Gasoline evaporation is an important anthropogenic source of atmospheric volatile organic compounds（VOCs）. Total OH reactivity for gasoline vapor was measured from 4 kinds of gasoline for the first time by comparati...Gasoline evaporation is an important anthropogenic source of atmospheric volatile organic compounds（VOCs）. Total OH reactivity for gasoline vapor was measured from 4 kinds of gasoline for the first time by comparative reactivity method（CRM） using proton transfer reaction mass spectrometer（PTR-MS）.Compositions of 56 PAMS（photochemical assessment monitoring station） nonmethane hydrocarbons（NMHCs） were measured for both liquid and headspace of gasoline. We found high abundance of alkenes and aromatics in gasoline. The calculated OH reactivity derived from quantified NMHCs speciation accounted for only 57 ？ 4% of total reactivity obtained from CRM method. N-Alkenes, only 6 wt% in liquid gasoline, contributed to 70% of calculated reactivity. We assume that the undetected branched alkenes are the possible reason for the missing reactivity. We suggest that the priority of gasoline quality improvement is to reduce alkenes content in gasoline in term of reactivity-based control.展开更多
Considerable efforts have been devoted to characterising the chemical components of vehicle exhaust.However,these components may not accurately reflect the contribution of vehicle exhaust to atmospheric reactivity bec...Considerable efforts have been devoted to characterising the chemical components of vehicle exhaust.However,these components may not accurately reflect the contribution of vehicle exhaust to atmospheric reactivity because of the presence of species not accounted for(“missing species”)given the limitations of analytical instruments.In this study,we improved the laser photolysis–laser-induced fluorescence(LP-LIF)technique and applied it to directly measure the total OH reactivity(TOR)in exhaust gas from light-duty gasoline vehicles in China.The TOR for China Ⅰ to Ⅵ-a vehicles was 15.6,16.3,8.4,2.6,1.5,and 1.6×10^(4) sec^(-1),respectively,reflecting a notable drop as emission standards were upgraded.The TOR was comparable between cold and warm starts.The missing OH reactivity(MOR)values for China Ⅰ to Ⅳ vehicles were close to zero with a cold start but were much higher with a warm start.The variations in oxygenated volatile organic compounds(OVOCs)under different emission standards and for the two start conditions were similar to those of the MOR,indicating that OVOCs and the missing species may have similar production processes.Online measurement revealed that the duration of the stable driving stage was the primary factor leading to the production of OVOCs and missing species.Our findings underscore the importance of direct measurement of TOR from vehicle exhaust and highlight the necessity of adding OVOCs and other organic reactive gases in future upgrades of emission standards,such that the vehicular contribution to atmospheric reactivity can be more effectively controlled.展开更多
基金funded by the National Natural Science Foundation (Nos. 41125018, 41330635)
文摘Gasoline evaporation is an important anthropogenic source of atmospheric volatile organic compounds（VOCs）. Total OH reactivity for gasoline vapor was measured from 4 kinds of gasoline for the first time by comparative reactivity method（CRM） using proton transfer reaction mass spectrometer（PTR-MS）.Compositions of 56 PAMS（photochemical assessment monitoring station） nonmethane hydrocarbons（NMHCs） were measured for both liquid and headspace of gasoline. We found high abundance of alkenes and aromatics in gasoline. The calculated OH reactivity derived from quantified NMHCs speciation accounted for only 57 ？ 4% of total reactivity obtained from CRM method. N-Alkenes, only 6 wt% in liquid gasoline, contributed to 70% of calculated reactivity. We assume that the undetected branched alkenes are the possible reason for the missing reactivity. We suggest that the priority of gasoline quality improvement is to reduce alkenes content in gasoline in term of reactivity-based control.
基金supported by the National Natural Science Foundation of China(Nos.91644221 and 41627809)the National Key Research and Development Program of China(Nos.2016YFC0202201 and 2018YFC0213904)the Key-Area Research and Development Program of Guangdong Province(No.2019B110206001).
文摘Considerable efforts have been devoted to characterising the chemical components of vehicle exhaust.However,these components may not accurately reflect the contribution of vehicle exhaust to atmospheric reactivity because of the presence of species not accounted for(“missing species”)given the limitations of analytical instruments.In this study,we improved the laser photolysis–laser-induced fluorescence(LP-LIF)technique and applied it to directly measure the total OH reactivity(TOR)in exhaust gas from light-duty gasoline vehicles in China.The TOR for China Ⅰ to Ⅵ-a vehicles was 15.6,16.3,8.4,2.6,1.5,and 1.6×10^(4) sec^(-1),respectively,reflecting a notable drop as emission standards were upgraded.The TOR was comparable between cold and warm starts.The missing OH reactivity(MOR)values for China Ⅰ to Ⅳ vehicles were close to zero with a cold start but were much higher with a warm start.The variations in oxygenated volatile organic compounds(OVOCs)under different emission standards and for the two start conditions were similar to those of the MOR,indicating that OVOCs and the missing species may have similar production processes.Online measurement revealed that the duration of the stable driving stage was the primary factor leading to the production of OVOCs and missing species.Our findings underscore the importance of direct measurement of TOR from vehicle exhaust and highlight the necessity of adding OVOCs and other organic reactive gases in future upgrades of emission standards,such that the vehicular contribution to atmospheric reactivity can be more effectively controlled.
