Encarnación Ruiz-Agudo

Mechanism of leached layer formation during chemical weathering of silicate minerals

The dissolution of most common multicomponent silicate minerals and glasses is typically incongruent, as shown by the nonstoichiometric release of the solid phase components. This results in the formation of so-called surface leached layers. Due to the important effects these leached layers may have on mineral dissolution rates and secondary mineral formation, they have attracted a great deal of research. However, the mechanism of leached layer formation is a matter of vigorous debate. Here we report on an in situ atomic force microscopy (AFM) study of the dissolution of wollastonite, CaSiO 3 , as an example of leached layer formation during dissolution. Our in situ AFM results provide, for the first time, clear direct experimental evidence that leached layers are formed in a tight interface-coupled two-step process: stoichiometric dissolution of the pristine mineral surfaces and subsequent precipitation of a secondary phase (most likely amorphous silica) from a supersaturated boundary layer of fluid in contact with the mineral surface. This occurs despite the fact that the bulk solution is undersaturated with respect to the secondary phase. Our results differ significantly from the concept of preferential leaching of cations, as postulated by most currently accepted incongruent dissolution models. This interface-coupled dissolution-precipitation model has important implications in understanding and evaluating dissolution kinetics of major rock-forming minerals.

Influence of Substrate Mineralogy on Bacterial Mineralization of Calcium Carbonate: Implications for Stone Conservation

ABSTRACT The influence of mineral substrate composition and structure on bacterial calcium carbonate productivity and polymorph selection was studied. Bacterial calcium carbonate precipitation occurred on calcitic (Iceland spar single crystals, marble, and porous limestone) and silicate (glass coverslips, porous sintered glass, and quartz sandstone) substrates following culturing in liquid medium (M-3P) inoculated with different types of bacteria (Myxococcus xanthus, Brevundimonas diminuta, and a carbonatogenic bacterial community isolated from porous calcarenite stone in a historical building) and direct application of sterile M-3P medium to limestone and sandstone with their own bacterial communities. Field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), powder X-ray diffraction (XRD), and 2-dimensional XRD (2D-XRD) analyses revealed that abundant highly oriented calcite crystals formed homoepitaxially on the calcitic substrates, irrespective of the bacterial type. Conversely, scattered spheroidal vaterite entombing bacterial cells formed on the silicate substrates. These results show that carbonate phase selection is not strain specific and that under equal culture conditions, the substrate type is the overruling factor for calcium carbonate polymorph selection. Furthermore, carbonate productivity is strongly dependent on the mineralogy of the substrate. Calcitic substrates offer a higher affinity for bacterial attachment than silicate substrates, thereby fostering bacterial growth and metabolic activity, resulting in higher production of calcium carbonate cement. Bacterial calcite grows coherently over the calcitic substrate and is therefore more chemically and mechanically stable than metastable vaterite, which formed incoherently on the silicate substrates. The implications of these results for technological applications of bacterial carbonatogenesis, including building stone conservation, are discussed.

Direct observations of mineral-fluid reactions using atomic force microscopy; the specific example of calcite

Abstract Atomic force microscopy (AFM) enables in situ observations of mineral-fluid reactions to be made at a nanoscale. During the past 20 years, the direct observation of mineral surfaces at molecular resolution during dissolution and growth has made significant contributions toward improvements in our understanding of the dynamics of mineral-fluid reactions at the atomic scale. Observations and kinetic measurements of dissolution and growth from AFM experiments give valuable evidence for crystal dissolution and growth mechanisms, either confirming existing models or revealing their limitations. Modifications to theories can be made in the light of experimental evidence generated by AFM. Significant changes in the kinetics and mechanisms of crystallization and dissolution processes occur when the chemical and physical parameters of solutions, including the presence of impurity molecules or background electrolytes, are altered. Calcite has received considerable attention in AFM studies due to its central role in geochemical and biomineralization processes. This review summarizes the extensive literature on the dissolution and growth of calcite that has been generated by AFM studies, including the influence of fluid characteristics such as supersaturation, solution stoichiometry, pH, temperature and the presence of impurities.

Alcohol Dispersions of Calcium Hydroxide Nanoparticles for Stone Conservation

Alcohol dispersions of Ca(OH)2 nanoparticles, the so-called nanolimes, are emerging as an effective conservation material for the consolidation of stone, mortars, and plasters present in old masonry and/or mural paintings. To better understand how this treatment operates, to optimize its performance and broaden its applications, here we study the nano and microstructural characteristics, carbonation behavior, and consolidation efficacy of colloidal alcohol dispersions of Ca(OH)2 nanoparticles produced by both homogeneous (commercial nanolime) and heterogeneous phase synthesis (aged slaked lime and carbide lime putties). We observe that the alcohol not only provides a high colloidal stability to Ca(OH)2 particles, but also affects the kinetics of carbonation and CaCO3 polymorph selection. This is due to the pseudomorphic replacement of Ca(OH)2 particles by calcium alkoxides upon reaction with ethanol or 2-propanol. The extent of this replacement reaction depends on Ca(OH)2 size and time. Hydrolysis of alkoxides speeds up the carbonation process and increases the CaCO3 yield. The higher degree of transformation into calcium alkoxide of both the commercial nanolime and the carbide lime fosters metastable vaterite formation, while calcite precipitation is promoted upon carbonation of the aged slaked lime due its lower reactivity, which limits calcium alkoxide formation. A higher consolidation efficacy in terms of strength gain of treated porous stone is achieved in the latter case, despite the fact that the carbonation is much faster and reaches a higher yield in the former ones. Formation of alkoxides, which has been neglected in previous studies, needs to be considered when applying nanolime treatments. These results show that the use Ca(OH)2 nanoparticle dispersions prepared with either aged slaked lime or carbide lime putties is an economical and effective conservation alternative to commercial nanolimes produced by homogeneous phase synthesis. Ultimately, this study contributes to show that nanotechnology can help saving the built and sculptural heritage.

Formation of amorphous calcium carbonate and its transformation into mesostructured calcite

Amorphous calcium carbonate (ACC) is a key precursor of crystalline CaCO3 biominerals and biomimetic materials. Despite recent extensive research, its formation and amorphous-to-crystalline transformation are not, however, fully understood. Here we show that hydrated ACC nanoparticles form after spinodal liquid–liquid phase separation and transform via dissolution/(re)precipitation into poorly hydrated and anhydrous ACC nanoparticles that aggregate, forming a range of 1D, 2D and 3D structures. The formation of these structures appears to be achieved by oriented attachment (OA), facilitated by the calcite medium-range order of ACC nanoparticles. Both electron irradiation processes in the TEM and under humid air exposure at room temperature of the latter ACC structures result in pseudomorphs of single crystalline mesostructured calcite. While the high-vacuum/e-beam heating leads to solid-state transformation, the transformation in air occurs via an interface-coupled dissolution/precipitation mechanism. Our results differ significantly from the currently accepted model, which considers that the low T ACC-to-calcite transformation in air and during biomineralization is a solid-state process. These results may help to better understand how calcite biominerals form after ACC and offer the possibility of biomimetically preparing single crystalline calcite structures after ACC by tuning pH2O at room temperature.

Direct nanoscale observations of CO2 sequestration during brucite [Mg(OH)2] dissolution

The dissolution and carbonation of brucite on (001) cleavage surfaces was investigated in a series of in situ and ex situ atomic force microscopy (AFM) experiments at varying pH (2-12), temperature (23-40 °C), aqueous NaHCO(3) concentration (10(-5)-1 M), and PCO(2) (0-1 atm). Dissolution rates increased with decreasing pH and increasing NaHCO(3) concentration. Simultaneously with dissolution of brucite, the growth of a Mg-carbonate phase (probably dypingite) was directly observed. In NaHCO(3) solutions (pH 7.2-9.3,), precipitation of Mg-carbonates was limited. Enhanced precipitation was, however, observed in acidified NaHCO(3) solutions (pH 5, DIC ≈ 25.5 mM) and in solutions that were equilibrated under a CO(2) atmosphere (pH 4, DIC ≈ 25.2 mM). Nucleation predominantly occurred in areas of high dissolution such as deep step edges suggesting that the carbonation reaction is locally diffusion-transport controlled. More extensive particle growth was also observed after ex situ experiments lasting for several hours. This AFM study contributes to an improved understanding of the mechanism of aqueous brucite carbonation at low temperature and pressure conditions and has implications for carbonation reactions in general.

Kinetics of Calcium Phosphate Nucleation and Growth on Calcite: Implications for Predicting the Fate of Dissolved Phosphate Species in Alkaline Soils

Unraveling the kinetics of calcium orthophosphate (Ca-P) precipitation and dissolution is important for our understanding of the transformation and mobility of dissolved phosphate species in soils. Here we use an in situ atomic force microscopy (AFM) coupled with a fluid reaction cell to study the interaction of phosphate-bearing solutions with calcite surfaces. We observe that the mineral surface-induced formation of Ca-P phases is initiated with the aggregation of clusters leading to the nucleation and subsequent growth of Ca-P phases on calcite, at various pH values and ionic strengths relevant to soil solution conditions. A significant decrease in the dissolved phosphate concentration occurs due to the promoted nucleation of Ca-P phases on calcite surfaces at elevated phosphate concentrations and more significantly at high salt concentrations. Also, kinetic data analyses show that low concentrations of citrate caused an increase in the nucleation rate of Ca-P phases. However, at higher concentrations of citrate, nucleation acceleration was reversed with much longer induction times to form Ca-P nuclei. These results demonstrate that the nucleation-modifying properties of small organic molecules may be scaled up to analyze Ca-P dissolution-precipitation processes that are mediated by a more complex soil environment. This in situ observation, albeit preliminary, may contribute to an improved understanding of the fate of dissolved phosphate species in diverse soil systems.

The mechanism of thermal decomposition of dolomite: New insights from 2D-XRD and TEM analyses

Abstract Despite being studied for more than one century, no consensus exists regarding the ultimate mechanism(s) of the thermal decomposition of dolomite [(CaMg(CO3)2]. To shed light on such a reaction, dolomite single crystals were calcined in air between 500 and 1000 °C, and in situ, in a TEM (high vacuum), following irradiation with the electron beam. In situ TEM shows that the decomposition involves the initial formation of a face centered cubic mixed oxide (Ca0.5Mg0.5O) with reactant/product orientation relationships [001]dolomite//<111>oxide, <4̄41>dolomite//<100>oxide, {112̄0}dolomite//{110}oxide, {112̄8}dolomite//{110}oxide and {101̄4}dolomite^{100}oxide~12°. This phase undergoes de-mixing into oriented crystals of Mg-poor CaO and Ca-poor MgO solid solutions upon long-term e-beam exposure. Ex situ TEM, XRD, 2D-XRD, and FESEM analyses show the formation of porous pseudomorphs made up of oxide nanocrystals with similar parent/product orientation relationships, but with limited Ca/Mg substitution (up to ~9-11%) due to de-mixing (spinodal decomposition) of the metastable (Ca,Mg)O precursor. High ion diffusivity at T > 500 °C (ex situ experiments) favors the formation of pure CaO and MgO crystals during coarsening via oriented aggregation and sintering. These results show that the thermal decomposition of dolomite is topotactic and independent of pCO2. Formation of Mg-calcite nanocrystals (up to ~8 mol% Mg) during the so-called “half decomposition” is observed at 650-750 °C. This transient phase formed topotactically following the reaction of CaO nanocystals (solid solution with ~9 mol% Mg) with CO2 present in the air and/or released upon further dolomite decomposition. With increasing T, Mg-calcite transformed into calcite, which underwent decomposition following the known topotactic relationship: {101̄4}calcite//{110}CaO and <4̄41>calcite//<110>CaO. These observations solve the long standing controversy on the mechanism of the “two-stage” decomposition of dolomite, which assumed the direct formation of calcite during the so-called “half decomposition.”

Posner's cluster revisited: direct imaging of nucleation and growth of nanoscale calcium phosphate clusters at the calcite-water interface

Although many in vitro studies have looked at calcium phosphate (Ca–P) mineralization, they have not emphasized the earliest events and the pathway of crystallization from solvated ions to the final apatitic mineral phase. Only recently has it become possible to unravel experimentally the processes of Ca–P formation through a cluster-growth model. Here we use mineral replacement reactions by the interaction of phosphate-bearing solutions with calcite surfaces in a fluid cell of an atomic force microscope (AFM) and reveal that the mineral surface-induced formation of an apatitic phase proceeds through the nucleation and aggregation of nanosized clusters with dimensions similar to those of Posners clusters, which subsequently form stable amorphous calcium phosphate (ACP) plates prior to the transformation to the final crystalline phase. Our direct AFM observations provide evidence for the existence of stable Posners clusters even though no organic template is applied.

Dissolution and Carbonation of Portlandite [Ca(OH)2] Single Crystals

The dissolution and carbonation of portlandite (Ca(OH)2) single crystals was studied by a combination of in situ Atomic Force Microscopy, Scanning Electron Microscopy, and two-dimensional X-ray diffraction. The dissolution of portlandite {0001} surfaces in water proceeds by the formation and expansion of pseudohexagonal etch pits, with edges parallel to ⟨100⟩ directions. Etch pits on {010} surfaces are elongated along ⟨001⟩, with edges parallel to ⟨101⟩. The interaction between carbonate-bearing solutions and portlandite results in the dissolution of the substrate coupled with the precipitation of thick islands of CaCO3 that appear oriented on the portlandite substrate. Ex situ carbonation of portlandite in contact with air results in the formation of pseudomorphs that fully preserve the external shape of the original portlandite single crystals. Our observations suggest that portlandite carbonation in contact with air and carbonate-bearing solutions occurs by a similar mechanism, i.e. coupled dissolution-precipitation. Calcite grows epitaxially on {0001} portlandite surfaces with the following orientation: ⟨001⟩Cc∥ ⟨001⟩Port. Apparently, no porosity is generated during the reaction, which progresses through the formation of fractures. Our results are of relevance to many processes in which the carbonation of portlandite takes place, such as CO2 capture and storage or the carbonation of cementitious materials.