Experimental determination of REE partition coefficients between zircon,garnet and melt: a key to understanding high‐T crustal processes

The partitioning of rare earth elements (REE) between zircon, garnet and silicate melt was determined using synthetic compositions designed to represent partial melts formed in the lower crust during anatexis. The experiments, performed using internally heated gas pressure vessels at 7 kbar and 900–1000 °C, represent equilibrium partitioning of the middle to heavy REE between zircon and garnet during high‐grade metamorphism in the mid to lower crust. The D_REE (zircon/garnet) values show a clear partitioning signature close to unity from Gd to Lu. Because the light REE have low concentrations in both minerals, values are calculated from strain modelling of the middle to heavy REE experimental data; these results show that zircon is favoured over garnet by up to two orders of magnitude. The resulting general concave‐up shape to the partitioning pattern across the REE reflects the preferential incorporation of middle REE into garnet, with D_Gd (zircon/garnet) ranging from 0.7 to 1.1, D_Ho (zircon/garnet) from 0.4 to 0.7 and D_Lu (zircon/garnet) from 0.6 to 1.3. There is no significant temperature dependence in the zircon–garnet REE partitioning at 7 kbar and 900–1000 °C, suggesting that these values can be applied to the interpretation of zircon–garnet equilibrium and timing relationships in the ultrahigh‐T metamorphism of low‐Ca pelitic and aluminous granulites.     

有效全岩成分的计算方法及其在变质相平衡模拟中的应用

变质相平衡模拟是变质岩领域近几十年最重要的进展之一，它已经成为确定变质作用P-T-t轨迹和探索变质演化过程的有力工具。变质岩的矿物组合不但与其形成的温度（T）和压力（P）条件有关，而且受控于岩石的全岩成分（X）。但是变质岩通常是不均匀的并且往往保留两期以上的矿物组合，因此计算不同成分域或不同变质演化期次的有效全岩成分是模拟P-T视剖面图的核心问题之一。在中-低温变质岩中，石榴石变斑晶的生长会不断地将其核部成分"冻结"而不参与后续变质反应，这导致根据实测全岩成分计算的P-T视剖面图无法有效地模拟石榴石幔部或边部生长阶段的变质演化过程。"瑞利分馏法"和"球体积法"利用电子探针实测的石榴石成分环带可以模拟计算石榴石各个生长阶段所对应的有效全岩成分，本文推荐使用这两个方法来处理石榴石变斑晶的分馏效应问题。相比较而言，石榴石在高温变质岩中通常无法保留生长阶段的成分环带特征，这是因为石榴石成分在高温条件下会发生扩散再平衡，并同时与多数基质矿物达到热力学平衡，这时一般不需要考虑石榴石的分馏效应。但是高温变质岩通常会发生部分熔融并伴随熔体的迁移，进而改变岩石的有效全岩成分。因此，通过P-T视剖面图模拟熔体迁移前后的变质演化过程需要使用"相平衡法"计算迁移的熔体成分以及熔体迁移前后岩石的有效全岩成分。此外，后成合晶与反应边是变质岩中最常见的退变质反应结构，但是后成合晶或反应边中的矿物之间并未达到热力学平衡。这种情况需要结合岩相学观察和矿物成分，利用最小二乘法确定后成合晶或反应边中发生的平衡反应方程式，进而获取变质反应发生时的有效全岩成分并通过计算P-T视剖面图来估算退变质的温压条件。除此之外，岩石体系中三价铁（Fe₂O₃）和H₂O含量的估算一直以来都是相平衡模拟研究中的难点，本文推荐使用P/T-X（Fe³⁺/Fe^tot，MH₂O）视剖面图来确定这两个组分的含量，这是因为P/T-X图可以估算各个变质演化阶段或特定矿物组合的Fe₂O₃或H₂O含量。     

Challenges in high-pressure granulite metamorphism in the era of pseudosections: reaction textures, compositional zoning and tectonic interpretation with examples from the Bohemian Massif

High‐pressure granulites are an important record of geodynamic processes in overthickened or subducted continental crust. Orthopyroxene‐free assemblages in granitic (ternary feldspar(s) + quartz + garnet + kyanite + rutile), intermediate (ternary feldspar(s) + quartz + garnet + clinopyroxene ± kyanite ±rutile ± titanite) and basic (garnet + clinopyroxene + plagioclase ± quartz + rutile) compositions indicate formation conditions at mantle depths. Clinopyroxene compositions in Variscan high‐pressure granulites are unusual in that they include omphacite (in plagioclase‐bearing rocks thus not eclogite) and Al‐rich diopside (i.e. indicating high Ca‐Tschermak content), with both yielding temperatures above 900 °C. Problems such as compositional zoning, multiple generations of key phases in reaction domains and unmixing of high‐temperature solid‐solution phases during cooling (ternary feldspars, omphacite) clearly indicate disequilibrium and require very careful interpretation as to which phases and compositions possibly represent a former equilibrium association. Pressure–temperature (P–T) determination by the pseudosection method, although allowing prediction of mineral assemblages, compositions and molar proportions for a fixed bulk composition for modelled P–T conditions, still requires reliable activity–composition information for the key phases feldspar and clinopyroxene as well as an interpretation of former equilibrium compositions in the investigated samples, i.e. the same restrictions applying to conventional thermobarometry. The interpretations of some recently determined pseudosections for the composition of Variscan clinopyroxene‐bearing high‐pressure granulites contradict numerous published P–T paths. However, quantitative information from thermobarometry or pseudosections must be integrated with key petrographic observations. In the case of the Variscan example, it is argued that petrographic observations and published P–T paths are consistent with mineral assemblages predicted in pseudosections and support existing tectonometamorphic models.     

Using calculated chemical potential relationships to account for coronas around kyanite: an example from the Bohemian Massif

Corona textures around kyanite, involving for example zoned plagioclase separating kyanite from the matrix, reflect the instability of kyanite with the matrix on changing P–T conditions, commonly related to decompression. The chemical potential gradients set up between the kyanite and the matrix as a consequence of slow Al diffusion drive corona development, with the zoning of the plagioclase reflecting the gradients. Calculated mineral equilibria are used to account for corona textures involving plagioclase ± garnet around kyanite, and replacement of kyanite by plagioclase + spinel symplectite, in quartz + plagioclase + K‐feldspar + garnet + kyanite granulite facies gneiss from the Blanský les massif in the Bohemian massif, Czech Republic. In the garnet‐bearing coronas, a commonly discontinuous garnet layer lies between the kyanite and the continuous plagioclase layer in the corona, with both the garnet and the plagioclase appearing mainly to replace matrix rather than kyanite. The garnet layer commonly extends around kyanite from original matrix garnet adjacent to the kyanite. Where garnet is missing in the corona, the kyanite itself may be replaced by a spinel–plagioclase corona. In a local equilibrium model, the mineral and mineral compositional spatial relationships are shown to correspond to paths in μ(Na₂O)–μ(CaO)–μ(K₂O)–μ(FeO)–μ(MgO)–μ(SiO₂) in the model chemical system, Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂ (NCKFMAS). The discontinuous nature of the garnet layer in coronas is accounted for by the effect of the adjacent original garnet on the chemical potential relationships. The replacement of kyanite by spinel + plagioclase appears to be metastable with respect to replacement by corundum + plagioclase, possibly reflecting the difficulty of nucleating corundum.     

Petrochronology of oxidized granulites from southern Peru

Sapphirine–quartz granulites from the Cocachacra region of the Arequipa Massif in southern Peru record early Neoproterozoic ultrahigh‐temperature metamorphism. Phase equilibrium modelling and zircon petrochronology are used to quantify timing and pressure–temperature (P–T) conditions of metamorphism. Modelling of three magnetite‐bearing sapphirine–quartz samples indicates peak temperatures of >950°C at ~0.7 GPa and a clockwise P–T evolution. Elevated concentrations of Al in orthopyroxene are also consistent with ultrahigh‐temperature conditions. Neoblastic zircon records ages of c. 1.0–0.9 Ga that are interpreted to record protracted ultrahigh‐temperature metamorphism. Th/U ratios of zircon of up to 100 reflect U‐depleted whole‐rock compositions. Concentrations of heavy rare earth elements in zircon do not show systematic trends with U–Pb age but do correlate with variable whole‐rock compositions. Very large positive Ce anomalies in zircon from two samples probably relate to strongly oxidizing conditions during neoblastic zircon crystallization. Low concentrations of Ti‐in‐zircon (<10 ppm) are interpreted to result from reduced titania activities due to the strongly oxidized nature of the granulites and the sequestration of titanium‐rich minerals away from the reaction volume. Whole‐rock compositions and oxidation state have a strong influence on the trace element composition of metamorphic zircon, which has implications for interpreting the geological significance of ages retrieved from zircon in oxidized metamorphic rocks.     

Separating metamorphic events in the Fosdick migmatite–granite complex,West Antarctica

The Fosdick migmatite–granite complex in West Antarctica records evidence for two high‐temperature metamorphic events, the first during the Devonian–Carboniferous and the second during the Cretaceous. The conditions of each high‐temperature metamorphic event, both of which involved melting and multiple melt‐loss events, are investigated using phase equilibria modelling during successive melt‐loss events, microstructural observations and mineral chemistry. In situ SHRIMP monazite and TIMS Sm–Nd garnet ages are integrated with these results to constrain the timing of the two events. In areas that preferentially preserve the Devonian–Carboniferous (M₁) event, monazite grains in leucosomes and core domains of monazite inclusions in Cretaceous cordierite yield an age of c. 346 Ma, which is interpreted to record the timing of monazite growth during peak M₁ metamorphism (～820–870 °C, 7.5–11.5 kbar) and the formation of garnet–sillimanite–biotite–melt‐bearing assemblages. Slightly younger monazite spot ages between c. 331 and 314 Ma are identified from grains located in fractured garnet porphyroblasts, and from inclusions in plagioclase that surround relict garnet and in matrix biotite. These ages record the growth of monazite during garnet breakdown associated with cooling from peak M₁ conditions. The Cretaceous (M₂) overprint is recorded in compositionally homogeneous monazite grains and rim domains in zoned monazite grains. This monazite yields a protracted range of spot ages with a dominant population between c. 111 and 96 Ma. Rim domains of monazite inclusions in cordierite surrounding garnet and in coarse‐grained poikiloblasts of cordierite yield a weighted mean age of c. 102 Ma, interpreted to constrain the age of cordierite growth. TIMS Sm–Nd ages for garnet are similar at 102–99 Ma. Mineral equilibria modelling of the residual protolith composition after Carboniferous melt loss and removal of inert M₁ garnet constrains M₂ conditions to ～830–870 °C and ～6–7.5 kbar. The modelling results suggest that there was growth and resorption of garnet during the M₂ event, which would facilitate overprinting of M₁ compositions during the M₂ prograde metamorphism. Measured garnet compositions and Sm–Nd diffusion modelling of garnet in the migmatitic gneisses suggest resetting of major elements and the Sm–Nd system during the Cretaceous M₁ overprint. The c. 102–99 Ma garnet Sm–Nd ‘closure’ ages correspond to cooling below 700 °C during the rapid exhumation of the Fosdick migmatite–granite complex.     

Phase equilibria modelling of kyanite‐bearing anatectic paragneisses from the central Grenville Province

Kyanite‐bearing paragneisses from the Manicouagan Imbricate Zone and its footwall (high‐P belt of the central Grenville Province) preserve evidence of partial melting with development of metamorphic textures involving biotite–garnet ± kyanite ± plagioclase ± K‐feldspar–quartz. Garnet in these rocks displays a variety of zoning patterns with respect to Ca. Pseudosection modelling in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (NCKFMASHTO) system using measured bulk rock compositions accounts for the textural evolution of two aluminous and two sub‐aluminous samples from the presumed thermal peak to conditions at which retained melt solidified. The prograde features are best explained by pseudosections calculated with compositions to account for melt loss. The intersection of isopleths of grossular content and Fe/(Fe + Mg) relating to large porphyroblasts of garnet provide constraints on the P–T conditions of the metamorphic peak. These P–T estimates are considered to be minima because of the potential for diffusional modification of the composition of garnet at high‐T and during the early stages of cooling. However, they are consistent with textural observations and pseudosection topology, with peak assemblages best preserved in rocks for which the calculated pseudosections predict only small changes in mineral proportions in the P–T interval, in which retrograde reactions are inferred to have occurred between the thermal peak and the solidus. Maximum P–T conditions (14.5–15.5 kbar and 840–890 °C) and steep retrograde P–T paths inferred for rocks from the Manicouagan Imbricate Zone are comparable with those determined for mafic rocks from the same area. In contrast, maximum P–T conditions of 12.5–13 kbar and 815–830 °C and flatter P–T paths are inferred for the rocks of the footwall to the Manicouagan Imbricate Zone. The general consistency between textures, mineral compositions and the topologies of the calculated pseudosections suggests that the pseudosection approach is an appropriate tool for inferring the P–T evolution of high‐P anatectic quartzo‐feldspathic rocks.     

Coexistence of garnet blueschist and eclogite in South Tianshan,NW China: dependence of P–T evolution and bulk‐rock composition

Coexisting garnet blueschist and eclogite from the Chinese South Tianshan high‐pressure (HP)–ultrahigh‐pressure (UHP) belt consist of similar mineral assemblages involving garnet, omphacite, glaucophane, epidote, phengite, rutile/sphene, quartz and hornblendic amphibole with or without paragonite. Eclogite assemblages generally contain omphacite >50 vol.% and a small amount of glaucophane (<5 vol.%), whereas blueschist assemblages have glaucophane over 30 vol.% with a small amount of omphacite which is even absent in the matrix. The coexisting blueschist and eclogite show dramatic differences in the bulk‐rock compositions with higher X(CaO) [=CaO/(CaO + MgO + FeO_total + MnO + Na₂O)] (0.33–0.48) and lower A/CNK [=Al₂O₃/(CaO + Na₂O + K₂O)] (0.35–0.56) in eclogite, but with lower X(CaO) (0.09–0.30) and higher A/CNK (0.65–1.28) in garnet blueschist. Garnet in both types of rocks has similar compositions and exhibits core–rim zoning with increasing grossular and pyrope contents. Petrographic observations and phase equilibria modelling with pseudosections calculated using thermocalc in the NCKMnFMASHO system for the coexisting garnet blueschist and eclogite samples suggest that the two rock types share similar P–T evolutional histories involving a decompression with heating from the P_max to the T_max stage and a post‐T_max decompression with slightly cooling stage, and similar P–T conditions at the T_max stage. The post‐T_max decompression is responsible for lawsonite decomposition, which results in epidote growth, glaucophane increase and omphacite decrease in the blueschist, or in an overprinting of the eclogitic assemblage by a blueschist assemblage. Calculated P–X(CaO), P–A/CNK and P–X(CO₂) pseudosections indicate that blueschist assemblages are favoured in rocks with lower X(CaO) (<0.28) and higher A/CNK (>0.75) or fluid composition with higher X(CO₂) (>0.15), but eclogite assemblages preferentially occur in rocks with higher X(CaO) and lower A/CNK or fluid composition with lower X(CO₂). Moreover, phase modelling suggests that the coexistence of blueschist and eclogite depends substantially on P–T conditions, which would commonly occur in medium temperatures of 500–590 °C under pressures of ~17–22 kbar. The modelling results are in good accordance with the measured bulk‐rock compositions and modelled temperature results of the coexisting garnet blueschist and eclogite from the South Tianshan HP–UHP belt.     

Apparent oxygen isotope equilibrium during progressive foliation development and porphyroblast growth in metapelites: implications for stable isotope and conventional thermometry

The assumption of oxygen isotope and major element equilibrium during prograde metamorphism was tested using staurolite‐grade pelitic schists that have undergone sequential porphyroblast growth and multiple episodes of recrystallization of matrix minerals and foliation development. Textural relationships are used to infer a metamorphic history that involves garnet growth followed by staurolite growth, with each porphyroblast growth event followed by at least one period of recrystallization of matrix minerals. Conventional geothermobarometry using Qtz–Grt–Pl–Ms–Bt ± St equilibria yields peak P–T conditions of c. 625 °C at 9–11 kbar, consistent with KMnFMASH petrogenetic grid predictions for stability of the assemblage Grt + St + Bt. Qtz–Grt oxygen isotope fractionations yield apparent temperatures of c. 590 °C and Qtz–St fractionations yield an apparent temperature of c. 595 °C. Diffusional modelling indicates that quartz isotopic compositions were reset by c. 30 °C via retrograde isotopic diffusional exchange with micas. The isotopic temperatures appear to be in excellent agreement with one another, and suggest oxygen isotope equilibrium was attained between garnet and staurolite at c. 625 °C. However, the agreement of Qtz–Grt and Qtz–Str isotopic temperatures is not consistent with petrographic observations (garnet grew before staurolite) and petrogenetic grid constraints that predict that garnet grows over a temperature interval of c. 525–550 °C. Given that: (i) oxygen diffusion rates in staurolite and garnet are slow enough to render an individual porphyroblast effectively closed to exchange after it forms; and (ii) matrix minerals are able to exchange isotopes via recrystallization during each period of deformation; garnet and staurolite could not have simultaneously achieved oxygen isotope equilibrium with each other or with minerals in the recrystallized matrix. Thus, the Qtz–Grt fractionations, which yield apparent temperatures that are in apparent agreement with peak metamorphic temperature and apparent temperatures for Qtz–St fractionations, cannot be fractionations resulting from equilibrium isotopic exchange. Instead, they are apparent fractionations between porphyroblasts formed at different temperature and times in the prograde P–T–D path, and quartz that recrystallized and exchanged with micas and plagioclase during several phases of deformation.     

Petrochemistry, oxygen isotopes and U-Pb SHRIMP geochronology of mafic–ultramafic bodies from the Sulu UHP terrane, China

Two Rongcheng eclogite‐bearing peridotite bodies (Chijiadian and Macaokuang) occur as lenses within the country rock gneiss of the northern Sulu terrane. The Chijiadian ultramafic body consists of garnet lherzolite, whereas the Macaokuang body is mainly meta‐dunite. Both ultramafics are characterized by high MgO contents, low fertile element concentrations and total REE contents, which suggests that they were derived from depleted, residual mantle. High FeO contents, an LREE‐enriched pattern and trace‐element contents indicate that the bulk‐rock compositions of these ultramafic rocks were modified by metasomatism. Oxygen‐isotope compositions of analysed garnet, olivine, clinopyroxene and orthopyroxene from these two ultramafic bodies are between +5.2‰ and +6.2‰ (δ¹⁸O), in the range of typical mantle values (+5.1 to +6.6‰). The eclogite enclosed within the Chijiadian lherzolite shows an LREE‐enriched pattern and was formed by melts derived from variable degrees (0.005–0.05) of partial melting of peridotite. It has higher δ¹⁸O values (+7.6‰ for garnet and +7.7‰ for omphacite) than those of lherzolite. Small O‐isotope fractionations (ΔCpx‐Ol: 0.4‰, ΔCpx‐Grt: 0.1‰, ΔGrt‐Ol: 0.3–0.4‰) in both eclogite and ultramafic rocks suggest isotopic equilibrium at high temperature. The P–T estimates suggest that these rocks experienced subduction‐zone ultrahigh‐pressure (UHP) metamorphism at ～700–800 °C, 5 GPa, with a low geothermal gradient. Zircon from the Macaokuang eclogite contains inclusions of garnet and diopside. The 225 ± 2 Ma U/Pb age obtained from these zircon may date either the prograde conditions just before peak metamorphism or the UHP metamorphic event, and therefore constrains the timing of subduction‐related UHP metamorphism for the Rongcheng mafic–ultramafic bodies.     

Pseudosection modelling and garnet Lu–Hf geochronology of HP amphibole schists constrain the closure of an ocean basin between the northern and southern Lhasa blocks,central Tibet

The P–T–t path of high‐P metamorphic rocks in subduction zones may reveal valuable information regarding the tectonic processes along convergent plate boundaries. Herein, we present a detailed petrological, pseudosection modelling and radiometric dating study of several amphibole schists of oceanic affinity from the Lhasa Block, Tibet. The amphibole schists experienced an overall clockwise P–T path that was marked by post‐P_max heating–decompression and subsequent isothermal decompression following the attainment of peak high‐P and low‐T conditions (~490°C and 1.6 GPa). Pseudosection modelling shows that the amphibole schists underwent water‐unsaturated conditions during prograde metamorphism, and the stability field of the assemblage extends to lower temperatures and higher pressures within the water‐unsaturated condition relative to water‐saturated model along the prograde path. The high‐P amphibole schists were highly reduced during retrograde metamorphism. Precise evaluation of the ferric iron conditions determined from the different compositions of epidote inclusions in garnet and matrix epidote is crucial for a true P–T estimate by garnet isopleth thermobarometry. Lu–Hf isotope analyses on garnet size separates from a garnet‐bearing amphibole schist yield four two‐point garnet–whole‐rock isochron ages from 228.2 ± 1.2 Ma to 224.3 ± 1.2 Ma. These Lu–Hf dates are interpreted to constrain the period of garnet growth and approximate the timing of prograde metamorphism because of the low peak metamorphic temperature of the rock and the well‐preserved Mn/Lu growth zoning in garnet. The majority of zircon U–Pb dates provide no constraints on the timing of metamorphism; however, two concordant U–Pb dates of 222.4 ± 3.9 Ma and 223.3 ± 4.2 Ma were obtained from narrow and uncommon metamorphic rims. Coexistence of zircon and sphene in the samples implies that the metamorphic zircon growth was likely assisted by retrogression of rutile to sphene during exhumation. The near coincident radiometric dates of zircon U–Pb and garnet Lu–Hf indicate rapid burial and exhumation of the amphibole schists, suggesting a closure time of c. 224–223 Ma for the fossil ocean basin between the northern and southern Lhasa blocks.     

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.     

Metamorphism of ultrahigh‐pressure eclogites from the Kebuerte Valley,South Tianshan,NW China: phase equilibria and P–T path

Eclogites from the Kebuerte Valley, Chinese South Tianshan, consist of garnet, omphacite, phengite, paragonite, glaucophane, hornblendic amphibole, epidote, quartz and accessory rutile, titanite, apatite and carbonate minerals with occasional presence of coesite or quartz pseudomorphs after coesite. The eclogites are grouped into two: type I contains porphyroblastic garnet, epidote, paragonite and glaucophane in a matrix dominated by omphacite where the proportion of omphacite and garnet is >50 vol.%; and type II contains porphyroblastic epidote in a matrix consisting mainly of fine‐grained garnet, omphacite and glaucophane where the proportion of omphacite and garnet is <50 vol.%. Garnet in both types of eclogites mostly exhibits core–rim zoning with increasing grossular (X_gr) and pyrope (X_py) contents, but a few porphyroblastic garnet grains in type I eclogite shows core–mantle zoning with increasing X_py and a slight decrease in X_gr, and mantle–rim zoning with increases in both X_gr and X_py. Garnet rims in type I eclogite have higher X_py than in type II. Petrographic observations and phase equilibria modelling with pseudosections calculated using thermocalc in the NCKMnFMASHO system for three representative samples suggest that the eclogites have experienced four stages of metamorphism: stage I is the pre‐peak temperature prograde heating to the pressure peak (P_max) which was recognized by the garnet core–mantle zoning with increasing X_py and decreasing X_gr. The P–T conditions at P_max constrained from garnet mantle or core compositions with minimum X_gr content are 29–30 kbar at 526–540 °C for type I and 28.2 kbar at 518 °C for type II, suggesting an apparent thermal gradient of ～5.5 °C km^?1. Stage II is the post‐P_max decompression and heating to the temperature peak (T_max), which was modelled from the garnet zoning with increasing X_gr and X_py contents. The P–T conditions at T_max, defined using the garnet rim compositions with maximum X_py content and the Si content in phengite, are 24–27 kbar at 590 °C for type I and 22 kbar at 540 °C for type II. Stage III is the post‐T_max isothermal decompression characterized by the decomposition of lawsonite, which may have resulted in the release of a large amount of fluid bound in the rocks, leading to the formation of epidote, paragonite and glaucophane porphyroblasts. Stage IV is the late retrograde evolution characterized by the overprint of hornblendic amphibole in eclogite and the occurrence of epidote–amphibole facies mineral assemblages in the margins or in the strongly foliated domains of eclogite blocks due to fluid infiltration. The P–T estimates obtained from conventional garnet–clinopyroxene–phengite thermobarometry for the Tianshan eclogites are roughly consistent with the P–T conditions of stage II at T_max, but with large uncertainties in temperature. On the basis of these metamorphic stages or P–T paths, we reinterpreted that the recently reported zircon U–Pb ages for eclogite may date the T_max stage or the later decompression stage, and the widely distributed (rutile‐bearing) quartz veins in the eclogite terrane may have originated from the lawsonite decomposition during the decompression stage rather than from the transition from blueschist to eclogite as previously proposed.     

Phase equilibria constraints on melting of stromatic migmatites from Ronda (S. Spain): insights on the formation of peritectic garnet

Stromatic metatexites occurring structurally below the contact with the Ronda peridotite (Ojén nappe, Betic Cordillera, S Spain) are characterized by the mineral assemblage Qtz+Pl+Kfs+Bt+Sil+Grt+Ap+Gr+Ilm. Garnet occurs in low modal amount (2–5 vol.%). Very rare muscovite is present as armoured inclusions, indicating prograde exhaustion. Microstructural evidence of melting in the migmatites includes pseudomorphs after melt films and nanogranite and glassy inclusions hosted in garnet cores. The latter microstructure demonstrates that garnet crystallized in the presence of melt. Re‐melted nanogranites and preserved glassy inclusions show leucogranitic compositions. Phase equilibria modelling of the stromatic migmatite in the MnO–Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂–O₂–C (MnNCaKFMASHOC) system with graphite‐saturated fluid shows P–T conditions of equilibration of 4.5–5 kbar, 660–700 °C. These results are consistent with the complete experimental re‐melting of nanogranites at 700 °C and indicate that nanogranites represent the anatectic melt generated immediately after entering supersolidus conditions. The P–T estimate for garnet and melt development does not, however, overlap with the low‐temperature tip of the pure melt field in the phase diagram calculated for the composition of preserved glassy inclusions in garnet in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O (NCKFMASH) system. A comparison of measured melt compositions formed immediately beyond the solidus with results of phase equilibria modelling points to the systematic underestimation of FeO, MgO and CaO in the calculated melt. These discrepancies are present also when calculated melts are compared with low‐T natural and experimental melts from the literature. Under such conditions, the available melt model does not perform well. Given the presence of melt inclusions in garnet cores and the P–T estimates for their formation, we argue that small amounts (<5 vol.%) of peritectic garnet may grow at low temperatures (≤700 °C), as a result of continuous melting reactions consuming biotite.     

The duration of near‐peak metamorphism from diffusion modelling of garnet zoning

Garnet in a staurolite–kyanite zone sample from central Vermont displays a bell‐shaped Mn growth zoning with diffusional modification over the outer 100 μm. The diffusion is driven by the prograde net transfer reaction garnet + chlorite = kyanite + biotite as is evidenced by a well‐defined resorption zone on the rim. Analysis of the reaction history and resorbed garnet composition suggests that the peak temperature attained was 620–660 °C. Diffusional modelling of the rim diffusion provides an estimate of the duration of the metamorphic episode over which significant garnet diffusion occurs. The duration is a function of the assumed peak temperature and garnet diffusivities and range from a few hundred thousand years to a few million years. Such short durations require rapid tectonic burial and exhumation of relatively thin tectonic slices.     

Phase equilibrium modelling of the amphibolite to granulite facies transition in metabasic rocks (Ivrea Zone,NW Italy)

The development of thermodynamic models for tonalitic melt and the updated clinopyroxene and amphibole models now allow the use of phase equilibrium modelling to estimate P–T conditions and melt production for anatectic mafic and intermediate rock types at high‐T conditions. The Permian mid‐lower crustal section of the Ivrea Zone preserves a metamorphic field gradient from mid amphibolite facies to granulite facies, and thus records the onset of partial melting in metabasic rocks. Interlayered metabasic and metapelitic rocks allows the direct comparison of P–T estimates and partial melting between both rock types with the same metamorphic evolution. Pseudosections for metabasic compositions calculated in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (NCKFMASHTO) system are presented and compared with those of metapelitic rocks calculated with consistent end‐member data and a–x models. The results presented in this study show that P–T conditions obtained by phase equilibria modelling of both metabasic and metapelitic rocks give consistent results within uncertainties, allowing integration of results obtained for both rock types. In combination, the calculations for both metabasic and metapelitic rocks allows an updated and more precisely constrained metamorphic field gradient for Val Strona di Omegna to be defined. The new field gradient has a slightly lower dP/dT which is in better agreement with the onset of crustal thinning of the Adriatic margin during the Permian inferred in recent studies.     

Rare eclogite‐mafic granulite in felsic granulite in Blanský les: precursor of intermediate granulite in the Bohemian Massif?

Mafic granulite, generated from eclogite, occurs in felsic granulite at Kle?, Blanský les, in the Bohemian Massif. This is significant because such eclogite is very rare within the felsic granulite massifs. Moreover, at this locality, strong interaction has occurred between the mafic granulite and the adjacent felsic granulite producing intermediate granulite, such intermediate granulite being of enigmatic origin elsewhere. The mafic granulite involves garnet from the original eclogite, containing large idiomorphic inclusions of omphacite, plagioclase and quartz, as well as rutile. The edge of the garnet is replaced by a plagioclase corona, with the garnet zoned towards the corona and also the inclusions. The original omphacite–quartz–?plagioclase matrix has recrystallized to coarse‐grained polygonal (‘equilibrium’‐textured) plagioclase‐diopsidic clinopyroxene–orthopyroxene also with brown amphibole commonly in the vicinity of garnet. Somewhat larger quartz grains are embedded in this matrix, along with minor ilmenite, rutile and zircon. Combining the core garnet composition with core inclusion compositions gives a pressure of the order of 18 kbar from assemblage and isopleths on a P?T pseudosection, with temperature poorly constrained, but most likely >900 °C. From this P?T pseudosection, the recrystallization of the matrix took place at ~12 kbar, and from Zr‐in‐rutile thermometry, at relatively hot conditions of 900–950 °C. It is largely at these conditions that the eclogite/mafic granulite interacted with the felsic granulite to make intermediate granulite (see next paper).     

Using calculated chemical potential relationships to account for replacement of kyanite by symplectite in high pressure granulites

Calculated mineral equilibria are used to account for the formation of sapphirine–plagioclase, spinel–plagioclase and corundum–plagioclase symplectites replacing kyanite in quartz–plagioclase–garnet–kyanite granulite facies gneisses from the Southern Domain of the Athabasca granulite terrane, a segment of the Snowbird tectonic zone in northern Saskatchewan, Canada. Metamorphic conditions of >14 kbar and 800 °C are established for the high pressure, garnet–kyanite assemblage using constraints from P–T pseudosections and Zr‐in‐rutile thermometry. Replacement of kyanite by symplectites reflects the reaction of kyanite with the matrix following near‐isothermal decompression to <10 kbar. The chemical potential gradients developed between the kyanite and the matrix led to diffusion that attempted to flatten the gradients, kyanite persisting as a stable phase while it is consumed by symplectite from its edge. In this local equilibrium model, the mineral and mineral compositional spatial relationships are shown to correspond to paths in μ(Na₂O)–μ(CaO)–μ(K₂O)–μ(FeO)–μ(MgO) in the model chemical system, Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂ (NCKFMAS), with SiO₂ and Al₂O₃ taken to be completely immobile. The values of μ(Na₂O) and μ(CaO) are constrained by fixing P–T conditions and choosing appropriate μ(Na₂O) and μ(CaO) values that correspond to the observed plagioclase compositions. μ(FeO)–μ(MgO) diagrams show the corresponding spatial relationships with kyanite and the symplectite phases. These results demonstrate that the replacement of kyanite by sapphirine–plagioclase and spinel–plagioclase appears to be metastable with respect to replacement by corundum–plagioclase. Replacement by corundum–plagioclase does also occur, apparently overprinting pre‐existing symplectite and also kyanite. Ignoring corundum, the resulting diagrams account for the spatial relationships and compositions observed in the spinel–plagioclase and sapphirine–plagioclase symplectites. They are predicted to occur over both a wide range of P–T conditions (6–11 kbar, 650–850 °C) and plagioclase compositions (X_An = 0.5–0.9). The wide range of P–T conditions that may result in identical spatial and compositional relationships suggests that such reaction textures may be of limited use in accurately quantifying the P–T conditions of retrograde metamorphism.     

Chloritoid–glaucophane schist in the north Qilian orogen, NW China: phase equilibria and P–T path from garnet zonation

Chloritoid–glaucophane‐bearing rocks are widespread in the high‐pressure belt of the north Qilian orogen, NW China. They are interbedded and cofacial with felsic schists originated from greywackes, mafic garnet blueschists and low‐T eclogites. Two representative chloritoid–glaucophane‐bearing assemblages are chloritoid + glaucophane + garnet + talc + quartz (sample Q5‐49) and chloritoid + glaucophane + garnet + phengite + epidote + quartz (sample Q5‐12). Garnet in sample Q5‐49 is coarse‐, medium‐ and fine‐grained and shows two types of zonation patterns. In pattern I, X_grs is constant as X_py rises, and in pattern II X_grs decreases as X_py rises. Phase equilibrium modelling in the NC(K)MnFMASH system with Thermocalc 3.25 indicates that pattern I can be formed during progressive metamorphism in lawsonite‐stable assemblages, while pattern II zonation can be formed with further heating after lawsonite has been consumed. Garnet growth in Q5‐49 is consistent with a continuous progressive metamorphic process from ～14.5 kbar at 470 °C to ～22.5 kbar at 560 °C. Garnet in sample Q5‐12 develops with pattern I zonation, which is consistent with a progressive metamorphic process from ～21 kbar at 540 °C to ～23.5 kbar at 580 °C with lawsonite present in the whole garnet growth. The latter sample shows the highest P–T conditions of the reported chloritoid–glaucophane‐bearing assemblages. Phase equilibrium calculation in the NCKFMASH system with a recent mixing model of amphibole indicates that chloritoid + glaucophane paragenesis does not have a low‐pressure limit of 18–19 kbar as previously suggested, but has a much larger pressure range from 7–8 to 27–30 kbar, with the low‐pressure part being within the stability field of albite.     

Garnet zoning and the identification of equilibrium mineral compositions in high-pressure–temperature granulites from the Moldanubian Zone, Austria

A detailed investigation of the compositional variation in garnet has been undertaken in a garnet–pyroxene‐bearing granulite from the high‐grade Gföhl Unit, Moldanubian Zone, Lower Austria. Textural observations, together with the interpretation of the preserved garnet chemistry, enables the recognition of both prograde core and peak metamorphic garnet mantle growth stages, an extremely rare feature in high‐P–T granulite facies rocks. Initial thermobarometric calculations undertaken across whole garnet zoning profiles show how correct interpretation of a zoning profile is essential if the maximum peak metamorphic P–T conditions are to be recovered. The effect of retrograde decompression‐ and cooling‐driven reactions on inclusion and host garnet compositions has also been assessed. The results indicate that caution should be exercised when utilizing inclusion and adjacent garnet compositions for the thermobarometric evaluation of peak metamorphic equilibration conditions. Peak P–T conditions were determined by the TWEEQU thermobarometric method, utilizing the core compositions of matrix phases combined with the interpreted high‐P–T garnet mantle composition, to give 15.6 kbar and 1090 °C, consistent with previously determined results for Moldanubian granulites. Similar high‐P–T estimates are also provided by a re‐evaluation of previously published results for a granulite sample from the same lithological unit, using a modified interpretation of garnet and plagioclase compositional data. The new estimates presented confirm the previously disputed idea that the Gföhl Unit underwent a high‐pressure granulite facies stage and is therefore distinctly different from the underlying tectonostratigraphic units. It is emphasized that any interpretation of the peak metamorphic conditions in high‐grade rocks must be based on detailed petrographic observations combined with a thorough understanding of the co‐existing equilibrium mineral compositions.