Volatile Organic Compounds Mixing Ratios Research Articles

Effects of rigorous emission controls on reducing ambient volatile organic compounds in Beijing, China

102 volatile organic compound (VOC) species were measured online using a gas chromatography–mass spectrometry/flame ionization detector (GC–MS/FID) at an urban site in Beijing in 11 August to 3 September 2015, when a series of rigorous air quality control measures were implemented in Beijing city and neighbouring provinces. Positive matrix factorization (PMF) was applied to identify emission sources from 1h averaged values of VOC data. Based on the online VOC data and the PMF analysis results, the effectiveness of different control measures were investigated. The PMF results were compared with an emission inventory data. Results show that the rigorous air quality restrictions implemented were successful. The averaged ambient VOC mixing ratios during the emission control period and non-control period were 27.53 and 45.42ppbv, respectively. The mixing ratios of total VOC during the control period were reduced by 40%. Alkanes were the most abundant chemical group in the two periods, followed by oxygenated volatile organic compounds (OVOCs). Almost all quantified VOC species decreased during the control period. Tracers of industrial sources and vehicle exhaust reduced most, including some halocarbons, esters and aromatics. Eight sources were resolved by online PMF analysis for ambient VOCs in Beijing. Contributions of those sources varied significantly during the control and non-control period. Compared with the values before control, contributions of vehicle-related sources were most reduced, followed by solvent utilization. Reductions of vehicle-related sources, solvent utilization, secondary formation, fuel combustion, and biogenic were responsible for 65%, 19%, 10%, 5%, and 1% of the reductions in ambient VOCs. Both PMF results and emission inventory data indicated that the control measure on traffic was very effective in reducing ambient VOCs in Beijing, with the emission reductions of about 50%.

Overview of VOC emissions and chemistry from PTR-TOF-MS measurements during the SusKat-ABC campaign: high acetaldehyde, isoprene and isocyanic acid in wintertime air of the Kathmandu Valley

Abstract. The Kathmandu Valley in Nepal suffers from severe wintertime air pollution. Volatile organic compounds (VOCs) are key constituents of air pollution, though their specific role in the valley is poorly understood due to insufficient data. During the SusKat-ABC (Sustainable Atmosphere for the Kathmandu Valley–Atmospheric Brown Clouds) field campaign conducted in Nepal in the winter of 2012–2013, a comprehensive study was carried out to characterise the chemical composition of ambient Kathmandu air, including the determination of speciated VOCs, by deploying a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) – the first such deployment in South Asia. In the study, 71 ion peaks (for which measured ambient concentrations exceeded the 2σ detection limit) were detected in the PTR-TOF-MS mass scan data, highlighting the chemical complexity of ambient air in the valley. Of the 71 species, 37 were found to have campaign average concentrations greater than 200 ppt and were identified based on their spectral characteristics, ambient diel profiles and correlation with specific emission tracers as a result of the high mass resolution (m ∕ Δm > 4200) and temporal resolution (1 min) of the PTR-TOF-MS. The concentration ranking in the average VOC mixing ratios during our wintertime deployment was acetaldehyde (8.8 ppb) > methanol (7.4 ppb) > acetone + propanal (4.2 ppb) > benzene (2.7 ppb) > toluene (1.5 ppb) > isoprene (1.1 ppb) > acetonitrile (1.1 ppb) > C8-aromatics ( ∼ 1 ppb) > furan ( ∼ 0.5 ppb) > C9-aromatics (0.4 ppb). Distinct diel profiles were observed for the nominal isobaric compounds isoprene (m ∕ z = 69.070) and furan (m ∕ z = 69.033). Comparison with wintertime measurements from several locations elsewhere in the world showed mixing ratios of acetaldehyde ( ∼ 9 ppb), acetonitrile ( ∼ 1 ppb) and isoprene ( ∼ 1 ppb) to be among the highest reported to date. Two "new" ambient compounds, namely formamide (m ∕ z = 46.029) and acetamide (m ∕ z = 60.051), which can photochemically produce isocyanic acid in the atmosphere, are reported in this study along with nitromethane (a tracer for diesel exhaust), which has only recently been detected in ambient studies. Two distinct periods were selected during the campaign for detailed analysis: the first was associated with high wintertime emissions of biogenic isoprene and the second with elevated levels of ambient acetonitrile, benzene and isocyanic acid from biomass burning activities. Emissions from biomass burning and biomass co-fired brick kilns were found to be the dominant sources for compounds such as propyne, propene, benzene and propanenitrile, which correlated strongly with acetonitrile (r2 > 0.7), a chemical tracer for biomass burning. The calculated total VOC OH reactivity was dominated by acetaldehyde (24.0 %), isoprene (20.2 %) and propene (18.7 %), while oxygenated VOCs and isoprene collectively contributed to more than 68 % of the total ozone production potential. Based on known secondary organic aerosol (SOA) yields and measured ambient concentrations in the Kathmandu Valley, the relative SOA production potential of VOCs were benzene > naphthalene > toluene > xylenes > monoterpenes > trimethylbenzenes > styrene > isoprene. The first ambient measurements from any site in South Asia of compounds with significant health effects such as isocyanic acid, formamide, acetamide, naphthalene and nitromethane have been reported in this study. Our results suggest that mitigation of intense wintertime biomass burning activities, in particular point sources such biomass co-fired brick kilns, would be important to reduce the emission and formation of toxic VOCs (such as benzene and isocyanic acid) in the Kathmandu Valley.

Sources of long-lived atmospheric VOCs at the rural boreal forest site, SMEAR II

Abstract. In this study a long-term volatile organic compound (VOCs) concentration data set, measured at the SMEAR II (Station for Measuring Ecosystem–Atmosphere Relations) boreal forest site in Hyytiälä, Finland during the years 2006–2011, was analyzed in order to identify source areas and profiles of the observed VOCs. VOC mixing ratios were measured using proton transfer reaction mass spectrometry. Four-day HYSPLIT 4 (Hybrid Single Particle Lagrangian Integrated Trajectory) backward trajectories and the Unmix 6.0 receptor model were used for source area and source composition analysis. Two major forest fire events in Russia took place during the measurement period. The effect of these fires was clearly visible in the trajectory analysis, lending confidence to the method employed with this data set. Elevated volume mixing ratios (VMRs) of non-biogenic VOCs related to forest fires, e.g. acetonitrile and aromatic VOCs, were observed. Ten major source areas for long-lived VOCs (methanol, acetonitrile, acetaldehyde, acetone, benzene, and toluene) observed at the SMEAR II site were identified. The main source areas for all the targeted VOCs were western Russia, northern Poland, Kaliningrad, and the Baltic countries. Industrial areas in northern continental Europe were also found to be source areas for certain VOCs. Both trajectory and receptor analysis showed that air masses from northern Fennoscandia were less polluted with respect to both the VOCs studied and other trace gases (CO, SO2 and NOx), compared to areas of eastern and western continental Europe, western Russia, and southern Fennoscandia.

Characterization of ambient volatile organic compounds and their sources in Beijing, before, during, and after Asia-Pacific Economic Cooperation China 2014

Abstract. Ambient volatile organic compounds (VOCs) were measured using an online system, gas chromatography–mass spectrometry/flame ionization detector (GC-MS/FID), in Beijing, China, before, during, and after Asia-Pacific Economic Cooperation (APEC) China 2014, when stringent air quality control measures were implemented. Positive matrix factorization (PMF) was applied to identify the major VOC contributing sources and their temporal variations. The secondary organic aerosols potential (SOAP) approach was used to estimate variations of precursor source contributions to SOA formation. The average VOC mixing ratios during the three periods were 86.17, 48.28, and 72.97 ppbv, respectively. The mixing ratios of total VOC during the control period were reduced by 44 %, and the mixing ratios of acetonitrile, halocarbons, oxygenated VOCs (OVOCs), aromatics, acetylene, alkanes, and alkenes decreased by approximately 65, 62, 54, 53, 37, 36, and 23 %, respectively. The mixing ratios of all measured VOC species decreased during control, and the most affected species were chlorinated VOCs (chloroethane, 1,1-dichloroethylene, chlorobenzene). PMF analysis indicated eight major sources of ambient VOCs, and emissions from target control sources were clearly reduced during the control period. Compared with the values before control, contributions of vehicular exhaust were most reduced, followed by industrial manufacturing and solvent utilization. Reductions of these three sources were responsible for 50, 26, and 16 % of the reductions in ambient VOCs. Contributions of evaporated or liquid gasoline and industrial chemical feedstock were slightly reduced, and contributions of secondary and long-lived species were relatively stable. Due to central heating, emissions from fuel combustion kept on increasing during the whole campaign; because of weak control of liquid petroleum gas (LPG), the highest emissions of LPG occurred in the control period. Vehicle-related sources were the most important precursor sources likely responsible for the reduction in SOA formation during this campaign.

A method for stable carbon isotope ratio and concentration measurements of ambient aromatic hydrocarbons

Abstract. A technique for compound-specific analysis of stable carbon isotope ratios and concentration of ambient volatile organic compounds (VOCs) is presented. It is based on selective VOC sampling onto adsorbent-filled cartridges by passing large volumes of air (up to 80 L) through the cartridge. The hydrocarbons are recovered by thermal desorption followed by two-step cryogenic trapping and then are separated by gas chromatography in the laboratory. Once separated, individual VOCs are subjected to online oxidation in a combustion interface and isotope ratio analysis by isotope ratio mass spectrometry. The method allows measurements of stable carbon isotope ratios of ambient aromatic VOCs present in low pptV to ppbV levels with an accuracy of typically better than 0.5 ‰. The precision of concentration measurements is better than 10%. Examples of measurements conducted as part of a joint Environment Canada–York University (EC-YU) measurement campaign at a semi-rural location demonstrate that the ability to make accurate measurements in air with low VOC mixing ratios is important to avoid bias from an overrepresentation of samples that are strongly impacted by recent emissions.

Stable Carbon Isotope Ratios and the Photochemical Age of Atmospheric Volatile Organic Compounds

The dependence of ozone formation on the mixing ratios of volatile organic compounds (VOCs) and nitrogen oxides (NOx) has been widely studied. In addition to the atmospheric levels of VOCs and NOx, the extent of photochemical processing of VOCs has a strong impact on ozone levels. Although methods for measuring atmospheric mixing ratios of VOCs and NOx are well established and results of those measurements are widely available, determination of the extent of photochemical processing of VOCs, known as photochemical age (PCA), is difficult. In this article a recently developed methodology for the determination of PCA for individual compounds based on the change in their stable carbon isotope composition is used to investigate the dependence between ozone and VOC or NOx mixing ratios at a rural site in Ontario, Canada, during fall and winter. The results show that under these conditions the variability in VOC mixing ratios is predominantly a result of the varying impact of local emissions and not a result of changes in the extent of atmospheric processing. This explains why the mixing ratio of ozone shows no systematic dependence on the mixing ratios of VOCs or NOx in this environment and at this time of the year.

Volatile organic compounds in the western Mediterranean basin: urban and rural winter measurements during the DAURE campaign

Abstract. Atmospheric volatile organic compounds (VOCs) have key environmental and biological roles, but little is known about the daily VOC mixing ratios in Mediterranean urban and natural environments. We measured VOC mixing ratios concurrently at an urban and a rural site during the winter DAURE campaign in the northeastern Iberian Peninsula, by means of PTR-MS at both locations: a PTR-Quad-MS at the urban site and a PTR-ToF-MS at the rural site. All VOC mixing ratios measured were higher at the urban site (e.g. acetaldehyde, isoprene, benzene, and toluene with averages up to 1.68, 0.31, 0.58 and 2.71 ppbv, respectively), with the exception of some short-chain oxygenated VOCs such as acetone (with similar averages of 0.7–1.6 ppbv at both sites). The average diurnal pattern also differed between the sites. Most of the VOCs at the urban location showed their highest mixing ratios in the morning and evening. These peaks coincided with traffic during rush hour, the main origin of most of the VOCs analyzed. Between these two peaks, the sea breeze transported the urban air inland, thus helping to lower the VOC loading at the urban site. At the rural site, most of the measured VOCs were advected by the midday sea breeze, yielding the highest daily VOC mixing ratios (e.g. acetaldehyde, isoprene, benzene, and toluene with averages up to 0.65, 0.07, 0.19, and 0.41 ppbv, respectively). Only biogenic monoterpenes showed a clear local origin at this site. In addition, the concentrations of fine particulate matter observed at both sites, together with the synoptic meteorological conditions and radio-sounding data, allowed the identification of different atmospheric scenarios that had a clear influence on the measured VOC mixing ratios. These results highlight the differences and relationships in VOC mixing ratios between nearby urban and rural areas in Mediterranean regions. Further research in other urban-rural areas is warranted to better understand the urban-rural influence on atmospheric VOC mixing ratios under different atmospheric conditions.

The characteristics, seasonal variation and source apportionment of VOCs at Gongga Mountain, China

The mixing ratio, composition and variability of volatile organic compounds (VOCs) were measured from 2008 through 2011 at Gongga Mountain Forest Ecosystem Research Station (102°00′E, 29°33′N, elevation 1640 m), a remote station in southwest China. Weekly samples were collected in the Gongga Mountain area and were analyzed using a three-stage preconcentration method coupled with GC–MS. An advance receptor model positive matrix factorization (PMF) was applied to identify and apportion the sources of VOCs. The results show that the measured VOC mixing ratio at Gongga Mountain is dominated by aromatics (35.7%) and alkanes (30.8%), followed by halocarbons (21.6%) and alkenes (11.9%). The general trend of seasonal variation shows higher mixing ratios in spring and lower mixing ratios in autumn. The effect of alkanes and aromatics on the seasonal variation of total volatile organic compounds (TVOCs) is significant. Five sources were resolved by the PMF model: (1) gasoline-related emission (the combination of gasoline exhaust and gas vapor), which contributes 35.1% of the measured VOC mixing ratios; (2) solvent use, contributing 21.8%; (3) fuel combustion, contributing 29.1%; (4) biogenic emission, contributing 5.2%; and (5) industrial, commercial and domestic sources, contributing 8.7%. The effect on this area of the long-range transport of air pollutants from highly polluted areas is significant.

Multiyear trends in volatile organic compounds in Los Angeles, California: Five decades of decreasing emissions

Airborne measurements of volatile organic compounds (VOCs) were performed during CalNex 2010 (California Research at the Nexus of Air Quality and Climate Change) in the Los Angeles (LA) basin in May–June 2010 and during ITCT2k2 (Intercontinental Transport and Chemical Transformation) in May 2002. While CO2 enhancements in the basin were similar between the two years, the ΔCO/ΔCO2 ratio had decreased by about a factor of two. The ΔVOC/ΔCO emission ratios stayed relatively constant between the two years. This indicates that, relative to CO2, VOCs in the LA basin also decreased by about a factor of two since 2002. These data are compared with the results from various previous field campaigns dating back as early as 1960 and from the extensive air quality monitoring system in the LA basin going back to 1980. The results show that the mixing ratios of VOCs and CO have decreased by almost two orders of magnitude during the past five decades at an average annual rate of about 7.5%. Exceptions to this trend are the small alkanes ethane and propane, which have decreased slower due to the use and production of natural gas. A comparison with trends in London, UK shows that, due to stricter regulations at the time, VOC mixing ratios in LA decreased earlier than in London, albeit at a slower rate, such that typical mixing ratios in both cities in 2008 were at about the same level.

Ozone and alkyl nitrate formation from the Deepwater Horizon oil spill atmospheric emissions

Ozone (O3), alkyl nitrates (RONO2), and other photochemical products were formed in the atmosphere downwind from the Deepwater Horizon (DWH) oil spill by photochemical reactions of evaporating hydrocarbons with NOx (=NO + NO2) emissions from spill response activities. Reactive nitrogen species and volatile organic compounds (VOCs) were measured from an instrumented aircraft during daytime flights in the marine boundary layer downwind from the area of surfacing oil. A unique VOC mixture, where alkanes dominated the hydroxyl radical (OH) loss rate, was emitted into a clean marine environment, enabling a focused examination of O3 and RONO2 formation processes. In the atmospheric plume from DWH, the OH loss rate, an indicator of potential O3 formation, was large and dominated by alkanes with between 5 and 10 carbons per molecule (C5–C10). Observations showed that NOx was oxidized very rapidly with a 0.8 h lifetime, producing primarily C6–C10 RONO2 that accounted for 78% of the reactive nitrogen enhancements in the atmospheric plume 2.5 h downwind from DWH. Both observations and calculations of RONO2 and O3 production rates show that alkane oxidation dominated O3 formation chemistry in the plume. Rapid and nearly complete oxidation of NOx to RONO2 effectively terminated O3 production, with O3 formation yields of 6.0 ± 0.5 ppbv O3 per ppbv of NOx oxidized. VOC mixing ratios were in large excess of NOx, and additional NOx would have formed additional O3 in this plume. Analysis of measurements of VOCs, O3, and reactive nitrogen species and calculations of O3 and RONO2 production rates demonstrate that NOx‐VOC chemistry in the DWH plume is explained by known mechanisms.

Influence of extensive compressed natural gas (CNG) usage on air quality

Compressed Natural Gas (CNG) is an inexpensive, indigenous energy resource which currently accounts for the majority of automobile and domestic energy consumption in Bangladesh. This extensive CNG usage, particularly within the capital city, Dhaka, heavily influences the atmospheric composition (and hence air quality), yet to date measurements of trace gases in regions dominated by CNG emissions are relatively limited. Here we report continuous observations of the atmospherically important trace gases O3, CO, SO2, NOx and volatile organic compounds (VOC), in ambient air in Dhaka City, Bangladesh, during May 2011. The average mixing ratios of O3, CO, SO2 ,a nd NO x for the measurement period were 18.9, 520.9, 7.6 and 21.5 ppbv, respectively. The ratios of CO to NO reveal that emissions from gasoline and CNG-fuelled vehicles were dominant during the daytime (slope of w26), while in contrast, owing to restrictions imposed on diesel fuelled vehicles entering Dhaka City, emissions from these vehicles only became significant during the night (slope of w10). The total VOC mixing ratio in Dhaka was w5e10 times higher than the levels reported in more developed Asian cities such as Tokyo and Bangkok, which consequently gives rise to a higher ozone formation potential (OFP). However, the most abundant VOC in Dhaka were the relatively long-lived ethane and propane (with mean mixing ratios of w115 and w30 ppbv, respectively), and as a consequence, the ozone formation potential per ppb carbon (ppbC) was lower in Dhaka than in Tokyo and Bangkok. Thus the atmospheric composition of air influenced by extensive CNG combustion may be characterized by high VOC mixing ratios, yet mixing ratios of the photochemical pollutant ozone do not drastically exceed the levels typical of Asian cities with considerably lower VOC levels.

Contrasting winter and summer VOC mixing ratios at a forest site in the Western Mediterranean Basin: the effect of local biogenic emissions

Abstract. Atmospheric volatile organic compounds (VOCs) are involved in ozone and aerosol generation, thus having implications for air quality and climate. VOCs and their emissions by vegetation also have important ecological roles as they can protect plants from stresses and act as communication cues between plants and between plants and animals. In spite of these key environmental and biological roles, the reports on seasonal and daily VOC mixing ratios in the literature for Mediterranean natural environments are scarce. We conducted seasonal (winter and summer) measurements of VOC mixing ratios in an elevated (720 m a.s.l.) holm oak Mediterranean forest site near the metropolitan area of Barcelona (NE Iberian Peninsula). Methanol was the most abundant compound among all the VOCs measured in both seasons. While aromatic VOCs showed almost no seasonal variability, short-chain oxygenated VOCs presented higher mixing ratios in summer, presumably due to greater emission by vegetation and increased photochemistry, both enhanced by the high temperatures and solar radiation in summer. Isoprenoid VOCs showed the biggest seasonal change in mixing ratios: they increased by one order of magnitude in summer, as a result of the vegetation's greater physiological activity and emission rates. The maximum diurnal concentrations of ozone increased in summer too, most likely due to more intense photochemical activity and the higher levels of VOCs in the air. The daily variation of VOC mixing ratios was mainly governed by the wind regime of the mountain, as the majority of the VOC species analyzed followed a very similar diel cycle. Mountain and sea breezes that develop after sunrise advect polluted air masses to the mountain. These polluted air masses had previously passed over the urban and industrial areas surrounding the Barcelona metropolitan area, where they were enriched in NOx and in VOCs of biotic and abiotic origin. Moreover, these polluted air masses receive additional biogenic VOCs emitted in the local valley by the vegetation, thus enhancing O3 formation in this forested site. The only VOC species that showed a somewhat different daily pattern were monoterpenes because of their local biogenic emission. Isoprene also followed in part the daily pattern of monoterpenes, but only in summer when its biotic sources were stronger. The increase by one order of magnitude in the concentrations of these volatile isoprenoids highlights the importance of local biogenic summer emissions in these Mediterranean forested areas which also receive polluted air masses from nearby or distant anthropic sources.

Identification of volatile organic compounds in suburban Bangkok, Thailand and their potential for ozone formation

Measurement of Volatile Organic Compound (VOC) was carried out in suburban Bangkok during July 2–8, 2008. Analysis was performed using GC-FID and GC-MS. High mixing ratios of VOCs detected during the morning and evening are most likely due to vehicular emissions. Averaged VOC mixing ratios revealed distinct difference between mixing ratios of weekdays and weekend, which the latter were found to be lower. The most abundance species were propane and toluene. Ratios of benzene over toluene suggested that additional toluene mixing ratios was owing to industrial emission, which was particularly larger during weekdays. Comparison between C2Cl4 and CH3Cl mixing ratios obtained for suburban Tokyo reveal a relatively lower influence of biomass burning than suburban Bangkok. Elucidating by Ozone Formation Potential, toluene was found to contribute the most to O3 production followed by ethylene, m-,p-xylene, and propylene.

Diurnally resolved particulate and VOC measurements at a rural site: indication of significant biogenic secondary organic aerosol formation

Abstract. We report simultaneous measurements of volatile organic compound (VOC) mixing ratios including C6 to C8 aromatics, isoprene, monoterpenes, acetone and organic aerosol mass loadings at a rural location in southwestern Ontario, Canada by Proton-Transfer-Reaction Mass Spectrometry (PTR-MS) and Aerosol Mass Spectrometry (AMS), respectively. During the three-week-long Border Air Quality and Meteorology Study in June–July 2007, air was sampled from a range of sources, including aged air from the polluted US Midwest, direct outflow from Detroit 50 km away, and clean air with higher biogenic input. After normalization to the diurnal profile of CO, a long-lived tracer, diurnal analyses show clear photochemical loss of reactive aromatics and production of oxygenated VOCs and secondary organic aerosol (SOA) during the daytime. Biogenic VOC mixing ratios increase during the daytime in accord with their light- and temperature-dependent sources. Long-lived species, such as hydrocarbon-like organic aerosol and benzene show little to no photochemical reactivity on this timescale. From the normalized diurnal profiles of VOCs, an estimate of OH concentrations during the daytime, measured O3 concentrations, and laboratory SOA yields, we calculate integrated local organic aerosol production amounts associated with each measured SOA precursor. Under the assumption that biogenic precursors are uniformly distributed across the southwestern Ontario location, we conclude that such precursors contribute significantly to the total amount of SOA formation, even during the period of Detroit outflow. The importance of aromatic precursors is more difficult to assess given that their sources are likely to be localized and thus of variable impact at the sampling location.

Global comparison of VOC and CO observations in urban areas

Speciated volatile organic compound (VOC) and carbon monoxide (CO) measurements from the Marylebone Road site in central London from 1998 through 2008 are presented. Long-term trends show statistically significant decreases for all the VOCs considered, ranging from −3% to −26% per year. Carbon monoxide decreased by −12% per year over the measurement period. The VOC trends observed at the kerbside site in London showed greater rates of decline relative to trends from monitoring sites in rural England (Harwell) and a remote high-altitude site (Hohenpeissenberg), which showed decreases for individual VOCs from −2% to −13% per year. Over the same 1998 through 2008 period VOC to CO ratios for London remained steady, an indication that emissions reduction measures affected the measured compounds equally. Relative trends comparing VOC to CO ratios between Marylebone Road and Hohenpeissenberg showed greater similarities than absolute trends, indicating that emissions reductions measures in urban areas are reflected by regional background locations. A comparison of VOC mixing ratios and VOC to CO ratios was undertaken for London and other global cities. Carbon monoxide and VOCs (alkanes greater than C 5 , alkenes, and aromatics) were found to be strongly correlated (>0.8) in the Annex I countries, whereas only ethene and ethyne were strongly correlated with CO in the non-Annex I countries. The correlation results indicate significant emissions from traffic-related sources in Annex I countries, and a much larger influence of other sources, such as industry and LPG-related sources in non-Annex I countries. Yearly benzene to ethyne ratios for London from 2000 to 2008 ranged from 0.17 to 0.29 and compared well with previous results from US cities and three global megacities.

Measurements of volatile organic compounds in the middle of Central East China during Mount Tai Experiment 2006 (MTX2006): observation of regional background and impact of biomass burning

Abstract. The measurement of volatile organic compounds (VOCs) was carried out at the summit of Mount Tai, located in the center of the Central East China (CEC) region, in June 2006 as part of the Mount Tai Experiment 2006 (MTX2006), which focused on the ozone and aerosol chemistry in the region. Temporal variations of simple VOCs between 2 June and 28 June revealed the characteristics of an aged air mass with minimum local influence. A comparison of VOCs observed at Mount Tai with other Chinese sites revealed relatively similar VOC levels to remote sites and, as expected, a lower level compared to more polluted sites. However, relatively high acetylene and benzene levels at Mount Tai were evidently indicated from comparison with normalized VOC profile by ethane suggested for Beijing. Owing to a shift in boundary layer height, we observed considerable differences between daytime and nighttime VOC mixing ratios. This suggests that the site potentially has a very useful characteristic of being able to measure regional polluted air and the free troposphere regional background air quality. Influence of emissions from biomass burning in the region was evidently found to be extensive during the first half of the campaign (2–15 June), using fire spot data coupling with backward trajectory analysis. Agricultural residue burning was suggested as the primary source of emissions elucidated by the slope of the correlation plot between CH3Cl and CO obtained during the first half of the campaign.

Fluxes and concentrations of volatile organic compounds above central London, UK

Abstract. Concentrations and fluxes of eight volatile organic compounds (VOCs) were measured during October 2006 from a high telecom tower above central London, as part of the CityFlux contribution to the REPARTEE I campaign. A continuous flow disjunct eddy covariance technique with analysis by proton transfer reaction mass spectrometry was used. Daily averaged VOC mixing ratios were within the range 1–19 ppb for the oxygenated compounds (methanol, acetaldehyde and acetone) and 0.2–1.3 ppb for the aromatics (benzene, toluene and C2-benzenes). Typical VOC fluxes were in the range 0.1–1.0 mg m−2 h−1. There was a non-linear relationship between VOC fluxes and traffic density for most of the measured compounds. Traffic activity was estimated to account for approximately 70% of the aromatic compound fluxes, whereas non-traffic related sources were found to be more important for methanol and isoprene fluxes. The measured fluxes were comparable to the estimates of the UK national atmospheric emission inventory for the aromatic VOCs and CO. In contrast, fluxes of the oxygenated compounds were about three times larger than inventory estimates. For isoprene and acetonitrile this difference was many times larger. At temperatures over 25° C it is estimated that more than half the isoprene observed in central London is of biogenic origin.

Volatile organic compounds measured in summer in Beijing and their role in ground‐level ozone formation

Beijing has long suffered from serious ground‐level ozone pollution, and volatile organic compounds (VOCs) play a key role in ozone formation. To understand the chemical speciation of VOCs in Beijing, nonmethane hydrocarbons (NMHCs) and oxygenated VOCs (OVOCs) were measured in summer in Beijing and nearby provinces (VOCs in this work means NMHCs+OVOCs). A variation of VOC mixing ratios and chemical speciation from 2004 to 2006 was observed at an urban site in Beijing. The typical VOC species, e.g., propane, propene, and toluene, had comparable or lower mixing ratios than levels found in other cities that previously hosted the Olympic Games, while the mixing ratios for isoprene were higher. The chemical compositions of VOCs within Beijing were heavily influenced by vehicular emissions and differed from those obtained in Tianjin and Hebei Province. OVOCs were an important component, accounting for 54% and 37% in the VOC mixing ratio in 2005 and 2006, respectively, and about 40% of the OH loss rates. The main reactive VOC compounds were aldehydes and alkenes. By using isoprene chemistry and the ratio of ethylbenzene to mp‐xylene, the initial mixing ratios of VOCs were estimated. The VOCs had similar variation patterns to ambient ozone and peroxyacetyl nitrate (PAN) concentrations. The correlation between daily maximum ozone concentrations and initial VOCs revealed that ozone formation was sensitive to VOCs for both urban (Peking University, PKU) and rural (Yufa) sites. A reduction in NOx would lead to a decrease in ozone at Yufa, but would cause increased ozone at the PKU site.

Abundances and Flux Estimates of Volatile Organic Compounds from a Dairy Cowshed in Germany

Animal husbandry and manure treatment have been specifically documented as significant sources of methane, ammonia, nitrous oxide, and particulate matter. Although volatile organic compounds (VOCs) are also produced, much less information exists concerning their impact. We report on chemical ionization mass spectrometry and photo-acoustic spectroscopy measurements of mixing ratios of VOCs over a 2-wk measurement period in a large cowshed at the Federal Agricultural Research Centre (FAL) in Mariensee, Germany. The high time resolution of these measurements enables insight into the sources of the emissions in a typical livestock management setting. During feeding hours and solid manure removal, large mixing ratio spikes of several VOCs were observed and correlated with simultaneous methane, carbon dioxide, and ammonia level enhancements. The subsequent decay of cowshed concentration due to passive cowshed ventilation was used to model emission rates, which were dominated by ethanol and acetic acid, followed by methanol. Correlations of VOC mixing ratios with methane or ammonia were also used to calculate cowshed emission factors and to estimate potential nationwide VOC emissions from dairy cows. The results ranged from around 0.1 Gg carbon per year (1 Gg = 10(9) g) for nonanal and dimethylsulfide, several Gg carbon per year for volatile fatty acids and methanol, to over 10 Gg carbon per year of emitted ethanol. While some estimates were not consistent between the two extrapolation methods, the results indicate that animal husbandry VOC emissions are dominated by oxygenated compounds and may be a nationally but not globally significant emission to the atmosphere.

A study of VOC reactivity in the Houston-Galveston air mixture utilizing an extended version of SAPRC-99 chemical mechanism

The Houston-Galveston area is the region where National Ambient Air Quality Standard (NAAQS) for ozone is often violated. Emissions from industrial sources contribute significantly to elevated ozone concentrations and make air composition quite unique in comparison to typical urban composition. In this study, source-oriented reactivity of individual organic compounds, released in urban and industrial areas inside Houston-Galveston region, with regard to ozone formation is determined. The CMAQ model and an extended version of SAPRC-99 mechanism, representing 26 additional individual compounds explicitly, is employed for the model simulations. The incremental volatile organic compound (VOC) reactivities calculated for the Houston-Galveston conditions show variations with respect to the differences in the air compositions between urban and industrial areas as well as meteorological conditions. The compounds with the highest reactivities, such as 2-methyl-2-butene, trans-2-butene and cis-2-butene, were found to be most sensitive to the environment in which they were released. According to the reactivities weighted by VOC mixing ratios, ethene, propene and formaldehyde show the highest impact on ozone formation. Reactivities of most investigated compounds estimated for the Houston-Galveston air conditions are in good agreement with the ‘reference’ maximum incremental reactivity (MIR) scale.