Iron isotope fractionation in subduction-related high-pressure metabasites (Ile de Groix,France)

Characterisation of mass transfer during subduction is fundamental to understand the origin of compositional heterogeneities in the upper mantle. Fe isotopes were measured in high-pressure/low-temperature metabasites (blueschists, eclogites and retrograde greenschists) from the Ile de Groix (France), a Variscan high-pressure terrane, to determine if the subducted oceanic crust contributes to mantle Fe isotope heterogeneities. The metabasites have δ⁵⁶Fe values of +0.16 to +0.33‰, which are heavier than typical values of MORB and OIB, indicating that their basaltic protolith derives from a heavy-Fe mantle source. The δ⁵⁶Fe correlates well with Y/Nb and (La/Sm)_PM ratios, which commonly fractionate during magmatic processes, highlighting variations in the magmatic protolith composition. In addition, the shift of δ⁵⁶Fe by +0.06 to 0.10‰ compared to basalts may reflect hydrothermal alteration prior to subduction. The δ⁵⁶Fe decrease from blueschists (+0.19 ± 0.03 to +0.33 ± 0.01‰) to eclogites (+0.16 ± 0.02 to +0.18 ± 0.03‰) reflects small variations in the protolith composition, rather than Fe fractionation during metamorphism: newly-formed Fe-rich minerals allowed preserving bulk rock Fe compositions during metamorphic reactions and hampered any Fe isotope fractionation. Greenschists have δ⁵⁶Fe values (+0.17 ± 0.01 to +0.27 ± 0.02‰) similar to high-pressure rocks. Hence, metasomatism related to fluids derived from the subducted hydrothermally altered metabasites might only have a limited effect on mantle Fe isotope composition under subsolidus conditions, owing to the large stability of Fe-rich minerals and low mobility of Fe. Subsequent melting of the heavy-Fe metabasites at deeper levels is expected to generate mantle Fe isotope heterogeneities.     

Variation of mineral composition,fabric and oxygen fugacity from massive to foliated eclogites during exhumation of subducted ocean crust in the North Qilian suture zone,NW China

Eclogites from the North Qilian suture zone are high‐pressure low‐temperature metamorphic rocks of ocean crust protolith, and occur in both massive and foliated varieties as individual blocks of tens to hundreds of metres in size. The massive type is weakly deformed and shows granoblastic texture characterized by a coarse‐grained peak mineral assemblage of Grt¹ + Omp¹ + Ph + Rt ± Lws (or retrograde Cz). In contrast, the foliated type is strongly deformed and shows a fine‐grained retrograde mineral assemblage of Grt² + Omp² + Cz + Gln + Ph. Both total FeO and aegirine contents in omphacite, as well as X_Fe[=Fe³⁺/(Fe³⁺ + Al^VI)] in clinozoisite/epidote, increase significantly from massive to foliated eclogites. Lattice preferred orientation (LPO) of omphacite, determined by electron back‐scatter diffraction analysis, is characterized by weak and strong SL‐type fabrics for massive and foliated eclogites, respectively. Clinozoisite/epidote also developed SL‐type fabric, but different from the LPOs of omphacite in <010> and <001> axes, owing to their opposite crystallographic long and short axis definitions. The transition of deformation mechanism from dislocation creep to diffusive mass transfer (DMT) creep in omphacite and the concomitant retrograde metamorphism both are efficiently facilitated when the original coarse‐grained Omp¹ + Grt¹ + Lws assemblage is dynamically recrystallized and retrogressed into the fine‐grained Fe³⁺‐rich assemblage of Omp² + Grt² + Cz + Gln. The DMT process with concomitant anisotropic growth assisted by fluids is considered to be an important deformation mechanism for most minerals in the foliated eclogite. P–T estimates yielded 2.3–2.6 GPa and 485?510 °C for the massive eclogite and 1.8–2.2 GPa and 450?480 °C for the foliated eclogite. The significant increase in total Fe and Fe³⁺ contents in omphacite and clinozoisite/epidote from massive to foliated eclogite suggests changes in mineral compositions accompanied by an increase in oxygen fugacity during ductile deformation associated with exhumation. The LPO transition of omphacite, clinozoisite and rutile from weak SL‐type in massive eclogites to strong SL‐type in foliated eclogites is interpreted to represent the increment of shear strain during exhumation along the ‘subduction channel’.     

Age and P–T conditions of the Gridino‐type eclogite in the Belomorian Province,Russia

Although eclogites in the Belomorian Province have been regarded as Archean in age and among the oldest in the world, there are also multiple studies that have proposed a Paleoproterozoic age. Here, we present new data for the Gridino‐type eclogites, which occur as boudins and metamorphosed dykes within tonalite–trondhjemite–granodiorite gneisses. Zircon from these eclogites has core and rim structures. The cores display high Th/U ratios (0.18–0.45), negative Eu anomalies and strong enrichment in HREE, and have Neoarchean U–Pb ages of c. 2.70 Ga; they are interpreted to be magmatic in origin. Zircon cores have δ¹⁸O of 5.64–6.07‰ suggesting the possibility of crystallization from evolved mantle‐derived magmas. In contrast, the rims, which include the eclogite facies minerals omphacite and garnet, are characterized by low Th/U ratios (<0.035) and flat HREE patterns, and yield U–Pb ages of c. 1.90 Ga; they are interpreted to be metamorphic in origin. Zircon rims have elevated δ¹⁸O of 6.23–6.80‰, which was acquired during eclogite facies metamorphism. Based on petrography and phase equilibria modelling, we recognize a prograde epidote amphibolite facies mineral assemblage, the peak eclogite facies mineral assemblage and a retrograde high‐P amphibolite facies mineral assemblage. The peak metamorphic conditions of 695–755°C at >18 kbar for the Gridino‐type eclogites suggest an apparent thermal gradient of <39–42°C/kbar for the Lapland–Kola collisional orogeny.     

Low δ18O eclogites from the Kokchetav massif, northern Kazakhstan

Oxygen isotopic compositions of silicates in eclogites and whiteschists from the Kokchetav massif were analyzed by whole‐grain CO₂‐laser fluorination methods. Systematic analyses yield extremely low δ¹⁸O for eclogites, as low as ?3.9‰ for garnet; these values are comparable with those reported for the Dabie‐Sulu UHP eclogites. Oxygen isotopic compositions are heterogeneous in samples of eclogite, even on an outcrop scale. Schists have rather uniform oxygen isotope values compared to eclogites, and low δ¹⁸O is not observed. Isotope thermometry indicates that both eclogites and schists achieved high‐temperature isotopic equilibration at 500–800 °C. This implies that retrograde metamorphic recrystallization barely modified the peak‐metamorphic oxygen isotopic signatures. A possible geological environment to account for the low‐δ¹⁸O basaltic protolith is a continental rift, most likely subjected to the conditions of a cold climate. After the basalt interacted with low δ¹⁸O meteoric water, it was tectonically inserted into the surrounding sedimentary units prior to, or during subduction and UHP metamorphism.     

Oxygen isotope composition of syngenetic inclusions in diamond from the Finsch Mine,RSA

Oxygen isotope data have been obtained for silicate inclusions in diamonds, and similar associated minerals in peridotitic and eclogitic xenoliths from the Finsch kimberlite by laser-fluorination. Oxygen isotope analyses of syngenetic inclusions weighing 20–400 μg have been obtained by laser heating in the presence of ClF₃. ¹⁸O/¹⁶O ratios are determined on oxygen converted to CO₂ over hot graphite and, for samples weighing less than 750 μg (producing <12 μmoles O₂) enhanced CO production in the graphite reactor causes a systematic shift in both δ¹³C and δ¹⁸O that varies as a function of sample weight. A “pressure effect” correction procedure, based on the magnitude of δ¹³C (CO₂) depletion relative to δ¹³C (graphite), is used to obtain corrected δ¹⁸O values for inclusions with an accuracy estimated to be ±0.3‰ for samples weighing 40 μg.Syngenetic inclusions in host diamonds with similar δ¹³C values (−8.4‰ to −2.7‰) have oxygen isotope compositions that vary significantly, with a clear distinction between inclusions of peridotitic (+4.6‰ to +5.6‰) and eclogitic paragenesis (+5.7‰ to +8.0‰). The mean δ¹⁸O composition of olivine inclusions is indistinguishable from that of typical peridotitic mantle (5.25 ± 0.22‰) whereas syngenetic purple garnet inclusions possess relatively low δ¹⁸O values (5.00 ± 0.33‰). Reversed oxygen isotope fractionation between olivine and garnet in both diamond inclusions and diamondiferous peridotite xenoliths suggests that garnet preserves subtle isotopic disequilibrium related to genesis of Cr-rich garnet and/or exchange with the diamond-forming fluid. Garnet in eclogite xenoliths in kimberlite show a range of δ¹⁸O values from +2.3‰ to +7.3‰ but garnets in diamondiferous eclogites and as inclusions in diamond all have values >4.7‰.     

Magnesium Isotope Compositions of Natural Reference Materials

This study presents a chemical protocol for the separation of Mg that is particularly adapted to alkali‐rich samples (granite, soil, plants). This protocol was based on a combination of two pre‐existing methods: transition metals were first removed from the sample using an AG‐MP1 anion‐exchange resin, followed by the separation of alkalis (Na, K) and bivalent cations (Ca²⁺, Mn²⁺ and Sr²⁺) using a AG50W‐X12 cation‐exchange resin. This procedure allowed Mg recovery of ～ 10 0 ± 8%. The [Σcations]/[Mg] molar ratios in all of the final Mg fractions were lower than 0.05. The Mg isotope ratios of eleven reference materials were analysed using two different MC‐ICP‐MS instruments (Isoprobe and Nu Plasma). The long‐term reproducibility, assessed by repeated measurements of Mg standard solutions and natural reference materials, was 0.14‰. The basalt (BE‐N), limestone (Cal‐S) and seawater (BCR‐403) reference materials analysed in this study yielded δ²⁶Mg mean values of ?0.28 ± 0.08‰, ?4.37 ± 0.11‰ and ?0.89 ± 0.10‰ respectively, in agreement with published data. The two continental rocks analysed, diorite (DR‐N) and granite (GA), yielded δ²⁶Mg mean values of ?0.50 ± 0.08‰ and ?0.75 ± 0.14‰, respectively. The weathering products, soil (TILL‐1) and river water (NIST SRM 1640), gave δ²⁶Mg values of ?0.40 ± 0.07‰ and ?1.27 ± 0.14‰, respectively. We also present, for the first time, the Mg isotope composition of bulk plant and organic matter. Rye flour (BCR‐381), sea lettuce (Ulva lactuva) (BCR‐279), natural hairgrass (Deschampsia flexuosa) and lichen (BCR‐482) reference materials gave δ²⁶Mg values of ?1.10 ± 0.14‰, ?0.90 ± 0.19‰, ?0.50 ± 0.22‰ and ?1.15 ± 0.27‰ respectively. Plant δ²⁶Mg values fell within the range defined by published data for chlorophylls.     

Eclogite-facies fluid infiltration: constraints from δ18O zoning in garnet

In situ analysis reveals that eclogite-facies garnets are zoned in δ¹⁸O with lower values in the core and rims that are ~1.5 to 2.5 ‰ higher. This pattern is present in 9 out of 12 garnets analyzed by SIMS from four orogenic eclogite terranes, and correlates with an increase in the mole fraction of pyrope and Mg/Fe ratio from core to rim, indicating prograde garnet growth. At the maximum temperatures and the time-scales experienced by these garnets, calculated intragranular diffusion distances for oxygen are small (<5 μm), indicating that δ¹⁸O records primary growth zoning and not diffusive exchange. The oxygen isotope gradients are larger than could form due to temperature changes during closed-system mineral growth. Thus, gradients reflect the compositions of fluids infiltrating during prograde metamorphism. Values of δ¹⁸O in garnet cores range from ?1 to 15 ‰, likely preserving the composition of the eclogite protoliths. Two garnet cores from the Almenningen eclogite in the Western Gneiss Region, Norway, have δ¹⁸O ~?1 ‰ and are the first negative δ¹⁸O eclogites identified in the region. In contrast with orogenic eclogites, seven high δ¹⁸O garnets (>5 ‰) from two kimberlites are homogeneous in δ¹⁸O, possibly due to diffusive exchange, which is possible for prolonged periods at higher mantle temperatures. Homogeneity of δ¹⁸O in garnets outside the normal mantle range (5–6 ‰) may be common in kimberlitic samples.     

P–T evolution and episodic zircon growth in barroisite eclogites of the Lanterman Range,northern Victoria Land,Antarctica

Prograde P–T–t paths of eclogites are often ambiguous owing to high variance of mineral assemblages, large uncertainty in isotopic age determinations and/or variable degree of retrograde equilibration. We investigated these issues using the barroisite eclogites from the Lanterman Range, northern Victoria Land, Antarctica, which are relatively uncommon but free of retrogression. These eclogites revealed three stages of prograde metamorphism, defining two distinctive P–T trajectories, M_1–2 and M₃. Inclusion minerals in garnet porphyroblasts suggest that initial prograde assemblages (M₁) consist of garnet+omphacite+barroisite/Mg‐pargasite+epidote+phengite+paragonite+rutile/titanite+quartz, and subsequent M₂ assemblages of garnet+omphacite+barroisite+phengite+rutile±quartz. The inclusion‐rich inner part of garnet porphyroblasts preserves a bell‐shaped Mn profile of the M₁, whereas the inclusion‐poor outer part (M₂) is typified by the outward decrease in Ca/Mg and X_Fe (=Fe²⁺/(Fe²⁺+Mg)) values. A pseudosection modelling employing fractionated bulk‐rock composition suggests that the eclogites have initially evolved from ~15 to 20 kbar and 520–570°C (M₁) to ~22–25 kbar and 630–650°C (M₂). The latter is in accordance with P–T conditions estimated from two independent geothermobarometers: the garnet–clinopyroxene–phengite (~25 ± 3 kbar and 660 ± 100°C) and Zr‐in‐rutile (~650–700°C at 22–27 kbar). The second segment (M_3A–B) of prograde P–T path is recorded in the grossular‐rich overgrowth rim of garnet. Apart from disequilibrium growth of the M_3A garnet, ubiquitous overgrowth of the M_3B garnet permits us to estimate the P–T conditions at ~26 ± 3 kbar and 720 ± 80°C. The cathodoluminescence (CL) imaging of zircon grains separated from a barroisite eclogite revealed three distinct zones with bright rim, dark mantle and moderately dark core. Eclogitic phases such as garnet, omphacite, epidote and rutile are present as fine‐grained inclusions in the mantle and rim of zircon, in contrast to their absence in the core. The sensitive high‐resolution ion microprobe U–Pb dating on metamorphic mantle domains and neoblasts yielded a weighted mean ²⁰⁶Pb/²³⁸U age of 515 ± 4 Ma (tσ), representing the time of the M₂ stage. On the other hand, overgrowth rims as well as bright‐CL neoblasts of zircon were dated at 498 ± 11 Ma (tσ), corresponding to the M₃. Average burial rates estimated from the M₂ and M₃ ages are too low (<2 mm/year) for cold subduction regime (~5–10°C/km), suggesting that an exhumation stage intervened between two prograde segments of P–T path. Thus, the P–T–t evolution of barroisite eclogites is typified by two discrete episodes with an c. 15 Ma gap during the middle Cambrian subduction of the Antarctic Ross Orogeny.     

Iron isotope compositions of carbonatites record melt generation, crystallization, and late-stage volatile-transport processes

Carbonatites define the largest range in Fe isotope compositions yet measured for igneous rocks, recording significant isotopic fractionations between carbonate, oxide, and silicate minerals during generation in the mantle and subsequent differentiation. In contrast to the relatively restricted range in δ⁵⁶Fe values for mantle-derived basaltic magmas (δ⁵⁶Fe?=?0.0?±?0.1‰), calcite from carbonatites have δ⁵⁶Fe values between ?1.0 and +0.8‰, similar to the range defined by whole-rock samples of carbonatites. Based on expected carbonate-silicate fractionation factors at igneous or mantle temperatures, carbonatite magmas that have modestly negative δ⁵⁶Fe values of ~ ?0.3‰ or lower can be explained by equilibrium with a silicate mantle. More negative δ⁵⁶Fe values were probably produced by differentiation processes, including crystal fractionation and liquid immiscibility. Positive δ⁵⁶Fe values for carbonatites are, however, unexpected, and such values seem to likely reflect interaction between low-Fe carbonates and Fe³⁺-rich fluids at igneous or near-igneous temperatures; the expected δ⁵⁶Fe values for Fe²⁺-bearing fluids are too low to produced the observed positive δ⁵⁶Fe values of some carbonatites, indicating that Fe isotopes may be a valuable tracer of redox conditions in carbonatite complexes. Further evidence for fluid-rock or fluid-magma interactions comes from the common occurrence of Fe isotope disequilibrium among carbonate, oxide, silicate, and sulfide minerals in the majority of the carbonatites studied. The common occurrence of Fe isotope disequilibrium among minerals in carbonatites may also indicate mixing of phenocyrsts from distinct magmas. Expulsion of Fe³⁺-rich brines into metasomatic aureols that surround carbonatite complexes are expected to produce high-δ⁵⁶Fe fenites, but this has yet to be tested.     

Transformation of garnet epidote amphibolite to eclogite, western Dabie Mountains, China

Omphacite and garnet coronas around amphibole occur in amphibolites in the Hong'an area, western Dabie Mountains, China. These amphibolites consist of an epidote–amphibolite facies assemblage of amphibole, garnet, albite, clinozoisite, paragonite, ilmenite and quartz, which is incompletely overprinted by an eclogite facies assemblage of garnet, omphacite and rutile. Coronas around amphibole can be divided into three types: an omphacite corona; a garnet–omphacite–rutile corona; and, a garnet–omphacite corona with less rutile. Chemographic analysis for local reaction domains in combination with petrographical observations show that reactions Amp + Ab + Pg = Omp +Czo + Qtz + H₂O, and Amp + Ab = Omp ± Czo + Qtz + H₂O may lead to the development of omphacite coronas. The garnet–omphacite–rutile corona was formed from the reaction Amp + Ab + Czo + Ilm ± Qtz = Omp + Grt + Rt + H₂O. In garnet–omphacite coronas, the garnet corona grew during an early stage of epidote amphibolite facies metamorphism, whereas omphacite probably formed by the reactions forming the omphacite corona during the eclogite facies stage. It is estimated that these reactions occurred at 0.8–1.4 GPa and 480–610 °C using the garnet–clinopyroxene thermometer and omphacite barometer in the presence of albite.     

Phase equilibria and metamorphic evolution of glaucophane‐bearing UHP eclogites from the Western Dabieshan Terrane,Central China

Glaucophane‐bearing ultrahigh pressure (UHP) eclogites from the western Dabieshan terrane consist of garnet, omphacite, glaucophane, kyanite, epidote, phengite, quartz/coesite and rutile with or without talc and paragonite. Some garnet porphyroblasts exhibit a core–mantle zoning profile with slight increase in pyrope content and minor or slight decrease in grossular and a mantle–rim zoning profile characterized by a pronounced increase in pyrope and rapid decrease in grossular. Omphacite is usually zoned with a core–rim decrease in j(o) [=Na/(Ca + Na)]. Glaucophane occurs as porphyroblasts in some samples and contains inclusions of garnet, omphacite and epidote. Pseudosections calculated in the NCKMnFMASHO system for five representative samples, combined with petrographic observations suggest that the UHP eclogites record four stages of metamorphism. (i) The prograde stage, on the basis of modelling of garnet zoning and inclusions in garnet, involves P–T vectors dominated by heating with a slight increase in pressure, suggesting an early slow subduction process, and P–T vectors dominated by a pronounced increase in pressure and slight heating, pointing to a late fast subduction process. The prograde metamorphism is predominated by dehydration of glaucophane and, to a lesser extent, chlorite, epidote and paragonite, releasing ～27 wt% water that was bound in the hydrous minerals. (ii) The peak stage is represented by garnet rim compositions with maximum pyrope and minimum grossular contents, and P–T conditions of 28.2–31.8 kbar and 605–613 °C, with the modelled peak‐stage mineral assemblage mostly involving garnet + omphacite + lawsonite + talc + phengite + coesite ± glaucophane ± kyanite. (iii) The early decompression stage is characterized by dehydration of lawsonite, releasing ～70–90 wt% water bound in the peak mineral assemblages, which results in the growth of glaucophane, j(o) decrease in omphacite and formation of epidote. And, (iv) The late retrograde stage is characterized by the mineral assemblage of hornblendic amphibole + epidote + albite/oligoclase + quartz developed in the margins or strongly foliated domains of eclogite blocks due to fluid infiltration at P–T conditions of 5–10 kbar and 500–580 °C. The proposed metamorphic stages for the UHP eclogites are consistent with the petrological observations, but considerably different from those presented in the previous studies.     

Petrochemistry, oxygen isotopes and U-Pb SHRIMP geochronology of mafic–ultramafic bodies from the Sulu UHP terrane, China

Two Rongcheng eclogite‐bearing peridotite bodies (Chijiadian and Macaokuang) occur as lenses within the country rock gneiss of the northern Sulu terrane. The Chijiadian ultramafic body consists of garnet lherzolite, whereas the Macaokuang body is mainly meta‐dunite. Both ultramafics are characterized by high MgO contents, low fertile element concentrations and total REE contents, which suggests that they were derived from depleted, residual mantle. High FeO contents, an LREE‐enriched pattern and trace‐element contents indicate that the bulk‐rock compositions of these ultramafic rocks were modified by metasomatism. Oxygen‐isotope compositions of analysed garnet, olivine, clinopyroxene and orthopyroxene from these two ultramafic bodies are between +5.2‰ and +6.2‰ (δ¹⁸O), in the range of typical mantle values (+5.1 to +6.6‰). The eclogite enclosed within the Chijiadian lherzolite shows an LREE‐enriched pattern and was formed by melts derived from variable degrees (0.005–0.05) of partial melting of peridotite. It has higher δ¹⁸O values (+7.6‰ for garnet and +7.7‰ for omphacite) than those of lherzolite. Small O‐isotope fractionations (ΔCpx‐Ol: 0.4‰, ΔCpx‐Grt: 0.1‰, ΔGrt‐Ol: 0.3–0.4‰) in both eclogite and ultramafic rocks suggest isotopic equilibrium at high temperature. The P–T estimates suggest that these rocks experienced subduction‐zone ultrahigh‐pressure (UHP) metamorphism at ～700–800 °C, 5 GPa, with a low geothermal gradient. Zircon from the Macaokuang eclogite contains inclusions of garnet and diopside. The 225 ± 2 Ma U/Pb age obtained from these zircon may date either the prograde conditions just before peak metamorphism or the UHP metamorphic event, and therefore constrains the timing of subduction‐related UHP metamorphism for the Rongcheng mafic–ultramafic bodies.     

大别山北部榴辉岩的Sm-Nd年龄测定及其对麻粒相退变质时间的制约

报道了大别山北部三个榴辉岩样品的矿物 Sm- Nd等时线年龄，它们分别为 (210± 6) Ma或 (214± 6) Ma、 (208± 38) Ma和 (208± 4) Ma。氧同位素研究表明，这些样品中的石榴子石与绿辉石之间处于氧同位素平衡状态，因此，该 Sm- Nd等时线定年结果可靠。本区榴辉岩的高压麻粒岩相退变质阶段的冷却年龄为 210 Ma左右；榴辉岩的钕同位素初始比ε Nd(t)(两个样品一个为－ 10左右，另一个为－ 2)基本上表现为陆壳岩石特征，可能类似于南部超高压带中的榴辉岩，为印支期扬子陆壳俯冲变质成因。它们的全岩δ 18O值较低，为＋ 2.4‰～＋ 3.6‰，可能指示其原岩同大别山南部超高压带中榴辉岩一样，在板块俯冲之前，经受过高温地表水热液蚀变。年代学结果表明，大别山北部榴辉岩在 230～ 210 Ma期间经历的是一等温或升温过程，这与大别山南部含柯石英榴辉岩在这一时期的快速冷却过程形成强烈对比，这对理解俯冲陆壳中不同构造岩片折返过程的差异有重要意义。     

Petrological sStudies of Jilang Eclogite and Constraints on the Subduction and Exhumation Processes of the Paleo‐Tethys Oceanic Crust

The (ultra‐) high pressure eclogites from Sumdo area, recorded the subduction and exhumation process of the Paleo‐Tethys oceanic crust. Previous studies showed that there are significant differences in temperature and pressure conditions of the eclogites in four regions, e.g. Sumdo, Xindaduo, Bailang and Jilang. The cause of this differences remains unclear. Studying the peak metamorphic conditions and P‐T path of Sumdo eclogite is of great significance to reveal the subduction and exhumation mechanism of Paleo‐Tethys ocean. In this paper, we choose the Jilang eclogite as an example, which has a mineral assemblage of garnet, omphacite, phengite, hornblende, rutile, epidote, quartz and symplectit (diopside + amphibole + plagioclase), and minor biotite. Garnet has a “dirty” core with abundant mineral inclusions and a “clear” rim with less mineral inclusions, showing typical growth zoning. From the core to the rim, Prp content in garnet increasing while Grs content decreasing. P‐T pseudosection calculated with Domino constrained peak P‐T conditions of Jilang eclogite as 563°C, 2.4 GPa. Combined with petrographical observation, four stages of metamorphism have been recognized: (1) early stage prograde metamorphism represent by the core of garnet and mineral inclusions therein; (2) peak metamorphism represent by the rim of garnet, omphacite, phengite, glaucophane, rutile and quartz; (3) first stage of retrograde metamorphism characterized by decomposition of lawsonite to zoisite; (4) second stage of retrograde metamorphism characterized by symplectites surrounding omphacite and cornona rimmed garnet. Jilang eclogite shows a clockwise P‐T path, and near isothermal decompression during exhumation. It differs from eclogites in other area, which are hosted by garnet‐bearing mica schists or serpentinites. Jilang eclogites are enclosed in metamorphic quartzites, with relatively low P‐T conditions. We infer that the Jilang eclogite was derived from the shallow part of the subduction zone, and was exhumated by low density materials in the subduction channel.     

Iron isotope fractionation during biogeochemical cycle: Information from suspended particulate matter (SPM) in Aha Lake and its tributaries,Guizhou, China

Iron isotope compositions of suspended particulate matters (SPM) collected from the Aha Lake, an artificial lake in the karst area of Yun-Gui Plateau, and its tributaries in summer and winter were investigated for our understanding of the behavior of Fe isotopes during iron biogeochemical cycling in lake. δ⁵⁶Fe values of SPM display statistically negative shift relative to IRMM-014. Samples from the lake display a range from ?1.36‰ to ?0.10‰ in summer and from ?0.30‰ to ?0.07‰ in winter, while river samples vary from ?0.88‰ to 0.07‰ in summer and from ?0.35‰ to ?0.03‰ in winter. The average iron isotope composition of aerosol samples is + 0.10‰, which is very similar to that of igneous rocks (0.09‰). The SPM in most rivers and water column showed seasonal variation in δ⁵⁶Fe value: the δ⁵⁶Fe values of SPM in summer were lower than in winter. The seasonal variation in δ⁵⁶Fe value of the riverine SPM should be ascribed to the change in source of particulate Fe and geochemical process in the watershed: More particulate Fe was leached from soil and produced by weathering of pyrite widely distributed in coal-containing strata. It is suggested that both allochthonous inputs and the redox iron cycling control the variations of δ⁵⁶Fe values for SPM in lake.During summer stratification, an Fe cycle named “ferrous wheel” is established near the redox boundary where the upwardly diffusing Fe(II) is oxidized and the reactive Fe oxides formed will continuously sink back into the reduction zone to complete the cycle. The δ⁵⁶Fe values for SPM reach the minima, ?0.88‰ for DB station and ?1.36‰ for LJK station, just near the redox boundary as a result of the Fe cycling, where a rough 45% to 76% of Fe in these particles was produced by the repetitive cycle. Due to random transportation and diffusion, δ⁵⁶Fe values of the particles near the redox zone distributed into approximately a Gaussian shape. The good negative correlation existed between δ⁵⁶Fe values and Fe/Al ratios for DB station, suggesting that they together can be used as good indicators of the redox-driven Fe transformations.     

High‐Precision Iron Isotope Analysis of Geological Reference Materials by High‐Resolution MC‐ICP‐MS

We report high‐precision iron isotopic data for twenty‐two commercially available geological reference materials, including silicates, carbonatite, shale, carbonate and clay. Accuracy was checked by analyses of synthetic solutions with known Fe isotopic compositions but different matrices ranging from felsic to ultramafic igneous rocks, high Ca and low Fe limestone, to samples enriched in transition group elements (e.g., Cu, Co and Ni). Analyses over a 2‐year period of these synthetic samples and pure Fe solutions that were processed through the whole chemistry procedure yielded an average δ⁵⁶Fe value of ?0.001 ± 0.025‰ (2s, n = 74), identical to the expected true value of 0. This demonstrates a long‐term reproducibility and accuracy of < 0.03‰ for determination of ⁵⁶Fe/⁵⁴Fe ratios. Reproducibility and accuracy were further confirmed by replicate measurements of the twenty‐two RMs, which yielded results that perfectly match the mean values of published data within quoted uncertainties. New recommended values and associated uncertainties are presented for interlaboratory calibration in the future.     

Quartz and orthopyroxene exsolution lamellae in clinopyroxene and the metamorphic P–T path of Belomorian eclogites

The Shirokaya Salma eclogite‐bearing complex is located in the Archean–Palaeoproterozoic Belomorian Province (Russia). Its eclogites and eclogitic rocks show multiple clinopyroxene breakdown textures, characterized by quartz–amphibole, orthopyroxene and plagioclase lamellae. Representative samples, a fresh eclogite, two partly retrograded eclogites, and a strongly retrograded eclogitic rock, were collected for this study. Two distinct mineral assemblages—(1) omphacite+garnet+quartz+rutile±amphibole and (2) clinopyroxene+garnet+amphibole+plagioclase+quartz+rutile+ilmenite±orthopyroxene—are described. Based on phase equilibria modelling, these assemblages correspond to the eclogite and granulite facies metamorphism that occurred at 16–18 kbar, 750–800°C and 11–15 kbar, 820–850°C, respectively. The quartz–amphibole lamellae in clinopyroxene formed during retrogression with water ingress, but do not imply UHP metamorphism. The superfine orthopyroxene lamellae developed due to breakdown of an antecedent clinopyroxene (omphacite) during retrogression that was triggered by decompression from the peak of metamorphism, while the coarser orthopyroxene grains and rods formed afterwards. The P–T path reconstructed for the Shirokaya Salma eclogites is comparable to that of the adjacent 1.9 Ga Uzkaya Salma eclogite (Belomorian Province), and those of several other Palaeoproterozoic high‐grade metamorphic terranes worldwide, facts allowing us to debate the exact timing of eclogite facies metamorphism in the Belomorian Province.     

Inter-mineral Fe isotope variations in mantle-derived rocks and implications for the Fe geochemical cycle

Iron isotope and major- and minor-element compositions of coexisting olivine, clinopyroxene, and orthopyroxene from eight spinel peridotite mantle xenoliths; olivine, magnetite, amphibole, and biotite from four andesitic volcanic rocks; and garnet and clinopyroxene from seven garnet peridotite and eclogites have been measured to evaluate if inter-mineral Fe isotope fractionation occurs in high-temperature igneous and metamorphic minerals and if isotopic fractionation is related to equilibrium Fe isotope partitioning or a result of open-system behavior. There is no measurable fractionation between silicate minerals and magnetite in andesitic volcanic rocks, nor between olivine and orthopyroxene in spinel peridotite mantle xenoliths. There are some inter-mineral differences (up to 0.2‰ in ⁵⁶Fe/⁵⁴Fe) in the Fe isotope composition of coexisting olivine and clinopyroxene in spinel peridotites. The Fe isotope fractionation observed between clinopyroxene and olivine appears to be a result of open-system behavior based on a positive correlation between the Δ⁵⁶Fe_{clinopyroxene-olivine} fractionation and the δ⁵⁶Fe value of clinopyroxene and olivine. There is also a significant difference in the isotopic compositions of garnet and clinopyroxene in garnet peridotites and eclogites, where the average Δ⁵⁶Fe_{clinopyroxene-garnet} fractionation is +0.32 ± 0.07‰ for six of the seven samples. The one sample that has a lower Δ⁵⁶Fe_{clinopyroxene-garnet} fractionation of 0.08‰ has a low Ca content in garnet, which may reflect some crystal chemical control on Fe isotope fractionation. The Fe isotope variability in mantle-derived minerals is interpreted to reflect subduction of isotopically variable oceanic crust, followed by transport through metasomatic fluids. Isotopic variability in the mantle might also occur during crystal fractionation of basaltic magmas within the mantle if garnet is a liquidus phase. The isotopic variations in the mantle are apparently homogenized during melting processes, producing homogenous Fe isotope compositions during crust formation.     

Oscillatory zoning in garnet from the Willsboro Wollastonite Skarn, Adirondack Mts, New York: a record of shallow hydrothermal processes preserved in a granulite facies terrane

Oscillatory zoning in low δ¹⁸O skarn garnet from the Willsboro wollastonite deposit, NE Adirondack Mts, NY, USA, preserves a record of the temporal evolution of mixing hydrothermal fluids from different sources. Garnet with oscillatory zoning are large (1–3 cm diameter) euhedral crystals that grew in formerly fluid filled cavities. They contain millimetre‐scale oscillatory zoning of varying grossular–andradite composition (X_Adr = 0.13–0.36). The δ¹⁸O values of the garnet zones vary from 0.80 to 6.26‰ VSMOW and correlate with X_Adr. The shape, pattern and number of garnet zones varies from crystal to crystal, as does the magnitude of the correlated chemistry changes, suggesting fluid system variability, temporal and/or spatial, over the time of garnet growth. The zones of correlated Fe content and δ¹⁸O indicate that a high Fe³⁺/Al, high δ¹⁸O fluid mixed with a lower Fe³⁺/Al and δ¹⁸O fluid. The high δ¹⁸O, Fe enriched fluids were likely magmatic fluids expelled from crystallizing anorthosite. The low δ¹⁸O fluids were meteoric in origin. These are the first skarn garnet with oscillatory zoning reported from granulite facies rocks. Geochronologic, stable isotope, petrologic and field evidence indicates that the Adirondacks are a polymetamorphic terrane, where localized contact metamorphism around shallowly intruded anorthosite was followed by a regional granulite facies overprint. The growth of these garnet in equilibrium with meteoric and magmatic fluids indicates an origin in the shallow contact aureole of the anorthosite prior to regional metamorphism. The zoning was preserved due to the slow diffusion of oxygen and cations in the large garnet and protection from deformation and recrystallization in zones of low strain in thick, rigid, garnetite layers. The garnet provide new information about the hydrothermal system adjacent to the shallowly intruded massif anorthosite that predates regional metamorphism in this geologically complex, polymetamorphic terrane.     

REE concentrations of garnet and omphacite in eclogites from the Dabie Mountain, central China

Distributions of the rare-earth elements (REE) in omphacite and garnet and REE behaviors during metamorphic processes were discussed. The REE concentrations of garnet and omphacite in six eclogite samples from the Dabie Mountain, central China, were measured by inductively coupled plasma-mass spectrometry (ICP-MS). The correlation of δEu ratios between garnet and omphacite indicated that chemical equilibrium of REE distribution between garnet and omphacite could be achieved during ultra-high pressure (UHP) metamorphism. Most of the partition coefficients (Kd=CiOmp/CiGrt) of light rare-earth elements (LREE) are higher than 1. However the partition coefficients of heavy rare-earth elements (HREE) are lower than 1. This indicated that the LREE inclined to occupy site M2 in omphacite, but the HREEs tended to occupy eightfold coordinated site in garnet during the eclogite formation. The REE geochemistry of the eclogites indicated that LREE could be partially lost during the prograde metamorphic process of protolith, but be introduced into the rocks during the symplectite formation. LREE are more active than HREE during the UHP metamorphism. The results are favorable to highlighting the REE behavior and evolution of UHP metamorphic rocks.