The geochemical cycling of reactive chlorine through the marine troposphere
Heterogeneous reactions involving sea‐salt aerosol in the marine troposphere are the major global source for volatile inorganic chlorine. We measured reactant and product species hypothesized to be associated with these chemical transformations as a function of phase, particle size, and altitude ove...
Published in: | Global Biogeochemical Cycles |
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1990
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ftharvardudash:oai:dash.harvard.edu:1/14121823 2023-05-15T17:34:44+02:00 The geochemical cycling of reactive chlorine through the marine troposphere Keene, William C. Pszenny, Alexander A. P. Jacob, Daniel James Duce, Robert A. Galloway, James N. Schultz-Tokos, Joseph J. Sievering, Herman Boatman, Joe F. 1990 application/pdf http://nrs.harvard.edu/urn-3:HUL.InstRepos:14121823 https://doi.org/10.1029/GB004i004p00407 en_US eng Wiley-Blackwell doi:10.1029/GB004i004p00407 Global Biogeochem. Cycles Keene, William C., Alexander A. P. Pszenny, Daniel J. Jacob, Robert A. Duce, James N. Galloway, Joseph J. Schultz-Tokos, Herman Sievering, and Joe F. Boatman. 1990. “The Geochemical Cycling of Reactive Chlorine through the Marine Troposphere.” Global Biogeochemical Cycles 4 (4) (December): 407–430. doi:10.1029/gb004i004p00407. 0886-6236 http://nrs.harvard.edu/urn-3:HUL.InstRepos:14121823 Journal Article 1990 ftharvardudash https://doi.org/10.1029/GB004i004p00407 https://doi.org/10.1029/gb004i004p00407 2022-04-05T06:46:44Z Heterogeneous reactions involving sea‐salt aerosol in the marine troposphere are the major global source for volatile inorganic chlorine. We measured reactant and product species hypothesized to be associated with these chemical transformations as a function of phase, particle size, and altitude over the North Atlantic Ocean during the summer of 1988. Concentrations of HCl were typically less than 1.0 ppbv near the sea surface and decreased with altitude and with distance from the U.S. east coast. Concentrations of Cl volatilized from aerosols were generally equivalent to the corresponding concentrations of HCl and ranged from less than detection limits to 125 nmol m STP. Highest absolute and percentage losses of particulate Cl were typically associated with elevated concentrations of anthropogenic combustion products. Concentrations of product nss SO and N0 in coarse aerosol fractions indicate that on average only 38% of measured Cl deficits could be accounted for by the combined effects of acid‐base desorption and reactions involving nonacidic N gases. We hypothesize a mechanism for the Cl loss initiated by reaction of O at sea‐salt aerosol surfaces, generating Cl followed by rapid photochemical conversion of Cl to HCl via Cl atoms (Cl˙) and eventual recapture of HCl by the aerosol. Simulations with a zero‐dimension (0‐D) photochemical model suggest that oxidation by Cl˙ may be an important tropospheric sink for dimethyl sulfide and hydrocarbons. Under low‐NO conditions, the rapid cycling of reactive Cl would provide a catalytic loss mechanism for O, which would possibly explain the low O concentrations often observed above the world's oceans. Engineering and Applied Sciences Version of Record Article in Journal/Newspaper North Atlantic Harvard University: DASH - Digital Access to Scholarship at Harvard Global Biogeochemical Cycles 4 4 407 430 |
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Open Polar |
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Harvard University: DASH - Digital Access to Scholarship at Harvard |
op_collection_id |
ftharvardudash |
language |
English |
description |
Heterogeneous reactions involving sea‐salt aerosol in the marine troposphere are the major global source for volatile inorganic chlorine. We measured reactant and product species hypothesized to be associated with these chemical transformations as a function of phase, particle size, and altitude over the North Atlantic Ocean during the summer of 1988. Concentrations of HCl were typically less than 1.0 ppbv near the sea surface and decreased with altitude and with distance from the U.S. east coast. Concentrations of Cl volatilized from aerosols were generally equivalent to the corresponding concentrations of HCl and ranged from less than detection limits to 125 nmol m STP. Highest absolute and percentage losses of particulate Cl were typically associated with elevated concentrations of anthropogenic combustion products. Concentrations of product nss SO and N0 in coarse aerosol fractions indicate that on average only 38% of measured Cl deficits could be accounted for by the combined effects of acid‐base desorption and reactions involving nonacidic N gases. We hypothesize a mechanism for the Cl loss initiated by reaction of O at sea‐salt aerosol surfaces, generating Cl followed by rapid photochemical conversion of Cl to HCl via Cl atoms (Cl˙) and eventual recapture of HCl by the aerosol. Simulations with a zero‐dimension (0‐D) photochemical model suggest that oxidation by Cl˙ may be an important tropospheric sink for dimethyl sulfide and hydrocarbons. Under low‐NO conditions, the rapid cycling of reactive Cl would provide a catalytic loss mechanism for O, which would possibly explain the low O concentrations often observed above the world's oceans. Engineering and Applied Sciences Version of Record |
format |
Article in Journal/Newspaper |
author |
Keene, William C. Pszenny, Alexander A. P. Jacob, Daniel James Duce, Robert A. Galloway, James N. Schultz-Tokos, Joseph J. Sievering, Herman Boatman, Joe F. |
spellingShingle |
Keene, William C. Pszenny, Alexander A. P. Jacob, Daniel James Duce, Robert A. Galloway, James N. Schultz-Tokos, Joseph J. Sievering, Herman Boatman, Joe F. The geochemical cycling of reactive chlorine through the marine troposphere |
author_facet |
Keene, William C. Pszenny, Alexander A. P. Jacob, Daniel James Duce, Robert A. Galloway, James N. Schultz-Tokos, Joseph J. Sievering, Herman Boatman, Joe F. |
author_sort |
Keene, William C. |
title |
The geochemical cycling of reactive chlorine through the marine troposphere |
title_short |
The geochemical cycling of reactive chlorine through the marine troposphere |
title_full |
The geochemical cycling of reactive chlorine through the marine troposphere |
title_fullStr |
The geochemical cycling of reactive chlorine through the marine troposphere |
title_full_unstemmed |
The geochemical cycling of reactive chlorine through the marine troposphere |
title_sort |
geochemical cycling of reactive chlorine through the marine troposphere |
publisher |
Wiley-Blackwell |
publishDate |
1990 |
url |
http://nrs.harvard.edu/urn-3:HUL.InstRepos:14121823 https://doi.org/10.1029/GB004i004p00407 |
genre |
North Atlantic |
genre_facet |
North Atlantic |
op_relation |
doi:10.1029/GB004i004p00407 Global Biogeochem. Cycles Keene, William C., Alexander A. P. Pszenny, Daniel J. Jacob, Robert A. Duce, James N. Galloway, Joseph J. Schultz-Tokos, Herman Sievering, and Joe F. Boatman. 1990. “The Geochemical Cycling of Reactive Chlorine through the Marine Troposphere.” Global Biogeochemical Cycles 4 (4) (December): 407–430. doi:10.1029/gb004i004p00407. 0886-6236 http://nrs.harvard.edu/urn-3:HUL.InstRepos:14121823 |
op_doi |
https://doi.org/10.1029/GB004i004p00407 https://doi.org/10.1029/gb004i004p00407 |
container_title |
Global Biogeochemical Cycles |
container_volume |
4 |
container_issue |
4 |
container_start_page |
407 |
op_container_end_page |
430 |
_version_ |
1766133653759328256 |