Limits to Crystallization Pressure.

Crystallization pressure drives deformation and damage in monuments, buildings, and the Earth's crust. Even though the phenomenon has been known for 170 years, there is no agreement between theoretical calculations of the maximum attainable pressure and experimentally measured pressures. We have therefore developed a novel experimental technique to image the nanoconfined crystallization process while controlling the pressure and applied it to calcite. The results show that displacement by crystallization pressure is arrested at pressures well below the thermodynamic limit. We use existing molecular dynamics simulations and atomic force microscopy data to construct a robust model of the disjoining pressure in this system and thereby calculate the absolute distance between the surfaces. On the basis of the high-resolution experiments and modeling, we formulate a novel mechanism for the transition between damage and adhesion by crystallization that may find application in Earth and materials sciences and in conservation of cultural heritage.

Ca2+ Ions Decrease Adhesion between Two (104) Calcite Surfaces as Probed by Atomic Force Microscopy.

Solution composition-sensitive disjoining pressure acting between the mineral surfaces in fluid-filled granular rocks and materials controls their cohesion, facilitates the transport of dissolved species, and may sustain volume-expanding reactions leading to fracturing or pore sealing. Although calcite is one of the most abundant minerals in the Earth's crust, there is still no complete understanding of how the most common inorganic ions affect the disjoining pressure (and thus the attractive or repulsive forces) operating between calcite surfaces. In this atomic force microscopy study, we measured adhesion acting between two cleaved (104) calcite surfaces in solutions containing low and high concentrations of Ca2+ ions. We detected only low adhesion between calcite surfaces, which was weakly modulated by the varying Ca2+ concentration. Our results show that the more hydrated calcium ions decrease the adhesion between calcite surfaces with respect to monovalent Na+ at a given ionic strength, and thus Ca2+ can sustain relatively thick water films between contacting calcite grains even at high overburden pressures. These findings suggest a possible loss of cohesion and continued progress of reaction-induced fracturing for weakly charged minerals in the presence of strongly hydrated ionic species.

A sample cell for the study of enzyme-induced carbonate precipitation at the grain-scale and its implications for biocementation.

Biocementation is commonly based on microbial-induced carbonate precipitation (MICP) or enzyme-induced carbonate precipitation (EICP), where biomineralization of [Formula: see text] in a granular medium is used to produce a sustainable, consolidated porous material. The successful implementation of biocementation in large-scale applications requires detailed knowledge about the micro-scale processes of [Formula: see text] precipitation and grain consolidation. For this purpose, we present a microscopy sample cell that enables real time and in situ observations of the precipitation of [Formula: see text] in the presence of sand grains and calcite seeds. In this study, the sample cell is used in combination with confocal laser scanning microscopy (CLSM) which allows the monitoring in situ of local pH during the reaction. The sample cell can be disassembled at the end of the experiment, so that the precipitated crystals can be characterized with Raman microspectroscopy and scanning electron microscopy (SEM) without disturbing the sample. The combination of the real time and in situ monitoring of the precipitation process with the possibility to characterize the precipitated crystals without further sample processing, offers a powerful tool for knowledge-based improvements of biocementation.

Calcite seed-assisted microbial induced carbonate precipitation (MICP).

Microbial-induced calcium carbonate precipitation (MICP) is a biological process inducing biomineralization of CaCO3. This can be used to form a solid, concrete-like material. To be able to use MICP successfully to produce solid materials, it is important to understand the formation process of the material in detail. It is well known that crystallization surfaces can influence the precipitation process. Therefore, we present in this contribution a systematic study investigating the influence of calcite seeds on the MICP process. We focus on the changes in the pH and changes of the optical density (OD) signal measured with absorption spectroscopy to analyze the precipitation process. Furthermore, optical microscopy was used to visualize the precipitation processes in the sample and connect them to changes in the pH and OD. We show, that there is a significant difference in the pH evolution between samples with and without calcite seeds present and that the shape of the pH evolution and the changes in OD can give detailed information about the mineral precipitation and transformations. In the presented experiments we show, that amorphous calcium carbonate (ACC) can also precipitate in the presence of initial calcite seeds and this can have implications for consolidated MICP materials.

Microbial-induced calcium carbonate precipitation: an experimental toolbox for in situ and real time investigation of micro-scale pH evolution.

Concrete is the second most consumed product by humans, after water. However, the production of conventional concrete causes more than 5% of anthropogenic CO2 emissions and therefore there is a need for emission-reduced construction materials. One method to produce a solid, concrete-like construction material is microbial-induced calcium carbonate precipitation (MICP). To get a better understanding of MICP it is important to be able to follow local pH changes in dissolution and precipitation processes of CaCO3. In this work we present a new method to study processes of MICP at the micro-scale in situ and in real time. We present two different methods to monitor the pH changes during the precipitation process of CaCO3. In the first method, the average pH of small sample volumes is measured in real time, and pH changes are subsequently correlated with processes in the sample by comparing to optical microscope results. The second method is introduced to follow local pH changes at a grain scale in situ and in real time. Furthermore, local pH changes during the dissolution of CaCO3 crystals are monitored. We demonstrate that these two methods are powerful tools to investigate the pH changes for both MICP precipitation and CaCO3 dissolution for knowledge-based improvement of MICP-based material properties.

Nucleation in confinement generates long-range repulsion between rough calcite surfaces.

Fluid-induced alteration of rocks and mineral-based materials often starts at confined mineral interfaces where nm-thick water films can persist even at high overburden pressures and at low vapor pressures. These films enable transport of reactants and affect forces acting between mineral surfaces. However, the feedback between the surface forces and reactivity of confined solids is not fully understood. We used the surface forces apparatus (SFA) to follow surface reactivity in confinement and measure nm-range forces between two rough calcite surfaces in NaCl, CaCl2, or MgCl2 solutions with ionic strength of 0.01, 0.1 or 1 M. We observed long-range repulsion that could not be explained by changes in calcite surface roughness, surface damage, or by electrostatic or hydration repulsion, but was correlated with precipitation events which started at µm-thick separations. We observed a submicron-sized precipitate that formed in the confined solution. This liquid-like viscous precipitate did not undergo any spontaneous ripening into larger crystals, which suggested that confinement prevented its dehydration. Nucleation was significantly postponed in the presence of Mg2+. The long-range repulsion generated by nucleation between confined mineral surfaces can have a crucial influence on evolution of the microstructure and therefore the macroscopic strength of rocks and materials.

Towards a low CO2 emission building material employing bacterial metabolism (2/2): Prospects for global warming potential reduction in the concrete industry.

The production of concrete is one of the most significant contributors to global greenhouse gas emissions. This work focuses on bio-cementation-based products and their potential to reduce global warming potential (GWP). In particular, we address a proposed bio-cementation method employing bacterial metabolism in a two-step process of limestone dissolution and recrystallisation (BioZEment). A scenario-based techno-economic analysis (TEA) is combined with a life cycle assessment (LCA), a market model and a literature review of consumers' willingness to pay, to compute the expected reduction of global GWP. Based on the LCA, the GWP of 1 ton of BioZEment is found to be 70-83% lower than conventional concrete. In the TEA, three scenarios are investigated: brick, precast and onsite production. The results indicate that brick production may be the easiest way to implement the products, but that due to high cost, the impact on global GWP will be marginal. For precast production the expected 10% higher material cost of BioZEment only produces a marginal increase in total cost. Thus, precast production has the potential to reduce global GWP from concrete production by 0-20%. Significant technological hurdles remain before BioZEment-based products can be used in onsite construction scenarios, but in this scenario, the potential GWP reduction ranges from 1 to 26%. While the potential to reduce global GWP is substantial, significant efforts need to be made both in regard to public acceptance and production methods for this potential to be unlocked.

Towards a low CO2 emission building material employing bacterial metabolism (1/2): The bacterial system and prototype production.

The production of concrete for construction purposes is a major source of anthropogenic CO2 emissions. One promising avenue towards a more sustainable construction industry is to make use of naturally occurring mineral-microbe interactions, such as microbial-induced carbonate precipitation (MICP), to produce solid materials. In this paper, we present a new process where calcium carbonate in the form of powdered limestone is transformed to a binder material (termed BioZEment) through microbial dissolution and recrystallization. For the dissolution step, a suitable bacterial strain, closely related to Bacillus pumilus, was isolated from soil near a limestone quarry. We show that this strain produces organic acids from glucose, inducing the dissolution of calcium carbonate in an aqueous slurry of powdered limestone. In the second step, the dissolved limestone solution is used as the calcium source for MICP in sand packed syringe moulds. The amounts of acid produced and calcium carbonate dissolved are shown to depend on the amount of available oxygen as well as the degree of mixing. Precipitation is induced through the pH increase caused by the hydrolysis of urea, mediated by the enzyme urease, which is produced in situ by the bacterium Sporosarcina pasteurii DSM33. The degree of successful consolidation of sand by BioZEment was found to depend on both the amount of urea and the amount of glucose available in the dissolution reaction.

Adhesive forces between two cleaved calcite surfaces in NaCl solutions: The importance of ionic strength and normal loading.

The mechanical strength of calcite bearing rocks is influenced by pore fluid chemistry due to the variation in nano-scale surface forces acting at the grain contacts or close to the fracture tips. The adhesion of two contacting surfaces, which affects the macroscopic strength of the material, is not only influenced by the fluid chemistry but also by the surface topography. In this paper, we use Atomic Force Microscope (AFM) to measure the interfacial forces between two freshly cleaved calcite surfaces in CaCO3-saturated solutions with varying NaCl concentration. We show that calcite contacts become stronger with increasing NaCl concentration (>100 mM), as a result of progressively weaker secondary hydration and increasing attraction due to instantaneous ion-ion correlation. Moreover, we discuss the effect of normal applied force (Fn) and surface roughness on the measured adhesion forces (Fad). We show that the measured pull-off force (adhesion) is linearly correlated with the magnitude of Fn, where an increase in applied force results in increased adhesion. This is attributed to a larger number of contacting surface asperities and thus increase in real contact area and the contact-bond strength. We discuss that the possible variation in local topography at contacts, together with strong dependence on ionic strength of the solution, can explain the inconsistent behavior of calcite rocks in NaCl solutions.

Surface Forces Apparatus Measurements of Interactions between Rough and Reactive Calcite Surfaces.

nm-Range forces acting between calcite surfaces in water affect macroscopic properties of carbonate rocks and calcite-based granular materials and are significantly influenced by calcite surface recrystallization. We suggest that the repulsive mechanical effects related to nm-scale surface recrystallization of calcite in water could be partially responsible for the observed decrease of cohesion in calcitic rocks saturated with water. Using the surface forces apparatus, we simultaneously followed the calcite reactivity and measured the forces in water in two surface configurations: between two rough calcite surfaces (CC) and between rough calcite and a smooth mica surface (CM). We used nm-scale rough, polycrystalline calcite films prepared by atomic layer deposition. We measured only repulsive forces in CC in CaCO3-saturated water, which was related to roughness and possibly to repulsive hydration effects. Adhesive or repulsive forces were measured in CM in CaCO3-saturated water depending on calcite roughness, and the adhesion was likely enhanced by electrostatic effects. The pull-off adhesive force in CM became stronger with time, and this increase was correlated with a decrease of roughness at contacts, the parameter which could be estimated from the measured force-distance curves. That suggested a progressive increase of real contact areas between the surfaces, caused by gradual pressure-driven deformation of calcite surface asperities during repeated loading-unloading cycles. Reactivity of calcite was affected by mass transport across nm- to µm-thick gaps between the surfaces. Major roughening was observed only for the smoothest calcite films, where gaps between two opposing surfaces were nm-thick over µm-sized areas and led to force of crystallization that could overcome confining pressures of the order of MPa. Any substantial roughening of calcite caused a significant increase of the repulsive mechanical force contribution.

Microscopic modeling of confined crystal growth and dissolution.

We extend the (1+1)-dimensional fluid solid-on-solid (SOS) model to include a confining flat surface opposite to the SOS surface subject to a constant load. This load is balanced by a repulsive surface-surface interaction given by an ansatz which agrees with known analytical solutions in the limit of two separated flat surfaces. Mechanical equilibrium is imposed at all times by repositioning the confining surface. By the use of kinetic Monte Carlo (KMC) we calculate how the equilibrium concentration (deposition rate) depends on the applied load, and find it to reproduce analytical thermodynamics independent of the parameters of the interaction ansatz. We also study the dependency between the surface roughness and the saturation level as we vary the surface tension, and expand on previous analyses of the asymmetry between growth and dissolution by parametrizing the linear growth rate constant for growth and dissolution separately. We find the presence of a confining surface to affect the speed of growth and dissolution equally.

Developing a general interaction potential for hydrophobic and hydrophilic interactions.

We review direct force measurements on a broad class of hydrophobic and hydrophilic surfaces. These measurements have enabled the development of a general interaction potential per unit area, W(D) = -2γ(i)Hy exp(-D/D(H)) in terms of a nondimensional Hydra parameter, Hy, that applies to both hydrophobic and hydrophilic interactions between extended surfaces. This potential allows one to quantitatively account for additional attractions and repulsions not included in the well-known combination of electrostatic double layer and van der Waals theories, the so-called Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The interaction energy is exponentially decaying with decay length D(H) ≈ 0.3-2 nm for both hydrophobic and hydrophilic interactions, with the exact value of D(H) depending on the precise system and conditions. The pre-exponential factor depends on the interfacial tension, γ(i), of the interacting surfaces and Hy. For Hy > 0, the interaction potential describes interactions between partially hydrophobic surfaces, with the maximum hydrophobic interaction (i.e., two fully hydrophobic surfaces) corresponding to Hy = 1. Hydrophobic interactions between hydrophobic monolayer surfaces measured with the surface forces apparatus (SFA) are shown to be well described by the proposed interaction potential. The potential becomes repulsive for Hy < 0, corresponding to partially hydrophilic (hydrated) interfaces. Hydrated surfaces such as mica, silica, and lipid bilayers are discussed and reviewed in the context of the values of Hy appropriate for each system.