Insights into the origin of carbonaceous chondrite organics from their triple oxygen isotope composition

International audienceDust grains of organic matter were the main reservoir of C and N in the forming Solar System and are thus considered to be an essential ingredient for the emergence of life. However, the physical environment and the chemical mechanisms at the origin of these organic grains are still highly debated. In this study, we report high-precision triple oxygen isotope composition for insoluble organic matter isolated from three emblematic carbonaceous chondrites, Orgueil, Murchison, and Cold Bokkeveld. These results suggest that the O isotope composition of carbonaceous chondrite insoluble organic matter falls on a slope 1 correlation line in the triple oxygen isotope diagram. The lack of detectable mass-dependent O isotopic fractionation, indicated by the slope 1 line, suggests that the bulk of carbonaceous chondrite organics did not form on asteroi-dal parent bodies during low-temperature hydrothermal events. On the other hand, these O isotope data, together with the H and N isotope characteristics of insoluble organic matter, may indicate that parent bodies of different carbonaceous chondrite types largely accreted organics formed locally in the protosolar nebula, possibly by photochemical dissociation of C-rich precursors

Predicting instrumental mass fractionation (IMF) of stable isotope SIMS analyses by response surface methodology (RSM) [Dataset]

The dataset contains four files. File S1 corresponds to cathodoluminescence and BSE images of standard minerals. File S2 contains geochemical data of mineral standards ans samples obtained by SIMS and EPMA. File S3 contains the parameters used to obtain response surface models of IMF in mineral standards. File S4 is a response surface methodology tutorial.Instrumental mass fractionation (IMF) of isotopic SIMS analyses (Cameca 1280HR, CRPG Nancy) was predicted by response surface methodology (RSM) for 18O/16O determinations of plagioclase, K-feldspar and quartz. The three predictive response surface models combined instrumental and compositional inputs. The instrumental parameters were: (i) X and Y position, (ii) LT1DefX and LT1DefY electrostatic deflectors, (iii) chamber pressure and, (iv) primary-ion beam intensity. The compositional inputs included: (i) anorthite content (An%) for the plagioclase model and, (ii) orthoclase (Or%) and barium (BaO%) contents for the K-feldspar model. The three models reached high predictive powers. The coefficients R2 and prediction-R2 were, respectively, 90.47% and 86.74% for plagioclase, 87.56% and 83.17% for K-feldspar and 94.29% and 91.59% for quartz. The results show that RSM can be confidently applied to IMF prediction in stable isotope SIMS analyses by the use of instrumental and compositional variables.

Origin of volatiles emitted by Plinian mafic eruptions of the Chikurachki volcano, Kurile arc, Russia : trace element, boron and sulphur isotope constraints

Author Posting. © The Author(s), 2017. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Chemical Geology 478 (2018): 131-147, doi:10.1016/j.chemgeo.2017.10.009.Chikurachki is a 1816-m high stratovolcano on Paramushir Island, Kurile arc, Russia, which has repeatedly produced highly explosive eruptions of mafic composition. The present work is aimed at constraining the origin of volatile components (CO2, H2O, F, S, and Cl), along with B and S isotopic compositions in a series of phenocryst-hosted melt inclusions and groundmass glasses from basaltic andesite pyroclasts of the 1853, 1986, and prehistoric Plinian eruptions of the volcano. The ranges of volatile concentrations in melt inclusions (47–1580 μg/g CO2, 0.4–4.2 wt% H2O, 399–633 μg/g F, 619–3402 μg/g S and 805–1240 μg/g Cl) imply a sudden pressure release from ~ 460 through ~ 35 MPa that corresponds to ~ 1.2–16-km-depth range of magma ascent upon decompression. We conclude that rapid ascent of the volatile-rich basaltic magmas from ~ 16-km initial depth accompanied by near-surface bubble nucleation and growth, and subsequent magma fragmentation appear to be a primary reason for the Plinian character of the Chikurachki eruptions. Significant negative correlations of S with K, Zr, Nb, Ba, La, Ce, Pr (R = − 0.8 to − 0.9), no clear relationships of S with H2O, CO2 and Cl, but strong positive correlations of S/K2O with H2O/K2O, Cl/K2O and F/K2O preclude magma degassing to be the only process affecting volatile concentrations dissolved in the melt. The δ34S values of the studied inclusion and groundmass glasses range from − 1.6 to + 12.3‰, decrease with decreasing S, show significant positive correlations with H2O/K2O, Cl/K2O and F/Zr, and negative correlations with a number of incompatible trace elements. Neither open- nor close-system magma degassing can account for the observed range of δ34S. The δ11B values of the melt inclusions range from − 7.0 to + 2.4‰ with 13–23 μg/g B. The relationships of δ11B with B/K2O and B/Nb are inconsistent with magma contamination at shallow crustal depths. Linear character of 1/S vs. δ34S relationship suggests two-component mixing. The possible mixing end-members could be the magmas having similar major and trace element compositions, but strongly contrasting volatile contents and S isotopes. Based on the behaviour of fluid-mobile vs. fluid-immobile incompatible trace elements, we conclude that the subduction component likely represents a mixture of subduction sediment-derived melt with up to 60% of slab-derived fluid. Admixture of ~ 1–8% of the inferred subduction component to the depleted mantle wedge source is required to account for the compositional range of the Chikurachki melt inclusions, and ~ 0.4–10% to constrain the composition of Kurile arc mafic magmas.This work was benefited from the NENIMF financial support of AAG during his training as a SIMS research specialist, the NSF grant EAR 0911093 to AAG, and partially from the Russian Science Foundation grant #16-17-10145 to VSK and MEZ

Quantification of the CO2 budget and H2O–CO2 systematics in subduction-zone magmas through the experimental hydration of melt inclusions in olivine at high H2O pressure

Highlights • Melt inclusions from Klyuchevskoy were homogenized at 1150 °C and PH2O=500 MPaPH2O=500 MPa. • High-P experiments can recover initial H2O and CO2 contents in dehydrated inclusions. • Isothermal (de)hydration results in linear trend of CO2 and H2O in inclusion glasses. • Parental Klyuchevskoy magmas contain ∼3800 ppm CO2 and 4–5 wt.% H2O. • At least 80% of CO2 is slab-derived in the Klyuchevskoy magmas with CO2/Nb ∼3000. Abstract Reliable evaluation of CO2 contents in parental arc magmas, which can be preserved in melt inclusions in phenocrysts, is required to verify the proposed efficiency of CO2 recycling at convergent margins. Quantification of bulk CO2 concentration in melt inclusions requires their complete homogenization. Using samples from lavas from the Bulochka vent of Klyuchevskoy Volcano (Kamchatka), we applied a novel experimental approach to homogenize and re-equilibrate naturally dehydrated (<1 wt.% H2O) melt inclusions from high-Fo (85–91 mol.%) olivine. The experiments were performed at temperatures of 1150–1400 °C, pressures of up to 500 MPa, under dry to H2O-saturated conditions and with oxygen fugacity ranging from CCO to QFM+3.3. No homogenization was achieved at dry conditions. Complete dissolution of fluid bubbles (homogenization) in the melt inclusions was achieved at H2O pressures of 500 MPa and temperature of 1150 °C, when water content in the melt inclusions reached 4–5 wt.% H2O. The CO2 content in the homogenized inclusions is 3800±140 ppm3800±140 ppm and CO2/Nb = 3000 ± 420, which are the highest values reported so far for the typical middle-K primitive arc melts and fall within the range of values inferred from the magmatic flux and volcanic gas data for primary arc magma compositions. About 83% of the CO2 in Klyuchevskoy magmas is likely to be derived from the subducting slab and can be attributed to flux melting with a fluid having a CO2/H2O ratio of ∼0.06. The H2O and CO2 contents in the melt inclusions after hydrous experiments were found to correlate positively with each other and negatively with the volume of fluid bubble, reflecting increasing internal pressure in melt inclusions with increasing melt hydration. Therefore, similar trends observed in some natural sets of melt inclusions can be attributed to a partial dehydration of melts after entrapment, operating simultaneously with or following post-entrapment crystallization. Our study implies that the process of post-entrapment dehydration can be completely reversed under high pressure experimental conditions. If temperature, redox conditions and pressure of melt inclusion entrapment can be independently estimated, then our novel experimental approach (homogenization at high H2O pressure) can be used to reconstruct the initial CO2 content and also the entire composition of melt inclusions in olivine, including their initial H2O content, from any type of volcanic rock. With this approach volatiles in ancient lavas can also be determined, expanding our knowledge of volatile recycling further back in Earth history

Enriched, HIMU-type peridotite and depleted recycled pyroxenite in the Canary plume : a mixed-up mantle

Author Posting. © Elsevier B.V., 2009. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Earth and Planetary Science Letters 277 (2009): 514-524, doi:10.1016/j.epsl.2008.11.013.The Earth’s mantle is chemically and isotopically heterogeneous, and a component of recycled oceanic crust is generally suspected in the convecting mantle [Hofmann and White, 1982. Mantle plumes from ancient oceanic crust. Earth Planet. Sci. Lett. 57, 421-436]. Indeed, the HIMU component (high μ = 238U/204Pb), one of four isotopically distinct end-members in the Earth’s mantle, is generally attributed to relatively old (≥1-2 Ga) recycled oceanic crust in the form of eclogite/pyroxenite, e.g. [Zindler and Hart, 1986. Chemical geodynamics. Ann. Rev. Earth Planet. Sci. 14, 493-571]. Although the presence of the recycled component is generally supported by element and isotopic data, little is known about its physical state at mantle depths. Here we show that the concentrations of Ni, Mn and Ca in olivine from the Canarian shield stage lavas, which can be used to asses the physical nature of the source material (peridotite versus olivine-free pyroxenite) [Sobolev et al., 2007. The amount of recycled crust in sources of mantle-derived melts. Science 316, 412-417], correlate strongly with bulk rock Sr, Nd and Pb isotopic ratios. The most important result following from our data is that the enriched, HIMU-type (having higher 206Pb/204Pb than generally found in the other mantle endmembers) signature of the Canarian hotspot magmas was not caused by a pyroxenite/eclogite constituent of the plume but appears to have been primarily hosted by peridotite. This implies that the old (older than ~1 Ga) ocean crust, which has more evolved radiogenic isotope compositions, was stirred into/reacted with the mantle so that there is not significant eclogite left, whereas younger recycled oceanic crust with depleted MORB isotopic signature (<1 Ga) can be preserved as eclogite, which when melted can generate reaction pyroxenite.This work was supported by Wolfgang Paul Award, Alexander von Humboldt Foundation, to AVS, the Max Planck Society, DFG grants SCHM 250/64 and 82-1, HA3097/2 to HUS, KH and FH, NSF Grant EAR-9105113 to KH, Russian Basic Research Foundation and Russian Academy of Sciences

Oxygen isotopes and volatile contents of the Gorgona komatiites, Colombia: A confirmation of the deep mantle origin of H2O

We report O isotopes in olivine grains (Fo89–93) and volatile contents (CO2, H2O, F, S, Cl) in olivine-hosted melt inclusions from one Gorgona picrite and five komatiites with the aim of constraining the origin of H2O in these magmas. These samples have previously been analysed for major and trace elements and volatile concentrations (H2O, S, Cl) and B isotopes in melt inclusions. A distinctive feature of the included melts is relatively high contents of volatile components and boron, which show positive anomalies in, otherwise depleted, primitive mantle normalised trace and rare earth element patterns and range in δ11B from −11.5 to 15.6‰. In this study, the olivines were systematically analysed for O isotopes (1) in the centre of grains, (2) near the grain boundaries and, (3) as close as possible to the studied melt inclusions. The majority of olivines (∼66%) are “mantle”-like, ‰‰ 4.8‰≤δ18O≤5.5‰ , with a subordinate but still significant number (∼33%) above, and only 2 grains below, this range. There is no systematic difference between the central and marginal parts of the grains. Higher than “mantle” δ18OOl values are ascribed to low-T (<300 °C) serpentinisation along inner fractures and grain boundaries of olivine phenocrysts. The measured concentrations of volatile components in the melt inclusions corrected for the effects of post-entrapment crystallisation and H2O–CO2 exsolution in inclusion shrinkage bubbles are: 286–1748 μg/g CO2, 0.2–0.86 wt.% H2O, 48–82 μg/g F, 398–699 μg/g S and 132–198 μg/g Cl. They correspond to a pressure of 86±44MPa or ∼2.5-km crustal depth of olivine crystallisation. The correlations of S and, to a lesser extent, of H2O, with highly incompatible lithophile elements and the correlation of F with Cl, but no relationships of H2O with Cl, rule out shallow depth magma degassing and/or crustal contamination. Our new δ18O olivine and volatile component data combined with the existing, highly variable δ11B values for melt inclusions also support the deep mantle origin of H2O (and probably other volatiles) in the Gorgona mafic and ultramafic magmas

Insights into crustal assimilation by Icelandic basalts from boron isotopes in melt inclusions from the 1783–1784 Lakagígar eruption

Author Posting. © The Author(s), 2012. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 94 (2012): 164-180, doi:10.1016/j.gca.2012.07.002.The boron isotope system has great potential for tracing alteration and assimilation in basaltic systems due to the very low concentrations of B in mantle-derived melts and the strong isotopic contrast between the mantle and surface materials. However, variability in B concentrations and isotope ratios in basalts can also be interpreted to reflect inputs from enriched regions of the mantle, as the extent of mantle heterogeneity with respect to boron remains poorly delineated. We have determined boron concentrations and isotope ratios in fresh, glassy, plagioclase-hosted melt inclusions and unaltered scoriaceous matrix glasses from four localities associated with the 1783-1784 Lakagígar (Laki Fissure) eruption, Iceland. Boron concentrations range from 0.59-1.25 ppm in the melt inclusions, and from 1.25-1.65 ppm in the matrix glasses, while δ11BNBS-951 ranges from - 7.8‰ to -16.5‰ in the melt inclusions and -10.5‰ to -16.9‰ in the matrix glasses. In contrast to previous studies of boron in basaltic melt inclusions from other fissure swarms in Iceland (Gurenko and Chaussidon, 1997, Chem. Geol. 135, 21-34), the Lakagígar melt inclusions display a significant range of boron concentrations and isotope ratios at constant K2O wt.%, which is more consistent with B addition by assimilation of altered basalt than it is with mixing between depleted and enriched mantle sources. Assimilation of freshwater-altered crustal materials at depth may impart a light δ11B signature such as that observed in the Lakagígar melt inclusions and tephra host glasses. Considering boron concentrations and isotope ratios in the Lakagígar glasses and previously studied altered Icelandic basalts, together with volatile equilibration depths of the Lakagígar melt inclusions, we propose that a) mantle-derived magmas formed beneath Lakagígar assimilated ~5-20% altered crust at a depth of ~3-4 km or more, probably during magma accumulation in sills formed at the boundaries of low-density hyaloclastite layers; and b) the magma subsequently underwent extensive mixing and homogenization prior to eruption, quite possibly within the magma chamber beneath the Grímsvötn central volcano, assimilating an additional ~10% of altered crust at that time, for a total of up to 30% crustal assimilation. We hypothesize that volatiles including H2O, CO2, S, F, and Cl, which were responsible for the majority of the considerable casualties attributed to the Lakagígar eruption, were added together with isotopically light B by assimilation of hydrothermally altered crustal materials.This work was supported by a PSU-EMS Miller Award to MDF, NSF 761 EAR 09117456 to PCL, and awards to MNB by the GSA Northeast Division Grant for Undergraduate Research, the Dept. of Geosciences Undergraduate Senior Thesis Grant, and PSU Undergraduate Research Discovery Grant

Boninite-like intraplate magmas from Manihiki Plateau Require Ultra-depleted and Enriched Source Components

The Ontong Java and Manihiki oceanic plateaus are believed to have formed through high-degree melting of a mantle plume head. Boninite-like, low-Ti basement rocks at Manihiki, however, imply a more complex magma genesis compared with Ontong Java basement lavas that can be generated by ∼30% melting of a primitive mantle source. Here we show that the trace element and isotope compositions of low-Ti Manihiki rocks can best be explained by re-melting of an ultra-depleted source (possibly a common mantle component in the Ontong Java and Manihiki plume sources) re-enriched by ≤1% of an ocean-island-basalt-like melt component. Unlike boninites formed via hydrous flux melting of refractory mantle at subduction zones, these boninite-like intraplate rocks formed through adiabatic decompression melting of refractory plume material that has been metasomatized by ocean-island-basalt-like melts. Our results suggest that caution is required before assuming all Archaean boninites were formed in association with subduction processes

Oxygen isotope heterogeneity of the mantle beneath the Canary Islands : insights from olivine phenocrysts

Author Posting. © The Author(s), 2010. This is the author's version of the work. It is posted here by permission of Springer for personal use, not for redistribution. The definitive version was published in Contributions to Mineralogy and Petrology 162 (2011): 349-363, doi:10.1007/s00410-010-0600-5.A relatively narrow range of oxygen isotopic ratios (δ18O = 5.05.4‰) is preserved in olivine of mantle xenoliths, mid-ocean ridge (MORB) and most ocean island basalts (OIB). The values in excess of this range are generally attributed either to the presence of a recycled component in the Earth’s mantle or to shallow level contamination processes. A viable way forward to trace source heterogeneity is to find a link between chemical (elemental and isotopic) composition of the earlier crystallized mineral phases (olivine) and the composition of their parental magmas, then using them to reconstruct the composition of source region. The Canary hotspot is one of a few that contains ~1-2 Ga old recycled ocean crust that can be traced to the core-mantle boundary using seismic tomography and whose origin is attributed to the mixing of at least three main isotopically distinct mantle components i.e., HIMU, DMM and EM. This work reports ion microprobe and single crystal laser fluorination oxygen isotope data of 148 olivine grains also analyzed for major and minor elements in the same spot. The olivines are from 20 samples resembling the most primitive shield stage picrite through alkali basalt to basanite series erupted on Gran Canaria, Tenerife, La Gomera, La Palma and El Hierro, Canary Islands, for which shallow level contamination processes were not recognized. A broad range of δ18Oolivine values from 4.6 to 6.1‰ was obtained and explained by stable, long-term oxygen isotope heterogeneity of crystal cumulates present under different volcanoes. These cumulates are thought to have crystallized from mantle derived magmas uncontaminated at crustal depth, representing oxygen isotope heterogeneity of source region. A relationship between Ni×FeO/MgO and δ18Oolivine values found in one basanitic lava erupted on El Hierro, the westernmost island of the Canary Archipelago, was used to estimate oxygen isotope compositions of partial melts presumably originated from peridotite (HIMU-type component inherited its radiogenic isotope composition from ancient, ~12 Ga, recycled ocean crust) and pyroxenite (young, <1 Ga, recycled oceanic crust preserved as eclogite with depleted MORB-type isotopic signature) components of the Canary plume. The model calculations yield 5.2 and 5.9±0.3‰ for peridotite and pyroxenite derived melts, respectively, which appeared to correspond closely to the worldwide HIMU-type OIB and upper limit N-MORB δ18O values. This difference together with the broad range of δ18O variations found in the Canarian olivines cannot be explained by thermodynamic effects of oxygen isotopic fractionation and are believed to represent true variations in the mantle, due to oceanic crust and continental lithosphere recycling.This work was supported by the CNRS “poste rouge” grant to AG, the NSF EAR-CAREER-0844772 grant to IB and the CRPG-CNRS and at its initial stage by the DFG (grant SCHM 250/64) and the Alexander von Humboldt Foundation (Wolfgang Paul Award to A.V. Sobolev who provided access to the electron microprobe at the Max Planck Institute, Mainz, Germany)

Boron isotopic composition of olivine-hosted melt inclusions from Gorgona komatiites, Colombia : new evidence supporting wet komatiite origin

Author Posting. © The Author(s), 2011. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Earth and Planetary Science Letters 312 (2011): 201–212, doi:10.1016/j.epsl.2011.09.033.A fundamental question in the genesis of komatiites is whether 30 these rocks originate from partial melting of dry and hot mantle, 400−500°C hotter than typical sources of MORB and OIB magmas, or if they were produced by hydrous melting of the source at much lower temperatures, similar or only moderately higher than those known today. Gorgona Island, Colombia, is a unique place where Phanerozoic komatiites occur and whose origin is directly connected to the formation of the Caribbean Large Igneous Province. The genesis of Gorgona komatiites remains controversial, mostly because of the uncertain origin of volatile components which they appear to contain. These volatiles could equally result from shallow level magma contamination, melting of a “damp” mantle or fluid-induced partial melting of the source due to devolatilization of the ancient subducting plate. We have analyzed boron isotopes of olivine40 hosted melt inclusions from the Gorgona komatiites. These inclusions are characterized by relatively high contents of volatile components and boron (0.2−1.0 wt.% H2O, 0.05−0.08 wt.% S, 0.02−0.03 wt.% Cl, 0.6−2.0 μg/g B), displaying positive anomalies in the overall depleted, primitive mantle (PM) normalized trace element and REE spectra ([La/Sm]n = 0.16−0.35; [H2O/Nb]n = 8−44; [Cl/Nb]n = 27−68; [B/Nb]n = 9-30, assuming 300 μg/g H2O, 8 μg/g Cl and 0.1 μg/g B in PM; Kamenetsky et al., 2010. Composition and temperature of komatiite melts from Gorgona Island constrained from olivine-hosted melt inclusions. Geology 38, 1003–1006). The inclusions range in δ11B values from −11.5 to +15.6 ± 2.2‰ (1 SE), forming two distinct trends in a δ11B vs. B-concentration diagram. Direct assimilation of seawater, seawater-derived components, altered oceanic crust or marine sediments by ascending komatiite magma cannot readily account for the volatile contents and B isotope variations. Alternatively, injection of <3% of a 11B enriched fluid to the mantle source could be a plausible explanation for the δ11B range that also may explain the H2O, Cl and B excess.Financial support to AAG during data acquisition and manuscript preparation was provided by Northeast National Ion Microprobe Facility (Woods Hole Oceanographic Institution, USA) and the Centre de Recherches Pétrographiqueset Géochimiques (France). This research was also supported by the Australian Research Council (Research Fellowship and Discovery grants to VSK). We acknowledge partial support of the Alexander von Humboldt Foundation, Germany (F.W. Bessel Award to VSK and Wolfgang Paul Award to A.V. Sobolev who provided access to the electron microprobe at the Max Planck Institute, Mainz, Germany