Filtern
Volltext vorhanden
- nein (2)
Erscheinungsjahr
- 2018 (2) (entfernen)
Dokumenttyp
- Wissenschaftlicher Artikel (2) (entfernen)
Sprache
- Englisch (2) (entfernen)
Gehört zur Bibliographie
- ja (2)
Schlagworte
- ABSH-system (1)
- Batch experiments (1)
- Black shales (1)
- Dora-Maira (1)
- Flowback (1)
- NOR (1)
- Radioactivity (1)
- Raman spectroscopy (1)
- Unconventional gas production (1)
- dumortierite (1)
- magnesiodumortierite (1)
- synthesis (1)
- tetrahedral boron (1)
- ultrahigh-pressure (UHP) (1)
Institut
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.
We performed leaching tests at elevated temperatures and pressures with an Alum black shale from Bomholm, Denmark and a Posidonia black shale from Lower Saxony, Germany. The Alum shale is a carbonate free black shale with pyrite and barite, containing 74.4 mu g/g U. The Posidonia shales is a calcareous shale with pyrite but without detectable amounts of barite containing 3.6 mu g/g U. Pyrite oxidized during the tests forming sulfuric acid which lowered the pH on values between 2 and 3 of the extraction fluid from the Alum shale favoring a release of U from the Alum shale to the fluid during the short-term and in the beginning of the long-term experiments. The activity concentration of U-238 is as high as 23.9 mBq/ml in the fluid for those experiments. The release of U and Th into the fluid is almost independent of pressure. The amount of uranium in the European shales is similar to that of the Marcellus Shale in the United States but the daughter product of U-238, the Ra-226 activity concentrations in the experimentally derived leachates from the European shales are quite low in comparison to that found in industrially derived flowback fluids from the Marcellus shale. This difference could mainly be due to missing Cl in the reaction fluid used in our experiments and a lower fluid to solid ratio in the industrial plays than in the experiments due to subsequent fracking and minute cracks from which Ra can easily be released.