Simulation chamber study of the spectral mass absorption, scattering, and extinction cross-sections (MAC, MSC, MEC) of fresh and aged combustion aerosols

Carbonaceous soot particles are formed during incomplete combustion of fossil fuels, biofuels or biomass and are considered to be a significant proportion of aerosol emission, especially in polluted areas, and to contain light-absorbing carbon fractions. The light-absorbing carbon components make these particles exhibit positive radiative forcing and thus they contribute to atmospheric warming processes. The exact contribution to this process however still has significant uncertainties. One of the sources of uncertainty is related to the capacity to accurately describe soot spectral optical properties (MAC/MSC/MEC - mass absorption/scattering/extinction cross-sections in m²g^-1; CRI - complex refractive index), due to significant uncertainties for key measurements like the absorption coefficient or absorbing mass fraction. A second source is considered to be the change of the optical properties with the variable physico-chemical state of soot (e.g. chemical composition, morphology, primary particle size, aggregate size distribution, coating and mixing state) which depends on (i) the combustion conditions/sources  and is (ii) known to change during atmospheric lifetime due to ageing and mixing processes.

The present work aims at providing new measurements of soot spectral optical properties and investigating their dependence on particles’ physico-chemical state and the role of measurement uncertainties. For this, a set of original experiments was performed in the 4.3m³ CESAM atmospheric simulation chamber (https://cesam.cnrs.fr/) on soot aerosols generated by a commercial propane diffusion flame soot generator (miniCAST model 6204 TYPE C, JING). In these experiments, the variability of soot properties due to (i) generation and (ii) atmospheric ageing was explored. Different combustion conditions going from fuel–leaner to fuel-richer were set to produce soot aerosol with different effective densities, EC/TC-ratios ranging from 0.8 ± 0.1 to 0.0 ± 0.1 and size distributions with median diameters between 30 and 120 nm. Selected aerosols were subjected to ageing in a N₂/O₂ atmosphere under simulated atmospheric conditions (humid, with/without illumination, up to 26 hours lifetime). In these conditions, physical and chemical ageing, under the presence of different gaseous phases (O₃, SO₂) and addition of a second aerosol phase produced by photo-oxidation of SO₂ or the ozonolysis of α-pinene, led to changes in the physico-chemical properties of the soot.

State-of-the-art techniques were used to generate an extensive dataset of physico-chemical parameters (mass concentration, morphology, effective density, composition, size distribution) and spectral optical properties (absorption, scattering, extinction coefficients) for different soot aerosols and different ageing states of these. The absorption coefficient in particular was measured by both filter-based (AE - Aethalometer, MAAP - Multi-Angle Absorption Photometer, MWAA – Multi-Wavelength Absorbance Analyzer, PP_UniMI - Polar Photometer by University of Milano) and extinction minus scattering techniques. The MAC, MSC and MEC datasets, retrieved by combining these measurements, will be presented for the ensemble of chamber experiments and the variability of these parameters in link with variations in the particles’ physico-chemical properties will be discussed together with key relevant uncertainties.