A revisit of the interaction of gaseous ozone with aqueous iodide. Estimating the contributions of the surface and bulk reactions

The main source of atmospheric iodine is the heterogeneous reaction of aqueous iodide (I‐ ) with ozone (O3), which takes place in surface seawater and probably in sea‐salt aerosols. However, there are seemingly contradictory conclusions about whether this heterogeneous reaction occurs in the bulk of...

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Detalles Bibliográficos
Autores: Moreno, Carolina, Gálvez González, Óscar, López-Arza Moreno, Vicente, Espíldora García, Eva María, Baeza Romero, María Teresa
Tipo de recurso: artículo
Fecha de publicación:2018
País:España
Institución:Universidad de Castilla-La Mancha
Repositorio:RUIdeRA. Repositorio Institucional de la UCLM
OAI Identifier:oai:ruidera.uclm.es:10578/29042
Acceso en línea:http://hdl.handle.net/10578/29042
Access Level:acceso abierto
Palabra clave:gaseous ozone
aqueous iodide
atmospheric iodine
ozone (O3)
surface seawater
Descripción
Sumario:The main source of atmospheric iodine is the heterogeneous reaction of aqueous iodide (I‐ ) with ozone (O3), which takes place in surface seawater and probably in sea‐salt aerosols. However, there are seemingly contradictory conclusions about whether this heterogeneous reaction occurs in the bulk of the aqueous phase, via O3 dissolution, or at the aqueous surface, via O3 adsorption. In this work, the ozone uptake coefficient has been calculated as a function of the concentration of aqueous iodide ([I‐ ]aq) and gaseous ozone near the aqueous surface ([O3]gs) by estimating parameters of the resistor model using results of previous studies. The calculated uptake coefficients suggest that the aqueous‐phase reaction dominates at low I ‐ concentrations (about <10‐4 mol/L), regardless of [O3]gs, and also at sufficiently high [O3]gs (about >10 ppm), regardless of [I‐ ]aq. In contrast, the surface reaction dominates at high [I‐ ]aq (about >10‐4 mol/L) as long as [O3]gs is low enough (about <10 ppm). This trend is able to reconcile previous studies of this reaction, and is a consequence of several factors, including the high surface excess of both reactants ozone and iodide. Given the typical O3 concentrations in the troposphere and the possible I ‐ concentrations and O3 solubilities in sea‐salt aerosols, the surface reaction may compete with the aqueous phase reaction in sea‐salt aerosols, unlike in surface seawater, where the aqueous‐phase reaction prevails. The rate constant of the surface reaction has been estimated as (5‐500)10^‐13 cm2 molecule‐1 s‐1 .