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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]

Understanding and quantifying the global methane (CH4) budget is important for assessing realistic pathways to mitigate climate change. Emissions and atmospheric concentrations of CH4 continue to increase, maintaining CH4 as the second most important human-influenced greenhouse gas in terms of climate forcing after carbon dioxide (CO2). The relative importance of CH4 compared to CO2 for temperature change is related to its shorter atmospheric lifetime, stronger radiative effect, and acceleration in atmospheric growth rate over the past decade, the causes of which are still debated. Two major challenges in reducing uncertainties in the factors explaining the well-observed atmospheric growth rate arise from diverse, geographically overlapping CH4 sources and from the uncertain magnitude and temporal change in the destruction of CH4 by short-lived and highly variable hydroxyl radicals (OH). To address these challenges, we have established a consortium of multi-disciplinary scientists under the umbrella of the Global Carbon Project to improve, synthesise and update the global CH4 budget regularly and to stimulate new research on the methane cycle. Following Saunois et al. (2016, 2020), we present here the third version of the living review paper dedicated to the decadal CH4 budget, integrating results of top-down CH4 emission estimates (based on in-situ and greenhouse gas observing satellite (GOSAT) atmospheric observations and an ensemble of atmospheric inverse-model results) and bottom-up estimates (based on process-based models for estimating land-surface emissions and atmospheric chemistry, inventories of anthropogenic emissions, and data-driven extrapolations). We present a budget for the most recent 2010–2019 calendar decade (the latest period for which full datasets are available), for the previous decade of 2000–2009 and for the year 2020. The revision of the bottom-up budget in this edition benefits from important progress in estimating inland freshwater emissions, with better accounting of emissions from lakes and ponds, reservoirs, and streams and rivers. This budget also reduces double accounting across freshwater and wetland emissions and, for the first time, includes an estimate of the potential double accounting that still exists (average of 23 Tg CH4 yr-1). Bottom-up approaches show that the combined wetland and inland freshwater emissions average 248 [159–369] Tg CH4 yr-1 for the 2010–2019 decade. Natural fluxes are perturbed by human activities through climate, eutrophication, and land use. In this budget, we also estimate, for the first time, this anthropogenic component contributing to wetland and inland freshwater emissions. Newly available gridded products also allowed us to derive an almost complete latitudinal and regional budget based on bottom-up approaches. For the 2010–2019 decade, global CH4 emissions are estimated by atmospheric inversions (top-down) to be 575 Tg CH4 yr-1 (range 553–586, corresponding to the minimum and maximum estimates of the model ensemble). Of this amount, 369 Tg CH4 yr-1 or ~65 % are attributed to direct anthropogenic sources in the fossil, agriculture and waste and anthropogenic biomass burning (range 350–391 Tg CH4 yr-1or 63–68 %). For the 2000–2009 period, the atmospheric inversions give a slightly lower total emission than for 2010–2019, by 32 Tg CH4 yr-1 (range 9–40). Since 2012, global direct anthropogenic CH4 emission trends have been tracking scenarios that assume no or minimal climate mitigation policies proposed by the Intergovernmental Panel on Climate Change (shared socio-economic pathways SSP5 and SSP3). Bottom-up methods suggest 16 % (94 Tg CH4 yr-1) larger global emissions (669 Tg CH4 yr-1, range 512–849) than top-down inversion methods for the 2010–2019 period. The discrepancy between the bottom-up and the top-down budgets has been greatly reduced compared to the previous differences (167 and 156 Tg CH4 yr-1 in Saunois et al. (2016, 2020), respectively), and for the first time uncertainty in bottom-up and top-down budgets overlap. The latitudinal distribution from atmospheric inversion-based emissions indicates a predominance of tropical and southern hemisphere emissions (~65 % of the global budget, <30° N) compared to mid (30° N–60° N, ~30 % of emissions) and high-northern latitudes (60° N–90° N, ~4 % of global emissions). This latitudinal distribution is similar in the bottom-up budget though the bottom-up budget estimates slightly larger contributions for the mid and high-northern latitudes, and slightly smaller contributions from the tropics and southern hemisphere than the inversions. Although differences have been reduced between inversions and bottom-up, the most important source of uncertainty in the global CH4 budget is still attributable to natural emissions, especially those from wetlands and inland freshwaters. We identify five major priorities for improving the CH4 budget: i) producing a global, high-resolution map of water-saturated soils and inundated areas emitting CH4 based on a robust classification of different types of emitting ecosystems; ii) further development of process-based models for inland-water emissions; iii) intensification of CH4 observations at local (e.g., FLUXNET-CH4 measurements, urban-scale monitoring, satellite imagery with pointing capabilities) to regional scales (surface networks and global remote sensing measurements from satellites) to constrain both bottom-up models and atmospheric inversions; iv) improvements of transport models and the representation of photochemical sinks in top-down inversions, and v) integration of 3D variational inversion systems using isotopic and/or co-emitted species such as ethane as well as information in the bottom-up inventories on anthropogenic super-emitters detected by remote sensing (mainly oil and gas sector but also coal, agriculture and landfills) to improve source partitioning. The data presented here can be downloaded from https://doi.org/10.18160/GKQ9-2RHT (Martinez et al., 2024). [ABSTRACT FROM AUTHOR]

Reports on the effect of liquefied petroleum gas (LPG) leakage to the atmosphere of Mexico City, Mexico. Dominant nonmethane hydrocarbons (NMHC) in the city's atmosphere; High concentration of NMHCs; Collection of samples; Composition of LPG used in the city.

Presents research which estimated the atmospheric residence time for methyl bromide (CH3Br). Use of Junge's 1963 general proposal; Methyl bromide in the atmosphere; Its sources; Consistency of findings with previous research.

NASA's Student Airborne Research Program (SARP) has completed 13 years of airborne student research since its inception in 2009. The 8-week summer internship program provides students, typically rising undergraduate seniors, with an opportunity to get hands-on experience in making Earth system measurements using NASA's airborne science platforms. Students also make complementary surface-based measurements, analyze airborne and surface data in the context of related data (e.g. coincident satellite measurements or prior-year SARP data), and present results to peers, program leadership, agency management, and the community. The program splits its time between the NASA Armstrong flight facility in Palmdale, California, and the University of California, Irvine. It is implemented with participation of faculty advisors (who provide many of the instruments used) and graduate student mentors, under the overall leadership of the NASA Earth Science Division. Disciplinary foci include atmospheric gases and aerosols, ocean biology, and terrestrial ecology using both in situ and remote sensing instruments. Students are also taken on site visits to nearby laboratories and facilities and attend lectures from visiting faculty and NASA agency personnel. The program engages approximately 30 students per year, with overall approximate gender balance. The program has a high rate of STEM retention, and its alumni are actively engaged in graduate and postgraduate programs in Earth system science and other disciplines. A summary of scientific and programmatic outcomes and a description of how the program has evolved will be presented. [ABSTRACT FROM AUTHOR]

In this study, the WRF-Chem v4.4 model was utilized to evaluate the sensitivity of O 3 simulations with three bottom-up emission inventories (EDGAR-HTAP v2 and v3 and KORUS v5) using surface and aircraft data in East Asia during the Korea-United States Air Quality (KORUS-AQ) campaign period in 2016. All emission inventories were found to reproduce the diurnal variations of O 3 and its main precursor NO 2 as compared to the surface monitor data. However, the spatial distributions of the daily maximum 8 h average (MDA8) O 3 in the model do not completely align with the observations. The model MDA8 O 3 had a negative (positive) bias north (south) of 30° N over China. All simulations underestimated the observed CO by 50 %–60 % over China and South Korea. In the Seoul Metropolitan Area (SMA), EDGAR-HTAP v2 and v3 and KORUS v5 simulated the vertical shapes and diurnal patterns of O 3 and other precursors effectively, but the model underestimated the observed O 3 , CO, and HCHO concentrations. Notably, the model aromatic volatile organic compounds (VOCs) were significantly underestimated with the three bottom-up emission inventories, although the KORUS v5 shows improvements. The model isoprene estimations had a positive bias relative to the observations, suggesting that the Model of Emissions of Gases and Aerosols from Nature (MEGAN) version 2.04 overestimated isoprene emissions. Additional model simulations were conducted by doubling CO and VOC emissions over China and South Korea to investigate the causes of the model O 3 biases and the effects of the long-range transport on the O 3 over South Korea. The doubled CO and VOC emission simulations improved the model O 3 simulations for the local-emission-dominant case but led to the model O 3 overestimations for the transport-dominant case, which emphasizes the need for accurate representations of the local VOC emissions over South Korea. [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]

Proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) is a technique commonly used to measure ambient volatile organic compounds (VOCs) in urban, rural, and remote environments. PTR-ToF-MS is known to produce artifacts from ion fragmentation, which complicates the interpretation and quantification of key atmospheric VOCs. This study evaluates the extent to which fragmentation and other ionization processes impact urban measurements of the PTR-ToF-MS ions typically assigned to isoprene (m/z 69, C 5 H 8 H +), acetaldehyde (m/z 45, CH 3 CHO +), and benzene (m/z 79, C 6 H 6 H +). Interferences from fragmentation are identified using gas chromatography (GC) pre-separation, and the impact of these interferences is quantified using ground-based and airborne measurements in a number of US cities, including Las Vegas, Los Angeles, New York City, and Detroit. In urban regions with low biogenic isoprene emissions (e.g., Las Vegas), fragmentation from higher-carbon aldehydes and cycloalkanes emitted from anthropogenic sources may contribute to m/z 69 by as much as 50 % during the day, while the majority of the signal at m/z 69 is attributed to fragmentation during the night. Interferences are a higher fraction of m/z 69 during airborne studies, which likely results from differences in the reactivity between isoprene and the interfering species along with the subsequent changes to the VOC mixture at higher altitudes. For other PTR masses, including m/z 45 and m/z 79, interferences are observed due to fragmentation and O 2+ ionization of VOCs typically used in solvents, which are becoming a more important source of anthropogenic VOCs in urban areas. We present methods to correct these interferences, which provide better agreement with GC measurements of isomer-specific molecules. These observations show the utility of deploying GC pre-separation for the interpretation PTR-ToF-MS spectra. [ABSTRACT FROM AUTHOR]

In this study, the WRF-Chem v4.4 model was utilized to evaluate three bottom-up emission inventories (EDGAR-HTAP v2, v3, and KORUS v5) using surface and aircraft data in East Asia during the Korea-United States Air Quality (KORUS-AQ) campaign period in 2016. All emission inventories were found to reproduce the diurnal variations of O3 and NO2 as compared to the surface monitor data. However, the spatial distributions of the daily maximum 8-hour average (MDA8) O3 in the model do not completely align with the observations. The model MDA8 O3 had a negative (positive) bias north (south) of 30°N over China. All simulations underestimated the observed CO by 50-60% over China and South Korea. In the Seoul Metropolitan Area (SMA), EDGAR-HTAP v2, v3, and KORUS v5 simulated the vertical shapes and diurnal patterns of O3 and other precursors effectively, but the model underestimated the observed O3, CO and HCHO concentrations. Notably, the model aromatic VOCs were significantly underestimated with the three bottom-up emission inventories, although the KORUS v5 shows improvements. The model isoprene estimations had a positive bias relative to the observations, suggesting that the Model of Emissions of Gases and Aerosols from Nature (MEGAN) version 2.04 overestimated isoprene emissions. Additional model simulations were conducted by doubling CO and VOC emissions over China and South Korea to investigate the causes of the model O3 biases and the effects of the long-range transport on the O3 over South Korea. The doubled CO and VOC emission simulations improved the model O3 simulations for the local emission dominant case, but led to the model O3 overestimations for the transport dominant case, which emphasizes the need for accurate representations of the local VOC emissions over South Korea. [ABSTRACT FROM AUTHOR]

Proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) is a technique commonly used to measure ambient volatile organic compounds (VOCs) in urban, rural, and remote environments. PTR-ToF-MS is known to produce artifacts from ion fragmentation, which complicates the interpretation and quantification of key atmospheric VOCs. This study evaluates the extent to which fragmentation and other ionization processes impacts urban measurements of the PTR-ToF-MS ions typically assigned to isoprene (m/z 69, C5H8H+), acetaldehyde (m/z 45, CH3CHO+), and benzene (m/z 79, C6H6H+). Interferences from fragmentation are identified using gas-chromatography (GC) pre-separation and the impact of these interferences are quantified using ground-based and airborne measurements in a number of US cities, including Las Vegas, Los Angeles, New York City, and Detroit. In urban regions with low biogenic isoprene emissions (e.g., Las Vegas), fragmentation from higher carbon aldehydes and cycloalkanes emitted from anthropogenic sources may contribute to m/z 69 by as much as 50% during the day, while the majority of the signal at m/z 69 is attributed to fragmentation during the night. Interferences are a higher fraction of m/z 69 during airborne studies, which likely results from differences in the reactivity between isoprene and the interfering species along with the subsequent changes to the VOC mixture at higher altitudes. For other PTR masses, including m/z 45 and m/z 79, interferences are observed due to the fragmentation and secondary ionization of VOCs typically used in solvents, which are becoming a more important source of anthropogenic VOCs in urban areas. We present methods to correct these interferences, which provide better agreement with GC measurements of isomer specific molecules. These observations show the utility of deploying GC pre-separation for the interpretation PTR-ToF-MS spectra. [ABSTRACT FROM AUTHOR]

Model intercomparison studies often report a large spread in simulation results, but quantifying the causes of these differences is hindered by the fact that several processes contribute to the model spread simultaneously. Here we use the Multi‐Scale Infrastructure for Chemistry and Aerosols (MUSICA) version 0 to investigate the model resolution dependencies of simulated chemical species, with a focus on the differences between global uniform grid and regional refinement grid simulations with the same modeling framework. We construct two global (ne30 [∼112 km] and ne60 [∼56 km]) and two regional refinement grids over Korea (ne30x8 [∼14 km] and ne30x16 [∼7 km]). The grid resolution can change chemical concentrations by an order of magnitude in the boundary layer, and the importance increases as the species' reactivity increases (e.g., up to 50% and 1,000% changes for ethane and xylenes, respectively). The diurnal cycle of oxidants (OH, O3, and NO3) also varies with the grid resolution, which leads to different oxidation pathways of volatile organic compounds (e.g., the fraction of monoterpenes reacting with NO3 in Seoul around midnight is 90% for ne30, but 65% for ne30x16). The models with high‐resolution grids usually do a better job at reproducing aircraft observations during the KORUS‐AQ campaign, but not always, implying compensating errors in the coarse grid simulations. For example, ozone is better reproduced by the coarse grid due to the artificial mixing of NOx. When developing new chemical mechanisms and evaluating models over urban areas, the uncertainties associated with model resolution should be considered. Plain Language Summary: A new model framework, the Multi‐Scale Infrastructure for Chemistry and Aerosols version 0 (MUSICAv0), has been developed at NCAR to enable a computationally feasible global modeling framework while still resolving chemistry at urban scales. Using the MUSICAv0 framework with different horizontal grid resolutions (∼112, ∼56, ∼14, and ∼7 km), this work examines how much horizontal grid resolution can affect simulated chemical concentrations in 3D chemistry models. Model concentrations can vary up to 10 times between ∼112 and ∼7 km grids over urban areas at the surface. On the other hand, a region‐specific emission inventory with detailed local information is essential for some chemical species, although it is generally less important than the grid resolution for many chemical species. The model with a high‐resolution grid better reproduces observations in general, but in some cases compensating errors result in better comparisons for the coarse grid. This work suggests that the effects of grid resolution should not be ignored when evaluating new chemical mechanisms and chemistry models in future studies, and high grid resolution in 3D models is needed to simulate air pollutants over urban and downwind regions. Key Points: The dependence of simulated chemical species on model resolution is quantified in a single modeling frameworkModel evaluations can be substantially affected by grid resolution, especially for urban surface and aircraft measurements at low altitudesGrid resolution strongly impacts the oxidation of volatile organic compounds through differences in diurnal variation of oxidants [ABSTRACT FROM AUTHOR]

The Satellite Coastal and Oceanic Atmospheric Pollution Experiment (SCOAPE) cruise in the Gulf of Mexico was conducted in May 2019 by NASA and the Bureau of Ocean Energy Management to determine the feasibility of using satellite data to measure air quality in a region of concentrated oil and natural gas (ONG) operations. SCOAPE addressed both technological and scientific issues related to measuring NO2 columns over the outer continental shelf. Featured were nitrogen dioxide (NO2) instruments (Pandora, Teledyne API analyzer) at Cocodrie, LA (29.26°, −90.66°), and on the Research Vessel Point Sur operating off the Louisiana coast with measurements of ozone, carbon monoxide, and volatile organic compounds (VOCs). The findings: (a) all NO2 observations revealed two atmospheric regimes over the Gulf, the first influenced by tropical air in 10–14 May, the second influenced by flow from urban areas on 15–17 May; (b) comparisons of OMI v4 and TROPOMI v1.3 TC (total column) NO2 data with shipboard Pandora NO2 column observations averaged 13% agreement with the largest difference during 15–17 May (∼20%). At Cocodrie, the satellite–Pandora agreement was ∼5%. (c) Three new‐model Pandora instruments displayed a TC NO2 precision of 0.01 Dobson Units (∼5%); (d) regions of smaller, older natural gas operations showed high methane readings from leakage; elevated VOCs were also detected. Neither satellite nor spectrometer captured the magnitude of ambient NO2 variability near ONG platforms. Given an absence of regular air quality monitoring over the Gulf of Mexico, SCOAPE data constitute a baseline against which future observations can be compared. Plain Language Summary: The Satellite Coastal and Oceanic Atmospheric Pollution Experiment (SCOAPE) cruise in the Gulf of Mexico (GOM) conducted on the Research Vessel Point Sur in May 2019 investigated the feasibility of using satellite data to measure air quality in a region of concentrated oil and natural gas (ONG) operations. SCOAPE addressed both technological and scientific issues related to measuring NO2 columns in a prototypical coastal environment. The results are as follows. First, measurements from SCOAPE demonstrated that satellite NO2 data can be used to monitor ONG activity over the GOM. Second, during SCOAPE both OMI and TROPOMI TC (total column) NO2 amounts were higher over land and sometimes the near‐shore ONG‐rich Gulf, than over deepwater regions farther offshore. This was confirmed by Pandora spectrometer "ground truth" TC NO2 data measured throughout SCOAPE on shore and on ship. Third, SCOAPE established the reliability and precision of a new generation of Pandora spectrometers. Fourth, comparisons of satellite and Pandora TC NO2 data in SCOAPE confirm previous land–water interface studies that point to limitations in satellite NO2 in coastal regions. Finally, neither satellite nor spectrometer captures the magnitude of ambient ("nose‐level") NO2 variability in a region dotted with hundreds of ONG platforms. Key Points: Shipboard Pandora NO2 columns and surface O3, NO2, CO, and volatile organic compounds (VOCs) over the Gulf of Mexico (GOM), May 2019, displayed two air quality (AQ) regimesGOM AQ was dominated by continental NO2 sources and near‐shore VOC; deepwater oil platforms were in a clean marine regimePandora and satellite total column NO2 over GOM agreed overall within 5% in clean, clear‐sky conditions along the coast and 13% over water [ABSTRACT FROM AUTHOR]

An obituary for atmospheric chemist F. Sherwood Rowland is presented.

Organosulfur compounds (OSCs) are naturally emitted via various processes involving phytoplankton and algae in marine regions, from animal metabolism, and from biomass decomposition inland. These compounds are malodorant and reactive. Their oxidation to methanesulfonic and sulfuric acids leads to the formation and growth of atmospheric particles, which are known to influence clouds and climate, atmospheric chemical processes. In addition, particles in air have been linked to negative impacts on visibility and human health. Accurate measurements of the OSC precursors are thus essential to reduce uncertainties in their sources and contributions to particle formation in air. Two different approaches, proton-transfer reaction time-offlight mass spectrometry (PTR-ToF-MS) and canister sampling coupled to gas chromatography with flame ionization detector (GC-FID), are compared for both laboratory standards (dimethyl sulfide, DMS; dimethyl disulfide, DMDS; dimethyl trisulfide, DMTS; and methanethiol, MTO) and for a complex sample. Results show that both techniques produce accurate quantification of DMS. While PTR-ToF-MS provides real-time measurements of all four OSCs individually, significant fragmentation of DMDS and DMTS occurs, which can complicate their identification in complex mixtures. Canister sampling coupled with GC-FID provides excellent sensitivity for DMS, DMDS, and DMTS. However, MTO was observed to react on metal surfaces to produce DMDS and, in the presence of hydrogen sulfide, even DMTS. Avoiding metal in sampling systems seems to be necessary for measuring all but dimethyl sulfide in air. [ABSTRACT FROM AUTHOR]

Organosulfur compounds (OSCs) are naturally emitted via various processes involving phytoplankton and algae in marine regions, from animal metabolism, and from biomass decomposition inland. These compounds are malodorant and reactive. Their oxidation to methanesulfonic and sulfuric acids leads to the formation and growth of atmospheric particles, which are known to influence clouds and climate, atmospheric chemical processes. In addition, particles in air have been linked to negative impacts on visibility and human health. Accurate measurements of the OSC precursors are thus essential to reduce uncertainties in their sources and contributions to particle formation in air. Two different approaches, proton-transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) and canister sampling coupled to gas chromatography with flame ionization detector (GC-FID), are compared for both laboratory standards (dimethyl sulfide, DMS; dimethyl disulfide, DMDS; dimethyl trisulfide, DMTS; and methanethiol, MTO) and for a complex sample. Results show that both techniques produce accurate quantification of DMS. While PTR-ToF-MS provides real-time measurements of all four OSCs individually, significant fragmentation of DMDS and DMTS occurs, which can complicate their identification in complex mixtures. Canister sampling coupled with GC-FID provides excellent sensitivity for DMS, DMDS, and DMTS. However, MTO was observed to react on metal surfaces to produce DMDS and, in the presence of hydrogen sulfide, even DMTS. Avoiding metal in sampling systems seems to be necessary for measuring all but dimethyl sulfide in air. [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]

A seven-year record of surface ozone measurements from Denali National Park, Alaska shows a persistent spring maximum. These data, combined with measurements of NOx, hydrocarbons, O3, and PAN from a continental site in Alaska during the spring of 1995 are used as the basis for a sensitivity study to explore tropospheric photochemistry in this region. Because of the relatively high concentrations of NOx (mean of 116, median of 91 pptv), the net tendency was for photochemical ozone production. The range of net O3 production for average conditions measured at this site during spring is between 0.96-3.9 ppbv/day depending on the assumptions used; in any case, this production must contribute to the observed springtime maximum in O3. Model calculations showed that of the anthropogenic ozone precursors, only NOx had a strong effect on the rate of ozone production; the measured concentrations of anthropogenic hydrocarbons did not significantly affect the ozone budget. Naturally produced biogenic hydrocarbons, such as isoprene, may also have a significant effect on ozone production, even at concentrations of a few 10's of pptv. An observed temperature-isoprene relationship from a boreal site in Canada indicates that isoprene may be present during the Alaskan spring. Measurements of isoprene taken during the spring of 1996 suggest that reactive biogenic hydrocarbon emissions begin before the emergence of leaves on deciduous trees and that the concentrations were sufficient to accelerate ozone production. [ABSTRACT FROM AUTHOR]

Local surface travel needs in the People's Republic of China (mainland China) have traditionally been met largely by nonpolluting bicycles. A major automobile manufacturing/importing effort has begun in thecountry over the last decade, and planning documents indicate that the Chinese may strive to acquire more than 100 million vehicles earlyin the next century. By analogy with large automotive fleets alreadyexisting in the western world, both regional and global scale pollution effects are to be expected from the increase. The present work adopts the latest projections of Chinese automobile manufacture and performs some quantitative assessments of the extent of pollution generation. Focus for the investigation is placed upon the oxidant ozone. Emissions of the precursor species nitrogen oxides and volatile organics are constructed based on data for the current automotive sector inthe eastern portion of the United States. Ozone production is first estimated from measured values for continental/oceanic scale yields relative to precursor oxidation. The estimates are then corroborated through idealized two dimensional modeling of the photochemistry taking place in springtime air flow off the Asian land mass and toward thePacific Ocean. The projected fleet sizes could increase coastal and remote oceanic ozone concentrations by tens of parts per billion (ppb) in the lower troposphere. Influences on the tropospheric aerosol system and on the major greenhouse gas carbon dioxide are treated peripherally. Nitrogen oxides created during the vehicular internal combustion process will contribute to nitrate pollution levels measured in the open Pacific. The potential for soot and fugitive dust increases should be considered as the automotive infrastructure develops. Sincethe emerging Chinese automotive transportation system will representa substantial addition to the global fleet and all the carbon in gasoline is eventually oxidized completely, a significant rise in globalcarbon [ABSTRACT FROM AUTHOR]

Urban air pollution is rapidly becoming a major environmental problem of public concern in several developing countries of the world. Jeddah, the second-largest city in Saudi Arabia, is subject to high air pollution that has severe implications for the health of the exposed population. Fine particulate matter (PM2.5) samples were collected for 24 h daily, during a 1-year campaign from 2013 to 2014. This study presents a detailed investigation of PM2.5 mass, chemical composition, and sources covering all four seasons of the year. Samples were analyzed for black carbon (BC), trace elements (TEs), and water-soluble ionic species (IS). The chemical compositions were statistically examined, and the temporal and seasonal patterns were characterized using descriptive analysis, correlation matrices, and elemental enrichment factor (EF). Source apportionment and source locations were performed on PM2.5 samples using the positive matrix factorization (PMF) model, elemental enrichment factor, and air-mass back trajectory analysis. The 24-h mean PM2.5 and BC concentrations ranged from 33.9 ± 9.1–58.8 ± 25 µg/m3 and 1.8 ± 0.4–2.4 ± 0.6 µg/m3, respectively. Atmospheric PM2.5 concentrations were well above the 24-h WHO guideline of 15 µg/m3, with overall results showing significant temporal and seasonal variability. EF defined two broad categories of TEs: anthropogenic (Ni, V, Cu, Zn, Cl, Pb, S, Lu, and Br), and earth-crust derived (Al, Si, Mg, K, Ca, Ti, Cr, Mn, Fe, and Sr). The five identified factors resulting from PMF were (1) fossil-fuels/oil combustion (45.3%), (2) vehicular emissions (19.1%), (3) soil/dust resuspension (15.6%), (4) industrial mixed dust (13.5%), and (5) sea-spray (6.5%). This study highlights the importance of focusing control strategies, not only on reducing PM concentration but also on the reduction of components of the PM as well, to effectively protect human health and the environment. [ABSTRACT FROM AUTHOR]

Organic aerosols (OA) represent a significant fraction of total submicron particulate matter (PM1) concentrations globally, including densely populated megacities such as Seoul. However, scientific understanding of the atmospheric formation and removal processes of OA, especially for secondary organic aerosols (SOA), is still highly uncertain. In this study, we examine the characteristics of SOA formation in Seoul during spring‐summer 2016 and fall‐winter 2017/2018, using airborne and ground observations along with a 3‐D global chemical transport model, GEOS‐Chem. We use four different SOA schemes in the model, including simplified and complex volatility‐based frameworks, and evaluate them by comparing the simulations with the observations to examine how our scientific understanding embedded in each SOA scheme affects the observed biases. Our analysis of the model performance of each scheme also provides the most suitable approach in simulating SOA in a typical urban environment. Comparisons of the simulated versus observed OA concentrations show that model biases range from −72% to +118%, with considerable variability among different schemes and seasons. We find that the inclusion of semi/intermediate volatile precursors, in addition to the traditional precursors, and chemical aging (functionalization) are important factors to simulate surface SOA concentrations in Seoul. However, a comparison of observed and simulated SOA/∆CO enhancement ratios suggests that most schemes underpredict SOA aging in upper levels in the boundary layer. We also find that the simplified SOA scheme can reproduce observed OA but often shows overestimation in surface air, indicating that uncertainties exist in bottom‐up emissions and precursor parameterization in Seoul. Plain Language Summary: We compare four different modeling approaches for simulating secondary organic aerosol (SOA) formation, accounting for a significant fraction of total fine particulate matter concentrations in Seoul, Korea. Using GEOS‐Chem, a chemical transport model, we find that current SOA schemes show large variabilities. Including an additional precursor species and further oxidation (i.e., chemical aging) of simulated SOA improves model performance. We also find that a simplified scheme with less computational cost can reproduce observed values but generally shows an overestimation in Seoul, indicating uncertainties in parameterization. Key Points: Model evaluation of simulated organic aerosols (OA) using different secondary organic aerosols (SOA) schemes in Seoul shows large variabilityThe inclusion of semi/intermediate volatile precursors and chemical aging are important factors in reducing model biasesThe simplified SOA scheme can reproduce observed OA, but uncertainties exist in precursor parameterization in Seoul [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]

Since 2012, studies in mice, rats, and humans have suggested that abnormalities in purinergic signaling may be a final common pathway for many genetic and environmental causes of autism spectrum disorder (ASD). The current study in mice was conducted to characterize the bioenergetic, metabolomic, breathomic, and behavioral features of acute hyperpurinergia triggered by systemic injection of the purinergic agonist and danger signal, extracellular ATP (eATP). Responses were studied in C57BL/6J mice in the maternal immune activation (MIA) model and controls. Basal metabolic rates and locomotor activity were measured in CLAMS cages. Plasma metabolomics measured 401 metabolites. Breathomics measured 98 volatile organic compounds. Intraperitoneal eATP dropped basal metabolic rate measured by whole body oxygen consumption by 74% ± 6% (mean ± SEM) and rectal temperature by 6.2˚ ± 0.3˚C in 30 minutes. Over 200 metabolites from 37 different biochemical pathways where changed. Breathomics showed an increase in exhaled carbon monoxide, dimethylsulfide, and isoprene. Metabolomics revealed an acute increase in lactate, citrate, purines, urea, dopamine, eicosanoids, microbiome metabolites, oxidized glutathione, thiamine, niacinamide, and pyridoxic acid, and decreased folate-methylation-1-carbon intermediates, amino acids, short and medium chain acyl-carnitines, phospholipids, ceramides, sphingomyelins, cholesterol, bile acids, and vitamin D similar to some children with ASD. MIA animals were hypersensitive to postnatal exposure to eATP or poly(IC), which produced a rebound increase in body temperature that lasted several weeks before returning to baseline. Acute hyperpurinergia produced metabolic and behavioral changes in mice. The behaviors and metabolic changes produced by ATP injection were associated with mitochondrial functional changes that were profound but reversible. [ABSTRACT FROM AUTHOR]

Understanding and quantifying the global methane (CH4) budget is important for assessing realistic pathways to mitigate climate change. Atmospheric emissions and concentrations of CH4 continue to increase, making CH4 the second most important human-influenced greenhouse gas in terms of climate forcing, after carbon dioxide (CO2). The relative importance of CH4 compared to CO2 depends on its shorter atmospheric lifetime, stronger warming potential, and variations in atmospheric growth rate over the past decade, the causes of which are still debated. Two major challenges in reducing uncertainties in the atmospheric growth rate arise from the variety of geographically overlapping CH4 sources and from the destruction of CH4 by short-lived hydroxyl radicals (OH). To address these challenges, we have established a consortium of multidisciplinary scientists under the umbrella of the Global Carbon Project to synthesize and stimulate new research aimed at improving and regularly updating the global methane budget. Following Saunois et al. (2016), we present here the second version of the living review paper dedicated to the decadal methane budget, integrating results of top-down studies (atmospheric observations within an atmospheric inverse-modelling framework) and bottom-up estimates (including process-based models for estimating land surface emissions and atmospheric chemistry, inventories of anthropogenic emissions, and data-driven extrapolations). For the 2008–2017 decade, global methane emissions are estimated by atmospheric inversions (a top-down approach) to be 576 Tg CH4 yr -1 (range 550–594, corresponding to the minimum and maximum estimates of the model ensemble). Of this total, 359 Tg CH4 yr -1 or ∼ 60 % is attributed to anthropogenic sources, that is emissions caused by direct human activity (i.e. anthropogenic emissions; range 336–376 Tg CH4 yr -1 or 50 %–65 %). The mean annual total emission for the new decade (2008–2017) is 29 Tg CH4 yr -1 larger than our estimate for the previous decade (2000–2009), and 24 Tg CH4 yr -1 larger than the one reported in the previous budget for 2003–2012 (Saunois et al., 2016). Since 2012, global CH4 emissions have been tracking the warmest scenarios assessed by the Intergovernmental Panel on Climate Change. Bottom-up methods suggest almost 30 % larger global emissions (737 Tg CH4 yr -1 , range 594–881) than top-down inversion methods. Indeed, bottom-up estimates for natural sources such as natural wetlands, other inland water systems, and geological sources are higher than top-down estimates. The atmospheric constraints on the top-down budget suggest that at least some of these bottom-up emissions are overestimated. The latitudinal distribution of atmospheric observation-based emissions indicates a predominance of tropical emissions (∼ 65 % of the global budget, < 30 ∘ N) compared to mid-latitudes (∼ 30 %, 30–60 ∘ N) and high northern latitudes (∼ 4 %, 60–90 ∘ N). The most important source of uncertainty in the methane budget is attributable to natural emissions, especially those from wetlands and other inland waters. Some of our global source estimates are smaller than those in previously published budgets (Saunois et al., 2016; Kirschke et al., 2013). In particular wetland emissions are about 35 Tg CH4 yr -1 lower due to improved partition wetlands and other inland waters. Emissions from geological sources and wild animals are also found to be smaller by 7 Tg CH4 yr -1 by 8 Tg CH4 yr -1 , respectively. However, the overall discrepancy between bottom-up and top-down estimates has been reduced by only 5 % compared to Saunois et al. (2016), due to a higher estimate of emissions from inland waters, highlighting the need for more detailed research on emissions factors. Priorities for improving the methane budget include (i) a global, high-resolution map of water-saturated soils and inundated areas emitting methane based on a robust classification of different types of emitting habitats; (ii) further development of process-based models for inland-water emissions; (iii) intensification of methane observations at local scales (e.g., FLUXNET- CH4 measurements) and urban-scale monitoring to constrain bottom-up land surface models, and at regional scales (surface networks and satellites) to constrain atmospheric inversions; (iv) improvements of transport models and the representation of photochemical sinks in top-down inversions; and (v) development of a 3D variational inversion system using isotopic and/or co-emitted species such as ethane to improve source partitioning. The data presented here can be downloaded from 10.18160/GCP-CH4-2019 (Saunois et al., 2020) and from the Global Carbon Project. [ABSTRACT FROM AUTHOR]

Organic nitrates (RONO2) are an important NOx sink. In warm, rural environments dominated by biogenic emissions, nocturnal NO3‐initiated production of RONO2 is competitive with daytime OH‐initiated RONO2 production. However, in urban areas, OH‐initiated production of RONO2 has been assumed dominant and NO3‐initiated production considered negligible. We show evidence for nighttime RONO2 production similar in magnitude to daytime production during three aircraft campaigns in chemically distinct summertime environments: Studies of Emissions and Atmospheric Composition, Clouds, and Climate Coupling by Regional Surveys (SEAC4RS) in the rural Southeastern United States, Front Range Air Pollution and Photochemistry Experiment (FRAPPÉ) in the Colorado Front Range, and Korea‐United States Air Quality Study (KORUS‐AQ) around the megacity of Seoul. During each campaign, morning observations show RONO2 enhancements at constant, near‐background Ox (≡ O3+NO2) concentrations, indicating that the RONO2 are from a non‐photochemical source, whereas afternoon observations show a strong correlation between RONO2 and Ox resulting from photochemical production. We show that there are sufficient precursors for nighttime RONO2 formation during all three campaigns. This evidence impacts our understanding of nighttime NOx chemistry. Plain Language Summary: Nitrogen oxides are pollutants emitted during combustion which are involved in ozone and secondary aerosol production. One way in which nitrogen oxides are removed from the atmosphere is via chemistry that converts them to organic nitrates. This conversion of nitrogen oxides to organic nitrates has been thought to occur primarily during the day when the chemistry is driven by sunlight. Here we show evidence that nighttime processes generate similar quantities of organic nitrates to those produced by sunlight‐driven processes. Key Points: We show evidence for nocturnal production of organic nitrates similar in magnitude to daytime photochemical productionSignificant nocturnal production of organic nitrates observed from three aircraft campaigns in distinct environmentsNighttime production of organic nitrates impacts our understanding of the nighttime lifetime and fate of NOx [ABSTRACT FROM AUTHOR]

The Community Earth System Model version 2 (CESM2) includes a detailed representation of chemistry throughout the atmosphere in the Community Atmosphere Model with chemistry and Whole Atmosphere Community Climate Model configurations. These model configurations use the Model for Ozone and Related chemical Tracers (MOZART) family of chemical mechanisms, covering the troposphere, stratosphere, mesosphere, and lower thermosphere. The new MOZART tropospheric chemistry scheme (T1) has a number of updates over the previous version (MOZART‐4) in CESM, including improvements to the oxidation of isoprene and terpenes, organic nitrate speciation, and aromatic speciation and oxidation and thus improved representation of ozone and secondary organic aerosol precursors. An evaluation of the present‐day simulations of CESM2 being provided for Climate Model Intercomparison Project round 6 (CMIP6) is presented. These simulations, using the anthropogenic and biomass burning emissions from the inventories specified for CMIP6, as well as online calculation of emissions of biogenic compounds, lightning NO, dust, and sea salt, indicate an underestimate of anthropogenic emissions of a variety of compounds, including carbon monoxide and hydrocarbons. The simulation of surface ozone in the southeast United States is improved over previous model versions, largely due to the improved representation of reactive nitrogen and organic nitrate compounds resulting in a lower ozone production rate than in CESM1 but still overestimates observations in summer. The simulation of tropospheric ozone agrees well with ozonesonde observations in many parts of the globe. The comparison of NOx and PAN to aircraft observations indicates the model simulates the nitrogen budget well. Plain Language Summary: The set of chemical reactions for tropospheric chemistry used in the Community Earth System Model version 2 (CESM2) has been updated significantly over CESM1 in the Community Atmosphere Model with chemistry (CAM‐chem) and Whole Atmosphere Community Climate Model (WACCM) configurations. The emissions used for the CESM2 simulations are documented here, with anthropogenic and biomass burning emissions based on the specified inventories for Climate Model Intercomparison Project 6 (CMIP6), and emissions of biogenic compounds, lightning NO, dust, and sea salt are calculated online and dependent on the simulated meteorology. Evaluation of the CAM‐chem and WACCM configurations of CESM2 with observations indicate an underestimate of anthropogenic emissions of a variety of compounds, including carbon monoxide and hydrocarbons. The updated chemistry leads to an improvement in the simulation of tropospheric ozone. Key Points: This paper fully documents the significant updates to the chemistry mechanisms in version 2 of the Community Earth System ModelThe new tropospheric chemistry scheme improves representation of isoprene oxidation as well as other ozone precursors over earlier versionsThe simulation of tropospheric ozone is improved in comparison to observations [ABSTRACT FROM AUTHOR]

Understanding and quantifying the global methane (CH4) budget is important for assessing realistic pathways to mitigate climate change. Atmospheric emissions and concentrations of CH4 are continuing to increase, making CH4 the second most important human-influenced greenhouse gas in terms of climate forcing, after carbon dioxide (CO2). Assessing the relative importance of CH4 in comparison to CO2 is complicated by its shorter atmospheric lifetime, stronger warming potential, and atmospheric growth rate variations over the past decade, the causes of which are still debated. Two major difficulties in reducing uncertainties arise from the variety of geographically overlapping CH4 sources and from the destruction of CH4 by short-lived hydroxyl radicals (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 new research aimed at improving and regularly updating the global methane budget. Following Saunois et al. (2016), we present here the second version of the living review paper dedicated to the decadal methane budget, integrating results of top-down studies (atmospheric observations within an atmospheric inverse-modelling framework) and bottom-up estimates (including process-based models for estimating land surface emissions and atmospheric chemistry, inventories of anthropogenic emissions, and data-driven extrapolations). For the 2008–2017 decade, global methane emissions are estimated by atmospheric inversions (top-down approach) to be 572 Tg CH4 yr−1 (range 538–593, corresponding to the minimum and maximum estimates of the ensemble), of which 357 Tg CH4 yr−1 or ~ 60 % are attributed to anthropogenic sources (range 50–65 %). This total emission is 27 Tg CH4 yr−1 larger than the value estimated for the period 2000–2009 and 24 Tg CH4 yr−1 larger than the one reported in the previous budget for the period 2003–2012 (Saunois et al. 2016). Since 2012, global CH4 emissions have been tracking the carbon intensive scenarios developed by the Intergovernmental Panel on Climate Change (Gidden et al., 2019). Bottom-up methods suggest larger global emissions (737 Tg CH4 yr−1, range 583–880) than top-down inversion methods, mostly because of larger estimated natural emissions from sources such as natural wetlands, other inland water systems, and geological sources. However the strength of the atmospheric constraints on the top-down budget, suggest that these bottom-up emissions are overestimated. The latitudinal distribution of atmospheric-based emissions indicates a predominance of tropical emissions (~ 65 % of the global budget, < 30° N) compared to mid (~ 30 %, 30° N–60° N) and high northern latitudes (~ 4 %, 60° N–90° N). Our analyses suggest that uncertainties associated with estimates of anthropogenic emissions are smaller than those of natural sources, with top-down inversions yielding larger uncertainties than bottom-up inventories and models. The most important source of uncertainty in the methane budget is attributable to natural emissions, especially those from wetlands and other inland waters. Some global source estimates are smaller compared to the previously published budgets (Saunois et al. 2016; Kirschke et al. 2013), particularly for vegetated wetland emissions that are lower by about 35 Tg CH4 yr−1 due to efforts to partition vegetated wetlands and inland waters. Emissions from geological sources are also found to be smaller by 7 Tg CH4 yr−1, and wild animals by 8 Tg CH4 yr−1. However the overall discrepancy between bottom-up and top-down estimates has been reduced by only 5 % compared to Saunois et al. (2016), due to a higher estimate of freshwater emissions resulting from recent research and the integration of emissions from estuaries. Priorities for improving the methane budget include: i) a global, high-resolution map of water-saturated soils and inundated areas emitting methane based on a robust classification of different types of emitting habitats; ii) further development of process-based models for inland-water emissions; iii) intensification of methane observations at local scales (e.g., FLUXNET-CH4 measurements and urban monitoring to constrain bottom-up land surface models, and at regional scales (surface networks and satellites) to constrain atmospheric inversions; iv) improvements of transport models and the representation of photochemical sinks in top-down inversions, and v) development of a 3D variational inversion system using isotopic and/or co-emitted species such as ethane. [ABSTRACT FROM AUTHOR]

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]

National-scale emissions of carbon tetrachloride (CCl4) are derived based on inverse modeling of atmospheric observations at multiple sites across the United States from the National Oceanic and Atmospheric Administration's flask air sampling network. We estimate an annual average US emission of 4.0 (2.0-6.5) Gg CCl4 y-1 during 2008-2012, which is almost two orders of magnitude larger than reported to the US Environmental Protection Agency (EPA) Toxics Release Inventory (TRI) (mean of 0.06 Gg y-1) but only 8% (3-22%) of global CCl4 emissions during these years. Emissive regions identified by the observations and consistently shown in all inversion results include the Gulf Coast states, the San Francisco Bay Area in California, and the Denver area in Colorado. Both the observation-derived emissions and the US EPA TRI identified Texas and Louisiana as the largest contributors, accounting for one- to two-thirds of the US national total CCl4 emission during 2008-2012. These results are qualitatively consistent with multiple aircraft and ship surveys conducted in earlier years, which suggested significant enhancements in atmospheric mole fractions measured near Houston and surrounding areas. Furthermore, the emission distribution derived for CCl4 throughout the United States is more consistent with the distribution of industrial activities included in the TRI than with the distribution of other potential CCl4 sources such as uncapped landfills or activities related to population density (e.g., use of chlorine-containing bleach). [ABSTRACT FROM AUTHOR]

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 (~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 (T-D, exploiting atmospheric observations within an atmospheric inverse-modelling framework) and bottom-up models, inventories, and data-driven approaches (B-U, 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 T-D inversions at 558 & Tg & CH4 & yr-1 (range [540-568]). About 60 & % of global emissions are anthropogenic (range [50-65 & %]). B-U approaches suggest larger global emissions (736 & Tg & CH4 & yr-1 [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 T-D budget, it is likely that some of the individual emissions reported by the B-U approaches are overestimated, leading to too large global emissions. Latitudinal data from T-D emissions indicate a predominance of tropical emissions (~64 & % of the global budget, < & 30° & N) as compared to mid (~32 & %, 30° & N-60° & N) and high northern latitudes (~ & 4 & %, 60° & N-90° & N). T-D inversions consistently infer lower emissions in China (~58 & Tg & CH4 & yr-1 [51-72], -14 & %) and higher emissions in Africa (86 & Tg & CH4 & yr-1 [73-108], +19 & %) than B-U values used as prior estimates. Overall, uncertainties for anthropogenic emissions appear smaller than those from natural sources, and the uncertainties on source categories appear larger for T-D inversions than for B-U inventories and models. The most important source of uncertainty on the methane budget is attributable to emissions from wetland and other inland waters. We show that the wetland extent could contribute for 30-40 & % on the estimated range for wetland emissions. Other priorities for improving the methane budget include: i) the development of process-based models for inland-water emissions, ii) the intensification of methane observations at local scale (flux measurements) to constrain B-U land surface models, and at regional scale (surface networks and satellites) to constrain T-D inversions, iii) improvements in the estimation of atmospheric loss by OH, and iv) improvements of the transport models integrated in T-D inversions. The data presented here can be downloaded from the Carbon Dioxide Information Analysis Center (doi:10.3334/CDIAC/Global_Methane_Budget_2016). [ABSTRACT FROM AUTHOR]

Particulate air pollution is a health concern. This study determines the microscopic make-up of different varieties of sand particles collected at a sand dune site in Badr, Saudi Arabia in 2012. Three categories of sand were studied: black sand, white sand, and volcanic sand. The study used multiple high resolution electron microscopies to study the morphologies, emission source types, size, and elemental composition of the particles, and to evaluate the presence of surface "coatings or contaminants" deposited or transported by the black sand particles. White sand was comprised of natural coarse particles linked to wind-blown releases from crustal surfaces, weathering of igneous/metamorphic rock sources, and volcanic activities. Black sand particles exhibited different morphologies and microstructures (surface roughness) compared with the white sand and volcanic sand. Morphological Scanning Electron Microscopy (SEM) and Laser Scanning Microscopy (LSM) analyses revealed that the black sand contained fine and ultrafine particles (50 to 500 nm ranges) and was strongly magnetic, indicating the mineral magnetite or elemental iron. Aqueous extracts of black sands were acidic (pH = 5.0). Fe, C, O, Ti, Si, V, and S dominated the composition of black sand. Results suggest that carbon and other contaminant fine particles were produced by fossil-fuel combustion and industrial emissions in heavily industrialized areas of Haifa and Yanbu, and transported as cloud condensation nuclei to Douf Mountain. The suite of techniques used in this study has yielded an in-depth characterization of sand particles. Such information will be needed in future environmental, toxicological, epidemiological, and source apportionment studies. [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]

Sulfuric acid (H2SO4), formed from oxidation of sulfur dioxide (SO2) emitted during fossil fuel combustion, is a major precursor of new airborne particles, which have well-documented detrimental effects on health, air quality, and climate. Another precursor is methanesulfonic acid (MSA), produced simultaneously with SO2 during the atmospheric oxidation of organosulfur compounds (OSCs), such as dimethyl sulfide. In the present work, a multidisciplinary approach is used to examine how contributions of H2SO4 and MSA to particle formation will change in a large coastal urban area as anthropogenic fossil fuel emissions of SO2 decline. The 3-dimensional University of California Irvine-California Institute of Technology airshed model is used to compare atmospheric concentrations of gas phase MSA, H2SO4, and SO2 under current emissions of fossil fuel-associated SO2 and a best-case futuristic scenario with zero fossil fuel sulfur emissions. Model additions include results from (i) quantum chemical calculations that clarify the previously uncertain gas phase mechanism of formation of MSA and (ii)a combination of published and experimental estimates of OSC emissions, such as those from marine, agricultural, and urban processes, which include pet waste and human breath. Results show that in the zero anthropogenic SO2 emissions case, particle formation potential from H2SO4 will drop by about two orders of magnitude compared with the current situation. However, particles will continue to be generated from the oxidation of natural and anthropogenic sources of OSCs, with contributions from MSA and H2SO4 of a similar order of magnitude. This could be particularly important in agricultural areas where there are significant sources of OSCs. [ABSTRACT FROM AUTHOR]

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. [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]

The airways of cystic fibrosis (CF) patients are chronically colonized by patient-specific polymicrobial communities. The conditions and nutrients available in CF lungs affect the physiology and composition of the colonizing microbes. Recent work in bioreactors has shown that the fermentation product 2,3-butanediol mediates cross-feeding between some fermenting bacteria and Pseudomonas aeruginosa, and that this mechanism increases bacterial current production. To examine bacterial fermentation in the respiratory tract, breath gas metabolites were measured and several metagenomes were sequenced from CF and non-CF volunteers. 2,3-butanedione was produced in nearly all respiratory tracts. Elevated levels in one patient decreased during antibiotic treatment, and breath concentrations varied between CF patients at the same time point. Some patients had high enough levels of 2,3-butanedione to irreversibly damage lung tissue. Antibiotic therapy likely dictates the activities of 2,3-butanedione-producing microbes, which suggests a need for further study with larger sample size. Sputum microbiomes were dominated by P. aeruginosa, Streptococcus spp. and Rothia mucilaginosa, and revealed the potential for 2,3-butanedione biosynthesis. Genes encoding 2,3-butanedione biosynthesis were disproportionately abundant in Streptococcus spp, whereas genes for consumption of butanedione pathway products were encoded by P. aeruginosa and R. mucilaginosa. We propose a model where low oxygen conditions in CF lung lead to fermentation and a decrease in pH, triggering 2,3-butanedione fermentation to avoid lethal acidification. We hypothesize that this may also increase phenazine production by P. aeruginosa, increasing reactive oxygen species and providing additional electron acceptors to CF microbes. [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]

Blood is the specimen of choice for most laboratory tests for diagnosis and disease monitoring. Sampling exhaled breath is a noninvasive alternative to phlebotomy and has the potential for real-time monitoring at the bedside. Improved instrumentation has advanced breath analysis for several gaseous compounds from humans. However, application to small animal models of diseases and physiology has been limited. To extend breath analysis to mice, we crafted a means for collecting nose-only breath samples from groups and individual animals who were awake. Samples were subjected to gas chromatography and mass spectrometry procedures developed for highly sensitive analysis of trace volatile organic compounds (VOCs) in the atmosphere. We evaluated the system with experimental systemic infections of severe combined immunodeficiency Mus musculus with the bacterium Borrelia hermsii. Infected mice developed bacterial densities of ∼107 per ml of blood by day 4 or 5 and in comparison to uninfected controls had hepatosplenomegaly and elevations of both inflammatory and anti-inflammatory cytokines. While 12 samples from individual infected mice on days 4 and 5 and 6 samples from uninfected mice did not significantly differ for 72 different VOCs, carbon monoxide (CO) was elevated in samples from infected mice, with a mean (95% confidence limits) effect size of 4.2 (2.8–5.6), when differences in CO2 in the breath were taken into account. Normalized CO values declined to the uninfected range after one day of treatment with the antibiotic ceftriaxone. Strongly correlated with CO in the breath were levels of heme oxygenase-1 protein in serum and HMOX1 transcripts in whole blood. These results (i) provide further evidence of the informativeness of CO concentration in the exhaled breath during systemic infection and inflammation, and (ii) encourage evaluation of this noninvasive analytic approach in other various other rodent models of infection and for utility in clinical management. [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]

During the Deepwater Horizon (DWH) oil spill, a wide range of gas and aerosol species were measured from an aircraft around, downwind, and away from the DWH site. Additional hydrocarbon measurements were made from ships in the vicinity. Aerosol particles of respirable sizes were on occasions a significant air quality issue for populated areas along the Gulf Coast. Yields of organic aerosol particles and emission factors for other atmospheric pollutants were derived for the sources from the spill, recovery, and cleanup efforts. Evaporation and subsequent secondary chemistry produced organic particulate matter with a mass yield of 8 ± 4% of the oil mixture reaching the water surface. Approximately 4% by mass of oil burned on the surface was emitted as soot particles. These yields can be used to estimate the effects on air quality for similar events as well as for this spill at other times without these data. Whereas emission of soot from burning surface oil was large during the episodic burns, the mass flux of secondary organic aerosol to the atmosphere was substantially larger overall. We use a regional air quality model to show that some observed enhancements in organic aerosol concentration along the Gulf Coast were likely due to the DWH spill. In the presence of evaporating hydrocarbons from the oil, NOx emissions from the recovery and cleanup operations produced ozone. [ABSTRACT FROM AUTHOR]

Detailed airborne, surface, and subsurface chemical measurements, primarily obtained in May and June 2010, are used to quantify initial hydrocarbon compositions along different transport pathways (i.e., in deep subsurface plumes, in the initial surface slick, and in the atmosphere) during the Deepwater Horizon oil spill. Atmospheric measurements are consistent with a limited area of surfacing oil, with implications for leaked hydrocarbon mass transport and oil drop size distributions. The chemical data further suggest relatively little variation in leaking hydrocarbon composition over time. Although readily soluble hydrocarbons made up ∼25% of the leaking mixture by mass, subsurface chemical data show these compounds made up ∼69% of the deep plume mass; only ∼31% of the deep plume mass was initially transported in the form of trapped oil droplets. Mass flows along individual transport pathways are also derived from atmospheric and subsurface chemical data. Subsurface hydrocarbon composition, dissolved oxygen, and dispersant data are used to assess release of hydrocarbons from the leaking well. We use the chemical measurements to estimate that (7.8 ± 1.9) × 106 kg of hydrocarbons leaked on June 10, 2010, directly accounting for roughly three-quarters of the total leaked mass on that day. The average environmental release rate of (10.1 ± 2.0) × 106 kg/d derived using atmospheric and subsurface chemical data agrees within uncertainties with the official average leak rate of (10.2 ± 1.0) × 106 kg/d derived using physical and optical methods. [ABSTRACT FROM AUTHOR]

After methane, ethane is the most abundant hydrocarbon in the remote atmosphere. It is a precursor to tropospheric ozone and it influences the atmosphere's oxidative capacity through its reaction with the hydroxyl radical, ethane's primary atmospheric sink. Here we present the longest continuous record of global atmospheric ethane levels. We show that global ethane emission rates decreased from 14.3 to 11.3 teragrams per year, or by 21 per cent, from 1984 to 2010. We attribute this to decreasing fugitive emissions from ethane's fossil fuel source-most probably decreased venting and flaring of natural gas in oil fields-rather than a decline in its other major sources, biofuel use and biomass burning. Ethane's major emission sources are shared with methane, and recent studies have disagreed on whether reduced fossil fuel or microbial emissions have caused methane's atmospheric growth rate to slow. Our findings suggest that reduced fugitive fossil fuel emissions account for at least 10-21 teragrams per year (30-70 per cent) of the decrease in methane's global emissions, significantly contributing to methane's slowing atmospheric growth rate since the mid-1980s. [ABSTRACT FROM AUTHOR]

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]

Methane and ethane are the most abundant hydrocarbons in the atmosphere and they affect both atmospheric chemistry and climate. Both gases are emitted from fossil fuels and biomass burning, whereas methane (CH4) alone has large sources from wetlands, agriculture, landfills and waste water. Here we use measurements in firn (perennial snowpack) air from Greenland and Antarctica to reconstruct the atmospheric variability of ethane (C2H6) during the twentieth century. Ethane levels rose from early in the century until the 1980s, when the trend reversed, with a period of decline over the next 20?years. We find that this variability was primarily driven by changes in ethane emissions from fossil fuels; these emissions peaked in the 1960s and 1970s at 14-16 teragrams per year (1?Tg = 1012?g) and dropped to 8-10?Tg?yr?1 by the turn of the century. The reduction in fossil-fuel sources is probably related to changes in light hydrocarbon emissions associated with petroleum production and use. The ethane-based fossil-fuel emission history is strikingly different from bottom-up estimates of methane emissions from fossil-fuel use, and implies that the fossil-fuel source of methane started to decline in the 1980s and probably caused the late twentieth century slow-down in the growth rate of atmospheric methane. [ABSTRACT FROM AUTHOR]