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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Minor contributions of daytime monoterpenes are major contributors to atmospheric reactivity
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.
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- Award ID(s):
- 1837882
- PAR ID:
- 10399084
- Date Published:
- Journal Name:
- Biogeosciences
- Volume:
- 20
- Issue:
- 1
- ISSN:
- 1726-4189
- Page Range / eLocation ID:
- 45 to 55
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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