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Abstract. Tropical tropospheric ozone (TTO) is important for the global radiation budget because the longwave radiative effect of tropospheric ozone is higher in the tropics than midlatitudes. In recent decades the TTO burden has increased, partly due to the ongoing shift of ozone precursor emissions from midlatitude regions toward the Equator. In this study, we assess the distribution and trends of TTO using ozone profiles measured by high-quality in situ instruments from the IAGOS (In-Service Aircraft for a Global Observing System) commercial aircraft, the SHADOZ (Southern Hemisphere ADditional OZonesondes) network, and the ATom (Atmospheric Tomographic Mission) aircraft campaign, as well as six satellite records reporting tropical tropospheric column ozone (TTCO): TROPOspheric Monitoring Instrument (TROPOMI), Ozone Monitoring Instrument (OMI), OMI/Microwave Limb Sounder (MLS), Ozone Mapping Profiler Suite (OMPS)/Modern-Era Retrospective analysis for Research and Applications version 2 (MERRA-2), Cross-track Infrared Sounder (CrIS), and Infrared Atmospheric Sounding Interferometer (IASI)/Global Ozone Monitoring Experiment 2 (GOME2). With greater availability of ozone profiles across the tropics we can now demonstrate that tropical India is among the most polluted regions (e.g., western Africa, tropical South Atlantic, Southeast Asia, Malaysia and Indonesia), with present-day 95th percentile ozone values reaching 80 nmol mol−1 in the lower free troposphere, comparable to midlatitude regions such as northeastern China and Korea. In situ observations show that TTO increased between 1994 and 2019, with the largest mid- and upper-tropospheric increases above India, Southeast Asia, and Malaysia and Indonesia (from 3.4 ± 0.8 to 6.8 ± 1.8 nmol mol−1 decade−1), reaching 11 ± 2.4 and 8 ± 0.8 nmol mol−1 decade−1 close to the surface (India and Malaysia–Indonesia, respectively). The longest continuous satellite records only span 2004–2019 but also show increasing ozone across the tropics when their full sampling is considered, with maximum trends over Southeast Asia of 2.31 ± 1.34 nmol mol−1 decade−1 (OMI) and 1.69 ± 0.89 nmol mol−1 decade−1 (OMI/MLS). In general, the sparsely sampled aircraft and ozonesonde records do not detect the 2004–2019 ozone increase, which could be due to the genuine trends on this timescale being masked by the additional uncertainty resulting from sparse sampling. The fact that the sign of the trends detected with satellite records changes above three IAGOS regions, when their sampling frequency is limited to that of the in situ observations, demonstrates the limitations of sparse in situ sampling strategies. This study exposes the need to maintain and develop high-frequency continuous observations (in situ and remote sensing) above the tropical Pacific Ocean, the Indian Ocean, western Africa, and South Asia in order to estimate accurate and precise ozone trends for these regions. In contrast, Southeast Asia and Malaysia–Indonesia are regions with such strong increases in ozone that the current in situ sampling frequency is adequate to detect the trends on a relatively short 15-year timescale. 

Abstract. 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 (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 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 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. Smoke from wildfires is a significant source of air pollution, which can adversely impact air quality and ecosystems downwind. With the recently increasing intensity and severity of wildfires, the threat to air quality is expected to increase. Satellite-derived biomass burning emissions can fill in gaps in the absence of aircraft or ground-based measurement campaigns and can help improve the online calculation of biomass burning emissions as well as the biomass burning emissions inventories that feed air quality models. This study focuses on satellite-derived NOx emissions using the high-spatial-resolution TROPOspheric Monitoring Instrument (TROPOMI) NO2 dataset. Advancements and improvements to the satellite-based determination of forest fire NOx emissions are discussed, including information on plume height and effects of aerosol scattering and absorption on the satellite-retrieved vertical column densities. Two common top-down emission estimation methods, (1) an exponentially modified Gaussian (EMG) and (2) a flux method, are applied to synthetic data to determine the accuracy and the sensitivity to different parameters, including wind fields, satellite sampling, noise, lifetime, and plume spread. These tests show that emissions can be accurately estimated from single TROPOMI overpasses.The effect of smoke aerosols on TROPOMI NO2 columns (via air mass factors, AMFs) is estimated, and these satellite columns and emission estimates are compared to aircraft observations from four different aircraft campaigns measuring biomass burning plumes in 2018 and 2019 in North America. Our results indicate that applying an explicit aerosol correction to the TROPOMI NO2 columns improves the agreement with the aircraft observations (by about 10 %–25 %). The aircraft- and satellite-derived emissions are in good agreement within the uncertainties. Both top-down emissions methods work well; however, the EMG method seems to output more consistent results and has better agreement with the aircraft-derived emissions. Assuming a Gaussian plume shape for various biomass burning plumes, we estimate an average NOx e-folding time of 2 ±1 h from TROPOMI observations. Based on chemistry transport model simulations and aircraft observations, the net emissions of NOx are 1.3 to 1.5 times greater than the satellite-derived NO2 emissions. A correction factor of 1.3 to 1.5 should thus be used to infer net NOx emissions from the satellite retrievals of NO2. 

Oceans emit large quantities of dimethyl sulfide (DMS) to the marine atmosphere. The oxidation of DMS leads to the formation and growth of cloud condensation nuclei (CCN) with consequent effects on Earth’s radiation balance and climate. The quantitative assessment of the impact of DMS emissions on CCN concentrations necessitates a detailed description of the oxidation of DMS in the presence of existing aerosol particles and clouds. In the unpolluted marine atmosphere, DMS is efficiently oxidized to hydroperoxymethyl thioformate (HPMTF), a stable intermediate in the chemical trajectory toward sulfur dioxide (SO 2 ) and ultimately sulfate aerosol. Using direct airborne flux measurements, we demonstrate that the irreversible loss of HPMTF to clouds in the marine boundary layer determines the HPMTF lifetime ( τ HPMTF < 2 h) and terminates DMS oxidation to SO 2 . When accounting for HPMTF cloud loss in a global chemical transport model, we show that SO 2 production from DMS is reduced by 35% globally and near-surface (0 to 3 km) SO 2 concentrations over the ocean are lowered by 24%. This large, previously unconsidered loss process for volatile sulfur accelerates the timescale for the conversion of DMS to sulfate while limiting new particle formation in the marine atmosphere and changing the dynamics of aerosol growth. This loss process potentially reduces the spatial scale over which DMS emissions contribute to aerosol production and growth and weakens the link between DMS emission and marine CCN production with subsequent implications for cloud formation, radiative forcing, and climate. 

Abstract. Anthropogenic secondary organic aerosol (ASOA), formed from anthropogenicemissions of organic compounds, constitutes a substantial fraction of themass of submicron aerosol in populated areas around the world andcontributes to poor air quality and premature mortality. However, theprecursor sources of ASOA are poorly understood, and there are largeuncertainties in the health benefits that might accrue from reducinganthropogenic organic emissions. We show that the production of ASOA in 11urban areas on three continents is strongly correlated with the reactivityof specific anthropogenic volatile organic compounds. The differences inASOA production across different cities can be explained by differences inthe emissions of aromatics and intermediate- and semi-volatile organiccompounds, indicating the importance of controlling these ASOA precursors.With an improved model representation of ASOA driven by the observations,we attribute 340 000 PM2.5-related premature deaths per year to ASOA, which isover an order of magnitude higher than prior studies. A sensitivity casewith a more recently proposed model for attributing mortality to PM2.5(the Global Exposure Mortality Model) results in up to 900 000 deaths. Alimitation of this study is the extrapolation from cities with detailedstudies and regions where detailed emission inventories are available toother regions where uncertainties in emissions are larger. In addition tofurther development of institutional air quality management infrastructure,comprehensive air quality campaigns in the countries in South and CentralAmerica, Africa, South Asia, and the Middle East are needed for furtherprogress in this area. 

Dimethyl sulfide (DMS), emitted from the oceans, is the most abundant biological source of sulfur to the marine atmosphere. Atmospheric DMS is oxidized to condensable products that form secondary aerosols that affect Earth’s radiative balance by scattering solar radiation and serving as cloud condensation nuclei. We report the atmospheric discovery of a previously unquantified DMS oxidation product, hydroperoxymethyl thioformate (HPMTF, HOOCH 2 SCHO), identified through global-scale airborne observations that demonstrate it to be a major reservoir of marine sulfur. Observationally constrained model results show that more than 30% of oceanic DMS emitted to the atmosphere forms HPMTF. Coincident particle measurements suggest a strong link between HPMTF concentration and new particle formation and growth. Analyses of these observations show that HPMTF chemistry must be included in atmospheric models to improve representation of key linkages between the biogeochemistry of the ocean, marine aerosol formation and growth, and their combined effects on climate. 

We use a 0-D photochemical box model and a 3-D global chemistry-climate model, combined with observations from the NOAA Southeast Nexus (SENEX) aircraft campaign, to understand the sources and sinks of glyoxal over the Southeast United States. Box model simulations suggest a large difference in glyoxal production among three isoprene oxidation mechanisms (AM3ST, AM3B, and MCM v3.3.1). These mechanisms are then implemented into a 3-D global chemistry-climate model. Comparison with field observations shows that the average vertical profile of glyoxal is best reproduced by AM3ST with an effective reactive uptake coefficient γglyx of 2 × 10-3, and AM3B without heterogeneous loss of glyoxal. The two mechanisms lead to 0-0.8 µg m-3 secondary organic aerosol (SOA) from glyoxal in the boundary layer of the Southeast U.S. in summer. We consider this to be the lower limit for the contribution of glyoxal to SOA, as other sources of glyoxal other than isoprene are not included in our model. In addition, we find that AM3B shows better agreement on both formaldehyde and the correlation between glyoxal and formaldehyde (RGF = [GLYX]/[HCHO]), resulting from the suppression of δ-isoprene peroxy radicals (δ-ISOPO2). We also find that MCM v3.3.1 may underestimate glyoxal production from isoprene oxidation, in part due to an underestimated yield from the reaction of IEPOX peroxy radicals (IEPOXOO) with HO2. Our work highlights that the gas-phase production of glyoxal represents a large uncertainty in quantifying its contribution to SOA.