Heat capacity and phase equilibria of wadeite-type K2Si4O9

The low-temperature heat capacity (C _p) of Si-wadeite (K₂Si₄O₉) synthesized with a piston cylinder device was measured over the range of 5–303 K using the heat capacity option of a physical properties measurement system. The entropy of Si-wadeite at standard temperature and pressure calculated from the measured heat capacity data is 253.8 ± 0.6 J mol⁻¹ K⁻¹, which is considerably larger than some of the previous estimated values. The calculated phase transition boundaries in the system K₂O–Al₂O₃–SiO₂ are generally consistent with previous experimental results. Together with our calculated phase boundaries, seven multi-anvil experiments at 1,400 K and 6.0–7.7 GPa suggest that no equilibrium stability field of kalsilite + coesite intervenes between the stability field of sanidine and that of coesite + kyanite + Si-wadeite, in contrast to previous predictions. First-order approximations were undertaken to calculate the phase diagram in the system K₂Si₄O₉ at lower pressure and temperature. Large discrepancies were shown between the calculated diagram compared with previously published versions, suggesting that further experimental or/and calorimetric work is needed to better constrain the low-pressure phase relations of the K₂Si₄O₉ polymorphs. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

超高压变质岩矿物中的显微构造缺陷:来自TEM和FTIR研究的证据

超高压变质矿物的某些显微构造缺陷可能指示了岩石短暂和快速抬升过程。文中报道了中国大别山双河地区超高压硬玉石英岩矿物显微构造缺陷的透射电镜(TEM)和Fourier变换红外光谱(FTIR)的研究结果。用TEM研究方法,在硬玉石英岩中硬玉包裹体内发现了亚微米级天然蒙钠长石(MA,C2/m)、高钠长石(HA,C)和低钠长石(LA,C)三种多形变体。表明岩石在折返过程经历过高温变质作用(>930℃),以及退变质过程的快速冷却;在石英包裹体内发现了纳米级柯石英和石盐子矿物,提供了柯石英转变为石英以及峰期变质条件下高盐流体存在的证据。"名义上无水矿物"(NAMs)的结构水(OH/H2O)是以缺陷形式赋存于矿物结构中。FTIR分析结果显示硬玉、石榴石、金红石和石英中结构水的平均含量分别为1000×10-6、(900~1600)×10-6、>2000×10-6和<4×10-6,硬玉石英岩全岩含水量为(490~600)×10-6,表明在高压-超高压变质作用过程中,地壳或原岩中的水可以通过这些NAMs携带到地球深部。该类显微构造缺陷可能是大陆碰撞造山带在高应变速率下的局部弱化和深部断层作用的结果。     

Geochemistry of amphibolitized eclogites and cross-cutting tonalitic–trondhjemitic dykes in the Metamorphic Kimi Complex in East Rhodope (N.E. Greece): implications for partial melting at the base of a thickened crust

In the ultra-high pressure Metamorphic Kimi Complex widespread tonalitic–trondhjemitic dykes, with an intrusion age ca. 65–63 Ma, cross-cut boudins and layers of amphibolitized eclogites. Geochemical investigation proclaims the tied genetic relationship of the amphibolitized eclogites and the associated tonalitic–trondhjemitic dykes. The major and trace element contents and rare earth element patterns of the amphibolitized eclogites indicate formation of their protoliths by fractional crystallization of tholeiitic magmas in a back-arc environment. The tonalites and trondhjemites are characterized by moderate to high Sr contents (>130 ppm), and low Y (<8.2 ppm) and heavy rare earth element contents (Yb content of 0.19–0.88 ppm). The chemical composition of the tonalitic and trondhjemitic dykes are best explained by partial melting of a tholeiitic source like the amphibolitized eclogites with residual garnet and amphibole, at the base of a thickened crust during Early Tertiary subduction/accretion at the southern margins of the European continent.     

Cretaceous isochron ages from K–Ar and Ar / Ar dating of eclogitic rocks in the Tso Morari Complex, western Himalaya, India

The Tso Morari Complex, which is thought to be originally the margin of the Indian continent, is composed of pelitic gneisses and schists including mafic rock lenses (eclogites and basic schists). Eclogites studied here have the mineral assemblage Grt + Omp + Ca-Amp + Zo + Phn + Pg + Qtz + Rt. They also have coesite pseudomorph in garnet and quartz rods in omphacite, suggesting a record of ultrahigh-pressure metamorphism. They occur only in the cores of meter-scale mafic rock lenses intercalated with the pelitic schists. Small mafic lenses and the rim parts of large lenses have been strongly deformed to form the foliation parallel to that of the pelitic schists and show the mineral assemblages of upper greenschist to amphibolite facies metamorphism. The garnet–omphacite thermometry and the univariant reaction relations for jadeite formation give 13–21 kbar at 600 °C and 16–18 kbar at 750 °C for the eclogite formation using the jadeite content of clinopyroxene (X_Jd = 0.48).

Phengites in pelitic schists show variable Si / Al and Na / K ratios among grains as well as within single grains, and give K–Ar ages of 50–87 Ma. The pelitic schist with paragonite and phengite yielded K–Ar ages of 83.5 Ma (K = 4.9 wt.%) for paragonite–phengite mixture and 85.3 Ma (K = 7.8 wt.%) for phengite and an isochron age of 91 ± 13 Ma from the two dataset. The eclogite gives a plateau age of 132 Ma in Ar/Ar step-heating analyses using single phengite grain and an inverse isochron age of 130 ± 39 Ma with an initial ⁴⁰Ar / ³⁶Ar ratio of 434 ± 90 in Ar/Ar spot analyses of phengites and paragonites. The Cretaceous isochron ages are interpreted to represent the timing of early stage of exhumation of the eclogitic rocks assuming revised high closure temperature (500 °C) for phengite K–Ar system. The phengites in pelitic schists have experienced retrograde reaction which modified their chemistry during intense deformation associated with the exhumation of these rocks with the release of significant radiogenic ⁴⁰Ar from the crystals. The argon release took place in the schists that experienced the retrogression to upper greenschist facies metamorphisms from the eclogite facies conditions.     

Preservation/exhumation of ultrahigh-pressure subduction complexes

Ultrahigh-pressure (UHP) metamorphic terranes reflect subduction of continental crust to depths of 90–140 km in Phanerozoic contractional orogens. Rocks are intensely overprinted by lower pressure mineral assemblages; traces of relict UHP phases are preserved only under kinetically inhibiting circumstances. Most UHP complexes present in the upper crust are thin, imbricate sheets consisting chiefly of felsic units ± serpentinites; dense mafic and peridotitic rocks make up less than  10% of each exhumed subduction complex. Roundtrip prograde–retrograde P–T paths are completed in 10–20 Myr, and rates of ascent to mid-crustal levels approximate descent velocities. Late-stage domical uplifts typify many UHP complexes.

Sialic crust may be deeply subducted, reflecting profound underflow of an oceanic plate prior to collisional suturing. Exhumation involves decompression through the P–T stability fields of lower pressure metamorphic facies. Scattered UHP relics are retained in strong, refractory, watertight host minerals (e.g., zircon, pyroxene, garnet) typified by low rates of intracrystalline diffusion. Isolation of such inclusions from the recrystallizing rock matrix impedes back reaction. Thin-aspect ratio, ductile-deformed nappes are formed in the subduction zone; heat is conducted away from UHP complexes as they rise along the subduction channel. The low aggregate density of continental crust is much less than that of the mantle it displaces during underflow; its rapid ascent to mid-crustal levels is driven by buoyancy. Return to shallow levels does not require removal of the overlying mantle wedge. Late-stage underplating, structural contraction, tectonic aneurysms and/or plate shallowing convey mid-crustal UHP décollements surfaceward in domical uplifts where they are exposed by erosion. Unless these situations are mutually satisfied, UHP complexes are completely transformed to low-pressure assemblages, obliterating all evidence of profound subduction.     

Mineral and fluid inclusions in zircon of UHP metamorphic rocks from the CCSD-main drill hole: A record of metamorphism and fluid activity

The Chinese Continental Scientific Drilling (CCSD) main drill hole (0–3000 m) in Donghai, southern Sulu orogen, consists of eclogite, paragneiss, orthogneiss, schist and garnet peridotite. Detailed investigations of Raman, cathodoluminescence, and microprobe analyses show that zircons from most eclogites, gneisses and schists have oscillatory zoned magmatic cores with low-pressure mineral inclusions of Qtz, Pl, Kf and Ap, and a metamorphic rim with relatively uniform luminescence and eclogite-facies mineral inclusions of Grt, Omp, Phn, Coe and Rt. The chemical compositions of the UHP metamorphic mineral inclusions in zircon are similar to those from the matrix of the host rocks. Similar UHP metamorphic P–T conditions of about 770 °C and 32 kbar were estimated from coexisting minerals in zircon and in the matrix. These observations suggest that all investigated lithologies experienced a joint in situ UHP metamorphism during continental deep subduction. In rare cases, magmatic cores of zircon contain coesite and omphacite inclusions and show patchy and irregular luminescence, implying that the cores have been largely altered possibly by fluid–mineral interaction during UHP metamorphism.

Abundant H₂O–CO₂, H₂O- or CO₂-dominated fluid inclusions with low to medium salinities occur isolated or clustered in the magmatic cores of some zircons, coexisting with low-P mineral inclusions. These fluid inclusions should have been trapped during magmatic crystallization and thus as primary. Only few H₂O- and/or CO₂-dominated fluid inclusions were found to occur together with UHP mineral inclusions in zircons of metamorphic origin, indicating that UHP metamorphism occurred under relatively dry conditions. The diversity in fluid inclusion populations in UHP rocks from different depths suggests a closed fluid system, without large-scale fluid migration during subduction and exhumation.     

Calculated Phase Relations in the System Na2O-CaO-K2O-FeO-MgO-Al2O3-SiO2-H2O with Applications to UHP Eclogites and Whiteschists

Pressure–temperature grids in the system Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O and its subsystems have been calculatedin the range 15–45 kbar and 550–900°C, usingan internally consistent thermodynamic dataset and new thermodynamicmodels for amphibole, white mica, and clinopyroxene, with thesoftware THERMOCALC. Minerals considered for the grids includegarnet, omphacite, diopside, jadeite, hornblende, actinolite,glaucophane, zoisite, lawsonite, kyanite, coesite, quartz, talc,muscovite, paragonite, biotite, chlorite, and plagioclase. Compatibilitydiagrams are used to illustrate the phase relationships in thegrids. Coesite-bearing eclogites and a whiteschist from Chinaare used to demonstrate the ability of pseudosections to modelphase relationships in natural ultrahigh-pressure metamorphicrocks. Under water-saturated conditions, chlorite-bearing assemblagesin Mg- and Al-rich eclogites are stable at lower temperaturesthan in Fe-rich eclogites. The relative temperature stabilityof the three amphiboles is hornblende > actinolite > glaucophane(amphibole names used sensu lato). Talc-bearing assemblagesare stable only at low temperature and high pressure in Mg-and Al-rich eclogites. For most eclogite compositions, talccoexists with lawsonite, but not zoisite, in the stability fieldof coesite. Water content contouring of pressure–temperaturepseudosections, along with appropriate geotherms, provides newconstraints concerning dehydration of such rocks in subductingslabs. Chlorite and lawsonite are two important H₂O-carriersin subducting slabs. Depending on bulk composition and pressure–temperaturepath, amphibole may or may not be a major H₂O-carrier to depth.In most cases, dehydration to make ultrahigh-pressure eclogitestakes place gradually, with H₂O content controlled by divariantor higher variance assemblages. Therefore, fluid fluxes in subductionzones are likely to be continuous, with the rate of dehydrationchanging with changing pressure and temperature. Further, eclogitesof different bulk compositions dehydrate differently. Dehydrationof Fe-rich eclogite is nearly complete at relatively shallowdepth, whereas Mg- and Al-rich eclogites dehydrate continuouslydown to greater depth. KEY WORDS: dehydration; eclogites; phase relations; THERMOCALC; UHP metamorphism; whiteschists     

Evolution from Oceanic Subduction to Continental Collision: a Case Study from the Northern Tibetan Plateau Based on Geochemical and Geochronological Data

Two apparently distinct, sub-parallel, paleo-subduction zonescan be recognized along the northern margin of the Tibetan Plateau:the North Qilian Suture Zone (oceanic-type) with ophioliticmélanges and high-pressure eclogites and blueschistsin the north, and the North Qaidam Belt (continental-type) inthe south, an ultrahigh-pressure (UHP) metamorphic terrane comprisingpelitic and granitic gneisses, eclogites and garnet peridotites.Eclogites from both belts have protoliths broadly similar tomid-ocean ridge basalts (MORB) or oceanic island basalts (OIB)in composition with overlapping metamorphic ages (480–440Ma, with weighted mean ages of 464 ± 6 Ma for North Qilianand 457 ± 7 Ma for North Qaidam), determined by zirconU–Pb sensitive high-resolution ion microprobe dating.Coesite-bearing zircon grains in pelitic gneisses from the NorthQaidam UHP Belt yield a peak metamorphic age of 423 ±6 Ma, 40 Myr younger than the age of eclogite formation, anda retrograde age of 403 ± 9 Ma. These data, combinedwith regional relationships, allow us to infer that these twoparallel belts may represent an evolutionary sequence from oceanicsubduction to continental collision, and continental underthrusting,to final exhumation. The Qilian–Qaidam Craton was probablya fragment of the Rodinia supercontinent with a passive marginand extended oceanic lithosphere in the north, which was subductedbeneath the North China Craton to depths >100 km at c. 423Ma and exhumed at c. 403 Ma (zircon rim ages in pelitic gneiss). KEY WORDS: HP and UHP rocks; subduction belts; zircon SHRIMP ages; Northern Tibetan Plateau     

Ca-rich Garnet-Clinopyroxene Rocks at Hujialin in the Su-Lu Terrane (Eastern China): Deeply Subducted Arc Cumulates?

Layers of Ca-rich garnet–clinopyroxene rocks enclosedin a serpentinite body at Hujialin, in the Su–Lu terraneof eastern China, preserve igneous textures, relict spinel ingarnet, and exsolution lamellae of Ca-rich garnet, ilmenite/magnetite,Fe-rich spinel, and also amphibole in clinopyroxene. In termsof their major and trace element compositions, the studied samplesform a trend from arc cumulates towards Fe–Ti gabbros.Reconstructed augite compositions plot on the trend for clinopyroxenein arc cumulates. These data suggest that the rocks crystallizedfrom mantle-derived magmas differentiated to various extentsbeneath an arc. The Ca-rich garnet + diopside assemblage isinferred to have formed by compressing Ca-rich augite, whereasthe relatively Mg-rich cores of garnet porphyroblasts may haveformed at the expense of spinel. The protolith cumulates weresubducted from near the crust–mantle boundary (c. 1 GPa)deep into the upper mantle (4·8 ± 0·6 GPaand 750 ± 50°C). Negatively sloped P–T pathsfor the garnet–clinopyroxene rocks and the corollary ofcorner flow induced subduction of mantle wedge peridotite arenot supported by the available data. Cooling with, or without,decompression of the cumulates after the igneous stage probablyoccurred prior to deep subduction. KEY WORDS: arc cumulates; Ca-rich garnet; garnet–clinopyroxene rocks; Su–Lu terrane; UHP metamorphism     

中国大陆科学钻探工程主孔榴辉岩的岩石学研究

中国大陆科学钻探工程5000m主孔位于苏鲁超高压变质带南部。该钻孔0～2000m主要由榴辉岩、片麻岩、石榴石橄榄岩和少量片岩和石英岩组成。累积厚度达1000多米的榴辉岩具有不同的矿物组成、不同的矿物含量和不同的全岩化学成分,可划分成富Si的石英榴辉岩、富Ti的金红石榴辉岩、富Al的多硅白云母和蓝晶石榴辉岩、富Mg的双矿物榴辉岩和具有正常玄武岩成分的普通榴辉岩。榴辉岩的原岩包括基性层状侵入岩和变质表壳岩。榴辉岩全岩成分对石榴石和绿辉石中某些化学组分的含量有明显控制,而且直接影响到变质条件估算的准确性。扩散成分环带的广泛发育表明超高压矿物在早期退变质过程中发生了成分再平衡。这一事实以及具有成分生长环带石榴石变斑晶的存在,为榴辉岩形成在更高温度(>940℃)和更高压力(>4.5GPa)条件下提供了有力的证据。