Cornelius Fischer

Converged surface roughness parameters—A new tool to quantify rock surface morphology and reactivity alteration

The quantification of surface topography is essential in understanding the processes of dissolution and precipitation occurring at the rock-water interface. As a new approach to quantify rock surface alteration in the micrometer to nanometer scale we utilize the convergence of well-known surface roughness parameters. This approach allows the quantification of rock surface size and amplitude as well as its state of alteration during fluid-rock interaction. Vertical scanning interferometry (VSI) is our tool of choice for measuring rock surface topography because of its high vertical resolution and large field of view. Here, we present a case study to demonstrate the potential of surface roughness convergence for quantifying rock surface alteration during weathering. Black slates show different concentrations of organic matter (OM) due to different oxidative weathering ranks. Roughness and surface size data indicate that the original smooth slate surface with deviations of only some tens of nanometers was altered to a rough surface with pore diameters at a scale of some hundreds of nanometers up to several microns. Surface roughness data of a sample profile of three weathering stages (small, medium, large OM decrease) primarily indicate an increase of the OM’s surface area and roughness during weathering. However, during further weathering, surface area and roughness were decreased. From these data we conclude that those parts of the OM that do not directly adjoin to the slate’s clay minerals have a higher reactivity. This means that during ongoing OM weathering the rock surface reactivity and topography are controlled by the extent of OM degradation. Because both reactivity and topography of the observed surface will alter during reaction, it must be concluded that a constant term of “reactive” surface area must not be used to calculate the dissolution rates.

Retention of latex colloids on calcite as a function of surface roughness and topography.

Adhesion of colloidal particles to mineral and rock surfaces is important for environmental and technological processes. Surface topography variations of mineral and rock surfaces at the submicrometer scale may play a significant role in colloid retention in the environment. Here, we present colloid deposition data on calcite as a function of submicrometer surface roughness based on surface data over a field of view of several square millimeters, sufficient to trace the pattern of common inhomogeneities on mineral surfaces. A freshly cleaved calcite crystal was reacted to produce a well-defined etch pit density of approximately 3.4 +/- 1.2 to 8.3 +/- 1.6 [10(-3) microm(-2)] and etch pit depth ranging from approximately 4 to 50 nm. This surface was exposed at the point of zero charge (PZC) of calcite to a colloidal suspension. We used a bimodal particle size distribution of nonfunctionalized polystyrene latex spheres with average diameters of 499 and 903 nm. Vertical scanning interferometry (VSI) was applied to quantify calcite surface topography variations as well as the retention of latex colloids. For both particle sizes, the experiments showed a positive correlation between the surface roughness (Rq) and the number of adsorbed particles. Etch pits were preferred sites for colloidal deposition in contrast to surface steps. The majority of adsorbed particles were trapped at etch pit walls compared to etch pit bottoms. Increasing pit density (D) and depth (d) resulted in an increase of colloidal retention. Deposition of smaller particles exceeded that of the larger-sized fraction of the bimodal system investigated here. Our results show that colloidal deposition at rough mineral and rock surfaces is an important geochemical process. The results about surface roughness dependent particle adsorption will foster the understanding and predictability of colloidal retention for a multitude of natural and technical processes.

Deposition of Latex Colloids at Rough Mineral Surfaces: An Analogue Study Using Nanopatterned Surfaces

Deposition of latex colloids on a structured silicon surface was investigated. The surface with well-defined roughness and topography pattern served as an analogue for rough mineral surfaces with half-pores in the submicrometer size. The silicon topography consists of a regular pit pattern (pit diameter = 400 nm, pit spacing = 400 nm, pit depth = 100 nm). Effects of hydrodynamics and colloidal interactions in transport and deposition dynamics of a colloidal suspension were investigated in a parallel plate flow chamber. The experiments were conducted at pH ∼ 5.5 under both favorable and unfavorable adsorption conditions using carboxylate functionalized colloids to study the impact of surface topography on particle retention. Vertical scanning interferometry (VSI) was applied for both surface topography characterization and the quantification of colloidal retention over large fields of view. The influence of particle diameter variation (d = 0.3-2 μm) on retention of monodisperse as well as polydisperse suspensions was studied as a function of flow velocity. Despite electrostatically unfavorable conditions, at all flow velocities, an increased retention of colloids was observed at the rough surface compared to a smooth surface without surface pattern. The impact of surface roughness on retention was found to be more significant for smaller colloids (d = 0.3, 0.43 vs. 1, 2 μm). From smooth to rough surfaces, the deposition rate of 0.3 and 0.43 μm colloids increased by a factor of ∼2.7 compared to a factor of 1.2 or 1.8 for 1 and 2 μm colloids, respectively. For a substrate herein, with constant surface topography, the ratio between substrate roughness and radius of colloid, Rq/rc, determined the deposition efficiency. As Rq/rc increased, particle-substrate overall DLVO interaction energy decreased. Larger colloids (1 and 2 μm) beyond a critical velocity (7 × 10(-5) and 3 × 10(-6) m/s) (when drag force exceeds adhesion force) tend to detach from the surface irrespective of the impact of roughness. For polydisperse solutions, an increase in the polydispersity and flow velocity resulted in a reduction of colloid deposition efficiency due to the resulting enhanced double-layer repulsion. Quantification of surface topography variations of two endmembers of natural grain surfaces showed that half-pore depths and roughness of sedimentary quartz grains are mainly in the micrometer range. Grains with diagenetically formed quartz overgrowths, however, show surface roughness mainly in the submicrometer range. Thus, surface topography features applied in the here presented analogue study and resulting variation in particle retention can serve as quantitative analogue for particle reactions in diagenetically altered quartz sands and sandstones. The reported impact of particle polydispersity can have an important application for quantitative prediction of retention of varying types of minerals, such as different clay minerals in the environment under prevailing unfavorable conditions.

Direct Measurement of Surface Dissolution Rates in Potential Nuclear Waste Forms: The Example of Pyrochlore

The long-term stability of ceramic materials that are considered as potential nuclear waste forms is governed by heterogeneous surface reactivity. Thus, instead of a mean rate, the identification of one or more dominant contributors to the overall dissolution rate is the key to predict the stability of waste forms quantitatively. Direct surface measurements by vertical scanning interferometry (VSI) and their analysis via material flux maps and resulting dissolution rate spectra provide data about dominant rate contributors and their variability over time. Using pyrochlore (Nd2Zr2O7) pellet dissolution under acidic conditions as an example, we demonstrate the identification and quantification of dissolution rate contributors, based on VSI data and rate spectrum analysis. Heterogeneous surface alteration of pyrochlore varies by a factor of about 5 and additional material loss by chemo-mechanical grain pull-out within the uppermost grain layer. We identified four different rate contributors that are responsible for the observed dissolution rate range of single grains. Our new concept offers the opportunity to increase our mechanistic understanding and to predict quantitatively the alteration of ceramic waste forms.

Site-specific retention of colloids at rough rock surfaces.

The spatial deposition of polystyrene latex colloids (d = 1 μm) at rough mineral and rock surfaces was investigated quantitatively as a function of Eu(III) concentration. Granodiorite samples from Grimsel test site (GTS), Switzerland, were used as collector surfaces for sorption experiments. At a scan area of 300 × 300 μm(2), the surface roughness (rms roughness, Rq) range was 100-2000 nm, including roughness contribution from asperities of several tens of nanometers in height to the sample topography. Although, an increase in both roughness and [Eu(III)] resulted in enhanced colloid deposition on granodiorite surfaces, surface roughness governs colloid deposition mainly at low Eu(III) concentrations (≤5 × 10(-7) M). Highest deposition efficiency on granodiorite has been found at walls of intergranular pores at surface sections with roughness Rq = 500-2000 nm. An about 2 orders of magnitude lower colloid deposition has been observed at granodiorite sections with low surface roughness (Rq < 500 nm), such as large and smooth feldspar or quartz crystal surface sections as well as intragranular pores. The site-specific deposition of colloids at intergranular pores is induced by small scale protrusions (mean height = 0.5 ± 0.3 μm). These protrusions diminish locally the overall DLVO interaction energy at the interface. The protrusions prevent further rolling over the surface by increasing the hydrodynamic drag required for detachment. Moreover, colloid sorption is favored at surface sections with high density of small protrusions (density (D) = 2.6 ± 0.55 μm(-1), asperity diameter (φ) = 0.6 ± 0.2 μm, height (h) = 0.4 ± 0.1 μm) in contrast to surface sections with larger asperities and lower asperity density (D = 1.2 ± 0.6 μm(-1), φ = 1.4 ± 0.4 μm, h = 0.6 ± 0.2 μm). The study elucidates the importance to include surface roughness parameters into predictive colloid-borne contaminant migration calculations.

Products and timing of diagenetic processes in Upper Rotliegend sandstones from Bebertal (North German Basin, Parchim Formation, Flechtingen High, Germany)

Aeolian-fluvial Upper Rotliegend sandstones from Bebertal outcrops (Flechtingen High, North Germany) are an analogue for deeply buried Permian gas reservoir sandstones of the North German Basin (NGB). We present a paragenetic sequence as well as thermochronological constraints to reconstruct the diagenetic evolution and to identify periods of enhanced mesodiagenetic fluid–rock reactions in sandstones from the southern flank of the NGB. Bebertal sandstones show comparatively high concentrations of mesodiagenetically formed K-feldspar but low concentrations of illite cements. Illite-rich grain rims were found to occur preferentially directly below sedimentary bounding surfaces, i.e. aeolian superimposition surfaces, and indicate the lowest intergranular volume. Illite grain rims also indicate sandstone sections with low quartz and feldspar cement concentrations but high loss of intergranular volume due to compaction. 40Ar–39Ar age determination of pronounced K-feldspar grain overgrowths and replacements of detrital grains indicates two generations: an early (Triassic) and a late (Jurassic) generation. The latter age range is similar to published diagenetic illite ages from buried Rotliegend reservoir sandstones. The first generation suggests an early intense mesodiagenetic fluid flow with remarkably high K+ activity synchronous with fast burial of proximal, initial graben sediments on the southern flank of the NGB. Accordingly, zircon fission-track data indicate that the strata already reached the zircon partial annealing zone of approximately 200°C during early mesodiagenesis. Zircon (U–Th)/He ages (92 ± 12 Ma) as well as apatite fission-track ages (~ 71–75 Ma) indicate the termination of mesodiagenetic processes, caused by rapid exhumation of the Flechtingen High during Late Cretaceous basin inversion.

Relationship between micrometer to submicrometer surface roughness and topography variations of natural iron oxides and trace element concentrations.

The surface area and roughness of natural iron oxide precipitations were quantified by 3D optical microscopy in order to get information about fluid-rock interface topography in high-permeability zones. Converged surface roughness data of microscale to submicroscale topography show the predominance of macroporous half-pores (>500 nm) and the occurrence of smaller half-pores (<500 nm) that dominate the BET surface area of iron oxides. A relationship was found between the occurrence of macroporous surface structures (micrometer range) and the uranium content of iron oxide encrustations. Iron-normalized uranium concentrations of an X-ray amorphous iron oxide encrustation correlate linearly with maximum topography heights of 1 to 2 mum on hand specimen subsamples. Our study shows the potential importance of micrometer- to submicrometer-size surface features, whose environmental impact is often ignored.

Deposition of mineral colloids on rough rock surfaces

Deposition of colloids on mineral and rock surfaces is an important mechanism to alter surface reactivity and to govern contaminant migration. Particle retention in aquifers occurs predominantly under electrostatically unfavorable conditions owing to the prevailing negative charge of both mineral colloids and rock surfaces. Mineral and rock surfaces show often an irregular surface topography and roughness variations over several orders of magnitude. This complicates the colloid-surface attachment predictability and results in poor understanding towards retention efficiency. Here we study the impact of submicron-scale morphology on the interaction between rock surfaces and mineral colloids. Colloid retention experiments using micrite surfaces were performed under electrostatically unfavorable conditions. Results showed a positive and linear correlation between adsorbed particle density and surface roughness (RMS roughness <100 nm). The existence of a minimum roughness range, required for initial colloid deposition was detected. Deposition occurred mainly at micrite grain boundaries that acted as surface steps. Linear deposition kinetics was found at constant flow rates. The site-specific impact of surface roughness was studied using nanostructured silicon wafer surfaces as a well-defined analog material. Experimental results from deposition on such surfaces suggest that the surface step density on collector surfaces is a critical parameter for quantitative prediction of colloid deposition. The importance of colloidal retention is highlighted for the diagenetic evolution of rocks, especially due to inhibition mechanisms that has consequences for cement mineral distribution and concentration as well as resulting reservoir quality. For further quantitative prediction and modeling of retention on rock surfaces, we suggest the application of an energy potential function that includes beside DLVO contribution the impact of particle kinetic energy (via fluid-flow velocity) as well as the impact of reactive site density (via surface roughness parameter data).

Performance of polarization-based stereoscopy screens

AbstractThe screen is a key part of stereoscopic display systems using polarization to separate the different channels for each eye. The system crosstalk, characterizing the imperfection of the screen in terms of preserving the polarization of the incoming signal, and the scattering rate, characterizing the ability of the screen to deliver the incoming light to the viewers, determine the image quality of the system. Both values will depend on the viewing angle. In this work we measure the performance of three silver screens and three rear-projection screens. Additionally, we measure the surface texture of the screens using white-light interferometry. While part of our optical results can be explained by the surface roughness, more work is needed to understand the optical properties of the screens from a microscopic model.

Correlation between sub-micron surface roughness of iron oxide encrustations and trace element concentrations.

Iron oxide encrustations are formed on black slate surfaces during oxidative weathering of iron sulfide and phosphate bearing, organic matter-rich slates. Synchronously, trace elements are released during ongoing weathering. Laser ablation ICP-MS analyses of a weathered and encrusted slate showed that major portions of the V, Cu, As, Mo, Pb, Th, and U reside in the encrustation.Recently a potential relationship between several micrometer to 500 nm surface topography roughness of such encrustations and its uranium concentration was shown. Based on laser scanning microscopy measurements, the present study shows that this interrelation must be expanded to small submicron-sized half-pores with diameters between 100 nm and 500 nm. We demonstrate that the relationship is not limited to topography variations of a single encrustation in the hand-specimen scale. Surface topography and geochemical analyses of iron oxide encrustations from several locations but from the same geochemical environment and with similar weathering history showed that the concentrations of U, P, Cu, and Zn correlate inversely with the surface roughness parameter F. This parameter represents the total surface area and is - in this case - a proxy for the root-mean square surface roughness Rq.This study substantiates the environmental importance that micrometer- to submicrometer topography variations of fluid-rock interfaces govern the trapping of trace elements.