On the survival of intergranular coesite in UHP eclogite

Coesite is typically found as inclusions in rock‐forming or accessory minerals in ultrahigh‐pressure (UHP) metamorphic rocks. Thus, the survival of intergranular coesite in UHP eclogite at Yangkou Bay (Sulu belt, eastern China) is surprising and implies locally “dry” conditions throughout exhumation. The dominant structures in the eclogites at Yangkou are a strong D₂ foliation associated with tight‐to‐isoclinal F₂ folds that are overprinted by close‐to‐tight F₃ folds. The coesite‐bearing eclogites occur as rootless intrafolial isoclinal F₁ fold noses wrapped by a composite S₁–S₂ foliation in interlayered phengite‐bearing quartz‐rich schists. To evaluate controls on the survival of intergranular coesite, we determined the number density of intergranular coesite grains per cm² in thin section in two samples of coesite eclogite (phengite absent) and three samples of phengite‐bearing coesite eclogite (2–3 vol.% phengite), and measured the amount of water in garnet and omphacite in these samples, and also in two samples of phengite‐bearing quartz eclogite (6–7 vol.% phengite, coesite absent). As coesite decreases in the mode, the amount of primary structural water stored in the whole rock, based on the nominally anhydrous minerals (NAMs), increases from 107/197 ppm H₂O in the coesite eclogite to 157–253 ppm H₂O in the phengite‐bearing coesite eclogite to 391/444 ppm H₂O in the quartz eclogite. In addition, there is molecular water in the NAMs and modal water in phengite. If the primary concentrations reflect differences in water sequestered during the late prograde evolution, the amount of fluid stored in the NAMs at the metamorphic peak was higher outside of the F₁ fold noses. During exhumation from UHP conditions, where NAMs became H₂O saturated, dehydroxylation would have generated a free fluid phase. Interstitial fluid in a garnet–clinopyroxene matrix at UHP conditions has dihedral angles >60°, so at equilibrium fluid will be trapped in isolated pores. However, outside the F₁ fold noses strong D₂ deformation likely promoted interconnection of fluid and migration along the developing S₂ foliation, enabling conversion of some or all of the intergranular coesite into quartz. By contrast, the eclogite forming the F₁ fold noses behaved as independent rigid bodies within the composite S₁–S₂ foliation of the surrounding phengite‐bearing quartz‐rich schists. Primary structural water concentrations in the coesite eclogite are so low that H₂O saturation of the NAMs is unlikely to have occurred. This inherited drier environment in the F₁ fold noses was maintained during exhumation by deformation partitioning and strain localization in the schists, and the fold noses remained immune to grain‐scale fluid infiltration from outside allowing coesite to survive. The amount of inherited primary structural water and the effects of strain partitioning are important variables in the survival of coesite during exhumation of deeply subducted continental crust. Evidence of UHP metamorphism may be preserved in similar isolated structural settings in other collisional orogens.     

Calculated phase equilibria for a morb composition in a P–T range, 450–650 °C and 18–28 kbar: the stability of eclogite

Lower temperature eclogite (with T = 600 °C) represents a significant part of the occurrences of eclogite in orogenic belts. ‘True’ eclogite, with, for example, garnet + omphacite >70%, is well represented in such an occurrence. Calculated phase equilibria in Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (NCKFMASHTO), for just one rock composition – that of a representative mid‐ocean ridge basalt, morb – are used to see under what circumstances ‘true’ eclogite is predicted to occur. The variables considered are not only pressure (P) and temperature (T) but also water content and oxidation state. The latter two variables are known to exert a significant control on mineral assemblage but are difficult to establish retrospectively from the observed rocks themselves. It is found that whereas oxidation state does have a strong effect on mineral assemblage, the key control on developing ‘true’ eclogite is shown to be temperature and water content. If temperature is established to be <600 °C, water content has to be low (less or much less than that for H₂O saturation) in order for ‘true’ eclogite to form. Moreover, unless pressure is at the high end in the range considered, lawsonite eclogite and ‘true’ eclogite will tend to be mutually exclusive, with the former requiring high water content at the lower temperature where it occurs, but the latter requiring low water content.     

Calcium and Magnesium‐bearing Sabugalite from the Tono Uranium Deposit,Central Japan

Calcium and magnesium‐bearing sabugalite occurs as aggregations of yellowish platy crystals in veinlets or druses in conglomerate from the oxidized parts of the Tono uranium deposit, Central Japan. X‐ray powder diffractometry of this mineral has reflections consistent with previous powder diffraction data of sabugalite. It is included in the monoclinic system with space group C2/m and calculated cell parameters of a = 19.68Å, b = 9.89Å, c = 9.82Å α = γ = 90°, β‐96.93° and V = 1897.83ų. Chemical analysis yields a formula of (Ca_0.10 Mg_0.09)_Σ0.19Al_0.53(UO₂)_2.04((PO₄)_1.99(AsO₄)_0.01)_Σ2.00·11.22H₂O. EMPA mapping shows that the mineral is compositionally uniform with no micron‐scale layering. Charge of cations including Ca and Mg in the cation‐H₂O layer is 1.98 being identical to that of autunite group minerals. This suggests that the charge balance in the cation‐H₂O layer of the mineral could be made by the alkaline earth or alkaline elements rather than by hydrogen ions.     

Mineral oxygen isotope and hydroxyl content changes in ultrahigh-pressure eclogite–gneiss contacts from Chinese Continental Scientific Drilling Project cores

A combined study of mineral O isotopes and hydroxyl contents was carried out for the contacts between ultrahigh‐pressure eclogite and gneiss from main hole of the Chinese Continental Scientific Drilling Project in the Sulu orogen. While there is a large δ¹⁸O variation from ?8.3 to 7.3‰ for all minerals, different styles of mineral‐pair fractionation occur at the boundaries of different lithologies. Both equilibrium and disequilibrium O isotope fractionations are observed between quartz and the other minerals, with reversed fractionations between omphacite and garnet in some samples of eclogite. This suggests that both eclogite and gneiss acquired their negative δ¹⁸O values by meteoric‐hydrothermal alteration of their protoliths at high temperatures before subduction, and that fluid‐assisted O isotope exchange did take place across the boundary of different lithologies at local scales during amphibolite‐facies retrogression. Fourier Transform Infrared Spectroscopy analysis yielded H₂O concentrations of 50 to 1144 p.p.m. (by weight) for garnet and 139 to 751 p.p.m. for omphacite. The state of equilibrium or disequilibrium O isotope fractionations between omphacite and garnet are correlated with variations in their water content at local scales, indicating that the internally derived fluid plays a critical role in retrograde metamorphism during exhumation. The retrograde metamorphism results in mineral reactions and O isotope disequilibria between some of the minerals, but the fluid for retrogression was derived from the decompression exsolution of structural hydroxyl and thus internally buffered in the O isotope composition. A quantitative estimate suggests that a hand specimen (3 × 6 × 9 cm) of eclogite composed of 70% garnet and 30% omphacite can release 0.316 g water by the decompression exsolution of structural hydroxyl, which can form 14.4 g amphibole during exhumation. This provides sufficient amounts of water for the amphibolite‐facies retrogression.     

Phase equilibria modelling of blueschist and eclogite from the Sanbagawa metamorphic belt of southwest Japan reveals along‐strike consistency in tectonothermal architecture

The Sanbagawa metamorphic belt of southwest Japan is one of the type localities of subduction‐related high‐P metamorphism. However, variable pressure–temperature (P–T) paths and metabasic assemblages have been reported for eclogite units in the region, leading to uncertainty about the subduction zone paleo‐thermal structure and associated tectonometamorphic conditions. To analyse this variation, phase equilibria modelling was applied to the three main high‐P metabasic rock types documented in the region – glaucophane eclogite, barroisite eclogite and garnet blueschist – with modelling performed over a range of P, T, bulk rock H₂O and bulk rock ferric iron conditions using thermocalc . All samples are calculated to share a common steep prograde P–T path to similar peak conditions of ～16–20 kbar and 560–610 °C. The results establish that regional assemblage variation is systematic, with the alternation in peak amphibole phase due to peak conditions overlapping the glaucophane–barroisite solvus, and bulk composition effects stabilizing blueschist v. eclogite facies assemblages at similar P–T conditions. Furthermore, the results reveal that a steep prograde P–T path is common to all eclogite units in the Sanbagawa belt, indicating that metamorphic conditions were consistent along strike. All localities are compatible with predictions made by a ridge approach model, which attributes eclogite facies metamorphism and exhumation of the Sanbagawa belt to the approach of a spreading ridge.     

Details of the gabbro‐to‐eclogite transition determined from microtextures and calculated chemical potential relationships

Permian‐aged metagabbros from the eclogite type‐locality in the eastern European Alps were partially to completely transformed to eclogite during Eoalpine intracontinental subduction. Microtextures developed along a preserved fluid infiltration and reaction front in the gabbros record the incipient gabbro‐to‐eclogite transition, allowing the details of the eclogitization process to be investigated. Original, anorthite‐rich igneous plagioclase is pervasively replaced by fine‐grained intergrowths of clinozoisite, kyanite and Na‐rich plagioclase. Where plagioclase was in contact with igneous orthopyroxene, 100–200 μm thick bimineralic coronae of symplectic kyanite and diopsidic clinopyroxene form along the edges of the grains. The rims of igneous orthopyroxene develop a complementary bimineralic corona of diopsidic clinopyroxene and garnet. Igneous clinopyroxene does not show any breakdown textures; however, jadeite content gradually increases towards the rims. In addition, exsolution lamellae inherited from the igneous clinopyroxene become progressively more jadeitic as eclogitization proceeds. Given that the igneous plagioclase is pervasively replaced by clinozoisite, kyanite and Na‐rich plagioclase, whereas kyanite–diopside symplectites are confined to narrow rim zones, we suggest that the development of these textures was controlled by the (im)mobility of different elements on different length scales. The presence of hydrous minerals in the core of anhydrous plagioclase indicates that H₂O diffusivity occurred on a mm‐scale. By contrast, the size of the anhydrous diopside–kyanite and diopside–garnet symplectites indicate that Fe–Mg–Ca–Na diffusivity was limited to a 10s of μm scale. Chemical potential relations calculated in the idealized NCASH chemical system show that the clinozoisite–kyanite–albite intergrowths formed due to an increase of μH₂O to plagioclase, whereas all other elements remained effectively immobile on the scale of this texture. Fluid conditions indicated by this texture span from virtually dry conditions (0.15) to H₂O‐saturation, and therefore does not imply that the rocks were ever fluid‐saturated. Calculations in the CMAS and NCFMAS systems show that the gabbro‐to‐eclogite transition is characterized by the growth of garnet, diopsidic clinopyroxene and kyanite due to diffusion of Ca (+ Na) and Mg (+ Fe) along a μCaO (+ Na₂O)–μMgO (+ FeO) chemical potential gradient developed between orthopyroxene and plagioclase compositional domains. The anhydrous nature of the textures indicate that the gabbro‐to‐eclogite transition is not driven by hydration; however, increased μH₂O acts as a catalyst that increases diffusivity of all elements and rates of dissolution–precipitation, allowing the overstepped metamorphic reactions to occur. Our results show that crustal eclogite formation requires low H₂O content, confirming that true eclogites are dry rocks.     

Fractionation of bulk rock composition due to porphyroblast growth: effects on eclogite facies mineral equilibria, Pam Peninsula, New Caledonia

Chemically zoned porphyroblasts in metamorphic rocks indicate that diffusional processes could not maintain equilibrium conditions on a grain scale during porphyroblast growth or establish it afterwards. An effect of this inability to maintain equilibrium is the progressive removal of elements forming garnet cores from any metamorphic reaction that occurs at the porphyroblast boundaries or in the matrix of the rock. To examine this effect on mineral assemblages, the Bence–Albee matrix correction was applied to X‐ray intensity maps collected using eclogite samples from northern New Caledonia in order to determine the chemical composition of all parts of the sample. The manipulation of these element maps allows a quantitative analysis of the fractionation of the bulk rock composition between garnet cores and the matrix. A series of calculated equilibrium‐volume compositions represents the change in matrix chemistry with progressive elemental fractionation as a consequence of prograde garnet growth under high‐P conditions. Pressure–temperature pseudosections are calculated for these compositions, in the CaO–Na₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O system. Assemblages, modal proportions and mineral textures observed in the New Caledonian eclogites can be closely modelled by progressively ‘removing’ elements forming garnet cores from the bulk rock composition. The pseudosections demonstrate how chemical fractionation effects the peak metamorphic assemblage, prograde textures and the development of retrograde assemblages.     

Intermediate granulite produced by transformation of eclogite at a felsic granulite contact,in Blanský les,Bohemian Massif

Layers or bodies of intermediate granulite on scales from a centimetre to a hundred metres occur commonly within the felsic granulite massifs of the Bohemian Massif. Their origin is enigmatic in that they commonly have complex microstructures that are difficult to interpret, and therefore even the sequence of crystallization of minerals is uncertain. At Kle?, in the Blanský les massif, there is a revealing outcrop in a low‐strain zone in which it is clear that intermediate granulite can form by the interaction of felsic granulite with eclogite. The eclogite, retains garnet from its eclogite heritage, the grains at least partially isolated from the matrix by a plagioclase corona. The original omphacite‐dominated matrix of the eclogite now consists of recrystallized diopsidic clinopyroxene, orthopyroxene and plagioclase, with minor brown amphibole and quartz. The modification of the eclogite is dominated by the addition of just K₂O and H₂O, rather than all the elements that would be involved if the process was one of pervasive melt infiltrations. This suggests that the main process involved is diffusion, with the source being the felsic granulite, or local partial melt of the granulite. The diffusion occurred at ~950 °C and 12 kbar, with the main observed effects being (i) the un‐isolation and preferential destruction of the interior part of some of the garnet grains by large idiomorphic ternary feldspar; (ii) textural modification of the matrix primarily involving the recrystallization of clinopyroxene into large poikiloblasts containing inclusions of ternary plagioclase; and (iii) conversion of low‐K plagioclase in the matrix into ternary feldspar by incorporation of the diffused‐in K₂O. The phase equilibria in the intermediate granulite are consistent with the chemical potential relationships that would be superimposed on the original eclogite by the felsic granulite at 950 °C and 12 kbar.     

Fluid generation and evolution during exhumation of deeply subducted UHP continental crust: Petrogenesis of composite granite–quartz veins in the Sulu belt,China

Composite granite–quartz veins occur in retrogressed ultrahigh pressure (UHP) eclogite enclosed in gneiss at General's Hill in the central Sulu belt, eastern China. The granite in the veins has a high‐pressure (HP) mineral assemblage of dominantly quartz+phengite+allanite/epidote+garnet that yields pressures of 2.5–2.1 GPa (Si‐in‐phengite barometry) and temperatures of 850–780°C (Ti‐in‐zircon thermometry) at 2.5 GPa (~20°C lower at 2.1 GPa). Zircon overgrowths on inherited cores and new grains of zircon from both components of the composite veins crystallized at c. 221 Ma. This age overlaps the timing of HP retrograde recrystallization dated at 225–215 Ma from multiple localities in the Sulu belt, consistent with the HP conditions retrieved from the granite. The ε_Hf(t) values of new zircon from both components of the composite veins and the Sr–Nd isotope compositions of the granite consistently lie between values for gneiss and eclogite, whereas δ¹⁸O values of new zircon are similar in the veins and the crustal rocks. These data are consistent with zircon growth from a blended fluid generated internally within the gneiss and the eclogite, without any ingress of fluid from an external source. However, at the peak metamorphic pressure, which could have reached 7 GPa, the rocks were likely fluid absent. During initial exhumation under UHP conditions, exsolution of H₂O from nominally anhydrous minerals generated a grain boundary supercritical fluid in both gneiss and eclogite. As exhumation progressed, the volume of fluid increased allowing it to migrate by diffusing porous flow from grain boundaries into channels and drain from the dominant gneiss through the subordinate eclogite. This produced a blended fluid intermediate in its isotope composition between the two end‐members, as recorded by the composite veins. During exhumation from UHP (coesite) eclogite to HP (quartz) eclogite facies conditions, the supercritical fluid evolved by dissolution of the silicate mineral matrix, becoming increasingly solute‐rich, more ‘granitic’ and more viscous until it became trapped. As crystallization began by diffusive loss of H₂O to the host eclogite concomitant with ongoing exhumation of the crust, the trapped supercritical fluid intersected the solvus for the granite–H₂O system, allowing phase separation and formation of the composite granite–quartz veins. Subsequently, during the transition from HP eclogite to amphibolite facies conditions, minor phengite breakdown melting is recorded in both the granite and the gneiss by K‐feldspar+plagioclase+biotite aggregates located around phengite and by K‐feldspar veinlets along grain boundaries. Phase equilibria modelling of the granite indicates that this late‐stage melting records P–T conditions towards the end of the exhumation, with the subsolidus assemblage yielding 0.7–1.1 GPa at <670°C. Thus, the composite granite–quartz veins represent a rare example of a natural system recording how the fluid phase evolved during exhumation of continental crust. The successive availability of different fluid phases attending retrograde metamorphism from UHP eclogite to amphibolite facies conditions will affect the transport of trace elements through the continental crust and the role of these fluids as metasomatic agents interacting with the mantle wedge in the subduction channel.     

Experimental study of metamorphic reactions and dehydration processes at the blueschist–eclogite transition during warm subduction

The transition between blueschist and eclogite plays an important role in subduction zones via dehydration and densification processes in descending oceanic slabs. There are a number of previous petrological studies describing potential mineral reactions taking place at the transition. An experimental determination of such reactions could help constrain the pressure–temperature conditions of the transition as well as the processes of dehydration. However, previous experimental contributions have focused on the stability of spontaneously formed hydrous minerals in basaltic compositions rather than on reactions among already formed blueschist facies minerals. Therefore, this study conducted three groups of experiments to explore the metamorphic reactions among blueschist facies minerals at conditions corresponding to warm subduction, where faster reaction rates are possible on the time scale of laboratory experiments. The first group of experiments was to establish experimental reversals of the reaction glaucophane+paragonite to jadeite+pyrope+quartz+H₂O over the range of 2.2–3.5 GPa and 650–820°C. This reaction has long been treated as key to the blueschist–eclogite transition. However, only the growth of glaucophane+paragonite was observed at the intersectional stability field of both paragonite and jadeite+quartz, confirming thermodynamic calculations that the reaction is not stable in the system Na₂O–MgO–Al₂O₃–SiO₂–H₂O. The second set of experiments involved unreversed experiments using glaucophane+zoisite ±quartz in low‐Fe and Ca‐rich systems and were run at 1.8–2.4 GPa and 600–780°C. These produced omphacite+paragonite/kyanite+H₂O accompanied by compositional shifts in the sodium amphibole, glaucophane, towards sodium–calcium amphiboles such as winchite (?(CaNa)(Mg₄Al)Si₈O₂₂(OH)₂) and barroisite (?(CaNa)(Mg₃Al₂)(AlSi₇)O₂₂(OH)₂). This suggests that a two‐step dehydration occurs, first involving the breakdown of glaucophane+zoisite towards a paragonite‐bearing assemblage, then the breakdown of paragonite to release H₂O. It also indicates that sodium–calcium amphibole can coexist with eclogite phases, thereby extending the thermal stability of amphibole to greater subduction zone depths. The third set of experiments was an experimental investigation at 2.0–2.4 GPa and 630–850°C involving a high‐Fe (Fe#=Fe_total/(Fe_total+Mg)≈0.36) natural glaucophane, synthetic paragonite and their eclogite‐forming reaction products. The results indicated that garnet and omphacite grew over most of these pressure–temperature conditions, which demonstrates the importance of Fe‐rich glaucophane in forming the key eclogite assemblage of garnet+omphacite, even under warm subduction zone conditions. Based on the experiments of this study, reaction between glaucophane+zoisite is instrumental in controlling dehydration processes at the blueschist–eclogite transition during warm subduction.     

Constraining the P–T path of a MORB-type eclogite using pseudosections, garnet zoning and garnet-clinopyroxene thermometry: an example from the Bohemian Massif

A mid‐ocean ridge basalt (MORB)‐type eclogite from the Moldanubian domain in the Bohemian Massif retains evidence of its prograde path in the form of inclusions of hornblende, plagioclase, clinopyroxene, titanite, ilmenite and rutile preserved in zoned garnet. Prograde zoning involves a flat grossular core followed by a grossular spike and decrease at the rim, whereas Fe/(Fe + Mg) is also flat in the core and then decreases at the rim. In a pseudosection for H₂O‐saturated conditions, garnet with such a zoning grows along an isothermal burial path at c. 750 °C from 10 kbar in the assemblage plagioclase‐hornblende‐diopsidic clinopyroxene‐quartz, then in hornblende‐diopsidic clinopyroxene‐quartz, and ends its growth at 17–18 kbar. From this point, there is no pseudosection‐based information on further increase in pressure or temperature. Then, with garnet‐clinopyroxene thermometry, the focus is on the dependence on, and the uncertainties stemming from the unknown Fe³⁺ content in clinopyroxene. Assuming no Fe³⁺ in the clinopyroxene gives a serious and unwarranted upward bias to calculated temperatures. A Fe³⁺‐contributed uncertainty of ±40 °C combined with a calibration and other uncertainties gives a peak temperature of 760 ± 90 °C at 18 kbar, consistent with no further heating following burial to eclogite facies conditions. Further pseudosection modelling suggests that decompression to c. 12 kbar occurred essentially isothermally from the metamorphic peak under H₂O‐undersaturated conditions (c. 1.3 mol.% H₂O) that allowed the preservation of the majority of garnet with symplectitic as well as relict clinopyroxene. The modelling also shows that a MORB‐type eclogite decompressed to c. 8 kbar ends as an amphibolite if it is H₂O saturated, but if it is H₂O‐undersaturated it contains assemblages with orthopyroxene. Increasing H₂O undersaturation causes an earlier transition to SiO₂ undersaturation on decompression, leading to the appearance of spinel‐bearing assemblages. Granulite facies‐looking overprints of eclogites may develop at amphibolite facies conditions.     

Petrogenesis and implications of jadeite‐bearing kyanite eclogite from the Sanbagawa belt (SW Japan)

Jadeite‐bearing kyanite eclogite has been discovered in the Iratsu body of the Sanbagawa belt, SW Japan. The jadeite + kyanite assemblage is stable at higher pressure–temperature (P–T) conditions or lower H₂O activity [a(H₂O)] than paragonite, although paragonite‐bearing eclogite is common in the Sanbagawa belt. The newly discovered eclogite is a massive metagabbro with the peak‐P assemblage garnet + omphacite + jadeite + kyanite + phengite + quartz + rutile. Impure jadeite is exclusively present as inclusions in garnet. The compositional gap between the coexisting omphacite (P2/n) and impure jadeite (C2/c) suggests relatively low metamorphic temperatures of 510–620 °C. Multi‐equilibrium thermobarometry for the assemblage garnet + omphacite + kyanite + phengite + quartz gives peak‐P conditions of ~2.5 GPa, 570 °C. Crystallization of jadeite in the metagabbro is attributed to Na‐ and Al‐rich effective bulk composition due to the persistence of relict Ca‐rich clinopyroxene at the peak‐P stage. By subtracting relict clinopyroxene from the whole‐rock composition, pseudosection modelling satisfactorily reproduces the observed jadeite‐bearing assemblage and mineral compositions at ~2.4–2.5 GPa, 570–610 °C and a(H₂O) >0.6. The relatively high pressure conditions derived from the jadeite‐bearing kyanite eclogite are further supported by high residual pressures of quartz inclusions in garnet. The maximum depth of exhumation in the Sanbagawa belt (~80 km) suggests decoupling of the slab–mantle wedge interface at this depth.     

Occurrence of negative open variances in ternary systems

Parameters of the hypothetical open arrays were computed for a total of 20 published sets of chemical analyses of igneous rocks in oxide, mole, cation, and cation weight-percentage forms. Negative open variances in the full (11 variables) data sets were eliminated by using a linear transformation of the raw data. For the 13 variables (11 oxides, the sum of the alkalies and total iron as FeO) 286 different simple ternary combinations can be formed. The CaO-Na₂O-K₂O (CNK) and total iron-serum of the alkalies-MgO (FMA) combinations are of frequent use in depicting “differentiation trends” within a series of igneous rocks. In each of the 20 data sets the estimated open variances of Na₂O in the CNK and total iron in the FMA combinations are negative. Elimination of negative open variances in the full data array does not eliminate negative open variances in these ternary combinations. Greater than 50 percent of the 29,172 ternary combinations examined contain a negative open variance.     

Water Content of Basalt Erupted on the ocean floor

Deep sea pillow basalts dredged from the ocean floor show that vesicularity changes with composition as well as with depth. Alkalic basalts are more vesicular than tholeiitic basalts erupted at the same depth. The vesicularity data, when related to experimentally determined solubility of water in basalt, indicate that K-poor oceanic tholeiites originally contained about 0.25 percent water, Hawaiian tholeiites of intermediate K-content, about 0.5 percent water, and alkali-rich basalts, about 0.9 percent water. Analyses of fresh basalt pillows show a systematic increase of H₂O⁺ as the rocks become more alkalic. K-poor oceanic tholeiites contain 0.06–0.42 percent H₂O⁺, Hawaiian tholeiites, 0.31–0.60 percent H₂O⁺, and alkali rich basalts 0.49–0.98 percent H₂O⁺. The contents of K₂O, P₂O₅, F, and Cl increase directly with an increase in H₂O⁺ content such that at 1.0 weight percent H₂O⁺, K₂O is 1.58 percent, P₂O₅ is 0.55 percent, F is 0.07 percent, and Cl is 0.1 percent. The measured weight percent of deuterium on the rim of one Hawaiian pillow is –6.0 (relative to SMOW); this value, which is similar to other indications of magmatic water, suggests that no appreciable sea water was absorbed by the pillow during or subsequent to eruption on the ocean floor.Concentrations of volatile constituents in the alkali basalt melts relative to tholeiitic melts can be explained by varying degrees of partial melting of mantle material or by fractional crystallization of a magma batch.Publication authorized by the Director, U.S. Geological Survey.     

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.     

Hydrothermal Fluid Sources of the Fengjia Barite–fluorite Deposit in Southeast Sichuan,China: Evidence from Fluid Inclusions and Hydrogen and Oxygen Isotopes

The Fengjia barite–fluorite deposit in southeast Sichuan is a stratabound ore deposit which occurs mainly in Lower Ordovician carbonate rocks. Here we present results from fluid inclusion and oxygen and hydrogen isotope studies to determine the nature and origin of the hydrothermal fluids that generated the deposit. The temperature of the ore‐forming fluid shows a range of 86 to 302 °C. Our detailed microthermometric data show that the temperature during mineralization of the fluorite and barite in the early ore‐forming stage was higher than that during the formation of the calcite in the late ore‐forming stage. The salinity varied substantially from 0.18% to 21.19% NaCl eqv., whereas the density was around 1.00 g/cm³. The fluid composition was mainly H₂O (>91.33%), followed by CO₂, CH₄ and traces of C₂H₆, CO, Ar, and H₂S. The dominant cation was Na⁺ and the dominant anion Cl^‐, followed by Ca²⁺, SO₄^2‐, K⁺, and Mg²⁺, indicating a mid–low‐temperature, mid‐low‐salinity, low‐density NaCl–H₂O system. Our results demonstrate that the temperature decreased during the ore‐forming process and the fluid system changed from a closed reducing environment to an open oxidizing environment. The hydrogen and oxygen isotope data demonstrate that the hydrothermal fluids in the study area had multiple sources, primarily formation water, as well as meteoric water and metamorphic water. Combined with the geological setting and mineralization features we infer that the stratabound barite–fluorite deposits originated from mid–low‐temperature hydrothermal fluids and formed vein filling in the fault zone.     

Petrochemical variations among mildly peralkaline (comendite) obsidians from the oceans and continents

Eleven new analyses and modes of comendite obsidians are presented, and compared with all available data on similar rocks. Most specimens are aphyric or contain only sparse phenocrysts, most commonly alkali feldspar. The oxides SiO₂, Al₂O₃, Na₂O and K₂O total over ninety percent by weight in all analyses. Iron, as FeO, is the only other constituent rising above one percent by weight. When the analyses are projected into the system Na₂O-K₂O-Al₂O₃-SiO₂, oceanic and continental samples group differently. Oceanic specimens have a compositional spread ranging from trachytic to the quartz-feldspar cotectic zone, consistent with derivation through a trachyte magma stem. Continental comendites show a strong correlation with the experimentally determined quartz-feldspar minima along a path of increasing peralkalinity. These differences presumably reflect the contrasting environments of magma generation, and suggest an origin by partial melting within the continental crust for the continental comendite obsidians.     

Tale of the Kulet eclogite from the Kokchetav Massive,Kazakhstan: Initial tectonic setting and transition from amphibolite to eclogite

The Kulet eclogite in the Kokchetav Massif, northern Kazakhstan, is identified as recording a prograde transformation from the amphibolite facies through transitional coronal eclogite to fully recrystallized eclogite (normal eclogite). In addition to minor bodies of normal eclogite with an assemblage of Grt + Omp + Qz + Rt ± Ph and fine‐grained granoblastic texture (type A), most are pale greyish green bodies consisting of both coronal and normal eclogites (type B). The coronal eclogite is characterized by coarse‐grained amphibole and zoisite of amphibolite facies, and the growth of garnet corona along phase boundaries between amphibole and other minerals as well as the presence of eclogitic domains. The Kulet eclogites experienced a four‐stage metamorphic evolution: (I) pre‐eclogite stage, (II) transition from amphibolite to eclogite, (III) a peak eclogite stage with prograde transformation from coronal eclogite to UHP eclogite and (IV) retrograde metamorphism. Previous studies made no mention of the presence of amphibole or zoisite in either the pre‐eclogite stage or coronal eclogite, and so did not identify the four‐stage evolution recognized here. P–T estimates using thermobarometry and Xprp and Xgrs isopleths of eclogitic garnet yield a clockwise P–T path and peak conditions of 27–33 kbar and 610–720 °C, and 27–35 kbar and 560–720 °C, respectively. P–T pseudosection calculations indicate that the coexistence of coronal and normal eclogites in a single body is chiefly due to different bulk compositions of eclogite. All eclogites have tholeiitic composition, and show flat or slightly LREE‐enriched patterns [(La/Lu)_N = 1.1–9.6] and negative Ba, Sr and Sc and positive Th, U and Ti anomalies. However, normal eclogite has higher TiO₂ (1.35–2.65 wt%) and FeO (12.11–16.72 wt%) and REE contents than those of coronal eclogite (TiO₂ < 0.9 wt% and FeO < 12.11 wt%) with one exception. Most Kulet eclogites plot in the MORB and IAB fields in the 2Nb–Zr/4–Y and TiO₂–FeO/MgO diagrams, although displacement from the MORB–OIB array indicates some degree of crustal involvement. All available data suggest that the protoliths of the Kulet eclogites were formed at a passive continent marginal basin setting. A schematic model involving subduction to 180–200 km at 537–527 Ma, followed by slab breakoff at 526–507 Ma, exhumation and recrystallization at crustal depths is applied to explain the four‐stage evolution of the Kulet eclogite.     

Eclogites from the south Tianshan, NW China: petrological characteristic and calculated mineral equilibria in the Na2O–CaO–FeO–MgO–Al2O3–SiO2–H2O system

Eclogites from the south Tianshan, NW China are grouped into two types: glaucophane and hornblende eclogites, composed, respectively, of garnet + omphacite + glaucophane + paragonite + epidote + quartz and garnet + omphacite + hornblende (sensu lato) + paragonite + epidote + quartz, plus accessory rutile and ilmenite. These eclogites are diverse both in mineral composition and texture not only between the two types but also among the different selected samples within the glaucophane eclogite. Using thermocalc 3.1 and recent models of activity–composition relation for minerals, a P–T projection and a series of P–T pseudosections for specific samples of eclogite have been calculated in the system Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O (NCFMASH) with quartz and water taken to be in excess. On the basis of these phase diagrams, the phase relations and P–T conditions are well delineated. The three selected samples of glaucophane eclogite AK05, AK11 and AK17 are estimated to have peak P–T conditions, respectively, of 540–550 °C at c. 16 kbar, c. 560 °C at 15–17 kbar and c. 580 °C at 15–19 kbar, and two samples of hornblende eclogite AK10 and AK30 of 610–630 °C and 17–18 kbar. Together with H₂O‐content contours in the related P–T pseudosections and textural relations, both types of eclogite are inferred to show clockwise P–T paths, with the hornblende eclogite being transformed from the glaucophane eclogite assemblage dominantly through increasing temperature.     

Eclogite and carpholite-bearing metasedimentary rocks in the North Qilian suture zone, NW China: implications for Early Palaeozoic cold oceanic subduction and water transport into mantle

Low‐temperature eclogite and eclogite facies metapelite together with serpentinite and marble occur as blocks within foliated blueschist that was originated from greywacke matrix; they formed a high‐pressure low‐temperature (HPLT) subduction complex (mélange) in the North Qilian oceanic‐type suture zone, NW China. Phengite–eclogite (type I) and epidote–eclogite (type II) were recognized on the basis of mineral assemblage. Relic lawsonite and lawsonite pseudomorphs occur as inclusions in garnet from both types of eclogite. Garnet–omphacite–phengite geothermobarometry yields metamorphic conditions of 460–510 °C and 2.20–2.60 GPa for weakly deformed eclogite, and 475–500 °C and 1.75–1.95 GPa for strongly foliated eclogite. Eclogite facies metasediments include garnet–omphacite–phengite–glaucophane schist and various chloritoid‐bearing schists. Mg‐carpholite was identified in some high‐Mg chloritoid schists. P–T estimates yield 2.60–2.15 GPa and 495–540 °C for Grt–Omp–Phn–Gln schist, and 2.45–2.50 GPa and 525–530 °C for the Mg‐carpholite schist. Mineral assemblages and P–T estimates, together with isotopic ages, suggest that the oceanic lithosphere as well as pelagic to semi‐pelagic sediments have been subducted to the mantle depths (≥75 km) before 460 Ma. Blueschist facies retrogression occurred at c. 454–446 Ma and led to eclogite deformation and dehydration of lawsonite during exhumation. The peak P–Tconditions for eclogite and metapelite in the North Qilian suture zone demonstrate the existence of cold subduction‐zone gradients (6–7 °C km^?1), and this cold subduction brought a large amount of H₂O to the deep mantle in the Early Palaeozoic times.