Thorsten Geisler

Control of silicate weathering by interface-coupled dissolution-precipitation processes at the mineral-solution interface

The mechanism of surface coating formation (the so-called surface altered layers [SALs] or leached layers) during weathering of silicate minerals is controversial and hinges on understanding the saturation state of the fluid at the dissolving mineral surface. Here we present in-situ data on the evolution of the interfacial fluid composition during dissolution of wollastonite (CaSiO3), obtained using interferometry and micro pH and ion-selective electrodes. Steep concentration gradients develop at the mineral interface as soon as it makes contact with the solution. This interfacial fluid becomes supersaturated with respect to amorphous silica that forms a surface coating, limiting fluid access to the mineral surface and hence affecting the dissolution rate. The thickness of the supersaturated zone and the precipitated layer depends on the relative rates of mass transport and surface reaction in the system; this effect could contribute to the discrepancy between dissolution rates measured in the field and in the laboratory. As well, our results have implications for predictions of silicate weathering rates and hence climate evolution, as different assumptions on dissolution mechanisms affect calculations on CO2 drawdown during weathering and consequent effects on estimates of global mean temperatures.

The role of Th-U minerals in assessing the performance of nuclear waste forms

Abstract Materials designed for nuclear waste disposal include a range of ceramics, glass ceramics and glass waste forms. Those with crystalline phases have provided the momentum for studies of minerals as a means to understand aspects of waste-form crystal chemistry, behaviour in aqueous systems and radiation damage over geological periods of time. Although the utility of natural analogue studies varies, depending upon the degree of analogy to the proposed geological repository and other factors such as chemical composition, the available data suggest that Th-U host phases such as brannerite, monazite, pyrochlore, zircon and zirconolite are resistant generally to dissolution in aqueous fluids at low temperatures. Geochemical durability may or may not extend to hydrothermal systems depending on the specifics of fluid composition, temperature and pressure. At elevated temperatures, for example, davidite may break down to new phase assemblages including titanite, ilmenite and rutile. Perovskite is generally less resistant to dissolution at low temperatures and breaks down to TiO2, releasing A-site cations to the aqueous fluid. Studies of radiation damage indicate that the oxide and silicate phases become amorphous as a result of the gradual accumulation of alpha-recoil collision cascades. Monazite tends to remain crystalline on geological time scales, a very attractive property that potentially eliminates major changes in physical properties such as density and volume, thereby reducing the potential for cracking, which is a major concern for zircon. In spite of recent success in describing the behaviour of Th-U minerals in geological systems, considerable work remains in order to understand the P-T-X conditions during alteration and T-t history of the host rocks.

Subduction zone forearc serpentinites as incubators for deep microbial life

Significance We document organic matter encapsulated in rock clasts from a oceanic serpentinite mud volcano above the Izu–Bonin–Mariana subduction zone (Pacific Ocean). Although we cannot pinpoint the exact origin of the organic matter, chemical analysis of the constituents resembles molecular signatures that could be produced by microbial life deep within or below the mud volcano. Considering the known temperature limit for life, 122 °C, and the subduction zone forearc geotherm where such mud volcanoes are located, we estimate that life could exist as deep as ∼10,000 m below the seafloor. This is considerably deeper than other active serpentinizing regions such as midocean ridges and could have provided sheltered ecosystems for life to survive the more violent phases of Earth’s history. Serpentinization-fueled systems in the cool, hydrated forearc mantle of subduction zones may provide an environment that supports deep chemolithoautotrophic life. Here, we examine serpentinite clasts expelled from mud volcanoes above the Izu–Bonin–Mariana subduction zone forearc (Pacific Ocean) that contain complex organic matter and nanosized Ni–Fe alloys. Using time-of-flight secondary ion mass spectrometry and Raman spectroscopy, we determined that the organic matter consists of a mixture of aliphatic and aromatic compounds and functional groups such as amides. Although an abiotic or subduction slab-derived fluid origin cannot be excluded, the similarities between the molecular signatures identified in the clasts and those of bacteria-derived biopolymers from other serpentinizing systems hint at the possibility of deep microbial life within the forearc. To test this hypothesis, we coupled the currently known temperature limit for life, 122 °C, with a heat conduction model that predicts a potential depth limit for life within the forearc at ∼10,000 m below the seafloor. This is deeper than the 122 °C isotherm in known oceanic serpentinizing regions and an order of magnitude deeper than the downhole temperature at the serpentinized Atlantis Massif oceanic core complex, Mid-Atlantic Ridge. We suggest that the organic-rich serpentinites may be indicators for microbial life deep within or below the mud volcano. Thus, the hydrated forearc mantle may represent one of Earth’s largest hidden microbial ecosystems. These types of protected ecosystems may have allowed the deep biosphere to thrive, despite violent phases during Earth’s history such as the late heavy bombardment and global mass extinctions.

Petrogenesis of alkaline basalt-hosted sapphire megacrysts. Petrological and geochemical investigations of in situ sapphire occurrences from the Siebengebirge Volcanic Field, Germany

Megacrystic sapphires are frequently associated with alkaline basalts, most notably in Asia and Australia, although basalt is not generally normative in corundum. Most of these sapphire occurrences are located in alluvial or eluvial deposits, making it difficult to study the enigmatic relationship between the sapphires and their host rocks. Here, we present detailed petrological and geochemical investigations of in situ megacrystic sapphires within alkaline basalts from the Cenozoic Siebengebirge Volcanic Field (SVF) in Germany. Markedly, the sapphires show several micrometer thick spinel coronas at the contact with the host basalt, indicating chemical disequilibrium between the sapphire and the basaltic melt, supporting a xenogenetic relationship. However, in situ U–Pb dating of a Columbite Group inclusion within one Siebengebirge sapphire using laser ablation–inductively coupled plasma–mass spectrometry (LA–ICP–MS) indicates a close genetic relationship between sapphire crystallization and alkaline mafic volcanism in the SVF. The syngenetic mineral inclusion suite including carbonates, members of the Pyrochlore, Betafite and Columbite Groupe minerals, as well as a high abundance of HFSE and of gaseous low-density CO2 inclusions support a parentage of a highly evolved, MgO and FeO deficient carbonatitic melt. We identified CO2 to be the link between alkaline basaltic volcanism and the xenocrystic sapphires. Only alkaline volcanic suites can build up enough CO2 in this magma chamber upon fractionation so that at high degrees of fractionation a carbonatitic melt exsolves which in turn can crystallize sapphires.

Evidence for Lattice Strain and Non-ideal Behavior in the (La1−xEux)PO4 Solid Solution from X-ray Diffraction and Vibrational Spectroscopy

The monazite-type solid solution of LaPO

Topotactic formation of ferrisicklerite from natural triphylite under hydrothermal conditions

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Towards a unifying mechanistic model for silicate glass corrosion

and EuPO

CO2 fluid inclusions in Jack Hills zircons

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An international initiative on long-term behavior of high-level nuclear waste glass

has been studied by X-ray diffraction, infrared (IR) and Raman spectroscopic techniques. A substantial excess molar volume has been derived from the X-ray data, and the Raman and IR spectra show band broadening typical for mixing of cations of different size on the cation sublattice. The IR spectra were interpreted by the autocorrelation method and the excess autocorrelation parameter

The mechanism of borosilicate glass corrosion revisited

Delta{corr}^{ex}