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  1. Free, publicly-accessible full text available October 13, 2023
  2. Free, publicly-accessible full text available June 7, 2023
  3. Abstract. Organic nitrate (RONO2) formation in the atmosphere represents a sink of NOx(NOx = NO + NO2) and termination of the NOx/HOx(HOx = HO2 + OH) ozone formation and radical propagation cycles, can act as a NOx reservoirtransporting reactive nitrogen, and contributes to secondary organic aerosol formation. While some fraction of RONO2 is thought to reside in the particle phase, particle-phase organic nitrates (pRONO2) are infrequently measured and thus poorly understood. There is anincreasing prevalence of aerosol mass spectrometer (AMS) instruments, which have shown promise for determining the quantitative total organic nitratefunctional group contribution to aerosols. A simple approach that relies on the relative intensities of NO+ and NO2+ ions inthe AMS spectrum, the calibrated NOx+ ratio for NH4NO3, and the inferred ratio for pRONO2 hasbeen proposed as a way to apportion the total nitrate signal to NH4NO3 and pRONO2. This method is increasingly beingapplied to field and laboratory data. However, the methods applied have been largely inconsistent and poorly characterized, and, therefore, adetailed evaluation is timely. Here, we compile an extensive survey of NOx+ ratios measured for variouspRONO2 compounds and mixtures from multiple AMS instruments, groups, and laboratory and field measurements. All data and analysispresented here are for use with the standard AMS vaporizer. We show that,more »in the absence of pRONO2 standards, thepRONO2 NOx+ ratio can be estimated using a ratio referenced to the calibrated NH4NO3 ratio, aso-called “Ratio-of-Ratios” method (RoR = 2.75 ± 0.41). We systematically explore the basis for quantifyingpRONO2 (and NH4NO3) with the RoR method using ground and aircraft field measurements conducted over a largerange of conditions. The method is compared to another AMS method (positive matrix factorization, PMF) and other pRONO2 andrelated (e.g., total gas + particle RONO2) measurements, generally showing good agreement/correlation. A broad survey of ground andaircraft AMS measurements shows a pervasive trend of higher fractional contribution of pRONO2 to total nitrate with lower totalnitrate concentrations, which generally corresponds to shifts from urban-influenced to rural/remote regions. Compared to ground campaigns,observations from all aircraft campaigns showed substantially lower pRONO2 contributions at midranges of total nitrate(0.01–0.1 up to 2–5 µg m−3), suggesting that the balance of effects controlling NH4NO3 and pRONO2formation and lifetimes – such as higher humidity, lower temperatures, greater dilution, different sources, higher particle acidity, andpRONO2 hydrolysis (possibly accelerated by particle acidity) – favors lower pRONO2 contributions for thoseenvironments and altitudes sampled.« less
  4. Abstract. Glyoxal (CHOCHO), the simplest dicarbonyl in thetroposphere, is a potential precursor for secondary organic aerosol (SOA)and brown carbon (BrC) affecting air quality and climate. The airbornemeasurement of CHOCHO concentrations during the KORUS-AQ (KORea–US AirQuality study) campaign in 2016 enables detailed quantification of lossmechanisms pertaining to SOA formation in the real atmosphere. Theproduction of this molecule was mainly from oxidation of aromatics (59 %)initiated by hydroxyl radical (OH). CHOCHO loss to aerosol was found to bethe most important removal path (69 %) and contributed to roughly∼ 20 % (3.7 µg sm−3 ppmv−1 h−1,normalized with excess CO) of SOA growth in the first 6 h in SeoulMetropolitan Area. A reactive uptake coefficient (γ) of∼ 0.008 best represents the loss of CHOCHO by surface uptakeduring the campaign. To our knowledge, we show the first field observationof aerosol surface-area-dependent (Asurf) CHOCHO uptake, which divergesfrom the simple surface uptake assumption as Asurf increases in ambientcondition. Specifically, under the low (high) aerosol loading, the CHOCHOeffective uptake rate coefficient, keff,uptake, linearly increases(levels off) with Asurf; thus, the irreversible surface uptake is areasonable (unreasonable) approximation for simulating CHOCHO loss toaerosol. Dependence on photochemical impact and changes in the chemical andphysical aerosol properties “free water”, as well as aerosol viscosity,are discussed as other possible factors influencing CHOCHO uptakemore »rate. Ourinferred Henry's law coefficient of CHOCHO, 7.0×108 M atm−1, is ∼ 2 orders of magnitude higher than thoseestimated from salting-in effects constrained by inorganic salts onlyconsistent with laboratory findings that show similar high partitioning intowater-soluble organics, which urges more understanding on CHOCHO solubilityunder real atmospheric conditions.« less
  5. Abstract. The evolution of organic aerosol (OA) and aerosol sizedistributions within smoke plumes is uncertain due to the variability inrates of coagulation and OA condensation/evaporation between different smokeplumes and at different locations within a single plume. We use aircraftdata from the FIREX-AQ campaign to evaluate differences in evolving aerosolsize distributions, OA, and oxygen to carbon ratios (O:C) between and withinsmoke plumes during the first several hours of aging as a function of smokeconcentration. The observations show that the median particle diameterincreases faster in smoke of a higher initial OA concentration (>1000 µg m−3), with diameter growth of over 100 nm in 8 h – despite generally having a net decrease in OA enhancementratios – than smoke of a lower initial OA concentration (<100 µg m−3), which had net increases in OA. Observations of OA and O:Csuggest that evaporation and/or secondary OA formation was greater in lessconcentrated smoke prior to the first measurement (5–57 min afteremission). We simulate the size changes due to coagulation and dilution andadjust for OA condensation/evaporation based on the observed changes in OA.We found that coagulation explains the majority of the diameter growth, withOA evaporation/condensation having a relatively minor impact. We found thatmixing between the core and edges of the plume generally occurred ontimescalesmore »of hours, slow enough to maintain differences in aging betweencore and edge but too fast to ignore the role of mixing for most of our cases.« less
  6. Abstract. Fires emit sufficient sulfur to affect local and regional airquality and climate. This study analyzes SO2 emission factors andvariability in smoke plumes from US wildfires and agricultural fires, as well as theirrelationship to sulfate and hydroxymethanesulfonate (HMS) formation.Observed SO2 emission factors for various fuel types show goodagreement with the latest reviews of biomass burning emission factors,producing an emission factor range of 0.47–1.2 g SO2 kg−1 C.These emission factors vary with geographic location in a way that suggeststhat deposition of coal burning emissions and application ofsulfur-containing fertilizers likely play a role in the larger observedvalues, which are primarily associated with agricultural burning. A 0-D boxmodel generally reproduces the observed trends of SO2 and total sulfate(inorganic + organic) in aging wildfire plumes. In many cases, modeled HMSis consistent with the observed organosulfur concentrations. However, acomparison of observed organosulfur and modeled HMS suggests that multipleorganosulfur compounds are likely responsible for the observations but thatthe chemistry of these compounds yields similar production and loss rates asthat of HMS, resulting in good agreement with the modeled results. Weprovide suggestions for constraining the organosulfur compounds observedduring these flights, and we show that the chemistry of HMS can alloworganosulfur to act as an S(IV) reservoir under conditions of pH > 6 andmore »liquid water content>10−7 g sm−3. This canfacilitate long-range transport of sulfur emissions, resulting in increasedSO2 and eventually sulfate in transported smoke.« less
  7. Abstract. Secondary organic aerosol (SOA) is a dominant contributor of fine particulate matter in the atmosphere, but the complexity of SOA formation chemistry hinders the accurate representation of SOA in models. Volatility-based SOA parameterizations have been adopted in many recent chemistry modeling studies and have shown a reasonable performance compared to observations. However, assumptions made in these empirical parameterizations can lead to substantial errors when applied to future climatic conditions as they do not include the mechanistic understanding of processes but are rather fitted to laboratory studies of SOA formation. This is particularly the case for SOA derived from isoprene epoxydiols (IEPOX SOA), for which we have a higher level of understanding of the fundamental processes than is currently parameterized in most models. We predict future SOA concentrations using an explicit mechanism and compare the predictions with the empirical parameterization based on the volatility basis set (VBS) approach. We then use the Community Earth System Model 2 (CESM2.1.0) with detailed isoprene chemistry and reactive uptake processes for the middle and end of the 21st century under four Shared Socioeconomic Pathways (SSPs): SSP1–2.6, SSP2–4.5, SSP3–7.0, and SSP5–8.5. With the explicit chemical mechanism, we find that IEPOX SOA is predicted to increasemore »on average under all future SSP scenarios but with some variability in the results depending on regions and the scenario chosen. Isoprene emissions are the main driver of IEPOX SOA changes in the future climate, but the IEPOX SOA yield from isoprene emissions also changes by up to 50 % depending on the SSP scenario, in particular due to different sulfur emissions. We conduct sensitivity simulations with and without CO2 inhibition of isoprene emissions that is highly uncertain, which results in factor of 2 differences in the predicted IEPOX SOA global burden, especially for the high-CO2 scenarios (SSP3–7.0 and SSP5–8.5). Aerosol pH also plays a critical role in the IEPOX SOA formation rate, requiring accurate calculation of aerosol pH in chemistry models. On the other hand, isoprene SOA calculated with the VBS scheme predicts a nearly constant SOA yield from isoprene emissions across all SSP scenarios; as a result, it mostly follows isoprene emissions regardless of region and scenario. This is because the VBS scheme does not consider heterogeneous chemistry; in other words, there is no dependency on aerosol properties. The discrepancy between the explicit mechanism and VBS parameterization in this study is likely to occur for other SOA components as well, which may also have dependencies that cannot be captured by VBS parameterizations. This study highlights the need for more explicit chemistry or for parameterizations that capture the dependence on key physicochemical drivers when predicting SOA concentrations for climate studies.« less
  8. Abstract. Secondary organic aerosol derived from isopreneepoxydiols (IEPOX-SOA) is thought to contribute the dominant fraction oftotal isoprene SOA, but the current volatility-based lumped SOAparameterizations are not appropriate to represent the reactive uptake ofIEPOX onto acidified aerosols. A full explicit modeling of this chemistryis however computationally expensive owing to the many species and reactionstracked, which makes it difficult to include it in chemistry–climate modelsfor long-term studies. Here we present three simplified parameterizations(version 1.0) for IEPOX-SOA simulation, based on an approximateanalytical/fitting solution of the IEPOX-SOA yield and formation timescale.The yield and timescale can then be directly calculated using the globalmodel fields of oxidants, NO, aerosol pH and other key properties, and drydeposition rates. The advantage of the proposed parameterizations is thatthey do not require the simulation of the intermediates while retaining thekey physicochemical dependencies. We have implemented the newparameterizations 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&thinsp;% yield parameterization), and comparedall of them to the case with detailed fully explicit chemistry. The bestparameterization (PAR3) captures the global tropospheric burden of IEPOX-SOAand its spatiotemporal distribution (R2=0.94) vs. thosesimulated by the full chemistry, while being more computationally efficient(∼5 times faster),more »and accurately captures the response tochanges in NOx and SO2 emissions. On the other hand, the constant3&thinsp;% yield that is now the default in GEOS-Chem deviates strongly (R2=0.66), as does the VBS (R2=0.47, 49&thinsp;% underestimation), withneither parameterization capturing the response to emission changes. Withthe advent of new mass spectrometry instrumentation, many detailed SOAmechanisms are being developed, which will challenge global and especiallyclimate models with their computational cost. The methods developed in thisstudy can be applied to other SOA pathways, which can allow includingaccurate SOA simulations in climate and global modeling studies in thefuture.

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