Ions and ion pairs are the species that lead to CaCO3 nucleation.

In viscous, organic-rich aerosol particles containing iron, sunlight may induce anoxic conditions that stabilize reactive oxygen species (ROS) and carbon-centered radicals (CCRs). In laboratory experiments, we show mass loss, iron oxidation and radical formation and release from photoactive organic particles containing iron. Our results reveal a range of temperature and relative humidity, including ambient conditions, that control ROS build up and CCR persistence in photochemically active, viscous organic particles. We find that radicals can attain high concentrations, altering aerosol chemistry and exacerbating health hazards of aerosol exposure. Our physicochemical kinetic model confirmed these results, implying that oxygen does not penetrate such particles due to the combined effects of fast reaction and slow diffusion near the particle surface, allowing photochemically-produced radicals to be effectively trapped in an anoxic organic matrix.

Nature possesses a unique control over the formation of CaCO 3 crystals that imparts fascinating mechanical properties to many CaCO 3 -based biomaterials. This high level of control is, at least in part, achieved through the use of certain soluble additives that influence the crystallization of amorphous CaCO 3 (ACC). Inspired by nature, excellent work has been performed to elucidate the influence of additives on the crystallization of ACC that is dispersed in bulk aqueous solutions or subjected to elevated temperatures. By contrast, very little is known about the influence of additives on the crystallization of ACC when exposed to a humid environment or elevated pressures. This incomplete understanding restricts the range of properties that can be obtained in synthetic CaCO 3 -based biomaterials. To address this shortcoming, we study the influence of additives on the humidity-and pressure-induced crystallization of ACC. We find that the humidity-induced crystallization of ACC follows a distinctly different pathway than the pressure-induced one. As a result, the influence of additives on the crystallization kinetics of ACC, and hence, the size, morphology, structure, and orientation of the resulting CaCO 3 crystals, differs considerably. These insights offer new opportunities to design CaCO 3 -based biomaterials whose mechanical properties more closely resemble natural ones.

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.