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F.M. acknowledges funding from the European Research Council (ERC) under Horizon 2020 Framework Programme/ERC Grant Agreement 637503 (Pristine). F.M. and M.C. acknowledge the financial support of the UnivEarthS Labex Program at Sorbonne Paris Cité (Grants ANR-10-LABX-0023 and ANR-11-IDEX-0005-02). Parts of this work were supported by IPGP Plateau d’Analyse haute Résolution (PARI) and by Region Île-de-France Sesame Grant 12015908. Indirect evidence for the presence of a felsic continental crust, such as the elevated 49Ti/47Ti ratios in Archean shales, has been used to argue for ongoing subduction at that time and therefore plate tectonics. However, rocks of intermediate to felsic compositions can be produced in both plume and island arc settings. The fact that Ti behaves differently during magma differentiation in these two geological settings might result in contrasting isotopic signatures. Here, we demonstrate that, at a given SiO2 content, evolved plume rocks (tholeiitic) are more isotopically fractionated in Ti than differentiated island arc rocks (mainly calc-alkaline). We also show that the erosion of crustal rocks from whether plumes (mafic in average) or island arcs (intermediate in average) can all produce sediments having quite constant 49Ti/47Ti ratios being 0.1–0.3 per mille heavier than that of the mantle. This suggests that Ti isotopes are not a direct tracer for the SiO2 contents of crustal rocks. Ti isotopes in crustal sediments are still a potential proxy to identify the geodynamical settings for the formation of the crust but only if combined with additional SiO2 information. Postprint

This work is a contribution to the HiTech AlkCarb project and was funded by the European Union's Horizon 2020 research and innovation programme under grant agreement No. 689909. W.H. also acknowledges support from a UKRI Future Leaders Fellowship (MR/S033505/1). A.J.B. is funded by the NERC National Environment Isotope Facility award (NE/S011587/1) and the Scottish Universities Environmental Research Centre. Alkaline igneous complexes are often rich in rare earth elements (REE) and other metals essential for modern technologies. Although a variety of magmatic and hydrothermal processes explain the occurrence of individual deposits, one common feature identified in almost all studies, is a REE-enriched parental melt sourced from the lithospheric mantle. Fundamental questions remain about the origin and importance of the mantle source in the genesis of REE-rich magmas. In particular, it is often unclear whether localized enrichments within an alkaline province reflect heterogeneity in the mantle source lithology (caused by prior subduction or plume activity) or variations in the degree of partial melting and differentiation of a largely homogeneous source. Sulfur isotopes offer a means of testing these hypotheses because they are unaffected by high temperature partial melting processes and can fingerprint different mantle sources. Although one must be careful to rule out subsequent isotope fractionation during magma ascent, degassing and crustal interactions. Here, we present new S concentration and isotope (δ34S) measurements, as well as a compilation of major and trace element data, for a suite of alkaline magmatic units and crustal lithologies from the Mesoproterozoic Gardar Province. Samples span all phases of Gardar magmatism (1330–1140 Ma) and include regional dykes, rift lavas and the alkaline complexes Motzfeldt and Ilímaussaq, which represent two of Europe's largest REE deposits. We show that the vast majority of our 115 samples have S contents >100 ppm and δ34S of −1 to 5‰. Only 8 samples (with low S contents

his project has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement No. 643084 (BASE-LiNE Earth), and was also supported by the collaborative research initiative CHARON (DFG Research Group 1644 – Phase II) funded by the German Research Foundation. Brachiopods present a key fossil group for Phanerozoic palaeo-environmental and palaeo-oceanographical reconstructions, owing to their good preservation and abundance in the geological record. Yet to date, hardly any geochemical proxies have been calibrated in cultured brachiopods and only little is known on the mechanisms that control the incorporation of various key elements into brachiopod calcite. To evaluate the feasibility and robustness of multiple Element/Ca ratios as proxies in brachiopods, specifically Li/Ca, B/Ca, Na/Ca, Mg/Ca, Sr/Ca, Ba/Ca, as well as Li/Mg, we cultured Magellania venosa, Terebratella dorsata and Pajaudina atlantica under controlled experimental settings over a period of more than two years with closely monitored ambient conditions, carbonate system parameters and elemental composition of the culture medium. The experimental setup comprised of two control aquariums (pH0 = 8.0 and 8.15, T = 10 °C) and treatments where pCO2−pH (pH1 = 7.6 and pH2 = 7.35), temperature (T = 16 °C) and chemical composition of the culture medium were manipulated. Our results indicate that the incorporation of Li and Mg is strongly influenced by temperature, growth effects as well as carbonate chemistry, complicating the use of Li/Ca, Mg/Ca and Li/Mg ratios as straightforward reliable proxies. Boron partitioning varied greatly between the treatments, however without a clear link to carbonate system parameters or other environmental factors. The partitioning of both Ba and Na varied between individuals, but was not systematically affected by changes in the ambient conditions. We highlight Sr as a potential proxy for DIC, based on a positive trend between Sr partitioning and carbonate chemistry in the culture medium. To explain the observed dependency and provide a quantitative framework for exploring elemental variations, we devise the first biomineralisation model for brachiopods, which results in a close agreement between modelled and measured Sr distribution coefficients. We propose that in order to sustain shell growth under increased DIC, a decreased influx of Ca2+ to the calcifying fluid is necessary, driving the preferential substitution of Sr2+ for Ca2+ in the crystal lattice. Finally, we conducted micro-computed tomography analyses of the shells grown in the different experimental treatments. We present pore space – punctae – content quantification that indicates that shells built under increased environmental stress, and in particular elevated temperature, contain relatively more pore space than calcite, suggesting this parameter as a potential novel proxy for physiological stress and even environmental conditions. Publisher PDF