Eric Hellebrand

MPI‐DING reference glasses for in situ microanalysis: New reference values for element concentrations and isotope ratios

We present new analytical data of major and trace elements for the geological MPI-DING glasses KL2-G, ML3B-G, StHs6/80-G, GOR128-G, GOR132-G, BM90/21-G, T1-G, and ATHO-G. Different analytical methods were used to obtain a large spectrum of major and trace element data, in particular, EPMA, SIMS, LA-ICPMS, and isotope dilution by TIMS and ICPMS. Altogether, more than 60 qualified geochemical laboratories worldwide contributed to the analyses, allowing us to present new reference and information values and their uncertainties (at 95% confidence level) for up to 74 elements. We complied with the recommendations for the certification of geological reference materials by the International Association of Geoanalysts (IAG). The reference values were derived from the results of 16 independent techniques, including definitive (isotope dilution) and comparative bulk (e.g., INAA, ICPMS, SSMS) and microanalytical (e.g., LA-ICPMS, SIMS, EPMA) methods. Agreement between two or more independent methods and the use of definitive methods provided traceability to the fullest extent possible. We also present new and recently published data for the isotopic compositions of H, B, Li, O, Ca, Sr, Nd, Hf, and Pb. The results were mainly obtained by high-precision bulk techniques, such as TIMS and MC-ICPMS. In addition, LA-ICPMS and SIMS isotope data of B, Li, and Pb are presented.

Coupled major and trace elements as indicators of the extent of melting in mid-ocean-ridge peridotites

Rocks in the Earths uppermost sub-oceanic mantle, known as abyssal peridotites, have lost variable but generally large amounts of basaltic melt, which subsequently forms the oceanic crust. This process preferentially removes from the peridotite some major constituents such as aluminium, as well as trace elements that are incompatible in mantle minerals (that is, prefer to enter the basaltic melt), such as the rare-earth elements. A quantitative understanding of this important differentiation process has been hampered by the lack of correlation generally observed between major- and trace-element depletions in such peridotites. Here we show that the heavy rare-earth elements in abyssal clinopyroxenes that are moderately incompatible are highly correlated with the Cr/(Cr + Al) ratios of coexisting spinels. This correlation deteriorates only for the most highly incompatible elements—probably owing to late metasomatic processes. Using electron- and ion-microprobe data from residual abyssal peridotites collected on the central Indian ridge, along with previously published data, we develop a quantitative melting indicator for mantle residues. This procedure should prove useful for relating partial melting in peridotites to geodynamic variables such as spreading rate and mantle temperature.

Ancient, highly heterogeneous mantle beneath Gakkel ridge, Arctic Ocean

The Earth’s mantle beneath ocean ridges is widely thought to be depleted by previous melt extraction, but well homogenized by convective stirring. This inference of homogeneity has been complicated by the occurrence of portions enriched in incompatible elements. Here we show that some refractory abyssal peridotites from the ultraslow-spreading Gakkel ridge (Arctic Ocean) have very depleted 187Os/188Os ratios with model ages up to 2 billion years, implying the long-term preservation of refractory domains in the asthenospheric mantle rather than their erasure by mantle convection. The refractory domains would not be sampled by mid-ocean-ridge basalts because they contribute little to the genesis of magmas. We thus suggest that the upwelling mantle beneath mid-ocean ridges is highly heterogeneous, which makes it difficult to constrain its composition by mid-ocean-ridge basalts alone. Furthermore, the existence of ancient domains in oceanic mantle suggests that using osmium model ages to constrain the evolution of continental lithosphere should be approached with caution.

Deep melting and sodic metasomatism underneath the highly oblique-spreading Lena Trough (Arctic Ocean)

Abstract Abyssal peridotites collected along the highly oblique-spreading Lena Trough north of Greenland and Spitsbergen have mineral compositions that are similar to residual abyssal peridotites, except for high sodium concentrations in clinopyroxene (cpx). Most samples are lherzolites with light rare earth element (REE)-depleted cpx trace element patterns, but significantly fractionated middle to heavy REE ratios at relatively high heavy REE concentrations. Such characteristics can only be explained by initial melting of a garnet peridotite followed by low degrees of melting in the stability field of spinel peridotite. The residual garnet signature requires either a high potential temperature of the upwelling mantle, or elevated solidus-lowering water contents. The limited spinel field melting suggests a deep cessation of melt extraction, possibly because of the presence of a thick lithospheric cap. This is consistent with the extremely low effective spreading rate and the vicinity to a passive continental margin, which allow conductive cooling to reach deeper levels than commonly estimated for faster mid-ocean ridges. High sodium concentrations in cpx are neither explainable by melt refertilization, nor by a simple diffusion mechanism. The efficient fractionation of sodium from the light REE requires post-melting metasomatism, which is typically restricted to the subcontinental lithosphere. This might imply that the Lena Trough peridotites represent unroofed subcontinental mantle, from which no melt was extracted during the opening of the Lena Trough. It is more likely that sodic metasomatism occurred after partial melting underneath the Lena Trough, and that such an enrichment process is responsible for elevated sodium concentrations in abyssal peridotites elsewhere. Sodium in cpx of residual peridotites can therefore not serve as an indicator of partial melting or melt refertilization.

Mantle melting beneath Gakkel Ridge (Arctic Ocean): abyssal peridotite spinel compositions

Abstract The ultraslow spreading Gakkel Ridge represents one of the most extreme spreading environments on the Earth. Full spreading rates there of 0.6–1.3 cm/year and Na8.0 in basalts of 3.3 imply an extremely low degree of mantle partial melting. For this reason, the complementary degree of melting registered by abyssal peridotite melting residues is highly interesting. In a single sample of serpentinized peridotite from Gakkel Ridge, we found spinels which, though locally altered, have otherwise unzoned and thus primary compositions in the cores of the grains. These reflect a somewhat higher degree of melting of the uppermost oceanic mantle than indicated by basalt compositions. Cr/(Cr+Al) ratios of these grains lie between 0.23 and 0.24, which is significantly higher than spinels from peridotites collected along the faster spreading Mid-Atlantic and Southwest Indian Ridges. Crustal thickness at Gakkel Ridge can be calculated from the peridotite spinel compositions, and is thicker than the crustal thickness of less than 4 km estimated from gravity data, or predicted from global correlations between spreading rate and seismically determined crustal thickness. The reason for this unexpected result may be local heterogeneity due to enhanced melt focussing at an ultraslow spreading ridge.

Stacked gabbro units and intervening mantle: A detailed look at a section of IODP Leg 305, Hole U1309D

Hole U1309D (Integrated Ocean Drilling Program (IODP) Legs 304/305) penetrated 1415 m into the seafloor of the Atlantis Massif, an oceanic core complex at 30°N, Mid-Atlantic Ridge. More than 96% of all recovered rocks are gabbroic. On the basis of a mineral chemical overview, we suggest that between ≤800 and 1100 m below sea floor (mbsf), a magmatic unit occurs, ranging from olivine gabbro and troctolite in the lower part to gabbronorite and oxide gabbro in the upper part. Below 1235 mbsf, massive gabbronorites/oxide gabbros were drilled and they may represent the roof of an underlying magmatic unit. The focus here is on the zone where both units interact and screens, totaling 50 m, of a microstructurally distinct, olivine-rich troctolite occur. We argue that the olivine-rich troctolite is a former mantle rock which was converted to a crust-mantle transition zone dunite at the base of the upper magmatic unit. Later, as melts derived from the lower magmatic unit percolated through it, it was equilibrated to a more evolved chemistry and transformed to a fine-grained, olivine-rich troctolite. Our main arguments against a possible cumulate nature of the olivine-rich troctolite are the lack of a systematic downhole trend in compatible elements within the olivine-rich troctolite, its distinctly fine-grained microstructure, the high Cr content of cpx, and its Ni-rich olivine composition. The high NiO for a given Mg/(Mg + Fe) in the olivine-rich troctolite can be modeled by simple equilibration of relict mantle olivine with a mildly evolved melt. Evidence for the percolation of evolved melts through the olivine-rich troctolites are Ti-rich, interstitial pyroxenes and, as inclusions in Cr-spinel, highly evolved amphiboles and orthopyroxenes plus the occurrence of millimeter-scale noritic veins. The percolation by evolved melts would also be the major difference to otherwise conceptually similar rocks from the ophiolitic crust-mantle transition zone.

Petrogenesis of crustal wehrlites in the Oman ophiolite: Experiments and natural rocks

In the Wadi Haymiliyah of the Oman ophiolite (Haylayn block), discordant wehrlite bodies ranging in size from tens to hundreds of meters intrude the lower crust at different levels. We combined investigations on natural wehrlites from the Wadi In the Wadi Haymiliyah of the Oman ophiolite (Haylayn block), discordant wehrlite bodies ranging in size from tens to hundreds of meters intrude the lower crust at different levels. We combined investigations on natural wehrlites from the Wadi Haymiliyah section with an experimental study on the phase relations in a wehrlitic system in order to constrain the petrogenesis of the crustal wehrlites of the Oman ophiolite. Secondary ion mass spectrometry analyses of clinopyroxenes from different wehrlite bodies imply that the clinopyroxenes were crystallized from tholeiitic, mid-ocean ridge (MORB)-type melts. The presence of primary magmatic amphiboles in some wehrlites suggests a formation under hydrous conditions. Significantly enhanced Sr-87/Sr-86 isotope ratios of separates from these amphiboles imply that the source of the corresponding magmatic fluids was either seawater or subduction zone-related. The experiments revealed that under wet conditions at relatively low temperatures, a MORB magma has the potential to produce wehrlite in the ocean crust by accumulation of early olivine and clinopyroxene. These show typically high Mg# which is a consequence of the oxidizing effect of the prevailing high aH(2)O. First plagioclases crystallizing after clinopyroxene under wet conditions are high in An content, in contrast to the corresponding dry system. Trace element compositions of clinopyroxenes of those wehrlites from the Moho transition zone are too depleted in HREE to be in equilibrium with present-day MORB, implying a genetic relation to the V2 lavas of the Oman ophiolite, which are interpreted to be the result of fluid-enhanced melting of previously depleted mantle. We present a model on the petrogenesis of the crustal wehrlites in an upper mantle wedge above an initial, shallow subduction zone at the beginning of the intraoceanic thrusting.

Diversity of melt conduits in the Izu-Bonin-Mariana forearc mantle: Implications for the earliest stage of arc magmatism

ABSTRACT Magmatic processes during the earliest stage of subduction initiation are still not well understood. We examined peridotites recovered from an exhumed crust-mantle section exposed along the landward slopes of the northern Izu-Bonin Trench using the Japan Agency for Marine-Earth Science and Technology9s remotely operated vehicle KAIKO7000II . Based on the Cr# [Cr/(Cr + Al) atomic ratio] of spinel, two distinctive groups, (1) high-Cr# (>0.8) dunite and (2) medium-Cr# (0.4–0.6) dunite, occur close to each other and are associated with refractory harzburgite. Two distinctive melts were in equilibrium with these dunites: a boninitic melt for the high-Cr# dunite and a mid-oceanic ridge basalt (MORB)–like melt for the medium-Cr# dunite. The TiO 2 content of the latter melt is lower than typical MORB compositions. We suggest that the medium-Cr# dunite was a melt conduit for a basalt recently reported from the Mariana forearc that was erupted at the inception of subduction. The wide range of variation in the Cr#s of spinels in dunites from the Izu-Bonin-Mariana forearc probably reflects changing melt compositions from MORB-like melts to boninitic melts in the forearc setting due to an increase of slab-derived hydrous fluids and/or melts during subduction initiation.

Phase transition in BCx system under high-pressure and high-temperature: Synthesis of cubic dense BC3 nanostructured phase

We synthesized a cubic BC3 (c-BC3) phase, by direct transformation from graphitic phases at a pressure of 39 GPa and temperature of 2200 K in a laser-heated diamond anvil cell. A combination of x-ray diffraction, electron diffraction, transmission electron microscopy (TEM) imaging, and electron energy loss spectroscopy (EELS) measurements lead us to conclude that the obtained phase is hetero-nano-diamond, c-BC3. High-resolution TEM imaging of the c-BC3 specimen recovered at ambient conditions demonstrates that the c-BC3 is a single, uniform, nanocrystalline phase with a grain size of about 3–5 nm. The EELS measurements show that the atoms inside the cubic structure are bonded by sp3 bonds. The zero-pressure lattice parameter of the c-BC3 calculated from diffraction peaks was found to be a = 3.589 ± 0.007 A. The composition of the c-BC3 is determined from EELS measurements. The ratio of carbon to boron, C/B, is approximately 3 (2.8 ± 0.7).

Phosphorus zoning reveals dendritic architecture of olivine

Quantitative spot analyses were acquired with the JEOL JXA-8500F field-emission gun electron probe micro-analyzer of the University of Hawaii – Manoa over two sessions. Olivine was analyzed during the first session with an electron beam tuned at 20 keV, 50 nA and 10 µm probe diameter. The elements were acquired using five analyzing crystals as followed: one LiFH for Cr and Ni, one LiF for Fe and Mn, one PETJ for Ca and Ti, one PETH for P, and two TAPJ crystals for Al, Si and Mg. The standards used were Verma garnet for Mn, San Carlos olivine USNM 111312/444 for Fe, Si, Mg and Ni, sphene glass for Ti, chromite USNM 117075 for Al and Cr, and fluor-apatite USNM 104021 for Ca and P. The on-peak and off-peak counting times were each 20 s for Si, Al and Mg, 30 s for Mn, Ti and Ni, 35 s for Fe, Ca and Cr, and 70 s for P. The off-peak correction method was linear for major elements and exponential for trace elements Ti, Al, Cr and P, using Probe for EPMA software. Detection limits are in the range 0.005 – 0.01 wt%. Precision and accuracy (1) are 0.4 – 2 % for major elements (reported in weight percent oxide), 3 – 5 % for minor elements (Ca, Mn and Ni – reported in µg/g) and 20 – 70 % for trace elements (Al, P, Ti, and Cr – reported in µg/g in Table DR1), based on repeated analyses of San Carlos olivine standard (USNM 111312/444). Matrix glasses and melt inclusions were analysed during the second session with a beam tuned at 15 keV, 15 nA and 10 µm probe diameter. Elements were acquired using one LiFH for Ti and Cr, one LiF for Fe and Mn, one PETH for Ca and K, and two TAPJ crystals for Mg, Al, Na and Si (Na measured first). The standards were Verma garnet for Mn, Kakanui augite USNM 122142 for Al, Fe, Si, Mg and Ca, sphene glass for Ti, chromite USNM 117075 for Cr, Amelia albite for Na, and orthoclase OR-1 for K. The on-peak and off-peak counting times were 30 s for all elements. Detection limits for Cr2O3 and S are 0.02 wt%. Precision is better than 1% for all elements (1), except Na and K (<3%). Accuracy (1) is better than 5 % for all elements.