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1. Modeling Diurnal Variation of Biogenic SOA Formation via Multiphase Reaction of Biogenic Hydrocarbons

   https://doi.org/10.5194/acp-2022-327  

   Han, S. ; Jang, M. ( January 2022 , Atmospheric chemistry and physics discussion)

   The daytime oxidation of biogenic hydrocarbons is attributed to both OH radicals and O3, while nighttime chemistry is dominated by the reaction with O3 and NO3 radicals. Here, the diurnal pattern of Secondary Organic Aerosol (SOA) originating from biogenic hydrocarbons was intensively evaluated under varying environmental conditions (temperature, humidity, sunlight intensity, NOx levels, and seed conditions) by using the UNIfied Partitioning Aerosol phase Reaction (UNIPAR) model, which comprises multiphase gas-particle partitioning and in-particle chemistry. The oxidized products of three different hydrocarbons (isoprene, α-pinene, and β-caryophyllene) were predicted by using near explicit gas mechanisms for four different oxidation paths (OH, O3, NO3, and O(3P)) during day and night. The gas mechanisms implemented the Master Chemical Mechanism (MCM v3.3.1), the reactions that formed low volatility products via peroxy radical (RO2) autoxidation, and self- and cross-reactions of nitrate-origin RO2. In the model, oxygenated products were then classified into volatility-reactivity base lumping species, which were dynamically constructed under varying NOx levels and aging scales. To increase feasibility, the UNIPAR model that equipped mathematical equations for stoichiometric coefficients and physicochemical parameters of lumping species was integrated with the SAPRC gas mechanism. The predictability of the UNIPAR model was demonstrated by simulating chamber-generated SOA data undermore »varying environments day and night. Overall, the SOA simulation decoupled to each oxidation path indicated that the nighttime isoprene SOA formation was dominated by the NO3-driven oxidation, regardless of NOx levels. However, the oxidation path to produce the nighttime α-pinene SOA gradually transited from the NO3-initiated reaction to ozonolysis as NOx levels decreased. For daytime SOA formation, both isoprene and α-pinene were dominated by the OH-radical initiated oxidation. The contribution of the O(3P) path to all biogenic SOA formation was negligible in daytime. Sunlight during daytime promotes the decomposition of oxidized products via photolysis and thus, reduces SOA yields. Nighttime α-pinene SOA yields were significantly higher than daytime SOA yields, although the nighttime α-pinene SOA yields gradually decreased with decreasing NOx levels. For isoprene, nighttime chemistry yielded higher SOA mass than daytime at the higher NOx level (isoprene/NOx > 5 ppbC/ppb). The daytime isoprene oxidation at the low NOx level formed epoxy-diols that significantly contributed SOA formation via heterogeneous chemistry. For isoprene and α-pinene, daytime SOA yields gradually increased with decreasing NOx levels. The daytime SOA produced more highly oxidized multifunctional products and thus, it was generally more sensitive to the aqueous reactions than the nighttime SOA. β-Caryophyllene, which rapidly oxidized and produced SOA with high yields, showed a relatively small variation in SOA yields from changes in environmental conditions (i.e., NOx levels, seed conditions, and diurnal pattern), and its SOA formation was mainly attributed to ozonolysis day and night. To mimic the nighttime α-pinene SOA formation under the polluted urban atmosphere, α-pinene SOA formation was simulated in the presence of gasoline fuel. The simulation suggested the growth of α-pinene SOA in the presence of gasoline fuel gas by the enhancement of the ozonolysis path under the excess amount of ozone, which is typical in urban air. We concluded that the oxidation of the biogenic hydrocarbon with O3 or NO3 radicals is a source to produce a sizable amount of nocturnal SOA, despite of the low emission at night.« less
2. OH and HO₂ radical chemistry in a midlatitude forest: measurements and model comparisons

   https://doi.org/10.5194/acp-20-9209-2020  

   Lew, Michelle M. ; Rickly, Pamela S. ; Bottorff, Brandon P. ; Reidy, Emily ; Sklaveniti, Sofia ; Léonardis, Thierry ; Locoge, Nadine ; Dusanter, Sebastien ; Kundu, Shuvashish ; Wood, Ezra ; et al ( January 2020 , Atmospheric Chemistry and Physics)

   Abstract. Reactions of the hydroxyl (OH) and peroxy (HO2 and RO2) radicals playa central role in the chemistry of the atmosphere. In addition to controlling the lifetimes ofmany trace gases important to issues of global climate change, OH radical reactionsinitiate the oxidation of volatile organic compounds (VOCs) which can lead to the production ofozone and secondary organic aerosols in the atmosphere. Previous measurements of these radicalsin forest environments characterized by high mixing ratios of isoprene and low mixing ratios ofnitrogen oxides (NOx) (typically less than 1–2 ppb) have shown seriousdiscrepancies with modeled concentrations. These results bring into question our understanding ofthe atmospheric chemistry of isoprene and other biogenic VOCs under low NOxconditions. During the summer of 2015, OH and HO2 radical concentrations, as well as totalOH reactivity, were measured using laser-induced fluorescence–fluorescence assay by gasexpansion (LIF-FAGE) techniques as part of the Indiana Radical Reactivity and Ozone productioN InterComparison (IRRONIC). This campaign took place in a forested area near Indiana University's Bloomington campus which is characterized by high mixing ratios of isoprene (average daily maximum ofapproximately 4 ppb at 28 ∘C) and low mixing ratios of NO (diurnal averageof approximately 170 ppt). Supporting measurements of photolysis rates, VOCs,NOx, and other species were used to constrain a zero-dimensional boxmore »model basedon the Regional Atmospheric Chemistry Mechanism (RACM2) and the Master Chemical Mechanism (MCM 3.2),including versions of the Leuven isoprene mechanism (LIM1) for HOx regeneration(RACM2-LIM1 and MCM 3.3.1). Using an OH chemical scavenger technique, the study revealed thepresence of an interference with the LIF-FAGE measurements of OH that increased with bothambient concentrations of ozone and temperature with an average daytime maximum equivalentOH concentration of approximately 5×106 cm−3. Subtraction of theinterference resulted in measured OH concentrations of approximately4×106 cm−3 (average daytime maximum) that were in better agreement with modelpredictions although the models underestimated the measurements in the evening. The addition ofversions of the LIM1 mechanism increased the base RACM2 and MCM 3.2 modeled OH concentrationsby approximately 20 % and 13 %, respectively, with the RACM2-LIM1 mechanism providing thebest agreement with the measured concentrations, predicting maximum daily OH concentrationsto within 30 % of the measured concentrations. Measurements of HO2 concentrationsduring the campaign (approximately a 1×109 cm−3 average daytime maximum)included a fraction of isoprene-based peroxy radicals(HO2*=HO2+αRO2) and were found to agree with modelpredictions to within 10 %–30 %. On average, the measured reactivity was consistent with thatcalculated from measured OH sinks to within 20 %, with modeled oxidation productsaccounting for the missing reactivity, however significant missing reactivity (approximately40 % of the total measured reactivity) was observed on some days.« less
3. Formation of condensable organic vapors from anthropogenic and biogenic volatile organic compounds (VOCs) is strongly perturbed by NO_<i>x</i> in eastern China

   https://doi.org/10.5194/acp-21-14789-2021  

   Liu, Yuliang ; Nie, Wei ; Li, Yuanyuan ; Ge, Dafeng ; Liu, Chong ; Xu, Zhengning ; Chen, Liangduo ; Wang, Tianyi ; Wang, Lei ; Sun, Peng ; et al ( January 2021 , Atmospheric Chemistry and Physics)

   Abstract. Oxygenated organic molecules (OOMs) are the crucial intermediates linkingvolatile organic compounds (VOCs) to secondary organic aerosols (SOAs) in theatmosphere, but comprehensive understanding of the characteristics of OOMsand their formation from VOCs is still missing. Ambient observations ofOOMs using recently developed mass spectrometry techniques are stilllimited, especially in polluted urban atmospheres where VOCs and oxidants areextremely variable and complex. Here, we investigate OOMs, measured by anitrate-ion-based chemical ionization mass spectrometer at Nanjing ineastern China, through performing positive matrix factorization on binnedmass spectra (binPMF). The binPMF analysis reveals three factors aboutanthropogenic VOC (AVOC) daytime chemistry, three isoprene-relatedfactors, three factors about biogenic VOC (BVOC) nighttime chemistry, andthree factors about nitrated phenols. All factors are influenced by NOxin different ways and to different extents. Over 1000 non-nitro moleculeshave been identified and then reconstructed from the selected solution ofbinPMF, and about 72 % of the total signals are contributed bynitrogen-containing OOMs, mostly regarded as organic nitrates formed throughperoxy radicals terminated by nitric oxide or nitrate-radical-initiatedoxidations. Moreover, multi-nitrates account for about 24 % of the totalsignals, indicating the significant presence of multiple generations,especially for isoprene (e.g., C5H10O8N2 andC5H9O10N3). Additionally, the distribution of OOMconcentration on the carbon number confirms their precursors are driven by AVOCsmixed with enhanced BVOCsmore »during summer. Our results highlight the decisiverole of NOx in OOM formation in densely populated areas, and we encouragemore studies on the dramatic interactions between anthropogenic and biogenicemissions.« less
4. Observational constraints on glyoxal production from isoprene oxidation and its contribution to organic aerosol over the Southeast United States

   https://doi.org/10.1002/2016JD025331  

   Provider: John Wiley & Sons, Ltd Content:text/plain ; charset="UTF-8" TY - JOUR Li, Jingyi ; Mao, Jingqiu ; Min, Kyung-Eun ; Washenfelder, Rebecca A. ; Brown, Steven S. ; Kaiser, Jennifer ; Keutsch, Frank N. ; Volkamer, Rainer ; Wolfe, Glenn M. ; et al ( July 2016 , Journal of geophysical research. Atmospheres)

   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 anmore »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.« less
5. Direct measurements of ozone response to emissions perturbations in California

   https://doi.org/10.5194/acp-22-4929-2022  

   Wu, Shenglun ; Lee, Hyung Joo ; Anderson, Andrea ; Liu, Shang ; Kuwayama, Toshihiro ; Seinfeld, John H. ; Kleeman, Michael J. ( January 2022 , Atmospheric Chemistry and Physics)

   Abstract. A new technique was used to directly measure O3 response to changes inprecursor NOx and volatile organic compound (VOC) concentrations in the atmosphere using threeidentical Teflon smog chambers equipped with UV lights. One chamberserved as the baseline measurement for O3 formation, one chamber addedNOx, and one chamber added surrogate VOCs (ethylene, m-xylene,n-hexane). Comparing the O3 formation between chambers over a3-hour UV cycle provides a direct measurement of O3 sensitivity toprecursor concentrations. Measurements made with this system at Sacramento,California, between April–December 2020 revealed that theatmospheric chemical regime followed a seasonal cycle. O3 formation wasVOC-limited (NOx-rich) during the early spring, transitioned toNOx-limited during the summer due to increased concentrations ofambient VOCs with high O3 formation potential, and then returned toVOC-limited (NOx-rich) during the fall season as the concentrations ofambient VOCs decreased and NOx increased. This seasonal pattern ofO3 sensitivity is consistent with the cycle of biogenic emissions inCalifornia. The direct chamber O3 sensitivity measurements matchedsemi-direct measurements of HCHO/NO2 ratios from the TROPOsphericMonitoring Instrument (TROPOMI) aboard the Sentinel-5 Precursor (Sentinel-5P) satellite. Furthermore, the satellite observations showed thatthe same seasonal cycle in O3 sensitivity occurred over most of theentire state of California, with only the urban cores of the very largecities remaining VOC-limited across all seasons. The O3-nonattainmentdays (MDA8 O3>70 ppb)more »have O3 sensitivity in theNOx-limited regime, suggesting that a NOx emissions controlstrategy would be most effective at reducing these peak O3concentrations. In contrast, a large portion of the days with MDA8 O3concentrations below 55 ppb were in the VOC-limited regime, suggesting thatan emissions control strategy focusing on NOx reduction would increaseO3 concentrations. This challenging situation suggests that emissionscontrol programs that focus on NOx reductions will immediately lowerpeak O3 concentrations but slightly increase intermediate O3concentrations until NOx levels fall far enough to re-enter theNOx-limited regime. The spatial pattern of increasing and decreasingO3 concentrations in response to a NOx emissions control strategyshould be carefully mapped in order to fully understand the public healthimplications.« less