Characterization and prediction of tailpipe ammonia emissions from in-use China 5/6 light-duty gasoline vehicles
Lewei Zeng1, Fengbin Wang2,3, Shupei Xiao1, Xuan Zheng1(), Xintong Li4, Qiyuan Xie4, Xiaoyang Yu4, Cheng Huang5, Qingyao Hu5, Yan You6, Ye Wu7
1. College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, China 2. State Key Laboratory of Engines, Tianjin University, Tianjin 300072, China 3. China Automotive Technology and Research Center Co. Ltd., Tianjin 300300, China 4. CATARC Automotive Test Center (Guangzhou) Co. Ltd., Guangzhou 511300, China 5. State Environmental Protection Key Laboratory of Cause and Prevention of Urban Air Pollution Complex, Shanghai Academy of Environmental Sciences, Shanghai 200233, China 6. National Observation and Research Station of Coastal Ecological Environments in Macao, Macao Environmental Research Institute, Macau University of Science and Technology, Macao SAR 999078, China 7. School of Environment, State Key Joint Laboratory of Environment Simulation and Pollution Control, Tsinghua University, Beijing 100084, China
● 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.
P M Abelló, Iglesias V Medina, los Santos López M A de, J Álvarez-Flórez. (2021). Real drive cycles analysis by ordered power methodology applied to fuel consumption, CO2, NOx and PM emissions estimation. Frontiers of Environmental Science & Engineering, 15(1): 4 https://doi.org/10.1007/s11783-020-1296-z
2
P Bielaczyc, A Szczotka, A Swiatek, J Woodburn. (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 https://doi.org/10.4271/2012-01-1095
3
A F Bouwman, D S Lee, W A H Asman, F J Dentener, K W Van Der Hoek, J G J Olivier. (1997). A global high-resolution emission inventory for ammonia. Global Biogeochemical Cycles, 11(4): 561–587 https://doi.org/10.1029/97GB02266
4
J J Cao, Z X Shen, J C Chow, J G Watson, S C Lee, X X Tie, K F Ho, G H Wang, Y M Han. (2012). Winter and summer PM2.5 chemical compositions in fourteen Chinese cities. Journal of the Air & Waste Management Association, 62(10): 1214–1226 https://doi.org/10.1080/10962247.2012.701193
5
EPA (2021). Overview of EPA’s Motor Vehicle Emission Simulator (MOVES3). Washington, DC: U.S. Environmental Protection Agency
6
N J Farren, J Davison, R A Rose, R L Wagner, D C Carslaw. (2020). Underestimated ammonia emissions from road vehicles. Environmental Science & Technology, 54(24): 15689–15697 https://doi.org/10.1021/acs.est.0c05839
7
N J Farren, J Davison, R A Rose, R L Wagner, D C Carslaw. (2021). Characterisation of ammonia emissions from gasoline and gasoline hybrid passenger cars. Atmospheric Environment, 11: 100117 https://doi.org/10.1016/j.aeaoa.2021.100117
8
J L Feng, Z G Guo, T R Zhang, X H Yao, C K Chan, M Fang. (2012). Source and formation of secondary particulate matter in PM2.5 in Asian continental outflow. Journal of Geophysical Research, 117: D03302 https://doi.org/10.1029/2011JD016400
9
L W Gong, R Lewicki, R J Griffin, F K Tittel, C R Lonsdale, R G Stevens, J R Pierce, Q G J Malloy, S A Travis, L M Bobmanuel. et al.. (2013). Role of atmospheric ammonia in particulate matter formation in Houston during summertime. Atmospheric Environment, 77: 893–900 https://doi.org/10.1016/j.atmosenv.2013.04.079
10
N V Heeb, A M Forss, S Brühlmann, R Lüscher, C J Saxer, P Hug. (2006). Three-way catalyst-induced formation of ammonia—velocity- and acceleration-dependent emission factors. Atmospheric Environment, 40(31): 5986–5997 https://doi.org/10.1016/j.atmosenv.2005.12.035
11
C S Ho, J F Peng, U H Yun, Q J Zhang, H J Mao. (2022). Impacts of methanol fuel on vehicular emissions: a review. Frontiers of Environmental Science & Engineering, 16(9): 121 https://doi.org/10.1007/s11783-022-1553-4
12
T Huai, T D Durbin, J W Miller, J T Pisano, C G Sauer, S H Rhee, J M Norbeck. (2003). Investigation of NH3 emissions from new technology vehicles as a function of vehicle operating conditions. Environmental Science & Technology, 37(21): 4841–4847 https://doi.org/10.1021/es030403+
13
T Huai, T D Durbin, T Younglove, G Scora, M Barth, J M Norbeck. (2005). Vehicle specific power approach to estimating on-road NH3 emissions from light-duty vehicles. Environmental Science & Technology, 39(24): 9595–9600 https://doi.org/10.1021/es050120c
14
C Huang, Q Y Hu, S R Lou, J J Tian, R N Wang, C Xu, J Y An, H J Ren, D Ma, Y F Quan, Y J Zhang, L Li. (2018). Ammonia emission measurements for light-duty gasoline vehicles in China and implications for emission modeling. Environmental Science & Technology, 52(19): 11223–11231 https://doi.org/10.1021/acs.est.8b03984
15
X Huang, Y Song, M M Li, J F Li, Q Huo, X H Cai, T Zhu, M Hu, H S Zhang. (2012). A high-resolution ammonia emission inventory in China. Global Biogeochemical Cycles, 26(1): GB1030 https://doi.org/10.1029/2011GB004161
16
ICCT (2021). ICCT’s Comments and Technical Recommendations on Future Euro 7/VII Emission Standards. Berlin: The International Council on Clean Transportation
17
J L Jiménez-Palacios (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
Y N Kang, M X Liu, Y Song, X Huang, H Yao, X H Cai, H S Zhang, L Kang, X J Liu, X Y Yan. et al.. (2016). High-resolution ammonia emissions inventories in China from 1980 to 2012. Atmospheric Chemistry and Physics, 16(4): 2043–2058 https://doi.org/10.5194/acp-16-2043-2016
19
Y Liu, Y K Liang, H Z N Yu, X P An, J Y Li. (2021a). Comparative analysis of China light-duty vehicle test cycle for passenger car and other typical driving cycles. E3S Web of Conferences, 241: 02002 https://doi.org/10.1051/e3sconf/202124102002
20
Y C Liu, J L Zhan, F X Zheng, B Y Song, Y S Zhang, W Ma, C J Hua, J L Xie, X L Bao, C Yan. et al.. (2022). Dust emission reduction enhanced gas-to-particle conversion of ammonia in the North China Plain. Nature Communications, 13(1): 6887 https://doi.org/10.1038/s41467-022-34733-4
21
Y S Liu, Y S Ge, J W Tan, H L Wang, Y Ding. (2021b). Research on ammonia emissions characteristics from light-duty gasoline vehicles. Journal of Environmental Sciences-China, 106: 182–193 https://doi.org/10.1016/j.jes.2021.01.021
22
C Livingston, P Rieger, A Winer. (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 https://doi.org/10.1016/j.atmosenv.2009.04.009
23
M Masiol, P K Hopke, H D Felton, B P Frank, O V Rattigan, M J Wurth, G H LaDuke. (2017). Source apportionment of PM2.5 chemically speciated mass and particle number concentrations in New York City. Atmospheric Environment, 148: 215–229 https://doi.org/10.1016/j.atmosenv.2016.10.044
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
W J Meng, Q R Zhong, X Yun, X Zhu, T B Huang, H Z Shen, Y L Chen, H Chen, F Zhou, J F Liu. et al.. (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 https://doi.org/10.1021/acs.est.6b03694
27
Z Y Meng, X B Xu, W L Lin, B Z Ge, Y L Xie, B Song, S H Jia, R Zhang, W Peng, Y Wang. et al.. (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 https://doi.org/10.5194/acp-18-167-2018
28
S M Platt, Haddad I El, S M Pieber, A A Zardini, R Suarez-Bertoa, M Clairotte, K R Daellenbach, R J Huang, J G Slowik, S Hellebust. et al.. (2017). Gasoline cars produce more carbonaceous particulate matter than modern filter-equipped diesel cars. Scientific Reports, 7(1): 4926 https://doi.org/10.1038/s41598-017-03714-9
29
S M Platt, Haddad I El, A A Zardini, M Clairotte, C Astorga, R Wolf, J G Slowik, B Temime-Roussel, N Marchand, I Ježek. et al.. (2013). Secondary organic aerosol formation from gasoline vehicle emissions in a new mobile environmental reaction chamber. Atmospheric Chemistry and Physics, 13(18): 9141–9158 https://doi.org/10.5194/acp-13-9141-2013
30
T Selleri, A Melas, P Bonnel, R Suarez-Bertoa. (2022). NH3 and CO emissions from fifteen Euro 6d and Euro 6d-TEMP gasoline-fuelled vehicles. Catalysts, 12(3): 245 https://doi.org/10.3390/catal12030245
31
M Shelef, H S Gandhi. (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
R Suarez-Bertoa, C Astorga. (2016). Isocyanic acid and ammonia in vehicle emissions. Transportation Research Part D, Transport and Environment, 49: 259–270 https://doi.org/10.1016/j.trd.2016.08.039
33
R Suarez-Bertoa, P Mendoza-Villafuerte, F Riccobono, M Vojtisek, M Pechout, A Perujo, C Astorga. (2017). On-road measurement of NH3 emissions from gasoline and diesel passenger cars during real world driving conditions. Atmospheric Environment, 166: 488–497 https://doi.org/10.1016/j.atmosenv.2017.07.056
34
R Suarez-Bertoa, A A Zardini, C Astorga. (2014). Ammonia exhaust emissions from spark ignition vehicles over the New European Driving Cycle. Atmospheric Environment, 97: 43–53 https://doi.org/10.1016/j.atmosenv.2014.07.050
35
R Suarez-Bertoa, A A Zardini, V Lilova, D Meyer, S Nakatani, F Hibel, J Ewers, M Clairotte, L Hill, C Astorga. (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 https://doi.org/10.1007/s11356-015-4267-3
36
W Tan, S H Xie, W P Shan, Z H Lian, L J Xie, A N Liu, F Gao, L Dong, H He, F D Liu. (2022). CeO2 doping boosted low-temperature NH3-SCR activity of FeTiOx catalyst: a microstructure analysis and reaction mechanistic study. Frontiers of Environmental Science & Engineering, 16(5): 60 https://doi.org/10.1007/s11783-022-1539-2
37
C Wang, S S Yin, L Bai, X C Zhang, X K Gu, H Zhang, Q Lu, R Q Zhang. (2018). High-resolution ammonia emission inventories with comprehensive analysis and evaluation in Henan, China, 2006–2016. Atmospheric Environment, 193: 11–23 https://doi.org/10.1016/j.atmosenv.2018.08.063
38
C X Wang, J W Tan, G Harle, H M Gong, W Z Xia, T T Zheng, D X Yang, Y S Ge, Y K Zhao. (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 https://doi.org/10.1021/acs.est.9b03893
39
X Wang, Y S Ge, H M Gong, Z J Yang, J W Tan, L J Hao, S Su. (2019b). Ammonia emissions from China-6 compliant gasoline vehicles tested over the WLTC. Atmospheric Environment, 199: 136–142 https://doi.org/10.1016/j.atmosenv.2018.11.027
40
X Y Wang, R H Zhang, W Yu. (2019c). The effects of PM2.5 concentrations and relative humidity on atmospheric visibility in Beijing. Journal of Geophysical Research. Atmospheres, 124(4): 2235–2259 https://doi.org/10.1029/2018JD029269
41
Y J Wang, Y F Wen, S J Zhang, G J Zheng, H T Zheng, X Chang, C Huang, S X Wang, Y Wu, J M Hao. (2023). Vehicular ammonia emissions significantly contribute to urban PM2.5 pollution in two Chinese megacities. Environmental Science & Technology, 57(7): 2698–2705 https://doi.org/10.1021/acs.est.2c06198
42
Y F Xing, Y H Xu, M H Shi, Y X Lian. (2016). The impact of PM2.5 on the human respiratory system. Journal of Thoracic Disease, 8(1): E69–E74
43
L Xu, J E Penner. (2012). Global simulations of nitrate and ammonium aerosols and their radiative effects. Atmospheric Chemistry and Physics, 12(20): 9479–9504 https://doi.org/10.5194/acp-12-9479-2012
44
Y Yang, X Z Zheng, W Ren, J F Liu, X L Fu, S G Meng, S F Chen, C Cai. (2022). Recent advances in special morphologic photocatalysts for NOx removal. Frontiers of Environmental Science & Engineering, 16(11): 137 https://doi.org/10.1007/s11783-022-1573-0
45
X N Yu, L Shen, X H Hou, L Yuan, Y P Pan, J L An, S Q Yan. (2020). High-resolution anthropogenic ammonia emission inventory for the Yangtze River Delta, China. Chemosphere, 251: 126342 https://doi.org/10.1016/j.chemosphere.2020.126342
46
J Y Zheng, S S Yin, D W Kang, W W Che, L J Zhong. (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 https://doi.org/10.5194/acp-12-7041-2012
47
X Zheng, L He, X He, S Zhang, Y Cao, J Hao, Y Wu. (2022). Real-time black carbon emissions from light-duty passenger vehicles using a portable emissions measurement system. Engineering (Beijing), 16: 73–81 https://doi.org/10.1016/j.eng.2020.11.009
48
Y Q Zhong, B X Xia, J W Shi, P Ning, C N Zhang, X Y Han, J M Hao. (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 https://doi.org/10.1007/s11783-022-1535-6
49
Y Zhou, S Y Cheng, J L Lang, D S Chen, B B Zhao, C Liu, R Xu, T T Li. (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 https://doi.org/10.1016/j.atmosenv.2015.01.069
50
R C Zhu, J N Hu, L Q He, L Zu, X F Bao, Y T Lai, S Su. (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 https://doi.org/10.1007/s11783-020-1306-1