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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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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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Frumkin, A., & Gvirtzman, H. (2006). Cross-formational rising groundwater at an artesian karstic basin: the Ayalon Saline Anomaly, Israel. Journal of Hydrology, 318(1), 316–333.
Abstract: It is proposed that a geothermal artesian karstic system at the central part of the Yarkon–Taninim aquifer creates the ‘Ayalon Saline Anomaly’ (ASA), whose mechanism has been under debate for several decades. A 4-year-long detailed groundwater monitoring was carried out at 68 new shallow boreholes in the Ayalon region, accompanied by a comprehensive survey of karstic voids. Results indicate the rising of warm-brackish groundwater through highly permeable swarms of karstic shafts, serving as an outflow of the artesian geothermal system. The ASA area contains ‘hot spots’, where groundwater contrasts with ‘normal’ water hundreds of meters away. The ASA temperature reaches 30°C (∼5°C warmer than its surroundings), chloride concentration reaches 528mg/l (50–100mg/l in the surrounding), H2S concentration reaches 5.6mg/l (zero all around) and pH value is 7.0 (compared with 7.8 around). Subsequently, the hydrothermal water flows laterally of at the watertable horizon through horizontal conduits, mixing with ‘normal’ fresh water which had circulated at shallow depth. Following rainy seasons, maximal watertable rise is observed in the ASA compared to its surroundings. Regional hydrogeology considerations suggest that the replenishment area for the ASA water is at the Samaria Mountains, east of the ASA. The water circulates to a great depth while flowing westward, and a cross-formational upward flow is then favored close the upper sub-aquifer’s confinement border.
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Klaus, J., Külls, C., & Dahan, O. (2008). Evaluating the recharge mechanism of the Lower Kuiseb Dune area using mixing cell modeling and residence time data. Journal of Hydrology, 358(3-4), 304–316.
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Morin, E., Grodek, T., Dahan, O., Benito, G., Külls, C., Jacoby, Y., et al. (2009). Flood routing and alluvial aquifer recharge along the ephemeral arid Kuiseb River, Namibia. Journal of Hydrology, 368(1-4), 262–275.
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