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RESEARCH ARTICLE

Experimental simulation of stratospheric ozone reactions with chloroalkane organic pollutants

Serguei V. Savilov A C , Natalia E. Strokova https://orcid.org/0000-0003-4529-2580 A , Anton S. Ivanov A and Igor I. Morozov B
+ Author Affiliations
- Author Affiliations

A M. V. Lomonosov Moscow State University, Department of Chemistry, Moscow 119991, Russia.

B N. N. Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, Moscow 119991, Russia.

C Corresponding author. Email: savilov@chem.msu.ru

Environmental Chemistry 18(1) 31-37 https://doi.org/10.1071/EN20073
Submitted: 21 May 2020  Accepted: 23 September 2020   Published: 22 October 2020

Environmental context. Chlorinated organic atmospheric pollutants, which can be produced naturally or anthropogenically, are considered as a factor responsible for stratospheric ozone depletion. Based on experimental simulations and low temperature vibrational spectroscopy, this work reports a mechanism for the reaction of chloroalkanes with ozone. This reaction leads to the formation of the photochemically reactive chlorine oxide species. Kinetics and implications of the reactions are discussed.

Abstract. The present work deals with the important problem of stratospheric ozone depletion and an investigation of the atmospheric decay of organic pollutants. The products of the heterogeneous reactions of ozone with chloroethane and 1-chloropropane in a flow-through vacuum electric discharge unit under conditions similar those observed in the stratosphere are studied by low-temperature infrared (IR) absorption spectroscopy. Taking into account the literature data, a scheme for the interaction of ozone with halogen-substituted alkanes at low temperatures is proposed, which shows the formation of chlorine oxides that have high photochemical activity and can cause damage to the ozone layer even when present in small concentrations. The conversion of chloroalkanes over time demonstrates the first-order-decay behaviour of the investigated processes.

Keywords: atmospheric pollutants, IR spectroscopy, low-temperature reactions, ozone depletion, stratospheric ozone.


References

Andrady A, Aucamp P, Austin A, Bais A, Ballaré C, Barnes P, Bernhard G, Bornman J, Caldwell M, De Gruijl F, et al (2015). Environmental effects of ozone depletion and its interactions with climate change: 2014 assessment Executive summary. Photochemical & Photobiological Sciences 14, 14–18.
Environmental effects of ozone depletion and its interactions with climate change: 2014 assessment Executive summaryCrossref | GoogleScholarGoogle Scholar |

Azarpazhooh A, Limeback H (2008). The application of ozone in dentistry: A systematic review of literature. Journal of Dentistry 36, 104–116.
The application of ozone in dentistry: A systematic review of literatureCrossref | GoogleScholarGoogle Scholar | 18166260PubMed |

Barbe A, Secroun C, Jouve P (1974). Infrared Spectra of 16O3 and 18O3: Darling and Dennison Resonance and Anharmonic Potential Function of Ozone. Journal of Molecular Spectroscopy 49, 171–182.
Infrared Spectra of 16O3 and 18O3: Darling and Dennison Resonance and Anharmonic Potential Function of OzoneCrossref | GoogleScholarGoogle Scholar |

Barletta B, Carreras-Sospedra M, Cohan A, Nissenson P, Dabdub D, Meinardi S, Atlas E, Lueb R, Holloway JS, Ryerson TB, Pederson J, VanCuren RA, Blake DR (2013). Emission estimates of HCFCs and HFCs in California from the 2010 CalNex study. Journal of Geophysical Research, D, Atmospheres 118, 2019–2030.
Emission estimates of HCFCs and HFCs in California from the 2010 CalNex studyCrossref | GoogleScholarGoogle Scholar |

Bekki S, Rap A, Poulain V, Dhomse S, Marchand M, Lefevre F, Forster PM, Szopa S, Chipperfield MP (2013). Climate impact of stratospheric ozone recovery. Geophysical Research Letters 40, 2796–2800.
Climate impact of stratospheric ozone recoveryCrossref | GoogleScholarGoogle Scholar |

Beltrán A, Andrés J, Noury S, Silvi B (1999). Structure and Bonding of Chlorine Oxides and Peroxides: ClOx, ClOx- (x = 1−4), and Cl2Ox (x = 1−8). The Journal of Physical Chemistry A 103, 3078–3088.
Structure and Bonding of Chlorine Oxides and Peroxides: ClOx, ClOx- (x = 1−4), and Cl2Ox (x = 1−8)Crossref | GoogleScholarGoogle Scholar |

Bey I, Jacob DJ, Yantosca RM, Logan JA, Field BD, Fiore AM, Li Q, Liu HY, Mickley LJ, Schultz MG (2001). Global modeling of tropospheric chemistry with assimilated meteorology: Model description and evaluation. Journal of Geophysical Research 106, 23073–23095.
Global modeling of tropospheric chemistry with assimilated meteorology: Model description and evaluationCrossref | GoogleScholarGoogle Scholar |

Carazzo G, Jellinek AM (2013). Particle sedimentation and diffusive convection in volcanic ash-clouds. Journal of Geophysical Research. Solid Earth 118, 1420–1437.
Particle sedimentation and diffusive convection in volcanic ash-cloudsCrossref | GoogleScholarGoogle Scholar |

Cheng BM, Lee YP (1989). Production and trapping of gaseous dimeric ClO: The infrared spectrum of chlorine peroxide (ClOOCl) in solid argon. The Journal of Chemical Physics 90, 5930–5935.
Production and trapping of gaseous dimeric ClO: The infrared spectrum of chlorine peroxide (ClOOCl) in solid argonCrossref | GoogleScholarGoogle Scholar |

Demir-Duz H, Aktürk AS, Ayyildiz O, Álvarez MG, Contreras S (2020). Reuse and recycle solutions in refineries by ozone-based advanced oxidation processes: A statistical approach. Journal of Environmental Management 263, 110346
Reuse and recycle solutions in refineries by ozone-based advanced oxidation processes: A statistical approachCrossref | GoogleScholarGoogle Scholar | 32174517PubMed |

Ebbing DD, Gammon SD (2009). ‘General chemistry.’ (Houghton Mifflin Company: New York, NY)

Ehrenhauser FS, Khadapkar K, Wang Y, Hutchings JW, Delhomme O, Kommalapati RR, Herckes P, Wornat MJ, Valsaraj KT (2012). Processing of atmospheric polycyclic aromatic hydrocarbons by fog in an urban environment. Journal of Environmental Monitoring 14, 2566–2579.
Processing of atmospheric polycyclic aromatic hydrocarbons by fog in an urban environmentCrossref | GoogleScholarGoogle Scholar | 22968314PubMed |

Faxon CB, Allen DT (2013). Chlorine chemistry in urban atmospheres: a review. Environmental Chemistry 10, 221–233.
Chlorine chemistry in urban atmospheres: a reviewCrossref | GoogleScholarGoogle Scholar |

Fraser PJ, Dunse BL, Manning AJ, Walsh S, Wang RHJ, Krummel PB, Steele LP, Porter LW, Allison C, O’Doherty S, Simmonds PG, Mühle J, Weiss RF, Prinn RG (2014). Australian carbon tetrachloride emissions in a global context. Environmental Chemistry 11, 77–88.
Australian carbon tetrachloride emissions in a global contextCrossref | GoogleScholarGoogle Scholar |

Gent PR, Danabasoglu G, Donner LJ, Holland MM, Hunke EC, Jayne SR, Lawrence DM, Neale RB, Rasch PJ, Vertenstein M, Worley PH, Yang Z-L, Zhang M (2011). The Community Climate System Model Version 4. Journal of Climate 24, 4973–4991.
The Community Climate System Model Version 4Crossref | GoogleScholarGoogle Scholar |

Grothe H, Willner H (1994). Chlorine Trioxide: Spectroscopic Properties, Molecular Structure, and Photochemical Behavior. Angewandte Chemie International Edition in English 33, 1482–1484.
Chlorine Trioxide: Spectroscopic Properties, Molecular Structure, and Photochemical BehaviorCrossref | GoogleScholarGoogle Scholar |

Grothe H, Willner H (1996). Chlorine Tetraoxide. Angewandte Chemie International Edition in English 35, 768–769.
Chlorine TetraoxideCrossref | GoogleScholarGoogle Scholar |

Guzel-Seydim ZB, Greene AK, Seydim AC (2004). Use of ozone in the food industry. Lebensmittel-Wissenschaft + Technologie 37, 453–460.
Use of ozone in the food industryCrossref | GoogleScholarGoogle Scholar |

Guzmán MI, Colussi AJ, Hoffmann MR (2006). Photogeneration of Distant Radical Pairs in Aqueous Pyruvic Acid Glasses. The Journal of Physical Chemistry A 110, 931–935.
Photogeneration of Distant Radical Pairs in Aqueous Pyruvic Acid GlassesCrossref | GoogleScholarGoogle Scholar | 16419992PubMed |

Guzman MI, Athalye RR, Rodriguez JM (2012). Concentration Effects and Ion Properties Controlling the Fractionation of Halides during Aerosol Formation. The Journal of Physical Chemistry A 116, 5428–5435.
Concentration Effects and Ion Properties Controlling the Fractionation of Halides during Aerosol FormationCrossref | GoogleScholarGoogle Scholar | 22591185PubMed |

Hamilton GA, Ribner BS, Hellman TM (1968). The mechanism of alkane oxidation by ozone. In ‘Oxidation of organic compounds’. (Ed. FR Mayo) pp. 15–25. (American Chemical Society: Washington DC)

Hobbs PV (2000). ‘Introduction to Atmospheric Chemistry’, Cambridge, Cambridge University Press.

Hull LA, Hisatsune IC, Heicklen J (1972). Low-temperature infrared studies of simple alkene-ozone reactions. Journal of the American Chemical Society 94, 4856–4864.
Low-temperature infrared studies of simple alkene-ozone reactionsCrossref | GoogleScholarGoogle Scholar |

Jacobs J, Kronberg M, Mueller HSP, Willner H (1994). An Experimental Study on the Photochemistry and Vibrational Spectroscopy of Three Isomers of Cl2O2 Isolated in Cryogenic Matrixes. Journal of the American Chemical Society 116, 1106–1114.
An Experimental Study on the Photochemistry and Vibrational Spectroscopy of Three Isomers of Cl2O2 Isolated in Cryogenic MatrixesCrossref | GoogleScholarGoogle Scholar |

Jurado-Alameda E, García-Román M, Altmajer-Vaz D, Jiménez-Pérez JL (2012). Assessment of the use of ozone for cleaning fatty soils in the food industry. Journal of Food Engineering 110, 44–52.
Assessment of the use of ozone for cleaning fatty soils in the food industryCrossref | GoogleScholarGoogle Scholar |

Keyte IJ, Harrison RM, Lammel G (2013). Chemical reactivity and long-range transport potential of polycyclic aromatic hydrocarbons – a review. Chemical Society Reviews 42, 9333–9391.
Chemical reactivity and long-range transport potential of polycyclic aromatic hydrocarbons – a reviewCrossref | GoogleScholarGoogle Scholar | 24077263PubMed |

Kopitzky R, Grothe H, Willner H (2002). Chlorine Oxide Radicals ClOx (x = 1–4) Studied by Matrix Isolation spectroscopy. Chemistry – A European Journal 8, 5601–5621.
Chlorine Oxide Radicals ClOx (x = 1–4) Studied by Matrix Isolation spectroscopyCrossref | GoogleScholarGoogle Scholar |

Koten IA (1940). Laboratory synthesis of ethyl chloride. Journal of Chemical Education 17, 461
Laboratory synthesis of ethyl chlorideCrossref | GoogleScholarGoogle Scholar |

Laturnus F, Fahimi I, Gryndler M, Hartmann A, Heal M, Matucha M, Schöler HF, Schroll R, Svensson T (2005). Natural Formation and Degradation of Chloroacetic Acids and Volatile Organochlorines in Forest Soil. Challenges to understanding (12 pp). Environmental Science and Pollution Research International 12, 233–244.
Natural Formation and Degradation of Chloroacetic Acids and Volatile Organochlorines in Forest Soil. Challenges to understanding (12 pp)Crossref | GoogleScholarGoogle Scholar | 16137159PubMed |

Lunin VV, Popovich MP, Tkachenko SN (1998). ‘Physical chemistry of ozone (in Russian).’ (MSU Publishing: Moscow)

McLinden CA, Olsen SC, Hannegan B, Wild O, Prather MJ, Sundet J (2000). Stratospheric ozone in 3-D models: A simple chemistry and the cross-tropopause flux. Journal of Geophysical Research 105, 14653–14665.
Stratospheric ozone in 3-D models: A simple chemistry and the cross-tropopause fluxCrossref | GoogleScholarGoogle Scholar |

McRoberts WC, Keppler F, Harper DB, Hamilton JTG (2015). Seasonal changes in chlorine and methoxyl content of leaves of deciduous trees and their impact on release of chloromethane and methanol at elevated temperatures. Environmental Chemistry 12, 426–437.
Seasonal changes in chlorine and methoxyl content of leaves of deciduous trees and their impact on release of chloromethane and methanol at elevated temperaturesCrossref | GoogleScholarGoogle Scholar |

Mehrjouei M, Müller S, Möller D (2015). A review on photocatalytic ozonation used for the treatment of water and wastewater. Chemical Engineering Journal 263, 209–219.
A review on photocatalytic ozonation used for the treatment of water and wastewaterCrossref | GoogleScholarGoogle Scholar |

Middlebrook AM, Tolbert MA (2000). ‘Stratospheric ozone depletion.’ (University Science Books: Sausalito, CA)

Nakata M, Sugie M, Takeo H, Matsumura C, Fukuyama T, Kuchitsu K (1981). Structure of dichlorine monoxide as studied by microwave spectroscopy. Determination of equilibrium structure by a modified mass dependence method. Journal of Molecular Spectroscopy 86, 241–249.
Structure of dichlorine monoxide as studied by microwave spectroscopy. Determination of equilibrium structure by a modified mass dependence methodCrossref | GoogleScholarGoogle Scholar |

Nawrocki J (2013). Catalytic ozonation in water: Controversies and questions. Discussion paper. Applied Catalysis B: Environmental 142–143, 465–471.
Catalytic ozonation in water: Controversies and questions. Discussion paperCrossref | GoogleScholarGoogle Scholar |

Nishijima W, Okuda T, Nakai S, Okada M (2014). A green procedure using ozone for Cleaning-in-Place in the beverage industry. Chemosphere 105, 106–111.
A green procedure using ozone for Cleaning-in-Place in the beverage industryCrossref | GoogleScholarGoogle Scholar | 24613443PubMed |

Park C (1976). Rates of reactions chlorine monoxide + chlorine monoxide. far. molecular chlorine + molecular oxygen and chlorine monoxide + atomic oxygen. far. atomic chlorine + molecular oxygen at elevated temperatures. Journal of Physical Chemistry 80, 565–571.
Rates of reactions chlorine monoxide + chlorine monoxide. far. molecular chlorine + molecular oxygen and chlorine monoxide + atomic oxygen. far. atomic chlorine + molecular oxygen at elevated temperaturesCrossref | GoogleScholarGoogle Scholar |

Park C (1977). Reaction rates for ozone + hydrochloric acid. fwdarw. atomic oxygen + molecular oxygen + hydrochloric acid, atomic chlorine + ozone. fwdarw. chlorine monoxide + molecular oxygen, and hydrochloric acid + atomic oxygen. fwdarw. hydroxyl + atomic chlorine at elevated temperatures. Journal of Physical Chemistry 81, 499–504.
Reaction rates for ozone + hydrochloric acid. fwdarw. atomic oxygen + molecular oxygen + hydrochloric acid, atomic chlorine + ozone. fwdarw. chlorine monoxide + molecular oxygen, and hydrochloric acid + atomic oxygen. fwdarw. hydroxyl + atomic chlorine at elevated temperaturesCrossref | GoogleScholarGoogle Scholar |

Rae ID (2008). Something in the air: connections between global warming, ozone depletion, POPs and particulates. Environmental Chemistry 5, 1–4.
Something in the air: connections between global warming, ozone depletion, POPs and particulatesCrossref | GoogleScholarGoogle Scholar |

Rehr A, Jansen M (1992). Investigations on solid chlorine dioxide: temperature-dependent crystal structure, IR spectrum, and magnetic susceptibility. Inorganic Chemistry 31, 4740–4742.
Investigations on solid chlorine dioxide: temperature-dependent crystal structure, IR spectrum, and magnetic susceptibilityCrossref | GoogleScholarGoogle Scholar |

Ruecker A, Weigold P, Behrens S, Jochmann M, Barajas XLO, Kappler A (2015). Halogenated hydrocarbon formation in a moderately acidic salt lake in Western Australia – role of abiotic and biotic processes. Environmental Chemistry 12, 406–414.
Halogenated hydrocarbon formation in a moderately acidic salt lake in Western Australia – role of abiotic and biotic processesCrossref | GoogleScholarGoogle Scholar |

Ryerson TB, Andrews AE, Angevine WM, Bates TS, Brock CA, Cairns B, Cohen RC, Cooper OR, De Gouw JA, Fehsenfeld FC, et al (2013). The 2010 California Research at the Nexus of Air Quality and Climate Change (CalNex) field study. Journal of Geophysical Research, D, Atmospheres 118, 5830–5866.
The 2010 California Research at the Nexus of Air Quality and Climate Change (CalNex) field studyCrossref | GoogleScholarGoogle Scholar |

Sander SP, Friedl RR, Barker JR, Golden DM, Kurylo MJ, Sciences GE, Wine PH, Abbatt JPD, Burkholder JB, Kolb CE, Moortgat GK, Huie RE, Orkin VL (2011). Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies. Evaluation Number 17. JPL Publication 10-06, pp. 1–334.

Savilov SV, Yagodovskaya TV (2002). The role of HCl and HBr in heterogeneous processes of stratospheric ozone decomposition. In ‘Global atmospheric change and its impact on regional air quality’. (Ed. I Barnes) pp. 167–171. (Springer Netherlands: Dordrecht)

Savilov SV, Yagodovskaya TV, Zosimov AV, Lunin VV (2003). Chlorine and bromine oxides: synthesis, structure, and role in heterogeneous processes of stratospheric ozone decomposition. Ninth Joint International Symposium on Atmospheric and Ocean Optics/Atmospheric Physics, 2003, Tomsk, Russia, pp. 7–12.

Sciorsci RL, Lillo E, Occhiogrosso L, Rizzo A (2020). Ozone therapy in veterinary medicine: A review. Research in Veterinary Science 130, 240–246.
Ozone therapy in veterinary medicine: A reviewCrossref | GoogleScholarGoogle Scholar | 32234614PubMed |

Semblante GU, Hai FI, Dionysiou DD, Fukushi K, Price WE, Nghiem LD (2017). Holistic sludge management through ozonation: A critical review. Journal of Environmental Management 185, 79–95.
Holistic sludge management through ozonation: A critical reviewCrossref | GoogleScholarGoogle Scholar | 27815004PubMed |

Shindell DT (1997). The Potential Influence of ClO·O2 on Stratospheric Ozone Depletion Chemistry. Journal of Atmospheric Chemistry 26, 323–335.
The Potential Influence of ClO·O2 on Stratospheric Ozone Depletion ChemistryCrossref | GoogleScholarGoogle Scholar |

Smith SJ, West JJ, Kyle P (2011). Economically consistent long-term scenarios for air pollutant emissions. Climatic Change 108, 619–627.
Economically consistent long-term scenarios for air pollutant emissionsCrossref | GoogleScholarGoogle Scholar |

Socrates G (2004). ‘Infrared and Raman characteristic group frequencies: tables and charts.’ (John Wiley & Sons: Hoboken, NJ)

Steinbrecht W, Hegglin MI, Harris N, Weber M (2018). Is global ozone recovering?. Comptes Rendus Geoscience 350, 368–375.
Is global ozone recovering?Crossref | GoogleScholarGoogle Scholar |

Strahan SE, Douglass AR, Newman PA (2013). The contributions of chemistry and transport to low arctic ozone in March 2011 derived from Aura MLS observations. Journal of Geophysical Research, D, Atmospheres 118, 1563–1576.
The contributions of chemistry and transport to low arctic ozone in March 2011 derived from Aura MLS observationsCrossref | GoogleScholarGoogle Scholar |

Strokova NE, Savilov SV, Morozov II, Yagodovskaya TV, Lunin VV (2015). Laboratory simulations of the interaction between ozone and chloroacetic acids in the conditions close to stratospheric. Russian Journal of Physical Chemistry A 89, 28–37.
Laboratory simulations of the interaction between ozone and chloroacetic acids in the conditions close to stratosphericCrossref | GoogleScholarGoogle Scholar |

Torres R, Lapidus GT (2016). Platinum, palladium and gold leaching from magnetite ore, with concentrated chloride solutions and ozone. Hydrometallurgy 166, 185–194.
Platinum, palladium and gold leaching from magnetite ore, with concentrated chloride solutions and ozoneCrossref | GoogleScholarGoogle Scholar |

Vysokikh TA, Yagodovskaya TV, Savilov SV, Lunin VV (2007a). The interaction of ozone with chlorobezene. Zhurnal Fizicheskoi Himii 81, 1010–1014. [in Russian]

Vysokikh TA, Mukhamedzyanova DF, Yagodovskaya TV, Savilov SV, Lunin VV (2007b). The interaction of CH3Cl, CH2Cl2, CHCl3, and CCl4 with ozone on the surface of ice under stratospheric conditions. Russian Journal of Physical Chemistry A 81, 1836–1839.
The interaction of CH3Cl, CH2Cl2, CHCl3, and CCl4 with ozone on the surface of ice under stratospheric conditionsCrossref | GoogleScholarGoogle Scholar |

Wen Q, Chen Q (2020). An Overview of Ozone Therapy for Treating Foot Ulcers in Patients With Diabetes. The American Journal of the Medical Sciences
An Overview of Ozone Therapy for Treating Foot Ulcers in Patients With DiabetesCrossref | GoogleScholarGoogle Scholar | 32534720PubMed |

Yagodovskaya TV, Savilov SV, Zosimov AV, Lunin VV (2000). Interaction of ozone with HCl, adsorbed on the ice surface at 77 K. Zhurnal Fizicheskoi Himii 74, 1028–1030.

Yang B, Wang Y, Zhang W, Liu C, Shu X, Shu J (2012). Heterogeneous ozonolysis of pirimicarb and isopropalin: mechanism of ozone-induced N-dealkylation and carbonylation reactions. Environmental Chemistry 9, 521–528.
Heterogeneous ozonolysis of pirimicarb and isopropalin: mechanism of ozone-induced N-dealkylation and carbonylation reactionsCrossref | GoogleScholarGoogle Scholar |

Yang K, Yu J, Guo Q, Wang C, Yang M, Zhang Y, Xia P, Zhang D, Yu Z (2017a). Comparison of micropollutants’ removal performance between pre-ozonation and post-ozonation using a pilot study. Water Research 111, 147–153.
Comparison of micropollutants’ removal performance between pre-ozonation and post-ozonation using a pilot studyCrossref | GoogleScholarGoogle Scholar | 28068535PubMed |

Yang Y, Ok YS, Kim K-H, Kwon EE, Tsang YF (2017b). Occurrences and removal of pharmaceuticals and personal care products (PPCPs) in drinking water and water/sewage treatment plants: A review. The Science of the Total Environment 596–597, 303–320.
Occurrences and removal of pharmaceuticals and personal care products (PPCPs) in drinking water and water/sewage treatment plants: A reviewCrossref | GoogleScholarGoogle Scholar | 28437649PubMed |