Melt/rock interaction in remains of refertilized Archean lithospheric mantle in Jiaodong Peninsula, North China Craton: Li isotopic evidence

Li contents and its isotopes of minerals in mantle peridotite xenoliths from late Cretaceous mafic dikes, analyzed in situ by Cameca IMS-1280, reveal the existence of melt/rock interaction in remains of refertilized Archean lithospheric mantle in Qingdao, Jiaodong Peninsula, North China Craton. Two groups of peridotites exist, i.e., low-Mg# lherzolite and high-Mg# harzburgites. The low-Mg# lherzolite has a relatively homogeneous Li concentration (ol: 2.01–2.11 ppm; opx: 1.77–1.88 ppm; cpx: 1.75–1.93 ppm) and Li isotopic composition (δ⁷Li in ol: 4.2–7.6‰; in opx: 6.0–8.3‰; in cpx: 5.3–8.4‰). The similarity in δ⁷Li value to the fresh MORB provides further evidence for the argument that the low-Mg# lherzolite could be the fragment of the newly accreted lithospheric mantle. The high-Mg# harzburgites have heterogeneous Li abundances (ol: 0.83–2.09 ppm; opx: 0.92–1.94 ppm; cpx: 1.12–4.89 ppm) and Li isotopic compositions (δ⁷Li in ol: −0.5 to +11.5‰; in opx: −6.2 to +11.1‰; in cpx: −34.3 to +10.1‰), showing strong disequilibrium in Li partitioning and Li isotope fractionation between samples. The cores of most minerals in these high-Mg# harzburgites have relatively homogeneous δ⁷Li values, which are higher than those of fresh MORB, but similar to those previously reported for arc lavas. These harzburgites have enriched trace elemental and Sr–Nd isotopic compositions. These observations indicate that in the early Mesozoic the lithospheric mantle beneath the southeastern North China Craton was similar to that in arc settings, which is metasomatized by subducted crustal materials. Extremely low δ⁷Li preserved in cpxs requires diffusive fractionation of Li isotopes from later-stage melt into the minerals. Thus, the Li data provide further evidence that the Archean refractory lithospheric mantle represented by the high-Mg# harzburgites was refertilized through melt/rock interaction and transformed to the Mesozoic less refractory and incompatible element and Sr–Nd isotopes enriched lithospheric mantle.     

Melt evolution in subarc mantle: evidence from heating experiments on spinel-hosted melt inclusions in peridotite xenoliths from the andesitic Avacha volcano (Kamchatka,Russia)

Glass-bearing inclusions hosted by Cr-spinel in harzburgite xenoliths from Avacha are grouped based on homogenization temperatures and daughter minerals into high-T (1,200°C; opx + cpx), intermediate (900–1,100°C; cpx ± amph), and low-T (900°C; amph) and are commonly accompanied by larger “melt pockets”. Unlike previous work on unheated inclusions and interstitial glass in xenoliths from Kamchatka, the homogenized glass compositions in this study are not affected by low-pressure melt fractionation during transport and cooling or by interaction with host magma. Primary melt compositions constrained for each inclusion type differ in major and trace element abundances and were formed by different events, but all are silica saturated, Ca-rich, and K-poor, with enrichments in LREE, Sr, Rb, and Ba and negative Nb anomalies. These melts are inferred to have been formed with participation of fluids produced by dehydration of slab materials. The high-T inclusions trapped liquids produced by ancient high-degree, fluid-induced melting in the mantle wedge. The low-T inclusions are related to percolation of low-T melts or hydrous fluids in arc mantle lithosphere. Melt pockets arise from localized heating and fluid-assisted melting induced by rising magmas shortly before the entrapment of the xenoliths. The “high-T” melt inclusions in Avacha xenoliths are unique in preserving evidence of ancient, high-T melting events in arc mantle, whereas the published data appear to characterize pre-eruption enrichment events.     

Li同位素在斜顽辉石、镁铝榴石及镁铝尖晶石晶格内扩散与分馏的理论计算研究

斜顽辉石、镁铝榴石和镁铝尖晶石作为辉石族、石榴石族以及尖晶石族中的重要端元,是地球上地幔主要组成矿物。Li同位素是重要的地幔地球化学示踪剂,其在橄榄石、辉石和石榴石等地幔矿物中的扩散分馏的性质对理解Li同位素作为地幔地球化学示踪剂非常重要。我们通过经典力场经验势方法,从原子尺度上计算研究了不同温压条件下Li同位素在斜顽辉石、镁铝榴石和镁铝尖晶石晶格中分别通过不同的填隙机制和取代空位机制迁移的活化能和其在不同晶格位上的分馏效应。我们发现Li同位素是通过取代空位机制在斜顽辉石、镁铝榴石和镁铝尖晶石中进行迁移扩散。Li同位素在不同晶格位上的分馏作用计算表明,在三种矿物中重同位素7Li会更多地进入晶格填隙位中,而6Li则相对更多进入Mg位。温度是影响这种分馏作用的一个关键因素,相应的结果可用来解释地幔Li同位素组成特征及冷却条件下的同位素分馏等科学问题。     

Evidence of a mantle contribution in the genesis of magmatic rocks from the Neogene Batu Hijau district in the Sunda Arc, South Western Sumbawa, Indonesia

Whole-rock geochemical and radiogenic data are combined with in situ trace and isotopic analyses of amphibole grains to characterize the source and the emplacement mechanisms of the magmas of the Sunda arc in the Batu Hijau district, Sumbawa, Indonesia. The low-K calc-alkaline magmatic suite in the area is characterized by a distinctively juvenile signature (¹⁴³Nd/¹⁴⁴Nd ~0.5130). Whole-rock trace element and Pb isotopic data (²⁰⁷Pb/²⁰⁴Pb ~15.603) suggest the involvement of a minimal (<0.1%) sediment component in arc petrogenesis. During the petrogenesis of the calc-alkaline plutons, the involvement of fluids that were not entirely derived from the dehydration of a subducting slab is reflected in the mineral chemistry of the primary hydrous magmatic amphiboles, which contain very low B and Li concentrations. We argue that the B- and Li-poor fluids implicated in the petrogenesis of the calc-alkaline melts were at least partially derived from dehydration of uprising asthenospheric mantle. The δD values of selected hydrous magmatic amphibole grains range between ca. −70‰ and 0‰, consistent with an original mantle-derived signature, which was subsequently modified due to a de-hydrogenation process. We put forward the hypothesis that in the Batu Hijau district an arc-transverse fault system facilitated the rise of asthenosphere-derived melts above a kink, or tear, in the subducting Indian Ocean Plate that underlies the Sunda arc. The melts ascended to upper-crustal levels and underwent fractionation while interacting with the arc crust or metasomatized lithospheric mantle wedge. As a result of this study, we emphasize the significance of crustal-scale faults as conduits that connect the mantle to upper-crustal levels in arc settings. The de-hydrogenation process that the tonalite plutons underwent in the Batu Hijau district may have been crucial to the genesis of associated Cu–Au porphyry mineralization and the development of the Pliocene Batu Hijau deposit. Consequently, we argue that deep structures may facilitate the efficient release of mineralizing fluids at high crustal-levels.     

Insights into Li and Li isotope cycling and sub-arc metasomatism from veined mantle xenoliths,Kamchatka

Harzburgitic xenoliths cut by pyroxenite veins from Avachinsky volcano, Kamchatka, are derived from the sub-arc mantle and record element transfer from the slab to the arc. Olivine and orthopyroxene in the harzburgites have Li isotopic compositions (δ⁷Li = +2.8 to +5.6) comparable to estimates of the upper mantle (δ⁷Li ~ +4 ± 2). The pyroxenite veins, which represent modal metasomatism and may therefore provide information about the metasomatic agent, have mantle-normalized trace element characteristics that suggest overprinting of their mantle source by an aqueous, slab-derived fluid. These include relative enrichments of Pb over Ce, U over Th and Sr over Nd. Li is enriched relative to the HREE, and ortho- and clinopyroxene from the veins are in Li elemental and isotopic equilibrium with each other and the surrounding harzburgite. Vein samples (δ⁷Li = +3.0 to +5.0) do not record a significant slab-derived δ⁷Li signature. These observations can be reconciled if slab Li diffusively re-equilibrates in the mantle wedge. Modeling demonstrates that Li equilibration of small (1–2 cm width) veins or melt conduits is achieved at mantle wedge temperatures within 10¹–10⁵ years. We conclude that strongly fractionated Li isotopic signatures cannot be sustained for long periods in the sub-arc mantle, at least at shallow (<70 km) depths. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Controls on magmatism in an island arc environment: study of lavas and sub-arc xenoliths from the Tabar–Lihir–Tanga–Feni island chain, Papua New Guinea

The Tabar–Lihir–Tanga–Feni (TLTF) islands of Papua New Guinea mainly comprise high-K calc-alkaline and silica undersaturated alkaline rocks that have geochemical features typical for subduction-related magmatism. Numerous sedimentary, mafic, and ultramafic xenoliths recovered from Tubaf seamount, located on the flank of Lihir Island, provide a unique opportunity to study the elemental and isotopic composition of the crust and mantle wedge beneath the arc and to evaluate their relationships to the arc magmatism in the region. The sedimentary and mafic xenoliths show that the crust under the islands is composed of sedimentary sequences and oceanic crust with Pacific affinity. A majority of the ultramafic xenoliths contain features indicating wide spread metasomatism in the mantle wedge under the TLTF arc. Leaching experiments reveal that the metasomatized ultramafic xenoliths contain discrete labile phases that can account for up to 50% or more of elements such as Cu, Zn, Rb, U, Pb, and light REE (rare-earth elements), most likely introduced in the xenoliths via hydrous fluids released from a subducted slab. The leaching experiments demonstrated that the light REE enrichment pattern can be more or less removed from the metasomatized xenoliths and the residual phases exhibit REE patterns that range from flat to light REE depleted. Sr–Nd isotopic data for the ultramafic residues show a coupled behavior of increasing ⁸⁷Sr/⁸⁶Sr with decreasing ¹⁴³Nd/¹⁴⁴Nd ratios. The labile phases in the ultramafic xenoliths, represented by the leachates, show decoupling between Sr and Nd with distinctly more radiogenic ⁸⁷Sr/⁸⁶Sr than the residues. Both leachates and residues exhibit very wide range in their Pb isotopic compositions, indicating the involvement of three components in the mantle wedge under the TLTF islands. Two of the components can be identified as Pacific Oceanic mantle and Pacific sediments. Some of the ultramafic samples and clinopyroxene separates, however, exhibit relatively low ²⁰⁶Pb/²⁰⁴Pb at elevated ²⁰⁷Pb/²⁰⁴Pb suggesting that the third component is either Indian Ocean-type mantle or Australian subcontinental lithospheric mantle. Geochemical data from the ultramafic xenoliths indicate that although the mantle wedge in the area was extensively metasomatized, it did not significantly contribute to the isotopic and incompatible trace element compositions of TLTF lavas. Compared to the mantle samples, the TLTF lavas have very restricted Pb isotopic compositions that lie within the Pacific MORB range, indicating that magma compositions were dominated by melts released from a stalled subducted slab with Pacific MORB affinity. Interaction of slab melts with depleted peridotitic component in the mantle wedge, followed by crystal fractionation most likely generated the geochemical characteristics of the lavas in the area. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Multistage melt/fluid-peridotite interactions in the refertilized lithospheric mantle beneath the North China Craton: constraints from the Li–Sr–Nd isotopic disequilibrium between minerals of peridotite xenoliths

Elemental and Li–Sr–Nd isotopic data of minerals in spinel peridotites hosted by Cenozoic basalts allow us to refine the existing models for Li isotopic fractionation in mantle peridotites and constrain the melt/fluid-peridotite interaction in the lithospheric mantle beneath the North China Craton. Highly elevated Li concentrations in cpx (up to 24 ppm) relative to coexisting opx and olivine (<4 ppm) indicate that the peridotites experienced metasomatism by mafic silicate melts and/or fluids. The mineral δ⁷Li vary greatly, with olivine (+0.7 to +5.4‰) being isotopically heavier than coexisting opx (−4.4 to −25.9‰) and cpx (−3.3 to −21.4‰) in most samples. The δ⁷Li in pyroxenes are considerably lower than the normal mantle values and show negative correlation with their Li abundances, likely due to recent Li ingress attended by diffusive fractionation of Li isotopes. Two exceptional samples have olivine δ⁷Li of −3.0 and −7.9‰, indicating the existence of low δ⁷Li domains in the mantle, which could be transient and generated by meter-scale diffusion of Li during melt/fluid-peridotite interaction. The ¹⁴³Nd/¹⁴⁴Nd (0.5123–0.5139) and ⁸⁷Sr/⁸⁶Sr (0.7018–0.7062) in the pyroxenes also show a large variation, in which the cpx are apparently lower in ⁸⁷Sr/⁸⁶Sr and slightly higher in ¹⁴³Nd/¹⁴⁴Nd than coexisting opx, implying an intermineral Sr–Nd isotopic disequilibrium. This is observed more apparently in peridotites having low ⁸⁷Sr/⁸⁶Sr and high ¹⁴³Nd/¹⁴⁴Nd ratios than in those with high ⁸⁷Sr/⁸⁶Sr and low ¹⁴³Nd/¹⁴⁴Nd, suggesting that a relatively recent interaction existed between an ancient metasomatized lithospheric mantle and asthenospheric melt, which transformed the refractory peridotites with highly radiogenic Sr and unradiogenic Nd isotopic compositions to the fertile lherzolites with unradiogenic Sr and radiogenic Nd isotopic compositions. Therefore, we argue that the lithospheric mantle represented by the peridotites has been heterogeneously refertilized by multistage melt/fluid-peridotite interactions.     

Lithium elemental and isotopic disequilibrium in minerals from peridotite xenoliths from Shangzhi,NE China: products of recent melt/fluid-peridotite interaction

Lithium elemental and isotopic disequilibrium has frequently been observed in the continental and oceanic mantle xenoliths, but its origin remains controversial. Here, we present a combined elemental and Li isotopic study on variably metasomatised peridotite xenoliths entrained in the Cenozoic basalts from Shangzhi in Northeast (NE) China that provides insight into this issue. Li concentration (0.3–2.7 ppm) and δ⁷Li (mostly 2‰–6‰) in olivine from the Shangzhi peridotites are similar to the normal mantle values and show roughly negative correlations with the indices of melt extraction (such as modal olivine and whole rock MgO). These features are consistent with variable degrees of partial melting. In contrast, clinopyroxene from the Shangzhi xenoliths shows significant Li enrichment (0.9–6.1 ppm) and anomalously light δ⁷Li (??13.8‰ to 7.7‰) relative to normal mantle values. Such features can be explained by Li diffusion from silicate melts or Li-rich fluids occurring over a very short time (several minutes to several hours). Moreover, the light Li isotopic compositions preserved in some bulk samples also indicate that these percolated melts/fluids have not had enough time to isotopically equilibrate with the bulk peridotite. We thus emphasize that Li isotopic fractionation in the Shangzhi mantle xenoliths is mainly related to Li diffusion from silicate melts or Li-rich fluids that took place shortly before or coincident with their entrainment into the host magmas.     

Trace element and Pb–B–Li isotope systematics of olivine-hosted melt inclusions: insights into source metasomatism beneath Stromboli (southern Italy)

We studied the elemental and isotopic (Pb, B and Li isotopes) composition of melt inclusions hosted in highly forsteritic (Fo_83–91) olivines that were collected from San Bartolo lava and pumice (ST79p, ST82p and ST531p) samples erupted by Stromboli in historical times. The studied melt inclusions have primitive calcalkaline to shoshonitic basaltic compositions. They cover a compositional range far wider than that exhibited by the whole-rocks and differ in key trace element ratios. San Bartolo melt inclusions are characterized by lower incompatible trace element abundances, higher ratios between fluid-mobile (B, Pb, U and LILE) and less fluid-mobile (REE, Th, HFSE) elements and lower La/Yb ratios relative to the pumice-hosted melt inclusions and pumiceous melts erupted during paroxysmal events. Trace elements, along with different Pb, B and Li isotopic signatures, attest to source heterogeneity on the small scale and provide new insights into subducted components beneath Stromboli. Results of a mixing model suggest that metasomatism of the mantle source of pumice-hosted melt inclusions was driven by solute-rich high-pressure fluids (<20%) expelled from the deep portion of the slab. Heterogeneous Pb isotopic composition together with light δ¹¹B (−8.6 to −13.7‰) and δ⁷Li (+2.3 to −1.7‰) indicates that high-pressure liquids were released in variable proportions from highly dehydrated metabasalts and metasediments. On the other hand, the elemental and isotopic (δ¹¹B ~ −1.9 to −5.9‰) composition of San Bartolo melt inclusions is better explained by the addition of a prevalent aqueous component (~2 to 4%) escaped at shallower depths from sediments and altered basaltic crust in almost equivalent proportions, with a smaller contribution by high-pressure fluids. Owing to the high-angle dip of the subducted cold Ionian slab, aqueous fluids and high-pressure fluids would rise through the mantle wedge and locally superimpose on each other, thus giving origin to variously metasomatized mantle domains.     

New insights into the origin of O–Hf–Os isotope signatures in arc lavas from Tonga–Kermadec

O, Hf and Os isotope data are presented for lavas from the highly depleted Tonga–Kermadec arc. O isotope values overlap with those of MORB limiting the amount of interaction with the arc crust. δ¹⁸O does not increase northwards as would be expected from the ~ 4 fold increase in subduction rate if slab-derived fluids had high ¹⁸O/¹⁶O ratios. Thus, the overall northward decrease in HFSE concentrations likely reflects depletion due to prior melt extraction, not increasing extents of melting. Hf isotopes are strongly negatively correlated with Be isotopes consistent with mixing of subducted pelagic sediment into the mantle wedge and do not require Hf to be fluid mobile. With the exception of a boninite from the north Tongan trench, the northern Tonga lavas do not overlap the Hf isotope composition of either the Samoan plume or the subducting Louisville volcaniclastic sediments. Thus, the Pb isotope signatures in these lavas must have been added by fluids and sediment melts derived from the Louisville volcaniclastics with minimal mobilisation of Hf. This suggests conservative behaviour for this element due to the formation of residual zircon during partial melting of the subducted sediments. ¹⁸⁷Os/¹⁸⁸Os ranges from 0.1275 to 0.4731 and the higher Os isotope ratios reflect the sensitivity of this system to even minor interaction with altered arc crust. Conversely, the lowest Os ratios are subchondritic and indicate that transfer of radiogenic Os from the slab is not all pervasive and provide an important constraint on the composition of the mantle wedge. Remarkably, the least radiogenic sample is a dacite demonstrating that evolved magmas can develop by fractionation from mantle-derived magmas with minimal interaction with the arc crust.     

Lithium isotopic systematics of peridotite xenoliths from Hannuoba, North China Craton: Implications for melt-rock interaction in the considerably thinned lithospheric mantle

Li concentrations and isotopic compositions of coexisting minerals (ol, opx, and cpx) from peridotite xenoliths entrained in the Hannuoba Tertiary basalts, North China Craton, provide insight into Li isotopic fractionation between mantle minerals during melt-rock interaction in the considerably thinned lithospheric mantle. Bulk analyses of mineral separates show significant enrichment of Li in cpx (2.4-3.6 ppm) relative to olivine (1.2-1.8 ppm), indicating that these peridotites have been affected by mantle metasomatism with mafic silicate melts. Bulk olivine separates (δ⁷Li ∼ +3.3‰ to +6.4‰) are isotopically heavier than coexisting pyroxenes (δ⁷Li ∼ −3.3‰ to −8.2‰ in cpx, and −4.0‰ to −6.7‰ in opx). Such large variation suggests Li elemental and isotopic disequilibrium. This conclusion is supported by results from in situ SIMS analyses of mineral grains where significant Li elemental and isotopic zonations exist. The olivine and opx have lower Li concentrations and heavier Li isotopes in the rims than in the cores. This reverse correlation of δ⁷Li with Li concentrations indicates diffusive fractionation of Li isotopes. However, the zoning patterns in coexisting cpx show isotopically heavier rims with higher Li abundances. This positive correlation between δ⁷Li and Li concentrations suggests a melt mixing trend. We attribute Li concentration and isotope zonation in minerals to the effects of two-stage diffusive fractionation coupled with melt-rock interaction. The earliest melts may have been derived from the subducted oceanic slab with low δ⁷Li values produced by isotopic fractionation during the dehydration of the seawater-altered slab. Melts at later stages were derived from the asthenosphere and interacted with the peridotites, producing the Li elemental and isotopic zoning in mineral grains. These data thus provide evidence for multiple-stage peridotite-melt interaction in the lithospheric mantle beneath the northern North China Craton.     

Lithium Isotopic Geochemistry in Subduction Zones: Retrospects and Prospects

Subduction zones involve many complex geological processes, including the release of slab-derived fluids, fluid/rock interactions, partial melting, isotopic fractionations, elemental transporting, and crust/mantle interactions. Lithium (Li) isotopes (6Li and 7Li) have relative mass difference up to 16%, being the largest among metal elements. Thus, Li isotopes have advantage to interprete trace various geological processes. Most importantly, during crust/mantle interactions in deep subduction zones, surface materials and mantle rocks usually have distinct Li isotopic compositions. Li isotopes can be potential tracer for subduction processes, from the onset of subduction to the release of Li from subducted slabs and interaction with mantle wedge, as well as the fate of Li in slab-derived fluids and residual slabs. Moreover, the Li isotopic composition of subducting output materials can provide useful information for understanding global Li circulation. With developments in measurement and expansion of Li isotopic database, Li isotopic geochemistry will provide more inference and be a powerful tracer for understanding subduction-related processes. This work retrospected the application of Li isotopes in tracing successive subduction processes, and made some prospects for further studies of Li isotopes.     

An origin of the along-arc compositional variation in the Izu-Bonin arc system

The Izu-Bonin arc system is sediment-poor(～400 m thick with no accretionary prism) and,therefore,the influence of the altered oceanic crust(AOC) is most likely the source of the documented along-arc lava compositional variations,especially in Pb isotopes.Izu-Bonin arc lava geochemistry suggests an influx of subduction component from an Indian-type AOC.However,samples drilled from the western Pacific geochemical reference site at Integrated Ocean Drilling Program Site 1149 implies subduction of a Pacific-type AOC.To solve the apparent discrepancy of slab input versus arc output in this arc system,samples of the AOC were dredged from vertical fault scarps of the subducting Pacific Plate along a transect from 27.5°N to 34.50 N.Samples range from tholeiitic to mildly alkalic mid-ocean ridge basalts as well as trachybasalts,basaltic trachyandesites,tephrites,and phono-tephrites.Isotope ratios also exhibit a range of values(~(87)Sr/~(86)Sr=0.70282-0.70673,143 Nd/144 Nd=0.512552-0.513174,~(206)Pb/204 Pb=18.43-20.00,207 Pb/204 Pb=15.40-15.67,~(208)Pb/~(204)Pb=37.75-39.55).Our results suggest that there is a geochemical variation in the AOC that is neither completely due to seawater or hydrothermal alteration,nor to petrogenetic processes.Rather,this variation is the result of the Pacific-Izanagi Ridge system tapping into a heterogeneous,plume-polluted mantle source during the Mid-Cretaceous volcanic event.The observed Pacific-type AOC is not responsible for the Indian-type Pb isotopic signature of Izu-Bonin arc lavas.This leads us to propose an alternative scenario where the Izu-Bonin arc lava Indian-type Pb isotopic signature originates from slab-derived fluids interacting and adsorbing Pb from an Indian-type mantle wedge through zone-refining.     

Boron-isotope fractionation between tourmaline and fluid: an experimental re-investigation

The fractionation of boron isotopes between synthetic dravitic tourmaline and fluid was determined by hydrothermal experiments between 400 and 700°C at 200 MPa and at 500°C, 500 MPa. Tourmaline was crystallized from an oxide mix in presence of water that contained boron in excess. In one series of experiments, [B]_fluid/[B]_tour was 9 after the run; in another series it was 0.1. All experiments produced tourmaline as the sole boron-bearing solid, along with traces of quartz and talc. Powder XRD and Rietveld refinements revealed no significant amounts of tetrahedrally coordinated boron in tourmaline. ¹¹B always preferentially fractionated into the fluid. For experiments where [B]_fluid/[B]_tour was 9, a consistent temperature-dependent boron isotope fractionation curve resulted, approximated by Δ¹¹B_{(tour–fluid)} = −4.20 · [1,000/T (K)] + 3.52; R ² = 0.77, and valid from 400 to 700°C. No pressure dependence was observed. The fractionation (−2.7 ± 0.5‰ at 400°C; and −0.8 ± 0.5‰ at 700°C) is much lower than that previously presented by Palmer et al. (1992). Experiments where [B]_fluid/[B]_tour was 0.1 showed a significant larger apparent fractionation of up to −4.7‰. In one of these runs, the isotopic composition of handpicked tourmaline crystals of different size varied by 1.3‰. This is interpreted as resulting from fractional crystallization of boron isotopes during tourmaline growth due to the small boron reservoir of the fluid relative to tourmaline, thus indicating larger fractionation than observed at equilibrium. The effect is eliminated or minimized in experiments with very high boron excess in the fluid. We therefore suggest that values given by the above relation represent the true equilibrium fractionations.     

Hydrothermal alteration of hemi-pelagic sediments: experimental evaluation of geochemical processes in shallow subduction zones

Laboratory hydrothermal experiments provide unique information regarding the fate of volatile and/or incompatibles (e.g. B, Li, and As) during oceanic crust subduction. Examination of chemical redistribution between the subducted slab, mantle wedge, arc volcanics and overlying ocean water during subduction is critical to gain further insight into arc volcanism and chemical oceanic budgets. For instance, efficient mobilization of B at shallow depths may be a key aspect of its oceanic budget, and can help to explain the systematics of B-δ¹¹B and B-¹⁰Be in arc lavas. Fluid–rock interactions at elevated temperatures and pressures in accretionary prisms were studied using a rocking autoclave hydrothermal apparatus to monitor sediment–porewater interaction over the range of 25 to 350°C, at 800 bars. Clay-rich hemi-pelagic sediments from the décollement zone of Ocean Drilling Program Site 808, Nankai Trough, were reacted with NaCl–CaCl₂ solutions at water/rock ratios of ∼3.5 to 1.5 (w/w) to mimic alteration processes in the shallow subduction zone. Fluids were extracted at 25–50°C intervals and were analyzed for major and trace chemical constituents. The fluid chemistry changed significantly during the course of these experiments, but there was generally only minor modification of the solid phase; only B, Li, As, Br, and Pb are significantly depleted. During the heating cycle, dissolved Na, Mg and SO₄ decreased sharply and NH₄, SiO₂, K, B, and Li increased at T⩾300°C. Calcium drops gradually at low temperatures, but concentrations rise sharply at T⩾300°C. Decomposition of organic matter, SO₄²⁻ depletion, and Mg-fixation dominate at low temperatures; however, albitization of calcic plagioclase leads to marked Na depletions and Ca enrichments at T⩾300°C. Dissolved SiO₂ remained below saturation with respect to quartz and amorphous silica throughout the entire experiment. B and Li mobilization with large isotopic fractionations occurred at low temperature. Exchangeable B (δ¹¹B=∼15‰) is completely leached before reaching 150°C. Substantial O₂ exchange between fluids and the solid phase occurred at T⩾200°C in the spiked experiment, where δ¹⁸O varies more than 100‰ in the fluids. During retrograde cooling, dissolved Mg, SO₄, Ca, Si, K and Sr are released as a result of carbonate or anhydrite dissolution, and marked B re-adsorption occurred at temperatures below 60°C.     

Lithium isotopes in Guatemalan and Franciscan HP-LT rocks: Insights into the role of sediment-derived fluids during subduction

High-pressure, low-temperature (HP-LT) rocks from a Cretaceous age subduction complex occur as tectonic blocks in serpentinite mélange along the Motagua Fault (MF) in central Guatemala. Eclogite and jadeitite among these are characterized by trace element patterns with enrichments in fluid mobile elements, similar to arc lavas. Eclogite is recrystallized from MORB-like altered oceanic crust, presumably at the boundary between the down-going plate and overlying mantle wedge. Eclogite geochemistry, mineralogy and petrography suggest a two step petrogenesis of (1) dehydration during prograde metamorphism at low temperatures (<500 °C) followed by (2) partial rehydration/fertilization at even lower T during exhumation. In contrast, Guatemalan jadeitites are crystallized directly from low-T aqueous fluid as veins in serpentinizing mantle during both subduction and exhumation. The overall chemistry and mineralogy of Guatemalan eclogites are similar to those from the Franciscan Complex, California, implying similar P-T-x paths.Li concentrations (?90 ppm) in mineral separates and whole rocks (WR) from Guatemalan and Franciscan HP-LT rocks are significantly higher than MORB (4-6 ppm), but similar to HP-LT rocks globally. Li isotopic compositions range from −5‰ to +5‰ for Guatemalan HP-LT rocks, and −4‰ to +1‰ for Franciscan eclogites, overlapping previous findings for other HP-LT suites. The combination of Li concentrations greater than MORB, and Li isotopic values lighter than MORB are inconsistent with a simple dehydration model. We prefer a model in which Li systematics in Guatemalan and Franciscan eclogites reflect reequilibration with subduction fluids during exhumation. Roughly 5-10% of the Li in these fluids is derived from sediments.Model results predict that the dehydrated bulk ocean crust is isotopically lighter (δ⁷Li ? +1 ± 3‰) than the depleted mantle (∼+3.5 ± 0.5‰), while the mantle wedge beneath the arc is the isotopic complement of the bulk crust. A subduction fluid with an AOC-GLOSS composition over the full range of model temperatures (50-600 °C) gives an average fluid δ⁷Li (∼+7 ± 5‰ 1σ) that is isotopically heavier than the depleted mantle. If the lowest temperature steps are excluded (50-260 °C) as too cold to participate in circulation of the mantle wedge, then the average subduction fluid (δ⁷Li = +4 ± 2.3‰ 1σ, is indistinguishable from depleted mantle. Because of the relatively compatible nature of Li in metamorphic minerals, the most altered part of the crust (uppermost extrusives), may retain a Li isotopic signature (∼+5 ± 3‰) heavier than the bulk crust. The range of Li isotopic values for OIB, IAB and MORB overlap, making it is difficult to resolve which of these components may contribute to the recycled component in the mantle using δ⁷Li alone.     

Adakite-like volcanism of Ecuador: lower crust magmatic evolution and recycling

In the Northern Andes of Ecuador, a broad Quaternary volcanic arc with significant across-arc geochemical changes sits upon continental crust consisting of accreted oceanic and continental terranes. Quaternary volcanic centers occur, from west to east, along the Western Cordillera (frontal arc), in the Inter-Andean Depression and along the Eastern Cordillera (main arc), and in the Sub-Andean Zone (back-arc). The adakite-like signatures of the frontal and main arc volcanoes have been interpreted either as the result of slab melting plus subsequent slab melt–mantle interactions or of lower crustal melting, fractional crystallization, and assimilation processes. In this paper, we present petrographic, geochemical, and isotopic (Sr, Nd, Pb) data on dominantly andesitic to dacitic volcanic rocks as well as crustal xenolith and cumulate samples from five volcanic centers (Pululagua, Pichincha, Ilalo, Chacana, Sumaco) forming a NW–SE transect at about 0° latitude and encompassing the frontal (Pululagua, Pichincha), main (Ilalo, Chacana), and back-arc (Sumaco) chains. All rocks display typical subduction-related geochemical signatures, such as Nb and Ta negative anomalies and LILE enrichment. They show a relative depletion of fluid-mobile elements and a general increase in incompatible elements from the front to the back-arc suggesting derivation from progressively lower degrees of partial melting of the mantle wedge induced by decreasing amounts of fluids released from the slab. We observe widespread petrographic evidence of interaction of primary melts with mafic xenoliths as well as with clinopyroxene- and/or amphibole-bearing cumulates and of magma mixing at all frontal and main arc volcanic centers. Within each volcanic center, rocks display correlations between evolution indices and radiogenic isotopes, although absolute variations of radiogenic isotopes are small and their values are overall rather primitive (e.g., ε_Nd = +1.5 to +6, ⁸⁷Sr/⁸⁶Sr = 0.7040–0.70435). Rare earth element patterns are characterized by variably fractionated light to heavy REE (La/Yb_N = 5.7–34) and by the absence of Eu negative anomalies suggesting evolution of these rocks with limited plagioclase fractionation. We interpret the petrographic, geochemical, and isotopic data as indicating open-system evolution at all volcanic centers characterized by fractional crystallization and magma mixing processes at different lower- to mid-crustal levels as well as by assimilation of mafic lower crust and/or its partial melts. Thus, we propose that the adakite-like signatures of Ecuadorian rocks (e.g., high Sr/Y and La/Yb values) are primarily the result of lower- to mid-crustal processing of mantle-derived melts, rather than of slab melts and slab melt–mantle interactions. The isotopic signatures of the least evolved adakite-like rocks of the active and recent volcanoes are the same as those of Tertiary ”normal” calc-alkaline magmatic rocks of Ecuador suggesting that the source of the magma did not change through time. What changed was the depth of magmatic evolution, probably as a consequence of increased compression induced by the stronger coupling between the subducting and overriding plates associated with subduction of the aseismic Carnegie Ridge.     

The effect of chrysotile nanotubes on the serpentine-fluid Li-isotopic fractionation

We determined the lithium isotope fractionation between synthetic Li-bearing serpentine phases lizardite, chrysotile, antigorite, and aqueous fluid in the P,T range 0.2–4.0 GPa, 200–500°C. For experiments in the systems lizardite-fluid and antigorite-fluid, ⁷Li preferentially partitioned into the fluid and Δ⁷Li values followed the T-dependent fractionation of Li-bearing mica-fluid (Wunder et al. 2007). By contrast, for chrysotile-fluid experiments, ⁷Li weakly partitioned into chrysotile. This contrasting behavior might be due to different Li environments in the three serpentine varieties: in lizardite and antigorite lithium is sixfold coordinated, whereas in chrysotile lithium is incorporated in two ways, octahedrally and as Li-bearing water cluster filling the nanotube cores. Low-temperature IR spectroscopic measurements of chrysotile showed significant amounts of water, whose freezing point was suppressed due to the Li contents and the confined geometry of the fluid within the tubes. The small inverse Li-isotopic fractionation for chrysotile-fluid results from intra-crystalline Li isotope fractionation of octahedral Li^[6] with preference to ⁶Li and lithium within the channels (Li^[Ch]) of chrysotile, favoring ⁷Li. The nanotubes of chrysotile possibly serve as important carrier of Li and perhaps also of other fluid-mobile elements in serpentinized oceanic crust. This might explain higher Li abundances for low-T chrysotile-bearing serpentinites relative to high-T serpentinites. Isotopically heavy Li-bearing fluids of chrysotile nanotubes could be released at relatively shallow depths during subduction, prior to complete chrysotile reactions to form antigorite. During further subduction, fluids produced during breakdown of serpentine phases will be depleted in ⁷Li. This behavior might explain some of the Li-isotopic heterogeneities observed for serpentinized peridotites.     

Melt- versus fluid-induced metasomatism in spinel to garnet wedge peridotites (Ulten Zone, Eastern Italian Alps): clues from trace element and Li abundances

The peridotite bodies of the Ulten Zone (Upper Austroalpine, Italian Eastern Alps) are enclosed in Variscan migmatites and derive from a mantle wedge environment. They display the progressive transformation of porphyroclastic spinel peridotites (T=1,200°C; P=1.5 GPa) into fine-grained garnet–amphibole peridotites (T=850°C; P=3 GPa). Detailed bulk-rock and mineral trace element analyses of a sample suite documenting the entire metamorphic evolution of the peridotites revealed several stages of metasomatism. The spinel peridotites derive from a depleted mantle that became enriched in some large ion lithophile element (LILE) and light rare earth elements (LREE). The same signature pertains to clinopyroxene and orthopyroxene, indicating that this metasomatic signature was acquired at the recorded temperature of 1,200°C. Such a temperature is considerably above the wet peridotite solidus and hence the metasomatic agent must have been a hydrous melt. Moreover, the Li-enrichment of the spinel-facies pyroxenes (up to 24 ppm Li) reflects disequilibrium distribution after exchange with a presumably mafic melt. ^cpx/opx D _Li=3–7 and ^cpx/ol D _Li=2.7–8 indicate that the spinel-facies clinopyroxene hosts higher Li amounts than the coexisting minerals. LREE fractionation, variable LREE enrichment, LILE enrichment with respect to HFSE (average clinopyroxene Pb _N /Nb _N =16–90) in spinel lherzolites can be related to chromatographic effects of porous melt flow. The significant enrichment of pyroxenes from the spinel lherzolites in Pb, U and Li indicates that the metasomatic melt was subduction-related. All these features suggest that the spinel lherzolites formed a mantle wedge layer percolated by melts carrying recycled crustal components and rising from a deeper source of subduction magmas. The garnet + amphibole peridotites equilibrated at temperatures well below the wet solidus in the presence of an aqueous fluid. Bulk-rock trace element patterns display pronounced positive anomalies in Cs, Ba, Pb and U and moderate enrichment in Li, indicating addition of a crustal component to the mantle rocks. Amphibole hosts most of these trace elements. Clinopyroxene displays high LILE/HFSE (Pb _N /Nb _N =300–600), low Ce/Pb (1.4–2.7 in garnet-facies clinopyroxene compared with 2.6–24.5 in the spinel-facies one) and variable LILE and LREE enrichments. The coupled increase of modal amphibole, Sr and Pb, together with positive Pb–Sr and Pb–U correlations, further indicate that incompatible element influx in these samples was fluid-mediated. In the garnet-facies samples, amphibole and, interestingly, olivine have similarly high Li concentrations as clinopyroxene, leading to ^cpx/amph D _Li=0.7 and ^cpx/ol D _Li=0.7–0.8, the latter being up to ten times lower than in the spinel-facies rocks. Due to its high modal abundance, olivine is the main host of Li in the garnet–amphibole peridotites. The observed metasomatic features provide evidence for the infiltration of an aqueous fluid in the mantle wedge above a subducting slab. This fluid most likely derived from subducted crustal rocks that underwent partial melting. Successive retrograde re-equilibration during exhumation of the garnet peridotite is accompanied by garnet and clinopyroxene breakdown and amphibole formation. This process produced minor changes, such as an increase of HREE and Li in amphibole, and an increase of Li in olivine. The general trace element signature remains essentially unchanged during retrogression and further hydration, indicating that fluids with a similar composition to the one present at the garnet–amphibole peridotite formation, were responsible for increased amphibole formation. The combined evidence from the metamorphic and metasomatic evolution indicates that the peridotites experienced first corner flow in a mantle wedge, followed by subduction and finally entrapment and exhumation within a crustal slab. During their entire history the Ulten peridotites were percolated first by melts and then by aqueous fluids, which added recycled crustal components to the mantle wedge.     

俯冲隧道内不同深度的壳幔相互作用:地幔楔超镁铁质岩的镁同位素记录

在不同的俯冲深度,俯冲板片会释放出不同来源和组成的熔/流体进入俯冲隧道中,并进而影响上覆地幔楔及衍生岛弧岩浆的地球化学组成.然而,如何识别俯冲隧道中不同深度熔/流体组分的来源一直是俯冲带研究中的难点.对不同深度来源的地幔楔超基性岩进行了Mg同位素研究,发现了Mg同位素具有示踪俯冲板块熔/流体来源的能力.首先,研究了美国加州Franciscan杂岩中一套经历了多期次流体交代作用的浅部来源（< ~60 km）的变质超基性岩.这些部分蛇纹石化的地幔楔超基性岩在蛇纹石脱水形成滑石的过程中会释放轻Mg同位素进入流体,而重Mg同位素更多地残留在滑石相中;随后进一步受俯冲板块来源流体的交代形成具有高CaO和轻Mg同位素组成的透闪石化变橄榄岩,暗示流体中含有源自俯冲板片的、富集轻Mg同位素的碳酸盐,说明在弧前~60 km深度,部分含Mg碳酸盐（方解石）可以在俯冲隧道中发生溶解并迁移交代上覆地幔楔橄榄岩.对深部地幔楔来源（~160 km）的大别造山带毛屋地区超镁铁质岩体岩相学和元素地球化学研究结果证实了其交代成因.结合多相包裹体、元素地球化学以及前人估计的温-压条件,推测交代介质更接近超临界流体.锆石U-Pb年代学研究揭示,交代作用主要发生在古生代洋壳俯冲阶段（454±58 Ma）,超高压变质作用则发生在三叠纪陆壳俯冲阶段（232.8±7.9 Ma）.古生代锆石中大量的碳酸盐矿物包裹体和重O同位素特征说明古生代洋壳俯冲交代过程中有沉积碳酸盐组分加入.全岩和单矿物的Mg同位素组成均显著低于地幔值以及大别新元古代榴辉岩,说明交代的碳酸盐组分来源应为循环的沉积富Mg碳酸盐,暗示了在俯冲带深部富Mg沉积碳酸盐在超临界流体中会发生溶解迁移.由于沉积碳酸盐具有独特的、显著富集轻Mg同位素组成的特征,这种交代作用会造成地幔楔局部具有异常的Mg同位素组成,从而解释目前观察到的岛弧火山岩的Mg同位素特征.因此,Mg同位素是示踪俯冲碳酸盐与上覆地幔楔相互作用的有效工具.