Assessing sulfur redox state and distribution in abyssal serpentinites using XANES spectroscopy

Sulfur is one of the main redox sensitive and volatile elements involved in chemical transfers between earth surface and the deep mantle. At mid-oceanic ridges, sulfur cycle is highly influenced by serpentinite formation which acts as a sink of sulfur under various oxidation states (S 2 − , S − , S 0 and S 6 + ). Sulfur sequestration in serpentinites is usually attributed to the crystallization of secondary minerals, such as sulfides (e.g. pyrite, pyrrhotite) or sulfates (e.g. anhydrite). However, the role of serpentine minerals as potential sulfur carriers is not constrained. We investigate the distribution and redox state of sulfur at micro-scale combining in situ spectroscopic (X-ray absorption near-edge structure: XANES) and geochemical (SIMS) measurements in abyssal serpentinites from the SWIR (South West Indian Ridge), the Rainbow and the MARK (Mid-Atlantic Ridge, Kane Fracture Zone) areas. These serpentinites are formed in different tectono-metamorphic settings and provide a meaningful database to understand the fate of sulfur during seafloor serpentinization. XANES spectra of serpentinite powders show that the sulfur budget of the studied samples is dominated by oxidized sulfur (S 6 + / S = 0.6–1) although sulfate micro- phases, such as barite and anhydrite, are absent. Indeed, μ -XANES analyses of mesh, bastite and antigorite veins in thin sections and of serpentine grains rather suggest the presence of S 6 + ions incorporated into serpentine minerals. The structural incorporation of S in serpentine minerals is also supported by X- ray fluorescence mapping revealing large areas (1600 μm 2 ) of serpentinite where S is homogeneously distributed. Our observations show that serpentine minerals can incorporate high S concentrations, from 140 to 1350 ppm, and that this can account for 60 to 100% of the sulfur budget of abyssal serpentinites. Serpentine minerals thus play an important role in S exchanges between the hydrosphere and the mantle at mid-oceanic ridges and may participate to S recycling in subduction zones.NERC Deep Volatiles Consortium Grant NE/M000303/

Zinc isotope evidence for sulfate-rich fluid transfer across subduction zones

Subduction zones modulate the chemical evolution of the Earth?s mantle. Water and volatile elements in the slab are released as fluids into the mantle wedge and this process is widely considered to result in the oxidation of the sub-arc mantle. However, the chemical composition and speciation of these fluids, which is critical for the mobility of economically important elements, remain poorly constrained. Sulfur has the potential to act both as oxidizing agent and transport medium. Here we use zinc stable isotopes ( \ensuremathδ 66 Zn) in subducted Alpine serpentinites to decipher the chemical properties of slab- derived fluids. We show that the progressive decrease in \ensuremathδ 66Zn with metamorphic grade is correlated with a decrease in sulfur content. As existing theoretical work predicts that Zn-SO42- complexes preferentially incorporate heavy \ensuremathδ 66Zn, our results provide strong evidence for the release of oxidized, sulfate-rich, slab serpentinite-derived fluids to the mantle wedge.This work was supported by an ERC Starting Grant (HabitablePlanet; 306655) and a NERC Deep Volatiles Consortium Grant (NE/M0003/1) awarded to H.W. H.W. and P.B. also acknowledge salary support from a NERC Advanced Fellowship (NE/F014295/2) and ERC Starting Grant (279828, MASE), respectivel

The behavior of iron and zinc stable isotopes accompanying the subduction of mafic oceanic crust: A case study from Western Alpine ophiolites

Arc lavas display elevated Fe3+/ΣFe ratios relative to MORB. One mechanism to explain this is the mobilization and transfer of oxidized or oxidizing components from the subducting slab to the mantle wedge. Here we use iron and zinc isotopes, which are fractionated upon complexation by sulfide, chloride, and carbonate ligands, to remark on the chemistry and oxidation state of fluids released during prograde metamorphism of subducted oceanic crust. We present data for metagabbros and metabasalts from the Chenaillet massif, Queyras complex, and the Zermatt-Saas ophiolite (Western European Alps), which have been metamorphosed at typical subduction zone P-T conditions and preserve their prograde metamorphic history. There is no systematic, detectable fractionation of either Fe or Zn isotopes across metamorphic facies, rather the isotope composition of the eclogites overlaps with published data for MORB. The lack of resolvable Fe isotope fractionation with increasing prograde metamorphism likely reflects the mass balance of the system, and in this scenario Fe mobility is not traceable with Fe isotopes. Given that Zn isotopes are fractionated by S-bearing and C-bearing fluids, this suggests that relatively small amounts of Zn are mobilized from the mafic lithologies in within these types of dehydration fluids. Conversely, metagabbros from the Queyras that are in proximity to metasediments display a significant Fe isotope fractionation. The covariation of δ56Fe of these samples with selected fluid mobile elements suggests the infiltration of sediment derived fluids with an isotopically light signature during subduction

Iron and zinc stable isotope evidence for open-system high-pressure dehydration of antigorite serpentinite in subduction zones

Subducted serpentinites have the potential to control the exchange of volatile and redox sensitive elements (e.g., Fe, S, C, N) between the slab, the mantle wedge and the deep mantle. Here we examine the mobility of iron and zinc in serpentinite-derived fluids by using their stable isotopes (δ56Fe and δ66Zn) in high-pressure subducted meta-serpentinites from the Cerro del Almirez massif (Spain). This massif preserves a metamorphic front between antigorite (Atg-serpentinite) and antigorite-olivine-orthopyroxene (transitional lithologies) -bearing serpentinites, and chlorite-bearing harzburgite (Chl-harzburgite), displaying granofels, spinifex and fine-grained recrystallized textures. Those rocks were formed at eclogite facies conditions (1.6�1.9 GPa and 680�710 °C). The mean δ56Fe of all the Cerro del Almirez meta- serpentinites (+0.05 ± 0.01 �) is identical within an error to that of primitive mantle (+0.03 ± 0.03 �). A positive correlation between δ56Fe and indices of peridotite protolith fertility (e.g., Al2O3/SiO2) suggests that the δ56Fe values of Cerro del Almirez samples predominantly reflect protolith compositional variations, likely produced by prior episodes of melt extraction. In contrast, the Zn concentrations (Zn = 34�67 ppm) and isotope signatures (δ66Zn = +0.18 � +0.55 �) of the Cerro del Almirez samples show a broad range of values, distinct to those of the primitive mantle (Zn = 54 ppm; δ66Zn = +0.16 ± 0.06 �). The Atg- serpentinites (Zn = 34�46 ppm; δ66Zn = +0.23 ± 0.06 �) display similar Zn and δ66Zn values to those of slab serpentinites from other high-pressure meta-ophiolites. Both Zn and δ66Zn increase in transitional lithologies (Zn = 45�67 ppm; δ66Zn = +0.30 ± 0.06 �) and Chl-harzburgites with granofels (Zn = 38� 59 ppm; δ66Zn = +0.33 ± 0.04 �) or spinifex (Zn = 48�66 ppm; δ66Zn = +0.43 ± 0.09 �) textures. Importantly, Cerro del Almirez transitional lithologies and Chl-harzburgites display abnormally high Zn relative to abyssal peridotites and serpentinites (29�45 ppm) and a positive correlation exists between Zn and δ66Zn. This correlation is interpreted to reflect the mobilization of Zn by subduction zone fluids at high pressures and temperatures coupled with significant Zn stable isotope fractionation. An increase in Zn and δ66Zn from Atg-serpentinite to Chl-harzburgite is associated with an increase in U/Yb, Sr/Y, Ba/Ce and Rb/Ce, suggesting that both Zn and δ66Zn record the interaction of the transitional lithologies and the Chl- harzburgites with fluids that had equilibrated with metasedimentary rocks. Quantitative models show that metasediment derived fluids can have isotopically heavy Zn as a consequence of sediment carbonate dissolution and subsequent Zn complexation with carbonate species in the released fluids (e.g., ZnHCO3(H2O)5+ or ZnCO3(H2O)3). Our models further demonstrate that Zn complexation with reduced carbon species cannot produce fluids with heavy δ66Zn signature and hence explain the δ66Zn variations observed in the Chl-harzburgites. The most straightforward explanation for the heavy δ66Zn of the Cerro del Almirez samples is thus serpentinite dehydration accompanied by the open system infiltration of the massif by oxidized, carbonate-rich sediment-derived fluids released during prograde subduction-related metamorphism

Mariana Serpentinite Mud Volcanism Exhumes Subducted Seamount Materials: Implications for the Origin of Life.

The subduction of seamounts and ridge features at convergent plate boundaries plays an important role in the deformation of the overriding plate and influences geochemical cycling and associated biological processes. Active serpentinization of forearc mantle and serpentinite mud volcanism on the Mariana forearc (between the trench and active volcanic arc) provides windows on subduction processes.  Here, we present (1) the first observation of an extensive exposure of an undeformed Cretaceous seamount currently being subducted at the Mariana Trench inner slope; (2) vertical deformation of the forearc region related to subduction of Pacific Plate seamounts and thickened crust; (3) recovered Ocean Drilling Program and International Ocean Discovery Program cores of serpentinite mudflows that confirm exhumation of various Pacific Plate lithologies, including subducted reef limestone; (4) petrologic, geochemical and paleontological data from the cores that show that Pacific Plate seamount exhumation covers greater spatial and temporal extents; (5) the inference that microbial communities associated with serpentinite mud volcanism may also be exhumed from the subducted plate seafloor and/or seamounts; and (6) the implications for effects of these processes with regard to evolution of life. This article is part of a discussion meeting issue ‘Serpentine in the Earth system’

Correspondências entre Joachim Le Breton e a corte portuguesa na Europa: o nascimento da Missão Artística de 1816

A series of documents kept at the National Archive of Tombo Tower in Lisbon offers us important tools to understand the origin of the 1 81 6 Artistic Mission. Although some Brazilian historians have already explored this field extensively - including Afonso d'Escragnolle Taunay, Mário Barata and Mário Pedrosa in their invaluable publications, not to mention Jean-Baptiste Debret in his writings - it is important to shed new light on this subject so that we may understand how the project of art and industrial education was conceived in Europe byJoachim Le Breton. How did the Mission's project come about? This paper proposes to review certain letters kept at the Tombo Tower and exchanged between Portuguese diplomats and Le Breton in 1815, while the latter was still in Paris, for the ultimate purpose of retracing the first steps of this story.Uma série de documentos conservados no Arquivo Nacional da Torre do Tombo, em Lisboa, oferece-nos ainda instrumentos significativos para a compreensão da origem da Missão Artística de 1816. Embora alguns historiadores brasileiros tenham já explorado intensamente este campo, dentre os quais as preciosas publicações de Afonso d'Escragnolle Taunay, Mário Barata e Mário Pedrosa - destacando-se também os escritos deJean-Baptiste Debret -, convém buscar novas luzes para entender a concepção do projeto de ensino artístico e industrial, ainda na Europa, pelas mãos de Joachim Le Breton. Como surgiu o projeto da Missão? Este artigo tem como objetivo a análise de algumas correspondências conservadas na Torre do Tombo, trocadas entre Le Breton e os diplomatas portugueses em 1815, ainda em Paris, visando à recuperação dos primeiros passos desta história

Mariana serpentinite mud volcanism exhumes subducted seamount materials: implications for the origin of life

The subduction of seamounts and ridge features at convergent plate boundaries plays an important role in the deformation of the overriding plate and influences geochemical cycling and associated biological processes. Active serpentinization of forearc mantle and serpentinite mud volcanism on the Mariana forearc (between the trench and active volcanic arc) provides windows on subduction processes. Here, we present (1) the first observation of an extensive exposure of an undeformed Cretaceous seamount currently being subducted at the Mariana Trench inner slope; (2) vertical deformation of the forearc region related to subduction of Pacific Plate seamounts and thickened crust; (3) recovered Ocean Drilling Program and International Ocean Discovery Program cores of serpentinite mudflows that confirm exhumation of various Pacific Plate lithologies, including subducted reef limestone; (4) petrologic, geochemical and paleontological data from the cores that show that Pacific Plate seamount exhumation covers greater spatial and temporal extents; (5) the inference that microbial communities associated with serpentinite mud volcanism may also be exhumed from the subducted plate seafloor and/or seamounts; and (6) the implications for effects of these processes with regard to evolution of life.Copyright 2020 The Authors. Published by the Royal Society under the terms of the Creative Commons Attribution License http://creativecommons.org/licenses/ by/4.0/, which permits unrestricted use, provided the original author and source are credited