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Atmospheric heterogeneous reaction of chlorobenzene on mineral α-Fe2O3 particulates: a chamber experiment study

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Abstract

Despite the large emission of chlorinated volatile organic compounds (CVOCs) into the atmosphere, the ultimate fate of these compounds remains largely unknown. Herein, we explore the photochemical conversion of an important class of CVOCs, namely chlorobenzene (CB), on mineral α-Fe2O3 particulates under atmospheric relevant conditions. A series of chamber reactions composed of the CB with/without SO2 or NO2 are performed, followed by in situ diffuse reflectance infrared Fourier transform spectroscopy measurements and density functional theory calculations. We show that CB can be considerably degraded by α-Fe2O3 under light irradiation, whereas the reaction is markedly suppressed by adding SO2 or NO2 owing to their competitive adsorption and surface acidification. In particular, we discover that CB can be ultimately converted into polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) under dark state or light irradiation, suggesting a possible origin of atmospheric PCDD/Fs from this overlooked photochemical source.

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References

  • Atkinson R, Aschmann S M, Winer A M, Pitts J NJr (1985). Atmospheric gas-phase loss processes for chlorobenzene, benzotrifluoride, and 4-chlorobenzotrifluoride, and generalization of predictive techniques for atmospheric lifetimes of aromatic-compounds. Archives of Environmental Contamination and Toxicology, 14(4): 417–425

    Article  CAS  Google Scholar 

  • Cai C, Li J, He Y, Jia J (2023). Target the neglected VOCs emission from iron and steel industry in China for air quality improvement. Frontiers of Environmental Science & Engineering, 17(8): 95

    Article  CAS  Google Scholar 

  • Cao Y Q, Ma Q X, Chu B W, He H (2023). Homogeneous and heterogeneous photolysis of nitrate in the atmosphere: state of the science, current research needs, and future prospects. Frontiers of Environmental Science & Engineering, 17(4): 48

    Article  CAS  Google Scholar 

  • Chen J Y, Yi J J, Ji Y M, Zhao B C, Ji Y P, Li G Y, An T C (2020a). Enhanced H-abstraction contribution for oxidation of xylenes via mineral particles: Implications for particulate matter formation and human health. Environmental Research, 186: 109568

    Article  CAS  Google Scholar 

  • Chen T, Sun C, Wang T J, Lomnicki S, Zhan M X, Li X D, Lu S Y, Yan J H (2020b). Formation of DF, PCDD/Fs and EPFRs from 1,2,3-trichlorobenzene over metal oxide/silica surface. Waste Management (New York, N.Y.), 118: 27–35

    Article  CAS  Google Scholar 

  • Chen Z L, Lin X Q, Lu S Y, Li X D, Qiu Q L, Wu A J, Ding J M, Yan J H (2018). Formation pathways of PCDD/Fs during the co-combustion of municipal solid waste and coal. Chemosphere, 208: 862–870

    Article  CAS  Google Scholar 

  • Cui H X, Cheng T T, Chen J M, Xu Y F, Fang W F (2008). A simulated heterogeneous reaction of SO2 on the surface of hematite at different temperatures. Acta Physico-Chimica Sinica, 24(12): 2331–2336 (in Chinese)

    Article  CAS  Google Scholar 

  • Day D A, Liu S, Russell L M, Ziemann P J (2010). Organonitrate group concentrations in submicron particles with high nitrate and organic fractions in coastal southern California. Atmospheric Environment, 44(16): 1970–1979

    Article  CAS  Google Scholar 

  • Deng W, Dai Q G, Lao Y J, Shi B B, Wang X Y (2016). Low temperature catalytic combustion of 1,2-dichlorobenzene over CeO2-TiO2 mixed oxide catalysts. Applied Catalysis B: Environmental, 181: 848–861

    Article  CAS  Google Scholar 

  • Du C T, Kong L D, Zhanzakova A, Tong S Y, Yang X, Wang L, Fu H B, Cheng T T, Chen J M, Zhang S C (2019). Impact of adsorbed nitrate on the heterogeneous conversion of SO2 on alpha-Fe2O3 in the absence and presence of simulated solar irradiation. Science of the Total Environment, 649: 1393–1402

    Article  CAS  Google Scholar 

  • Duan Z H, Scheutz C, Kjeldsen P (2021). Trace gas emissions from municipal solid waste landfills: a review. Waste Management (New York, N.Y.), 119: 39–62

    Article  CAS  Google Scholar 

  • Ebrahimbabaie P, Pichtel J (2021). Biotechnology and nanotechnology for remediation of chlorinated volatile organic compounds: current perspectives. Environmental Science and Pollution Research International, 28(7): 7710–7741

    Article  CAS  Google Scholar 

  • Edney E O, Kleindienst T E, Corse E W (1986). Room-temperature rate constants for the reaction of oh with selected chlorinated and oxygenated hydrocarbons. International Journal of Chemical Kinetics, 18(12): 1355–1371

    Article  CAS  Google Scholar 

  • Fang Q L, Zhu B Z, Sun Y L, Zhu Z C, Xu M G, Ge T T (2019a). Mechanistic insight into the selective catalytic reduction of NO by NH3 over α-Fe2O3 (001): a density functional theory study. Catalysis Science & Technology, 9(1): 116–124

    Article  CAS  Google Scholar 

  • Fang X, Park S, Saito T, Tunnicliffe R, Ganesan A L, Rigby M, Li S, Yokouchi Y, Fraser P J, Harth C M, et al. (2019b). Rapid increase in ozone-depleting chloroform emissions from China. Nature Geoscience, 12(2): 89–93

    Article  CAS  Google Scholar 

  • Froese K L, Hutzinger O (1996). Polychlorinated benzene, phenol, dibenzo-p-dioxin, and dibenzofuran in heterogeneous combustion reactions of acetylene. Environmental Science & Technology, 30(3): 998–1008

    Article  CAS  Google Scholar 

  • Fu H B, Wang X, Wu H B, Yin Y, Chen J M (2007). Heterogeneous uptake and oxidation of SO2 on iron oxides. Journal of Physical Chemistry C, 111(16): 6077–6085

    Article  CAS  Google Scholar 

  • Ge X, Wexler A S, Clegg S L (2011). Atmospheric amines–Part I. A review. Atmospheric Environment, 45(3): 524–546

    Article  CAS  Google Scholar 

  • George I, Abbatt J (2010). Heterogeneous oxidation of atmospheric aerosol particles by gas-phase radicals. Nature Chemistry, 2(9): 713–722

    Article  CAS  Google Scholar 

  • Gu Y F, Cai T, Gao X H, Xia H Q, Sun W, Zhao J, Dai Q G, Wang X Y (2019). Catalytic combustion of chlorinated aromatics over WOx/CeO2 catalysts at low temperature. Applied Catalysis B: Environmental, 248: 264–276

    Article  CAS  Google Scholar 

  • Guan J K, Zhou L S, Li W Q, Hu D, Wen J, Huang B C (2021). Improving the performance of Gd addition on catalytic activity and SO2 resistance over MnOx/ZSM-5 catalysts for low-temperature NH3-SCR. Catalysts, 11(3): 324

    Article  CAS  Google Scholar 

  • He X, Ma Z C, Xi X, Kudesi A, Wang J M (2022). Heterogeneous reaction of toluene/NO2/O3 on alpha-Fe2O3 nanoparticles: the impacts of O3, light illumination, and relative humidity on the formation of N-containing organic compounds (NOC). Environmental Science. Nano, 9(9): 3318–3330

    Article  CAS  Google Scholar 

  • Hettiarachchi E, Grassian V H (2022). Heterogeneous reactions of α-pinene on mineral surfaces: formation of organonitrates and α-pinene oxidation products. Journal of Physical Chemistry A, 126(25): 4068–4079

    Article  CAS  Google Scholar 

  • Hixson B C, Jordan J W, Wagner E L, Bevsek H M (2011). Reaction products and kinetics of the reaction of NO2 with gamma-Fe2O3. Journal of Physical Chemistry A, 115(46): 13364–13369

    Article  CAS  Google Scholar 

  • Huang H L, Huang H B, Zhan Y J, Liu G Y, Wang X M, Lu H X, Xiao L, Feng Q Y, Leung D Y C (2016). Efficient degradation of gaseous benzene by VUV photolysis combined with ozone-assisted catalytic oxidation: performance and mechanism. Applied Catalysis B: Environmental, 186: 62–68

    Article  CAS  Google Scholar 

  • Kanwal A, Sajjad S, Leghari S A K, Yousaf Z (2021). Cascade electron transfer in ternary CuO/α-Fe2O3/γ-Al2O3 nanocomposite as an effective visible photocatalyst. Journal of Physics and Chemistry of Solids, 151: 109899

    Article  CAS  Google Scholar 

  • Kislov V V, Nguyen T L, Mebel A M, Lin S H, Smith S C (2004). Photodissociation of benzene under collision-free conditions: an ab initio/Rice-Ramsperger-Kassel-Marcus study. Journal of Chemical Physics, 120(15): 7008–7017

    Article  CAS  Google Scholar 

  • Li H L, Dong F Q, Bian L, Huo T T, Zhou L, Luo W G, Zhang J, Zheng F, Lv Z Z, He X C, et al. (2022). Heterogeneous oxidation mechanism of SO2 on α-Fe2O3 (001) catalyst by HONO: effect of oxygen defect. Colloid and Interface Science Communications, 46: 100572

    Article  CAS  Google Scholar 

  • Lichtenberger J, Amiridis M D (2004). Catalytic oxidation of chlorinated benzenes over V2O5/TiO2 catalysts. Journal of Catalysis, 223(2): 296–308

    Article  CAS  Google Scholar 

  • Liu C, Ma Q, Liu Y, Ma J, He H (2012). Synergistic reaction between SO2 and NO2 on mineral oxides: a potential formation pathway of sulfate aerosol. Physical Chemistry Chemical Physics, 14(5): 1668–1676

    Article  CAS  Google Scholar 

  • Liu F D, Asakura K, He H, Shan W P, Shi X Y, Zhang C B (2011a). Influence of sulfation on iron titanate catalyst for the selective catalytic reduction of NOx with NH3. Applied Catalysis B: Environmental, 103(3–4): 369–377

    Article  CAS  Google Scholar 

  • Liu S L, Wang B G, He J, Tang X D, Luo W, Wang C (2011b). Source fingerprints of volatile organic compounds emitted from a municipal solid waste incineration power plant in Guangzhou, China. International Conference on Environment Science and Engineering (ICESE), Bali Island, Indonesia

  • Long Y P, Su Y T, Xue Y H, Wu Z B A, Weng X L (2021). V2O5-WO3/TiO2 catalyst for efficient synergistic control of NOx and chlorinated organics: insights into the arsenic effect. Environmental Science & Technology, 55(13): 9317–9325

    Article  CAS  Google Scholar 

  • Lunt M F, Park S, Li S, Henne S, Manning A J, Ganesan A L, Simpson I J, Blake D R, Liang Q, O’doherty S, et al. (2018). Continued emissions of the ozone-depleting substance carbon tetrachloride from eastern Asia. Geophysical Research Letters, 45(20): 11423–11430

    Article  CAS  Google Scholar 

  • Lv S Y, Liu Q Y, Zhao Y X, He S G (2021). Photooxidation of isoprene by titanium oxide cluster anions with dimensions up to a nanosize. Journal of the American Chemical Society, 143(10): 3951–3958

    Article  CAS  Google Scholar 

  • Ma Y F, Wang P Y, Lin X Q, Chen T, Li X D (2021). Formation and inhibition of polychlorinated-rho-dibenzodioxins and dibenzofurans from mechanical grate municipal solid waste incineration systems. Journal of Hazardous Materials, 403(5): 123812

    Article  CAS  Google Scholar 

  • Montzka S A, Dutton G S, Yu P, Ray E, Portmann R W, Daniel J S, Kuijpers L, Hall B D, Mondeel D, Siso C, et al. (2018). An unexpected and persistent increase in global emissions of ozone-depleting CFC-11. Nature, 557(7705): 413–417

    Article  CAS  Google Scholar 

  • Nagao M, Suda Y (1989). Adsorption of benzene, toluene, and chlorobenzene on titanium-dioxide. Langmuir, 5(1): 42–47

    Article  CAS  Google Scholar 

  • Niu H J Y, Li K Z, Chu B W, Su W K, Li J H (2017). Heterogeneous reactions between toluene and NO2 on mineral particles under simulated atmospheric conditions. Environmental Science & Technology, 51(17): 9596–9604

    Article  CAS  Google Scholar 

  • Peng A P, Gao J, Chen Z Y, Wang Y, Li H, Ma L Q, Gu C (2018). Interactions of gaseous 2-chlorophenol with Fe3+-saturated montmorillonite and their toxicity to human lung cells. Environmental Science & Technology, 52(9): 5208–5217

    Article  CAS  Google Scholar 

  • Pitts J NJr, Grosjean D, Vancauwenberghe K, Schmid J P, Fitz D R (1978). Photo-oxidation of aliphatic-amines under simulated atmospheric conditions: formation of nitrosamines, nitramines, amides, and photo-chemical oxidant. Environmental Science & Technology, 12(8): 946–953

    Article  CAS  Google Scholar 

  • Ponczek M, George C (2018). Kinetics and product formation during the photooxidation of butanol on atmospheric mineral dust. Environmental Science & Technology, 52(9): 5191–5198

    Article  CAS  Google Scholar 

  • Potter P M, Guan X, Lomnicki S M (2018). Synergy of iron and copper oxides in the catalytic formation of PCDD/Fs from 2-monochlorophenol. Chemosphere, 203: 96–103

    Article  CAS  Google Scholar 

  • Qi J H, Liu X H, Yao X H, Zhang R F, Chen X J, Lin X H, Gao H W, Liu R H (2018). The concentration, source and deposition flux of ammonium and nitrate in atmospheric particles during dust events at a coastal site in northern China. Atmospheric Chemistry and Physics, 18(2): 571–586

    Article  CAS  Google Scholar 

  • Ren Z Y, Lu Y, Li Q S, Sun Y Z, Wu C M, Ding Q (2018). Occurrence and characteristics of PCDD/Fs formed from chlorobenzenes production in China. Chemosphere, 205: 267–274

    Article  CAS  Google Scholar 

  • Ryder O S, Campbell N R, Shaloski M, Al-Mashat H, Nathanson G M, Bertram T H (2015). Role of organics in regulating ClNO2 production at the air–sea interface. Journal of Physical Chemistry A, 119(31): 8519–8526

    Article  CAS  Google Scholar 

  • Ryu J Y (2008). Formation of chlorinated phenols, dibenzo-p-dioxins, dibenzofurans, benzenes, benzoquinnones and perchloroethylenes from phenols in oxidative and copper(II) chloride-catalyzed thermal process. Chemosphere, 71(6): 1100–1109

    Article  CAS  Google Scholar 

  • USEPA (1994). Method 1613: Tetra- through Octa-Chlorinated Dioxins and Furans by Isotope Dilution HRGC/HRMS. Cincinnati, OH: USEPA

    Google Scholar 

  • USEPA (1999). Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air. 2nd ed. Cincinnati, OH: USEPA

    Google Scholar 

  • Wang B G, Feng Z C, Zhou Y, Liu H X (2009). VOC components in the air caused by the local polyurethane synthetic leather industries in the Pearl River Delta region. China Environment Science, 29(9): 914–918 (in Chinese)

    Google Scholar 

  • Wang D, Zhang H J, Fan Y, Ren M H, Cao R, Chen J P (2019a). Electrophilic chlorination of naphthalene in combustion flue gas. Environmental Science & Technology, 53(10): 5741–5749

    Article  CAS  Google Scholar 

  • Wang J, Wang X, Liu X L, Zeng J L, Guo Y Y, Zhu T Y (2015). Kinetics and mechanism study on catalytic oxidation of chlorobenzene over V2O5/TiO2 catalysts. Journal of Molecular Catalysis A Chemical, 402: 1–9

    Article  CAS  Google Scholar 

  • Wang P, Zhu S, Vrekoussis M, Brasseur G P, Wang S, Zhang H (2022). Is atmospheric oxidation capacity better in indicating tropospheric O3 formation? Frontiers of Environmental Science & Engineering, 16(5): 65

    Article  Google Scholar 

  • Wang X W, Jiang W Y, Yin R Q, Sun P F, Lu Y H, Wu Z B, Weng X L (2020). The role of surface sulfation in mediating the acidity and oxidation ability of nickel modified ceria catalyst for the catalytic elimination of chlorinated organics. Journal of Colloid and Interface Science, 574: 251–259

    Article  CAS  Google Scholar 

  • Wang Z W, Li S, Xie S H, Liu Y X, Dai H X, Guo G S, Deng J G (2019b). Supported ultralow loading Pt catalysts with high H2O-,CO2-, and SO2-resistance for acetone removal. Applied Catalysis A, General, 579(5): 106–115

    Article  CAS  Google Scholar 

  • Wu R R, Wang S N, Wang L M (2014). Atmospheric oxidation mechanism of chlorobenzene. Chemosphere, 111: 537–544

    Article  CAS  Google Scholar 

  • Xie C Y, Sun Y L, Zhu B Z (2021). The promoting mechanism of doping Mn, Co, and Ce on gas adsorption property and anti-SO2 oxidation over γ-Fe2O3 (001) surface: a density functional theory study. Colloids and Surfaces. A, Physicochemical and Engineering Aspects, 628(5): 127218

    Article  CAS  Google Scholar 

  • Yang L L, Liu G R, Zheng M H, Zhao Y Y, Jin R, Wu X L, Xu Y (2017). Molecular mechanism of dioxin formation from chlorophenol based on electron paramagnetic resonance spectroscopy. Environmental Science & Technology, 51(9): 4999–5007

    Article  CAS  Google Scholar 

  • Yang W W, Ma Q X, Liu Y C, Ma J Z, Chu B W, He H (2019). The effect of water on the heterogeneous reactions of SO2 and NH3 on the surfaces of α-Fe2O3 and γ-Al2O3. Environmental Science. Nano, 6(9): 2749–2758

    Article  CAS  Google Scholar 

  • Yu Y X, Tan W, An D Q, Wang X W, Liu A N, Zou W X, Tang C J, Ge C Y, Tong Q, Sun J F, et al. (2021). Insight into the SO2 resistance mechanism on γ-Fe2O3 catalyst in NH3-SCR reaction: a collaborated experimental and DFT study. Applied Catalysis B: Environmental, 281: 119544

    Article  CAS  Google Scholar 

  • Zhang Y, Li G, Wu P, Zhuang K, Shen K, Wang S, Huang T (2020). Effect of SO2 on the low-temperature denitrification performance of Ho-modified Mn/Ti catalyst. Chemical Engineering Journal, 400(15): 122597

    Article  CAS  Google Scholar 

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 22176169, 52070168), the Key R&D Plan of Zhejiang Province (No. 2023C03127), and the Fundamental Research Funds for the Central Universities (No. 226-2022-00150).

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Authors and Affiliations

  1. Key Laboratory of Environment Remediation and Ecological Health (Ministry of Education), College of Environmental and Resource Sciences, Zhejiang University, Hangzhou, 310058, China

    Meiling Chen, Yuetan Su, Ruizhe Li, Zhongbiao Wu & Xiaole Weng

  2. ZJU-Hangzhou Global Scientific and Technological Innovation Center, Zhejiang University, Hangzhou, 311215, China

    Meiling Chen & Xiaole Weng

  3. School of Automation (School of Artificial Intelligence), Hangzhou Dianzi University, Hangzhou, 310018, China

    Mengjie Yin & Kezhou Liu

  4. Zhejiang Provincial Engineering Research Centre of Industrial Boiler & Furnace Flue Gas Pollution Control, Hangzhou, 311200, China

    Zhongbiao Wu & Xiaole Weng

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  1. Meiling Chen
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  2. Mengjie Yin
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  3. Yuetan Su
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  4. Ruizhe Li
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  5. Kezhou Liu
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  6. Zhongbiao Wu
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  7. Xiaole Weng
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Correspondence to Xiaole Weng.

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The authors declare no conflict of interest.

Highlights

• Photochemical conversion of chlorobenzene (CB) on α-Fe2O3 was evaluated.

• CB can be considerably degraded by α-Fe2O3 under light irradiation.

• Photochemical conversion of CB is markedly suppressed by adding SO2 or NO2.

• CB can be ultimately converted into PCDD/Fs under dark state or light irradiation.

• Photochemical conversion complements an overlooked source of natural PCDD/Fs.

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Chen, M., Yin, M., Su, Y. et al. Atmospheric heterogeneous reaction of chlorobenzene on mineral α-Fe2O3 particulates: a chamber experiment study. Front. Environ. Sci. Eng. 17, 134 (2023). https://doi.org/10.1007/s11783-023-1734-9

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  • DOI: https://doi.org/10.1007/s11783-023-1734-9

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