The production of formaldehyde and hydroxyacetone in methacrolein photooxidation: New insights into mechanism and effects of water vapor

Methacrolein(MACR) is an abundant multifunctional carbonyl compound with high reactivity in the atmosphere. In this study, we investigated the hydroxyl radical initiated oxidation of MACR at various NO/MACR ratios(0 to 4.04) and relative humidities( 3% to80%) using a flow tube. Meanwhile, a box model based on the Master Chemical Mechanism was performed to test our current understanding of the mechanism. In contrast to the reasonable predictions for hydroxyacetone production, the modeled yields of formaldehyde(HCHO) were twice higher than the experimental results. The discrepancy was ascribed to the existence of unconsidered non-HCHO forming channels in the chemistry of CH_3-UC(=CH_2)OO, which account for approx. 50%. In addition, the production of hydroxyacetone and HCHO were affected by water vapor as well as the initial NO/MACR ratio. The yields of HCHO were higher under humid conditions than that under dry condition. The yields of hydroxyacetone were higher under humid conditions at low-NO_x level, while lower at high-NOxlevel. The reasonable explanation for the lower hydroxyacetone yield under humid conditions at high-NO_x level is that water vapor promotes the production of Umethacrolein nitrate in the reaction of HOCH_2 C(CH_3)(OO)CHO with NO due to the peroxy radical-water complex formation, which was evidenced by calculational results. And the minimum equilibrium constant of this water complex formation was estimated to be 1.89 × 10~(-18) cm~3/molecule. These results provide new insights into the MACR oxidation mechanism and the effects of water vapor.     

Sources of methacrolein and methyl vinyl ketone and their contributions to methylglyoxal and formaldehyde at a receptor site in Pearl River Delta

Methacrolein(MACR) and methyl vinyl ketone(MVK) are two major intermediate products from the photochemical oxidation of isoprene, the most important biogenic volatile organic compound. In addition, MACR and MVK have primary emissions. Investigating the sources and evolution of MACR and MVK could provide helpful information for the oxidative capacity of the atmosphere. In this study, hourly measurements of isoprene, MACR, and MVK were conducted at a receptor site in the Pearl River Delta region(PRD), i.e., the Heshan site(HS), from 22 October to 20 November, 2014. The average mixing ratios of isoprene,MACR and MVK were 151 ± 17, 91 ± 6 and 79 ± 6 pptv, respectively. The daily variations and the ratios of MVK/MACR during daytime and nighttime suggested that other sources besides isoprene photooxidation influenced the MACR and MVK abundances at the HS.Positive matrix factorization was utilized to resolve the sources of MACR and MVK. Five sources were identified and quantified, including biogenic emissions, biomass burning,secondary formation, diesel, and gasoline vehicular emissions. Among them, secondary formation made the greatest contribution to observed MACR and MVK with average contributions of ～ 45% and ～ 70%, respectively. Through the yields of secondary products from the oxidation of MACR and MVK by the OH radical and the concentrations of MACR and MVK, it was found that methylglyoxal and formaldehyde were the main oxidation products of MACR and MVK at the HS site. Overall, this study evaluated the roles of primary emissions on ambient levels of MACR and MVK and advanced the understanding of photochemical oxidation of MACR and MVK in the PRD.