Intermediate and semi-volatility organic compounds (I/SVOCs) emission from Chinese vehicles: volatility distribution, influencing factors, and implication for SOA formation

Abstract

Intermediate and semi-volatility organic compounds (I/SVOCs) are crucial precursors for secondary organic aerosols (SOA). Vehicles are major sources of I/SVOCs, yet their emission profiles remain insufficiently characterized. We conducted dynamometer tests on eight in-use gasoline and diesel vehicles (DVs), employing non-targeted analysis with comprehensive two-dimensional gas chromatography coupled with high-resolution mass spectrometry (GC × GC-TOFMS) to investigate vehicular I/SVOC emissions at the molecular level. A total of 438 and 424 compounds were identified and (semi)-quantified in the gas and particle phases, respectively. DVs exhibited higher emission factors (376.7 ± 74.9 mg/(kg·fuel)) compared to gasoline vehicles (GVs) (114.4 ± 42.1 mg/(kg·fuel)) across both phases. Alkanes (29.7%–41.9%), single-ring aromatics (2.6%–29.8%), and cycloalkanes (1.0%–13.1%) were dominant I/SVOCs groups. Oxygenated I/SVOCs were more abundant in particulate phases (40.3%–56.8%) than in gas phases (14.4%–15.3%). Upgrading emission standards reduced organic emissions by 89.2% from China IV to China VI for DVs, particularly in the particle phase. Cold-start conditions resulted in higher I/SVOC emissions (528.4 mg/(kg·fuel)) than hot-starts (224.8 mg/(kg·fuel)) due to reduced combustion efficiency and suboptimal after-treatment performance at low temperatures. Our composition-based SOA estimation method improved SOA predictions by 1.5 and 1.2 times for diesel and GVs, respectively, compared to the traditional bin approach. These findings provide valuable insights into the molecular composition of vehicular I/SVOCs and their environmental impacts.

Graphical abstract

Keywords

Vehicle emissions / Non-targeted analysis / I/SVOCs / Chemical fingerprinting / SOA formation potential

Highlight

	● I/SVOCs profile and volatility distributions from vehicles were established.
	● Stricter emission standards reduced organic emissions but increased I/SVOC fraction.
	● Speciation analysis enhanced SOA prediction accuracy compared to GC-MS.

References

[1] Alam M S, Zeraati-Rezaei S, Liang Z, Stark C, Xu H, MacKenzie A R, Harrison R M. (2018). Mapping and quantifying isomer sets of hydrocarbons (≥C12 ) in diesel exhaust, lubricating oil and diesel fuel samples using GC×GC-ToF-MS. Atmospheric Measurement Techniques, 11(5): 3047–3058

[2] Alam M S, Zeraati-Rezaei S, Xu H, Harrison R M. (2019). Characterization of gas and particulate phase organic emissions (C9–C37) from a diesel engine and the effect of abatement devices. Environmental Science & Technology, 53(19): 11345–11352

[3] Algrim L B, Ziemann P J. (2016). Effect of the keto group on yields and composition of organic aerosol formed from OH radical-initiated reactions of ketones in the presence of NO_x. Journal of Physical Chemistry A, 120(35): 6978–6989

[4] AlgrimL BZiemann P J (2019). Effect of the hydroxyl group on yields and composition of organic aerosol formed from OH radical-initiated reactions of alcohols in the presence of NO_x. ACS Earth & Space Chemistry, 3(3): 413–423

[5] An Z, Li X, Shi Z, Williams B J, Harrison R M, Jiang J. (2021). Frontier review on comprehensive two-dimensional gas chromatography for measuring organic aerosol. Journal of Hazardous Materials Letters, 2: 100013

[6] An Z, Ren H, Xue M, Guan X, Jiang J. (2020). Comprehensive two-dimensional gas chromatography mass spectrometry with a solid-state thermal modulator for in-situ speciated measurement of organic aerosols. Journal of Chromatography. A, 1625: 461336

[7] Cao X, Yao Z, Shen X, Ye Y, Jiang X. (2016). On-road emission characteristics of VOCs from light-duty gasoline vehicles in Beijing, China. Atmospheric Environment, 124: 146–155

[8] Chacon-Madrid H J, Donahue N M. (2011). Fragmentation vs. functionalization: chemical aging and organic aerosol formation. Atmospheric Chemistry and Physics, 11(20): 10553–10563

[9] Chan A W H, Chan M N, Surratt J D, Chhabra P S, Loza C L, Crounse J D, Yee L D, Flagan R C, Wennberg P O, Seinfeld J H. (2010). Role of aldehyde chemistry and NO_x concentrations in secondary organic aerosol formation. Atmospheric Chemistry and Physics, 10(15): 7169–7188

[10] Chan A W H, Kautzman K E, Chhabra P S, Surratt J D, Chan M N, Crounse J D, Kürten A, Wennberg P O, Flagan R C, Seinfeld J H. (2009). Secondary organic aerosol formation from photooxidation of naphthalene and alkylnaphthalenes: implications for oxidation of intermediate volatility organic compounds (IVOCs). Atmospheric Chemistry and Physics, 9(9): 3049–3060

[11] Dallüge J, Beens J, Brinkman U A T. (2003). Comprehensive two-dimensional gas chromatography: a powerful and versatile analytical tool. Journal of Chromatography. A, 1000(1−2): 69–108

[12] Donahue N M, Kroll J H, Pandis S N, Robinson A L. (2012). A two-dimensional volatility basis set – Part 2: Diagnostics of organic-aerosol evolution. Atmospheric Chemistry and Physics, 12(2): 615–634

[13] Drozd G T, Zhao Y, Saliba G, Frodin B, Maddox C, Oliver Chang M C, Maldonado H, Sardar S, Weber R J, Robinson A L. . (2019). Detailed speciation of intermediate volatility and semi-volatile organic compound emissions from gasoline vehicles: effects of cold-starts and implications for secondary organic aerosol Formation. Environmental Science & Technology, 53(3): 1706–1714

[14] Drozd G T, Zhao Y, Saliba G, Frodin B, Maddox C, Weber R J, Chang M C O, Maldonado H, Sardar S, Robinson A L. . (2016). Time resolved measurements of speciated tailpipe emissions from motor vehicles: trends with emission control technology, cold start effects, and speciation. Environmental Science & Technology, 50(24): 13592–13599

[15] Du Z, Hu M, Peng J, Zhang W, Zheng J, Gu F, Qin Y, Yang Y, Li M, Wu Y. . (2018). Comparison of primary aerosol emission and secondary aerosol formation from gasoline direct injection and port fuel injection vehicles. Atmospheric Chemistry and Physics, 18(12): 9011–9023

[16] Gentner D R, Jathar S H, Gordon T D, Bahreini R, Day D A, El Haddad I, Hayes P L, Pieber S M, Platt S M, De Gouw J. . (2017). Review of urban secondary organic aerosol formation from gasoline and diesel motor vehicle emissions. Environmental Science & Technology, 51(3): 1074–1093

[17] Harvey R M, Petrucci G A. (2015). Control of ozonolysis kinetics and aerosol yield by nuances in the molecular structure of volatile organic compounds. Atmospheric Environment, 122: 188–195

[18] Hatch L E, Luo W, Pankow J F, Yokelson R J, Stockwell C E, Barsanti K C. (2015). Identification and quantification of gaseous organic compounds emitted from biomass burning using two-dimensional gas chromatography–time-of-flight mass spectrometry. Atmospheric Chemistry and Physics, 15(4): 1865–1899

[19] He X, Zheng X, You Y, Zhang S, Zhao B, Wang X, Huang G, Chen T, Cao Y, He L. . (2022a). Comprehensive chemical characterization of gaseous I/SVOC emissions from heavy-duty diesel vehicles using two-dimensional gas chromatography time-of-flight mass spectrometry. Environmental Pollution, 305: 119284

[20] He X, Zheng X, Zhang S, Wang X, Chen T, Zhang X, Huang G, Cao Y, He L, Cao X. . (2022b). Comprehensive characterization of particulate intermediate-volatility and semi-volatile organic compounds (I/SVOCs) from heavy-duty diesel vehicles using two-dimensional gas chromatography time-of-flight mass spectrometry. Atmospheric Chemistry and Physics, 22(21): 13935–13947

[21] Huang C, Hu Q, Li Y, Tian J, Ma Y, Zhao Y, Feng J, An J, Qiao L, Wang H. . (2018). Intermediate volatility organic compound emissions from a large cargo vessel operated under real-world conditions. Environmental Science & Technology, 52(21): 12934–12942

[22] Huang D D, Hu Q, He X, Huang R J, Ding X, Ma Y, Feng X, Jing S A, Li Y, Lu J. . (2024). Obscured contribution of oxygenated Intermediate-volatility organic compounds to secondary organic aerosol formation from gasoline vehicle emissions. Environmental Science & Technology, 58(24): 10652–10663

[23] Huang L, Bohac S V, Chernyak S M, Batterman S A. (2015). Effects of fuels, engine load and exhaust after-treatment on diesel engine SVOC emissions and development of SVOC profiles for receptor modeling. Atmospheric Environment, 102: 228–238

[24] Huo Y, Guo Z, Li Q, Wu D, Ding X, Liu A, Huang D, Qiu G, Wu M, Zhao Z. . (2021a). Chemical fingerprinting of HULIS in particulate matters emitted from residential coal and biomass combustion. Environmental Science & Technology, 55(6): 3593–3603

[25] Huo Y, Guo Z, Liu Y, Wu D, Ding X, Zhao Z, Wu M, Wang L, Feng Y, Chen Y. . (2021b). Addressing unresolved complex mixture of I/SVOCs emitted from incomplete combustion of solid fuels by nontarget analysis. Journal of Geophysical Research: Atmospheres, 126(23): e2021JD035835

[26] Jathar S H, Gordon T D, Hennigan C J, Pye H O, Pouliot G, Adams P J, Donahue N M, Robinson A L. (2014). Unspeciated organic emissions from combustion sources and their influence on the secondary organic aerosol budget in the United States. Proceedings of the National Academy of Sciences of the United States of America, 111(29): 10473–10478

[27] Laszakovits J R, Mackay A A. (2022). Data-based chemical class regions for van krevelen diagrams. Journal of the American Society for Mass Spectrometry, 33(1): 198–202

[28] Li L, Li J, Qin M, Xie X, Hu J, Zhang Y. (2024). Variations in summertime ozone in Nanjing between 2015 and 2020: roles of meteorology, radical chain length and ozone production efficiency. Frontiers of Environmental Science & Engineering, 18(11): 137

[29] Li L, Ping T, Nakao S, Cocker D R III. (2016). Impact of molecular structure on secondary organic aerosol formation from aromatic hydrocarbon photooxidation under low-NO_x conditions. Atmospheric Chemistry and Physics, 16(17): 10793–10808

[30] Liu P, Wu Y, Li Z, Lv Z, Zhang J, Liu Y, Song A, Wang T, Wu L, Mao H. . (2024). Tailpipe volatile organic compounds (VOCs) emissions from Chinese gasoline vehicles under different vehicle standards, fuel types, and driving conditions. Atmospheric Environment, 323: 120348

[31] Liu T, Wang Z, Huang D D, Wang X, Chan C K. (2018). Significant production of secondary organic aerosol from emissions of heated cooking oils. Environmental Science & Technology Letters, 5(1): 32–37

[32] Loza C L, Craven J S, Yee L D, Coggon M M, Schwantes R H, Shiraiwa M, Zhang X, Schilling K A, Ng N L, Canagaratna M R. . (2014). Secondary organic aerosol yields of 12-carbon alkanes. Atmospheric Chemistry and Physics, 14(3): 1423–1439

[33] Lu Q, Zhao Y, Robinson A L. (2018). Comprehensive organic emission profiles for gasoline, diesel, and gas-turbine engines including intermediate and semi-volatile organic compound emissions. Atmospheric Chemistry and Physics, 18(23): 17637–17654

[34] Mader B T, Pankow J F. (2001). Gas/solid partitioning of semivolatile organic compounds (SOCs) to air filters. 3. An analysis of gas adsorption artifacts in measurements of atmospheric SOCs and organic carbon (OC) when using Teflon membrane filters and quartz fiber filters. Environmental Science & Technology, 35(17): 3422–3432

[35] Matsumoto K, Hayano T, Uematsu M. (2003). Positive artifact in the measurement of particulate carbonaceous substances using an ambient carbon particulate monitor. Atmospheric Environment, 37(33): 4713–4717

[36] Mcdonald B C, De Gouw J A, Gilman J B, Jathar S H, Akherati A, Cappa C D, Jimenez J L, Lee-Taylor J, Hayes P L, Mckeen S A. . (2018). Volatile chemical products emerging as largest petrochemical source of urban organic emissions. Science, 359(6377): 760–764

[37] Peng J, Hu M, Du Z, Wang Y, Zheng J, Zhang W, Yang Y, Qin Y, Zheng R, Xiao Y. . (2017). Gasoline aromatics: a critical determinant of urban secondary organic aerosol formation. Atmospheric Chemistry and Physics, 17(17): 10743–10752

[38] Peng J, Hu M, Shang D, Wu Z, Du Z, Tan T, Wang Y, Zhang F, Zhang R. (2021). Explosive secondary aerosol formation during severe haze in the North China Plain. Environmental Science & Technology, 55(4): 2189–2207

[39] Presto A A, Miracolo M A, Kroll J H, Worsnop D R, Robinson A L, Donahue N M. (2009). Intermediate-volatility organic compounds: a potential source of ambient oxidized organic aerosol. Environmental Science & Technology, 43(13): 4744–4749

[40] Qi L, Zhao J, Li Q, Su S, Lai Y, Deng F, Man H, Wang X, Shen X E, Lin Y. . (2021). Primary organic gas emissions from gasoline vehicles in China: Factors, composition and trends. Environmental Pollution, 290: 117984

[41] Qiao L, Gao L, Liu Y, Huang D, Li D, Zheng M. (2022). Recognition and health impacts of organic pollutants with significantly different proportions in the gas phase and size-fractionated particulate phase in ambient air. Environmental Science & Technology, 56(11): 7153–7162

[42] Robinson A L, Donahue N M, Shrivastava M K, Weitkamp E A, Sage A M, Grieshop A P, Lane T E, Pierce J R, Pandis S N. (2007). Rethinking organic aerosols: semivolatile emissions and photochemical aging. Science, 315(5816): 1259–1262

[43] Shrivastava M, Cappa C D, Fan J, Goldstein A H, Guenther A B, Jimenez J L, Kuang C, Laskin A, Martin S T, Ng N L. . (2017). Recent advances in understanding secondary organic aerosol: Implications for global climate forcing. Reviews of Geophysics, 55(2): 509–559

[44] Song K, Guo S, Gong Y, Lv D, Wan Z, Zhang Y, Fu Z, Hu K, Lu S. (2023a). Non-target scanning of organics from cooking emissions using comprehensive two-dimensional gas chromatography-mass spectrometer (GC×GC-MS). Applied Geochemistry, 151: 105601

[45] Song K, Guo S, Gong Y, Lv D, Zhang Y, Wan Z, Li T, Zhu W, Wang H, Yu Y. . (2022). Impact of cooking style and oil on semi-volatile and intermediate volatility organic compound emissions from Chinese domestic cooking. Atmospheric Chemistry and Physics, 22(15): 9827–9841

[46] Song K, Tang R, Zhang J, Wan Z, Zhang Y, Hu K, Gong Y, Lv D, Lu S, Tan Y. . (2023b). Molecular fingerprints and health risks of smoke from home-use incense burning. Atmospheric Chemistry and Physics, 23(21): 13585–13595

[47] Stewart G J, Acton W J F, Nelson B S, Vaughan A R, Hopkins J R, Arya R, Mondal A, Jangirh R, Ahlawat S, Yadav L. . (2021). Emissions of non-methane volatile organic compounds from combustion of domestic fuels in Delhi, India. Atmospheric Chemistry and Physics, 21(4): 2383–2406

[48] Tang R, Lu Q, Guo S, Wang H, Song K, Yu Y, Tan R, Liu K, Shen R, Chen S. . (2021). Measurement report: distinct emissions and volatility distribution of intermediate-volatility organic compounds from on-road Chinese gasoline vehicles: implication of high secondary organic aerosol formation potential. Atmospheric Chemistry and Physics, 21(4): 2569–2583

[49] Wagner T, Wyszyński M L. (1996). Aldehydes and ketones in engine exhaust emissions: a review. Proceedings of the Institution of Mechanical Engineers. Part D, Journal of Automobile Engineering, 210(2): 109–122

[50] Wu Y, Fan X, Liu Y, Zhang J, Wang H, Sun L, Fang T, Mao H, Hu J, Wu L. . (2023a). Source apportionment of VOCs based on photochemical loss in summer at a suburban site in Beijing. Atmospheric Environment, 293: 119459

[51] Wu Y, Liu Y, Liu P, Sun L, Song P, Peng J, Li R, Wei N, Wu L, Wang T. . (2023b). Evaluating vehicular exhaust and evaporative emissions via VOC measurement in an underground parking garage. Environmental Pollution, 333: 122022

[52] Zeng L, Wang F, Xiao S, Zeng X, Li X, Xie Q, Yu X, Huang C, Hu Q, You Y. . (2024). Characterization and prediction of tailpipe ammonia emissions from in-use China 5/6 light-duty gasoline vehicles. Frontiers of Environmental Science & Engineering, 18(1): 6

[53] Zhang J, Peng J, Song A, Du Z, Guo J, Liu Y, Yang Y, Wu L, Wang T, Song K. . (2024a). Secondary organic aerosol formation potential from vehicular non-tailpipe emissions under real-world driving conditions. Environmental Science & Technology, 58(12): 5419–5429

[54] ZhangJ, Peng J, SongA, LvZ, TongH, DuZ, GuoJ, WuL, WangT, HallquistM, et al. (2023).Marked impacts of transient conditions on potential secondary organic aerosol production during rapid oxidation of gasoline exhausts. npj Climate and Atmospheric Science, 6(1): 59

[55] Zhang X, He X, Cao Y, Chen T, Zheng X, Zhang S, Wu Y. (2024b). Comprehensive characterization of speciated volatile organic compounds (VOCs), gas-phase and particle-phase intermediate- and semi-volatile volatility organic compounds (I/S-VOCs) from Chinese diesel trucks. Science of the Total Environment, 912: 168950

[56] Zhang Y, Wang X, Wen S, Herrmann H, Yang W, Huang X, Zhang Z, Huang Z, He Q, George C. (2016). On-road vehicle emissions of glyoxal and methylglyoxal from tunnel tests in urban Guangzhou, China. Atmospheric Environment, 127: 55–60

[57] Zhao B, Wang S, Hao J. (2024). Challenges and perspectives of air pollution control in China. Frontiers of Environmental Science & Engineering, 18(6): 68

[58] Zhao J, Lv Z, Qi L, Zhao B, Deng F, Chang X, Wang X, Luo Z, Zhang Z, Xu H. . (2022). Comprehensive assessment for the impacts of S/IVOC emissions from mobile sources on SOA formation in China. Environmental Science & Technology, 56(23): 16695–16706

[59] Zhao Y, Hennigan C J, May A A, Tkacik D S, De Gouw J A, Gilman J B, Kuster W C, Borbon A, Robinson A L. (2014). Intermediate-volatility organic compounds: a large source of secondary organic aerosol. Environmental Science & Technology, 48(23): 13743–13750

[60] Zhao Y, Lambe A T, Saleh R, Saliba G, Robinson A L. (2018). Secondary organic aerosol production from gasoline vehicle exhaust: effects of engine technology, cold start, and emission certification standard. Environmental Science & Technology, 52(3): 1253–1261

[61] Zhao Y, Nguyen N T, Presto A A, Hennigan C J, May A A, Robinson A L. (2015). Intermediate volatility organic compound emissions from on-road diesel vehicles: chemical composition, emission factors, and estimated secondary organic aerosol production. Environmental Science & Technology, 49(19): 11516–11526

[62] Zhao Y, Nguyen N T, Presto A A, Hennigan C J, May A A, Robinson A L. (2016). Intermediate volatility organic compound emissions from on-road gasoline vehicles and small off-road gasoline engines. Environmental Science & Technology, 50(8): 4554–4563

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