Measurements Of Nonmethane Hydrocarbons Research Articles

Comparison of NMHC measurements between 2010 and 2020 in Wuxi City, Yangtze River Delta region: Levels, compositions, sources, and impacts

Field observation analyses of volatile organic compounds (VOCs) have gained significant attention due to their potential explaining atmospheric temporal trends. This study measured non-methane hydrocarbons (NMHCs) in Wuxi City, located in the Yangtze River Delta (YRD) of China, in 2010 and 2020. The aim was to gain a better understanding of the ten-year change of VOCs in terms of their mixing ratios, sources, role in ozone, secondary organic aerosol (SOA) formation, and health risks. The average NMHC level 2020 was 20.67 ppbv, which indicated a 20% drop from 2010. A notable shift was observed in the chemical composition of NMHCs. The contribution of alkanes increased from 45% to 62% in 2020, while that of the aromatics decreased from 25% in 2010 to 21% in 2020. Ratio analysis and receptor modelling for 2010 and 2020 were used to identify the source changes of VOC species. The source apportionment model showed that the contribution of vehicle exhaust decreased from 34.5% to 20.9% from 2010 to 2020, and that of the solvent increased from 15.1% to 25.3%. The chemical reactivity results suggested that aromatics played significant roles in photochemical reactions in Wuxi City. The ozone formation potential (OFP) and SOA potential of VOCs also showed decreasing trends from 2010 to 2020. The total OFP of alkenes decreased by 34.0%, from 30.6 to 20.2 ppbvO3/ppbv. The total non-carcinogenic risk value for the key VOC species was 0.034 in 2010 and 0.024 in 2020. Although the carcinogenic risks for benzene have decreased significantly, the value is still above the acceptable carcinogenic risk level. The results of this study demonstrate the effectiveness of air pollution control measures in Wuxi City and highlight the positive impacts on reducing secondary pollution and health risks in this region over one decade.

Obtaining accurate non-methane hydrocarbon data for ambient air in urban areas: comparison of non-methane hydrocarbon data between indirect and direct methods

Abstract. Since non-methane hydrocarbons (NMHCs) include numerous species of volatile organic compounds (VOCs), they are the only indicators that can characterize the total amount of VOCs in ambient air. More than 90 % of NMHC instruments in the market use the indirect method for NMHC determination, utilizing a gas chromatograph to determine the concentrations of total hydrocarbons (THCs) and methane in air. However, we found indirect NMHC measurements incorrectly characterized the low NMHC concentrations in the urban air. These measurements were hindered by the uncertain changes in the errors associated with low THC concentrations, humidity and macroscopic substances (oxygen) in the atmosphere. In this study, we conducted intercomparisons between 10 instruments in the market using different operation principles; among these, two used the direct method, and eight used the indirect method. For the indirect method, experiments showed that when the NMHC concentration was 50 ppb C, the errors in the measurement results were 32 % (CH4) and 98 % (THC) when compared to theoretical values. The oxygen content in the sample gas directly affected the response of the THC. The effect of increased oxygen content on the analysis of oxygen-containing substances was more significant than that of the increase in hydrocarbon substances. The response of dry zero was blank, and the response value increased non-linearly with relative humidity (RH). RH had a great impact on low NMHC concentrations of nearly 50 %. For the direct method, although various flow designs were applied for different instruments, the results indicated that they generally showed lower interference and higher accuracy for the ambient NMHC measurements. With the online direct methods, we obtained more reliable data and characteristics for low-concentration NMHCs in downtown Shanghai. The median of hourly data was 163.1 ppb C, and the highest ratio of the maximum and minimum concentrations of NMHCs reached 9.56 in a single day.

Observation-based sources evolution of non-methane hydrocarbons (NMHCs) in a megacity of China

Both concentrations and emissions of many air pollutants have been decreasing due to implement of control measures in China, in contrast to the fact that an increase in emissions of non-methane hydrocarbons (NMHCs) has been reported. This study employed seven years continuous NMHCs measurements and the related activities data of Shanghai, a megacity in China, to explore evolution of emissions and effectiveness of air pollution control measures. The mixing ratio of NMHCs showed no statistical interannual changes, of which their compositions exhibited marked changes. This resulted in a decreasing trend of ozone formation potential by 3.8%/year (p < 0.05, the same below), which should be beneficial to ozone pollution mitigation as its production in Shanghai is in the NMHCs-limited regime. Observed alkanes, aromatics and acetylene changed by +3.7%/year, -5.9%/year and -7.4%/year, respectively, and alkenes showed no apparent trend. NMHCs sources were apportioned by a positive matrix factorization model. Accordingly, vehicular emissions (-5.9%/year) and petrochemical industry emissions (-7.1%/year) decreased significantly, but the decrease slowed down; significant reduction in solvent usage (-9.0%/year) appeared after 2010; however, emissions of natural gas (+12.6%/year) and fuel evaporation (with an increasing fraction) became more important. The inconsistency between observations and inventories was found in interannual trend and speciation as well as source contributions, emphasizing the need for further validation in NMHCs emission inventory. Our study confirms the effectiveness of measures targeting mobile and centralized emissions from industrial sources and reveals a need focusing on fugitive emissions, which provided new insights into future air policies in polluted region.

Tower-based measurements of NMHCs and OVOCs in the Pearl River Delta: Vertical distribution, source analysis and chemical reactivity

Measurements of vertical distribution of volatile organic compounds (VOCs) have attracted wide attentions, which could help to understand atmospheric oxidation mechanism and provide implications for VOC control. This study measured the non-methane hydrocarbons (NMHCs) and oxygenated VOCs (OVOCs) simultaneously for the first time at three different heights, namely ground, 118 m and 488 m, in the Canton Tower located in the urban core of the Pearl River Delta (PRD). The results show that NMHCs decreased while some OVOC species such as formaldehyde and acetaldehyde increased with increasing height. It was mainly attributed to the dilution and chemical loss of NMHCs but secondary production of OVOCs during vertical transport. Ratio analysis and receptor modeling indicate that vehicle exhausts (47%) and fuel evaporation (39%) were major sources of the total NMHCs. Interestingly, industry contributed much more at 118 m, probably affected by organic gas discharge from the high chimney of industrial factories. The chemical reactivities in terms of OH radical loss rate (LOH), ozone formation potential (OFP) and secondary organic aerosol potential (SOAP) were lowest at 118 m, smaller than those influenced by high fresh NMHC emissions at ground and strong formation of secondary species (e.g. OVOCs) at 488 m. OH exposure estimated by isoprene and m,p-xylene/ethylbenzene was different depending on their time scale of vertical turbulent mixing and chemical loss. OVOC species measured at different heights were positively correlated with Ox (R = 0.48–0.87), indicating that OVOCs were largely contributed by secondary formation in photochemical process. The tower measurements of NMHCs and OVOCs provided a unique opportunity to investigate the VOC distribution and chemical behaviors, which could give important information for understanding O3 and PM2.5 pollution mechanism in the PRD region with fast developing urban setting and substantially changing air quality.

Evaluation of offline sampling for atmospheric C3-C11 non-methane hydrocarbons

The concentration variation of C3-C11 non-methane hydrocarbons (NMHCs) collected in several types of commercial flexible bags and adsorption tubes was systematically investigated using a gas chromatography-flame ionization detector (GC-FID) system. The percentage loss of each NMHC in the polyvinyl fluoride (PVF) bags was less than 5% during a 7-hr storage period; significant NMHCs loss was detected in aluminum foil composite film and fluorinated ethylene propylene bags. The thermal desorption efficiency of NMHCs for adsorption tubes filled Carbopack B and Carboxen1000 sorbents was greater than 95% at 300℃, and the loss of NMHCs in the adsorption tubes during 20-days storage at 4℃ was less than 8%. The thermal desorption efficiency for C11 NMHCs in the adsorption tube filled with Carbograph 1 and Carbosieve SⅢ absorbents was less than 40% at 300℃, and pyrolysis of the absorbents at 330℃ interfered significantly with the measurements of some alkenes. The loss of alkenes was significant when NMHCs were sampled by cryo-enrichment at -90℃ in the presence of O3 for the online NMHC measurements, and negligible for enrichment using adsorption tubes at 25℃. Although O3 scrubbers have been widely used to eliminate the influence of O3 on NMHC measurements, the loss of NMHCs with carbon numbers greater than 8 was more than 10%. Therefore, PVF bags and adsorption tubes filled Carbopack B and Carboxen1000 sorbents were recommended for the sampling of atmospheric NMHCs.

Ambient Non-Methane Hydrocarbons (NMHCs) Measurements in Baoding, China: Sources and Roles in Ozone Formation

Ambient non-methane hydrocarbons (NMHCs) are important precursors of ozone (O3) and secondary organic aerosol (SOA). Online and offline measurements of NMHCs were conducted during September 2015 in Baoding, Hebei province of China, in order to investigate their sources and roles in ozone formation. Average levels of total NMHCs online measured at the urban site were 44.5 ± 26.7 ppb. Aromatics was the largest contributor to NMHCs levels and OH reactivity, with fraction of 27.1% and 35.9%, respectively. Based on offline measurements at eight sites, we found that toluene, ethylbenzene, and m,p-xylene displayed the highest level at the site close to automobile manufacturing factories, followed by downwind receptor sites and other sites. Positive matrix factorization (PMF) model was then used to analyze NMHCs sources. Four factors were identified, including traffic-related emission, automobile manufacturing coating, biogenic emission, and NG/LPG usage and background. Average relative contribution of automobile manufacturing coating to NMHCs levels during the entire online measurement period was 33.4%, and this value increased to 42% during two O3 pollution days. Sensitivity of O3 formation to NMHCs and NOX during an O3 pollution episode were analyzed using a box model based on observations. Relative incremental reactivity (RIR) results suggested that O3 formation was in NOx-titration regime (i.e., highly NMHCs-limited regime). Further scenario analyses on relationship of O3 formation with reduction of NOx and anthropogenic NMHCs (AHC) indicated that AHC and NOx should be reduced by a ratio greater than two and three to achieve 5% and 10% O3 control objectives, respectively. The largest RIR value for anthropogenic NMHC species was from xylenes, which were also an important contributor to SOA formation and dominantly from sources related to automobile manufacturing coating and traffic emission. This means reducing NMHCs emission from automobile manufacturing coating and traffic emission should be given priority for synergetic control of O3 and PM2.5.

An increasing role for solvent emissions and implications for future measurements of volatile organic compounds

Volatile organic compounds (VOCs) are a broad class of air pollutants which act as precursors to tropospheric ozone and secondary organic aerosols. Total UK emissions of anthropogenic VOCs peaked in 1990 at 2,840 kt yr−1 and then declined to approximately 810 kt yr−1 in 2017 with large reductions in road transport and fugitive fuel emissions. The atmospheric concentrations of many non-methane hydrocarbons (NMHC) in the UK have been observed to fall over this period in broadly similar proportions. The relative contribution to emissions from solvents and industrial processes is estimated to have increased from approximately 35% in 1990 to approximately 63% in 2017. In 1992, UK national monitoring quantified 19 of the 20 most abundant individual anthropogenic VOCs emitted (all were NMHCs), but by 2017 monitoring captured only 13 of the top 20 emitted VOCs. Ethanol is now estimated to be the most important VOC emitted by mass (in 2017 approx. 136 kt yr−1 and approx. 16.8% of total emissions) followed by n-butane (52.4 kt yr−1) and methanol (33.2 kt yr−1). Alcohols have grown in significance representing approximately 10% of emissions in 1990 rising to approximately 30% in 2017. The increased role of solvent emissions should now be reflected in European monitoring strategies to verify total VOC emission reduction obligations in the National Emissions Ceiling Directive. Adding ethanol, methanol, formaldehyde, acetone, 2-butanone and 2-propanol to the existing NMHC measurements would provide full coverage of the 20 most significant VOCs emitted on an annual mass basis.This article is part of a discussion meeting issue ‘Air quality, past present and future’.

Non-methane hydrocarbon (C&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;–C&amp;lt;sub&amp;gt;8&amp;lt;/sub&amp;gt;) sources and sinks around the Arabian Peninsula

Abstract. Atmospheric non-methane hydrocarbons (NMHCs) have been extensively studied around the globe due to their importance to atmospheric chemistry and their utility in emission source and chemical sink identification. This study reports on shipborne NMHC measurements made around the Arabian Peninsula during the AQABA (Air Quality and climate change in the Arabian BAsin) ship campaign. The ship traversed the Mediterranean Sea, the Suez Canal, the Red Sea, the northern Indian Ocean, and the Arabian Gulf, before returning by the same route. The Middle East is one of the largest producers of oil and gas (O&amp;amp;G), yet it is among the least studied. Atmospheric mixing ratios of C2–C8 hydrocarbons ranged from a few ppt in unpolluted regions (Arabian Sea) to several ppb over the Suez Canal and Arabian Gulf (also known as the Persian Gulf), where a maximum of 166.5 ppb of alkanes was detected. The ratio between i-pentane and n-pentane was found to be 0.93±0.03 ppb ppb−1 over the Arabian Gulf, which is indicative of widespread O&amp;amp;G activities, while it was 1.71±0.06 ppb ppb−1 in the Suez Canal, which is a characteristic signature of ship emissions. We provide evidence that international shipping contributes to ambient C3–C8 hydrocarbon concentrations but not to ethane, which was not detected in marine traffic exhausts. NMHC relationships with propane differentiated between alkane-rich associated gas and methane-rich non-associated gas through a characteristic enrichment of ethane over propane atmospheric mixing ratios. Utilizing the variability–lifetime relationship, we show that atmospheric chemistry governs the variability of the alkanes only weakly in the source-dominated areas of the Arabian Gulf (bAG=0.16) and along the northern part of the Red Sea (bRSN=0.22), but stronger dependencies are found in unpolluted regions such as the Gulf of Aden (bGA=0.58) and the Mediterranean Sea (bMS=0.48). NMHC oxidative pair analysis indicated that OH chemistry dominates the oxidation of hydrocarbons in the region, but along the Red Sea and the Arabian Gulf the NMHC ratios occasionally provided evidence of chlorine radical chemistry. These results demonstrate the utility of NMHCs as source/sink identification tracers and provide an overview of NMHCs around the Arabian Peninsula.

Revelation of Coupling Biogenic with Anthropogenic Isoprene by Highly Time-Resolved Observations

ABSTRACTInter-annual variations of atmospheric isoprene in a major metropolis, Taipei, were reported based on a two-year continuous measurements of non-methane hydrocarbons (NMHCs) with an hourly resolution. It is by far the largest dataset ever collected in the urban subtropical environment with thriving vegetation and traffic flows. The dataset revealed the detailed interplay between the two major sources of biogenic and vehicular throughout the year. To separate the vehicular contribution from the biogenic one for the ambient isoprene, ethylene was used as an indicator of traffic emissions. While dramatic surge of isoprene was observed at noontime in hot months with the highest average peak mixing ratio of 1.6 ppbv in August, its abundance decreased to 0.2 ppbv on average in cold months. The vehicular contribution to ambient isoprene was largely masked over by the noontime surge of isoprene in hot seasons, but was still able to be vaguely observed on the slopes of the isoprene peaks mimicking the rush-hour features of ethylene. In winter, the diurnal variations of isoprene were very similar to those of ethylene, which suggests that ambient isoprene in cold months was almost of traffic origin. This study based on the continuous dataset could enhance the key findings in previous flask studies in the same metropolis. While canister sampling had a major advantage of area coverage, the highly time-resolved fixed-site monitoring could better reveal the evolution process from a biogenically overwhelmed condition in hot months to the condition where the biogenic source weakened to reveal the traffic source in cold months.

Compilation of a source profile database for hydrocarbon and OVOC emissions in China

Source profiles are essential for quantifying the role of volatile organic compound (VOC) emissions in air pollution. This study compiled a database of VOC source profiles in China, with 75 species drawn from five major categories: transportation, solvent use, biomass burning, fossil fuel burning, and industrial processes. Source profiles were updated for diesel vehicles, biomass burning, and residential coal burning by measuring both hydrocarbons and oxygenated VOCs (OVOCs), while other source profiles were derived from the available literature. The OVOCs contributed 53.8% of total VOCs in the profiles of heavy - duty diesel vehicle exhaust and 12.4%–46.3% in biomass and residential coal burning, which indicated the importance of primary OVOCs emissions from combustion-related sources. Taking the national emission inventory from 2008 as an example, we established an approach for assigning source profiles to develop a speciation-specific VOC and OVOC emission inventory. The results showed that aromatics contributed 30% of the total 26 Tg VOCs, followed by alkanes (24%), alkenes (19%) and OVOCs (12%). Aromatics (7.9 Tg) were much higher than in previous results (1.1 Tg and 3.4 Tg), while OVOCs (3.1 Tg) were comparable with the 3.3 Tg and 4.3 Tg reported in studies using profiles from the US. The current emission inventories were built based on emission factors from non-methane hydrocarbon measurements, and therefore the proportions from OVOC emissions was neglected, leading to up to 30% underestimation of total VOC emissions. As a result, there is a need to deploy appropriate emission factors and source profiles that include OVOC measurements to reduce the uncertainty of estimated emissions and chemical reactivity potential.

Influence of oil and gas field operations on spatial and temporal distributions of atmospheric non-methane hydrocarbons and their effect on ozone formation in winter

Abstract. Emissions from oil and natural gas development during winter in the Upper Green River basin of Wyoming are known to drive episodic ozone (O3) production. Contrasting O3 distributions were observed in the winters of 2011 and 2012, with numerous episodes (hourly O3 ≥ 85 ppbv) in 2011 compared to none in 2012. The lack of O3 episodes in 2012 coincided with a reduction in measured ambient levels of total non-methane hydrocarbons (NMHC). Measurements of speciated NMHC, and other air quality parameters, were performed to better understand emission sources and to determine which compounds are most active in promoting O3 formation. Positive matrix factorization (PMF) analyses of the data were carried out to help achieve these goals. PMF analyses revealed three contributing factors that were identified with different emission source types: factor 1, combustion/traffic; factor 2, fugitive natural gas; and factor 3, fugitive condensate. Compositional signatures of the three contributing factors were identified through comparison with independently derived emission source profiles. Fugitive emissions of natural gas and of condensate were the two principal emission source types for NMHC. A water treatment and recycling facility was found to be a significant source of NMHC that are abundant in condensate, in particular toluene and m+p-xylene. Emissions from water treatment have an influence upon peak O3 mixing ratios at downwind measurement sites.

Trends of non-methane hydrocarbons (NMHC) emissions in Beijing during 2002–2013

Abstract. Non-methane hydrocarbons (NMHCs) play a critical role in the photochemical production of ozone (O3) and organic aerosols. Obtaining an accurate understanding on temporal trends of NMHC emissions is essential for predicting air quality changes and evaluating the effectiveness of current control measures. In this study, we evaluated temporal trends of anthropogenic NMHC emissions during August in Beijing based on ambient measurements during selected summer periods at an urban site in Beijing from 2002 to 2013. In the contrast to the results from the most recent inventory (Multi-resolution Emission Inventory for China, MEIC), which reported that anthropogenic NMHC emissions during August increased by 28% from 2004 to 2012, whereas mixing ratios of NMHCs measured at this urban site decreased by 37% during the same time period. A positive matrix factorization (PMF) model was applied to these NMHC measurements for source apportionment. The results showed that the relative contributions of vehicular exhaust and gasoline evaporation to measured NMHC concentrations decreased by 66% during August from 2004 to 2012, comparable to the relative decline of 67% for transportation-related NMHC emissions reported by the MEIC inventory. This finding indicates that the implementation of stricter emissions standards for new vehicles and specific control measures for in-use vehicles has been effective for reducing transportation-related NMHC emissions. In addition, the PMF results suggested that there were no significant temporal changes in NMHC concentrations from solvent use and industry during August from 2004 to 2012, in contrast with the rapid rate of increase (8.8% yr−1) reported by the MEIC inventory. To re-evaluate the NMHC emissions trends for solvent use and industry, annual variations in NMHC / NOx ratios were compared between ambient measurements at the PKU site and the MEIC inventory. In contrast to the significant rise in NMHC / NOx ratios from the MEIC inventory, the measured NMHC / NOx ratios declined by 14% during August from 2005 to 2012. The inferred NMHC / NOx ratios based on PMF results exhibited a comparable decline of 11% to measured ratios. These results indicate that the increase rate for NMHC emissions from solvent use and industry in Beijing might be overestimated in the current inventory; therefore, additional research is necessary to verify the NMHC emission trends for this source.

Network monitoring of speciated vs. total non-methane hydrocarbon measurements

The total non-methane hydrocarbon (TNMHC) level in the atmosphere is defined as the level of total hydrocarbons minus the level of methane. TNMHC observations are made in selected air quality stations (AQS) of Environmental Protection Agency (EPA) across Taiwan. The AQS network is also complemented by a network of photochemical assessment monitoring stations (PAMS) to provide hourly observations of 56 speciated non-methane hydrocarbons (NMHCs). In this study, the relationship between the AQS and PAMS TNMHC values was cross-examined for the period of 2007–2011 at four sites that conducted both types of measurements. Although the two observations differ in their methods of collection, the variations in the two datasets showed high synchronicity. However, because some of the NMHCs were missed in the summation of 56 species, the PAMS TNMHC values were consistently lower than those of the AQS TNMHC by an average of 30%.Although total hydrocarbon (THC) instruments can provide instantaneous TNMHC mixing ratios (by subtracting methane) to approximate the levels of volatile organic compounds (VOCs), they lack speciated information, which is invaluable to establishing the link between the observation site and specific source influences. In contrast, PAMS observations with speciation information can be used to complement this deficiency. Examples of this complementarity were illustrated by comparing four common sites, with two mainly affected by urban/traffic emissions and two primarily affected by industrial emissions. The chemical composition of the air samples varied significantly between the four sites. Ethylene and propylene were found to be prominent at the two industrial sites, linking these samples strongly to the petrochemical industry nearby. This compositional signature was even more pronounced for the sample peak values. These findings suggest that network monitoring of TNMHCs may not be sufficient, and the lack of compositional information can be complemented by the more elaborate monitoring means such as PAMS deployed only at critical sites to provide both area coverage and speciation knowledge.

Vertical distributions of non-methane hydrocarbons and halocarbons in the lower troposphere over northeast China

Abstract Vertical distributions of air pollutants are crucial for understanding the key processes of atmospheric transport and for evaluating chemical transport models. In this paper, we present measurements of non-methane hydrocarbons (NMHCs) and halocarbons obtained from an intensive aircraft study over northeast (NE) China in summer 2007. Most compounds exhibited a typical negative profile of decreasing mixing ratios with increasing altitude, although the gradients differed with different species. Three regional plumes with enhanced VOC mixing ratios were discerned and characterized. An aged plume transported from the northern part of the densely populated North China Plain (NCP; i.e. Beijing–Tianjin area) showed relatively higher levels of HCFC-22, 1,2-dichloroethane (1,2-DCE) and toluene. In comparison, the plume originating from Korea had higher abundances of CFC-12, tetrachloroethene (C2Cl4) and methyl chloride (CH3Cl), while regional air masses from NE China contained more abundant light alkanes. By comparing these results with the earlier PEM-West B (1994) and TRACE-P (2001) aircraft measurements, continuing declining trends were derived for methyl chloroform (CH3CCl3), tetrachloromethane (CCl4) and C2Cl4 over the greater China–northwestern Pacific region, indicating the accomplishment of China in reducing these compounds under the Montreal protocol. However, the study also provided evidence for the continuing emissions of several halocarbons in China in 2007, such as CFCs (mainly from materials in stock) and HCFCs.

A five year record of high-frequency in situ measurements of non-methane hydrocarbons at Mace Head, Ireland

Abstract. Continuous high-frequency in situ measurements of a range of non-methane hydrocarbons have been made at Mace Head since January 2005. Mace Head is a background Northern Hemispheric site situated on the eastern edge of the Atlantic. Five year measurements (2005–2009) of six C2–C5 non-methane hydrocarbons have been separated into baseline Northern Hemispheric and European polluted air masses, among other sectors. Seasonal cycles in baseline Northern Hemispheric air masses and European polluted air masses arriving at Mace Head have been studied. Baseline air masses show a broad summer minima between June and September for shorter lived species, longer lived species show summer minima in July/August. All species displayed a winter maxima in February. European air masses showed baseline elevated mole fractions for all non-methane hydrocarbons. Largest elevations (of up to 360 ppt for ethane maxima) from baseline data were observed in winter maxima, with smaller elevations observed during the summer. Analysis of temporal trends using the Mann-Kendall test showed small (&lt;6 % yr−1) but statistically significant decreases in the butanes and i-pentane between 2005 and 2009 in European air. No significant trends were found for any species in baseline air.

Evidence of Reactive Aromatics As a Major Source of Peroxy Acetyl Nitrate over China

We analyze the observations of near-surface peroxy acetyl nitrate (PAN) and its precursors in Beijing, China in August of 2007. The levels of PAN are remarkably high (up to 14 ppbv), surpassing those measured over other urban regions in recent years. Analyses employing a 1-D version of a chemical transport model (Regional chEmical and trAnsport Model, REAM) indicate that aromatic non-methane hydrocarbons (NMHCs) are the dominant (55-75%) PAN source. The major oxidation product of aromatics that produces acetyl peroxy radicals is methylglyoxal (MGLY). PAN and O(3) in the observations are correlated at daytime; aromatic NMHCs appear to play an important role in O(3) photochemistry. Previous NMHC measurements indicate the presence of reactive aromatics at high levels over broad polluted regions of China. Aromatics are often ignored in global and (to a lesser degree) regional 3D photochemical transport models; their emissions over China as well as photochemistry are quite uncertain. Our findings suggest that critical assessments of aromatics emissions and chemistry (such as the yields of MGLY) are necessary to understand and assess ozone photochemistry and regional pollution export in China.

Nonmethane hydrocarbon measurements at a suburban site in Changsha City, China

The concentration, composition, and variability of nonmethane hydrocarbons (NMHCs) and carbon monoxide (CO) were characterized in a suburban region of south-central China. Weekly samples were collected in 2007 in the Changsha suburban area and analyzed with a three-stage preconcentration method coupled with GC–MS. A time series of NMHC measurements showed seasonal variation, with a higher level occurring in winter and a lower level in summer. Toluene was the most abundant species with an average concentration of 2.51 ± 1.87 ppbv, followed by benzene (2.04 ± 1.30 pptv). According to the level of identified NMHCs, vehicular exhaust appears to be the main source of NMHCs in Changsha. Among alkanes, the highest level is propane with a concentration of 1.31 ± 0.71 ppbv, it indicated an extensive use and leakage of liquefied petroleum gas (LPG) in Changsha. The concentrations of NMHCs were influenced by the wind direction; a high level of NMHCs was carried by winds from southern China. Significant biogenic isoprene emissions were observed, with good correlation between isoprene level and temperature. Finally, when the typical individual NMHC species and CO in the morning and afternoon were compared, the shorter lifetime of NMHC species relative to CO could explain the poorer correlation observed in the afternoon.

Nonmethane hydrocarbons at Pico Mountain, Azores: 1. Oxidation chemistry in the North Atlantic region

Measurements of nonmethane hydrocarbons (NMHC) at the Pico Mountain observatory at 2225 m asl on Pico Island, Azores, Portugal, from August 2004 to August 2005 (in part overlapping with the field campaign of the International Consortium on Atmospheric Research on Transport and Transformation study) were used to investigate NMHC sources and seasonal oxidation chemistry in the central North Atlantic region. Levels of anthropogenic NMHC were characteristic of the marine free troposphere. Their concentrations were low compared to continental sites at higher northern latitudes, but higher than data reported from a similarly located Pacific mountain site at Mauna Loa Observatory, Hawaii. These higher NMHC levels are indicative of a greater influence of the adjacent continents on air composition at Pico. Substantially enhanced NMHC concentrations during the summers of 2004 and 2005 were attributed to long‐range transport of biomass burning plumes originating from fires in northern Canada, Alaska, and Siberia. This finding exemplifies the continuing impact of biomass burning plumes on atmospheric composition and chemistry many days downwind of these emission sources. Seasonal cycles with lower NMHC concentrations and lower ratios of more reactive to less reactive NMHC during summer reflect the higher degree of photochemical processing occurring during transport. The NMHC concentrations indicate no significant role of chlorine atom oxidation on NMHC. Ozone above 35 ppbv was measured at Pico Mountain throughout all seasons. Enhanced ozone levels were observed in air that had relatively “fresh” photochemical signatures (e.g., ln [propane]/[ethane] &gt; −2.5). During spring‐summer air that was more processed (“older” air with ln [propane]/[ethane] &lt; −2.5) on average had lower ozone levels (down to &lt;20 ppbv). This relationship indicates that conditions in the lower free troposphere over the mid–North Atlantic during the spring and summer lead to net photochemical ozone destruction while air is photochemically aging during transport to Pico. This behavior contrasts to that in the mid–North Pacific where other recent studies have found that the photochemistry is more nearly ozone neutral.

New off-line aircraft instrumentation for non-methane hydrocarbon measurements

New off-line instrumentation was developed to implement measurements of non-methane hydrocarbons (NMHC) on (French) research aircraft. NMHC are collected on multisorbent tubes by AMOVOC (Airborne Measurements Of Volatile Organic Compounds), a new automatic sampler. AMOVOC is a versatile and portable sampler targeting a wide range of NMHC at high frequency (sampling time of 10 min). Multisorbent tubes are analyzed on the ground by short-path thermal desorption coupled with gas chromatography and mass spectrometry. The development and optimization of both NMHC sampling and analysis are reported here. On the one hand, the paper points out technical choices that were made according to aircraft constraints and avoiding sample loss or contamination. On the other hand, it describes analytical optimization, tube storage stability, and moisture removal. The method shows high selectivity, sensitivity (limit of detection less than 10 ppt) and precision (less than 24%). Finally, NMHC data collected on French aircraft during the African Monsoon Multidisciplinary Analysis campaign are reported for the first time. The results highlight instrumentation validity and protocol efficiency for NMHC measurements in the lower and upper troposphere.

Sampling, storage, and analysis of C 2–C 7 non-methane hydrocarbons from the US National Oceanic and Atmospheric Administration Cooperative Air Sampling Network glass flasks

An analytical technique was developed to analyze light non-methane hydrocarbons (NMHC), including ethane, propane, iso-butane, n-butane, iso-pentane, n-pentane, n-hexane, isoprene, benzene and toluene from whole air samples collected in 2.5 l-glass flasks used by the National Oceanic and Atmospheric Administration, Earth System Research Laboratory, Global Monitoring Division (NOAA ESRL GMD, Boulder, CO, USA) Cooperative Air Sampling Network. This method relies on utilizing the remaining air in these flasks (which is at below-ambient pressure at this stage) after the completion of all routine greenhouse gas measurements from these samples. NMHC in sample aliquots extracted from the flasks were preconcentrated with a custom-made, cryogen-free inlet system and analyzed by gas chromatography (GC) with flame ionization detection (FID). C 2–C 7 NMHC, depending on their ambient air mixing ratios, could be measured with accuracy and repeatability errors of generally ≤10–20%. Larger deviations were found for ethene and propene. Hexane was systematically overestimated due to a chromatographic co-elution problem. Saturated NMHC showed less than 5% changes in their mixing ratios in glass flask samples that were stored for up to 1 year. In the same experiment ethene and propene increased at ∼30% yr −1. A series of blank experiments showed negligible contamination from the sampling process and from storage (<10 pptv yr −1) of samples in these glass flasks. Results from flask NMHC analyses were compared to in-situ NMHC measurements at the Global Atmospheric Watch station in Hohenpeissenberg, Germany. This 9-months side-by-side comparison showed good agreement between both methods. More than 94% of all data comparisons for C 2–C 5 alkanes, isoprene, benzene and toluene fell within the combined accuracy and precision objectives of the World Meteorological Organization Global Atmosphere Watch (WMO-GAW) for NMHC measurements.