Heavy aerosol loading threatens human health across the globe and is typically related to photochemical processing associated with emission of organic, inorganic and trace metal compounds. Aerosol particles dominated by organic solutes may attain a high or ultra-high viscosity (> 1012 Pa s) becoming solid-like in cold and dry air, limiting diffusion of organic and reactive molecules through the particle volume, thus slowing chemistry. In contrast, illumination and thus photochemistry to produce radicals may occur through the bulk of light absorbing particles irrespective of diffusion limitations, but its efficiency is not well constrained. We investigated iron oxidation state changes in particles containing various concentrations of citric acid, iron(III)-citrate, copper(II)-citrate and copper(II) salts using environmental X-ray spectromicroscopy with control of relative humidity, RH, and temperature, T. Chemical images of single aerosol particles with resolution currently as low as 35 × 35 nm2 were acquired in a humidified microreactor revealing spatial gradients in the concentration of iron(II), iron(III), copper(I) and copper(II) compounds. We have also quantified the CO2 formation from coated wall flowtube experiments due to decarboxylation subsequent to ligand to metal charge transfer and the condensed and gas phase products using proton-transfer reaction mass spectrometry to characterize the complex chemical reaction scheme. We observed that iron was largely reduced in particles despite being in an oxygen atmosphere immediately after exposure to atmospherically relevant UV light exposure i.e. using 375 nm LED and a measured intensity of 3 W m‑2 for 15 min. This implies that oxygen uptake, diffusion, reactive oxygen species generation and metal reoxidation reactions were slow compared to photochemical reduction. When relative humidity, RH < 50%, there was significant oxidation only near the surface of particles extending over scales of tens of nanometers. At higher RH, particles became more homogeneously oxidized. We concluded that O2 reaction and diffusion is limited and results in organic radical persistence in particles. In the presence of copper, iron was immediately oxidized after UV exposure, which is in sharp contrast to particles without copper. If oxygen is limited, and therefore cannot quickly reoxidize iron, then copper oxidation reactions or cross iron-copper redox reactions must generate more radicals than expected. We aim to improve the kinetic treatment of radical production from copper and iron, which can affect redox cycling in organic aerosol. Such information is necessary for the accurate prediction of aerosol phase radical generation, chemical loss of oxygenated organic aerosol dominated by carboxyl functionalities and identifying diffusion limitations leading to the preservation of reactive oxygen species and free radicals.

Here we demonstrate a method for performing X-ray absorption spectroscopy (XAS) on airborne aerosols. XAS provides unique insight into elemental composition, chemical and phase state, local coordination and electronic structure of both crystalline and amorphous matter. The aerosol is generated from different salt solutions using a commercial atomizer and dried using a diffusion drier. Embedded in a carrier gas, the aerosol is guided into the experimental chamber for XAS analysis. Typical particle sizes range from some 10 to a few 100 nm. Inside the chamber the aerosol bearing gas is then confined into a region of about 1-2 cm3 in size, by a pure flow of helium, generating a stable free-flowing stream of aerosol. It is hit by a monochromatic X-ray beam, and the emitted fluorescent light is used for spectroscopic analysis. Using an aerosol generated from CaCl2, KCl, and (NH4)2SO4 salt solutions, we demonstrate the functionality of the system in studying environmentally relevant systems. In addition, we show that the detection limits are sufficient to also observe subtle spectroscopic signatures in XAS spectra with integration times of about 1-2 hours using a bright undulator beamline. This novel setup opens new research opportunities for studying the nucleation of new phases in multicomponent aerosol systems in situ, and for investigating (photo-) chemical reactions on airborne matter, as relevant to both atmospheric science and also for general chemical application.

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.

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 CaCO3 crystals that imparts fascinating mechanical properties to many CaCO3-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 CaCO3 (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 CaCO3-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 CaCO3 crystals, differs considerably. These insights offer new opportunities to design CaCO3-based biomaterials whose mechanical properties more closely resemble natural ones.

A facile aerosol-based method for the synthesis of pure and stable amorphous calcium carbonate (ACC) is presented. The method relies on the instantaneous carbonation of calcium hydroxide aerosols with carbon dioxide followed by rapid drying of the freshly formed ACC. The ACC display extended stability against humidity induced crystallization.

Under ambient conditions, marine organisms are able to synthesize a variety of functional materials, ranging from eye lenses to protective shells through the meticulous control over magnesium incorporation into calcite during its crystallization. The mechanistic understanding of how they achieve such exquisite control, at a constant magnesium-to-calcium ratio and at ambient conditions, is important in the development of bioinspired functional materials. However, the replication of these processes in the laboratory is still challenging. Herein, we present a systematic study on how to tune magnesium incorporation into calcite and polymorph selection in the Ca-Mg-CO3 system through the precise control of the inorganic solutions chemistry at ambient conditions of temperature and pressure, and at a magnesium-to-calcium ratio of 5:1, which is analogous to the ratio found in most seas. By varying the pH, cation-to-anion ratio, and solution concentration, the controlled synthesis of magnesium calcites with 10-45% magnesium was achieved at room temperature. The mechanism of formation is consistent with that observed during biomineralization, during which an intermediate magnesium-rich amorphous calcium carbonate (Mg-ACC) phase forms first and later transforms into high magnesium calcite. Once crystallization occurs, the magnesium calcites that form are stable in solution and exhibit slow growth through Ostwald ripening. Our findings suggest that the precise control of saturation levels is key in driving nucleation and crystallization.

Baryte is of interest to nuclear waste disposal as the main scavenger of Ra-226, a long-lived nuclide playing a major role in the safety assessment of planned disposal sites. In specific repository setups, Ba and Ra released from the nuclear waste will react with sulphate-rich pore water, potentially leading to formation of Ra-bearing baryte. Baryte has a complex kinetic behaviour and its precipitation may strongly be inhibited. Because highly supersaturated solutions may persist metastably, it can be anticipated that the migration of Ra through the repository near-field will strongly depend on parameters related to nucleation and precipitation kinetics, so that thermodynamic equilibrium calculations will not be sufficient for a reliable prediction of Ra-226 mobility. In this study, we implement Classical Nucleation Theory (CNT) and a saturation-state dependent precipitation rate equation into a Lattice-Boltzmann (LB) reactive transport code to model Ra-bearing baryte precipitation within a porous medium analogous to fragmented nuclear waste glass. In the simulations, baryte precipitation is induced by counter-diffusion of BaCl2 and Na2SO4 solutions. Radium co-precipitation is taken into account by assuming a fixed partition coefficient and constant Ra concentration at the BaCl2 injection boundary. Both homogeneous and heterogeneous growth were considered. Critical CNT parameters, particularly supersaturation-dependent induction times, were calibrated against independent turbidity and X-ray absorption experiments. The model allows exploring the influence of baryte nucleation/precipitation kinetics on the partitioning of Ra between aqueous phase and solid at the pore (micrometre) scale. Our results indicate that quantitative knowledge of kinetic and nucleation parameters is essential to predict radionuclide transport towards the geosphere in nuclear waste repository systems.

The understanding of nucleation and crystallization is fundamental in science and technology. In solution, these processes are complex involving multiple transformations from ions and ion pairs through amorphous intermediates to multiple crystalline phases. X-ray absorption spectroscopy (XAS), which is sensitive to liquid, amorphous and crystalline phases offers prospects of demystifying these processes. However, for low Z elements the use of in situ X-ray absorption spectroscopy requires the tender X-ray range, which is often limited by vacuum requirements thereby complicating these measurements. To overcome these challenges, we developed a versatile and user-friendly droplet-based in situ X-ray absorption spectroscopy cell for studying crystallization processes. Time-resolved in situ experiments under ambient conditions are carried out in the cell whilst the cell is mounted in the vacuum chamber of a tender X-ray beamline. By following changes in the Ca K-edge X-ray absorption near edge structure (XANES), we captured in situ the intermediate phases involved during calcium carbonate crystallization from aqueous solutions. In addition, through linear combination fitting it was possible to qualitatively observe the evolution of each phase during the reaction demonstrating the potential of the cell in studying complex multiphase chemical processes.

Mechanisms of CaCO3 nucleation from solutions that depend on multistage pathways and the existence of species far more complex than simple ions or ion pairs have recently been proposed. Herein, we provide a tightly coupled theoretical and experimental study on the pathways that precede the initial stages of CaCO3 nucleation. Starting from molecular simulations, we succeed in correctly predicting bulk thermodynamic quantities and experimental data, including equilibrium constants, titration curves, and detailed x- ray absorption spectra taken from the supersaturated CaCO3 solutions. The picture that emerges is in complete agreement with classical views of cluster populations in which ions and ion pairs dominate, with the concomitant free energy landscapes following classical nucleation theory.

A comparative study of ex-situ and in-operando X-ray diffraction experiments using the fast lithium ion conductor Li 0.18 Sr 0.66 Ti 0.5 Nb 0.5 O 3 will be presented.Ex-situ analysis of synchrotron X-ray diffraction data suggests that a single phase material exists for all discharges to as low as 0.422 V.For samples with higher lithium content, it is possible to determine the lithium position from the X-ray data.However, in-operando X-ray diffraction reveals a kinetically driven two phase region on cycling below 1 V. Monitoring the change in unit cell dimension during electrochemical cycling showed a reduction in the rate of unit cell expansion part way through the first discharge and during the second discharge, caused by a drop in lithium diffusion into the bulk material for higher lithium contents.A more significant change is a jump in the unit cell expansion once the lithium content exceeds one lithium ion per vacant site, caused by damping of octahedral rotations.This provides a link between lithium content and octahedral rotations.Using in-operando diffraction may therefore enable to determine the strength of octahedral rotations in defect perovskites and allow correlations with the large variance of ionic conductivities in these materials. References[1] W. R. Brant, D. Li, Q. Gu & S. Schmid, J. Power Sources 302, 126 -134 (2016).Comparison of ex-situ and operando X-ray diffraction techniques for investigating lithium insertion defect perovskite Li 0.18 Sr 0.66 Ti 0.5 Nb 0.5 O 3 .[2