Free Standard AU & NZ Shipping For All Book Orders Over $80!
Register      Login
Environmental Chemistry Environmental Chemistry Society
Environmental problems - Chemical approaches
Shopping Cart: ( empty )
You are here: Home > Journals > EN > EN24030
RESEARCH ARTICLE
Contents Vol 21(6)

Diversity of ammonia sources in Tianjin: nitrogen isotope analyses and simulations of aerosol ammonium

Libin Wu https://orcid.org/0009-0006-3898-1192 A # , Yiwen Zhang B # , Yunting Xiao A , Jialei Zhu A , Zongbo Shi https://orcid.org/0000-0002-7157-543X C , Yuantao Wang A , Hong Xu D , Wei Hu A , Junjun Deng A , Miao Tang D * and Pingqing Fu A *
+ Author Affiliations
- Author Affiliations

A Institute of Surface-Earth System Science, School of Earth System Science, Tianjin University, Tianjin, 300072, PR China.

B School of Biological and Environmental Engineering, Tianjin Vocational Institute, Tianjin, 300410, PR China.

C School of Geography, Earth & Environmental Sciences, University of Birmingham, Birmingham, B15 2TT, UK.

D Tianjin Eco-Environmental Monitoring Center, Tianjin, 300191, PR China.

* Correspondence to: tangmiao32@163.com, fupingqing@tju.edu.cn
# These authors contributed equally to this paper

Handling Editor: Noel Aquilina

Environmental Chemistry 21, EN24030 https://doi.org/10.1071/EN24030
Submitted: 12 April 2024  Accepted: 17 August 2024  Published: 18 September 2024

© 2024 The Author(s) (or their employer(s)). Published by CSIRO Publishing.

Abstract

Environmental context

Atmospheric particulate NH4+, primarily produced from the reaction of NH3 and acids, is an important component of PM2.5. In this study, nitrogen stable isotope analyses and an atmospheric chemistry model were used to estimate the contribution of major NH3 sources to particulate NH4+ in Tianjin, a megacity in North China Plain (NCP). Our research has implications for investigations of NH3 emission sources and relevant pollution control in Tianjin and NCP.

Rationale

The North China Plain (NCP) has been identified as an NH3 emission hotspot. Source apportionment of NH3 is a prerequisite for controlling NH3 or NH4+ pollution. Nitrogen stable isotope (δ15N) analysis is a promising method for NH3 source apportionment but its accuracy is still in question.

Methodology

In this study, daytime and nighttime PM2.5 samples were collected from two sites in Tianjin, NCP, in autumn. Concentrations and δ15N of particulate NH4+ were then measured. Nitrogen stable isotope analyses and isotope mixing model (MixSIAR), and an atmospheric chemistry model (WRF-CMAQ-ISAM) were used to estimate the sources of NH3 in Tianjin.

Results

Results from the MixSIAR and WRF-CMAQ-ISAM models suggested that all the sources including livestock breeding, N-fertiliser application, fossil fuels, NH3 slip (especially from traffic), human waste and biomass burning (mostly from bioapplication) were non-negligible to NH3 and NH4+ in Tianjin. This high complexity is due to significant agricultural and industrial production and residential life in Tianjin and the surrounding regions. Our results indicate all NH3 sources need to be considered if we want to reduce NH4+ pollution in Tianjin in autumn.

Keywords: ammonia, nitrogen isotope analyses, North China Plain, particulate ammonium, PM2.5, source apportionment, Tianjin, WRF-CMAQ-ISAM model.

References

Altieri KE, Fawcett SE, Hastings MG (2021) Reactive nitrogen cycling in the atmosphere and ocean. Annual Review of Earth and Planetary Sciences 49, 523-550.
| Crossref | Google Scholar |

An ZS, Huang R-J, Zhang RY, Tie XX, Li GH, Cao JJ, Zhou WJ, Shi ZG, Han YM, Gu ZL, Ji YM (2019) Severe haze in northern China: a synergy of anthropogenic emissions and atmospheric processes. Proceedings of the National Academy of Sciences of the United States of America 116(18), 8657-8666.
| Crossref | Google Scholar | PubMed |

Bhattarai N, Wang SX, Pan YP, Xu QC, Zhang YL, Chang YH, Fang YT (2021) δ15N-stable isotope analysis of NHx: An overview on analytical measurements, source sampling and its source apportionment. Frontiers of Environmental Science & Engineering 15(6), 126.
| Crossref | Google Scholar | PubMed |

Boylan JW, Russell AG (2006) PM and light extinction model performance metrics, goals, and criteria for three-dimensional air quality models. Atmospheric Environment 40, 4946-4959.
| Crossref | Google Scholar |

Chan CK, Yao XH (2008) Air pollution in mega cities in China. Atmospheric Environment 42, 1-42.
| Crossref | Google Scholar |

Chang YH, Liu XJ, Deng CR, Dore AJ, Zhuang GS (2016) Source apportionment of atmospheric ammonia before, during, and after the 2014 APEC summit in Beijing using stable nitrogen isotope signatures. Atmospheric Chemistry and Physics 16, 11635-11647.
| Crossref | Google Scholar |

Chen MX, Zhou Y, Hu MG, Zhou YL (2020) Influence of urban scale and urban expansion on the urban heat island effect in metropolitan areas: case study of Beijing–Tianjin–Hebei urban agglomeration. Remote Sensing 12(21), 3491.
| Crossref | Google Scholar |

Chen Z-L, Song W, Hu C-C, Liu X-J, Chen GY, Walters WW, Michalski G, Liu C-Q, Fowler D, Liu X-Y (2022) Significant contributions of combustion-related sources to ammonia emissions. Nature Communications 13, 7710.
| Crossref | Google Scholar | PubMed |

Cheng BR, Yue SY, Hu W, Ren LJ, Deng JJ, Wu LB, Fu PQ (2020) Summertime fluorescent bioaerosol particles in the coastal megacity Tianjin, North China. Science of The Total Environment 723, 137966.
| Crossref | Google Scholar | PubMed |

Erisman JW, Sutton MA, Galloway J, Klimont Z, Winiwarter W (2008) How a century of ammonia synthesis changed the world. Nature Geoscience 1(10), 636-639.
| Crossref | Google Scholar |

Fan YB, Liu C-Q, Li LJ, Ren LJ, Ren H, Zhang ZM, Li QK, Wang S, Hu W, Deng JJ, Wu LB, Zhong SJ, Zhao Y, Pavuluri CM, Li XD, Pan XL, Sun YL, Wang ZF, Kawamura K, Shi ZB, Fu PQ (2020) Large contributions of biogenic and anthropogenic sources to fine organic aerosols in Tianjin, North China. Atmospheric Chemistry and Physics 20(1), 117-137.
| Crossref | Google Scholar |

Felix JD, Elliott EM, Gish TJ, McConnell LL, Shaw SL (2013) Characterizing the isotopic composition of atmospheric ammonia emission sources using passive samplers and a combined oxidation‐bacterial denitrifier approach. Rapid Communications in Mass Spectrometry 27, 2239-2246.
| Crossref | Google Scholar | PubMed |

Felix JD, Berner A, Wetherbee GA, Murphy SF, Heindel RC (2023) Nitrogen isotopes indicate vehicle emissions and biomass burning dominate ambient ammonia across Colorado’s Front Range urban corridor. Environmental Pollution 316(1), 120537.
| Crossref | Google Scholar | PubMed |

Feng SJ, Xu W, Cheng MM, Ma YX, Wu LB, Kang JH, Wang K, Tang AH, Collett JL, Jr, Fang YT, Goulding K, Liu XJ, Zhang FS (2022) Overlooked nonagricultural and wintertime agricultural NH3 emissions in Quzhou County, North China Plain: evidence from 15N-stable isotopes. Environmental Science & Technology Letters 9(2), 127-133.
| Crossref | Google Scholar |

Gruber N, Galloway JN (2008) An earth-system perspective of the global nitrogen cycle. Nature 451(7176), 293-296.
| Crossref | Google Scholar | PubMed |

Han SQ, Hao TY, Yang X, Yang YC, Luo ZW, Zhang YF, Tang YX, Lu MM (2023) Land-sea difference of the planetary boundary layer structure and its influence on PM2.5 – observation and numerical simulation. Science of The Total Environment 858, 159881.
| Crossref | Google Scholar | PubMed |

Hauglustaine DA, Balkanski Y, Schulz M (2014) A global model simulation of present and future nitrate aerosols and their direct radiative forcing of climate. Atmospheric Chemistry and Physics 14(20), 11031-11063.
| Crossref | Google Scholar |

He PZ, Xie ZQ, Chi XY, Yu XW, Fan SD, Kang H, Liu C, Zhan HC (2018) Atmospheric Δ17O(NO3−) reveals nocturnal chemistry dominates nitrate production in Beijing haze. Atmospheric Chemistry and Physics 18, 14465-14476.
| Crossref | Google Scholar |

Heaton THE, Spiro B, Robertson SMC (1997) Potential canopy influences on the isotopic composition of nitrogen and sulphur in atmospheric deposition. Oecologia 109, 600-607.
| Crossref | Google Scholar | PubMed |

Huang X, Song Y, Li M, Li J, Huo Q, Cai X, Zhu T, Hu M, Zhang H (2012) A high-resolution ammonia emission inventory in China. Global Biogeochemical Cycles 26, GB1030.
| Crossref | Google Scholar |

Jin L, Luo XS, Fu PQ, Li XD (2017) Airborne particulate matter pollution in urban China: a chemical mixture perspective from sources to impacts. National Science Review 4, 593-610.
| Crossref | Google Scholar |

Kang YN, Liu MX, Song Y, Huang X, Yao H, Cai XH, Zhang HS, Kang L, Liu XJ, Yan XY, He H, Zhang Q, Shao M, Zhu T (2016) High-resolution ammonia emissions inventories in China from 1980 to 2012. Atmospheric Chemistry and Physics 16, 2043-2058.
| Crossref | Google Scholar |

Kawashima H, Kurahashi T (2011) Inorganic ion and nitrogen isotopic compositions of atmospheric aerosols at Yurihonjo, Japan: implications for nitrogen sources. Atmospheric Environment 45, 6309-6316.
| Crossref | Google Scholar |

Kawashima H, Ono S (2019) Nitrogen isotope fractionation from ammonia gas to ammonium in particulate ammonium chloride. Environmental Science & Technology 53(18), 10629-10635.
| Crossref | Google Scholar | PubMed |

Kong L, Tang X, Zhu J, Wang ZF, Pan YP, Wu HJ, Wu L, Wu QZ, He YX, Tian SL, Xie YZ, Liu ZR, Sui WX, Han LN, Carmichael G (2019) Improved inversion of monthly ammonia emissions in China based on the Chinese ammonia monitoring network and ensemble Kalman filter. Environmental Science & Technology 53(21), 12529-12538.
| Crossref | Google Scholar | PubMed |

Kwok RHF, Napelenok SL, Baker KR (2013) Implementation and evaluation of PM2.5 source contribution analysis in a photochemical model. Atmospheric Environment 80, 398-407.
| Crossref | Google Scholar |

Li Y, Schichtel BA, Walker JT, Schwede DB, Chen X, Lehmann CMB, Puchalski MA, Gay DA, Collett JL, Jr (2016) Increasing importance of deposition of reduced nitrogen in the United States. Proceedings of the National Academy of Sciences of the United States of America 113(21), 5874-5879.
| Crossref | Google Scholar | PubMed |

Li ZJ, Xiao HW, Walters WW, Hastings MG, Min J, Song LL, Lu WZ, Wu LB, Yan WD, Liu SG, Fang YT (2024) Nitrogen isotopic characteristics of aerosol ammonium in a Chinese megacity indicate the reduction from vehicle emissions during the lockdown period. Science of The Total Environment 922, 171265.
| Crossref | Google Scholar | PubMed |

Lim S, Hwang J, Lee M, Czimczik CI, Xu XM, Savarino J (2022) Robust evidence of 14C, 13C, and 15N analyses indicating fossil fuel sources for total carbon and ammonium in fine aerosols in Seoul megacity. Environmental Science & Technology 56, 6894-6904.
| Crossref | Google Scholar | PubMed |

Liu XJ, Zhang Y, Han WX, Tang AH, Shen JL, Cui ZL, Vitousek P, Erisman JW, Goulding K, Christie P, Fangmeier A, Zhang FS (2013) Enhanced nitrogen deposition over China. Nature 494(7438), 459-462.
| Crossref | Google Scholar | PubMed |

Liu DW, Fang YT, Tu Y, Pan YP (2014) Chemical method for nitrogen isotopic analysis of ammonium at natural abundance. Analytical Chemistry 86, 3787-3792.
| Crossref | Google Scholar | PubMed |

Liu MX, Huang X, Song Y, Tang J, Cao JJ, Zhang XY, Zhang Q, Wang SX, Xu TT, Kang L, Cai XH, Zhang HS, Yang F, Wang HA, Yu JZ, Lau AKH, He LG, Huang XF, Duan L, Ding A, Xue L, Gao J, Liu B, Zhu T (2019) Ammonia emission control in China would mitigate haze pollution and nitrogen deposition, but worsen acid rain. Proceedings of the National Academy of Sciences of the United States of America 116(16), 7760-7765.
| Crossref | Google Scholar | PubMed |

Liu PF, Dong JW, Song HQ, Zheng YW, Shen XY, Wang CK, Wang YS, Yang DY (2024) Response of fine particulate matter and ozone concentrations to meteorology and anthropogenic precursors over the “2+26” cities of northern China. Chemosphere 352, 141439.
| Crossref | Google Scholar | PubMed |

Pan YP, Tian SL, Liu DW, Fang YT, Zhu XY, Zhang Q, Zheng B, Michalski G, Wang YS (2016) Fossil fuel combustion-related emissions dominate atmospheric ammonia sources during severe haze episodes: evidence from 15N-stable isotope in size-resolved aerosol ammonium. Environmental Science & Technology 50, 8049-8056.
| Crossref | Google Scholar | PubMed |

Pan YP, Tian SL, Zhao YH, Zhang L, Zhu XY, Gao J, Huang W, Zhou YB, Song Y, Zhang Q, Wang YS (2018a) Identifying ammonia hotspots in China using a national observation network. Environmental Science & Technology 52(7), 3926-3934.
| Crossref | Google Scholar |

Pan YP, Tian SL, Liu DW, Fang YT, Zhu XY, Gao M, Wentworth GR, Michalski G, Huang XJ, Wang YS (2018b) Source apportionment of aerosol ammonium in an ammonia-rich atmosphere: an isotopic study of summer clean and hazy days in urban Beijing. Journal of Geophysical Research: Atmospheres 123, 5681-5689.
| Crossref | Google Scholar |

Pan YP, Gu MN, Song LL , Tian SL, Wu DM, Walters WW, Yu XN, Lü XM, Ni X, Wang YJ, Cao J, Liu XJ, Fang YT, Wang YS (2020) Systematic low bias of passive samplers in characterizing nitrogen isotopic composition of atmospheric ammonia. Atmospheric Research 243, 105018.
| Crossref | Google Scholar |

Rathbone C, Ullah S (2023) Ammonia emissions from nitrogen fertilised agricultural soils: controlling factors and solutions for emission reduction. Environmental Chemistry 21, EN23010.
| Crossref | Google Scholar |

Stevens CJ (2019) Nitrogen in the environment. Science 363(6427), 578-580.
| Crossref | Google Scholar | PubMed |

Stock B, Semmens B (2016) MixSIAR: v3.1.2 (3.1.2). Zenodo, 16 March 2016. doi:10.5281/zenodo.47719

Tao J, Zhang LM, Cao JJ, Zhang RJ (2017) A review of current knowledge concerning PM2.5 chemical composition, aerosol optical properties and their relationships across China. Atmospheric Chemistry and Physics 17, 9485-9518.
| Crossref | Google Scholar |

Tianjin Ecology and Environmental Bureau (2020) 2019天津市生态环境状况公报: Tianjin Ecology and Environment Statement 2019. (天津市生态环境局) Available at https://sthj.tj.gov.cn/YWGZ7406/HJZL9827/HJZKGB866/TJSLNHJZKGB6653/202109/W020210913630141433433.pdf [In Chinese with title in Chinese and English]

Urey HC (1947) The thermodynamic properties of isotopic substances. Journal of the Chemical Society 1947, 562-581.
| Crossref | Google Scholar | PubMed |

Van Damme M, Clarisse L, Whitburn S, Hadji-Lazaro J, Hurtmans D, Clerbaux C, Coheur P-F (2018) Industrial and agricultural ammonia point sources exposed. Nature 564, 99-103.
| Crossref | Google Scholar | PubMed |

Walters WW, Chai J, Hastings MG (2019) Theoretical phase resolved ammonia–ammonium nitrogen equilibrium isotope exchange fractionations: applications for tracking atmospheric ammonia gas-to-particle conversion. ACS Earth and Space Chemistry 3(1), 79-89.
| Crossref | Google Scholar |

Walters WW, Song LL, Chai J, Fang YT, Colombi N, Hastings MG (2020) Characterizing the spatiotemporal nitrogen stable isotopic composition of ammonia in vehicle plumes. Atmospheric Chemistry and Physics 20(19), 11551-11567.
| Crossref | Google Scholar |

Walters WW, Karod M, Willcocks E, Baek BH, Blum DE, Hastings MG (2022) Quantifying the importance of vehicle ammonia emissions in an urban area of northeastern USA utilizing nitrogen isotopes. Atmospheric Chemistry and Physics 22(20), 13431-13448.
| Crossref | Google Scholar |

Wang GH, Zhang RY, Gomez ME, Yang LX, Zamora ML, Hu M, Lin Y, Peng JF, Guo S, Meng JJ, Li JJ, Cheng CL, Hu TF, Ren YQ, Wang YS, Gao J, Cao JJ, An ZS, Zhou WJ, Li GH, Wang JY, Tian PF, Marrero-Ortiz W, Secrest J, Du ZF, Zheng J, Shang DJ, Zeng LM, Shao M, Wang WG, Huang Y, Wang Y, Zhu YJ, Li YX, Hu JX, Pan BW, Cai L, Cheng YT, Ji YM, Zhang F, Rosenfeld D, Liss PS, Duce RA, Kolb CE, Molina MJ (2016) Persistent sulfate formation from London fog to Chinese haze. Proceedings of the National Academy of Sciences of the United States of America 113, 13630-13635.
| Crossref | Google Scholar | PubMed |

Wang YJ, Wen YF, Zhang SJ, Zheng GJ, Zheng HT, Chang X, Huang C, Wang SX, Wu Y, Hao JM (2023) Vehicular ammonia emissions significantly contribute to urban PM2.5 pollution in two Chinese megacities. Environmental Science & Technology 57, 2698-2705.
| Crossref | Google Scholar | PubMed |

Warner JX, Dickerson RR, Wei Z, Strow LL, Wang Y, Liang Q (2017) Increased atmospheric ammonia over the world’s major agricultural areas detected from space. Geophysical Research Letters 44, 2875-2884.
| Crossref | Google Scholar | PubMed |

Wu LB, Liu XD, Fang YT, Hou SJ, Xu LQ, Wang XY, Fu PQ (2018) Nitrogen cycling in the soil–plant system along a series of coral islands affected by seabirds in the South China Sea. Science of The Total Environment 627, 166-175.
| Crossref | Google Scholar | PubMed |

Wu Y, Wang P, Yu S, Wang L, Li P, Li Z, Mehmood K, Liu W, Wu J, Lichtfouse E, Rosenfeld D, Seinfeld JH (2018) Residential emissions predicted as a major source of fine particulate matter in winter over the Yangtze River Delta, China. Environmental Chemistry Letters 16, 1117-1127.
| Crossref | Google Scholar |

Wu LB, Ren H, Wang P, Chen J, Fang YT, Hu W, Ren LJ, Deng JJ, Song Y, Li J, Sun YL, Wang ZF, Liu C-Q, Ying Q, Fu PQ (2019) Aerosol ammonium in the urban boundary layer in Beijing: insights from nitrogen isotope ratios and simulations in summer 2015. Environmental Science & Technology Letters 6(7), 389-395.
| Crossref | Google Scholar |

Wu LB, Yue SY, Shi ZB, Hu W, Chen J, Ren H, Deng JJ, Ren LJ, Fang YT, Yan H, Li WJ, Harrison RM, Fu PQ (2021) Source forensics of inorganic and organic nitrogen using δ15N for tropospheric aerosols over Mt Tai. npj Climate and Atmospheric Science 4, 8.
| Crossref | Google Scholar |

Wu LB, Wang P, Zhang Q, Ren H, Shi ZB, Hu W, Chen J, Xie QR, Li LJ, Yue SY, Wei LF, Song LL, Zhang YG, Wang ZH, Chen S, Wei W, Wang XM, Zhang YL, Kong SF, Ge BZ, Yang T, Fang YT, Ren LJ, Deng JJ, Sun YL, Wang ZF, Zhang HL, Hu JL, Liu C-Q, Harrison RM, Ying Q, Fu PQ (2024) Dominant contribution of combustion-related ammonium during haze pollution in Beijing. Science Bulletin 69(7), 978-987.
| Crossref | Google Scholar | PubMed |

Xiao H, Ding SY, Ji CW, Li QK, Li XD (2022) Combustion related ammonia promotes PM2.5 accumulation in autumn in Tianjin, China. Atmospheric Research 275, 106225.
| Crossref | Google Scholar |

Xiao YT, Yang JB, Cui LH, Deng JJ, Fu PQ, Zhu JL (2023) Weakened sea–land breeze in a coastal megacity driven by urbanization and ocean warming. Earth’s Future 11, e2022EF003341.
| Crossref | Google Scholar |

Xiao H, Ding SY, Li XD (2024) Sources of NH4+ in PM2.5 and their seasonal variations in urban Tianjin China: new insights from the seasonal δ15N values of NH3 source. Journal of Geophysical Research: Atmospheres 129, e2023JD040169.
| Crossref | Google Scholar |

Yan FH, Chen WH, Wang XM, Jia SG, Mao JY, Cao JC, Chang M (2024) Significant increase in ammonia emissions in China: considering nonagricultural sectors based on isotopic source apportionment. Environmental Science & Technology 58(5), 2423-2433.
| Crossref | Google Scholar | PubMed |

Yang T, Li HY, Xu WQ, Song YF, Xu L, Wang HB, Wang FT, Sun YL, Wang ZF, Fu PQ (2024) Strong impacts of regional atmospheric transport on the vertical distribution of aerosol ammonium over Beijing. Environmental Science & Technology Letters 11(1), 29-34.
| Crossref | Google Scholar |

Yuan XL, Zhang MF, Wang QS, Wang YT, Zuo J (2017) Evolution analysis of environmental standards: effectiveness on air pollutant emissions reduction. Journal of Cleaner Production 149, 511-520.
| Crossref | Google Scholar |

Yue SY, Zhu JL, Chen S, Xie QR, Li W, Li LJ, Ren H, Su SH, Li P, Ma H, Fan YB, Cheng BR, Wu LB, Deng JJ, Hu W, Ren LJ, Wei LF, Zhao WY, Tian Y, Pan XL, Sun YL, Wang ZF, Wu FC, Liu C-Q, Su H, Penner JE, Pöschl U, Andreae MO, Cheng YF, Fu PQ (2022) Brown carbon from biomass burning imposes strong circum-Arctic warming. One Earth 5(3), 293-304.
| Crossref | Google Scholar |

Zhang YY, Benedict KB, Tang AH, Sun YL, Fang YT, Liu XJ (2020) Persistent non-agricultural and periodic agricultural emissions dominate sources of ammonia in urban Beijing: evidence from 15N stable isotope in vertical profiles. Environmental Science & Technology 54(1), 102-109.
| Crossref | Google Scholar | PubMed |

Zhang ZY, Zeng Y, Zheng NJ, Luo L, Xiao HW, Xiao HY (2020) Fossil fuel-related emissions were the major source of NH3 pollution in urban cities of northern China in the autumn of 2017. Environmental Pollution 256, 113428.
| Crossref | Google Scholar | PubMed |

Zhang YB, Chen X, Yu SC, Wang LQ, Li Z, Li MY, Liu WP, Li PF, Rosenfeld D, Seinfeld JH (2021) City-level air quality improvement in the Beijing–Tianjin–Hebei region from 2016/17 to 2017/18 heating seasons: attributions and process analysis. Environmental Pollution 274, 116523.
| Crossref | Google Scholar | PubMed |

Zong Z, Ren CH, Shi XL, Sun ZY, Huang X, Tian CG, Li J, Zhang G, Fang YT, Gao HW (2023) Isotopic comparison of ammonium between two summertime field campaigns in 2013 and 2021 at a background site of north China. Science of The Total Environment 905, 167304.
| Crossref | Google Scholar | PubMed |