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Equilibria between Ti oxides and silicate melt lead to Ti isotope fractionation in terrestrial samples, with isotopically light Ti oxides and isotopically heavy coexisting melt. However, while Ti is mostly tetravalent in terrestrial samples, around 10% of the overall Ti is trivalent at fO2 relevant to lunar magmatism (~ IW-1). The different valences of Ti in lunar samples, could additionally influence Ti stable isotope fractionation during petrogenesis of lunar basalts to an unknown extent. We performed an experimental approach using gas mixing furnaces to investigate the effect of Ti oxide formation at different fO2 on Ti stable isotope fractionation during mare basalt petrogenesis. Two identical bulk compositions were equilibrated simultaneously during each experiment to guarantee comparability. One experiment was investigated with the EPMA to characterize the petrology of experimental run products, whereas the second experiment was crushed, and fabricated phases (i.e., oxides, silicates and glass) were handpicked, separated and digested. An aliquot of each sample was mixed with a Ti double-spike, before Ti was separated from matrix and interfering elements using a modified HFSE chemistry. Our study shows fO2-dependent fractionation within seven samples from air to IW-1, especially ∆49Tiarmalcolite-melt and ∆49Tiarmalcolite-orthopyroxene become more fractionated from oxidized to reduced conditions (− 0.092 ± 0.028-  − 0.200 ± 0.033 ‰ and  − 0.089 ± 0.027- − 0.250 ± 0.049 ‰, respectively), whereas ∆49Tiorthopyroxene-melt shows only a minor fractionation (− 0.002 ± 0.017-0.050 ± 0.025 ‰). The results of this study show that Ti isotope fractionation during mare basalt petrogenesis is expected to be redox dependent and mineral-melt fractionation as commonly determined for terrestrial fO2 may not be directly applied to a lunar setting. This is important for the evaluation of Ti isotope fractionation resulting from lunar magmatism, which takes place under more reducing conditions compared to the more oxidized terrestrial magmatism.

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ABSTRACT:We present new U-Pb zircon ages and Sm-Nd-Pb isotopic data for volcanic and hypabyssal acid rocks from the northernmost exposure of the Acampamento Velho Formation in the NW portion of the Sul-Rio-Grandense Shield, Brazil. The first volcanic episode, grouped in the high-Ti rhyolites from the Tupanci hill, shows age of 579 ± 5.6 Ma, which is in agreement with the post-collisional Acampamento Velho Formation volcanism in the Bom Jardim Group of the Camaquã Basin. A poorly constrained age of 558 +/-39 Ma was obtained for rhyolites from the low-Ti group at the Picados Hill, which may indicate a younger acid volcanism, or a greater time span for the volcanism of the Acampamento Velho Formation in southernmost Brazil. Regarding magmatic sources, Sm/Nd isotopic data coupled to Pb isotopes and a review of trace element geochemistry indicate different amounts of Paleoproterozoic (Dom Feliciano, Pinheiro Machado Suite) to Neoproterozoic (Rio Vacacaí terrane) lower crust melting. Our data, coupled with literature data, contribute to a better understanding of the stratigraphic evolution for the Neoproterozoic post-collisional volcanic successions of the Camaquã Basin in the Sul-Rio-Grandense Shield. KEYWORDS:Volcanism; Acampamento Velho Formation; Camaquã Basin; Tupanci; Geochronology. RESUMO: Novas idades obtidas por meio do método U-Pb em zircão e dados isotópicos Sm-Nd-Pb são apresentados para as rochas vulcânicas e hipabssais ácidas da exposição mais setentrional da Formação Acampamento

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