Skip to main content
SpringerLink
Log in

Effect of NOX, O3 and NH3 on sulfur isotope composition during heterogeneous oxidation of SO2: a laboratory investigation

  • Published:
Air Quality, Atmosphere & Health Aims and scope Submit manuscript

Abstract

Sulfate aerosol is a major fraction of haze, playing an important role in aerosol formation and aging processes. To understand the mechanism of sulfate formations, the characteristics of sulfur isotope composition were determined during different heterogeneous oxidation reactions of sulfur dioxide on the surface of α-Fe2O3. Although NH3 was more beneficial to the formation of sulfate, compared with NOX and O3, 34S tended to enrich the lighter sulfur isotopes in the presence of NH3. Furthermore, in consideration of the potential competitive effects of NOX, O3, and NH3 in the heterogeneous oxidation processes, the contributions of each gas were evaluated via Rayleigh distillation model. Notably, the oxidation by NOX contributed 67.5±10 % of the whole sulfate production, which is higher than that of O3 (13.3±10 %) and NH3 (19.2±10 %) on the basic of the average fractionation factor. The observed δ34S values of sulfate aerosols were negatively correlated with sulfur oxidation ratios, owing to the sulfur isotopic fractionations during the sulfate formation processes. Given the isotope mass balance, the overall δ34Ssulfate approached the δ34Semission as oxidation of SO2 progressed, suggesting that NOX played a major rather than a sole role in the different heterogeneous oxidation processes of SO2 on the mineral dust surface.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

Data availability

Data will be supplied upon request.

References

  • Anderson TL, Charlson RJ (2003) Climate forcing by aerosols-a hazy picture. Science 300(5622):1103–1104

    Article  CAS  PubMed  Google Scholar 

  • Chen HM, Zhuang B, Liu J, Wang T, Li S, Xie M, Li M, Chen P, Zhao M (2019) Characteristics of ozone and particles in the near-surface atmosphere in the urban area of the Yangtze River Delta, China. Atmos Chem Phys 19(7):4153–4175

    Article  CAS  ADS  Google Scholar 

  • Chen SL, Guo ZY, Guo ZB, Guo QJ, Zhang YL, Zhu B, Zhang HX (2017a) Sulfur isotopic fractionation and its implication: Sulfate formation in PM2.5 and coal combustion under different conditions. Atmos Environ 119:142–149

    Google Scholar 

  • Chen S, Xu L, Zhang Y, Chen B, Wang X, Zhang X, Zhen M, Chen J, Wang W, Sun Y, Fu P, Wang Z, Li W (2017b) Direct observations of organic aerosols in common wintertime hazes in North China: insights into direct emissions from Chinese residential stoves. Atmos Chem Phys 17(2):1259–1270

    Article  CAS  ADS  Google Scholar 

  • Cheng YF, Zheng G, Wei C, Cheng Y, Zheng G, Wei C, Mu Q, Zheng B, Wang Z, Gao M, Zhang Q, He K, Carmichael G, Pöschl U, Su H (2016) Reactive nitrogen chemistry in aerosol water as a source of sulfate during haze events in China. Sci Adv 2(12):e1601530

    Article  PubMed  PubMed Central  ADS  Google Scholar 

  • Cheng Y, Yan L, Huang Y, Wang Q, Morawska L, Gu ZL, Cao JJ, Zhang LY, Li BW, Wang Y (2019) Characterization of particle size distributions during winter haze episodes in urban air. Atmos Res 228:55–67

    Article  CAS  Google Scholar 

  • Chu B, Zhang X, Liu Y, He H, Sun Y, Jiang J, Li J, Hao J (2016) Synergetic formation of secondary inorganic and organic aerosol: effect of SO2 and NH3 on particle formation and growth. Atmos Chem Phys 16(22):14219–14230

    Article  CAS  ADS  Google Scholar 

  • Ding T, Valkiers S, Kipphardt H, Bièvre PD, Taylor PDP, Gonfiantini R, Krouse R (2001) Calibrated sulfur isotope abundance ratios of three IAEA sulfur isotope reference materials and V-CDT with a reassessment of the atomic weight of sulfur. Geochim Cosmochim Acta 65(15):2433–2437

    Article  CAS  ADS  Google Scholar 

  • Fuzzi S (1978) Study of iron (III) catalysed sulphur dioxide oxidation aqueous solution over a wide rang of pH. Atmos Environ 12:1439–1442

    Article  CAS  ADS  Google Scholar 

  • Gao M, Carmichael GR, Wang Y, Ji D, Liu Z, Wang Z (2016) Improving simulations of sulfate aerosols during winter haze over Northern China: the impacts of heterogeneous oxidation by NO2. Front Environ Sci Eng 10(5):1–11

    Article  Google Scholar 

  • Gao M, Liu Z, Zheng B, Ji D, Sherman P, Song S, Xin J, Liu C, Wang Y, Zhang Q, Xin J, Jiang J, Wang Z, Carmichael GR, McElroy MB (2020) China’s emission control strategies have suppressed unfavorable influences of climate on wintertime PM2.5 concentrations in Beijing since 2002. Atmos. Chem Phys 20(3):1497–1505

    CAS  ADS  Google Scholar 

  • Ge S, Wang G, Zhang S, Li D, Xie Y, Wu C, Yuan Q, Chen J, Zhang H (2019) Abundant NH3 in China enhances atmospheric HONO production by promoting the heterogeneous reaction of SO2 with NO2. Environ Sci Technol 53:14339–14347

    Article  CAS  PubMed  ADS  Google Scholar 

  • Grewling Ł, Bogawski P, Kryza M, Magyar D, Sikoparija B, Skjoth CA, Udvardy U, Werner M, Smith M (2019) Concomitant occurrence of anthropogenic air pollutants, mineral dust and fungal spores during long-distance transport of ragweed pollen. Environ Pollut 254:112948

    Article  CAS  PubMed  Google Scholar 

  • Guo H, Weber RJ, Nenes A (2017) High levels of ammonia do not raise fine particle pH sufficiently to yield nitrogen oxide-dominated sulfate production. Sci Rep 7(1):12109

    Article  PubMed  PubMed Central  ADS  Google Scholar 

  • Guo ZB, Shi L, Chen SL, Jiang W, Wei Y, Rui ML, Zeng G (2016) Sulfur isotopic fractionation and source appointment of PM2.5 in Nanjing region around the second session of the Youth Olympic Games. Atmos Res 174:9–17

    Article  ADS  Google Scholar 

  • Han X, Guo Q, Liu C, Fu P, Strauss H, Yang J, Hu J, Wei L, Ren H, Peters M, Wei R, Tian L (2016a) Using stable isotopes to trace sources and formation processes of sulfate aerosols from Beijing, China. Sci Rep 6(1):29958

    Article  CAS  PubMed  PubMed Central  ADS  Google Scholar 

  • Han X, Guo Q, Liu C, Strauss H, Yang J, Hu J, Wei R, Tian L, Kong J, Peters M (2016b) Effect of the pollution control measures on PM2.5 during the 2015 China Victory Day Parade: Implication from water-soluble ions and sulfur isotope. Environ Pollut 218:230–241

    Article  CAS  PubMed  Google Scholar 

  • Han X, Guo Q, Strauss H, Liu C, Hu J, Guo Z, Wei R, Peters M, Tian L, Kong J (2017) Multiple sulfur isotope constraints on sources and formation processes of sulfate in Beijing PM2.5 Aerosol. Environ Sci Technol 51(14):7794–7803

    Article  CAS  PubMed  ADS  Google Scholar 

  • Hanisch F, Crowley JN (2003) Ozone decomposition on Saharan dust: an experimental Investigation. Atmos Chem Phys 3:119–130

    Article  CAS  ADS  Google Scholar 

  • Harris E, Sinha B, Foley S, Crowley JN, Borrmann S, Hoppe P (2012a) Sulfur isotope fractionation during heterogeneous oxidation of SO2 on mineral dust. Atmos Chem Phys 12(11):4867–4884

    Article  CAS  ADS  Google Scholar 

  • Harris E, Sinha B, Hoppe P, Ono S (2013b) High-precision measurements of 33S and 34S fractionation during SO2 oxidation reveal causes of seasonality in SO2 and sulfate isotopic composition. Environ Sci Technol 47(21):12174–12183

    Article  CAS  PubMed  ADS  Google Scholar 

  • Harris E, Sinha B, Hoppe P, Crowley JN, Ono S, Foley S (2012b) Sulfur isotope fractionation during oxidation of sulfur dioxide: gas-phase oxidation by OH radicals and aqueous oxidation by H2O2, O3 and iron catalysis. Atmos Chem Phys 12(1):407–424

    Article  CAS  ADS  Google Scholar 

  • Harris E, Sinha B, Pinxteren DV, Tilgner A, Fomba KW, Schneider J, Roth A, Gnauk T, Fahlbusch B, Mertes S, Lee T, Collett J, Foley S, Borrmann S, Hoppe P, Herrmann H (2013a) Enhanced role of transition metal ion catalysis during in-cloud oxidation of SO2. Science 340(6133):727–730

    Article  CAS  PubMed  ADS  Google Scholar 

  • Huang R, Zhang Y, Bozzetti C, Ho K, Cao J, Han Y, Daellenbach KR, Slowik JG, Platt SM, Canonaco F, Zotter P, Wolf R, Pieber SM, Bruns EA, Crippa M, Ciarelli G, Piazzalunga A, Schwikowski M, Abbaszade G et al (2014) High secondary aerosol contribution to particulate pollution during haze events in China. Nature 514(7521):218–222

    Article  CAS  PubMed  ADS  Google Scholar 

  • Jiang B, Xia D (2017) Role identification of NH3 in atmospheric secondary new particle formation in haze occurrence of China. Atmos Environ 163:107–117

    Article  CAS  ADS  Google Scholar 

  • Kong LD, Zhao X, Sun ZY, Yang YW, Fu HB, Zhang SC, Cheng TT, Yang X, Wang L, Chen JM (2014) The effects of nitrate on the heterogeneous uptake of sulfur dioxide on hematite. Atmos Chem Phys 14(17):9451–9467

    Article  CAS  ADS  Google Scholar 

  • Li J, Michalski G, Davy P, Harvey M, Katzman T, Wilkins B (2018a) Investigating source contributions of size-aggregated aerosols collected in Southern Ocean and Baring Head, New Zealand using sulfur isotopes. Geophys Res Lett 45(8):3717–3727

    Article  ADS  Google Scholar 

  • Li L, Hoffmann MR, Colussi AJ (2018b) Role of nitrogen dioxide in the production of sulfate during Chinese haze-aerosol episodes. Environ Sci Technol 52(5):2686–2693

    Article  CAS  PubMed  ADS  Google Scholar 

  • Li J, Zhang Y, Cao F, Zhang W, Fan M, Lee X, Michalski G (2020) Stable sulfur isotopes revealed a major role of transition-metal-ion catalyzed SO2 oxidation in haze episodes. Environ Sci Technol 54(5):2626–2634

    Article  CAS  PubMed  ADS  Google Scholar 

  • Li R, Wang Z, Cui L, Fu H, Zhang L, Kong L, Chen W, Chen J (2019) Air pollution characteristics in China during 2015-2016: Spatiotemporal variations and key meteorological factors. Sci Total Environ 648:902–915

    Article  CAS  PubMed  ADS  Google Scholar 

  • Liu Y, Pellikka PKE, Li HSB, Fang XQ (2019) Detection of the dispersion and residence of volcanic SO 2 and sulfate aerosol from Nabro in 2011 . Atmospheric Environ 197:36–44

    Article  CAS  ADS  Google Scholar 

  • Liu T, Chan AW, Abbatt JP (2021) Multiphase oxidation of sulfur dioxide in aerosol particles: implications for sulfate formation in polluted environments. Environ Sci Technol 55(8):4227–4242

    Article  CAS  PubMed  ADS  Google Scholar 

  • Liu TY, Clegg SL, Abbatt JPD (2020a) Fast oxidation of sulfur dioxide by hydrogen peroxide in deliquesced aerosol particles. Proc Natl Acad Sci USA 117:1354–1359

    Article  CAS  PubMed  PubMed Central  ADS  Google Scholar 

  • Liu Y, Zhang Y, Lian C, Yan C, Feng Z, Zheng F, Fan X, Chen Y, Wang W, Chu B, Wang Y, Cai J, Du W, Daellenbach KR, Kangasluoma J, Bianchi F, Kujansuu J, Petäjä T, Wang X et al (2020b) The promotion effect of nitrous acid on aerosol formation in wintertime in Beijing: the possible contribution of traffic-related emissions. Atmos. Chem Phys 20:13023–13040

    CAS  ADS  Google Scholar 

  • Liu X, Li J, Qu Y, Han T, Hou L, Gu J, Chen C, Yang Y, Liu X, Yang T, Zhang Y, Tian H, Hu M (2012) Formation and evolution mechanism of regional haze: a case study in the megacity Beijing, China. Atmos Chem Phys 13:4501–4514

    Article  ADS  Google Scholar 

  • Ma J, Chu B, Liu J, Liu Y, Zhang H, He H (2018) NOX promotion of SO2 conversion to sulfate: An important mechanism for the occurrence of heavy haze during winter in Beijing. Environ Pollut 233:662–669

    Article  CAS  PubMed  Google Scholar 

  • Ma S, Chai J, Jiao K, Ma L, Zhu S, Wu K (2017) Environmental influence and countermeasures for high humidity flue gas discharging from power plants. Renew Sust Energ Rev 73:225–235

    Article  CAS  Google Scholar 

  • Ma T, Furutani H, Duan F, Kimoto T, Jiang JK, Zhang Q, Xu XB, Wang Y, Gao J, Geng GN, Li M, Song SJ, Ma YL, Che F, Wang J, Zhu LD, Huang T, Toyoda M, He KB (2020) Contribution of hydroxymethanesulfonate (HMS) to severe winter haze in the North China Plain. Atmos Chem Phys 20:5887–5897

    Article  ADS  Google Scholar 

  • Pandis SN, Seinfeld JH (1989) Sensitivity analysis of a chemical mechanism for aqueous-phase atmospheric chemistry. J Geophys Res 94(D1):1105

    Article  CAS  ADS  Google Scholar 

  • Robinson ES, Shah RU, Messier K, Gu P, Li HZ, Apte JS, Robinson AL, Presto AA (2019) Land-use regression modeling of source-resolved fine particulate matter components from mobile sampling. Environ Sci Technol 53(15):8925–8937

    Article  CAS  PubMed  ADS  Google Scholar 

  • Rosenfeld D, Sherwood S, Wood R, Donner L (2014) Climate effects of aerosol-cloud interactions. Science 343(6169):379–380

    Article  CAS  PubMed  ADS  Google Scholar 

  • Tadic M, Trpkov D, Kopanja L, Vojnovic S, Panjan M (2019) Hydrothermal synthesis of hematite (α-Fe2O3) nanoparticle forms: synthesis conditions, structure, particle shape analysis, cytotoxicity and magnetic properties. J Alloys Compd 792:599–609

    Article  CAS  Google Scholar 

  • Usher CR, Michel AE, Grassian VH (2003) Reactions on Mineral Dust. Chem Rev 103(12):4883–4940

    Article  CAS  PubMed  Google Scholar 

  • Wang F, Liu X, Lv S, Zhang S, Wu C, Liu S, Lei YL, Chen YB, Li R, Wang G (2023) Increasing role of phenolic oxidative branch in daytime oxidation process of aromatics in Chinese haze period. Sci Total Environ 857:159578

    Article  CAS  PubMed  ADS  Google Scholar 

  • Wang G, Zhang R, Gomez M, Yang L, Zamora M, Hu M, Lin Y, Peng J, Guo S, Meng J, Li J, Cheng C, Hu T, Ren Y, Wang Y, Gao J, Cao J, An Z, Zhou W et al (2016) Persistent sulfate formation from London Fog to Chinese haze. P Natl Acad Sci USA 113(48):13630–13635

    Article  CAS  ADS  Google Scholar 

  • Wang J, Li J, Ye J, Zhao J, Wu Y, Hu J, Liu D, Nie D, Shen F, Huang X, Huang DD, Ji D, Sun X, Xu W, Guo J, Song S, Qin Y, Liu P, Turner JR et al (2020) Fast sulfate formation from oxidation of SO2 by NO2 and HONO observed in Beijing haze. Nat Commun 11:2844

    Article  CAS  PubMed  PubMed Central  ADS  Google Scholar 

  • Wang T, Liu M, Liu M, Song Y, Xu Z, Shang F, Huang X, Liao WL, Wang WG, Ge MF, Cao JJ, Hu JN, Tang GG, Pan YP, Hu M, Zhu T (2022) Sulfate formation apportionment during winter haze events in North China. Environ Sci Technol 56:7771–7778

    Article  CAS  PubMed  ADS  Google Scholar 

  • Xu M, Qiu P, He Y, Guo S, Bai Y, Zhang H, Zhao S, Shen XY, Zhu B, Guo QJ, Guo Z (2021) Sulfur isotope composition during heterogeneous oxidation of SO2 on mineral dust: The effect of temperature, relative humidity, and light intensity. Atmos Res 254:105513

    Article  CAS  Google Scholar 

  • Xu W, Li Q, Shang J, Liu J, Feng X, Zhu T (2015) Heterogeneous oxidation of SO2 by O3-aged black carbon and its dithiothreitol oxidative potential. J Environ Sci 36:56–62

    Article  Google Scholar 

  • Xue J, Yu X, Yuan ZB, Griffith SM, Stephen M, Lan AKH, Seinfeld JH, Yu JZ (2019) Efficient control of atmospheric sulfate production based on three formation regimes. Nat Geosci 12(12):977–982

    Article  CAS  ADS  Google Scholar 

  • Yang DA, Bardoux G, Assayag N, Laskar C, Widory D, Cartigny P (2018) Atmospheric SO2 oxidation by NO2 plays no role in the mass independent sulfur isotope fractionation of urban aerosols. Atmos Res 193:109–117

    Google Scholar 

  • Yang W, He H, Ma Q, Ma J, Liu Y, Liu P, Mu Y (2016) Synergistic formation of sulfate and ammonium resulting from reaction between SO2 and NH3 on typical mineral dust. Phys Chem Chem Phys 18(2):956–964

    Article  CAS  PubMed  Google Scholar 

  • Yinon L, Thurston G (2017) An evaluation of the health benefits achieved at the time of an air quality intervention in three Israeli cities. Environ Int 102:66–73

    Article  PubMed  PubMed Central  Google Scholar 

  • Zhang Q, He KB, Huo H (2012) Cleaning China’s air. Nature 484:161–162

    Article  CAS  PubMed  ADS  Google Scholar 

  • Zhang T, Li X, Wang M, Chen H, Yao M (2019) Microbial aerosol chemistry characteristics in highly polluted air. Sci China Chem 62:1051–1063

    Article  CAS  Google Scholar 

  • Zhao D, Zhu T, Chen Q, Liu Y, Zhang Z (2011) Raman micro-spectrometry as a technique for investigating heterogeneous reactions on individual atmospheric particles. Sci China Chem 54(1):154–160

    Article  CAS  Google Scholar 

Download references

Acknowledgments

We gratefully acknowledge the financial supports from the National Natural Science Foundation of China (Nos. 41873016, 51908293, 51908294 and 41625006), Jiangsu Province 333 Talent Project (BRA2018033).

Funding

We gratefully acknowledge the financial supports from the National Natural Science Foundation of China (Nos. 41873016, 51908293, 51908294 and 41625006), Jiangsu Province 333 Talent Project (BRA2018033).

Author information

Authors and Affiliations

  1. Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control (AEMPC), Collaborative Innovation Center of Atmospheric Environment and Equipment Technology (CIC-AEET), School of Environmental Science and Engineering, Nanjing University of Information Science and Technology, Nanjing, 210044, China

    Zhaobing Guo, Qingxiang Qian, Mingyi Xu & Pengxiang Qiu

  2. Collaborative Innovation Center on Forecast and Evaluation of Meteorological Disasters and Key Laboratory of Meteorological Disaster, Ministry of Education (KLME), Nanjing University of Information Science & Technology, Nanjing, 210044, China

    Bin Zhu

  3. Center for Environmental Remediation, Institute of Geographic Sciences and Natural Resources Research, Chinese Academy of Sciences, Beijing, 100101, China

    Qingjun Guo

Authors
  1. Zhaobing Guo
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Qingxiang Qian
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Mingyi Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Bin Zhu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Qingjun Guo
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Pengxiang Qiu
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

ZBG designed the methodology, administrated the project and wrote the original draft. MYX performed model simulations and analyzed the data. QXQ conducted the investigation process. BZ, QJG wrote the review and commentary. PXQ reviewed and revised the paper.

Corresponding author

Correspondence to Pengxiang Qiu.

Ethics declarations

Ethical approval

Not applicable because we did not work directly with humans, but the possible health risk in the ambient air.

Consent to participate

Not applicable because we did not work directly with humans, but the possible health risk in the ambient air.

Consent to publish

Not applicable because we did not work directly with humans, but the possible health risk in the ambient air.

Competing interests

We declare that we have no financial and personal relationships with other people or organizations that can inappropriately influence our work, there is no professional or other personal interest of any nature or kind in any product, service and/or company that could be construed as influencing the manuscript entitled “Effect of NOX, O3 and NH3 on sulfur isotope composition during heterogeneous oxidation of SO2: a laboratory investigation”.

Additional information

Publisher’s Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Guo, Z., Qian, Q., Xu, M. et al. Effect of NOX, O3 and NH3 on sulfur isotope composition during heterogeneous oxidation of SO2: a laboratory investigation. Air Qual Atmos Health (2024). https://doi.org/10.1007/s11869-024-01543-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s11869-024-01543-0

Keywords

Search

Navigation