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, lizarditeserpentinites, 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...

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, δ 66 Zn 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; δ 66 Zn = +0.24 ± 0.01 to +0.31 ± 0.02‰) to OIB (Zn = 74 ± 9 to 124 ± 7 ppm; δ 66 Zn = +0.21 ± 0.07 to +0.40 ± 0.04‰). Unlike MORB, the high Zn and δ 66 Zn 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 δ 66 Zn of OIB relative to MORB and mantle peridotites, reflecting the contribution of isotopically heavy C-bearing phases (δ 66 Zn = +0.91 ± 0.24‰) to the mantle source (δ 66 Zn = +0.16 ± 0.06‰). Our study thus emphasizes the use of Zn and δ 66 Zn 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.

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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 (δ 56 Fe), 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 δ 56 Fe variation. Unexpected negative correlations between serpentinite bulk δ 56 Fe, fluid-mobile element concentrations (e.g., B, As) and Fe 3+ /ΣFe 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.

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Simple chromatographic isolation of nickel in just two steps prior to Ni stable isotope ratio analysis by MC-ICP-MS.

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