Before We Inject: Assessing the Impact of Silica-Based Aerosols on Stratospheric Chemistry via a Kinetic Model Informed by Molecular Dynamics

Stratospheric aerosol injection (SAI) has been proposed as a geoengineering strategy to mitigate global warming by increasing Earth's albedo. Silica-based materials, such as diamond-doped silica aerogels, have shown promising optical properties, but their impact on stratospheric chemistry, ozone one in particular, remains largely unknown. Here, we present first-principles molecular dynamics (MD) simulations of the heterogeneous reaction between hydrogen chloride (HCl) and chlorine nitrate (ClONO₂), two main reservoirs of stratospheric chlorine and nitrogen species, on a dry and hydroxylated α-quartz silica interface, a surface that serves as a proxy for silica-based aerosols under low relative humidity and stratospheric conditions. Our results reveal a barrierless reaction pathway toward the formation of chlorine gas (Cl₂), a major contributor to stratospheric ozone loss. We design a heterogeneous kinetic model informed by our MD simulation and available experimental data: despite the barrierless formation of Cl₂, the higher surface affinities and partial pressures of HNO₃ and HCl compared to those of ClONO₂ result in a negligible reaction probability, <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msub><mml:mi>γ</mml:mi><mml:mrow><mml:mrow><mml:mi>C</mml:mi><mml:mi>l</mml:mi><mml:mi>O</mml:mi><mml:mi>N</mml:mi></mml:mrow><mml:msub><mml:mi>O</mml:mi><mml:mn>2</mml:mn></mml:msub></mml:mrow></mml:msub></mml:math>, upon chlorine nitrate collision with the silica surface. Since <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msub><mml:mi>γ</mml:mi><mml:mrow><mml:mrow><mml:mi>C</mml:mi><mml:mi>l</mml:mi><mml:mi>O</mml:mi><mml:mi>N</mml:mi></mml:mrow><mml:msub><mml:mi>O</mml:mi><mml:mn>2</mml:mn></mml:msub></mml:mrow></mml:msub></mml:math> enters as a proportionality constant in the definition of the heterogeneous reaction rate, our kinetic model indicates that the injection of silica-based aerosols may have only a limited impact on stratospheric ozone depletion driven by HCl and ClONO₂ chemistry. At the same time, our findings also underscore the scarcity of experimental data, the need of better theoretical frameworks for the inclusion of MD results into kinetic models, and the urgency for further experimental validations of silica-based SAI technologies before their deployment in climate intervention strategies.