Geology and geochemistry of the Jianchaling hydrothermal nickel deposit: T–pH–fO2–fS2 conditions and nickel precipitation mechanism

The Jianchaling nickel deposit in the Bikou Terrane (Shaanxi Province, China) occurs along the boundaries between granite porphyry and carbonated ultramafic rocks (carbonated serpentinite, talc–carbonate rocks, and listwaenite). Serpentine– magnetite, serpentine– magnesite– magnetite, and magnesite– talc– quartz– pyrite– violarite– millerite– chalcopyrite assemblage formed in carbonated ultramafic rocks during hydrothermal activities. Ni-bearing sulphides, coexisting with magnesite, postdated magnetite in carbonated ultramafic rocks. Compared with serpentinite, Ni, Co, Cu, Mn, and Pb concentrate in talc–carbonate rocks. The fact that the NiO contents of magnetite decrease with progressive carbonation of serpentinite suggests that Ni from magnetite concentrated in fluid and contributed to the formation of the Jianchaling nickel deposit. Sulphides precipitated from fluid with log fO₂ value varying from −34.5 to −31.8 and log fS₂ value varying from −10.3 to −9.2. High pH and HS⁻ activities triggered by transformation of serpentine into magnesite–talc–quartz assemblage promoted precipitation of Ni-bearing sulphides, and finally formed the Jianchaling hydrothermal nickel deposit.     

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.     

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.     

CO2 sequestration and extreme Mg depletion in serpentinized peridotite clasts from the Devonian Solund basin, SW-Norway

The conglomerates of the Solund Devonian basin of SW-Norway contain numerous (locally up to 20 vol.%) peridotitic clasts with concentric mm- to 10-cm thick zones of varying red to black color. The peridotite clasts show a clear, alteration-related textural evolution. The least-altered rocks are partly serpentinized peridotites, showing a typical mesh texture with veins of serpentine, magnesite and Ni-rich magnetite surrounding olivine (Fo₉₁) relicts and its Mg-depleted, clay-like alteration product (deweylite assemblage). In the more advanced ophicarbonate stage, the mesh cells contain calcite, silica and are surrounded by talc. In the final stage, quartz, calcite, and hematite dominate the mineralogy and occur together with minor amounts of chromite, talc, Cr-chlorite, and Cr-hydroandradite. In tandem with this textural evolution is a decrease in MgO from 40 to 2.5 wt% and a CaO increase from 1 to 35 wt%. All peridotite clasts are characterized by high Cr and Ni concentrations. The chemistry and the textural evolution show that the clasts formed by an extreme Mg-mobilization from the peridotite, with development of secondary porosity and subsequent precipitation of calcite. MgO removed from the clasts after burial is in part consumed by replacement reactions in the sediment matrix around the clasts where Mg-free minerals (e.g., almandine) are replaced by Mg-bearing minerals (e.g., talc). Calculated apparent ⁸⁷Sr/⁸⁶Sr ratios of the clasts at 385 Ma (0.7124-0.7139), corresponding to the inferred age of sediment deposition and incipient clast alteration, indicate interaction with diagenetic basinal fluids. We explain the reaction history as a three stage process involving (a) partial serpentinization of olivine in an oceanic environment (b) breakdown of olivine relicts to the deweylite assemblage resulting in mobilization of MgO under (near-) surface conditions in a tropical Devonian climate and (c) further Mg-mobilization and replacement of the deweylite assemblage by calcite and quartz after diagenesis. Sedimentary basins with abundant weathered peridotite represent potential sites for a permanent CO₂ storage by formation of calcite in a low-temperature environment.     

Geochemical constraints on the origin and tectonic setting of the serpentinized peridotites from the Paleoproterozoic Nyong series,Eseka area,SW Cameroon

Serpentinized rocks closely associated with Paleoproterozoic eclogitic metabasites were recently discovered at Eseka area in the northwestern edge of the Congo craton in southern Cameroon. Here, we present new field data, petrography, and first comprehensible whole-rock geochemistry data and discuss the protolith and tectonic significance of these serpentinites in the region. The studied rock samples are characterized by pseudomorphic textures, including mesh microstructure formed by serpentine intergrowths with cores of olivine, bastites after pyroxene. Antigorite constitutes almost the whole bulk of the rocks and is associated (to the less amount) with tremolite, talc, spinel, and magnetite. Whole-rock chemistry of the Eseka serpentinites led to the distinction of two types. Type 1 has high MgO (> 40 wt%) content and high Mg# values (88.80) whereas Type 2 serpentinite samples display relatively low MgO concentration and Mg# values (< 40 and 82.88 wt%, respectively). Both types have low Al/Si and high Mg/Si ratios than the primitive mantle, reflecting a refractory abyssal mantle peridotite protolith. Partial melting modeling indicates that these rocks were derived from melting of spinel peridotite before serpentinization. Bulk rock high-Ti content is similar to the values of subducted serpentinites (> 50 ppm). This similarity, associated with the high Cr contents, spinel-peridotite protolith compositions and Mg/Si and Al/Si ratios imply that the studied serpentinites were formed in a subduction-related environment. The U-shaped chondrite normalized-REE patterns of serpentinized peridotites, coupled with similar enrichments in LREE and HFSE, suggest the refertilized nature due to melt/rock interaction prior to serpentinization. Based on the results, we suggest that the Eseka serpentinized peridotites are mantle residues that suffered a high degree of partial melting in a subduction-related environment, especially in Supra Subduction Zone setting. These new findings suggest that the Nyong series in Cameroon represents an uncontested Paleoproterozoic suture zone between the Congo craton and the São Francisco craton in Brazil.

     

Serpentinization of abyssal peridotites from the MARK area, Mid-Atlantic Ridge: sulfur geochemistry and reaction modeling

The opaque mineralogy and the contents and isotope compositions of sulfur in serpentinized peridotites from the MARK (Mid-Atlantic Ridge, Kane Fracture Zone) area were examined to understand the conditions of serpentinization and evaluate this process as a sink for seawater sulfur. The serpentinites contain a sulfur-rich secondary mineral assemblage and have high sulfur contents (up to 1 wt.%) and elevated δ³⁴S_sulfide (3.7 to 12.7‰). Geochemical reaction modeling indicates that seawater-peridotite interaction at 300 to 400°C alone cannot account for both the high sulfur contents and high δ³⁴S_sulfide. These require a multistage reaction with leaching of sulfide from subjacent gabbro during higher temperature (∼400°C) reactions with seawater and subsequent deposition of sulfide during serpentinization of peridotite at ∼300°C. Serpentinization produces highly reducing conditions and significant amounts of H₂ and results in the partial reduction of seawater carbonate to methane. The latter is documented by formation of carbonate veins enriched in ¹³C (up to 4.5‰) at temperatures above 250°C. Although different processes produce variable sulfur isotope effects in other oceanic serpentinites, sulfur is consistently added to abyssal peridotites during serpentinization. Data for serpentinites drilled and dredged from oceanic crust and from ophiolites indicate that oceanic peridotites are a sink for up to 0.4 to 6.0 × 10¹² g seawater S yr⁻¹. This is comparable to sulfur exchange that occurs in hydrothermal systems in mafic oceanic crust at midocean ridges and on ridge flanks and amounts to 2 to 30% of the riverine sulfate source and sedimentary sulfide sink in the oceans. The high concentrations and modified isotope compositions of sulfur in serpentinites could be important for mantle metasomatism during subduction of crust generated at slow spreading rates.     

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.     

Mineralogy and chemistry of Cu-Fe-Ni sulfides in orogenic-type spinel peridotite bodies from Ariege (Northeastern Pyrenees,France)

Mantle-derived peridotite bodies of Ariège are composed of spinel lherzolites and harzburgites ranging from remarkably fresh (less than 5% serpentinized) samples with protogranular texture to secondary foliated samples, which are generally 10%–20% serpentinized. The foliated samples have passed through two cycles of deformation and re-crystallization, the earlier ones occurring at temperatures above 950° C for 15 kbar pressure, the later ones at temperatures between 950° and 750° C for 8–15 kbar. Microscopic investigation of 140 samples reveals an accessoy sulfide component which is more abundant in lherzolie than in harzburgite. This component occurs in two differet textural locations, either as inclusions trapped within silicates during the first stage of re-crystallization or as interstitial grains among silicates. Mineralogy and chemistry of both sulfide occurrences are quite similar, at least in samples less than 5% serpentinized. In these fresh samples, sulfides are composed of complex intergrowths between nickel-rich pentlandite and pyrite, coexisting with minor primary pyrrhotite (Fe₇S₈) and chalcopyrite. Pentlandite and pyrite are interpreted as low-temperature breakdown products of upper mantle monosulfide solid solutions. The mineralogy and chemistry of interstitial sulfides in serpentinized rocks vary in parallel with the degree of serpentinization. In samples less than 10% serpentinized, primary pyrrhotite grades into FeS. In samples more than 10% serpentinized, pyrite is replaced by secondary pyrrhotite, and then disappears totally, whereas the coexisting pentlandite is Fe-enriched and replaced by mackinawite. This sequence of alteration indicates a decrease of sulfur fugacity, resulting from serpentinization of olivine at temperatures below 300° C. This is also the case for the inclusions which have been fractured during the tectonic emplacement of the host peridotites within the crust. The presence of non-equilibrium sulfide assemblages in both cases reflects the sluggishness of solid state reactions at near-surface temperatures. It is inferred from these results that sulfides disseminated within orogenic peridotite massifs are so sensitive to serpentinization that most sulfur fugacity estimates based on fractured inclusions and intergranular sulfides are unreliable.     

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.     

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.     

On Silica Activity and Serpentinization

Serpentinites have the lowest silica activity of common crustalrocks. At the serpentinization front, where olivine, serpentine,and brucite are present, silica activities (relative to quartz)are of the order of 10^–2·5 to 10^–5, dependingon the temperature. Here we argue that this low silica activityis the critical property that produces the unusual geochemicalenvironments characteristic of serpentinization. The formationof magnetite is driven by the extraction of silica from theFe₃Si₂O₅(OH)₄ component of serpentine, producing extremely reducingconditions as evinced by the rare iron alloys that partiallyserpentinized peridotites contain. The incongruent dissolutionof diopside to form Ca²⁺, serpentine, and silica becomes increasinglyfavored at lower T, producing the alkalic fluids characteristicof serpentinites. The interaction of these fluids with adjacentrocks produces rodingites, and we argue that desilication isalso part of the rodingite-forming process. The low silica activityalso explains the occurrence of low-silica minerals such ashydrogrossular, andradite, jadeite, diaspore, and corundum inserpentinites or rocks adjacent to serpentinites. The tendencyfor silica activity to decrease with decreasing temperaturemeans that the presence of certain minerals in serpentinitescan be used as indicators of the temperature of serpentinization.These include, with decreasing temperature, diopside, andraditeand diaspore. Because the assemblage serpentine + brucite marksthe lowest silica activity reached in most serpentinites, thepresence and distribution of brucite, which commonly is a crypticphase in serpentinites, is critical to interpreting the processesthat lead to the hydration of any given serpentinite. KEY WORDS: serpentinization; serpentinites; silica activity; oxygen fugacity; rodingites; magnetization of serpentinites     

Metamorphism of peritotites in the mantle wedge above the subduction zone: Hydration of the lithospheric mantle

Two areas with different types of hydration (serpentinization), which occurred in two settings distinct in temperatures, pressures, and stresses, are spatially individualized in the ophiolitic ultramafic massifs of the Polar Urals. The high-temperature hydration of ultramafic rocks occurred in the lithosphere of the mantle wedge directly above the subducted slab. The initial conditions of hydration are limited to 1.2–2 GPa and 650–700°C; a stable assemblage of olivine + antigorite + magnetite → amphibole → talc → chlorite was formed at 0.9–1.2 GPa and 550–600°C. The low-temperature mesh lizardite–chrysotile serpentinization occurred in the crustal, near-surface conditions. Both types of hydration were accompanied by release of hydrogen, which participates in abiogenic CH₄ synthesis in the presence of CO₂ dissolved in water.     

Neoproterozoic ophiolitic peridotites along the Allaqi-Heiani suture, South Eastern Desert, Egypt

The Wadi Allaqi ophiolite along the Egyptian-Sudanese border defines the southernmost ophiolitic assemblage and suture zone in the Eastern Desert. Ophiolite assemblages comprise nappes composed mainly of mafic and ultramafic rocks that were tectonically emplaced and replaced by serpentine and carbonates along shear zones probably due to CO₂-metasomatism. Serpentinites, altered slices of the upper mantle, represent a distinctive lithology of dismembered ophiolites of the western YOSHGAH suture. Microscopically, they are composed of more than 90 % serpentine minerals with minor opaque minerals, carbonate, brucite and talc. The mineral chemistry and whole-rock chemical data reported here indicate that the serpentinized peridotites formed as highly-depleted mantle residues. They show compositions consistent with formation in a suprasubduction zone environment. They are depleted in Al₂O₃ and CaO similar to those in fore-arc peridotites. Also, high Cr# (Cr/ (Cr+Al)) in the relict chrome spinels (average ~0.72) indicates that these are residual after extensive partial melting, similar to spinels in modern fore-arc peridotites. Therefore, the studied serpentinites represent fragments of an oceanic lithosphere that formed in a fore-arc environment, which belongs to an ophiolitic mantle sequence formed in a suprasubduction zone.     

Sulfur in peridotites and gabbros at Lost City (30°N, MAR): Implications for hydrothermal alteration and microbial activity during serpentinization

Variations in sulfur mineralogy and chemistry of serpentinized peridotites and gabbros beneath the Lost City Hydrothermal Field at the southern face of the Atlantis Massif (Mid-Atlantic Ridge, 30°N) were examined to better understand serpentinization and alteration processes and to study fluid fluxes, redox conditions, and the influence of microbial activity in this active, peridotite-hosted hydrothermal system. The serpentinized peridotites are characterized by low total sulfur contents and high bulk δ³⁴S values close to seawater composition. Low concentrations of ³⁴S-enriched sulfide phases and the predominance of sulfate with seawater-like δ³⁴S values indicate oxidation, loss of sulfide minerals and incorporation of seawater sulfate into the serpentinites. The predominance of pyrite in both serpentinites and gabbros indicates relatively high fO₂ conditions during progressive serpentinization and alteration, which likely result from high fluid fluxes during hydrothermal circulation and evolution of the Lost City system from temperatures of ∼250 to 150 °C. Sulfate and sulfide minerals in samples from near the base of hydrothermal carbonate towers at Lost City show δ³⁴S values that reflect the influence of microbial activity. Our study highlights the variations in sulfur chemistry of serpentinized peridotites in different marine environments and the influence of long-lived, moderate temperature peridotite-hosted hydrothermal system and high seawater fluxes on the global sulfur cycle.     

The compositional variation of synthetic sodic amphiboles at high and ultra-high pressures

Sodic amphiboles in high pressure and ultra-high pressure (UHP) metamorphic rocks are complex solid solutions in the system Na₂O–MgO–Al₂O₃–SiO₂–H₂O (NMASH) whose compositions vary with pressure and temperature. We conducted piston-cylinder experiments at 20–30?kbar and 700–800?°C to investigate the stability and compositional variations of sodic amphiboles, based on the reaction glaucophane=2jadeite+talc, by using the starting assemblage of natural glaucophane, talc and quartz, with synthetic jadeite. A close approach to equilibrium was achieved by performing compositional reversals, by evaluating compositional changes with time, and by suppressing the formation of Na-phyllosilicates. STEM observations show that the abundance of wide-chain structures in the synthetic amphiboles is low. An important feature of sodic amphibole in the NMASH system is that the assemblage jadeite–talc?±?quartz does not fix its composition at glaucophane. This is because other amphibole species such as cummingtonite (Cm), nyböite (Nyb), Al–Na-cummingtonite (Al–Na-Cm) and sodium anthophyllite (Na-Anth) are also buffered via the model reactions: 3cummingtonite?+?4quartz?+?4H₂O=7talc, nyböite?+?3quartz=3jadeite?+?talc, 3Al–Na-cummingtonite + 11quartz + 2H₂O=6jadeite + 5talc, and 3 sodium anthophyllite?+?13quartz?+?4H₂O=3 jadeite + 7talc. We observed that at all pressures and temperatures investigated, the compositions of newly grown amphiboles deviate significantly from stoichiometric glaucophane due to varying substitutions of Al^IV for Si, Mg on the M(4) site, and Na on the A-site. The deviation can be described chiefly by two compositional vectors: [Na^AAl^IV]<=>[□^ASi] (edenite) toward nyböite, and [Na^(M4)Al^VI]<=>[Mg^(M4)Mg^VI] toward cummingtonite. The extent of nyböite and cummingtonite substitution increases with temperature and decreases with pressure in the experiments. Similar compositional variations occur in sodic amphiboles from UHP rocks. The experimentally calibrated compositional changes therefore may prove useful for thermobarometric applications.     

Mantle peridotite in newly discovered far-inland subduction complex,southwest Arizona: initial report

The latest Cretaceous to early Palaeogene Orocopia Schist and related units are generally considered a low-angle subduction complex that underlies much of southern California and Arizona. A recently discovered exposure of Orocopia Schist at Cemetery Ridge west of Phoenix, Arizona, lies exceptionally far inland from the continental margin. Unexpectedly, this body of Orocopia Schist contains numerous blocks, as large as ~300 m, of variably serpentinized mantle peridotite. These are unique; elsewhere in the Orocopia and related schists, peridotite is rare and completely serpentinized. Peridotite and metaperidotite at Cemetery Ridge are of three principal types: (1) serpentinite and tremolite serpentinite, derived from dunite; (2) partially serpentinized harzburgite and olivine orthopyroxenite (collectively, harzburgite); and (3) granoblastic or schistose metasomatic rocks, derived from serpentinite, made largely of actinolite, calcic plagioclase, hercynite, and chlorite. In the serpentinite, paucity of relict olivine, relatively abundant magnetite (5%), and elevated Fe³⁺/Fe indicate advanced serpentinization. Harzburgite contains abundant orthopyroxene, only slightly serpentinized, and minor to moderate (1–15%) relict olivine. Mantle tectonite fabric is locally preserved. Several petrographic and geochemical characteristics of the peridotite at Cemetery Ridge are ambiguously similar to either abyssal or mantle-wedge (suprasubduction) peridotites and serpentinites. Least ambiguous are orthopyroxene compositions. Orthopyroxene is distinctively depleted in Al₂O₃, Cr₂O₃, and CaO, indicating mantle-wedge affinities. Initial interpretation of field and petrologic data suggests that the peridotite blocks in the Orocopia Schist subduction complex at Cemetery Ridge may be derived from the leading corner or edge of a mantle wedge, presumably in (pre-San Andreas fault) southwest California. However, derivation from a subducting plate is not precluded.     

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.     

Fluid–rock interaction during seprentinization of oceanic ultramafic rocks hosting the Lost City hydrothermal field, 30° N,MAR

The estimation of the fluid/rock (W/R) ratio during serpentinization on the basis of oxygen isotope characteristics is peculiar, because this process is accompanied by not only changes in the stoichiometric proportions of oxygen in fluid and rock, but also by the formation of associated minerals. These factors should be taken into account for environments when the volume of aqueous fluid is limited, for instance, for serpentinization of the deep-seated rocks of oceanic lithosphere under low spreading rates. We studied isotope characteristics of samples collected in dives of submersible MIR during Cruise 50 of the R/V Akademik Mstislav Keldysh along vertical profile on the southern slope of the Atlantis Massif, which hosts the Lost City hydrothermal field. Almost all studied serpentinites have homogenous strontium isotope composition corresponding to the composition of the modern seawater. Oxygen isotope composition of these serpentinites shows systematic variations from 2. 6 to 6.1‰ with sampling depth, which indicates the preservation of stratigraphic position of samples in the sequence of the Atlantis Massif and the global serpentinization of the entire plutonic sequence. The value of the fluid–rock ratio during serpentinization in a system closed to fluid was estimated using the dissolution–crystallization model. This model takes into account the variable stoichiometry of oxygen and the effect of the simultaneous crystallization of brucite on the oxygen isotope composition of newly formed serpentine. The results show that at moderately elevated temperatures (≈300°C) and 0.1 < W/R < 5, fluid, crystallizing serpentine, and brucite are characterized by sharp variations in oxygen isotope composition: 1.3–7.8, 2.5–8.9, and 4.5–1.9‰, respectively. The model explains the observed range of δ¹⁸O in the serpentinized harzburgites of the Atlantis Massif. According to our estimates, the rocks of the studied sequence of the Atlantis Massif were serpentinized at 270–350°C and W/R = 0.7–3. For lower temperature serpentinization, for instance, at T = 250°C, the W/R ratio can be as high as 6. The present-day serpentinization of the deepseated zones of the Atlantis Massif with the Lost City fluid participance proceeds at T > 270°C and W/R ratio <1. These conditions are similar to those of serpentinization of harzburgites from the lower parts of the studied sequence of the Atlantis Massif.     

The production of iron oxide during peridotite serpentinization: Influence of pyroxene

Serpentinization produces molecular hydrogen(H2)that can support communities of microorganisms in hydrothermal fields;H2 results from the oxidation of ferrous iron in olivine and pyroxene into ferric iron,and consequently iron oxide(magnetite or hematite)forms.However,the mechanisms that control H2 and iron oxide formation are poorly constrained.In this study,we performed serpentinization experiments at 311℃ and 3.0 kbar on olivine(with 5% pyroxene),orthopyroxene,and peridotite.The results show that serpentine and iron oxide formed when olivine and orthopyroxene individually reacted with a saline starting solution.Olivine-derived serpentine had a significantly lower FeO content(6.57±1.30 wt.%)than primary olivine(9.86 wt.%),whereas orthopyroxene-derived serpentine had a comparable FeO content(6.26±0.58 wt.%)to that of primary orthopyroxene(6.24 wt.%).In experiments on peridotite,olivine was replaced by serpentine and iron oxide.However,pyroxene transformed solely to serpentine.After 20 days,olivine-derived serpentine had a FeO content of 8.18±1.56 wt.%,which was significantly higher than that of serpentine produced in olivine-only experiments.By contrast,serpentine after orthopyroxene had a slightly higher FeO content(6.53±1.01 wt.%)than primary orthopyroxene.Clinopyroxene-derived serpentine contained a significantly higher FeO content than its parent mineral.After 120 days,the FeO content of olivine-derived serpentine decreased significantly(5.71±0.35 wt.%),whereas the FeO content of orthopyroxene-derived serpentine increased(6.85±0.63 wt.%)over the same period.This suggests that iron oxide preferentially formed after olivine serpentinization.Pyroxene in peridotite gained some Fe from olivine during the serpentinization process,which may have led to a decrease in iron oxide production.The correlation between FeO content and SiO_2 or AI_2 O_3 content in olivine-and orthopyroxene-derived serpentine indicates that aluminum and silica greatly control the production of iron oxide.Based on our results and data from natural serpentinites reported by other workers,we propose that aluminum may be more influential at the early stages of peridotite serpentinization when the production of iron oxide is very low,whereas silica may have a greater control on iron oxide production during the late stages instead.     

Carbonate alteration of ophiolitic rocks in the Arabian–Nubian Shield of Egypt: sources and compositions of the carbonating fluid and implications for the formation of Au deposits

Ultramafic portions of ophiolitic fragments in the Arabian–Nubian Shield (ANS) show pervasive carbonate alteration forming various degrees of carbonated serpentinites and listvenitic rocks. Notwithstanding the extent of the alteration, little is known about the processes that caused it, the source of the CO₂ or the conditions of alteration. This study investigates the mineralogy, stable (O, C) and radiogenic (Sr) isotope composition, and geochemistry of suites of variably carbonate altered ultramafics from the Meatiq area of the Central Eastern Desert (CED) of Egypt. The samples investigated include least-altered lizardite (Lz) serpentinites, antigorite (Atg) serpentinites and listvenitic rocks with associated carbonate and quartz veins. The C, O and Sr isotopes of the vein samples cluster between ?8.1‰ and ?6.8‰ for δ¹³C, +6.4‰ and +10.5‰ for δ¹⁸O, and ⁸⁷Sr/⁸⁶Sr of 0.7028–0.70344, and plot within the depleted mantle compositional field. The serpentinites isotopic compositions plot on a mixing trend between the depleted-mantle and sedimentary carbonate fields. The carbonate veins contain abundant carbonic (CO₂±CH₄±N₂) and aqueous-carbonic (H₂O-NaCl-CO₂±CH₄±N₂) low salinity fluid, with trapping conditions of 270–300°C and 0.7–1.1 kbar. The serpentinites are enriched in Au, As, S and other fluid-mobile elements relative to primitive and depleted mantle. The extensively carbonated Atg-serpentinites contain significantly lower concentrations of these elements than the Lz-serpentinites suggesting that they were depleted during carbonate alteration. Fluid inclusion and stable isotope compositions of Au deposits in the CED are similar to those from the carbonate veins investigated in the study and we suggest that carbonation of ANS ophiolitic rocks due to influx of mantle-derived CO₂-bearing fluids caused break down of Au-bearing minerals such as pentlandite, releasing Au and S to the hydrothermal fluids that later formed the Au-deposits. This is the first time that gold has been observed to be remobilized from rocks during the lizardite–antigorite transition.