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Extraction and Characterization of Surfactants from Atmospheric Aerosols
Published on: April 21, 2017
Quantified Interfacial Affinity of Hydrogen Sulfate and Sulfate Speciation in Model Marine Aerosol Particles
Leslie M Ritchie1, Madison B Lester1, Arun K Sharma2
1Department of Biology, Chemistry, and Environmental Science, Christopher Newport University, Newport News, Virginia23606, United States.
Abstract:
Heterogeneous reactions occurring in atmospheric aerosols are crucial components of multiple chemical reaction cycles. Sulfate species exert substantial influence on many heterogeneous reaction mechanisms due to their abundance and speciation. Despite the importance of sulfate species on heterogeneous reactions, quantitative descriptions of interfacial affinity and sulfate species partitioning at interfaces remain incomplete. Here, we quantify the interfacial properties of HSO4-, using cetyltrimethylammonium hydrogen sulfate (CTAHS) reverse micelles (RMs), as model marine aerosol particles. Infrared spectra (IR) of CTAHS RMs were collected and analyzed using multivariate curve resolution-alternating least-squares (MCR-ALS). MCR-ALS analysis reveals that four distinct species contribute to the observed IR spectra, which we assign as CTA+-HSO4- contact pairs (CPs), interfacial HSO4-, core HSO4-, and core SO42-. Computational studies reveal that the CTA+-HSO4- CPs exist in two distinct orientations at the interface. Spectral contributions from each chemical species are used to determine the quantitative interfacial affinity (χInt.) of HSO4-. Our observations indicate that the cationic charge of the interface alters the ionic distribution of sulfate species compared to air-water interfaces, placing H3O+ below HSO4-.
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