Microbialites are widespread in modern and fossil hypersaline environments, where they provide a unique sedimentary archive. Authigenic mineral precipitation in modern microbialites results from a complex interplay between microbial metabolisms, organic matrices and environmental parameters. Here, we combined mineralogical and microscopic analyses with measurements of metabolic activity in order to characterise the mineralisation of microbial mats forming microbialites in the Great Salt Lake (Utah, USA). Our results show that the mineralisation process takes place in three steps progressing along geochemical gradients produced through microbial activity. First, a poorly crystallized Mg-Si phase precipitates on alveolar extracellular organic matrix due to a rise of the pH in the zone of active oxygenic photosynthesis. Second, aragonite patches nucleate in close proximity to sulfate reduction hotspots, as a result of the degradation of cyanobacteria and extracellular organic matrix mediated by, among others, sulfate reducing bacteria. A final step consists of partial replacement of aragonite by dolomite, possibly in neutral to slightly acidic porewater. This might occur due to dissolution-precipitation reactions when the most recalcitrant part of the organic matrix is degraded. The mineralisation pathways proposed here provide pivotal insight for the interpretation of microbial processes in past hypersaline environments.
This present study provides an overview of the clay-mineral reactions involved in the chloritization process in a mixed-layer mineral series, and focuses on the properties of the resulting lowtemperature chlorites (formed at <220°C) in diagenetic and hydrothermal systems. According to the literature, most chlorite species occurring in low-temperature geological systems are derived fromspecific clay precursors except for direct precipitates from solution in veins. In addition, three main types of clay-mineral series have been associated with these chloritization processes: saponite-to-chlorite, berthierineto- chlorite and kaolinite-to-sudoite reactions. The conversion of saponite to chlorite results in the most common sequence of trioctahedral clay minerals related to the occurrence of Mg-Fe trioctahedral chlorite in a wide variety of hydrothermal and diagenetic to very low-grade metamorphism environments. Two models were proposed in the literature to describe the saponite-to-chlorite conversion through corrensite. The first model is a continuous transition model based on solid-state transformation (SST) mechanisms and is valid in rock-dominated systems (closed micro-systems with very low fluid-rock ratios). The second model is a stepwise transition model based on dissolution-crystallization mechanisms (DC) and is efficient in fluid-dominated systems (open systems with high fluid-rock ratio). The berthierine to Fechlorite transition results in a sequence of trioctahedral phases which are related to chloritization processes in iron-rich and reducing environments. This transformation is a cell-preserved phase transition dominated by a SST mechanismthat operates simultaneously in different domains of the parental mineral and may be considered as a polymorphic mineral reaction. Finally, the conversion of kaolinite to sudoite (Al-Mg ditrioctahedral chlorite) has not been documented like the other two aforementioned conversion series. Despite the scarcity of detailed investigations, the conversion of kaolinite to sudoite through tosudite is considered a stepwise mineral reaction that is dominated by a DC mechanism. From a compilation of literature data, it appears that several parameters of hydrothermal and diagenetic chlorites differ, including the minimal temperature, the textural and structural characteristics and the extents of compositional fields. In hydrothermal systems, discrete chlorite occurs at a minimal temperature near 200°C, regardless of its chemical composition. In diagenetic systems, discrete chlorite occurs at minimal temperatures that vary according to its crystal chemistry (100–120°C for Mg-chlorite as opposed to 40–120°C for Fe chlorite). The strong discrepancy between the lowest temperature at which Mg- and Fe-chlorite form in buried sediments and in geothermal systems should result from drastically different heating rates, heat-flow conditions and tectonism between basins at passivemargins and geothermal systems at active margins. The morphology, structure and compositional fields of the diagenetic Fe-rich chlorite may have been inherited from those of the berthierine precursor. All of the chlorite species formed through theDC mechanism have good geothermometry potential. However, the SST mechanism in which berthierine is transformed into chlorite could have unexplored consequences regarding the use of the chemistry (including stable isotope composition) of diagenetic Fe-chlorite for reconstructing the burial history of sediments. Further investigations regarding the formationmechanisms of mixed-layerminerals are required to provide us with insight to understand the chloritization process in low-temperature geological systems.
In modern stromatolites, mineralization results from a complex interplay between microbial metabolisms, the organic matrix, and environmental parameters. Here, we combined biogeochemical, mineralogical, and microscopic analyses with measurements of metabolic activity to characterize the mineralization processes and products in an emergent (<18 months) hypersaline microbial mat. While the nucleation of Mg silicates is ubiquitous in the mat, the initial formation of a Ca-Mg carbonate lamina depends on (i) the creation of a high-pH interface combined with a major change in properties of the exopolymeric substances at the interface of the oxygenic and anoxygenic photoautotrophic layers and (ii) the synergy between two major players of sulfur cycle, purple sulfur bacteria, and sulfate-reducing bacteria. The repetition of this process over time combined with upward growth of the mat is a possible pathway leading to the formation of a stromatolite.
Aluminum phosphate-sulfate (APS) minerals occur as disseminated crystals in a wide range of geological environments near the Earth's surface, including weathering, sedimentary, diagenetic, hydrothermal, metamorphic and also postmagmatic systems. Their general formula is AB 3 (XO 4 ) 2 (OH) 6 , in which A, B and X represent three different crystallographic sites. These minerals are known to incorporate a great number of chemical elements in their lattice and to form complex solid-solution series controlled by the physicochemical conditions of their formation (Eh, pH, activities of constituent cations, P and T). These minerals are particularly widespread and spatially related to hydrothermal clay-mineral parageneses in the East Alligator River Uranium Field (EARUF) environment associated with uranium orebodies in the Proterozoic Kombolgie basin of the Northern Territories, Australia. This field contains several high-grade unconformity-related uranium deposits, including Jabiluka and Ranger. Both petrography and chemical data are used to discuss the significance of APS minerals in the alteration processes from the EARUF. The wide range of chemical compositions recorded in APS is essentially due to coupled substitutions of Sr for the LREE and of S for P at the A and X sites, respectively. The major variations of the APS solid-solution series mainly consist of the relative proportions of svanbergite, goyazite and florencite end-members. The APS minerals result from the interaction of oxidizing and relatively acidic fluids with aluminous host-rocks enriched in monazite. The spatial distribution of these minerals and their compositional variation around the uranium orebodies allow us to consider them as good tracers of redox and pH paleo-conditions responsible for the development of fronts during the alteration processes, and hence as potential tools for mineral exploration. SOMMAIRELes sulfates-phosphates d'aluminium (APS) sont des minéraux ubiquistes disséminés dans un grand nombre d'environnements géologiques: sédimentaire, diagénétique hydrothermal, métamorphique, magmatique. Leur formule générale est AB 3 (XO 4 ) 2 (OH) 6 , dans laquelle A, B et X correspondent à trois sites cristallographiques. Ces minéraux sont connus pour intégrer un grand nombre d'éléments chimiques dans leur structure sous la forme de nombreuses solutions solides dont la nature est contrôlée par les conditions de formation (Eh, pH, activités des éléments chimiques, P et T). Ces minéraux sont particulièrement répandus dans le district de l'East Alligator River Uranium Field (Territoires du Nord, Australie), où ils accompagnent les altérations argileuses autour des gisements d'uranium de type discordance, d'âge protérozoïque. Ce district contient plusieurs gisements d'uranium, de rang économique, tel que Jabiluka et Ranger. Les observations pétrographiques et les analyses chimiques effectuées lors de cette étude ont été utilisées pour discuter de l'intérêt des APS au niveau des altérations observées dans le district de l'East Alligator River Ura...
Sudoites exhibit different crystal-chemical and textural properties which may be related to the structural and valence state of Fe. Mössbauer spectroscopic analysis shows that all Fe previously analyzed using a microprobe (from 1 wt.% to 7.2 wt.% total Fe as Fe2O3) is structural and occurs in both oxidation states (40% Fe2+ and ∼60% Fe3+). Electron microprobe analyses from ∼200 sudoites indicate that Fe occurs in both octahedral sheets according to three main types of substitution: Fe3+ = octahedral Al; Fe2+ = Mg; and Fe3+ + Fe2++ □ = 3Mg. Decreasing tetrahedral substitution balances Fe3+ substitution in the trioctahedral sheet. Increasing octahedral Fe results in a more dioctahedral character of sudoite.X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, differential thermal analysis (DTA) and scanning electron microscope-transmission electron microscope (SEM-TEM) analyses showed that increasing octahedral Fe is associated with decreased stacking order and thermal stability due to the greater number of defects. In addition, with increasing octahedral Fe in sudoite, particles became smaller and more anhedral and consequently less stable with increasing Fe content. These structural and textural variations are interpreted as a result of the distortion of the sudoite structure by substitutions of Fe3+ with larger ionic radii for Al and Mg octahedral cations and by the formation of octahedral vacancies.
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