高温高压下水和氯化钠溶液的物理化学性质研究

高温高压下水和氯化钠溶液的物理化学性质研究徐有生（中国科学院地球化学研究所，贵阳５５０００２）关键词高温高压水和ＮａＣｌ溶液物理化学性质水和ＮａＣｌ溶液是地质上最常见的溶液，了解其物理化学性质有助于研究水溶液在地球内部各种地质作用和地质过程中所起的作...     

Influence of tectonic overpressure on P–T paths of HP–UHP rocks in continental collision zones: thermomechanical modelling

The principle of lithostatic pressure is habitually used in metamorphic geology to calculate burial/exhumation depth from pressure given by geobarometry. However, pressure deviation from lithostatic, i.e. tectonic overpressure/underpressure due to deviatoric stress and deformation, is an intrinsic property of flow and fracture in all materials, including rocks under geological conditions. In order to investigate the influences of tectonic overpressure on metamorphic P–T paths, 2D numerical simulations of continental subduction/collision zones were conducted with variable brittle and ductile rheologies of the crust and mantle. The experiments suggest that several regions of significant tectonic overpressure and underpressure may develop inside the slab, in the subduction channel and within the overriding plate during continental collision. The main overpressure region that may influence the P–T paths of HP–UHP rocks is located in the bottom corner of the wedge‐like confined channel with the characteristic magnitude of pressure deviation on the order of ～0.3 GPa and 10–20% from the lithostatic values. The degree of confinement of the subduction channel is the key factor controlling this magnitude. Our models also suggest that subducted crustal rocks, which may not necessarily be exhumed, can be classified into three different groups: (i) UHP‐rocks subjected to significant (≥0.3 GPa) overpressure at intermediate subduction depth (50–70 km, P = 1.5–2.5 GPa) then underpressured at depth ≥100 km (P ≥ 3 GPa); (ii) HP‐rocks subjected to ≥0.3 GPa overpressure at peak P–T conditions reached at 50–70 km depth in the bottom corner of the wedge‐like confined subduction channel (P = 1.5–2.5 GPa); (iii) lower‐pressure rocks formed at shallower depths (≤40 km depth, P ≤ 1 GPa), which are not subjected to significant overpressure and/or underpressure.     

Petrological model of the northern Izu–Bonin–Mariana arc crust: constraints from high-pressure measurements of elastic wave velocities of the Tanzawa plutonic rocks, central Japan

Ultrasonic compressional wave velocities (Vp) and shear wave velocities (Vs) were measured with varying pressure up to 1.0 GPa in a temperature range from 25 to 400 °C for a suite of tonalitic–gabbroic rocks of the Miocene Tanzawa plutonic complex, central Japan, which has been interpreted as uplifted and exposed deep crust of the northern Izu–Bonin–Mariana (IBM) arc. The Vp values of the tonalitic–gabbroic rocks increase rapidly at low pressures from 0.1 to 0.4 GPa, and then become nearly constant at higher pressures above 0.4 GPa. The Vp values at 1.0 GPa and 25 °C are 6.3–6.6 km/s for tonalites (56.4–71.1 wt.% SiO₂), 6.8 km/s for a quartz gabbro (53.8 wt.% SiO₂), and 7.1–7.3 km/s for a hornblende gabbro (43.2–47.7 wt.% SiO₂). Combining the present data with the P wave velocity profile of the northern IBM arc, we infer that 6-km-thick tonalitic crust exists at mid-crustal depth (6.1–6.3 km/s Vp) overlying 2-km-thick hornblende gabbroic crust (6.8 km/s Vp). Our model shows large differences in acoustic impedance between the tonalite and hornblende gabbro layers, being consistent with the strong reflector observed at 12-km-depth in the IBM arc. The measured Vp of Tanzawa hornblende-bearing gabbroic rocks (7.1–7.3 km/s) is significantly lower than that Vp modeled for the lowermost crustal layer of the northern IBM arc (7.3–7.7 km/s at 15–22 km depth). We propose that the IBM arc consists of a thick tonalitic middle crust and a mafic lower crust.     

An anticlockwise P–T–t path at high‐pressure,high‐temperature conditions for a migmatitic gneiss from the island of Fjørtoft,Western Gneiss Region,Norway, indicates two burial events during the Caledonian orogeny

The Blåhø Nappe on the island of Fjørtoft, which represents an isolated portion of the Seve Nappe Complex in the Western Gneiss Region, Norway, has been suggested to have experienced two deep burial cycles during the Caledonian orogeny. However, evidence on this multiple burial process by the derivation of a pressure–temperature–time (P–T–t) path has never been given in the literature. In this study, the ‘diamondiferous’ kyanite–garnet gneiss from the Blåhø Nappe on Fjørtoft was revisited to determine if such a process was correct. Two types of garnet, porphyroblastic garnet‐1 and fine‐grained garnet‐2, were recognized in the gneiss. The core of garnet‐1 is poor in Ca and documents P–T conditions of 1.2–1.3 GPa at c. 880°C based on pseudosection modelling. The inner rims of garnet‐1 and the core of garnet‐2 are both richer in Ca, recording P–T conditions of 1.35–1.45 GPa and 770–820°C. Application of conventional geothermobarometry on the outer rim of garnet‐1 and the rim of garnet‐2 yielded retrograde P–T conditions of 0.75–0.90 GPa and 610–685°C. These estimates define an anticlockwise P–T path at pressures below 1.5 GPa. Accessory monazite was dated with the electron microscope. Relicts of detrital monazite in the gneiss point to Sveconorwegian and possibly also Cryogenian provenance for the detritus of the sedimentary protolith. Metamorphic monazite in the gneiss records a wide age range from 460 to 380 Ma, with a peak c. 435 Ma and a shoulder at 395 Ma. These data suggest that the original (Ediacaran?) Baltica margin sediment (gneiss protolith) was transported to the base of an overlying plate during the early Caledonian (pre‐Scandian) orogeny. A long residence time of the metasedimentary rock at this base caused its heating to 880°C and homogenization of the early garnet chemistry. The late Caledonian (Scandian) collision between Baltica and Laurentia led to further burial, during which the studied gneiss was close to the former surface of the downgoing continental plate and, thus, cooled. The reconstructed P–T–t path confirms the multiple burial history of the Blåhø Nappe but contradicts previous ideas of deep burial of the Fjørtoft gneiss to more than 100 km.     

Mesozoic to Cenozoic tectono‐metamorphic history of the South Pamir–Hindu Kush (Chitral,NW Pakistan): Insights from phase equilibria modelling,and garnet–monazite petrochronology

The Karakoram–Hindu Kush–Pamir and adjacent Tibetan plateau belt comprise a series of Gondwana‐derived crustal fragments that successively accreted to the Eurasian margin in the Mesozoic as the result of the progressive Tethys ocean closure. These domains provide unique insights into the thermal and structural history of the Mesozoic to Cenozoic Eurasian plate margin, which are critical to inform the initial boundary conditions (e.g. crustal thickness, structure and thermo‐mechanical properties) for the subsequent development of the large and hot Tibetan–Himalaya orogen, and the associated crustal deformation processes. Using a combination of microstructural analyses, thermobarometry modelling and U–Th–Pb monazite and Lu–Hf garnet geochronology, the study reappraises the metamorphic history of exposed mid‐crustal metapelites in the Chitral region of the South Pamir–Hindu Kush (NW Pakistan). This study also demonstrates that trace elements in monazite (especially Y and Dy), combined with thermodynamical modelling and Lu–Hf garnet dating, provides a powerful integrated toolbox for constraining long‐lived and polyphased tectono‐metamorphic histories in all their spatial and temporal complexity. Rocks from the Chitral region were progressively deformed and metamorphosed at sub‐ and supra‐solidus conditions through at least four distinct episodes from the Mesozoic to the Cenozoic. Rocks were first metamorphosed at ~400–500°C and ~0.3 GPa in the Late Triassic–Early Jurassic (210–185 Ma), likely in response to the accretion of the Karakoram during the Cimmerian orogeny. Pressure and temperature subsequently increased by ~0.3 GPa and 100°C in the Early‐ to Mid Cretaceous (140–80 Ma), coinciding with the intrusion of calcalkaline granitic plutons across the Karakoram and Pamir regions. This event is interpreted as the record of crustal thickening and the development of a proto‐plateau within the Eurasian margin due to a long‐lived episode of slab flattening in an Andean‐type margin. Peak metamorphism was reached in the Late Eocene–Early Oligocene (40–30 Ma) at conditions of 580–600°C and ~0.6 GPa and 700–750°C and 0.7–0.8 GPa for the investigated staurolite schists and sillimanite migmatites respectively. This crustal heating up to moderate anatexis likely resulted in the underthrusting of the Indian plate after a NeoTethyan slab‐break off or to the Tethyan Himalaya–Lhasa microcontinent collision and subsequent oceanic slab flattening. Near‐isothermal decompression/exhumation followed in the Late Oligocene (28–23 Ma) as marked by a pressure decrease in excess of ~0.1 GPa. This event was coeval with the intrusion of the 24 Ma Garam Chasma leucogranite. This rapid exhumation is interpreted to be related to the reactivation of the South Pamir–Karakoram suture zone during the ongoing collision with India. The findings of this study confirm that significant crustal shortening and thickening of the south Eurasian margin occurred during the Mesozoic in an accretionary‐type tectonic setting through successive episodes of terrane accretions and probably slab flattening, transiently increasing the coupling at the plate interface. Moreover, they indicate that the south Eurasian margin was already hot and thickened prior to Cenozoic collision with India, which has important implications for orogen‐scale strain‐accommodation mechanisms.     

On the petrology of brittle precursors of shear zones – An expression of concomitant brittle deformation and fluid–rock interactions in the ‘ductile’ continental crust?

The inherited localization model for shear zone development suggests that ductile deformation in the middle and lower continental crust is localized on mechanical anisotropies, like fractures, referred to as shear zone brittle precursors. In the Neves area (Western Tauern Window, Eastern Alps), although the structural control of these brittle precursors on ductile strain localization is well established, the relative timing of the brittle deformation and associated localized fluid flow with respect to ductile deformation remains in most cases a matter of debate. The present petrological study, carried out on a brittle precursor of a shear zone affecting the Neves metagranodiorite, aims to determine whether brittle and ductile deformations are concomitant and therefore relate to the same tectonic event. The brittle precursor consists of a 100–500 µm wide recrystallized zone with a host mineral‐controlled stable mineral assemblage composed of plagioclase–garnet–quartz–biotite–zoisite±white mica±pyrite. Plagioclase and garnet preserve an internal compositional zoning interpreted as the fingerprint of Alpine metamorphism and fluid–rock interactions concomitant with the brittle deformation. Phase equilibrium modelling of this garnet‐bearing brittle precursor shows that metamorphic garnet and plagioclase both nucleated at 0.6 ± 0.05 GPa, 500 ± 20°C and then grew along a prograde path to 0.75 ± 0.05 GPa, 530 ± 20°C. These amphibolite facies conditions are similar to those inferred from ductile shear zones from the same area, suggesting that both brittle and ductile deformation were active in the ductile realm above 500°C for a depth range between 17 and 21 km. We speculate that the Neves area fulfils most of the required conditions to have hosted slow earthquakes during Alpine continental collision, that is, coupled frictional and viscous deformation under high‐fluid pressure conditions ~450°C. Further investigation of this potential geological record is required to demonstrate that slow earthquakes may not be restricted to subduction zones but are also very likely to occur in modern continental collision settings.     

Dehydration Temperature of Serpentine at Elevated Temperatures and Pressures by Electrical Conductivity Method and Its Implications

Dehydration temperatures of serpentine were measured in the pressure range between 1.0GPa and 5.0GPa by using the electrical conductivity metod simultaneously at high temperatures and high pressures.The results show that with increasing pressure th dehydration temperature of antigorite increases slightly below 2.0GPa ,but drops markedly above2.0GPa .This strongly suggests that high pressure would favor the dehydration of serpentine minerals and the water released thereby would be an important source of fluids involved in magmatism in a subduction zone and mantle metasomatism,Meanwhile,the greatly enhanced electric conductivity in the presence of water may be one of the reasons underlying the occurrence of a high-conductivity zone in the lower crust.     

Phase transitions in the system CaCO<Subscript>3</Subscript> at high P and T determined by in situ vibrational spectroscopy in diamond anvil cells and first-principles simulations

The stability of the high-pressure CaCO₃ calcite (cc)-related polymorphs was studied in experiments that were performed in conventional diamond anvil cells (DAC) at room temperature as a function of pressure up to 30 GPa as well as in internally heated diamond anvil cells (DAC-HT) at pressures and temperatures up to 20 GPa and 800 K. To probe structural changes, we used Raman and FTIR spectroscopy. For the latter, we applied conventional and synchrotron mid-infrared as well as synchrotron far-infrared radiation. Within the cc-III stability field (2.2–15 GPa at room temperature, e.g., Catalli and Williams in Phys Chem Miner 32(5–6):412–417, 2005), we observed in the Raman spectra consistently three different spectral patterns: Two patterns at pressures below and above 3.3 GPa were already described in Pippinger et al. (Phys Chem Miner 42(1):29–43, 2015) and assigned to the phase transition of cc-IIIb to cc-III at 3.3 GPa. In addition, we observed a clear change between 5 and 6 GPa that is independent of the starting material and the pressure path and time path of the experiments. This apparent change in the spectral pattern is only visible in the low-frequency range of the Raman spectra—not in the infrared spectra. Complementary electronic structure calculations confirm the existence of three distinct stability regions of cc-III-type phases at pressures up to about 15 GPa. By combining experimental and simulation data, we interpret the transition at 5–6 GPa as a re-appearance of the cc-IIIb phase. In all types of experiments, we confirmed the transition from cc-IIIb to cc-VI at about 15 GPa at room temperature. We found that temperature stabilizes cc-VI to lower pressure. The reaction cc-IIIb to cc-VI has a negative slope of ?7.0 × 10^?3 GPa K^?1. Finally, we discuss the possibility of the dense cc-VI phase being more stable than aragonite at certain pressure and temperature conditions relevant to the Earth’s mantle.     

Experimental studies At 5–12 GPa of the Ondermatjie hypabyssal kimberlite

Liquidus and sub-liquidus phase relationships are reported for melts formed from an aphanitic kimberlite composition crystallized at 5–12 GPa and 900–1400 °C. The liquidus phase over the pressure range investigated is forsteritic olivine. This is followed with decreasing temperature by olivine plus garnet as the initial sub-liquidus solid phase assemblage. Supra-solidus assemblages consist of olivine+garnet+clinopyroxene+Mg-ilmenite+liquid at 5–7 GPa or olivine+garnet+clinopyroxene+hematite–ilmenite solid solutions (+/−perovskite)+liquid at 8–12 GPa. Phlogopite forms as a near-solidus phase only at 900 °C and 6 GPa. Orthopyroxene does not form at any temperature and pressure. All garnets formed at 6–7 GPa are Ti-rich almandine–grossular–pyrope solid solutions and not Cr-pyrope, whereas garnets formed above 8 GPa are Ti- and Fe³⁺-rich and have no natural counterparts. Quenched liquids are represented by magnesite at 10–12 GPa and Mg–Ca-carbonates at lower pressures. In addition to forming discrete crystals, Mg-ilmenite and hematite–ilmenite solid solutions occur as lamellar intergrowths that are identical in texture to naturally occurring intergrowths. Mg-ilmenite compositions at 6–7 GPa are similar to those of the natural occurrences, whereas clinopyroxenes are richer in Ca. The effects of graphite versus platinum capsules on the oxygen fugacity of the experimental charges and the composition of the olivine, clinopyroxene, Fe–Ti-oxides and garnets formed are described. These experimental data are interpreted to indicate that kimberlite magmas are unlikely to be formed by very small degrees of partial melting of a simple homogeneous carbonated garnet lherzolite mantle. It is proposed that kimberlite magmas form by extensive partial melting of metasomatized mantle, i.e. mineralogically complex carbonate-bearing veins in a lherzolitic/harzburgitic substrate, and that lamellar ilmenite–clinopyroxene intergrowths represent the products of non-equilibrium growth in kimberlite magma.     

Evaluation of a constitutive model for clays and sands: Part I – sand behaviour

This paper evaluates the performance of a generalized effective stress soil model for predicting the rate independent behaviour of freshly deposited sands, while a companion paper describes model capabilities for clays and silts. Most material parameters can be obtained from standard laboratory data, including hydrostatic or one‐dimensional compression, drained and undrained triaxial shear testing. A compilation of data on compression behaviour allows for estimation of compression parameters when this type of data is not available. Extensive comparisons of model predictions with measured data from undrained triaxial shear tests shows that the model gives excellent predictions of the transition from dilative to contractive shear response as the confining pressure and/or the initial formation void ratio increases. A parametric study of drained response shows that the model describes realistically the variation of peak friction angle and dilation rate as a function of confining pressure and density when compared with an empirical correlation valid for many sands. The proposed formulation predicts a unique critical state locus for both drained and undrained triaxial testing which is non‐linear over the entire range of stresses and is in excellent agreement with recent experimental data. Overall, the model provides excellent predictions of the stress–strain–strength relationships over a wide range of confining pressures and formation densities. Copyright © 2002 John Wiley & Sons, Ltd.     

Geochronology and Ore‐Forming Fluids of the Baizhangyan W–Mo Deposit in the Chizhou Area,Middle‐Lower Yangtze Valley,SE‐China

The Baizhangyan skarn‐porphyry type W–Mo deposit is located in a newly defined Mo–W–Pb–Zn metallogenic belt, which is in the south of Middle‐Lower Yangtze Valley Cu–Fe–Au polymetallic metallogenic belt in SE China. The W–Mo orebodies occur mainly within the contact zone between fine‐grained granite and Sinian limestone strata. There are two types of W–Mo mineralization: major skarn W–Mo mineralization and minor granite‐hosted disseminated Mo mineralization which was traced by drilling at depth. Eight molybdenite samples from Mo‐bearing ores yield Re–Os dates that overlap within analytical error, with a weighted average age of 134.1 ± 2.2 Ma. These dates are in close agreement with SIMS U–Pb concordant zircon age for fine‐grained granite at 133.3 ± 1.3 Ma, indicating that crystallization of the granite and hydrothermal molybdenite formation were coeval and likely cogenetic. The Baizhangyan W–Mo deposit formed in the Early Cretaceous extensional tectonic setting at the Middle‐Lower Yangtze Valley metallogenic belt and the Jaingnan Ancient Continent. Based on mineral compositions and crosscutting relationships of veinlets, hydrothermal alteration and mineralization, the ore mineral paragenesis of the Baizhangyan deposit is divided into four stages: skarn stage (I), oxide stage (II), sulfide stage (III), and carbonate stage (IV). Fluid inclusions in garnet, scheelite, quartz and calcite from W–Mo ores are mainly aqueous‐rich (L + V) type inclusions. Following garnet deposition at stage I, the high‐temperature fluids gave way to progressively cooler, more dilute fluids associated with tungsten–molybdenite–base metal sulfide deposition (stage II and stage III) (162–360°C, 2.7–13.2 wt % NaCl equivalent) and carbonate deposition (stage IV) (137–190°C, 0.9–5 wt % NaCl equiv.). Hydrogen‐oxygen isotope data from minerals of different stages suggest that the ore‐forming fluids consisted of magmatic water, mixed in various proportions with meteoric water. From stage I to stage IV, there is a systematic decrease in the homogenization temperature of the fluid‐inclusion fluids and calculated δ¹⁸O values of the fluids. These suggest that increasing involvement of formation water or meteoric water during the fluid ascent resulted in successive deposition of scheelite and molybdenite at Baizhangyan.     

Prograde and retrograde metamorphic fabrics – a key for understanding burial and exhumation in orogens (Bohemian Massif)

In the Orlica–?nie?nik Dome (NE Bohemian massif), alternating belts of orthogneiss with high‐pressure rocks and belts of mid‐crustal metasedimentary–metavolcanic rocks commonly display a dominant subvertical fabric deformed into a subhorizontal foliation. The first macroscopic foliation is subvertical, strikes NE–SW and is heterogeneously folded by open to isoclinal folds with subhorizontal axial planes parallel to the heterogeneously developed flat‐lying foliation. The metamorphic evolution of the mid‐crustal metasedimentary rocks involved successive crystallization of chlorite–muscovite–ilmenite–plagioclase–garnet, followed by staurolite‐bearing and then kyanite‐bearing assemblages in the subvertical fabric. This was followed by garnet retrogression, with syntectonic crystallization of sillimanite and andalusite parallel to the shallow‐dipping foliation. Elsewhere, andalusite and cordierite statically overgrew the flat‐lying fabric. With reference to a P–T pseudosection for a representative sample, the prograde succession of mineral assemblages and the garnet zoning pattern with decreasing grossular, spessartine and X_Fe are compatible with a P–T path from 3.5–5 kbar/490–520 °C to peak conditions of 6–7 kbar/～630 °C suggesting burial from 12 to 25 km with increasing temperature. Using the same pseudosection, the retrograde succession of minerals shows decompression to sillimanite stability at ～4 kbar/～630 °C and to andalusite–cordierite stability at 2–3 kbar indicating exhumation from 25 km to around 9–12 km. Subsequent exhumation to ～6 km occurred without apparent formation of a deformation fabric. The structure and petrology together with the spatial distribution of the metasedimentary–metavolcanic rocks, and gneissic and high‐pressure belts are compatible with a model of burial of limited parts of the upper and middle crust in narrow cusp‐like synclines, synchronous with the exhumation of orogenic lower crust represented by the gneissic and high‐pressure rocks in lobe‐shaped and volumetrically more important anticlines. Converging P–T–D paths for the metasedimentary rocks and the adjacent high‐pressure rocks are due to vertical exchanges between cold and hot vertically moving masses. Finally, the retrograde shallow‐dipping fabric affects both the metasedimentary–metavolcanic rocks and the gneissic and high‐pressure rocks, and indicates that the ～15‐km exhumation was mostly accommodated by heterogeneous ductile thinning associated with unroofing of a buoyant crustal root.     

高温高压下电导-温度曲线方法进行蛇纹石的脱水温度测量及其意义

在1．0～5．0GPa压力范围内，运用高温同时高压下电导测量方法确定了蛇纹石的脱水温度。实验结果表明，压力小于2.0GPa时叶蛇纹石的脱水温度随压力的增大呈微弱升高趋势，压力大于2．0GPa时其脱水温度随压力的增大明显降低，意味着较高压力下有利于脱水反应的发生，是俯冲带岩浆作用及地幔交代作用流体的重要来源。蛇纹石脱水后，由于自由水的存在导致其电导明显增加，可能是高导层产生的原因之一。     

Synthesis of Fluid Inclusion Reference Materials in the H2O–NaCl–CH4 System

In this study, we detail procedures to synthesise inclusions of fluids of known composition under diagenetic conditions – low temperatures (50–180 °C) and pressures (2–25 MPa) – hosted by quartz. Pre‐existing microcavities in polished quartz chips were used, decrepitated and rinsed before being healed in an autoclave. Each synthesis required around 4 weeks. A range of biphase liquid–vapour inclusions in the H₂O–CH₄–NaCl system, similar to natural ones, were synthesised in quartz, varying the content of all three components. The quartz chips were checked before and after synthesis by optical microscopy, microthermometry and Raman spectroscopy. The method was used to build a series of calibration curves relating methane‐to‐water count ratios to the methane content of aqueous fluid inclusions. Good correlation was obtained between Raman band area ratios and the expected CH₄ solubilities from equations of state. The chosen procedure's main advantages, compared with other published methods, are as follows: quicker healing of the microfractures at lower temperatures, larger inclusions, simple quartz sample preparation, control of fluid inclusion composition and the use of commercial reactors. Such reference material inclusions allow the calibration of Raman microspectrometers with the objective of PTX reconstruction of palaeofluid migration in petroleum reservoirs.     

Integrated garnet and zircon–titanite geochronology constrains the evolution of ultra‐high–pressure terranes: An example from the Sulu orogen

Dating ultra‐high–pressure (UHP) metamorphic rocks provides important timing constraints on deep subduction zone processes. Eclogites, deeply subducted rocks now exposed at the surface, undergo a wide range of metamorphic conditions (i.e. deep subduction and exhumation) and their mineralogy can preserve a detailed record of chronologic information of these dynamic processes. Here, we present an approach that integrates multiple radiogenic isotope systems in the same sample to provide a more complete timeline for the subduction–collision–exhumation processes, based on eclogites from the Dabie–Sulu orogenic belt in eastern China, one of the largest UHP terranes on Earth. In this study, we integrate garnet Lu–Hf and Sm–Nd ages with zircon and titanite U–Pb ages for three eclogite samples from the Sulu UHP terrane. We combine this age information with Zr‐in‐rutile temperature estimates, and relate these multiple chronometers to different P–T conditions. Two types of rutile, one present as inclusions in garnet and the other in the matrix, record the temperatures of UHP conditions and a hotter stage, subsequent to the peak pressure (‘hot exhumation') respectively. Garnet Lu–Hf ages (c. 238–235 Ma) record the initial prograde growth of garnet, while coupled Sm–Nd ages (c. 219–213 Ma) reflect cooling following hot exhumation. The maximum duration of UHP conditions is constrained by the age difference of these two systems in garnet (c. 235–220 Ma). Complementary zircon and titanite U–Pb ages of c. 235–230 Ma and c. 216–206 Ma provide further constraints on the timing of prograde metamorphism and the ‘cold exhumation' respectively. We demonstrate that timing of various metamorphic stages can thus be determined by employing complementary chronometers from the same samples. These age results, combined with published data from adjacent areas, show lateral diachroneity in the Dabie–Sulu orogeny. Three sub‐blocks are thus defined by progressively younger garnet ages: western Dabie (243–238 Ma), eastern Dabie–northern Sulu (238–235 Ma) and southern Sulu terranes (225–220 Ma), which possibly correlate to different crustal slices in the recently proposed subduction channel model. These observed lateral chronologic variations in a large UHP terrane can possibly be extended to other suture zones.     

Electrical conductivity of dry and hydrous NaAlSi<Subscript>3</Subscript>O<Subscript>8</Subscript> glasses and liquids at high pressures

We report the first study of electrical conductivities of silicate melts at very high pressures (up to 10 GPa) and temperatures (up to 2,173 K). Impedance spectroscopy was applied to dry and hydrous albite (NaAlSi₃O₈) glasses and liquids (with 0.02–5.7 wt% H₂O) at 473–1,773 K and 0.9–1.8 GPa in a piston-cylinder apparatus, using a coaxial cylindrical setup. Measurements were also taken at 473–2,173 K and 6–10 GPa in two multianvil presses, using simple plate geometry. The electrical conductivity of albite melts is found to increase with temperature and water content but to decrease with pressure. However, at 6 GPa, conductivity increases rapidly with temperature above 1,773 K, so that at temperatures beyond 2,200 K, conductivity may actually increase with pressure. Moreover, the effect of water in enhancing conductivity appears to be more pronounced at 6 GPa than at 1.8 GPa. These observations suggest that smaller fractions of partial melt than previously assumed may be sufficient to explain anomalously high conductivities, such as in the asthenosphere. For dry melt at 1.8 GPa, the activation energy at T > 1,073 K is higher than that at T < 1,073 K, and the inflection point coincides with the rheological glass transition. Upon heating at 6–10 GPa, dry albite glass often shows a conductivity depression starting from ~1,173 K (due to crystallization), followed by rapid conductivity enhancement when temperature approaches the albite liquidus. For hydrous melts at 0.9–1.8 GPa, the activation energies for conductivity at ≥1,373 K are lower than those at <973 K, with a complex transition pattern in between. Electrical conductivity and previously reported Na diffusivity in albite melt are consistent with the Nernst–Einstein relation, suggesting the dominance of Na transport for electrical conduction in albite melts.     

Garnet and spinel lherzolite assemblages in MgO–Al2O3–SiO2 and CaO–MgO–Al2O3–SiO2: thermodynamic models and an experimental conflict

The recent publication of an updated thermodynamic dataset for petrological calculations provides an opportunity to illustrate the relationship between experimental data and the dataset, in the context of a new set of activity–composition models for several key minerals. These models represent orthopyroxene, clinopyroxene and garnet in the system CaO–MgO–Al₂O₃–SiO₂ (CMAS), and are valid up to 50 kbar and at least 1800 °C; they are the first high‐temperature models for these phases to be developed for the Holland & Powell dataset. The models are calibrated with reference to phase‐relation data in the subsystems CaO–MgO–SiO₂ (CMS) and MgO–Al₂O₃–SiO₂ (MAS), and will themselves form the basis of models in larger systems, suitable for calculating phase equilibria in the crust and mantle. In the course of calibrating the models, it was necessary to consider the reaction orthopyroxene + clinopyroxene + spinel = garnet + forsterite in CMAS, representing a univariant transition between simple spinel and garnet lherzolite assemblages. The high‐temperature segment of this reaction has been much disputed. We offer a powerful thermodynamic argument relating this reaction to the equivalent reaction in MAS, that forces us to choose between good model fits to the data in MAS or to the more recent data in CMAS. We favour the fit to the MAS data, preserving conformity with a large body of experimental and thermodynamic data that are incorporated as constraints on the activity–composition modelling via the internally consistent thermodynamic dataset.     

Olivine‐bearing symplectites in fractured garnet from eclogite,Moldanubian Zone (Bohemian Massif) – a short‐lived,granulite facies event

Recent petrological studies on high‐pressure (HP)–ultrahigh‐pressure (UHP) metamorphic rocks in the Moldanubian Zone, mainly utilizing compositional zoning and solid phase inclusions in garnet from a variety of lithologies, have established a prograde history involving subduction and subsequent granulite facies metamorphism during the Variscan Orogeny. Two temporally separate metamorphic events are developed rather than a single P–T loop for the HP–UHP metamorphism and amphibolite–granulite facies overprint in the Moldanubian Zone. Here further evidence is presented that the granulite facies metamorphism occurred after the HP–UHP rocks had been exhumed to different levels of the middle or upper crust. A medium‐temperature eclogite that is part of a series of tectonic blocks and lenses within migmatites contains a well‐preserved eclogite facies assemblage with omphacite and prograde zoned garnet. Omphacite is partly replaced by a symplectite of diopside + plagioclase + amphibole. Garnet and omphacite equilibria and pseudosection calculations indicate that the HP metamorphism occurred at relatively low temperature conditions of ~600 °C at 2.0–2.2 GPa. The striking feature of the rocks is the presence of garnet porphyroblasts with veins filled by a granulite facies assemblage of olivine, spinel and Ca‐rich plagioclase. These minerals occur as a symplectite forming symmetric zones, a central zone rich in olivine that is separated from the host garnet by two marginal zones consisting of plagioclase with small amounts of spinel. Mineral textures in the veins show that they were first filled mostly by calcic amphibole, which was later transformed into granulite facies assemblages. The olivine‐spinel equilibria and pseudosection calculations indicate temperatures of ~850–900 °C at pressure below 0.7 GPa. The preservation of eclogite facies assemblages implies that the granulite facies overprint was a short‐lived process. The new results point to a geodynamic model where HP–UHP rocks are exhumed to amphibolite facies conditions with subsequent granulite facies heating by mantle‐derived magma in the middle and upper crust.     

The initial garnet‐in reaction involving siderite–rhodochrosite,garnet re‐equilibration and P–T–t paths of graphitic schists in the Black Hills orogen,South Dakota,USA

It is generally thought that garnet in metapelites is produced by continuous reactions involving chlorite or chloritoid. Recent publications have suggested that the equilibrium temperatures of garnet‐in reactions may be significantly overstepped in regionally metamorphosed terranes. The growth of small spessartine–almandine garnet crystals on Mn‐siderite at the garnet isograd in graphitic metapelites in the Proterozoic Black Hills orogen, South Dakota, demonstrates that Mn‐siderite was the principal reactant that produced the initial garnet in the schists. Moreover, the positions of garnet compositions in isobaric, T–(C/H) pseudosections for the schists show that the temperature of the garnet‐in reaction from Mn‐siderite was overstepped minimally at the most. In the Black Hills, garnet was initially produced during regional metamorphism beginning at c. 1755 Ma due to the collision of Wyoming and Superior cratons, and was subsequently partially or fully re‐equilibrated at more elevated temperatures and pressures during intrusion of the Harney Peak Granite (HPG) at c. 1715 Ma. Garnet occurs in graphitic schists in garnet, staurolite and sillimanite zones, the latter being a product of contact metamorphism by HPG. During metamorphism, coexisting fluid contained both CO₂ and CH₄. In the garnet zone, garnet crystals contain petrographically distinct cores with inclusions of quartz, graphite and other minerals. Centres of the cores have distinctly elevated Y concentrations that mark the positions of garnet nucleation. The elevated Y is thought to have come from the Mn‐siderite onto which Y was probably absorbed during precipitation in an ocean. In the upper garnet and staurolite zones, the cores were overgrown by inclusion‐poor mantles. Mantles are highly zoned and have more elevated Fe and Mg and lower Mn and Ca than cores. The growth of mantles is attributed to late‐orogenic heating by leucogranite magmas and attendant influx of H₂O that caused consumption of graphite in rock matrices. A portion of the Proterozoic terrane that includes the HPG is surrounded by four large faults. In this ‘HPG block’, garnet is inclusion‐poor and its composition does not preserve its early growth history. This garnet appears to have re‐equilibrated by internal diffusion of its major components and/or recrystallization of an earlier inclusion‐rich garnet. It has equilibrated within the kyanite stability range, and together with remnant kyanite in the high‐strain aureole of the HPG, indicates that the HPG block had a ≥6 kbar history. The HPG block has undergone decompression during emplacement of the HPG. The decompression is evident in occurrences of retrograde andalusite and cordierite in the thermal aureole of the HPG. The data support a polybaric metamorphic history of the Black Hills orogen with different segments of the orogen having their own clockwise P–T–t paths.     

Evolution of mineralizing fluids in the Zn–Pb–Cu(–Ag ± Au) skarn and epithermal deposits of the world-class San Martín district, Zacatecas, Mexico

Mineralizing fluids at the San Martín skarn show an evolution characterized by prograde and retrograde associations. The prograde mineral associations consist of (1) a massive garnet zone, (2) a tremolite ± garnet zone, and (3) a late association of quartz, sphalerite, calcite and fluorite lining the vugs in the garnet zone. The fluids of the prograde associations exhibit decreasing temperatures of homogenization (Th) and variable salinities. The fluids of the massive garnet zone have salinities of 36 wt.% NaCl equiv. and Th of 645 to 570 °C, corresponding to pressures of 1055 bar. At the tremolite ± garnet zone, Th range from 438 to 354 °C. In the late association at the endoskarn, the following evolution can be drawn: (a) salinities of 50 to 42 wt.% NaCl equiv., and Th of 455 to 346 °C in quartz, (b) salinities of 46 wt.% NaCl equiv., and Th of 415 to 410 °C in sphalerite, (c) salinities of 50 to 37 wt.% NaCl equiv., and Th of 479 to 310 °C in calcite, (d) salinities of 33 to 28 wt.% NaCl equiv. and of 24 to 22 wt.% KCl in fluorite, and (e) two types of fluids with salinities of 2 and 39 wt.% NaCl equiv. and Th 344 and 300 °C, respectively, in later saccharoidal quartz segregations. The retrograde mineral associations comprise pervasive propylitic alteration to carbonization, and mantos with sulfides. Fluids in epidote have salinities of 7.6 wt.% NaCl equiv. and Th of 287 to 252 °C, and in calcite have salinities of 9.2 to 1 wt.% NaCl equiv. and Th of 188 to 112 °C. Fluids in the sulfide assemblages in the mantos have salinities of 8 to 3 wt.% NaCl equiv. and Th 300 °C, with corresponding pressures of 94 bar. Fluids in late epithermal veins close to the intrusive body have salinities of 10 to 5 wt.% NaCl equiv. and Th of 275 to 200 °C, and distal veins show salinities of 2 to 1 wt.% NaCl equiv. and Th of 160 °C.