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Dumortierite was synthesized in piston-cylinder experiments at 2.5-4.0 GPa, 650-700 degrees C in the Al2O3 -B2O3-SiO2-H2O (ABSH) system. Electron-microprobe (EMP) analyses reveal significant boron-excess (up to 0.26 B-[4] per formula unit, pfu) and silicon-deficiency relative to the ideal anhydrous dumortierite stoichiometry Al7BSi3O18 . The EMP data in conjunction with results from single-crystal Raman spectroscopy and powder X-ray diffraction provide evidence that silicon at the tetrahedral site is replaced by excess boron via the substitution Si-[4] <--> B-[4] + H. The Raman spectrum of synthetic dumortierite in the frequency region 2000 4000 cm(-1) comprises eight bands, of which six are located at frequencies below 3400 cm(-1). This points to strong hydrogen bonding, most likely O2-H center dot center dot center dot O7 and O7-H center dot center dot center dot O2, arising from a high number of octahedral vacancies at the All site and substitution of trivalent Al3+ and B3+ for Si4+ at Si1 and Si2 sites, causing decreasing acceptor-donor distances and lower incident valence at the acceptor oxygen. Contrary to the synthetic high-pressure ABSH-dumortierite, magnesiodumortierite from the Dora-Maira Massif, which is assumed to have formed at similar conditions (2.5-3.0 GPa, 700 degrees C), does not show any B-excess. Tourmaline shows an analogous behaviour in that magnesium-rich (e.g., dravitic) tourmaline formed at high pressure shows no or only minor amounts of tetrahedral boron, whereas natural aluminum-rich tourmaline and synthetic olenitic tourmaline formed at high pressures can incorporate significant amounts of tetrahedral boron. Two mechanisms might account for this discrepancy: (i) Structural avoidance of Mg-[6]-(OR3+)-R-[4] configurations in magnesiodumortierite due to charge deficieny at the oxygens O2 and O7 and strong local distortion of M1 due to decreased O2-O7 bond length, and/or (ii) decreasing fluid mobility of boron in Al-rich systems at high pressures.
Graphite forms the endpoint for organic carbon metamorphism; it is extremely resilient to physical, biological and chemical degradation. Carbonaceous materials (CM) contained within sediments, collected across Taiwan and from the Gaoping submarine canyon, were analyzed using Raman spectroscopy to determine the crystallinity. This allowed the erosional and orogenic movements of petrogenic organic carbon (OCpetro) during the Taiwanese orogeny to be deduced. After automatically fitting and classifying spectra, the distribution of four groups of CM within the sediments provides evidence that many forms of OCpetro have survived at least one previous cycle of erosion, transport and burial before forming rocks in the Western Foothills of the island. There is extensive detrital graphite present in rocks that have not experienced high-grade metamorphism, and graphite flakes are also found in recently deposited marine sediments off Taiwan. The tectonic and geological history of the island shows that these graphite flakes must have survived at least three episodes of recycling. Therefore, transformation to graphite during burial and orogeny is a mechanism for stabilizing organic carbon over geological time, removing biospheric carbon from the active carbon cycle and protecting it from oxidation during future erosion events.
A great number of Central Asian wall paintings, archeological materials, architectural fragments, and textiles, as well as painting fragments on silk and paper, make up the so called Turfan Collection at the Asian Art Museum in Berlin. The largest part of the collection comes from the Kucha region, a very important cultural center in the third to ninth centuries. Between 1902 and 1914, four German expeditions traveled along the northern Silk Road. During these expeditions, wall paintings were detached from their original settings in Buddhist cave complexes. This paper reports a technical study of a wall painting, existing in eight fragments, from the Buddhist cave no. 40 (Ritterhohle). Its original painted surface is soot blackened and largely illegible. Gruwedel, leader of the first and third expeditions, described the almost complete destruction of the rediscovered temple complex and evidence of fire damage. The aim of this case study is to identify the materials used for the wall paintings. Furthermore, soot deposits as well as materials from conservation interventions were of interest. Non-invasive analyses were preferred but a limited number of samples were taken to provide more precise information on the painting technique. By employing optical and scanning electron microscopy, energy dispersive X-ray spectroscopy, micro X-ray fluorescence spectroscopy, X-ray diffraction analysis, and Raman spectroscopy, a layer sequence of earthen render, a ground layer made of gypsum, and a paint layer containing a variety of inorganic pigments were identified.
Gas hydrates are ice-like crystalline compounds made of water cavities that retain various types of guest molecules. Natural gas hydrates are CH4-rich but also contain higher hydrocarbons as well as CO2, H2S, etc. They are highly dependent of local pressure and temperature conditions. Considering the high energy content, natural gas hydrates are artificially dissociated for the production of methane gas. Besides, they may also dissociate in response to global warming. It is therefore crucial to investigate the hydrate nucleation and growth process at a molecular level. The understanding of how guest molecules in the hydrate cavities respond to warming climate or gas injection is also of great importance.
This thesis is concerned with a systematic investigation of simple and mixed gas hydrates at conditions relevant to the natural hydrate reservoir in Qilian Mountain permafrost, China. A high-pressure cell that integrated into the confocal Raman spectroscopy ensured a precise and continuous characterization of the hydrate phase during formation/dissociation/transformation processes with a high special and spectral resolution. By applying laboratory experiments, the formation of mixed gas hydrates containing other hydrocarbons besides methane was simulated in consideration of the effects from gas supply conditions and sediments. The results revealed a preferential enclathration of different guest molecules in hydrate cavities and further refute the common hypothesis of the coexistence of hydrate phases due to a changing feed gas phase. However, the presence of specific minerals and organic compounds in sediments may have significant impacts on the coexisting solid phases. With regard to the dissociation, the formation damage caused by fines mobilization and migration during hydrate decomposition was reported for the first time, illustrating the complex interactions between fine grains and hydrate particles. Gas hydrates, starting from simple CH4 hydrates to binary CH4—C3H8 hydrates and multi-component mixed hydrates were decomposed by thermal stimulation mimicking global warming. The mechanisms of guest substitution in hydrate structures were studied through the experimental data obtained from CH4—CO2, CH4—mixed gas hydrates and mixed gas hydrates—CO2 systems. For the first time, a second transformation behavior was documented during the transformation process from CH4 hydrates to CO2-rich mixed hydrates. Most of the crystals grew or maintained when exposed to CO2 gas while some others decreased in sizes and even disappeared over time. The highlight of the two last experimental simulations was to visualize and characterize the hydrate crystals which were at different structural transition stages. These experimental simulations enhanced our knowledge about the mixed gas hydrates in natural reservoirs and improved our capability to assess the response to global warming.
Zircon (ZrSiO4), hafnon (HfSiO4) and five intermediate compositions were synthesized from a Pb silicate melt. The resulting crystals were 20-300 mu m in size and displayed sector and growth zoning. Raman spectra were acquired at locations in the sample for which preceding electron microprobe (EMP) analyses revealed sufficient compositional homogeneity. The dataset documents shifts of Raman bands with changing composition. In this study, bands that have previously not been reported were found for the intermediate compositions and for pure hafnon, in particular at wavenumbers less than 200 cm(-1). For these external modes, the dataset provides new insight into the compositional dependence of their frequencies. Density-functional theory calculations support the observations and are used for a detailed interpretation of the spectra. The pitfalls of the EMP analysis along the zircon-hafnon join are highlighted.