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Recent thermodynamic and experimental studies have suggested that volatile organic compounds (e.g., methane, formate, and acetate) can be produced and stabilized in subduction zones, potentially playing an important role in the deep carbon cycle. However, field evidence for the high-pressure production and storage of solid organic compounds is missing. Here, we examine forearc serpentinite clasts recovered by drilling mud volcanoes above the Mariana subduction zone. Notable correlations between carbon and iron stable-isotope signatures and fluid-mobile element (B, As and Sb) concentrations provide evidence for the percolation of slab-derived CO 2 -rich aqueous fluids through the forearc mantle. The presence of carbonaceous matter rich in aliphatic moieties within high-temperature clasts (>350°C) demonstrates that molecular hydrogen production associated with forearc serpentinization is an efficient mechanism for the reduction and conversion of slab-derived CO 2 -rich fluids into solid organic compounds. These findings emphasize the need to consider the forearc mantle as an important reservoir of organic carbon on Earth.

This study presents a new classification of a ∼100-m-thick crater suevite sequence in the recent International Ocean Discovery Program (IODP)-International Continental Scientific Drilling Program (ICDP) Expedition 364 Hole M0077A drill core to better understand the formation of suevite on top of the Chicxulub peak ring. We provide an extensive data set for this succession that consists of whole-rock major and trace element compositional data (n = 212) and petrographic data supported by digital image analysis. The suevite sequence is subdivided into three units that are distinct in their petrography, geochemistry, and sedimentology, from base to top: the ∼5.6-m-thick non-graded suevite unit, the ∼89-m-thick graded suevite unit, and the ∼3.5-m-thick bedded suevite unit. All of these suevite units have isolated Cretaceous planktic foraminifera within their clastic groundmass, which suggests that marine processes were responsible for the deposition of the entire M0077A suevite sequence. The most likely scenario describes that the first ocean water that reached the northern peak ring region entered through a N-NE gap in the Chicxulub outer rim. We estimate that this ocean water arrived at Site M0077 within 30 minutes after the impact and was relatively poor in rock debris. This water caused intense quench fragmentation when it interacted with the underlying hot impact melt rock, and this resulted in the emplacement of the ∼5.6-m-thick hyaloclastite-like, non-graded suevite unit. In the following hours, the impact structure was flooded by an ocean resurge rich in rock debris, which caused the phreatomagmatic processes to stop and the ∼89-m-thick graded suevite unit to be deposited. We interpret that after the energy of the resurge slowly dissipated, oscillating seiche waves took over the sedimentary regime and formed the ∼3.5-m-thick bedded suevite unit. The final stages of the formation of the impactite sequence (estimated to be

The Moroccan Anti-Atlas orogenic belt encloses several Precambrian inliers comprising two major Neoproterozoic ophiolitic complexes: the Sirwa and Bou Azzer ophiolites. These ophiolites expose crustal and mantle units, thrusting over fragments of a long-lived intra-oceanic arc system. We present a detailed geochronological and petro-geochemical study of three mafic/ultramafic units of these two ophiolites: the Khzama sequence (Sirwa ophiolite) and the Northern and Southern Aït Ahmane sequences (Bou Azzer ophiolite). The crystallization of layered metagabbros from the Bou Azzer ophiolite (North Aït Ahmane sequence) has been dated here at 759 ± 2 Ma (U-Pb on zircons). This new age for the Bou Azzer ophiolite is similar to the formation of the Sirwa ophiolite (762 Ma) and suggests that both units formed during the same spreading event. Metabasalts of the three units show tholeiitic signature but with variable subduction-related imprints marked by LILE enrichments, HFSE depletions and variable Ti contents, similar to modern back-arc basin basalts (BABB). Their back-arc origin is also supported by the geochemical signature of ultramafic units showing very low contents in major and trace incompatible elements (Al2O3: 0.12–1.53 wt%, Ti: 3.5–64.2 ppm and Nb: 0.004–0.10 ppm), attesting of a highly refractory protolith. This is in agreement with the high Cr (0.44–0.81) and low to intermediate Mg (0.25–0.73) of their constitutive Cr-spinels. Dynamic melting models suggest that these serpentinites experienced intense and polyphased hydrous melting events, strongly influenced by supra-subduction zone SSZ-fluid influx and subduction-related melt percolation. Being particularly affected by these SSZ-melt/rock interactions and closer to arc units to the south, the Sirwa ophiolite and the South Aït Ahmane unit of the Bou Azzer ophiolite likely represent an early stage of the arc-back-arc system, which has been more influenced by the magmatic products of the arc activity compared to the North Aït Ahmane unit of the Bou Azzer ophiolite., SCOPUS: ar.j, info:eu-repo/semantics/published

The Earth’s mantle is currently divided into the African and Pacific domains, separated by the circum-Pacific subduction girdle, and each domain features a large low shear-wave velocity province (LLSVP) in the lower mantle. However, it remains controversial as to whether the LLSVPs have been stationary through time or dynamic, changing in response to changes in global subduction geometry. Here we compile radiogenic isotope data on plume-induced basalts from ocean islands and oceanic plateaus above the two LLSVPs that show distinct lead, neodymium and strontium isotopic compositions for the two mantle domains. The African domain shows enrichment by subducted continental material during the assembly and breakup of the supercontinent Pangaea, whereas no such feature is found in the Pacific domain. This deep-mantle geochemical dichotomy reflects the different evolutionary histories of the two domains during the Rodinia and Pangaea supercontinent cycles and thus supports a dynamic relationship between plate tectonics and deep-mantle structures. Earth’s deep-mantle domains are geochemically distinct. The African domain is enriched in subducted material, which suggests a different history from the Pacific domain and a dynamic relationship between plate tectonics and deep-mantle structures.

Subduction zones are active sites of chemical exchange between the Earth’s surface and deep interior and play a fundamental role in regulating planet habitability. However, the mechanisms by which redox sensitive elements (e.g., iron, carbon and sulfur) are cycled during subduction remains unclear. Here we use Fe stable isotopes (δ56Fe), which are sensitive to redox-related processes, to examine forearc serpentinite clasts recovered from deep sea drilling of mud volcanoes formed above the Mariana subduction zone in the Western Pacific. We show that serpentinisation of the forearc by slab-derived fluids produces dramatic δ56Fe variation. Unexpected negative correlations between serpentinite bulk δ56Fe, fluid-mobile element concentrations (e.g., B, As) and Fe3+/ƩFe suggest a concomitant oxidation of the mantle wedge through the transfer of isotopically light iron by slab-derived fluids. This process must reflect the transfer of either sulfate- or carbonate-bearing fluids that preferentially complex isotopically light Fe.

Atmospheric deposition is a key mode of iron (Fe) input to ocean regions where low concentrations of this micronutrient limit marine primary production. Various natural particles (e.g., mineral dust, volcanic ash) and anthropogenic particles (e.g., from industrial processes, biomass burning) can deliver Fe to the ocean, and assessment of their relative importance in supplying Fe to seawater requires knowledge of both their deposition flux and their Fe solubility (a proxy for Fe bioavailability). Iron isotope (

Mineral dust is a natural tracer of atmospheric composition and climate variability. Yet, there is still much to be known about the Southern Hemisphere dust cycle during the last Pleistocene. Major efforts have attempted to solve the ‘puzzle’ of the origin of the potential source areas that contribute dust to the Southern Ocean and East Antarctica (EA). Here we present a comprehensive geochemical characterization of an important potential source area, which role as a dust supplier to different environments of the SH has significantly been underestimated, that is, the Southern Africa (SAF) region. On the basis of Sr-Nd-Pb isotope ratios and rare earth element concentrations analyzed in sediments collected along the major dust-producing areas in the Namibian coast (Kuiseb, Omaruru and Huab riverbeds and the Namibian sand sea region), this study demonstrates for the first time that SAF emerges as the second most important dust source to EA during interglacial times.

This study aims to better understand the development of group identity, mobility, and health in the Early Medieval Meuse Valley. This is achieved by combining existing demographic and palaeopathological information from 73 cremation deposits from Echt, the Netherlands, with new strontium isotope ratios (87Sr/86Sr) and strontium concentrations ([Sr]) that are performed on pars petrosa, diaphysis, and rib fragments. Although the surrounding Early Medieval cemeteries practiced inhumation, the initial burial community of Echt persisted in expressing the divergent burial ritual of cremation. Thirty-two radiocarbon dates demonstrate the fifth- to sixth-century cremation deposits to be chronologically separated from the seventh-century inhumations that were preserved in situ, suggesting a subsequent burial community replaced cremation with inhumation in the seventh century. Nutritionally inadequate diets may have contributed to the relatively high prevalence of porotic hyperostosis (~ 34%), resulting from decreasing foods supplies caused by deteriorating climatic conditions. The inhabitants are postulated to have mainly consumed foods originating from the land directly surrounding their farmsteads, expressed by the great variability in the 87Sr/86Sr of the diaphyses and ribs (0.7096 to 0.7131), matching the geological complexity of the area. The lack of significant differences between the 87Sr/86Sr and [Sr] of ribs and diaphyses connotes little change in the geological origin of the foods occurred over time, stressing the importance of the yield of local harvests. In contrast, large differences in childhood (i.e. pars petrosa) vs. adult (i.e. ribs and diaphyses) 87Sr/86Sr suggest the regional movement of individuals to possibly support inter-farmstead relationships (e.g. via marriages)., SCOPUS: ar.j, info:eu-repo/semantics/published

We present a workflow to conduct a full characterization of medium to coarse-grained igneous rocks, using portable, non-invasive, and reproducible approaches. This includes: (i) Image Analysis (IA) to quantify mineral phase proportions, grain size distribution using the Weka trainable machine learning algorithm. (ii) Portable X-ray fluorescence spectrometer (PXRF, Bruker Tracer IV) to quantify the whole-rock's chemical composition. For this purpose, a specific calibration method dedicated to igneous rocks using the open-source CloudCal app was developed. It was then validated for several key elements (Si, Al, K, Ti, Ca, Fe, Mn, Sr, Ga, Ba, Rb, Zn, Nb, Zr, and Y) by analyzing certified standard reference igneous rocks. (iii) Portable Magnetic Susceptibilimeter (pMS, Bartington MS2K system) to constrain the mineralogical contribution of the samples. The operational conditions for these three methods were tested and optimized by analyzing five unprepared surfaces of igneous rocks ranging from a coarse-grained alkaline granite to a fine-grained porphyric diorite and hence, covering variable grain sizes, mineralogical contents, and whole-rock geochemical compositions. For pMS and PXRF tools, one hundred analyses were conducted as a 10 cm × 10 cm square grid on each sample. Bootstrap analysis was implemented to establish the best grid size sampling to reach an optimized reproducibility of the whole-rock signature. For PXRF analysis, averaged compositions were compared to PXRF analysis on press-pellets and laboratory WD-XRF analysis on fused disk and solution ICP-OES (for major) and solution-ICPMS (for trace element concentrations). Ultimately, this workflow was applied in the field on granitoids from three Roman quarrying sites in the Lavezzi archipelago (southern Corsica) and tested against the Bonifacio granitic War Memorial, for which its provenance is established. Our results confirm this information and open the door to geoarchaeological provenance studies with a high spatial resolution., SCOPUS: ar.j, info:eu-repo/semantics/published

The Mariana forearc is a unique setting on Earth where serpentinite mud volcanoes exhume clasts originating from depths of 15 km and more from the forearc mantle. These peridotite clasts are variably serpentinized by interaction with slab derived fluid, and provide a record of forearc mantle dynamics and changes in geochemistry with depth. During International Oceanic Discovery Program (IODP) Expedition 366, we recovered serpentinized ultramafic clasts contained within serpentinite muds of three different mud volcanoes located at increasing distance from the Mariana trench and at increasing depth to the slab/mantle interface: Yinazao (distance to the trench: 55 km / depth to the slab/mantle interface: 13 km), Fantangisña (62 km / 14 km) and Asùt Tesoru (72 km / 18 km). Four different types of ultramafic clasts were recovered: blue serpentinites, lizardite-serpentinites, antigorite/lizardite- and antigorite-serpentinites. Lizardite-serpentinites are primarily composed of orange serpentine, forming mesh and bastite textures. Raman and microprobe analyses revealed that these textures contain a mixture of Fe-rich brucite (XMg ~ 0.84) and lizardite/chrysotile. Antigorite/lizardite- and antigorite-serpentinites record the progressive recrystallization of mesh and bastite textures to antigorite, magnetite and pure Fe-poor brucite (XMg ~ 0.92). Oxygen isotope compositions of clasts and pore fluids showed that the transition from lizardite to antigorite is due to the increase in temperature from 200 °C to about 400 °C within the forearc area above the slab/mantle interface. Lizardite-, antigorite/lizardite- and antigorite-serpentinites displayed U-shaped chondrite normalized Rare Earth Element (REE) patterns and are characterized by high fluid mobile element concentrations (Cs, Li, Sr, As, Sb, B, Li) relative to abyssal peridotites and/or primitive mantle. The recrystallization of lizardite to antigorite is accompanied by a decrease in Cs, Li and Sr, and an increase in As and Sb concentrations in the bulk clasts, whereas B concentrations are relatively constant. Some clasts are overprinted by blue serpentine, often in association with sulfides. Most of these blue serpentinites were recovered at Yinazao and the uppermost units of Fantangisña and Asùt Tesoru suggesting alteration in the shallower portions of the forearc, possibly during exhumation of the clasts. This episode of alteration resulted in a flattening of REE spectra and an increase of Zn concentrations in serpentinites. Otherwise, no systematic changes of ultramafic clasts chemistry or mineralogy were observed with increasing depth to the slab. The samples document previously undescribed prograde metamorphic events in the shallow portions of the Mariana subduction zone, consistent with a continuous burial of the serpentinized forearc mantle during subduction. Similar processes, induced by the interaction with fluids released from the downgoing slab, likely occur in subduction zones worldwide. At greater depth, breakdown of brucite and antigorite will result in the massive transfer of fluids and fluid mobile elements, such as As, Sb and B, to the source of arc magmas., SCOPUS: ar.j, info:eu-repo/semantics/published

Studies of the Fe, Cu, and Zn isotopic compositions of volcanic rocks and sulfides provide an important tool for understanding magmatic, hydrothermal, and alteration processes, thereby enabling the determination of both transition metal sources and the quantification of the petrologic environmental impacts of hydrothermal activities. In this study, the δ56Fe and δ57Fe values of the mid-ocean ridge basalts (MORBs) are higher than those of the seafloor hydrothermal fluids, while the reverse is true for the δ66Zn and δ68Zn values, suggesting that basalt-fluid interactions preferentially incorporate isotopically light Fe and heavy Zn into the fluids, resulting in the relative enrichment of heavier Fe and lighter Zn isotopes in altered basaltic rocks. Most of the δ56Fe values (−1.96 to +0.11‰) of the sulfide minerals are within the range of the vent fluids, but they are significantly lower than those of the MORBs and back-arc basin basalts (BABBs), suggesting that the Fe in the sulfides was mainly derived from the fluids. However, the majority of the chalcopyrite δ56Fe and δ57Fe values are higher than those of the sphalerite and pyrite. This suggests that high-temperature sulfide minerals are enriched in 56Fe and 57Fe, whereas medium- and low-temperature sulfides are depleted in 56Fe and 57Fe. Moreover, the δ65Cu (−0.88 to −0.16‰) and δ66Zn (−0.39 to −0.03‰) values of the sulfide minerals are significantly lower than those of the MORBs, BABBs, and fluids, suggesting that 63Cu and 64Zn were preferentially removed from the fluids and incorporated into the chalcopyrite and sphalerite, respectively. Consequently, vent fluid injection and deposition can cause the heavier Cu and Zn isotopic compositions of hydrothermal plumes, seawater, and sediments., SCOPUS: ar.j, info:eu-repo/semantics/published

The ability to trace and quantify sediment provenance in northwestern Patagonia is increasingly needed to properly understand modern sediment erosion and transport processes in this rapidly changing environment, and to accurately interpret sediment records from adjacent basins in terms of climate and environmental change. Nonetheless, no study so far has systematically evaluated the effectiveness of different tracers to reconstruct sediment provenance in this region. To fill this gap, we assess the effectiveness of commonly-used provenance indicators, including bulk mineralogy, major and rare earth element (REE) geochemistry, and Sr and Nd isotopes, to reconstruct sediment provenance in northwestern Patagonia. First, the ability of these tracers to discriminate between the main sources of sediment in the region is investigated, mostly using data compiled from the literature. Then, the potential of these tracers for provenance reconstruction is assessed by comparing the composition of sediments from six major Chilean rivers between 44 and 48°S to lithological proportions in their respective watersheds. The results suggest that mineralogy, major element geochemistry, and REE geochemistry can be used as qualitative tracers of sediment provenance. However, the compositional overlap between the sources and the relatively large variability within them prevent quantitative reconstructions. By comparison, 87Sr/86Sr and εNd allow to clearly differentiate between the sources, most likely due to significant age differences between the main lithologies, and to estimate the relative contribution of each source. End-member mixing results based on Sr and Nd isotopes show that the relative source contributions are in general agreement with the lithological proportions in the river watersheds. Differences between estimated contributions and lithological proportions in the watersheds are interpreted as the result of the high regional precipitation gradient and unequal glacier distribution, which lead to variable erosion rates across the study area. Our results demonstrate the suitability of 87Sr/86Sr and εNd for quantitative provenance reconstruction in northwestern Patagonia. They constitute a strong basis for the interpretation of sediment archives from the Patagonian fjords and from the eastern South Pacific, and they should be particularly useful to quantitatively investigate modern and past earth-surface processes., SCOPUS: ar.j, info:eu-repo/semantics/published

There is a lack of certified reference materials with an organic matrix for which metal isotope ratios have been certified. Here, we have determined the iron, copper and zinc stable isotopic compositions for six reference materials of biological origin with diverse matrices, i.e. BCR-380R (whole milk), BCR-383 (beans), ERM-CE464 (tuna fish), SRM-1577c (bovine liver), DORM-4 (fish protein) and TORT-3 (lobster hepatopancreas) in three different labs. The concentrations for six major and sixteen trace elements, spanning almost four orders of magnitude, were also measured and the results obtained show an excellent agreement with certified values, demonstrating that the dissolution step was quantitative for all the standards. By taking literature data into account, 39 possible pair-wise comparisons of mean iron, copper and zinc isotopic values (δ values) could be made. Results of Tukey multiple comparisons of means yielded 11 significantly different pairs. Most of these differences are of the same order of magnitude as the estimated mean expanded uncertainties (U, k = 2) (±0.10‰, ±0.05‰, and ±0.05‰ for the δ56Fe, δ65Cu and δ66Zn values, respectively). The present inter-comparison study finally proposes nineteen new preferred values for the Cu, Zn and Fe isotopic compositions of six reference materials of biological origin., SCOPUS: ar.j, info:eu-repo/semantics/published

The Archean continental lithosphere consists of a dominantly felsic continental crust, made of tonalite-trondhjemite-granodiorite (TTG) and subordinate granitoids, and a cratonic lithospheric mantle, made of highly refractory peridotites. Whether they stemmed from the same process of differentiation from the primitive mantle, or were two distinct components that were physically juxtaposed, remains debated. Metal stable isotope ratios are sensitive to magmatic and metamorphic processes and do not evolve with time. Therefore, stable isotope ratios are complementary to radiogenic isotope ratios, and they allow direct comparisons to be made between different terrestrial components without age corrections. Isotopes of iron and zinc, metals ubiquitous in Earth’s lithosphere, can be tracers of lithospheric formation and evolution because they are affected by partial melting (Fe, Zn), redox state (Fe), and the presence of sulfides (Fe, Zn). Here, using stable Fe and Zn isotopic data from Archean samples of the lithospheric mantle and the continental crust, we show that Fe and Zn isotopes define a linear array, best explained by their coupled fractionation behavior during magmatic processes. Our data show that high degrees of partial melting (>30%) during the formation of the cratonic mantle and mafic protocrust, and reworking of the early crust significantly fractionate Fe and Zn isotopes. Conversely, Fe and Zn isotope ratios in the TTG are similar to those in Archean mafic rocks, suggesting an origin by fractional crystallization of basalt, and implying limited Fe and Zn isotopic fractionation, instead of partial melting of mafic crust. Moreover, the absence of Fe and Zn isotope decoupling due to redox effects, melt (fluid)–rock or sediment-rock interaction, and decarbonation indicates that subduction, at least as we understand it now, is not required to explain the Fe and Zn isotope composition of the Archean lithosphere.

Water and iron are believed to be key constituents controlling the strength and density of the lithosphere and, therefore, play a crucial role in the long-term stability of cratons. On the other hand, metasomatism can modify the water and iron abundances in the mantle and possibly triggers thermo-mechanical erosion of cratonic keels. Whether local or large scale processes control water distribution in cratonic mantle remains unclear, calling for further investigation. Spinel peridotite xenoliths in alkali basalts of the Cenozoic Tok volcanic field sampled the lithospheric mantle beneath the southeastern margin of the Siberian Craton. The absence of garnet-bearing peridotite among the xenoliths, together with voluminous eruptions of basaltic magma, suggests that the craton margin, in contrast to the central part, lost its deep keel. The Tok peridotites experienced extensive and complex metasomatic reworking by evolved, Ca-Fe-rich liquids that transformed refractory harzburgite to lherzolite and wehrlite. We used polarized Fourier transform infrared spectroscopy (FTIR) to obtain water content in olivine, orthopyroxene (Opx), and clinopyroxene (Cpx) of 14 Tok xenoliths. Olivine, with a water content of 0–3 ppm H2O, was severely degassed, probably during emplacement and cooling of the host lava flow. Orthopyroxene (49–106 ppm H2O) and clinopyroxene (97–300 ppm H2O) are in equilibrium. The cores of the pyroxene grains, unlike olivine, experienced no water loss due to dehydration or addition attributable to interaction with the host magma. The water contents of Opx and Cpx are similar to those from the Kaapvaal, Tanzania, and North China cratons, but the Tok Opx has less water than previously studied Opx from the central Siberian craton (Udachnaya, 28–301 ppm; average 138 ppm). Melting models suggest that the water contents of Tok peridotites are higher than in melting residues, and argue for a post-melting (metasomatic) origin.Moreover, the water contents in Opx and Cpx of Tok peridotites are decoupled from iron enrichments or other indicators of melt metasomatism (e.g., CaO and P2O5). Such decoupling is not seen in the Udachnaya and Kaapvaal peridotites but is similar to observations on Tanzanian peridotites. Our data suggest that iron enrichments in the southeastern Siberian craton mantle preceded water enrichment. Pervasive and large-scale, iron enrichment in the lithospheric mantle may strongly increase its density and initiate a thermo-magmatic erosion. By contrast, the distribution of water in xenoliths is relatively “recent” and was controlled by local metasomatic processes that operate shortly before the volcanic eruption. Hence, water abundances in minerals of Tok mantle xenoliths appear to represent a snapshot of water in the vicinity of the xenolith source regions.

Subduction at convergent margins introduces a range of sedimentary and crustal materials into the mantle, providing the most dominant form of heterogeneity in the source of oceanic basalts. Yet, the relationship between geochemical variability and lithologic heterogeneities in the Earth's mantle remains controversial. In this paper, we comprehensively review Zn, δ66Zn and Sr-Nd isotope systematics in near-primary basalts erupted at mid-ocean ridges (MORB) and ocean islands (OIB) to help constrain the nature and proportion of the carbon (C) bearing slab-derived component in their mantle sources. We show that Zn elemental and isotopic composition of oceanic basalts differs according to their tectonic settings, increasing from MORB (Zn = 62 ± 10 to 73 ± 11 ppm; δ66Zn = +0.24 ± 0.01 to +0.31 ± 0.02‰) to OIB (Zn = 74 ± 9 to 124 ± 7 ppm; δ66Zn = +0.21 ± 0.07 to +0.40 ± 0.04‰). Unlike MORB, the high Zn and δ66Zn recorded in OIB cannot be explained by partial melting of a fertile peridotite mantle source only. Importantly, global correlations between Zn content and Sr-Nd isotopes in oceanic basalts suggest that the Zn enrichment in OIB is inherited from a recycled component in their mantle source rather than melting processes. We demonstrate that involvement of neither typical MORB-like oceanic crust nor subducted sediments can achieve the whole range of Zn composition in OIB. Instead, addition of ≤6% C-bearing oceanic crust to a fertile peridotite mantle fully resolves the Zn heterogeneity of OIB, both in terms of magnitude of Zn enrichment and global trends with Sr-Nd isotopes. Such scenario is corroborated by the elevated δ66Zn of OIB relative to MORB and mantle peridotites, reflecting the contribution of isotopically heavy C-bearing phases (δ66Zn = +0.91 ± 0.24‰) to the mantle source (δ66Zn = +0.16 ± 0.06‰). Our study thus emphasizes the use of Zn and δ66Zn systematics to track the nature and origin of mantle carbon, highlighting the role of subduction in the deep carbon cycle. Finally, the positive correlation between Zn content and temperature of magma generation of oceanic basalts suggests that hotter mantle plumes are more likely to carry a higher proportion of dense C-bearing eclogite. Zinc systematics therefore may provide evidence that the presence of heterogeneous domains in the source of OIB is, at least partly, linked to plume thermal buoyancy, bringing new insights into mantle dynamics., SCOPUS: re.j, info:eu-repo/semantics/published

This paper presents the results of a study using strontium, oxygen and carbon isotopes, strontium concentrations, infrared analyses and radiocarbon dating to investigate human mobility and landscape use as seen in individuals from the Neolithic court tomb of Parknabinnia, Co. Clare, Ireland. Taking advantage of the recent demonstration that it is possible to obtain reliable in vivo strontium isotope signals from calcined bone, we compare measurements on cremated bone (n = 4) and uncremated tooth enamel (n = 4). The results suggest that two out of four uncremated enamel samples can be considered ‘local’ while the other two, and all four cremated bone samples, represent ‘non-local’ individuals. New radiocarbon dates obtained on two of the cremated bone fragments place them in the Chalcolithic/Early Bronze Age, contrasting with the Neolithic dates previously obtained on the uncremated remains, demonstrating re-use of the monument. Assuming that our small sample is representative, it seems that the court tomb was used for burial by both ‘locals’ and ‘non-locals’ during the Neolithic and predominantly by ‘non-locals’ in the Chalcolithic/Early Bronze Age. This stands in contrast to the nearby Early Neolithic portal tomb of Poulnabrone where only one individual (of 17 analysed) appears to be an ‘outsider’. Our results suggest that, even within a small region, mobility and landscape use may have differed significantly within the Neolithic and also between the Neolithic and the Chalcolithic/Early Bronze Age., SCOPUS: ar.j, info:eu-repo/semantics/published

Strontium isotopes are used in archaeology, ecology, forensics, and other disciplines to study the origin of artefacts, humans, animals and food items. Strontium in animal and human tissues such as bone and teeth originates from food and drink consumed during life, leaving an isotopic signal corresponding to their geographical origin (i.e. where the plants grew, the animals grazed and the drinking water passed through). To contextualise the measurements obtained directly on animal and human remains, it is necessary to have a sound baseline of the isotopic variation of biologically available strontium in the landscape. In general, plants represent the main source of strontium for humans and animals as they usually contain much higher strontium concentrations than animal products (meat and milk) or drinking water. The observed difference between the strontium isotope composition of geological bedrock, soils and plants from the same locality warrants direct measurement of plants to create a reliable baseline. Here we present the first baseline of the biologically available strontium isotope composition for the island of Ireland based on 228 measurements on plants from 140 distinct locations. The isoscape shows significant variation in strontium isotope composition between different areas of Ireland with values as low as 0.7067 for the basalt outcrops in County Antrim and values of up to 0.7164 in the Mourne Mountains. This variability confirms the potential for studying mobility and landscape use of past human and animal populations in Ireland. Furthermore, in some cases, large differences were observed between different types of plants from the same location, highlighting the need to measure more than one plant sample per location for the creation of BASr baselines., SCOPUS: ar.j, info:eu-repo/semantics/published

Although several authors have previously reported the limited Roman quarrying activity in Corsica, recent research programs revealed a real basin of granitoid quarries in the archipelago of Lavezzi (Strait of Bonifacio, southern Corsica). A series of fundamental archaeological questions have arisen for which a geological expertise could provide new answers: (i) what was the quarrying strategy during Roman times in the Strait of Bonifacio area, (ii) is it possible to characterize and catalogue the quarried granitic rock materials and establish ‘quarry-to-monument’ relationships (i.e. comparisons with building stones and quarries), and (iii) how to identify and constrain the timing of major phases of quarrying activity (discrimination of Roman activities relative to modern footprints in the quarries)?To achieve these goals, our geoarchaeological study proposes a pluri-disciplinary, innovative, non-destructive methodological strategy, coupling techniques of digital photogrammetry, field petrography, mineralogical and chemical analyses by portable magnetic susceptibilimeter (pMS) and portable X-Ray Fluorescence spectrometer (pXRF) respectively, and physical rock properties using a Schmidt Hammer. The field geochemical measurements were calibrated by laboratory major and trace element analyses on ICP-OES and HR-ICP-MS, respectively. Here, we present preliminary results of two field campaigns. These results indicate that a statistically significant number of measurements by pMS and pXRF from the same representative area of the studied rocks – natural rocks or building stones, can be used to discriminate different quarried sites and identifying distinct rock sources. Several profiles of rebound measurements at the rock surface using the Schmidt Hammer (indicative of the degree to which a rock surface has been weathered and by extension, exposed) might help revealing the initial volume of natural rock massifs before their initial extraction. Our study provides original and reproducible techniques contributing to significantly improve geoarchaeometric investigations and brings key information on the quarrying activity in southern Corsica during Roman times along with its implications on the Mediterranean commercial exchange trades.

A compact isotope ratio sensor based on laser absorption spectroscopy at 2.7 μm was developed for high precision and simultaneous measurements of the D/H, 18O/16O and 17O/16O isotope ratios in glacier water. Measurements of the oxygen and hydrogen isotope ratios in glacier water demonstrate a 1σ precision of 0.3‰ for δ18O, 0.2‰ for δ17O, and 0.5‰ for δ2H, respectively. The δvalues of the working standard glacier water obtained by the calibrated sensor system is basically identical to the IRMS measurement results with a very high calibration accuracy from 0.17‰ to 0.75‰. Preliminary results on the reproducibility measurements display a standard deviation of 0.13‰ for δ18O, 0.13‰ for δ17O, and 0.64‰ for δ2H, respectively., SCOPUS: ar.j, info:eu-repo/semantics/published

A compact isotope ratio sensor based on laser absorption spectroscopy at 2.7 μm was developed for high precision and simultaneous measurements of the D/H

Multi-isotope analyses suggest cultural differentiation as the primary reason for Late Neolithic variability in burial location., The coexistence of cultural identities and their interaction is a fundamental topic of social sciences that is not easily addressed in prehistory. Differences in mortuary treatment can help approach this issue. Here, we present a multi-isotope study to track both diet and mobility through the life histories of 32 broadly coeval Late Neolithic individuals interred in caves and in megalithic graves of a restricted region of northern Iberia. The results show significant differences in infant- and child-rearing practices, in subsistence strategies, and in landscape use between burial locations. From this, we posit that the presence of communities with distinct lifestyles and cultural backgrounds is a primary reason for Late Neolithic variability in burial location in Western Europe and provides evidence of an early “them and us” scenario. We argue that this differentiation could have played a role in the building of lasting structures of socioeconomic inequality and, occasionally, violent conflict.

International audience; A recent paper by Miszczak et al. (2020) examines metal contamination of mires in Poland and Norway. The authors conclude that lead (Pb) records in ombrotrophic peatlands cannot be used to reconstruct the chronological history of anthropogenic activities due to post-depositional mobility of the metal. We contest this general conclusion which stands in contrast with a significant body of literature demonstrating that Pb is largely immobile in the vast majority of ombrotrophic peatlands. Our aim is to reaffirm the crucial contribution that peat records have Science of the Total Environment xxx (xxxx) xxx ⁎ Corresponding author at: Instituto Franco-Argentino para el Estudio del Clima y sus Impactos (j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / s c i t o t e n v made to our knowledge of atmospheric Pb contamination. In addition, we reiterate the necessity of following established protocols to produce reliable records of anthropogenic Pb contamination in environmental archives.

Nickel stable isotope ratios have attracted a growing interest across the (bio)geochemical and environmental sciences since the late 2000s. Accuracy and precision of Multi-Collector Inductively Coupled-Plasma Mass Spectrometry (MC-ICP-MS) measurements depend crucially on efficient chemical purification of the target analyte to avoid spectral and non-spectral interferences and artificial on-column fractionation. In the case of Ni, this has been previously achieved by cumbersome chemical isolation protocols involving non-aqueous media, Ni-specific resin or complexing agent and up to five successive chromatographic columns. Since the advent of MC-ICP-MS, sample throughput in isotopic analysis has increased significantly, but the Ni isolation procedures do not allow for large numbers of samples to be processed. Advances in Ni isotope geochemistry have thus been relatively slow compared to those of other transition elements (e.g. Cu, Zn, Fe). Here, we present an innovative and straightforward two-step procedure for quantitative isolation of Ni from igneous silicate matrix prior to MC-ICP-MS analysis to help bridge that gap. Nickel is purified taking advantage of the selective adsorption of chemical elements from hydrochloric and acetic acids onto the widespread AG1-X8 (200-400 mesh) anion exchange resin, without using Ni-specific compounds nor pH-tuning. A single pass through the two successive columns results in a quantitative recovery (≥96%) of Ni as a pure Ni fraction, reducing preparation costs and time, eluent volumes and total procedural blank contribution (, SCOPUS: ar.j, info:eu-repo/semantics/published

During the time period December 2019 – January 2020, a lot of biomass burning has been ongoing in the Southern Hemisphere. This led to a large amount of fine dust being emitted and transported into the atmosphere of the Southern Hemisphere. With the dispersion model FLEXPART, we will simulate these fires, using the CAMS Global Fire Assimilation System (GFAS) which assimilates fire radiative power (FRP) observations from satellite-based sensors in order to reproduce daily estimates of biomass burning emissions. Also information on the injection height is available.Aerosol fluxes and sources in Antarctica and its closely associated Southern Ocean are poorly constrained, in particular the particle chemistry. A detailed understanding of present-day atmospheric transport pathways of particles and of volatile organic compounds (VOC) from source to deposition in Antarctica remains essential to document biogeochemical cycles and the relative importance of natural and anthropogenic compounds. Within the CHASE project (chase.meteo.be), the Royal Meteorological Institute of Belgium, Ghent University and the Université Libre de Bruxelles are doing research at the Belgian research station Princess Elisabeth (71.9°S, 23.3°E; East Antarctica, Dronning Maud Land) on the physical-chemical composition of both atmospheric particles, particles in surface snow particles as well as of VOCs. Since 2018, samples are taken both near the Belgian research station Princess Elisabeth (active sampling with pumps) and on a transect to the coast (passive samplers and surface snow samples). In this contribution we will thoroughly investigate the atmospheric transport pathways of the recent biomass burning plumes, and in particular to what extent parts of these plumes have reached Antarctica. The measured chemical signatures of atmospheric particles and VOCs will help to constrain the simulations of the dispersion model.

Atmospheric metal pollution is a major health concern whose roots pre-date industrialization. This study pertains the analyses of ancient human skeletons and compares them with natural archives to trace historical environmental exposure at the edge of the Roman Empire in NW Iberia. The novelty of our approach relies on the combination of mercury, lead and lead isotopes. We found over a 700-year period that rural Romans incorporated two times more mercury and lead into their bones than post-Romans inhabiting the same site, independent of sex or age. Atmospheric pollution sources contributed on average 57% (peaking at 85%) of the total lead incorporated into the bones in Roman times, which decreased to 24% after the decline of Rome. These values and accompanying changes in lead isotopic composition mirror changes in atmospheric Pb deposition recorded in local peatlands. Thus, skeletons are a time-transgressive archive reflecting contaminant exposure., SCOPUS: ar.j, info:eu-repo/semantics/published

Identifying the provenance of mineral dust depositions in Antarctica is crucial to reconstruct Southern Hemisphere (SH) atmospheric circulation, validate numerical models, evaluate their contribution as micronutrients in the Southern Ocean and assess their control on the climate changes. For the last few decades, it has been demonstrated Southern South America (SSA) is the main precursor of dust reaching Antarctica during both ice ages and interglacial periods (e.g. Gili et al., 2017, 2016). However, the origin of modern dust depositions on the Antarctic continent is still poorly constrained. Back in the nineties, together with SSA, Australia, New Zealand, and Southern Africa were firstly identified as dust contributors to East Antarctica (EA) (e.g. Delmonte et al., 2004a). Since then, only SSA and Australian dust sources benefited from detailed studies. While some works identified the Makgadikgadi and Etosha Pans as southern Africa's major mineral dust sources in the SH, it was not until recently the Namib Desert coastal areas were described as another important regional dust sources. Within the Namib Desert and along the coast, the Kuiseb (K), Omaruru (O) and Huab (H) dry riverbeds are the three main areas identified as the dustiest ones with the higher frequency of dust emission events (Von Holdt et al., 2017). Here we use Sr, Nd and Pb isotopes (measured on HR-MC-ICP-MS) to characterize and evaluate the influence of this region in Southern Africa as a dust source to EA. Samples collected in K, O and H desertic areas were analyzed together with snow samples collected along a ~250 km N-S transect (defined from the coast to inland) at seven different sampling sites in the surroundings of Dronning Maud Land, EA. In addition, using the bulk of the Huab region, dust aerosols were generated into an atmospheric simulation chamber (CESAM) to reproduce, mechanically the saltation and sandblasting processes responsible for the release of mineral dust in natural conditions. Our isotopic results show Namibia’s coast emerged as another possible source end-member, together with some regions in SSA, that supply dust to EA during warmer periods.References:Delmonte, B., Basile-Doelsch, I., Petit, J.R., Maggi, V., Revel-Rolland, M., Michard, A., Jagoutz, E., Grousset, F., 2004. Comparing the EPICA and Vostok dust records during the last 220,000 years: stratigraphical correlation and provenance in glacial periods. Earth-Sci. Rev. 66, 63–87.Gili, S., Gaiero, D.M., Goldstein, S.L., Chemale, F. Jr., Koester, E., Jweda, J., Vallelonga, P., Kaplan, M.R., 2016. Provenance of dust to Antarctica: a lead isotopic perspective. Geophys. Res. Lett. 43. http://dx.doi.org/10.1002/2016GL068244.Gili, S., D.M. Gaiero, S.L. Goldstein, F. Chemale, J. Jweda, M.R. Kaplan, R.A. Becchio, and E. Koester (2017). Glacial/interglacial changes of Southern Hemisphere wind circulation from the geochemistry of South American dust. Earth Planet. Sci. Lett., 469, 98-109, doi: 10.1016/j.epsl.2017.04.007.Von Holdt, JR., Eckardt FD., and Wiggs GFS., 2017. Landsat identifies aeolian dust emission dynamics at the landform scale. Remote Sensing of Environment 198., 229–243.

The southern westerly winds (SWW) play a major role in climate variability in Southern Hemisphere mid- and high-latitudes, regulating rainfall, ocean circulation, and the Southern Ocean carbon sink. Despite their importance, little is known about millennial scale changes in the SWW and how they have influenced the climate system in the past and interacted with the Earth's surface elements, such as dust, nutrients and carbon. Here we present a dust record from a 6.6 kyr old peat core in Amsterdam Island (AMS) situated at the northern edge of the SWW (37°S) in the Southern Indian Ocean. Mineral dust flux was used to track atmospheric dust production, long-distance transport and subsequent deposition. Dust provenance was determined from rare earth element (REE) and Nd isotopic signatures (εNd) in the peat core, compared with a reference dataset of Southern Hemisphere dust sources. Using a multi-proxy mixing model, the εNd and REE ratios show a relatively uniform mixture of ca. 40% local, 15% Southern African and 45% Southern South American dust sources since 6.6 cal kyr BP. However, from 1910 AD onwards, there is a doubling in the contribution from Southern Africa (32%). Two mineral dust flux minima occur at 6.2–4.9 cal kyr BP and 3.9–2.7 cal kyr BP, interpreted as periods with equatorward-shifted and/or strengthened SWW at the northern edge of the wind belt. Conversely, periods of higher dust flux at 6.6–6.2 cal kyr BP, 4.9–3.9 cal kyr BP, and 1.4 cal kyr BP onwards are interpreted as poleward-shifted and/or weakened SWW. These interpretations are based on the findings that higher (lower) wind speeds lead to enhanced (less) removal of distal dust on the way to AMS, by wet deposition and turbulence. Published Holocene SWW records at the northern edge of the wind belt (33–41°S) covering South-America, Southern-Africa and Australia, show much variability over the last 6.6 kyr. We suggest this reflects complex regional climate variability in the different SH longitudinal sectors, indicating that SWW are not zonally homogeneous at the northern edge of the wind belt. The recent shift in dust provenance is not accompanied by enhanced total dust deposition at AMS. We therefore suggest that human impact (e.g. land use changes) and drier climate conditions in Southern Africa have led to enhanced dust mobilization., SCOPUS: ar.j, info:eu-repo/semantics/published

Cremated human remains from Stonehenge provide direct evidence on the life of those few select individuals buried at this iconic Neolithic monument. The practice of cremation has, however, precluded the application of strontium isotope analysis of tooth enamel as the standard chemical approach to study their origin. New developments in strontium isotopic analysis of cremated bone reveal that at least 10 of the 25 cremated individuals analysed did not spend their lives on the Wessex chalk on which the monument is found. Combined with the archaeological evidence, we suggest that their most plausible origin lies in west Wales, the source of the bluestones erected in the early stage of the monument’s construction. These results emphasise the importance of inter-regional connections involving the movement of both materials and people in the construction and use of Stonehenge., SCOPUS: ar.j, info:eu-repo/semantics/published

Wet atmospheric deposition can account for up to 50% of the total iron input to surface waters, so establishing the extent to which kinetic and equilibrium isotope effects can influence aerosol soluble δ56Fe values is imperative to trace and constrain aerosol sources using Fe isotopes and to understand the differences found between δ56Fe values for bulk and soluble phases of aerosols. In this context, changes in iron solubility and isotopic composition of dissolved Fe during simulated atmospheric processing of industrial ash was investigated. Kinetic and equilibrium experiments were performed under UV/VIS light using ash from a Fe–Mn alloy metallurgical plant and a synthetic solution that mimics cloud water chemistry. The nature of the Fe species of the industrial ash was investigated by Mossbauer Spectroscopy, whereas ash and dissolved δ56Fe values were measured by MC-ICP-MS. Mossbauer Spectroscopy revealed that α-hematite, magnetite, and poorly crystallized manganoferrite nanoparticles are the main Fe species. In the early-stage dissolution (until 60 min) a Fe isotope fractionation (Δ56Fesolution-bulk ash) of −0.284 ± 0.103‰ was found at the minimum contact time evaluated herein (i.e., 5 min) due to kinetic isotopic effects. In the late-stage dissolution (after 60 min) a Δ56Fesolution-ash of 0.227 ± 0.091‰ was found due to equilibrium isotopic effects. The kinetic isotope effect within one ash surface monolayer was modeled with an enrichment factor (e) of −1‰ in 56Fe/54Fe ratio. Iron fractional dissolution undergone during different atmospheric processing time scales may release Fe with contrasted isotope compositions to solution, changing the original soluble Fe isotope signature (which is linked to its source). This might be especially important when the dissolution process goes from kinetic to near-equilibrium conditions, in which higher amounts of Fe are progressively released from ash surface.

International audience; Zinc is an essential micronutrient that is ultimately released during mineral weathering. In soils, organic matter plays a key role in influencing Zn partitioning and therefore on Zn biogeochemical cycling. Soil organic matter is partitioned between carbon that is more readily available for decomposition by microorganisms, and more stable carbon transiently preserved from decomposition. The role of the stable pool of soil organic matter on Zn biogeochemical cycling remains poorly understood. The pool of stable carbon is controlled by combination with mineral constituents or is material that is intrinsically resistant to decomposition. The Zn stable isotopes are fractionated by interactions between Zn and soil mineral and organic constituents. This study reports the Zn isotope composition of five Icelandic soil profiles derived from the same parent basalt and characterized by contrasting degrees of weathering and organic matter content (δ66Zn = + 0.10 ± 0.05 to + 0.35 ± 0.02‰), the distribution of reactive mineral constituents available to form associations with soil organic matter, and the amount of stable organic carbon. Throughout these soils, the δ66Zn isotope variations are little influenced by mineral constituents, but rather by soil organic matter content. These data suggest that a combination of organic matter accumulation and Zn loss by leaching is required to explain the observed decrease in Zn concentration in soils and lighter soil δ66Zn with increasing organic carbon content. These results suggest that the presence of stable organic carbon in soils provides a pool of light Zn, attributed to the Zn isotope signature of organic matter partially preserved from decomposition. Crucially, this stable organic carbon pool may also contribute to the formation of the light Zn isotope sink reported in organic-rich marine sediments, a key output required to explain the oceanic mass balance of Zn isotopes.

International audience; We present a petrological, geochronological and geochemical study of Neoproterozoic ophiolitic units exposed in the Pan-African orogenic belt (Moroccan Anti-Atlas). These units comprise two main complexes: (i) the Khzama ophiolite (in the Sirwa window) to the west and (ii) the Aït Ahmane ophiolite to the east (in the Bou Azzer inlier). Both complexes mainly consist in serpentinized ultramafics associated with rare chromite pods and pyroxenites, which are in tectonic contact with mafic units made of isotropic and layered metagabbros and metabasalts dykes. Khzama ophiolite has been dated at 762 Ma (U-Pb zircon dating on plagiogranite dykes) and we dated Aït Ahmane ophiolite at 745.9 ± 7.4 Ma (U-Pb zircon dating on a layered metagabbro). The precursors of Aït Ahmane and Khzama serpentinites are spinel harzburgites associated with minor dunitic lenses, both entirely serpentinized. Bulk rock composition shows low contents in incompatible major and trace elements (Al2O3: 0.2-1.3 wt.% and Ti: 3-38 ppm) and in HREE ([Yb]N

Determining the extent of mantle mixing during the Hadean-Archean is an integral factor in our understanding of early geodynamic processes as well as the speed and degree of mantle homogenisation. If a dynamic convecting mantle was the predominant regime it would be expected that early formed isotopic anomalies would be quickly homogenised, whilst in a stagnant lid regime these anomalies might last for hundreds of millions of years. Archean terranes are dominated by felsic tonalite, trondhjemite and granodiorite rocks, as such these rocks have been the main rock type studied, even though they are not formed by primary mantle melts. Therefore, in this study, we have focused on mafic rock samples as tracers of primary mantle melting, from the relatively unknown West African craton. The mafic rocks have undergone metamorphism to granulite facies with the majority of samples retrogressed to amphibolite facies. Major element compositions reveal that the protolith was tholeiitic basalt. The majority of trace elements display limited mobility, as primary correlations with Zr are still present. Trace element patterns are typical for Archean mafic rocks, with Nb-Ta and Ti depletions. The meta-basalts yield a 147 Sm- 143 Nd errorchron with an age of 3300 ± 300 Ma, with initial εNd of +4.4. The Nd compositions indicate that the meta-basalts have experienced minimal crustal assimilation and retain primary geochemical attributes. A positive initial εNd for the meta-basalts suggests that the magmatic protolith evolved from an already differentiated source. Nevertheless, 142 Nd compositions are within error of modern day terrestrial, as such, the protolith for these samples either did not experience any early differentiation, or that mantle convection had homogenised any anomalous signal. These results highlight the lack of large (>±8 µ 142 Nd) 142 Nd anomalies detected from outside the North Atlantic and Superior Cratons, suggesting that Archean mantle dynamics was complex, with different processes occurring on different parts of Earth, similar to today., SCOPUS: ar.j, info:eu-repo/semantics/published

International audience

Ultramafic hosted hydrothermal deposits are ubiquitous along slow-spreading ridges such as the Mid-Atlantic Ridge (MAR; e.g. Ashadzé Rainbow, Lost City) where they exert a major control on the cycling of economically important elements (e.g. Zn, Cu, Ni). However, the origin of metal mobility in these environments remains unclear. Here we use Zn (δ66Zn), Cu (δ65Cu) and Fe (δ56Fe) stable isotopes to explore the mobility of metals during (1) the serpentinization of the Rainbow massif basement in a seawater dominated system at low temperature (350 °C) mineralization of serpentinites through seawater-derived fluids that interacted with gabbro prior to interacting with serpentinite near hydrothermal sites (stockworks). The Rainbow samples display among the largest range of isotopic variations ever reported for ultramafic rocks (−0.10‰ ≤ δ66Zn ≤ +0.47‰; −0.93‰ ≤ δ65Cu ≤ +0.24‰; −0.15‰ ≤ δ56Fe ≤ +0.25‰). These variations reflect a two-stage process. (1) Serpentinization of the ultramafic basement is accompanied by a decrease in Zn (26–41 ppm) and Cu (1–13 ppm) concentrations and an increase of δ66Zn (+0.30–+0.47‰) in peridotites relative to primitive mantle (Zn ∼ 55 ppm, Cu ∼ 20 ppm, δ66Zn ∼ +0.16‰). Striking correlations between δ66Zn and indices of serpentinization (LOI and Fe/3+ΣFe) show preferential leaching of isotopically light Zn by fluids during the serpentinization of the massif. This isotopic fractionation is controlled by the dissolution of both mantle sulfides and/or spinels and Zn complexation with chlorine in fluids. At this stage, Fe seems to be immobile as attested by correlations between δ56Fe and indices of peridotite fertility (e.g. Al2O3/SiO2). (2) The mineralization of serpentinites near the Rainbow stockwork is accompanied by an increase in Fe/3+ΣFe (>0.7), FeO (up to 19.8 wt%), Zn (≫50 ppm) and Cu (≫20 ppm) concentrations. The δ66Zn and δ65Cu values progressively decrease with indices of serpentinite mineralization (e.g. Zn, Cu, Fe/3+ΣFe), while several samples display abnormally high δ56Fe (up to 0.25‰) relative to primitive mantle (δ56Fe ∼ 0.025‰), suggesting a high mobility of Zn, Cu and Fe in high temperature hydrothermal fluids. These isotopic fractionations can be explained by the local oxidation of sulfur bearing fluids in contact with seawater. This process enhances metal precipitation as well as the formation of Fe3+-bearing phases, such as magnetite, beneath the stockwork, explaining the presence of magnetic anomalies below the Rainbow hydrothermal field. Our study shows that the mobility of metals in hydrothermal fluids can be enhanced by both peridotite interaction with seawater or with fluid that interacted with deeper mafic bodies and then flowed to the surface. These processes may generate hydrothermal deposits with distinct metal signatures., SCOPUS: ar.j, info:eu-repo/semantics/published