On the potential importance of the gas phase reaction CH3O2 + ClO → ClOO + CH3O and the heterogeneous reaction HOCl + HCl → H2O + Cl2 in “ozone hole” chemistry

Crutzen, Paul J.; Müller, Rolf; Brühl, C.; Peter, Thomas

doi:10.1029/92gl01172

Cited by 138 publications

(144 citation statements)

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“…For the Arctic high latitude ozone loss, this cycle may be of comparable importance as the BrO-C10 cycle (Table 2). Since it is strongly dependent on solar illumination [Crutzen et al, 1992], it is triggered earlier during southward excursions if variations in latitude are considered, so that in this case, the HC1 activation, and thus the ozone depletion, is slightly stronger ( Ozone depletion simulated in the model from 15.12.91 to 15.3.92 for temperature T (as in Fig. 1) …”

Section: Model Results and Observationsmentioning

confidence: 99%

Chlorine chemistry and the potential for ozone depletion in the Arctic stratosphere in the winter of 1991/92

Müller¹,

Peter²,

Crutzen³

et al. 1994

Geophysical Research Letters

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105

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Section: Model Results and Observationsmentioning

confidence: 99%

Chlorine chemistry and the potential for ozone depletion in the Arctic stratosphere in the winter of 1991/92

Müller¹,

Peter²,

Crutzen³

et al. 1994

Geophysical Research Letters

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105

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“…Cycle C1 was first formulated by Crutzen et al (1992), demonstrating the importance of Reaction (R3) for ozone hole chemistry. Reaction (R3) is essential for the production of a HO 2 radical from the CH 3 formed in Reaction (R4).…”

Section: Maintenance Of Chlorine Activationmentioning

confidence: 99%

“…(Salawitch et al, 1988;Crutzen et al, 1992;Portmann et al, 1996). The further chemical activation to near-zero HCl values, as observed in Antarctic winter and in cold winters in the Arctic (Jaeglé et al, 1997;Santee et al, 2005Santee et al, , 2008Manney et al, 2011;Wegner et al, 2012), requires the reproduction of partners (e.g.…”

Section: Introductionmentioning

confidence: 99%

“…In particular, we apply a detailed analysis of the temporal development of the rates of the key chemical processes based on a unique algorithm for the determination of chemical pathways (Lehmann, 2004). We demonstrate that for the efficacy of the HCl null cycles it is essential that the heterogeneous reaction (Prather, 1992;Crutzen et al, 1992) HOCl + HCl → Cl 2 + H 2 O (R2) and the gas-phase reaction )…”

Section: Introductionmentioning

confidence: 99%

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The maintenance of elevated active chlorine levels in the Antarctic lower stratosphere through HCl null cycles

Müller¹,

Grooß²,

Zafar

et al. 2018

Atmos. Chem. Phys.

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Abstract. The Antarctic ozone hole arises from ozone destruction driven by elevated levels of ozone destroying ("active") chlorine in Antarctic spring. These elevated levels of active chlorine have to be formed first and then maintained throughout the period of ozone destruction. It is a matter of debate how this maintenance of active chlorine is brought about in Antarctic spring, when the rate of formation of HCl (considered to be the main chlorine deactivation mechanism in Antarctica) is extremely high. Here we show that in the heart of the ozone hole (16-18 km or 85-55 hPa, in the core of the vortex), high levels of active chlorine are maintained by effective chemical cycles (referred to as HCl null cycles hereafter). In these cycles, the formation of HCl is balanced by immediate reactivation, i.e. by immediate reformation of active chlorine. Under these conditions, polar stratospheric clouds sequester HNO 3 and thereby cause NO 2 concentrations to be low. These HCl null cycles allow active chlorine levels to be maintained in the Antarctic lower stratosphere and thus rapid ozone destruction to occur. For the observed almost complete activation of stratospheric chlorine in the lower stratosphere, the heterogeneous reaction HCl + HOCl is essential; the production of HOCl occurs via HO 2 + ClO, with the HO 2 resulting from CH 2 O photolysis. These results are important for assessing the impact of changes of the future stratospheric composition on the recovery of the ozone hole. Our simulations indicate that, in the lower stratosphere, future increased methane concentrations will not lead to enhanced chlorine deactivation (through the reaction CH 4 + Cl −→ HCl+CH 3 ) and that extreme ozone destruction to levels below ≈ 0.1 ppm will occur until mid-century.

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“…The submodel PSC is based on the "Mainz Photochemical Box Model" (Crutzen et al, 1992;Müller et al, 1994;Grooß, 1996;Meilinger, 2000) and was improved and extended by Buchholz (2005) and Kirner (2008). The submodel PSC simulates the number densities, mean radii and surface areas of liquid sulphuric acid aerosols, STS, NAT and ice particles.…”

Section: The Submodel Pscmentioning

confidence: 99%

Contribution of liquid, NAT and ice particles to chlorine activation and ozone depletion in Antarctic winter and spring

Kirner

Müller²,

Ruhnke

et al. 2015

Atmos. Chem. Phys.

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Abstract. Heterogeneous reactions in the Antarctic stratosphere are the cause of chlorine activation and ozone depletion, but the relative roles of different types of polar stratospheric clouds (PSCs) in chlorine activation is an open question. We use multi-year simulations of the chemistryclimate model ECHAM5/MESSy for Atmospheric Chemistry (EMAC) to investigate the impact that the various types of PSCs have on Antarctic chlorine activation and ozone loss.One standard and three sensitivity EMAC simulations have been performed. In all simulations a Newtonian relaxation technique using the ERA-Interim reanalysis was applied to simulate realistic synoptic conditions. In the three sensitivity simulations, we only changed the heterogeneous chemistry on PSC particles by switching the chemistry on liquid, nitric acid trihydrate (NAT) and ice particles on and off. The results of these simulations show that the significance of heterogeneous reactions on NAT and ice particles for chlorine activation and ozone depletion in Antarctic winter and spring is small in comparison to the significance of heterogeneous reactions on liquid particles. Liquid particles alone are sufficient to activate almost all of the available chlorine, with the exception of the upper PSC regions between 10 and 30 hPa, where temporarily ice particles show a relevant contribution. Shortly after the first PSC occurrence, NAT particles contribute a small fraction to chlorine activation.Heterogeneous chemistry on liquid particles is responsible for more than 90 % of the ozone depletion in Antarctic spring in the model simulations. In high southern latitudes, heterogeneous chemistry on ice particles causes only up to 5 DU of additional ozone depletion in the column and heterogeneous chemistry on NAT particles less than 0.5 DU.The simulated HNO 3 , ClO and O 3 results agree closely with observations from the Microwave Limb Sounder (MLS) onboard NASA's Aura satellite.

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On the potential importance of the gas phase reaction CH₃O₂ + ClO → ClOO + CH₃O and the heterogeneous reaction HOCl + HCl → H₂O + Cl₂ in “ozone hole” chemistry

Cited by 138 publications

References 25 publications

Chlorine chemistry and the potential for ozone depletion in the Arctic stratosphere in the winter of 1991/92

Chlorine chemistry and the potential for ozone depletion in the Arctic stratosphere in the winter of 1991/92

The maintenance of elevated active chlorine levels in the Antarctic lower stratosphere through HCl null cycles

Contribution of liquid, NAT and ice particles to chlorine activation and ozone depletion in Antarctic winter and spring

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