A cold Early Palaeozoic subduction zone in the North Qilian Mountains, NW China: petrological and U-Pb geochronological constraints

The north Qilian high‐pressure (HP)/low‐temperature (LT) metamorphic belt is composed mainly of blueschists, eclogites and greenschist facies rocks. It formed within an Early Palaeozoic accretionary wedge associated with the subduction of the oceanic crust and is considered to be one of the best preserved HP/LT metamorphic belts in China. Here we report new lawsonite‐bearing eclogites and eclogitic rocks enclosed within epidote blueschists in the North Qilian Mountains. Five samples contain unaltered lawsonite coexisting with omphacite and phengite as inclusions in garnet, indicating eclogite facies garnet growth and lawsonite pseudomorphs were observed in garnet from an additional 11 eclogites and eclogitic rocks. Peak pressure conditions estimated from lawsonite omphacite‐phengite‐garnet assemblages were 2.1–2.4 GPa at temperatures of 420–510 °C, in or near the stability field of lawsonite eclogite, and implying formation under an apparent geothermal gradient of 6–8 °C km^?1, consistent with metamorphism in a cold subduction zone. SHRIMP U‐Pb dating of zircon from two lawsonite‐bearing eclogitic metabasites yields ages of 489 ± 7 Ma and 477 ± 16 Ma, respectively. CL images and mineral inclusions in zircon grains indicate that these ages reflect an eclogite facies metamorphism. An age of 502 ± 16 Ma is recorded in igneous cores of zircon grains from one lawsonite pseudomorph‐bearing eclogite, which is in agreement with the formation age of Early Ordovician for some ophiolite sequences in the North Qilian Mountains, and may be associated with a period of oceanic crust formation. The petrological and chronological data demonstrate the existence of a cold Early Palaeozoic subduction zone in the North Qilian Mountains.     

Geology, Fluid Inclusion and Isotopic Study of the Neoproterozoic Suoi Thau Copper Deposit, Northwest Vietnam

The Sin Quyen-Lung Po district is an important Cu metallogenic province in Vietnam, but there are few temporal and genetic constraints on deposits from this belt. Suoi Thau is one of the representative Cu deposits associated with granitic intrusion. The deposit consists of ore bodies in altered granite or along the contact zone between granite and Proterozoic meta-sedimentary rocks. The Cu-bearing intrusion is sub-alkaline I-type granite. It has a zircon U-Pb age of ~776 Ma, and has subduction-related geochemical signatures. Geochemical analysis reveals that the intrusion may be formed by melting of mafic lower crust in a subduction regime. Three stages of alteration and mineralization are identified in the Suoi Thau deposit, i.e., potassic alteration; silicification and Cu mineralization; and phyllic alteration. Two-phase aqueous fluid inclusions in quartz from silicification stage show wide ranges of homogenization temperatures(140–383℃) and salinities(4.18wt%–19.13wt%). The high temperature and high salinity natures of some inclusions are consistent with a magmatic derivation of the fluids, which is also supported by the H-O-S isotopes. Fluids in quartz have δD values of –41.9‰ to –68.8‰. The fluids in isotopic equilibrium with quartz have δ~(18)O values ranging from 7.9‰ to 9.2‰. These values are just plotted in the compositional field of magmatichydrothermal fluids in the δD_(water) versus δ~(18)O_(water) diagram. Sulfide minerals have relatively uniform δ~(34)S values from 1.84‰ to 3.57‰, which is supportive of a magmatic derivation of sulfur. The fluid inclusions with relatively low temperatures and salinities most probably represent variably cooled magmatic-hydrothermal fluids. The magmatic derivation of fluids and the close spatial relationship between Cu ore bodies and intrusion suggest that the Cu mineralization most likely had a genetic association with granite. The Suoi Thau deposit, together with other deposits in the region, may define a Neoproterozoic subduction-related ore-forming belt.     

Transformation of Fe–Ti gabbro to coronite, eclogite and amphibolite in the Baie du Nord segment, Manicouagan Imbricate Zone, eastern Grenville Province

Fe–Ti gabbros from the Baie du Nord Segment of the Manicouagan Imbricate Zone, metamorphosed under high P–T conditions during the Grenvillian orogeny, have been the focus of a detailed micropetrological study. Textures and mineral chemistry suggest that the mineral assemblages represent progressive stages of metamorphic transformation resulting in the formation of coronas, pseudomorphs after igneous phases (transitional) and true, granoblastic eclogites. The transitional and eclogitic samples also have coronas which are developed locally around igneous xenocrysts of plagioclase and olivine. The deformed margins of coronitic Fe–Ti gabbros are transformed to amphibolite and contain clinopyroxene-bearing leucosomes with garnet poikiloblasts that are indicative of high-P–T dehydration melting. Interpretation of garnet zoning and thermobarometry suggest that the highest P–T conditions are recorded by coronas around xenocrysts (c. 720–800 °C at 14–17 kbar) and garnet–clinopyroxene cores in granoblastic assemblages (c. 740–820 °C at 13–17 kbar) in the eclogitic samples. Re-equilibration during the early stages of exhumation at high-T conditions (>700 °C) affected all samples, and is evidenced by the widespread development of pargasite-bearing plagioclase collars in the coronitic and transitional metagabbros and by widespread re-equilibration of the eclogites giving lower P–T estimates at grain boundaries. However, the difference in calculated pressure conditions between coronite and eclogite samples is consistent with increasing pressure (depth) from the coronites (11–13 kbar) to the eclogites (13–17 kbar). The P–T conditions recorded by these rocks define a metamorphic field gradient which suggests high heat flow through the lower crust during the Grenvillian orogeny.     

Hydrothermal Alteration and Mineralization of Middle Jurassic Dexing Porphyry Cu-Mo Deposit, Southeast China

The Dexing deposit is located in a NE‐trending magmatic belt along the southeastern margin of the Yangtze Craton. It is the largest porphyry copper deposit in China, consisting of three porphyry copper orebodies of Zhushahong, Tongchang and Fujiawu from northwest to southeast. It contains 1168 Mt of ores with 0.5% Cu and 0.01% Mo. The Dexing deposit is hosted by Middle Jurassic granodiorite porphyries and pelitic schist of Proterozoic age. The Tongchang granodiorite porphyry has a medium K cal‐alkaline series, with medium K₂O content (1.94–2.07 wt%), and low K₂O/(Na₂O + K₂O) (0.33–0.84) ratios. They have high large‐ion lithophile elements, high light rare‐earth elements, and low high‐field‐strength elements. The hydrothermal alteration at Tongchang is divided into four alteration mineral assemblages and related vein systems. They are early K‐feldspar alteration and A vein; transitional (chlorite + illite) alteration and B vein; late phyllic (quartz + muscovite) alteration and D vein; and latest carbonate, sulfate and oxide alteration and hematite veins. Primary fluid inclusions in quartz from phyllic alteration assemblage include liquid‐rich (type 1), vapor‐rich (type 2) and halite‐bearing ones (type 3). These provide trapping pressures of 20–400 ´ 10⁵ Pa of fluids responsible for the formation of D veins. Igneous biotite from least altered granochiorite porphyry and hydrothermal muscovite in mineralized granodiorite porphyry possess δ¹⁸O and δD values of 4.6‰ and ?87‰ for biotite and 7.1–8.9‰, ?71 to ?73‰ for muscovite. Stable isotopic composition of the hydrothermal water suggests a magmatic origin. The carbon and oxygen isotope for hydrothermal calcite are ?4.8 to ?6.2‰ and 6.8–18.8‰, respectively. The δ³⁴S of pyrite in quartz vein ranges from ?0.1 to 3‰, whereas δ³⁴S for chalcopyrite in calcite veins ranges from 4 to 5‰. These are similar to the results of previous studies, and suggest a magmatic origin for sulfur. Results from alteration assemblages and vein system observation, as well as geochemical, fluid inclusion, stable isotope studies indicate that the involvement of hydrothermal fluids exsolved from a crystallizing melt are responsible for the formation of Tongchang porphyry Cu‐Mo orebodies in Dexing porphyry deposit.     

Serpentinites of the Zermatt-Saas ophiolite complex and their texture evolution

The Zermatt‐Saas serpentinite complex is an integral member of the Penninic ophiolites of the Central Alps and represents the mantle part of the oceanic lithosphere of the Tethys. Metamorphic textures of the serpentinite preserve the complex mineralogical evolution from primary abyssal peridotite through ocean‐floor hydration, subduction‐related high‐pressure overprint, meso‐Alpine greenschist facies metamorphism, and late‐stage hydrothermal alteration. The early ocean floor hydration of the spinel harzburgites is still visible in relic pseudomorphic bastite and locally preserved mesh textures. The primary serpentine minerals were completely replaced by antigorite. The stable assemblage in subduction‐related mylonitic serpentinites is antigorite–olivine–magnetite ± diopside. The mid‐Tertiary greenschist facies overprint is characterized by minor antigorite recrystallization. Textural and mineral composition data of this study prove that the hydrated mineral assemblages remained stable during high‐pressure metamorphism of up to 2.5 GPa and 650 °C. The Zermatt‐Saas serpentinites thus provide a well documented example for the lack of dehydration of a mantle fragment during subduction to 75 km depth.     

Fabric development in a fragment of tethyan oceanic lithosphere from the piemonte ophiolite nappe of the western Alps, Valtournanche, Italy

South of the Matterhorn the Valtournanche cuts through Alpine serpentinites, metagabbros, meta-pillowbasalts and metasediments—dismembered remnants of the Jurassic Tethyan oceanic crust, reassembled in the Piemonte ophiolite nappe. This study deals with a serpentinized ultramafic to mafic layered complex stemming from a spreading ridge environment. Cumulus fabrics of various kinds can be read through antigorite pseudomorphs, still allowing the detailed reconstruction of deep oceanic crust. Relics of igneous and metamorphic olivine prove crustal conditions during deformation. Fracturing of cumulus olivine was succeeded by plastic flow that activated low-temperature slip systems. Concomitant recrystallization produced metaperidotite only along shear zones, which are ascribed to subduction of the oceanic crust. At the turning point from subduction to obduction a static metamorphic event resulted in recovery and grain growth of recrystallized olivine. Afterwards serpentinization of the complex took place still under static conditions. Deformation of the serpentinite led to a sequence of four phases, involving non-penetrative cleavage formation, stretching and folding. This deformation is structurally related to obduction of the complex although partly accompanied by subduction zone metamorphism. Final movements of the ophiolites were due to cataclastic thrusting forming subnappe boundaries.     

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‰.     

Geochemistry of Neoproterozoic mafic intrusions in the Panzhihua district (Sichuan Province,SW China): Implications for subduction-related metasomatism in the upper mantle

Metasomatism above subduction zones is an important process that produces heterogeneous mantle and thus a diversity of igneous rocks. In the Panzhihua district, on the western margin of the Yangtze Block (SW China), two Neoproterozoic mafic intrusions, one olivine gabbro and one hornblende gabbro, have identical ages of 746 ± 10 and 738 ± 23 Ma. Both of the gabbros are tholeiitic in composition and have arc-like geochemical compositions. The hornblende gabbros have K₂O concentrations ranging from 0.70 to 1.69 wt.% and show enrichment of Rb, Ba, U, Th and Pb and depletion of Nb,Ta and Ti. They have variable ⁸⁷Sr/⁸⁶Sr ratios (0.7045–0.7070) with constant ɛNd(t) values (−0.12 to −0.93). The olivine gabbros have relatively low K₂O (0.19–0.43 wt.%), are depleted in Rb and Th relative to Ba and U, and have obvious negative Nb–Ta and Zr–Hf anomalies on primitive mantle-normalized trace element diagrams. Their ɛNd(t) values range from −0.64 to −1.73 and initial ⁸⁷Sr/⁸⁶Sr ratios from 0.7070 to 0.7075. Both types of gabbro experienced fractional crystallization of clinopyroxene, plagioclase, amphibole and minor Fe–Ti oxide. The parental magmas of the olivine and hornblende gabbros were formed by about 20% partial melting of garnet–spinel lherzolite and spinel lherzolite, respectively. According to trace elemental ratios, the hornblende gabbros were probably derived from a source strongly modified by subducted slab fluids, whereas the olivine gabbros came from a mantle source modified by subducted slab melts. The close association of the olivine gabbros and hornblende gabbros suggests that a steep subduction zone existed along the western margin of the Yangtze Block during Neoproterozoic time. Thus, the giant Neoproterozoic magmatic event in South China was subduction-related.     

Low δO in the Icelandic mantle and its origins: Evidence from Reykjanes Ridge and Icelandic lavas

Oxygen isotope ratios have been determined using laser fluorination techniques on olivine and plagioclase phenocrysts and bulk glasses from the Reykjanes Ridge and Iceland. δ¹⁸O in Reykjanes Ridge olivines shows hyperbolic correlations with Sr-Nd-Pb isotope ratios that terminate at δ¹⁸O = +4.5‰ at compositions almost identical to those of moderately enriched lavas on the Reykjanes Peninsula, Iceland. Samples with low δ¹⁸O show no indication of contamination by oceanic crust such as elevated Cl/K, and are too deep to have been influenced by meteoric water hydrothermal systems. They cannot represent Icelandic melts contaminated in the crust and transferred laterally along the ridge since fissure systems are strongly oblique to the ridge axis. It follows that Icelandic mantle advected along the ridge has low δ¹⁸O. The hyperbolic ¹⁴³Nd/¹⁴⁴Nd-δ¹⁸O correlation appears to be more strongly curved than magma mixing trajectories and suggests that melt fractions are ∼4.5× greater and source Nd contents ∼9× greater in the mantle at 63°N compared with that at 60°N. Primitive lavas from the Reykjanes Peninsula show linear correlations between olivine δ¹⁸O and ¹⁴³Nd/¹⁴⁴Nd or ²⁰⁶Pb/²⁰⁴Pb, extending to δ¹⁸O of +4.3‰ at ¹⁴³Nd/¹⁴⁴Nd close to the lowest ratios observed in Icelandic magmas. These correlations cannot be produced by melt mixing or crustal contamination because these would yield strongly hyperbolic trajectories. Lower δ¹⁸O seen in more evolved samples from the Eastern Rift Zone may reflect crustal contamination, though there is some evidence of a mantle source with lower δ¹⁸O in eastern Iceland. It is very difficult to explain the low δ¹⁸O of enriched Icelandic mantle sources on current understanding of mantle and crustal oxygen isotopes. There is no obvious reason why such low-δ¹⁸O sources should not contribute to other ocean islands. No oceanic crustal lithologies exist that could produce the low-δ¹⁸O enriched sources by recycling into the mantle, and there is no evidence for changes in δ¹⁸O of ophiolite suites with time, nor of changes during high-P metamorphism. Low δ¹⁸O appears to be associated with high ³He/⁴He, and we speculate that this signature may be characteristic of the host mantle into which ocean crust was recycled.     

Interdependence of deformation, fluid infiltration and reaction progress recorded in eclogitic metagranitoids (Sesia Zone, Western Alps)

The effects of high-strain deformation and fluid infiltration during Alpine eclogite facies metamorphism have been studied across ductile shear zones in relatively undeformed metagranitoids at Monte Mucrone (Sesia Zone, Western Alps, Italy). Microfabrics together with bulk rock and stable isotope data indicate that the mineralogical and chemical variations are related to the degree of deformation, rather than to changes in P-T conditions or tectonic position. Transformation of meta-quartz diorite to recrystallized eclogitic mylonites involved the breakdown of biotite and plagioclase and required the influx of H₂O. Bulk-rock geochemical data show that ductile deformation to form eclogitic mylonites involved an increase in volume with a weight percent gain in H₂O and Si and variable loss of K, Na, Ca and Al. δ¹⁸O changes systematically across ductile shear zones into the undeformed country rocks. Constant values in shear zone centres indicate advection parallel to the shear zone and within 10 cm of the mylonites. A dominant component of diffusive oxygen exchange perpendicular to the shear zones produced isotopic fronts, evident from a gradual increase in δ¹⁸O values to the reference values of the country rocks. The degree of isotopic shift within the shear zones reflects increasing deformation and degree of reaction progress. Multiple phases of Alpine deformation and mineral growth are recognized in the Monte Mucrone metagranitoids, and in some cases, eclogite facies shear zones were reactivated under greenschist facies conditions. The results of this study suggest that high-strain deformation provided pathways for both synkinematic and post-kinematic metamorphic fluids which were necessary for complete reactions. Relict igneous fabrics, as well as the presence of corona textures around biotite and pseudomorphs after primary igneous plagioclase in the least deformed rocks, indicate a paucity of hydrous fluids and support the conclusion that fluid movement was channelled rather than pervasive.     

The role of granites in volcanic-hosted massive sulphide ore-forming systems: an assessment of magmatic�Chydrothermal contributions

Assessment of geological, geochemical and isotopic data indicates that a significant subgroup of volcanic-hosted massive sulphide (VHMS) deposits has a major or dominant magmatic?Chydrothermal source of ore fluids and metals. This group, which is typically characterised by high Cu and Au grades, includes deposits such as those in the Neoarchean Doyon-Bousquet-LaRonde and Cambrian Mount Lyell districts. These deposits are distinguished by aluminous advanced argillic alteration assemblages or metamorphosed equivalents intimately associated with ore zones. In many of these deposits, ??³⁴S_sulphide is low, with a major population below ?3??; ??³⁴S_sulphate differs from coexisting seawater and ??³⁴S_{sulphate?Csulphide}????20?C30??. These characteristics are interpreted as the consequence of disproportionation of magmatic SO₂ as magmatic?Chydrothermal fluids ascended and cooled and as a definitive evidence for a significant magmatic?Chydrothermal contribution. Other characteristics that we consider diagnostic of significant magmatic?Chydrothermal input into VHMS ore fluids include uniformly high (>3 times modern seawater values) salinities or very ¹⁸O-enriched (??¹⁸O?>?5??) ore fluids. We do not consider other criteria [e.g. variable salinity, moderately high ??¹⁸O_fluid (2?C5??), ??³⁴S_sulphide near 0??, metal assemblages or a spatial association with porphyry Cu or other clearly magmatic-hydrothermal deposits] that have been used previously to advocate significant magmatic?Chydrothermal contributions to be diagnostic as they can be produced by non-magmatic processes known to occur in VHMS mineral systems. However, in general, a small magmatic?Chydrothermal contribution cannot be excluded in most VHMS systems considered. Conclusive data that imply minimal magmatic?Chydrothermal contributions are only available in the Paleoarchean Panorama district where coeval seawater-dominated and magmatic?Chydrothermal systems appear to have been physically separated. This district, which is characterised by chloritic and sericitic alteration assemblages and lacks aluminous advanced argillic alteration assemblages, is typical of many VHMS deposits around the world, suggesting that for ??garden variety?? VHMS deposits, a significant magmatic?Chydrothermal contribution is not required. Other than deposits associated with advanced argillic alteration assemblages, the only deposit for which we ascribe a major magmatic?Chydrothermal contribution is the Devonian Neves Corvo deposit. This deposit differs from other deposits in the Iberian Pyrite Belt and around the world in being extremely Sn-rich, with the Sn closely associated with Cu and in having formed from high ¹⁸O-rich fluids (??¹⁸O_fluid ??8.5??). We consider these characteristics, particularly the last, as diagnostic of a significant magmatic hydrothermal contribution. Our analysis indicates that two subgroups of VHMS deposits have a major magmatic?Chydrothermal contribution: Cu/Au-rich deposits with aluminous alteration assemblages and reduced, very Sn-rich deposits in which Sn was introduced in a high-temperature ore assemblage. Comparison with ??normal?? VHMS deposits suggests that these subgroups of VHMS deposits may form in specialised tectonic environments. The Cu/Au-rich deposits appear to form adjacent to magmatic arcs, an environment conducive to the generation of hydrous, oxidised melts by melting metasomatised mantle in the wedge above the subducting slab. This contrasts with the back-arc setting of ??normal?? VHMS deposits in which relatively dry granites (In this contribution, we use the term granite sensu latto) formed by decompression melting drive seawater-dominated hydrothermal circulation. The tectonic setting of highly Sn-rich VHMS deposits such as Neves Corvo is less clear; however, thick continental crust below the ore-hosting basin may be critical, as it is in other Sn deposits.     

Zircon geochemistry of two contrasting types of eclogite: Implications for the tectonic evolution of the North Qaidam UHPM belt,northern Tibet

Compared to the extensively documented ultrahigh-pressure metamorphism at North Qaidam, the pre-metamorphic history for both continental crust and oceanic crust is poorly constrained. Trace element compositions, U–Pb ages, O and Lu–Hf isotopes obtained for distinct zircon domains from eclogites metamorphosed from both continental and oceanic mafic rocks are linked to unravel the origin and multi-stage magmatic/metamorphic evolution of eclogites from the North Qaidam ultrahigh-pressure metamorphic (UHPM) belt, northern Tibet.For continental crust-derived eclogite, magmatic zircon cores from two samples with U–Pb ages of 875–856 Ma have both very high δ¹⁸O (10.6 ± 0.5‰) and mantle-like δ¹⁸O (averaging at 5.2 ± 0.7‰), high Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, and steep MREE-HREE distribution patterns (chondrite-normalized) with negative Eu anomalies. Combined with positive ε_Hf (t) of 3.9–14.3 and T_DM (1.2–0.8 Ga and 1.3–1.0 Ga, respectively), they are interpreted as being crystallized from either subduction-related mantle wedge or recycled material in the mantle. While the metamorphic rims from the eclogites have U–Pb ages of 436–431 Ma, varying (inherited, lower, and elevated) oxygen isotopes compared with cores, low Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, and flat HREE distribution patterns with no Eu anomalies. These reflect both solid-state recrystallization from the inherited zircon and precipitation from external fluids at metamorphic temperatures of 595–622 °C (T_Ti-in-zircon).For oceanic crust-derived eclogite, the magmatic cores (510 ± 19 Ma) and metamorphic rims (442.0 ± 3.7 Ma) also show distinction for Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, and the REE patterns and Eu anomalies. Combined with the mantle-like δ¹⁸O signature of 5.1 ± 0.3 ‰ and two groups of model age (younger T_DM close to the apparent ages and older > 700 Ma), two possible pools, juvenile and inherited, were involved in mixing of mantle-derived magma with crustal components. The relatively high δ¹⁸O of 6.6 ± 0.3‰ for metamorphic zircon rims suggests either the protolith underwent hydrothermal alteration prior to the ~ 440 Ma oceanic crust subduction, or external higher δ¹⁸O fluid activities during UHP metamorphism at ~ 440 Ma.Therefore, the North Qaidam UHPM belt witnesses multiple tectonic evolution from Late Mesoproterozoic–Neoproterozoic assembly/breakup of the Rodinia supercontinent with related magmatic emplacement, then Paleozoic oceanic subduction, and finally transition of continental subduction/collision related to UHP metamorphism.     

Extreme oxygen isotope signature of meteoric water in magmatic zircon from metagranite in the Sulu orogen, China: Implications for Neoproterozoic rift magmatism

Unusual ¹⁸O depletion, with δ¹⁸O values as negative as −10‰ to −4‰ relative to VSMOW, was reported in zircons from ultrahigh-pressure eclogite-facies metamorphic rocks in the Dabie-Sulu orogenic belt, China. But it is critical for the negative δ¹⁸O zircons to be distinguished between magmatic and metamorphic origins, because the ¹⁸O depletion can be acquired by high-T eclogite-facies metamorphism of meteoric-hydrothermally altered low δ¹⁸O rocks. While zircon O diffusion kinetics has placed a reasonable constraint on this, zircon trace element compositions can provide a straightforward distinction between the magmatic and metamorphic origins. This paper reports our finding of unusual ¹⁸O depletion in zircon from granitic gneiss in the northeastern end of the Sulu orogen. Zircon δ¹⁸O values vary from −7.8‰ to −3.1‰ along a profile of 50 m length at Zaobuzhen. They are close to extremely low δ¹⁸O values of −9.0‰ to −5.9‰ for metagranite at Qinglongshan and adjacent areas in the southwestern end of the Sulu orogen. CL imaging suggests that the low δ¹⁸O zircons at Zaobuzhen are primarily of magmatic origin, but underwent different degrees of metamorphic modification. Zircon U-Pb dating yields middle Neoproterozoic ages of 751 ± 27 to 779 ± 25 Ma for protolith crystallization and Triassic ages of 214 ± 10 to 241 ± 33 Ma for metamorphic resetting. However, no metamorphic modification occurs in zircon REE patterns that only indicate magmatic recrystallization and hydrothermal alteration, respectively. Thus, the negative δ¹⁸O zircons are interpreted as crystallizing from negative δ¹⁸O magmas due to melting of meteoric-hydrothermally altered negative δ¹⁸O rocks in an active rift setting at about 780 Ma. The variation in zircon δ¹⁸O values indicates considerable O isotope heterogeneity in its granitic protolith. Zircon Lu-Hf isotope analyses give positive ε_Hf(t) values of 1.6-4.1 and Hf model ages of 1.18-1.30 Ga. This suggests that the granitic protolith was derived from the mid-Neoproterozoic reworking of late Mesoproterozoic juvenile crust. The metagranites at Zaobuzhen and Qinglongshan, about 450 km apart, are two known occurrences of the unusually low δ¹⁸O zircons below −6‰ so far reported in the Sulu orogen. They are similar to each other in both protolith and metamorphic ages, so that they share the same nature of both Neoproterozoic protolith and Triassic metamorphism. Therefore, the locally negative δ¹⁸O zircons may register centers of low δ¹⁸O magmatism during the supercontinental rifting.     

Oxygen isotopic variability associated with multiple stages of serpentinization, Duke Island Complex, southeastern Alaska

Ultramafic rocks of the Duke Island Complex in southeastern Alaska crystallized in a supra-subduction zone setting, but the serpentinization of olivine-bearing rocks involved the incursion of late-stage meteoric waters. Three textural types of serpentine (primarily lizardite) have been identified which in part reflect progress in reactions during multiple stages of fluid infiltration. The overall mesh texture of serpentine has been subdivided into a massive-type, found in dunites and wehrlites, and a dendritic-type found in wehrlites and olivine clinopyroxenites. Serpentine veins represent a late-stage in the hydrothermal alteration process. Both FeO contents and δ¹⁸O values of the three textural types of serpentine are variable at the centimeter scale. Magnetite abundance in association with serpentine is also variable with up to 5 vol% of magnetite found in samples with dendritic serpentine. Continued reaction of FeO-bearing serpentine with fluid appears to control the formation of most magnetite. Oxygen isotope ratios of the three textural types of serpentine are distinct, with the massive variety characterized by δ¹⁸O values between −3‰ and 3‰, the dendritic variety showing values between 2‰ and 6‰ and the veins having the highest values between 4‰ and 10‰. Although the δ¹⁸O values may vary by as much as 5‰ on the centimeter scale, δD values tend to show relatively less variation with over 90% of the measured values between −100‰ and −120‰. The O and H isotopic values are consistent with the involvement of meteoric water that had undergone variable degrees of isotopic exchange with country rocks prior to reacting with olivine in the Duke Island Complex. Small-scale variability in both serpentine FeO content and δ¹⁸O values suggests that chemical and isotopic equilibria may have not been attained at larger than centimeter scales. Oxygen isotopic variability in serpentine produced during relatively low-temperature hydrothermal alteration is in large part a function of exchange mediated via fluid flow through microfractures.     

H2O and Ultrahigh-Pressure Subsolidus Phase Relations for Mafic and Ultramafic Systems

Experimental studies show that aqueous fluid-mediated mineralogic solution/redeposition mechanisms are orders faster than solid-solid transformations; hence the presence of a separate aqueous fluid markedly enhances reaction rates, whereas its total absence impedes mineralogic transformations. Where does this volatile component come from? For typical subduction-zone P-T trajectories, amphibole constitutes the major OH-bearing phase in most deep-seated metamorphic rocks of basaltic composition; other hydrous minerals are of minor abundance. Clinoamphiboles dehydrate at pressures of-2.0 to 2.4 GPa, but devolatilization may be delayed slightly by pressure overstepping; thus mafic blueschists and barroisitic amphibolites expel H₂O at arc melt-generation depths of ～100 km, and commonly achieve the stable eclogitic phase configuration. Serpentinized mantle beneath the oceanic crust devolatilizes at comparable conditions. Only where metagabbroic rocks are completely dry and coarse grained are low-pressure assemblages metastably preserved. For realistic subduction-zone geothermal gradients, white micas ± biotites remain stable in sialic crust to pressures exceeding 3.5 GPa. Accordingly, under conditions attending descent to great depths, mica-rich quartzofeldspathic schists and gneisses that constitute the continental crust fail to evolve substantial amounts of H₂O, and transform incompletely to stable eclogite-facies assemblages. The deep underflow of partly hydrated oceanic lithosphere thus generates most of the deep-seated volatile flux—and consequent partial melting to produce the calc-alkaline suite along and above a subduction zone; where large volumes of micaceous sialic materials are carried down to extreme depths, volatile flux severely diminishes.     

Oxygen and Carbon Isotope Study of Calcite and Dolomite in the Disseminated Au-Ag Telluride Bulawan Deposit, Negros Island, Philippines

Abstract: The disseminated Au‐Ag telluride Bulawan deposit, Negros island, Philippines, is hosted by dacite porphyry breccia pipes which formed in a Middle Miocene dacite porphyry stock. Electrum and Au‐Ag tellurides occur mostly as grains intergrown with or filling voids between sphalerite, pyrite, chalcopyrite, galena and tennantite. Calcite, quartz and rare dolomite are the principal gangue minerals. Four types of alteration were recognized in the deposit, namely; propylitic, K‐feldspar‐sericitic, sericitic and carbonate alteration. Carbonate alteration is correlatable to the gold deposition stage and occurs mostly along fault zones. The δ¹⁸O and δ¹³C compositions of calcite and dolomite in propylite zone and ore‐stage dacite porphyry breccia were determined. The δ¹⁸O values of calcite in propylitized andesite range from +12.2 to +14.7%, and their δ¹³C values range from ‐6.1 to ‐1.0%. The δ¹⁸O values of calcite and dolomite in sericite‐ and carbonate‐altered, mineralized dacite porphyry breccia and dacite porphyry rocks range from +15.1 to +23.1%, and the δ¹³C values of calcite and dolomite range from ‐3.9 to +0.9%. The δ¹⁸O and δ¹³C values of the hydrothermal fluids were estimated from inferred temperatures of formation on the basis of fluid inclusion microthermometry. The δ¹⁸O values of hydrothermal fluid for the propylitic alteration were calculated to be +8.5 ‐ +9.5%, assuming 375°C. On the other hand, the δ¹⁸O values of ore solutions for base metal and Au mineralization were computed to be +13.6 ‐ +14.6%, assuming 270°C. The hydrothermal fluids that formed the Bulawan deposit are dilute and ¹⁸O‐enriched fluids which reacted with ¹⁸O‐ and ¹³C‐rich wallrocks such as limestone.     

Geochemistry and oxygen isotopic composition of olivine in kimberlites from the Arkhangelsk province: Contribution of mantle metasomatism

The paper presents data on the composition of olivine macrocrysts from two Devonian kimberlite pipes in the Arkhangelsk diamond province: the Grib pipe (whose kimberlite belongs to type I) and Pionerskaya pipe (whose kimberlite is of type II, i.e., orangeite). The dominant olivine macrocrysts in kimberlites from the two pipes significantly differ in geochemical and isotopic parameters. Olivine macrocrysts in kimberlite from the Grib pipe are dominated by magnesian (Mg# = 0.92–0.93), Ti-poor (Ti < 70 ppm) olivine possessing low Ti/Na (0.05–0.23), Zr/Nb (0.28–0.80), and Zn/Cu (3–20) ratios and low Li concentrations (1.2–2.0 ppm), and the oxygen isotopic composition of this olivine δ¹⁸O = 5.64‰ is higher than that of olivine in mantle peridotites (δ¹⁸O = 5.18 ± 0.28‰). Olivine macrocrysts in kimberlite from the Pionerskaya pipe are dominated by varieties with broadly varying Mg# = 0.90–0.93, high Ti concentrations (100–300 ppm), high ratios Ti/Na (0.90–2.39), Zr/Nb (0.31–1.96), and Zn/Cu (12–56), elevated Li concentrations (1.9–3.4 ppm), and oxygen isotopic composition δ¹⁸O = 5.34‰ corresponding to that of olivine in mantle peridotites. The geochemical and isotopic traits of low-Ti olivine macrocrysts from the Grib pipe are interpreted as evidence that the olivine interacted with carbonate-rich melts/fluids. This conclusion is consistent with the geochemical parameters of model melt in equilibrium with the low-Ti olivine that are similar to those of deep carbonatite melts. Our calculations indicate that the variations in the δ¹⁸O of the olivine relative the “mantle range” (toward both higher and lower values) can be fairly significant: from 4 to 7‰ depending on the composition of the carbonate fluid. These variations were formed at interaction with carbonate fluid, whose δ¹⁸O values do not extend outside the range typical of mantle carbonates. The geochemical parameters of high-Ti olivine macrocrysts from the Grib pipe suggest that their origin was controlled by the silicate (water–silicate) component. This olivine is characterized by a zoned Ti distribution, with the configuration of this distribution between the cores of the crystals and their outer zones showing that the zoning of the cores and outer zones is independent and was produced during two episodes of reaction interaction between the olivine and melt/fluid. The younger episode (when the outer zone was formed) likely involved interaction with kimberlite melt. The transformation of the composition of the cores during the older episode may have been of metasomatic nature, as follows from the fact that the composition varies from grain to grain. The metasomatic episode most likely occurred shortly before the kimberlite melt was emplaced and was related to the partial melting of pyroxenite source material.     

The formation of high temperature clay minerals from basalt alteration during hydrothermal discharge on the East Pacific Rise axis at 21°N

Aluminous, high-temperature clay minerals form from alteration of tholeiitic basaltic glass and calcic plagioclase during hydrothermal venting on the crest of the East Pacific Rise at 21°N. The clay alteration assemblages are layered crusts (up to 1 mm thick) completely replacing glass and calcic plagioclase adjacent to surfaces exposed to hydrothermal fluids. The interiors of the affected basalt samples have unaltered appearances and oxygen isotopic compositions just slightly heavier than that of MORB. The surficial alteration crusts are mixtures of beidellitic smectite (aluminous, dioctahedral), randomly interstratified mixed-layer Al-rich chlorite/smectite, minor chlorite, an x-ray amorphous aluminosilicate material, and possible minor serpentine (amesite). A δ¹⁸O value of +4.1 ± 0.2%. (SMOW) is determined for the beidellitic smectite. Assuming that this smectite equilibrated with hydrothermal fluid having an oxygen isotope value between that of seawater (0%.) and 350°C hydrothermal fluid from EPR, 21°N vents (+1.6%.), an equilibration temperature between 290°C and 360°C is calculated for the beidellitic smectite. This is substantially higher than any previously reported temperature for an oceanic smectite. The mixed-layer Al-rich chlorite/smectite has a δ¹⁸O value of +3.5%., which corresponds to equilibration at 295°–360°C. The aluminous composition of the alteration assemblage is uncommon for clay minerals produced by submarine hydrothermal basalt alteration. We suggest that this assemblage is largely the product of high-temperature interaction between basalt glass + plagioclase and Mg-poor, acidic hydrothermal fluids, with possibly some contribution of Mg from bottom seawater, and that the aluminous clays either incorporate Al³⁺ remobilized from basalt by lowpH hydrothermal fluids, or are residual phases remaining after intense alteration of basaltic glass + plagioclase.     

The application of C isotope measurements to the identification of the sources of C in diamonds: a review

In the past decade, the isotopic compositions of C in > 600 inclusion-bearing diamonds have been determined. Such analyses have revealed the following isotopic characteristics: (1) peridotitic diamonds, which typically contain garnet, chromite, olivine and/or orthopyroxene inclusions with refractory compositions (high Mg, Cr), have δ¹³C values predominantly between −10 and −1‰, with a sharp peak in the distribution near −5‰; (2) eclogitic diamonds, which commonly contain inclusions of omphacitic clinopyroxene, Cr-poor pyrope, and/or eclogitic accessory minerals such as rutile, kyanite, coesite or sanidine, have δ¹³C values between −34 and +3‰, with a smaller peak near −5‰; (3) the isotopic compositions obtained for suites of diamonds from individual occurrences are, in general, unique and do not resemble the range and distribution obtained by amalgamating the diamond isotope data from a number of localities; (4) isotopic zoning patterns and heterogeneities are found in some diamonds; cores of coated diamonds tend to be depleted in¹³C relative to the rims, and within single octahedral diamonds δ¹³C variations of nearly 6‰ have been reported.Because expected C isotope fractionations at mantle temperatures are small, attempts to model the full range of diamond isotope values through fractionating a homogeneous mantle C source have been unsuccessful. Nevertheless, fractionation is probably responsible for some of the observed variation in δ¹³C values. Two other models have also been proposed to account for the diamond characteristics outlined above. The “primordial model” suggests that the range and distribution of C isotope compositions are inherited from primordial C in the mantle which has an inhomogeneous isotopic composition, such as that found in meteorites. The “subduction model” suggests that subducted, crustal C is the source of C in diamonds, as organic and inorganic C compounds in the crust exhibit a range of δ¹³C values similar to that observed in diamonds. This paper reviews the C isotope characteristics of diamonds and compares the models which have been proposed to explain the origins of these characteristics.     

Alpine olivine- and titanian clinohumite-bearing assemblages in the Erro-Tobbio peridotite (Voltri Massif, NW Italy)

The microstructures in the Erro-Tobbio peridotite indicate several stages of recrystallization of olivine + titanian clinohumite-bearing assemblages. The development of these assemblages is closely associated with serpentinite mylonites, in which they occur in shear bands and foliations and are inferred to have grown synkinematically, in veins, and as post-kinematic radial aggregates. In the peridotite wall-rock adjacent to these mylonites, the same assemblages have recrystallized statically at the expense of original olivine and pyroxenes, mesh-textured chrysolite and antigorite veins. In addition, the olivine-bearing assemblage occurs in widespread vein systems. The brittle deformation of the peridotite resulting in the development of these vein systems is closely related to ductile deformation of metagabbroic dykes in the peridotite. Although early metasomatism resulted in extensive rodingitization of the gabbros, some dykes show an eclogitic assemblage of Na-clinopyroxene + garnet + chloritoid + chlorite ± talc. These observations, the microstructures and the mineral chemistry all suggest that the assemblages in the ultramafic rocks and metagabbros developed during a prograde evolution towards high pressures (>13–16 kbar, 450–550° C), and during subsequent decompression. This metamorphic evolution is considered to be related to Late Cretaceous intraoceanic subduction in the Alps-Apennine system and closure of the Piedmont-Ligurian basin.