Oxide- and Silicate-Water Interfaces and Their Roles in Technology and the Environment.

Interfacial reactions drive all elemental cycling on Earth and play pivotal roles in human activities such as agriculture, water purification, energy production and storage, environmental contaminant remediation, and nuclear waste repository management. The onset of the 21st century marked the beginning of a more detailed understanding of mineral aqueous interfaces enabled by advances in techniques that use tunable high-flux focused ultrafast laser and X-ray sources to provide near-atomic measurement resolution, as well as by nanofabrication approaches that enable transmission electron microscopy in a liquid cell. This leap into atomic- and nanometer-scale measurements has uncovered scale-dependent phenomena whose reaction thermodynamics, kinetics, and pathways deviate from previous observations made on larger systems. A second key advance is new experimental evidence for what scientists hypothesized but could not test previously, namely, interfacial chemical reactions are frequently driven by "anomalies" or "non-idealities" such as defects, nanoconfinement, and other nontypical chemical structures. Third, progress in computational chemistry has yielded new insights that allow a move beyond simple schematics, leading to a molecular model of these complex interfaces. In combination with surface-sensitive measurements, we have gained knowledge of the interfacial structure and dynamics, including the underlying solid surface and the immediately adjacent water and aqueous ions, enabling a better definition of what constitutes the oxide- and silicate-water interfaces. This critical review discusses how science progresses from understanding ideal solid-water interfaces to more realistic systems, focusing on accomplishments in the last 20 years and identifying challenges and future opportunities for the community to address. We anticipate that the next 20 years will focus on understanding and predicting dynamic transient and reactive structures over greater spatial and temporal ranges as well as systems of greater structural and chemical complexity. Closer collaborations of theoretical and experimental experts across disciplines will continue to be critical to achieving this great aspiration.

Direct Nanoscale Imaging Reveals the Mechanism by Which Organic Acids Dissolve Vivianite through Proton and Ligand Effects.

The coprecipitation of iron (Fe) and phosphorus (P) in natural environments limits their bioavailability. Plant root-secreted organic acids can dissolve Fe-P precipitates, but the molecular mechanism underlying mobilizing biogenic elements from highly insoluble inorganic minerals remains poorly understood. Here, we investigated vivianite (Fe3(PO4)2·8H2O) dissolution by organic acids (oxalic acid (OA), citric acid (CA), and 2'-dehydroxymugineic acid (DMA)) at three different pH values (4.0, 6.0, and 8.0). With increasing pH, the vivianite dissolution efficiency by OA and CA was decreased while that by DMA was increased, indicating various dissolution mechanisms of different organic acids. Under acidic conditions, weak ligand OA (HC2O4- > C2O42- at pH 4.0 and C2O42- at pH 6.0) dissolved vivianite through the H+ effect to form irregular pits, but under alkaline condition (pH 8.0), the completely deprotonated OA was insufficient to dissolve vivianite. At pH 4.0, CA (H2Cit- > HCit2- > H3Cit) dissolved vivianite to form irregular pits through a proton-promoted mechanism, while at pH 6.0 (HCit2- > Cit3-) and pH 8.0 (Cit3-), CA dissolved vivianite to form near-rhombohedral pits through a ligand-promoted mechanism. At three pH values ((H0)DMA3- > (H1)DMA2- at pH 4.0, (H0)DMA3- at pH 6.0, and (H0)DMA3- and one deprotonated imino at pH 8.0), strong ligand DMA dissolved vivianite to form near-rhombohedral pits via ligand-promoted mechanisms. Raman spectroscopy showed that the deprotonated carboxyl groups (COO-) and imino groups were bound to Fe on the vivianite (010) face. The surface free energy of vivianite coated with OA decreased from 29.32 mJ m-2 to 24.23 mJ m-2 and then to 13.47 mJ m-2 with increasing pH, and that coated with CA resulted in a similar pH-dependent vivianite surface free-energy decrease while that coated with DMA increased the vivianite surface free energy from 31.92 mJ m-2 to 39.26 mJ m-2 and then to 49.93 mJ m-2. Density functional theory (DFT)-based calculations confirmed these findings. Our findings provide insight into the mechanism by which organic acids dissolved vivianite through proton and ligand effects.

Molecular mechanisms for the humic acid-enhanced formation of the ordered secondary structure of a conserved catalytic domain in phytase.

Changes in the secondary structure of phytase, particularly the conserved active catalytic domain (ACD, SRHGVRAPHD) are extremely important for the varied catalytic activity during hydrolyzing phytate in the presence of humic acid (HA). However, little is known about the molecular-scale mechanisms of how HA influences the secondary structure of ACD found in phytase. First, in situ surface-enhanced Raman spectroscopy (SERS) results show the secondary structure transformation of ACD from the unordered random coil to the ordered ß-sheet structure after treatment with HA. Then, we use an atomic force microscopy (AFM)-based single-molecule force spectroscopy (SMFS) technique that can in situ directly probe the single-molecule interaction of ACD with HA and underlying changes in ACD secondary structure in the approach-retraction cycles in real time. Based on the SMFS results, we further detect the HA-enhanced formation of H-bonding between amide groups in the ACD backbone after noncovalently interacting with HA in the absence of phytate. Following the addition of phytate, the calculated contour length (Lc) and the free energies (ΔGb) of functional groups within ACD(-1/2) binding to mica/HA collectively demonstrate the formation of the organized intermediate structural state of ACD following its covalent binding to phytate. These spectroscopic and single-molecule determinations provide the molecular-scale understanding regarding the detailed mechanisms of HA-enhancement of the ordered ß-sheet secondary structure of ACD through chemical functionalities in ACD noncovalently interacting with HA. Therefore, we suggest that similar studies of the interactions of other soil enzymes and plant nutrients may reveal predominant roles of dissolved organic matter (DOM) in controlling elemental cycling and fate for sustainable agriculture development.

Dissolution and Precipitation Dynamics at Environmental Mineral Interfaces Imaged by In Situ Atomic Force Microscopy.

Chemical reactions at the mineral-solution interface control important interfacial processes, such as geochemical element cycling, nutrient recovery from eutrophicated waters, sequestration of toxic contaminants, and geological carbon storage by mineral carbonation. By time-resolved in situ imaging of nanoscale mineral interfacial reactions, it is possible to clarify the mechanisms governing mineral-fluid reactions.In this Account, we present a concise summary of this topic that addresses a current challenge at the frontier of understanding mineral interfaces and their importance to a wide range of mineral re-equilibration processes in the presence of a fluid aqueous phase. We have used real-time nanoscale imaging of liquid-cell atomic force microscopy (AFM) to observe the in situ coupling of the dissolution-precipitation process, whereby the dissolution of a parent mineral phase is coupled at mineral interfaces with the precipitation of another product phase, chemically different from the parent. These nanoscale observations allow for the identification of dissolution and growth rates through systematically investigating various minerals, including calcite (CaCO3), siderite (FeCO3), cerussite (PbCO3), magnesite (MgCO3), dolomite (CaMg(CO3)2), brushite (CaHPO4·2H2O), brucite (Mg(OH)2), portlandite (Ca(OH)2), and goethite (α-FeOOH), in various reacting aqueous fluids containing solution species, such as arsenic, phosphate, organo- or pyrophosphate, CO2, selenium, lead, cadmium, iron, chromium, and antimony. We detected the in situ replacement of these parent mineral phases by product phases, identified through a variety of analytical methods such as Raman spectroscopy, high-resolution transmission electron microscopy, and various X-ray techniques, as well as modeling by geochemical simulation using PHREEQC. As a consequence of the coupled processes, sequestration of toxic elements and hazardous species and inorganic and organic carbon, and limiting or promoting recovery of nutrients can be achieved at nano- and macroscopic scales.We also used in situ AFM to quantitatively measure the retreat rates of molecular steps and directly observe the morphology changes of dissolution etch pits on calcium phosphates in organic acid solutions present in most rhizosphere environments. By molecular modeling using density functional theory (DFT), we explain the origin of dissolution etch pit evolution through specific stereochemistry and molecular recognition and provide an energetic basis by calculating the binding energies of chemical functionalities on organic acids to direction-specific steps on mineral surfaces. In addition, we further quantified precipitation kinetics of calcium phosphates (Ca-P's) on typical mineral surfaces at the nanoscale in environmentally relevant solutions with various organic molecules, by measurements obtained from sequential images obtained by liquid-cell AFM. In situ dynamic force spectroscopy (DFS) was used to determine binding energies of single-molecules with different chemical functionalities found in natural organic matter at mineral-fluid interfaces. Quantifying molecular organo-mineral bonding or binding energies mechanistically explains phosphate precipitation and transformation. From DFS measurements, molecular-scale interactions of mineral-natural organic matter (DNA, proteins, and polysaccharides) associations were determined. With this powerful tool, single-molecule determinations of polysaccharide-amorphous iron oxide or hematite interactions provided the mechanistic origin of the phase- or facet-dependent adsorption. These systematic investigations and findings significantly contribute to a more quantitative prediction of the fate of nutrients and contaminants, chemical element cycling, and potential geological carbon capture and nuclear waste storage in aqueous environments.

Phosphorylated/Nonphosphorylated Motifs in Amelotin Turn Off/On the Acidic Amorphous Calcium Phosphate-to-Apatite Phase Transformation.

Amelotin (AMTN) as a matrix protein exerts a direct effect on biomineralization by modulating apatite (HAP) formation during the dental enamel maturation stage through the specific interaction of a potentially phosphorylated Ser-Ser-Glu-Glu-Leu (SSEEL) peptide fragment with calcium phosphate (Ca-P) surfaces. However, the roles of (non)phosphorylation of this evolutionarily conserved subdomain within AMTN remain poorly understood. Here, we show, by time-resolved atomic force microscopy (AFM) imaging of in situ HAP crystallization via the HPO42--rich amorphous calcium phosphate (acidic ACP), the on/off switching of the phase transformation process through a nonphosphorylation-to-phosphorylation transition of the SSEEL motif. Using high-resolution transmission electron microscopy (HRTEM), we observed that the acidic ACP phase is stabilized by the phosphorylated SSEEL motif, delaying its transformation to HAP, whereas the nonphosphorylated counterpart promotes HAP formation by accelerating the dissolution-recrystallization of the acidic ACP substrate. Dynamic force spectroscopy measurements demonstrate greater binding energies of nonphosphorylated SSEEL to the acidic ACP substrate by the formation of molecular peptide-ACP bonding, explaining the enhanced dissolution of the acidic ACP substrate by stronger complexion with surface Ca2+ ions. Our findings demonstrate direct evidence for the switching role of (non)phosphorylation of an evolutionarily conserved subdomain within AMTN in controlling the phase transition of growing enamel and designing tissue regeneration biomaterials.

Molecular Understanding of Humic Acid-Limited Phosphate Precipitation and Transformation.

Phosphorus (P) availability is widely assumed to be limited by the formation of metal (Ca, Fe, or Al) phosphate precipitates that are modulated by soil organic matter (SOM), but the SOM-precipitate interactions remain uncertain because of their environmental complexities. Here, we present a model system by quantifying the in situ nanoscale nucleation kinetics of calcium phosphates (Ca-Ps) on mica in environmentally relevant aqueous solutions by liquid-cell atomic force microscopy. We find that Ca-P precipitate formation is slower when humic acid (HA) concentration is higher. High-resolution transmission electron microscopy observations demonstrate that HA strongly stabilizes amorphous calcium phosphate (ACP), delaying its subsequent transformation to thermodynamically more stable phases. Consistent with the formation of molecular organo-mineral bonding, dynamic force spectroscopy measurements display larger binding energies of organic ligands with certain chemical functionalities on HA to the initially formed ACP than to mica that are responsible for stabilization of ACP through stronger HA-ACP interactions. Our results provide direct evidence for the proposed importance of SOM in inhibiting Ca-P precipitation/transformation. We suggest that similar studies of binding strength in SOM-Fe/Al-P may reveal how both organic matter and metal ions control P availability and fate, and thus the eventual P management for agronomical and environmental sustainability.

Molecular-Scale Investigations Reveal Noncovalent Bonding Underlying the Adsorption of Environmental DNA on Mica.

Mineral-soil organic matter (SOM including DNA, proteins, and polysaccharides) associations formed through various interactions, play a key role in regulating long-term SOM preservation. The mechanisms underlying DNA-mineral and DNA-protein/polysaccharide interactions at nanometer and molecular scales in environmentally relevant solutions remain uncertain. Here, we present a model mineral-SOM system consisting of mineral (mica)-nucleic acid (environmental DNA, eDNA)/protein (bovine serum albumin)/polysaccharide (alginate), and combine atomic force microscopy (AFM)-based dynamic force spectroscopy and PeakForce quantitative nanomechanical mapping using DNA-decorated tips. Single-molecule binding and adhesion force of eDNA to mineral and to mineral adsorbed by protein/polysaccharide reveal the noncovalent bonds and that systematically changing ion compositions, ionic strength, and pH result in significant differences in organic-organic and organic-mineral binding energies. Consistent with the bond-strength measurements, protein, rather than polysaccharide, promotes mineral-bound DNA molecules by ex situ AFM deposition observations in relatively high concentrations of divalent cation-containing acidic solutions. These molecular-scale determinations and nanoscale observations should substantially improve our understanding of how environmental factors influence the organic-mineral interfacial interactions through the synergy of collective noncovalent and/or covalent bonds in mineral-organic associations.

Direct Observations of the Occlusion of Soil Organic Matter within Calcite.

Global soil carbon cycling plays a key role in regulating and stabilizing the earth's climate change because of soils with amounts of carbon at least three times greater than those of other ecological systems. Soil minerals have also been shown to underlie the persistence of soil organic matter (SOM) through both adsorption and occlusion, but the microscopic mechanisms that control the latter process are poorly understood. Here, using time-resolved in situ atomic force microscopy (AFM) to observe how calcite, a representative mineral in alkaline soils, interacts with humic substances, we show that following adsorption, humic substances are gradually occluded by the advancing steps of spirals on the calcite (1014) face grown in relatively high supersaturated solutions, through the embedment, compression, and closure of humic substance particles into cavities. This occlusion progress is inhibited by phytate at high concentrations (10-100 µM) due to the formation of phytate-Ca precipitates on step edges to prevent the step advancement, whereas phytate at relatively low concentrations (≤1 µM) and oxalate at high concentrations (100 µM) have little effect on this process. These in situ observations may provide new insights into the organo-mineral interaction, resulting in the incorporation of humic substances into minerals with a longer storage time to delay degradation in soils. This will improve our understanding of carbon cycling and immobilization in soil ecological systems.

Humic Acids Limit the Precipitation of Cadmium and Arsenate at the Brushite-Fluid Interface.

Bioavailability and mobility of cadmium (Cd2+) and arsenate (As5+) in soils can be effectively lowered through the dissolution of brushite (dicalcium phosphate dihydrate, CaHPO4·2H2O) coupled with the precipitation of a more stable mineral phase containing both Cd and As. Due to the ubiquitous presence of humic acid (HA) in soil environments, it is more complex to predict the fate of dissolved Cd and As during such sequestration. Here, we used in situ atomic force microscopy (AFM) to image the kinetics of simultaneous precipitation of Cd and As at the brushite-fluid interface in the presence of HA. Results show that HA inhibits the formation of both amorphous and crystalline Cd(5- x)Ca x(PO4)(3- y)(AsO4) y(OH) on the (010) face of brushite. A combination of X-ray photoelectron spectroscopy (XPS) and real-time surface-enhanced Raman spectroscopy (SERS) reveals that part of As5+ reduction into As3+ with HA and [HA-Cd] complexation occurs, modulating the concentrations of free Cd2+ and As5+ ions to inhibit subsequent precipitation of a Cd(5- x)Ca x(PO4)(3- y)(AsO4) y(OH) phase on the dissolving brushite surface. A combination of AFM imaging, SERS analyses, and PhreeqC simulations suggests that environmentally relevant humic substances can limit the precipitation of Cd and As at mineral surfaces through a mechanism of oxidation/reduction and aqueous/surface complexation. This may exacerbate the transportation of these contaminants into waters by subsurface fluid flow, and research attempts to weaken the negative effect of HA are needed.

Dynamics and Molecular Mechanism of Phosphate Binding to a Biomimetic Hexapeptide.

Phosphorus (P) recovery from wastewater is essential for sustainable P management. A biomimetic hexapeptide (SGAGKT) has been demonstrated to bind inorganic P in P-rich environments, however the dynamics and molecular mechanisms of P-binding to the hexapeptide still remain largely unknown. We used dynamic force spectroscopy (DFS) to directly distinguish the P-unbound and P-bound SGAGKT adsorbed to a mica (001) surface by measuring the single-molecule binding free energy (Δ Gb). Using atomic force microscopy (AFM) to determine real-time step retreat velocities of triangular etch pits formed at the nanoscale on the dissolving (010) face of brushite (CaHPO4·2H2O) in the presence of SGAGKT, we observed that SGAGKT peptides promoted in situ dissolution through an enhanced P-binding driven by hydrogen bonds in a P-loop being capable of discriminating phosphate over arsenate, concomitantly forming a thermodynamically favored SGAGKT-HPO42- complexation at pH 8.0 and relatively low ionic strength, consistent with the DFS and isothermal titration calorimetry (ITC) determinations. The findings reveal the thermodynamic and kinetic basis for binding of phosphate to SGAGKT and provide direct evidence for phosphate discrimination in phosphate/arsenate-rich environments.

Direct Observation of Simultaneous Immobilization of Cadmium and Arsenate at the Brushite-Fluid Interface.

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.

Sequestration of Antimony on Calcite Observed by Time-Resolved Nanoscale Imaging.

Antimony, which has damaging effects on the human body and the ecosystem, can be released into soils, ground-, and surface waters either from ore minerals that weather in near surface environments, or due to anthropogenic releases from waste rich in antimony, a component used in batteries, electronics, ammunitions, plastics, and many other industrial applications. Here, we show that dissolved Sb can interact with calcite, a widespread carbonate mineral, through a coupled dissolution-precipitation mechanism. The process is imaged in situ, at room temperature, at the nanometer scale by using an atomic force microscope equipped with a flow-through cell. Time-resolved imaging allowed following the coupled process of calcite dissolution, nucleation of precipitates at the calcite surface and growth of these precipitates. Sb(V) forms a precipitate, whereas Sb(III) needs to be oxidized to Sb(V) before being incorporated in the new phase. Scanning-electron microscopy and Raman spectroscopy allowed identification of the precipitates as two different calcium-antimony phases (Ca2Sb2O7). This coupled dissolution-precipitation process that occurs in a boundary layer at the calcite surface can sequester Sb as a solid phase on calcite, which has environmental implications as it may reduce the mobility of this hazardous compound in soils and groundwaters.

Imaging Organophosphate and Pyrophosphate Sequestration on Brucite by in Situ Atomic Force Microscopy.

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.

In Situ Nanoscale Imaging of Struvite Formation during the Dissolution of Natural Brucite: Implications for Phosphorus Recovery from Wastewaters.

As phosphorus (P) resources are diminishing, the recovery of this essential nutrient from wastewaters becomes an increasingly interesting option. P-recovery through the controlled crystallization of struvite (MgNH4PO4·6H2O), a potential slow-release fertilizer, is highly attractive, but costly if large amounts of Mg have to be added. In this context, natural Mg-minerals like brucite (Mg(OH)2) could provide more cost-effective Mg-sources compared to high-grade Mg-compounds such as MgCl2. Here we used in situ atomic force microscopy (AFM) to study the interactions of ammonium phosphate solutions with brucite (001) cleavage surfaces. Brucite dissolution was strongly enhanced in the presence of H2PO4- ions, most likely due to the formation of negatively charged surface complexes. Simultaneously with brucite dissolution, we directly observed the formation of a new phase that was identified as struvite by Raman spectroscopy. Our results suggest that brucite dissolution and struvite precipitation were coupled at the mineral-fluid interface within a thin fluid boundary layer. An interpretation is proposed where the heterogeneous nucleation and growth of struvite occurs via a particle-mediated process involving the formation of primary nanoparticles, followed by their continuous aggregation, fusion and possible transformation to crystalline struvite. These observations have implications for the feasibility of using brucite in phosphorus recovery processes.

Visualizing Organophosphate Precipitation at the Calcite-Water Interface by in Situ Atomic-Force Microscopy.

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.

In situ imaging of interfacial precipitation of phosphate on Goethite.

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.

Modelling the effects of salt solutions on the hydration of calcium ions.

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.

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.

Sequestration of selenium on calcite surfaces revealed by nanoscale imaging.

Calcite, a widespread natural mineral at the Earth's surface, is well-known for its capacity to sequester various elements within its structure. Among these elements, selenium is important because of its high toxicity in natural systems and for human health. In the form of selenite (Se((IV))), selenium can be incorporated into calcite during growth. Our in situ atomic force microscopy observations of calcite surfaces during contact with selenium-bearing solutions demonstrate that another process of selenium trapping can occur under conditions in which calcite dissolves. Upon the injection of solutions containing selenium in two states of oxidation (either Se((IV)) or Se((VI))), precipitates were observed forming while calcite was still dissolving. In the presence of selenate (Se((VI))), the precipitates formed remained small during the observation period. When injecting selenite (Se((IV))), the precipitates grew significantly and were identified as CaSeO3·H2O, based on SEM observations, Raman spectroscopy, and thermodynamic calculations. An interpretation is proposed where the dissolution of calcite increases the calcium concentration in a thin boundary layer in contact with the surface, allowing the precipitation of a selenium phase. This process of dissolution-precipitation provides a new mechanism for selenium sequestration and extends the range of thermodynamic conditions under which such a process is efficient.

Coupled dissolution and precipitation at the cerussite-phosphate solution interface: implications for immobilization of lead in soils.

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.