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Atmospheric aerosol particles with a high viscosity may become inhomogeneously mixed during chemical processing. Models have predicted gradients in condensed phase reactant concentration throughout particles as the result of diffusion and chemical reaction limitations, termed chemical gradients. However, these have never been directly observed for atmospherically relevant particle diameters. We investigated the reaction between ozone and aerosol particles composed of xanthan gum and FeCl 2 and observed the in situ chemical reaction that oxidized Fe 2+ to Fe 3+ using X-ray spectromicroscopy. Iron oxidation state of particles as small as 0.2 μm in diameter were imaged over time with a spatial resolution of tens of nanometers. We found that the loss off Fe 2+ accelerated with increasing ozone concentration and relative humidity, RH. Concentric 2-D column integrated profiles of the Fe 2+ fraction, α , out of the total iron were derived and demonstrated that particle surfaces became oxidized while particle cores remained unreacted at RH = 0–20%. At higher RH, chemical gradients evolved over time, extended deeper from the particle surface, and Fe 2+ became more homogeneously distributed. We used the kinetic multi-layer model for aerosol surface and bulk chemistry (KM-SUB) to simulate ozone reaction constrained with our observations and inferred key parameters as a function of RH including Henry's Law constant for ozone, H O3 , and diffusion coefficients for ozone and iron, D O3 and D Fe , respectively. We found that H O3 is higher in our xanthan gum/FeCl 2 particles than for water and increases when RH decreased from about 80% to dry conditions. This coincided with a decrease in both D O3 and D Fe . In order to reproduce observed chemical gradients, our model predicted that ozone could not be present further than a few nanometers from a particle surface indicating near surface reactions were driving changes in iron oxidation state. However, the observed chemical gradients in α observed over hundreds of nanometers must have been the result of iron transport from the particle interior to the surface where ozone oxidation occurred. In the context of our results, we examine the applicability of the reacto-diffusive framework and discuss diffusion limitations for other reactive gas-aerosol systems of atmospheric importance.
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Rate of atmospheric brown carbon whitening governed by environmental conditions
Biomass burning organic aerosol (BBOA) in the atmosphere contains many compounds that absorb solar radiation, called brown carbon (BrC). While BBOA is in the atmosphere, BrC can undergo reactions with oxidants such as ozone which decrease absorbance, or whiten. The effect of temperature and relative humidity (RH) on whitening has not been well constrained, leading to uncertainties when predicting the direct radiative effect of BrC on climate. Using an aerosol flow-tube reactor, we show that the whitening of BBOA by oxidation with ozone is strongly dependent on RH and temperature. Using a poke-flow technique, we show that the viscosity of BBOA also depends strongly on these conditions. The measured whitening rate of BrC is described well with the viscosity data, assuming that the whitening is due to oxidation occurring in the bulk of the BBOA, within a thin shell beneath the surface. Using our combined datasets, we developed a kinetic model of this whitening process, and we show that the lifetime of BrC is 1 d or less below ∼1 km in altitude in the atmosphere but is often much longer than 1 d above this altitude. Including this altitude dependence of the whitening rate in a chemical transport model causes a large change in the predicted warming effect of BBOA on climate. Overall, the results illustrate that RH and temperature need to be considered to understand the role of BBOA in the atmosphere.
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- Award ID(s):
- 1936642
- PAR ID:
- 10485352
- Publisher / Repository:
- AAAS
- Date Published:
- Journal Name:
- Proceedings of the National Academy of Sciences
- Volume:
- 119
- Issue:
- 38
- ISSN:
- 0027-8424
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1073/pnas.2205610119
