Garnet–chloritoid–kyanite assemblages: eclogite facies indicators of subduction constraints in orogenic belts

The assemblage garnet–chloritoid–kyanite is shown to be quite common in high‐pressure eclogite facies metapelites from orogenic belts around the world, and occurs over a narrowly restricted range of temperature ～550–600 °C, between 20 and 25 kbar. This assemblage is favoured particularly by large Al₂O₃:K₂O ratios allowing the development of kyanite in addition to garnet and chloritoid. Additionally, ferric iron and manganese also help stabilize chloritoid in this assemblage. Pseudosections for several bulk compositions illustrate these high‐pressure assemblages, and a new thermodynamic model for white mica to include calcium and ferric iron was required to complete the calculations. It is extraordinary that so many orogenic eclogite facies rocks, both mafic eclogites sensu stricto as well as metapelites with the above assemblage, all yield temperatures within the range of 520–600 °C and peak pressures ～23±3 kbar. Subduction of oceanic crust and its entrained associated sedimentary material must involve the top of the slab, where mafic and pelitic rocks may easily coexist, passing through these P–T conditions, such that rocks, if they proceed to further depths, are generally not returned to the surface. This, together with the tightly constrained range in peak temperatures which such eclogites experience, suggests thermal weakening being a major control on the depths at which crustal material is decoupled from the downgoing slab.     

Influence of ferric iron on phase equilibria in greenschist facies assemblages: the hematite‐rich metasedimentary rocks from the Monti Pisani (Northern Apennines)

We have investigated the effects of different Fe₂O₃ bulk contents on the calculated phase equilibria of low‐T/intermediate‐P metasedimentary rocks. Thermodynamic modelling within the MnO–Na₂O–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (MnNKFMASHTO) chemical system of chloritoid‐bearing hematite‐rich metasedimentary rocks from the Variscan basement of the Pisani Mountains (Northern Apennines, Italy) fails to reproduce the observed mineral compositions when the bulk Fe₂O₃ is determined through titration. The mismatch between observed and computed mineral compositions and assemblage is resolved by tuning the effective ferric iron content by P–XFe₂O₃ diagrams, obtaining equilibration conditions of 475 °C and 9–10 kbar related to a post‐compressional phase of the Alpine collision. The introduction of ferric iron affects the stability of the main rock‐forming silicates that often yield important thermobaric information. In Fe₂O₃‐rich compositions, garnet‐ and carpholite‐in curves shift towards higher temperatures with respect to the Fe₂O₃‐free systems. The presence of a ferric‐iron oxide (hematite) prevents the formation of biotite in the mineral assemblage even at temperatures approaching 550 °C. The use of P–T–XFe₂O₃ phase diagrams may also provide P–T information in common greenschist facies metasedimentary rocks.     

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。     

Metamorphism and phase relations in carbonate rocks from the Nevado-Filábride Complex (Cordilleras Béticas, Spain): application of the Ttn + Rt + Cal + Qtz + Gr buffer

Phase relations and metamorphic conditions have been studied in metacarbonate rocks from the Nevado-Filábride Complex (Cordilleras Béticas) through forward modeling. In many rock samples, the assemblage titanite + rutile + calcite + quartz + graphite buffered the composition of the C-O-H fluid present during metamorphism. Over a wide range of P-T conditions, fluid compositions computed for this buffer are essentially binary H₂O-CO₂ mixtures. This buffer also constrains the chemical potentials of TiO₂, CaO and SiO₂. Consequently it is possible to make a thermodynamic projection through these components to predict the stable phase relations consistent with the buffer. Using this method, phase relations have been analyzed in a rock containing the buffer assemblage and paragonite, albite, phengite, epidote, and chlorite. The equilibrium P-T conditions for this assemblage are constrained, by minimization of the differences between predicted and observed mineral compositions, to be 560 ± 15 °C and 9.5 ± 1 kbar. Conditions obtained compare well with those estimated from other studies in different lithologic units. The inferred metamorphic fluid composition is H₂O-rich (). Received: 11 October 1995 / Accepted 5 August 1996     

On the importance of minding one’s Ps and Ts: metamorphic processes and quantitative petrology

This Special Issue comprises a selection of the papers given at a two‐day discussion meeting held at the University of Melbourne, Australia in June 2009 to celebrate Roger Powell’s 60th birthday. At this milestone, it is fitting to review Roger’s career to date. He has published ～200 scientific papers on topics that range from low‐ to high‐grade metamorphism, from low‐ to ultrahigh‐pressure (UHP) metamorphism, and from thermodynamics to kinetics. Most of Roger’s papers are multi‐authored and address important questions in the petrogenesis of metamorphic rocks. Roger is widely known for his work with Tim Holland to develop the most complete internally consistent dataset of thermodynamic properties of end members of phases necessary to undertake calculations on the conditions of formation and modification of metamorphic rocks. Additionally, Roger and Tim have developed activity–composition models for many of these phases, building on their important methodological developments in formulating such models. Roger is also responsible for the ongoing development of thermocalc , a thermodynamic calculation software package that may be used to undertake a wide range of phase diagram calculations, including P–T projections, P–T, P–X and T–X, compatibility diagrams and μ–μ diagrams. Together, Roger and Tim have changed the way we carry out quantitative phase equilibria studies. However, Roger’s contributions to metamorphic petrology go well beyond the development of phase equilibria methods and mineral thermodynamics. He has contributed significantly to our understanding of a range of metamorphic processes, and with an extensive array of co‐authors has shown how phase equilibria can be used to understand the evolution of metamorphic rocks in general terms as well as in specific terranes. The papers in this Special Issue cover the range from the stabilization of the continents to understanding the formation of orogenic gold deposits, from the stability of sapphirine–quartz‐bearing assemblages to the crystallization of melt in migmatites, from the effects of ferric iron and sulphur on the stability of metamorphic mineral assemblages in general to the effects of ferric iron and H₂O on the stability of eclogite in particular, and to the quantification of UHP metamorphism. It is our hope that in reading these contributions, you will be stimulated to seek a better understanding of metamorphic processes and to improve our quantification of the variables in metamorphism.     

Stability of sapphirine + quartz in the oxidized rocks of the Wilson Lake terrane,Labrador: calculated equilibria in NCKFMASHTO

The equilibrium coexistence of sapphirine + quartz is inferred to record temperatures in excess of 980 °C, based on the stability of this assemblage in the simplified chemical system FeO–MgO–Al₂O₃–SiO₂ (FMAS) system. However, the potential for sapphirine to contain significant Fe³⁺ suggests that the stability of sapphirine + quartz could extend to lower temperatures than those constrained in this ideal system. The Wilson Lake terrane in the Grenville Province of central Labrador preserves sapphirine + quartz‐bearing assemblages in highly oxidized bulk compositions, and provides an opportunity to explore the stability of sapphirine + quartz in such rock compositions within the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (NCKFMASHTO) chemical system. Starting with the phase equilibria in FeO–MgO–Al₂O₃–SiO₂–TiO₂–O (FMASTO), expansion into K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (KFMASHTO) allows the effect of the stability of the additional phases, biotite, K‐feldspar and melt, on the stability of sapphirine + quartz to be assessed. These phase relations are evaluated generally using P–T projections, and the ultimate extension into NCKFMASHTO is done with pseudosections. Conditions of peak metamorphism in the Wilson Lake terrane are constrained using P–T pseudosections, and the appropriate H₂O and O contents to use in the modelled compositions are investigated using T–M_H2O and T–M_O pseudosections. The peak P–T estimates from a sapphirine + quartz‐bearing sample are ～960 to 935 °C at ～10 to 8.6 kbar, similar to estimates from orthopyroxene + sillimanite + quartz ± garnet‐bearing samples. Whereas the sapphirine + quartz‐bearing sample is more Fe‐rich than the orthopyroxene + sillimanite‐bearing sample on an all‐Fe‐as‐FeO basis, once the oxidation state is taken into account, the former is effectively more magnesian than the latter, accounting for the sapphirine occurrence.     

The Crossite Content of Ca-Amphibole as a Guide to Pressure of Metamorphism

A correlation between the crossite component (NaM₄) in Ca-amphiboleand pressure of metamorphism has long been recognized (Shido& Miyashiro, 1959), but only recently has the reaction beenidentified which buffers this aspect of amphibole composition(Brown, 1974): Ca-amphibole+iron oxide+albite+chloriteI+H₂O (±stilp,qtz) = crossite+epidote (±muscovite, qtz). The exact stoichiometry of the reaction depends on compositionalvariables in the minerals, especially Fe²⁺/Mg and Fe³⁺/Al. Ca-amphiboleshould have fixed NaM₄, at any given T and P, where it coexistswith iron oxide, albite, and chlorite. Comparison of Ca-amphibole composition with mineral assemblage,in rocks from Otago, N.Z., and elsewhere, supports this hypothesis.In any terrane NaM₄ is nearly constant at a particular metamorphicgrade where amphibole exists in the buffering assemblage, butvaries widely outside of this assemblage. Variations in Fe²⁺/Mgand Fe³⁺/Al in the amphibole have relatively little effect onNaM₄, but in high pressure amphiboles NaM₄ varies inverselywith Al^iv. Ca-amphiboles from high pressure areas have substantially moreNaM₄ (Otago, 0.6 of 2.0) than those from lower pressure areas(Sierra contact aureoles, 0.1). These relations suggest thatin the buffering assemblage, the NaM₄ content of Ca-amphiboleshould be a useful relative barometer for low to medium grademetamorphic rocks.     

The stability of sapphirine + clinopyroxene: implications for phase relations in the CaO-MgO-Al2O3-SiO2 system under deep-crustal and upper mantle conditions

Reaction textures and chemographic relations in sapphirine-bearing basic granulites at Finero, Italy, suggest that sapphirine and aluminous diopside were formed in mutual equilibrium from an inferred early spinel-bearing assemblage. Finero appears to be the only known locality where this association has been found in situ, although it is also known from kimberlite and breccia pipe nodules elsewhere. The reactions deduced to have occurred in these rocks suggest the existence of stable invariant points involving the phases sapphirine-spinel-orthopyroxene-clinopyroxene-garnet-anorthite and sapphirine-two pyroxenes-garnetanorthite-kyanite (or sillimanite) in the CMAS end-member system. P-T estimates for the relevant rocks, and the available experimental data, suggest that these points lie at around 800°–900° C, 9–11 kbar. A semi-quantitative petrogenetic grid, incorporating these invariant points with previously determined univariant reactions, is proposed. It is inferred that sapphirine+diopside are stable relative to spinel-bearing assemblages below 900° C. The relatively low temperature explains why sapphirine has not to date been reported from experimental work on the CMAS system. It also suggests that sapphirine may be an important aluminous phase in Mg-rich metagabbros under conditions corresponding to the base of the continental crust, despite the observed rarity of such rocks at the surface.     

Ephesite,Na(LiAl2) [Al2Si2O10] (OH)2: II. Thermodynamic analysis of its stability and compatibility relations,and its geological occurrences

The trioctahedral mica ephesite, Na(LiAl₂) [Al₂Si₂O₁₀] (OH)₂, has a large -T stability field in the quaternary system NaAlSiO₄-LiAlSiO₄-Al₂O₃-H₂O. At temperatures below 400–500° C it coexists with diaspore, while at higher temperatures it occurs with corundum, until it decomposes to nepheline +eucryptite+corundum+H₂O at 600–800° C (Fig. 1). Nature faithfully reflects these phase relations; ephesite is found to coexist with diaspore or corundum in silicadeficient metamorphosed rocks or in hydrothermally altered nepheline-syenite pegmatite.Thermodynamic analysis of phase relations of ephesite in the silica saturated portion of the quinary system NaAlSiO₄-LiAlSiO₄-Al₂O₃-SiO₂-H₂O shows that the assemblage quartz+ephesite is always metastable with respect to paragonite+spodumene or paragonite+petalite at temperatures down to approximately 300° C (Fig. 3). At lower temperatures, a number of other phases like bikitaite, cookeite, Na-montmorillonite, and analcime are stabilized. Stability and compatibility relations involving these phases are presently not amenable to thermodynamic treatment due to lack of suitable data. Nevertheless, the absence of the assemblage quartz+ephesite in nature seems to vindicate our conclusion that it is metastable down to at least 300° C.The frequently encountered assemblage quartzspodumene (or petalite)-microcline-albite of some lithium pegmatites contains muscovite (±lepidolite), rather than paragonite. The absence of paragonite in such rocks is best explained by the inherent metastability of the phase-pair paragonite+microcline with respect to muscovite+albite. The pegmatite bulk compositions plot in the four-phase field spodumene (petalite)-microcline-muscovite-albite, cutting out paragonite from the observed assemblage Thus, absence of paragonite-spodumene or paragonitepetalite in nature reflects lack of suitable bulk compositions in rocks.     

Textures and phase relationships in ferrous granulites from Tidjenouine (Hoggar, Algeria): fayalite–ferrossilite–quartz secondary assemblage

Ferrous granulites in the area of Tidjénouine (Central Hoggar) exhibit a remarkable mineralogical composition characterized by the association orthoferrossilite–fayalite–quartz. These granulites are metamorphosed mafic igneous rocks showing the juxtaposition of different metamorphic parageneses. Peak paragenesis with garnet–clinopyroxene–amphibole–plagioclase–quartz reach to assemblage with orthopyroxene–plagioclase₂. Secondary orthopyroxene reacted with garnet to produce symplectites with fayalite + plagioclase + quartz. The latest stage corresponds to an orthopyroxene–fayalite–quartz–plagioclase assemblage. The metamorphic history of the ferrous granulites is inferred by combining the study of phase relations with the construction of a petrogenetic grid and pseudosection in the CFMASH and CFAS systems using the Thermocalc program of [J. Metamorph. Geol. 6 (1988) 173]. The evolution of paragenetic minerals indicates a metamorphic P–T path through the following conditions: 7.1 ± 1 kbar at 880 °C, 4.9 ± 1.6 kbar at 750 °C and 3–4 kbar at 700 °C, which is consistent with a clockwise P–T path recorded throughout the area.     

The stoichiometric effects of ferric iron substitutions in serpentine from microprobe data

ABSTRACT

Given that secondary magnetite is common in serpentinites, it is clear that serpentinites are oxidized rocks. Questions remain, however, concerning the distribution of ferric iron among magnetite and serpentine minerals and the role of ferric iron-rich serpentine in the formation of secondary magnetite. Direct determination of ferric iron in serpentine is not possible using an electron microprobe. We show, however, that the stoichiometic effects of ferric iron substitutions are detectable, although not quantifiable, by microprobe. First, we demonstrate that for studies that provide both microprobe analyses of major elements of serpentine and Mössbauer analysis of ferric iron, substitution effects are obvious. Next, it is equally clear that the early veins forming at the onset of olivine hydration (type 1 veins) show no indication of the presence of ferric serpentine, although a small amount of ferric ‘brucite’ may occur. Finally, we show that secondary (type 2) veins, which form as the system becomes open to fluids in equilibrium with plagioclase or pyroxene, contain, in addition to significant alumina, stoichiometric indications of ferric iron substitution. The serpentine in these veins is magnesian, usually with Mg#s around 96–98. Thus, even if a significant proportion of this iron is ferric, it comprises only a small fraction of the total ferric iron budget of the rock. Given that reduced iron is known to be abundant in early-formed brucite and early-formed serpentine and given that brucite, in particular, is absent from evolved serpentine veins, we propose that most magnetite in serpentinites forms as a tertiary product via oxidation of brucite.     

Crystal-liquid relationships in some ultrabasic dykes and their petrological significance

Phase relations have been determined at one atmosphere and an oxygen fugacity of 10^–8 atmospheres for a number of rocks from two differentiated ultrabasic dykes. It is demonstrated that these are consistent with other petrological evidence and that they support the view that the dykes were differentiated mechanically during intrusion. Crystal-liquid relations during the equilibrium crystallization of one of these rocks were determined by electron probe microanalysis. Over part of the temperature range where the three phase assemblage olivine+spinel+liquid exists an anomalous relationship was found. Immediately below the liquidus crystallization is normal with the olivine and liquid both becoming relatively enriched in iron as temperature decreases. When spinel starts to crystallize the iron enrichment in the liquid is suppressed and the forsterite content of the olivine actually increases until at lower temperatures a normal trend of iron enrichment is resumed. This phenomenon is tentatively attributed to the crystallization of the spinel under conditions of constant oxygen fugacity.     

A comparison of observed and thermodynamically predicted phase equilibria and mineral compositions in mafic granulites

Recently published activity–composition (a–x) relations for minerals in upper amphibolite‐ and granulite facies intermediate and basic rocks have expanded our ability to interpret the petrological evolution of these important components of the lower continental crust. If such petrological modelling is to be reliable, the abundances and compositions of phases calculated at the interpreted conditions of metamorphic equilibration should resemble those in the sample under study. Here, petrological modelling was applied to six granulite facies rocks that formed in different tectonic environments and reached different peak metamorphic pressure–temperature (P–T) conditions. While phase assemblages matching those observed in each sample can generally be calculated at P–T conditions that approximate those of peak metamorphism, a consistent discrepancy was found between the calculated and observed compositions of amphibole and clinopyroxene. In amphibole, Si, Ca and A‐site K are underestimated by the model, while Al and A‐site Na are overestimated; comparatively, in clinopyroxene, Mg and Si are generally underestimated, while Fe²⁺ and Al are typically overestimated, compared to observed values. One consequence is a reversal in the Fe–Mg distribution coefficient (K_D) between amphibole and clinopyroxene compared to observations. Some of these mismatches are attributed to the incorrect partitioning of elements between the predicted amphibole and clinopyroxene compositions; however, other discrepancies are the result of the incorrect prediction of major substitution vectors in amphibole and clinopyroxene. These compositional irregularities affect mineral modal abundance estimates and in turn the position and size (in P–T space) of mineral assemblage fields, the effect becoming progressively more marked as the modal abundance of hornblende increases; hence, this study carries implications for estimating P–T conditions of high‐temperature metabasites using these new a–x relations.     

Petrology and tectonic significance of metabasite slivers in the Lesser and Higher Himalayan domains of Sikkim,India

The metamorphic history of the Himalayas has been constrained mostly through studies of the ubiquitous metapelitic rocks. Non‐eclogitic metabasite rock lenses that occur intercalated with the metapelites have received little attention and it is not clear whether they share a common metamorphic history. This study reports the results of a petrological study of the metabasite lenses (dm³–m³) from the Lesser Himalayan (LH) and the Higher Himalayan (HH) domains in Sikkim. These have similar bulk chemical compositions and chemical affinities (sub‐alkaline tholeiitic basalts), with plagioclase and amphibole as the dominant mineralogical constituents. Garnet and clinopyroxene occur in some samples depending on small variations in bulk chemistry; and orthopyroxene is developed as a retrograde phase in some rocks. Minor phases are ilmenite, chlorite, titanite and rutile. The rocks were metamorphosed at similar conditions (～9–12 kbar, 800 °C). Minor differences in bulk chemical composition lead to different phase assemblages and mineral chemistry in adjacent metabasite lenses, a feature that is used to demonstrate that metamorphic conditions (peak P–T as well as retrograde P–T path) can be reliably retrieved through a combination of pseudosection analysis and kinetically constrained individual thermobarometry. The peak P–T conditions of the metabasites from this region are independent of the present geographic or tectonic (i.e. within the LH or HH) location of the samples and they differ from the conditions at which the regional metapelites (i.e. metapelites not immediately adjacent to the metabasite lenses) were metamorphosed. Metapelites that are immediately adjacent to the metabasite lenses differ in their appearance, phase assemblage and recorded P–T history from those of the regional metapelites, either because they were emplaced as slivers along with the metabasites, or because they were modified when they came in contact with the metabasites. The retrograde P–T paths of the LH and HH metabasites are different: the HH samples underwent steep decompression whereas the LH followed a more gentle exhumation path. The P–T conditions of peak metamorphism (9–12 kbar, 800 °C) are commensurate with a thermal perturbation at the base of a crust of average thickness and may be the signature of a widespread (samples found across different regions in the Himalaya) and long‐lasting (e.g. homogeneous garnet compositions) crustal underplating event that occurred during the early stages (?subduction) of the Himalayan orogeny, or earlier if the metamorphism was pre‐Himalayan.     

Influence of pH and dissolved Si on Fe isotope fractionation during dissimilatory microbial reduction of hematite

Microbial dissimilatory iron reduction (DIR) has been identified as a mechanism for production of aqueous Fe(II) that has low ⁵⁶Fe/⁵⁴Fe ratios in modern and ancient suboxic environments that contain ferric oxides or hydroxides. These studies suggest that DIR could have played an important role in producing distinct Fe isotope compositions in Precambrian banded iron formations or other marine sedimentary rocks. However, the applicability of experimental studies of Fe isotope fractionation produced by DIR in geochemically simple systems to ancient marine environments remains unclear. Here we report Fe isotope fractionations produced during dissimilatory microbial reduction of hematite by Geobacter sulfurreducens in the presence and absence of dissolved Si at neutral and alkaline pH. Hematite reduction was significantly decreased by Si at alkaline (but not neutral) pH, presumably due to Si polymerization at the hematite surface. The presence of Si altered Fe isotope fractionation factors between aqueous Fe(II) or sorbed Fe(II) and reactive Fe(III), reflecting changes in bonding environment of the reactive Fe(III) component at the oxide surface. Despite these changes in isotopic fractionations, our results demonstrate that microbial Fe(III) oxide reduction produces Fe(II) with negative δ⁵⁶Fe values under conditions of variable pH and dissolved Si, similar to the large inventory of negative δ⁵⁶Fe in Neoarchean and Paleoproterozoic age marine sedimentary rocks.     

Phase relations of biotite and stilpnomelane in the greenschist facies

Phase relations of biotite and stilpnomelane and associated silicate minerals have been studied in rocks of the greenschist facies, chiefly from Otago, New Zealand and western Vermont, but also from Scotland, Minnesota-Michigan iron range, and northwest Washington. That stilpnomelane in the greenschicht facies crystallizes initially with nearly all iron in the ferrous state is indicated by chemical analyses, high p-T experiments, and phase relationships. Alteration of stilpnomelane after metamorphism not only oxidizes iron but leaches potassium; corrections for both effects must be made in using analyses of brown stilpnomelane in studies of phase relations. Two discontinuous reactions which produce biotite at the biotite isograd have been identified:

1. muscovite+stilpnomelane+actinolite→ biotite+chlorite+epidote
2. chlorite+microcline→ biotite+muscovite. Biotite produced by the first of these reactions has a limited range of variation in Fe/Mg. As grade advances within the biotite zone more magnesian and ferruginous biotites become stable in consequence of the two continuous reactions:
3. muscovite+actinolite+chlorite→ biotite (Mg-rich)+epidote
4. muscovite+stilpnomelane→ biotite (Fe-rich)+chlorite.

Stilpnomelane is stable in muscovite-free rocks throughout the biotite zone, and even up to the grade at which hornblende becomes stable. Phengitic muscovite is stable throughout the biotite zone in New Zealand and thus apparently does not contribute to the formation of biotite until a higher grade is reached.     

Zoned sodic amphibole: Petrologic indicator of changing pressure and temperature during tectonism in the Bathurst Area,New Brunswick,Canada

Amphibole, zoned from an actinolite core through a barroisite layer to a crossite or ferroglaucophane rim, coexists with epidote, chlorite, albite, quartz, phengite, sphene, magnetite, and calcite in metabasites of the Tetagouche Group near Bathurst, New Brunswick. Stratigraphic, structural and regional-metamorphic evidence suggests that these rocks were situated in the hangingwall of a SE-dipping subduction zone during the Taconian Orogeny. Using microprobe analyses of the coexisting minerals, a dehydration reaction and a subsequent hydration reaction have been balanced in the system SiO₂-Al₂O₃-TiO₂-Fe₂O₃-(Fe, Mg, Mn)O-CaO-Na₂O-K₂O-H₂O, so as to describe the development of the zoned amphiboles. Relatively large coefficients for magnetite in these reactions accord with the absence of sodic amphibole in associated magnetite-free metabasites, indicating that ferric iron has a significant effect on the transition from greenschist to epidote-blueschist fades. Relatively small residuals of FeO, MgO and MnO show that these components are only weakly partitioned between the reactant and product assemblages. The procedure of Holland and Richardson (1979) has been used to calculate apparentP-T paths that trace the growth histories of the zoned amphiboles from a low-P environment to a high-P environment. Although the apparent pressure-change is implausibly large and the final temperature implausibly low, it is clear that the Bathurst metabasites followed a very differentP-T path than those of the Austrian Alps, despite their identical mineral assemblage.     

Revised activity–composition models for clinopyroxene and amphibole

Recent activity–composition models for clinopyroxene and amphibole are revised to provide better consistency with observed phase relations in natural rocks. For clinopyroxene, the calibration in NCFMAS is retained, but the incorporation of acmite is revised to improve the partitioning of ferric iron between coexisting clinopyroxenes. For amphibole, the NCFMASH calibration is retained, but the addition of ferric iron is changed to provide consistency with the clinopyroxenes. The thermodynamics of orthoamphibole (gedrite) is also adjusted to resolve an unrelated inconsistency. The effects of these improvements are illustrated through comparison of calculated pseudosections produced with the existing and new models with natural data from lawsonite eclogites.     

Quantitative determination of metamorphic reaction history: mass balance relations between groundmass and mineral inclusion assemblages in metamorphic rocks

Qualitative and quantitative information about metamorphic reaction history and PT paths may be obtained from mineral inclusions in garnet by comparing the mineralogy, distribution, and compositions of paragenetically-related inclusions with minerals in the groundmass assemblage. Using the algebraic technique of singular value decomposition (SVD), we document mass balance relations between inclusion and groundmass assemblages in metapelitic rocks from two metamorphic terranes that experienced different peak metamorphic conditions, and whose transition from inclusion to groundmass assemblage records different PT path segments relative to peak conditions. We calculate mass balances relating an inclusion assemblage consisting in part of armored relics of chloritoid to groundmass mineral assemblages in a kyanite-staurolite mica schist from the Solitude Range, British Columbia, and an inclusion assemblage of kyanite, staurolite, and rutile to groundmass minerals in a sillimanite-cordierite gneiss from the Skagit Gneiss, North Cascade Range, Washington. Mass balances for each rock are consistent with reaction histories inferred from petrographic observations. In the Solitude Range schist, the results of mass balance calculations are consistent with the growth of staurolite and garnet at the expense of chloritoid during prograde metamorphism and suggest that chlorite, although not preserved as an inclusion, was involved in initial staurolite growth. In the Skagit sillimanite gneiss, mass balance relations exist between the inclusion suite, which formed during high pressure metamorphism, and the associated groundmass assemblage, which equilibrated at high temperature but much lower pressure. Mass balance does not exist between the groundmass of the Skagit sillimanite gneiss and the groundmass of a nearby kyanite-staurolite schist that has been proposed as a possible lower-grade equivalent of the sillimanite-bearing rocks. These results indicate that, although compositional modification and selective preservation of minerals must be taken into account, mineral inclusion suites may nevertheless preserve enough compositional information to allow reconstruction of complete or nearly complete pre-existing assemblages. This information may not be retrievable from any other source if no lower-grade equivalents of the rocks of interest are exposed.     

Interaction of deformation and metamorphism during subduction and exhumation of hydrated oceanic mantle: Insights from the Western Alps

Petrological investigations supported by multi‐scale structural analysis of eclogitized serpentinite in the Zermatt–Saas Zone of the Western Alps allows for the determination of mineral assemblages related to successive fabrics, upon which the P–T–d–t path of these hydrated mantle rocks can be inferred. Serpentinites of the upper Valtournanche, with lenses and dykes of metagabbro and meta‐rodingite, display an Alpine polyphase metamorphic evolution from eclogite to epidote‐amphibolite facies conditions associated with three successive foliations having different parageneses in these rocks. Serpentinite mainly consists of serpentine with minor magnetite; however, where S1 and S2 foliations are pervasive, metamorphic olivine, together with Ti‐clinohumite and clinopyroxene, are also found. The mineral assemblage associated with D1 includes serpentine1, clinopyroxene1, opaque minerals, titanite ± olivine1, Ti‐clinohumite1 and ilmenite; the D2 assemblage is the same (±chlorite) but minerals have different compositions. The assemblage associated with D3 comprises serpentine3, opaque minerals, ±chlorite3, ilmenite and amphibole3. Ti‐clinohumite is associated with veins that are older than D2 and pre‐date D3. Veins that post‐date D3 are characterized by amphibole + chlorite or by serpentine. P–T conditions for S2 parageneses evaluated using two pseudosections for different bulk compositions suggest that these rocks experienced pressures >2.5 ± 0.3 GPa at temperatures slightly higher than 600 °C. The late epidote–amphibolite facies re‐equilibration associated with D3 and D4 developed during late syn‐exhumation deformation related to folding and testifies to a small temperature decrease. These results, which were integrated in the regional framework, suggest that different portions of the Zermatt–Saas Zone registered different P–T peak conditions and underwent different exhumation paths. In addition, the inferred P–T–d–t path suggests that the Valtournanche serpentinites re‐equilibrated close to the UHP conditions registered by the Cignana meta‐cherts. These results imply that tectonic slices exhumed after UHP metamorphism might be wider than previously reported or that small‐size UHP units, tectonically sampled during the Alpine convergence, are more abundant than those that have been detected to date.