在线分析宁波市北仑区VOCs组成、趋势及来源

利用VOCs在线监测技术，对2010年宁波市北仑区空气内的VOCs的浓度、组成、变化规律及来源进行分析研究。结果表明，在北仑区域内的16种VOCs中，苯、甲苯、二甲苯、乙苯和己烷的比例占到了总数的82．9％，且该5种有机物浓度存在较为典型的季节性变化规律和日变化规律；采用CMD模型法对VOCs的来源进行解析后发现，北仑区域内的VOCs主要来源于汽车尾气、汽油蒸气和石油液化气，而且汽车尾气的贡献值要比一些大城市低得多，且夏季和冬季的成分源贡献率存在明显差异。     

Regional and seasonal characteristics of emission sources of fine airborne particulate matter collected in the center and suburbs of Tokyo, Japan as determined by multielement analysis and source receptor models

Airborne particulate matter, suspected to induce adverse effects on human health, have been one of the most important concerns regarding recent air pollution issues in Japan. To characterize regional and seasonal variations in emission sources of fine airborne particulate matter (d < 2 microm), monthly samples (n = 36 for each site) were collected at urban (Tokyo), suburban (Maebashi), and mountainous (Akagi) sites in Japan from April 2003 to March 2006. Multielement analysis of chemical species (Na, Al, K, Ca, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Sb, and Pb) was performed by inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry. The combined source receptor model, which consists of positive matrix factorization and chemical mass balance, determined the contributions of nine emission sources (local and continental soils, road dust, coal and oil combustion, waste incineration, steel industry, brake wear, and diesel exhaust) to the observed elemental concentrations. Large regional differences were identified in the source contributions among the observational sites. Diesel exhaust was identified as the most significant source (70% of identified contributions) at the urban site. Local and continental soils, coal combustion, and diesel exhaust were intricately assigned (20-30% each) to the suburban site. Continental soil was the predominant source (65%) at the mountainous site. Respective significant source contributions dominated the seasonal variations of total elemental concentrations at each site. These results suggest that a better understanding of the regional and seasonal characteristics of impacting emission sources will be important for improving regional environments.     

典型化工园区大气中挥发性有机物污染调查

对常州市某典型化工园区大气中挥发性有机物(VOCs)污染状况进行了调查。结果表明,该化工园区大气中检出挥发性有机物共有58种,组分有芳香烃、饱和烷烃、卤代烃、烯烃、醛酯类化合物及其他类;苯、甲苯、乙苯、二甲苯为主要挥发性有机污染物,质量浓度为1.0~194μg/m~3;均未超出参考标准的限值。背景点位和园区点位大气中主要ρ总(VOCs)在秋冬季最高,敏感点大气VOCs随季节变化也较为明显;园区T1和T2ρ总(VOCs)年均值高于敏感点位,背景点位年均值最低;园区点位除了汽车尾气排放之外,溶剂的挥发和生产工艺中污染物的排放也增加了大气中苯系物的浓度,同时也对敏感点位和对照点位的大气质量产生了一定的影响。     

中国沿海三省主要饮用水源有机物监测

采用固相萃取、吹扫捕集和气相色谱-质谱联用仪(GC-MS)对江苏、浙江、山东省的21个主要地表饮用水源、126份水样中的25种VOCs、38种SVOCs进行定量检测。结果有19种VOCs、10种SVOCs至少在一个水源地多次被检出,其中挥发性氯代烃、苯系物、氯代苯类、酚类、硝基苯类、酞酸酯类、农药为中国或美国环境保护局提出的"水中优先控制污染物",最高检出量为27.79μg/L。三省主要地表水受到有机物轻度污染,水体中VOCs、SVOCs含量尚未超过《地表水环境质量标准》(GB 3838-2002)和《生活饮用水卫生标准》(GB 5749-2006)限值,工业废水排放及农田雨水径流是地表水有机物的重要来源。     

PM2.5 and volatile organic compounds (VOCs) in ambient air: a focus on the effect of meteorology

PM(2.5) and VOCs (benzene, toluene, m-p-o-xylenes) concentrations were measured in an urban and a suburban site in Athens, Greece, during the period between April and November 2004. This period, which is considered to be the warmer period in Greece, is characterized by the development of sea-breeze over the Attica Basin. Additionally strong Northern, North-eastern winds called "The Etesians", predominate during the summer months (July-August), acting positively to the dispersion of pollutants. In this campaign, 24 days with sea-breeze development were observed, 15 days with northern winds, 6 days with southern winds while the rest of the days presented no specific wind profile. Maximum concentrations of PM(2.5), VOCs and nitrogen oxides, were detected during the days with sea-breeze, while minimum concentrations during the days with northern winds. Ozone was the only pollutant that appeared to have higher concentrations in the background site and not in the city centre, where benzene presented strong negative correlation with ozone, indicating the photochemical reaction of hydrocarbons that lead to the ozone formation. The BTX ratios were similar for both sites and wind profiles, indicating common sources for those pollutants. T/B ratio ranged in low levels, between 3-5 for site A and 2-5 for site B, suggesting vehicles emissions as the main sources of volatile compounds. Finally, the strong correlations of PM(2.5) and benzene concentrations, between the two sampling sites, indicate that both the city centre and the background site, are affected by the same sources, under common meteorological conditions (sea-breeze, northern winds).     

Comprehensive screening and priority ranking of volatile organic compounds in Daliao River,China

An analytical strategy for comprehensive screening of target and non-target volatile organic compounds (VOCs) in surface water was developed, and it was applied to the analysis of VOCs in water samples from Daliao River. The target VOCs were quantified using purge and trap-gas chromatography-mass spectrometry (P&T-GC/MS). Among 20 water samples, 34 VOCs were detected at least once. For the screening of non-target VOCs, the double distillation apparatus was used for the pre-concentration of VOCs prior to P&T-GC/MS analysis. Subsequently, deconvolution software and NIST mass spectral library were applied for the identification of the non-target compounds. A total of 17 non-target VOCs were identified. The most frequently detected VOCs (detection frequencies >80 %) included toluene, benzene, naphthalene, 1,2-dichloroethane, 1,1,2-trichloroethane, and methyl tert-butyl ether. The distribution of VOCs obviously varied according to the sampling sites. The total concentrations of VOCs in water samples collected from the heavily industrialized cities (Anshan and Liaoyang) and the busy port city (Yingkou) were relatively high. The top ten priority VOCs, including naphthalene, 1,2-dichloroethane, o-xylene, 1,3-dichlorobenzene, tetrachloroethene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, ethylbenzene, m-xylene, and p-xylene, were obtained by the ranking of the detected VOCs according to their occurrence and ecological effects. These compounds should be given more attention in monitoring and drainage control strategies.     

春季广州城区空气中VOCs来源解析

2013年4月在广州市区对大气中挥发性有机化合物(VOCs)进行了观测,对其变化特征和来源进行了分析。结果表明,观测期间测得的VOC总平均混合比为41.35×10~(-9),表现为烷烃芳香烃烯烃炔烃;利用PMF解析出观测时段内影响广州市区的9个VOCs主要来源,各源占比情况依次为:LPG排放老化VOC汽油挥发石化、未知源汽油车排放油漆溶剂柴油车排放天然源;与机动车相关和工业相关的来源分别占到了大气VOCs的46.8%和21.0%。     

A study of ground-level ozone pollution, ozone precursors and subtropical meteorological conditions in central Taiwan

Hourly concentrations of ozone (O(3)), 55 volatile organic compounds (VOCs, ozone precursors) and nitrogen oxides (NOx) were measured at an upwind urban site, a downwind suburban site, and a rural site in central Taiwan, from January 2003 to December 2006. VOC and NOx mean concentrations showed a gradient from high to low across the urban (56 ppb and 34 ppb), suburban (38 ppb and 27 ppb) and rural sites (25 ppb and 21 ppb) but a reverse gradient in ozone across these sites (24, 27, and 29 ppb, respectively). Although there was about twice the difference in VOC concentrations between the urban and rural sites, nearly 65% ozone formation potential was contributed to by the same 9 VOCs. Seasonal patterns showed peak ozone levels in autumn and minima in summer at the urban site, but minima in winter at the downwind suburban and rural sites. Ozone precursor levels, on the other hand, were lowest in summer and highest in winter. The diurnal pattern showed that ozone levels peaked one hour later at the rural site than at the urban site. The ethylbenzene to m,p-xylene ratio, an indicator of the age of the air mass, increased from 0.4 at the urban site to 0.6 at the suburban site and 0.8 at the rural site during daily peak ozone times. This finding suggests the transport of ozone and precursors from upwind to downwind producing elevated ozone levels in the suburban and rural areas. Ozone episodes occurred mostly in days with a mean midday UV index of 6.5 (1 UV index=100 J m(-2)) and wind speed at 1.3 m s(-1) at all three sites.     

机动车排放尾气中挥发性有机污染物对环境空气质量影响初探

采用气相色谱/质谱检测技术,对汽油和柴油、汽油车和柴油车排放气体以及天津市环境空气中主要挥发性有机污染物(VOCs)的组成种类及比例进行探析.结果表明,机动车排放的尾气中主要有机污染物为芳香烃类、烷烃类和烯烃类化合物,其中芳香烃类含量最高;汽油车排放的芳香烃类化合物浓度高于柴油车排放的浓度;机动车尾气对交通区域空气质量的影响高于工厂区(非化工区)、生活小区和公园.     

Characterizations of volatile organic compounds during high ozone episodes in Beijing,China

Air samples were collected in Beijing from June through August 2008, and concentrations of volatile organic compounds (VOCs) in those samples are here discussed. This sampling was performed to increase understanding of the distributions of their compositions, illustrate the overall characteristics of different classes of VOCs, assess the ages of air masses, and apportion sources of VOCs using principal compound analysis/absolute principal component scores (PCA/APCS). During the sampling periods, the relative abundance of the four classes of VOCs as determined by the concentration-based method was different from that determined by the reactivity approach. Alkanes were found to be most abundant (44.3–50.1%) by the concentration-based method, but aromatic compounds were most abundant (38.2–44.5%) by the reactivity approach. Aromatics and alkenes contributed most (73–84%) to the ozone formation potential. Toluene was the most abundant compound (11.8–12.7%) during every sampling period. When the maximum incremental reactivity approach was used, propene, toluene, m,p-xylene, 1-butene, and 1,2,4-trimethylbenzene were the five most abundant compounds during two sampling periods. X/B, T/B, and E/B ratios in this study were lower than those found in other cities, possibly due to the aging of the air mass at this site. Four components were extracted from application of PCA to the data. It was found that the contribution of vehicle exhaust to total VOCs accounted for 53% of VOCs, while emissions due to the solvent use contributed 33% of the total VOCs. Industrial sources contributed 3% and biogenic sources contributed 11%. The results showed that vehicle exhausts (i.e., unburned vehicle emissions + vehicle internal engine combustion) were dominant in VOC emissions during the experimental period. The solvent use made the second most significant contribution to ambient VOCs.     

Airborne particulate-associated polyaromatic hydrocarbons,n-alkanes,elemental and organic carbon in three European cities

Total suspended particulate (TSP) samples were collected weekly over a period of one year at four European sites during 1995/6. Two sites were in London-a Central London site (CL, St Paul's Cathedral) and a suburban North London site (NL, Bounds Green); the other two sites were in Porto, Portugal and Vienna, Austria. TSP was collected using a low volume sampler. Organic carbon (OC) and elemental carbon (EC) concentrations were measured using a thermal-optical carbon analyser. Parallel samplers collected TSP for subsequent GC-MS analysis of thirty-nine combustion-associated organic compounds; 16 polyaromatic hydrocarbons (PAHs) and 23 n-alkanes. OC and EC correlate well at all sites (r2 = 0.39-0.65), although the London inter-site correlations were low, suggesting that local sources of OC and EC have a significant influence on local concentrations. Concentrations do not vary widely across the four urban sites, despite the significant differences in urban characteristics. Seasonal patterns of OC:EC ratios were similar at the London and Vienna sites, with highest ratios in autumn and winter, and annual mean OC:EC ratios were identical at these sites. The Carbon Preference Index (CPI) indicated vehicle emissions to have a stronger influence over particulate concentrations at the Vienna and central London sites; there was a stronger biogenic signature in north London and Porto. In addition, two PAH compounds (pyrene and fluoranthene) previously associated with diesel exhaust, were correlated with OC and EC concentrations at the London and Vienna sites.     

2020年江苏省机动车排放污染分布特征及与大气质量耦合性研究

依据生态环境部2021年6月发布的《排放源统计调查产排污核算方法和系数手册》,结合本地实测数据,在对汽油车颗粒物(PM)排放系数进行测算的基础上,核算了2020年江苏省机动车PM、氮氧化物(NO_(X))、挥发性有机物(VOC_(S))的排放总量,分析了机动车排放污染分布特征及与大气质量的耦合关系。结果表明:2020年江苏省机动车PM、NO_(X)、VOC_(S)排放量分别为0.5×10^(4),3.71×10^(5),1.17×10^(5) t。从区域分布来看,苏州、南京、无锡3市的3项污染物排放总量及NO_(X)、VOC_(S)排放量均位列前3位,PM排放量位列前3位的是苏州、徐州、无锡。从车型、燃料类型和排放阶段来看,国Ⅳ及以下排放标准的汽油小型客车是机动车VOC_(S)排放控制的重点,国Ⅲ排放标准的重型柴油货车是机动车PM和NO_(X)排放控制的重点。分析区域机动车PM排放量与大气中PM_(2.5)来源解析结果的耦合关系,其间存在不同程度的正相关性,控制机动车污染对改善大气环境会产生积极成效,南京、徐州和盐城3市的成效会尤为明显。     

宁波市环境空气中VOCs污染状况及变化趋势分析

基于近7年来的连续监测数据,对宁波市环境空气中挥发性有机物(VOCs)的污染状况及变化趋势进行了初步分析。研究表明:在宁波市环境空气中检测出94种VOCs,其主要成分是饱和烷烃、芳烃、烯烃、卤代烃、卤代芳烃、含氧有机物等,有37种属有毒有害物质,其中苯系物含量最高;宁波市环境空气中苯系物的污染程度与国内外城市基本处于同一水平,近年来的污染状况变化不大,没有明显恶化;空间分布特征显示一类保护区VOCs的排放以天然源为主,二类各功能区VOCs的排放由天然源和局部人为污染源共同形成,三类区以工业污染源排放为主;时间变化趋势显示VOCs在冬季和春季的平均浓度比其他季节高,VOCs的日变化基本呈现2个主浓度峰值特征,跟城市交通流量变化具有很好相关性。     

Application of CMB model for source apportionment of polycyclic aromatic hydrocarbons (PAHs) in coastal surface sediments from Rizhao offshore area, China

Polycyclic aromatic hydrocarbons (PAHs) in coastal surface sediments from Rizhao offshore area were analyzed by gas chromatography–mass spectrometry. A chemical mass balance (CMB) model developed by the U.S. Environmental Protection Agency (EPA), CMB8.2, was used to apportion sources of PAHs. Seven possible sources, including coal residential, coal power plant, diesel engines exhaust, gasoline engines exhaust, coke oven, diesel oil leaks, and wood burning, were chosen as the major contributors for PAHs in coastal surface sediments. To establish the fingerprints of the seven sources, source profiles were collected from literatures. After including degradation factors, the modified model results indicate that diesel oil leaks, diesel engines exhaust, and coal burning were the three major sources of PAHs. The source contributions estimated by the EPA’s CMB8.2 model were 9.25%, 15.05%, and 75.70% for diesel oil leaks, diesel engines exhaust, and coal burning, respectively.     

Pollution characteristics of volatile organic compounds in the atmosphere of Haicang District in Xiamen City, Southeast China

The compositions, spatial distributions, seasonal variations and ozone formation potential (OFP) of volatile organic compounds (VOCs) were investigated in the atmosphere of Haicang District, Xiamen City, Southeast China. Twenty-four types of VOCs were measured in this study, and ethanol, methylene chloride, toluene, ethyl acetate and isopropyl alcohol were the abundant species based on concentration rank. The concentrations of total VOCs (TVOCs) in industrial areas were higher than those in residential and administrative areas and background site. For industrial areas, the TVOCs concentrations in summer were higher than those in winter, which might result from higher emissions from industrial activities because of stronger evaporation in summer. In contrast, non-industrial areas showed higher concentrations in winter due to the unfavorable meteorological conditions. The spatial distribution of BTEX (benzene, toluene, ethylbenzene and xylene) followed the order of industrial areas > residential and administrative areas > background site, and the concentrations in summer were lower than those in winter for most sites. The high ratios (8.9-14.0) of T/B in this study indicated that industrial emissions were the main sources in this district. X/B ratios were used to assess the ages of air parcels and provided evidence of the transport of air parcels among these sites. Total OFP (TOFP) showed the trend of increase with the increase of TVOCs, and toluene was found as the major contributor to TOFP.     

Emissions of VOCs at Urban Petrol Retail Distribution Centres in India (Delhi and Mumbai)

Air pollution has assumed gigantic proportion killing almost half a million Asians every year. Urban pollution mainly comprises of emissions from buses, trucks, motorcycle other forms of motorized transport and its supporting activities. As Asia's cities continue to expand the number of vehicles have risen resulting in greater pollution. Fugitive emissions from retail distribution center in urban area constitute a major source. Petrol vapours escape during refueling adding pollutants like benzene, toluene, ethylbenzene and xylene to ambient air. This paper discusses a study on fugitive emissions of Volatile Organic Compounds (VOC) at some refueling station in two metropolitan cities of India, i.e., Mumbai and Delhi. Concentration of VOCs in ambient air at petrol retail distribution center is estimated by using TO-17 method. Concentration of benzene in ambient air in Delhi clearly shows the effect of intervention in use of petroleum and diesel fuel and shift to CNG. Chemical Mass Balance (CMB) model is used to estimate source contributions. At Delhi besides diesel combustion engines, refueling emissions are also major sources. At Mumbai evaporative emissions are found to contribute maximum to Total VOC (TVOC) concentration in ambient air.     

Influence of Relative Humidity and Ozone on the Sampling of Volatile Organic Compounds on Carbotrap/Carbosieve Adsorbents

By using a dynamic dilution system, the atmospheric measurement of 11 selected toxics VOCs (ethylene, acetylene, propene, 1-butene, 1,3-butadiene, 1-pentene, 1-hexene, benzene, toluene, ethylbenzene, m+p-xylene) from the list WHO of 1996 and TO-14 method of US EPA by preconcentration by thermal desorption (TD), analysis by gas chromatography (GC), identification and quantification with a flame ionisation detector (FID) was developed and validated in term of metrology, especially the techniques of sampling of these VOCs with adsorbents cartridges "Air Toxics" when used with an "UMEG sampler" equipped in the inlet with a nafion membrane. In particular the influence of climatic conditions (temperature and relative humidity) and the influence of chemical factors like ozone, on the representativity of sampling were studied. Experiments made with various humidities showed that the addition of a nafion membrane in the inlet of the sampling system was required. Without this membrane, losses of compounds were observed for RH >50%. With this membrane, storage for 2 weeks in a refrigerator, as for canisters, did not induce a loss of compounds. No significative decrease of concentrations of the studied VOCs after 14 days storage, which are known to react with ozone, were observed with an ozone concentrations of 55 ppb. One explanation is that nafion membrane, placed in the inlet of the sampler, will neutralize ozone before entering the sampling tubes. This observation is in accordance with literature which states that the sampling of VOCs on Carbotrap cartridges without ozone scrubber induce a loss of compounds.     

Organic Liquids Storage Tanks Volatile Organic Compounds (VOCS) Emissions Dispersion and Risk Assessment in Developing Countries: The Case of Dar-Es-Salaam City, Tanzania

The emission estimation of nine volatile organic compounds (VOCs) from eight organic liquids storage tanks companies in Dar-es-Salaam City Tanzania has been done by using US EPA standard regulatory storage tanks emission model (TANKS 4.9b). Total VOCs atmospheric emission has been established to be 853.20 metric tones/yr. It has been established further that petrol storage tanks contribute about 87% of total VOCs emitted, while tanks for other refined products and crude oil were emitting 10% and 3% of VOCs respectively. Of the eight sources (companies), the highest emission value from a single source was 233,222.94 kg/yr and the lowest single source emission value was 6881.87 kg/yr. The total VOCs emissions estimated for each of the eight sources were found to be higher than the standard level of 40,000 kg/yr per source for minor source according to US EPA except for two sources, which were emitting VOCs below the standard level. The annual emissions per single source for each of the VOCs were found to be below the US EPA emissions standard which is 2,000~kg/yr in all companies except the emission of hexane from company F1 which was slightly higher than the standard. The type of tanks used seems to significantly influence the emission rate. Vertical fixed roof tanks (VFRT) emit a lot more than externally floating roof tanks (EFRT) and internally floating roof tanks (IFRT). The use of IFRT and EFRT should be encouraged especially for storage of petrol which had highest atmospheric emission contribution. Model predicted atmospheric emissions are less than annual losses measured by companies in all the eight sources. It is possible that there are other routes for losses beside atmospheric emissions. It is therefore important that waste reduction efforts in these companies are directed not only to reducing atmospheric emissions, but also prevention of the spillage and leakage of stored liquid and curbing of the frequently reported illegal siphoning of stored products. Emission rates for benzene, toluene, and xylene were used as input to CALPUFF air dispersion model for the calculation of spatial downwind concentrations from area sources. By using global positioning system (GPS) and geographical information system (GIS) the spatial benzene concentration contributed by organic liquid storage tanks has been mapped for Dar-es-Salaam City. Highest concentrations for all the three toxic pollutants were observed at Kigamboni area, possibly because the area is located at the wind prevailing direction from the locations of the storage tanks. The model predicted concentrations downwind from the sources were below tolerable concentrations by WHO and US-OSHA. The highest 24 hrs averaging time benzene concentration was used for risk assessment in order to determine maximum carcinogenic risk amongst the population exposed at downwind. Established risk for adult and children at 2.9×10^-3 and 1.9×10^-3 respectively, are higher than the acceptable US-EPA risk of 1×10^-6. It is very likely that the actual VOCs concentrations in some urban areas in Tanzania including Dar-es-Salaam City are much higher than the levels reported in this study when other sources such as petrol stations and motor vehicles on the roads are considered. Tanzania Government therefore need to put in place: an air quality policy and legislation, establish air quality guidelines and acquire facilities which will enable the implementation of air quality monitoring and management programmes.     

南通市夏季VOCs污染特征与来源研究

运用大气挥发性有机物(VOCs)快速在线连续自动监测系统,于2018年7月对南通市区环境空气中VOCs进行观测,分析VOCs的浓度状况、组成特征、对臭氧生成潜势的贡献及主要来源。结果表明:观测期间共检出100种VOCs,总挥发性有机物(TVOCs)的平均体积分数为(38. 18±23. 63)×10^-9,各物种体积分数从大到小顺序依次为烷烃>含氧有机物>芳香烃>卤代烃>烯、炔烃;芳烃和烯烃是最主要的活性物种,间/对二甲苯、甲苯、邻二甲苯等是VOCs的关键活性组分;利用PMF模型解析得到VOCs的主要污染来源是工业排放与溶剂使用、机动车尾气排放、燃料挥发排放和生物源排放。     

VOCs走航观测在城市污染源排查中的应用

为推进城市空气质量精细化管理工作的实施,实现VOCs污染源精准排查,2019年3-4月,利用单光子电离飞行时间质谱对青岛市重点区域进行了VOCs走航观测。在排查到的污染源中,工业区的VOCs浓度较生活区整体偏高,且生活区、工业区夜间的VOCs浓度均较白天高。VOCs各类组分中,生活区白天苯系物、卤代烃、烯烃、烷烃的占比均在20%左右,夜间苯系物占比明显升高;工业区苯系物在白天和夜间的占比均最高,其他组分相对较小。浓度较高的前10位VOCs物种中,生活区白天烯烃物种占主导,夜间烷烃物种的比重明显增加;工业区苯系物、烯烃物种在白天和夜间的比重均较大,烷烃物种较小。生活区VOCs的污染源主要为机动车尾气排放和油品挥发,工业区主要为企业排放。烯烃和苯系物臭氧生成贡献较烷烃高,特别是丁烯、戊烯、己烯、甲苯、二甲苯/乙苯、三甲苯贡献显著,建议作为优控物种重点管控。