Uptake of stratospheric species on minerals proposed for stratospheric aerosol injection

Abstract

Solid mineral-based particles have been proposed as alternatives to sulfates for climate intervention by stratospheric aerosol injection, as a means for improving optical or chemical characteristics and thereby minimize risks and uncertainties. However, the heterogeneous reactivity of solid particles with stratospheric trace gases, and possible implications to the ozone layer, is currently not fully constrained, particularly at stratospheric concentrations. We present a systematic comparative study of the uptake of HNO3, HCl, and NO2 on calcite, alumina, crystalline silica (quartz), and amorphous silica, using complementary Knudsen cell and flow reactor techniques. We find that NO2 uptake is weak on all surfaces, with estimated removal timescales indicating negligible impact on stratospheric nitrogen chemistry. Conversely, HCl uptake is substantial, with a pronounced concentration dependence consistent with surface site limited Langmuir adsorption. Extracting adsorption isotherms, we find that HCl surface coverage at stratospheric concentrations differs by four orders of magnitude between the surfaces, with calcite adsorbing the most and amorphous silica the least, suggesting a dominant role of surface acid-base character. Using HCl surface coverage as a proxy for ClONO2 reactive uptake, we estimate that amorphous silica could deplete substantially less ozone than calcite or alumina under equivalent injection scenarios. We find a marked difference between crystalline and amorphous silica, underscoring the sensitivity of heterogeneous chemistry to surface microstructure and the importance of selecting particles with low-reactivity surfaces in addition to considering bulk characteristics. Our findings motivate the development of particles with surfaces tailored for minimizing SAI risks and uncertainties, including minimal reactivity with stratospheric gases and background sulfate aerosols.