Characterization and prediction of tailpipe ammonia emissions from in-use China 5/6 light-duty gasoline vehicles

Abstract

● Rich combustion strategy in cold-start period caused more NH₃ emission.

● NH₃ emitting events were tightly related to start and stop conditions.

● NH₃ emissions were regulated by the catalytic temperature in TWC.

● NH₃ EFs strongly correlated with combustion efficiency, engine and vehicle speeds.

● Three prediction methods were established to reproduce real-world NH₃ emissions.

On-road tailpipe ammonia (NH₃) emissions contribute to urban secondary organic aerosol formation and have direct or indirect adverse impacts on the environment and human health. To understand the tailpipe NH₃ emission characteristics, we performed comprehensive chassis dynamometer measurements of NH₃ emission from two China 5 and two China 6 light-duty gasoline vehicles (LDGVs) equipped with three-way catalytic converters (TWCs). The results showed that the distance-based emission factors (EFs) were 12.72 ± 2.68 and 3.18 ± 1.37 mg/km for China 5 and China 6 LDGVs, respectively. Upgrades in emission standards were associated with a reduction in tailpipe NH₃ emission. In addition, high NH₃ EFs were observed during the engine warm-up period in cold-start cases owing to the intensive emissions of incomplete combustion products and suitable catalytic temperature in the TWCs. Notably, based on the instantaneous NH₃ emission rate, distinct NH₃–emitting events were detected under high/extra high velocity or rapid acceleration. Furthermore, NH₃ emission rates correlated well with engine speed, vehicle specific power, and modified combustion efficiency, which were more easily accessible. These strong correlations were applied to reproduce NH₃ emissions from China 5/6 LDGVs. The predicted NH₃ EFs under different dynamometer and real-world cycles agreed well with existing measurement and prediction results, revealing that the NH₃ EFs of LDGVs in urban routes were within 8.55–11.62 mg/km. The results presented here substantially contribute to improving the NH₃ emission inventory for LDGVs and predicting on-road NH₃ emissions in China.

Graphical abstract

Keywords

NH ₃ instantaneous emissions / Catalytic temperature / Vehicle specific power / Combustion efficiency / Emission prediction

References

[1] Abelló P M, Medina Iglesias V, de los Santos López M A, Álvarez-Flórez J. (2021). Real drive cycles analysis by ordered power methodology applied to fuel consumption, CO₂, NO_x and PM emissions estimation. Frontiers of Environmental Science & Engineering, 15(1): 4

[2] Bielaczyc P, Szczotka A, Swiatek A, Woodburn J. (2012). A comparison of ammonia emission factors from light-duty vehicles operating on gasoline, liquefied petroleum gas (LPG) and compressed natural gas (CNG). SAE International Journal of Fuels and Lubricants, 5(2): 751–759

[3] Bouwman A F, Lee D S, Asman W A H, Dentener F J, Van Der Hoek K W, Olivier J G J. (1997). A global high-resolution emission inventory for ammonia. Global Biogeochemical Cycles, 11(4): 561–587

[4] Cao J J, Shen Z X, Chow J C, Watson J G, Lee S C, Tie X X, Ho K F, Wang G H, Han Y M. (2012). Winter and summer PM_2.5 chemical compositions in fourteen Chinese cities. Journal of the Air & Waste Management Association, 62(10): 1214–1226

[5] EPA (2021). Overview of EPA’s Motor Vehicle Emission Simulator (MOVES3). Washington, DC: U.S. Environmental Protection Agency

[6] Farren N J, Davison J, Rose R A, Wagner R L, Carslaw D C. (2020). Underestimated ammonia emissions from road vehicles. Environmental Science & Technology, 54(24): 15689–15697

[7] Farren N J, Davison J, Rose R A, Wagner R L, Carslaw D C. (2021). Characterisation of ammonia emissions from gasoline and gasoline hybrid passenger cars. Atmospheric Environment, 11: 100117

[8] Feng J L, Guo Z G, Zhang T R, Yao X H, Chan C K, Fang M. (2012). Source and formation of secondary particulate matter in PM_2.5 in Asian continental outflow. Journal of Geophysical Research, 117: D03302

[9] Gong L W, Lewicki R, Griffin R J, Tittel F K, Lonsdale C R, Stevens R G, Pierce J R, Malloy Q G J, Travis S A, Bobmanuel L M. . (2013). Role of atmospheric ammonia in particulate matter formation in Houston during summertime. Atmospheric Environment, 77: 893–900

[10] Heeb N V, Forss A M, Brühlmann S, Lüscher R, Saxer C J, Hug P. (2006). Three-way catalyst-induced formation of ammonia—velocity- and acceleration-dependent emission factors. Atmospheric Environment, 40(31): 5986–5997

[11] Ho C S, Peng J F, Yun U H, Zhang Q J, Mao H J. (2022). Impacts of methanol fuel on vehicular emissions: a review. Frontiers of Environmental Science & Engineering, 16(9): 121

[12] Huai T, Durbin T D, Miller J W, Pisano J T, Sauer C G, Rhee S H, Norbeck J M. (2003). Investigation of NH₃ emissions from new technology vehicles as a function of vehicle operating conditions. Environmental Science & Technology, 37(21): 4841–4847

[13] Huai T, Durbin T D, Younglove T, Scora G, Barth M, Norbeck J M. (2005). Vehicle specific power approach to estimating on-road NH₃ emissions from light-duty vehicles. Environmental Science & Technology, 39(24): 9595–9600

[14] Huang C, Hu Q Y, Lou S R, Tian J J, Wang R N, Xu C, An J Y, Ren H J, Ma D, Quan Y F, Zhang Y J, Li L. (2018). Ammonia emission measurements for light-duty gasoline vehicles in China and implications for emission modeling. Environmental Science & Technology, 52(19): 11223–11231

[15] Huang X, Song Y, Li M M, Li J F, Huo Q, Cai X H, Zhu T, Hu M, Zhang H S. (2012). A high-resolution ammonia emission inventory in China. Global Biogeochemical Cycles, 26(1): GB1030

[16] ICCT (2021). ICCT’s Comments and Technical Recommendations on Future Euro 7/VII Emission Standards. Berlin: The International Council on Clean Transportation

[17] Jiménez-PalaciosJ L (1999). Understanding and quantifying motor vehicle emissions with vehicle specific power and TILDAS remote sensing. Dissertation for the Doctoral Degree. Cambridge: Massachusetts Institute of Technology

[18] Kang Y N, Liu M X, Song Y, Huang X, Yao H, Cai X H, Zhang H S, Kang L, Liu X J, Yan X Y. . (2016). High-resolution ammonia emissions inventories in China from 1980 to 2012. Atmospheric Chemistry and Physics, 16(4): 2043–2058

[19] Liu Y, Liang Y K, Yu H Z N, An X P, Li J Y. (2021a). Comparative analysis of China light-duty vehicle test cycle for passenger car and other typical driving cycles. E3S Web of Conferences, 241: 02002

[20] Liu Y C, Zhan J L, Zheng F X, Song B Y, Zhang Y S, Ma W, Hua C J, Xie J L, Bao X L, Yan C. . (2022). Dust emission reduction enhanced gas-to-particle conversion of ammonia in the North China Plain. Nature Communications, 13(1): 6887

[21] Liu Y S, Ge Y S, Tan J W, Wang H L, Ding Y. (2021b). Research on ammonia emissions characteristics from light-duty gasoline vehicles. Journal of Environmental Sciences-China, 106: 182–193

[22] Livingston C, Rieger P, Winer A. (2009). Ammonia emissions from a representative in-use fleet of light and medium-duty vehicles in the California South Coast Air Basin. Atmospheric Environment, 43(21): 3326–3333

[23] Masiol M, Hopke P K, Felton H D, Frank B P, Rattigan O V, Wurth M J, LaDuke G H. (2017). Source apportionment of PM_2.5 chemically speciated mass and particle number concentrations in New York City. Atmospheric Environment, 148: 215–229

[24] MEE (2013). Limits and measurement methods for emissions from light-duty vehicles (CHINA 5). Beijing: Ministry of Ecology and Environment of the People’s Republic of China (in Chinese)

[25] MEE (2016). Limits and measurement methods for emissions from light-duty vehicles (CHINA 6). Beijing: Ministry of Ecology and Environment of the People’s Republic of China (in Chinese)

[26] Meng W J, Zhong Q R, Yun X, Zhu X, Huang T B, Shen H Z, Chen Y L, Chen H, Zhou F, Liu J F. . (2017). Improvement of a global high-resolution ammonia emission inventory for combustion and industrial sources with new data from the residential and transportation sectors. Environmental Science & Technology, 51(5): 2821–2829

[27] Meng Z Y, Xu X B, Lin W L, Ge B Z, Xie Y L, Song B, Jia S H, Zhang R, Peng W, Wang Y. . (2018). Role of ambient ammonia in particulate ammonium formation at a rural site in the North China Plain. Atmospheric Chemistry and Physics, 18(1): 167–184

[28] Platt S M, El Haddad I, Pieber S M, Zardini A A, Suarez-Bertoa R, Clairotte M, Daellenbach K R, Huang R J, Slowik J G, Hellebust S. . (2017). Gasoline cars produce more carbonaceous particulate matter than modern filter-equipped diesel cars. Scientific Reports, 7(1): 4926

[29] Platt S M, El Haddad I, Zardini A A, Clairotte M, Astorga C, Wolf R, Slowik J G, Temime-Roussel B, Marchand N, Ježek I. . (2013). Secondary organic aerosol formation from gasoline vehicle emissions in a new mobile environmental reaction chamber. Atmospheric Chemistry and Physics, 13(18): 9141–9158

[30] Selleri T, Melas A, Bonnel P, Suarez-Bertoa R. (2022). NH₃ and CO emissions from fifteen Euro 6d and Euro 6d-TEMP gasoline-fuelled vehicles. Catalysts, 12(3): 245

[31] Shelef M, Gandhi H S. (1974). Ammonia formation in the catalytic reduction of nitric oxide. III. The role of water gas shift, reduction by hydrocarbons, and steam reforming. Industrial & Engineering Chemistry Product Research and Development, 13(1): 80–85

[32] Suarez-Bertoa R, Astorga C. (2016). Isocyanic acid and ammonia in vehicle emissions. Transportation Research Part D, Transport and Environment, 49: 259–270

[33] Suarez-Bertoa R, Mendoza-Villafuerte P, Riccobono F, Vojtisek M, Pechout M, Perujo A, Astorga C. (2017). On-road measurement of NH₃ emissions from gasoline and diesel passenger cars during real world driving conditions. Atmospheric Environment, 166: 488–497

[34] Suarez-Bertoa R, Zardini A A, Astorga C. (2014). Ammonia exhaust emissions from spark ignition vehicles over the New European Driving Cycle. Atmospheric Environment, 97: 43–53

[35] Suarez-Bertoa R, Zardini A A, Lilova V, Meyer D, Nakatani S, Hibel F, Ewers J, Clairotte M, Hill L, Astorga C. (2015). Intercomparison of real-time tailpipe ammonia measurements from vehicles tested over the new world-harmonized light-duty vehicle test cycle (WLTC). Environmental Science and Pollution Research International, 22(10): 7450–7460

[36] Tan W, Xie S H, Shan W P, Lian Z H, Xie L J, Liu A N, Gao F, Dong L, He H, Liu F D. (2022). CeO₂ doping boosted low-temperature NH₃-SCR activity of FeTiO_x catalyst: a microstructure analysis and reaction mechanistic study. Frontiers of Environmental Science & Engineering, 16(5): 60

[37] Wang C, Yin S S, Bai L, Zhang X C, Gu X K, Zhang H, Lu Q, Zhang R Q. (2018). High-resolution ammonia emission inventories with comprehensive analysis and evaluation in Henan, China, 2006–2016. Atmospheric Environment, 193: 11–23

[38] Wang C X, Tan J W, Harle G, Gong H M, Xia W Z, Zheng T T, Yang D X, Ge Y S, Zhao Y K. (2019a). Ammonia formation over Pd/Rh three-way catalysts during lean-to-rich fluctuations: the effect of the catalyst aging, exhaust temperature, lambda, and duration in rich conditions. Environmental Science & Technology, 53(21): 12621–12628

[39] Wang X, Ge Y S, Gong H M, Yang Z J, Tan J W, Hao L J, Su S. (2019b). Ammonia emissions from China-6 compliant gasoline vehicles tested over the WLTC. Atmospheric Environment, 199: 136–142

[40] Wang X Y, Zhang R H, Yu W. (2019c). The effects of PM_2.5 concentrations and relative humidity on atmospheric visibility in Beijing. Journal of Geophysical Research. Atmospheres, 124(4): 2235–2259

[41] Wang Y J, Wen Y F, Zhang S J, Zheng G J, Zheng H T, Chang X, Huang C, Wang S X, Wu Y, Hao J M. (2023). Vehicular ammonia emissions significantly contribute to urban PM_2.5 pollution in two Chinese megacities. Environmental Science & Technology, 57(7): 2698–2705

[42] Xing Y F, Xu Y H, Shi M H, Lian Y X. (2016). The impact of PM_2.5 on the human respiratory system. Journal of Thoracic Disease, 8(1): E69–E74

[43] Xu L, Penner J E. (2012). Global simulations of nitrate and ammonium aerosols and their radiative effects. Atmospheric Chemistry and Physics, 12(20): 9479–9504

[44] Yang Y, Zheng X Z, Ren W, Liu J F, Fu X L, Meng S G, Chen S F, Cai C. (2022). Recent advances in special morphologic photocatalysts for NO_x removal. Frontiers of Environmental Science & Engineering, 16(11): 137

[45] Yu X N, Shen L, Hou X H, Yuan L, Pan Y P, An J L, Yan S Q. (2020). High-resolution anthropogenic ammonia emission inventory for the Yangtze River Delta, China. Chemosphere, 251: 126342

[46] Zheng J Y, Yin S S, Kang D W, Che W W, Zhong L J. (2012). Development and uncertainty analysis of a high-resolution NH₃ emissions inventory and its implications with precipitation over the Pearl River Delta region, China. Atmospheric Chemistry and Physics, 12(15): 7041–7058

[47] Zheng X, He L, He X, Zhang S, Cao Y, Hao J, Wu Y. (2022). Real-time black carbon emissions from light-duty passenger vehicles using a portable emissions measurement system. Engineering (Beijing), 16: 73–81

[48] Zhong Y Q, Xia B X, Shi J W, Ning P, Zhang C N, Han X Y, Hao J M. (2022). Particle-bound polycyclic aromatic hydrocarbons in typical urban of Yunnan-Guizhou Plateau: Characterization, sources and risk assessment. Frontiers of Environmental Science & Engineering, 16(9): 114

[49] Zhou Y, Cheng S Y, Lang J L, Chen D S, Zhao B B, Liu C, Xu R, Li T T. (2015). A comprehensive ammonia emission inventory with high-resolution and its evaluation in the Beijing–Tianjin–Hebei (BTH) region, China. Atmospheric Environment, 106: 305–317

[50] Zhu R C, Hu J N, He L Q, Zu L, Bao X F, Lai Y T, Su S. (2021). Effects of ambient temperature on regulated gaseous and particulate emissions from gasoline-, E10- and M15-fueled vehicles. Frontiers of Environmental Science & Engineering, 15(1): 14

RIGHTS & PERMISSIONS

Higher Education Press