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Climate change will bring about changes in meteorological and ecological factors that are currently used in global-scale models to calculate biogenic emissions. By comparing long-term datasets of biogenic compounds to modeled emissions, this work seeks to improve understanding of these models and their driving factors. We compare speciated biogenic volatile organic compound (BVOC) measurements at the Virginia Forest Research Laboratory located in Fluvanna County, VA, USA, for the year 2020 with emissions estimated by the Model of Emissions of Gases and Aerosols from Nature version 3.2 (MEGANv3.2). The emissions were subjected to oxidation in a 0-D box model (F0AM v4.3) to generate time series of modeled concentrations. We find that default light-dependent fractions (LDFs) in the emissions model do not accurately represent observed temporal variability in regional observations. Some monoterpenes with a default light dependence are better represented using light-independent emissions throughout the year (LDFα-pinene=0, as opposed to 0.6), while others are best represented using a seasonally or temporally dependent light dependence. For example, limonene has the highest correlation between modeled and measured concentrations using an LDF =0 for January through April and roughly 0.74–0.97 in the summer months, in contrast to the default value of 0.4. The monoterpenes β-thujene, sabinene, and γ-terpinene similarly have an LDF that varies throughout the year, with light-dependent behavior in summer, while camphene and α-fenchene follow light-independent behavior throughout the year. Simulations of most compounds are consistently underpredicted in the winter months compared to observed concentrations. In contrast, day-to-day variability in the concentrations during summer months are relatively well captured using the coupled emissions–chemistry model constrained by regional concentrations of NOX and O3. 

Abstract. Emissions from natural sources are driven by various external stimuli such as sunlight, temperature, and soil moisture. Once biogenic volatile organic compounds (BVOCs) are emitted into the atmosphere, they rapidly react with atmospheric oxidants, which has significant impacts on ozone and aerosol budgets. However, diurnal, seasonal, and interannual variability in these species are poorly captured in emissions models due to a lack of long-term, chemically speciated measurements. Therefore, increasing the monitoring of these emissions will improve the modeling of ozone and secondary organic aerosol concentrations. Using 2 years of speciated hourly BVOC data collected at the Virginia Forest Research Lab (VFRL) in Fluvanna County, Virginia, USA, we examine how minor changes in the composition of monoterpenes between seasons are found to have profound impacts on ozone and OH reactivity. The concentrations of a range of BVOCs in the summer were found to have two different diurnal profiles, which, we demonstrate, appear to be driven by light-dependent versus light-independent emissions. Factor analysis was used to separate the two observed diurnal profiles and determine the contribution from each emission type. Highly reactive BVOCs were found to have a large influence on atmospheric reactivity in the summer, particularly during the daytime. These findings reveal the need to monitor species with high atmospheric reactivity, even though they have low concentrations, to more accurately capture their emission trends in models. 

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. 

Abstract. Despite the significant contribution of biogenic volatileorganic compounds (BVOCs) to organic aerosol formation and ozone productionand loss, there are few long-term, year-round, ongoing measurements oftheir volume mixing ratios and quantification of their impacts onatmospheric reactivity. To address this gap, we present 1 year of hourlymeasurements of chemically resolved BVOCs between 15 September 2019 and15 September 2020, collected at a research tower in Central Virginiain a mixed forest representative of ecosystems in the Southeastern US.Mixing ratios of isoprene, isoprene oxidation products, monoterpenes, andsesquiterpenes are described and examined for their impact on the hydroxyradical (OH), ozone, and nitrate reactivity. Mixing ratios of isoprene rangefrom negligible in the winter to typical summertime 24 h averages of 4–6 ppb, while monoterpenes have more stable mixing ratios in the range of tenths of a part per billion up to ∼2 ppb year-round. Sesquiterpenes aretypically observed at mixing ratios of <10 ppt, but this representsa lower bound in their abundance. In the growing season, isoprene dominatesOH reactivity but is less important for ozone and nitrate reactivity.Monoterpenes are the most important BVOCs for ozone and nitrate reactivitythroughout the year and for OH reactivity outside of the growing season. Tobetter understand the impact of this compound class on OH, ozone, andnitrate reactivity, the role of individual monoterpenes is examined. Despitethe dominant contribution of α-pinene to total monoterpene mass, theaverage reaction rate of the monoterpene mixture with atmospheric oxidantsis between 25 % and 30 % faster than α-pinene due to thecontribution of more reactive but less abundant compounds. A majority ofreactivity comes from α-pinene and limonene (the most significantlow-mixing-ratio, high-reactivity isomer), highlighting the importance ofboth mixing ratio and structure in assessing atmospheric impacts ofemissions. 

Abstract Reductions in anthropogenic emissions have drawn increasing attention to the role of the biosphere in O₃production chemistry in U.S. cities. We report the results of chemical transport model sensitivity simulations exploring the relative impacts of biogenic isoprene and soil nitrogen oxides (NOx) emissions on O₃and its temporal variability. We compare scenarios with high and low anthropogenic NOx emissions representing the reductions that have occurred in recent decades. As expected, summertime O₃concentrations become less sensitive to perturbations in biogenic isoprene emissions as anthropogenic NOx emissions decline. However, we demonstrate for the first time that across policy relevant O₃nonattainment areas of the United States, O₃becomes more sensitive to perturbations in soil NOx emissions than to identical perturbations in isoprene emissions. We show that interannual variability in soil NOx emissions may now have larger impacts on interannual O₃variability than isoprene emissions in many areas where the latter would have dominated in the recent past. 

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 uptake 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.