Step Retreat Research Articles

Reconstructing dynamics of the Baltic Ice Stream Complex during deglaciation of the Last Scandinavian Ice Sheet

Abstract. Landforms left behind by the last Scandinavian Ice Sheet (SIS) offer an opportunity to investigate controls governing ice sheet dynamics. Terrestrial sectors of the ice sheet have received considerable attention from landform and stratigraphic investigations. In contrast, despite its geographical importance, the Baltic Sea remains poorly constrained due to limitations in bathymetric data. Both ice-sheet-scale investigations and regional studies at the southern periphery of the SIS have considered the Baltic depression to be a preferential route for ice flux towards the southern ice margin throughout the last glaciation. During the deglaciation the Baltic depression hosted the extensive Baltic Ice Lake, which likely exerted a considerable control on ice dynamics. Here we investigate the Baltic depression using newly available bathymetric data and peripheral topographic data. These data reveal an extensive landform suite stretching from Denmark in the west to Estonia in the east and from the southern European coast to the Åland Sea, comprising an area of 0.3 million km2. We use these landforms to reconstruct aspects of the ice dynamic history of the Baltic sector of the ice sheet. Landform evidence indicates a complex retreat pattern that changes from lobate ice margins with splaying lineations to parallel mega-scale glacial lineations (MSGLs) in the deeper depressions of the Baltic Basin. Ice margin still-stands on underlying geological structures indicate the likely importance of pinning points during deglaciation, resulting in a stepped retreat signal. Over the span of the study area we identify broad changes in the ice flow direction, ranging from SE–NW to N–S and then to NW–SE. MSGLs reveal distinct corridors of fast ice flow (ice streams) with widths of 30 km and up to 95 km in places, rather than the often-interpreted Baltic-wide (300 km) accelerated ice flow zone. These smaller ice streams are interpreted as having operated close behind the ice margin during late stages of deglaciation. Where previous ice-sheet-scale investigations inferred a single ice source, our mapping identifies flow and ice margin geometries from both Swedish and northern Bothnian sources. We anticipate that our landform mapping and interpretations may be used as a framework for more detailed empirical studies by identifying targets to acquire high-resolution bathymetry and sediment cores and also for comparison with numerical ice sheet modelling.

Different Dissolution Molecular Pathways of Azilsartan Crystals with Different Forms Revealed by In Situ Atomic Force Microscopy.

Here, using in situ atomic force microscopy (AFM), the dissolution behaviors and dissolution molecular pathways of two azilsartan crystals, the isopropanol solvate (AZ-IPA), and form I (AZ-I), in pure water and 6-30% poly(ethylene glycol) (PEG) aqueous solutions are revealed. The dissolution behaviors of step retreat and etch pit formation are observed on the (100) faces of the two crystals, with a single step corresponding to one molecular monolayer in crystal structures. Etching rates of pits increase with PEG concentration. Furthermore, our results show that AZ-IPA dissolves by the direct detachment of molecules from the step front to solution. Such a mechanism remains even when the PEG concentration changes. However, AZ-I dissolves primarily by the surface diffusion mechanism involving molecular detachment from the step front at first and then diffusion over the terraces before desorption into solution. PEG promotes the dissolution of AZ-I crystals by favoring the molecular detachment from the step front.

Testing hypotheses of albite dissolution mechanisms at near-equilibrium using Si isotope tracers

Here, we demonstrate the potential advantages of using isotope tracers to test hypotheses of reaction mechanisms near-equilibrium. Using non-traditional stable Si isotopes as tracers, we measured albite unidirectional dissolution rates (r+) across a range of Gibbs free energy of reaction (ΔrG) close to equilibrium (−26 to −2 kJ/mol). Thirteen batch experiment series were conducted at 50 °C and pH ∼ 8 ± 0.25. Different distances from equilibrium were achieved by a stepwise increase of concentrations of Si (0–600 μM), Al (0–10 μM), and Na (0–1000 μM). The temperature, pH, sample preparation, and reaction duration were kept identical to isolate the ΔrG effect. Secondary phase precipitation, which is difficult to avoid in near-equilibrium, near-neutral pH experiments renders the rate measurement method based on changes in Si and Al concentration unworkable, but it should not impact the Si isotope ratios-based rates.The resulting r+ values were nearly constant in the experimental ΔrG range, signaling no major ΔrG-related switch of reaction mechanisms. Our results suggest that the switch from etch pit opening at far-from-equilibrium to step retreat at near-equilibrium does not operate under circum-neutral pH in low-temperature systems; this mechanism switch was proposed based on experimental data in alkaline solutions at hydrothermal temperatures. The nearly constant r+ values at pH 5–8 also suggest that an H2O-catalyzed reaction mechanism dominant at circumneutral pH, in addition to the H+- and OH–-catalyzed reaction mechanisms dominant at acidic and alkaline pH, respectively.The experimental results have implications for geochemical modeling of low-temperature geological and environmental processes. The results suggest that a term of H2O-catalyzed reaction mechanism should be included in rate laws and that the parallel rate law with a mechanism-switch is not applicable in the pH range of 5–8.

Modeling the kinetics of calcite dissolution in neutral and alkaline solutions

Using kinetic Monte Carlo simulations and scaling approaches, we describe the far from equilibrium calcite dissolution in neutral to alkaline solution and in scales ranging from the molecule detachment from surfaces to that of crystalline grains. The parameters of the thermally activated model are calibrated by the velocities of terrace steps and densities of monolayer pits measured in atomic force microscopy works. The application to nanosized crystalline grains shows that they dissolve at room temperature with significant edge rounding, large rates compared to laboratory estimates, and activation energy equal to that of molecule detachment at kink sites. A different kinetic regime is predicted for grains with typical macroscopic sizes or for high temperatures, in which pit nucleation at flat surfaces and step retreat lead to more uniform dissolution. The extrapolation of high temperature simulation data to room temperature gives dissolution rate 0.3–1.4 μmol/(m2 s) and activation energy 64±3 kJ/mol for macroscopic grains with various densities of surface steps. This rate agrees with the smallest values obtained in a recent compilation of laboratory data in alkaline conditions and the activation energy agrees with laboratory estimates. Grains with high densities of kink sites are shown to dissolve with rates ∼101-102 times larger; these estimates are used to predict the contribution of dislocations and explain the largest values of that compilation.

An atomic force microscopy study of calcite dissolution in seawater

We present the first examination of calcite dissolution in seawater using Atomic Force Microscopy (AFM). We quantify step retreat velocity and etch pit density to compare dissolution in seawater to low ionic strength water, and also to compare calcite dissolution under AFM conditions to those conducted in bulk solution experiments (e.g. Subhas et al., 2015, Dong et al., 2018). Bulk dissolution rates and step retreat velocities are slower at high and mid-saturation state (Ω) values and become comparable to low ionic strength water rates at low Ω. The onset of defect-assisted etch pit formation in seawater is at Ω ∼ 0.85 (defined as Ωcritical), higher than in low ionic strength water (Ω ∼ 0.54). There is an abrupt increase in etch pit density (from ∼106 cm−2 to ∼108 cm−2) occurring when Ω falls below 0.7 in seawater, compared to Ω ∼ 0.1 in low ionic strength water, suggesting a transition from defect-assisted dissolution to homogeneous dissolution much closer to equilibrium in seawater. The step retreat velocity (v) does not scale linearly with undersaturation (1-Ω) across an Ω range of 0.4 to 0.9 in seawater, potentially indicating a high order correlation between kink rate and Ω for non-Kossel crystals such as calcite, or surface complexation processes during calcite dissolution in seawater.

A new varve sequence from Windermere, UK, records rapid ice retreat prior to the Lateglacial Interstadial (GI-1)

Annually laminated sediments (varves) provide excellent temporal resolution to study rapid environmental change, but are rare in the early part of the Last Termination (∼19–∼11.7 ka BP). We present a new >400 varve year (vyr) varve sequence in two floating parts from Windermere, a lake at the southern margin of the mountains of northwest England. This sequence records the final retreat of the Windermere glacier at the southern edge of the Lake District Ice Cap during the transition from Heinrich Stadial 1 (∼18–∼14.7 ka BP) into the Lateglacial Interstadial (∼14.7–∼12.9 ka BP).Laminated sediments from four lake cores from Windermere's northern and southern basins were investigated and shown to be varved. These sequences are integrated with seismic reflection evidence to reconstruct south-to-north deglaciation. Seismic and sedimentological evidence is consistent with gradual stepped ice retreat along the entire southern basin and into the northern basin between 255 and 700 vyr prior to the appearance of significant biota in the sediment that heralded the Lateglacial Interstadial, and had retreated past a recessional moraine (RM8) in the northern basin by 121 vyr prior to the interstadial. The Lateglacial Interstadial age of this biota-bearing unit was confirmed by 14C-dating, including one date from the northernmost core of ∼13.5 cal ka BP. A change in mineralogy in all four cores as the glacier retreated north of the Dent Group (the northernmost source of calcareous bedrock) and a decrease in coarse grains in the varves shows that the ice had retreated along the entire North Basin at ∼70 vyr prior to the Lateglacial Interstadial. The estimated retreat rate is 70–114 m yr−1 although buried De Geer moraines, if annual, may indicate retreat of 120 m yr−1 with a ≥3 year stillstand at a recessional moraine halfway along the basin. The glacier then retreated north of the lake basin, becoming land-terminating and retreating at 92.5–49 m yr−1.The northernmost core has a varve sequence ending at least 111 vyr after the other core chronologies, due to the increased proximity to remnant ice in the catchment uplands into the early Lateglacial Interstadial. We show that almost all of the glacier retreat in the Windermere catchment occurred before the abrupt warming at the onset of the Lateglacial Interstadial, in keeping with similar findings from around the Irish Sea Basin, and suggesting a similar retreat timescale for other radial valley glaciers of the Lake District Ice Cap. The seismic and core evidence also show the potential for a much longer varve chronology extending at least 400 and potentially over 1000 vyr further back into Heinrich Stadial 1 (18–14.7 ka BP), suggesting that glacier retreat in the Windermere valley initiated at least before 15.5 ka BP and perhaps 16 ka BP.

Left High and Dry: Deglaciation of Dogger Bank, North Sea, Recorded in Proglacial Lake Evolution

Reconstructions of palaeo-ice sheet retreat in response to climate warming using offshore archives can provide vital analogues for future ice-sheet behaviour. At the Last Glacial Maximum, Dogger Bank, in the southern North Sea, was covered by the Eurasian Ice Sheet. However, the maximum extent and behaviour of the ice sheet in the North Sea basin is poorly constrained. We reveal ice-marginal dynamics and maximum ice extent at Dogger Bank through sedimentological and stratigraphic investigation of glacial and proglacial lake sediments. We use a large, integrated subsurface dataset of shallow seismic reflection and geotechnical data collected during windfarm site investigation. For the first time, an ice stream is identified at Dogger Bank, based on preserved subglacial bedforms, eskers and meltwater channels. During ice-sheet advance, a terminal thrust-block moraine complex formed, whose crest runs approximately north-northeast to south-southwest. Subsequent ice stream shutdown caused stagnation of ice, and rapid retreat of the ice-sheet margin. The moraine complex, and outwash head from an adjacent ice-sheet lobe to the west, dammed a large (approximately 750 km2) proglacial lake. Subsequent sedimentation infilled the lake with 30 m of glacial outwash sediments. A lobate subaqueous fan formed at the ice-sheet margin, which thins towards the southeast with iceberg scours and ice-rafted debris at the base, and is onlapped by lake sediments calibrated to core as alternating clay and silt laminae, interpreted to be varves. The lake became isolated from the retreating ice-sheet margin, and ice-sheet retreat slowed. Sediment-laden meltwater was supplied to the ice-distal proglacial lake for c. 1500-2000 years. Subsequent ice-sheet retreat off Dogger Bank was more rapid due to the negative subglacial slope. The stepped retreat of rapid downwasting, slow retreat, and a final rapid phase off Dogger Bank occurred after the LGM at around 27 ka and before formation of a ribbon lake, dated previously to 23 ka and approximately 60 metres lower in elevation, formed to the north of Dogger Bank. The complicated stratigraphic architecture revealed through these data improves forecasting of ground conditions for turbine footings at Dogger Bank, an important step in the provision of clean, sustainable energy.

In Situ Nanoscale Investigation of Step Retreat on Fluoranthene Crystal Surfaces.

Fluoranthene, a polycyclic aromatic hydrocarbon, has been detected on Earth as well as in asteroids and meteorites and may have played a role in the formation of life. Increasing the ionic strength of aqueous solutions has been observed to lower the fluoranthene solubility, but it is unclear how solution composition controls the release rate of fluoranthene to an aqueous solution. To elucidate this, we performed in situ atomic force microscopy experiments in which we characterized the sublimation and dissolution behavior of fluoranthene crystal surfaces. From this, we quantify the step retreat rate upon exposure to air, deionized water, and a 0.4 M NaCl or 0.1 M MgSO4 solution. Surface roughness is the main factor that determines the dissolution or sublimation rate. The results imply that during fluoranthene remediation or breakdown in meteorites and asteroids, ionic strength will be more important than chemical composition for controlling fluoranthene release into solution.

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.

A kinetic pressure effect on calcite dissolution in seawater

This study provides laboratory data of calcite dissolution rate as a function of seawater undersaturation state (1 − Ω) under variable pressure. 13C-labeled calcite was dissolved in unlabeled seawater and the evolving δ13C composition of the fluid was monitored over time to evaluate the dissolution rate. Results show that dissolution rates are enhanced by a factor of 2–4 at 700 dbar compared to dissolution at the same Ω under ambient pressure (10 dbar). This dissolution rate enhancement under pressure applies over an Ω range of 0.65–1 between 10 dbar and 700 dbar. Above 700 dbar (up to 2500 dbar), dissolution rates become independent of pressure. The observed enhancement is well beyond the uncertainty associated with the thermodynamic properties of calcite under pressure (partial molar volume ΔV), and thus should be interpreted as a kinetic pressure effect on calcite dissolution. Dissolution at ambient pressure and higher pressures yield non-linear dissolution kinetics, the pressure effect does not significantly change the reaction order n in Rate = k(1 − Ω)n, which is shown to vary from 3.1 ± 0.3 to 3.8 ± 0.5 from 10 dbar to 700 dbar over Ω = 0.65–0.9. Furthermore, two different dissolution mechanisms are indicated by a discontinuity in the rate-undersaturation relationship, and seen at both ambient and higher pressures. The discontinuity, Ωcritical = 0.87 ± 0.05 and 0.90 ± 0.03 at 10 dbar and 1050 dbar respectively, are similar within error. The reaction order, n, at Ω > 0.9 is 0.47 ± 0.27 and 0.46 ± 0.15 at 10 dbar and 700 dbar respectively. This Ωcritical is considered to be the threshold between step retreat dissolution and defect-assisted dissolution. The kinetic enhancement of dissolution rates at higher pressures is related to a decrease in the interfacial energy barrier at dissolution sites. The impact of pressure on the calcite dissolution kinetics implies that sinking particles would dissolve at shallower depths than previously thought.

Trough geometry was a greater influence than climate-ocean forcing in regulating retreat of the marine-based Irish-Sea Ice Stream

Marine terminating ice streams are a major component of contemporary ice sheets and are likely to have a fundamental influence on their future evolution and concomitant contribution to sea-level rise. To accurately predict this evolution requires that modern day observations can be placed into a longer-term context and that numerical ice sheet models used for making predictions are validated against known evolution of former ice masses. New geochronological data document a stepped retreat of the paleo−Irish Sea Ice Stream from its Last Glacial Maximum limits, constraining changes in the time-averaged retreat rates between well-defined ice marginal positions. The timing and pace of this retreat is compatible with the sediment-landform record and suggests that ice marginal retreat was primarily conditioned by trough geometry and that its pacing was independent of ocean-climate forcing. We present and integrate new luminescence and cosmogenic exposure ages in a spatial Bayesian sequence model for a north-south (173km) transect of the largest marine-terminating ice stream draining the last British−Irish Ice Sheet. From the south and east coasts of Ireland, initial rates of ice margin retreat were as high as 300−600 m a−1, but retreat slowed to 26 m a−1 as the ice stream became topographically constricted within St George’s Channel, a sea channel between Ireland to the west and Great Britain to the east, and then stabilized (retreating at only 3 m a−1) at the narrowest point of the trough during the climatic warming of Greenland Interstadial 2 (GI-2: 23.3−22.9 ka). Later retreat across a normal bed-slope during the cooler conditions of Greenland Stadial 2 was unexpectedly rapid (152 m a−1). We demonstrate that trough geometry had a profound influence on ice margin retreat and suggest that the final rapid retreat was conditioned by ice sheet drawdown (dynamic thinning) during stabilization at the trough constriction, which was exacerbated by increased calving due to warmer ocean waters during GI-2.

Study of Iron-Bearing Dolomite Dissolution at Various Temperatures: Evidence for the Formation of Secondary Nanocrystalline Iron-Rich Phases on the Dolomite Surface

We investigated the dissolution of a natural Fe-containing dolomite [Ca1.003Mg0.972Fe0.024Mn0.002(CO3)2] under acidic conditions (pH 3–5.5) with atomic force microscopy (AFM) at 20 °C and with batch dissolution experiments at 80 °C. Dolomite dissolution proceeded by two identified mechanisms: removal of dolomite layers through spreading and coalescence of etch pits nucleated at defect points, and stepped retreat from surface edges. The dolomite dissolution rate increased when pH decreased (from 0.410 nm s–1 at pH 3 to 0.035 nm s–1 at pH 5). Rates calculated from edge retreat (vedges) and from etch-pit spreading rates (vsum) were consistent; the etch-pit digging rate was almost 10 times slower than its spreading rate. Nanocrystalline secondary phases precipitated in the course of dolomite dissolution at pH 3 and 80 °C were identified as (nano)hematite, ferrihydrite, and an ankerite like mineral using X-ray diffraction, transmission electron microscopy, MicroRaman and X-ray photoelectron spectrometry. In ad...

Exploring dynamic surface processes during silicate mineral (wollastonite) dissolution with liquid cell TEM.

Most liquid cell transmission electron microscopy (LC TEM) studies focus on nanoparticles or nanowires, in large part because the preparation and study of materials in this size range is straightforward. By contrast, this is not true for samples in the micrometre size range, in large part because of the difficulties associated with sample preparation starting from a 'bulk' material. There are also many advantages inherent to the study of micrometre-sized samples compared to their nanometre-sized counterparts. Here, we present a liquid cell transmission electron study that employed an innovative sample preparation technique using focused ion beam (FIB) milling to fabricate micrometre-sized electron transparent lamellae that were then welded to the liquid cell substrate. This technique, for which we have described in detail all of the fabrication steps, allows for samples having dimensions of several square micrometres to be observed by TEM in situ in a liquid. We applied this technique to test whether we could observe and measure in situ dissolution of a crystalline material called wollastonite, a calcium silicate mineral. More specifically, this study was used to observe and record surface dynamics associated with step and terrace edge movement, which are ultimately linked to the overall rate of dissolution. The wollastonite lamella underwent chemical reactions in pure deionized water at ambient temperature in a liquid cell with a 5-μm-spacer thickness. The movement of surface steps and terraces was measured periodically over a period of almost 5 h. Quite unexpectedly, the one-dimensional rates of retreat of these surface features were not constant, but changed over time. In addition, there were noticeable quantitative differences in retreat rates as a function crystallographic orientation, indicating that surface retreat is anisotropic. Several bulk rates of dissolution were also determined (1.6-4.2 • 10-7 mol m-2 s-1 ) using the rates of retreat of representative terraces and steps, and were found to be within one order of magnitude of dissolution rates in the literature based on aqueous chemistry data.

Understanding the mechanisms of solid-water reactions through analysis of surface topography.

The topography of a reactive surface contains information about the reactions that form or modify the surface and, therefore, it should be possible to characterize reactivity using topography parameters such as surface area, roughness, or fractal dimension. As a test of this idea, we consider a two-dimensional (2D) lattice model for crystal dissolution and examine a suite of topography parameters to determine which may be useful for predicting rates and mechanisms of dissolution. The model is based on the assumption that the reactivity of a surface site decreases with the number of nearest neighbors. We show that the steady-state surface topography in our model system is a function of, at most, two variables: the ratio of the rate of loss of sites with two neighbors versus three neighbors (d(2)/d(3)) and the ratio of the rate of loss of sites with one neighbor versus three neighbors (d(1)/d(3)). This means that relative rates can be determined from two parameters characterizing the topography of a surface provided that the two parameters are independent of one another. It also means that absolute rates cannot be determined from measurements of surface topography alone. To identify independent sets of topography parameters, we simulated surfaces from a broad range of d(1)/d(3) and d(2)/d(3) and computed a suite of common topography parameters for each surface. Our results indicate that the fractal dimension D and the average spacing between steps, E[s], can serve to uniquely determine d(1)/d(3) and d(2)/d(3) provided that sufficiently strong correlations exist between the steps. Sufficiently strong correlations exist in our model system when D>1.5 (which corresponds to D>2.5 for real 3D reactive surfaces). When steps are uncorrelated, surface topography becomes independent of step retreat rate and D is equal to 1.5. Under these conditions, measures of surface topography are not independent and any single topography parameter contains all of the available mechanistic information about the surface. Our results also indicate that root-mean-square roughness cannot be used to reliably characterize the surface topography of fractal surfaces because it is an inherently noisy parameter for such surfaces with the scale of the noise being independent of length scale.

In-Situ Atomic Force Microscopy Study of the Dissolution of Nanoporous SAPO-34 and SAPO-18

In-situ atomic force microscopy has been used to investigate the dissolution behavior of industrially relevant silicoaluminophosphate catalysts SAPO-34 and SAPO-18. Spiral growth is prevalent on these materials and it is common for the spirals to be composites of multiple dislocation sources. The spirals dissolve via classical step retreat and the structure dissolves in a two-step process via unstable intermediates. The data support the proposition that the terminating surface of SAPO-34 is composed of double 6-rings. SAPO-34 and SAPO-18 both dissolve by removal of the same structural units with similar mechanisms.

Direct Nanoscale Imaging of Calcium Oxalate Crystallization on Brushite Reveals the Mechanisms Underlying Stone Formation

A mixture of calcium oxalate and calcium phosphate is a source of chronic human disease, forming kidney stones. However, the mechanisms of pathological biomineralization and its modulation by natural inhibitors such as osteopontin (OPN) proteins are poorly defined at the nanoscale. Here, the in vitro formation of calcium oxalate monohydrate (COM) concretions having brushite nidi is observed using in situ atomic force microscopy (AFM) in a simulated acidic urinary milieu. We quantify the dissolution kinetics of the [101]Cc, [1̅00]Cc, and [101̅]Cc steps on the brushite (CaHPO4·2H2O, DCPD) (010) surfaces by oxalate, two urinary constituents. In support of clinical observations, we further demonstrate the inhibitory effect of phosphorylated OPN peptides on the step retreat rates through step-specific interactions, this in turn regulating the kinetics of COM nucleation and aggregation at the expense of brushite crystals by means of the interfacial mineral replacement reactions. The definition of respective roles for DCPD and OPN peptides thereby offers general insights concerning the control of kidney stone formation and the mechanisms through which aberrant crystallization kinetics is inhibited.

In situ observation of biotite (001) surface dissolution at pH 1 and 9.5 by advanced optical microscopy.

Laser confocal differential interference contrast microscopy (LCM-DIM) allows for the study of the reactivity of surface minerals with slow dissolution rates (e.g., phyllosilicates). With this technique, it is possible to carry out in situ inspection of the reacting surface in a broad range of pH, ionic strength and temperature providing useful information to help unravel the dissolution mechanisms of phyllosilicates. In this work, LCM-DIM was used to study the mechanisms controlling the biotite (001) surface dissolution at pH 1 (11 and 25 °C) and pH 9.5 (50 °C). Step edges are the preferential sites of dissolution and lead to step retreat, regardless of the solution pH. At pH 1, layer swelling and peeling takes place, whereas at pH 9.5 fibrous structures (streaks) form at the step edges. Confocal Raman spectroscopy characterization of the reacted surface could not confirm if the formation of a secondary phase was responsible for the presence of these structures.

In situ AFM study on barite (0 0 1) surface dissolution in NaCl solutions at 30 °C

This paper reports in situ observations on barite (001) surface dissolution behavior in 0.1–0.001M NaCl solutions at 30°C using atomic force microscopy (AFM). The step retreating on barite (001) surfaces changed with increasing NaCl solution concentrations. In solutions with a higher NaCl concentration (⩾0.01M), many steps showed curved or irregular fronts during the later experimental stage, while almost all steps in solutions with a lower NaCl concentration exhibited straight or angular fronts, even during the late stage. The splitting phenomenon of the initial 〈hk0〉 one-layer steps (7.2Å) into two half-layer steps (3.6Å) occurred in all NaCl solutions, while that of the initial [010] one-layer steps observed only in the 0.1M NaCl solution. The step retreat rates increased with an increasing NaCl solution concentration. We observed triangular etch pit and deep etch pit formation in all NaCl solutions, which tended to form late in solutions with lower NaCl concentrations. The deep etch pit morphology changed with increasing NaCl solution concentrations. A hexagonal form elongated in the [010] direction was bounded by the {100}, {310}, and (001) faces in a 0.001M NaCl solution, and a rhombic form was bounded by the {510} and (001) faces in 0.01M and 0.1M NaCl solutions. An intermediate form was observed in a 0.005M NaCl solution, which was defined by {100}, a curved face tangent to the [010] direction, {310}, and (001) faces: the intermediate form appeared between the hexagonal and rhombic forms in solutions with lower and higher NaCl concentrations, respectively. The triangular etch pit and deep etch pit growth rates also increased with the NaCl solution concentration. Combining the step and face retreat rates in NaCl solutions estimated in this AFM study as well as the data on the effect of water temperature on the retreat rates reported in our earlier study, we produced two new findings. One finding is that the retreat rates increase by approximately two-fold when the NaCl solution concentration increases by one order of magnitude, and the other finding is that the retreat rate increase due to a one order of magnitude increase in the NaCl concentration corresponds to an increase of approximately 8°C in water temperature. This correlation may help to understand and evaluate increasing dissolution kinetics induced by the different mechanisms where barite dissolution is promoted by the catalytic effect of Na+ and Cl− ions (through an increase in the NaCl solution concentration) or by an increase in the hydration of Ba2+ and SO42− (through an increase in water temperature).

Direct Imaging of Nanoscale Dissolution of Dicalcium Phosphate Dihydrate by an Organic Ligand: Concentration Matters

Unraveling the kinetics and mechanisms of sparingly soluble calcium orthophosphate (Ca-P) dissolution in the presence of organic acids at microscopic levels is important for an improved understanding in determining the effectiveness of organic acids present in most rhizosphere environments. Herein, we use in situ atomic force microscopy (AFM) coupled with a fluid reaction cell to image dissolution on the (010) face of brushite, CaHPO4 · 2H2O, in citrate-bearing solutions over a broad concentration range. We directly measure the dependence of molecular step retreat rate on citrate concentration at various pH values and ionic strengths, relevant to soil solution conditions. We find that low concentrations of citrate (10-100 μM) induced a reduction in step retreat rates along both the [100]Cc and [101]Cc directions. However, at higher concentrations (exceeding 0.1 mM), this inhibitory effect was reversed with step retreat speeds increasing rapidly. These results demonstrate that the concentration-dependent modulation of nanoscale Ca-P phase dissolution by citrate may be applied to analyze the controversial role of organic acids in enhancing Ca-P mineral dissolution in a more complex rhizosphere environment. These in situ observations may contribute to resolving the previously unrecognized interactions of root exudates (low molecular weight organic acids) and sparingly soluble Ca-P minerals.

Cholesterol Monohydrate Dissolution in the Presence of Bile Acid Salts

The molecular-level dissolution of cholesterol monohydrate single crystal (001) surfaces was systematically investigated in aqueous solutions of chenodeoxycholate (CDC) and ursodeoxycholate (UDC) using in situ atomic force microscopy (AFM). Dissolution via the layer-by-layer step retreat of monolayers was observed in solutions where the bile salt concentration exceeded the critical micelle concentration (cmc). Studies performed in CDC solution revealed markedly lower cmc values than in UDC. An abrupt transition from sporadic to continuous dissolution between ∼4–7 mM CDC was consistent with a previously proposed 2-step model for micelle formation. In contrast, cholesterol dissolution in UDC was apparent at ∼14 mM with no abrupt change in dissolution rate with increasing UDC concentration. Comparison with previous dissolution studies performed in aqueous ethanol (Cryst. Growth Des. 2005, 5, 2146–2153) reveal key differences in micelle-mediated versus bulk dissolution mechanisms.