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In the efforts at controlling automobile emissions, it is important to know in what extent air pollutants from on-road vehicles could be truly reduced. In 2014 we conducted tests in a heavily trafficked tunnel in south China to characterize emissions of volatile organic compounds (VOC) from on-road vehicle fleet and compared our results with those obtained in the same tunnel in 2004. Alkanes, aromatics, and alkenes had average emission factors (EFs) of 338, 63, and 42 mg km −1 in 2014 against that of 194, 129, and 160 mg km −1 in 2004, respectively. In 2014, LPG-related propane, n-butane and i-butane were the top three non-methane hydrocarbons (NMHCs) with EFs of 184 ± 21, 53 ± 6 and 31 ± 3 mg km −1 ; the gasoline evaporation marker i-pentane had an average EF of 17 ± 3 mg km −1 ; ethylene and propene were the top two alkenes with average EFs of 16 ± 1 and 9.7 ± 0.9 mg km −1 , respectively; isoprene had no direct emission from vehicles; toluene showed the highest EF of 11 ± 2 mg km −1 among the aromatics; and acetylene had an average EF of 7 ± 1 mg km −1 . While EFs of total NMHCs decreased only 9% from 493 ± 120 mg km −1 in 2004 to 449 ± 40 mg km −1 in 2014, their total ozone formation potential (OFP) decreased by 57% from 2.50 × 10 3 mg km −1 in 2004 to 1.10 × 10 3 mg km −1 in 2014, and their total secondary organic aerosol formation potential (SOAFP) decreased by 50% from 50 mg km −1 in 2004 to 25 mg km −1 in 2014. The large drop in ozone and SOA formation potentials could be explained by reduced emissions of reactive alkenes and aromatics, due largely to fuel transition from gasoline/diesel to LPG for taxis/buses and upgraded vehicle emission standards. [ABSTRACT FROM AUTHOR]

Peroxy acetyl nitrate (PAN) is a key component of photochemical smog and plays an important role in atmospheric chemistry. Though it has been known that PAN is produced via reactions of nitrogen oxides (NOx) with some volatile organic compounds (VOCs), it is difficult to quantify the contributions of individual precursor species. Here we use an explicit photochemical model – Master Chemical Mechanism (MCM) model – to dissect PAN formation and identify principal precursors, by analyzing measurements made in Beijing in summer 2008. PAN production was sensitive to both NOx and VOCs. Isoprene was the predominant VOC precursor at suburb with biogenic impact, whilst anthropogenic hydrocarbons dominated at downtown. PAN production was attributable to a relatively small class of compounds including NOx, xylenes, trimethylbenzenes, trans/cis-2-butenes, toluene, and propene. MCM can advance understanding of PAN photochemistry to a species level, and provide more relevant recommendations for mitigating photochemical pollution in large cities. [ABSTRACT FROM AUTHOR]

Abstract: Multiyear (2000–2006) seasonal measurements of carbon monoxide, hydrocarbons, halogenated species, dimethyl sulfide, carbonyl sulfide and C1–C4 alkyl nitrates at the South Pole are presented for the first time. At the South Pole, short-lived species (such as the alkenes) typically were not observed above their limits of detection because of long transit times from source regions. Peak mixing ratios of the longer lived species with anthropogenic sources were measured in late winter (August and September) with decreasing mixing ratios throughout the spring. In comparison, compounds with a strong oceanic source, such as bromoform and methyl iodide, had peak mixing ratios earlier in the winter (June and July) because of decreased oceanic production during the winter months. Dimethyl sulfide (DMS), which is also oceanically emitted but has a short lifetime, was rarely measured above 5 pptv. This is in contrast to high DMS mixing ratios at coastal locations and shows the importance of photochemical removal during transport to the pole. Alkyl nitrate mixing ratios peaked during April and then decreased throughout the winter. The dominant source of the alkyl nitrates in the region is believed to be oceanic emissions rather than photochemical production due to low alkane levels. Sampling of other tropospheric environments via a Twin Otter aircraft included the west coast of the Ross Sea and large stretches of the Antarctic Plateau. In the coastal atmosphere, a vertical gradient was found with the highest mixing ratios of marine emitted compounds at low altitudes. Conversely, for anthropogenically produced species the highest mixing ratios were measured at the highest altitudes, suggesting long-range transport to the continent. Flights flown through the plume of Mount Erebus, an active volcano, revealed that both carbon monoxide and carbonyl sulfide are emitted with an OCS/CO molar ratio of 3.3 × 10−3 consistent with direct observations by other investigators within the crater rim. [Copyright &y& Elsevier]

Mexico City is the world’s largest and most polluted urban center. We examine the distribution of methane and other hydrocarbons within the Valley of Mexico, using it as a model for the role developing megacities will play in the next century of geochemical cycling. Seventy-five whole air samples were analyzed with multivariate statistical techniques, including factor analysis using principal components. Methane concentrations are highly variable in space and time, due to air circulations and source distribution. Landfills and open sewage canals are major inputs. Emissions into and out from the valley are modeled to be ∼515 t per day. Per capita emission is 0.01 t per annum per person, consistent with the global average for human related anaerobic generation. Natural gas leaks are small, and likely to be higher in other developing megacities; Mexican natural gas use has been discouraged out of earthquake safety concerns. In contrast, liquefied petroleum gas loss constitutes the major emission of propane and butane estimated at a leak rate of 5–10%. Kyoto and other environmental conventions have ignored methane as a greenhouse gas. Our analysis underscores the need to consider methane and other hydrocarbons, and the urbanization process, in future emission protocols. [Copyright &y& Elsevier]

Investigating the long-term trends of alkyl nitrates (RONO 2) is of great importance for evaluating the variations of photochemical pollution. Mixing ratios of C 1 –C 5 RONO 2 were measured in autumn Hong Kong from 2002 to 2016, and the average level of 2-butyl nitrate (2-BuONO 2) always ranked first. The C 1 –C 4 RONO 2 all showed increasing trends (p < 0.05), and 2-BuONO 2 had the largest increase rate. The enhancement in C 3 RONO 2 was partially related to elevated propane, and dramatic decreases (p < 0.05) in both nitrogen monoxide (NO) and nitrogen dioxide (NO 2) also led to the increased RONO 2 formation. In addition, an increase of hydroxyl (OH) and hydroperoxyl (HO 2) radicals (p < 0.05) suggested enhanced atmospheric oxidative capacity, further resulting in the increases of RONO 2. Source apportionment of C 1 –C 4 RONO 2 specified three typical sources of RONO 2 , including biomass burning emission, oceanic emission, and secondary formation, of which secondary formation was the largest contributor to ambient RONO 2 levels. Mixing ratios of total RONO 2 from each source were quantified and their temporal variations were investigated. Elevated RONO 2 from secondary formation and biomass burning emission were two likely causes of increased ambient RONO 2. By looking into the spatial distributions of C 1 –C 5 RONO 2 , regional transport from the Pearl River Delta (PRD) was inferred to build up RONO 2 levels in Hong Kong, especially in the northwestern part. In addition, more serious RONO 2 pollution was found in western PRD region. This study helps build a comprehensive understanding of RONO 2 pollution in Hong Kong and even the entire PRD. Image 1 • C 1 –C 4 RONO 2 levels all kept increasing during the past 15 years in Hong Kong. • Enhanced atmospheric oxidative capacity facilitated photochemical formation of RONO 2. • Elevated biomass burning emissions built up primary RONO 2. • Regional transport from inland China possibly contributed to the elevated RONO 2 as well. Elevated secondary formation and biomass burning emission caused RONO 2 increase from 2002 to 2016. [ABSTRACT FROM AUTHOR]

Ports are major air pollution sources impacting downwind communities with emissions from port activities, nearby energy and other heavy industries, truck, train, and vessel traffic, and commuting traffic. The Ports of Los Angeles/Long Beach, denoted Ports, are the western hemisphere's largest, with plans for port electrification to reduce air pollution. The covid19 shutdown impacted the Ports, providing a real-world experiment on the effects of electrification on exposure to neighboring communities. Eight in situ surveys with a mobile air quality laboratory (14 trace gases, aerosols, and meteorology) were conducted spanning the covid19 shutdown to characterize the resultant air quality changes. These data were combed with time series (2015-) from six Port area air quality stations and TROPOMI satellite nitrogen dioxide NO 2 column XNO 2. In situ surveys showed dramatic NO 2 decreases from Jul. 2019 to May 2020 (during the shutdown), with NO 2 only returning towards pre-covid levels by Jul. 2022. Lesser covid19 NO 2 decreases were observed by the air quality station data and satellite XNO 2 for the Los Angeles Basin; both showed NO 2 decrease during the shutdown and an extended time for recovery to more normal concentration (and underlying economic activity) - until 2022 - far longer than the shutdown. Overall, ozone, O 3 increased, signifying that O 3 , formation is volatile organic hydrocarbons, VOH, limited, with the strongest O 3 source(s) arriving from offshore. This finding suggests efforts to purely address air quality by electrification without addressing area VOH emissions could potentially lessen, perhaps significantly, the expected air quality and health improvements in downwind communities. The Ports' area industrial sites were identified as driving these VOHs, as the inverse relationship between NO 2 and O 3 persisted during the shutdown when non-industrial VOH sources would have decreased. [Display omitted] • Mobile air quality surveyed the Los Angeles & Long Beach Ports during covid19. • Surveys, air quality station and satellite data found dramatic covid19 NO 2 decreases. • Recovery to normal pollution levels was slow - multiyear. • Ozone increased during covid19, indicating VOH-limited ozone formation. [ABSTRACT FROM AUTHOR]

Nighttime concentrations of the gas phase nitrate radical (NO 3 ) were successfully measured during a four week field campaign in an arid urban location, Reno Nevada, using long-path Differential Optical Absorbance Spectrometry (DOAS). While typical concentrations of NO 3 ranged from 5 to 20 ppt, elevated concentrations were observed during a wildfire event. Horizontal mixing in the free troposphere was considerable because the sampling site was above the stable nocturnal boundary layer every night and this justified a box modeling approach. Process analysis of box model simulations showed NO 3 accounted for approximately half of the loss of internal olefins, 60% of the isoprene loss, and 85% of the α-pinene loss during the nighttime hours during a typical night of the field study. The NO 3 + aldehyde reactions were not as important as anticipated. On a polluted night impacted by wildfires upwind of the sampling location, NO 3 reactions were more important. Model simulations overpredicted NO 2 concentrations for both case studies and inorganic chemistry was the biggest influence on NO 3 concentrations and on nitric acid formation. The overprediction may be due to additional NO 2 loss processes that were not included in the box model, as deposition and N 2 O 5 uptake had no significant effect on NO 2 levels. [ABSTRACT FROM AUTHOR]

Abstract: While it is well known that combustion of ethanol as a biofuel will lead to enhanced emissions of methane, ethene (ethylene), acetaldehyde, formaldehyde, and oxides of nitrogen (primarily NO) when compared to gasoline alone, especially during cold starts or if catalytic converters are not operating properly, the impacts of increases in atmospheric ethene levels from combustion of fuels with higher ethanol content has not received much attention. Ethene is a well known and potent plant growth hormone and exposure to agricultural crops and natural vegetation results in yield reductions especially when combined with higher levels of PAN and ozone also expected from the increased use of ethanol/gasoline blends. We report here some baseline measurements of ethene obtained in 2002 in the southwestern and south central United States. These data indicate that current ethene background levels are less than 1 ppb. Anticipated increases in fuel ethanol content of E30 or greater is expected to lead to higher atmospheric levels of ethene on regional scales due to its atmospheric lifetime of 1.5–3 days. These background measurements are discussed in light of the potential enhancement of ethene levels expected from the anticipated increases in ethanol use as a renewable biofuel. [Copyright &y& Elsevier]

We present data collected from a number of snow-covered environments including two polar locations (Summit, Greenland and the South Pole) and two mid-latitude regions (a remote site in northern Michigan, and Niwot Ridge, Colorado). At each site, concentrations of and were enhanced within the interstitial air near the snow surface, compared to levels in boundary layer air. Fluxes of from surface snow to the atmosphere were observed at each site except Niwot Ridge, where appeared to have a sink. The mid-latitude sites showed significant emissions of , mostly originating at the ground surface and traveling up through the snow, while at the polar locations emissions from firn air were relatively small. In general, methyl halide mixing ratios in firn air were significantly greater at Summit than at the South Pole, with Summit showing a strong diurnal cycle in the production of alkyl halides that was well correlated with actinic radiation and firn temperature. We suggest that the most likely route to alkyl halide formation is through an acid catalyzed nucleophilic substitution of an alcohol type function by a halide, both of which should be preferentially segregated to the quasi-liquid layer at the surface of the snow grains. A series of experiments using a snow-filled quartz chamber irradiated by natural sunlight allowed estimation of emission trends that were hard to measure in the natural snowpack. These static chamber experiments confirmed significant production of the primary alkyl halides, following the order . Our observations at all four locations, including polar and mid-latitude sites, imply that alkyl halide production may be associated with all surface snows. [Copyright &y& Elsevier]

Abstract: We report selected carbon species emission indices (EIs) for a Rolls Royce RB211-535-E4 turbofan engine that were acquired during the NASA EXperiment to Characterize Aircraft Volatile Aerosol and Trace-species Emissions (EXCAVATE). Conducted during winter 2002, the mission focused upon characterizing the exhaust constituents of the NASA Boeing 757 aircraft during ground-based operation. Carbon species concentrations were determined by chromatographic analyses of whole air samples collected 10m behind the engine exit plane as engine power was varied from ground idle to about 60% of maximum rated thrust. Ambient air samples were also collected and analyzed to facilitate correction of calculated EIs for background concentrations. Results are consistent with previous observations and indicate that, on a relative basis, turbine engines emit considerable amounts of light hydrocarbon species at idle, but significantly lesser amounts at higher engine powers. [Copyright &y& Elsevier]

Alkyl nitrates (RONO 2 ) are an important class of nitrogen oxides reservoirs in the atmosphere and play a key role in tropospheric photochemistry. Despite the increasing concern for photochemical air pollution over China, the knowledge of characteristics and formation mechanisms of alkyl nitrates in this region is limited. We analyzed C 1 -C 5 alkyl nitrates measured in Beijing at a polluted urban site in summer 2008 and at a downwind rural site in summers of both 2005 and 2008. Although the abundances of NO x and hydrocarbons were much lower at the rural site, the mixing ratios of RONO 2 were comparable between both sites, emphasizing the regional nature of alkyl nitrate pollution. Regional transport of urban plumes governed the elevated RONO 2 levels at the rural site. The concentrations of C 1 -C 2 RONO 2 were significantly higher at the rural site in 2008 compared to 2005 despite a decline in NO x and anthropogenic VOCs, mainly owing to enhanced contributions from biogenic VOCs. The photochemical formation regimes of RONO 2 were evaluated by both a simplified sequential reaction model and a detailed master chemical mechanism box model. The observed C 4 -C 5 RONO 2 levels can be well explained by the photochemical degradation of n -butane and n -pentane, while the sources of C 1 -C 3 RONO 2 were rather complex. In addition to the C 1 -C 3 alkanes, biogenic VOCs and reactive aromatics were also important precursors of methyl nitrate, and alkenes and long-chain alkanes contributed to the formation of C 2 -C 3 RONO 2 . This study provides insights into the spatial distribution, inter-annual variation and photochemical formation mechanisms of alkyl nitrate pollution over the Beijing area. [ABSTRACT FROM AUTHOR]

Vehicular emission is one of the important anthropogenic pollution sources for volatile organic compounds (VOCs). Four characterization campaigns were conducted at a representative urban roadside environment in Hong Kong between May 2011 and February 2012. Carbon monoxide (CO) and VOCs including methane (CH 4 ), non-methane hydrocarbons (NMHCs), halocarbons, and alkyl nitrates were quantified. Both mixing ratios and compositions of the target VOCs show ignorable seasonal variations. Except CO, liquefied petroleum gas (LPG) tracers of propane, i -butane and n -butane are the three most abundant VOCs, which increased significantly as compared with the data measured at the same location in 2003. Meanwhile, the mixing ratios of diesel- and gasoline tracers such as ethyne, alkenes, aromatics, halogenated, and nitrated hydrocarbons decreased by at least of 37%. The application of advanced multivariate receptor modeling technique of positive matrix factorization (PMF) evidenced that the LPG fuel consumption is the largest pollution source, accounting for 60 ± 5% of the total quantified VOCs at the roadside location. The sum of ozone formation potential (OFP) for the target VOCs was 300.9 μg-O 3 m −3 , which was 47% lower than the value of 567.3 μg-O 3 m −3 measured in 2003. The utilization of LPG as fuel in public transport (i.e., taxis and mini-buses) contributed 51% of the sum of OFP, significantly higher than the contributions from gasoline- (16%) and diesel-fueled (12%) engine emissions. Our results demonstrated the effectiveness of the switch from diesel to LPG-fueled engine for taxis and mini-buses implemented by the Hong Kong Special Administrative Region (HKSAR) Government between the recent ten years, in additional to the execution of substitution to LPG-fueled engine and restrictions of the vehicular emissions in compliance with the updated European emission standards. [ABSTRACT FROM AUTHOR]

Air pollution emissions from ports are major sources of contaminant exposures to downwind communities. Elevated pollutant concentrations relate to emissions from port activities and nearby heavy industries including refining. Methane (CH 4) in the 66 Refinery plume, located west of the Los Angeles Port, provided a real-world validation opportunity for in situ -derived emissions in comparison with imaging spectroscopy-derived emissions. Airborne remote sensing data were acquired by the airborne thermal infrared Mako imaging spectrometer, while contemporaneous in situ meteorology and trace gas measurements and air samples were collected using a ground based mobile system, SISTER™ (Standard Instrumentation Suite: Truck Enabled for Response). SISTER measures 13 trace gases, meteorology, aerosol size distributions, and vertical aerosol profiles at up to highway speeds. Real-time data visualization is used to target sample collection. SISTER & Mako data were collected 19 June 2020 with additional SISTER data including air samples collected 16 July 2020. In situ CH 4 emissions were derived from two series of inversion plume models with different numbers of plumes for comparison with Mako reference emissions. The informed series used Mako spatial data, whereas the uninformed series did not. In situ survey data and air samples also were collected for two nearby oil wells and found significantly elevated alkanes through undecane and aromatics in the refinery and oil well plumes compared to nearby reference air. Remote sensing CH 4 emissions were 69 g s−1 (2.18 Gg yr−1), within 20% of the informed in situ emissions of 87 g s−1 (2.73 Gg yr−1) and within 10% of four-plume uninformed emissions of 80 g s−1 (2.51 Gg yr−1). On an annualized basis, this is 10% of estimated US refining CH 4 emissions. Derived emissions were robust – agreeing within 10–20% for the various models; however, partitioning between plumes was very poor for the uninformed plumes because neglecting wind veering caused emissions mis-assignment. Monte Carlo simulation emission uncertainties were 12–13% for 19 June and 24–25% for 16 July when emissions were much lower, 0.25 Gg CH 4 yr−1. This study emphasized the importance of fine-scale structure in winds with respect to characterizing emissions at the sub-facility (kilometer) scale, while also showing robust estimation of emissions at the facility scale by in situ survey for a wide range of models. Wind structure on kilometer and smaller scales plays a key role in understanding the fate of emissions. • Concurrent in situ and airborne remote sensing CH 4 plume data were collected. • Very good agreement (<10%) between remote sensing and in situ derived emissions. • Kilometer-scale wind structure (particularly veering) was critical in the agreement. • Plume was significantly elevated over ambient for a wide range of alkanes and aromatics. [ABSTRACT FROM AUTHOR]

Abstract: The &#x201c;Industrial Heartland&#x201d; of Alberta is Canada's largest hydrocarbon processing center, with more than 40 major chemical, petrochemical, and oil and gas facilities. Emissions from these industries affect local air quality and human health. This paper characterizes ambient levels of 77 volatile organic compounds (VOCs) in the region using high-precision measurements collected in summer 2010. Remarkably strong enhancements of 43 VOCs were detected, and concentrations in the industrial plumes were often similar to or even higher than levels measured in some of the world's largest cities and industrial regions. For example maximum levels of propene and i-pentane exceeded 100 ppbv, and 1,3-butadiene, a known carcinogen, reached 27 ppbv. Major VOC sources included propene fractionation, diluent separation and bitumen processing. Emissions of the measured VOCs increased the hydroxyl radical reactivity (k OH), a measure of the potential to form downwind ozone, from 3.4 s&#x2212;1 in background air to 62 s&#x2212;1 in the most concentrated plumes. The plume value was comparable to polluted megacity values, and acetaldehyde, propene and 1,3-butadiene contributed over half of the plume k OH. Based on a 13-year record (1994&#x2013;2006) at the county level, the incidence of male hematopoietic cancers (leukemia and non-Hodgkin lymphoma) was higher in communities closest to the Industrial Heartland compared to neighboring counties. While a causal association between these cancers and exposure to industrial emissions cannot be confirmed, this pattern and the elevated VOC levels warrant actions to reduce emissions of known carcinogens, including benzene and 1,3-butadiene. [ABSTRACT FROM AUTHOR]

Abstract: Ambient air measurements of volatile organic compounds (VOCs) and oxygenated volatile organic compounds (OVOCs) were conducted and characterised during a two-year grid study in the Pearl River Delta (PRD) region of southern China. The present grid study pioneered the systematic investigation of the nature and characteristics of complex VOC and OVOC sources at a regional scale. The largest contributing VOCs, accounting over 80% of the total VOCs mixing ratio, were toluene, ethane, ethyne, propane, ethene, butane, benzene, pentane, ethylbenzene, and xylenes. Sub-regional VOC spatial characteristics were identified, namely: i) relatively fresh pollutants, consistent with elevated vehicular and industrial activities, around the PRD estuary; and ii) a concentration gradient with higher mixing ratios of VOCs in the west as compared with the eastern part of PRD. Based on alkyl nitrate aging determination, a high hydroxyl radical (OH) concentration favoured fast hydrocarbon reactions and formation of locally produced ozone. The photochemical reactivity analysis showed aromatic hydrocarbons and alkenes together consisted of around 80% of the ozone formation potential (OFP) among the key VOCs. We also found that the OFP from OVOCs should not be neglected since their OFP contribution was more than one-third of that from VOCs alone. These findings support the choice of current air pollution control policy which focuses on vehicular sources but warrants further controls. Industrial emissions and VOCs emitted by solvents should be the next targets for ground-level ozone abatement. [Copyright &y& Elsevier]

South Korea routinely experiences poor air quality with ozone and small particles exceeding air quality standards. To build a better understanding of this problem, in 2016, the KORea-United States cooperative Air Quality (KORUS-AQ) study collected surface and airborne measurements of many chemical species, including the reactive gases hydroxyl (OH) and hydroperpoxyl (HO 2). Several different results are reported here. First, OH and HO 2 measured on the NASA DC-8 agree to within uncertainties with values calculated by two different box models, both in statistical comparisons and as a function of altitude from the surface to 8 km. These comparisons show substantial scatter, likely due to both variability in instrument performance and the difficulty in interpolating measurements made with frequencies different from those of the model time step. Second, OH and HO 2 calculated by a model including HO 2 uptake on aerosol particles in the chemical mechanism are inconsistent with observations. Third, in the planetary boundary layer over both ocean and land, measured and model-calculated OH reactivity are sometimes different, and this missing OH reactivity, which is as much as ∼4 s−1, increased from April to June and originated primarily from the Korean peninsula. Fourth, repeated missed approaches at the Seoul Air Base during several days show that the changes in the sum of ozone and nitrogen dioxide are consistent with ozone production rates calculated from HO 2 either observed or modeled by the Langley Research Center model. • For South Korea, observed and modeled OH and HO 2 agree to within uncertainties. • Modeled aerosol uptake of hydroperoxyl is inconsistent with observed hydroperoxyl. • Missing OH reactivity came from Korea and increased from spring to summer. • Observed ozone changes are consistent with calculated ozone production. [ABSTRACT FROM AUTHOR]

Abstract: As part of the third NASA Aircraft Particle Emissions Experiment (APEX-3, November 2005), whole air samples were collected to determine the emission rates of volatile organic compounds (VOCs) from aircraft equipped with three different gas-turbine engines (an Allison Engine 3007-A1E, a Pratt–Whitney 4158, and a Rolls–Royce RB211-535E4B). Samples were collected 1 m behind the engine exhaust plane of the engines while they were operated at powers ranging from idle up to 30% of maximum rated thrust. Exhaust emission indices (mass emitted per kilogram of fuel used) for CO and non-methane hydrocarbons (NMHCs) were calculated based on enhancements over background relative to CO2. Emissions of all NMHCs were greatest at low power with values decreasing by an order of magnitude with increasing power. Previous studies have shown that scaling idle hydrocarbon emissions to formaldehyde or ethene (which are typically emitted at a ratio of 1-to-1 at idle) reduces variability amongst engine types. NMHC emissions were found to scale at low power, with alkenes contributing over 50% of measured NMHCs. However, as the power increases hydrocarbon emissions no longer scale to ethene, as the aromatics become the dominant species emitted. This may be due in part to a shift in combustion processes from thermal cracking (producing predominantly alkenes) to production of new molecules (producing proportionally more aromatics) as power increases. The formation of these aromatics is an intermediate step in the production of soot, which also increases with increasing power. The increase in aromatics relative to alkenes additionally results in a decrease in the hydroxyl radical reactivity and ozone formation potential of aircraft exhaust. Samples collected 30 m downwind of the engine were also analyzed for NMHCs and carbonyl compounds (acetone, 2-butanone and C1–C9 aldehydes). Formaldehyde was the predominant carbonyl emitted; however, the ratio of ethene-to-formaldehyde varied between the aircraft, possibly due to the sampling of transient emissions such as engine start-up and power changes. A large portion of the measured emissions (27–42% by mass) in the plume samples was made up of hazardous air pollutants (HAPs) with oxygenated compounds being most significant. [Copyright &y& Elsevier]

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. [Copyright &y& Elsevier]

Abstract: This paper presents an evaluation of the consistency of an urban state-of-the-art hydrocarbon (HC) emission inventory. The evaluation was conducted through the comparison of this inventory with hourly HC measurements during two summer months in the centre of Marseille, on the Mediterranean French coast. Factors of under or overestimation could be calculated for each compound on the basis of a systematic HC to HC ratio analysis. These results, associated with a deep analysis of the speciation profiles, show that most of the common and highly concentrated hydrocarbons (such as butanes) are too much predominant in the emission speciation, while the heavy and less common species (branched alkanes, substituted aromatics) are under-represented in the inventory. The urban diffuse sources appear here as one critical point of the inventories. The disagreements were shown to have a strong incidence on the representation of the air mass reactivity. In a last step, the identified uncertainties in emissions were implemented in an air-quality model for sensitivity studies. It was shown that the observed biases in the inventory could affect the regional ozone production, with a probable impact on ozone peaks of 2–10 ppbv over the area. [ABSTRACT FROM AUTHOR]

Abstract: We present a study of the seasonal and diurnal variability of carbon monoxide and selected volatile organic compounds in the Los Angeles area. Measurements were made during four different nine-day field campaigns in April/May, September, and November, 2007, and February, 2008, at the Mt. Wilson sampling site, which is located at an elevation of approximately 1700 m in the San Gabriel Mountains overlooking Pasadena and the Los Angeles basin. The results were used to characterize the Mt. Wilson site as a representative location for monitoring integrated Los Angeles basin emissions, and, by reference to carbon monoxide emissions, to estimate average annual emissions. The considerable seasonal variability of many hydrocarbons, in both their measured mixing ratios and their relationship to carbon monoxide, was indicative of variable source strengths. Most interestingly, perturbation of C4 hydrocarbon ratios suggested an enhanced role for chlorine chemistry during the month of September, likely as the result of Los Angeles’ coastal location. Such coastal influence was confirmed by observations of enhanced mixing ratios of marine halocarbons, as well as air mass back trajectories. [Copyright &y& Elsevier]

Abstract: Methane (CH4) and carbon monoxide (CO) mixing ratios were measured at an air quality monitoring station near the Mt. Wilson (MW) Observatory in southern California starting in the spring of 2007. Diurnal variation and mixing ratio correlation (R 2 = 0.81) were observed. The correlation results observed agree with previous aircraft measurements collected over the greater Los Angeles (LA) metropolitan area. The consistent agreement between CH4 and CO indicates these gases are well-mixed before reaching the sampling site and the emission source contributions of both compounds are reasonably constant. Since CH4 and CO are considered non-reactive on the time scale of dispersion within the LA urban area and their emission sources are likely to be similarly distributed (e.g., associated with human activities) they are subject to similar scales of atmospheric transport and dilution. This behavior allows the relationship of CH4 and CO to be applied for estimation of CH4 emissions using well-documented CO emissions. Applying this relationship a “top–down” CH4 inventory was calculated for LA County based on the measurements observed at MW and compared with the California Air Resources Board (CARB) “bottom–up” CH4 emissions inventory based on the Intergovernmental Panel on Climate Change recommended methodologies. The “top–down” CH4 emissions inventory is approximately one-third greater than CARB''s “bottom–up” inventory for LA County. Considering the uncertainties in both methodologies, the different CH4 emissions inventory approaches are in good agreement, although some under and/or uninventoried CH4 sources may exist. [Copyright &y& Elsevier]

A sampling campaign was conducted in the city of Milan, Italy before and during a transportation strike in January 2004. This strike provided a unique opportunity to investigate the influence of public transportation on the air quality in a major metropolitan area. Twenty-four air samples were collected each day around the city on January 2nd, 7th and 9th. The samples were analyzed for methane, carbon monoxide, non-methane hydrocarbons (NMHCs), halocarbons and alkyl nitrates. Significant differences in the mixing ratios were observed among the three days of sampling, with January 2nd showing the lowest concentrations as a result of decreased activity in the city during the holiday season. January 9th showed the highest NMHC concentrations because of increased vehicular activity in the city due to a public transportation strike. This paper investigates the correlation between the increased number of vehicles and decreased air quality because of a reduction in public transportation. Computer simulations were able to reproduce measurements of ozone production during the January 2004 strike and a July 2005 strike. The measurements and simulations suggest that reduced VOC emissions due to the existence of public transportation lowers peak ozone by 11–33% during the summer months. [Copyright &y& Elsevier]

The Pearl River Delta (PRD) region can be considered one of the most economically developed areas of mainland China. In September 2005, a total of 96 whole air samples were collected in Guangzhou and Dongguan, two important urban centers of the PRD region. Guangzhou is considered the economic center of Guangdong province, and Dongguan is a rapidly expanding industrial city. Here, we report mixing ratios of 50 nonmethane hydrocarbons (NMHCs) that were quantified in the ambient air of these PRD centers. The discussion focuses on understanding the main sources responsible for NMHC emissions, and evaluating the role of the identified sources towards ozone formation. Propane was the most abundant species in Guangzhou, with an average mixing ratio of 6.8ppbv (±0.7ppbv S.E.), compared to 2.5±0.2ppbv in Dongguan. Toluene was the most abundant hydrocarbon in Dongguan (6.1±0.8ppbv, compared to 5.9±0.7ppbv in Guangzhou). Based on an analysis of the correlation between vehicular-emitted compounds and the measured NMHCs, together with the benzene-to-toluene (B/T) ratio, vehicular emission appears to be the dominant source of NMHCs measured in Guangzhou. By contrast, selected species (including toluene) in many of the Dongguan samples were influenced by an additional source, most likely related to industrial activities. A specific B/T ratio (<0.20) is proposed here and used as indicator of samples strongly affected by industrial emissions. The ozone formation potential (OFP) is calculated, and the role of the different NMHCs associated with industrial and combustion sources is evaluated. [Copyright &y& Elsevier]

Abstract: Between 1999 and 2005 a sampling campaign was conducted to identify and quantify the major species of atmospheric nonmethane hydrocarbons (NMHCs) in United States cities. Whole air canister samples were collected in 28 cities and analyzed for methane, carbon monoxide (CO) and NMHCs. Ambient mixing ratios exhibited high inter- and intra-city variability, often having standard deviations in excess of 50% of the mean value. For this reason, ratios of individual NMHC to CO, a combustion tracer, were examined to facilitate comparison between cities. Ratios were taken from correlation plots between the species of interest and CO, and most NMHCs were found to have correlation coefficients (r 2) greater than 0.6, particularly ethene, ethyne and benzene, highlighting the influence of vehicular emissions on NMHC mixing ratios. Notable exceptions were the short-chain alkanes, which generally had poor correlations with CO. Ratios of NMHC vs. CO were also used to identify those cities with unique NMHC sources. [Copyright &y& Elsevier]

Experiments were performed at Summit, Greenland (72°34′ N, 38°29′ W) to investigate hydroxyl mixing ratios in the sunlit surface snowpack (or firn). We added a carefully selected mixture of hydrocarbon gases (with a wide range of hydroxyl reactivities) to a UV and visible light transparent flow chamber containing undisturbed natural firn. The relative decrease in mixing ratios of these gases allowed estimation of the lower limit mixing ratio of hydroxyl radicals in the near-surface firn pore spaces. Hydroxyl mixing ratios in the firn air followed a diurnal cycle in summer 2003 (10–12 July), with peak values of more than 3.2×106 moleculescm−3 between 13:00 and 16:00 local time. The minimum value estimated was 1.1×106 moleculescm−3 at 20:00 local time. Results during spring of 2004 showed lower, but rapidly increasing, peak hydroxyl mixing ratios of 1.1×106 moleculescm−3 in the early afternoon on 15 April and 1.5×106 moleculescm−3 on 1 May. Our firn hydroxyl estimates were similar to directly measured above-snow ambient levels during the spring field season, but were only about 30% of ambient levels during summer. [Copyright &y& Elsevier]

Abstract: During this study 158 whole air samples were collected in 45 Chinese cities in January and February 2001. The spatial distribution of different classes of halocarbons in the Chinese urban atmosphere, including chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), Halon-1211, and other chlorinated compounds is presented and discussed. Most of these compounds were enhanced compared to background levels. However, the mean enhancement of CFCs was relatively small, with CFC-12 and CFC-11 increases of 6% (range 1–31%) and 10% (range 2–89%), respectively, with respect to the global background. On the contrary, strongly enhanced levels of CFC replacement compounds and halogenated compounds used as solvents were measured. The average Halon-1211 concentration exceeded the background of 4.3pptv by 75% and was higher than 10pptv in several cities. Methyl chloride mixing ratios were also strongly elevated (78% higher than background levels), which is likely related to the widespread use of coal and biofuel in China. [Copyright &y& Elsevier]

Abstract: Mixing ratios of seven C1–C5 alkyl nitrates (RONO2) were measured during a 16-month study (August 2001–December 2002) at Tai O, a coastal site 30km west of central Hong Kong in the Pearl River Delta, the fastest-growing industrial region in the world. The C3–C4 (rather than C1–C2) RONO2 were most abundant throughout the study, showing the importance of photochemical (rather than marine) RONO2 production in the sampled air. A lack of methyl nitrate (MeONO2) enhancement during summer, when the prevailing winds are from the ocean, indicates that the South China Sea is not a region of strong RONO2 emissions. By contrast, MeONO2 levels during pollution episodes (up to 25 parts per trillion by volume (pptv)) were the highest that our group has recorded during urban photochemical RONO2 production, as opposed to marine emissions or biomass burning. The highest summed RONO2 level of the study (204pptv) was measured in the afternoon of 7 November 2002, during an intense pollution episode that captured the highest ozone (O3) level ever recorded in Hong Kong (203ppbv). During pollution episodes, the average ratio of O3 to summed RONO2 was roughly 1000:1 in freshly polluted air (ethyne/CO∼3–5pptv/ppbv) and 500:1 in very freshly polluted air (ethyne/CO∼6–8pptv/ppbv). Ozone and RONO2 share a common photochemical source, and their good correlation in pollution plumes shows that RONO2 can be used as a tracer of photochemical O3 production. Even MeONO2 showed similar diurnal variations as the C2–C5 RONO2, indicating a strong photochemical source despite its very slow photochemical production from methane oxidation. The decomposition of longer-chain alkoxy radicals also does not explain the high MeONO2 levels, and rough calculations show that methoxy radical reaction with NO2 appears to be a viable alternate pathway for MeONO2 production in polluted atmospheres, though further measurements and modeling are required to confirm this mechanism. [Copyright &y& Elsevier]

Abstract: Whole air samples were collected in 43 Chinese cities in January and February 2001, and methane and nonmethane hydrocarbon (NMHC) concentrations for those samples are here discussed. In order to identify the main sources of the hydrocarbons in these cities, cross-correlations with the general combustion tracer ethyne and the gasoline marker i-pentane were investigated. Most of the identified NMHCs correlated with ethyne or i-pentane suggesting that their primary source is combustion or gasoline evaporation. To differentiate between vehicular and other combustion sources, the benzene to toluene ratio characteristic of the Chinese vehicular fleet was calculated using roadside samples (collected in 25 cities). Cities where the main source of the NMHCs was traffic related were identified. The slope resulting from the correlation of selected gases was used to identify the likely sources of the NMHCs measured. Vehicular emissions were found to be an important source of isoprene in some cities. Different VOC mixing ratio distributions throughout the country were also investigated. This paper gives a general overview of urban VOCs in many Chinese cities. Future more rigorous studies will be necessary to further characterize VOC sources in China. [Copyright &y& Elsevier]

Volatile organic compounds (VOCs) were measured at the South Pole (SP) from late Austral spring to mid-summer 2000 as part of the Investigation of Sulfur Chemistry in the Antarctic Troposphere Program (ISCAT-2000). This paper focuses on VOCs that are directly emitted from the ocean, specifically dimethyl sulfide (DMS), methyl nitrate (CH3ONO2), methyl iodide (CH3I) and bromoform (CHBr3). A partial seasonal cycle of these gases was also recorded during the year following ISCAT-2000. During the summer, the SP periodically receives relatively fresh marine air containing short-lived oceanic trace gases, such as DMS (τ≈1 day). However, DMS was not detected at the SP until January even though DMS emissions from the Southern Ocean typically start peaking in November and elevated levels of other ocean-derived VOCs, including CH3ONO2 and CHBr3, were observed in mid-November. We speculate that in November and December most of the DMS is oxidized before it reaches the SP: a strong correlation between CH3ONO2 and methane sulfonate (MSA), an oxidation product of DMS, supports this hypothesis. Based on a limited number of samples taken over the course of one year, CH3ONO2 apparently accumulates to a quasi-steady-state level over the SP in winter, most likely due to continuing emissions of the compound coupled with a lower rate of photochemical destruction. Oceanic emissions were concluded to be the dominant source of alkyl nitrates at the SP; this is in sharp contrast to northern high latitudes where total alkyl nitrate mixing ratios are dominated by urban sources. [Copyright &y& Elsevier]

Mixing ratios of carbon monoxide (CO), methane (CH[sub 4]), non-methane hydrocarbons, halocarbons and alkyl nitrates (a total of 72 species) were determined for 78 whole air samples collected during the winter of 1998-1999 in Karachi, Pakistan. This is the first time that volatile organic compound (VOC) levels in Karachi have been extensively characterized. The overall air quality of the urban environment was determined using air samples collected at six locations throughout Karachi. Methane (6.3 ppmv) and ethane (93 ppbv) levels in Karachi were found to be much higher than in other cities that have been studied. The very high CH[sub 4] levels highlight the importance of natural gas leakage in Karachi. The leakage of liquefied petroleum gas contributes to elevated propane and butane levels in Karachi, although the propane and butane burdens were lower than in other cities (e.g., Mexico City, Santiago). High levels of benzene (0.3-19 ppbv) also appear to be of concern in the Karachi urban area. Vehicular emissions were characterized using air samples collected along the busiest thoroughfare of the city (M.A. Jinnah Road). Emissions from vehicular exhaust were found to be the main source of many of the hydrocarbons reported here. Significant levels of isoprene (1.2 ppbv) were detected at the roadside, and vehicular exhaust is estimated to account for about 20% of the isoprene observed in Karachi. 1,2-Dichloroethane, a lead scavenger added to leaded fuel, was also emitted by cars. The photochemical production of ozone (O[sub 3]) was calculated for CO and the various VOCs using the Maximum Incremental Reactivity (MIR) scale. Based on the MIR scale, the leading contributors to O[sub 3] production in Karachi are ethene, CO, propene, m-xylene and toluene. [ABSTRACT FROM AUTHOR]

Measurements at Summit, Greenland, performed from June-August 1999, showed significant enhancement in concentrations of several trace gases in the snowpack (firn) pore air relative to the atmosphere. We report here measurements of alkenes, halocarbons, and alkyl nitrates that are typically a factor of 2-10 higher in concentration within the firn air than in the ambient air 1-10m above the snow. Profiles of concentration to a depth of 2m into the firn show that maximum values of these trace gases occur between the surface and 60 cm depth. The alkenes show highest pore mixing ratios very close to the surface, with mixing ratios in the order ethene > propene > 1-butene. Mixing ratios of the alkyl iodides and alkyl nitrates peak slightly deeper in the firn, with mixing ratios in order of methyl > ethyl > propyl. These variations are likely consistent with different near-surface photochemical production mechanisms. Diurnal mixing ratio variations within the firn correlate well with actinic flux for all these gases, with a temporal offset between the solar maximum and peak concentrations, lengthening with depth. Using a snow-filled chamber under constant flow conditions, we calculated production rates for the halocarbons and alkenes that ranged between 10[sup 3]-10[sup 5] and 10[sup 6] molecules cm[sup -3] s[sup -1], respectively. Taken together, these results suggest that photochemistry associated with the surface snowpack environment plays an important role in the oxidative capacity of the local atmospheric boundary layer, and influences post-depositional chemistry, which in turn may affect the interpretation of certain aspects of the ice core records collected previously at Summit. [ABSTRACT FROM AUTHOR]

Halocarbons are widely used in the Greater Pearl River Delta (PRD) region of China. To study the long-term trends, source changes and emissions of major halocarbons, a total of 1505 canister air samples were collected in the Greater PRD region during 2001–2018. Mixing ratios of CFCs decreased significantly over the past 18 years except for CFC-114, which significantly increased in the Greater PRD, consistent with the recent observations of significant CFC-114 emissions in East Asia. Declines in CFCs in the Greater PRD region were faster than those at the background Mauna Loa (MLO) site, indicating effective control regulations. Source apportionment simulations showed that refrigeration applications, including refrigeration industry and CFCs replacement, were the main sources of halocarbons. During the study period, refrigeration industry experienced a progressive decline in both mixing ratio and percentage, while the contribution of CFCs replacement remained increasing. Contribution of solvent use in electronic industry traced by C 2 Cl 4 dramatically decreased during the study period, and stayed at a low level in recent years. Based on the measured ratios of halocarbons to CO, the estimated total halocarbon emissions in 2016 were 46.5 ± 16.7 Gg for the Greater PRD region. This study provides useful information for examining the evolving emission status of halocarbons in the Greater PRD region in response to control strategies and changing usage. • Mixing ratios of CFCs decreased over the past 18 years except for CFC-114, which increased in the Greater PRD region. • Refrigeration applications were the main sources of halocarbons in the Greater PRD region. • Refrigeration industry dominated by CFCs decreased during the past 18 years, while source of CFCs replacement increased. • The estimated total halocarbon emissions in 2016 were 46.5 ± 16.7 Gg for the whole Greater PRD region. [ABSTRACT FROM AUTHOR]

The nonlinear chemical processes involved in ozone production (P(O 3)) have necessitated using proxy indicators to convey information about the primary dependence of P(O 3) on volatile organic compounds (VOCs) or nitrogen oxides (NO x). In particular, the ratio of remotely sensed columns of formaldehyde (HCHO) to nitrogen dioxide (NO 2) has been widely used for studying O 3 sensitivity. Previous studies found that the errors in retrievals and the incoherent relationship between the column and the near-surface concentrations are a barrier in applying the ratio in a robust way. In addition to these obstacles, we provide calculational-observational evidence, using an ensemble of 0-D photochemical box models constrained by DC-8 aircraft measurements on an ozone event during the Korea-United States Air Quality (KORUS-AQ) campaign over Seoul, to demonstrate the chemical feedback of NO 2 on the formation of HCHO is a controlling factor for the transition line between NO x -sensitive and NO x -saturated regimes. A fixed value (~2.7) of the ratio of the chemical loss of NO x (LNO x) to the chemical loss of HO 2 +RO 2 (LRO x) perceptibly differentiates the regimes. Following this value, data points with a ratio of HCHO/NO 2 less than 1 can be safely classified as NO x -saturated regime, whereas points with ratios between 1 and 4 fall into one or the other regime. We attribute this mainly to the HCHO-NO 2 chemical relationship causing the transition line to occur at larger (smaller) HCHO/NO 2 ratios in VOC-rich (VOC-poor) environments. We then redefine the transition line to LNO x /LRO x ~2.7 that accounts for the HCHO-NO 2 chemical relationship leading to HCHO = 3.7 × (NO 2 – 1.14 × 1016 molec.cm-2). Although the revised formula is locally calibrated (i.e., requires for readjustment for other regions), its mathematical format removes the need for having a wide range of thresholds used in HCHO/NO 2 ratios that is a result of the chemical feedback. Therefore, to be able to properly take the chemical feedback into consideration, the use of HCHO = a × (NO 2 – b) formula should be preferred to the ratio in future works. We then use the Geostationary Trace gas and Aerosol Sensor Optimization (GeoTASO) airborne instrument to study O 3 sensitivity in Seoul. The unprecedented spatial (250 × 250 m2) and temporal (~every 2 h) resolutions of HCHO and NO 2 observations form the sensor enhance our understanding of P(O 3) in Seoul; rather than providing a crude label for the entire city, more in-depth variabilities in chemical regimes are observed that should be able to inform mitigation strategies correspondingly. • Ozone sensitivity over Seoul on an exceptionally degraded air quality day. • Various thresholds for HCHO/NO 2 should be defined to label chemical regimes. • The inherent dependence of HCHO production on NO x levels complicates the ratio. • We redesign the formula to reflect the chemical feedback of NO x on HCHO. • GeoTASO provides in-depth variabilities in chemical regimes over Seoul. [ABSTRACT FROM AUTHOR]