Photochemical degradation of iron(III) citrate/citric acid aerosol quantified with the combination of three complementary experimental techniques and a kinetic process model

Iron(III) carboxylate photochemistry plays an important role in aerosol aging, especially in the lower troposphere. These complexes can absorb light over a broad wavelength range, inducing the reduction of iron(III) and the oxidation of carboxylate ligands. In the presence of inline-formulaO₂, the ensuing radical chemistry leads to further decarboxylation, and the production of inline-formula^.OH, inline-formula $M3inlinescrollmathmlchem{\mathrm{normal\; HO}}_{\mathrm{normal\; 2}}^{.}$ 23pt13ptsvg-formulamathimg2c010506db919fad645157cdabe19d7d acp-21-315-2021-ie00001.svg23pt13ptacp-21-315-2021-ie00001.png , peroxides, and oxygenated volatile organic compounds, contributing to particle mass loss. The inline-formula^.OH, inline-formula $M5inlinescrollmathmlchem{\mathrm{normal\; HO}}_{\mathrm{normal\; 2}}^{.}$ 23pt13ptsvg-formulamathimg6b488196364f76983e4f000eb49165d7 acp-21-315-2021-ie00002.svg23pt13ptacp-21-315-2021-ie00002.png , and peroxides in turn reoxidize iron(II) back to iron(III), closing a photocatalytic cycle. This cycle is repeated, resulting in continual mass loss due to the release of inline-formulaCO₂ and other volatile compounds. In a cold and/or dry atmosphere, organic aerosol particles tend to attain highly viscous states. While the impact of reduced mobility of aerosol constituents on dark chemical reactions has received substantial attention, studies on the effect of high viscosity on photochemical processes are scarce. Here, we choose iron(III) citrate (inline-formulaFe^III(Cit)) as a model light-absorbing iron carboxylate complex that induces citric acid (CA) degradation to investigate how transport limitations influence photochemical processes. Three complementary experimental approaches were used to investigate kinetic transport limitations. The mass loss of single, levitated particles was measured with an electrodynamic balance, the oxidation state of deposited particles was measured with X-ray spectromicroscopy, and inline-formula $M8inlinescrollmathmlchem{\mathrm{normal\; HO}}_{\mathrm{normal\; 2}}^{.}$ 23pt13ptsvg-formulamathimge415bab72aa30c7cb24864dedd33f404 acp-21-315-2021-ie00003.svg23pt13ptacp-21-315-2021-ie00003.png radical production and release into the gas phase was observed in coated-wall flow-tube experiments. We observed significant photochemical degradation with up to 80 % mass loss within 24 h of light exposure. Interestingly, we also observed that mass loss always accelerated during irradiation, resulting in an increase of the mass loss rate by about a factor of 10. When we increased relative humidity (RH), the observed particle mass loss rate also increased. This is consistent with strong kinetic transport limitations for highly viscous particles. To quantitatively compare these experiments and determine important physical and chemical parameters, a numerical multilayered photochemical reaction and diffusion (PRAD) model was developed that treats chemical reactions and the transport of various species. The PRAD model was tuned to simultaneously reproduce all experimental results as closely as possible and captured the essential chemistry and transport during irradiation. In particular, the photolysis rate of inline-formulaFe^III, the reoxidation rate of inline-formulaFe^II, inline-formula $M11inlinescrollmathmlchem{\mathrm{normal\; HO}}_{\mathrm{normal\; 2}}^{.}$ 23pt13ptsvg-formulamathimg5f107cc8d9047ff8575335410c056d32 acp-21-315-2021-ie00004.svg23pt13ptacp-21-315-2021-ie00004.png production, and the diffusivity of inline-formulaO₂ in aqueous inline-formulaFe^III(Cit) inline-formula∕ CA system as function of RH and inline-formulaFe^III(Cit) inline-formula∕ CA molar ratio could be constrained. This led to satisfactory agreement within modelpage316 uncertainty for most but not all experiments performed. Photochemical degradation under atmospheric conditions predicted by the PRAD model shows that release of inline-formulaCO₂ and repartitioning of organic compounds to the gas phase may be very important when attempting to accurately predict organic aerosol aging processes.