Source appointment of volatile organic compounds and evaluation of anthropogenic monoterpene emission estimates in Atlanta, Georgia

Abstract

Emissions of monoterpenes from volatile chemical products (VCPs) have been shown to contribute substantially to secondary organic aerosol (SOA) formation in a number of cities across the US. In the southeast US (SE US), monoterpenes are the dominant precursor to SOA production. Previous studies have assumed that monoterpenes are primarily biogenic in origin. We examine that assumption here using a total of nine months of volatile organic compound (VOC) observations spanning across 2020 and 2021 which are made via proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) in Atlanta, Georgia. The dataset is resolved via non-negative matrix factorization (NNMF) into two biogenic, four anthropogenic, and two secondary factors. NNMF results show that VCP sources contribute to 0.28 ± 0.17 ppb of monoterpenes, or about 26% of all monoterpenes in the summer and 53% in the winter. Interannual comparison suggest minimum impact of the COVID-19 pandemic on atmospheric VOC composition in Atlanta during the second half of 2020. Comparison of NNMF anthropogenic monoterpenes-to-benzene ([Manthro/B]) and anthropogenic-to-total monoterpenes ([Manthro/MT]) ratios with emission ratios in the National Emission Inventory 2016v1 modeling platform (NEI16) and Fuel-Based Inventory of Vehicle Emissions and Volatile Chemical Products (FIVE-VCP) suggests that NEI16 underestimates anthropogenic monoterpene emissions by as much as 70% in Atlanta. FIVE-VCP estimates higher anthropogenic monoterpene emissions than NEI16 and provides better agreement with observations, especially during winter months. Anthropogenic monoterpenes may impact as much as 17% of total summertime SOA formation in Atlanta and the SE US, with potential additional influence of limonene from anthropogenic monoterpene sources due to its higher reactivity and SOA yield potential.