对人体健康影响评估值超过美国环保署可接受水平.调查更全面的室内VOCs数据,探索对各类因素影响机制,提出更有效降低VOCs对人体健康影响的措施将是未来室内空气治理重点发展方向.     

Volatile organic compounds concentration profiles and control strategy in container manufacturing industry: Case studies in China

Volatile organic compounds (VOCs), important precursors of ozone (O₃) and fine particulate matter (PM_2.5), are the key to curb the momentum of O₃ growth and further reducing PM_2.5 in China. Container manufacturing industry is one of the major VOC emitters, and more than 96% containers of the world are produced in China, with the annual usage of coatings of over 200,000 tons in recent years. This is the first research on the emission characteristics of VOCs in Chinese container manufacturing industry, including concentration and ozone formation potential (OFP) of each species. The result shows that the largest amounts of VOCs are emitted during the pretreatment process, followed by the paint mixing process and primer painting process, and finally other sprays process. The average VOC concentrations in the workshops, the exhausts before treatment and the exhausts after treatment are ranging from 82.67–797.46 , 170–1,812.65 , 66.20–349.63 mg/m³, respectively. Benzenes, alcohols and ethers are main species, which contribute more than 90% OFP together. Based on the emission characteristics of VOCs and the technical feasibility, it is recommended to set the emission limit in standard of benzene to 1.0 mg/m³, toluene to 10 mg/m³, xylene to 20 mg/m³, benzenes to 40 mg/m³, alcohols and ethers to 50 mg/m³, and VOCs to 100 mg/m³. The study reports the industry emission characteristics and discusses the standard limits, which is a powerful support to promote VOCs emission reduction, and to promote the coordinated control of PM_2.5 and O₃ pollution.     

南宁市冬季挥发性有机物特征及其来源分析

为了解南宁市冬季期间挥发性有机物（VOCs）污染特征及来源,采用在线连续监测系统于2020年12月9日~2021年2月22日在南宁市区对116种VOCs进行了在线连续观测.结果显示,观测期间VOCs体积分数为37.57x10^-9,烷烃、烯烃、芳香烃、OVOCs及卤代烃体积分数占VOCs比例分别为44%、15%、8%、19%和11%.VOCs体积分数白天低,夜晚高;采用OH消耗速率（L_OH）和臭氧生成潜势（OFP）估算了观测期间VOCs大气化学反应活性,结果表明醛酮类、芳香烃和烯烃是主要的活性物质;使用气溶胶生成系数法（FAC）估算了VOCs对二次有机气溶胶（SOA）的贡献,发现芳香烃对SOA生成贡献最大,占比为98%,其中苯、间/对二甲苯和甲苯为优势物种;正交矩阵因子（PMF）解析结果表明,冬季期间南宁市VOCs主要来源于：机动车尾气排放源（30.1%）>固定燃烧及生物质燃烧源（22.2%）>工业工艺排放源（16.8%）,而OFP贡献较高的源分别为溶剂使用源（23.9%）、固定燃烧及生物质燃烧源（22%）、机动车尾气排放源（21.8%）.因此,机动车尾气排放源和固定燃烧及生物质燃烧源应为南宁市冬季的优先管控源类,其次为工业工艺排放源、溶剂使用源.     

食用植物油加工VOCs排放特征

获取了菜籽和大豆植物油加工行业VOCs排放系数、成分谱和臭氧生成贡献,并对其全国VOCs排放量进行了计算.结果表明,菜籽油加工过程VOCs排放系数为1.20kg/t菜籽用量和6.32kg/t菜籽油产量,大豆油加工过程VOCs排放系数为0.36kg/t大豆用量和2.35kg/t大豆油产量.菜籽油和大豆油加工排放的VOCs主要来自于有机溶剂挥发.VOCs排放占比最大的物种是正己烷,其次是甲基戊烷（包括3-甲基戊烷和2-甲基戊烷）,再次是甲基环戊烷.植物油加工行业OFP为931.47μg/m³,其中,烷烃贡献最大,占比为61.90%;其次是烯烃和OVOCs,占比分别为19.61%和15.14%,.2019年中国大豆和油菜籽植物油加工VOCs排放量为5.12万t,大豆和油菜籽植物油分别贡献65.4%和34.6%,山东、湖北、江苏、广东、河南、广西、天津、河北、湖南、福建是贡献最大的10个省份,合计占比72.0%.