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The adsorption behaviour of micro-organisms during the initial attachment stage of biofilm formation affects subsequent stages. The available area for attachment and the chemophysical properties of a surface affect microbial attachment performance. This study focused on the initial attachment behaviour of Klebsiella aerogenes on monazite by measuring the ratio of planktonic against sessile subpopulations (P:S ratio), and the potential role of extracellular DNA (eDNA). eDNA production, effects of physicochemical properties of the surface, particle size, total available area for attachment, and the initial inoculation size on the attachment behaviour were tested. K. aerogenes attached to monazite immediately after exposure to the ore; however, the P:S ratio significantly (p = 0.05) changed in response to the particle size, available area, and inoculation size. Attachment occurred preferentially on larger-sized (~50 µm) particles, and either decreasing the inoculation size or increasing the available area further promoted attachment. Nevertheless, a portion of the inoculated cells always remained in a planktonic state. K. aerogenes produced lower eDNA in response to the changed surface chemical properties when monazite was replaced by xenotime. Using pure eDNA to cover the monazite surface significantly (p ≤ 0.05) hindered bacterial attachment due to the repulsive interaction between the eDNA layer and bacteria.

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Microbial attachment and biofilm formation is a ubiquitous behaviour of microorganisms and is the most crucial prerequisite of contact bioleaching. Monazite and xenotime are two commercially exploitable minerals containing rare earth elements (REEs). Bioleaching using phosphate solubilizing microorganisms is a green biotechnological approach for the extraction of REEs. In this study, microbial attachment and biofilm formation of Klebsiella aerogenes ATCC 13048 on the surface of these minerals were investigated using confocal laser scanning microscopy (CLSM) and scanning electron microscopy (SEM). In a batch culture system, K. aerogenes was able to attach and form biofilms on the surface of three phosphate minerals. The microscopy records showed three distinctive stages of biofilm development for K. aerogenes commencing with initial attachment to the surface occurring in the first minutes of microbial inoculation. This was followed by colonization of the surface and formation of a mature biofilm as the second distinguishable stage, with progression to dispersion as the final stage. The biofilm had a thin-layer structure. The colonization and biofilm formation were localized toward physical surface imperfections such as cracks, pits, grooves and dents. In comparison to monazite and xenotime crystals, a higher proportion of the surface of the high-grade monazite ore was covered by biofilm which could be due to its higher surface roughness. No selective attachment or colonization toward specific mineralogy or chemical composition of the minerals was detected. Finally, in contrast to abiotic leaching of control samples, microbial activity resulted in extensive microbial erosion on the high-grade monazite ore.

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Cadmium (Cd2+) and Arsenate (As5+) are the main toxic elements in soil environments and are easily taken up by plants. Unraveling the kinetics of the adsorption and subsequent precipitation/immobilization on mineral surfaces is of considerable importance for predicting the fate of these dissolved species in soils. Here we used in situ atomic force microscopy (AFM) to image the dissolution on the (010) face of brushite (dicalcium phosphate dihydrate, CaHPO4·2H2O) in CdCl2- or Na2HAsO4-bearing solutions over a broad pH and concentration range. During the initial dissolution processes, we observed that Cd or As adsorbed on step edges to modify the morphology of etch pits from the normal triangular shape to a four-sided trapezium. Following extended reaction times, the respective precipitates were formed on brushite through a coupled dissolution-precipitation mechanism. In the presence of both CdCl2 and Na2HAsO4 in reaction solutions at pH 8.0, high-resolution transmission electron microscopy (HRTEM) showed a coexistence of both amorphous and crystalline phases, i.e., a mixed precipitate of amorphous and crystalline Cd(5- x)Ca x(AsO4)(3- y)(PO4) yOH phases was detected. These direct dynamic observations of the transformation of adsorbed species to surface precipitates may improve the mechanistic understanding of the calcium phosphate mineral interface-induced simultaneous immobilization of both Cd and As and subsequent sequestration in diverse soils.

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The chemical composition of the continental crust cannot be adequately explained by current models for its formation, because it is too rich in Ni and Cr compared to that which can be generated by any of the proposed mechanisms. Estimates of the crust composition are derived from average sediment, while crustal growth is ascribed to amalgamation of differentiated magmatic rocks at continental margins. Here we show that chemical weathering of Ni- and Cr-rich, undifferentiated ultramafic rock equivalent to ~1.3 wt% of today's continental crust compensates for low Ni and Cr in formation models of the continental crust. Ultramafic rock weathering produces a residual that is enriched in Ni and also silica. In the light of potentially large volumes of ultramafic rock and high atmospheric CO2 concentrations during the Archean, chemical weathering must therefore have played a major role in forming compositionally evolved components of the early Earth's crust.

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Mineral surfaces play a critical role in the solar nebula as a catalytic surface for chemical reactions and potentially acted as a source of water during Earth's accretion by the adsorption of water molecules to the surface of interplanetary dust particles. However, nothing is known about how mineral surfaces respond to short-lived thermal fluctuations that are below the melting temperature of the mineral. Here we show that mineral surfaces react and rearrange within minutes to changes in their local environment despite being far below their melting temperature. Polished surfaces of the rock and planetary dust-forming silicate mineral olivine ((Mg,Fe)2SiO4) show significant surface reorganization textures upon rapid heating resulting in surface features up to 40 nm in height observed after annealing at 1200 °C. Thus, high-temperature fluctuations should provide new and highly reactive sites for chemical reactions on nebula mineral particles. Our results also may help to explain discrepancies between short and long diffusion profiles in experiments where diffusion length scales are of the order of 100 nm or less.

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In order to evaluate the organic phosphorus (OP) and pyrophosphate (PyroP) cycle and their fate in the environment, it is critical to understand the effects of mineral interfaces on the reactivity of adsorption and precipitation of OP and PyroP. Here, in situ atomic force microscopy (AFM) is used to directly observe the kinetics of coupled dissolution-precipitation on cleaved (001) surfaces of brucite [Mg(OH)2] in the presence of phytate, glucose-6-phosphate (G6P) and pyrophosphate, respectively. AFM results show that the relative order of contribution to mineral surface adsorption and precipitation is phytate > pyrophosphate > G6P under the same solution conditions and can be quantified by the induction time of OP/PyroP-Mg nucleation in a boundary layer at the brucite-water interface. Calculations of solution speciation during brucite dissolution in the presence of phytate or pyrophosphate at acidic pH conditions show that the solutions may reach supersaturation with respect to Mg5H2Phytate.6H2O as a Mg-phytate phase or Mg2P2O7 as a Mg-pyrophosphate phase that becomes thermodynamically stable before equilibrium with brucite is reached. This is consistent with AFM dynamic observations for the new phase formations on brucite. Direct nanoscale observations of the transformation of adsorption/complexation-surface precipitation, combined with spectroscopic characterizations and species simulations may improve the mechanistic understanding of organophosphate and pyrophosphate sequestration by mineral replacement reactions through a mechanism of coupled dissolution-precipitation occurring at mineral-solution interfaces in the environment.

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Esters of phosphoric acid constitute a large fraction of the total organic phosphorus (OP) in the soil environment and, thus, play an important role in the global phosphorus cycle. These esters, such as glucose-6-phosphate (G6P), exhibit unusual reactivity toward various mineral particles in soils, especially those containing calcite. Many important processes of OP transformation, including adsorption, hydrolysis, and precipitation, occur primarily at mineral-fluid interfaces, which ultimately governs the fate of organophosphates in the environment. However, little is known about the kinetics of specific mineral-surface-induced adsorption and precipitation of organophosphates. Here, by using in situ atomic-force microscopy (AFM) to visualize the dissolution of calcite (1014) faces, we show that the presence of G6P results in morphology changes of etch pits from the typical rhombohedral to a fan-shaped form. This can be explained by a site-selective mechanism of G6P-calcite surface interactions that stabilize the energetically unfavorable (0001) or (0112) faces through step-specific adsorption of G6P. Continuous dissolution at calcite (1014)-water interfaces caused a boundary layer at the calcite-water interface to become supersaturated with respect to a G6P-Ca phase that then drives the nucleation and growth of a G6P-Ca precipitate. Furthermore, after the introduction of the enzyme alkaline phosphatase (AP), the precipitates were observed to contain a mixture of components associated with G6P-Ca, amorphous calcium phosphate (ACP)-hydroxyapatite (HAP) and dicalcium phosphate dihydrate (DCPD). These direct dynamic observations of the transformation of adsorption- and complexation-surface precipitation and enzyme-mediated pathways may improve the mechanistic understanding of the mineral-interface-induced organophosphate sequestration in the soil environment.

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Adsorption and subsequent immobilization of orthophosphate on iron oxides is of considerable importance in soil fertility and eutrophication studies. Here, in situ atomic force microscopy (AFM) has been used to probe the interaction of phosphate-bearing solutions with goethite, α-FeOOH, (010) cleavage surfaces. During the dissolution of goethite we observed simultaneous nucleation of nanoparticles (1.0-3.0 nm in height) of iron phosphate (Fe-P) phases at the earliest nucleation stages, subsequent aggregation to form secondary particles (about 6.0 nm in height) and layered precipitates under various pH values and ionic strengths relevant to acid soil solution conditions. The heterogeneous nucleation rates of Fe-P precipitates at phosphate concentrations ranging from 5.0 to 50.0 mM were quantitatively defined. Enhanced goethite dissolution in the presence of high concentration NaCl or AlCl3 leads to a rapid increase in Fe-P nucleation rates, whereas low concentration MgCl2 inhibits goethite dissolution, this in turn influences Fe-P nucleation. Moreover, kinetic data analyses show that low concentrations of citrate caused an increase in the nucleation rate of Fe-P phases. However, at higher concentrations of citrate, nucleation acceleration was reversed with much longer induction times to form Fe-P nuclei. These in situ observations may improve the mechanistic understanding of processes resulting in phosphate immobilization by goethite-rich acid soils in the presence of various inorganic and organic additive molecules.

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Classical molecular dynamics simulations of several aqueous alkali halide salt solutions have been used to determine the effect of electrolytes on the structure of water and the hydration properties of calcium ions. Compared with the simulations of Ca(2+) ions in pure liquid water, the frequency of water exchange in the first hydration shell of calcium, which is a fundamental process in controlling the reactivity of calcium(ii) aqua-ions, is drastically reduced in the presence of other electrolytes in solution. The strong stabilization of the hydration shell of Ca(2+) occurs not only when the halide anions are directly coordinated to calcium, but also when the alkali and halide ions are placed at or outside the second coordination shell of Ca(2+), suggesting that the reactivity of the first solvation shell of the calcium ion can be influenced by the specific affinity of other ions in solution for the water molecules coordinated to Ca(2+). Analysis of the hydrogen-bonded structure of water in the vicinity of the calcium ion shows that the average number of hydrogen bonds per water molecules, which is 1.8 in pure liquid water, decreases as the concentration of alkali-halide salts in solution increases, and that the temporal fluctuations of hydrogen bonds are significantly larger than those obtained for Ca(2+) in pure liquid water. This effect has been explained in terms of the dynamics of reorganization of the O-H···X(-) (X = F, Cl and Br) hydrogen bond. This work shows the importance of solution composition in determining the hydrogen-bonding network and ligand-exchange dynamics around metal ions, both in solution and at the mineral-water interfaces, which in turn has implications for interactions occurring at the mineral-water interface, ultimately controlling the mobilization of ions in the environment as well as in industrial processes.

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In situ atomic force microscopy (AFM) has been used to study the interaction of phosphate-bearing solutions with cerussite, PbCO3, (010) surfaces. During the dissolution of cerussite we observed simultaneous growth of needle-shaped or spherical pyromorphite phases. This occurred at two different pH values and ionic strengths relevant to soil solution conditions. The initial dissolution processes occurring at the cerussite solid-phosphate solution interface were clearly distinguished, and heterogeneous nucleation and growth rates of pyromorphites at phosphate concentrations ranging from 0.1 µM to 10 mM were quantitatively defined. Enhanced cerussite dissolution in the presence of high salt (NaCl or NaF) concentrations leads to an increase in pyromorphite nucleation and growth rates. The newly formed pyromorphites were found to be stable upon contact with water or citrate-bearing solutions under acidic or alkaline conditions in the pH range 4-8. These in situ observations may improve the mechanistic understanding of processes resulting in lead immobilization in diverse soil systems as well as to enhance the effectiveness of phosphate-based treatments for remediation of lead-polluted soils.

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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.

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Magnesite growth in chloride and sulfate-rich solutions has been examined at 90 °C in situ using phase-shift interferometry (PSI) and ex situ using atomic force microscopy (AFM) to evaluate the feasibility of cosequestering SO2 and CO2 in Mg-rich rocks. Although sulfate may assist desolvation at the magnesite surface, evidence for enhanced growth was only found at specific surface sites. The overall growth rates fit with those observed for chloride experiments in similarly saturated solutions. Thus, the formation of Mg-SO4 ion pairs in solution, which lowers the supersaturation with respect to magnesite, will have the dominant effect during sequestration. Lowering the activity of Mg(2+) ions in solution also inhibited the nucleation of other hydrated Mg-carbonate phases. As no evidence was found for sulfate incorporation into the growing magnesite, the presence of sulfate in solution will be detrimental to CO2 sequestration and is not expected to be cosequestered. The PSI data also emphasize the variability of reactivity over the surface and how this changes as a function of solution saturation and composition.

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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.

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The presence of water in the Earth has long been an enigma. However, computer modelling techniques have shown that the adsorption of water onto the fractal surfaces of interplanetary dust particles, which are present in the planetary accretion disk, is sufficiently strong to provide a viable origin of terrestrial water.

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Large-scale olivine carbonation has been proposed as a potential method for sequestering CO(2) emissions. For in situ carbonation techniques, understanding the relationship between the formation of carbonate and other phases is important to predict the impact of possible passivating layers on the reaction. Therefore, we have conducted reactions of olivine with carbonated saline solutions in unstirred batch reactors. Altering the reaction conditions changed the Mg-carbonate morphology. We propose that this corresponded to changes in the ability of the system to precipitate hydromagnesite or magnesite. During high-temperature reactions (200 degrees C), an amorphous silica-enriched phase was precipitated that was transformed to lizardite as the reaction progressed. Hematite was also precipitated in the initial stages of these reactions but dissolved as the reaction proceeded. Comparison of the experimental observations with reaction models indicates that the reactions are governed by the interfacial fluid composition. The presence of a new Mg-silicate phase and the formation of secondary products at the olivine surface are likely to limit the extent of olivine to carbonate conversion.

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Spicules of calcareous sponges are elaborately shaped skeletal elements that nonetheless show characteristics of calcite single-crystals. Our atomic force microscopic and transmission electron microscopic investigation of the triradiate spicules of the sponge Pericharax heteroraphis reveals a nano-cluster structure with mostly well-aligned small crystal domains and pockets with accumulated domain misalignments. Combined high-resolution and energy-filtering transmission electron microscopy revealed carbon enrichments located in between crystal domain boundaries, which strongly suggests an intercalated network-like proteinaceous organic matrix. This matrix is proposed to be involved in the nano-clustered calcite precipitation via a transient phase that may enable a 'brick-by-brick' formation of composite and yet single-crystalline spicules with elaborate morphologies. This composite cluster structure reduces the brittleness of the material by dissipating strain energy and deflecting crack propagation from the calcite cleavage planes, but the lattice symmetry and anisotropic growth properties of calcite still play a major role in the morphogenesis of these unusual calcite single-crystals. Our structural, crystallographic, textural, and chemical analysis of sponge spicules corroborates the view that nano-clustered crystal growth, induced by organic matrices, is a basic characteristic of biomineralisation that enables the production of composite materials with elaborate morphologies.

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A selection of recent results illustrating the application of off-axis electron holography to the study of magnetic microstructure in closely-spaced nanoparticles and nanowires is reviewed. Examples are taken from the characterization of FeNi nanoparticle chains, Co nanoparticle rings, two-dimensional arrays of naturally occurring magnetite crystals in minerals, and single crystalline Co nanowires. Approaches that can be used to separate the magnetic signal of interest from the mean inner potential contribution to the measured holographic phase shift are described, and the spatial and phase resolution that can be achieved are discussed.

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Pure calcium carbonate (calcite and aragonite) solid materials of different particle size (100-200 microm fragments and millimeter-sized single crystals) were interacted with Pb in aqueous solutions at room temperature under atmospheric PCO2. In the case of the micrometer-sized samples, the macroscopic investigation using a batch-type treatment procedure (solutions between 10 and 1000 mg/L Pb) and ICP-AES, SEM-EDS, and powder-XRD showed that the metal is readily removed from the aqueous media by both materials and indicated the sorption processes (mainly surface precipitation leading to overgrowth of cerussite and hydrocerussite crystals) taking place in parallel with surface dissolution processes. The various processes occurring at the calcium carbonate solid-water interface were clearly distinguished and defined in the case of the millimeter-sized samples interacted with 1000 mg/L Pb using a combination of wet-chemical, in-situ (AFM) and ex-situ (AFM, SEM) microscopic, and surface spectroscopic (XPS, 12C-RBS) techniques. The in-situ AFM data revealed the dissolution processes on the surface of the calcium carbonates and the simultaneous heterogeneous nucleation of lead carbonate phases and confirmed the secondary dissolution of lead carbonate crystals grown epitaxially from the initial nuclei. The XPS spectra confirmed that adsorption of Pb occurs simultaneously to dissolution at short interaction times (less than approximately 10 min, prior to precipitation-nucleation/crystal growth) in the case of both CaCO3 polymorphs and that the calcite surface with adsorbed Pb may have an aragonite-type character. The 12C-RBS spectra indicated that absorption (incorporation of Pb2+ ions) also takes place in parallel at the surface layers of the calcium carbonates, resulting in formation of solid solutions.

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