Marschall Horst R.

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Marschall

First Name

Horst R.

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0000-0002-0609-682X

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Effects of fluid-rock interaction on 40Ar/39Ar geochronology in high-pressure rocks (Sesia-Lanzo Zone, Western Alps)

( 2013-10-13) Halama, Ralf ; Konrad-Schmolke, Matthias ; Sudo, Masafumi ; Marschall, Horst R. ; Wiedenbeck, Michael

in situ UV laser spot 40Ar/39Ar analyses of distinct phengite types in eclogite-facies rocks from the Sesia-Lanzo Zone (Western Alps, Italy) were combined with SIMS boron isotope analyses as well as boron (B) and lithium (Li) concentration data to link geochronological information with constraints on fluid-rock interaction. In weakly deformed samples, apparent 40Ar/39Ar ages of phengite cores span a range of ∼20 Ma, but inverse isochrons define two distinct main high-pressure (HP) phengite core crystallization periods of 88-82 Ma and 77-74 Ma, respectively. The younger cores have on average lower B contents (∼36 mg/g) than the older ones (∼43-48 mg/g), suggesting that loss of B and resetting of the Ar isotopic system were related. Phengite cores have variable d11B values (-18 to -10 ‰), indicating the lack of km scale B homogenization during HP crystallization. Overprinted phengite rims in the weakly deformed samples generally yield younger apparent 40Ar/39Ar ages than the respective cores. They also show variable effects of heterogeneous excess 40Ar incorporation and Ar loss. One acceptable inverse isochron age of 77.1 ±1.1 Ma for rims surrounding older cores (82.6 ±0.6 Ma) overlaps with the second period of core crystallization. Compared to the phengite cores, all rims have lower B and Li abundances but similar d11B values (-15 to -9 ‰), reflecting internal redistribution of B and Li and internal fluid buffering of the B isotopic composition during rim growth. The combined observation of younger 40Ar/39Ar ages and boron loss, yielding comparable values of both parameters only in cores and rims of different samples, is best explained by a selective metasomatic overprint. In low permeability samples, this overprint caused recrystallization of phengite rims, whereas higher permeability in other samples led to complete recrystallization of phengite grains. Strongly deformed samples from a several km long, blueschist-facies shear zone contain mylonitic phengite that forms a tightly clustered group of relatively young apparent 40Ar/39Ar ages (64.7 to 68.8 Ma), yielding an inverse isochron age of 65.0 ±3.0 Ma. Almost complete B and Li removal in mylonitic phengite is due to leaching into a fluid. The B isotopic composition is significantly heavier than in phengites from the weakly deformed samples, indicating an external control by a high-d11B fluid (d11B = +7 ±4 ‰). We interpret this result as reflecting phengite recrystallization related to deformation and associated fluid flow in the shear zone. This event also caused partial resetting of the Ar isotope system and further B loss in more permeable rocks of the adjacent unit. We conclude that geochemical evidence for pervasive or limited fluid flow is crucial for the interpretation of 40Ar/39Ar data in partially metasomatized rocks.
Fluid-induced breakdown of white mica controls nitrogen transfer during fluid–rock interaction in subduction zones

( 2016-09) Halama, Ralf ; Bebout, Gray ; Marschall, Horst R. ; John, Timm

In order to determine the effects of fluid–rock interaction on nitrogen elemental and isotopic systematics in high-pressure metamorphic rocks, we investigated three different profiles representing three distinct scenarios of metasomatic overprinting. A profile from the Chinese Tianshan (ultra)high-pressure–low-temperature metamorphic belt represents a prograde, fluid-induced blueschist–eclogite transformation. This profile shows a systematic decrease in N concentrations from the host blueschist (~26 μg/g) via a blueschist–eclogite transition zone (19–23 μg/g) and an eclogitic selvage (12–16 μg/g) towards the former fluid pathway. Eclogites and blueschists show only a small variation in δ15Nair (+2.1 ± 0.3‰), but the systematic trend with distance is consistent with a batch devolatilization process. A second profile from the Tianshan represents a retrograde eclogite–blueschist transition. It shows increasing, but more scattered, N concentrations from the eclogite towards the blueschist and an unsystematic variation in δ15N values (δ15N = + 1.0 to +5.4‰). A third profile from the high-P/T metamorphic basement complex of the Southern Armorican Massif (Vendée, France) comprises a sequence from an eclogite lens via retrogressed eclogite and amphibolite into metasedimentary country rock gneisses. Metasedimentary gneisses have high N contents (14–52 μg/g) and positive δ15N values (+2.9 to +5.8‰), and N concentrations become lower away from the contact with 11–24 μg/g for the amphibolites, 10–14 μg/g for the retrogressed eclogite, and 2.1–3.6 μg/g for the pristine eclogite, which also has the lightest N isotopic compositions (δ15N = + 2.1 to +3.6‰). Overall, geochemical correlations demonstrate that phengitic white mica is the major host of N in metamorphosed mafic rocks. During fluid-induced metamorphic overprint, both abundances and isotopic composition of N are controlled by the stability and presence of white mica. Phengite breakdown in high-P/T metamorphic rocks can liberate significant amounts of N into the fluid. Due to the sensitivity of the N isotope system to a sedimentary signature, it can be used to trace the extent of N transport during metasomatic processes. The Vendée profile demonstrates that this process occurs over several tens of metres and affects both N concentrations and N isotopic compositions.
Mesoproterozoic subduction under the eastern edge of the Kalahari-Grunehogna Craton preceding Rodinia assembly : the Ritscherflya detrital zircon record, Ahlmannryggen (Dronning Maud Land, Antarctica)

( 2013-07-11) Marschall, Horst R. ; Hawkesworth, Chris J. ; Leat, Philip T.

The reconstruction of the palaeogeography and supercontinent amalgamation processes in the Precambrian is generally guided by the age of magmatic and metamorphic rocks in orogenic belts, which formed along the sutures of colliding continents or smaller terranes (e.g., Wareham et al., 1998; Dalziel et al., 2000). Yet, the investigation and interpretation of these belts becomes increasingly difficult with increasing age of the orogenic cycles, due to metamorphic overprint, fragmentation by subsequent rifting processes, erosive loss, and covering by younger deposits or by ice. An alternative and important recorder of geodynamic processes are clastic sediments that are fed from the eroding orogenic belts and are deposited on stable cratonic platforms, where they may escape erosion and high-grade metamorphism for billions of years. These clastic sediment deposits generally contain abundant detrital zircon, which provides an age record of the eroded orogenic belts, reflecting a large number of rock types. The age spectra of detrital zircon recovered from sedimentary basins can be used to distinguish between different tectonic settings in which the sediments were deposited, such as convergent margins, collisional orogens or extensional settings (von Eynatten & Dunkl, 2012; Cawood et al., 2012). The supercontinent Rodinia formed by convergence and collision of all the major landmasses between 1200 and 950Ma, i.e. in the late Mesoproterozoic (Hoffman, 1991; Li et al., 2008). Key evidence for the collisions is found in the late Mesoproterozoic orogenic belts, which span thousands of kilometres through North and South America, southern Africa, Australia, Asia and East Antarctica. Yet, the paleogeographic reconstruction of Rodinia is still uncertain, and at least three different configurations have been discussed (Li et al., 2008). Issues arise in part from the uncertainties in terrane boundaries within East Antarctica and possible connections to the African Kalahari Craton. At least one major late Mesoproterozoic (Stenian) suture must be located in Dronning Maud Land (DML; East Antarctica), but its location and the extent of possible crustal blocks are still enigmatic (Jacobs et al., 2008a).
Sulfur loss from subducted altered oceanic crust and implications for mantle oxidation

(European Association of Geochemistry, 2020-04-02) Walters, Jesse B. ; Cruz‐Uribe, Alicia M. ; Marschall, Horst R.

Oxygen fugacity (fO2) is a controlling factor of the physics of Earth’s mantle; however, the mechanisms driving spatial and secular changes in fO2 associated with convergent margins are highly debated. We present new thermodynamic models and petrographic observations to predict that oxidised sulfur species are produced during the subduction of altered oceanic crust. Sulfur loss from the subducting slab is a function of the protolith Fe3+/ΣFe ratio and subduction zone thermal structure, with elevated sulfur fluxes predicted for oxidised slabs in cold subduction zones. We also predict bi-modal release of sulfur-bearing fluids, with a low volume shallow flux of reduced sulfur followed by an enhanced deep flux of sulfate and sulfite species, consistent with oxidised arc magmas and associated copper porphyry deposits. The variable SOx release predicted by our models both across and among active margins may introduce fO2 heterogeneity to the upper mantle.
Development and evolution of detachment faulting along 50 km of the Mid-Atlantic Ridge near 16.5°N

(John Wiley & Sons, 2014-12-05) Smith, Deborah K. ; Schouten, Hans A. ; Dick, Henry J. B. ; Cann, Johnson R. ; Salters, Vincent J. M. ; Marschall, Horst R. ; Ji, Fuwu ; Yoerger, Dana R. ; Sanfilippo, Alessio ; Parnell-Turner, Ross ; Palmiotto, Camilla ; Zheleznov, Alexei ; Bai, Hailong ; Junkin, Will ; Urann, Ben ; Dick, Spencer ; Sulanowska, Margaret ; Lemmond, Peter ; Curry, Scott

A multifaceted study of the slow spreading Mid-Atlantic Ridge (MAR) at 16.5°N provides new insights into detachment faulting and its evolution through time. The survey included regional multibeam bathymetry mapping, high-resolution mapping using AUV Sentry, seafloor imaging using the TowCam system, and an extensive rock-dredging program. At different times, detachment faulting was active along ∼50 km of the western flank of the study area, and may have dominated spreading on that flank for the last 5 Ma. Detachment morphologies vary and include a classic corrugated massif, noncorrugated massifs, and back-tilted ridges marking detachment breakaways. High-resolution Sentry data reveal a new detachment morphology; a low-angle, irregular surface in the regional bathymetry is shown to be a finely corrugated detachment surface (corrugation wavelength of only tens of meters and relief of just a few meters). Multiscale corrugations are observed 2–3 km from the detachment breakaway suggesting that they formed in the brittle layer, perhaps by anastomosing faults. The thin wedge of hanging wall lavas that covers a low-angle (6°) detachment footwall near its termination are intensely faulted and fissured; this deformation may be enhanced by the low angle of the emerging footwall. Active detachment faulting currently is limited to the western side of the rift valley. Nonetheless, detachment fault morphologies also are present over a large portion of the eastern flank on crust >2 Ma, indicating that within the last 5 Ma parts of the ridge axis have experienced periods of two-sided detachment faulting.
Arc magmas sourced from melange diapirs in subduction zones

( 2012-10-11) Marschall, Horst R. ; Schumacher, John C.

At subduction zones, crustal material is recycled back into the mantle. A certain proportion, however, is returned to the overriding plate via magmatism. The magmas show a characteristic range of compositions that have been explained by three-component mixing in their source regions: hydrous fluids derived from subducted altered oceanic crust and components derived from the thin sedimentary veneer are added to the depleted peridotite in the mantle beneath the volcanoes. However, currently no uniformly accepted model exists for the physical mechanism that mixes the three components and transports them from the slab to the magma source. Here we present an integrated physico-chemical model of subduction zones that emerges from a review of the combined findings of petrology, modelling, geophysics, and geochemistry: Intensely mixed metamorphic rock formations, so-called mélanges, form along the slab-mantle interface and comprise the characteristic trace-element patterns of subduction-zone magmatic rocks. We consider mélange formation the physical mixing process that is responsible for the geochemical three-component pattern of the magmas. Blobs of low-density mélange material, so-called diapirs, rise buoyantly from the surface of the subducting slab and provide a means of transport for well-mixed materials into the mantle beneath the volcanoes, where they produce melt. Our model provides a consistent framework for the interpretation of geophysical, petrological and geochemical data of subduction zones.
Preferential formation of chlorite over talc during si‐metasomatism of ultramafic rocks in subduction zones

(American Geophysical Union, 2022-09-21) Codillo, Emmanuel A. ; Klein, Frieder ; Marschall, Horst R.

Talc formation via silica‐metasomatism of ultramafic rocks is believed to play key roles in subduction zone processes. Yet, the conditions of talc formation remain poorly constrained. We used thermodynamic reaction‐path models to assess the formation of talc at the slab‐mantle interface and show that it is restricted to a limited set of pressure–temperature conditions, protolith, and fluid compositions. In contrast, our models predict that chlorite formation is ubiquitous at conditions relevant to the slab‐mantle interface of subduction zones. The scarcity of talc and abundance of chlorite is evident in the rock record of exhumed subduction zone terranes. Talc formation during Si‐metasomatism may thus play a more limited role in volatile cycling, strain localization, and in controlling the decoupling‐coupling transition of the plate interface. Conversely, the observed and predicted ubiquity of chlorite corroborates its prominent role in slab‐mantle interface processes that previous studies attributed to talc.
Extreme magnesium isotope fractionation at outcrop scale records the mechanism and rate at which reaction fronts advance

( 2014-10) Pogge von Strandmann, Philip A. E. ; Dohmen, Ralf ; Marschall, Horst R. ; Schumacher, John C. ; Elliott, Tim

Isotopic fractionation of cationic species during diffusive transport provides novel means of constraining the style and timing of metamorphic transformations. Here we document a major (~1‰) decrease in the Mg isotopic composition of the reaction front of an exhumed contact between rocks of subducted crust and serpentinite, in the Syros mélange zone. This isotopic perturbation extends over a notable length-scale (~1 m), implicating diffusion of Mg through an intergranular fluid network over a period of ~100 kyr. These novel observations confirm models of diffusion-controlled growth of reaction zones formed between rocks of contrasting compositions, such as found at the slab-mantle interface in subduction zones. The results also demonstrate that diffusive processes can result in exotic stable isotope compositions of major elements with implications for mantle xenoliths and complex intrusions.
Variations of Li and Mg isotope ratios in bulk chondrites and mantle xenoliths

( 2011-06-21) Pogge von Strandmann, Philip A. E. ; Elliott, Tim ; Marschall, Horst R. ; Coath, Chris ; Lai, Yi-Jen ; Jeffcoate, Alistair B. ; Ionov, Dmitri A.

We present whole rock Li and Mg isotope analyses of 33 ultramafic xenoliths from the terrestrial mantle, which we compare with analyses of 30 (mostly chondritic) meteorites. The accuracy of our new Mg isotope ratio measurement protocol is substantiated by a combination of standard addition experiments, the absence of mass independent effects in terrestrial samples and our obtaining identical values for rock standards using 2 different separation chemistries and 3 different mass-spectrometric introduction systems. Carbonaceous, ordinary and enstatite chondrites have irresolvable mean stable Mg isotopic compositions (δ25Mg = -0.14 ± 0.06; δ26Mg = - 0.27 ± 0.12‰, 2sd), but our enstatite chondrite samples have lighter δ7Li (by up to ~3‰) than our mean carbonaceous and ordinary chondrites (3.0 ± 1.5‰, 2sd), possibly as a result of spallation in the early solar system. Measurements of equilibrated, fertile peridotites give mean values of δ7Li = 3.5 ± 0.5‰, δ25Mg = -0.10 ± 0.03‰ and δ26Mg = -0.21 ± 0.07‰. We believe these values provide a useful estimate of the primitive mantle and they are within error of our average of bulk carbonaceous and ordinary chondrites. A fuller range of fresh, terrestrial, ultramafic samples, covering a variety of geological histories, show a broad positive correlation between bulk δ7Li and δ26Mg, which vary from -3.7 to +14.5‰, and -0.36 to +0.06‰, respectively. Values of δ7Li and δ26Mg lower than our estimate of primitive mantle are strongly linked to kinetic isotope fractionation, occurring during transport of the mantle xenoliths. We suggest Mg and Li diffusion into the xenoliths is coupled to H loss from nominally anhydrous minerals following degassing. Diffusion models suggest that the co-variation of Mg and Li isotopes requires comparable diffusivities of Li and Mg in olivine. The isotopically lightest samples require ~5-10 years of diffusive ingress, which we interpret as a time since volatile loss in the host magma. Xenoliths erupted in pyroclastic flows appear to have retained their mantle isotope ratios, likely as a result of little prior degassing in these explosive events. High δ7Li, coupled with high [Li], in rapidly cooled arc peridotites may indicate that these samples represent fragments of mantle wedge that has been metasomatised by heavy, slab-derived fluids. If such material is typically stirred back into the convecting mantle, it may account for the heavy δ7Li seen in some oceanic basalts.
Isotopic compositions of sulfides in exhumed high-pressure terranes: Implications for sulfur cycling in subduction zones

(American Geophysical Union, 2019-06-14) Walters, Jesse B. ; Cruz‐Uribe, Alicia M. ; Marschall, Horst R.

Subduction is a key component of Earth's long‐term sulfur cycle; however, the mechanisms that drive sulfur from subducting slabs remain elusive. Isotopes are a sensitive indicator of the speciation of sulfur in fluids, sulfide dissolution‐precipitation reactions, and inferring fluid sources. To investigate these processes, we report δ34S values determined by secondary ion mass spectroscopy in sulfides from a global suite of exhumed high‐pressure rocks. Sulfides are classified into two petrogenetic groups: (1) metamorphic, which represent closed‐system (re)crystallization from protolith‐inherited sulfur, and (2) metasomatic, which formed during open system processes, such as an influx of oxidized sulfur. The δ34S values for metamorphic sulfides tend to reflect their precursor compositions: −4.3 ‰ to +13.5 ‰ for metabasic rocks, and −32.4 ‰ to −11.0 ‰ for metasediments. Metasomatic sulfides exhibit a range of δ34S from −21.7 ‰ to +13.9 ‰. We suggest that sluggish sulfur self‐diffusion prevents isotopic fractionation during sulfide breakdown and that slab fluids inherit the isotopic composition of their source. We estimate a composition of −11 ‰ to +8 ‰ for slab fluids, a significantly smaller range than observed for metasomatic sulfides. Large fractionations during metasomatic sulfide precipitation from sulfate‐bearing fluids, and an evolving fluid composition during reactive transport may account for the entire ~36 ‰ range of metasomatic sulfide compositions. Thus, we suggest that sulfates are likely the dominant sulfur species in slab‐derived fluids.
Boron isotope analysis of silicate glass with very low boron concentrations by secondary ion mass spectrometry

( 2014-02) Marschall, Horst R. ; Monteleone, Brian D.

Here we present an improved method for the determination of the boron isotopic composition of volcanic glasses with boron concentrations of as low as 0.4–2.5 μg g−1, as is typical for mid-ocean ridge basalt glasses. The analyses were completed by secondary ion mass spectrometry using a Cameca 1280 large-radius ion microprobe. Transmission and stability of the instrument and analytical protocol were optimised, which led to an improvement of precision and reduction in surface contamination and analysis time compared with earlier studies. Accuracy, reproducibility (0.4–2.3‰, 2 RSD), measurement repeatability (2 RSE = 2.5–4.0‰ for a single spot with [B] = 1 μg g−1), matrix effects (≪ 0.5‰ among komatiitic, dacitic and rhyolitic glass), machine drift (no internal drift; long-term drift: ~ 0.1‰ hr−1), contamination (~ 3–8 ng g−1) and machine background (0.093 s−1) were quantified and their influence on samples with low B concentrations was determined. The newly developed set-up was capable of determining the B isotopic composition of basaltic glass with 1 μg g−1 B with a precision and accuracy of ± 1.5‰ (2 RSE) by completing 4–5 consecutive spot analyses with a spatial resolution of 30 μm × 30 μm. Samples with slightly higher concentrations (≥ 2.5 μg g−1) could be analysed with a precision of better than ± 2‰ (internal 2 RSE) with a single spot analysis, which took 32 min.
Geochemical evidence for mélange melting in global arcs

(American Association for the Advancement of Science., 2017-04-07) Nielsen, Sune G. ; Marschall, Horst R.

In subduction zones, sediments and hydrothermally altered oceanic crust, which together form part of the subducting slab, contribute to the chemical composition of lavas erupted at the surface to form volcanic arcs. Transport of this material from the slab to the overlying mantle wedge is thought to involve discreet melts and fluids that are released from various portions of the slab. We use a meta-analysis of geochemical data from eight globally representative arcs to show that melts and fluids from individual slab components cannot be responsible for the formation of arc lavas. Instead, the data are compatible with models that first invoke physical mixing of slab components and the mantle wedge, widely referred to as high-pressure mélange, before arc magmas are generated.
Fossil records of early solar irradiation and cosmolocation of the CAI factory: a reappraisal

(American Association for the Advancement of Science, 2021-09-29) Bekaert, David V. ; Auro, Maureen E. ; Shollenberger, Quinn R. ; Liu, Ming-Chang ; Marschall, Horst R. ; Burton, Kevin W. ; Jacobsen, Benjamin ; Brennecka, Gregory A. ; MacPherson, Glenn J. ; von Mutius, Richard ; Sarafian, Adam ; Nielsen, Sune G.

Calcium-aluminum–rich inclusions (CAIs) in meteorites carry crucial information about the environmental conditions of the nascent Solar System prior to planet formation. Based on models of 50V–10Be co-production by in-situ irradiation, CAIs are considered to have formed within ~0.1 AU from the proto-Sun. Here, we present vanadium (V) and strontium (Sr) isotopic co-variations in fine- and coarse-grained CAIs and demonstrate that kinetic isotope effects during partial condensation and evaporation best explain V isotope anomalies previously attributed to solar particle irradiation. We also report initial excesses of 10Be and argue that CV CAIs possess essentially a homogeneous level of 10Be, inherited during their formation. Based on numerical modeling of 50V–10Be co-production by irradiation, we show that CAI formation during protoplanetary disk build-up likely occurred at greater heliocentric distances than previously considered, up to planet-forming regions (~1AU), where solar particle fluxes were sufficiently low to avoid substantial in-situ irradiation of CAIs.
Fluid‐mediated mass transfer between mafic and ultramafic rocks in subduction zones

(American Geophysical Union, 2022-07-11) Codillo, Emmanuel A. ; Klein, Frieder ; Dragovic, Besim ; Marschall, Horst R. ; Baxter, Ethan ; Scambelluri, Marco ; Schwarzenbach, Esther M.

Metasomatic reaction zones between mafic and ultramafic rocks exhumed from subduction zones provide a window into mass-transfer processes at high pressure. However, accurate interpretation of the rock record requires distinguishing high-pressure metasomatic processes from inherited oceanic signatures prior to subduction. We integrated constraints from bulk-rock geochemical compositions and petrophysical properties, mineral chemistry, and thermodynamic modeling to understand the formation of reaction zones between juxtaposed metagabbro and serpentinite as exemplified by the Voltri Massif (Ligurian Alps, Italy). Distinct zones of variably metasomatized metagabbro are dominated by chlorite, amphibole, clinopyroxene, epidote, rutile, ilmenite, and titanite between serpentinite and eclogitic metagabbro. Whereas the precursor serpentinite and oxide gabbro formed and were likely already in contact in an oceanic setting, the reaction zones formed by diffusional Mg-metasomatism between the two rocks from prograde to peak, to retrograde conditions in a subduction zone. Metasomatism of mafic rocks by Mg-rich fluids that previously equilibrated with serpentinite could be widespread along the subduction interface, within the subducted slab, and the mantle wedge. Furthermore, the models predict that talc formation by Si-metasomatism of serpentinite in subduction zones is limited by pressure-dependent increase in the silica activity buffered by the serpentine-talc equilibrium. Elevated activities of aqueous Ca and Al species would also favor the formation of chlorite and garnet. Accordingly, unusual conditions or processes would be required to stabilize abundant talc at high P-T conditions. Alternatively, a different set of mineral assemblages, such as serpentine- or chlorite-rich rocks, may be controlling the coupling-decoupling transition of the plate interface.
Tourmaline reference materials for the In situ analysis of oxygen and lithium isotope ratio compositions

(International Association of Geoanalysts, 2020-10-19) Wiedenbeck, Michael ; Trumbull, Robert B. ; Rosner, Martin ; Boyce, Adrian ; Fournelle, John H. ; Franchi, Ian A. ; Halama, Ralf ; Harris, Chris ; Lacey, Jack H. ; Marschall, Horst R. ; Meixner, Anette ; Pack, Andreas ; Pogge von Strandmann, Philip A. E. ; Spicuzza, Michael J. ; Valley, John W. ; Wilke, Franziska D.H.

Three tourmaline reference materials sourced from the Harvard Mineralogical and Geological Museum (schorl 112566, dravite 108796 and elbaite 98144), which are already widely used for the calibration of in situ boron isotope measurements, are characterised here for their oxygen and lithium isotope compositions. Homogeneity tests by secondary ion mass spectrometry (SIMS) showed that at sub‐nanogram test portion masses, their 18O/16O and 7Li/6Li isotope ratios are constant within ± 0.27‰ and ± 2.2‰ (1s), respectively. The lithium mass fractions of the three materials vary over three orders of magnitude. SIMS homogeneity tests showed variations in 7Li/28Si between 8% and 14% (1s), which provides a measure of the heterogeneity of the Li contents in these three materials. Here, we provide recommended values for δ18O, Δ’17O and δ7Li for the three Harvard tourmaline reference materials based on results from bulk mineral analyses from multiple, independent laboratories using laser‐ and stepwise fluorination gas mass spectrometry (for O), and solution multi‐collector inductively coupled plasma‐mass spectroscopy (for Li). These bulk data also allow us to assess the degree of inter‐laboratory bias that might be present in such data sets. This work also re‐evaluates the major element chemical composition of the materials by electron probe microanalysis and investigates these presence of a chemical matrix effect on SIMS instrumental mass fractionation with regard to δ18O determinations, which was found to be < 1.6‰ between these three materials. The final table presented here provides a summary of the isotope ratio values that we have determined for these three materials. Depending on their starting mass, either 128 or 512 splits have been produced of each material, assuring their availability for many years into the future.
Fluorine and chlorine in mantle minerals and the halogen budget of the Earth’s mantle

( 2017-05-01) Urann, Benjamin M. ; Le Roux, Véronique ; Hammond, Keiji ; Marschall, Horst R. ; Lee, Cin-Ty A.

The fluorine (F) and chlorine (Cl) contents of arc magmas have been used to track the composition of subducted components, and the F and Cl contents of MORB have been used to estimate the halogen content of depleted MORB mantle (DMM). Yet, the F and Cl budget of the Earth's upper mantle, and their distribution in peridotite minerals, remains to be constrained. Here we developed a method to measure low concentrations of halogens (≥ 0.4 μg/g F and ≥ 0.3 μg/g Cl) in minerals by secondary ion mass spectroscopy. We present a comprehensive study of F and Cl in natural olivine, orthopyroxene, clinopyroxene, and amphibole in seventeen samples from different tectonic settings. We support the hypothesis that F in olivine is controlled by melt polymerization, and that F in pyroxene is controlled by their Na and Al contents, with some effect of melt polymerization. We infer that Cl compatibility ranks as follows: amphibole > clinopyroxene > olivine ~ orthopyroxene, while F compatibility ranks as follows: amphibole > clinopyroxene > orthopyroxene ≥ olivine, depending on the tectonic context. In addition, we show that F, Cl, Be and B are correlated in pyroxenes and amphibole. F and Cl variations suggest that interaction with slab melts and fluids can significantly alter the halogen content of mantle minerals. In particular, F in oceanic peridotites is mostly hosted in pyroxenes, and proportionally increases in olivine in subduction-related peridotites. The mantle wedge is likely enriched in F compared to un-metasomatized mantle, while Cl is always low (< 1 μg/g) in all tectonic settings studied here. The bulk anhydrous peridotite mantle contains 1.4–31 μg/g F and 0.14–0.38 μg/g Cl. The bulk F content of oceanic-like peridotites (2.1–9.4 μg/g) is lower than DMM estimates, consistent with F-rich eclogite in the source of MORB. Furthermore, the bulk Cl budget of all anhydrous peridotites studied here is lower than previous DMM estimates. Our results indicate that nearly all MORB may be somewhat contaminated by seawater-rich material and that the Cl content of DMM could be overestimated. With this study, we demonstrate that the halogen contents of natural peridotite minerals are a unique tool to understand the cycling of halogens, from ridge settings to subduction zones.
Emplacement and high-temperature evolution of gabbros of the 16.5 degrees N oceanic core complexes (Mid-Atlantic Ridge): Insights into the compositional variability of the lower oceanic crust.

(American Geophysical Union, 2018-12-05) Sanfilippo, Alessio ; Dick, Henry JB ; Marschall, Horst R. ; Lissenberg, C. Johan ; Urann, Ben

This study reports the composition of the oceanic crust from the 16.5°N region of the Mid‐Atlantic Ridge, a spreading ridge segment characterized by a complex detachment fault system and three main oceanic core complexes (southern, central, and northern OCCs). Lithologies recovered from the core complexes include both greenschist facies and weathered pillow basalt, diabase, peridotite, and gabbro, while only weathered and fresh pillow basalt was dredged from the rift valley floor. The gabbros are compositionally bimodal, with the magmatic crust in the region formed by scattered intrusions of chemically primitive plutonic rocks (i.e., dunites and troctolites), associated with evolved oxide‐bearing gabbros. We use thermodynamic models to infer that this distribution is expected in regions where small gabbroic bodies are intruded into mantle peridotites. The occurrence of ephemeral magma chambers located in the lithospheric mantle enables large proportions of the melt to be erupted after relatively low degrees of fractionation. A large proportion of the dredged gabbros reveal evidence for deformation at high‐temperature conditions. In particular, chemical changes in response to deformation and the occurrence of very high‐temperature ultramylonites (>1000 °C) suggest that the deformation related to the oceanic detachment commenced at near‐solidus conditions. This event was likely associated with the expulsion of interstitial, evolved magmas from the crystal mush, a mechanism that enhanced the formation of disconnected oxide‐gabbro seams or layers often associated with crystal‐plastic fabrics in the host gabbros. This granulite‐grade event was soon followed by hydrothermal alteration revealed by the formation of amphibole‐rich veins at high‐temperature conditions (~900 °C).
The boron and lithium isotopic composition of mid-ocean ridge basalts and the mantle

( 2017-03-17) Marschall, Horst R. ; Wanless, V. Dorsey ; Shimizu, Nobumichi ; Pogge von Strandmann, Philip ; Elliott, Tim ; Monteleone, Brian D.

A global selection of 56 mid-ocean ridge basalt (MORB) glasses were analysed for Li and B abundances and isotopic compositions. Analytical accuracy and precision of analyses constitute an improvement over previously published MORB data and allow a more detailed discussion of the Li and B systematics of the crust-mantle system. Refined estimates for primitive mantle abundances ([Li]=1.39±0.10[Li]=1.39±0.10 μg/g and [B]=0.19±0.02[B]=0.19±0.02 μg/g) and depleted mantle abundances ([Li]=1.20±0.10[Li]=1.20±0.10 μg/g and [B]=0.077±0.010[B]=0.077±0.010 μg/g) are presented based on mass balance and on partial melting models that utilise observed element ratios in MORB. Assimilation of seawater (or brine) or seawater-altered material beneath the ridge, identified by high Cl/KCl/K, causes significant elevation of MORB δ11Bδ11B and variable elevation in δ7Liδ7Li. The B isotope ratio is, hence, identified as a reliable indicator of assimilation in MORB and values higher than −6‰ are strongly indicative of shallow contamination of the magma. The global set of samples investigated here were produced at various degrees of partial melting and include depleted and enriched MORB from slow and fast-spreading ridge segments with a range of radiogenic isotope signatures and trace element compositions. Uncontaminated (low-Cl/KCl/K) MORB show no significant boron isotope variation at the current level of analytical precision, and hence a homogenous B isotopic composition of δ11B=-7.1±0.9‰δ11B=-7.1±0.9‰ (mean of six ridge segments; 2SD). Boron isotope fractionation during mantle melting and basalt fractionation likely is small, and this δ11Bδ11B value reflects the B isotopic composition of the depleted mantle and the bulk silicate Earth, probably within ±0.4‰. Our sample set shows a mean δ7Li=+3.5±1.0‰δ7Li=+3.5±1.0‰ (mean of five ridge segments; 2SD), excluding high-Cl/KCl/K samples. A significant variation of 1.0–1.5‰ exists among various ridge segments and among samples within individual ridge segments, but this variation is unrelated to differentiation, assimilation or mantle source indicators, such as radiogenic isotopes or trace elements. It, therefore, seems likely that kinetic fractionation of Li isotopes during magma extraction, transport and storage may generate δ7Liδ7Li excursions in MORB. No mantle heterogeneities, such as those generated by deeply recycled subducted materials, are invoked in the interpretation of the Li and B isotope data presented here, in contrast to previous work on smaller data sets. Lithium and boron budgets for the silicate Earth are presented that are based on isotope and element mass balance. A refined estimate for the B isotopic composition of the bulk continental crust is given as δ11B=-9.1±2.4‰δ11B=-9.1±2.4‰. Mass balance allows the existence of recycled B reservoirs in the deep mantle, but these are not required. However, mass balance among the crust, sediments and seawater shows enrichment of 6Li6Li in the surface reservoirs, which requires the existence of 7Li7Li-enriched material in the mantle. This may have formed by the subduction of altered oceanic crust since the Archaean.
Arc-like magmas generated by mélange-peridotite interaction in the mantle wedge

(Nature Publishing Group, 2018-07-20) Codillo, Emmanuel A. ; Le Roux, Véronique ; Marschall, Horst R.

The mechanisms of transfer of crustal material from the subducting slab to the overlying mantle wedge are still debated. Mélange rocks, formed by mixing of sediments, oceanic crust, and ultramafics along the slab-mantle interface, are predicted to ascend as diapirs from the slab-top and transfer their compositional signatures to the source region of arc magmas. However, the compositions of melts that result from the interaction of mélanges with a peridotite wedge remain unknown. Here we present experimental evidence that melting of peridotite hybridized by mélanges produces melts that carry the major and trace element abundances observed in natural arc magmas. We propose that differences in nature and relative contributions of mélanges hybridizing the mantle produce a range of primary arc magmas, from tholeiitic to calc-alkaline. Thus, assimilation of mélanges into the wedge may play a key role in transferring subduction signatures from the slab to the source of arc magmas.
The ascent of subduction zone mélanges: Experimental constraints on mélange rock densities and solidus temperatures

(Elsevier, 2023-09-27) Codillo, Emmanuel A. ; Le Roux, Veronique ; Klein, Benjamin Z. ; Behn, Mark D. ; Marschall, Horst R. ; Bebout, Gray E.

Mélanges are mixtures of subducted materials and serpentinized mantle rocks that form along the slab-mantle interface in subduction zones. It has been suggested that mélange rocks may be able to ascend from the slab-top into the overlying mantle, as solid or partially molten buoyant diapirs, and transfer their compositional signatures to the source regions of arc magmas. However, their ability to buoyantly rise is in part tied to their phase equilibria during melting and residual densities after melt extraction, all of which are poorly constrained. Here, we report a series of piston-cylinder experiments performed at 1.5–2.5 GPa and 500–1050 °C on three natural mélange rocks that span a range of mélange compositions. Using phase equilibria, solidus temperatures, and densities for all experiments, we show that melting of mélanges is unlikely to occur along the slab-top at pressures ≤ 2.5 GPa, so that diapirism into the hotter mantle wedge would be required for melting to initiate. For the two metaluminous mélange compositions, diapir formation is favored up to pressures of at least 2.5 GPa. For the peraluminous mélange composition investigated, diapir buoyancy is possible at 1.5 GPa but limited at 2.5 GPa due to the formation of high-density garnet, primarily at the expense of chlorite. We also evaluate whether thermodynamic modeling (Perple_X) can accurately reproduce the phase equilibria, solidus temperatures, and density evolution of mélange compositions. Our analysis shows good agreement between models and experiments in mélange compositions with low initial water contents and low-pressure (≤ 1.5 GPa) conditions. However, discrepancies between the thermodynamic models and experiments become larger at higher pressures and high-water contents, highlighting the need for an improved thermodynamic database that can model novel bulk compositions beyond the canonical subducting lithologies. This study provides experimental constraints on mélange buoyancy that can inform numerical models of mélange diapirism and influence the interpretations of both geophysical signals and geochemical characteristics of magmas in subduction zones.

Marschall Horst R.

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