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Environ Sci Process Impacts ; 21(1): 63-73, 2019 Jan 23.
Artigo em Inglês | MEDLINE | ID: mdl-30534711


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.

Atmosfera/química , Brometos/química , Bromo/química , Ozônio/química , Ácido Cítrico/química , Compostos Orgânicos , Oxirredução , Ozônio/análise , Sais , Compostos de Sódio/química , Solubilidade , Temperatura , Viscosidade
Nat Commun ; 8(1): 700, 2017 09 26.
Artigo em Inglês | MEDLINE | ID: mdl-28951540


Oxidation of bromide in aqueous environments initiates the formation of molecular halogen compounds, which is important for the global tropospheric ozone budget. In the aqueous bulk, oxidation of bromide by ozone involves a [Br•OOO-] complex as intermediate. Here we report liquid jet X-ray photoelectron spectroscopy measurements that provide direct experimental evidence for the ozonide and establish its propensity for the solution-vapour interface. Theoretical calculations support these findings, showing that water stabilizes the ozonide and lowers the energy of the transition state at neutral pH. Kinetic experiments confirm the dominance of the heterogeneous oxidation route established by this precursor at low, atmospherically relevant ozone concentrations. Taken together, our results provide a strong case of different reaction kinetics and mechanisms of reactions occurring at the aqueous phase-vapour interface compared with the bulk aqueous phase.Heterogeneous oxidation of bromide in atmospheric aqueous environments has long been suspected to be accelerated at the interface between aqueous solution and air. Here, the authors provide spectroscopic, kinetic and theoretical evidence for a rate limiting, surface active ozonide formed at the interface.

Angew Chem Int Ed Engl ; 54(30): 8728-31, 2015 Jul 20.
Artigo em Inglês | MEDLINE | ID: mdl-26069026


Identification of active species and the rate-determining reaction steps are crucial for optimizing the performance of oxygen-storage materials, which play an important role in catalysts lowering automotive emissions, as electrode materials for fuel cells, and as antioxidants in biomedicine. We demonstrated that active Ce(3+) species in a ceria-supported platinum catalyst during CO oxidation are short-lived and therefore cannot be observed under steady-state conditions. Using time-resolved resonant X-ray emission spectroscopy, we quantitatively correlated the initial rate of Ce(3+) formation under transient conditions to the overall rate of CO oxidation under steady-state conditions and showed that ceria reduction is a kinetically relevant step in CO oxidation, whereas a fraction of Ce(3+) was present as spectators. This approach can be applied to various catalytic processes involving oxygen-storage materials and reducible oxides to distinguish between redox and nonredox catalytic mechanisms.