Active chlorine release from marine aerosols: Roles for reactive iodine and nitrogen species

McFiggans, G.; Cox, R. A.; Mössinger, J.; Allan, B. J.; Plane, J. M. C.

doi:10.1029/2001jd000383

Cited by 71 publications

(71 citation statements)

References 56 publications

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“…In line with previous studies, the system modelled was for the uptake of hypoiodous acid (HOI) at ambient temperature and humidity, an important mechanism as identified by McFiggans et al (2002). Other processes can and will be modelled as part of the halogen-aerosol interaction studies within RHAMBLE and will be the subject of future publications.…”

Section: Heterogeneous and Multiphase Chemistrymentioning

confidence: 86%

Composition and properties of atmospheric particles in the eastern Atlantic and impacts on gas phase uptake rates

et al. 2009

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Abstract. Marine aerosol composition continues to represent a large source of uncertainty in the study of climate and atmospheric chemistry. In addition to their physical size and chemical composition, hygroscopicity plays a significant role, increasing the particles' surface areas and scattering potential. Simultaneous aerosol measurements were performed on board the RRS Discovery and at the Cape Verde atmospheric observatory during the Aerosol Composition and Modelling in the Marine Environment (ACMME) and Reactive Halogens in the Marine Boundary Layer (RHAMBLE) experiments. These included online measurements of number and dry size and bulk collection for offline analysis of aqueous ions. In addition, the measurements on board the Discovery included online measurements of composition using an Aerodyne Aerosol Mass Spectrometer, optical absorption using a Multi Angle Absorption Photometer, ambient humidity size distribution measurements using a humidified differential mobility particle sizer (DMPS) and optical particle counter (OPC) and hygroscopicity measurements with a hygroscopicity tandem differential mobility analyser (HT-DMA).Good agreement between platforms in terms of the sea salt (ss) and non sea salt (nss) modes was found during the period when the Discovery was in close proximity to Cape Verde and showed a composition consistent with remote marine air. As the Discovery approached the African coast, the aerosol showed signs of continental influence such as an increaseCorrespondence to: J. D. Allan (james.allan@manchester.ac.uk) in particle number, optical absorption, enhancement of the nss mode and dust particles. The Cape Verde site was free of this influence during this period. Chloride and bromide showed concentrations with significant deviations from seawater relative to sodium, indicating that atmospheric halogen processing (and/or acid displacement for chloride) had taken place. The time dependent ambient size distribution was synthesised using humidified DMPS and OPC data, corrected to ambient humidity using HTDMA data. Heterogeneous uptake rates of hypoiodous acid (HOI) were also predicted and the nss accumulation mode was found to be the most significant part of the size distribution, which could act as an inert sink for this species. The predicted uptake rates were enhanced by around a factor of 2 during the African influence period due to the addition of both coarse and fine particles.The hygroscopicity of the nss fraction was modelled using the Aerosol Diameter Dependent Equilibrium Model (AD-DEM) using the measured composition and results compared with the HTDMA data. This was the first time such a reconciliation study with this model has been performed with marine data and good agreement was reached within the resolution of the instruments. The effect of hygroscopic growth on HOI uptake was also modelled and ambient uptake rates were found to be approximately doubled compared to equivalent dry particles.

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Section: Heterogeneous and Multiphase Chemistrymentioning

confidence: 86%

Composition and properties of atmospheric particles in the eastern Atlantic and impacts on gas phase uptake rates

et al. 2009

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“…The product of acid-catalysed dihalogen release following I + (HOI, INO 2 , INO 3 ) uptake was updated from I 2 as in Sherwen et al (2016a) to yield IBr and ICl following McFiggans et al (2002). Acidity is calculated online through titra- Table 2.…”

Section: Rxn Id Reactionmentioning

confidence: 99%

Global impacts of tropospheric halogens (Cl, Br, I) on oxidants and composition in GEOS-Chem

et al. 2016

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Abstract. We present a simulation of the global present-day composition of the troposphere which includes the chemistry of halogens (Cl, Br, I). Building on previous work within the GEOS-Chem model we include emissions of inorganic iodine from the oceans, anthropogenic and biogenic sources of halogenated gases, gas phase chemistry, and a parameterised approach to heterogeneous halogen chemistry. Consistent with Schmidt et al. (2016) we do not include sea-salt debromination. Observations of halogen radicals (BrO, IO) are sparse but the model has some skill in reproducing these. Modelled IO shows both high and low biases when compared to different datasets, but BrO concentrations appear to be modelled low. Comparisons to the very sparse observations dataset of reactive Cl species suggest the model represents a lower limit of the impacts of these species, likely due to underestimates in emissions and therefore burdens.Inclusion of Cl, Br, and I results in a general improvement in simulation of ozone (O 3 ) concentrations, except in polar regions where the model now underestimates O 3 concentrations. Halogen chemistry reduces the global tropospheric O 3 burden by 18.6 %, with the O 3 lifetime reducing from 26 to 22 days. Global mean OH concentrations of 1.28 × 10 6 molecules cm −3 are 8.2 % lower than in a simulation without halogens, leading to an increase in the CH 4 lifetime (10.8 %) due to OH oxidation from 7.47 to 8.28 years. Oxidation of CH 4 by Cl is small (∼ 2 %) but Cl oxidation of other VOCs (ethane, acetone, and propane) can be significant (∼ 15-27 %). Oxidation of VOCs by Br is smaller, representing 3.9 % of the loss of acetaldehyde and 0.9 % of the loss of formaldehyde.

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“…The inorganic iodine reaction scheme used here is adapted from McFiggans et al (2000McFiggans et al ( , 2002, Calvert and Lindberg (2004a, b), and Saiz-Lopez et al (2008). Organic iodine compounds are not included.…”

Section: Atmosmentioning

confidence: 99%

Interactions of bromine, chlorine, and iodine photochemistry during ozone depletions in Barrow, Alaska

et al. 2015

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Abstract. The springtime depletion of tropospheric ozone in the Arctic is known to be caused by active halogen photochemistry resulting from halogen atom precursors emitted from snow, ice, or aerosol surfaces. The role of bromine in driving ozone depletion events (ODEs) has been generally accepted, but much less is known about the role of chlorine radicals in ozone depletion chemistry. While the potential impact of iodine in the High Arctic is more uncertain, there have been indications of active iodine chemistry through observed enhancements in filterable iodide, probable detection of tropospheric IO, and recently, observation of snowpack photochemical production of I 2 . Despite decades of research, significant uncertainty remains regarding the chemical mechanisms associated with the bromine-catalyzed depletion of ozone, as well as the complex interactions that occur in the polar boundary layer due to halogen chemistry. To investigate this, we developed a zero-dimensional photochemical model, constrained with measurements from the 2009 OA-SIS field campaign in Barrow, Alaska. We simulated a 7-day period during late March that included a full ozone depletion event lasting 3 days and subsequent ozone recovery to study the interactions of halogen radicals under these different conditions. In addition, the effects of iodine added to our Base Model were investigated. While bromine atoms were primarily responsible for ODEs, chlorine and iodine were found to enhance the depletion rates and iodine was found to be more efficient per atom at depleting ozone than Br. The interaction between chlorine and bromine is complex, as the presence of chlorine can increase the recycling and production of Br atoms, while also increasing reactive bromine sinks under certain conditions. Chlorine chemistry was also found to have significant impacts on both HO 2 and RO 2 , with organic compounds serving as the primary reaction partner for Cl atoms. The results of this work highlight the need for future studies on the production mechanisms of Br 2 and Cl 2 , as well as on the potential impact of iodine in the High Arctic.

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Active chlorine release from marine aerosols: Roles for reactive iodine and nitrogen species

Cited by 71 publications

References 56 publications

Composition and properties of atmospheric particles in the eastern Atlantic and impacts on gas phase uptake rates

Composition and properties of atmospheric particles in the eastern Atlantic and impacts on gas phase uptake rates

Global impacts of tropospheric halogens (Cl, Br, I) on oxidants and composition in GEOS-Chem

Interactions of bromine, chlorine, and iodine photochemistry during ozone depletions in Barrow, Alaska

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