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Motor vehicles are among the major sources of pollutants and greenhouse gases in urban areas and a transition to "zero emission vehicles" is underway worldwide. However, emissions associated with brake and tire wear will remain. We show here that previously unrecognized volatile and semi-volatile organic compounds, which have a similarity to biomass burning emissions are emitted during braking. These include greenhouse gases or, these classified as Hazardous Air Pollutants, as well as nitrogen-containing organics, nitrogen oxides and ammonia. The distribution and reactivity of these gaseous emissions are such that they can react in air to form ozone and other secondary pollutants with adverse health and climate consequences. Some of the compounds may prove to be unique markers of brake emissions. At higher temperatures, nucleation and growth of nanoparticles is also observed. Regions with high traffic, which are often disadvantaged communities, as well as commuters can be impacted by these emissions even after combustion-powered vehicles are phased out.

Nitryl chloride (ClNO2) is a radical reservoir species that releases chlorine radicals upon photolysis. An integrated analysis of the impact of ClNO2 on regional photochemistry in the Seoul metropolitan area (SMA) during the Korea-United States Air Quality Study (KORUS-AQ) 2016 field campaign is presented. Comprehensive multiplatform observations were conducted aboard the NASA DC-8 and at two ground sites (Olympic Park, OP; Taehwa Research Forest, TRF), representing an urbanized area and a forested suburban region, respectively. Positive correlations between daytime Cl2 and ClNO2 were observed at both sites, the slope of which was dependent on O3 levels. The possible mechanisms are explored through box model simulations constrained with observations. The overall diurnal variations in ClNO2 at both sites appeared similar but the nighttime variations were systematically different. For about half of the observation days at the OP site the level of ClNO2 increased at sunset but rapidly decreased at around midnight. On the other hand, high levels were observed throughout the night at the TRF site. Significant levels of ClNO2 were observed at both sites for 4-5 h after sunrise. Airborne observations, box model calculations, and back-trajectory analysis consistently show that these high levels of ClNO2 in the morning are likely from vertical or horizontal transport of air masses from the west. Box model results show that chlorine-radical-initiated chemistry can impact the regional photochemistry by elevating net chemical production rates of ozone by 25% in the morning.

Approximately 3 billion people worldwide cook with solid fuels, such as wood, charcoal, and agricultural residues. These fuels, also used for residential heating, are often combusted in inefficient devices, producing carbonaceous emissions. Between 2.6 and 3.8 million premature deaths occur as a result of exposure to fine particulate matter from the resulting household air pollution (Health Effects Institute, 2018a; World Health Organization, 2018). Household air pollution also contributes to ambient air pollution; the magnitude of this contribution is uncertain. Here, we simulate the distribution of the two major health-damaging outdoor air pollutants (PM2:5 and O3) using state-of-thescience emissions databases and atmospheric chemical transport models to estimate the impact of household combustion on ambient air quality in India. The present study focuses on New Delhi and the SOMAARTH Demographic, Development, and Environmental Surveillance Site (DDESS) in the Palwal District of Haryana, located about 80 km south of New Delhi. The DDESS covers an approximate population of 200 000 within 52 villages. The emissions inventory used in the present study was prepared based on a national inventory in India (Sharma et al., 2015, 2016), an updated residential sector inventory prepared at the University of Illinois, updated cookstove emissions factors from Fleming et al. (2018b), and PM2:5 speciation from cooking fires from Jayarathne et al. (2018). Simulation of regional air quality was carried out using the US Environmental Protection Agency Community Multiscale Air Quality modeling system (CMAQ) in conjunction with the Weather Research and Forecasting modeling system (WRF) to simulate the meteorological inputs for CMAQ, and the global chemical transport model GEOS-Chem to generate concentrations on the boundary of the computational domain. Comparisons between observed and simulated O3 and PM2:5 levels are carried out to assess overall airborne levels and to estimate the contribution of household cooking emissions.

Emissions of C2-C5 alkanes from the U.S. oil and gas sector have changed rapidly over the last decade. We use a nested GEOS-Chem simulation driven by updated 2011NEI emissions with aircraft, surface and column observations to 1) examine spatial patterns in the emissions and observed atmospheric abundances of C2-C5 alkanes over the U.S., and 2) estimate the contribution of emissions from the U.S. oil and gas industry to these patterns. The oil and gas sector in the updated 2011NEI contributes over 80% of the total U.S. emissions of ethane (C2H6) and propane (C3H8), and emissions of these species are largest in the central U.S. Observed mixing ratios of C2-C5 alkanes show enhancements over the central U.S. below 2 km. A nested GEOS-Chem simulation underpredicts observed C3H8 mixing ratios in the boundary layer over several U.S. regions and the relative underprediction is not consistent, suggesting C3H8 emissions should receive more attention moving forward. Our decision to consider only C4-C5 alkane emissions as a single lumped species produces a geographic distribution similar to observations. Due to the increasing importance of oil and gas emissions in the U.S., we recommend continued support of existing long-term measurements of C2-C5 alkanes. We suggest additional monitoring of C2-C5 alkanes downwind of northeastern Colorado, Wyoming and western North Dakota to capture changes in these regions. The atmospheric chemistry modeling community should also evaluate whether chemical mechanisms that lump larger alkanes are sufficient to understand air quality issues in regions with large emissions of these species.

East Asia is the strongest global source region for anthropogenic black carbon (BC), the most important light-absorbing aerosol contributing to direct radiative climate forcing. To provide extended observational constraints on regional BC distributions and impacts, in situ measurements of BC were obtained with a single particle soot photometer during the May/June 2016 Korean-United States Air Quality aircraft campaign (KORUS-AQ) in South Korea. Unique chemical tracer relationships were associated with BC sourced from different regions. The extent and variability in vertical BC mass burden for 48 profiles over a single site near Seoul were investigated using back trajectory and chemical tracer analysis. Meteorologically driven changes in transport influenced the relative importance of different source regions, impacting observed BC loadings at all altitudes. Internal mixing and size distributions of BC further demonstrated dependence on source region: BC attributed to China had a larger mass median diameter (180 ± 13 nm) than BC attributed to South Korea (152 ± 25 nm), and BC associated with long-range transport was less thickly coated (60 ± 4 nm) than that sourced from South Korea (75 ± 16 nm). The column BC direct radiative effect at the top of the atmosphere was estimated to be 1.0+0.90.5 W/m2, with average values for different meteorological periods varying by a factor of 2 due to changes in the BC vertical profile. During the campaign, BC sourced from South Korea (≤ 31%), China (22%), and Russia (14%) were the most significant single-region contributors to the column direct radiative effect.

Carbon tetrachloride (CCl4) is an ozone-depleting substance, accounting for about 10% of the chlorine in the troposphere. Under the terms of the Montreal Protocol, its production for dispersive uses was banned from 2010. In this work we show that, despite the controls on production being introduced, CCl4 emissions from the eastern part of China did not decline between 2009 and 2016. This finding is in contrast to a recent bottom-up estimate, which predicted a significant decrease in emissions after the introduction of production controls. We find eastern Asian emissions of CCl4 to be 16 (9-24) Gg/year on average between 2009 and 2016, with the primary source regions being in eastern China. The spatial distribution of emissions that we derive suggests that the source distribution of CCl4 in China changed during the 8-year study period, indicating a new source or sources of emissions from China's Shandong province after 2012.

Air quality in rural India is impacted by residential cooking and heating with biomass fuels. In this study, emissions of CO, CO2, and 76 volatile organic compounds (VOCs) and fine particulate matter (PM2.5) were quantified to better understand the relationship between cook fire emissions and ambient ozone and secondary organic aerosol (SOA) formation. Cooking was carried out by a local cook, and traditional dishes were prepared on locally built chulha or angithi cookstoves using brushwood or dung fuels. Cook fire emissions were collected throughout the cooking event in a Kynar bag (VOCs) and on polytetrafluoroethylene (PTFE) filters (PM2.5). Gas samples were transferred from a Kynar bag to previously evacuated stainless-steel canisters and analyzed using gas chromatography coupled to flame ionization, electron capture, and mass spectrometry detectors. VOC emission factors were calculated from the measured mixing ratios using the carbon-balance method, which assumes that all carbon in the fuel is converted to CO2, CO, VOCs, and PM2.5 when the fuel is burned. Filter samples were weighed to calculate PM2.5 emission factors. Dung fuels and angithi cookstoves resulted in significantly higher emissions of most VOCs (p < 0.05). Utilizing dung-angithi cook fires resulted in twice as much of the measured VOCs compared to dung-chulha and 4 times as much as brushwood-chulha, with 84.0, 43.2, and 17.2g measured VOCkgg fuel carbon, respectively. This matches expectations, as the use of dung fuels and angithi cookstoves results in lower modified combustion efficiencies compared to brushwood fuels and chulha cookstoves. Alkynes and benzene were exceptions and had significantly higher emissions when cooking using a chulha as opposed to an angithi with dung fuel (for example, benzene emission factors were 3.18gkgg fuel carbon for dung-chulha and 2.38gkgg fuel carbon for dung-angithi). This study estimated that 3 times as much SOA and ozone in the maximum incremental reactivity (MIR) regime may be produced from dung-chulha as opposed to brushwood-chulha cook fires. Aromatic compounds dominated as SOA precursors from all types of cook fires, but benzene was responsible for the majority of SOA formation potential from all chulha cook fire VOCs, while substituted aromatics were more important for dung-angithi. Future studies should investigate benzene exposures from different stove and fuel combinations and model SOA formation from cook fire VOCs to verify public health and air quality impacts from cook fires.

We use a global model, TOMCAT, and an inverse model, INVICAT, to estimate emissions of ethane (C2H6) between 2008 and 2014 by assimilating surface flask observations. We find that baseline global emissions in 2008 need to increase by a factor of 2.04–2.11 in order for the model to capture C2H6 observations, indicating large biases in current emission inventories. Most of this increase occurs over North America and Eurasia, with temperate North American emissions accounting for 23–26% of the total global emission increase and temperate Eurasian emissions accounting for 35–37%. Further to this, recent peer-reviewed analysis of long-term observational records shows an increase in C2H6 in the Northern Hemisphere since ~2009. Our results indicate that annual global emissions of C2H6 have increased at a rate of 0.27 ± 0.54–0.33 ± 0.44 Tg/yr2 between 2008 and 2014. A statistically significant positive trend of 0.20 ± 0.11–0.24 ± 0.13 Tg/yr2 (p ≤ 0.01) is found in temperate North America, resulting in emissions that are 31–32% larger in 2014 than in 2008. Our results corroborate previous studies' conclusions that a rapid increase in oil and natural gas production in United States over this time period is likely a large driver of the change in emissions.

Deep convective clouds are critically important to the distribution of atmospheric constituents throughout the troposphere but are difficult environments to study. The Deep Convective Clouds and Chemistry (DC3) study in 2012 provided the environment, platforms, and instrumentation to test oxidation chemistry around deep convective clouds and their impacts downwind. Measurements on the NASA DC-8 aircraft included those of the radicals hydroxyl (OH) and hydroperoxyl (HO2), OH reactivity, and more than 100 other chemical species and atmospheric properties. OH, HO2, and OH reactivity were compared to photochemical models, some with and some without simplified heterogeneous chemistry, to test the understanding of atmospheric oxidation as encoded in the model. In general, the agreement between the observed and modeled OH, HO2, and OH reactivity was within the combined uncertainties for the model without heterogeneous chemistry and the model including heterogeneous chemistry with small OH and HO2 uptake consistent with laboratory studies. This agreement is generally independent of the altitude, ozone photolysis rate, nitric oxide and ozone abundances, modeled OH reactivity, and aerosol and ice surface area. For a sunrise to midday flight downwind of a nighttime mesoscale convective system, the observed ozone increase is consistent with the calculated ozone production rate. Even with some observed-to-modeled discrepancies, these results provide evidence that a current measurement-constrained photochemical model can simulate observed atmospheric oxidation processes to within combined uncertainties, even around convective clouds. For this DC3 study, reduction in the combined uncertainties would be needed to confidently unmask errors or omissions in the model chemical mechanism.

To understand the chemical mechanisms of controlling factors in ozone (O3) formation in early summer in Seoul, a comprehensive study encompassing measurement and modeling was conducted under the Megacity Air Pollution Study-Seoul (MAPS-Seoul) campaign. From May 18 to June 12, 2015, O3 and peroxyacetyl nitrate (PAN) were measured, along with their precursors, including NOx and volatile organic compounds (VOCs), at the Korea Institute of Science and Technology, located in northeast Seoul. VOCs were sampled in a canister twice a day (at 09:30 and 15:00) and analyzed via gas chromatography. The meteorological conditions and chemical regimes of the air masses were clearly distinguished during the study period. In May, NOx concentrations were higher with more pronounced diurnal cycles of precursors and O3 under constant westerly winds. By contrast, stagnant conditions developed in June, which reduced the inflow of primary emissions from the downtown area but increased the influence from the neighboring forest under high temperatures. As a result, the ratio of O3 to odd oxygen was higher in June, indicating a less efficient removal of O3 by NOx. In the same context, the air mass was chemically more aged with a higher NO2/NOx ratio and enhanced OH reactivity of oxygenated and biogenic VOCs in June. The overall measurement results suggest that O3 formation is slightly more sensitive to VOCs than to NOx in Seoul during this season, when O3 concentrations are the highest of the year.

Fine particulate matter (PM2.5) samples collected at Mount (Mt.) Tai in the North China Plain during summer 2014 were analyzed for dicarboxylic acids and related compounds (oxocarboxylic acids and α-dicarbonyls) (DCRCs). The total concentration of DCRCs was 1050±580 and 1040±490ng m-3 during the day and night, respectively. Although these concentrations were about 2 times lower than similar measurements in 2006, the concentrations reported here were about 1-13 times higher than previous measurements in other major cities in the world. Molecular distributions of DCRCs revealed that oxalic acid (C2) was the dominant species (50%), followed by succinic acid (C4) (12%) and malonic acid (C3) (8%). WRF modeling revealed that Mt. Tai was mostly in the free troposphere during the campaign and long-range transport was a major factor governing the distributions of the measured compounds at Mt. Tai. A majority of the samples (79%) had comparable concentrations during the day and night, with their day-night concentration ratios between 0.9 and 1.1. Multi-day transport was considered an important reason for the similar concentrations. Correlation analyses of DCRCs and their gas precursors and between C2 and sulfate indicated precursor emissions and aqueous-phase oxidations during long-range transport also likely play an important role, especially during the night. Source identification indicated that anthropogenic activities followed by photochemical aging accounted for about 60% of the total variance and were the dominant source at Mt. Tai. However, biomass burning was only important during the first half of the measurement period. Measurements of potassium (K+) and DCRCs were about 2 times higher than those from the second half of the measurement period. The concentration of levoglucosan, a biomass burning tracer, decreased by about 80% between 2006 and 2014, indicating that biomass burning may have decreased between 2006 and 2014.

Emissions of airborne particles from biomass burning are a significant source of black carbon (BC) and brown carbon (BrC) in rural areas of developing countries where biomass is the predominant energy source for cooking and heating. This study explores the molecular composition of organic aerosols from household cooking emissions with a focus on identifying fuel-specific compounds and BrC chromophores. Traditional meals were prepared by a local cook with dung and brushwood-fueled cookstoves in a village in Palwal district, Haryana, India. Cooking was done in a village kitchen while controlling for variables including stove type, fuel moisture, and meal. Fine particulate matter (PM2.5) emissions were collected on filters, and then analyzed via nanospray desorption electrospray ionization-high-resolution mass spectrometry (nano-DESI-HRMS) and high-performance liquid chromatography-photodiode array-high-resolution mass spectrometry (HPLC-PDA-HRMS) techniques. The nano-DESI-HRMS analysis provided an inventory of numerous compounds present in the particle phase. Although several compounds observed in this study have been previously characterized using gas chromatography methods a majority of the species in the nano-DESI spectra were newly observed biomass burning compounds. Both the stove (chulha or angithi) and the fuel (brushwood or dung) affected the composition of organic aerosols. The geometric mean of the PM2.5 emission factor and the observed molecular complexity increased in the following order: brushwood-chulha (7.3±1.8 g kg-1 dry fuel, 93 compounds), dung-chulha (21.1±4.2 g kg-1 dry fuel, 212 compounds), and dung-angithi (29.8±11.5 g kg-1 dry fuel, 262 compounds). The mass-normalized absorption coefficient (MACbulk) for the organic-solvent extractable material for brushwood PM2.5 was 3.7±1.5 and 1.9±0.8m2 g-1 at 360 and 405 nm, respectively, which was approximately a factor of two higher than that for dung PM2.5. The HPLC-PDA-HRMS analysis showed that, regardless of fuel type, the main chromophores were CxHyOz lignin fragments. The main chromophores accounting for the higher MACbulk values of brushwood PM2.5 were C8H10O3 (tentatively assigned to syringol), nitrophenols C8H9NO4, and C10H10O3 (tentatively assigned to methoxycinnamic acid).

Carbonyls are an important group of volatile organic compounds (VOCs) that play critical roles in tropospheric chemistry. To better understand the formation mechanisms of carbonyl compounds, extensive measurements of carbonyls and related parameters were conducted in Beijing in summer 2008. Formaldehyde (11.17 ± 5.32 ppbv), acetone (6.98 ± 3.01 ppbv), and acetaldehyde (5.27 ± 2.24 ppbv) were the most abundant carbonyl species. Two dicarbonyls, glyoxal (0.68 ± 0.26 ppbv) and methylglyoxal (MGLY; 1.10 ± 0.44 ppbv), were also present in relatively high concentrations. An observation-based chemical box model was used to simulate the in situ production of formaldehyde, acetaldehyde, glyoxal, and MGLY and quantify their contributions to ozone formation and ROx budget. All four carbonyls showed similar formation mechanisms but exhibited different precursor distributions. Alkenes (mainly isoprene and ethene) were the dominant precursors of formaldehyde, while both alkenes (e.g., propene, i-butene, and cis-2-pentene) and alkanes (mainly i-pentane) were major precursors of acetaldehyde. For dicarbonyls, both isoprene and aromatic VOCs were the dominant parent hydrocarbons of glyoxal and MGLY. Photolysis of oxygenated VOCs was the dominant source of ROx radicals (approximately >80% for HO2 and approximately >70% for RO2) in Beijing. Ozone production occurred under a mixed-control regime with carbonyls being the key VOC species. Overall, this study provides some new insights into the formation mechanisms of carbonyls, especially their parent hydrocarbon species, and underlines the important role of carbonyls in radical chemistry and ozone pollution in Beijing. Reducing the emissions of alkenes and aromatics would be an effective way to mitigate photochemical pollution in Beijing.

Determining the leakage rates of halogenated refrigerants from operating mobile air conditioning systems (MACs) is a challenging task. Here, we take advantage of a heavily trafficked tunnel with a traffic flow of over 40,000 motor vehicles per day in south China. We carried out measurements in 2014 on hot and humid days, and therefore, it is reasonable to assume that essentially all of the MAC units would be turned on to ensure the thermo-comfort of the occupants. Thus, we obtained the leakage rates of the three most important refrigerants from the operating MACs aboard the on-road vehicles. The emission factors (EFs) of HFC-134a, HCFC-22, and CFC-12 from the on-road operating MACs are 1.27 ± 0.11, 0.47 ± 0.04, and 0.17 ± 0.04 mg km-1 veh-1, respectively. Normalized by the percentages of vehicles using different refrigerants in their MACs, the emission rates of HFC-134a, HCFC-22, and CFC-12 are 52.2, 329, and 59.5 mg h-1 veh-1, respectively. This emission rate of HFC-134a is approximately 10 times higher than those previously reported in Europe for stationary conditions and a whole-lifetime average of fugitive losses. The unusually high leakage rates suggest that improving the leak tightness of MACs in China would help to greatly lower their emissions. The global warming potentials associated with refrigerant leakage is equal to 1.4% of the CO2 directly emitted due to fuel consumptions.

High mixing ratios of ozone (O3) in the northern Front Range (NFR) of Colorado are not limited to the urban Denver area but were also observed in rural areas where oil and gas activity is the primary source of O3 precursors. On individual days, oil and gas O3 precursors can contribute in excess of 30 ppb to O3 growth and can lead to exceedances of the EPA O3 National Ambient Air Quality Standard. Data used in this study were gathered from continuous surface O3 monitors for June–August 2013–2015 as well as additional flask measurements and mobile laboratories that were part of the FRAPPE/DISCOVER-AQ field campaign of July–August 2014. Overall observed O3 levels during the summer of 2014 were lower than in 2013, likely due to cooler and damper weather than an average summer. This study determined the median hourly surface O3 mixing ratio in the NFR on summer days with limited photochemical production to be approximately 45–55 ppb. Mobile laboratory and flask data collected on three days provide representative case studies of different O3 formation environments in and around Greeley, Colorado. Observations of several gases (including methane, ethane, CO, nitrous oxide) along with O3 are used to identify sources of O3 precursor emissions. A July 23 survey demonstrated low O3 (45–60 ppb) while August 3 and August 13 surveys recorded O3 levels of 75–80 ppb or more. August 3 exemplifies influence of moderate urban and high oil and gas O3 precursor emissions. August 13 demonstrates high oil and gas emissions, low agricultural emissions, and CO measurements that were well correlated with ethane from oil and gas, suggesting an oil and gas related activity as a NOx and O3 precursor source. Low isoprene levels indicated that they were not a significant contributor to O3 precursors measured during the case studies.

As intermediate products of photochemical reactions, alkyl nitrates (RONO2) regulate ozone (O3) formation. In this study, a photochemical box model incorporating master chemical mechanism well reproduced the observed RONO2 at an urban and a mountainous site, with index of agreement in the range of 0.66–0.73. The value 0.0003 was identified to be the most appropriate branching ratio for C1 RONO2, with the error less than 50%. Although levels of the parent hydrocarbons and nitric oxide (NO) were significantly higher at the urban site than the mountainous site, the production of C2–C3 RONO2 was comparable to or even lower than at the mountainous site, due to the lower concentrations of oxidative radicals in the urban environment. Based on the profiles of air pollutants at the mountainous site, the formation of C2–C4 RONO2 was limited by NOx (volatile organic compounds (VOCs)) when total volatile organic compounds (TVOCs)/NOx was higher (lower) than 10.0 ± 0.4 parts per billion by volume (ppbv)/ppbv. This dividing ratio decreased (p

Following the recent Global Carbon Project (GCP) synthesis of the decadal methane (CH4) budget over 2000-2012 (Saunois et al., 2016), we analyse here the same dataset with a focus on quasi-decadal and inter-annual variability in CH4 emissions. The GCP dataset integrates results from top-down studies (exploiting atmospheric observations within an atmospheric inverse-modelling framework) and bottom-up models (including process-based models for estimating land surface emissions and atmospheric chemistry), inventories of anthropogenic emissions, and data-driven approaches. The annual global methane emissions from top-down studies, which by construction match the observed methane growth rate within their uncertainties, all show an increase in total methane emissions over the period 2000-2012, but this increase is not linear over the 13 years. Despite differences between individual studies, the mean emission anomaly of the top-down ensemble shows no significant trend in total methane emissions over the period 2000-2006, during the plateau of atmospheric methane mole fractions, and also over the period 2008-2012, during the renewed atmospheric methane increase. However, the top-down ensemble mean produces an emission shift between 2006 and 2008, leading to 22 [16-32]Tg CH4yr-1 higher methane emissions over the period 2008-2012 compared to 2002-2006. This emission increase mostly originated from the tropics, with a smaller contribution from mid-latitudes and no significant change from boreal regions. The regional contributions remain uncertain in top-down studies. Tropical South America and South and East Asia seem to contribute the most to the emission increase in the tropics. However, these two regions have only limited atmospheric measurements and remain therefore poorly constrained. The sectorial partitioning of this emission increase between the periods 2002-2006 and 2008-2012 differs from one atmospheric inversion study to another. However, all top-down studies suggest smaller changes in fossil fuel emissions (from oil, gas, and coal industries) compared to the mean of the bottom-up inventories included in this study. This difference is partly driven by a smaller emission change in China from the top-down studies compared to the estimate in the Emission Database for Global Atmospheric Research (EDGARv4.2) inventory, which should be revised to smaller values in a near future. We apply isotopic signatures to the emission changes estimated for individual studies based on five emission sectors and find that for six individual top-down studies (out of eight) the average isotopic signature of the emission changes is not consistent with the observed change in atmospheric 13CH4. However, the partitioning in emission change derived from the ensemble mean is consistent with this isotopic constraint. At the global scale, the top-down ensemble mean suggests that the dominant contribution to the resumed atmospheric CH4 growth after 2006 comes from microbial sources (more from agriculture and waste sectors than from natural wetlands), with an uncertain but smaller contribution from fossil CH4 emissions. In addition, a decrease in biomass burning emissions (in agreement with the biomass burning emission databases) makes the balance of sources consistent with atmospheric 13CH4 observations. In most of the top-down studies included here, OH concentrations are considered constant over the years (seasonal variations but without any inter-annual variability). As a result, the methane loss (in particular through OH oxidation) varies mainly through the change in methane concentrations and not its oxidants. For these reasons, changes in the methane loss could not be properly investigated in this study, although it may play a significant role in the recent atmospheric methane changes as briefly discussed at the end of the paper.

Over the past 10 years (2005-2014), ground-level O3 in Hong Kong has consistently increased in all seasons except winter, despite the yearly reduction of its precursors, i.e. nitrogen oxides (NOx = NO + NO2), total volatile organic compounds (TVOCs), and carbon monoxide (CO). To explain the contradictory phenomena, an observation-based box model (OBM) coupled with CB05 mechanism was applied in order to understand the influence of both locally produced O3 and regional transport. The simulation of locally produced O3 showed an increasing trend in spring, a decreasing trend in autumn, and no changes in summer and winter. The O3 increase in spring was caused by the net effect of more rapid decrease in NO titration and unchanged TVOC reactivity despite decreased TVOC mixing ratios, while the decreased local O3 formation in autumn was mainly due to the reduction of aromatic VOC mixing ratios and the TVOC reactivity and much slower decrease in NO titration. However, the decreased in situ O3 formation in autumn was overridden by the regional contribution, resulting in elevated O3 observations. Furthermore, the OBM-derived relative incremental reactivity indicated that the O3 formation was VOC-limited in all seasons, and that the long-term O3 formation was more sensitive to VOCs and less to NOx and CO in the past 10 years. In addition, the OBM results found that the contributions of aromatics to O3 formation decreased in all seasons of these years, particularly in autumn, probably due to the effective control of solvent-related sources. In contrast, the contributions of alkenes increased, suggesting a continuing need to reduce traffic emissions. The findings provide updated information on photochemical pollution and its impact in Hong Kong.

Satellite-based measurements of the column CH2O/NO2 ratio have previously been used to estimate near-surface ozone (O3) sensitivity (i.e., NOx or VOC limited), and the forthcoming launch of air quality-focused geostationary satellites provides a catalyst for reevaluating the ability of satellite-measured CH2O/NO2 to be used in this manner. In this study, we use a 0-D photochemical box model to evaluate O3 sensitivity and find that the relative rate of radical termination from radical-radical interactions to radical-NOx interactions (referred to as LROx/LNOx) provides a good indicator of maximum O3 production along NOx ridgelines. Using airborne measurements from NASA's Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relative to Air Quality (DISCOVER-AQ) deployments in Colorado, Maryland, and Houston, we show that in situ measurements of CH2O/NO2 can be used to indicate O3 sensitivity, but there is an important “transition/ambiguous” range whereby CH2O/NO2 fails to categorize O3 sensitivity, and the range and span of this transition/ambiguous range varies regionally. Then, we apply these findings to aircraft-derived column density measurements from DISCOVER-AQ and find that inhomogeneities in vertical mixing in the lower troposphere further degrades the ability of column CH2O/NO2 to indicate near-surface O3 sensitivity (i.e., the transition/ambiguous range is much larger than indicated by in situ data alone), and we hypothesize that the global transition/ambiguous range is sufficiently large to make the column CH2O/NO2 ratio unuseful for classifying near-surface O3 sensitivity. Lastly, we present a case study from DISCOVER-AQ-Houston that suggests that O3 sensitivity on exceedance days may be substantially different than on nonexceedance days (which may be observable from space) and explore the diurnal evolution of O3 sensitivity, O3 production, and the column CH2O/NO2 ratio. The results of these studies suggest that although satellite measurements of CH2O/NO2 alone may not be sufficient for accurately classifying near-surface O3 sensitivity, new techniques offered by geostationary platforms may nonetheless provide methods for using space-based measurements to develop O3 mitigation strategies.

We examine three case studies during the Deep Convective Clouds and Chemistry (DC3) field experiment when storm inflow and outflow air were sampled for aerosol subsaturated hygroscopicity and the real part of refractive index (n) with a Differential Aerosol Sizing and Hygroscopicity Probe (DASH-SP) on the NASA DC-8. Relative to inflow aerosol particles, outflow particles were more hygroscopic (by 0.03 based on the estimated κ parameter) in one of the three storms examined. Two of three “control” flights with no storm convection reveal higher κ values, albeit by only 0.02, at high altitude (> 8 km) versus < 4 km. Entrainment modeling shows that measured κ values in the outflow of the three storm flights are higher than predicted values (by 0.03-0.11) based on knowledge of κ values from the inflow and clear air adjacent to the storms. This suggests that other process(es) contributed to hygroscopicity enhancements such as secondary aerosol formation via aqueous-phase chemistry. Values of n were higher in the outflow of two of the three storm flights, reaching as high as 1.54. More statistically significant differences were observed in control flights (no storms) where n decreased from 1.50-1.52 (< 4 km) to 1.49-1.50 (> 8 km). Chemical data show that enhanced hygroscopicity was coincident with lower organic mass fractions, higher sulfate mass fractions, and higher O: C ratios of organic aerosol. Refractive index did not correlate as well with available chemical data. Deep convection is shown to alter aerosol radiative properties, which has implications for aerosol effects on climate.

Recent measurements over the Northern Hemisphere indicate that the long-term decline in the atmospheric burden of ethane (C2H6) has ended and the abundance increased dramatically between 2010 and 2014. The rise in C2H6 atmospheric abundances has been attributed to oil and natural gas extraction in North America. Existing global C2H6 emission inventories are based on outdated activity maps that do not account for current oil and natural gas exploitation regions. We present an updated global C2H6 emission inventory based on 2010 satellite-derived CH4 fluxes with adjusted C2H6 emissions over the U.S. from the National Emission Inventory (NEI 2011). We contrast our global 2010 C2H6 emission inventory with one developed for 2001. The C2H6 difference between global anthropogenic emissions is subtle (7.9 versus 7.2 Tg yr-1), but the spatial distribution of the emissions is distinct. In the 2010 C2H6 inventory, fossil fuel sources in the Northern Hemisphere represent half of global C2H6 emissions and 95% of global fossil fuel emissions. Over the U.S., unadjusted NEI 2011 C2H6 emissions produce mixing ratios that are 14-50% of those observed by aircraft observations (2008-2014). When the NEI 2011 C2H6 emission totals are scaled by a factor of 1.4, the Goddard Earth Observing System Chem model largely reproduces a regional suite of observations, with the exception of the central U.S., where it continues to underpredict observed mixing ratios in the lower troposphere. We estimate monthly mean contributions of fossil fuel C2H6 emissions to ozone and peroxyacetyl nitrate surface mixing ratios over North America of ~ 1% and ~8%, respectively.

We present the first sector-specific analysis of methane (CH4) emissions from the San Francisco Bay Area (SFBA) using CH4 and volatile organic compound (VOC) measurements from six sites during September – December 2015. We apply a hierarchical Bayesian inversion to separate the biological from fossil-fuel (natural gas and petroleum) sources using the measurements of CH4 and selected VOCs, a source-specific 1 km CH4 emission model, and an atmospheric transport model. We estimate that SFBA CH4 emissions are 166–289 Gg CH4/yr (at 95% confidence), 1.3–2.3 times higher than a recent inventory with much of the underestimation from landfill. Including the VOCs, 82 ± 27% of total posterior median CH4 emissions are biological and 17 ± 3% fossil fuel, where landfill and natural gas dominate the biological and fossil-fuel CH4 of prior emissions, respectively.

From 2005 to 2013, volatile organic compounds (VOCs) and other trace gases were continuously measured at a suburban site in Hong Kong. The measurement data showed that the concentrations of most air pollutants decreased during these years. However, ozone (O3) and total non-methane hydrocarbon levels increased with the rate of 0.23 ± 0.03 and 0.34 ± 0.02 ppbv/year, respectively, pointing to the increasing severity of photochemical pollution in Hong Kong. The Hong Kong government has ongoing programs to improve air quality in Hong Kong, including a solvent program implemented during 2007-2011, and a diesel commercial vehicle (DCV) program since 2007. From before to after the solvent program, the sum of toluene, ethylbenzene and xylene isomers decreased continuously with an average rate of -99.1 ± 6.9 pptv/year, whereas the sum of ethene and propene increased by 48.2 ± 2.0 pptv/year from before to during the DCV program. Despite this, source apportionment results showed that VOCs emitted from diesel exhaust decreased at a rate of -304.5 ± 17.7 pptv/year, while solvent related VOCs decreased at a rate of -204.7 ± 39.7 pptv/year. The gasoline and liquefied petroleum gas vehicle emissions elevated by 1086 ± 34 pptv/year, and were responsible for the increases of ethene and propene. Overall, the simulated O3 rate of increase was lowered from 0.39 ± 0.03 to 0.16 ± 0.05 ppbv/year by the solvent and DCV programs, because O3 produced by solvent usage and diesel exhaust related VOCs decreased (p

Photochemical smog, characterized by high concentrations of ozone (O3) and fine particles (PM2.5) in the atmosphere, has become one of the top environmental concerns in China. Volatile organic compounds (VOCs), one of the key precursors of O3 and secondary organic aerosol (SOA) (an important component of PM2.5), have a critical influence on atmospheric chemistry and subsequently affect regional and global climate. Thus, VOCs have been extensively studied in many cities and regions in China, especially in the North China Plain, the Yangtze River Delta and the Pearl River Delta regions where photochemical smog pollution has become increasingly worse over recent decades. This paper reviews the main studies conducted in China on the characteristics and sources of VOCs, their relationship with O3 and SOA, and their removal technology. This paper also provides an integrated literature review on the formulation and implementation of effective control strategies of VOCs and photochemical smog, as well as suggestions for future directions of VOCs study in China.

Wildfires emit significant amounts of pollutants that degrade air quality. Plumes from three wildfires in the western U.S. were measured from aircraft during the Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) and the Biomass Burning Observation Project (BBOP), both in summer 2013. This study reports an extensive set of emission factors (EFs) for over 80 gases and 5 components of submicron particulate matter (PM1) from these temperate wildfires. These include rarely, or never before, measured oxygenated volatile organic compounds and multifunctional organic nitrates. The observed EFs are compared with previous measurements of temperate wildfires, boreal forest fires, and temperate prescribed fires. The wildfires emitted high amounts of PM1 (with organic aerosol (OA) dominating the mass) with an average EF that is more than 2 times the EFs for prescribed fires. The measured EFs were used to estimate the annual wildfire emissions of carbon monoxide, nitrogen oxides, total nonmethane organic compounds, and PM1 from 11 western U.S. states. The estimated gas emissions are generally comparable with the 2011 National Emissions Inventory (NEI). However, our PM1 emission estimate (1530 ± 570 Gg yr-1) is over 3 times that of the NEI PM2.5 estimate and is also higher thanthe PM2.5 emitted from all other sources in these states in the NEI. This study indicates that the source of OA from biomass burning in the western states is significantly underestimated. In addition, our results indicate that prescribed burning may be an effective method to reduce fine particle emissions.

The global methane (CH4) budget is becoming an increasingly important component for managing realistic pathways to mitigate climate change. This relevance, due to a shorter atmospheric lifetime and a stronger warming potential than carbon dioxide, is challenged by the still unexplained changes of atmospheric CH4 over the past decade. Emissions and concentrations of CH4 are continuing to increase, making CH4 the second most important human-induced greenhouse gas after carbon dioxide. Two major difficulties in reducing uncertainties come from the large variety of diffusive CH4 sources that overlap geographically, and from the destruction of CH4 by the very short-lived hydroxyl radical (OH). To address these difficulties, we have established a consortium of multi-disciplinary scientists under the umbrella of the Global Carbon Project to synthesize and stimulate research on the methane cycle, and producing regular (g1/4 biennial) updates of the global methane budget. This consortium includes atmospheric physicists and chemists, biogeochemists of surface and marine emissions, and socio-economists who study anthropogenic emissions. Following Kirschke et al. (2013), we propose here the first version of a living review paper that integrates results of top-down studies (exploiting atmospheric observations within an atmospheric inverse-modelling framework) and bottom-up models, inventories and data-driven approaches (including process-based models for estimating land surface emissions and atmospheric chemistry, and inventories for anthropogenic emissions, data-driven extrapolations). For the 2003-2012 decade, global methane emissions are estimated by top-down inversions at 558g Tgg CH4g yrg'1, range 540-568. About 60g % of global emissions are anthropogenic (range 50-65g %). Since 2010, the bottom-up global emission inventories have been closer to methane emissions in the most carbon-intensive Representative Concentrations Pathway (RCP8.5) and higher than all other RCP scenarios. Bottom-up approaches suggest larger global emissions (736g Tgg CH4g yrg'1, range 596-884) mostly because of larger natural emissions from individual sources such as inland waters, natural wetlands and geological sources. Considering the atmospheric constraints on the top-down budget, it is likely that some of the individual emissions reported by the bottom-up approaches are overestimated, leading to too large global emissions. Latitudinal data from top-down emissions indicate a predominance of tropical emissions (g1/4 64g % of the global budget, http://doi.org/10.3334/CDIAC/GLOBAL-METHANE-BUDGET-2016-V1.1) and the Global Carbon Project.

The Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE) campaign took place in and around the Kathmandu Valley and in the Indo-Gangetic Plain (IGP) of southern Nepal during April 2015. The source characterization phase targeted numerous important but undersampled (and often inefficient) combustion sources that are widespread in the developing world such as cooking with a variety of stoves and solid fuels, brick kilns, open burning of municipal solid waste (a.k.a. trash or garbage burning), crop residue burning, generators, irrigation pumps, and motorcycles. NAMaSTE produced the first, or rare, measurements of aerosol optical properties, aerosol mass, and detailed trace gas chemistry for the emissions from many of the sources. This paper reports the trace gas and aerosol measurements obtained by Fourier transform infrared (FTIR) spectroscopy, whole-air sampling (WAS), and photoacoustic extinctiometers (PAX; 405 and 870nm) based on field work with a moveable lab sampling authentic sources. The primary aerosol optical properties reported include emission factors (EFs) for scattering and absorption coefficients (EF Bscat, EF Babs, inm2kg-1 fuel burned), single scattering albedos (SSAs), and absorption Ångström exponents (AAEs). From these data we estimate black and brown carbon (BC, BrC) emission factors (gkg-1 fuel burned). The trace gas measurements provide EFs (gkg-1) for CO2, CO, CH4, selected non-methane hydrocarbons up to C10, a large suite of oxygenated organic compounds, NH3, HCN, NOx, SO2, HCl, HF, etc. (up to ∼ 80 gases in all). The emissions varied significantly by source, and light absorption by both BrC and BC was important for many sources. The AAE for dung-fuel cooking fires (4.63±0.68) was significantly higher than for wood-fuel cooking fires (3.01±0.10). Dung-fuel cooking fires also emitted high levels of NH3 (3.00±1.33gkg-1), organic acids (7.66±6.90gkg-1), and HCN (2.01±1.25gkg-1), where the latter could contribute to satellite observations of high levels of HCN in the lower stratosphere above the Asian monsoon. HCN was also emitted in significant quantities by several non-biomass burning sources. BTEX compounds (benzene, toluene, ethylbenzene, xylenes) were major emissions from both dung- (∼4.5gkg-1) and wood-fuel (∼1.5gkg-1) cooking fires, and a simple method to estimate indoor exposure to the many measured important air toxics is described. Biogas emerged as the cleanest cooking technology of approximately a dozen stove-fuel combinations measured. Crop residue burning produced relatively high emissions of oxygenated organic compounds (∼12gkg-1) and SO2 (2.54±1.09gkg-1). Two brick kilns co-firing different amounts of biomass with coal as the primary fuel produced contrasting results. A zigzag kiln burning mostly coal at high efficiency produced larger amounts of BC, HF, HCl, and NOx, with the halogenated emissions likely coming from the clay. The clamp kiln (with relatively more biomass fuel) produced much greater quantities of most individual organic gases, about twice as much BrC, and significantly more known and likely organic aerosol precursors. Both kilns were significant SO2 sources with their emission factors averaging 12.8±0.2gkg-1. Mixed-garbage burning produced significantly more BC (3.3±3.88gkg-1) and BTEX (∼4.5gkg-1) emissions than in previous measurements. For all fossil fuel sources, diesel burned more efficiently than gasoline but produced larger NOx and aerosol emission factors. Among the least efficient sources sampled were gasoline-fueled motorcycles during start-up and idling for which the CO EF was on the order of ∼700gkg-1 - or about 10 times that of a typical biomass fire. Minor motorcycle servicing led to minimal if any reduction in gaseous pollutants but reduced particulate emissions, as detailed in a companion paper (Jayarathne et al., 2016). A small gasoline-powered generator and an "insect repellent fire" were also among the sources with the highest emission factors for pollutants. These measurements begin to address the critical data gap for these important, undersampled sources, but due to their diversity and abundance, more work is needed.

Emissions from 15 agricultural fires in the southeastern U.S. were measured from the NASA DC-8 research aircraft during the summer 2013 Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) campaign. This study reports a detailed set of emission factors (EFs) for 25 trace gases and 6 fine particle species. The chemical evolution of the primary emissions in seven plumes was examined in detail for ~1.2 h. A Lagrangian plume cross-section model was used to simulate the evolution of ozone (O3), reactive nitrogen species, and organic aerosol (OA). Observed EFs are generally consistent with previous measurements of crop residue burning, but the fires studied here emitted high amounts of SO2 and fine particles, especially primary OA and chloride. Filter-based measurements of aerosol light absorption implied that brown carbon (BrC) was ubiquitous in the plumes. In aged plumes, rapid production of O3, peroxyacetyl nitrate (PAN), and nitrate was observed with ΔO3/ΔCO, ΔPAN/ΔNOy, and Δnitrate/ΔNOy reaching ~0.1, ~0.3, and ~0.3. For five selected cases, the model reasonably simulated O3 formation but underestimated PAN formation. No significant evolution of OA mass or BrC absorption was observed. However, a consistent increase in oxygen-to-carbon (O/C) ratios of OA indicated that OA oxidation in the agricultural fire plumes was much faster than in urban and forest fire plumes. Finally, total annual SO2, NOx, and CO emissions from agricultural fires in Arkansas, Louisiana, Mississippi, and Missouri were estimated (within a factor of ~2) to be equivalent to ~2% SO2 from coal combustion and ~1% NOx and ~9% CO from mobile sources.

We have developed semi-independent methods for determining CH2O scavenging efficiencies (SEs) during strong midlatitude convection over the western, south-central Great Plains, and southeastern regions of the United States during the 2012 Deep Convective Clouds and Chemistry (DC3) Study. The Weather Research and Forecasting model coupled with chemistry (WRF-Chem) was employed to simulate one DC3 case to provide an independent approach of estimating SEs and the opportunity to study CH2O retention in icewhen liquid drops freeze. Measurements of CH2O instorminflow and outflow were acquired on board the NASA DC-8 and the NSF/National Center for Atmospheric Research Gulfstream V (GV) aircraft employing cross-calibrated infrared absorption spectrometers. This study also relied heavily on the nonreactive tracers i-/n-butane and i-/n-pentane measured on both aircraft in determining lateral entrainment rates during convection as well as their ratios to ensure that inflow and outflow air masses did not have different origins. Of the five storm cases studied, the various tracermeasurements showed that the inflow and outflow from four storms were coherently related. The combined average of the various approaches from these storms yield remarkably consistent CH2O scavenging efficiency percentages of: 54%± 3% for 29 May; 54% ± 6% for 6 June; 58%± 13% for 11 June; and 41 ± 4% for 22 June. The WRF-Chem SE result of 53% for 29 May was achieved only when assuming complete CH2O degassing from ice. Further analysis indicated that proper selection of corresponding inflow and outflow time segments is more important than the particular mixing model employed.

One of the objectives of the Deep Convective Clouds and Chemistry (DC3) field experiment was to determine the scavenging of soluble trace gases by thunderstorms. We present an analysis of scavenging of hydrogen peroxide (H2O2) and methyl hydrogen peroxide (CH3OOH) from six DC3 cases that occurred in Oklahoma and northeast Colorado. Estimates of H2O2 scavenging efficiencies are comparable to previous studies ranging from 79 to 97% with relative uncertainties of 5–25%. CH3OOH scavenging efficiencies ranged from 12 to 84% with relative uncertainties of 18–558%. The wide range of CH3OOH scavenging efficiencies is surprising, as previous studies suggested that CH3OOH scavenging efficiencies would be

Single-point failures of natural gas infrastructure can hamper methane emission control strategies designed to mitigate climate change. The 23 October 2015 blowout of a well connected to the Aliso Canyon underground storage facility in California resulted in a massive release of natural gas. Analysis of methane and ethane data from dozens of plume transects, collected during 13 research-aircraft flights between 7 November 2015 and 13 February 2016, shows atmospheric leak rates of up to 60 metric tons of methane and 4.5 metric tons of ethane per hour. At its peak, this blowout effectively doubled the methane emission rate of the entire Los Angeles basin and, in total, released 97,100 metric tons of methane to the atmosphere.

Bulk aerosol composition and aerosol size distributions measured aboard the DC-8 aircraft during the Deep Convective Clouds and Chemistry Experiment mission in May/June 2012 were used to investigate the transport of mineral dust through nine storms encountered over Colorado and Oklahoma. Measurements made at low altitudes ( 9 km MSL). Storm mean outflow Ca2+ mass concentrations and total coarse (1 μm < diameter < 5 μm) aerosol volume (Vc) were comparable to mean inflow values as demonstrated by average outflow/inflow ratios greater than 0.5. A positive relationship between Ca2+, Vc, ice water content, and large (diameter > 50 μm) ice particle number concentrations was not evident; thus, the influence of ice shatter on these measurements was assumed small. Mean inflow aerosol number concentrations calculated over a diameter range (0.5 μm < diameter < 5.0 μm) relevant for proxy ice nuclei (NPIN) were ~15–300 times higher than ice particle concentrations for all storms. Ratios of predicted interstitial NPIN (calculated as the difference between inflow NPIN and ice particle concentrations) and inflow NPIN were consistent with those calculated for Ca2+ and Vc and indicated that on average less than 10% of the ingested NPIN were activated as ice nuclei during anvil formation. Deep convection may therefore represent an efficient transport mechanism for dust to the upper troposphere where these particles can function as ice nuclei cirrus forming in situ.

Formation of organic nitrates (RONO2) during oxidation of biogenic volatile organic compounds (BVOCs: isoprene, monoterpenes) is a significant loss pathway for atmospheric nitrogen oxide radicals (NOx), but the chemistry of RONO2 formation and degradation remains uncertain. Here we implement a new BVOC oxidation mechanism (including updated isoprene chemistry, new monoterpene chemistry, and particle uptake of RONO2) in the GEOS-Chem global chemical transport model with ∼25 × 25 km2 resolution over North America. We evaluate the model using aircraft (SEAC4RS) and ground-based (SOAS) observations of NOx, BVOCs, and RONO2 from the Southeast US in summer 2013. The updated simulation successfully reproduces the concentrations of individual gas- and particle-phase RONO2 species measured during the campaigns. Gas-phase isoprene nitrates account for 25-50% of observed RONO2 in surface air, and we find that another 10% is contributed by gas-phase monoterpene nitrates. Observations in the free troposphere show an important contribution from long-lived nitrates derived from anthropogenic VOCs. During both campaigns, at least 10% of observed boundary layer RONO2 were in the particle phase. We find that aerosol uptake followed by hydrolysis to HNO3 accounts for 60% of simulated gas-phase RONO2 loss in the boundary layer. Other losses are 20% by photolysis to recycle NOx and 15% by dry deposition. RONO2 production accounts for 20% of the net regional NOx sink in the Southeast US in summer, limited by the spatial segregation between BVOC and NOx emissions. This segregation implies that RONO2 production will remain a minor sink for NOx in the Southeast US in the future even as NOx emissions continue to decline.

High time resolution measurements of volatile organic compounds (VOCs) were collected using a proton-transfer-reaction quadrupole mass spectrometry (PTR-QMS) instrument at the Platteville Atmospheric Observatory (PAO) in Colorado to investigate how oil and natural gas (O&NG) development impacts air quality within the Wattenburg Gas Field (WGF) in the Denver-Julesburg Basin. The measurements were carried out in July and August 2014 as part of NASA’s “Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality” (DISCOVER-AQ) field campaign. The PTR-QMS data were supported by pressurized whole air canister samples and airborne vertical and horizontal surveys of VOCs. Unexpectedly high benzene mixing ratios were observed at PAO at ground level (mean benzene = 0.53 ppbv, maximum benzene = 29.3 ppbv), primarily at night (mean nighttime benzene = 0.73 ppbv). These high benzene levels were associated with southwesterly winds. The airborne measurements indicate that benzene originated from within the WGF, and typical source signatures detected in the canister samples implicate emissions from O&NG activities rather than urban vehicular emissions as primary benzene source. This conclusion is backed by a regional toluene-to-benzene ratio analysis which associated southerly flow with vehicular emissions from the Denver area. Weak benzene-to-CO correlations confirmed that traffic emissions were not responsible for the observed high benzene levels. Previous measurements at the Boulder Atmospheric Observatory (BAO) and our data obtained at PAO allow us to locate the source of benzene enhancements between the two atmospheric observatories. Fugitive emissions of benzene from O&NG operations in the Platteville area are discussed as the most likely causes of enhanced benzene levels at PAO.

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 (CH4), 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-O3 m-3, which was 47% lower than the value of 567.3 μg-O3 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.

The 1,1,1,2-tetrafluoroethane (HFC-134a), an important alternative to CFC-12 in accordance with the Montreal Protocol on Substances that Deplete the Ozone Layer, is a high global warming potential greenhouse gas. Here we evaluate variations in global and regional HFC-134a emissions and emission trends, from 1995 to 2010, at a relatively high spatial and temporal (3.75° in longitude × 2.5° in latitude and 8 day) resolution, using surface HFC-134a measurements. Our results show a progressive increase of global HFC-134a emissions from 19 ± 2 Gg/yr in 1995 to 167 ± 5 Gg/yr in 2010, with both a slowdown in developed countries and a 20%/yr increase in China since 2005. A seasonal cycle is also seen since 2002, which becomes enhanced over time, with larger values during the boreal summer.

Inhaled corticosteroids (ICS) and β2-agonists are the primary pharmacotherapies of asthma management. However, suboptimal medication compliance is common in asthmatics and is associated with increased morbidity. We hypothesized that exhaled breath measurements of the aerosol used in the inhaled medications might prove useful as surrogate marker for asthma medication compliance. To explore this, 10 healthy controls were recruited and randomly assigned to ICS (Flovent HFA) or short acting bronchodilators (Proventil HFA). Both inhalers contain HFA-134a as aerosol propellant. Exhaled breath sampling and pulmonary function tests were performed prior to the inhaler medication dispersion, immediately after inhalation, then at 2, 4, 6, 8, 24, and 48 hours postadministration. At baseline, mean (SD) levels of HFA-134a in the breath were 252 (156) pptv. Immediately after inhalation, HFA-134a breath levels increased to 300 × 106 pptv and were still well above ambient levels 24 hours postadministration. The calculated ratio of forced expiratory volume in 1 second over forced vital capacity did not change over time following inhaler administration. This study demonstrates, for the first time, that breath HFA-134a levels can be used to assess inhaler medication compliance. It may also be used to evaluate how effectively the medicine is delivered.

Nighttime concentrations of the gas phase nitrate radical (NO3) 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 NO3 ranged from 5 to 20ppt, 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 NO3 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 NO3+aldehyde reactions were not as important as anticipated. On a polluted night impacted by wildfires upwind of the sampling location, NO3 reactions were more important. Model simulations overpredicted NO2 concentrations for both case studies and inorganic chemistry was the biggest influence on NO3 concentrations and on nitric acid formation. The overprediction may be due to additional NO2 loss processes that were not included in the box model, as deposition and N2O5 uptake had no significant effect on NO2 levels.

A model intercomparison activity was inspired by the large suite of observations of atmospheric composition made during the International Polar Year (2008) in the Arctic. Nine global and two regional chemical transport models participated in this intercomparison and performed simulations for 2008 using a common emissions inventory to assess the differences in model chemistry and transport schemes. This paper summarizes the models and compares their simulations of ozone and its precursors and presents an evaluation of the simulations using a variety of surface, balloon, aircraft and satellite observations. Each type of measurement has some limitations in spatial or temporal coverage or in composition, but together they assist in quantifying the limitations of the models in the Arctic and surrounding regions. Despite using the same emissions, large differences are seen among the models. The cloud fields and photolysis rates are shown to vary greatly among the models, indicating one source of the differences in the simulated chemical species. The largest differences among models, and between models and observations, are in NOy partitioning (PAN vs. HNO3) and in oxygenated volatile organic compounds (VOCs) such as acetaldehyde and acetone. Comparisons to surface site measurements of ethane and propane indicate that the emissions of these species are significantly underestimated. Satellite observations of NO2 from the OMI (Ozone Monitoring Instrument) have been used to evaluate the models over source regions, indicating anthropogenic emissions are underestimated in East Asia, but fire emissions are generally overestimated. The emission factors for wildfires in Canada are evaluated using the correlations of VOCs to CO in the model output in comparison to enhancement factors derived from aircraft observations, showing reasonable agreement for methanol and acetaldehyde but underestimate ethanol, propane and acetone, while overestimating ethane emission factors.

©2015. American Geophysical Union. All Rights Reserved. As part of the Deep Convective Cloud and Chemistry (DC3) experiment, the National Science Foundation/National Center for Atmospheric Research (NCAR) Gulfstream-V (GV) and NASA DC-8 research aircraft probed the chemical composition of the inflow and outflow of two convective storms (north storm, NS, south storm, SS) originating in the Colorado region on 22 June 2012, a time when the High Park wildfire was active in the area. A wide range of trace species were measured on board both aircraft including biomass burning (BB) tracers hydrogen cyanide (HCN) and acetonitrile (ACN). Acrolein, a much shorter lived tracer for BB, was also quantified on the GV. The data demonstrated that the NS had ingested fresh smoke from the High Park fire and as a consequence had a higher VOC OH reactivity than the SS. The SS lofted aged fire tracers along with other boundary layer ozone precursors and was more impacted by lightning NOx (LNOx) than the NS. The NCAR master mechanism box model was initialized with measurements made in the outflow of the two storms. The NS and SS were predicted to produce 11 and 14ppbv of O3, respectively, downwind of the storm over 2days. Sensitivity tests revealed that the ozone production potential of the SS was highly dependent on LNOx. Normalized excess mixing ratios, ΔX/ΔCO, for HCN and ACN were determined in both the fire plume and the storm outflow and found to be 7.0±0.5 and 2.3±0.5pptvppbv-1, respectively, and 1.4±0.3pptvppbv-1 for acrolein in the outflow only.

In a joint NRL/Manila Observatory mission, as part of the Seven SouthEast Asian Studies program (7-SEAS), a 2-week, late September 2011 research cruise in the northern Palawan archipelago was undertaken to observe the nature of southwest monsoonal aerosol particles in the South China Sea/East Sea (SCS/ES) and Sulu Sea region. Previous analyses suggested this region as a receptor for biomass burning from Borneo and Sumatra for boundary layer air entering the monsoonal trough. Anthropogenic pollution and biofuel emissions are also ubiquitous, as is heavy shipping traffic. Here, we provide an overview of the regional environment during the cruise, a time series of key aerosol and meteorological parameters, and their interrelationships. Overall, this cruise provides a narrative of the processes that control regional aerosol loadings and their possible feedbacks with clouds and precipitation. While 2011 was a moderate El Ninõ-Southern Oscillation (ENSO) La Ninã year, higher burning activity and lower precipitation was more typical of neutral conditions. The large-scale aerosol environment was modulated by the Madden-Julian Oscillation (MJO) and its associated tropical cyclone (TC) activity in a manner consistent with the conceptual analysis performed by Reid et al. (2012). Advancement of the MJO from phase 3 to 6 with accompanying cyclogenesis during the cruise period strengthened flow patterns in the SCS/ES that modulated aerosol life cycle. TC inflow arms of significant convection sometimes span from Sumatra to Luzon, resulting in very low particle concentrations (minimum condensation nuclei CN < 150 cm-3, non-sea-salt PM2.5 < 1 μg m-3). However, elevated carbon monoxide levels were occasionally observed suggesting passage of polluted air masses whose aerosol particles had been rained out. Conversely, two drier periods occurred with higher aerosol particle concentrations originating from Borneo and Southern Sumatra (CN > 3000 cm-3 and non-sea-salt PM2.5 10-25 μg m-3). These cases corresponded with two different mechanisms of convection suppression: lower free-tropospheric dry-air intrusion from the Indian Ocean, and large-scale TC-induced subsidence. Veering vertical wind shear also resulted in aerosol transport into this region being mainly in the marine boundary layer (MBL), although lower free troposphere transport was possible on the western sides of Sumatra and Borneo. At the hourly time scale, particle concentrations were observed to be modulated by integer factors through convection and associated cold pools. Geostationary satellite observations suggest that convection often takes the form of squall lines, which are bowed up to 500 km across the monsoonal flow and 50 km wide. These squall lines, initiated by cold pools from large thunderstorms and likely sustained by a veering vertical wind shear and aforementioned mid-troposphere dry layers, propagated over 1500 km across the entirety of the SCS/ES, effectively cutting large swaths of MBL aerosol particles out of the region. Our conclusion is that while large-scale flow patterns are very important in modulating convection, and hence in allowing long-range transport of smoke and pollution, more short-lived phenomena can modulate cloud condensation nuclei (CCN) concentrations in the region, resulting in pockets of clean and polluted MBL air. This will no doubt complicate large scale comparisons of aerosol-cloud interaction.

Organosulfates are important secondary organic aerosol (SOA) components and good tracers for aerosol heterogeneous reactions. However, the knowledge of their spatial distribution, formation conditions, and environmental impact is limited. In this study, we report two organosulfates, an isoprene-derived isoprene epoxydiols (IEPOX) (2,3-epoxy-2-methyl-1,4-butanediol) sulfate and a glycolic acid (GA) sulfate, measured using the NOAA Particle Analysis Laser Mass Spectrometer (PALMS) on board the NASA DC8 aircraft over the continental U.S. during the Deep Convective Clouds and Chemistry Experiment (DC3) and the Studies of Emissions and Atmospheric Composition, Clouds, and Climate Coupling by Regional Surveys (SEAC4RS). During these campaigns, IEPOX sulfate was estimated to account for 1.4% of submicron aerosol mass (or 2.2% of organic aerosol mass) on average near the ground in the southeast U.S., with lower concentrations in the western U.S. (0.2-0.4%) and at high altitudes (

We analyzed the measurements of ozone (O3) and its precursors made at rural/suburban sites downwind of four large Chinese cities - Beijing, Shanghai, Guangzhou and Lanzhou, to elucidate their pollution characteristics, regional transport, in situ production, and impacts of heterogeneous processes. The same measurement techniques and observation-based model were used to minimize uncertainties in comparison of the results due to difference in methodologies. All four cities suffered from serious O3 pollution but showed different precursor distributions. The model-calculated in situ O3 production rates were compared with the observed change rates to infer the relative contributions of on-site photochemistry and transport. At the rural site downwind of Beijing, export of the well-processed urban plumes contributed to the extremely high O3 levels (up to an hourly value of 286 ppbv), while the O3 pollution observed at suburban sites of Shanghai, Guangzhou and Lanzhou was dominated by intense in situ production. The O3 production was in a volatile organic compound (VOC)-limited regime in both Shanghai and Guangzhou, and a NOx-limited regime in Lanzhou. The key VOC precursors are aromatics and alkenes in Shanghai, and aromatics in Guangzhou. The potential impacts on O3 production of several heterogeneous processes, namely, hydrolysis of dinitrogen pentoxide (N2O5), uptake of hydro peroxy radical (HO2) on particles and surface reactions of NO2 forming nitrous acid (HONO), were assessed. The analyses indicate the varying and considerable impacts of these processes in different areas of China depending on the atmospheric abundances of aerosol and NOx, and suggest the urgent need to better understand these processes and represent them in photochemical models.

In California, emission control strategies have been implemented to reduce air pollutants. Here we estimate the changes in nitrogen oxides (NOx = NO + NO2) emissions in 2005-2010 using a state-of-the-art four-dimensional variational approach. We separately and jointly assimilate surface NO2 concentrations and tropospheric NO2 columns observed by Ozone Monitoring Instrument (OMI) into the regional-scale Sulfur Transport and dEposition Model (STEM) chemical transport model on a 12 × 12 km2 horizontal resolution grid in May 2010. The assimilation generates grid-scale top-down emission estimates, and the updated chemistry fields are evaluated with independent aircraft measurements during the NOAA California Nexus (CalNex) field experiment. The emission estimates constrained only by NO2 columns, only by surface NO2, and by both indicate statewide reductions of 26%, 29%, and 30% from ~0.3 Tg N/yr in the base year of 2005, respectively. The spatial distributions of the emission changes differ in these cases, which can be attributed to many factors including the differences in the observation sampling strategies and their uncertainties, as well as those in the sensitivities of column and surface NO2 with respect to NOx emissions. The updates in California's NOx emissions reduced the mean error in modeled surface ozone in the Western U.S., even though the uncertainties in some urban areas increased due to their NOx-saturated chemical regime. The statewide reductions in NOx emissions indicated from our observationally constrained emission estimates are also reflected in several independently developed inventories: ~30% in the California Air Resources Board bottom-up inventory, ~4% in the 2008 National Emission Inventory, and ~20% in the annual mean top-down estimates by Lamsal et al. using the global Goddard Earth Observing System (GEOS)-Chem model and OMI NO2 columns. Despite the grid-scale differences among all top-down and bottom-up inventories, they all indicate stronger emission reductions in the urban regions. This study shows the potential of using space-/ground-based monitoring data and advanced data assimilation approach to timely and independently update NOx emission estimates on a monthly scale and at a fine grid resolution. The well-evaluated results here suggest that these approaches can be applied more broadly.

The non-methane organic compound (NMOC) emission rate is used to assess compliance with landfill gas emission regulations by the United States Environmental Protection Agency (USEPA). A recent USEPA Report (EPA/600/R-11/033) employed a ratio method to estimate speciated NMOC emissions (i.e., individual NMOC emissions): speciated NMOC emissions=measured methane (CH4) emission multiplied by the ratio of individual NMOCs concentration relative to CH4 concentration (CNMOCs/CCH4) in the landfill header gas. The objectives of this study were to (1) evaluate the efficacy of the ratio method in estimating speciated NMOC flux from landfills; (2) determine for what types of landfills the ratio method may be in error and why, using recent field data to quantify the spatial variation of (CNMOCs/CCH4) in landfills; and (3) formulate alternative models for estimating NMOC emissions from landfills for cases in which the ratio method results in biased estimates. This study focuses on emissions through landfill covers measured with flux chambers and evaluates the utility of the ratio method for estimating NMOC emission through this pathway. Evaluation of the ratio method was performed using CH4 and speciated NMOC concentration and flux data from 2012/2013 field sampling of four landfills, an unpublished landfill study, and literature data from three landfills. The ratio method worked well for landfills with thin covers (

Aircraft measurements, including non-methane hydrocarbons (NMHCs), long-lived halocarbons, carbon monoxide (CO), and ozone (O3) collected on board the NASA DC-8 during the Deep Convection, Clouds, and Chemistry (DC3) field campaign (May – June 2012), were used to investigate interactions and mixing between stratospheric intrusions and polluted air masses. Stratospherically influenced air masses were detected using a suite of long-lived halocarbons, including chlorofluorocarbons (CFCs) and HCFCs, as a tracer for stratospheric air. A large number of stratospherically influenced samples were found to have reduced levels of O3 and elevated levels of CO (both relative to background stratospheric air), indicative of mixing with anthropogenically influenced air. Using n-butane and propane as further tracers of anthropogenically influenced air, we show that this type of mixing was present both at low altitudes and in the upper troposphere (UT). At low altitudes, this mixing resulted in O3 enhancements consistent with those reported at surface sites during deep stratospheric intrusions, while in the UT, two case studies were performed to identify the process by which this mixing occurs. In the first case study, stratospheric air was found to be mixed with aged outflow from a convective storm, while in the second case study, stratospheric air was found to have mixed with outflow from an active storm occurring in the vicinity of a stratospheric intrusion. From these analyses, we conclude that deep convective events may facilitate the mixing between stratospheric air and polluted boundary layer air in the UT. Throughout the entire DC3 study region, this mixing was found to be prevalent: 72% of all samples that involve stratosphere-troposphere mixing show influence of polluted air. Applying a simple chemical kinetics analysis to these data, we show that during DC3, the instantaneous production of hydroxyl radical (OH) in these mixed stratospheric-polluted air masses was 11 ± 8 times higher than that of stratospheric air, and 4.2 ± 1.8 times higher than that of background upper tropospheric air.

Methyl chloroform (MCF) is a man-made chlorinated solvent contributing to the destruction of stratospheric ozone and is controlled under the "Montreal Protocol on Substances that Deplete the Ozone Layer" and its amendments, which called for its phase-out in 1996 in developed countries and 2015 in developing countries. Long-term, high-frequency observations of MCF carried out at three European sites show a constant decline in the background mixing ratios of MCF. However, we observe persistent non-negligible mixing ratio enhancements of MCF in pollution episodes, suggesting unexpectedly high ongoing emissions in Europe. In order to identify the source regions and to give an estimate of the magnitude of such emissions, we have used a Bayesian inversion method and a point source analysis, based on high-frequency long-term observations at the three European sites. The inversion identified southeastern France (SEF) as a region with enhanced MCF emissions. This estimate was confirmed by the point source analysis. We performed this analysis using an 11-year data set, from January 2002 to December 2012. Overall, emissions estimated for the European study domain decreased nearly exponentially from 1.1 Gg yrg'1 in 2002 to 0.32 Gg yrg'1 in 2012, of which the estimated emissions from the SEF region accounted for 0.49 Gg yrg'1 in 2002 and 0.20 Gg yrg'1 in 2012. The European estimates are a significant fraction of the total semi-hemisphere (30-90° N) emissions, contributing a minimum of 9.8% in 2004 and a maximum of 33.7% in 2011, of which on average 50% are from the SEF region. On the global scale, the SEF region is thus responsible for a minimum of 2.6% (in 2003) and a maximum of 10.3% (in 2009) of the global MCF emissions.

Air samples were collected concurrently at 05:00 A.M. and 10:00 A.M. local Beijing time (geomagnetic time + 8) at 84 sites during two grid-study campaigns on 29 September 2008 and 1 March 2009 in the Pearl River Delta region, in order to offer snapshots of ambient CFCs and hydrochlorofluorocarbons (HCFCs) in different seasons and to indicate the presence of local emission sources. Compared to the subtropical northern hemisphere background levels, mean mixing ratios of CFC-11, CFC-12, CFC-113, CFC-114, and HCFC-22 were enhanced by 7%–11%, 8%–11%, 5%–6%, 8%–9%, and 71%–135%, respectively. When data from this tudy were pooled together with previous observations in the region, ambient CFC-11, CFC-12, and CFC-113 unambiguously showed declines in mixing ratios, while HCFC-22 showed an increase. Spatial variations revealed potential emission hot spots in the region, and levels of CFCs and HCFC-22 were higher in September than in March due to many more refrigeration and air-conditioning activities during summer. Source apportioning by positive matrix factorization revealed that new input of CFCs and HCFC-22 into the ambient air was largely attributed to emission from air-conditioning and refrigerating activities instead of industry activities. Average emissions in the region estimated by the CO-tracer method were 0.8 ± 0.2, 1.4 ± 0.6, 0.2 ± 0.1, 0.1 ± 0.02, and 4.4 ± 1.0 Gg/yr for CFC-11, CFC-12, CFC-113, CFC-114, and HCFC-22, respectively, and they accounted for 5.5%–25.5% of the total estimated CFC and HCFC-22 emissions in China.