Microphysics of the aqueous bulk counters the water activity driven rate acceleration of bromide oxidation by ozone from 289–245 K.
Saved in:
| Title: | Microphysics of the aqueous bulk counters the water activity driven rate acceleration of bromide oxidation by ozone from 289–245 K. |
|---|---|
| Authors: | Edebeli, Jacinta1,2, Ammann, Markus1, Bartels-Rausch, Thorsten1 |
| Source: | Environmental Science: Processes & Impacts. Jan2019, Vol. 21 Issue 1, p63-73. 11p. |
| Subject Terms: | *Sea ice, *Ozone, Ozone generators, Microphysics, Sodium bromide, Atmospheric boundary layer, Bromides |
| Abstract: | The reaction of ozone with bromide is an initiation process in bromine activation resulting in the formation of reactive bromine species with impacts on the fate of compounds in the lower atmosphere. Environmental halide sources often contain organics, which are known to influence aqueous bulk reactivity. Here, we present a study investigating the temperature dependence of bromide oxidation by ozone using a coated wall flow tube reactor coated with an aqueous mixture of citric acid, as a proxy for oxidized secondary organic matter, and sodium bromide. Using the resistor model formulation, we quantify changes in the properties of the aqueous bulk relevant for the observed reactivity. The reactive uptake coefficient decreased from 2 × 10−6 at 289 K to 0.5 × 10−6 at 245 K. Our analysis indicates that the humidity-driven increase in concentration with a corresponding increase in the pseudo-first order reaction rate was countered by the colligative change in ozone solubility and the effect of the organic fraction via increased viscosity and decreased diffusivity of ozone as the temperature decreased. From our parameterization, we provide an extension of the temperature dependence of the reaction rate coefficients driving the oxidation of bromide, and assess the temperature-dependent salting effects of citric acid on ozone solubility. This study shows the effects of the organic species at relatively mild temperatures, between the freezing point and eutectic temperature of sea as is typical for the Earth's cryosphere. Thus, this study may be relevant for atmospheric models at different scales describing halogen activation in the marine boundary layer or free troposphere including matrices such as sea-spray aerosol and brine in sea ice, snow, and around mid-latitude salt lakes. [ABSTRACT FROM AUTHOR] |
| Copyright of Environmental Science: Processes & Impacts is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
| Database: | GreenFILE |
| FullText | Text: Availability: 0 |
|---|---|
| Header | DbId: 8gh DbLabel: GreenFILE An: 134862157 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
| IllustrationInfo | |
| Items | – Name: Title Label: Title Group: Ti Data: Microphysics of the aqueous bulk counters the water activity driven rate acceleration of bromide oxidation by ozone from 289–245 K. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Edebeli%2C+Jacinta%22">Edebeli, Jacinta</searchLink><relatesTo>1,2</relatesTo><br /><searchLink fieldCode="AR" term="%22Ammann%2C+Markus%22">Ammann, Markus</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Bartels-Rausch%2C+Thorsten%22">Bartels-Rausch, Thorsten</searchLink><relatesTo>1</relatesTo> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Environmental+Science%3A+Processes+%26+Impacts%22">Environmental Science: Processes & Impacts</searchLink>. Jan2019, Vol. 21 Issue 1, p63-73. 11p. – Name: Subject Label: Subject Terms Group: Su Data: *<searchLink fieldCode="DE" term="%22Sea+ice%22">Sea ice</searchLink><br />*<searchLink fieldCode="DE" term="%22Ozone%22">Ozone</searchLink><br /><searchLink fieldCode="DE" term="%22Ozone+generators%22">Ozone generators</searchLink><br /><searchLink fieldCode="DE" term="%22Microphysics%22">Microphysics</searchLink><br /><searchLink fieldCode="DE" term="%22Sodium+bromide%22">Sodium bromide</searchLink><br /><searchLink fieldCode="DE" term="%22Atmospheric+boundary+layer%22">Atmospheric boundary layer</searchLink><br /><searchLink fieldCode="DE" term="%22Bromides%22">Bromides</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: The reaction of ozone with bromide is an initiation process in bromine activation resulting in the formation of reactive bromine species with impacts on the fate of compounds in the lower atmosphere. Environmental halide sources often contain organics, which are known to influence aqueous bulk reactivity. Here, we present a study investigating the temperature dependence of bromide oxidation by ozone using a coated wall flow tube reactor coated with an aqueous mixture of citric acid, as a proxy for oxidized secondary organic matter, and sodium bromide. Using the resistor model formulation, we quantify changes in the properties of the aqueous bulk relevant for the observed reactivity. The reactive uptake coefficient decreased from 2 × 10−6 at 289 K to 0.5 × 10−6 at 245 K. Our analysis indicates that the humidity-driven increase in concentration with a corresponding increase in the pseudo-first order reaction rate was countered by the colligative change in ozone solubility and the effect of the organic fraction via increased viscosity and decreased diffusivity of ozone as the temperature decreased. From our parameterization, we provide an extension of the temperature dependence of the reaction rate coefficients driving the oxidation of bromide, and assess the temperature-dependent salting effects of citric acid on ozone solubility. This study shows the effects of the organic species at relatively mild temperatures, between the freezing point and eutectic temperature of sea as is typical for the Earth's cryosphere. Thus, this study may be relevant for atmospheric models at different scales describing halogen activation in the marine boundary layer or free troposphere including matrices such as sea-spray aerosol and brine in sea ice, snow, and around mid-latitude salt lakes. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Environmental Science: Processes & Impacts is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
| PLink | https://search.ebscohost.com/login.aspx?direct=true&site=eds-live&db=8gh&AN=134862157 |
| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1039/c8em00417j Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 11 StartPage: 63 Subjects: – SubjectFull: Sea ice Type: general – SubjectFull: Ozone Type: general – SubjectFull: Ozone generators Type: general – SubjectFull: Microphysics Type: general – SubjectFull: Sodium bromide Type: general – SubjectFull: Atmospheric boundary layer Type: general – SubjectFull: Bromides Type: general Titles: – TitleFull: Microphysics of the aqueous bulk counters the water activity driven rate acceleration of bromide oxidation by ozone from 289–245 K. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Edebeli, Jacinta – PersonEntity: Name: NameFull: Ammann, Markus – PersonEntity: Name: NameFull: Bartels-Rausch, Thorsten IsPartOfRelationships: – BibEntity: Dates: – D: 01 M: 01 Text: Jan2019 Type: published Y: 2019 Identifiers: – Type: issn-print Value: 20507887 Numbering: – Type: volume Value: 21 – Type: issue Value: 1 Titles: – TitleFull: Environmental Science: Processes & Impacts Type: main |
| ResultId | 1 |
