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Advanced in situ techniques based on electrons and X-rays are increasingly used to gain insights into fundamental materials dynamics in liquid media. Yet, ionizing radiation changes the solution chemistry. In this work, we show that ionizing radiation decouples the acidity from autoprotolysis. Consequently, pH is insufficient to capture the acidity of water-based systems under irradiation. Via radiolysis simulations, we provide a more conclusive description of the acid-base interplay. Finally, we demonstrate that acidity can be tailored by adjusting the dose rate and adding pH-irrelevant species. This opens up a huge parameter landscape for studies involving ionizing radiation., Comment: 21 pages, 9 figures (main: 8 pages, 3 figures + SI: 13 pages, 6 figures)

CaSO4 minerals (i.e. gypsum, anhydrite and bassanite) are widespread in natural and industrial environments. During the last several years, a number of studies have revealed that nucleation in the CaSO4-H2O system is non-classical, where the formation of crystalline phases involves several steps. Based on these recent insights we have formulated a tentative general model for calcium sulfate precipitation from solution. This model involves primary species that are formed through the assembly of multiple Ca2+ and SO42- ions into nanoclusters. These nanoclusters assemble into poorly ordered (i.e. amorphous) hydrated aggregates, which in turn undergo ordering into coherent crystalline units. The thermodynamic (meta)stability of any of the three CaSO4 phases is regulated by temperature, pressure and ionic strength with gypsum being the stable form at low temperatures and low to medium ionic strengths, and anhydrite the stable phase at high temperatures and lower temperature at high salinities. Bassanite is metastable across the entire phase diagram but readily forms as the primary phase at high ionic strengths across a wide range of temperatures, and can persist up to several months. Although the physicochemical conditions leading to bassanite formation in aqueous systems are relatively well established, nanoscale insights into the nucleation mechanisms and pathways are still lacking. To fill this gap, and to further improve our general model for calcium sulfate precipitation, we have conducted in situ scattering measurements at small- and wide-angles (SAXS/WAXS) and complemented these with in situ Raman spectroscopic characterization. Based on these experiments we show that the process of formation of bassanite from aqueous solutions is very similar to the formation of gypsum: it involves the aggregation of small primary species into larger disordered aggregates., Comment: 32 pages, Supporting Information p.31-32

Although clays are crucial mineral phases in Earth's weathering engine, it is unclear how they form in surface environments under (near-)ambient pressures and temperature. Most synthesis routes, attempting to give insights into the plausible mechanisms, rely on hydrothermal conditions, yet many geological studies showed that clays may actually form at moderate temperatures (< 100 deg. C) in most terrestrial settings. Here, we present the mechanism of the low-temperature (25-95 deg. C) crystallization of a synthetic Mg-clay, saponite. We describe the pathway at the various sub-stages of the reaction, as we derived from high-energy X-ray diffraction, infrared spectroscopy and transmission electron microscopy data. Our results reveal that saponite crystallizes via a two stage process: 1) a rapid (several minutes) co-precipitation where ~20% of the available magnesium becomes incorporated into an aluminosilicate network followed by 2) a much slower crystallization mechanism (many hours to days) where the remaining magnesium becomes gradually incorporated into the growing saponite sheet structure., Comment: manuscript + supporting information

Understanding the gypsum (CaSO4.2H2O) formation pathway from aqueous solution has been the subject of intensive research in the past years. This interest stems from the fact that gypsum appears to fall into a broader category of crystalline materials whose formation does not follow classical nucleation and growth theories. The pathways involve transitory precursor cluster species, yet the actual structural properties of such clusters are not very well understood. Here, we show how in situ high-energy X-ray diffraction experiments and molecular dynamics (MD) simulations can be combined to derive the structure of small CaSO4 clusters, which are precursors of crystalline gypsum. We fitted several plausible structures to the derived pair distribution functions and explored their dynamic properties using unbiased MD simulations based on both rigid ion and polarizable force fields. Determination of the structure and (meta)stability of the primary species is important from both a fundamental and applied perspective; for example, this will allow for an improved design of additives for greater control of the nucleation pathway., Comment: Pages 1-18: the main article; Pages 27-32 Supporting Information; Structural and trajectory files: https://github.com/tomaszstawski/CaSO4-Nanorods-Supporting-Information

Calcium sulfate minerals are found under the form of three crystalline phases: gypsum (CaSO4.2H2O), bassanite (CaSO4.0.5H2O), and anhydrite (CaSO4). Due to its relevance in natural and industrial processes, the formation pathways of these calcium sulphate phases from aqueous solution have been the subject of intensive research. There is a growing body of literature, that calcium sulfate forms essentially through a non-classical nanoparticle- or cluster-mediated crystallisation process. At the early stages of precipitation calcium sulfate crystals grow through the reorganization and coalescence of aggregates rather than through classical unit addition. Here, we show by using low-dose dark field (DF) transmission electron microscopy (TEM) and electron diffraction, that these re-structuring processes by no means continue until a near-perfectly homogeneous single crystal is obtained. Instead the growth process yields a final imperfect mesocrystal of the overall morphology resembling that of a single crystal, yet composed of smaller nano-domains. Hence, our data indicate that organic-free mesocrystal grown by a particle mediated-pathway may preserve a 'memory or 'imprint' of the non-classical growth process in the final crystal structure, something that has been largely overlooked until now. Furthermore, the nano-scale misalignment of the structural sub-units within crystals might propagate through the length-scales, and potentially is expressed macroscopically as misaligned zones/domains in large single crystals, e.g. as those observed in some of the giant crystals from the Naica Mine, Chihuahua, Mexico., Comment: 30 pages, 5 main figures, 1 supporting figure

A quantitative understanding of aggregation mechanisms leading to the formation of inorganic nanoparticles (NPs) and protein composites in aqueous media is of paramount interest for colloid chemistry. In particular, the interactions between silica (SiO2) NPs and lysozyme (LZM) have attracted attention, because LZM is well-known to adsorb strongly to silica NPs, while at the same time preserving its enzymatic activity. The inherent nature of the aggregation processes leading to NP-LZM composites involves structural changes at length-scales from few to hundreds of nanometres but also time scales << 1 second. To unravel these we used in situ synchrotron-based small-angle X-ray scattering (SAXS) and followed the subtle interparticle interactions in solution at a time resolution of 50 ms/frame (20 fps). We show that if the size of silica NPs (~5 nm diameter) is matched by the dimensions of LZM, the evolving scattering patterns contain a unique structure factor contribution originating from the presence of LZM. We developed a scattering model and applied it to analyse this structure function, which allowed us to extract structural information on the deformation of lysozyme molecules during aggregation, as well as to derive the mechanisms of composite formation., Comment: The script we developed as well as all the documentation and the selected scattering curves are available at: https://github.com/tomaszstawski/SilicaLysozymeSAXS

Can we control the crystallization of solid CaCO3 from supersaturated aqueous solutions and thus mimic a natural process predicted to occur in living organisms that produce biominerals? Here we show how we achieved this by confining the reaction between Ca2+ and CO32- ions to the environment of nanosized water cores of water-in-oil microemulsions. Using a combination of in situ small-angle X-ray scattering, high-energy X-ray diffraction, and low-dose liquid-cell scanning transmission electron microscopy, we elucidate how the presence of micellar interfaces leads to the formation of a solute CaCO3 phase that can be stabilized for extended periods of time inside micellar water nano-droplets. We can also control and >>on-demand<< trigger the actual precipitation and crystallization of solid CaCO3 phases through the targeted removal of the organic-inorganic interfaces., Comment: The associated video files cannot be uploaded. Please contact the authors if you want to view the videos

The formation of crystalline calcium sulfate (CaSO4*xH2O) polymorphs from aqueous solutions is assumed to occur via a single-step process following the classical nucleation paradigm. However, although recent research contradicts this classical picture and indicates that CaSO4*2H2O forms at room temperature through multiple steps at different length and time-scales, these steps have so far not been quantified. By using in situ and fast time-resolved small angle X-ray scattering (SAXS), we demonstrate that the nucleation and growth of CaSO4*2H2O involves at the very initial stages the formation of well-defined, primary species of < 3 nm in length (stage I). Stage II of the reaction is characterized by the arrangement of these primary species into domains, while in stage III these domains condense into larger aggregates. Based on volume fractions and electron density considerations we propose that the fast forming primary species from supersaturated aqueous CaSO4 solutions are composed of anhydrous Ca-SO4-cores. The first three stages of nucleation and aggregation of the primary species are followed by a final stage (stage IV), where the primary species grow within the aggregates, and eventually transform into gypsum (CaSO4*2H2O). This final stage was also confirmed through simultaneously collected wide-angle scattering (diffraction, WAXS) data, which clearly show the growth of gypsum during stage IV only. Our results demonstrate that CaSO4 formation is driven by the nucleation and aggregation of well-defined anhydrous Ca-SO4-cores that transform through hydration into gypsum through a complex nucleation and growth pathway., Comment: 41 pages of unformatted text, 5 main figures, 4 supporting figures