Biogenic secondary organic aerosols (SOAs) contribute to a large fraction of fine aerosols globally, impacting air quality and climate. The formation of biogenic SOA depends on not only emissions of biogenic volatile organic compounds (BVOCs) but also anthropogenic pollutants including primary organic aerosol, sulfur dioxide (SO2), and nitrogen oxides (NOx). However, the anthropogenic impact on biogenic SOA production (AIBS) remains unclear. Here we use the decadal trend and variability in observed organic aerosol (OA) in the southeast US, combined with a global chemistry–climate model, to better constrain AIBS. We show that the reduction in SO2 emissions can only explain 40 % of the decreasing decadal trend of OA in this region, constrained by the low summertime month-to-month variability in surface OA. We hypothesize that the rest of the OA decreasing trend is largely due to a reduction in NOx emissions. By implementing a scheme for monoterpene SOA with enhanced sensitivity to NOx, our model can reproduce the decadal trend and variability in OA in this region. Extending to a centennial scale, our model shows that global SOA production increases by 36 % despite BVOC reductions from the preindustrial period to the present day, largely amplified by AIBS. Our work suggests a strong coupling between anthropogenic and biogenic emissions in biogenic SOA production that is missing from current climate models.
Baublitz, C B., Arlene M Fiore, Olivia E Clifton, Jingqiu Mao, J Li, G Correa, Daniel M Westervelt, Larry W Horowitz, Fabien Paulot, and A Park Williams, April 2020: Sensitivity of tropospheric ozone over the Southeast USA to dry deposition. Geophysical Research Letters, 47(7), DOI:10.1029/2020GL087158. Abstract
Dry deposition (DD) is a major loss process for tropospheric ozone and some reactive nitrogen and carbon precursors. We investigate the response of summertime ozone and its production chemistry over the Southeast United States (USA) to variability in this sink. Turning off DD of oxidized nitrogen, ozone, or all species over the USA in the GFDL AM3 model increases regional mean surface ozone by 5, 18 or 25 ppb, respectively. Additional sensitivity simulations demonstrate that, assuming linearity, surface ozone has a similar sensitivity to ozone DD as to NOx emissions. Trends in ozone production efficiency derived from observed relationships between ozone and precursor oxidation products may not solely reflect precursor emission changes if ozone DD varies (e.g. with meteorology). We conclude that DD variability merits consideration when interpreting observed ozone trends. Quantifying the impact of changes in sinks versus sources will require long‐term DD measurements across the region of interest.
We describe the baseline model configuration and simulation characteristics of the Geophysical Fluid Dynamics Laboratory (GFDL)'s Atmosphere Model version 4.1 (AM4.1), which builds on developments at GFDL over 2013–2018 for coupled carbon‐chemistry‐climate simulation as part of the sixth phase of the Coupled Model Intercomparison Project. In contrast with GFDL's AM4.0 development effort, which focused on physical and aerosol interactions and which is used as the atmospheric component of CM4.0, AM4.1 focuses on comprehensiveness of Earth system interactions. Key features of this model include doubled horizontal resolution of the atmosphere (~200 to ~100 km) with revised dynamics and physics from GFDL's previous‐generation AM3 atmospheric chemistry‐climate model. AM4.1 features improved representation of atmospheric chemical composition, including aerosol and aerosol precursor emissions, key land‐atmosphere interactions, comprehensive land‐atmosphere‐ocean cycling of dust and iron, and interactive ocean‐atmosphere cycling of reactive nitrogen. AM4.1 provides vast improvements in fidelity over AM3, captures most of AM4.0's baseline simulations characteristics, and notably improves on AM4.0 in the representation of aerosols over the Southern Ocean, India, and China—even with its interactive chemistry representation—and in its manifestation of sudden stratospheric warmings in the coldest months. Distributions of reactive nitrogen and sulfur species, carbon monoxide, and ozone are all substantially improved over AM3. Fidelity concerns include degradation of upper atmosphere equatorial winds and of aerosols in some regions.
Li, J, Jingqiu Mao, Arlene M Fiore, R C Cohen, John D Crounse, A P Teng, P O Wennberg, B H Lee, Felipe D Lopez-Hilfiker, J A Thornton, Jeff Peischl, I B Pollack, Thomas B Ryerson, P R Veres, J M Roberts, J Andrew Neuman, John B Nowak, G M Wolfe, T F Hanisco, A Fried, H B Singh, Jack E Dibb, Fabien Paulot, and Larry W Horowitz, February 2018: Decadal changes in summertime reactive oxidized nitrogen and surface ozone over the Southeast United States. Atmospheric Chemistry and Physics, 18(3), DOI:10.5194/acp-18-2341-2018. Abstract
Widespread efforts to abate ozone (O3) smog have significantly reduced emissions of nitrogen oxides (NOx) over the past 2 decades in the Southeast US, a place heavily influenced by both anthropogenic and biogenic emissions. How reactive nitrogen speciation responds to the reduction in NOx emissions in this region remains to be elucidated. Here we exploit aircraft measurements from ICARTT (July–August 2004), SENEX (June–July 2013), and SEAC4RS (August–September 2013) and long-term ground measurement networks alongside a global chemistry–climate model to examine decadal changes in summertime reactive oxidized nitrogen (RON) and ozone over the Southeast US. We show that our model can reproduce the mean vertical profiles of major RON species and the total (NOy) in both 2004 and 2013. Among the major RON species, nitric acid (HNO3) is dominant (∼ 42–45 %), followed by NOx (31 %), total peroxy nitrates (ΣPNs; 14 %), and total alkyl nitrates (ΣANs; 9–12 %) on a regional scale. We find that most RON species, including NOx, ΣPNs, and HNO3, decline proportionally with decreasing NOx emissions in this region, leading to a similar decline in NOy. This linear response might be in part due to the nearly constant summertime supply of biogenic VOC emissions in this region. Our model captures the observed relative change in RON and surface ozone from 2004 to 2013. Model sensitivity tests indicate that further reductions of NOx emissions will lead to a continued decline in surface ozone and less frequent high-ozone events.
Mao, Jingqiu, A G Carlton, R C Cohen, W Brune, Steven S Brown, G M Wolfe, J L Jimenez, Havala O T Pye, N L Ng, Lu Xu, V Faye McNeill, Kostas Tsigaridis, B C McDonald, C Warneke, A Guenther, M J Alvarado, J A de Gouw, L J Mickley, E M Leibensperger, R. Mathur, Christopher G Nolte, R W Portmann, Nadine Unger, M Tosca, and Larry W Horowitz, February 2018: Southeast Atmosphere Studies: learning from model-observation syntheses. Atmospheric Chemistry and Physics, 18(4), DOI:10.5194/acp-18-2615-2018. Abstract
Concentrations of atmospheric trace species in the United States have changed dramatically over the past several decades in response to pollution control strategies, shifts in domestic energy policy and economics, and economic development (and resulting emission changes) elsewhere in the world. Reliable projections of the future atmosphere require models to not only accurately describe current atmospheric concentrations, but to do so by representing chemical, physical and biological processes with conceptual and quantitative fidelity. Only through incorporation of the processes controlling emissions and chemical mechanisms that represent the key transformations among reactive molecules can models reliably project the impacts of future policy, energy and climate scenarios. Efforts to properly identify and implement the fundamental and controlling mechanisms in atmospheric models benefit from intensive observation periods, during which collocated measurements of diverse, speciated chemicals in both the gas and condensed phases are obtained. The Southeast Atmosphere Studies (SAS, including SENEX, SOAS, NOMADSS and SEAC4RS) conducted during the summer of 2013 provided an unprecedented opportunity for the atmospheric modeling community to come together to evaluate, diagnose and improve the representation of fundamental climate and air quality processes in models of varying temporal and spatial scales.
This paper is aimed at discussing progress in evaluating, diagnosing and improving air quality and climate modeling using comparisons to SAS observations as a guide to thinking about improvements to mechanisms and parameterizations in models. The effort focused primarily on model representation of fundamental atmospheric processes that are essential to the formation of ozone, secondary organic aerosol (SOA) and other trace species in the troposphere, with the ultimate goal of understanding the radiative impacts of these species in the southeast and elsewhere. Here we address questions surrounding four key themes: gas-phase chemistry, aerosol chemistry, regional climate and chemistry interactions, and natural and anthropogenic emissions. We expect this review to serve as a guidance for future modeling efforts.
Northern India (23° N–31° N, 68° E–90° E) is one of the most densely populated and polluted regions in world. Accurately modeling pollution in the region is difficult due to the extreme conditions with respect to emissions, meteorology, and topography, but it is paramount in order to understand how future changes in emissions and climate may alter the region's pollution regime. We evaluate the ability of a developmental version of the new-generation NOAA GFDL Atmospheric Model, version 4 (AM4) to simulate observed wintertime fine particulate matter (PM2.5) and its relationship to meteorology over Northern India. We compare two simulations of GFDL-AM4 nudged to observed meteorology for the period 1980–2016 driven by pollutant emissions from two global inventories developed in support of the Coupled Model Intercomparison Project Phases 5 (CMIP5) and 6 (CMIP6), and compare results with ground-based observations from India's Central Pollution Control Board (CPCB) for the period 1 October 2015–31 March 2016. Overall, our results indicate that the simulation with CMIP6 emissions, produces improved concentrations of pollutants over the region relative to the CMIP5-driven simulation.
While the particulate concentrations simulated by AM4 are biased low overall, the model generally simulates the magnitude and daily variability of observed total PM2.5. Nitrate and organic matter are the primary components of PM2.5 over Northern India in the model. On the basis of correlations of the individual model components with total observed PM2.5 and correlations between the two simulations, meteorology is the primary driver of daily variability. The model correctly reproduces the shape and magnitude of the seasonal cycle of PM2.5, but the simulated diurnal cycle misses the early evening rise and secondary maximum found in the observations. Observed PM2.5 abundances are by far the highest within the densely populated Indo-Gangetic Plain, where they are closely related to boundary layer meteorology, specifically relative humidity, wind speed, boundary layer height, and inversion strength. The GFDL AM4 model reproduces the overall observed pollution gradient over Northern India as well as the strength of the meteorology-PM2.5 relationship in most locations.
The soluble fraction of aerosol Fe, mainly Fe(II), represents a large source of nutrient iron to the open ocean. Fe(II) may also play an important role in the adverse health effects of ambient aerosols. Our current understanding of the reduction of Fe(III) to Fe(II) in aerosols suggests that the major pathway is the photoreduction of Fe(III)–oxalate complexes, but this pathway cannot explain the observed nighttime Fe(II) in ambient aerosols and is also limited by the supply of oxalate. Here we propose a new pathway initiated by gaseous HO2 uptake, followed by Cu–Fe redox coupling, which can sustain nighttime Fe(II) and also dominate Fe(III) reduction in the absence of Fe(III)–oxalate complexes. Consequently, aqueous OH production is substantially enhanced via the Fenton reaction and sustained by the influx of HO2 from the gas phase. This mechanism is potentially the major mechanism for sustaining soluble Fe(II) in ambient aerosols and can be tested by a combination of modeling and aerosol Fe speciation measurements. We hypothesize that this mechanism may also be relevant to mineral Fe dissolution in dust aerosols.
Ng, N L., Steven S Brown, Alexander T Archibald, E L Atlas, R C Cohen, J N Crowley, Douglas A Day, N M Donahue, J L Fry, H Fuchs, R J Griffin, M I Guzman, H Hermann, Alma Hodzic, Y Iinuma, J L Jimenez, Astrid Kiendler-Scharr, B H Lee, D J Luecken, and Jingqiu Mao, et al., February 2017: Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms, and organic aerosol. Atmospheric Chemistry and Physics, 17(3), DOI:10.5194/acp-17-2103-2017. Abstract
Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO3) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than three decades, during which time a large body of research has emerged from laboratory, field and modeling studies. NO3-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms and organic aerosol yields for NO3-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO3 within the poorly mixed nocturnal atmosphere and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry-climate models.
This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first section summarizes the current literature on NO3-BVOC chemistry, with a particular focus on recent advances in instrumentation and models, and in organic nitrate and secondary organic aerosol (SOA) formation chemistry. Building on this current understanding, the second half of the review outlines impacts of NO3-BVOC chemistry on air quality and climate, and suggests critical research needs to better constrain this interaction to improve the predictive capabilities of atmospheric models.
Prather, Michael J., X Zhu, C Flynn, Sarah A Strode, J Rodriguez, S Steenrod, J Liu, Jean-Francois Lamarque, Arlene M Fiore, Larry W Horowitz, and Jingqiu Mao, et al., June 2017: Global Atmospheric Chemistry – Which Air Matters. Atmospheric Chemistry and Physics, 17(14), DOI:10.5194/acp-17-9081-2017. Abstract
An approach for analysis and modeling of global atmospheric chemistry is developed for application to measurements that provide a tropospheric climatology of those heterogeneously distributed, reactive species that control the loss of methane and the production and loss of ozone. We identify key species (e.g., O3, NOx, HNO3, HNO4, C2H3NO5, H2O, HOOH, CH3OOH, HCHO, CO, CH4, C2H6, acetaldehyde, acetone), and presume that they can be measured simultaneously in air parcels on the scale of a few km horizontally and a few tenths vertically. Six global models have prepared such climatologies (at model resolution) for August with emphasis on the vast central Pacific and Atlantic Ocean basins. We show clear differences in model generated reactivities as well as species covariances that could readily be discriminated with an unbiased climatology. A primary tool is comparison of multi-dimensional probability densities of key species weighted by frequency of occurrence as well as by the reactivity of the parcels with respect to methane and ozone. The reactivity-weighted probabilities tell us which parcels matter in this case. Testing 100-km scale models with 2-km measurements using these tools also addresses a core question about model resolution and whether fine-scale atmospheric structures matter to the overall ozone and methane budget. A new method enabling these six global chemistry-climate models to ingest an externally-sourced climatology and then compute air parcel reactivity is demonstrated. Such an observed climatology is anticipated from the NASA Atmospheric Tomography (ATom) aircraft mission (2015–2020), measuring the key species, executing profiles over the Pacific and Atlantic Ocean basins. This work is a core part of the design of ATom.
Fisher, J A., D J Jacob, K R Travis, P S Kim, Eloise A Marais, C Chan Miller, K Yu, L Zhu, R M Yantosca, M P Sulprizio, and Jingqiu Mao, et al., May 2016: Organic nitrate chemistry and its implications for nitrogen budgets in an isoprene- and monoterpene-rich atmosphere: constraints from aircraft (SEAC4RS) and ground-based (SOAS) observations in the Southeast US. Atmospheric Chemistry and Physics Discussions, 16(9), DOI:10.5194/acp-16-5969-2016. Abstract
Formation of organic nitrates (RONO2) during oxidation of biogenic volatile organic compounds (BVOCs: isoprene, monoterpenes) is a significant loss pathway for atmospheric nitrogen oxide radicals (NOx), but the chemistry of RONO2 formation and degradation remains uncertain. Here we implement a new BVOC oxidation mechanism (including updated isoprene chemistry, new monoterpene chemistry, and particle uptake of RONO2) in the GEOS-Chem global chemical transport model with ∼ 25 × 25 km2 resolution over North America. We evaluate the model using aircraft (SEAC4RS) and ground-based (SOAS) observations of NOx, BVOCs, and RONO2 from the Southeast US in summer 2013. The updated simulation successfully reproduces the concentrations of individual gas- and particle-phase RONO2 species measured during the campaigns. Gas-phase isoprene nitrates account for 25–50 % of observed RONO2 in surface air, and we find that another 10 % is contributed by gas-phase monoterpene nitrates. Observations in the free troposphere show an important contribution from long-lived nitrates derived from anthropogenic VOCs. During both campaigns, at least 10 % of observed boundary layer RONO2 were in the particle phase. We find that aerosol uptake followed by hydrolysis to HNO3 accounts for 60 % of simulated gas-phase RONO2 loss in the boundary layer. Other losses are 20 % by photolysis to recycle NOx and 15 % by dry deposition. RONO2 production accounts for 20 % of the net regional NOx sink in the Southeast US in summer, limited by the spatial segregation between BVOC and NOx emissions. This segregation implies that RONO2 production will remain a minor sink for NOx in the Southeast US in the future even as NOx emissions continue to decline.
Li, J, Jingqiu Mao, K-E Min, R A Washenfelder, Steven S Brown, J Kaiser, F N Keutsch, R Volkamer, G M Wolfe, T F Hanisco, I B Pollack, Marta Abalos, M Graus, J B Gilman, B M Lerner, C Warneke, J A de Gouw, Ann M Middlebrook, J Liao, A Welti, B H Henderson, V Faye McNeill, S R Hall, K Ullmann, Leo J Donner, Fabien Paulot, and Larry W Horowitz, August 2016: Observational constraints on glyoxal production from isoprene oxidation and its contribution to organic aerosol over the Southeast United States. Journal of Geophysical Research: Atmospheres, 121(16), DOI:10.1002/2016JD025331. Abstract
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.
Nault, Benjamin A., C Garland, P J Wooldridge, W Brune, Pedro Campuzano-Jost, John D Crounse, Douglas A Day, Jack E Dibb, S R Hall, L G Huey, J L Jimenez, Xiaoping Liu, and Jingqiu Mao, et al., April 2016: Observational Constraints on the Oxidation of NOx in the Upper Troposphere. Journal of Physical Chemistry A, 120(9), DOI:10.1021/acs.jpca.5b07824. Abstract
NOx (NOx ≡ NO + NO2) regulates O3 and HOx (HOx ≡ OH + HO2) concentrations in the upper troposphere. In the laboratory, it is difficult to measure rates and branching ratios of the chemical reactions affecting NOx at the low temperatures and pressures characteristic of the upper troposphere, making direct measurements in the atmosphere especially useful. We report quasi-Lagrangian observations of the chemical evolution of an air parcel following a lightning event that results in high NOx concentrations. These quasi-Lagrangian measurements obtained during the Deep Convective Clouds and Chemistry experiment are used to characterize the daytime rates for conversion of NOx to different peroxy nitrates, the sum of alkyl and multifunctional nitrates, and HNO3. We infer the following production rate constants [in (cm3/molecule)/s] at 225 K and 230 hPa: 7.2(±5.7) × 10–12 (CH3O2NO2), 5.1(±3.1) × 10–13 (HO2NO2), 1.3(±0.8) × 10–11 (PAN), 7.3(±3.4) × 10–12 (PPN), and 6.2(±2.9) × 10–12 (HNO3). The HNO3 and HO2NO2 rates are ∼30–50% lower than currently recommended whereas the other rates are consistent with current recommendations to within ±30%. The analysis indicates that HNO3 production from the HO2 and NO reaction (if any) must be accompanied by a slower rate for the reaction of OH with NO2, keeping the total combined rate for the two processes at the rate reported for HNO3 production above.
Nicely, J M., D C Anderson, T P Canty, R J Salawitch, G M Wolfe, E C Apel, S R Arnold, E L Atlas, N J Blake, J F Bresch, T L Campos, R R Dickerson, B N Duncan, Louisa K Emmons, M J Evans, R P Fernandez, Johannes Flemming, S R Hall, T F Hanisco, S B Honomichl, R S Hornbroook, V Huijnen, L Kaser, Douglas Kinnison, Jean-Francois Lamarque, and Jingqiu Mao, et al., June 2016: An observationally constrained evaluation of the oxidative capacity in the tropical western Pacific troposphere. Journal of Geophysical Research: Atmospheres, 121(12), DOI:10.1002/2016JD025067. Abstract
Hydroxyl radical (OH) is the main daytime oxidant in the troposphere and determines the atmospheric lifetimes of many compounds. We use aircraft measurements of O3, H2O, NO, and other species from the Convective Transport of Active Species in the Tropics (CONTRAST) field campaign, which occurred in the tropical western Pacific (TWP) during January–February 2014, to constrain a photochemical box model and estimate concentrations of OH throughout the troposphere. We find that tropospheric column OH (OHCOL) inferred from CONTRAST observations is 12 to 40% higher than found in chemical transport models (CTMs), including CAM-chem-SD run with 2014 meteorology as well as eight models that participated in POLMIP (2008 meteorology). Part of this discrepancy is due to a clear-sky sampling bias that affects CONTRAST observations; accounting for this bias and also for a small difference in chemical mechanism results in our empirically based value of OHCOL being 0 to 20% larger than found within global models. While these global models simulate observed O3 reasonably well, they underestimate NOx (NO + NO2) by a factor of 2, resulting in OHCOL ~30% lower than box model simulations constrained by observed NO. Underestimations by CTMs of observed CH3CHO throughout the troposphere and of HCHO in the upper troposphere further contribute to differences between our constrained estimates of OH and those calculated by CTMs. Finally, our calculations do not support the prior suggestion of the existence of a tropospheric OH minimum in the TWP, because during January–February 2014 observed levels of O3 and NO were considerably larger than previously reported values in the TWP.
We update and evaluate the treatment of nitrate aerosols in the Geophysical Fluid Dynamics Laboratory (GFDL) atmospheric model (AM3). Accounting for the radiative effects of nitrate aerosols generally improves the simulated aerosol optical depth, although nitrate concentrations at the surface are biased high. This bias can be reduced by increasing the deposition of nitrate to account for the near-surface volatilization of ammonium nitrate or by neglecting the heterogeneous production of nitric acid to account for the inhibition of N2O5 reactive uptake at high nitrate concentrations. Globally, uncertainties in these processes can impact the simulated nitrate optical depth by up to 25 %, much more than the impact of uncertainties in the seasonality of ammonia emissions (6 %) or in the uptake of nitric acid on dust (13 %). Our best estimate for present-day fine nitrate optical depth at 550 nm is 0.006 (0.005–0.008). We only find a modest increase of nitrate optical depth (< 30 %) in response to the projected changes in the emissions of SO2 (−40 %) and ammonia (+38 %) from 2010 to 2050. Nitrate burden is projected to increase in the tropics and in the free troposphere, but to decrease at the surface in the midlatitudes because of lower nitric acid concentrations. Our results suggest that better constraints on the heterogeneous chemistry of nitric acid on dust, on tropical ammonia emissions, and on the transport of ammonia to the free troposphere are needed to improve projections of aerosol optical depth.
Warneke, C, M Trainer, J A de Gouw, David D Parrish, D W Fahey, A R Ravishankara, Ann M Middlebrook, C A Brock, J M Roberts, Steven S Brown, J Andrew Neuman, B M Lerner, D Lack, D Law, G Hübler, I B Pollack, S Sjostedt, Thomas B Ryerson, J B Gilman, J Liao, J Holloway, Jeff Peischl, John B Nowak, Kenneth C Aikin, K-E Min, R A Washenfelder, M Graus, M Richardson, M Z Markovic, N L Wagner, A Welti, P R Veres, P Edwards, J P Schwarz, T Gordon, W P Dube, S A McKeen, Jerome Brioude, R Ahmadov, A Bougiatioti, Jack J Lin, A Nenes, G M Wolfe, T F Hanisco, B H Lee, Felipe D Lopez-Hilfiker, J A Thornton, F N Keutsch, J Kaiser, Jingqiu Mao, and C D Hatch, July 2016: Instrumentation and measurement strategy for the NOAA SENEX aircraft campaign as part of the Southeast Atmosphere Study 2013. Atmospheric Measurement Techniques, 9(7), DOI:10.5194/amt-9-3063-2016. Abstract
Natural emissions of ozone-and-aerosol-precursor gases such as isoprene and monoterpenes are high in the southeastern US. In addition, anthropogenic emissions are significant in the southeastern US and summertime photochemistry is rapid. The NOAA-led SENEX (Southeast Nexus) aircraft campaign was one of the major components of the Southeast Atmosphere Study (SAS) and was focused on studying the interactions between biogenic and anthropogenic emissions to form secondary pollutants. During SENEX, the NOAA WP-3D aircraft conducted 20 research flights between 27 May and 10 July 2013 based out of Smyrna, TN.
Here we describe the experimental approach, the science goals and early results of the NOAA SENEX campaign. The aircraft, its capabilities and standard measurements are described. The instrument payload is summarized including detection limits, accuracy, precision and time resolutions for all gas-and-aerosol phase instruments. The inter-comparisons of compounds measured with multiple instruments on the NOAA WP-3D are presented and were all within the stated uncertainties, except two of the three NO2 measurements.
The SENEX flights included day- and nighttime flights in the southeastern US as well as flights over areas with intense shale gas extraction (Marcellus, Fayetteville and Haynesville shale). We present one example flight on 16 June 2013, which was a daytime flight over the Atlanta region, where several crosswind transects of plumes from the city and nearby point sources, such as power plants, paper mills and landfills, were flown. The area around Atlanta has large biogenic isoprene emissions, which provided an excellent case for studying the interactions between biogenic and anthropogenic emissions. In this example flight, chemistry in and outside the Atlanta plumes was observed for several hours after emission. The analysis of this flight showcases the strategies implemented to answer some of the main SENEX science questions.
Wolfe, G M., J Kaiser, T F Hanisco, F N Keutsch, J A de Gouw, J B Gilman, M Graus, C D Hatch, J Holloway, Larry W Horowitz, B H Lee, B M Lerner, Felipe D Lopez-Hilfiker, and Jingqiu Mao, et al., March 2016: Formaldehyde production from isoprene oxidation across NOx regimes. Atmospheric Chemistry and Physics, 16(4), DOI:10.5194/acp-16-2597-2016. Abstract
The chemical link between isoprene and formaldehyde (HCHO) is a strong, nonlinear function of NOx (i.e., NO + NO2). This relationship is a linchpin for top-down isoprene emission inventory verification from orbital HCHO column observations. It is also a benchmark for overall photochemical mechanism performance with regard to VOC oxidation. Using a comprehensive suite of airborne in situ observations over the southeast US, we quantify HCHO production across the urban–rural spectrum. Analysis of isoprene and its major first-generation oxidation products allows us to define both a "prompt" yield of HCHO (molecules of HCHO produced per molecule of freshly emitted isoprene) and the background HCHO mixing ratio (from oxidation of longer-lived hydrocarbons). Over the range of observed NOx values (roughly 0.1–2 ppbv), the prompt yield increases by a factor of 3 (from 0.3 to 0.9 ppbv ppbv−1), while background HCHO increases by a factor of 2 (from 1.6 to 3.3 ppbv). We apply the same method to evaluate the performance of both a global chemical transport model (AM3) and a measurement-constrained 0-D steady-state box model. Both models reproduce the NOx dependence of the prompt HCHO yield, illustrating that models with updated isoprene oxidation mechanisms can adequately capture the link between HCHO and recent isoprene emissions. On the other hand, both models underestimate background HCHO mixing ratios, suggesting missing HCHO precursors, inadequate representation of later-generation isoprene degradation and/or underestimated hydroxyl radical concentrations. Detailed process rates from the box model simulation demonstrate a 3-fold increase in HCHO production across the range of observed NOx values, driven by a 100 % increase in OH and a 40 % increase in branching of organic peroxy radical reactions to produce HCHO.
Arnold, S R., Louisa K Emmons, S A Monks, K Law, D A Ridley, S Turquety, Simone Tilmes, J L Thomas, I Bouarar, V Huijnen, and Jingqiu Mao, et al., June 2015: Biomass burning influence on high latitude tropospheric ozone and reactive nitrogen in summer 2008: a multi-model analysis based on POLMIP simulations. Atmospheric Chemistry and Physics, 15(11), DOI:10.5194/acp-15-6047-2015. Abstract
We have evaluated tropospheric ozone enhancement in air dominated by biomass burning emissions at high laititudes (> 50˚ N) in July 2008, using 10 global chemical transport model simulations from the POLMIP multi-model comparison exercise. In model air masses dominated by fire emissions, Δ O3/ΔCO values ranged between 0.039 and 0.196 ppbv ppbv−1 (mean: 0.113 ppbv ppbv−1) in freshly fire-influenced air, and between 0.140 and 0.261 ppbv ppbv−1 (mean: 0.193 ppbv) in more aged fire-influenced air. These values are in broad agreement with the range of observational estimates from the literature. Model ΔPAN/ΔCO enhancement ratios show distinct groupings according to the meteorological data used to drive the models. ECMWF-forced models produce larger ΔPAN/ΔCO values (4.44–6.28 pptv ppbv−1) than GEOS5-forced models (2.02–3.02 pptv ppbv−1), which we show is likely linked to differences efficiency of vertical transport during poleward export from mid-latitude source regions. Simulations of a large plume of biomass burning and anthropogenic emissions exported from Asia towards the Arctic using a Lagrangian chemical transport model show that 4 day net ozone change in the plume is sensitive to differences in plume chemical composition and plume vertical position among the POLMIP models. In particular, Arctic ozone evolution in the plume is highly sensitive to initial concentrations of PAN, as well as oxygenated VOCs (acetone, acetaldehyde), due to their role in producing the peroxyacetyl radical PAN precursor. Vertical displacement is also important due to its effects on the stability of PAN, and subsequent effect on NOx abundance. In plumes where net ozone production is limited, we find that the lifetime of ozone in the plume is sensitive to hydrogen peroxide loading, due to the production of HO2 from peroxide photolysis, and the key role of HO2 + O3 in controlling ozone loss. Overall, our results suggest that emissions from biomass burning lead to large-scale photochemical enhancement in high latitude tropospheric ozone during summer.
Emmons, Louisa K., S R Arnold, S A Monks, V Huijnen, Simone Tilmes, K Law, J L Thomas, J-C Raut, I Bouarar, S Turquety, Y Long, B N Duncan, S Steenrod, Sarah A Strode, Johannes Flemming, and Jingqiu Mao, et al., June 2015: The POLARCAT Model Intercomparison Project (POLMIP): overview and evaluation with observations. Atmospheric Chemistry and Physics, 15(12), DOI:10.5194/acp-15-6721-2015. Abstract
Eleven 3D tropospheric chemistry models have been compared and evaluated with observations in the Arctic during the International Polar Year (IPY 2008). Large differences are seen among the models, particularly related to the model chemistry of volatile organic compounds (VOCs) and reactive nitrogen (NOx, PAN, HNO3) partitioning. Consistency among the models in the underestimation of CO, ethane and propane indicates the emission inventory is too low for these compounds.
Fu, T-M, Y Zheng, Fabien Paulot, Jingqiu Mao, and R M Yantosca, May 2015: Positive but variable sensitivity of August surface ozone to large-scale warming in the southeast United States. Nature Climate Change, 5(5), DOI:10.1038/nclimate2567. Abstract
Surface ozone, a major air pollutant toxic to humans and damaging to ecosystems(1,2), is produced by the oxidation of volatile organic compounds in the presence of nitrogen oxides (NOx = NO + NO2) and sunlight. Climate warming may affect future surface ozone levels(3-6) even in the absence of anthropogenic emission changes, but the direction of ozone change due to climate warming remains uncertain over the southeast US and other polluted forested areas(3-10). Here we use observations and simulations to diagnose the sensitivity of August surface ozone to large-scale temperature variations in the southeast US during 1988-2011. We show that the enhanced biogenic emissions and the accelerated photochemical reaction rates associated with warmer temperatures both act to increase surface ozone. However, the sensitivity of surface ozone to large-scale warming is highly variable on interannual and interdecadal timescales owing to variation in regional ozone advection. Our results have important implications for the prediction and management of future ozone air quality.
Monks, S A., S R Arnold, Louisa K Emmons, K Law, S Turquety, B N Duncan, Johannes Flemming, V Huijnen, Simone Tilmes, J Langner, and Jingqiu Mao, et al., March 2015: Multi-model study of chemical and physical controls on transport of anthropogenic and biomass burning pollution to the Arctic. Atmospheric Chemistry and Physics, 15(6), DOI:10.5194/acp-15-3575-2015. Abstract
Using observations from aircraft, surface stations and satellite, we comprehensively evaluate multi-model simulations of carbon monoxide (CO) and ozone (O3) in the Arctic and over lower latitude emission regions, as part of the POLARCAT Model Inter-comparison Project (POLMIP). Evaluation of eleven atmospheric models with chemistry shows that they generally underestimate CO throughout the Arctic troposphere, with the largest biases found during winter and spring. Negative CO biases are also found throughout the Northern Hemisphere, with multi-model mean gross errors (9–12%) suggesting models perform similarly over Asia, North America and Europe. A multi-model annual mean tropospheric OH (10.8 ± 0.6 × 105 molec cm−3) is found to be slightly higher than previous estimates of OH constrained by methyl chloroform, suggesting negative CO biases in models may be improved through better constraints on OH. Models that have lower Arctic OH do not always show a substantial improvement in their negative CO biases, suggesting that Arctic OH is not the dominant factor controlling the Arctic CO burden in these models. In addition to these general biases, models do not capture the magnitude of CO enhancements observed in the Arctic free troposphere in summer, suggesting model errors in the simulation of plumes that are transported from anthropogenic and biomass burning sources at lower latitudes. O3 in the Arctic is also generally underestimated, particularly at the surface and in the upper troposphere. Summer O3 comparisons over lower latitudes show several models overestimate upper tropospheric concentrations.
Simulated CO, O3 and OH all demonstrate a substantial degree of inter-model variability. Idealised CO-like tracers are used to quantitatively compare the impact of inter-model differences in transport and OH on CO in the Arctic troposphere. The tracers show that model differences in transport from Europe in winter and from Asia throughout the year are important sources of model variability at the Barrow. Unlike transport, inter-model variability in OH similarly affects all regional tracers at Barrow. Comparisons of fixed lifetime and OH-loss idealised CO-like tracers throughout the Arctic troposphere show that OH differences are a much larger source of inter-model variability than transport differences. The concentration of OH in the models is found to be correlated with inter-model differences in H2O, suggesting it to be an important driver of differences in simulated concentrations of CO and OH at high latitudes in these simulations. Despite inter-model differences in transport and OH, the relative contributions from the different source regions (North America, Europe and Asia) and different source types (anthropogenic and biomass burning) are comparable across the models. Fire emissions from the boreal regions in 2008 contribute 33, 43 and 19% to the total Arctic CO-like tracer in spring, summer and autumn, respectively, highlighting the importance of boreal fire emissions in controlling pollutant burdens in the Arctic.
Fischer, E V., D J Jacob, R M Yantosca, D B Millet, and Jingqiu Mao, et al., March 2014: Atmospheric peroxyacetyl nitrate (PAN): a global budget and source attribution. Atmospheric Chemistry and Physics, 14(5), DOI:10.5194/acp-14-2679-2014. Abstract
Peroxyacetyl nitrate (PAN) formed in the atmospheric oxidation of non-methane volatile organic compounds (NMVOCs) is the principal tropospheric reservoir for nitrogen oxide radicals (NOx = NO + NO2). PAN enables the transport and release of NOx to the remote troposphere with major implications for the global distributions of ozone and OH, the main tropospheric oxidants. Simulation of PAN is a challenge for global models because of the dependence of PAN on vertical transport as well as complex and uncertain NMVOC sources and chemistry. Here we use an improved representation of NMVOCs in a global 3-D chemical transport model (GEOS-Chem) and show that it can simulate PAN observations from aircraft campaigns worldwide. The immediate carbonyl precursors for PAN formation include acetaldehyde (44% of the global source), methylglyoxal (30%), acetone (7%), and a suite of other isoprene and terpene oxidation products (19%). A diversity of NMVOC emissions is responsible for PAN formation globally including isoprene (37%) and alkanes (14%). Anthropogenic sources are dominant in the extratropical Northern Hemisphere outside the growing season. Open fires appear to play little role except at high northern latitudes in spring, although results are very sensitive to plume chemistry and plume rise. Lightning NOx is the dominant contributor to the observed PAN maximum in the free troposphere over the South Atlantic.
Barkley, M P., and Jingqiu Mao, et al., June 2013: Top-down isoprene emissions over tropical South America inferred from SCIAMACHY and OMI formaldehyde columns. Journal of Geophysical Research, 18(12), DOI:10.1002/jgrd.50552. Abstract
We use formaldehyde (HCHO) vertical column measurements from the Scanning Imaging Absorption spectrometer for Atmospheric Chartography (SCIAMACHY) and Ozone Monitoring Instrument (OMI), and a nested-grid version of the GEOS-Chem chemistry transport model, to infer an ensemble of top-down isoprene emission estimates from tropical South America during 2006, using different model configurations and assumptions in the HCHO air-mass factor (AMF) calculation. Scenes affected by biomass burning are removed on a daily basis using fire count observations, and we use the local model sensitivity to identify locations where the impact of spatial smearing is small, though this comprises spatial coverage over the region. We find that the use of the HCHO column data more tightly constrains the ensemble isoprene emission range from 27–61 Tg C to 31–38 Tg C for SCIAMACHY, and 45–104 Tg C to 28–38 Tg C for OMI. Median uncertainties of the top-down emissions are about 60–260% for SCIAMACHY, and 10–90% for OMI. We find that the inferred emissions are most sensitive to uncertainties in cloud fraction and cloud top pressure (differences of ±10%), the a priori isoprene emissions (±20%), and the HCHO vertical column retrieval (±30%). Construction of continuous top-down emission maps generally improves GEOS-Chem's simulation of HCHO columns over the region, with respect to both the SCIAMACHY and OMI data. However, if local time top-down emissions are scaled to monthly mean values, the annual emission inferred from SCIAMACHY are nearly twice those from OMI. This difference cannot be explained by the different sampling of the sensors or uncertainties in the AMF calculation.
Mao, Jingqiu, Songmiao Fan, Marta Abalos, and K R Travis, January 2013: Radical loss in the atmosphere from Cu-Fe redox coupling in aerosols. Atmospheric Chemistry and Physics, 13(2), DOI:10.5194/acp-13-509-2013. Abstract
The hydroperoxyl radical (HO2) is a major precursor of OH and tropospheric ozone. OH is the main atmospheric oxidant, while tropospheric ozone is an important surface pollutant and greenhouse gas. Standard gas-phase models for atmospheric chemistry tend to overestimate observed HO2 concentrations, and this has been tentatively attributed to heterogeneous uptake by aerosol particles. It is generally assumed that HO2 uptake by aerosol involve conversion to H2O2, but this is of limited efficacy as an HO2 sink because H2O2 can photolyze to regenerate OH and from there HO2. Joint atmospheric observations of HO2 and H2O2 suggest that HO2 uptake by aerosols may in fact not produce H2O2. Here we propose a catalytic mechanism involving coupling of the transition metal ions (TMI) Cu(I)/Cu(II) and Fe(II)/Fe(III) to rapidly convert HO2 to H2O in aerosols. The implied HO2 uptake significantly affects global model predictions of tropospheric OH, ozone, and other species, improving comparisons to observations, and may have a major and previously unrecognized impact on atmospheric oxidant chemistry.
Biomass burning is one of the largest sources of trace gases and aerosols to the atmosphere, and has profound influence on tropospheric oxidants and radiative forcing. Using a fully coupled chemistry-climate model (GFDL AM3), we find that co-emission of trace gases and aerosol from present-day biomass burning increases the global tropospheric ozone burden by 5.1%, and decreases global mean OH by 6.3%. Gas and aerosol emissions combine to increase CH4 lifetime non-linearly. Heterogeneous processes are shown to contribute partly to the observed lower ΔO3/ΔCO ratios in northern high latitudes versus tropical regions. The radiative forcing from biomass burning is shown to vary non-linearly with biomass burning strength. At present-day emission levels, biomass burning produces a net radiative forcing of −0.19 W/m2 (−0.29 from short-lived species, mostly aerosol direct and indirect effects, +0.10 from CH4 and CH4-induced changes in O3 and stratospheric H2O), but increasing emissions to over 5 times present levels would result in a positive net forcing.
Mao, Jingqiu, Fabien Paulot, D J Jacob, R C Cohen, John D Crounse, P O Wennberg, Christoph A Keller, R Hudman, M P Barkley, and Larry W Horowitz, October 2013: Ozone and organic nitrates over the eastern United States: sensitivity to isoprene chemistry. Journal of Geophysical Research: Atmospheres, 118(19), DOI:10.1002/jgrd.50817. Abstract
We implement a new isoprene oxidation mechanism in a global 3-D chemical transport model (GEOS-Chem). Model results are evaluated with observations for ozone, isoprene oxidation products, and related species from the ICARTT aircraft campaign over the eastern United States in summer 2004. The model achieves an unbiased simulation of ozone in the boundary layer and the free troposphere, reflecting canceling effects from recent model updates for isoprene chemistry, bromine chemistry, and HO2 loss to aerosols. Simulation of the ozone-CO correlation is improved relative to previous versions of the model and this is attributed to a lower and reversible yield of isoprene nitrates, increasing the ozone production efficiency (OPE) per unit of nitrogen oxides (NOx ≡ NO + NO2). The model successfully reproduces the observed concentrations of organic nitrates (∑ANs) and their correlations with HCHO and ozone. ∑ANs in the model is principally composed of secondary isoprene nitrates, including a major contribution from nighttime isoprene oxidation. The correlations of ∑ANs with HCHO and ozone then provide sensitive tests of isoprene chemistry and argue in particular against a fast isomerization channel for isoprene peroxy radicals. ∑ANs can provide an important reservoir for exporting NOx from the US boundary layer. We find that the dependence of surface ozone on isoprene emission is positive throughout the US, even if NOx emissions are reduced by a factor of 4. Previous models showed negative dependences that we attribute to erroneous titration of OH by isoprene.
We describe and evaluate atmospheric chemistry in the newly developed Geophysical Fluid Dynamics Laboratory chemistry-climate model (GFDL AM3) and apply it to investigate the net impact of preindustrial (PI) to present (PD) changes in short-lived pollutant emissions (ozone precursors, sulfur dioxide, and carbonaceous aerosols) and methane concentration on atmospheric composition and climate forcing. The inclusion of online troposphere-stratosphere interactions, gas-aerosol chemistry, and aerosol-cloud interactions (including direct and indirect aerosol radiative effects) in AM3 enables a more complete representation of interactions among short-lived species, and thus their net climate impact, than was considered in previous climate assessments. The base AM3 simulation, driven with observed sea surface temperature (SST) and sea ice cover (SIC) over the period 1981–2007, generally reproduces the observed mean magnitude, spatial distribution, and seasonal cycle of tropospheric ozone and carbon monoxide. The global mean aerosol optical depth in our base simulation is within 5% of satellite measurements over the 1982–2006 time period. We conduct a pair of simulations in which only the short-lived pollutant emissions and methane concentrations are changed from PI (1860) to PD (2000) levels (i.e., SST, SIC, greenhouse gases, and ozone depleting substances are held at PD levels). From the PI to PD, we find that changes in short-lived pollutant emissions and methane have caused the tropospheric ozone burden to increase by 39% and the global burdens of sulfate, black carbon and organic carbon to increase by factors of 3, 2.4 and 1.4, respectively. Tropospheric hydroxyl concentration decreases by 7%, showing that increases in OH sinks (methane, carbon monoxide, non-methane volatile organic compounds, and sulfur dioxide) dominate over sources (ozone and nitrogen oxides) in the model. Combined changes in tropospheric ozone and aerosols cause a net negative top-of-the-atmosphere radiative forcing perturbation (−1.05 Wm-2) indicating that the negative forcing (direct plus indirect) from aerosol changes dominates over the positive forcing due to ozone increases, thus masking nearly half of the PI to PD positive forcing from long-lived greenhouse gases globally, consistent with other current generation chemistry-climate models.
Ren, X, and Jingqiu Mao, et al., June 2013: Atmospheric Oxidation Chemistry and Ozone Production: Results from SHARP 2009 in Houston, Texas. Journal of Geophysical Research: Atmospheres, 118(11), DOI:10.1002/jgrd.50342. Abstract
Ozone (O3) and secondary fine particles come from the atmospheric oxidation chemistry that involves the hydroxyl radical (OH) and hydroperoxyl radical (HO2), which are together called HOx. Radical precursors such as nitrous acid (HONO) and formaldehyde (HCHO) significantly affect the HOx budget in urban environments. These chemical processes connect surface anthropogenic and natural emissions to local and regional air pollution. Using the data collected during the Study of Houston Atmospheric Radical Precursors (SHARP) in spring 2009, we examine atmospheric oxidation chemistry and O3 production in this polluted urban environment. A numerical box model with five different chemical mechanisms was used to simulate the oxidation processes and thus OH and HO2 in this study. In general, the model reproduced the measured OH and HO2 with all five chemical mechanisms producing similar levels of OH and HO2, although midday OH was over-predicted and nighttime OH and HO2 were under-predicted. The calculated HOx production was dominated by HONO photolysis in the early morning and by the photolysis of O3 and oxygenated volatile organic compounds (OVOCs) in the midday. On average, the daily HOx production rate was 24.6 ppbv d-1, of which 30% was from O3 photolysis, 22% from HONO photolysis, 15% from the photolysis of OVOCs (other than HCHO), 14% from HCHO photolysis, and 13% from O3 reactions with alkenes. The O3 production was sensitive to volatile organic compounds (VOCs) in the early morning but was sensitive to NOx for most of afternoon. This is similar to the behavior observed in two previous summertime studies in Houston: the Texas Air Quality Study in 2000 (TexAQS 2000) and the TexAQS II Radical and Aerosol Measurement Project in 2006 (TRAMP 2006). Ozone production in SHARP exhibits a longer NOx-sensitive period than TexAQS 2000 and TRAMP 2006, indicating that NOx control may be an efficient approach for the O3 control in springtime for Houston. Results from this study provide additional support for regulatory actions to reduce NOx and reactive VOCs in Houston in order to reduce O3 and other secondary pollutants.
Worton, D R., and Jingqiu Mao, et al., October 2013: Observational Insights into Aerosol Formation from Isoprene. Environmental Science & Technology, 47(20), DOI:10.1021/es4011064. Abstract
Atmospheric photooxidation of isoprene is an important source of
secondary organic aerosol (SOA) and the
re is increasing evidence that anthro-
pogenic oxidant emissions can enhance t
his SOA formation. In this work, we use
ambient observations of organosulfates formed from isoprene epoxydiols
(IEPOX) and methacrylic acid epoxide (MAE) and a broad suite of che-
mical measurements to investigate the rela
tive importance of nitrogen oxide (NO/
NO
2
) and hydroperoxyl (HO
2
) SOA formation pathways from isoprene at a
forested site in California. In contrast to IEPOX, the calculated production rate of
MAE was observed to be independent of temperature. This is the result of the
very fast thermolysis of MPAN at high temperatures that a
ff
ects the distribution of
the MPAN reservoir (MPAN / MPA radical) reducing the fraction that can react
with OH to form MAE and subsequently SOA (F
MAE formation
). The strong
temperature dependence of F
MAE formation
helps to explain our observations of
similar concentrations of IEPOX-derived organosulfates (IEPOX-OS;
∼
1ngm
−
3
) and MAE-derived organosulfates (MAE-OS;
∼
1ngm
−
3
)
under cooler conditions (lower isoprene concentrations) and much higher IEPOX-OS (
∼
20 ng m
−
3
) relative to MAE-OS
(<0.0005 ng m
−
3
) at higher temperatures (higher isoprene concentrations). A kinetic model of IEPOX and MAE loss showed
that MAE forms 10
−
100 times more ring-opening products than IEPOX and that both are strongly dependent on aerosol water
content when aerosol pH is constant. However, the higher fraction of MAE ring opening products does not compensate for the
lower MAE production under warmer conditions (higher isoprene concentrations) resulting in lower formation of MAE-derived
products relative to IEPOX at the surface. In regions of high NO
x
, high isoprene emissions and strong vertical mixing the slower MPAN
thermolysis rate aloft could increase the fraction of MPAN that forms MAE resulting in a vertically varying isoprene SOA source.
Fischer, E V., D J Jacob, D B Millet, R M Yantosca, and Jingqiu Mao, January 2012: The role of the ocean in the global atmospheric budget of acetone. Geophysical Research Letters, 39, L01807, DOI:10.1029/2011GL050086. Abstract
Acetone is one of the most abundant carbonyl compounds in the atmosphere and it plays
an important role in atmospheric chemistry. The role of the ocean in the global atmospheric
acetone budget is highly uncertain, with past studies reaching opposite conclusions as to whether
the ocean is a source or sink. Here we use a global 3-D chemical transport model (GEOS-Chem)
simulation of atmospheric acetone to evaluate the role of air-sea exchange in the global budget.
Inclusion of updated (slower) photolysis loss in the model means that a large net ocean source is
not needed to explain observed acetone in marine air. We find that a simulation with a fixed
seawater acetone concentration of 15 nM based on observations can reproduce the observed
global patterns of atmospheric concentrations and air-sea fluxes. The Northern Hemisphere
oceans are a net sink for acetone while the tropical oceans are a net source. On a global scale the
ocean is in near-equilibrium with the atmosphere. Prescribing an ocean concentration of acetone
as a boundary condition in the model assumes that ocean concentrations are controlled by
internal production and loss, rather than by air-sea exchange. An implication is that the ocean
plays a major role in controlling atmospheric acetone. This hypothesis needs to be tested by
better quantification of oceanic acetone sources and sinks.
Lin, J-T, and Jingqiu Mao, et al., December 2012: Modeling uncertainties for tropospheric nitrogen dioxide columns affecting satellite-based inverse modeling of nitrogen oxides emissions. Atmospheric Chemistry and Physics, 12(24), DOI:10.5194/acp-12-12255-2012. Abstract
Errors in chemical transport models (CTMs) interpreting the relation between space-retrieved tropospheric column densities of nitrogen dioxide (NO2) and emissions of nitrogen oxides (NOx) have important consequences on the inverse modeling. They are however difficult to quantify due to lack of adequate in situ measurements, particularly over China and other developing countries. This study proposes an alternate approach for model evaluation over East China, by analyzing the sensitivity of modeled NO2 columns to errors in meteorological and chemical parameters/processes important to the nitrogen abundance. As a demonstration, it evaluates the nested version of GEOS-Chem driven by the GEOS-5 meteorology and the INTEX-B anthropogenic emissions and used with retrievals from the Ozone Monitoring Instrument (OMI) to constrain emissions of NOx. The CTM has been used extensively for such applications. Errors are examined for a comprehensive set of meteorological and chemical parameters using measurements and/or uncertainty analysis based on current knowledge. Results are exploited then for sensitivity simulations perturbing the respective parameters, as the basis of the following post-model linearized and localized first-order modification. It is found that the model meteorology likely contains errors of various magnitudes in cloud optical depth, air temperature, water vapor, boundary layer height and many other parameters. Model errors also exist in gaseous and heterogeneous reactions, aerosol optical properties and emissions of non-nitrogen species affecting the nitrogen chemistry. Modifications accounting for quantified errors in 10 selected parameters increase the NO2 columns in most areas with an average positive impact of 22% in July and 10% in January. This suggests a possible systematic model bias such that the top-down emissions will be overestimated by the same magnitudes if the model is used for emission inversion without corrections. The modifications however cannot account for the large model underestimates in cities and other extremely polluted areas (particularly in the north) as compared to satellite retrievals, likely pointing to underestimates of the a priori emission inventory in these places with important implications for understanding of atmospheric chemistry and air quality. Post-model modifications also have large impacts on surface ozone concentrations with the peak values in July over North China decreasing by about 15 ppb. Individually, modification for the uptake of the hydroperoxyl radical on aerosols has the largest impact for both NO2 and ozone, followed by various other parameters important for some species in some seasons. Note that these modifications are simplified and should be used with caution for error apportionment.
Mao, Jingqiu, et al., September 2012: Insights into hydroxyl measurements and atmospheric oxidation in a California forest. Atmospheric Chemistry and Physics, 12(17), DOI:10.5194/acp-12-8009-2012. Abstract
The understanding of oxidation in forest atmospheres is being challenged by measurements of unexpectedly large amounts of hydroxyl (OH). A significant number of these OH measurements were made by laser-induced fluorescence in low-pressure detection chambers (called Fluorescence Assay with Gas Expansion (FAGE)) using the Penn State Ground-based Tropospheric Hydrogen Oxides Sensor (GTHOS). We deployed a new chemical removal method to measure OH in parallel with the traditional FAGE method in a California forest. The new method gives on average only 40–60% of the OH from the traditional method and this discrepancy is temperature dependent. Evidence indicates that the new method measures atmospheric OH while the traditional method is affected by internally generated OH, possibly from oxidation of biogenic volatile organic compounds. The improved agreement between OH measured by this new technique and modeled OH suggests that oxidation chemistry in at least one forest atmosphere is better understood than previously thought.
Marais, Eloise A., D J Jacob, T P Kurosu, K Chance, J G Murphy, C Reeves, G Mills, S Casadio, D B Millet, M P Barkley, Fabien Paulot, and Jingqiu Mao, July 2012: Isoprene emissions in Africa inferred from OMI observations of formaldehyde columns. Atmospheric Chemistry and Physics, 12(14), DOI:10.5194/acp-12-6219-2012. Abstract
We use 2005–2009 satellite observations of formaldehyde (HCHO) columns from the OMI instrument to infer biogenic isoprene emissions at monthly 1 × 1° resolution over the African continent. Our work includes new approaches to remove biomass burning influences using OMI absorbing aerosol optical depth data (to account for transport of fire plumes) and anthropogenic influences using AATSR satellite data for persistent small-flame fires (gas flaring). The resulting biogenic HCHO columns (ΩHCHO) from OMI follow closely the distribution of vegetation patterns in Africa. We infer isoprene emission (EISOP) from the local sensitivity S = ΔΩHCHO / ΔEISOP derived with the GEOS-Chem chemical transport model using two alternate isoprene oxidation mechanisms, and verify the validity of this approach using AMMA aircraft observations over West Africa and a longitudinal transect across central Africa. Displacement error (smearing) is diagnosed by anomalously high values of S and the corresponding data are removed. We find significant sensitivity of S to NOx under low-NOx conditions that we fit to a linear function of tropospheric column NO2. We estimate a 40% error in our inferred isoprene emissions under high-NOx conditions and 40–90% under low-NOx conditions. Our results suggest that isoprene emission from the central African rainforest is much lower than estimated by the state-of-the-science MEGAN inventory.
Olson, J, J H Crawford, W Brune, and Jingqiu Mao, et al., August 2012: An analysis of fast photochemistry over high northern latitudes during spring and summer using in-situ observations from ARCTAS and TOPSE. Atmospheric Chemistry and Physics, 12(15), DOI:10.5194/acp-12-6799-2012. Abstract
Observations of chemical constituents and meteorological quantities obtained during the two Arctic phases of the airborne campaign ARCTAS (Arctic Research of the Composition of the Troposphere from Aircraft and Satellites) are analyzed using an observationally constrained steady state box model. Measurements of OH and HO2 from the Penn State ATHOS instrument are compared to model predictions. Forty percent of OH measurements below 2 km are at the limit of detection during the spring phase (ARCTAS-A). While the median observed-to-calculated ratio is near one, both the scatter of observations and the model uncertainty for OH are at the magnitude of ambient values. During the summer phase (ARCTAS-B), model predictions of OH are biased low relative to observations and demonstrate a high sensitivity to the level of uncertainty in NO observations. Predictions of HO2 using observed CH2O and H2O2 as model constraints are up to a factor of two larger than observed. A temperature-dependent terminal loss rate of HO2 to aerosol recently proposed in the literature is shown to be insufficient to reconcile these differences. A comparison of ARCTAS-A to the high latitude springtime portion of the 2000 TOPSE campaign (Tropospheric Ozone Production about the Spring Equinox) shows similar meteorological and chemical environments with the exception of peroxides; observations of H2O2 during ARCTAS-A were 2.5 to 3 times larger than those during TOPSE. The cause of this difference in peroxides remains unresolved and has important implications for the Arctic HOx budget. Unconstrained model predictions for both phases indicate photochemistry alone is unable to simultaneously sustain observed levels of CH2O and H2O2; however when the model is constrained with observed CH2O, H2O2 predictions from a range of rainout parameterizations bracket its observations. A mechanism suitable to explain observed concentrations of CH2O is uncertain. Free tropospheric observations of acetaldehyde (CH2CHO) are 2–3 times larger than its predictions, though constraint of the model to those observations is sufficient to account for less than half of the deficit in predicted CH2O. The box model calculates gross O2 formation during spring to maximize from 1–4 km at 0.8 ppbv d−1, in agreement with estimates from TOPSE, and a gross production of 2–4 ppbv d−1 in the boundary layer and upper troposphere during summer. Use of the lower observed levels of HO2 in place of model predictions decreases the gross production by 25–50%. Net O3 production is near zero throughout the ARCTAS-A troposphere, and is 1–2 ppbv in the boundary layer and upper altitudes during ARCTAS-B.
Ren, X, and Jingqiu Mao, et al., August 2012: Airborne intercomparison of HOx measurements using laser-induced fluorescence and chemical ionization mass spectrometry during ARCTAS. Atmospheric Measurement Techniques, 5(8), DOI:10.5194/amt-5-2025-2012. Abstract
The hydroxyl (OH) and hydroperoxyl (HO2) radicals, collectively called HOx, play central roles in tropospheric chemistry. Accurate measurements of OH and HO2 are critical to examine our understanding of atmospheric chemistry. Intercomparisons of different techniques for detecting OH and HO2 are vital to evaluate their measurement capabilities. Three instruments that measured OH and/or HO2 radicals were deployed on the NASA DC-8 aircraft throughout Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) in the spring and summer of 2008. One instrument was the Penn State Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS) for OH and HO2 measurements based on Laser-Induced Fluorescence (LIF) spectroscopy. A second instrument was the NCAR Selected-Ion Chemical Ionization Mass Spectrometer (SI-CIMS) for OH measurement. A third instrument was the NCAR Peroxy Radical Chemical Ionization Mass Spectrometer (PeRCIMS) for HO2 measurement. Formal intercomparison of LIF and CIMS was conducted for the first time on a same aircraft platform. The three instruments were calibrated by quantitative photolysis of water vapor by ultraviolet (UV) light at 184.9 nm with three different calibration systems. The absolute accuracies were ±32% (2σ) for the LIF instrument, ±65% (2σ) for the SI-CIMS instrument, and ±50% (2σ) for the PeRCIMS instrument. In general, good agreement was obtained between the CIMS and LIF measurements of both OH and HO2 measurements. Linear regression of the entire data set yields [OH]CIMS = 0.89 × [OH]LIF + 2.8 × 104 cm−3 with a correlation coefficient r2 = 0.72 for OH, and [HO2]CIMS = 0.86 × [HO2]LIF + 3.9 parts per trillion by volume (pptv, equivalent to pmol mol−1) with a correlation coefficient r2 = 0.72 for HO2. In general, the difference between CIMS and LIF instruments for OH and HO2 measurements can be explained by their combined measurement uncertainties. Comparison with box model results shows some similarities for both the CIMS and LIF measurements. First, the observed-to-modeled HO2 ratio increases greatly for higher NO mixing ratios, indicating that the model may not properly account for HOx sources that correlate with NO. Second, the observed-to-modeled OH ratio increases with increasing isoprene mixing ratios, suggesting either incomplete understanding of isoprene chemistry in the model or interferences in the measurements in environments where biogenic emissions dominate ambient volatile organic compounds.
Barkley, M P., and Jingqiu Mao, August 2011: Can a “state of the art” chemistry transport model simulate Amazonian tropospheric chemistry?Journal of Geophysical Research: Atmospheres, 116, D16302, DOI:10.1029/2011JD015893. Abstract
We present an evaluation of a nested high-resolution Goddard Earth Observing System (GEOS)-Chem chemistry transport model simulation of tropospheric chemistry over tropical South America. The model has been constrained with two isoprene emission inventories: (1) the canopy-scale Model of Emissions of Gases and Aerosols from Nature (MEGAN) and (2) a leaf-scale algorithm coupled to the Lund-Potsdam-Jena General Ecosystem Simulator (LPJ-GUESS) dynamic vegetation model, and the model has been run using two different chemical mechanisms that contain alternative treatments of isoprene photo-oxidation. Large differences of up to 100 Tg C yr−1 exist between the isoprene emissions predicted by each inventory, with MEGAN emissions generally higher. Based on our simulations we estimate that tropical South America (30–85°W, 14°N–25°S) contributes about 15–35% of total global isoprene emissions. We have quantified the model sensitivity to changes in isoprene emissions, chemistry, boundary layer mixing, and soil NOx emissions using ground-based and airborne observations. We find GEOS-Chem has difficulty reproducing several observed chemical species; typically hydroxyl concentrations are underestimated, whilst mixing ratios of isoprene and its oxidation products are overestimated. The magnitude of model formaldehyde (HCHO) columns are most sensitive to the choice of chemical mechanism and isoprene emission inventory. We find GEOS-Chem exhibits a significant positive bias (10–100%) when compared with HCHO columns from the Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY) and Ozone Monitoring Instrument (OMI) for the study year 2006. Simulations that use the more detailed chemical mechanism and/or lowest isoprene emissions provide the best agreement to the satellite data, since they result in lower-HCHO columns.
Huisman, A J., and Jingqiu Mao, et al., September 2011: Photochemical modeling of glyoxal at a rural site: observations and analysis from BEARPEX 2007. Atmospheric Chemistry and Physics, 11(17), DOI:10.5194/acp-11-8883-2011. Abstract
We present roughly one month of high time-resolution, direct, in situ measurements of gas-phase glyoxal acquired during the BEARPEX 2007 field campaign. The research site, located on a ponderosa pine plantation in the Sierra Nevada mountains, is strongly influenced by biogenic volatile organic compounds (BVOCs); thus this data adds to the few existing measurements of glyoxal in BVOC-dominated areas. The short lifetime of glyoxal of ~1 h, the fact that glyoxal mixing ratios are much higher during high temperature periods, and the results of a photochemical model demonstrate that glyoxal is strongly influenced by BVOC precursors during high temperature periods.
A zero-dimensional box model using near-explicit chemistry from the Leeds Master Chemical Mechanism v3.1 was used to investigate the processes controlling glyoxal chemistry during BEARPEX 2007. The model showed that MBO is the most important glyoxal precursor (~67 %), followed by isoprene (~26 %) and methylchavicol (~6 %), a precursor previously not commonly considered for glyoxal production. The model calculated a noon lifetime for glyoxal of ~0.9 h, making glyoxal well suited as a local tracer of VOC oxidation in a forested rural environment; however, the modeled glyoxal mixing ratios over-predicted measured glyoxal by a factor 2 to 5. Loss of glyoxal to aerosol was not found to be significant, likely as a result of the very dry conditions, and could not explain the over-prediction. Although several parameters, such as an approximation for advection, were found to improve the model measurement discrepancy, reduction in OH was by far the most effective. Reducing model OH concentrations to half the measured values decreased the glyoxal over-prediction from a factor of 2.4 to 1.1, as well as the overprediction of HO2 from a factor of 1.64 to 1.14. Our analysis has shown that glyoxal is particularly sensitive to OH concentration compared to other BVOC oxidation products. This relationship arises from (i) the predominantly secondary- or higher-generation production of glyoxal from (mainly OH-driven, rather than O3-driven) BVOC oxidation at this site and (ii) the relative importance of photolysis in glyoxal loss as compared to reaction with OH. We propose that glyoxal is a useful tracer for OH-driven BVOC oxidation chemistry.
Wang, Q, D J Jacob, J A Fisher, and Jingqiu Mao, et al., December 2011: Sources of carbonaceous aerosols and deposited black carbon in the Arctic in winter-spring: implications for radiative forcing. Atmospheric Chemistry and Physics, 11(23), DOI:10.5194/acp-11-12453-2011. Abstract
We use a global chemical transport model (GEOS-Chem CTM) to interpret observations of black carbon (BC) and organic aerosol (OA) from the NASA ARCTAS aircraft campaign over the North American Arctic in April 2008, as well as longer-term records in surface air and in snow (2007–2009). BC emission inventories for North America, Europe, and Asia in the model are tested by comparison with surface air observations over these source regions. Russian open fires were the dominant source of OA in the Arctic troposphere during ARCTAS but we find that BC was of prevailingly anthropogenic (fossil fuel and biofuel) origin, particularly in surface air. This source attribution is confirmed by correlation of BC and OA with acetonitrile and sulfate in the model and in the observations. Asian emissions are the main anthropogenic source of BC in the free troposphere but European, Russian and North American sources are also important in surface air. Russian anthropogenic emissions appear to dominate the source of BC in Arctic surface air in winter. Model simulations for 2007–2009 (to account for interannual variability of fires) show much higher BC snow content in the Eurasian than the North American Arctic, consistent with the limited observations. We find that anthropogenic sources contribute 90% of BC deposited to Arctic snow in January-March and 60% in April–May 2007–2009. The mean decrease in Arctic snow albedo from BC deposition is estimated to be 0.6% in spring, resulting in a regional surface radiative forcing consistent with previous estimates.