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

Abstract

Abstract. 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 O2, the ensuing radical chemistry leads to further decarboxylation, and the production of .OH, HO2., peroxides, and oxygenated volatile organic compounds, contributing to particle mass loss. The .OH, HO2., 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 CO2 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 (FeIII(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 HO2. 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 FeIII, the reoxidation rate of FeII, HO2. production, and the diffusivity of O2 in aqueous FeIII(Cit) ∕ CA system as function of RH and FeIII(Cit) ∕ CA molar ratio could be constrained. This led to satisfactory agreement within model uncertainty for most but not all experiments performed. Photochemical degradation under atmospheric conditions predicted by the PRAD model shows that release of CO2 and repartitioning of organic compounds to the gas phase may be very important when attempting to accurately predict organic aerosol aging processes.

Ice nucleation imaged with X-ray spectro-microscopy

“…107,108 In situ microreactors have been previously developed and used in the eld of atmospheric chemistry and physics for investigating water uptake and phase transformations, 81,[93][94][95][96][97] and chemical 98,99 and photochemical reaction cycling. 100,109 2.1 INXCell design and description Fig. 1 shows a schematic of the INXCell that highlights the two most important design features.…”

Nitrate Photolysis in Mixed Sucrose–Nitrate–Sulfate Particles at Different Relative Humidities

“…Organic compounds account for a large proportion (20–90%) of the mass of atmospheric particles , Dependent on their functional groups and molecular structures, some organics can make the particle viscous, impeding gas-particle partitioning, − water uptake, , and (photo)­chemical reactions. − Viscous particles thus become more “inert” toward heterogeneous oxidation due to the inefficient diffusion of gas-phase reactants. However, by generating oxidants within particles, nitrate photolysis may be an alternative route to promote oxidation and alter the physicochemical properties of the particles.…”

Growth of microaerophilic Fe(II)‐oxidizing bacteria using Fe(II) produced by Fe(III) photoreduction

“…To ensure that all available Fe(II) was produced by Fe(III) photoreduction, we selected a mixture of Fe(III) (in the form of ferrihydrite) and citrate as organic ligand. Fe(III) photoreduction of inorganic Fe(III) species is insignificant at circumneutral pH (King et al, 1993), but citrate forms photo-susceptible complexes with Fe(III) that readily undergo Fe(III) photoreduction upon exposure to blue or UV light (Dou et al, 2021;Faust & Zepp, 1993).…”

“…According to Dou et al (2021), the diffusivity factor (normalized to water) of O 2 is larger than the diffusivity factors of Fe(II) and Fe(III)citrate. Interestingly, O 2 did not reach the bottom of the inoculated gradient tubes in UV and blue light incubation after 6 days (as it did in the negative control tubes) but only penetrated 10-12 mm into the top layer from the air headspace (Figure 3f,g).…”