Measurement report: Summertime and wintertime VOCs in Houston: Source apportionment and spatial distribution of source origins

Abstract. The seasonal variations of volatile organic compounds (VOCs) was studied in the Houston metropolitan area in the summertime and wintertime of 2018. The analysis of hourly measurements obtained from the automated gas chromatograph (auto-GC) network showed the total VOC average concentrations of 28.68 ppbC in the summertime and 33.92 ppbC in the wintertime. The largest contributions came from alkane compounds, which accounted for 61 % and 82 % of VOCs in the summer and winter, respectively. We performed principal component analysis (PCA) and Positive Matrix Factorization (PMF) and identified seven factors in the summertime and six factors in the wintertime, among which alkane species formed three factors according to their rate of reactions in both seasons: (1) the emissions of long-lived tracers from oil and natural gas (ONG long-lived species), (2) fuel evaporation, and (3) the emissions of short-lived tracers from oil and natural gas (ONG short-lived species). Two other similar factors were (4) emissions of aromatic compounds and (5) alkene tracers of ethylene and propylene. Summertime factor 6 was associated with acetylene, and one extra summertime factor 7 was influenced by the biogenic emissions. The factor 6 of wintertime was affected by vehicle exhaust. Higher nighttime and lower daytime values of the ethylene/acetylene ratios during the summertime indicated the stronger impacts of ethylene photochemical degradation. Also, the exploration of the photochemical processes of the VOCs showed that the ethylene and propylene had the highest contributions to the summertime and wintertime ozone formation as well as the emissions of the isoprene, which showed a high impact on summertime ozone. Our results acknowledged that ethylene and propylene continue to be significant emissions of VOCs, and their emissions control would help the mitigation of the ozone of Ship Channel. Based on trajectory analysis, we identified main VOC emission sources in Houston Ship Channel (HSC) local industrial areas and regions south of the HSC. Ambient VOC concentrations measured at the HSC were influenced by the emissions from the petrochemical sectors and industrial complexes, especially from the Baytown refinery and Bayport industrial district next to the HSC and Galveston Bay refineries at the south of the study area.