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Multiphase Photochemistry of Iron-Chloride Containing Particles as a Source of Aqueous Chlorine Radicals and Its Effect on Sulfate Production

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    Anthropogenic Impacts on the Atmosphere

    Multiphase Photochemistry of Iron-Chloride Containing Particles as a Source of Aqueous Chlorine Radicals and Its Effect on Sulfate Production
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    Environmental Science & Technology

    Cite this: Environ. Sci. Technol. 2020, 54, 16, 9862–9871
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    https://doi.org/10.1021/acs.est.0c01540
    Published July 15, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    Photolysis of iron chlorides is a well-known photolytic source of Cl• in environmental waters. However, the role of particulate chlorine radicals (Cl• and Cl2•–) in their multiphase oxidative potential has been much less explored. Herein, we examine the effect of Cl•/Cl2•– produced from photolysis of particulate iron chlorides on atmospheric multiphase oxidation. As a model system, experiments on multiphase oxidation of SO2 by Cl•/Cl2•– were performed. Fast sulfate production from SO2 oxidation was observed with reactive uptake coefficients of ∼10–5, comparable to the values necessary for explaining the observations in the haze events in China. The experimental and modeling results found a good positive correlation between the uptake coefficient, γSO2, and the Cl• production rate, d[Cl•]/dt, as γSO2 = 5.3 × 10–6 × log(d[Cl•]/dt) + 4.9 × 10–5. When commonly found particulate dicarboxylic acids (oxalic acid or malonic acid) were added, sulfate production was delayed due to the competition of Fe3+ between chloride and the dicarboxylic acid for its complexation at the initial stage. After the delay, comparable sulfate production was observed. The present study highlights the importance of photochemistry of particulate iron chlorides in multiphase oxidation processes in the atmosphere.

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    • Text describing calculations of photon fluxes, kinetic modeling of sulfate production, calculations of reactive uptake coefficients of SO2, comparison of sulfate production pathways, •OH and Cl– reaction as a potential source of Cl•, and reactivity of glyoxal with chlorine radicals. Tables listing concentrations of chloride, iron, sulfate, and carboxylic acids observed in fine particles across China, reactions considered in the kinetic modeling, molar absorptivity and quantum yield of photolytic species, and initial conditions of each experiment and modeling results. Figures of schematic of experimental setup, wavelength-dependent intensity and photon fluxes of irradiation, replicate experiments, relative uncertainty of measured sulfate concentration, sulfate production as a function of irradiation intensity, pH-dependent distributions of iron complexes, variations of particle pH during reaction, time-dependent Raman spectra of the irradiated particle containing Fe3+, OA, and perchlorate, model fitting to measured sulfate production in the presence and absence of organic compounds, simulated concentrations of important species during reactions in the presence and absence of organic compounds, comparison of sulfate production pathways in the presence and absence of organic compounds, decay of glyoxal by chlorine radicals, emergence of new Raman peak during glyoxal oxidation by Cl•, photodecay of 2NB as a function of irradiation time, wavelength-dependent molar absorptivity of 2NB, and reaction mechanisms involving iron and malonate (PDF)

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    Environmental Science & Technology

    Cite this: Environ. Sci. Technol. 2020, 54, 16, 9862–9871
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.est.0c01540
    Published July 15, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

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