Gieré, Reto
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Publication Zirconolite: A Review of Localities Worldwide, and a Compilation of its Chemical Compositions(1996-06-01) Williams, C T; Gieré, RetoA compilation of the chemical data and brief review of the mineral zirconolite, essentially CaZrTi207, is presented. A total of 321 chemical analyses, 169 previously unpublished, from 39 of the 46 known terrestrial localities, and covering IO rock types are tabulated. A brief description of the minerals associated with zirconolite is outlined for each locality. Data from all zirconolite-bearing lunar rocks have also been compiled. The recently published nomenclature scheme for zirconolite is employed throughout.Publication Retention of Actinides in Natural Pyrochlores and Zirconolites(1994) Lumpkin, Gregory R; Hart, K P; McGlinn, P J; Payne, T E; Gieré, Reto; Williams, C TNatural pyrochlore and zirconolite undergo a crystalline-aperiodic transformation caused by alpha-decay of 232Th and 2380 at dose levels between 2 X 1014 and 3 X 1017 a/mg. The principal effects of the transformation are volume expansion and microfracturing, providing potential pathways for fluids. Geochemical alteration of the minerals may occur under hydrothermal conditions or in low temperature, near surface environments, but Th and U usually remain immobile and can be retained for time scales up to 109 years. However, the Th-U isotope systematics of a zirconolite-bearing vein and dolomite host rock may provide evidence for disequilibrium between 230Th, 234U and 238U.Publication Recalcitrant Pharmaceuticals in the Aquatic Environment: A Comparative Screening Study of Their Occurrence, Formation of Phototransformation Products and Their in Vitro Toxicity(2014-01-01) Bergheim, Marlies; Gminski, Richard; Spangenberg, Bernd; Dębiak, Malgorzata; Bürkle, Alexander; Mersch-Sundermann, Volker; Kümmerer, Klaus; Gieré, RetoData allowing for a complete environmental risk assessment of pharmaceuticals and their photoderatives in the environment are still scarce. In the present study, in vitro toxicity and both bio- and photopersistence of various pharmaceuticals (aciclovir, allopurinol, cetirizine, cimetidine, fluconazole, hydrochlorothiazide, lisinopril, phenytoin, primidone, ranitidine, sotalol, sulpiride, tramadol and valsartane) as well as their phototransformation products were evaluated in order to fill data gaps and to help prioritise them for further testing. Twelve out of the fourteen compounds investigated were found to be neither readily nor inherently biodegradable in the Organisation of Economic Cooperation and Development-biodegradability tests. The study further demonstrates that the photo-induced transformation of the pharmaceuticals was faster upon irradiation with a Hg lamp (UV light) than with a Xe lamp emitting a spectrum that mimics sunlight. Comparing the non-irradiated with the respective irradiated solutions, a higher acute and chronic toxicity against bacteria was found for the irradiated solutions of seven compounds (cetirizine, cimetidine, hydrochlorothiazide, ranitidine, sulpiride, tramadol and valsartane). No cyto- and genotoxic effects were found in human cervical (HeLa) and liver (Hep-G2) cells for any of the investigated compounds or their phototransformation products. This comparative study documents that phototransformation products can arise as a result of UV treatment of wastewater containing these pharmaceuticals. It further demonstrates that some phototransformation products may have a higher environmental risk potential than the respective parent compounds because some phototransformation products exhibited a higher bacterial toxicity.Publication Surface Crystal Chemistry of Phyllosilicates Using X-Ray Photoelectron Spectroscopy: A Review(2016-10-01) Elmi, Chiara; Guggenheim, Stephen; Gieré, RetoThe characterization of freshly cleaved mica surfaces for surface structure and chemical composition was briefly reviewed and focused on surface crystal chemistry using X-ray photoelectron spectroscopy (XPS) and other surface-sensitive techniques. This paper considers micas, which are useful as a first approximation for the behavior of many clay surfaces. Emphasis was given to phyllosilicate XPS binding energies (''chemical shift''), which were described and used to obtain oxidation state, layer charge, and chemical bonding information from the chemical shifts of different peaks. The chemical shift of the Si2p binding-energy to lower values can result from a negative charge increase because of Si4+ replacement by Al3+ and/or Fe3+. The apparent interlayer coordination number reduction from twelve to eight at muscovite and tetraferri-phlogopite (001) surfaces was indicated by the XPS measured K2p binding-energy and is consistent with bond relaxation. Although chemical shifts are valuable to distinguish chemical bonding and oxidation state, chemical shifts usually cannot distinguish between different Al coordination environments where Al is in both tetrahedral and octahedral sites.Publication Magnetite in the Human Body: Biogenic vs. Anthropogenic(2016-10-01) Gieré, RetoMagnetite is an iron-oxide mineral that occurs naturally on Earth. Because it is also an important component of many anthropogenic materials (e.g., coal fly ash) and synthetic products (e.g., black toner powders), magnetite can be released to the environment through human activities (1). In PNAS,Maher et al. (2) describe the abundant presence in the human brain of magnetite nanoparticles, some of which they attribute to air pollution. This finding could have major implications.Publication The Role of Th-U Minerals in Assessing the Performance of Nuclear Waste Forms(2014-10-01) Lumpkin, Gregory R; Gao, Yan; Gieré, Reto; Williams, C T; Mariano, Anthony; Geisler, ThorstenMaterials 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.Publication REE Zoning in Allanite Related to Changing Partition Coefficients During Crystallization: Implications for REE Behaviour in an Epidote-Bearing Tonalite(2006-08-01) Beard, J S; Sorensen, S S; Gieré, RetoAllanite is present in most samples of the tonalitic Bell Island Pluton, with an average mode near 0.05 wt.%. Allanite occurs as cores in igneous epidote-clinozoisite and exhibits characteristic and consistent zoning patterns. REE-rich cores (All40–70) grade out towards epidote-clinozoisite with REE below electron microprobe detection limits. La, Ce and Pr contents are highest in the REE-rich cores of zoned crystals. Nd and Sm contents both initially increase as total REE decreases and are highest in intermediate zones. Y contents are generally low throughout, but tend to be highest in analyses with All5–20. The zoning behaviour exhibited by the allanite, specifically the rimward increases in Nd, Sm, and Y, cannot be accounted for by simple fractionation and are best explained by increases in allanite/melt partition coefficients (Kd values) for these elements during crystallization. We propose that the variation in Kd values reflects modification of the allanite structure with changing REE content. These modifications are manifested by changes in colour, extinction, and pleochroism within the zoned crystals and include changes in unit-cell volume and dimensions. The changes in Kd values are large enough to result in crossing REE patterns within single allanite crystals. Fractional crystallization of zoned allanite can have noticeable effects on LREE contents and La/Sm (and almost certainly La/Lu) in magmas. In the Bell Island pluton, 80% of La, but <3% of Y is contained in allanite. Although some of the variation in the LREE chemistry of the pluton is attributable to statistical sampling error, much of it appears to reflect petrogenetic processes that controlled LREE abundance and, ultimately, allanite mode. One sample of Bell Island tonalite is depleted in LREE and has low La/Lu and La/Sm. These chemical features can be modelled by fractionation of zoned allanite.