Understanding and improving model representation of aerosol optical properties for a Chinese haze event measured during KORUS-AQ

KORUS-AQ was an international cooperative air quality field study in South Korea that measured local and remote sources of air pollution affecting the Korean Peninsula during May&ndash;June&nbsp;2016. Some of the largest aerosol mass concentrations were measured during a Chinese haze transport event (24&nbsp;May). Air quality forecasts using the WRF-Chem model with aerosol optical depth (AOD) data assimilation captured AOD during this pollution episode but overpredicted surface particulate matter concentrations in South Korea, especially PM2.5, often by a factor of 2 or larger. Analysis revealed multiple sources of model deficiency related to the calculation of optical properties from aerosol mass that explain these discrepancies. Using in situ observations of aerosol size and composition as inputs to the optical properties calculations showed that using a low-resolution size bin representation (four bins) underestimates the efficiency with which aerosols scatter and absorb light (mass extinction efficiency). Besides using finer-resolution size bins (8&ndash;16 bins), it was also necessary to increase the refractive indices and hygroscopicity of select aerosol species within the range of values reported in the literature to achieve better consistency with measured values of the mass extinction efficiency (6.7&thinsp;m2&thinsp;g&minus;1 observed average) and light-scattering enhancement factor (f(RH)) due to aerosol hygroscopic growth (2.2 observed average). Furthermore, an evaluation of the optical properties obtained using modeled aerosol properties revealed the inability of sectional and modal aerosol representations in WRF-Chem to properly reproduce the observed size distribution, with the models displaying a much wider accumulation mode. Other model deficiencies included an underestimate of organic aerosol density (1.0&thinsp;g&thinsp;cm&minus;3 in the model vs. observed average of 1.5&thinsp;g&thinsp;cm&minus;3) and an overprediction of the fractional contribution of submicron inorganic aerosols other than sulfate, ammonium, nitrate, chloride, and sodium corresponding to mostly dust (17&thinsp;%&ndash;28&thinsp;% modeled vs. 12&thinsp;% estimated from observations). These results illustrate the complexity of achieving an accurate model representation of optical properties and provide potential solutions that are relevant to multiple disciplines and applications such as air quality forecasts, health impact assessments, climate projections, solar power forecasts, and aerosol data assimilation. Full List of Authors: Pablo E. Saide1,2, Meng Gao3, Zifeng Lu4, Daniel L. Goldberg4, David G. Streets4, Jung-Hun Woo5, Andreas Beyersdorf6, Chelsea A. Corr7, Kenneth L. Thornhill8,18, Bruce Anderson8, Johnathan W. Hair8, Amin R. Nehrir8, Glenn S. Diskin8, Jose L. Jimenez9, Benjamin A. Nault9, Pedro Campuzano-Jost9, Jack Dibb10, Eric Heim10, Kara D. Lamb11, Joshua P. Schwarz11, Anne E. Perring12, Jhoon Kim13, Myungje Choi13,14, Brent Holben15, Gabriele Pfister16, Alma Hodzic16, Gregory R. Carmichael17, Louisa Emmons16, and James H. Crawford8 1Department of Atmospheric and Oceanic Sciences, University of California &ndash; Los Angeles, Los Angeles, CA, USA 2Institute of the Environment and Sustainability, University of California &ndash; Los Angeles, Los Angeles, CA, USA 3Department of Geography, Hong Kong Baptist University, Hong Kong SAR, China 4Energy Systems Division, Argonne National Laboratory, Lemont, IL 60439, USA 5Department of Technology Fusion Engineering, Konkuk University, Seoul, South Korea 6Department of Chemistry &amp; Biochemistry, California State University San Bernardino, San Bernardino, CA, USA 7USDA UV-B Monitoring and Research Program, Natural Resource Ecology Laboratory, Colorado State University, Fort Collins, CO, USA 8NASA Langley Research Center, Hampton, VA, USA 9Department of Chemistry, and Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO, USA 10Institute for the Study of Earth, Oceans, and Space, University of New Hampshire, Durham, NH, USA 11Chemical Sciences Laboratory, Earth System Research Laboratories, Boulder, CO, USA 12Department of Chemistry, Colgate University, Hamilton, NY, USA 13Department of Atmospheric Sciences, Yonsei University, Seoul, 03722, Korea 14Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA 91109, USA 15NASA Goddard Space Flight Center, Greenbelt, Maryland, USA 16Atmospheric Chemistry Observations and Modeling Lab, National Center for Atmospheric Research, Boulder, CO, USA 17Center for Global &amp; Regional Environmental Research, University of Iowa, Iowa City, Iowa, USA 18Science Systems and Applications Inc., Hampton, VA USA </ul

Integration of airborne and ground observations of nitryl chloride in the Seoul metropolitan area and the implications on regional oxidation capacity during KORUS-AQ 2016

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

Aerosol pH indicator and organosulfate detectability from aerosol mass spectrometry measurements

Aerosol sulfate is a major component of submicron particulate matter (PM1). Sulfate can be present as inorganic (mainly ammonium sulfate, AS) or organosulfate (OS). Although OS is thought to be a smaller fraction of total sulfate in most cases, recent literature argues that this may not be the case in more polluted environments. Aerodyne aerosol mass spectrometers (AMSs) measure total submicron sulfate, but it has been difficult to apportion AS vs. OS as the detected ion fragments are similar. Recently, two new methods have been proposed to quantify OS separately from AS with AMS data. We use observations collected during several airborne field campaigns covering a wide range of sources and air mass ages (spanning the continental US, marine remote troposphere, and Korea) and targeted laboratory experiments to investigate the performance and validity of the proposed OS methods. Four chemical regimes are defined to categorize the factors impacting sulfate fragmentation. In polluted areas with high ammonium nitrate concentrations and in remote areas with high aerosol acidity, the decomposition and fragmentation of sulfate in the AMS is influenced by multiple complex effects, and estimation of OS does not seem possible with current methods. In regions with lower acidity (pH \u3e 0) and ammonium nitrate (fraction of total mass \u3c 0.3), the proposed OS methods might be more reliable, although application of these methods often produced nonsensical results. However, the fragmentation of ambient neutralized sulfate varies somewhat within studies, adding uncertainty, possibly due to variations in the effect of organics. Under highly acidic conditions (when calculated pH \u3c 0 and ammonium balance \u3c 0.65), sulfate fragment ratios show a clear relationship with acidity. The measured ammonium balance (and to a lesser extent, the HySO+x / SO+x AMS ratio) is a promising indicator of rapid estimation of aerosol pH \u3c 0, including when gas-phase NH3 and HNO3 are not available. These results allow an improved understanding of important intensive properties of ambient aerosols

Quantitative detection of iodine in the stratosphere

Oceanic emissions of iodine destroy ozone, modify oxidative capacity, and can form new particles in the troposphere. However, the impact of iodine in the stratosphere is highly uncertain due to the lack of previous quantitative measurements. Here, we report quantitative measurements of iodine monoxide radicals and particulate iodine (Iy,part) from aircraft in the stratosphere. These measurements support that 0.77 ± 0.10 parts per trillion by volume (pptv) total inorganic iodine (Iy) is injected to the stratosphere. These high Iy amounts are indicative of active iodine recycling on ice in the upper troposphere (UT), support the upper end of recent Iy estimates (0 to 0.8 pptv) by the World Meteorological Organization, and are incompatible with zero stratospheric iodine injection. Gasphase iodine (Iy,gas) in the UT (0.67 ± 0.09 pptv) converts to Iy,part sharply near the tropopause. In the stratosphere, IO radicals remain detectable (0.06 ± 0.03 pptv), indicating persistent Iy,part recycling back to Iy,gas as a result of active multiphase chemistry. At the observed levels, iodine is responsible for 32% of the halogen-induced ozone loss (bromine 40%, chlorine 28%), due primarily to previously unconsidered heterogeneous chemistry. Anthropogenic (pollution) ozone has increased iodine emissions since preindustrial times (ca. factor of 3 since 1950) and could be partly responsible for the continued decrease of ozone in the lower stratosphere. Increasing iodine emissions have implications for ozone radiative forcing and possibly new particle formation near the tropopause.Fil: Koenig, Theodore K.. State University of Colorado at Boulder; Estados UnidosFil: Baidar, Sunil. State University of Colorado at Boulder; Estados UnidosFil: Campuzano Jost, Pedro. State University of Colorado at Boulder; Estados UnidosFil: Cuevas, Carlos Alberto. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Dix, Barbara. State University of Colorado at Boulder; Estados UnidosFil: Fernandez, Rafael Pedro. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; España. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto Interdisciplinario de Ciencias Básicas. - Universidad Nacional de Cuyo. Instituto Interdisciplinario de Ciencias Básicas; ArgentinaFil: Guo, Hongyu. State University of Colorado at Boulder; Estados UnidosFil: Hall, Samuel R.. National Center for Atmospheric Research; Estados UnidosFil: Kinnison, Douglas. National Center for Atmospheric Research; Estados UnidosFil: Nault, Benjamin A.. State University of Colorado at Boulder; Estados UnidosFil: Ullmann, Kirk. National Center for Atmospheric Research; Estados UnidosFil: Jimenez, Jose L.. State University of Colorado at Boulder; Estados UnidosFil: Saiz López, Alfonso. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Volkamer, Rainer. State University of Colorado at Boulder; Estados Unido

Interferences on aerosol acidity quantification due to gas-phase ammonia uptake onto acidic sulfate filter samples

Measurements of the mass concentration and chemical speciation of aerosols are important to investigate their chemical and physical processing from near emission sources to the most remote regions of the atmosphere. A common method to analyze aerosols is to collect them onto filters and analyze the filters offline; however, biases in some chemical components are possible due to changes in the accumulated particles during the handling of the samples. Any biases would impact the measured chemical composition, which in turn affects our understanding of numerous physicochemical processes and aerosol radiative properties. We show, using filters collected onboard the NASA DC-8 and NSF C-130 during six different aircraft campaigns, a consistent, substantial difference in ammonium mass concentration and ammonium-to-anion ratios when comparing the aerosols collected on filters versus an Aerodyne aerosol mass spectrometer (AMS). Another online measurement is consistent with the AMS in showing that the aerosol has lower ammonium-to-anion ratios than obtained by the filters. Using a gas uptake model with literature values for accommodation coefficients, we show that for ambient ammonia mixing ratios greater than 10 ppbv, the timescale for ammonia reacting with acidic aerosol on filter substrates is less than 30 s (typical filter handling time in the aircraft) for typical aerosol volume distributions. Measurements of gas-phase ammonia inside the cabin of the DC-8 show ammonia mixing ratios of 45±20 ppbv, consistent with mixing ratios observed in other indoor environments. This analysis enables guidelines for filter handling to reduce ammonia uptake. Finally, a more meaningful limit of detection for University of New Hampshire Soluble Acidic Gases and Aerosol (SAGA) filters collected during airborne campaigns is ∼0.2 µg sm−3 of ammonium, which is substantially higher than the limit of detection of ion chromatography. A similar analysis should be conducted for filters that collect inorganic aerosol and do not have ammonia scrubbers and/or are handled in the presence of human ammonia emissions

A simplified parameterization of isoprene-epoxydiol-derived secondary organic aerosol (IEPOX-SOA) for global chemistry and climate models: a case study with GEOS-Chem v11-02-rc

Secondary organic aerosol derived from isoprene epoxydiols (IEPOX-SOA) is thought to contribute the dominant fraction of total isoprene SOA, but the current volatility-based lumped SOA parameterizations are not appropriate to represent the reactive uptake of IEPOX onto acidified aerosols. A full explicit modeling of this chemistry is however computationally expensive owing to the many species and reactions tracked, which makes it difficult to include it in chemistry&ndash;climate models for long-term studies. Here we present three simplified parameterizations (version 1.0) for IEPOX-SOA simulation, based on an approximate analytical/fitting solution of the IEPOX-SOA yield and formation timescale. The yield and timescale can then be directly calculated using the global model fields of oxidants, NO, aerosol pH and other key properties, and dry deposition rates. The advantage of the proposed parameterizations is that they do not require the simulation of the intermediates while retaining the key physicochemical dependencies. We have implemented the new parameterizations into the GEOS-Chem v11-02-rc chemical transport model, which has two empirical treatments for isoprene SOA (the volatility-basis-set, VBS, approach and a fixed 3 % yield parameterization), and compared all of them to the case with detailed fully explicit chemistry. The best parameterization (PAR3) captures the global tropospheric burden of IEPOX-SOA and its spatiotemporal distribution (R2=0.94) vs. those simulated by the full chemistry, while being more computationally efficient (&sim;5 times faster), and accurately captures the response to changes in NOx and SO2 emissions. On the other hand, the constant 3 % yield that is now the default in GEOS-Chem deviates strongly (R2=0.66), as does the VBS (R2=0.47, 49 % underestimation), with neither parameterization capturing the response to emission changes. With the advent of new mass spectrometry instrumentation, many detailed SOA mechanisms are being developed, which will challenge global and especially climate models with their computational cost. The methods developed in this study can be applied to other SOA pathways, which can allow including accurate SOA simulations in climate and global modeling studies in the future.</p

Towards a Satellite Formaldehyde in situ Hybrid Estimate for Organic Aerosol Abundance

Organic aerosol (OA) is one of the main components of the global particulate burden and intimately links natural and anthropogenic emissions with air quality and climate. It is challenging to accurately represent OA in global models. Direct quantification of global OA abundance is not possible with current remote sensing technology; however, it may be possible to exploit correlations of OA with remotely observable quantities to infer OA spatiotemporal distributions. In particular, formaldehyde (HCHO) and OA share common sources via both primary emissions and secondary production from oxidation of volatile organic compounds (VOCs). Here, we examine OAHCHO correlations using data from summertime airborne campaigns investigating biogenic (NASA SEAC4RS and DC3), biomass burning (NASA SEAC4RS), and anthropogenic conditions (NOAA CalNex and NASA KORUS-AQ). In situ OA correlates well with HCHO (r=0.590.97), and the slope and intercept of this relationship depend on the chemical regime. For biogenic and anthropogenic regions, the OAHCHO slopes are higher in low NOx conditions, because HCHO yields are lower and aerosol yields are likely higher. The OAHCHO slope of wildfires is over 9 times higher than that for biogenic and anthropogenic sources. The OAHCHO slope is higher for highly polluted anthropogenic sources (e.g., KORUS-AQ) than less polluted (e.g., CalNex) anthropogenic sources. Near-surface OAs over the continental US are estimated by combining the observed in situ relationships with HCHO column retrievals from NASA's Ozone Monitoring Instrument (OMI). HCHO vertical profiles used in OA estimates are from climatology a priori profiles in the OMI HCHO retrieval or output of specific period from a newer version of GEOS-Chem. Our OA estimates compare well with US EPA IMPROVE data obtained over summer months (e.g., slope =0.600.62, r=0.56 for August 2013), with correlation performance comparable to intensively validated GEOS-Chem (e.g., slope =0.57, r=0.56) with IMPROVE OA and superior to the satellite-derived total aerosol extinction (r=0.41) with IMPROVE OA. This indicates that OA estimates are not very sensitive to these HCHO vertical profiles and that a priori profiles from OMI HCHO retrieval have a similar performance to that of the newer model version in estimating OA. Improving the detection limit of satellite HCHO and expanding in situ airborne HCHO and OA coverage in future missions will improve the quality and spatiotemporal coverage of our OA estimates, potentially enabling constraints on global OA distribution