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  1. The acidity of atmospheric aerosols controls their impacts on heterogeneous and multiphase reactions, cloud formation, and human health. Recently, it has been shown that multiphase buffering can shift aerosol pH substantially compared to bulk solutions. Here, we highlight a unique type of multiphase buffering for aerosols that occurs when organic acids partition from aqueous salt aerosols upon acidification with a strong acid. In this case, rather than lowering the pH of the aerosol, titration with strong acids lowers the organic fraction within the aerosol while maintaining constant pH. We investigate evaporation rates for the model system lactic acid as well as other atmospherically-relevant species such as acetic, butyric, and methacrylic acids. We demonstrate that the timescales for evaporation of organic acids from aerosols are on the order of minutes, comparable to acidification rates in the atmosphere. The organic acid evaporation we observe for lactic acid in salt aerosols is enhanced compared to bulk measurements within what is expected based on differences in surface to volume ratios, indicating surface effects are important. In addition, we show that a salting-out effect drives small organic molecules to the surface, where they quickly evaporate, reducing acidity and causing a “superbuffering” effect. Our results canmore »explain why aerosols in the pH range from 2 to 4 are able to resist further acidification by strong acids in the atmosphere. Overall, this work highlights unique properties of concentrated aerosols and demonstrates how inorganic ions and organic compounds together control multiphase buffering in the atmosphere.« less
    Free, publicly-accessible full text available February 16, 2024
  2. Free, publicly-accessible full text available December 6, 2023
  3. Free, publicly-accessible full text available December 6, 2023
  4. Abstract Ocean waves transfer sea spray aerosol (SSA) to the atmosphere, and these SSA particles can be enriched in organic matter relative to salts compared to seawater ratios. A fundamental understanding of the factors controlling the transfer of biogenic organic matter from the ocean to the atmosphere remains elusive. Field studies that focus on understanding the connection between organic species in seawater and SSA are complicated by the numerous processes and sources affecting the composition of aerosols in the marine environment. Here, an isolated ocean–atmosphere system enables direct measurements of the sea–air transfer of different classes of biogenic organic matter over the course of two phytoplankton blooms. By measuring excitation–emission matrices of bulk seawater, the sea surface microlayer, and SSA, we investigate time series of the transfer of fluorescent species including chlorophyll-a, protein-like substances, and humic-like substances. Herein, we show the emergence of different molecular classes in SSA at specific times over the course of a phytoplankton bloom, suggesting that SSA chemical composition changes over time in response to changing ocean biological conditions. We compare the temporal behaviors for the transfer of each component, and discuss the factors contributing to differences in transfer between phases.
    Free, publicly-accessible full text available December 1, 2023
  5. Abstract The reactive uptake of N 2 O 5 to aqueous aerosol is a major loss channel for nitrogen oxides in the troposphere. Despite its importance, a quantitative picture of the uptake mechanism is missing. Here we use molecular dynamics simulations with a data-driven many-body model of coupled-cluster accuracy to quantify thermodynamics and kinetics of solvation and adsorption of N 2 O 5 in water. The free energy profile highlights that N 2 O 5 is selectively adsorbed to the liquid–vapor interface and weakly solvated. Accommodation into bulk water occurs slowly, competing with evaporation upon adsorption from gas phase. Leveraging the quantitative accuracy of the model, we parameterize and solve a reaction–diffusion equation to determine hydrolysis rates consistent with experimental observations. We find a short reaction–diffusion length, indicating that the uptake is dominated by interfacial features. The parameters deduced here, including solubility, accommodation coefficient, and hydrolysis rate, afford a foundation for which to consider the reactive loss of N 2 O 5 in more complex solutions.
    Free, publicly-accessible full text available December 1, 2023
  6. Free, publicly-accessible full text available November 16, 2023
  7. Marine chromophoric dissolved organic matter (m-CDOM) mediates many vital photochemical processes at the ocean's surface. Isolating m-CDOM within the chemical complexity of marine dissolved organic matter has remained an analytical challenge. The SeaSCAPE campaign, a large-scale mesocosm experiment, provided a unique opportunity to probe the in situ production of m-CDOM across phytoplankton and microbial blooms. Results from mass spectrometry coupled with UV-VIS spectroscopy reveal production of a chemodiverse set of compounds well-correlated with increases in absorbance after a bacterial bloom, indicative of autochthonous m-CDOM production. Notably, many of the absorbing compounds were found to be enriched in nitrogen, which may be essential to chromophore function. From these results, quinoids, porphyrins, flavones, and amide-like compounds were identified via structural analysis and may serve as important photosensitizers in the marine boundary layer. Overall, this study demonstrates a step forward in identifying and characterizing m-CDOM using temporal mesocosm data and integrated UV-VIS spectroscopy and mass spectrometry analyses.
    Free, publicly-accessible full text available October 19, 2023
  8. Free, publicly-accessible full text available October 5, 2023