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Ingham, E. S., Cook, N. J., Cliff, J., Ciobanu, C. L., & Huddleston, A. (2014). A combined chemical, isotopic and microstructural study of pyrite from roll-front uranium deposits, Lake Eyre Basin, South Australia. Geochimica et Cosmochimica Acta, 125, 440–465.
Abstract: The common sulfide mineral pyrite is abundant throughout sedimentary uranium systems at Pepegoona, Pepegoona West and Pannikan, Lake Eyre Basin, South Australia. Combined chemical, isotopic and microstructural analysis of pyrite indicates variation in fluid composition, sulfur source and precipitation conditions during a protracted mineralization event. The results show the significant role played by pyrite as a metal scavenger and monitor of fluid changes in low-temperature hydrothermal systems. In-situ micrometer-scale sulfur isotope analyses of pyrite demonstrated broad-scale isotopic heterogeneity (δ34S=−43.9 to +32.4‰VCDT), indicative of complex, multi-faceted pyrite evolution, and sulfur derived from more than a single source. Preserved textures support this assertion and indicate a genetic model involving more than one phase of pyrite formation. Authigenic pyrite underwent prolonged evolution and recrystallization, evidenced by a genetic relationship between archetypal framboidal aggregates and pyrite euhedra. Secondary hydrothermal pyrite commonly displays hyper-enrichment of several trace elements (Mn, Co, Ni, As, Se, Mo, Sb, W and Tl) in ore-bearing horizons. Hydrothermal fluids of magmatic and meteoric origins supplied metals to the system but the geochemical signature of pyrite suggests a dominantly granitic source and also the influence of mafic rock types. Irregular variation in δ34S, coupled with oscillatory trace element zonation in secondary pyrite, is interpreted in terms of continuous variations in fluid composition and cycles of diagenetic recrystallization. A late-stage oxidizing fluid may have mobilized selenium from pre-existing pyrite. Subsequent restoration of reduced conditions within the aquifer caused ongoing pyrite re-crystallization and precipitation of selenium as native selenium. These results provide the first qualitative constraints on the formation mechanisms of the uranium deposits at Beverley North. Insights into depositional conditions and sources of both sulfide and uranium mineralization and an improved understanding of pyrite geochemistry can also underpin an effective vector for uranium exploration at Beverley North and other sedimentary systems of the Lake Eyre Basin, as well as in comparable geological environments elsewhere.
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Li, X., Shen, K., Li, Q., Deng, Y., Zhu, P., & Wang, D. (2018). Roll-over behavior in current-voltage curve introduced by an energy barrier at the front contact in thin film CdTe solar cell. Solar Energy, 165, 27–34.
Abstract: Roll-over phenomenon in the current–voltage (J–V) curve is often observed in a CdTe thin film solar cell. The roll-over phenomenon, which is occurred near the open-circuit voltage in a light J–V curve, is due to Schottky energy barrier formed at the CdTe/metal interface in a CdTe solar cell back contact. In this study we report a J–V roll-over phenomenon which is induced by an energy barrier at the front contact of a CdTe solar cell. Two kinds of oxides, namely, Al2O3 and SnO2, were deposited as high-resistance transparent (HRT) layer between the window layer CdS and the fluorine doped tin oxide (FTO) front electrode in CdTe solar cells. These two oxides present much different electronic band alignment with FTO and CdS. SnO2 formed almost no energy barrier with CdS, this allowed smooth transport for photo-generated electrons from CdTe to CdS and FTO. However, Al2O3 formed a high energy barrier with CdS. The rather high energy barrier with a value of 3.43 eV at the CdS/Al2O3 interface induced a J–V roll-over phenomenon in a CdTe thin film solar cell, which dramatically led to a quick decrease for the cell device efficiency. The electron transport at the FTO/Al2O3/CdS interface is governed by tunneling effect. The results presented in this study demonstrate that the band structure at the front electrode plays an important role for the performance of a CdTe thin film solar cell.
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Min, M., Xu, H., Chen, J., & Fayek, M. (2005). Evidence of uranium biomineralization in sandstone-hosted roll-front uranium deposits, northwestern China. Ore Geology Reviews, 26(3), 198–206.
Abstract: We show evidence that the primary uranium minerals, uraninite and coffinite, from high-grade ore samples (U3O8\textgreater0.3%) in the Wuyiyi, Wuyier, and Wuyisan sandstone-hosted roll-front uranium deposits, Xinjiang, northwestern China were biogenically precipitated and psuedomorphically replace fungi and bacteria. Uranium (VI), which was the sole electron acceptor, was likely to have been enzymically reduced. Post-mortem accumulation of uranium may have also occurred through physio-chemical interaction between uranium and negatively-charged cellular sites, and inorganic adsorption or precipitation reactions. These results suggest that microorganisms may have played a key role in formation of the sandstone- or roll-type uranium deposits, which are among the most economically significant uranium deposits in the world.
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Bonnetti, C., Zhou, L., Riegler, T., Brugger, J., & Fairclough, M. (2020). Large S isotope and trace element fractionations in pyrite of uranium roll front systems result from internally-driven biogeochemical cycle. Geochimica et Cosmochimica Acta, 282, 113–132.
Abstract: Complex pyrite textures associated with large changes in isotopic and trace element compositions are routinely assumed to be indicative of multi-faceted processes involving multiple fluid and sulfur sources. We propose that the features of ore-stage pyrite from roll front deposits across the world, revealed in exquisite detail via high-resolution trace element mapping by LA-ICP-MS, reflect the dynamic internal evolution of the biogeochemical processes responsible for sulfate reduction, rather than externally driven changes in fluid or sulfur sources through time. Upon percolation of oxidizing fluids into the reduced host-sandstones, roll front systems become self-organized, with a systematic reset of their activity cycle after each translation stage of the redox interface down dip of the aquifer. Dominantly reducing conditions at the redox interface favor the formation of biogenic framboidal pyrite (δ34S from −30.5 to −12.5‰) by bacterial sulfate reduction and the genesis of the U mineralization. As the oxidation front advances, oxidation of reduced sulfur minerals induces an increased supply of sulfate and metals in solution to the bacterial sulfate reduction zone that has similarly advanced down the flow gradient. Hence, this stage is marked by increased rates of the bacterial sulfate reduction associated with the crystallization of variably As-Co-Ni-Mo-enriched concentric pyrite (up to 10,000′s of ppm total trace contents) with moderately negative δ34S values (from −13.7 to −7.5‰). A final stage of pyrite cement with low trace element contents and heavier δ34S signature (from −6.9 to +18.8‰) marks the end of the roll front activity cycle and the transition from an open to a predominantly closed system behavior (negligible advection of fresh sulfate). Blocky pyrite cement is formed using the remaining sulfate, which now becomes quickly heavy according to a Rayleigh isotope fractionation process. This ends the cycle by depleting the nutrient supplies for the sulfate-reducing bacteria and cementing pore spaces within the host sandstone, effectively restricting fluid infiltration. This internally-driven roll front activity cycle results in systematic, large S isotope and trace element fractionation. Ultimately, the long-time evolution of the basin and fluid sources control the metal endowment and evolution of the system; these events, however, are unlikely to be preserved by the roll front, as a direct result of its hydrodynamic nature.
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Hebert, B., Baron, F., Robin, V., Lelievre, K., Dacheux, N., Szenknect, S., et al. (2019). Quantification of coffinite (USiO4) in roll-front uranium deposits using visible to near infrared (Vis-NIR) portable field spectroscopy. Journal of Geochemical Exploration, 199, 53–59.
Abstract: Coffinite (USiO4) is a common uranium-bearing mineral of roll-front uranium deposits. This mineral can be identified by the visible near infrared (Vis-NIR) portable field spectrometers used in mining exploration. However, due to the low detection limits and associated errors, the quantification of coffinite abundance in the mineralized sandstones or sandy sediments of roll-front uranium deposits using Vis-NIR spectrometry requires a specific methodological development. In this study, the 1135 nm absorption band area is used to quantify the abundance of coffinite. This absorption feature does not interfere with NIR absorption bands of any other minerals present in natural sands or sandstones of uranium roll-front deposits. The correlation between the 1135 nm band area and coffinite content was determined from a series of spectra measured from prepared mineral mixtures. The samples were prepared with a range of weighted amounts of arenitic sands and synthetic coffinite simulating the range of uranium concentration encountered in roll-front uranium deposits. The methodology presented in this study provides the quantification of the coffinite content present in sands between 0.03 wt% to 1 wt% coffinite with a detection limit as low as 0.005 wt%. The integrated area of the 1135 nm band is positively correlated with the coffinite content of the sand in this range, showing that the method is efficient to quantify coffinite concentrations typical of roll-front uranium deposits. The regression equation defined in this study was then used as a reference to predict the amount of natural coffinite in a set of mineralized samples from the Tortkuduk uranium roll-front deposit (South Kazakhstan).
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