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.

Abstract: The Complexe Terminal (CT) multi-layer aquifer is formed by Neogene/Paleogene sand deposits, Upper Senonian (Campanian-Maastrichtian limestones) and Turonian carbonates. The chemical composition and isotopes of carbon and uranium were investigated in groundwater sampled from the main hydrogeological units of the (CT) aquifer in southern Tunisia. We paid special attention to the variability of uranium contents and isotopes ratio (234U/238U) to provide a better understanding of the evolution of the groundwater system. Uranium concentrations range from 1.5 to 19.5 ppb, typical of oxic or mildly reducing conditions in groundwaters. The lowest concentrations are found southeast of the study area, where active recharge is supposed to take place. When looking at the isotope composition, it appears that all the samples, including those from carbonate levels, are in radioactive disequilibrium with significant 234U excess. A clear-cut distinction is observed between Turonian and Senonian carbonate aquifers on the one hand, with 234U/238U activity ratios between 1.1 and 1.8, and the sandy aquifer on the other hand, showing higher ratios from 1.8 to 3.2. The distribution of uranium in this complex aquifer system seems to be in agreement with the lithological variability and are ultimately a function of a number of physical and chemical factors including the uranium content of the hosting geological formation, water-rock interaction and mixing between waters having different isotopic signatures. Significant relationships also appear when comparing the uranium distribution with the major ions composition. It is noticeable that uranium is better correlated with sulfate, calcium and magnesium than with other major ions as chloride or bicarbonate. The 14C activities and δ13C values of DIC cover a wide range of values, from 1.1 pmc to 30.2 pmc and from −3.6‰ to −10.7‰, respectively. 14C model ages estimated by the Fontes and Garnier model are all younger than 22 Ka and indicate that the recharge of CT groundwater occurred mainly during the end of the last Glacial and throughout the Holocene.