Calculated stabilities of sodic phases in the Sambagawa metapelites and their implications

Pressure (P)–temperature (T) pseudosection analyses were carried out on metapelites from Sambagawa belt by using Perple_X 07 so as to determine mineral equilibria and the stability of sodic phases, in the model system MnO–Na₂O–K₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O–(CO₂) under high‐pressure (HP) conditions (0.5–2.5 GPa/400–600 °C). A pressure–X_NA [=Na/(Na+Al–2K–1.5Ca)] pseudosection at 500 °C is also calculated to examine the effect of Na/Al value of the bulk‐rock composition on the stabilities of sodic minerals. The bulk‐rock compositions of Sambagawa metapelite are variable in X_NA values. The calculation results of stable assemblages in metapelites under the blueschist and eclogite facies conditions indicate that: (i) paragonite and glaucophane are stable throughout the wide X_NA range of bulk‐rock compositions of host rocks; (ii) stable P–T conditions of sodic pyroxene enlarge with increasing X_NA value; and (iii) the stability field of paragonite enlarges with the presence of CO₂ in the metamorphic fluid. The suggested wide stability of paragonite in metapelites and the relationships between the stability of sodic pyroxene and the bulk‐rock compositions explain the reasons why (i) the occurrence of omphacite in metapelites from several subduction‐related terranes is rare; and (ii) paragonite commonly occurs as inclusions in garnet of metapelites from the Besshi region of the Sambagawa belt. Paragonite is an important sodic phase of HP metapelites, and a combination of paragonite and quartz with high residual pressure included in garnet may be a useful indicator to verify the evidence for the eclogite facies metamorphism recorded in metapelites.     

Amphibolites with staurolite and other aluminous minerals: calculated mineral equilibria in NCFMASH

Amphibolite facies mafic rocks that consist mainly of hornblende, plagioclase and quartz may also contain combinations of chlorite, garnet, epidote, and, more unusually, staurolite, kyanite, sillimanite, cordierite and orthoamphiboles. Such assemblages can provide tighter constraints on the pressure and temperature evolution of metamorphic terranes than is usually possible from metabasites. Because of the high variance of most of the assemblages, the phase relationships in amphibolites depend on rock composition, in addition to pressure, temperature and fluid composition. The mineral equilibria in the Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O (NCFMASH) model system demonstrate that aluminium content is critical in controlling the occurrence of assemblages involving hornblende with aluminous minerals such as sillimanite, kyanite, staurolite and cordierite. Except in aluminous compositions, these assemblages are restricted to higher pressures. The iron to magnesium ratio (X_Fe), and to a lesser extent, sodium to calcium ratio, have important roles in determining which (if any) of the aluminous minerals occur under particular pressure–temperature conditions. Where aluminous minerals occur in amphibolites, the P–T–X dependence of their phase relationships is remarkably similar to that in metapelitic rocks. The mineral assemblages of Fe‐rich amphibolites are typically dominated by garnet‐ and staurolite‐bearing assemblages, whereas their more Mg‐rich counterparts contain chlorite and cordierite. Assemblages involving staurolite–hornblende can occur over a wide range of pressures (4–10 kbar) at temperatures of 560–650 °C; however, except in the more aluminous, iron‐rich compositions, they occupy a narrow pressure–temperature window. Thus, although their occurrence in ‘typical’ amphibolites may be indicative of relatively high pressure metamorphism, in more aluminous compositions their interpretation is less straightforward.     

Hugoniot and sound velocity of antigorite and evidence for sluggish decomposition

Antigorite is one kind of hydrous serpentine that is present in meteorites and in the Earth mantle. In order to understand its dynamic behaviors, metastability and decomposition, shock experiments on antigorite have been conducted using a two-stage gas gun, and wave profiles of particle velocities have been measured to obtain the Hugoniot up to ~130 GPa and sound velocity at high pressures. The results show three regions of low-pressure phase below ~43 GPa and its metastable extension above a pressure of ~43 GPa for short durations of shock and high-pressure phase(s) above a pressure of ~43 GPa for long durations of shock. The dynamic behaviors of antigorite depend on not only the pressure but also the compression duration. Metastable extension state indicates that antigorite may survive beyond the stability depending on the shock conditions. Shock temperatures for antigorite are calculated along the Hugoniot. The pressure–density, sound velocity–pressure and shock temperature–pressure plots demonstrate that the decomposition reaction of antigorite into high-pressure phase(s) is accompanied by a volume expansion, sound velocity increase and temperature decrease, relative to the metastable extension phase above ~43 GPa. The decomposition should be sluggish and needs enough reaction time to complete and to overcome the activation energy. As a result of the high metastability of antigorite and possible decomposition assemblages, the hydrous serpentine (antigorite) may play a crucial role for the origin of water during the Earth accretion.     

Serpentinization: a review

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

An experimental investigation of antigorite dehydration in natural silica-enriched serpentinite

Piston cylinder experiments were performed to constrain the pressure and temperature conditions for two high-pressure antigorite dehydration reactions found in silica-enriched serpentinites from Cerro del Almirez (Nevado–Filábride Complex, Betic Cordillera, southern Spain). At 630–660°C and pressures greater than 1.6 GPa, antigorite first reacts with talc to form orthopyroxene ± chlorite + fluid. We show that orthopyroxene + antigorite is restricted to high-pressure metamorphism of silica-enriched serpentinite. This uncommon assemblage is helpful in constraining metamorphic conditions in cold subduction environments, where antigorite serpentinites have no diagnostic assemblages over a large pressure and temperature range. The second dehydration reaction leads to the breakdown of antigorite to olivine + orthopyroxene + chlorite + fluid. The maximum stability of antigorite is found at 680°C at 1.9 GPa, which also corresponds to the maximum pressure limit for tremolite coexisting with olivine + orthopyroxene. The high aluminium (3.70 wt% Al₂O₃) and chromium contents (0.59 wt% Cr₂O₃) of antigorite in the investigated starting material is responsible for the expansion of the serpentinite stability to 60–70°C higher temperatures at 1.8 GPa than the antigorite stability calculated in the Al-free system. The antigorite from our study has the highest Al–Cr contents among all experimental studies and therefore likely constraints the maximum stability of antigorite in natural systems. Comparison of experimental results with olivine–orthopyroxene–chlorite–tremolite assemblages outcropping in Cerro del Almirez indicates that peak metamorphic conditions were 680–710°C and 1.6–1.9 GPa.     

Antigorite equation of state and anomalous softening at 6 GPa: an in situ single-crystal X-ray diffraction study

The compressibility of antigorite has been determined up to 8.826(8) GPa, for the first time by single crystal X-ray diffraction in a diamond anvil cell, on a specimen from Cerro del Almirez. Fifteen pressure–volume data, up to 5.910(6) GPa, have been fit by a third-order Birch–Murnaghan equation of state, yielding V ₀ = 2,914.07(23) Å³, K _T0 = 62.9(4) GPa, with K′ = 6.1(2). The compression of antigorite is very anisotropic with axial compressibilities in the ratio 1.11:1.00:3.22 along a, b and c, respectively. The new equation of state leads to an estimation of the upper stability limit of antigorite that is intermediate with respect to existing values, and in better agreement with experiments. At pressures in excess of 6 GPa antigorite displays a significant volume softening that may be relevant for very cold subducting slabs.     

Calculated phase equilibria for MORB compositions: a reappraisal of the metamorphic evolution of lawsonite eclogite

Pseudosections calculated with thermocalc predict that lawsonite‐bearing assemblages, including lawsonite eclogite, will be common for subducted oceanic crust that experiences cool, fluid‐saturated conditions. For glaucophane–lawsonite eclogite facies conditions (500–600 °C and 18–28 kbar), MORB compositions are predicted in the NCKMnFMASHO system to contain glaucophane, garnet, omphacite, lawsonite, phengite and quartz, with chlorite at lower temperature and talc at higher temperature. In these assemblages, the pyrope content in garnet is mostly controlled by variations in temperature, and grossular content is strongly controlled by pressure. The silica content in phengite increases linearly with pressure. As the P–T conditions for these given isopleths are only subtly affected by common variations in bulk‐rock compositions, the P–T pseudosections potentially present a robust geothermobarometric method for natural glaucophane‐bearing eclogites. Thermobarometric results recovered both by isopleth and conventional approaches indicate that most natural glaucophane–lawsonite eclogites (Type‐L) and glaucophane–epidote eclogites (Type‐E) record similar peak P–T conditions within the lawsonite stability field. Decompression from conditions appropriate for lawsonite stability should result in epidote‐bearing assemblages through dehydration reactions controlled by lawsonite + omphacite = glaucophane + epidote + H₂O. Lawsonite and omphacite breakdown will be accompanied by the release of a large amount of bound fluid, such that eclogite assemblages are variably recrystallized to glaucophane‐rich blueschist. Calculated pseudosections indicate that eclogite assemblages form most readily in Ca‐rich rocks and blueschist assemblages most readily in Ca‐poor rocks. This distinction in bulk‐rock composition can account for the co‐existence of low‐T eclogite and blueschist in high‐pressure terranes.     

The metamorphic evolution of metapelitic granulites from Radok Lake, northern Prince Charles Mountains, east Antarctica; evidence for an anticlockwise P–T path

Mineral textures in metapelitic granulites from the northern Prince Charles Mountains, coupled with thermodynamic modelling in the K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃ (KFMASHTO) model system, point to pressure increasing with increasing temperature on the prograde metamorphic path, followed by retrograde cooling (i.e. an anticlockwise P–T path). Textural evidence for the increasing temperature part of the path is given by the breakdown of garnet and biotite to form orthopyroxene and cordierite in sillimanite‐absent rocks, and through the break‐down of biotite and sillimanite to form spinel, cordierite and garnet in more aluminous assemblages. This is equated to the advective addition of heat from the regional emplacement of granitic and charnockitic magmas dated at c. 980 Ma. A subsequent increase in pressure, inferred from the break‐down of spinel and quartz to sillimanite, cordierite and garnet in aluminous rocks, is attributed to crustal thickening related to upright folding dated at 940–910 Ma. The terrane attained peak metamorphic temperatures of c. 880 °C at pressures of c. 6.0–6.5 kbar during this event. Subsequent cooling is inferred from the localised breakdown of cordierite and garnet to form biotite and sillimanite that developed in the latter stages of the same event. The textural observations described are interpreted via the application of P–T and P–T–X pseudosections. The latter show that most rock compositions preserve only fragments of the overall P–T path; a result of different rock compositions undergoing mineral assemblage changes, or changes in mineral modal abundance, on different sections of the P–T path. The results also suggest that partial melting during granulite facies metamorphism, coupled with melt loss and dehydration, initiated a switch from pervasive ductile, to discrete ductile/brittle deformation, during retrograde cooling.     

Petrogenesis of the garnet peridotite and garnet-free peridotite of the Zhimafang ultramafic body in the Sulu ultrahigh-pressure metamorphic belt, eastern China

The CCSD‐PP1 drillhole penetrated a 110‐m‐thick sequence of the Zhimafang ultramafic body in the Sulu ultrahigh‐pressure (UHP) metamorphic belt, east China. The sequence consists of interlayered garnet‐bearing (Grt) and garnet‐free (GF) peridotite. Eleven layers of Grt‐peridotite, ranging from 1.2 to 9.5 m in thickness, have an aggregate thickness of 54.49 m, whereas eight layers of GF‐peridotite, ranging from 2.2 to 14.2 m in thickness, have a total thickness of 57.53 m. The boundaries between the two rock types are gradational. The Grt‐peridotites have slightly higher contents of Al₂O₃, CaO and SiO₂, and lower Mg^#s (0.90–0.92) than the GF‐peridotites (Mg^#s 0.91–0.93). Both contain low TiO₂ (<0.05 wt%) and have higher modal abundances of enstatite (average 10 vol.%) than diopside (1–5 vol.%), typical of depleted‐type upper mantle. The diopside in these rocks has high and relatively uniform Mg^# members (0.93–0.95), but highly variable Al₂O₃ (0.2–2.3 wt%), Na₂O (0.5–2.5 wt%) and Cr₂O₃ (0.38–2.09 wt%). Enstatite (En_92?93) contains very low Al₂O₃ (0–0.3 wt%). Both porphyroblastic and equigranular garnet are present. The equigranular varieties are zoned, from core to rim in Cr₂O₃ (3.4–4.2 wt%), MgO (18.4–17.5 wt%) and Al₂O₃ (21.1–20.1 wt%). Titania is very low in all the garnet, mostly <0.05 wt%. Chromite or chromium (Cr)‐spinel occur both in the Grt‐ and GF‐peridotite, and are characterized by high contents of Cr₂O₃ (49–58 wt%) and FeO (24–43 wt%), similar to that in iron‐rich Alpine‐type peridotites. Based on the bulk‐rock MgO–FeO compositions, the Zhimafang Grt‐peridotite probably underwent 20–30% partial melting, whereas the GF‐peridotite may have undergone as much as 35–40% partial melting, suggesting that the two rock types owe their differences to different degrees of partial melting rather than to pressure differences during metamorphism.     

俯冲带蛇纹岩的变质过程

俯冲带蛇纹岩是俯冲带流体的重要来源,特别是其深部脱水作用对地幔动力学影响深远,是研究俯冲带约80~200km深度范围的地球动力学的关键,因此研究蛇纹岩的变质作用过程及其相关特征矿物(组合)的温压稳定范围具有重要意义。蛇纹岩具有简单的矿物(组合):蛇纹石类、硅镁石类、磁铁矿、氢氧镁石、绿泥石、橄榄石、透辉石、角闪石、滑石等,并且这些矿物(组合)对温压变化不敏感从而很难用来判定蛇纹岩所经历的变质演化轨迹。近几十年来,研究者通过实验岩石学和野外地质观察,主要研究了蛇纹石类矿物和硅镁石类矿物的温压稳定范围,并且试图使用这些特征矿物(组合)来判定俯冲带蛇纹岩的峰期变质条件。本文总结了蛇纹岩中这些主要矿物的温压稳定范围和相关变质反应,并且以中国西南天山蛇纹岩为例,展示使用特征矿物(组合)和叶蛇纹石Al等值线判定蛇纹岩峰期温压条件在实际岩石中的应用。另外,早期对叶蛇纹石的研究表明:随着温压条件的变化,叶蛇纹石的晶体结构会发生相应的调整。表现为单位晶胞内硅氧四面体的个数(m值)发生变化:温度升高,m值变小;压力升高,m值变大,这个发现在高压实验和天然样品中得到了一定程度的验证。本文利用已知峰期温压范围的叶蛇纹石样品分别采用粉末制样法和离子减薄制样法,进行透射电镜测试(TEM)样品的m值,并通过统计的方法获得叶蛇纹石的m值的峰值。结果显示叶蛇纹石的m值的峰值在一定程度上可以用以指示温压条件。本文提出可以用矿物组合、叶蛇纹石Al等值线和叶蛇纹石m值峰值相结合的方法确定蛇纹岩的变质温压条件和P-T轨迹。     

Liquid compositions from low-pressure experimental melting of pelitic rock from Morton Pass, Wyoming, USA

Low‐pressure crystal‐liquid equilibria in pelitic compositions are important in the formation of low‐pressure, high‐temperature migmatites and in the crystallization of peraluminous leucogranites and S‐type granites and their volcanic equivalents. This paper provides data from vapour‐present melting of cordierite‐bearing pelitic assemblages and augments published data from vapour‐present and vapour‐absent melting of peraluminous compositions, much of which is at higher pressures. Starting material for the experiments was a pelitic rock from Morton Pass, Wyoming, with the major assemblage quartz‐K feldspar‐biotite‐cordierite, approximately in the system KFMASH. A greater range in starting materials was obtained by addition of quartz and sillimanite to aliquots of this rock. Sixty‐one experiments were carried out in cold‐seal apparatus at pressures of 1–3.5 kbar (particularly 2 kbar) and temperatures from 700 to 840 °C, with and without the addition of water. In the vapour‐present liquidus relations at 2 kbar near the beginning of melting, the sequence of reactions with increasing temperature is: Qtz + Kfs + Crd + Sil + Spl + V = L; Qtz + Kfs + Crd + Spl + Ilm + V = Bt + L; and Qtz + Bt + V = Crd + Opx + Ilm + L. Vapour‐absent melting starts at about 800 °C with a reaction of the form Qtz + Bt = Kfs + Crd + Opx + Ilm + L. Between approximately 1–3 kbar the congruent melting reaction is biotite‐absent, and biotite is produced by incongruent melting, in contrast to higher‐pressure equilibria. Low pressure melts from pelitic compositions are dominated by Qtz‐Kfs‐Crd. Glasses at 820–840 °C have calculated modes of approximately Qtz₄₂Kfs₄₆Crd₁₂. Granites or granitic leucosomes with more than 10–15% cordierite should be suspected of containing residual cordierite. The low‐pressure glasses are quite similar to the higher‐pressure glasses from the literature. However, X_Mg increases from about 0.1–0.3 with increasing pressure from 1 to 10 kbar, and the low‐temperature low‐pressure glasses are the most Fe‐rich of all the experimental glasses from pelitic compositions.     

Retrograde replacement of andalusite by Ca–Na mica in chloritoid-bearing metapelites. PTX modelling of rocks with different Al content in the MnNCKFMASH system

Andalusite porphyroblasts are totally pseudomorphosed by margarite–paragonite aggregates in aluminous pelites containing the peak mineral assemblage andalusite, chlorite, chloritoid, margarite, paragonite, quartz ± garnet, in a NW Iberia contact area. Equilibria at low P–T are investigated using new KFMASH and (mainly) MnCNKFMASH grids constructed with Thermocalc 3.21. P–T and T–X pseudosections with phase modal volume isopleths are constructed for compositions relatively richer and poorer in andalusite to model the assemblages in an andalusite‐bearing rock that contains a thin andalusite‐rich band (ARB) during retrogression. Their compositions, prior to retrogression, are used in the modelling, and have been retrieved by restoring the pseudomorph‐forming elements into the current‐depleted matrix, except for Al₂O₃ which is assumed to be immobile. Compositional differences between the thin band and the rest of the rock have not resulted in differences in andalusite porphyroblast retrogression. The absence of chloritoid resorbtion implies either a pressure increase at constant reacting‐system composition, or that its composition changed during retrogression at constant pressure, by becoming enriched in the progressively replaced andalusite porphyroblasts. T–X pseudosections at 1 kbar model this latter process using as end‐members in X, first, the restored original rock and ARB compositions, and, then the same process, taking into account the change in composition of both as retrogression proceeded. The MnNCKFMASH pseudosections of rocks with different Al contents facilitate making further deductions on the rock‐composition control of the resulting assemblages upon retrogression. Andalusite eventually disappears in relatively Al‐poor rocks, resulting, as in this study, in a rock formed by chloritoid–chlorite as the only FM minerals, plus margarite–paragonite pseudomorphs of andalusite. In rocks richer in Al, chlorite would progressively disappear and a kyanite/andalusite–chloritoid assemblage would eventually be stable at retrograde conditions. The Al‐silicate, stable during retrogression in Al‐rich rocks, indicates pressure conditions and hence the tectonic context under which retrogression took place.     

Domainal variations of U–Pb monazite ages and Rb–Sr whole-rock dates in polymetamorphic paragneisses (KTB Drill Core, Germany): influence of strain and deformation mechanisms on isotope systems

Polyphase metamorphic paragneisses from the drill core of the continental deep drilling project (KTB; NW Bohemian Massif) are characterized by peak pressures of about 8 kbar (medium‐P metamorphism) followed by strain accumulation at T >650 °C, initially by dislocation creep and subsequently by diffusion creep. U–Pb monazite ages and Rb–Sr whole‐rock data vary in the dm‐scale, indicating Ordovician and Mid‐Devonian metamorphic events. Such age variations are closely interconnected with dm‐scale domainal variations of microfabrics that indicate different predominant deformation mechanisms. U–Pb monazite age variations dependent on microfabric domains exceed grain‐size‐dependent age variations. In ‘mylonitic domains’ recording high magnitudes of plastic strain, dislocation creep and minor static annealing, monazite yields concordant and near concordant Lower Ordovician U–Pb ages, and the Rb–Sr whole‐rock system shows isotopic disequilibrium at an mm‐scale. In ‘mineral growth/mobilisate domains’, in which diffusive mass transfer was a major strain‐producing mechanism promoting diffusion creep of quartz and feldspar, and in which static recrystallization (annealing) reduced the internal free energy of the strained mineral aggregates, concordant U–Pb ages are Mid‐Devonian. Locally, in such domains, Rb–Sr dates among mm³‐sized whole‐rock slabs reflect post‐Ordovician resetting. In ‘transitional domains’, the U–Pb‐ages are discordant. We conclude that medium‐P metamorphism occurred at 484±2 Ma, and a second metamorphic event at 380–370 Ma (Mid‐Devonian) caused progressive strain in the rocks. Dislocation creep at high rates, even at high temperatures, does not reset the Rb–Sr whole‐rock system, while diffusion creep at low rates and stresses (i.e. low ε/D_eff ratios), static annealing and the presence of intergranular fluids locally assist resetting. At temperatures above 650 °C, diffusive Pb loss did not reset Ordovician U–Pb monazite ages, and in domains of overall high imposed strain rates and stresses, resetting was not assisted by dynamic recrystallization/crystal plasticity. However, during diffusion creep at low rates, Pb loss by dissolution and precipitation (‘recrystallization’) of monazite produces discordance and Devonian‐concordant U–Pb monazite ages. Hence, resetting of these isotope systems reflects neither changes of temperature nor, directly, the presence or absence of strain.     

Quantitative P–T–X constraints on orthopyroxene-bearing high-pressure granulites in felsic–metapelitic rocks: evidence from the Huangtuling granulite, Dabieshan Orogen

High‐pressure granulites are generally characterized by the absence of orthopyroxene. However, orthopyroxene is reported in a few high‐pressure, felsic–metapelitic granulites, such as the Huangtuling felsic high‐pressure granulite in the North Dabie metamorphic core complex in east‐central China, which rarely preserves the high‐pressure granulite facies assemblage of garnet + orthopyroxene + biotite + plagioclase + K‐feldspar + quartz. To investigate the effects of bulk‐rock composition on the stability of orthopyroxene‐bearing, high‐pressure granulite facies assemblages in the NCKFMASHTO (Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃) system, a series of P–T–X pseudosections based on the melt‐reintegrated composition of the Huangtuling felsic high‐pressure granulite were constructed. Calculations demonstrate that the orthopyroxene‐bearing, high‐pressure granulite facies assemblages are restricted to low X_Al [Al₂O₃/(Na₂O + CaO + K₂O + FeO + MgO + Al₂O₃) < 0.35, mole proportion] or high X_Mg [MgO/(MgO + FeO) > 0.85] felsic–metapelitic rock types. This study also reveals that the X_Al values in the residual felsic–metapelitic, high‐pressure granulites could be significantly reduced by a high proportion of melt loss. We suggest that orthopyroxene‐bearing, high‐pressure granulites occur in residual overthickened crustal basement under continental subduction–collision zones and arc–continent collision belts.     

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

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

Low‐P and high‐T metamorphism of basalts: Insights from the Sudbury impact melt sheet aureole and thermodynamic modelling

Low‐pressure and high‐temperature (LP–HT) metamorphism of basaltic rocks, which occurs globally and throughout geological time, is rarely constrained by forward phase equilibrium modelling, yet such calculations provide valuable supplementary thermometric information and constraints on anatexis that are not possible to obtain from conventional thermometry. Metabasalts along the southern margin of the Sudbury Igneous Complex (SIC) record evidence of high‐grade contact metamorphism involving partial melting and melt segregation. Peak metamorphic temperatures reached at least ~925°C at ~1–3 kbar near the SIC contact. Preservation of the peak mineral assemblage indicates that most of the generated melt escaped from these rocks leaving a residuum characterized by a plagioclase–orthopyroxene–clinopyroxene–ilmenite‐magnetite±melt assemblage. Peak temperatures reached ~875°C up to 500 m from the SIC lower contact, which marks the transition to metabasalts that only experienced incipient partial melting without melt loss. Metabasalts ~500 to 750 m from the SIC contact are characterized by a similar two‐pyroxene mineral assemblage, but typically contain abundant hornblende that overgrew clino‐ and orthopyroxene along an isobaric cooling path. Metabasalts ~750 to 1,000 m from the SIC contact are characterized by a hornblende–plagioclase–quartz–ilmenite assemblage indicating temperatures up to ~680°C. Mass balance and phase equilibria calculations indicate that anatexis resulted in 10–20% melt generation in the inner ~500 m of the aureole, with even higher degrees of melting towards the contact. Comparison of multiple models, experiments, and natural samples indicates that modelling in the Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O₂ (NCFMASHTO) system results in the most reliable predictions for the temperature of the solidus. Incorporation of K₂O in the most recent amphibole solution model now successfully predicts dehydration melting by the coexistence of high‐Ca amphibole and silicate melt at relatively low pressures (~1.5 kbar). However, inclusion of K₂O as a system component results in prediction of the solidus at too low a temperature. Although there are discrepancies between modelling predictions and experimental results, this study demonstrates that the pseudosection approach to mafic rocks is an invaluable tool to constrain metamorphic processes at LP–HT conditions.     

Highly ordered antigorite from Cerro del Almirez HP–HT serpentinites,SE Spain

The Cerro del Almirez ultramafic massif offers an example of high pressure and high temperature antigorite serpentinites. A sharp antigorite-out isograd separates them from Chl-harzburgites, consisting of olivine + enstatite + chlorite. Antigorite is characterized by aluminium contents as high as 4 wt.% Al₂O₃. The microstructural study shows that, prior to the transformation, antigorite is exceptionally ordered and consists of the polysome m = 17. No polysomatic defect occurs in antigorite forming most of the Cerro del Almirez serpentinites. Close to the antigorite-out isograd, limited disorder features may occur, mainly as (001) twins, reaction rims and reduction of m down to 14–15. Here, local recrystallization phenomena lead to sporadic growth of large antigorite and chlorite crystals.     

Contact metamorphic P–T–t paths from Sm–Nd garnet ages, phase equilibria modelling and thermobarometry: Garnet Ledge, south-eastern Alaska, USA

Sm–Nd garnet‐whole rock geochronology, phase equilibria, and thermobarometry results from Garnet Ledge, south‐eastern Alaska, provide the first precisely constrained P–T–t path for garnet zone contact metamorphism. Garnet cores from two crystals and associated whole rocks yield a four point isochron age for initial garnet growth of 89.9 ± 3.6 Ma. Garnet rims and matrix minerals from the same samples yield a five point isochron age for final garnet growth of 89 ± 1 Ma. Six size fractions of zircon from the adjacent pluton yield a concordant U–Pb age of 91.6 ± 0.5 Ma. The garnet core and rim, and zircon ages are compatible with single‐stage garnet growth during and/or after pluton emplacement. All garnet core–whole rock and garnet rim‐matrix data from the two samples constrain garnet growth duration to ≤5.5 my. A garnet mid‐point and the associated matrix from one of the two garnet crystals yield an age of 90.0 ± 1.0 Ma. This mid‐point result is logically younger than the 90.7 ± 5.6 Ma core–whole rock age and older than the 88.4 ± 2.5 Ma rim‐matrix age for this sample. A MnNaCaKFMASH phase diagram (P–T pseudosection) and the garnet core composition are used to predict that cores of garnet crystals grew at 610 ± 20 °C and 5 ± 1 kbar. This exceeds the temperature of the garnet‐in reaction by c. 50 °C and is compatible with overstepping of the garnet growth reaction during contact metamorphism. Intersection of three reactions involving garnet‐biotite‐sillimanite‐plagioclase‐quartz calculated by THERMOCALC in average P–T mode, and exchange thermobarometry were used to estimate peak metamorphic conditions of 678 ± 58 °C at 6.1 ± 0.9 kbar and 685 ± 50 °C at 6.3 ± 1 kbar, respectively. Integration of pressure, temperature, and age estimates yields a pressure‐temperature‐time path compatible with near isobaric garnet growth over an interval of c. 70 °C and c. 2.3 my.     

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.     

Adsorption Mechanism and Kinetic Characterization of Bituminous Coal under High Temperatures and Pressures in the Linxing‐Shenfu Area

The majority of coalbed methane(CBM) in coal reservoirs is in adsorption states in coal matrix pores. To reveal the adsorption behavior of bituminous coal under high-temperature and high-pressure conditions and to discuss the microscopic control mechanism affecting the adsorption characteristics, isothermal adsorption experiments under hightemperature and high-pressure conditions, low-temperature liquid nitrogen adsorption-desorption experiments and CO2 adsorption experiments were performed on coal samples. Results show that the adsorption capacity of coal is comprehensively controlled by the maximum vitrinite reflectance(Ro, max), as well as temperature and pressure conditions. As the vitrinite reflectance increases, the adsorption capacity of coal increases. At low pressures, the pressure has a significant effect on the positive effect of adsorption, but the effect of temperature is relatively weak. As the pressure increases, the effect of temperature on the negative effect of adsorption gradually becomes apparent, and the influence of pressure gradually decreases. Considering pore volumes of pores with diameters of 1.7-100 nm, the peak volume of pores with diameters 10-100 nm is higher than that from pores with diameters 1.7-10 nm, especially for pores with diameters of 40-60 nm, indicating that pores with diameters of 10-100 nm are the main contributors to the pore volume. The pore specific surface area shows multiple peaks, and the peak value appears for pore diameters of 2-3 nm, indicating that this pore diameter is the main contributor to the specific surface area. For pore diameters of 0.489-1.083 nm, the pore size distribution is bimodal, with peak values at 0.56-0.62 nm and 0.82-0.88 nm. The adsorption capability of the coal reservoir depends on the development degree of the supermicroporous specific surface area, because the supermicroporous pores are the main contributors to the specific pore area. Additionally, the adsorption space increases as the adsorption equilibrium pressure increases. Under the same pressure, as the maximum vitrinite reflectance increases, the adsorption space increases. In addition, the cumulative reduction in the surface free energy increases as the maximum vitrinite reflectance increases. Furthermore, as the pressure increases, the surface free energy of each pressure point gradually decreases, indicating that as the pressure increases, it is increasingly difficult to adsorb methane molecules.