Characteristic, source apportionment and effect of photochemical loss of ambient VOCs in an emerging megacity of Central China

Abstract

During the transportation from emission sources to sampling site, volatile organic compounds (VOCs) undergo photochemical losses which have significant effects for tropospheric ozone (O₃) formation and VOCs source apportionment. In this study, based on hourly speciated VOC data from May 23, to July 8, 2019 with high O₃ concentrations, the concentration level, chemical composition, and diurnal variation of observed VOCs were studied, and the initial concentration of VOCs was obtained by combining the local emission inventory in Zhengzhou, Central China. The impact of photochemical loss on source apportionment was evaluated using the Positive Matrix Factorization/Multilinear Engine 2-Species Ratio (PMF/ME2-SR) model based on observed and initial VOCs concentration (OC-PMF and IC-PMF). Results suggest that during the observed period, the average concentration of total VOCs (TVOCs) was 23.74 ± 9.20 ppbv, and alkanes (3.92 ± 2.40 ppbv) were the predominant component. The photochemical losses of TVOCs were approximately 10.15 ± 7.13 ppbv, with an average loss rate of 29.9%. The ozone formation potential (OFP) based on the initial VOCs concentration was 2.2 times higher than that observed VOCs concentration. Alkenes contributed the most to OFP and were also the largest contributors to photochemical losses. TVOC concentrations increased by 5.0% during O₃ pollution compared to non-O₃ pollution. Seven sources of VOCs were determined, including biomass burning, liquefied petroleum gas (LPG), vehicle emission, industrial emission, solvent usage, gasoline evaporation, and biogenic emission. Compared to the results of IC-PMF, the contributions of these sources in OC-PMF were underestimated by 15.4%, 14.4%, 13.0%, 11.7%, 31.5%, 7.6%, and 4.7%, respectively. This study still exhibits certain limitations in calculation method, and further exploration can be conducted in the future.