Particulate organic compounds emitted from experimental wildland fires in a Mediterranean ecosystem

Fine (PM_2.5) and coarse (PM_2.5–10) smoke particles from controlled biomass burnings of a shrub-dominated forest in Lousã Mountain, Portugal, enabled the quantification by chromatographic techniques of several molecular tracers for the combustion of Mediterranean forest ecosystems, which could be conducive to source apportionment studies. The major organic components in the smoke samples were pyrolysates of vegetation cuticles, mainly comprising steradienes and sterol derivatives, carbohydrates from the breakdown of cellulose, aliphatic lipids from vegetation waxes and methoxyphenols from the lignin thermal degradation. Most of these compounds are chiefly found in fine particles. Polycyclic aromatic hydrocarbons (PAH) were also present as minor constituents. Anhydrosugar and PAH molecular diagnostic ratios were applied as source assignment tools. Some biomarkers are reported for the first time in biomass burning smoke.     

Investigation of the motor vehicle exhaust contribution to primary fine particle organic carbon in urban air

Motor vehicle (MV) emissions and ambient particle concentrations under a variety of situations were studied in Toronto and Vancouver, Canada. Petroleum biomarkers (i.e., hopanes and steranes) were used to determine the fraction of fine particle organic carbon (OC) attributed to primary particles in MV exhaust. Source profiles obtained from a tunnel and from direct tailpipe emissions were applied to ambient measurements at locations ranging from rush hour traffic to a regional background site. The greatest amount of MV OC, 4.0 μgC m⁻³ out of 9.1 μgC m⁻³ or 43%, was observed 75 m south of a commuter highway during a period that included morning rush hour. Monthly estimates of MV-OC were determined for a downtown Toronto monitoring site for 2 years. Total OC concentrations were greater in the summer, due to secondary OC, but the amount of MV-OC did not exhibit a strong seasonal pattern. However, on a per cent basis, MV contributions from primary OC emissions were greatest in the winter (15–20%) and smallest in the summer (10–15%) with a two-year average of 14% of the OC or about 5% of the PM_2.5.     

Evolution of vehicle exhaust particles in the atmosphere

Aerosol mass spectrometer (AMS) measurements are used to characterize the evolution of exhaust particulate matter (PM) properties near and downwind of vehicle sources. The AMS provides time-resolved chemically speciated mass loadings and mass-weighted size distributions of nonrefractory PM smaller than 1 microm (NRPM1). Source measurements of aircraft PM show that black carbon particles inhibit nucleation by serving as condensation sinks for the volatile and semi-volatile exhaust gases. Real-world source measurements of ground vehicle PM are obtained by deploying an AMS aboard a mobile laboratory. Characteristic features of the exhaust PM chemical composition and size distribution are discussed. PM mass and number concentrations are used with above-background gas-phase carbon dioxide (CO2) concentrations to calculate on-road emission factors for individual vehicles. Highly variable ratios between particle number and mass concentrations are observed for individual vehicles. NRPM1 mass emission factors measured for on-road diesel vehicles are approximately 50% lower than those from dynamometer studies. Factor analysis of AMS data (FA-AMS) is applied for the first time to map variations in exhaust PM mass downwind of a highway. In this study, above-background vehicle PM concentrations are highest close to the highway and decrease by a factor of 2 by 200 m away from the highway. Comparison with the gas-phase CO2 concentrations indicates that these vehicle PM mass gradients are largely driven by dilution. Secondary aerosol species do not show a similar gradient in absolute mass concentrations; thus, their relative contribution to total ambient PM mass concentrations increases as a function of distance from the highway. FA-AMS of single particle and ensemble data at an urban receptor site shows that condensation of these secondary aerosol species onto vehicle exhaust particles results in spatial and temporal evolution of the size and composition of vehicle exhaust PM on urban and regional scales.     

Carbonyl compounds and dissolved organic carbon in rainwater of an urban atmosphere

This study investigates the occurrence of carbonyl compounds in rainwater at the city of Thessaloniki, Northern Greece. The concentrations of carbonyl compounds (as sum of 14 compounds) ranged from 21.8 to 592 μg/L, mean concentration 119 μg/L. Formaldehyde, acetaldehyde, hexanal, glyoxal, and methylglyoxal were the dominant compounds. DOC concentrations in rainwater ranged from 0.46 to 21.3 mg/L. UV–Vis and fluorescence spectra characteristics showed variation among rain events. Carbonyl compounds were negatively correlated with temperature exhibited relatively higher concentrations in cold season. They also influenced by storm origin with higher concentrations under terrestrial air masses. Calm conditions enhance the concentrations of DOC. Wash out is an effective removal mechanism of DOC.     

Volatile organic compounds (VOCs) in urban atmosphere of Hong Kong

The assessment of volatile organic compounds (VOCs) has become a major issue of air quality network monitoring in Hong Kong. This study is aimed to identify, quantify and characterize volatile organic compounds (VOCs) in different urban areas in Hong Kong. The spatial distribution, temporal variation as well as correlations of VOCs at five roadside sampling sites were discussed. Twelve VOCs were routinely detected in urban areas (Mong Kok, Kwai Chung, Yuen Long and Causeway Bay). The concentrations of VOCs ranged from undetectable to 1396 microg/m3. Among all of the VOC species, toluene has the highest concentration. Benzene, toluene, ethylbenzene and xylenes (BTEX) were the major constituents (more than 60% in composition of total VOC detected), mainly contributed from mobile sources. Similar to other Asian cities, the VOC levels measured in urban areas in Hong Kong were affected both by automobile exhaust and industrial emissions. High toluene to benzene ratios (average T/B ratio = 5) was also found in Hong Kong as in other Asian cities. In general, VOC concentrations in the winter were higher than those measured in the summer (winter to summer ratio > 1). As toluene and benzene were the major pollutants from vehicle exhausts, there is a necessity to tighten automobile emission standards in Hong Kong.     

上海市机动车尾气VOCs组成及其化学反应活性

采用钢罐采样-气相色谱/质谱法,采集并分析了上海市主要交通干道和隧道废气样品中挥发性有机物(VOCs)的污染水平。分析结果表明,交通干道和隧道废气样品的总挥发性有机污染物(TVOC)质量浓度分别为(227.1±40.9)、(2209.9±1228.0)μg/m3;隧道废气样品中的TVOC浓度是交通干道平均浓度的4.3～15.2倍;交通干道废气样品中VOCs主要组分与隧道废气样品中VOCs主要组分非常类似,说明交通干道废气样品中VOCs主要来源于机动车尾气排放。交通干道废气样品中TVOC的.OH消耗速率为(17.21±4.49)s-1,延安东路隧道和打浦路隧道废气样品中TVOC的.OH消耗速率分别为(300.37±120.78)、(138.09±25.30)s-1,烯烃对TVOC的.OH消耗速率贡献最大,其对废气化学反应活性贡献率在70%以上。交通干道和隧道废气样品中关键活性组分是C2～C5的烯烃组分,这些组分也是机动车尾气中的特征污染物,因此可以判断机动车尾气是上海市大气化学反应活性的最大贡献者。     

家具涂料的挥发性有机物排放特征及致癌风险估算

采用顶空实验装置采集家具涂料挥发蒸汽,通过不锈钢采样罐-气相色谱(GC)/质谱(MS)分析系统测量了溶剂型和水型涂料的挥发性有机物(VOCs)排放特征。结果表明,溶剂型涂料排放的总VOCs平均质量浓度为7.6mg/m3,远高于水型涂料的2.6mg/m3。溶剂型和水型涂料排放的VOCs主要以芳香烃和烷烃为主。溶剂型涂料和水型涂料排放的特征VOCs组分为甲苯、2-甲基戊烷、苯、正辛烷,分别占两种涂料总VOCs排放的41.8%(质量分数,下同)和31.2%、21.2%和9.6%、6.5%和5.6%、6.0%和4.8%。溶剂型涂料排放VOCs的臭氧生成潜势(OFP)和二次气溶胶生成潜势(SOAP)明显高于水型涂料,OFP和SOAP的主要贡献组分均为芳香烃物质。溶剂型涂料排放的苯的长期致癌风险是水型涂料的2.6~4.6倍,均远远高于可接受的暴露风险值1×10-6。     

Seasonal distribution of polar organic compounds in the urban atmosphere of two large cities from the North and South of Europe

Polar organic species, including n-alkanols, sterols, anhydrosugars, n-alkanoic acids, n-alkenoic acids and dicarboxylic acids were quantified to typify the composition of fine (PM_2.5) and coarse (PM_10–2.5) aerosols collected simultaneously at roadside and background sites in Oporto (Portugal) and Copenhagen (Denmark) during separate month-long intensive summer and winter campaigns. As a general trend, both cities exhibit roadside average concentrations higher than their correspondent urban background levels. The polar organics are more abundant in the fine fraction, exhibiting a seasonal pattern with high winter concentrations and low summer loads. Aerosols from both cities showed typical distributions of n-alkanols and n-alkanoic acids in the ranges C₁₂–C₂₈ and C₈–C₂₈, respectively. The <C₂₀ homologues, usually attributed to kitchen emissions, vehicular exhausts and microbial origins, dominated the fatty acid fraction. Linear alcohols were mainly represented by higher molecular weight homologues from vegetation waxes. Molecular tracer species for wood smoke (e.g. levoglucosan, mannosan and resinic acids) were found to contribute significantly to the urban aerosol, especially in winter. Ratios between these tracers indicated different biofuel contributions to the atmospheric particles of the two cities. Secondary constituents from both biogenic (e.g. pinonic acid) and anthropogenic precursors (e.g. phthalic and benzoic acids) were detected in both cities and seasons.     

Volatile organic compounds in the atmosphere of forests

The procedure of sampling and gas chromatographic-mass spectrometric analysis of air containing volatile emissions from living plants has been elaborated. The qualitative composition of volatile organic compounds (VOC) produced by 22 species of plants which are characteristic for Northern hemisphere forests has been studied. The emission rate of isoprene and terpenes for some of them has been determined. Terpene concentrations in coniferous forests of different regions of the U.S.S.R. have been also determined. The list of compounds identified includes more than 70 substances of different classes. Total terpene concentrations in the coniferous forests air usually vary from 3.5 to 35 μg⁻³. Strong influence of meteorological conditions on the emission rate and terpene concentrations in the air under the forest canopy has been noted.     

Ions in motor vehicle exhaust and their dispersion near busy roads

Measurements in the exhaust plume of a petrol-driven motor car showed that molecular cluster ions of both signs were present in approximately equal amounts. The emission rate increased sharply with engine speed while the charge symmetry remained unchanged. Measurements at the kerbside of nine motorways and five city roads showed that the mean total cluster ion concentration near city roads (603 cm^?3) was about one-half of that near motorways (1211 cm^?3) and about twice as high as that in the urban background (269 cm^?3). Both positive and negative ion concentrations near a motorway showed a significant linear increase with traffic density (R² = 0.3 at p < 0.05) and correlated well with each other in real time (R² = 0.87 at p < 0.01). Heavy duty diesel vehicles comprised the main source of ions near busy roads. Measurements were conducted as a function of downwind distance from two motorways carrying around 120–150 vehicles per minute. Total traffic-related cluster ion concentrations decreased rapidly with distance, falling by one-half from the closest approach of 2 m to 5 m of the kerb. Measured concentrations decreased to background at about 15 m from the kerb when the wind speed was 1.3 m s^?1, this distance being greater at higher wind speed. The number and net charge concentrations of aerosol particles were also measured. Unlike particles that were carried downwind to distances of a few hundred metres, cluster ions emitted by motor vehicles were not present at more than a few tens of metres from the road.     

Intake fraction of nonreactive motor vehicle exhaust in Hong Kong

The intake fraction (iF) of nonreactive constituents of exhaust from mobile vehicles in the urban area of Hong Kong is investigated using available monitoring data for carbon monoxide (CO) as a tracer of opportunity. Correcting for regional transport of carbon monoxide into Hong Kong, the annual-average iF for nonreactive motor vehicle emissions within the city is estimated to be around 270 per million. This estimated iF is much higher than values previously reported for vehicle emissions in US urban areas, Helsinki and Beijing, and somewhat lower than those reported for a densely populated street canyon in downtown Manhattan, New York City, or for emissions into indoor environments. The reported differences in intake fractions in various cities mainly result from the differences in local population densities. Our analysis highlights the importance of accounting for the influence of upwind transport of pollutants when using ambient data to estimate iF for an urban area. For vehicle exhaust in Hong Kong, it is found that the in/near vehicle microenvironment contributes similarly to the indoor home environment when accounting for the overall iF for children and adults.     

挥发性有机废气净化技术研究进展

综述了微波催化氧化、膜基吸收净化、生物过滤净化和纳米材料净化对废气中的挥发性有机化合物的研究进展及应用     

Effects of vehicle exhaust emissions on urban wild plant species

Very few investigations have examined the direct impacts of vehicle exhausts on plants and attempted to separate out the key pollutants responsible for observed effects. This paper describes a multi-phase investigation into this topic, using 12 herbaceous species typical of urban areas and representing different functional groups. Fumigations were conducted in solardomes with diesel exhaust pollutants at concentrations designed to simulate those close to a major highway in inner London. A wide range of effects were detected, including growth stimulation and inhibition, changes in gas exchange and premature leaf senescence. This was complemented by controlled fumigations with NO, NO(2) and their mixture, as well as a transect study away from a busy inner London road. All evidence suggested that NO(x) was the key phytotoxic component of exhaust emissions, and highlights the potential for detrimental effects of vehicle emissions on urban ecosystems.     

The hydrocarbon composition of exhaust emitted from gasoline fuelled vehicles

The non-methane hydrocarbon (NMHC) compositions of the exhausts from 67 vehicles in ‘on the road’ condition and driven through an urban driving cycle on a chassis dynamometer, have been determined. The major components were ethylene (11.2% w/w of NMHC), toluene (10.2%), acetylene (8.7%), m,p-Xylenes(6.5%), benzene (5.0%), propylene (5.0%) and i-pentane(4.8%). These compounds have also been reported as significant components in the exhausts from two similar populations of American vehicles.The NMHC compositions were found to be insensitive to the mass emission rates of hydrocarbons from the vehicles, except for the combustion-derived olefins, ethylene and propylene, which were affected by engine modifications introduced to satisfy emission control requirements. A close relationship was found between petrol composition and exhaust composition but this did not correspond simply to emissions of unburnt petrol. The aromatics are enriched relative to the alkanes in exhaust when compared with their proportions in the petrol.     

Sulfuric odorous compounds emitted from pig-feeding operations

The objective of the study was to quantify the concentration and emission levels of sulfuric odorous compounds emitted from pig-feeding operations. Five types of pig-housing rooms were studied: gestation, farrowing, nursery, growing and fattening rooms. The concentration range of sulfuric odorous compounds in these pig-housing rooms were 30–200 ppb for hydrogen sulfide (H₂S), 2.5–20 ppb for methyl mercaptan (CH₃SH), 1.5–12 ppb for dimethyl sulfide (DMS; CH₃SCH₃) and 0.5–7 ppb for dimethyl disulfide (DMDS; CH₃S₂CH₃), respectively. The emission rates of H₂S, CH₃SH, DMS and DMDS were estimated by multiplying the average concentration (mg m⁻³) measured near the air outlet by the mean ventilation rate (m³ h⁻¹) and expressed either per area (mg m⁻² h⁻¹) or animal unit (AU; liveweight of the pig, 500 kg) (mg pig⁻¹ h⁻¹). As a result, the emission rates of H₂S, CH₃SH, DMS and DMDS in the pig-housing rooms were 14–64, 0.8–7.3, 0.4–3.4 and 0.2–1.9 mg m⁻² h⁻¹, respectively, based on pig's activity space and 310–723, 18–80, 9–39 and 5–22 mg AU⁻¹ h⁻¹, respectively, based on pig's liveweight, which indicates that their emission rates were similar, whether based upon the pig's activity space or liveweight. In conclusion, the concentrations and emission rates of H₂S were highest in the fattening room followed by the growing, nursery, farrowing and gestation rooms whereas those of CH₃SH, DMS and DMDS concentrations were largest in the growing room followed by the nursery, gestation and farrowing rooms.     

On-road motor vehicle emissions and fuel consumption in urban driving conditions

This paper reports on the analysis of on-road vehicle speed, emission, and fuel consumption data collected by four instrumented vehicles. Time-, distance-, and fuel-based average fuel consumption, as well as CO, HC, NOx, and soot emission factors, were derived. The influences of instantaneous vehicle speed on emissions and fuel consumption were studied. It was found that the fuel-based emission factors varied much less than the time- and distance-based emission factors as instantaneous speed changed. The trends are similar to the results obtained from laboratory tests. The low driving speed contributed to a significant portion of the total emissions over a trip. Furthermore, the on-road data were analyzed using the modal approach. The four standard driving modes are acceleration, cruising, deceleration, and idling. It was found that the transient driving modes (i.e., acceleration and deceleration) were more polluting than the steady-speed driving modes (i.e., cruising and idling) in terms of g/km and g/sec. These results indicated that the on-road emission measurement is feasible in deriving vehicle emissions and fuel consumption factors in urban driving conditions.     

Use of biochar for the sorption of volatile organic compounds (VOCs) emitted from cattle manure

Environmental Science and Pollution Research - The ability of biochar to be used as filter or as additive for the adsorption of volatile organic compounds (VOCs) emitted from cattle manure is...     

Ambient levels of volatile organic compounds in the atmosphere of Greater Cairo

Ambient volatile organic compounds (VOCs) samples were collected at three locations, two in urban areas in Greater Cairo (Ramsis and Haram) and background one in rural area in Menofiya province (Kafr El-Akram), during the period of June, 2004–August, 2004. The highest concentrations of VOCs were found in Ramsis, whereas the lowest concentrations were detected in Kafr El-Akram, and the difference in mean concentrations were statistically significant (p<0.001). Among all of the measured VOCs species, the contribution of individual VOC to the total VOCs concentration were very similar in Ramsis and Haram locations, toluene was the most abundant compound followed by (m, p)-xylene. This similarity implies a similar emission sources of VOCs in both urban locations, vehicle exhausts are the dominant one. Greater Cairo has high levels of volatile aromatic hydrocarbons compared with many polluted cities in the world. The BTEX (benzene: toluene: ethylbenzene: xylenes) concentration ratios were (2.01:4.94:1:4.95), (2.03:4.91:1:4.87) and (2.31:2.98:1:2.59) in Ramsis, Haram and Kafr El-Akram, respectively. The average toluene/benzene (T/B), (m, p)-xylene/benzene ((m, p)-X/B) and o-xylene/benzene (o-X/B) concentration ratios were 2.45, 1.61and 0.85, respectively in Ramsis and 2.42, 1.61 and 0.78, respectively in Haram. The ratios in both urban locations were of the same magnitude and close to those obtained from automotive exhausts, indicating that the ambient BTEX originate mainly from motor vehicle emissions. However, the (T/B), ((m, p)-X/B) and (o-X/B) concentration ratios were 1.29, 0.71 and 0.41 in Kafr El-Akram, respectively. These ratios were lower than those found in Ramsis and Haram locations and in automotive exhaust, suggesting that the BTEX in Kafr El-Akram do not come from a local source and are exclusively results from the diffusion and dispersion of VOCs produced from the traffic density in the surrounding cities. Significant positive correlation coefficients (p<0.001) were found between the concentrations of BTEX compounds at the three sampling locations. The diurnal variation of VOCs concentrations in Ramsis location showed two daily peaks linked to traffic density.     

Concentrations and fluxes of organic compounds in the atmosphere of the Swedish west coast

Measurements of organic compounds in air and deposition have been carried out in parallel on the Swedish west coast. In this investigation the importance of long-range transport for the occurrence of organic compounds in deposition has been studied. Air samples were collected using a high volume sampler (HVS) and the deposition was sampled on a 1 m² Teflon-coated horizontal surface with runoff for the precipitation to an adsorbent. The samples were analyzed in order to identify and quantify different semivolatile compounds such as PAH and petrogenic hydrocarbons and chlorinated compounds such as PCB, HCH and HCB. Qualitative differences between the content of organic compounds in air and deposition during periods with varying levels of air pollution and different meteorological conditions have been studied and a comparison with other air pollutants, such as soot, has been carried out. The results of the measurements show that deposition of PAH and other hydrocarbons takes place continuously but the greatest amounts are measured in the deposition in connection with episodes together with heavy precipitation. The highest concentrations of PCB and HCH in the air were obtained during a warm dry period in May and the greatest amounts were deposited in a period in May with heavy precipitation.