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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]

Reactive halogens catalytically destroy O3 and therefore affect (1) stratospheric O3 depletion, and (2) the oxidative capacity of the troposphere. Reactive halogens also partition into the aerosol phase, but what governs halogen-aerosol partitioning is poorly constrained in models. In this work, we present global-scale measurements of non-sea-salt aerosol (nSSA) bromine and iodine taken during the NASA Atmospheric Tomography Mission (ATom). Using the Particle Analysis by Laser Mass Spectrometry instrument, we found that bromine and iodine are present in 8-26 % (interquartile range, IQR) and 12-44 % (IQR) of accumulation-mode nSSA, respectively. Despite being commonly found in nSSA, the mass concentrations of bromine and iodine in nSSA were low, 0.11-0.57 pmol mol-1 (IQR) and 0.04–0.24 pmol mol-1 (IQR), respectively. In the troposphere, we find two distinct sources of bromine and iodine to nSSA: (1) a primary source from biomass burning, and (2) a pervasive secondary source. In the stratosphere, nSSA bromine and iodine mass increased with increasing O3 concentrations; however, higher concentrations of stratospheric nSSA bromine and iodine were found in organic-rich particles that originated in the troposphere. Finally, we compared our ATom nSSA iodine measurements to the global chemical transport model GEOS-Chem; nSSA bromine concentrations could not be compared because they were not tracked in the model. We found that the model compared well to our ATom nSSA iodine measurements in the background atmosphere, but not in the marine boundary layer, biomass burning plumes, or in the stratosphere. [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]

The atmospheric sulfur cycle plays a key role in air quality, climate, and ecosystems, such as pollution, radiative forcing, new particle formation, and acid rain. In this study, we compare the spatially and temporally resolved measurements from the NASA Atmospheric Tomography (ATom) mission with simulations from five AeroCom III models for four sulfur species (dimethyl sulfide (DMS), sulfur dioxide (SO 2), particulate methanesulfonate (MSA), and particulate sulfate (SO 4)). We focus on remote regions over the Pacific, Atlantic, and Southern oceans from near the surface to ∼ 12 km altitude range covering all four seasons. In general, the differences among model results can be greater than 1 order of magnitude. Comparing with observations, model-simulated SO 2 is generally low, whereas SO 4 is generally high. Simulated DMS concentrations near the sea surface exceed observed levels by a factor of 5 in most cases, suggesting potential overestimation of DMS emissions in all models. With GEOS model simulations of tagging emission from anthropogenic, biomass burning, volcanic, and oceanic sources, we find that anthropogenic emissions are the dominant source of sulfate aerosol (40 %–60 % of the total amount) in the ATom measurements at almost all altitudes, followed by volcanic emissions (18 %–32 %) and oceanic sources (16 %–32 %). Similar source contributions can also be derived at broad ocean basins and on monthly scales, indicating the representativeness of ATom measurements for global ocean. Our work presents the first assessment of AeroCom sulfur study using ATom measurements, providing directions for improving sulfate simulations, which remain the largest uncertainty in radiative forcing estimates in aerosol climate models. [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]

Extensive airborne measurements of non-methane organic gases (NMOGs), methane, nitrogen oxides, reduced nitrogen species, and aerosol emissions from US wild and prescribed fires were conducted during the 2019 NOAA/NASA Fire Influence on Regional to Global Environments and Air Quality campaign (FIREX-AQ). Here, we report the atmospheric enhancement ratios (ERs) and inferred emission factors (EFs) for compounds measured on board the NASA DC-8 research aircraft for nine wildfires and one prescribed fire, which encompass a range of vegetation types. We use photochemical proxies to identify young smoke and reduce the effects of chemical degradation on our emissions calculations. ERs and EFs calculated from FIREX-AQ observations agree within a factor of 2, with values reported from previous laboratory and field studies for more than 80 % of the carbon- and nitrogen-containing species. Wildfire emissions are parameterized based on correlations of the sum of NMOGs with reactive nitrogen oxides (NO y) to modified combustion efficiency (MCE) as well as other chemical signatures indicative of flaming/smoldering combustion, including carbon monoxide (CO), nitrogen dioxide (NO 2), and black carbon aerosol. The sum of primary NMOG EFs correlates to MCE with an R2 of 0.68 and a slope of - 296 ± 51 g kg -1 , consistent with previous studies. The sum of the NMOG mixing ratios correlates well with CO with an R2 of 0.98 and a slope of 137 ± 4 ppbv of NMOGs per parts per million by volume (ppmv) of CO, demonstrating that primary NMOG emissions can be estimated from CO. Individual nitrogen-containing species correlate better with NO 2 , NO y , and black carbon than with CO. More than half of the NO y in fresh plumes is NO 2 with an R2 of 0.95 and a ratio of NO 2 to NO y of 0.55 ± 0.05 ppbv ppbv -1 , highlighting that fast photochemistry had already occurred in the sampled fire plumes. The ratio of NO y to the sum of NMOGs follows trends observed in laboratory experiments and increases exponentially with MCE, due to increased emission of key nitrogen species and reduced emission of NMOGs at higher MCE during flaming combustion. These parameterizations will provide more accurate boundary conditions for modeling and satellite studies of fire plume chemistry and evolution to predict the downwind formation of secondary pollutants, including ozone and secondary organic aerosol. [ABSTRACT FROM AUTHOR]

The sulfur cycle plays a key role in atmospheric air quality, climate, and ecosystems. In this study, we compare the spatial and temporal distribution of four sulfur-containing species, dimethyl sulfide (DMS), sulfur dioxide (SO2), particulate methanesulfonate (MSA), and particulate sulfate (SO4), that were measured during the airborne NASA Atmospheric Tomography (ATom) mission and simulated by five AeroCom-III models to analyze the budget of sulfur cycle from the models. This study focuses on remote regions over the Pacific, Atlantic, and Southern Oceans from near the ocean surface to ~12-km altitude range, and covers all four seasons. These regions provide us with highly heterogeneous natural and anthropogenic source environments, which is not usually the case for traditional continental studies. We examine the vertical and seasonal variations of these sulfur species over tropical, mid-, and high-latitude regions in both hemispheres. We identify their origins from land versus ocean and from anthropogenic versus natural sources with sensitivity studies by applying tagged tracers linking to emission types and regions. In general, the differences among model results can be greater than one-order of magnitude. Comparing with observations, simulated SO2 is generally low while SO4 is high, and the model-observation agreement is much better in ATom-4 (April-May, 2018). There are much larger DMS concentrations simulated close to the sea surface than observed, indicating that the DMS emissions may be too high from all models. Anthropogenic emissions are the dominant source (40-60% of the total amount) for atmospheric sulfate simulated at locations and times along the ATom flight tracks at almost every altitude, followed by volcanic emissions (18-32%) and oceanic sources (16-32%). Similar source contributions can also be derived at broad ocean basin and monthly scales, indicating that any reductions of anthropogenic sulfur emissions would have global impacts in modern times. [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]

Extensive airborne measurements of non-methane organic gases (NMOGs), methane, nitrogen oxides, reduced nitrogen-species, and aerosol emissions from US wild and prescribed fires were conducted during the 2019 NOAA/NASA Fire Influence on Regional to Global Environments and Air Quality campaign (FIREX-AQ). Here, we report the atmospheric enhancement ratios (ERs) and inferred emission factors (EFs) for compounds measured onboard the NASA DC-8 research aircraft for nine wildfires and one prescribed fire, which encompass a range of vegetation types. We use photochemical proxies to identify young smoke and reduce the effects of chemical degradation on our emissions calculations. ERs and EFs calculated from FIREX-AQ observations agree within a factor of 2 with values reported from previous laboratory and field studies for more than 80 % of the carbon- and nitrogen-containing species. Wildfire emissions are parameterized based on correlations of the sum of NMOGs with reactive nitrogen oxides (NOy) to modified combustion efficiency (MCE) as well as other chemical signatures indicative of flaming/smoldering combustion, including carbon monoxide (CO), nitrogen dioxide (NO2), and black carbon aerosol. The sum of primary NMOG EFs correlates to MCE with an R² of 0.68 and a slope of -296 ± 51 g kg-1, consistent with previous studies. The sum of the NMOG mixing ratios correlates well with CO with an R² of 0.98 and a slope of 137 ± 4 ppbv of NMOGs per ppmv of CO, demonstrating that primary NMOG emissions can be estimated from CO. Individual nitrogen-containing species correlate better with NO2, NOy, and black carbon than with CO. More than half of the NOy in fresh plumes is NO2 with an R² of 0.95 and a ratio of NO2 to NOy of 0.55 ± 0.05 ppbv ppbv-1, highlighting that fast photochemistry had already occurred in the sampled fire plumes. The ratio of NOy to the sum of NMOGs follows trends observed in laboratory experiments and increases exponentially with MCE, due to increased emission of key nitrogen species and reduced emission of NMOGs at higher MCE during flaming combustion. These parameterizations will provide more accurate boundary conditions for modeling and satellite studies of fire plume chemistry and evolution to predict the downwind formation of secondary pollutants, including ozone and secondary organic aerosol. [ABSTRACT FROM AUTHOR]

The availability of formaldehyde (HCHO) (a proxy for volatile organic compound reactivity) and nitrogen dioxide (NO 2) (a proxy for nitrogen oxides) tropospheric columns from ultraviolet–visible (UV–Vis) satellites has motivated many to use their ratios to gain some insights into the near-surface ozone sensitivity. Strong emphasis has been placed on the challenges that come with transforming what is being observed in the tropospheric column to what is actually in the planetary boundary layer (PBL) and near the surface; however, little attention has been paid to other sources of error such as chemistry, spatial representation, and retrieval uncertainties. Here we leverage a wide spectrum of tools and data to quantify those errors carefully. Concerning the chemistry error, a well-characterized box model constrained by more than 500 h of aircraft data from NASA's air quality campaigns is used to simulate the ratio of the chemical loss of HO 2 + RO 2 (LROx) to the chemical loss of NO x (LNOx). Subsequently, we challenge the predictive power of HCHO/NO2 ratios (FNRs), which are commonly applied in current research, in detecting the underlying ozone regimes by comparing them to LROx/LNOx. FNRs show a strongly linear (R2=0.94) relationship with LROx/LNOx , but only on the logarithmic scale. Following the baseline (i.e., ln(LROx/LNOx) = - 1.0 ± 0.2) with the model and mechanism (CB06, r2) used for segregating NOx -sensitive from VOC-sensitive regimes, we observe a broad range of FNR thresholds ranging from 1 to 4. The transitioning ratios strictly follow a Gaussian distribution with a mean and standard deviation of 1.8 and 0.4, respectively. This implies that the FNR has an inherent 20 % standard error (1σ) resulting from not accurately describing the ROx – HOx cycle. We calculate high ozone production rates (PO 3) dominated by large HCHO × NO 2 concentration levels, a new proxy for the abundance of ozone precursors. The relationship between PO 3 and HCHO × NO 2 becomes more pronounced when moving towards NOx -sensitive regions due to nonlinear chemistry; our results indicate that there is fruitful information in the HCHO × NO 2 metric that has not been utilized in ozone studies. The vast amount of vertical information on HCHO and NO 2 concentrations from the air quality campaigns enables us to parameterize the vertical shapes of FNRs using a second-order rational function permitting an analytical solution for an altitude adjustment factor to partition the tropospheric columns into the PBL region. We propose a mathematical solution to the spatial representation error based on modeling isotropic semivariograms. Based on summertime-averaged data, the Ozone Monitoring Instrument (OMI) loses 12 % of its spatial information at its native resolution with respect to a high-resolution sensor like the TROPOspheric Monitoring Instrument (TROPOMI) (> 5.5 × 3.5 km 2). A pixel with a grid size of 216 km 2 fails at capturing ∼ 65 % of the spatial information in FNRs at a 50 km length scale comparable to the size of a large urban center (e.g., Los Angeles). We ultimately leverage a large suite of in situ and ground-based remote sensing measurements to draw the error distributions of daily TROPOMI and OMI tropospheric NO 2 and HCHO columns. At a 68 % confidence interval (1σ), errors pertaining to daily TROPOMI observations, either HCHO or tropospheric NO 2 columns, should be above 1.2–1.5 × 10 16 molec. cm -2 to attain a 20 %–30 % standard error in the ratio. This level of error is almost non-achievable with the OMI given its large error in HCHO. The satellite column retrieval error is the largest contributor to the total error (40 %–90 %) in the FNRs. Due to a stronger signal in cities, the total relative error (< 50 %) tends to be mild, whereas areas with low vegetation and anthropogenic sources (e.g., the Rocky Mountains) are markedly uncertain (> 100 %). Our study suggests that continuing development in the retrieval algorithm and sensor design and calibration is essential to be able to advance the application of FNRs beyond a qualitative metric. [ABSTRACT FROM AUTHOR]

The availability of formaldehyde (HCHO) (a proxy for volatile organic compound reactivity) and nitrogen dioxide (NO2) (a proxy for nitrogen oxides) tropospheric columns from Ultraviolet-Visible (UV-Vis) satellites has motivated many to use their ratios to gain some insights into the near-surface ozone sensitivity. Strong emphasis has been placed on the challenges that come with transforming what is being observed in the tropospheric column to what is actually in the planetary boundary layer (PBL) and near to the surface; however, little attention has been paid to other sources of error such as chemistry, spatial representation, and retrieval uncertainties. Here we leverage a wide spectrum of tools and data to carefully quantify those errors. Concerning the chemistry error, a well-characterized box model constrained by more than 500 hours of aircraft data from NASA’s air quality campaigns is used to simulate the ratio of the chemical loss of HO2+RO2 (LROx) to the chemical loss of NOx (LNOx). Subsequently, we challenge the predictive power of HCHO / NO2 ratios (FNRs), which are commonly applied in current research, at detecting the underlying ozone regimes by comparing them to LROx / LNOx. FNRs show a strongly linear (R²=0.94) relationship to LROx / LNOx in the log-log scale. Following the baseline (i.e., ln(LROx / LNOx) = -1.0±0.2) with the model and mechanism (CB06, r2) used for segregating NOx-sensitive from VOC-sensitive regimes, we observe a broad range of FNR thresholds ranging from 1 to 4. The transitioning ratios strictly follow a Gaussian distribution with a mean and standard deviation of 1.8 and 0.4, respectively. This implies that FNR has an inherent 20 % standard error (1-sigma) resulting from not being able to fully describe the ROx-HOx cycle. We calculate high ozone production rates (PO3) dominated by large HCHO×NO2 concentration levels, a new proxy for the abundance of ozone precursors. The relationship between PO3 and HCHO×NO2 becomes more pronounced when moving towards NOx-sensitive regions due to non-linear chemistry; our results indicate that there is fruitful information in the HCHO×NO2 metric that has not been utilized in ozone studies. The vast amount of vertical information on HCHO and NO2 concentration from the air quality campaigns enables us to parameterize the vertical shapes of FNRs using a second-order rational function permitting an analytical solution for an altitude adjustment factor to partition the tropospheric columns to the PBL region. We propose a mathematical solution to the spatial representation error based on modeling isotropic semivariograms. With respect to a high-resolution sensor like TROPOspheric Monitoring Instrument (TROPOMI) (>5.5×3.5 km²), Ozone Monitoring Instrument (OMI) loses 12 % of spatial information at its native resolution. A pixel with a grid size of 216 km² fails at capturing ~65 % of the spatial information in FNRs at a 50 km length scale comparable to the size of a large urban center (e.g., Los Angeles). We ultimately leverage a large suite of in-situ and ground-based remote sensing measurements to draw the error distributions of daily TROPOMI and OMI tropospheric NO2 and HCHO columns. At 68 % confidence interval (1 sigma) errors pertaining to daily TROPOMI observations, either HCHO or tropospheric NO2 columns should be above 1.2–1.5×1016 molec.cm-2 to attain 20–30 % standard error in the ratio. This level of error is almost non-achievable with OMI given its large error in HCHO. The satellite column retrieval error is the largest contributor to the total error (40–90 %) in the FNRs. Due to a stronger signal in cities, the total relative error (<50 %) tends to be mild, whereas areas with low vegetation and anthropogenic sources (e.g., Rocky Mountains) are markedly uncertain (>100 %). Our study suggests that continuing development in the retrieval algorithm and sensor design and calibration is essential to be able to advance the application of FNRs beyond a qualitative metric. The availability of formaldehyde (HCHO) (a proxy for volatile organic compound reactivity) and nitrogen dioxide (NO2) (a proxy for nitrogen oxides) tropospheric columns from Ultraviolet-Visible (UV-Vis) satellites has motivated many to use their ratios to gain some insights into the near-surface ozone sensitivity. Strong emphasis has been placed on the challenges that come with transforming what is being observed in the tropospheric column to what is actually in the planetary boundary layer (PBL) and near to the surface; however, little attention has been paid to other sources of error such as chemistry, spatial representation, and retrieval uncertainties. Here we leverage a wide spectrum of tools and data to carefully quantify those errors. Concerning the chemistry error, a well-characterized box model constrained by more than 500 hours of aircraft data from NASA’s air quality campaigns is used to simulate the ratio of the chemical loss of HO2+RO2 (LROx) to the chemical loss of NOx (LNOx). Subsequently, we challenge the predictive power of HCHO / NO2 ratios (FNRs), which are commonly applied in current research, at detecting the underlying ozone regimes by comparing them to LROx / LNOx. FNRs show a strongly linear (R²=0.94) relationship to LROx / LNOx in the log-log scale. Following the baseline (i.e., ln(LROx / LNOx) = -1.0±0.2) with the model and mechanism (CB06, r2) used for segregating NOx-sensitive from VOC-sensitive regimes, we observe a broad range of FNR thresholds ranging from 1 to 4. The transitioning ratios strictly follow a Gaussian distribution with a mean and standard deviation of 1.8 and 0.4, respectively. This implies that FNR has an inherent 20 % standard error (1-sigma) resulting from not being able to fully describe the ROx-HOx cycle. We calculate high ozone production rates (PO3) dominated by large HCHO×NO2 concentration levels, a new proxy for the abundance of ozone precursors. The relationship between PO3 and HCHO×NO2 becomes more pronounced when moving towards NOx-sensitive regions due to non-linear chemistry; our results indicate that there is fruitful information in the HCHO×NO2 metric that has not been utilized in ozone studies. The vast amount of vertical information on HCHO and NO2 concentration from the air quality campaigns enables us to parameterize the vertical shapes of FNRs using a second-order rational function permitting an analytical solution for an altitude adjustment factor to partition the tropospheric columns to the PBL region. We propose a mathematical solution to the spatial representation error based on modeling isotropic semivariograms. With respect to a high-resolution sensor like TROPOspheric Monitoring Instrument (TROPOMI) (>5.5×3.5 km²), Ozone Monitoring Instrument (OMI) loses 12 % of spatial information at its native resolution. A pixel with a grid size of 216 km² fails at capturing ~65 % of the spatial information in FNRs at a 50 km length scale comparable to the size of a large urban center (e.g., Los Angeles). We ultimately leverage a large suite of in-situ and ground-based remote sensing measurements to draw the error distributions of daily TROPOMI and OMI tropospheric NO2 and HCHO columns. At 68 % confidence interval (1 sigma) errors pertaining to daily TROPOMI observations, either HCHO or tropospheric NO2 columns should be above 1.2–1.5×1016 molec.cm-2 to attain 20–30 % standard error in the ratio. This level of error is almost non-achievable with OMI given its large error in HCHO. The satellite column retrieval error is the largest contributor to the total error (40–90 %) in the FNRs. Due to a stronger signal in cities, the total relative error (<50 %) tends to be mild, whereas areas with low vegetation and anthropogenic sources (e.g., Rocky Mountains) are markedly uncertain (>100 %). Our study suggests that continuing development in the retrieval algorithm and sensor design and calibration is essential to be able to advance the application of FNRs beyond a qualitative metric. [ABSTRACT FROM AUTHOR]

Peat fires in Southeast Asia are a major source of trace gases and particles to the regional-global atmosphere that influence atmospheric chemistry, climate, and air quality. During the November 2015 record-high Ocean Niño Index (ONI, 2.6) our mobile smoke sampling team made the first, or rare, field measurements of numerous trace gases, aerosol optical properties, and aerosol chemistry and mass emissions for fires burning only peat in the Indonesian province of Central Kalimantan (on the island of Borneo). The measurements used Fourier transform infrared spectroscopy (FTIR), whole air sampling (WAS), photoacoustic extinctiometers (PAX, 401 and 870 nm), and detailed off-line analyses of particulate matter (PM) collected on filters. In September–November 2019 we measured peat fire trace gas emissions again, using WAS only, under El Niño–Southern Oscillation (ENSO)-neutral conditions (ONI, 0.3) in more remote areas of Central Kalimantan and also the Indonesian provinces of Riau, Jambi, and South Sumatra, all on the island of Sumatra. The 2019 measurements significantly expanded the geographic range and climate conditions sampled. This paper presents the 2019 results and synthesizes them with the previous fieldwork to converge on more robust regional average emission factors (EFs; grams of compound per kilogram of biomass burned) for authentic peat fires. In addition, samples of peat imported from Indonesia were burned in US laboratories, and the EFs and optical properties were characterized in more detail than in the field by a larger suite of instrumentation. We use the improved knowledge of regional emissions based on the expanded field measurements to select the most representative lab data and compute a synthesized, more "chemically complete" set of EFs and aerosol optical properties for tropical peat fires. The modified combustion efficiency (MCE) values for the peat smoke sampled in 2019 were within the range of MCEs sampled in 2015, but with a lower average in 2019 (0.718±0.021 , range 0.687–0.736) than 2015 (0.772±0.035 , range 0.693–0.835). Averaging the new and older data together suggests an updated MCE for tropical peat fires of ∼0.76. Despite the difference in MCE, the study-average methane emission factors (EF CH 4) were remarkably similar across the 2 years probing different regions: 9.42±2.51 g kg -1 in 2019 and 9.51±4.74 g kg -1 in 2015. When parsing the 2019 samples by province, the EFs for non-methane organic gases (NMOGs) were about 3 times higher in South Sumatra and Central Kalimantan than in Jambi and Riau, but the overall 2019 study average was only ∼15 % higher than the 2015 study average. South Sumatra peat fires emitted higher amounts of carbonyl and dimethyl sulfide, suggesting a volcanic or marine influence or effects of agricultural chemicals. The lab and fieldwork taken together provide EFs for 230 trace gases including CO 2 (1544 g kg -1), CO (315 g kg -1), and CH 4 (9.8 g kg -1). These are significant adjustments to IPCC-recommended EFs, -9 %, +50 %, and -53 %, respectively. We also report EFs for numerous NMOGs, 46 N-containing compounds, and 14 sulfur- or halogen-containing species. The use of high-resolution mass spectrometry in the lab allowed measurement of 82 % more NMOG mass than in the field. Gravimetrically measured EF PM 2.5 in the field in 2015 (17.3±5.8 g kg -1) was ∼20 % lower than the average from lab studies (22.4±10.4 g kg -1), perhaps due to higher field temperatures. Taken together the lab and field data show that the single-scattering albedo (SSA) was largely independent of wavelength and MCE in the visible (∼0.998), but lower at low MCE at 401 and 405 nm with a value of 0.958 at the study-average MCE. The absorption Ångström exponent (AAE) at the average MCE was 5.7. By far the largest PM component was weakly absorbing insoluble organic carbon. [ABSTRACT FROM AUTHOR]

Bromine released from the decomposition of short-lived brominated source gases contributes as a sink of ozone in the lower stratosphere. The two major contributors are CH2Br2 and CHBr3. In this study, we investigate the global seasonal distribution of these two substances, based on four High Altitude and Long Range Research Aircraft (HALO) missions, the HIAPER Pole-to-Pole Observations (HIPPO) mission, and the Atmospheric Tomography (ATom) mission. Observations of CH2Br2 in the free and upper troposphere indicate a pronounced seasonality in both hemispheres, with slightly larger mixing ratios in the Northern Hemisphere (NH). Compared to CH2Br2, CHBr3 in these regions shows larger variability and less clear seasonality, presenting larger mixing ratios in winter and autumn in NH mid to high latitudes. A clear CH2Br2 maximum is observed in the NH during autumn with a less pronounced similar feature in the Southern Hemisphere (SH). This suggests that transport processes may be different in both hemispheric autumn seasons, which implies that the influx of tropospheric air ("flushing") into the NH lowermost stratosphere is more efficient than in the SH. However, the SH database is insufficient to quantify this difference. We further compare the observations to model estimates of TOMCAT and CAM-Chem, both using the same emission inventory. The pronounced tropospheric seasonality of CH2Br2 in the SH is not reproduced by the models, presumably due to erroneous seasonal emissions or atmospheric photochemical decomposition efficiencies. In contrast, model simulations of CHBr3 show a pronounced seasonality in both hemispheres, which are not confirmed by observations. The distributions of both species in the lowermost stratosphere of the Northern and Southern Hemispheres are overall well captured by the models with the exception of southern hemispheric autumn, where both models present a bias that maximizes in the lowest 40 K above the tropopause, with considerably lower mixing ratios in the observations. Thus, both models reproduce equivalent "flushing" in both hemispheres, which is not confirmed by the available observations. Our study emphasises the need for more extensive 20 observations in the SH to fully understand the impact of CH2Br2and CHBr3 on lowermost stratospheric ozone loss and to help constraining emissions. [ABSTRACT FROM AUTHOR]

High levels of fine particulate matter (PM2.5) pollution in East Asia often exceed local air quality standards. Observations from the Korea–United States Air Quality (KORUS-AQ) field campaign in May and June 2016 showed that development of extreme pollution (haze) occurred through a combination of long-range transport and favorable meteorological conditions that enhanced local production of PM2.5. Atmospheric models often have difficulty simulating PM2.5 chemical composition during haze, which is of concern for the development of successful control measures. We use observations from KORUS-AQ to examine the ability of the GEOS-Chem chemical transport model to simulate PM2.5 composition throughout the campaign and identify the mechanisms driving the pollution event. At the surface, the model underestimates sulfate by - 64 % but overestimates nitrate by + 36 %. The largest underestimate in sulfate occurs during the pollution event, for which models typically struggle to generate elevated sulfate concentrations due to missing heterogeneous chemistry in aerosol liquid water in the polluted boundary layer. Hourly surface observations show that the model nitrate bias is driven by an overestimation of the nighttime peak. In the model, nitrate formation is limited by the supply of nitric acid, which is biased by + 100 % against aircraft observations. We hypothesize that this is due to a large missing sink, which we implement here as a factor of 5 increase in dry deposition. We show that the resulting increased deposition velocity is consistent with observations of total nitrate as a function of photochemical age. The model does not account for factors such as the urban heat island effect or the heterogeneity of the built-up urban landscape, resulting in insufficient model turbulence and surface area over the study area that likely results in insufficient dry deposition. Other species such as NH3 could be similarly affected but were not measured during the campaign. Nighttime production of nitrate is driven by NO2 hydrolysis in the model, while observations show that unexpectedly elevated nighttime ozone (not present in the model) should result in N2O5 hydrolysis as the primary pathway. The model is unable to represent nighttime ozone due to an overly rapid collapse of the afternoon mixed layer and excessive titration by NO. We attribute this to missing nighttime heating driving deeper nocturnal mixing that would be expected to occur in a city like Seoul. This urban heating is not considered in air quality models run at large enough scales to treat both local chemistry and long-range transport. Key model failures in simulating nitrate, mainly overestimated daytime nitric acid, incorrect representation of nighttime chemistry, and an overly shallow and insufficiently turbulent nighttime mixed layer, exacerbate the model's inability to simulate the buildup of PM2.5 during haze pollution. To address the underestimate in sulfate most evident during the haze event, heterogeneous aerosol uptake of SO2 is added to the model, which previously only considered aqueous production of sulfate from SO2 in cloud water. Implementing a simple parameterization of this chemistry improves the model abundance of sulfate but degrades the SO2 simulation, implying that emissions are underestimated. We find that improving model simulations of sulfate has direct relevance to determining local vs. transboundary contributions to PM2.5. During the haze pollution event, the inclusion of heterogeneous aerosol uptake of SO2 decreases the fraction of PM2.5 attributable to long-range transport from 66 % to 54 %. Locally produced sulfate increased from 1 % to 25 % of locally produced PM2.5 , implying that local emissions controls could have a larger effect than previously thought. However, this additional uptake of SO2 is coupled to the model nitrate prediction, which affects the aerosol liquid water abundance and chemistry driving sulfate–nitrate–ammonium partitioning. An additional simulation of the haze pollution with heterogeneous uptake of SO2 to aerosol and simple improvements to the model nitrate simulation results in 30 % less sulfate due to 40 % less nitrate and aerosol water, and this results in an underestimate of sulfate during the haze event. Future studies need to better consider the impact of model physical processes such as dry deposition and nighttime boundary layer mixing on the simulation of nitrate and the effect of improved nitrate simulations on the overall simulation of secondary inorganic aerosol (sulfate + nitrate + ammonium) in East Asia. Foreign emissions are rapidly changing, increasing the need to understand the impact of local emissions on PM2.5 in South Korea to ensure continued air quality improvements. [ABSTRACT FROM AUTHOR]

Here we use satellite observations of formaldehyde (HCHO) vertical column densities (VCD) from the TROPOspheric Monitoring Instrument (TROPOMI), aircraft measurements, combined with a nested regional chemical transport model (GEOS-Chem at 0.5×0.625∘ resolution), to better understand the variability and sources of summertime HCHO in Alaska. We first evaluate GEOS-Chem with in-situ airborne measurements during the Atmospheric Tomography Mission 1 (ATom-1) aircraft campaign. We show reasonable agreement between observed and modeled HCHO, isoprene, monoterpenes and the sum of methyl vinyl ketone and methacrolein (MVK + MACR) in the continental boundary layer. In particular, HCHO profiles show spatial homogeneity in Alaska, suggesting a minor contribution of biogenic emissions to HCHO VCD. We further examine the TROPOMI HCHO product in Alaska in summer, reprocessed by GEOS-Chem model output for a priori profiles and shape factors. For years with low wildfire activity (e.g., 2018), we find that HCHO VCDs are largely dominated by background HCHO (58 %–71 %), with minor contributions from wildfires (20 %–32 %) and biogenic VOC emissions (8 %–10 %). For years with intense wildfires (e.g., 2019), summertime HCHO VCD is dominated by wildfire emissions (50 %–72 %), with minor contributions from background (22 %–41 %) and biogenic VOCs (6 %–10 %). In particular, the model indicates a major contribution of wildfires from direct emissions of HCHO, instead of secondary production of HCHO from oxidation of larger VOCs. We find that the column contributed by biogenic VOC is often small and below the TROPOMI detection limit, in part due to the slow HCHO production from isoprene oxidation under low NO x conditions. This work highlights challenges for quantifying HCHO and its precursors in remote pristine regions. [ABSTRACT FROM AUTHOR]

Large wildfires influence regional atmospheric composition, but chemical complexity challenges model predictions of downwind impacts. Here, we elucidate key connections within gas-phase photochemistry and assess novel chemical processes via a case study of the 2013 California Rim Fire plume. Airborne in situ observations, acquired during the NASA Studies of Emissions, Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC 4 RS) mission, illustrate the evolution of volatile organic compounds (VOCs), oxidants, and reactive nitrogen over 12 h of atmospheric aging. Measurements show rapid formation of ozone and peroxyacyl nitrates (PNs), sustained peroxide production, and prolonged enhancements in oxygenated VOCs and nitrogen oxides (NO x). Observations and Lagrangian trajectories constrain a 0-D puff model that approximates plume photochemical history and provides a framework for evaluating process interactions. Simulations examine the effects of (1) previously unmeasured reactive VOCs identified in recent laboratory studies and (2) emissions and secondary production of nitrous acid (HONO). Inclusion of estimated unmeasured VOCs leads to a 250 % increase in OH reactivity and a 70 % increase in radical production via oxygenated VOC photolysis. HONO amplifies radical cycling and serves as a downwind NO x source, although impacts depend on how HONO is introduced. The addition of initial HONO (representing primary emissions) or particulate nitrate photolysis amplifies ozone production, while heterogeneous conversion of NO 2 suppresses ozone formation. Analysis of radical initiation rates suggests that oxygenated VOC photolysis is a major radical source, exceeding HONO photolysis when averaged over the first 2 h of aging. Ozone production chemistry transitions from VOC sensitive to NO x sensitive within the first hour of plume aging, with both peroxide and organic nitrate formation contributing significantly to radical termination. To simulate smoke plume chemistry accurately, models should simultaneously account for the full reactive VOC pool and all relevant oxidant sources. [ABSTRACT FROM AUTHOR]

Glyoxal (CHOCHO), the simplest dicarbonyl in the troposphere, is a potential precursor for secondary organic aerosol (SOA) and brown carbon (BrC) affecting air quality and climate. The airborne measurement of CHOCHO concentrations during the KORUS-AQ (KORea–US Air Quality study) campaign in 2016 enables detailed quantification of loss mechanisms pertaining to SOA formation in the real atmosphere. The production of this molecule was mainly from oxidation of aromatics (59 %) initiated by hydroxyl radical (OH). CHOCHO loss to aerosol was found to be the most important removal path (69 %) and contributed to roughly ∼ 20 % (3.7 µ g sm -3 ppmv -1 h -1 , normalized with excess CO) of SOA growth in the first 6 h in Seoul Metropolitan Area. A reactive uptake coefficient (γ) of ∼ 0.008 best represents the loss of CHOCHO by surface uptake during the campaign. To our knowledge, we show the first field observation of aerosol surface-area-dependent (Asurf) CHOCHO uptake, which diverges from the simple surface uptake assumption as Asurf increases in ambient condition. Specifically, under the low (high) aerosol loading, the CHOCHO effective uptake rate coefficient, keff,uptake , linearly increases (levels off) with Asurf ; thus, the irreversible surface uptake is a reasonable (unreasonable) approximation for simulating CHOCHO loss to aerosol. Dependence on photochemical impact and changes in the chemical and physical aerosol properties "free water", as well as aerosol viscosity, are discussed as other possible factors influencing CHOCHO uptake rate. Our inferred Henry's law coefficient of CHOCHO, 7.0×108 M atm -1 , is ∼ 2 orders of magnitude higher than those estimated from salting-in effects constrained by inorganic salts only consistent with laboratory findings that show similar high partitioning into water-soluble organics, which urges more understanding on CHOCHO solubility under real atmospheric conditions. [ABSTRACT FROM AUTHOR]

Aerosol indirect radiative forcing (IRF), which characterizes how aerosols alter cloud formation and properties, is very sensitive to the preindustrial (PI) aerosol burden. Dimethyl sulfide (DMS), emitted from the ocean, is a dominant natural precursor of non-sea-salt sulfate in the PI and pristine present-day (PD) atmospheres. Here we revisit the atmospheric oxidation chemistry of DMS, particularly under pristine conditions, and its impact on aerosol IRF. Based on previous laboratory studies, we expand the simplified DMS oxidation scheme used in the Community Atmospheric Model version 6 with chemistry (CAM6-chem) to capture the OH-addition pathway and the H-abstraction pathway and the associated isomerization branch. These additional oxidation channels of DMS produce several stable intermediate compounds, e.g., methanesulfonic acid (MSA) and hydroperoxymethyl thioformate (HPMTF), delay the formation of sulfate, and, hence, alter the spatial distribution of sulfate aerosol and radiative impacts. The expanded scheme improves the agreement between modeled and observed concentrations of DMS, MSA, HPMTF, and sulfate over most marine regions, based on the NASA Atmospheric Tomography (ATom), the Aerosol and Cloud Experiments in the Eastern North Atlantic (ACE-ENA), and the Variability of the American Monsoon Systems (VAMOS) Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-REx) measurements. We find that the global HPMTF burden and the burden of sulfate produced from DMS oxidation are relatively insensitive to the assumed isomerization rate, but the burden of HPMTF is very sensitive to a potential additional cloud loss. We find that global sulfate burden under PI and PD emissions increase to 412 Gg S (+ 29 %) and 582 Gg S (+ 8.8 %), respectively, compared to the standard simplified DMS oxidation scheme. The resulting annual mean global PD direct radiative effect of DMS-derived sulfate alone is - 0.11 W m -2. The enhanced PI sulfate produced via the gas-phase chemistry updates alone dampens the aerosol IRF as anticipated (- 2.2 W m -2 in standard versus - 1.7 W m -2 , with updated gas-phase chemistry). However, high clouds in the tropics and low clouds in the Southern Ocean appear particularly sensitive to the additional aqueous-phase pathways, counteracting this change (- 2.3 W m -2). This study confirms the sensitivity of aerosol IRF to the PI aerosol loading and the need to better understand the processes controlling aerosol formation in the PI atmosphere and the cloud response to these changes. [ABSTRACT FROM AUTHOR]

High levels of fine particulate matter (PM2.5) pollution in East Asia often exceed local air quality standards. Observations from the Korea United States-Air Quality (KORUS-AQ) field campaign in May and June 2016 showed that development of extreme pollution (haze) occurred through a combination of long-range transport and favorable meteorological conditions that enhanced local production of PM2.5. Atmospheric models often have difficulty simulating PM2.5 chemical composition during haze, which is of concern for the development of successful control measures. We use observations from KORUS-AQ to examine the ability of the GEOS-Chem chemical transport model to simulate PM2.5 composition throughout the campaign and identify the mechanisms driving the pollution event. In the surface level, the model underestimates campaign average sulfate aerosol by -64% but overestimates nitrate aerosol by 36%. The largest underestimate in sulfate occurs during the pollution event in conditions of high relative humidity, where models typically struggle to generate the high concentrations due to missing heterogeneous chemistry in aerosol liquid water in the polluted boundary layer. Hourly surface observations show that the model nitrate bias is driven by an overestimation of the nighttime peak. In the model, nitrate formation is limited by the supply of nitric acid, which is biased by +100% against aircraft observations. We hypothesize that this is due to a missing sink, which we implement here as a factor of five increase in dry deposition. We show that the resulting increased deposition velocity is consistent with observations of total nitrate as a function of photochemical age. The model does not account for factors such as the urban heat island effect or the heterogeneity of the built-up urban landscape resulting in insufficient model turbulence and surface area over the study area that likely results in insufficient dry deposition. Other species such as NH3 could be similarly affected but were not measured during the campaign. Nighttime production of nitrate is driven by NO2 hydrolysis in the model, while observations show that unexpectedly elevated nighttime ozone (not present in the model) should result in N2O5 hydrolysis as the primary pathway. The model is unable to represent nighttime ozone due to an overly rapid collapse of the afternoon mixed layer and excessive titration by NO. We attribute this to missing nighttime heating driving deeper nocturnal mixing that would be expected to occur in a city like Seoul. This urban heating is not considered in air quality models run at large enough scales to treat both local chemistry and long-range transport. Key model failures in simulating nitrate, mainly overestimated daytime nitric acid, incorrect representation of nighttime chemistry, and an overly shallow and insufficiently turbulent nighttime mixed layer, exacerbate the model's inability to simulate the buildup of PM2.5 during haze pollution. To address the underestimate in sulfate most evident during the haze event, heterogeneous aerosol uptake of SO2 is added to the model which previously only considered aqueous production of sulfate from SO2 in cloud water. Implementing a simple parameterization of this chemistry improves the model abundance of sulfate but degrades the SO2 simulation implying that emissions are underestimated. We find that improving model simulations of sulfate has direct relevance to determining local vs. transboundary contributions to PM2.5. During the haze pollution event, the inclusion of heterogeneous aerosol uptake of SO2 decreases the fraction of PM2.5 attributable to long-range transport from 66% to 54%. Locally-produced sulfate increased from 1% to 46% of locally-produced PM2.5, implying that local emissions controls would have a larger effect than previously thought. However, this additional uptake of SO2 is coupled to the model nitrate prediction which affects the aerosol liquid water abundance and chemistry driving sulfate-nitrate-ammonium partitioning. An additional simulation of the haze pollution with heterogeneous uptake of SO2 to aerosol and simple improvements to the model nitrate simulation results in 30% less sulfate due to 40% less nitrate and aerosol water, and results in an underestimate of sulfate during the haze event. Future studies need to better consider the impact of model physical processes such as dry deposition and boundary layer mixing on the simulation of nitrate and the effect of improved nitrate simulations on the overall simulation of secondary inorganic aerosol (sulfate+nitrate+ammonium) in East Asia. Foreign emissions are rapidly changing, increasing the need to understand the impact of local emissions on PM2.5 in South Korea to ensure continued air quality improvements. [ABSTRACT FROM AUTHOR]

In this study, we present a novel approach for assessing nearshore seepage atmospheric emissions through modeling of air quality station data, specifically a Gaussian plume inversion model. A total of 3 decades of air quality station meteorology and total hydrocarbon concentration, THC, data were analyzed to study emissions from the Coal Oil Point marine seep field offshore California. THC in the seep field directions was significantly elevated and Gaussian with respect to wind direction, θ. An inversion model of the seep field, θ -resolved anomaly, THC ′ (θ) -derived atmospheric emissions is given. The model inversion is for the far field, which was satisfied by gridding the sonar seepage and treating each grid cell as a separate Gaussian plume. This assumption was validated by offshore in situ data that showed major seep area plumes were Gaussian. Plume total carbon, TC (TC = THC + carbon dioxide, CO 2 , + carbon monoxide), 18 % was CO 2 and 82 % was THC; 85 % of THC was CH 4. These compositions were similar to the seabed composition, demonstrating efficient vertical plume transport of dissolved seep gases. Air samples also measured atmospheric alkane plume composition. The inversion model used observed winds and derived the 3-decade-average (1990–2021) field-wide atmospheric emissions of 83 400 ± 12 000 m 3 THC d -1 (27 Gg THC yr -1 based on 19.6 g mol -1 for THC). Based on a 50 : 50 air-to-seawater partitioning, this implies seabed emissions of 167 000 m 3 THC d -1. Based on atmospheric plume composition, C 1 –C 6 alkane emissions were 19, 1.3, 2.5, 2.2, 1.1, and 0.15 Gg yr -1 , respectively. The spatially averaged CH 4 emissions over the ∼ 6.3 km 2 of 25 × 25 m 2 bins with sonar values above noise were 5.7 µ M m -2 s -1. The approach can be extended to derive emissions from other dispersed sources such as landfills, industrial sites, or terrestrial seepage if source locations are constrained spatially. [ABSTRACT FROM AUTHOR]

Large wildfires markedly alter regional atmospheric composition, but chemical complexity challenges model predictions of downwind impacts. Here, we elucidate key facets of gas-phase photochemistry and assess novel chemical processes via a case study of the 2013 California Rim Fire plume. Airborne in situ observations, acquired during the NASA Studies of Emissions, Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) mission, illustrate the evolution of volatile organic compounds (VOC), oxidants, and reactive nitrogen over 12 hours of atmospheric aging. Measurements show rapid formation of ozone and peroxyacyl nitrates (PNs), sustained peroxide production, and prolonged enhancements in oxygenated VOC and nitrogen oxides (NO[sub x]). Measurements and Lagrangian trajectories constrain a 0-D puff model that approximates plume photochemical history and provides a framework for evaluating key processes. Simulations examine the effects of 1) previously -unmeasured reactive VOC identified in recent laboratory studies, and 2) emissions and secondary production of nitrous acid (HONO). Inclusion of estimated unmeasured VOC leads to a 250% increase in OH reactivity and a 70% increase in radical production via oxygenated VOC photolysis. HONO amplifies radical cycling and serves as a downwind NO[sub x] source, although two different HONO production mechanisms (particulate nitrate photolysis and heterogeneous NO[sub 2] conversion) exhibit markedly different effects on ozone, NO[sub x], and PNs. Analysis of radical initiation rates suggests that oxygenated VOC photolysis is a major radical source, exceeding HONO photolysis when averaged over the first 2 hours of aging. Ozone production chemistry transitions from VOC-sensitive to NO[sub x]-sensitive within the first hour of plume aging, with both peroxide and organic nitrate formation contributing significantly to radical termination. To simulate smoke plume chemistry accurately, models should simultaneously account for the full reactive VOC pool and all relevant oxidant sources. [ABSTRACT FROM AUTHOR]

Here we use satellite observations of HCHO vertical column densities (VCD) from the TROPOspheric Monitoring Instrument (TROPOMI), ground-based and aircraft measurements, combined with a nested regional chemical transport model (GEOS-Chem at 0.5°×0.625° resolution), to understand the variability and sources of summertime HCHO better in Alaska. We first evaluate GEOSChem with in-situ airborne measurements during Atmospheric Tomography Mission 1 (ATom-1) aircraft campaign and ground-based measurements from Multi-AXis Differential Optical Absorption Spectroscopy (MAX-DOAS). We show reasonable agreement between observed and modeled HCHO, isoprene and monoterpenes. In particular, HCHO profiles show spatial homogeneity in Alaska, suggesting a minor contribution of biogenic emissions to HCHO VCD. We further examine the TROPOMI HCHO product in Alaska during boreal summer, which is in good agreement with GEOSChem model results. We find that HCHO VCDs are dominated by free-tropospheric background in wildfire-free regions. During the summer of 2018, the model suggests that the background HCHO column, resulting from methane oxidation, contributes to 66 to 80% of the HCHO VCD, while wildfires contribute to 14% and biogenic VOC contributes to 5 to 9% respectively. For the summer of 2019, which had intense wildfires, the model suggests that wildfires contribute to 40 to 65%, and the background column accounts for 30 to 50% of HCHO VCD in June and July. In particular, the model indicates a major contribution of wildfires from direct emissions of HCHO, instead of secondary production of HCHO from oxidation of larger VOCs. We find that the column contributed by biogenic VOC is often small and below the TROPOMI detection limit. The source and variability of HCHO VCD above Alaska during summer is mainly driven by background methane oxidation and wildfires. This work discusses challenges for quantifying HCHO and its precursors in remote pristine regions. [ABSTRACT FROM AUTHOR]

Aerosol indirect radiative forcing (IRF), which characterizes how aerosols alter cloud formation and properties, is very sensitive to the preindustrial (PI) aerosol burden. Dimethyl sulfide (DMS), emitted from the ocean, is a dominant natural precursor of non-sea-salt sulfate in the PI and pristine present-day (PD) atmospheres. Here we revisit the atmospheric oxidation chemistry of DMS, particularly under pristine conditions, and its impact on aerosol IRF. Based on previous laboratory studies, we expand the simplified DMS oxidation scheme used in the Community Atmospheric Model version 6 with chemistry (CAM6-chem) to capture the OH-addition pathway as well as the H-abstraction pathway and the associated isomerization branch. These additional oxidation channels of DMS produce several stable intermediate compounds, e.g., methanesulfonic acid (MSA) and hydroperoxymethyl thioformate (HPMTF), delay the formation of sulfate, and hence, alter the spatial distribution of sulfate aerosol and radiative impacts. The expanded scheme improves the agreement between modeled and observed concentrations of DMS, MSA, HPMTF, and sulfate over most marine regions based on the NASA Atmospheric Tomography (ATom), the Aerosol and Cloud Experiments in the Eastern North Atlantic (ACE-ENA), and the VAMOS Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-REx) measurements. We find that the global HPMTF burden, as well as the burden of sulfate produced from DMS oxidation are relatively insensitive to the assumed isomerization rate, but the burden of HPMTF is very sensitive to a potential additional cloud loss. We find that global sulfate burden under PI and PD emissions increase to 412 Gg-S (+29%) and 582 Gg-S (+8.8%), respectively, compared to the standard simplified DMS oxidation scheme. The resulting annual mean global PD direct radiative effect of DMS-derived sulfate alone is -0.11 W m-2. The enhanced PI sulfate produced via the gas-phase chemistry updates alone dampens the aerosol IRF as anticipated (-2.2 W m-2 in standard versus -1.7 W m-2 with updated gas-phase chemistry). However, high clouds in the tropics and low clouds in the Southern Ocean appear particularly sensitive to the additional aqueous-phase pathways, counteracting this change (-2.3 W m-2). This study confirms the sensitivity of aerosol IRF to the PI aerosol loading, as well as the need to better understand the processes controlling aerosol formation in the PI atmosphere and the cloud response to these changes. [ABSTRACT FROM AUTHOR]

Glyoxal (CHOCHO), the simplest dicarbonyl in the troposphere, is an important precursor for secondary organic aerosol (SOA) and brown carbon (BrC) affecting air-quality and climate. The airborne measurement of CHOCHO concentrations during the KORUS-AQ (KORea-US Air Quality study) campaign in 2016 enables detailed quantification of loss mechanisms, pertaining to SOA formation in the real atmosphere. The production of this molecule was mainly from oxidation of aromatics (59%) initiated by hydroxyl radical (OH), of which glyoxal forming mechanisms are relatively well constrained. CHOCHO loss to aerosol was found to be the most important removal path (69 %) and contributed to roughly ~20 % (3.7 μg sm-3 ppmv-1 hr-1, normalized with excess CO) of SOA growth in the first 6 hours in Seoul Metropolitan Area. To our knowledge, we show the first field observation of aerosol surface-area (4smf)-dependent CHOCHO uptake, which diverges from the simple surface uptake assumption as ^surf increases in ambient condition. Specifically, under the low (high) aerosol loading, the CHOCHO effective uptake rate coefficient, ^uptake, linearly increases (levels off) with ^uf thus, the irreversible surface uptake is a reasonable (unreasonable) approximation for simulating CHOCHO loss to aerosol. [ABSTRACT FROM AUTHOR]

Anthropogenic secondary organic aerosol (ASOA), formed from anthropogenic emissions of organic compounds, constitutes a substantial fraction of the mass of submicron aerosol in populated areas around the world and contributes to poor air quality and premature mortality. However, the precursor sources of ASOA are poorly understood, and there are large uncertainties in the health benefits that might accrue from reducing anthropogenic organic emissions. We show that the production of ASOA in 11 urban areas on three continents is strongly correlated with the reactivity of specific anthropogenic volatile organic compounds. The differences in ASOA production across different cities can be explained by differences in the emissions of aromatics and intermediate- and semi-volatile organic compounds, indicating the importance of controlling these ASOA precursors. With an improved model representation of ASOA driven by the observations, we attribute 340 000 PM 2.5 -related premature deaths per year to ASOA, which is over an order of magnitude higher than prior studies. A sensitivity case with a more recently proposed model for attributing mortality to PM 2.5 (the Global Exposure Mortality Model) results in up to 900 000 deaths. A limitation of this study is the extrapolation from cities with detailed studies and regions where detailed emission inventories are available to other regions where uncertainties in emissions are larger. In addition to further development of institutional air quality management infrastructure, comprehensive air quality campaigns in the countries in South and Central America, Africa, South Asia, and the Middle East are needed for further progress in this area. [ABSTRACT FROM AUTHOR]

The details of aerosol processes and size distributions in the stratosphere are important for both heterogeneous chemistry and aerosol–radiation interactions. Using in situ, global-scale measurements of the size distribution of particles with diameters > 3 nm from the NASA Atmospheric Tomography Mission (ATom), we identify a mode of aerosol smaller than 12 nm in the lowermost stratosphere (LMS) at mid- and high latitudes. This mode is substantial only in the Northern Hemisphere (NH) and was observed in all four seasons. We also observe elevated SO 2 , an important precursor for new particle formation (NPF) and growth, in the NH LMS. We use box modelling and thermodynamic calculations to show that NPF can occur in the LMS conditions observed on ATom. Aircraft emissions are shown as likely sources of this SO 2 , as well as a potential source of nucleation mode particles directly emitted by or formed in the plume of the engines. These nucleation mode particles have the potential to grow to larger sizes and to coagulate with larger aerosol, affecting heterogeneous chemistry and aerosol–radiation interactions. Understanding all sources and characteristics of stratospheric aerosols is important in the context of anthropogenic climate change as well as proposals for climate intervention via stratospheric sulfur injection. This analysis not only adds to the, currently sparse, observations of the global impact of aviation, but also introduces another aspect of climate influence, namely a size distribution shift of the background aerosol distribution in the LMS. [ABSTRACT FROM AUTHOR]

The details of aerosol processes and size distributions in the stratosphere are important for both heterogeneous chemistry and aerosol-radiation interactions. Using in-situ, global-scale measurements of the size distribution of particles with diameters >3 nm from the NASA Atmospheric Tomography Mission (ATom), we identify a mode of ultrafine aerosol in the lowermost stratosphere (LMS) at mid and high latitudes. This mode is substantial only in the northern hemisphere (NH), and was observed in all four seasons. We also observe elevated SO2, an important precursor for new particle formation (NPF) and growth, in the NH LMS. We use box modelling and thermodynamic calculations to show that NPF can occur in the LMS conditions observed on ATom. Aircraft emissions are shown as likely sources of this SO2, as well as a potential source of ultrafine particles directly emitted by, or formed in the plume of the engines. These ultra-fine particles have the potential to grow to larger sizes, and to coagulate with larger aerosol, affecting heterogeneous chemistry and aerosol-radiation interactions. Understanding all sources and characteristics of stratospheric aerosol is important in the context of anthropogenic climate change as well as proposals for climate intervention via stratospheric sulphur injection. This analysis not only adds to the, currently sparse, observations of the global impact of aviation, but also introduces another aspect of climate influence, namely a size distribution shift of the background aerosol distribution in the LMS. [ABSTRACT FROM AUTHOR]

Global coupled chemistry–climate models underestimate carbon monoxide (CO) in the Northern Hemisphere, exhibiting a pervasive negative bias against measurements peaking in late winter and early spring. While this bias has been commonly attributed to underestimation of direct anthropogenic and biomass burning emissions, chemical production and loss via OH reaction from emissions of anthropogenic and biogenic volatile organic compounds (VOCs) play an important role. Here we investigate the reasons for this underestimation using aircraft measurements taken in May and June 2016 from the Korea–United States Air Quality (KORUS-AQ) experiment in South Korea and the Air Chemistry Research in Asia (ARIAs) in the North China Plain (NCP). For reference, multispectral CO retrievals (V8J) from the Measurements of Pollution in the Troposphere (MOPITT) are jointly assimilated with meteorological observations using an ensemble adjustment Kalman filter (EAKF) within the global Community Atmosphere Model with Chemistry (CAM-Chem) and the Data Assimilation Research Testbed (DART). With regard to KORUS-AQ data, CO is underestimated by 42 % in the control run and by 12 % with the MOPITT assimilation run. The inversion suggests an underestimation of anthropogenic CO sources in many regions, by up to 80 % for northern China, with large increments over the Liaoning Province and the North China Plain (NCP). Yet, an often-overlooked aspect of these inversions is that correcting the underestimation in anthropogenic CO emissions also improves the comparison with observational O 3 datasets and observationally constrained box model simulations of OH and HO 2. Running a CAM-Chem simulation with the updated emissions of anthropogenic CO reduces the bias by 29 % for CO, 18 % for ozone, 11 % for HO 2 , and 27 % for OH. Longer-lived anthropogenic VOCs whose model errors are correlated with CO are also improved, while short-lived VOCs, including formaldehyde, are difficult to constrain solely by assimilating satellite retrievals of CO. During an anticyclonic episode, better simulation of O 3 , with an average underestimation of 5.5 ppbv, and a reduction in the bias of surface formaldehyde and oxygenated VOCs can be achieved by separately increasing by a factor of 2 the modeled biogenic emissions for the plant functional types found in Korea. Results also suggest that controlling VOC and CO emissions, in addition to widespread NO x controls, can improve ozone pollution over East Asia. [ABSTRACT FROM AUTHOR]

Anthropogenic secondary organic aerosol (ASOA), formed from anthropogenic emissions of organic compounds, constitutes a substantial fraction of the mass of submicron aerosol in populated areas around the world and contributes to poor air quality and premature mortality. However, the precursor sources of ASOA are poorly understood, and there are large uncertainties in the health benefits that might accrue from reducing anthropogenic organic emissions. We show that the production of ASOA in 11 urban areas on three continents is strongly correlated with the anthropogenic reactivity of specific volatile organic compounds. The differences in ASOA production across different cities can be explained by differences in the emissions of aromatics and intermediate-and semi-volatile organic compounds, indicating the importance of controlling these ASOA precursors. With an improved modeling representation of ASOA driven by the observations, we attribute 340,000 PM2.5 premature deaths per year to ASOA, which is over an order of magnitude higher than prior studies. A sensitivity case with a more recently proposed model for attributing mortality to PM2.5 (the Global Exposure Mortality Model) results up to 900,000 deaths. A limitation of this study is the extrapolation from regions with detailed data to others where data is not available. Comprehensive air quality campaigns in the countries in South and Central America, Africa, South Asia, and the Middle East are needed for further progress in this area. [ABSTRACT FROM AUTHOR]

The absence of up-to-date emissions has been a major impediment to accurately simulating aspects of atmospheric chemistry and to precisely quantifying the impact of changes in emissions on air pollution. Hence, a nonlinear joint analytical inversion (Gauss–Newton method) of both volatile organic compounds (VOCs) and nitrogen oxide (NOx) emissions is made by exploiting the Smithsonian Astrophysical Observatory (SAO) Ozone Mapping and Profiler Suite Nadir Mapper (OMPS-NM) formaldehyde (HCHO) and the National Aeronautics and Space Administration (NASA) Ozone Monitoring Instrument (OMI) tropospheric nitrogen dioxide (NO2) columns during the Korea–United States Air Quality (KORUS-AQ) campaign over East Asia in May–June 2016. Effects of the chemical feedback of NOx and VOCs on both NO2 and HCHO are implicitly included by iteratively optimizing the inversion. Emission uncertainties are greatly narrowed (averaging kernels >0.8 , which is the mathematical presentation of the partition of information gained from the satellite observations with respect to the prior knowledge) over medium- to high-emitting areas such as cities and dense vegetation. The prior amount of total NOx emissions is mainly dictated by values reported in the MIX-Asia 2010 inventory. After the inversion we conclude that there is a decline in emissions (before, after, change) for China (87.94±44.09 Gg d -1 , 68.00±15.94 Gg d -1 , -23 %), North China Plain (NCP) (27.96±13.49 Gg d -1 , 19.05±2.50 Gg d -1 , -32 %), Pearl River Delta (PRD) (4.23±1.78 Gg d -1 , 2.70±0.32 Gg d -1 , -36 %), Yangtze River Delta (YRD) (9.84±4.68 Gg d -1 , 5.77±0.51 Gg d -1 , -41 %), Taiwan (1.26±0.57 Gg d -1 , 0.97±0.33 Gg d -1 , -23 %), and Malaysia (2.89±2.77 Gg d -1 , 2.25±1.34 Gg d -1 , -22 %), all of which have effectively implemented various stringent regulations. In contrast, South Korea (2.71±1.34 Gg d -1 , 2.95±0.58 Gg d -1 , + 9 %) and Japan (3.53±1.71 Gg d -1 , 3.96±1.04 Gg d -1 , +12 %) are experiencing an increase in NOx emissions, potentially due to an increased number of diesel vehicles and new thermal power plants. We revisit the well-documented positive bias (by a factor of 2 to 3) of MEGAN v2.1 (Model of Emissions of Gases and Aerosols from Nature) in terms of biogenic VOC emissions in the tropics. The inversion, however, suggests a larger growth of VOCs (mainly anthropogenic) over NCP (25 %) than previously reported (6 %) relative to 2010. The spatial variation in both the magnitude and sign of NOx and VOC emissions results in nonlinear responses of ozone production and loss. Due to a simultaneous decrease and increase in NOx/VOC over NCP and YRD, we observe a ∼53 % reduction in the ratio of the chemical loss of NOx (LNOx) to the chemical loss of ROx (RO2+HO2) over the surface transitioning toward NOx -sensitive regimes, which in turn reduces and increases the afternoon chemical loss and production of ozone through NO2+OH (-0.42 ppbv h -1) /HO2 (and RO2) +NO (+0.31 ppbv h -1). Conversely, a combined decrease in NOx and VOC emissions in Taiwan, Malaysia, and southern China suppresses the formation of ozone. Simulations using the updated emissions indicate increases in maximum daily 8 h average (MDA8) surface ozone over China (0.62 ppbv), NCP (4.56 ppbv), and YRD (5.25 ppbv), suggesting that emission control strategies on VOCs should be prioritized to curb ozone production rates in these regions. Taiwan, Malaysia, and PRD stand out as regions undergoing lower MDA8 ozone levels resulting from the NOx reductions occurring predominantly in NOx -sensitive regimes. [ABSTRACT FROM AUTHOR]

The global oxidation capacity, defined as the tropospheric mean concentration of the hydroxyl radical (OH), controls the lifetime of reactive trace gases in the atmosphere such as methane and carbon monoxide (CO). Models tend to underestimate the methane lifetime and CO concentrations throughout the troposphere, which is consistent with excessive OH. Approximately half of the oxidation of methane and non-methane volatile organic compounds (VOCs) is thought to occur over the oceans where oxidant chemistry has received little validation due to a lack of observational constraints. We use observations from the first two deployments of the NASA ATom aircraft campaign during July–August 2016 and January–February 2017 to evaluate the oxidation capacity over the remote oceans and its representation by the GEOS-Chem chemical transport model. The model successfully simulates the magnitude and vertical profile of remote OH within the measurement uncertainties. Comparisons against the drivers of OH production (water vapor, ozone, and NOy concentrations, ozone photolysis frequencies) also show minimal bias, with the exception of wintertime NOy. The severe model overestimate of NOy during this period may indicate insufficient wet scavenging and/or missing loss on sea-salt aerosols. Large uncertainties in these processes require further study to improve simulated NOy partitioning and removal in the troposphere, but preliminary tests suggest that their overall impact could marginally reduce the model bias in tropospheric OH. During the ATom-1 deployment, OH reactivity (OHR) below 3 km is significantly enhanced, and this is not captured by the sum of its measured components (cOHR obs) or by the model (cOHR mod). This enhancement could suggest missing reactive VOCs but cannot be explained by a comprehensive simulation of both biotic and abiotic ocean sources of VOCs. Additional sources of VOC reactivity in this region are difficult to reconcile with the full suite of ATom measurement constraints. The model generally reproduces the magnitude and seasonality of cOHR obs but underestimates the contribution of oxygenated VOCs, mainly acetaldehyde, which is severely underestimated throughout the troposphere despite its calculated lifetime of less than a day. Missing model acetaldehyde in previous studies was attributed to measurement uncertainties that have been largely resolved. Observations of peroxyacetic acid (PAA) provide new support for remote levels of acetaldehyde. The underestimate in both model acetaldehyde and PAA is present throughout the year in both hemispheres and peaks during Northern Hemisphere summer. The addition of ocean sources of VOCs in the model increases cOHR mod by 3 % to 9 % and improves model–measurement agreement for acetaldehyde, particularly in winter, but cannot resolve the model summertime bias. Doing so would require 100 Tg yr -1 of a long-lived unknown precursor throughout the year with significant additional emissions in the Northern Hemisphere summer. Improving the model bias for remote acetaldehyde and PAA is unlikely to fully resolve previously reported model global biases in OH and methane lifetime, suggesting that future work should examine the sources and sinks of OH over land. [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]

The absence of up-to-date emissions has been a major impediment to accurately simulate aspects of atmospheric chemistry, and to precisely quantify the impact of changes of emissions on air pollution. Hence, a non-linear joint analytical inversion (Gauss-Newton method) of both volatile organic compounds (VOC) and nitrogen oxides (NOx) emissions is made by exploiting the Smithsonian Astrophysical Observatory (SAO) Ozone Mapping and Profile Suite Nadir Mapper (OMPS-NM) formaldehyde (HCHO) and the National Aeronautics and Space Administration (NASA) Ozone Monitoring Instrument (OMI) tropospheric nitrogen dioxide (NO2) retrievals during the Korea-United States Air Quality (KORUS-AQ) campaign over East Asia in May-June 2016. Effects of the chemical feedback of NOx and VOCs on both NO2 and HCHO are implicitly included through iteratively optimizing the inversion. Emissions estimates are greatly improved (averaging kernels > 0.8) over medium- to high-emitting areas such as cities and dense vegetation. The amount of total NOx emissions is mainly dictated by values reported in the MIX-Asia 2010 inventory. After the inversion we conclude a decline in the emissions (before, after, change) for China (87.94 ± 44.09 Gg/day, 68.00 ± 15.94 Gg/day, -23 %), North China Plain (NCP) (27.96 ± 13.49 Gg/day, 19.05 ± 2.50 Gg/day, -32 %), Pearl River Delta (PRD) (4.23 ± 1.78 Gg/day, 2.70 ± 0.32 Gg/day, -36 %), Yangtze River Delta (YRD) (9.84 ± 4.68 Gg/day, 5.77 ± 0.51 Gg/day, -41 %), Taiwan (1.26 ± 0.57 Gg/day, 0.97 ± 0.33 Gg/day, -23 %), and Malaysia (2.89 ± 2.77 Gg/day, 2.25 ± 1.34 Gg/day, -22 %), all of which have effectively implemented various stringent regulations. In contrast, South Korea (2.71 ± 1.34 Gg/day, 2.95 ± 0.58 Gg/day, +9 %) and Japan (3.53 ± 1.71 Gg/day, 3.96 ± 1.04 Gg/day, +12 %) experience an increase in NOx emissions potentially due to risen number of diesel vehicles and new thermal power plants. We revisit the well-documented positive bias of the model in terms of biogenic VOC emissions in the tropics. The inversion, however, suggests a larger growth of VOC (mainly anthropogenic) over NCP (25 %) than previously reported (6 %) relative to 2010. The spatial variation in both magnitude and sign of NOx and VOC emissions results in non-linear responses of ozone production/loss. Due to simultaneous decrease/increase of NOx/VOC over NCP and YRD, we observe an ~ 53 % reduction in the ratio of the chemical loss of NOx (LNOx) to the chemical loss of ROx (RO2 + HO2) transitioning toward NOx-sensitive regimes, which in turn, reduces/increases the afternoon chemical loss/production of ozone through NO2 + OH (-0.42 ppbv hr-1)/HO2 (and RO2) + NO (+0.31 ppbv hr-1). Conversely, a combined decrease in NOx and VOC emissions in Taiwan, Malaysia, and the southern China suppresses the formation of ozone. Ultimately, model simulations indicate enhancements of maximum daily 8-hour average (MDA8) surface ozone over China (0.62 ppbv), NCP (4.56 ppbv), and YRD (5.25 ppbv) due to the non-linear ozone chemistry, suggesting that emissions standards should be extended to regulate VOCs to be able to curb ozone production rates. Taiwan, Malaysia, and PRD stand out as the regions undergoing lower MDA8 ozone levels resulting from the NOx reductions occurring predominantly in NOx-sensitive regimes. [ABSTRACT FROM AUTHOR]

The hydroxyl radical (OH) reacts with thousands of chemical species in the atmosphere, initiating their removal and the chemical reaction sequences that produce ozone, secondary aerosols, and gas-phase acids. OH reactivity, which is the inverse of OH lifetime, influences the OH abundance and the ability of OH to cleanse the atmosphere. The NASA Atmospheric Tomography (ATom) campaign used instruments on the NASA DC-8 aircraft to measure OH reactivity and more than 100 trace chemical species. ATom presented a unique opportunity to test the completeness of the OH reactivity calculated from the chemical species measurements by comparing it to the measured OH reactivity over two oceans across four seasons. Although the calculated OH reactivity was below the limit of detection for the ATom instrument used to measure OH reactivity throughout much of the free troposphere, the instrument was able to measure the OH reactivity in and just above the marine boundary layer. The mean measured value of OH reactivity in the marine boundary layer across all latitudes and all ATom deployments was 1.9 s -1 , which is 0.5 s -1 larger than the mean calculated OH reactivity. The missing OH reactivity, the difference between the measured and calculated OH reactivity, varied between 0 and 3.5 s -1 , with the highest values over the Northern Hemisphere Pacific Ocean. Correlations of missing OH reactivity with formaldehyde, dimethyl sulfide, butanal, and sea surface temperature suggest the presence of unmeasured or unknown volatile organic compounds or oxygenated volatile organic compounds associated with ocean emissions. [ABSTRACT FROM AUTHOR]

Ozone is a greenhouse gas and air pollutant that is harmful to human health and plants. During the summer in the southeastern US, many regional and global models are biased high for surface ozone compared to observations. Past studies have suggested different solutions including the need for updates to model representation of clouds, chemistry, ozone deposition, and emissions of nitrogen oxides (NOx) or biogenic hydrocarbons. Here, due to the high biogenic emissions in the southeastern US, more comprehensive and updated isoprene and terpene chemistry is added into CESM/CAM-chem (Community Earth System Model/Community Atmosphere Model with full chemistry) to evaluate the impact of chemistry on simulated ozone. Comparisons of the model results with data collected during the Studies of Emissions Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC 4 RS) field campaign and from the US EPA (Environmental Protection Agency) CASTNET (Clean Air Status and Trends Network) monitoring stations confirm the updated chemistry improves simulated surface ozone, ozone precursors, and NOx reservoir compounds. The isoprene and terpene chemistry updates reduce the bias in the daily maximum 8 h average (MDA8) surface ozone by up to 7 ppb. In the past, terpene oxidation in particular has been ignored or heavily reduced in chemical schemes used in many regional and global models, and this study demonstrates that comprehensive isoprene and terpene chemistry is needed to reduce surface ozone model biases. Sensitivity tests were performed in order to evaluate the impact of lingering uncertainties in isoprene and terpene oxidation on ozone. Results suggest that even though isoprene emissions are higher than terpene emissions in the southeastern US, remaining uncertainties in isoprene and terpene oxidation have similar impacts on ozone due to lower uncertainties in isoprene oxidation. Additionally, this study identifies the need for further constraints on the aerosol uptake of organic nitrates derived from isoprene and terpenes in order to reduce uncertainty in simulated ozone. Although the updates to isoprene and terpene chemistry greatly reduce the ozone bias in CAM-chem, a large bias remains. Evaluation against SEAC 4 RS field campaign results suggests future improvements to horizontal resolution and cloud parameterizations in CAM-chem may be particularly important for further reducing this bias. [ABSTRACT FROM AUTHOR]

The Kathmandu Valley in Nepal is a bowl-shaped urban basin that experiences severe air pollution that poses health risks to its 3.5 million inhabitants. As part of the Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE), ambient air quality in the Kathmandu Valley was investigated from 11 to 24 April 2015, during the pre-monsoon season. Ambient concentrations of fine and coarse particulate matter (PM 2.5 and PM 10 , respectively), online PM 1 , inorganic trace gases (NH3 , HNO3 , SO2 , and HCl), and carbon-containing gases (CO2 , CO, CH4 , and 93 non-methane volatile organic compounds; NMVOCs) were quantified at a semi-urban location near the center of the valley. Concentrations and ratios of NMVOC indicated origins primarily from poorly maintained vehicle emissions, biomass burning, and solvent/gasoline evaporation. During those 2 weeks, daily average PM 2.5 concentrations ranged from 30 to 207 µ g m -3 , which exceeded the World Health Organization 24 h guideline by factors of 1.2 to 8.3. On average, the non-water mass of PM 2.5 was composed of organic matter (48 %), elemental carbon (13 %), sulfate (16 %), nitrate (4 %), ammonium (9 %), chloride (2 %), calcium (1 %), magnesium (0.05 %), and potassium (1 %). Large diurnal variability in temperature and relative humidity drove corresponding variability in aerosol liquid water content, the gas–aerosol phase partitioning of NH3 , HNO3 , and HCl, and aerosol solution pH. The observed levels of gas-phase halogens suggest that multiphase halogen-radical chemistry involving both Cl and Br impacted regional air quality. To gain insight into the origins of organic carbon (OC), molecular markers for primary and secondary sources were quantified. Levoglucosan (averaging 1230±1154 ng m -3), 1,3,5-triphenylbenzene (0.8±0.6 ng m -3), cholesterol (2.9±6.6 ng m -3), stigmastanol (1.0 ±0.8 ng m -3), and cis-pinonic acid (4.5±1.9 ng m -3) indicate contributions from biomass burning, garbage burning, food cooking, cow dung burning, and monoterpene secondary organic aerosol, respectively. Drawing on source profiles developed in NAMaSTE, chemical mass balance (CMB) source apportionment modeling was used to estimate contributions to OC from major primary sources including garbage burning (18±5 %), biomass burning (17±10 %) inclusive of open burning and biomass-fueled cooking stoves, and internal-combustion (gasoline and diesel) engines (18±9 %). Model sensitivity tests with newly developed source profiles indicated contributions from biomass burning within a factor of 2 of previous estimates but greater contributions from garbage burning (up to three times), indicating large potential impacts of garbage burning on regional air quality and the need for further evaluation of this source. Contributions of secondary organic carbon (SOC) to PM 2.5 OC included those originating from anthropogenic precursors such as naphthalene (10±4 %) and methylnaphthalene (0.3±0.1 %) and biogenic precursors for monoterpenes (0.13±0.07 %) and sesquiterpenes (5±2 %). An average of 25 % of the PM 2.5 OC was unapportioned, indicating the presence of additional sources (e.g., evaporative and/or industrial emissions such as brick kilns, food cooking, and other types of SOC) and/or underestimation of the contributions from the identified source types. The source apportionment results indicate that anthropogenic combustion sources (including biomass burning, garbage burning, and fossil fuel combustion) were the greatest contributors to PM 2.5 and, as such, should be considered primary targets for controlling ambient PM pollution. [ABSTRACT FROM AUTHOR]

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

Ozone is a greenhouse gas and air pollutant that is harmful to human health and plants. During the summer in the southeastern U.S., many regional and global models are biased high for surface ozone compared to observations. Past studies have suggested different solutions including the need for updates to model representation of clouds, chemistry, ozone deposition, and emissions of nitrogen oxides (NOx) or biogenic hydrocarbons. Here due to the high biogenic emissions in the southeastern U.S., more comprehensive and updated isoprene and terpene chemistry is added into CESMTM/CAM-chem (Community Earth System Model/Community Atmosphere Model with chemistry) to evaluate the impact of chemistry on simulated ozone. Comparisons of the model results with data collected during the Studies of Emissions Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) field campaign and U.S. EPA CASTNET monitoring stations confirm the updated chemistry improves simulated surface ozone, ozone precursors, and NOx reservoir compounds. The isoprene and terpene chemistry updates reduce the bias in the daily maximum 8-hr average (MDA8) surface ozone by up to 7 ppb. In the past, terpene oxidation in particular has been ignored or heavily reduced in chemical schemes used in many regional and global models, and this study demonstrates comprehensive isoprene and terpene chemistry is needed to reduce surface ozone model biases. Sensitivity tests were performed in order to evaluate the impact of lingering uncertainties in isoprene and terpene oxidation on ozone. Results suggest that even though isoprene emissions are higher than terpene emissions in the southeastern U.S., remaining uncertainties in isoprene and terpene oxidation have similar impacts on ozone due to lower uncertainties in isoprene oxidation. Additionally, this study identifies the need for further constraints on aerosol uptake of organic nitrates derived from isoprene and terpenes in order to reduce uncertainty in simulated ozone. [ABSTRACT FROM AUTHOR]

The hydroxyl radical (OH) reacts with thousands of chemical species in the atmosphere, initiating their removal and the chemical reaction sequences that produce ozone, secondary aerosols, and gas-phase acids. OH reactivity, which is the inverse of OH lifetime, influences the OH abundance and the ability of OH to cleanse the atmosphere. The NASA Atmospheric Tomography (ATom) campaign used instruments on the NASA DC-8 aircraft to measure OH reactivity and more than 100 trace chemical species. ATom presented a unique opportunity to test the completeness of the OH reactivity calculated from the chemical species measurements by comparing it to the measured OH reactivity over two oceans across four seasons. Although the calculated OH reactivity was below the OH reactivity instrument's limit-of-detection for much of the free troposphere, the OHR instrument was able to measure the OH reactivity in and just above the marine boundary layer. The average measured value of OH reactivity in the marine boundary layer across all latitudes and all ATom phases was 1.9 s-1, which 0.5 s-1 larger than the average calculated OH reactivity. Concurrently, missing OH reactivity, the difference between the measured and calculated OH reactivity, was measured to be ~ 0.5-2.0 s-1 at some locations in the tropics and midlatitudes. Correlations of missing OH reactivity with formaldehyde, dimethyl sulfide, butanal, and sea surface temperature suggest the presence of unmeasured or unknown volatile organic compounds or oxygenated volatile organic compounds associated with ocean emissions. [ABSTRACT FROM AUTHOR]

We apply a high-resolution chemical transport model (GEOS-Chem CTM) with updated treatment of volatile organic compounds (VOCs) and a comprehensive suite of airborne datasets over North America to (i) characterize the VOC budget and (ii) test the ability of current models to capture the distribution and reactivity of atmospheric VOCs over this region. Biogenic emissions dominate the North American VOC budget in the model, accounting for 70 % and 95 % of annually emitted VOC carbon and reactivity, respectively. Based on current inventories anthropogenic emissions have declined to the point where biogenic emissions are the dominant summertime source of VOC reactivity even in most major North American cities. Methane oxidation is a 2 × larger source of nonmethane VOCs (via production of formaldehyde and methyl hydroperoxide) over North America in the model than are anthropogenic emissions. However, anthropogenic VOCs account for over half of the ambient VOC loading over the majority of the region owing to their longer aggregate lifetime. Fires can be a significant VOC source episodically but are small on average. In the planetary boundary layer (PBL), the model exhibits skill in capturing observed variability in total VOC abundance (R2=0.36) and reactivity (R2=0.54). The same is not true in the free troposphere (FT), where skill is low and there is a persistent low model bias (∼ 60 %), with most (27 of 34) model VOCs underestimated by more than a factor of 2. A comparison of PBL : FT concentration ratios over the southeastern US points to a misrepresentation of PBL ventilation as a contributor to these model FT biases. We also find that a relatively small number of VOCs (acetone, methanol, ethane, acetaldehyde, formaldehyde, isoprene + oxidation products, methyl hydroperoxide) drive a large fraction of total ambient VOC reactivity and associated model biases; research to improve understanding of their budgets is thus warranted. A source tracer analysis suggests a current overestimate of biogenic sources for hydroxyacetone, methyl ethyl ketone and glyoxal, an underestimate of biogenic formic acid sources, and an underestimate of peroxyacetic acid production across biogenic and anthropogenic precursors. Future work to improve model representations of vertical transport and to address the VOC biases discussed are needed to advance predictions of ozone and SOA formation. [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]

Approximately 3 billion people worldwide cook with solid fuels, such as wood, charcoal, and agricultural residues. These fuels, also used for residential heating, are often combusted in inefficient devices, producing carbonaceous emissions. Between 2.6 and 3.8 million premature deaths occur as a result of exposure to fine particulate matter from the resulting household air pollution (Health Effects Institute, 2018a; World Health Organization, 2018). Household air pollution also contributes to ambient air pollution; the magnitude of this contribution is uncertain. Here, we simulate the distribution of the two major health-damaging outdoor air pollutants (PM 2.5 and O3) using state-of-the-science emissions databases and atmospheric chemical transport models to estimate the impact of household combustion on ambient air quality in India. The present study focuses on New Delhi and the SOMAARTH Demographic, Development, and Environmental Surveillance Site (DDESS) in the Palwal District of Haryana, located about 80 km south of New Delhi. The DDESS covers an approximate population of 200 000 within 52 villages. The emissions inventory used in the present study was prepared based on a national inventory in India (Sharma et al., 2015, 2016), an updated residential sector inventory prepared at the University of Illinois, updated cookstove emissions factors from Fleming et al. (2018b), and PM 2.5 speciation from cooking fires from Jayarathne et al. (2018). Simulation of regional air quality was carried out using the US Environmental Protection Agency Community Multiscale Air Quality modeling system (CMAQ) in conjunction with the Weather Research and Forecasting modeling system (WRF) to simulate the meteorological inputs for CMAQ, and the global chemical transport model GEOS-Chem to generate concentrations on the boundary of the computational domain. Comparisons between observed and simulated O3 and PM 2.5 levels are carried out to assess overall airborne levels and to estimate the contribution of household cooking emissions. Observed and predicted ozone levels over New Delhi during September 2015, December 2015, and September 2016 routinely exceeded the 8 h Indian standard of 100 µ g m -3 , and, on occasion, exceeded 180 µ g m -3. PM 2.5 levels are predicted over the SOMAARTH headquarters (September 2015 and September 2016), Bajada Pahari (a village in the surveillance site; September 2015, December 2015, and September 2016), and New Delhi (September 2015, December 2015, and September 2016). The predicted fractional impact of residential emissions on anthropogenic PM 2.5 levels varies from about 0.27 in SOMAARTH HQ and Bajada Pahari to about 0.10 in New Delhi. The predicted secondary organic portion of PM 2.5 produced by household emissions ranges from 16 % to 80 %. Predicted levels of secondary organic PM 2.5 during the periods studied at the four locations averaged about 30 µ g m -3 , representing approximately 30 % and 20 % of total PM 2.5 levels in the rural and urban stations, respectively. [ABSTRACT FROM AUTHOR]

The Kathmandu Valley in Nepal is a bowl-shaped urban basin that experiences severe air pollution that poses health risks to its 3.5 million inhabitants. As part of the Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE), ambient air quality in the Kathmandu Valley was investigated from 11 to 24 April 2015, during the pre-monsoon season. Ambient concentrations of fine and coarse particulate matter (PM2.5 and PM10, respectively), online PM1, inorganic trace gases (NH3, HNO3, SO2, and HCl), and carbon-containing gases (CO2, CO, CH4, and 85 non-methane volatile organic compounds; NMVOC) were quantified at a semi-urban location near the center of the valley. Concentrations and ratios of NMVOC indicated that origins primarily from poorly-maintained vehicle emissions, biomass burning, and solvent/gasoline evaporation. During those two weeks, daily average PM2.5 concentrations ranged from 30 to 207 μg m-3, which exceeded the World Health Organization 24 hour guideline by factors of 1.2 to 8.3. On average, the non-water mass of PM2.5 was composed of organic matter (48 %), elemental carbon (13 %), sulfate (16 %), nitrate (4 %), ammonium (9 %), chloride (2 %), calcium (1 %), magnesium (0.05 %), and potassium (1 %). Large diurnal variability in temperature and relative humidity drove corresponding variability in aerosol liquid water content, the gas-aerosol phase partitioning of NH3, HNO3, and HCl, and aerosol solution pH. The observed levels of gas-phase halogens suggest that multiphase halogen-radical chemistry involving both Cl and Br impacted regional air quality. To gain insight into the origins of organic carbon (OC), molecular markers for primary and secondary sources were quantified. Levoglucosan (1230 ± 1153 ng m-3), 1,3,5-triphenylbenzene (0.8 ±0.5 ng m-3), cholesterol (3.0 ± 6.7 ng m-3), stigmastanol (1.4 ± 6.7 ng m-3), and cis-pinonic acid (4.5 ± 0.6 ng m-3) indicate contributions from biomass burning, garbage burning, food cooking, cow-dung burning, and monoterpene secondary organic aerosol, respectively. Drawing on source profiles developed in NAMaSTE, chemical mass balance (CMB) source apportionment modeling was used to estimate contributions to OC from major primary sources including garbage burning (18 ± 5 %), biomass burning (17 ± 10 %) inclusive of open burning and biomass-fueled cooking stoves, and internal-combustion (gasoline and diesel) engines (18 ± 9 %). Model sensitivity tests with newly-developed source profiles indicated contributions from biomass burning within a factor of two of previous estimates, but relatively greater contributions from garbage burning (up to three times), indicating large potential impacts of garbage burning on regional air quality and the need for further evaluation of this source. Contributions of secondary organic carbon (SOC) to PM2.5 OC included those originating from anthropogenic precursors for naphthalene (10 ± 4 %) and methylnaphthalene (0.3 ± 0.1 %) and biogenic precursors for monoterpenes (0.13 ± 0.07 %) and sesquiterpenes (5 ± 2 %). An average of 25 % of the PM2.5 OC was unapportioned, indicating the presence of additional sources (e.g., evaporative and/or industrial emissions such as brick kilns, food cooking, and other types of SOC) or underestimation of the contributions from the identified source types. The source apportionment results indicate that anthropogenic combustion sources (including biomass burning, garbage burning, and fossil-fuel combustion) were the greatest contributors to PM2.5 and, as such, should be considered primary targets for controlling ambient PM pollution. [ABSTRACT FROM AUTHOR]

We apply a high-resolution chemical transport model (GEOS-Chem CTM) with updated treatment of volatile organic compounds (VOCs) and a comprehensive suite of airborne datasets over North America to i) characterize the VOC budget, and ii) test the ability of current models to capture the distribution and reactivity of atmospheric VOCs, over this region. Biogenic emissions dominate the North American VOC budget in the model, accounting for 70 % and 95 % of annually emitted VOC-carbon and reactivity, respectively. Based on current inventories anthropogenic emissions have declined to the point where biogenic emissions are the dominant summertime source of VOC reactivity even in most major North American cities. Methane oxidation is a 2× larger source of non-methane VOCs (via production of formaldehyde and methyl hydroperoxide) over North America in the model than are anthropogenic emissions. However, anthropogenic VOCs account for over half the ambient VOC loading over the majority of the region owing to their longer aggregate lifetime. Fires can be a significant VOC source episodically but are small on average. In the planetary boundary layer (PBL), the model exhibits skill in capturing observed variability in total VOC-abundance (R2 = 0.36) and reactivity (R2 = 0.54). The same is not true in the free troposphere (FT), where skill is low and there is a persistent low model bias (~ 60 %), with most (27 of 34) model VOCs underestimated by more than a factor of 2. A comparison of PBL : FT concentration ratios over the southeastern US points to a misrepresentation of PBL ventilation as a contributor to these model FT biases. We also find that a relatively small number of VOCs (acetone, methanol, ethane, acetaldehyde, formaldehyde, isoprene + oxidation products, methyl hydroperoxide) drive a large fraction of total ambient VOC reactivity and associated model biases; research to improve understanding of their budgets is thus warranted. A source tracer analysis suggests a current overestimate of biogenic sources for hydroxyacetone, methyl ethyl ketone and glyoxal, an underestimate of biogenic formic acid sources, and an underestimate of peroxyacetic acid production across biogenic and anthropogenic precursors. Future work to improve model representations of vertical transport and to address the VOC biases discussed are needed to advance predictions of ozone and SOA formation. [ABSTRACT FROM AUTHOR]

Organic aerosol (OA) is an important fraction of submicron aerosols. However, it is challenging to predict and attribute the specific organic compounds and sources that lead to observed OA loadings, largely due to contributions from secondary production. This is especially true for megacities surrounded by numerous regional sources that create an OA background. Here, we utilize in situ gas and aerosol observations collected on board the NASA DC-8 during the NASA–NIER KORUS-AQ (Korea–United States Air Quality) campaign to investigate the sources and hydrocarbon precursors that led to the secondary OA (SOA) production observed over Seoul. First, we investigate the contribution of transported OA to total loadings observed over Seoul by using observations over the Yellow Sea coupled to FLEXPART Lagrangian simulations. During KORUS-AQ, the average OA loading advected into Seoul was ∼1 –3 µgsm-3. Second, taking this background into account, the dilution-corrected SOA concentration observed over Seoul was ∼140 µgsm-3ppmv-1 at 0.5 equivalent photochemical days. This value is at the high end of what has been observed in other megacities around the world (20–70 µgsm-3ppmv-1 at 0.5 equivalent days). For the average OA concentration observed over Seoul (13 µgsm-3), it is clear that production of SOA from locally emitted precursors is the major source in the region. The importance of local SOA production was supported by the following observations. (1) FLEXPART source contribution calculations indicate any hydrocarbons with a lifetime of less than 1 day, which are shown to dominate the observed SOA production, mainly originate from South Korea. (2) SOA correlated strongly with other secondary photochemical species, including short-lived species (formaldehyde, peroxy acetyl nitrate, sum of acyl peroxy nitrates, dihydroxytoluene, and nitrate aerosol). (3) Results from an airborne oxidation flow reactor (OFR), flown for the first time, show a factor of 4.5 increase in potential SOA concentrations over Seoul versus over the Yellow Sea, a region where background air masses that are advected into Seoul can be measured. (4) Box model simulations reproduce SOA observed over Seoul within 11 % on average and suggest that short-lived hydrocarbons (i.e., xylenes, trimethylbenzenes, and semi-volatile and intermediate-volatility compounds) were the main SOA precursors over Seoul. Toluene alone contributes 9 % of the modeled SOA over Seoul. Finally, along with these results, we use the metric ΔOA / ΔCO2 to examine the amount of OA produced per fuel consumed in a megacity, which shows less variability across the world than ΔOA/ΔCO. [ABSTRACT FROM AUTHOR]

Approximately 3 billion people worldwide cook with solid fuels, such as wood, charcoal, and agricultural residues. These fuels are often combusted in inefficient cookstoves, producing carbonaceous emissions. Between 2.6 and 3.8 million premature deaths occur as a result to exposure to fine particulate matter from the resulting household air pollution (Health Effects Institute, 2018a; World Health Organization, 2018). Household air pollution also contributes to ambient air pollution; the magnitude of this contribution is uncertain. Here, we simulate the distribution of the two major health-damaging outdoor air pollution species (PM2.5 and O3) using state-of-the-science emissions databases and atmospheric chemical transport models to estimate the impact of household combustion on ambient air quality in India. The present study focuses on New Delhi and the SOMAARTH Demographic, Development, and Environmental Surveillance Site (DDESS) in the Palwal District of Haryana, located about 80 km south of New Delhi. The DDESS covers an approximate population of 200 000 within 52 villages. The emissions inventory used in the present study was prepared based on a national inventory in India (Sharma et al., 2015, 2016), an updated residential sector inventory prepared at the University of Illinois, updated cookstove emissions factors from Fleming et al. (2018b), and PM2.5 speciation from cooking fires from Jayarathne et al. (2018). Simulation of regional air quality was carried out using the U.S. Environmental Protection Agency Community Multiscale Air Quality modeling system (CMAQ), in conjunction with the Weather Research and Forecasting modeling system (WRF) to simulate the meteorological inputs for CMAQ, and the global chemical transport model GEOS-Chem to generate concentrations on the boundary of the computational domain. Comparisons between observed and simulated O3 and PM2.5 levels are carried out to assess overall airborne levels and to estimate the contribution of household cooking emissions. Observed and predicted ozone levels over New Delhi during September 2015, December 2015, and September 2016 routinely exceeded 150 μg m-3, as compared with the 8-hour Indian standard of 100 μg m-3, and, on occasion, exceeded 200 μg m-3. PM2.5 levels are predicted over the SOMAARTH headquarters (September 2015 and September 2016), Bajada Pahari (a village in the surveillance site, September 2015, December 2015, and September 2016), and New Delhi (September 2015, December 2015, and September 2016). Predicted levels vary depending on the time of year but, on the whole, tend to be somewhat less than those observed. The predicted fractional impact of residential emissions on PM2.5 levels varies from about 0.30 in SOMAARTH HQ and Bajada Pahari to about 0.10 in New Delhi. Predicted levels of secondary organic PM2.5 during the periods studied at the three locations averaged about 5 μg m-3, representing approximately 10% of total PM2.5 levels, accentuating the dominant role played by primary carbonaceous emissions in all three locations. [ABSTRACT FROM AUTHOR]

Nitryl chloride (ClNO2) is a radical reservoir species that releases chlorine radicals upon photolysis. An integrated analysis of the impact of ClNO2 on regional photochemistry in the Seoul Metropolitan Area (SMA) during the Korean-United States-Air Quality (KORUS-AQ) 2016 field campaign is presented. Comprehensive multiplatform observations were conducted aboard the NASA DC-8 and at two ground sites (Olympic Park, OP; Taehwa Research Forest, TRF), representing an urbanized area and a forested region downwind, respectively. The overall diurnal variations of ClNO2 in both sites appeared similar but the night time variation were systematically different. For about half of the observation days at the OP site the level of ClNO2 increased at sunset but rapidly decreased at around midnight. On the other hand, high levels were sustained throughout the night at the TRF site. Significant levels of ClNO2 were sustained at both sites for 4–5 hours after sunrise. Airborne observations, box model calculations, and back trajectory analysis consistently show that this high levels of ClNO2 in the morning is likely due to the transport of air masses within the boundary layer. Box model results show that chlorine radical initiated chemistry can impact the regional photochemistry by elevating net ozone production rate up to ~25% in the morning. [ABSTRACT FROM AUTHOR]

Air quality in rural India is impacted by residential cooking and heating with biomass fuels. In this study, emissions of CO, CO2, and 76 volatile organic compounds (VOCs) and fine particulate matter (PM2.5) were quanti- fied to better understand the relationship between cook fire emissions and ambient ozone and secondary organic aerosol (SOA) formation. Cooking was carried out by a local cook, and traditional dishes were prepared on locally built chulha or angithi cookstoves using brushwood or dung fuels. Cook fire emissions were collected throughout the cooking event in a Kynar bag (VOCs) and on polytetrafluoroethylene (PTFE) filters (PM2.5). Gas samples were transferred from a Kynar bag to previously evacuated stainless-steel canisters and analyzed using gas chromatography coupled to flame ionization, electron capture, and mass spectrometry detectors. VOC emission factors were calculated from the measured mixing ratios using the carbon-balance method, which assumes that all carbon in the fuel is converted to CO2, CO, VOCs, and PM2.5 when the fuel is burned. Filter samples were weighed to calculate PM2.5 emission factors. Dung fuels and angithi cookstoves resulted in significantly higher emissions of most VOCs (p < 0:05). Utilizing dung--angithi cook fires resulted in twice as much of the measured VOCs compared to dung--chulha and 4 times as much as brushwood--chulha, with 84.0, 43.2, and 17.2 g measured VOCkg-1 fuel carbon, respectively. This matches expectations, as the use of dung fuels and angithi cookstoves results in lower modified combustion efficiencies compared to brushwood fuels and chulha cookstoves. Alkynes and benzene were exceptions and had significantly higher emissions when cooking using a chulha as opposed to an angithi with dung fuel (for example, benzene emission factors were 3.18 g kg-1 fuel carbon for dung--chulha and 2.38 g kg-1 fuel carbon for dung--angithi). This study estimated that 3 times as much SOA and ozone in the maximum incremental reactivity (MIR) regime may be produced from dung--chulha as opposed to brushwood--chulha cook fires. Aromatic compounds dominated as SOA precursors from all types of cook fires, but benzene was responsible for the majority of SOA formation potential from all chulha cook fire VOCs, while substituted aromatics were more important for dung--angithi. Future studies should investigate benzene exposures from different stove and fuel combinations and model SOA formation from cook fire VOCs to verify public health and air quality impacts from cook fires. [ABSTRACT FROM AUTHOR]

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