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The ca. 2.97 to 2.80 Ga Witwatersrand Supergroup, South Africa, represents the oldest intracontinental sedimentary basin of the Kaapvaal craton. Two volcanic units occur in this supergroup: the widespread Crown Formation lavas in the marine shale-dominated West Rand Group and the more geographically restricted Bird Member lavas, intercalated with fluvial to fluvio-deltaic sandstone and conglomerate of the Central Rand Group. These units remain poorly studied as they are rarely exposed and generally deeply weathered when cropping out. We report whole-rock major and trace elements, Hf and Nd-isotope whole-rock analyses of the lavas from core samples drilled in the south of the Witwatersrand basin and underground samples from the Evander Goldfield in the northeast. In the studied areas, both the Crown Formation and Bird Member are composed of two units of lava separated by sandstone. Whereas all the Crown Formation samples show a similar geochemical composition, the upper and lower volcanic units of the Bird Member present clear differences. However, the primitive mantle-normalized incompatible trace element concentrations of all Crown Formation and Bird Member samples show variously enriched patterns and marked negative Nb and Ta anomalies relative to Th and La. Despite the convergent geodynamic setting of the Witwatersrand Supergroup suggested by the literature, the Crown Formation and Bird Member are probably not related to subduction-related magmatism but more to decompression melting. Overall, the combined trace element and Sm-Nd isotopic data indicate melts from slightly to moderately depleted sources that were variably contaminated with crustal material. Greater contamination, followed by differentiation in different magma chambers, can explain the difference between the two signatures of the Bird Member. Finally, despite previous proposals for stratigraphically correlating the Witwatersrand Supergroup to the Mozaan Group of the Pongola Supergroup, their volcanic units are overall geochemically distinct.

The Hokuroku region of north-eastern Japan is endowed with important volcanic-hosted massive sulphide Zn–Pb–Cu deposits, which are considered the archetype of Kuroko (black ore) deposits worldwide. The bimodal, felsic-dominated volcanic succession that hosts the ore was deposited in a continental rift formed during continental extension in the final stages of the Miocene back-arc opening that led to the formation of the Japan Sea. In this study, we define some of the fundamental intensive parameters of this volcanism (temperature, pressure of crystallisation, fluid saturation, fO2) based on rock textures, and analyses of whole-rock samples, minerals and melt inclusions. Based on the melt inclusion analyses, we assess the behaviour of metals during magma evolution and degassing, and evaluate the possible implications for ore deposition. Plagioclase-melt geothermometry in felsic tuff and lava samples collected from both the units underlying and overlying the Kuroko indicates temperatures of 880–940 °C, and Fe–Ti oxide equilibrium indicates oxygen fugacity of ca. FMQ + 1.5. Melt inclusions have high-SiO2 rhyolite compositions (> 75 wt%, on an anhydrous basis), and the plot of normative mineral compositions in the granitic triplot indicates low pressure of magma stalling and crystallisation (

Archaean supracrustal rocks carry a record of mass-independently fractionated S that is interpreted to be derived from UV-induced photochemical reactions in an oxygen-deficient atmosphere. Experiments with photochemical reactions of SO2 gas have provided some insight into these processes. However, reconciling experimental results with the multiple S isotopic composition of the Archaean sedimentary record has proven difficult and represents one of the outstanding issues in understanding the Archaean surface S-cycle. We present quadruple S isotope data (32S, 33S, 34S, 36S) for pyrite from Mesoarchaean carbonaceous sediments of the Dominion Group, South Africa, deposited in an acidic volcanic lake, which help reconcile observations from the Archaean sedimentary record with the results of photochemical experiments. The data, which show low S/S ratios (mostly ≪ 1) and very negative S/S ratios (−4 and lower), contrast with the composition of most Archaean sedimentary sulfides and sulfates, having S/ (the so-called ‘Archaean reference array’), but match those of modern photochemical sulfate aerosols produced in the stratosphere, following super-large volcanic eruptions, and preserved in Antarctic ice. These data are also consistent with the results of UV-irradiation experiments of SO2 gas at variable gas pressure. The S isotope composition of the Dominion Group pyrite is here interpreted to reflect the products of photolysis in a low-oxygen-level atmosphere at high SO2 pressure during large volcanic eruptions, mixed with Archaean ‘background’ (having a composition broadly similar to the Archaean reference array) S pools. It is inferred that high sedimentation rates in a terrestrial basin resulted in an instantaneously trapped input of atmospheric S during short-lasted depositional intervals, which faithfully represents transient photochemical signals in comparison with marine sedimentary records.

International audience; Constraining the timing of eukaryogenesis and the divergence of eukaryotic clades is a major challenge in evolutionary biology. Here, we present trace metal concentration and zinc isotope data for c. 2.1 billion-year-old Francevillian Group pyritized structures, previously described as putative remnants of the first colonial multicellular organisms, and their host black shales. Relative to the host rocks, pyritized structures are strongly enriched in zinc, cobalt and nickel, by at least one order of magnitude, with markedly lighter zinc isotope compositions. A metabolic demand for high concentrations of aqueous zinc, cobalt, and nickel combined with preferential uptake of lighter zinc isotopes may indicate metalloenzyme utilization by eukaryotes in marine habitats c. 2.1 billion years ago. Once confirmed, this would provide a critical calibration point for eukaryogenesis, suggesting that this major evolutionary innovation may have happened contemporaneously with elevated atmospheric oxygen levels during the latter part of the Great Oxidation Event, some 400 million years earlier than is currently widely accepted.

Background Food allergy (FA) is a growing health problem worldwide. Effective strategies are advocated to limit the disease burden. Human milk (HM) could be considered as a protective factor against FA, but its mechanisms remain unclear. Butyrate is a gut microbiota‐derived metabolite able to exert several immunomodulatory functions. We aimed to define the butyrate concentration in HM, and to see whether the butyrate concentration detected in HM is able to modulate the mechanisms of immune tolerance. Methods HM butyrate concentration from 109 healthy women was assessed by GS‐MS. The effect of HM butyrate on tolerogenic mechanisms was assessed in in vivo and in vitro models. Results The median butyrate concentration in mature HM was 0.75 mM. This butyrate concentration was responsible for the maximum modulatory effects observed in all experimental models evaluated in this study. Data from mouse model show that in basal condition, butyrate up‐regulated the expression of several biomarkers of gut barrier integrity, and of tolerogenic cytokines. Pretreatment with butyrate significantly reduced allergic response in three animal models of FA, with a stimulation of tolerogenic cytokines, inhibition of Th2 cytokines production and a modulation of oxidative stress. Data from human cell models show that butyrate stimulated human beta defensin‐3, mucus components and tight junctions expression in human enterocytes, and IL‐10, IFN‐γ and FoxP3 expression through epigenetic mechanisms in PBMCs from FA children. Furthermore, it promoted the precursors of M2 macrophages, DCs and regulatory T cells. Conclusion The study's findings suggest the importance of butyrate as a pivotal HM compound able to protect against FA., Human milk contains a significant level of the short‐chain fatty acid butyrate. At concentration detectable in human milk, butyrate effectively modulates several tolerogenic mechanisms involved in the protection against food allergy. The protective role of human milk against food allergy could be related, at least in part, to the presence of an effective concentration of butyrate