A chamber study on isoprene - promoting the production of toluene - derived methylbutenedial in low NOx environment
ZHANG Yang1, HAN Shi-jie1, LI Qin-qin1, WANG Wen-lu1, XIAO Yang1, GUO Yan1, WANG Hao1,2,3, WANG Bo-guang1,2,3
1. Institute for Environmental and Climate Research, Jinan University, Guangzhou 511443, China; 2. Australia-China Centre for Air Quality Science and Management (Guangdong), Guangzhou 511443, China; 3. Guangdong-Hongkong-Macau Joint Laboratory of Collaborative Innovation for Environmental Quality, Guangzhou 511443, China
Abstract：Toluene and isoprene are typical anthropogenic volatile organic compounds (AVOCs) and biological volatile organic compounds (BVOCs), respectively. In this study, smog chamber experiments were carried out to simulate photochemical reactions of toluene and isoprene at low NOx levels. In order to investigate the effect of BVOCs on the chemical degradation of AVOCs during the interaction between anthropogenic and biogenic emissions, a proton-transfer-reaction time-of-flight mass spectrometry (PTR-TOF-MS) was used to monitor the real-time concentration variations of the key gaseous substances in the mixed system. The results show that isoprene inhibited the chemical degradation of toluene, which might be related to the competitive reactions with OH radicals between isoprene and toluene. Moreover, the earlier competitive reaction began, the more significant the inhibition effect was. And isoprene enhanced the production of toluene RO2 degradation pathway products, resulting in more unsaturated 1,4-dicarbonyl compounds (Butenedial, Methyl-butenedial) and dicarbonyl compounds (Glyoxal, Methylglyoxal). The increment in methylbutenedial was up to 38.6%. Also, the RO2• generated by the rapid oxidation of isoprene had less carbon number, which may have a rapid cross-reaction with the RO2• generated by toluene oxidation. The cross reaction was conducive to the generation and cleavage of toluene RO• and ultimately led to an increase of the products from toluene RO2 • channel. This study can improve an understanding of the impact of BVOCs on AVOCs degradation during the interaction process between anthropogenic and biogenic emissions, and provide insights into regional air pollution prevention and control in the future.
张扬, 韩士杰, 李勤勤, 王文路, 肖扬, 郭严, 王好, 王伯光. 低NOx环境异戊二烯促进甲苯生成甲基丁烯二醛的模拟实验[J]. 中国环境科学, 2022, 42(9): 4001-4008.
ZHANG Yang, HAN Shi-jie, LI Qin-qin, WANG Wen-lu, XIAO Yang, GUO Yan, WANG Hao, WANG Bo-guang. A chamber study on isoprene - promoting the production of toluene - derived methylbutenedial in low NOx environment. CHINA ENVIRONMENTAL SCIENCECE, 2022, 42(9): 4001-4008.
Ji Y, Zhao J, Terazono H, et al. Reassessing the atmospheric oxidation mechanism of toluene [J]. Proceedings of the National Academy of Sciences, 2017,114(31):8169-8174.
[2]
Kurtenbach R, Ackermann R, Becker K H, et al. Verification of the contribution of vehicular traffic to the total NMVOC emissions in germany and the importance of the NO3 chemistry in the city air [J]. Journal of Atmospheric Chemistry 42:395–411:2002.
[3]
Velasco E, Lamb B, Westberg H, et al. Distribution, magnitudes, reactivities, ratios and diurnal patterns of volatile organic compounds in the Valley of Mexico during the MCMA 2002 & 2003 field campaigns [J]. Atmospheric Chemistry and Physics, 2007,7:329-353.
[4]
Li M, Zhang Q, Zheng B, et al. Persistent growth of anthropogenic non-methane volatile organic compound (NMVOC) emissions in China during 1990~2017: Drivers, speciation and ozone formation potential [J]. Atmospheric Chemistry and Physics, 2019,19(13):8897-8913.
[5]
Karl T, Striednig M, Graus M, et al. Urban flux measurements reveal a large pool of oxygenated volatile organic compound emissions [J]. Proceedings of the National Academy of Sciences, 2018,115(6):1186- 1191.
[6]
Li B, Ho S S H, Gong S, et al. Characterization of VOCs and their related atmospheric processes in a central Chinese city during severe ozone pollution periods [J]. Atmospheric Chemistry and Physics, 2019,19(1):617-638.
[7]
Zhao Q, Bi J, Liu Q, et al. Sources of volatile organic compounds and policy implications for regional ozone pollution control in an urban location of Nanjing, East China [J]. Atmospheric Chemistry and Physics, 2020,20(6):3905-3919.
[8]
Wu R, Xie S. Spatial distribution of secondary organic aerosol formation potential in China derived from speciated anthropogenic volatile organic compound emissions [J]. Environmental Science & Technology, 2018,52(15):8146-8156.
[9]
Levine C, Marcillo A. Regarding several points of doubt of the structure of the olfactory bulb: as described by T. Blanes [J]. Anatomical Record-advances in Integrative Anatomy & Evolutionary Biology, 2008,291(7):751-62.
[10]
Samet J M, Chiu W A, Cogliano V, et al. The IARC monographs: Updated procedures for modern and transparent evidence synthesis in cancer hazard identification [J]. International Agency for Research on Cancer, 2020,112(1):30-37.
[11]
Moolla R, Curtis C J, Knight J. Occupational exposure of diesel station workers to BTEX compounds at a bus depot [J]. International Journal of Environmental Research and Public Health, 2015,12(4): 4101-4115.
[12]
王玉珏,胡 敏,李 晓,等.大气颗粒物中棕色碳的化学组成、来源和生成机制 [J]. 化学进展, 2020,32(5):627-641. Yujue Wang, Min Hu, Xiao Li, et al. Chemical Composition, Sources and Formation Mechanisms of Particulate Brown Carbon in the Atmosphere [J]. Progress in Chemistry, 2020,32(5):627-641.
[13]
Le B G, Becker K H. Chemical processes in atmospheric oxidation [J]. Eurotrac, 1997,551.51l-dc20:96-41132.
[14]
Bandow H, Washida N. Ring-cleavage reactions of aromatic hydrocarbons studied by FT-IR spectroscopy. II. Photooxidation of o-, m-, and p-xylenes in the NOx-air system [J]. Bulletin of the Chemical Society of Japan, 2006,58(9):2541-2548.
[15]
Wang S, Newland M J, Deng W, et al. Aromatic photo-oxidation, a new source of atmospheric acidity [J]. Environmental Science & Technology, 2020,54(13):7798-7806.
[16]
Arey J, Obermeyer G, Aschmann S M, et al. Dicarbonyl products of the OH radical-initiated reaction of a series of aromatic hydrocarbons [J]. Environmental Science & Technology, 2009,43(3):683-689.
[17]
Nehr S, Bohn B, Dorn H P, et al. Atmospheric photochemistry of aromatic hydrocarbons: OH budgets during SAPHIR chamber experiments [J]. Atmospheric Chemistry and Physics, 2014,14(13): 6941-6952.
[18]
贾 龙,徐 福.烟雾箱与数值模拟研究苯和乙苯的臭氧生成潜势 [J]. 环境科学, 2014,35(2):495-503. Long Jia, Yong fu Xu. Studies of Ozone Formation Potentials for Benzene and Ethylbenzene Using a Smog Chamber and Model Simulation [J]. Eevironmental Science, 2014,35(2):495-503.
[19]
Lu S, Li X, Liu Y, et al. Advances on atmospheric oxidation mechanism of typical aromatic hydrocarbons [J]. Acta Chimica Sinica, 2021,79(10):18.
[20]
Newland M J, Jenkin M E, Rickard A R. Elucidating the fate of the OH-adduct in toluene oxidation under tropospheric boundary layer conditions [J]. Proceedings of the National Academy of Sciences, 2017,114(38):E7856-7857.
[21]
Liu X, Jeffries H E, Sexton K G J E S, et al. Atmospheric photochemical degradation of 1,4-Unsaturated dicarbonyls [J]. Environmental Science & Technology, 1999,33(23):4212-4220.
[22]
Bierbach A, Barnes I, Becker K H, et al. Atmospheric chemistry of unsaturated carbonyls: Butenedial, 4-Oxo-2-pentenal, 3-Hexene-2, 5-dione, Maleic Anhydride, 3H-Furan-2-one, and 5-Methyl-3H- furan-2-one [J]. Environmental Science & Technology, 1994,28(4): 715-729.
[23]
Wu R, Pan S, Li Y, et al. Atmospheric oxidation mechanism of toluene [J]. Journal of Physical Chemistry A, 2014,118(25):4533-4547.
[24]
Smith D F, Mciver C D, Kleindienst T E J J O a C. Primary product distribution from the reaction of hydroxyl radicals with toluene at ppb NOx mixing ratios [J]. Journal of Atmospheric Chemistry, 1998,30(2): 209-228.
[25]
Birdsall A W, Elrod M J. Comprehensive NO-dependent study of the products of the oxidation of atmospherically relevant aromatic compounds [J]. Journal of Physical Chemistry A, 2011,115(21):5397-5407.
[26]
Zaytsev A, Koss A R, Breitenlechner M, et al. Mechanistic study of the formation of ring-retaining and ring-opening products from the oxidation of aromatic compounds under urban atmospheric conditions [J]. Atmospheric Chemistry and Physics, 2019,19(23):15117-15129.
[27]
Hoyle C R, Boy M, Donahue N M, et al. A review of the anthropogenic influence on biogenic secondary organic aerosol [J]. Atmospheric Chemistry and Physics, 2011,11(1):321-343.
[28]
Bryant D J, Dixon W J, Hopkins J R, et al. Strong anthropogenic control of secondary organic aerosol formation from isoprene in Beijing [J]. Atmospheric Chemistry and Physics, 2020,20(12):7531-7552.
[29]
Li L, Zhang B, Cao J, et al. Isoprenoid emissions from natural vegetation increased rapidly in eastern China [J]. Environmental Research, 2021,200(12):111462-111462.
[30]
Wei D, Fuentes J D, Gerken T, et al. Influences of nitrogen oxides and isoprene on ozone-temperature relationships in the Amazon rain forest [J]. Atmospheric Environment, 2019,206:280-292.
[31]
Makar P A, Staebler R M, Akingunola A, et al. The effects of forest canopy shading and turbulence on boundary layer ozone [J]. Nature Communications, 2017,8:15243.
[32]
Lv S, Gong D, Ding Y, et al. Elevated levels of glyoxal and methylglyoxal at a remote mountain site in southern China: Prompt in-situ formation combined with strong regional transport [J]. Science of the Total Environment, 2019,672:869-882.
[33]
Gong D, Wang H, Zhang S, et al. Low-level summertime isoprene observed at a forested mountaintop site in southern China: implications for strong regional atmospheric oxidative capacity [J]. Atmospheric Chemistry and Physics, 2018,18(19):14417-14432.
[34]
Qin M, Hu A, Mao J, et al. PM2.5 and O3 relationships affected by the atmospheric oxidizing capacity in the Yangtze River Delta, China [J]. Science of the Total Environment, 2022,810:152268.
[35]
Chen T, Jang M. Secondary organic aerosol formation from photooxidation of a mixture of dimethyl sulfide and isoprene [J]. Atmospheric Environment, 2012,46:271-278.
[36]
张诗炀,龚道程,王 好,等.南岭国家大气背景站异戊二烯的在线观测研究 [J]. 中国环境科学, 2017,37(7):2504-2512. Shi-yang Zhang, Dao-cheng Gong, et al. Online measurement of isoprene at a national air background monitoring station in the Nanling Mountains, South China [J]. China Environmental Science, 2017, 37(7):2504-2512.
[37]
Jaoui M, Edney E O, Kleindienst T E, et al. Formation of secondary organic aerosol from irradiated -pinene/toluene/NOx mixtures and the effect of isoprene and sulfur dioxide [J]. Journal of Geophysical Research, 2008,113:D09303.
[38]
Chen L, Bao K, Li K, et al. Ozone and secondary organic aerosol formation of toluene/NOx irradiations under complex pollution scenarios [J]. Aerosol & Air Quality Research, 2017,17(7):1660-1671.
[39]
De Gouw J, Warneke C. Measurements of volatile organic compounds in the earth's atmosphere using proton-transfer-reaction mass spectrometry [J]. Mass Spectrom Reviews, 2007,26(2):223-257.
[40]
Yuan B, Koss A R, Warneke C, et al. Proton-transfer-reaction mass spectrometry: Applications in atmospheric sciences [J]. Chemical Reviews, 2017,117(21):13187-13229.
[41]
Jorga S D, Kaltsonoudis C, Liangou A, et al. Measurement of formation rates of secondary aerosol in the ambient urban atmosphere using a dual smog chamber system [J]. Environmental Science & Technology, 2020,54(3):1336-1343.
[42]
Wang Y, Zhao Y, Li Z, et al. Importance of hydroxyl radical chemistry in isoprene suppression of particle formation from α-pinene ozonolysis [J]. Earth and Space Chemistry, 2021,5(3):487-499.
[43]
Jang M, Kamens R M. Characterization of secondary aerosol from the photooxidation of toluene in the presence of NOx and 1-propene [J]. Environmental Science & Technology, 2001,35(18):3626-3639.
[44]
Fan J W, Zhang R Y. Atmospheric oxidation mechanism of isoprene [J]. Environmental Chemistry, 2004,1:140-149.
[45]
Healy R M, Wenger J C, Metzger A, et al. Atmospheric chemistry and physics gas/particle partitioning of carbonyls in the photooxidation of isoprene and 1,3,5-trimethylbenzene [J]. Atmospheric Chemistry and Physics, 2008,8:3215-3230.
[46]
Pan G, Hu C J, et al. Direct detection of isoprene photooxidation products by using synchrotron radiation photoionization mass spectrometry [J]. Rapid Communications in Mass Spectrometry Rcm, 2011,26(2):189-194.
[47]
Wennberg P O, Bates K H, Crounse J D, et al. Gas-phase reactions of isoprene and its major oxidation products [J]. Chemical Reviews, 2018,118,7:3337–3390.
[48]
Kroll J H, Ng N L, Murphy S M, et al. Secondary organic aerosol formation from isoprene photooxidation [J]. Environmental Science & Technology, 2006,40(6):1869-1877.
[49]
Birdsall A W, Andreoni J F, Elrod M J. Investigation of the role of bicyclic peroxy radicals in the oxidation mechanism of toluene [J]. Journal of Physical Chemistry A, 2010,114(39):10655-10663.
[50]
Seuwen R, Warneck P. Oxidation of toluene in NOx free air: Product distribution and mechanism [J]. International Journal of Chemical Kinetics, 1996,28(5):315-332.
[51]
Mattias H, John C. Wenger, et al. The formation, properties and impact of secondary organic aerosol: current and emerging issues [J]. Atmospheric Chemistry and Physics, 2009,9:5155-5236.
[52]
Schwantes R H, Schilling K A, Mcvay R C, et al. Formation of highly oxygenated low-volatility products from cresol oxidation [J]. Atmospheric Chemistry and Physics, 2017,17(5):3453-3474.
[53]
Baltaretu C O, Lichtman E I, Hadler A B, et al. Primary atmospheric oxidation mechanism for toluene [J]. Journal of Physical Chemistry A, 2009,113(1):221-230.
[54]
Jenkin M E, Young J C, Rickard A R. The MCM v3.3.1degradation scheme for isoprene [J]. Atmospheric Chemistry and Physics, 2015, 15(20):11433-11459.
[55]
Moschonas N, Glavas S, Danalatos D. The effect of O2 and NO2 on the ring retaining products of the reaction of toluene with hydroxyl radicals [J]. Atmospheric Environment, 1996,127:875-881.
[56]
Jun Zhao, Renyi Zhang, et al. Quantification of hydroxycarbonyls from OH Isoprene reactions [J]. Journal of the American Chemical Society, 2004,126(9):2686–2687.
[57]
Tuazon E C, Atkinson R, et al. A product study of the gas-phase reaction of Isoprene with the OH radical in the presence of NOx [J]. International Journal of Chemical Kinetics, 1991,21(12):1221-1236.
[58]
Sprengnether M, Demerjian K, et al. Product analysis of the OH oxidation of isoprene and 1,3-butadiene in the presence of NO. [J]. Journal of Geophysical Research Atmospheres, 2002,107(D15):ACH 8-1-ACH 8-13.
[59]
Carlton A G, Wiedinmyer C, Kroll J H, et al. A review of Secondary Organic Aerosol (SOA) formation from isoprene [J]. Atmospheric Chemistry and Physics Discussions, 2009,9(14):4987-5005.
[60]
Baker J, Arey J, Atkinson R, et al. Formation and reaction of hydroxycarbonyls from the reaction of OH radicals with 1,3-butadiene and isoprene [J]. Environmental Science & Technology, 2005,84(11): 4091-4099.
