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1. Turbulent transport and reactions of plant-emitted hydrocarbons in an Amazonian rain forest

   https://doi.org/10.1016/j.atmosenv.2022.119094  

   Fuentes, Jose D.; Gerken, Tobias; Chamecki, Marcelo; Stoy, Paul; Freire, Livia; Ruiz-Plancarte, Jesus (June 2022, Atmospheric Environment)

   Professor Jian Zhen Yu (Ed.)

   using a combination of field experiments and numerical simulations. Specifically, Large Eddy Simulations (LES) were used to resolve emissions of isoprene and monoterpenes, turbulent transport, and air chemistry. The coupled chemistry-transport LES included the effects of isoprene and monoterpenes reactivity due to reactions with hydroxyl radical and ozone. The LES results are used to compute vertically resolved budgets of isoprene and monoterpenes in the rainforest canopy in response to emissions, turbulent transport, surface deposition, and air chemistry. Results indicated that emission and dispersion dominated the isoprene budget as the gases were transported out of the canopy space. In a region limited by nitrogen oxides (with prevailing nitric oxide levels of < 0.5 parts per billion), the in-canopy chemical destruction removed approximately 10% of locally emitted monoterpenes. Hydroxyl radical production rates from the ozonolysis of monoterpenes amounted to ≈ 2 × 106 radicals cm􀀀 3 s􀀀 1 and had similar magnitude to the light-dependent hydroxyl radical formation. One key conclusion was that the Amazonia rainforest abundantly emitted monoterpenes whose in-canopy ozonolysis yielded hydroxyl radicals in amounts similar to the magnitude of light-dependent formation. Reactions of monoterpenes and isoprene with hydroxyl radical and ozone were necessary for the maintenance of the Amazon rainforest canopy as a photochemically active environment suitable to generate oxidants and secondary organic aerosols. 

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2. OH, HO ₂ , and RO ₂ radical chemistry in a rural forest environment: measurements, model comparisons, and evidence of a missing radical sink

   https://doi.org/10.5194/acp-23-10287-2023  

   Bottorff, Brandon; Lew, Michelle M.; Woo, Youngjun; Rickly, Pamela; Rollings, Matthew D.; Deming, Benjamin; Anderson, Daniel C.; Wood, Ezra; Alwe, Hariprasad D.; Millet, Dylan B.; et al (September 2024, Atmospheric Chemistry and Physics)

   Abstract. The hydroxyl (OH), hydroperoxy (HO2), and organic peroxy (RO2)radicals play important roles in atmospheric chemistry. In the presence ofnitrogen oxides (NOx), reactions between OH and volatile organiccompounds (VOCs) can initiate a radical propagation cycle that leads to theproduction of ozone and secondary organic aerosols. Previous measurements ofthese radicals under low-NOx conditions in forested environmentscharacterized by emissions of biogenic VOCs, including isoprene andmonoterpenes, have shown discrepancies with modeled concentrations. During the summer of 2016, OH, HO2, and RO2 radical concentrationswere measured as part of the Program for Research on Oxidants:Photochemistry, Emissions, and Transport – Atmospheric Measurements ofOxidants in Summer (PROPHET-AMOS) campaign in a midlatitude deciduousbroadleaf forest. Measurements of OH and HO2 were made by laser-inducedfluorescence–fluorescence assay by gas expansion (LIF-FAGE) techniques,and total peroxy radical (XO2) mixing ratios were measured by the Ethane CHemical AMPlifier (ECHAMP) instrument. Supporting measurements ofphotolysis frequencies, VOCs, NOx, O3, and meteorological datawere used to constrain a zero-dimensional box model utilizing either theRegional Atmospheric Chemical Mechanism (RACM2) or the Master ChemicalMechanism (MCM). Model simulations tested the influence of HOxregeneration reactions within the isoprene oxidation scheme from the LeuvenIsoprene Mechanism (LIM1). On average, the LIM1 models overestimated daytimemaximum measurements by approximately 40 % for OH, 65 % for HO2,and more than a factor of 2 for XO2. Modeled XO2 mixing ratioswere also significantly higher than measured at night. Addition of RO2 + RO2 accretion reactions for terpene-derived RO2 radicals tothe model can partially explain the discrepancy between measurements andmodeled peroxy radical concentrations at night but cannot explain thedaytime discrepancies when OH reactivity is dominated by isoprene. Themodels also overestimated measured concentrations of isoprene-derivedhydroxyhydroperoxides (ISOPOOH) by a factor of 10 during the daytime,consistent with the model overestimation of peroxy radical concentrations.Constraining the model to the measured concentration of peroxy radicalsimproves the agreement with the measured ISOPOOH concentrations, suggestingthat the measured radical concentrations are more consistent with themeasured ISOPOOH concentrations. These results suggest that the models maybe missing an important daytime radical sink and could be overestimating therate of ozone and secondary product formation in this forest. 

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3. 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 under 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. 

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4. A new model mechanism for atmospheric oxidation of isoprene: global effects on oxidants, nitrogen oxides, organic products, and secondary organic aerosol

   https://doi.org/10.5194/acp-19-9613-2019  

   Bates, Kelvin H.; Jacob, Daniel J. (January 2019, Atmospheric Chemistry and Physics)

   Abstract. Atmospheric oxidation of isoprene, the most abundantly emitted non-methane hydrocarbon, affects the abundances of ozone (O3), the hydroxyl radical (OH), nitrogen oxide radicals (NOx), carbon monoxide (CO), oxygenated and nitrated organic compounds, and secondary organic aerosol (SOA). We analyze these effects in box models and in the global GEOS-Chem chemical transport model using the new reduced Caltech isoprene mechanism (RCIM) condensed from a recently developed explicit isoprene oxidation mechanism. We find many similarities with previous global models of isoprene chemistry along with a number of important differences. Proper accounting of the isomer distribution of peroxy radicals following the addition of OH and O2 to isoprene influences the subsequent distribution of products, decreasing in particular the yield of methacrolein and increasing the capacity of intramolecular hydrogen shifts to promptly regenerate OH. Hydrogen shift reactions throughout the mechanism lead to increased OH recycling, resulting in less depletion of OH under low-NO conditions than in previous mechanisms. Higher organonitrate yields and faster tertiary nitrate hydrolysis lead to more efficient NOx removal by isoprene and conversion to inorganic nitrate. Only 20 % of isoprene-derived organonitrates (excluding peroxyacyl nitrates) are chemically recycled to NOx. The global yield of formaldehyde from isoprene is 22 % per carbon and less sensitive to NO than in previous mechanisms. The global molar yield of glyoxal is 2 %, much lower than in previous mechanisms because of deposition and aerosol uptake of glyoxal precursors. Global production of isoprene SOA is about one-third from each of the following: isoprene epoxydiols (IEPOX), organonitrates, and tetrafunctional compounds. We find a SOA yield from isoprene of 13 % per carbon, much higher than commonly assumed in models and likely offset by SOA chemical loss. We use the results of our simulations to further condense RCIM into a mini Caltech isoprene mechanism (Mini-CIM) for less expensive implementation in atmospheric models, with a total size (108 species, 345 reactions) comparable to currently used mechanisms. 

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5. Composition, concentration, and oxidant reactivity of sesquiterpenes in the southeastern U.S.

   https://doi.org/10.1039/D2EA00059H  

   Frazier, Graham; McGlynn, Deborah F.; Barry, Laura E.; Lerdau, Manuel; Pusede, Sally E.; Isaacman-VanWertz, Gabriel (September 2022, Environmental Science: Atmospheres)

   Biogenic volatile organic compounds (BVOCs) contribute the majority of reactive organic carbon to the atmosphere and lead to aerosol formation through reaction with atmospheric oxidants including ozone and hydroxyl radicals. One class of BVOCs, sesquiterpenes, have a high reactivity with ozone but exist at lower concentrations compared to other BVOCs, and there are relatively few measurements of their concentrations in different environments or their importance in the atmospheric oxidant budget. To help close this knowledge gap, we examine concentrations of isomer-resolved sesquiterpene concentrations collected hourly at two sites in Virginia that are representative of different ecosystems in the southeastern US. Sesquiterpene concentrations are presented and discussed in relation to their diurnal patterns and used to estimate their contribution to reactivity with common gas-phase oxidants. Twenty-four sesquiterpenes were identified at the sites, eleven of which were observed at both sites. Total sesquiterpene concentrations were found to range between 0.8 and 2 ppt with no single isomer dominating throughout. Hydroxyl activity is similarly diverse, with no particular isomer dominating activity at either site. Ozone reactivity, however, was found to be dominated (∼3/4 total reactivity) by β-caryophyllene and humulene despite these compounds representing roughly only 10% of total sesquiterpene mass, highlighting their importance as the major driver of sesquiterpene-ozone reactivity. Average reaction rate constants for sesquiterpenes with ozone and hydroxyl radicals were calculated for both sites as a method to simplify future atmospheric modelling concerning sesquiterpenes. This work provides broad insight into the composition and impacts of sesquiterpenes, suggesting that sesquiterpene composition is relatively similar between sites. Furthermore, while the calculated average sesquiterpene-ozone reaction rate constants are at least an order of magnitude higher than that of more prevalent BVOC classes (isoprene and monoterpenes), their low concentrations suggest their impacts on atmospheric reactivity are expected to be limited to periods of high emissions. 

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