Geochemistry and petrogenesis of forearc peridotites, ODP Leg 125

ODP Leg 125 recovered peridotites from Conical Seamount in the Mariana forearc and Torishima Forearc Seamount in the Izu-Bonin forearc. The peridotites recovered comprise about 95% harzburgites and about 5% dunites, which are variably serpentinised (mostly 60-100%). The Leg 125 peridotites represent some of the first extant peridotites recovered from a forearc selling. A detailed petrographic, mineral and bulk-rock chemical study of the peridotites has been undertaken in order to elucidate information about melting and fluid processes in the forearc mantle wedge. The harzburgites are highly refractory in terms of their mineralogy and geochemistry. They have low modal clinopyroxene, highly magnesian olivine (Mg# = 91.1-93.6) and orthopyroxene (Mg# = 91.6-93.2) and chrome-rich spinels (Cr# = 60-80) and very low incompatible element contents (Ti <80 ppm). Furthermore they are more refractory than the most depleted abyssal peridotite, which suggests that the harzburgites can be interpreted as residues to extensive partial melting (>20%). The Ti concentrations in the clinopyroxene indicate that the harzburgites are residues to -25% fractional melting. However, petrographic and other geochemical information show that the Leg 125 harzburgites have had a complicated melting and enrichment history. Many samples have olivine fabrics which are interpreted as having formed beneath a spreading ridge. Orthopyroxenes have lobate grain boundaries often associated with fresh olivine neoblasts. This texture is interpreted as showing the incongruent melting of orthopyroxene, a process which happens at low pressures (-3 kb) and high water pressures. These two types of textures indicate that the peridotites have had a two stage melting history. Moreover, the V concentrations in the clinopyroxenes can be explained by -15% partial melting at low oxygen fugacities (FMQ-1), followed by 5- 10% melting at high oxygen fugacities (FMQ+1). Oxygen thermobarometry calculations are in accordance with the peridotites last equilibrating under oxygen fugacities of greater than FMQ+1.The bulk-rocks have chondrite-normalised REE patterns showing extreme U-shapes with [La/Sm](_N) ratios in the range 5.03-250.0 and [Sm/Yb](_N) ratios in the range 0.05 to 0.25; several samples have possible small positive Eu anomalies. On extended chondrite-normalised plots the bulk-rocks also show enrichments in Sr and Zr relative to their neighbouring REEs and are enriched in LREE, Rb, Cs, Ba, Sm, and Eu relative to abyssal peridotites. Covariation diagrams based on clinopyroxene data show that Sr, Ce, Nd, Sm, Eu and Zr are enriched in the clinopyroxenes and that the enrichment took place during or after melting. The enrichment component is most likely a melt derived from the underlying subduction zone. A multistage melting and enrichment model is proposed for the peridotites where they first melt 10-15% beneath a spreading ridge. The resulting depleted spinel Iherzolite is enriched and then melted again 10- 15% above the subduction zone to produce the spatially associated boninites. A final enrichment event takes place during and after this melting event to produce the characteristic trace element enrichments in the Leg 125 peridotites

Free energy of formation of clusters of sulphuric acid and water molecules determined by guided disassembly

We evaluate the grand potential of a cluster of two molecular species, equivalent to its free energy of formation from a binary vapour phase, using a nonequilibrium molecular dynamics technique where guide particles, each tethered to a molecule by a harmonic force, move apart to disassemble a cluster into its components. The mechanical work performed in an ensemble of trajectories is analysed using the Jarzynski equality to obtain a free energy of disassembly, a contribution to the cluster grand potential. We study clusters of sulphuric acid and water at 300 K, using a classical interaction scheme, and contrast two modes of guided disassembly. In one, the cluster is broken apart through simple pulling by the guide particles, but we find the trajectories tend to be mechanically irreversible. In the second approach, the guide motion and strength of tethering are modified in a way that prises the cluster apart, a procedure that seems more reversible. We construct a surface representing the cluster grand potential, and identify a critical cluster for droplet nucleation under given vapour conditions. We compare the equilibrium populations of clusters with calculations reported by Henschel et al. [J. Phys. Chem. A 118, 2599 (2014)] based on optimised quantum chemical structures

Spinful bosons in an optical lattice

We analyze the behavior of cold spin-1 particles with antiferromagnetic interactions in a one-dimensional optical lattice using density matrix renormalization group calculations. Correlation functions and the dimerization are shown and we also present results for the energy gap between ground state and the spin excited states. We confirm the anticipated phase diagram, with Mott-insulating regions of alternating dimerized S=1 chains for odd particle density versus on-site singlets for even density. We find no evidence for any additional ordered phases in the physically accessible region, however for sufficiently large spin interaction, on-site singlet pairs dominate leading, for odd density, to a breakdown of the Mott insulator or, for even density, a real-space singlet superfluid.Comment: Minor revisions and clarification

Boninite and Harzburgite from Leg 125 (Bonin-Mariana Forearc): A Case Study of Magma Genesis during the Initial Stages of Subduction

Holes drilled into the volcanic and ultrabasic basement of the Izu-Ogasawara and Mariana forearc terranes during Leg 125 provide data on some of the earliest lithosphere created after the start of Eocene subduction in the Western Pacific. The volcanic basement contains three boninite series and one tholeiite series. (1) Eocene low-Ca boninite and low-Ca bronzite andesite pillow lavas and dikes dominate the lowermost part of the deep crustal section through the outer-arc high at Site 786. (2) Eocene intermediate-Ca boninite and its fractionation products (bronzite andesite, andesite, dacite, and rhyolite) make up the main part of the boninitic edifice at Site 786. (3) Early Oligocene intermediate-Ca to high-Ca boninite sills or dikes intrude the edifice and perhaps feed an uppermost breccia unit at Site 786. (4) Eocene or Early Oligocene tholeiitic andesite, dacite, and rhyolite form the uppermost part of the outer-arc high at Site 782. All four groups can be explained by remelting above a subduction zone of oceanic mantle lithosphere that has been depleted by its previous episode of partial melting at an ocean ridge. We estimate that the average boninite source had lost 10-15 wt% of melt at the ridge before undergoing further melting (5-10%) shortly after subduction started. The composition of the harzburgite (<2% clinopyroxene, Fo content of about 92%) indicates that it underwent a total of about 25% melting with respect to a fertile MORB mantle. The low concentration of Nb in the boninite indicates that the oceanic lithosphere prior to subduction was not enriched by any asthenospheric (OIB) component. The subduction component is characterized by (1) high Zr and Hf contents relative to Sm, Ti, Y, and middle-heavy REE, (2) light REE-enrichment, (3) low contents of Nb and Ta relative to Th, Rb, or La, (4) high contents of Na and Al, and (5) Pb isotopes on the Northern Hemisphere Reference Line. This component is unlike any subduction component from active arc volcanoes in the Izu-Mariana region or elsewhere. Modeling suggests that these characteristics fit a trondhjemitic melt from slab fusion in amphibolite facies. The resulting metasomatized mantle may have contained about 0.15 wt% water. The overall melting regime is constrained by experimental data to shallow depths and high temperatures (1250°C and 1.5 kb for an average boninite) of boninite segregation. We thus envisage that boninites were generated by decompression melting of a diapir of metasomatized residual MORB mantle leaving the harzburgites as the uppermost, most depleted residue from this second stage of melting. Thermal constraints require that both subducted lithosphere and overlying oceanic lithosphere of the mantle wedge be very young at the time of boninite genesis. This conclusion is consistent with models in which an active transform fault offsetting two ridge axes is placed under compression or transpression following the Eocene plate reorganization in the Pacific. Comparison between Leg 125 boninites and boninites and related rocks elsewhere in the Western Pacific highlights large regional differences in petrogenesis in terms of mantle mineralogy, degree of partial melting, composition of subduction components, and the nature of pre-subduction lithosphere. It is likely that, on a regional scale, the initiation of subduction involved subducted crust and lithospheric mantle wedge of a range of ages and compositions, as might be expected in this type of tectonic setting

The “central state” and the almighty Dollar

New methods to determine the titanium (Ti) mass-dependent isotope fractionation of solar system materials to high precision were developed by combining internally normalised Ti isotope data with double-spike analyses utilising a 47Ti-49Ti double spike. The procedure includes a three-stage ion-exchange separation procedure to isolate Ti from the sample matrix that provides high-purity Ti fractions that are necessary for high-precision Ti isotope analyses. Analyses of sample aliquots that were spiked before and after the ion-exchange separation procedure demonstrate that Ti isotope fractionation can be induced by the separation procedure. This outcome requires the addition of the double spike before the ion exchange separation procedure in order to accurately determine the natural mass-dependent Ti isotope fractionation of samples. Multiple double spike analyses of an Alfa Aesar Ti standard performed over eight months yielded a reproducibility (2σ standard deviation) of 0.033‰ for δ49/47Ti (differences in 49Ti/47Ti relative to the OL-Ti standard). Terrestrial sample analyses display a 2σ reproducibility of 0.018 to 0.031‰ for δ49/47Ti. Titanium isotope results for three terrestrial USGS magmatic reference samples (AGV-2, BHVO-2 and BCR-2) agree well with literature data and therefore demonstrate the accuracy and precision of the presented methodologies. Achondritic meteorites display an overall range of 0.75‰ for δ49/47Ti. The ungrouped achondrite NWA 7325 has a more positive composition by 0.64‰ for δ49/47Ti compared to all other investigated samples likely reflecting Ti isotope fractionation induced by magmatic differentiation associated with highly reducing conditions and potentially associated with oxide and plagioclase formation. In contrast, eucrites with δ49/47Ti of -0.020 ± 0.070 and -0.003 ± 0.033 and the first mass-dependent Ti isotope data for an acapulcoite (Dhofar 125; δ49/47Ti = 0.094 ± 0.033) show only limited magmatic Ti isotope fractionation. Chondrites also display a relatively restricted range of 0.085‰ for δ49/47Ti, including one calcium‑aluminum rich inclusion (CAI) from Allende and the first mass-dependent Ti isotope data for two Rumuruti chondrites (NWA 753 and NWA 755). Furthermore, the mass-dependent Ti isotope composition of chondrites overlaps with that of eucrites and the acapulcoite Dhofar 125 indicating that nebular processes induce only limited Ti isotope fractionation. Additionally, the Ti isotope data indicate that thermal metamorphism also produced marginal Ti isotope fractionation at the bulk sample scale for chondrites. Small mass-dependent Ti isotope variations between different bulk meteorite samples are also evident, which might reflect sample heterogeneity. Importantly, the mass-dependent Ti isotope composition of the Earth and Moon overlap with the composition of the investigated chondrites, eucrites and acapulcoites within the 2 standard deviation uncertainties

Tellurium stable isotope fractionation in chondritic meteorites and some terrestrial samples

New methodologies employing a 125Te-128Te double-spike were developed and applied to obtain high precision mass-dependent tellurium stable isotope data for chondritic meteorites and some terrestrial samples by multiple-collector inductively coupled plasma mass spectrometry. Analyses of standard solutions produce Te stable isotope data with a long-term reproducibility (2SD) of 0.064‰ for δ130/125Te. Carbonaceous and enstatite chondrites display a range in δ130/125Te of 0.9‰ (0.2‰ amu−1) in their Te stable isotope signature, whereas ordinary chondrites present larger Te stable isotope fractionation, in particular for unequilibrated ordinary chondrites, with an overall variation of 6.3‰ for δ130/125Te (1.3‰ amu−1). Tellurium stable isotope variations in ordinary chondrites display no correlation with Te contents or metamorphic grade. The large Te stable isotope fractionation in ordinary chondrites is likely caused by evaporation and condensation processes during metamorphism in the meteorite parent bodies, as has been suggested for other moderately and highly volatile elements displaying similar isotope fractionation. Alternatively, they might represent a nebular signature or could have been produced during chondrule formation.Enstatite chondrites display slightly more negative δ130/125Te compared to carbonaceous chondrites and equilibrated ordinary chondrites. Small differences in the Te stable isotope composition are also present within carbonaceous chondrites and increase in the order CV-CO-CM−CI. These Te isotope variations within carbonaceous chondrites may be due to mixing of components that have distinct Te isotope signatures reflecting Te stable isotope fractionation in the early solar system or on the parent bodies and potentially small so-far unresolvable nucleosynthetic isotope anomalies of up to 0.27‰. The Te stable isotope data of carbonaceous and enstatite chondrites displays a general correlation with the oxidation state and hence might provide a record of the nebular formation environment.The Te stable isotope fractionation of the carbonaceous chondrites CI and CM (and CO potentially) overlap within uncertainty with data for terrestrial Te standard solutions, sediments and ore samples. Assuming the silicate Earth displays similar Te isotope fractionation as the studied terrestrial samples, the data indicate that the late veneer might have been delivered by material similar to CI or CM (or possibly) CO carbonaceous chondrites in terms of Te isotope composition.Nine terrestrial samples display resolvable Te stable isotope fractionation of 0.85 and 0.60‰ for δ130/125Te for sediment and USGS geochemical exploration reference samples, respectively. Tellurium isotopes therefore have the potential to become a new geochemical sedimentary proxy, as well as a proxy for ore-exploration

Sr isotopes in arcs revisited: tracking slab dehydration using δ88/86Sr and 87Sr/86Sr systematics of arc lavas

Dehydration of the subducting slab is a crucial process in the generation of hydrous convergent margin magmas, yet the exact processes of how and where the slab dehydrates and how these fluids are transported to the mantle wedge remain obscure. Strontium is a “fluid-mobile” element and as such well suited to investigate the source of slab-derived fluids. We employ mass-dependent Sr isotope systematics (δ88/86Sr; the deviation in 88Sr/86Sr of a sample relative to NIST SRM 987) of primitive arc lavas, in tandem with conventional radiogenic 87Sr/86Sr measurements, as a novel tracer of slab dehydration. To characterise the δ88/86Sr composition of subduction zone inputs, we present new δ88/86Sr data for subducting sediments, altered oceanic crust and MORB. Calcareous sediments are isotopically lighter and carbonate-free sediments are isotopically heavier than mid-ocean ridge basalts (MORB). Samples of the altered oceanic crust display elevated 87Sr/86Sr but only the most intensely altered sample has significantly higher δ88/86Sr than pristine MORB. Mafic arc lavas from the Aegean and Mariana arc invariably have a mass-dependent Sr isotope composition that is indistinguishable from MORB and lower 87Sr/86Sr than upper altered oceanic crust. This δ88/86Sr-87Sr/86Sr signature of the arc lavas, in combination with their high but variable Sr/Nd, can only be explained if it is provided by a fluid that acquired its Sr isotope signature in the deeper, less altered part of the subducted oceanic crust. We propose a model where the breakdown of serpentinite in the slab mantle releases a pulse of fluid at sub-arc depths. These fluids travel through and equilibrate with the overlying oceanic crust and induce wet partial melting of the upper altered crust and sediments. This hydrous melt is then delivered to the mantle source of arc magmas as a single metasomatic component. From mass balance it follows that the slab-derived fluid contributes >70% of the Sr budget of both Mariana and Aegean arc lavas. Whereas this fluid-dominated character is unsurprising for the sediment-poor Mariana arc, the Aegean arc sees the subduction of 3–6 km of calcareous sediments that were found to exert very little control on the Sr budget of the arc magmas and are overwhelmed by the fluid contribution

A re‐evaluation of the Plenus Cold Event, and the links between CO2, temperature, and seawater chemistry during OAE 2

International audienceThe greenhouse world of the mid‐Cretaceous (~94 Ma) was punctuated by an episode of abrupt climatic upheaval: Oceanic Anoxic Event 2 (OAE 2). High‐resolution climate records reveal considerable changes in temperature, carbon cycling, and ocean chemistry during this climatic perturbation. In particular, an interval of cooling has been detected in the English Chalk on the basis of an invasive boreal fauna and bulk oxygen‐isotope excursions registered during the early stages of OAE 2—a phenomenon known as the Plenus Cold Event (PCE), which has tentatively been correlated with climatic shifts worldwide.Here we present new high‐resolution neodymium‐, carbon‐, and oxygen‐isotope data, as well as elemental chromium concentrations and cerium anomalies, from the English Chalk exposed at Dover, UK, which we evaluate in the context of >400 records from across the globe. A negative carbon‐isotope excursion that correlates with the original ‘PCE’ is consistently expressed worldwide, and CO2 proxy records, where available, indicate a rise and subsequent fall in CO2 over the Plenus interval. However, variability in the timing and expression of cooling at different sites suggests that, although sea‐surface paleo‐temperatures may reflect a response to global CO2 change, local processes likely played a dominant role at many sites. Variability in the timing and expression of changes in water‐mass character, and problems in determining the driver of observed proxy changes, suggest that no single simple mechanism can link the carbon cycle to oceanography during the Plenus interval and other factors including upwelling and circulation patterns were locally important. As such, it is proposed that the Plenus carbon‐isotope event is a more reliable stratigraphic marker to identify the Plenus interval, rather than any climatic shifts that may have been overprinted by local effects

Understanding Far-Infrared Absorption in the S=1 Antiferromagnetic Chain Compound NENP

Infrared transmission measurements on the $S=1$ antiferromagnetic chain compound NENP in applied magnetic fields show a sharp absorption line at the field-shifted Haldane gap. This violates a wave-vector selection rule of the Hamiltonian normally used for NENP, as the gap excitations occur at the Brillouin zone boundary. We argue that the crystal structure admits terms which can explain the absorption lines. In addition, in an applied field, staggered orientations of the g-tensors produce a staggered magnetic field. This can explain the observation of a finite gap at all applied fields.Comment: 12 pages, revtex, preprint HU-CMT-93H9