Reto Gieré

Zirconolite, allanite and hoegbomite in a marble skarn from the Bergell contact aureole : Implications for mobility of Ti, Zr and REE

Zirconolite, allanite and hoegbomite are present as accessory phases in a metasomatically altered spinel-calcite-marble from the contact with the Bergell intrusives (Switzerland/Italy). Textural relationships indicate a step-wise alteration of spinel to 1) hoegbomite or corundum + magnetite, 2) margarite and 3) chlorite. Replacement of spinel by hoegbomite can be described by the substitution 1.94(Mg2+, Fe2+, Zn2+, Mn2+, Ca2+)⇋Ti4+ +0.12(OH−) where Al3+ and Fe3+ are held constant. The average composition of the Bergell hoegbomites is given by the formula Fe0.972+Mg0.69Zn0.04Ti0.17Al3.94Fe0.063+O7.98(OH)0.02 and seems to be imposed by the composition of pre-existing spinel. During the first two steps of spinel alteration, calcite was replaced by anorthite+phlogopite, and the rare earth element(REE)-bearing minerals zirconolite, allanite and sphene were formed. Allanites have characteristic chondrite-normalized REE patterns with enrichment in the light REE. The zirconolite patterns show a marked increase in concentration from La to Ce, followed by an almost constant section. Sphene lacks detectable La, and its REE patterns vary from grain to grain. Contemporaneous formation of phlogopite, REE-bearing minerals and hoegbomite during replacement of the spinel-calcite-marble indicates that the metamorphic fluid introduced potassium along with REE and other high valence cations (Ti4+, Zr4+, U4+, Th4A3804265, Nb5A3804265, Y3A3804265) possibly as polynuclear complexes. The abundance of fluorine-bearing phlogopite and fluor-apatite as well as their close association with REE-bearing minerals and hoegbomite suggests F− and PO43−as likely ligands for complexing of the above mentioned elements.

Micro- and nanochemistry of fly ash from a coal-fired power plant

Abstract Fly ash from a coal-fired power plant was investigated to obtain detailed information on its physical and chemical properties, and to gain an understanding of potential environmental and health impacts associated with its disposal in landfills. The studied material was produced through combustion of Illinois Basin coal and trapped within the power plant by an electrostatic precipitator. It is a finegrained, low-Ca fly ash containing primarily SiO2, Al2O3, and Fe2O3, and is enriched in many toxic elements (e.g., Be, Zn, As, Cd, Tl, Pb, and U) by a factor of up to 30 relative to coal. The ash consists of mainly hematite, magnetite, mullite, quartz, and amorphous material. These constituents occur mostly as spherical particles with diameters of less than 13 μm. We examined the physical, chemical, and structural characteristics of individual fly ash particles by scanning and transmission electron microscopy and electron probe microanalysis. The results demonstrate that, with the exception of complex plerospheres, individual particles are chemically fairly homogeneous, but a pronounced compositional variation exists among particles with similar physical and structural attributes. Electron microprobe data document that several trace elements, including U, are partitioned into the Ferich particles. Transmission electron microscopy revealed that various types of small (<1 μm) crystalline Ca-rich phases, including lime, are attached to the glass spheres, particularly the nonmagnetic glass. These crystals may contain substantial amounts of S. Even though only a few of these crystals were analyzed quantitatively, our data indicate that the Ca-rich and S-rich phases may be important hosts for trace elements such as V and Zn. The observed element partitioning and the existence of surface-attached crystals enriched in certain trace elements suggest that fly ash from coal-fired power plants might have a more deleterious environmental impact than is inferred from bulk analytical data.

REE-bearing minerals in a Ti-rich vein from the Adamello contact aureole (Italy)

AbstractZirconolite, aeschynite-(Ce), titanite and apatite have been found as minor or accessory minerals in a Ti-rich (TiO2=2.1–4.5 wt.%) hydrothermal vein occurring in dolomite marbles at the contact with a tonalite intrusion of the Tertiary Adamello batholith (northern Italy). The vein consists of four distinct mineral zones, comprising from margin to center: (1) forsterite+calcite, (2) pargasite+calcite+titanite+sulfides, (3) phlogopite +calcite+titanite+sulfides, and (4) titanian clinohumite +spinel+calcite+sulfides. Zirconolite occurs in two vein zones only: in the phlogopite zone it is invariably anhedral, often corroded, and exhibits complex chemical zonation patterns. In the titanian clinohumite zone zirconolite is idiomorphic and characterized by a pronounced discontinous chemical zoning, but shows no evidence of corrosion. The considerable compositional variation observed for zirconolite (in wt.%: ∑(REE2O3)=0.74–16.8, UO2=0.59–24.0, ThO2=0.67–17.1) is due to the zoning, and may be attributed to four major substitutions described by the exchange vectors:1.(Th, U) (Mg, Fe2+) Ca-1 Ti-12.REE Al Ca-1 Ti-13.REE Fe2+ (Nb, Ta) Ca-1 Ti-14.Hf Zr-1 Exchange vector (2) is effective at total REE2O3 contents up to approximately 5 wt.%, whereas vector (3) is operating at higher concentrations. Both titanite and aeschynite-(Ce) exhibit, like zirconolite, complex chemical zonation patterns which document that the trace element content of the metasomatic fluid was variable during the vein-forming process. As indicated by thermodynamic analysis of the phase assemblages, the vein zones containing the REE-bearing minerals formed at 500–600°C (Ptotal≈2 kbar) from a reducing fluid rich in H2S, HCl°, HF° and phosphorus, but relatively poor in CO2(XCO2 ≈0.2). Geochemical and isotopic data are consistent with the interpretation of the fluid as being derived from the nearby tonalite intrusion. The abundance of idiomorphic fluor-apatite as well as textural relations between apatite, the other REE-bearing minerals and the fluorine-bearing hydrous silicates suggest F- and PO43-to be the most likely ligands for complexing REE, Ti, Zr and other high-field-strength elements in the veinforming fluid. The corrosive features observed for zirconolite demonstrate that hydrothermal fluids are able to dissolve zirconolite, which is one of the main components of SYNROC-C, the most promising disposal option for high-level nuclear waste. Therefore, immobilization of radioactive waste in zirconolite can be guaranteed only if an effective sealing material prevents any hydrothermal fluid from access to the final disposal site.

Antimony sinks in the weathering crust of bullets from Swiss shooting ranges.

Shooting ranges represent sites heavily polluted by Pb, Sb, Cu, Ni, and Zn, which are released during the weathering of bullets. The pristine bullets are made of a Pb-Sb core, Fe mantle, and minor amounts of Cu, Ni, and Zn in an interlayer between the core and mantle. At two selected sampling sites (Losone and Lucerne, both in Switzerland), corroding bullets were collected to determine the sinks of Sb within the weathering crust of the bullets. Bulk Sb concentrations in the crust were found to be as high as 1.3 wt.%. The oxalate-extractable fraction of Fe showed that the amorphous Fe oxides (e.g., ferrihydrite) prevail over goethite and lepidocrocite, which were identified by bulk X-ray diffraction experiments. Crystalline Pb phases are litharge (only found by X-ray diffraction) and cerussite, which result from weathering of the Pb core. No distinct Sb minerals were identified by X-ray diffraction. Investigations with electron microprobe (EMP) showed that Sb is mostly accumulated in those regions in the weathering crust where there is also a high concentration of Fe. In the weathering crust from Losone, such Fe-rich regions with Sb are represented by material that cements or rims silicate mineral grains. The cement was identified as lepidocrocite by micro-Raman analysis. At Lucerne, Sb is found in Fe-oxide aggregates, in sawdust particles where it may be bound to organic matter, or in aggregates enriched in Pb and depleted in Fe. Bulk EXAFS experiments suggested that the Fe oxides are the most important sink for Sb. Our modelling of Sb next-nearest neighbours suggests two types of inner-sphere complexes on the surfaces of Fe oxides. These are edge- and corner-sharing adsorption complexes. Hence, the predominant sink of Sb in the weathering crust of the bullets at the selected shooting ranges is Fe oxides, amorphous or crystalline.

Determination of 25 elements in the complex oxide mineral zirconolite by analytical electron microscopy

Abstract In this paper we describe a technique for the determination of 25 elements in natural zirconolite using energy-dispersive analytical electron microscopy (AEM). The method presented here allows one to quantitatively investigate the chemistry of submicron-scale zones in complex oxide minerals. The effects of electron channeling, thickness variability and variations in detector resolution were minimized by using a controlled set of operating procedures and instrument parameters. To provide a high level of accurayy, kATI-factors were determined from standards for most of the 25 elements of interest, including all of the major elements. Each analytical spectrum is reduced to a set of raw peak counts (and errors) using a digital top-hat filter to suppress background followed by multiple least squares fitting of reference spectra. Counting times of 12–15 min per analysis were required to provide suitable counting statistics. Results are presented for zirconolite samples from the contact metamorphic aureole of the Bergell granodiorite intrusion, Switzerland-Italy. A comparison of 43 AEM analyses with 15 analyses obtained by wavelength-dispersive electron probe microanalysis (EPMA) shows that there is excellent agreement between the two data sets in the amounts of individual elements present, chemical trends and overall stoichiometry. An assessment of the combined data set shows that the major substitution mechanisms in the Bergell samples are coupled substitutions involving the M5,6- and M8-sites of the zirconolite structure: M8Ca2+ + M5,6Ti4+→M8REE3+ + M5,6(Al,Fe)3+ and M8Ca2+ + M5,6Ti4+→M8(Th,U)4+ + M5,6 (Mg,Fe)2+.

Nuclear waste forms

Abstract This review describes nuclear waste forms for high-level waste (HLW), that is, glasses, ceramics, and glass-ceramics, as well as for low- and intermediate-level waste (LILW), that is, cement, bitumen, glass, glassy slags, and ceramics. Ceramic waste forms have the highest chemical durability and radiation resistance, and are recommended for HLW and actinide (ACT) immobilization. Most radiation-resistant materials are based on phases with a fluorite-related structure (cubic zirconia-based solid solutions, pyrochlore, zirconolite, murataite). Glass is also a suitable matrix for HLW containing fission and corrosion products, and process contaminants such as Na salts. Within the framework of the HLW partitioning concept providing separation of short-lived (Cs, Sr) and long-lived (rare earth element-ACT) fractions, glass may be used for immobilization of the Cs-Sr-bearing fraction, whereas the rare earth-ACT fraction may be incorporated in ceramics. Glass-based materials or clay-based ceramics are the most promising LILW forms, but cement and bitumen may also be applied as matrices for low-level wastes (LLW).

Retention of Actinides in Natural Pyrochlores and Zirconolites

Natural pyrochlore and zirconolite undergo a crystalline-aperiodic transformation caused by alpha-decay of Th and U at dose levels between 2X10 and 3X10 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 ΙΟ years. However, the Th-U isotope systematics of a zirconolite-bearing vein and dolomite host rock may provide evidence for disequilibrium between Th, U and U.

Biodegradability and ecotoxicitiy of tramadol, ranitidine, and their photoderivatives in the aquatic environment

PurposeThis study was designed to assess the fate and the overall potential impacts of the widely prescribed drugs ranitidine and tramadol after their introduction into the aquatic environment.MethodsThe probability to detect these two drugs in the aquatic environment was studied by analyzing their abiotic and biotic degradation properties. For this purpose, samples were irradiated with different light sources, and three widely used biodegradability tests from the OECD series, the closed bottle test (OECD 301 D), the manometric respirometry test (OECD 301 F) and the Zahn–Wellens test (OECD 302 B), were conducted. The ecotoxicity of the photolytically formed transformation products was assessed by performing the bacterial growth inhibition test (EN ISO 10712). Furthermore, quantitative structure–activity relationship analysis and a risk analysis based on the calculation of the predicted environmental concentrations have also been conducted to assess the environmental risk potential of the transformation products. The possible formation of stable products by microbial or photolytical transformation has been investigated with DOC and LC-MS analytics.ResultsIn the present study, neither ranitidine, nor tramadol, nor their photoderivatives were found to be readily or inherently biodegradable according to test guidelines. The photolytic transformation was faster under a UV lamp compared to the reaction under an Xe lamp with a spectrum that mimics sunlight. No chronic toxicity against bacteria was found for ranitidine or its photolytic decomposition products, but a low toxicity was detected for the resulting mixture of the photolytic transformation products of tramadol.ConclusionsThe study demonstrates that transformation products may have a higher environmental risk potential than the respective parent compounds.

Transport and deposition of REE in H2S-rich fluids: evidence from accessory mineral assemblages

Abstract It is shown in four examples from geologically different environments that accessory or minor minerals rich in rare-earth elements (REE) are often texturally associated with base-metal sulfides. The examples demonstrate that REE can migrate in hydrothermal fluids containing large amounts of reduced sulfur (S −II _ species, i.e. H 2 S, HS − and S 2− . In certain fluids complexes of REE with S −II species may be important for the REE transport, but most probably only in the absence of other strong ligands such as fluoride, carbonate or possibly phosphate. Textural relationships and geochemical data suggest that the formation of REE-bearing minerals in S −II -rich environments is genetically related to the precipitation of basemetal sulfides.

Genotoxic effects of three selected black toner powders and their dimethyl sulfoxide extracts in cultured human epithelial A549 lung cells in vitro.

Until now, the adverse effects of toner powders on humans have been considered to be minimal. However, several recent reports have suggested possible significant adverse health effects from toner dust inhalation. The aim of this study was to evaluate the genotoxic potential of black toner powders in vitro. For the study of DNA damage, A549 cells were exposed to toner‐powder suspensions and to their DMSO extracts, and then subjected to the comet assay and to the in‐vitro cytokinesis block micronucleus test (CB‐MNvit). Cytotoxic effects of the toner samples were assessed by the erythrosin B assay. Furthermore, size, shape, and composition of the toner powders were investigated. None of the three toner powders or their DMSO extracts reduced cell viability; however, they did induce DNA damage and formed micronuclei at concentrations from 80 to 400 μg cm−2, although to a varying extent. All toner powders contain considerable amounts of the pigments carbon black and magnetite (Fe3O4) as well as small amounts of polycyclic aromatic hydrocarbons (PAHs). The overall results of our in‐vitro study suggest that the investigated toner‐powder samples are not cytotoxic but genotoxic. From the results of the physical and chemical characterization, we conclude that metals and metalloids as components of magnetite, or PAHs as components of the carbon‐bearing material, are responsible for the genotoxic effects. Further research is necessary to determine the relevance of these in‐vitro observations for private and occupational toner powder exposure. Environ. Mol. Mutagen., 2011.