Aqueous-Phase Reactive Uptake of Dicarbonyls as a Source of Organic Aerosol Over Eastern North America

We use a global 3-D atmospheric chemistry model (GEOS-Chem) to simulate surface and aircraft measurements of organic carbon (OC) aerosol over eastern North America during summer 2004 (ICARTT aircraft campaign), with the goal of evaluating the potential importance of a new secondary organic aerosol (SOA) formation pathway via irreversible uptake of dicarbonyl gases (glyoxal and methylglyoxal) by aqueous particles. Both dicarbonyls are predominantly produced in the atmosphere by isoprene, with minor contributions from other biogenic and anthropogenic precursors. Dicarbonyl SOA formation is represented by a reactive uptake coefficient γ = 2.9 × 10−3 and takes place mainly in clouds. Surface measurements of OC aerosol at the IMPROVE network in the eastern U.S. average 2.2 ± 0.7 μg C m−3 for July–August 2004 with little regional structure. The corresponding model concentration is 2.8 ± 0.8 μg C m−3, also with little regional structure due to compensating spatial patterns of biogenic, anthropogenic, and fire contributions. Aircraft measurements of water-soluble organic carbon (WSOC) aerosol average 2.2 ± 1.2 μg C m−3 in the boundary layer (<2 km) and 0.9 ± 0.8 μg C m−3 in the free troposphere (2–6 km), consistent with the model (2.0 ± 1.2 μg C m−3 in the boundary layer and 1.1 ± 1.0 μg C m−3 in the free troposphere). Source attribution for the WSOC aerosol in the model boundary layer is 27% anthropogenic, 18% fire, 28% semi-volatile SOA, and 27% dicarbonyl SOA. In the free troposphere it is 13% anthropogenic, 37% fire, 23% semi-volatile SOA, and 27% dicarbonyl SOA. Inclusion of dicarbonyl SOA doubles the SOA contribution to WSOC aerosol at all altitudes. Observed and simulated correlations of WSOC aerosol with other chemical variables measured aboard the aircraft suggest a major SOA source in the free troposphere compatible with the dicarbonyl mechanism.Earth and Planetary SciencesEngineering and Applied Science

Global Budgets of Atmospheric Glyoxal and Methylglyoxal, and Implications for Formation of Secondary Organic Aerosols

We construct global budgets of atmospheric glyoxal and methylglyoxal with the goal of quantifying their potential for global secondary organic aerosol (SOA) formation via irreversible uptake by aqueous aerosols and clouds. We conduct a detailed simulation of glyoxal and methylglyoxal in the GEOS-Chem global 3-D chemical transport model including our best knowledge of source and sink processes. Our resulting best estimates of the global sources of glyoxal and methylglyoxal are 45 Tg a−1 and 140 Tg a−1, respectively. Oxidation of biogenic isoprene contributes globally 47% of glyoxal and 79% of methylglyoxal. The second most important precursors are acetylene (mostly anthropogenic) for glyoxal and acetone (mostly biogenic) for methylglyoxal. Both acetylene and acetone have long lifetimes and provide a source of dicarbonyls in the free troposphere. Atmospheric lifetimes of glyoxal and methylglyoxal in the model are 2.9 h and 1.6 h, respectively, mostly determined by photolysis. Simulated dicarbonyl concentrations in continental surface air at northern midlatitudes are in the range 10–100 ppt, consistent with in situ measurements. On a global scale, the highest concentrations are over biomass burning regions, in agreement with glyoxal column observations from the SCIAMACHY satellite instrument. SCIAMACHY and a few ship cruises also suggest a large marine source of dicarbonyls missing from our model. The global source of SOA from the irreversible uptake of dicarbonyls in GEOS-Chem is 11 Tg C a−1, including 2.6 Tg C a−1 from glyoxal and 8 Tg C a−1 from methylglyoxal; 90% of this source takes place in clouds. The magnitude of the global SOA source from dicarbonyls is comparable to that computed in GEOS-Chem from the standard mechanism involving reversible partitioning of semivolatile products from the oxidation of monoterpenes, sesquiterpenes, isoprene, and aromatics.Earth and Planetary SciencesEngineering and Applied Science

Spatial Distribution of Isoprene Emissions from North America Derived from Dormaldehyde Column Measurements by the OMI Satellite Sensor

Space-borne formaldehyde (HCHO) column measurements from the Ozone Monitoring Instrument (OMI), with 13 × 24 km2 nadir footprint and daily global coverage, provide new constraints on the spatial distribution of biogenic isoprene emission from North America. OMI HCHO columns for June-August 2006 are consistent with measurements from the earlier GOME satellite sensor (1996–2001) but OMI is 2–14% lower. The spatial distribution of OMI HCHO columns follows that of isoprene emission; anthropogenic hydrocarbon emissions are undetectable except in Houston. We develop updated relationships between HCHO columns and isoprene emission from a chemical transport model (GEOS-Chem), and use these to infer top-down constraints on isoprene emissions from the OMI data. We compare the OMI-derived emissions to a state-of-science bottom-up isoprene emission inventory (MEGAN) driven by two land cover databases, and use the results to optimize the MEGAN emission factors (EFs) for broadleaf trees (the main isoprene source). The OMI-derived isoprene emissions in North America (June–August 2006) with 1° × 1° resolution are spatially consistent with MEGAN (R2 = 0.48–0.68) but are lower (by 4–25% on average). MEGAN overestimates emissions in the Ozarks and the Upper South. A better fit to OMI (R2 = 0.73) is obtained in MEGAN by using a uniform isoprene EF from broadleaf trees rather than variable EFs. Thus MEGAN may overestimate emissions in areas where it specifies particularly high EFs. Within-canopy isoprene oxidation may also lead to significant differences between the effective isoprene emission to the atmosphere seen by OMI and the actual isoprene emission determined by MEGAN.Earth and Planetary SciencesEngineering and Applied Science

Source attribution of particulate matter pollution over North China with the adjoint method

We quantify the source contributions to surface PM2.5 (fine particulate matter) pollution over North China from January 2013 to 2015 using the GEOS-Chem chemical transport model and its adjoint with improved model horizontal resolution (1/4 degrees x 5/16 degrees) and aqueous-phase chemistry for sulfate production. The adjoint method attributes the PM2.5 pollution to emissions from different source sectors and chemical species at the model resolution. Wintertime surface PM2.5 over Beijing is contributed by emissions of organic carbon (27% of the total source contribution), anthropogenic fine dust (27%), and SO2 (14%), which are mainly from residential and industrial sources, followed by NH3 (13%) primarily from agricultural activities. About half of the Beijing pollution originates from sources outside of the city municipality. Adjoint analyses for other cities in North China all show significant regional pollution transport, supporting a joint regional control policy for effectively mitigating the PM2.5 air pollution.China&apos;s National Basic Research Program [2014CB441303]; National Natural Science Foundation of China [41205103, 41475112]SCI(E)[email protected]

Parameterized Yields of Semivolatile Products from Isoprene Oxidation under Different NO_x Levels: Impacts of Chemical Aging and Wall-Loss of Reactive Gases

We developed a parametrizable box model to empirically derive the yields of semivolatile products from VOC oxidation using chamber measurements, while explicitly accounting for the multigenerational chemical aging processes (such as the gas-phase fragmentation and functionalization and aerosol-phase oligomerization and photolysis) under different NO_x levels and the loss of particles and gases to chamber walls. Using the oxidation of isoprene as an example, we showed that the assumptions regarding the NO_x-sensitive, multigenerational aging processes of VOC oxidation products have large impacts on the parametrized product yields and SOA formation. We derived sets of semivolatile product yields from isoprene oxidation under different NO_x levels. However, we stress that these product yields must be used in conjunction with the corresponding multigenerational aging schemes in chemical transport models. As more mechanistic insights regarding SOA formation from VOC oxidation emerge, our box model can be expanded to include more explicit chemical aging processes and help ultimately bridge the gap between the process-based understanding of SOA formation from VOC oxidation and the bulk-yield parametrizations used in chemical transport models

First Directly Retrieved Global Distribution of Tropospheric Column Ozone from GOME: Comparison with the GEOS-CHEM Model

We present the first directly retrieved global distribution of tropospheric column ozone from Global Ozone Monitoring Experiment (GOME) ultraviolet measurements during December 1996 to November 1997. The retrievals clearly show signals due to convection, biomass burning, stratospheric influence, pollution, and transport. They are capable of capturing the spatiotemporal evolution of tropospheric column ozone in response to regional or short time-scale events such as the 1997–1998 El Niño event and a 10–20 DU change within a few days. The global distribution of tropospheric column ozone displays the well-known wave-1 pattern in the tropics, nearly zonal bands of enhanced tropospheric column ozone of 36–48 DU at 20°S–30°S during the austral spring and at 25°N–45°N during the boreal spring and summer, low tropospheric column ozone of 33 DU at some northern high-latitudes during the spring. Simulation from a chemical transport model corroborates most of the above structures, with small biases of <±5 DU and consistent seasonal cycles in most regions, especially in the southern hemisphere. However, significant positive biases of 5–20 DU occur in some northern tropical and subtropical regions such as the Middle East during summer. Comparison of GOME with monthly-averaged Measurement of Ozone and Water Vapor by Airbus in-service Aircraft (MOZAIC) tropospheric column ozone for these regions usually shows good consistency within 1σ standard deviations and retrieval uncertainties. Some biases can be accounted for by inadequate sensitivity to lower tropospheric ozone, the different spatiotemporal sampling and the spatiotemporal variations in tropospheric column ozone.Earth and Planetary SciencesEngineering and Applied Science

Sensitivities of Ozone Air Pollution in the Beijing-Tianjin-Hebei Area to Local and Upwind Precursor Emissions Using Adjoint Modeling

Effective mitigation of surface ozone pollution entails detailed knowledge of the contributing precursors' sources. We use the GEOS-Chem adjoint model to analyze the precursors contributing to surface ozone in the Beijing-Tianjin-Hebei area (BTH) of China on days of different ozone pollution severities in June 2019. We find that BTH ozone on heavily polluted days is sensitive to local emissions, as well as to precursors emitted from the provinces south of BTH (Shandong, Henan, and Jiangsu, collectively the SHJ area). Heavy ozone pollution in BTH can be mitigated effectively by reducing NOx (from industrial processes and transportation), ≥C3 alkenes (from on-road gasoline vehicles and industrial processes), and xylenes (from paint use) emitted from both BTH and SHJ, as well as by reducing CO (from industrial processes, transportation, and power generation) and ≥C4 alkanes (from industrial processes, paint and solvent use, and on-road gasoline vehicles) emissions from SHJ. In addition, reduction of NOx, xylene, and ≥C3 alkene emissions within BTH would effectively decrease the number of BTH ozone-exceedance days. Our analysis pinpoint the key areas and activities for locally and regionally coordinated emission control efforts to improve surface ozone air quality in BTH

Space-based formaldehyde measurements as constrains on volatile organic compound emissions in east and south Asia and implications for ozone

We use a continuous 6-year record (1996–2001) of GOME satellite measurements of formaldehyde (HCHO) columns over east and south Asia to improve regional emission estimates of reactive nonmethane volatile organic compounds (NMVOCs), including isoprene, alkenes, HCHO, and xylenes. Mean monthly HCHO observations are compared to simulated HCHO columns from the GEOS-Chem chemical transport model using state-of-science, “bottom-up” emission inventories from Streets et al. (2003a) for anthropogenic and biomass burning emissions and Guenther et al. (2006) for biogenic emissions (MEGAN). We find that wintertime GOME observations can diagnose anthropogenic reactive NMVOC emissions from China, leading to an estimate 25% higher than Streets et al. (2003a). We attribute the difference to vehicular emissions. The biomass burning source for east and south Asia is almost 5 times the estimate of Streets et al. (2003a). GOME reveals a large source from agricultural burning in the North China Plain in June missing from current inventories. This source may reflect a recent trend toward in-field burning of crop residues as the need for biofuels diminishes. Biogenic isoprene emission in east and south Asia derived from GOME is 56 ± 30 Tg yr−1, similar to 52 Tg yr−1 from MEGAN. We find, however, that MEGAN underestimates emissions in China and overestimates emissions in the tropics. The higher Chinese biogenic and biomass burning emissions revealed by GOME have important implications for ozone pollution. We find 5 to 20 ppb seasonal increases in surface ozone in GEOS-Chem for central and northern China when using GOME-derived versus bottom-up emissions. Our methodology can be adapted for other regions of the world to provide top-down constraints on NMVOC emissions where multiple emission source types overlap in space and time.Earth and Planetary SciencesEngineering and Applied Science