Petrological and mineralogical studies of Pan-African serpentinites at Bir Al-Edeid area,central Eastern Desert,Egypt

The studied serpentinites occur as isolated masses, imbricate slices of variable thicknesses and as small blocks or lenses incorporated in the sedimentary matrix of the mélange. They are thrusted over the associated island arc calc-alkaline metavolcanics and replaced by talc-carbonates along shear zones. Lack of thermal effect of the serpentinites upon the enveloping country rocks, as well as their association with thrust faults indicates their tectonic emplacement as solid bodies. Petrographically, they are composed essentially of antigorite, chrysotile and lizardite with subordinate amounts of carbonates, chromite, magnetite, magnesite, talc, tremolite and chlorite. Chrysotile occurs as cross-fiber veinlets traversing the antigorite matrix, which indicate a late crystallization under static conditions. The predominance of antigorite over other serpentine minerals indicates that the serpentinites have undergone prograde metamorphism or the parent ultramafic rocks were serpentinized under higher pressure. The parent rocks of the studied serpentinites are mainly harzburgite and less commonly dunite and wehrlite due to the prevalence of mesh and bastite textures. The serpentinites have suffered regional metamorphism up to the greenschist facies, which occurred during the collisional stage or back-arc basin closure, followed by thrusting over a continental margin. The microprobe analyses of the serpentine minerals show wide variation in SiO₂, MgO, Al₂O₃, FeO and Cr₂O₃ due to different generations of serpentinization. The clinopyroxene relicts, from the partly serpentinized peridotite, are augite and similar to clinopyroxene in mantle-derived peridotites. The chromitite lenses associated with the serpentinites show common textures and structures typical of magmatic crystallization and podiform chromitites. The present data suggest that the serpentinites and associated chromitite lenses represent an ophiolitic mantle sequence from a supra-subduction zone, which were thrust over the continental margins during the collisional stage of back-arc basin.     

Supra-subduction affinity in the Neoproterozoic serpentinites in the Eastern Desert, Egypt: Evidence from mineral composition

Serpentinites in the Eastern Desert (ED) of Egypt represent integral components of the ophiolites. Metamorphic textures of the serpentinites preserve the complex mineralogical evolution from primary peridotite through metamorphism, and late-stage hydrothermal alteration. Two textural types are distinguished in the olivines of the present serpentinized peridotites, namely (a) highly-strained olivine grains with kink bands, as in the deformed mantle tectonites from ophiolites, and (b) non-strained grains. The latter may represent recrystallized crystals during later thermal metamorphic events due to the intrusion of granite. On the basis of X-ray diffraction analysis, antigorite is the main serpentine minerals with lesser chrysotile and lizardite which indicates that serpentinites were formed under prograde metamorphism. Relict primary minerals of the serpentinites are Cr-spinel, olivine and pyroxene. Chrome spinel relicts have high Cr# (0.60–0.80), whereas primary olivines are Mg-rich nature (Fo = 89–96). Geochemical compositions of serpentinites indicate that they formed not at mid-ocean ridges but at spreading centers associated with subduction zones and this could have happened in a supra-subduction zone either in the fore-arc or back-arc environments. Mineral compositions of primary chrome spinels and olivines are similar to those of modern fore-arcs. High Cr# in the relict chrome spinels and Fo in the primary olivines of serpentinites indicate that they are residual after extensive partial melting and originated by sea-floor spreading during subduction initiation.     

Petrology and metamorphic evolution of ultramafic rocks and dolerite dykes of the Betic Ophiolitic Association (Mulhacén Complex, SE Spain): evidence of eo-Alpine subduction following an ocean-floor metasomatic process

The Betic Ophiolitic Association, cropping out within the Mulhacén Complex (Betic Cordilleras), is made up of numerous metre- to kilometre-sized lenses of mafic and/or ultramafic and meta-sedimentary rocks. Pre-Alpine oceanic metasomatism and metamorphism caused the first stage of serpentinization in the ultramafic sequence of this association, which is characterized by local clinopyroxene (Cpx) breakdown and Ca-depletion, and complementary rodingitization of the basic dykes intruded in them. Subsequent eo-Alpine orogenic metamorphism developed eclogite facies assemblages in ultramafic and basic lithotypes, which were partly retrograded in Ab-Ep-amphibolite facies conditions during a meso-Alpine event. The heterogeneous development of the oceanic metasomatism in the ultramafic rock-types led to the patchy development of highly serpentinized Ca-depleted domains, without gradual transition to the host, and less serpentinized, Cpx-bearing ultramafites, mainly lherzolitic in composition. The high-pressure eo-Alpine recrystallization of these ultramafites in subduction conditions originated secondary harzburgites in the Ca-depleted domains, consisting of a spinifex-like textured olivine+orthopyroxene paragenesis, and a diopside+Ti-clinohumite paragenesis in the enclosing lherzolitic rocks. During the meso-Alpine event, secondary harzburgites were partly transformed into talc+antigorite serpentinites, whereas the diopside and clinohumite-bearing residual meta-lherzolites were mainly transformed into Cpx-bearing serpentinites. Relics of mantle-derived colourless olivine may be present in the more or less serpentinized secondary harzburgites. These relics are overgrown by the eo-Alpine brown pseudo-spinifex olivine, which contains submicroscopic inclusions of chromite, ilmenite and occasional halite and sylvite, inherited from its parental oceanic serpentine. The same type of mantle-derived olivine relics is also preserved within the Cpx-bearing serpentinites, although it has been partly replaced by the eo-Alpine Ti-clinohumite. The dolerite dykes included in the ultramafites were partly rodingitized in an oceanic environment. They were then transformed during the eo-Alpine event into meta-rodingites in their border zones and into eclogites towards the innermost, less-rodingitized portions. Estimated P–T conditions for the high-pressure assemblages in ultramafic and basic lithotypes range from 650 to 750°C and 16–25 kb.     

Serpentinization: a review

The common alteration assemblage produced by serpentinization of ultramafic rocks is: lizardite, chrysotile, magnetite±brucite±antigorite. Lizardite-chrysotile serpentinites are more common than antigorite; the presence of antigorite indicates that the serpentinite has undergone prograde metamorphism or that the periootite was serpentinized in a higher P,T regime than lizardite and chrysotile. The iron subsitution into serpentine minerals and brucite is a function of temperature at low f_O2, with increased temperature enhancing magnetite formation. The presence of awaruite and native Fe are strong evidence for a locally very reducing environment. Isotopic studies have shown a wide variety of origins for the fluids involved in serpentinization. The increased boron content of serpentinized rocks when compared to boron contents of the parent ultramafic body indicates a possible sea water origin for the fluids. Serpentinization takes place under both constant volume and constant chemical composition conditions. The factors in evaluating the importance of the two processes for an individual serpentinite are: (1) determination of the mineral assemblage and its paragenesis, (2) the structural and tectonic relationship of the ultramafic body to its country rock, (3) fluid access to the rock in duration and amount, and (4) timing of serpentinization - before, during or after emplacement into the crust.     

Three steps of serpentinization in an eclogitized oceanic serpentinization front (Lanzo Massif – Western Alps)

The Lanzo peridotite massif is a fragment of oceanic lithosphere generated in an ocean–continent transition context and eclogitized during alpine collision. Despite the subduction history, the massif has preserved its sedimentary oceanic cover, suggesting that it may have preserved its oceanic structure. It is an exceptional case for studying the evolution of a fragment of the lithosphere from its oceanization to its subduction and then exhumation. We present a field and petrological study retracing the different serpentinization episodes and their impact on the massif structure. The Lanzo massif is composed of slightly serpentinized peridotites (<20% serpentinization) surrounded by an envelope of foliated serpentinites (100% serpentinization) bordered by oceanic metabasalts and metasedimentary rocks. The limit between peridotites and serpentinites defines the front of serpentinization. This limit is sharp: it is marked by the presence of massive serpentinites (80% serpentinization) and, locally, by dykes of metagabbros and mylonitic gabbros. The deformation of these gabbros is contemporaneous with the emplacement of the magma. The presence of early lizardite in the peridotites testifies that serpentinization began during the oceanization, which is confirmed by the presence of meta‐ophicarbonates bordering the foliated serpentinite envelope. Two additional generations of serpentine occur in the ultramafic rocks. The first is a prograde antigorite that partially replaced the lizardite and the relict primary minerals of the peridotite during subduction, indicating that serpentinization is an active process at the ridge and in the subduction zone. Locally, this episode is followed by the deserpentinization of antigorite at peak P–T (estimated in eclogitized metagabbros at 2–2.5 GPa and 550–620 °C): it is marked by the crystallization of secondary olivine associated with chlorite and/or antigorite and of clinopyroxene, amphibole and chlorite assemblages. A second antigorite formed during exhumation partially to completely obliterating previous textures in the massive and foliated serpentinites. Serpentinites are an important component of the oceanic lithosphere generated in slow to ultraslow spreading settings, and in these settings, there is a serpentinization gradient with depth in the upper mantle. The seismic Moho limit could correspond to a serpentinization front affecting the mantle. This partially serpentinized zone constitutes a less competent level where, during subduction and exhumation, deformation and fluid circulation are localized. In this zone, the reaction kinetics are increased and the later steps of serpentinization obliterate the evidence of this progressive zone of serpentinization. In the Lanzo massif, this zone fully recrystallized into serpentinite during alpine subduction and collision. Thus, the serpentinite envelope represents the oceanic crust as defined by geophysicists, and the sharp front of serpentinization corresponds to an eclogitized seismic palaeo‐Moho.     

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.     

Serpentinites and their tectonic signature along the Northwest Zagros Thrust Zone, Kurdistan Region, Iraq

Two types of serpentinized peridotites are distinguished within the Northwest Zagros Thrust Zone (NW-ZTZ) in Kurdistan region of Iraq. One is found as lower members of ophiolite sequences, such as the Mawat and Penjwin ophiolites of the upper Cretaceous age. The other is represented by intraformational isolated serpentinite bodies in Betwat, Qaladeza, and Qalander areas within the Walash–Naopurdan volcano-sedimentary unit of the Paleocene to Eocene paleo-arc tectonic setting. Serpentinites within the NW-ZTZ consist mainly of lizardite and chrysotile, with subordinate amounts of syn-serpentinization magnetite, carbonates, chromium chlorite, tremolite, and talc as secondary minerals, and olivine, clinopyroxene, and chromian spinel as primary minerals. Minor antigorite is also found in the sheared serpentinites often found in ophiolite sequences. Petrological and geochemical studies of serpentinites from the NW-ZTZ show that, of the original protoliths of serpentinites, those associated with ophiolites are residual depleted harzburgite and dunite. The $ {\text{Cr}}\# \left( {{{ = {\text{ Cr}}} \mathord{\left/ {\vphantom {{ = {\text{ Cr}}} {\left( {{\text{Cr}} + {\text{Al}}} \right){\text{ atomic ratio}}}}} \right. \kern-0em} {\left( {{\text{Cr}} + {\text{Al}}} \right){\text{ atomic ratio}}}}} \right) $ of chromian spinel is more than 0.6, and the forsterite content of olivine is 91–92. On the other hand, the original protolith of isolated serpentinite bodies is less depleted harzburgite or depleted lherzolite, which has spinel with Cr# less than 0.6 and olivine with 90–91 forsterite contents. Whole rock chemistry of major, trace, and rare earth elements shows that the serpentinites of ophiolite sequences are depleted in CaO, Al₂O₃, and SiO₂, Sr, and Zr, and are enriched in MgO, Ni, and Cr, in comparison with the isolated serpentinites. Cr# of the disseminated unaltered chromian spinels indicates that the serpentinites of both types had been originated from the supra-subduction zone tectonic setting; the serpentinites of ophiolite sequences obducted and thrusted over the continental margin during the obduction of the Tethyth oceanic crust onto the Arabian continental margin during the upper Cretaceous period. Isolated serpentinite bodies represent serpentinized forearc mantle wedge peridotites emplaced by diapiric upwelling into non-accretionary forearc tectonic settings during the Paleocene to Eocene age.     

Paleozoic serpentinite-enclosed chromitites from Tehuitzingo (Acatlán Complex, southern Mexico): a petrological and mineralogical study

The serpentinites and associated chromitite bodies in Tehuitzingo (Acatlán Complex, southern Mexico) are in close relationship with eclogitic rocks enclosed within a metasedimentary sequence, suggesting that the serpentinites, chromitites and eclogitic rocks underwent a common metamorphic history.Primary chromites from the chromitite bodies at Tehuitzingo are of refractory-grade (Al-rich) and have a chemical composition similar to that expected to be found in an ophiolitic environment. The chromite grains in chromitites and serpentinites are systematically altered to ‘ferritchromite’. The alteration trend is usually characterized by a decrease in the Al, Mg and Cr contents coupled by an increase in Fe³⁺ and Fe²⁺.The Tehutizingo chromitites have low Platinum Group Elements (PGE) contents, ranging from 102 to 303 ppb. The chondrite-normalized PGE patterns are characterized by an enrichment in the Ir-subgroup elements (IPGE=Os, Ir, Ru) relative to the Pd-subgroup elements (PPGE=Rh, Pt, Pd). In addition, all chromitite samples display a negative slope from Ru to Pd [(Os+Ir+Ru)/(Pt+Pd)=4.78−14.13]. These patterns, coupled with absolute PGE abundances, are typical of ophiolitic chromitites elsewhere. Moreover, all the analyzed samples exhibit chondrite-normalized PGE patterns similar to those found for non-metamorphosed ophiolitic chromitites. Thus, the PGE distribution patterns found in the Tehuitzingo chromitites have not been significantly affected by any subsequent Paleozoic high-pressure (eclogite facies) metamorphic event.The chondrite-normalized PGE patterns of the enclosing serpentinites also indicate that the PGE distribution in the residual mantle peridotites exposed in Tehuitzingo was unaffected by high-pressure metamorphism, or subsequent hydrothermal alteration since the serpentinites show a similar pattern to that of partially serpentinized peridotites present in mantle sequences of non-metamorphosed ophiolites.Our main conclusion is that the chromitites and serpentinites from Tehuizingo experienced no significant redistribution (or concentration) of PGE during the serpentinization process or the high-pressure metamorphic path, or during subsequent alteration processes. If any PGE mobilization occurred, it was restricted to individual chromitite bodies without changing the bulk-rock PGE composition.Our data suggest that the Tehuitzingo serpentinites and associated chromitites are a fragment of oceanic lithosphere formed in an arc/back-arc environment, and represent an ophiolitic mantle sequence from a supra-subduction zone, the chemical composition of which remained essentially unchanged during the alteration and metamorphic events that affected the Acatlán Complex.     

Geochemistry and fore-arc evolution of upper mantle peridotites in the Cryogenian Bir Umq ophiolite,Arabian Shield,Saudi Arabia

ABSTRACT

The Bir Umq ophiolite is one of the most important ophiolitic successions in the Arabian Shield, and represents an excellent case for the study of the tectonomagmatic evolution of the earliest Precambrian events in the juvenile part of the Arabian-Nubian Shield (ANS). It is a dismembered ophiolite, which includes a serpentinized peridotite with small amounts of gabbro and mélange, and is overlain by the Sumayir formation. The mantle section of the Bir Umq ophiolite has been pervasively sheared and folded during its emplacement and is extensively serpentinized, carbonated and silicified, resulting in the common development of magnesite and listwaenite along the shear zones. Listwaenite occurs in the form of upstanding ridges due to its resistance to erosion. Antigorite is the main serpentine mineral, which, however, has low amounts of lizardite and chrysotile, indicating that the present serpentinites formed by prograde metamorphism. The ophiolitic rocks of Bir Umq have undergone regional metamorphism up to the greenschist to amphibolite facies. The presence of mesh and bastite textures indicates harzburgite and dunite protoliths. The serpentinized peridotite preserves rare relicts of primary minerals such as olivine, pyroxene and Cr-spinel. The serpentinized ultramafics of Bir Umq have high Mg# [molar Mg/(Mg+Fe²⁺); 0.90–0.93), low CaO, and Al₂O₃ contents similar to that of the environment of the suprasubduction zone. Additionally, they are characterized by the depletion of some compatible trace elements (e.g., Nb, Sr, Ta, Zr, Hf and REE), but show a wide variation in the Rb and Ba. Moreover, they are enriched in some elements that have affinities for Mg-rich minerals such as Ni, Cr, V, and Co. Fresh relics of olivine have high Fo (av. 0.91) and NiO (av. 0.42) contents, similar to those in the mantle olivine. The fresh Cr-spinel has high Cr# (0.68) and low TiO₂ content (av. 0.11), similar to those in modern fore-arc peridotites. The composition of both orth- and clinopyroxenes confirms the fore-arc affinity of the studied ultramafics. The present study indicates that the protoliths of the serpentinized ultramafics of Bir Umq have high partial melt degrees, which is consistent with the characteristics of ultramafic rocks formed in a subarc environment (fore-arc) within a suprasubduction zone system.     

A stable isotope study of serpentinization and metamorphism in the Highland Border Suite,Scotland, U.K.

$\text{D}\text{H}$ and ${}^{18}\text{O}{}^{16}\text{O}$ ratios have been measured for whole-rock samples and mineral separates from the mafic and ultramatic rocks of the Cambro-Ordovician Highland Border Suite. The H- and O- isotopic compositions of these rocks record individual stages in a relatively complex 500 Myr old hydrothermal/metamorphic history. Lizardite serpentinites (δD ～ ? 105‰; δ¹⁸O ～ + 6.2‰) record a premetamorphic history and indicate that parent harzburgites, dunites, and pyroxenites were serpentinized through low-temperature interaction with meteoric waters during cooling. The other rocks of the Highland Border Suite record subsequent interaction with metamorphic fluids. Amphibolite facies hornblende schists were produced through thrust-related (dynamothermal) metamorphism of spilitic pillow lavas. During dehydration, D-enriched fluids were driven off from the spilites thus leaving the hornblende schists to equilibrate with a relatively D-depleted internal fluid reservoir (δD ～ ? 45‰). The expelled D-enriched fluids may have mixed with more typical Dalradian metamorphic waters which then exchanged with the remaining mafic rocks and lizardite serpentinites during greenschist facies regional metamorphism to produce antigorite serpentinites (δD ～ ? 62‰; δ¹⁸O ～ + 8‰) and greenschist metaspilites (δD ～ ? 57‰; δ¹⁸O ～ + 7.3‰) with similar H- and O-isotopic compositions. Serpentinites which have been only partially metamorphosed show intermediate H-isotopic compositions between that of metamorphic antigorite (δD ～ ? 62‰) and non-metamorphic lizardite δD ～ ? 105‰) end members.     

Implications of the serpentine phase transition on the behaviour of beryllium and lithium-boron of subducted ultramafic rocks

The Totalp-Platta-Malenco ophiolites in the Eastern Central Alps offer a unique opportunity to study the behaviour of Li, Be and B in ultramafic rocks in response to serpentinization and to progressive Alpine metamorphism. These units represent the remnants of a former ocean-continent transition that was intensely serpentinized during exposure on the Jurassic seafloor of the Ligurian Tethys. From north to the south, three isograd reactions (lizardite⇒antigorite+brucite;lizardite+talc⇒antigorite;lizardite+tremolite⇒antigorite+diopside) have been used to quantify the evolution of the light element content of metamorphic minerals. We determined the Li, Be and B concentrations in major silicate minerals from the ultramafic bodies of Totalp, Platta and Malenco by secondary ion mass spectrometry. Mantle minerals have Be concentrations (e.g. <0.001-0.009 μg/g in olivine) similar to the metamorphic minerals that replace them (e.g. <0.001-0.016 μg/g in serpentine). The mantle signature of Be is thus neither erased during seafloor alteration nor by progressive metamorphism from prehnite-pumpellyite to epidote-amphibolite facies. In contrast, the Li and B inventories of metamorphic minerals are related to the lizardite-to-antigorite transition. Both elements display higher concentrations in the low-temperature serpentine polymorph lizardite (max. 156 μg/g Li, max. 318 μg/g B) than in antigorite (max. 0.11 μg/g Li, max. 12 μg/g B). Calculated average B/Li ratios for lizardite (∼1395) and antigorite (∼115) indicate that Li fractionates from B during the lizardite-to-antigorite transition during prograde metamorphism in ultramafic rocks. In subduction zones, this signature is likely to be recorded in the B-rich nature of forearc fluids.Relative to oceanic mantle the Be content of mantle clinopyroxene is much higher, but similar to Be values from mantle xenoliths and subduction-related peridotite massifs. These data support previous hypothesis that the mantle rocks from the Eastern Central Alps have a subcontinental origin. We conclude that Be behaves conservatively during subduction metamorphism of ultramafic rocks, at least at low-temperature, and thus retains the fingerprint of ancient subduction-related igneous events in mantle peridotites.     

Coexisting serpentine and quartz from carbonate-bearing serpentinized peridotite in the Samail Ophiolite, Oman

Tectonically exposed mantle peridotite in the Oman Ophiolite is variably serpentinized and carbonated. Networks of young carbonate veins are prevalent in highly serpentinized peridotite, particularly near low-temperature alkaline springs emanating from the peridotite. An unusual feature in some samples is the coexistence of serpentine and quartz, which is not commonly observed in serpentinites. This assemblage is unstable with respect to serpentine?+?talc or talc?+?quartz under most conditions. Serpentine in the carbonated serpentinites in this study is more iron rich than in most serpentinites reported in previous studies, and samples with co-existing quartz contain the most iron-rich serpentines. Calculations of thermodynamic equilibria in the MgO–SiO₂–H₂O–CO₂ system suggest that serpentine?+?quartz may be a stable assemblage at low temperatures (e.g., <~15–50?°C) and is stabilized to higher temperatures by preferential cation substitutions in serpentine over talc. Based on these calculations, serpentine?+?quartz assemblages could result from serpentinization at near-surface temperatures. Clumped isotope thermometry of carbonate veins yields temperatures within error of the observed temperatures in Oman groundwater for all samples analyzed, while the δ¹⁸O of water calculated to be in equilibrium with carbonate precipitated at those temperatures is within error of the observed isotopic composition of Oman groundwater for the majority of samples analyzed. As groundwater geochemistry suggests that carbonate precipitation and serpentinization occur concomitantly, this indicates that both hydration and carbonation of peridotite are able to produce extensive alteration at the relatively low temperatures of the near-surface weathering environment.     

Eclogites in the Makuti gneisses of Zimbabwe: implications for the tectonic evolution of the Zambezi Belt in southern Africa

The gneisses of the Makuti Group in north-west Zimbabwe are characterized by complex geometries that resulted from intense non-coaxial deformation in a crustal scale high-strain zone that accommodated extensional deformation along the axis of the Zambezi Belt at c. 800 Ma. Within low-strain domains in the Makuti gneisses, undeformed metagabbroic lenses preserve eclogite and granulite facies assemblages, which record a part of the metamorphic history that predates Pan-African events. Eclogitic rocks can be subdivided into: (1) corona-textured metagabbros that preserve igneous textures, and (2) garnet–omphacite rocks in which primary textures are destroyed. The lenses of eclogitic rocks are enveloped in a mantle of garnet–clinopyroxene–hornblende gneiss, which is a common rock type in the Makuti gneisses. The eclogites preserve multi-staged, domainal, symplectic reaction textures that developed progressively as the rocks experienced loading followed by decompression–heating. In the metagabbros, the original clinopyroxene, plagioclase and olivine domains acted separately during the peak of metamorphism, with plagioclase being replaced by garnet and kyanite, and olivine being replaced by orthopyroxene and possibly omphacite. The peak assemblage was overprinted by: (1) the multi-mineralic corona assemblage pargasite–orthopyroxene–spinel–plagioclase replacing garnet–kyanite–clinopyroxene (possibly at c. 19 kbar, 760±25 °C); (2) orthopyroxene–pargasite–plagioclase–scapolite coronas replacing orthopyroxene (15±1.5 kbar, 750±50 °C); and (3) moats of orthopyroxene–plagioclase replacing garnet (10±1 kbar, 760±50 °C). The garnet–omphacite rocks record similar peak conditions (15±1.1 kbar, 760±60 °C). Garnet–clinopyroxene–hornblende–plagioclase gneisses envelop the eclogites and record matrix conditions of 11±1.5 kbar at 730±50 °C using assemblages that are oriented in the regional fabric. These rocks are characterized by decompression-heating textures, reflecting temperature increases during exhumation of the Makuti gneisses. The eclogite facies rocks formed during a collisional event prior to 850 Ma. Their formation could be related to a suture zone that developed along the axis of the Zambezi Belt during the formation of Rodinia (between 1400 and 850 Ma). The main deformation-metamorphism in the Makuti gneisses occurred around 800 Ma and involved extension and exhumation of the high-P rocks (break-up of Rodinia), which experienced a high-T metamorphic overprint. Around 550–500 Ma, a collisional event associated with the formation of Gondwana resulted in renewed burial and metamorphic recrystallization of the Makuti gneisses.     

O–H isotope ratios of high pressure ultramafic rocks: implications for fluid sources and mobility in the subducted hydrous mantle

We examine the O-H isotope signatures of Alpine ultramafic rocks and eclogitic metagabbros of the Erro-Tobbio peridotite Unit (western Italian Alps), which record a subduction and exhumation cycle. Localization of subduction-related deformation along serpentinite mylonite shear zones favoured preservation of pre-subduction mantle and low temperature (oceanic) alteration assemblages within undeformed (meta)peridotite that underwent partial static recrystallization to high-pressure metamorphic parageneses. Bulk rock and mineral separate (clinopyroxene and serpentine) oxygen isotope ratios of the serpentinized mantle peridotites (5-8‰) are slightly enriched in ¹⁸O compared with those of the high-pressure metaperidotites and the serpentinite mylonites (4.4-7.6‰). The lowest values occur in high-pressure veins (3.5-5.7‰) and eclogitic metagabbros (3.1-5.3‰). These variations are comparable to variations observed in modern oceanic rocks and in non-subducted ophiolites. Preservation of pre-eclogitic '¹⁸O signatures of the Erro-Tobbio rocks and a lack of oxygen isotope re-equilibration between different shear zones imply local-scale fluid flow at low water/rock ratios and closed system behaviour during high-pressure metamorphism. Different serpentine generations show a bimodal distribution in 'D values: pre-eclogitic lizardite and chrysotile range from -102 to -77‰; high-pressure antigorite in the mylonites and in low strain metaperidotites range from -71 to -57‰ and -83 to -60‰, respectively. Comparable ranges occur in antigorite in the associated high-pressure veins, suggesting that the hydrogen signatures were acquired prior to veining. We propose that the isotopic variations reflect multiple events of fluid uptake in different geodynamic environments. The H- and O-isotope ratios in the eclogitic mylonites suggest that initial hydration occurred over a range of temperatures during local interaction with altered seawater along oceanic shear zones. The ¹⁸O-enriched and H-depleted compositions of chrysotile and lizardite in the mantle peridotites suggest that a second hydration event may have occurred as a result of interaction with metamorphic fluids at the early stages of burial in a forearc setting, where slabs undergo large-scale, low-temperature fluid fluxing. The oceanic mantle is thus a candidate for continuous hydration during its oceanic and early subduction history. The Erro-Tobbio unit thus represents an example of cycling of internally-derived fluids, whereby the different structural and textural domains behaved as relatively closed systems to fluid circulation during high-pressure metamorphism.     

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.     

On the Stability of Sulfides, Oxides, and Native Metals in Serpentinite

Topologic relations indicate that the lowest relative oxygenfugacity attained in magnetite-bearing serpentinites occursin the presence of the assemblage serpentine-olivine-brucite.This is consistent with the observation that Ni-Fe alloys arepreferentially associated with this assemblage, both in progrademetaserpentinites, where the stable serpentine mineral is antigorite,and in retrograde serpentinites, where either antigorite, lizardite,or chrysotile may be present. The presence of the Ni-Fe alloyindicates that the assemblage serpentine-olivine-brucite-magnetitein prograde metaserpentinites equilibrated with an oxygen fugacityfour to five log units below the FMQ buffer whereas in retrogradeenvironments it equilibrated at oxygen fugacities as low assix or seven log units below FMQ. In carbonate-bearing metaperidotitesthe oxygen fugacity is buffered by the assemblage Fe-Mg carbonate-Feoxide and this buffering allows the oxygen fugacity to attainvalues above those of the HM buffer for rocks with relativelyhigh XCo2, such as those containing the assemblage talc magnesite.A considerable gradient in fO₂ may therefore be present acrossa serpentinite body from a partially serpentinized core to acarbonatized margin. This gradient is reflected in the compositionof the Fe and Ni sulfides. Sulfur-rich sulfides, such as milleriteor vaesite and pyrite, occur in carbonate-rich peridotites whilethe S-poor sulfide heazlewoodite is found in carbonate-freeserpentinites, and native Ni-Fe alloys, commonly without anyassociated sulfide, are preferentially found in the highly reduced,partially serpentinized peridotites. Under proper conditions the strong gradient info can lead tomobilization of metals or sulfides. Josephinite nodules, forexample, are postulated to have formed during high-temperature,reversible serpentinization. In such a situation, the locationof the serpentinization front and its associated environmentof extreme reduction will be thermally fixed, forming a sitefor deposition of native metals. The Ca in solution will bedeposited along with the metals as diopside and andradite, silicatescommon in josephinite. The tendency for sulfides in metaperidotiteto show evidence of mobilization in bodies metamorphosed toupper greenschist facies or higher may be explained by the factthat above 400 ?C the carbonate-bearing portion of an ultramaficbody may be associated with a fluid dominated by SO₂. Underthese conditions, sulfides may be dissolved and transportedto more-reducing areas of the body, such as the carbonate-freeserpentinite or the contact with the country rock, where theywould be reprecipitated.     

胶-辽-吉造山带北辽河变基性岩的成因、地球化学属性及其构造意义

大规模出露于胶-辽-吉造山带的北辽河变基性岩(NLHmetabasicrocks)是恢复造山带构造演化的关键之一,然而,研究者们对这些变基性岩的成因和构造环境有很大争议,制约了对胶-辽-吉造山带早期构造演化的深入研究。基于详细的野外地质调查,本文对北辽河变基性岩进行了系统的岩石学研究并提供了新的全岩地球化学数据,结合前人的测试结果,我们对这些变基性岩的成因和构造环境进行了相关探讨。变基性岩侵入于北辽河群的大理岩和碎屑岩中,经历了一定程度的蚀变以及绿片岩相-角闪岩相变质。岩石类型包括变质辉长岩、变质辉绿岩、斜长角闪岩以及石榴斜长角闪岩;前两者具有明显的变余辉长或者辉绿结构,可见自形斜长石,少见原生矿物单斜辉石的残留;后两者主要由斜长石和角闪石组成,部分含有石榴子石变斑晶;此外,岩石中出现大量Fe-Ti氧化物(磁铁矿和钛铁矿)。地球化学研究表明,北辽河变基性岩均属于拉斑玄武岩系列(SiO_2=44.55%~54.11%,Nb/Y=0.16~0.31),以低TiO_2(0.69%~1.99%)和低MgO(多数5.47%~7.97%)为特征,轻稀土轻微富集((La/Sm)_N=1.22~2.66;(La/Yb)_N=1.66~4.56),并具有明显的Nb、Ta、P以及轻微的Zr、Ti亏损,岩石经历了橄榄石、单斜辉石和斜长石等矿物的三相结晶分异以及Fe-Ti氧化物(磁铁矿和钛铁矿)的堆晶;它们的微量元素配分型式类似于E-MORB和地壳岩石,并且地球化学组成与MORB相近,而不同于弧玄武岩和板内玄武岩;这些变基性岩的Ce/Pb(3.07~26.58)、(Ta/La)PM(0.47~1.45)以及(Hf/Sm)PM(0.91~1.15)显示出有限的俯冲相关流体的交代作用;此外,大多数不相容元素比值(例如Th/Nb、La/Nb及Th/La等)的变化趋势则表明北辽河变基性岩的岩浆源区不可能是大陆岩石圈地幔,并且在形成过程中经历了明显的地壳物质混染。基于这些野外地质调查和地球化学研究,我们认为北辽河变基性岩应形成于相对成熟的弧后盆地,这样一个形成环境也表明胶-辽-吉造山带在早期存在~2.1Ga的洋壳俯冲过程,该构造带应该是~1.9Ga岛弧与大陆碰撞形成的一条古元古代造山带。     

Subduction metamorphism of serpentinite‐hosted carbonates beyond antigorite‐serpentinite dehydration (Nevado‐Filábride Complex,Spain)

At sub‐arc depths, the release of carbon from subducting slab lithologies is mostly controlled by fluid released by devolatilization reactions such as dehydration of antigorite (Atg‐) serpentinite to prograde peridotite. Here we investigate carbonate–silicate rocks hosted in Atg‐serpentinite and prograde chlorite (Chl‐) harzburgite in the Milagrosa and Almirez ultramafic massifs of the palaeo‐subducted Nevado‐Filábride Complex (NFC, Betic Cordillera, S. Spain). These massifs provide a unique opportunity to study the stability of carbonate during subduction metamorphism at P–T conditions before and after the dehydration of Atg‐serpentinite in a warm subduction setting. In the Milagrosa massif, carbonate–silicate rocks occur as lenses of Ti‐clinohumite–diopside–calcite marbles, diopside–dolomite marbles and antigorite–diopside–dolomite rocks hosted in clinopyroxene‐bearing Atg‐serpentinite. In Almirez, carbonate–silicate rocks are hosted in Chl‐harzburgite and show a high‐grade assemblage composed of olivine, Ti‐clinohumite, diopside, chlorite, dolomite, calcite, Cr‐bearing magnetite, pentlandite and rare aragonite inclusions. These NFC carbonate–silicate rocks have variable CaO and CO₂ contents at nearly constant Mg/Si ratio and high Ni and Cr contents, indicating that their protoliths were variable mixtures of serpentine and Ca‐carbonate (i.e., ophicarbonates). Thermodynamic modelling shows that the carbonate–silicate rocks attained peak metamorphic conditions similar to those of their host serpentinite (Milagrosa massif; 550–600°C and 1.0–1.4 GPa) and Chl‐harzburgite (Almirez massif; 1.7–1.9 GPa and 680°C). Microstructures, mineral chemistry and phase relations indicate that the hybrid carbonate–silicate bulk rock compositions formed before prograde metamorphism, likely during seawater hydrothermal alteration, and subsequently underwent subduction metamorphism. In the CaO–MgO–SiO₂ ternary, these processes resulted in a compositional variability of NFC serpentinite‐hosted carbonate–silicate rocks along the serpentine‐calcite mixing trend, similar to that observed in serpentinite‐hosted carbonate‐rocks in other palaeo‐subducted metamorphic terranes. Thermodynamic modelling using classical models of binary H₂O–CO₂ fluids shows that the compositional variability along this binary determines the temperature of the main devolatilization reactions, the fluid composition and the mineral assemblages of reaction products during prograde subduction metamorphism. Thermodynamic modelling considering electrolytic fluids reveals that H₂O and molecular CO₂ are the main fluid species and charged carbon‐bearing species occur only in minor amounts in equilibrium with carbonate–silicate rocks in warm subduction settings. Consequently, accounting for electrolytic fluids at these conditions slightly increases the solubility of carbon in the fluids compared with predictions by classical binary H₂O–CO₂ fluids, but does not affect the topology of phase relations in serpentinite‐hosted carbonate‐rocks. Phase relations, mineral composition and assemblages of Milagrosa and Almirez (meta)‐serpentinite‐hosted carbonate–silicate rocks are consistent with local equilibrium between an infiltrating fluid and the bulk rock composition and indicate a limited role of infiltration‐driven decarbonation. Our study shows natural evidence for the preservation of carbonates in serpentinite‐hosted carbonate–silicate rocks beyond the Atg‐serpentinite breakdown at sub‐arc depths, demonstrating that carbon can be recycled into the deep mantle.     

Mineralogy,geochemistry, and geotectonic significance of the Neoproterozoic ophiolite of Wadi Arais area,south Eastern Desert,Egypt

ABSTRACT

The dismembered ophiolites in Wadi Arais area of the south Eastern Desert of Egypt are one of a series of Neoproterozoic ophiolites found within the Arabian–Nubian Shield (ANS). We present new major, trace, and rare earth element analyses and mineral composition data from samples of the Wadi Arais ophiolitic rocks with the goal of constraining their geotectonic setting. The suite includes serpentinized ultramafics (mantle section) and greenschist facies metagabbros (crustal section). The major and trace element characteristics of the metagabbro unit show a tholeiitic to calc-alkaline affinity. The serpentinized ultramafics display a bastite, or less commonly mesh, texture of serpentine minerals reflecting harzburgite and dunite protoliths, and unaltered relics of olivine, orthopyroxene, clinopyroxene, and chrome spinel can be found. Bulk-rock chemistry confirms harzburgite as the main protolith. The high Mg# (91.93–93.15) and low Al₂O₃/SiO₂ ratios (0.01–0.02) of the serpentinized peridotite, together with the high Cr# (>0.6) of their Cr-spinels and the high NiO contents (0.39–0.49 wt.%) of their olivines, are consistent with residual mantle rocks that experienced high degrees of partial melt extraction. The high Cr# and low TiO₂ contents (0.02–0.34 wt.%) of the Cr-spinels are most consistent with modern highly refractory fore-arc peridtotites and suggest that these rocks probably developed in a supra-subduction zone environment.     

Petrogenesis of garnet-bearing ultramafic rocks and associated eclogites in the Su-Lu ultrahigh-P metamorphic terrane, eastern China

Ultramafic blocks that themselves contain eclogite lenses in the Triassic Su-Lu ultrahigh-P terrane of eastern China range in size from hundreds of metres to kilometres. The ultramafic blocks are enclosed in quartzofeldspathic gneiss of early Proterozoic age. Ultramafic rocks include garnetiferous lherzolite, wehrlite, pyroxenite, and hornblende peridotite. Garnet lherzolites are relatively depleted in Al₂O₃ (<3.8wt%), CaO (<3.2%) and TiO₂ (<0.11 wt%), and are low in total REE contents (several p.p.m.), suggesting that the rocks are residual mantle material that was subjected to low degrees of partial melting. The eclogite lenses or layers within the ultramafic rocks are characterized by higher MgO and CaO, lower Al₂O₃ and TiO₂ contents, and a higher CaO/Al₂O₃ ratio compared to eclogites enclosed in the quartzofeldspathic gneiss. Scatter in the plots of major and trace elements vs. MgO, REE patterns and La, Sm and Lu contents suggest that some eclogites were derived from melts formed by various degrees (0.05–0.20) of partial melting of peridotite, and that other eclogites formed by accumulation of garnet and clinopyroxene ± trapped melt in the upper mantle. Both ultramafic and eclogitic rocks have experienced a complex metamorphic history. At least six stages of recrystallization occurred in the ultramafic rocks based on an analysis of reaction textures and mineral compositions. Stage I is a high temperature protolith assemblage of Ol + Opx + Cpx + Spl. Stage II consists of the ultrahigh-pressure assemblage Ol + Cpx + Opx + Grt. Stage III is manifested by the appearance of fine-grained garnet after coarse-grained garnet. Stage IV is characterized by formation of kelyphitic rims of fibrous Opx and Cpx around garnet, and replacement of garnet by spinel and pargasitic-hornblende. Stage V is represented by the assemblage Ol + Opx + Prg-Hbl + Spl. The mineral assemblages of stages VI_A and VI_B are Ol + Tr-Amp + Chl and Serp + Chl ± talc, respectively. Garnet and orthopyroxene all show a decrease in MgO with retrogressive recrystallization and Na₂O in clinopyroxene also decreases throughout this history. Eclogites enclosed within ultramafic blocks consist of Grt + Omp + Rt ± Qtz ± Phn. A few quartz-bearing eclogites contain rounded and oval inclusion of polycrystalline quartz aggregates after coesite in garnet and omphacite. Minor retrograde features include thin symplectic rims or secondary amphiboles after Cpx, and ilmenite after rutile. P-T estimates indicate that the ultrahigh-metamorphism (stage II) of ultramafic rocks occurred at 820-900d? C and 36-41 kbar and that peak metamorphism of eclogites occurred at 730-900d? C and >28 kbar. Consonant with earlier plate tectonic models, we suggest that these rocks were underplated at the base of the continental crust. The rocks then underwent ultrahigh-pressure metamorphism and were tectonically emplaced into thickened continental crust during the Triassic collision between the Sino-Korean and Yangtze cratons.