Heterogeneous and Photosensitized Oxidative Degradation Kinetics of the Plastic Additive Bisphenol-A in Sea Spray Aerosol Mimics

Abstract

Plastics have become ubiquitous in the world's oceans, and recent work indicates that they can transfer from the ocean to the atmosphere in sea spray aerosol (SSA). Hazardous chemical residues in plastics, including bisphenol-A (BPA), represent a sizable fraction of consumer plastics and have been measured consistently in air over both terrestrial and marine environments. However, the chemical lifetimes of BPA and mechanisms by which plastic residues degrade with respect to photochemical and heterogeneous oxidation processes in aerosols are unknown. Here, we present the photosensitized and OHinitiated heterogeneous oxidation kinetics of BPA in the aerosol phase consisting of pure-component BPA and internal mixtures of BPA, NaCl, and dissolved photosensitizing organic matter. We found that photosensitizers enhanced BPA degradation in binary-component BPA + photosensitizer aerosol mixtures when irradiated in the absence of OH. OH-initiated degradation of BPA was enhanced in the presence of NaCl with and without photosensitizing species. We attribute this enhanced degradation to greater mobility and thus reaction probability between BPA, OH, and reactive chlorine species (RCS) formed through reaction between OH and dissolved Cl − in the more liquid-like aerosol matrix in the presence of NaCl. Addition of the photosensitizers in the ternary-component BPA + NaCl + photosensitizer aerosol led to no enhancement in the degradation of BPA following light exposure compared to the binary-component BPA + NaCl aerosol. This was attributed to quenching of triplet state formation by dissolved Cl − in the less viscous aqueous aerosol mixtures containing NaCl. Based upon measured second-order heterogeneous reaction rates, the estimated lifetime of BPA with respect to heterogeneous oxidation by OH is one week in the presence of NaCl compared to 20 days in the absence of NaCl. This work highlights the important heterogeneous and photosensitized reactions and the role of phase state, which affect the lifetimes of hazardous plastic pollutants in SSA with implications for understanding pollutant transport and exposure risks in coastal marine environments.

Effects of Relative Humidity and Phase on the Molecular Detection of Nascent Sea Spray Aerosol Using Extractive Electrospray Ionization

“…A different explanation is the increased mobility of reactants resulting from the reduced SSA particle viscosity at higher RH. ,, This would heighten diffusive mixing and facilitate interactions between Na + at the particle surface and the molecular components in nascent SSA, akin to the enhanced reaction probabilities between molecules at the particle interface and in the bulk of lower viscosity aerosols at higher RH. ,, …”

“…The nascent SSA molecular composition was measured using an extractive electrospray ionization time-of-flight mass spectrometer (Aerodyne Research Inc. and Tofwerk AG). EESI exposes aerosol samples to electrospray droplets, producing a signal proportional to the mass concentration of aerosol components. ,,, The reagent ion spray was generated by passing the reagent solution through a 365 μm/150 μm OD/ID fused silica capillary (IDEX Health and Science, LLC) at 350 mbar, charged at −2500 V in negative mode and +2500 V in positive mode.…”

Enhanced HONO Formation from Aqueous Nitrate Photochemistry in the Presence of Marine Relevant Organics: Impact of Marine-Dissolved Organic Matter (m-DOM) Concentration on HONO Yields and Potential Synergistic Effects of Compounds within m-DOM

“…Overall, this study sheds light on the daytime HONO formation through m-DOM photosensitization of nitrates. Yet, the role of chloride ions in natural settings should be considered given recent findings. ,,, …”

“…Yet, the role of chloride ions in natural settings should be considered given recent findings. 15 , 61 , 63 , 64 …”