Reaction of zoning of garnet

Compositional zoning of garnet in metamorphic or igneous rocks preserves evidence of the equilibration history of the sample and can be interpreted in terms of a growth-fractionation, diffusion-exchange, or diffusion-reaction model. Diffusion zoning is usually assumed to result from exchange reactions between garnet and other phases as the partitioning coefficient varies in response to changing environmental conditions, primarily temperature. However, in many natural environments where garnet grew originally in divariant equilibrium with other phases, changing conditions can promote continuous or “divariant” reactions and consequent compositional shifts of phases that can be much greater in some systems showing these reactions than those related to the small changes of partitioning. Diffusional zoning related to overstepping of these continuous reactions must be related to incongruent reaction and necessitates formulation of a kinetic diffusion-reaction model involving moving phase boundaries as well as solid-state diffusion. Three samples containing zoned garnets from the metamorphic aureole around the Ronda ultramafic intrusion in southern Spain are used to illustrate two possible models of diffusion-reaction processes. The examples are particularly informative because the reactions are demonstrably irreversible and evidence of the reaction system is preserved. Partitioning data indicates that compositions of product phases are not in equilibrium with the original garnet and do not vary with extent of reaction; therefore, exchange reactions with garnet were not possible and garnet changed composition only by incongruent reaction. After a small amount of reaction, Mg/Fe of the rim composition approaches a value apparently in equilibrium with product phases, but the garnets are zoned inward to the original garnet composition preserved in the interior. Grossularite content is approximately constant and spessartite content variable but small, thus, the rim composition of pyrope or almandine is assumed to be fixed by the external reaction process and is taken as a boundary condition in the following models. The zoning profile of pyrope or almandine component between the fixed rim and core compositions (assumed to extend to ∞) is described in semiinfinite, half-space models appropriate for large garnets with narrow rims. The first model corresponds to a reaction system in which all garnet compositions are metastable (case 1) and zoning depends on the independent variables of the diffusion constant, velocity of the interface between garnet and matrix, and time. The second model, corresponding to systems in which the initial garnet composition is metastable but an equilibrium composition is stable (case 2), depends on the independent variables diffusion constant, time, and a function of reaction compositions. In case 1 the consumption velocity is assumed constant and a steady state zoning profile is reached at large time, whereas, in case 2, the velocity decreases with the concentration gradient and steady state is not possible. The models were tested using a reaction time estimated from cooling models of the aureole, mass of garnet consumed, determined petrographically, and phase compositions. The two cases are somewhat independent in that different parameters are independent variables. The estimate of the diffusion constant of 10^?18±2 cm²/sec (assumed to be a mutual or binary coefficient for almandine and pyrope) is considered reasonable for the temperature range of reaction (probably 600–900° C), and the two models are consistent considering the probable error and possible real temperature differences. It is obvious that details of the metamorphic reaction system must be known to successfully apply diffusion models. Kinetic models, involving consumption or growth of the phase as well as diffusion are probably necessary when dealing with natural rocks. Several possible and interesting complications, such as cross coupling between components, can be investigated if more data were available. Experimental determination of diffusion constants allow natural reaction rates to be estimated by this method. Diffusion zoning is an important consideration that could increase the efficiency of experimentation with chemically recalcitrant phases.     

A chemical equilibrium algorithm for highly non-ideal multiphase systems: Free energy minimization

A method is presented for calculating equilibrium phase assemblages in very nonideal systems. It may be applied to any system for which a thermodynamically consistent model of the free energy which satisfies the usual Maxwell relations and convexity criterion is available. The algorithm minimizes the Gibbs free energy by independently choosing stable reaction directions. The procedure is described in detail and various numerical problems encountered and strategies for dealing with them are discussed. It will be shown that the necessary and sufficient conditions for solution phase selection may be derived from the values of the Lagrange multipliers corresponding to constraints on phases that are not present in the system. The method for evaluating the solution phase Lagrangian multipliers and choosing the optimum composition with which to bring the new solution phase into the system involves a separate constrained minimization problem. This method is sufficiently general so that the correct phase assemblage is chosen free from external control. Special procedures for adding and removing phases including solution phases are also described.     

Progressive metamorphism in a crustal-scale shear zone: an example from the Léon region, north-west Brittany, France

This paper describes the progressive metamorphism and deformation of a series of metasediments, Le Conquet Schists and their higher grade equivalents, which occur as tectonically emplaced screens within a sequence of foliated gneisses, the Gneiss de Brest and Gneiss de Lesneven. The sequence exhibits a steep south to north increase in metamorphic grade from garnet-staurolite schist to sillimanite gneiss and sillimanite-K-feldspar migmatite. The relationship of mineral growth to foliation development has been established for individual screens. At least five phases of deformation (D1-D5) are preserved. Analysis of porphyroblast inclusion trails is used to demonstrate sequential mineral growth during the successive development of orthogonal foliations S1-S4. Porphyroblasts continued to grow during the subsequent development of C-S mylonite fabrics and extensional crenulation cleavages which are genetically related to a series of high-strain zones (D5). Mineral assemblages, phase relations and mineral chemistry are consistent with porphyroblast growth being the result of continuous reactions. Microstructure-porphyroblast relations are used to show that although mineral growth proceeded during continuous reactions, these only operated episodically. Phase relations, mineral chemistry and P-T estimates are used to constrain P-T trajectories and these are linked to the deformation histories within individual screens. A comparison between the resulting pressure-temperature-deformation paths is used to demonstrate that the metamorphic peak occurred progressively later and at successively lower pressures with increasing metamorphic grade. It is suggested that the early evolution of the belt is the result of crustal thickening by overthrusting. The subsequent history is one of progressive heating and unroofing of the higher grade rocks in a dextral strike-slip transtensional shear zone.     

Melting reactions and trace element relationships in selected specimens of migmatitic pelites from New Hampshire and Maine

Leucosomes and melanosomes in selected specimens of migmatitic, sillimanite-zone, pelitic schists are modal and chemical complements formed by segregation within originally homogeneous paleosomes. Systematic bulk chemical and modal variations in melanosomes can be used to infer the reactions by which leucosomes were generated.Trace element variations and relationships in melanosomes and leucosomes indicate that the migmatites behaved as closed systems during leucosome formation. Mass-balance evaluation of trace element relationships in the context of inferred leucosome-forming reactions suggest that trace elements essentially followed the melanosome phases initially containing them, as these phases reacted in leucosome generation. The trace element composition of a leucosome is given by the sum of those of the melanosome phases reacted, minus the trace element contents of any new solid melanosome phases produced by the reactions.Trace element relations are consistent with metamorphic equilibrium during leucosome generation, but suggest that once leucosome was segregated, equilibrium was not maintained between leucosome and melanosome.     

Phase relations of a simplified Marly rock system with application to the Western Hohe Tauern (Austria)

The regional distribution of metamorphic mineral assemblages in Mesozoic carbonate rocks of the Western Hohe Tauern allows the mapping of isograds based on the appearance of biotite+calcite and biotite+zoisite+calcite. The latter isograd corresponds approximately to the thermal maximum of the alpidic metamorphism in the central part of this area. An estimate of P, T, X _fluid conditions can be obtained from phase relations among muscovite, biotite, chlorite, margarite, tremolite, zoisite, anorthite, quartz, calcite, and dolomite in the system K₂O-CaO-MgO-Al₂O₃-SiO₂-H₂O-CO₂ which approximates the composition of marls. Calculations based on various experimental and thermodynamic data have been made with emphasis on phase relations pertinent to a group of carbonate rocks with very low Fe and Na contents in non-opaque minerals. Significant and opposite deviations from the phase relations for stochiometric end member mineral compositions are due to the substitutions F-OH and Mg+Si-2Al. Consistency of observed and calculated phase relations is favoured by high F-contents. For the majority of carbonate rocks in the high metamorphic zone, maximum temperatures around 550° C, minimum pressures of 4–6 kb, and relatively low XCO₂ values within the stability field of zoisite and of biotite+calcite+quartz are indicated.     

Pumpellyites and coexisting minerals in different low-grade metamorphic facies of Liguria, Italy

Pumpellyite from four-phase assemblages (pumpellyite + epidote + prehnite + chlorite; pumpellyite + epidote + actinolite + chlorite; pumpellyite + epidote + Na-amphibole + chlorite, together with common excess phases), considered to be low variance in a CaO-(MgO + FeO)-Al₂O₃-Fe₂O₃ (+Na₂O + SiO₂+ H₂O) system, have been examined in areas which underwent metamorphism in the prehnite-pumpellyite, pumpellyite-actinolite and low-temperature blueschist facies respectively. The analysed mineral assemblages are compared for nearly constant (basaltic) chemical composition at varying metamorphic grade and for varying chemical composition (basic, intermediate, acidic) at constant metamorphic conditions (low-temperature blueschist facies). In the studied mineral assemblages, coexisting phases approached near chemical equilibrium. At constant (basaltic) bulk rock composition the MgO content of pumpellyite increases, and the X_Fe3+ of both pumpellyite and epidote decreases with increasing metamorphic grade, the Fe³⁺ being preferentially concentrated in epidote. Both pumpellyite and epidote compositions vary with the bulk rock composition at isofacial conditions; pumpellyite becomes progressively enriched in Fe and depleted in Mg from basic to intermediate and acidic bulk rock compositions. The compositional comparison of pumpellyites from high-variance (1–3 phases) assemblages in various bulk rock compositions (basic, intermediate, acidic rocks, greywackes, gabbros) shows that the compositional fields of both pumpellyite and epidote are wide and variable, broadly overlapping the compositional effects observed at varying metamorphic grade in low-variance assemblages. The intrinsic stability of both Fe- and Al-rich pumpellyites extends across the complete range of the considered metamorphic conditions. Element partitioning between coexisting phases is the main control on the mineral composition at different P-T conditions.     

Reaction‐induced nucleation and growth v. grain coarsening in contact metamorphic,impure carbonates

The understanding of the evolution of microstructures in a metamorphic rock requires insights into the nucleation and growth history of individual grains, as well as the coarsening processes of the entire aggregate. These two processes are compared in impure carbonates from the contact metamorphic aureole of the Adamello pluton (N‐Italy). As a function of increasing distance from the pluton contact, the investigated samples have peak metamorphic temperatures ranging from the stability field of diopside/tremolite down to diagenetic conditions. All samples consist of calcite as the dominant matrix phase, but additionally contain variable amounts of other minerals, the so‐called second phases. These second phases are mostly silicate minerals and can be described in a KCMASHC system (K₂O, CaO, MgO, Al₂O₃, SiO₂, H₂O, CO₂), but with variable K/Mg ratios. The modelled and observed metamorphic evolution of these samples are combined with the quantification of the microstructures, i.e. mean grain sizes and crystal size distributions. Growth of the matrix phase and second phases strongly depends on each other owing to coupled grain coarsening. The matrix phase is controlled by the interparticle distances between the second phases, while the second phases need the matrix grain boundary network for mass transfer processes during both grain coarsening and mineral reactions. Interestingly, similar final mean grain sizes of primary second phase and second phases newly formed by nucleation are observed, although the latter formed later but at higher temperatures. Moreover, different kinetic processes, attributed to different driving forces for growth of the newly nucleated grains in comparison with coarsening processes of the pre‐existing phases, must have been involved. Chemically induced driving forces of grain growth during reactions are orders of magnitudes larger compared to surface energy, allowing new reaction products subjected to fast growth rates to attain similar grain sizes as phases which underwent long‐term grain coarsening. In contrast, observed variations in grain size of the same mineral in samples with a similar T–t history indicate that transport properties depend not only on the growth and coarsening kinetics of the second phases but also on the microstructure of the dominant matrix phase during coupled grain coarsening. Resulting microstructural phenomena such as overgrowth and therefore preservation of former stable minerals by the matrix phase may provide new constraints on the temporal variation of microstructures and provide a unique source for the interpretation of the evolution of metamorphic microstructures.     

The effect of Mn on mineral stability in metapelites

Calculations based on a KMnFMASH petrogenetic grid derived using an internally consistent thermodynamic dataset indicate that the principal effect of the presence of Mn in average subaluminous pelite compositions is to stabilize garnet to higher and lower pressures and temperatures over a wide range of bulk compositions. Garnet-bearing fields expand to lower temperatures and pressures with the addition of Mn, and garnet appears as an extra phase at low pressures. The addition of Mn also increases the number and extent of four AMnFM phase assemblages and stabilizes five AMnFM phases along univariant reactions. The KMnFMASH system predictions for typical subaluminous pelite bulk compositions match the sequence of isograds and assemblages observed in the Barrovian zones. The sequence of assemblages observed in the Stonehaven section can also be predicted if there is variation in bulk composition within the stratigraphic section. Mn appears to be less important in producing the sequence of isograds and garnet-absent assemblages in the low-pressure Buchan zones. The addition of Mn to the calculations does not change the sequence of isograds that are predicted to be stable in a regional metamorphic terrane, but the P – T  position of these isograds does change. In particular, the predicted temperature of the garnet-in isograd is lowered by as much as 100 °C by the addition of Mn to KFMASH. Mn also increases the range of metapelite bulk compositions that develop the assemblages traditionally identified as metapelite isograds.     

Redox evolution of western Tianshan subduction zone and its effect on deep carbon cycle

Knowing the phase relations of carbon-bearing phases at high-pressure(HP) and high-temperature(HT) condition is essential for understanding the deep carbon cycle in the subduction zones.In particular,the phase relation of carbon-bearing phases is also strongly influenced by redox condition of subduction zones,which is poorly explored.Here we summarized the phase relations of carbon-bearing phases(calcite,aragonite,dolomite,magnesite,graphite,hydrocarbon) in HP metamorphic rocks(marble,metapelite,eclogite) from the Western Tianshan subduction zone and high-pressure experiments.During prograde progress of subduction,carbonates in altered oceanic crust change from Ca-carbonate(calcite) to Ca,Mg-carbonate(dolomite),then finally to Mgcarbonate(magnesite) via Mg-Ca cation exchange reaction between silicate and carbonate,while calcite in sedimentary calcareous ooze on oceanic crust directly transfers to high-pressure aragonite in marble or amorphous CaCO3 in subduction zones.Redox evolution also plays a significant effect on the carbon speciation in the Western Tianshan subduction zone.The prograde oxygen fugacity of the Western Tianshan subduction zone was constrained by mineral assemblage of garnet-omphacite from FMQ-1.9 to FMQ-2.5 at its metamorphic peak(maximum P-T) conditions.In comparison with redox conditions of other subduction zones,Western Tianshan has the lowest oxygen fugacity.Graphite and light hydrocarbon inclusions were ubiqutously identified in Western Tianshan HP metamorphic rocks and speculated to be formed from reduction of Fe-carbonate at low redox condition,which is also confirmed by high-pressure experimental simulation.Based on petrological observation and high-pressure simulation,a polarized redox model of reducing slab but oxidizing mantle wedge in subduction zone is proposed,and its effect on deep carbon cycle in subduction zones is further discussed.     

超高压变质矿物中的多相固体包裹体研究进展

大陆碰撞过程中熔/流体的组成和演化是研究大陆深俯冲动力学的重要内容,而超高压岩石记录了大陆俯冲和折返过程中的熔/流体-岩石相互作用,因而是研究大陆碰撞过程中熔/流体组成和演化的天然实验室。大陆俯冲带高压/超高压变质矿物中多相固体包裹体作为熔/流体活动的直接记录,为我们提供了揭示超高压变质过程中熔/流体演化的重要制约。近年来,围绕超高压岩石中多相固体包裹体的形成时间、演化过程及其所反映的俯冲带超高压变质熔/流体的组成和性质,进行了大量的研究工作。超高压岩石中多相固体包裹体的发现,为理解峰期超高压变质流体的组成和演化提供了重要制约,同时也为研究俯冲板片-地幔楔界面的熔/流体交代作用提供了新的途径。本文从多相固体包裹体形成机制、结构形态特征、矿物化学成分及其地质地球化学意义等方面,对于超高压变质岩中多相固体包裹体的研究现状和存在的问题进行系统地总结和探讨,以期促进多相固体包裹体的岩石学和地球化学研究。     

Grain coarsening in polymineralic contact metamorphic carbonate rocks: The role of different physical interactions during coarsening

The microstructural evolution of polymineralic contact metamorphic calcite marbles (Adamello contact aureole) with variable volume fractions of second-phase minerals were quantitatively analyzed in terms of changes in grain size and nearest neighbor relations, as well as the volume fractions, dispersion and occurrences of the second phases as a function of changing metamorphic conditions. In all samples, the calcite grain size is controlled by pinning of grain boundaries by second phases, which can be expressed by the Zener parameter (Z), i.e., the ratio between size and volume fraction of the second phases. With increasing peak metamorphic temperature, both the sizes of matrix grains and second phases increase in dependence on the second-phase volume fraction. Two distinct coarsening trends are revealed: trend I with coupled grain coarsening limited by the growth of the second phases is either characterized by large-sized or a large number of closely spaced-second phase particles, and results finally in a dramatic increase in the calcite grain size with Z. Trend II is manifest by matrix controlled grain growth, which is retarded by the presence of single second-phase particles that are located on calcite grain boundaries. It is supported by grain boundary pinning induced by triple junctions, and the calcite grain size increases moderately with Z. The two different grain coarsening trends manifest the transition between relatively pure polymineralic aggregates (trend II) and microstructures with considerable second-phase volume fractions of up to 0.5. The variations might be of general validity for any polymineralic rock, which undergoes grain coarsening during metamorphism. The new findings are important for a better understanding of the initiation of strain localization based on the activation of grain size dependent deformation mechanisms.     

Nanochemo-mechanical signature of organic-rich shales: a coupled indentation–EDX analysis

The organic–inorganic nature of organic-rich source rocks poses several challenges for the development of functional relations that link mechanical properties with geochemical composition. With this focus in mind, we herein propose a method that enables chemo-mechanical characterization of this highly heterogeneous source rock at the micron and submicron length scale through a statistical analysis of a large array of energy-dispersive X-ray spectroscopy (EDX) data coupled with nanoindentation data. The ability to include elemental composition to the indentation probe via EDX is shown to provide a means to identify pure material phases, mixture phases, and interfaces between different phases. Employed over a large array, the statistical clustering of this set of chemo-mechanical data provides access to the properties of the fundamental building blocks of clay-dominated organic-rich source rocks. The versatility of the approach is illustrated through the application to a large number of source rocks of different origin, chemical composition, and organic content. We find that the identified properties exhibit a unique scaling relation between stiffness and hardness. This suggests that organic-rich shale properties can be reduced to their elementary constituents, with several implications for the development of predictive functional relations between chemical composition and mechanical properties of organic-rich source rocks such as the intimate interplay between clay-packing, organic maturity, and mechanical properties of porous clay/organic phase.     

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.     

Sector trilling in cordierite and equilibrium overstepping in metamorphism

The origin of sector trilling in cordierite is due to the hexagonal-orthorhombic Al, Si ordering transformation which under non-equilibrium conditions proceeds via a short-range ordered modulated structure. The growth of these distortion waves associated with progressive ordering produces a strain field which is minimized by a cyclic distribution of symmetrically equivalent modulations.Sector and complexly trilled cordierites in metamorphic rocks grew as the hexagonal polymorph with a considerable degree of Al, Si disorder. The enthalpy and entropy of disorder are evaluated from recent experimental work. The implication is that, in metamorphic rocks, substantial overstepping of stable equilibrium phase boundaries is required to nucleate hexagonal cordierite. Moreover, its composition coexisting with other phases will also be significantly different from that of the stable ordered form.     

Replacement textures in CAI and implications regarding planetary metamorphism

Textural and chemical features of five coarse-grained, calcium-aluminum-rich inclusions from the Allende meteorite indicate that some of the melilite in these inclusions was formed by a secondary metamorphic event and not by primary crystallization from a melt or by a sequential nebular condensation process. These inclusions contain embayed pyroxene surrounded by melilite. Physically separated pyroxene crystals are often in optical continuity indicating that they were once part of larger single crystals that have been partly replaced by melilite. Other evidences of metamorphism include reaction textures between melilite and spinel, and metamorphic textures such as kink-band-like features, lobate sutured grain boundaries, and 120° triple-points. This type of metamorphic process requires the addition of Ca which we propose came from calcite or by introduction of a fluid phase. We believe that the most likely environment for this metamorphic process is on a small planetary body, and not in the solar nebula. The results of this study are compatible with oxygen isotopic heterogeneities within CAI, and provide a mechanism for producing lower temperature alteration phases and the rim phases found in these inclusions. We conclude that planetary processes must thus be considered in the formation history of CAI, and that it is necessary to reconsider the classification system of these objects in light of the replacement process proposed here.     

Sulfides,oxides and sphene in high-pressure schists from New Caledonia

In the New Caledonia high-pressure schists pyrite, pyrrhotite, chalcopyrite, rutile and sphene are common phases while hematite and ilmenite are rare and magnetite is absent. The parageneses of these minerals were clarified from their occurrence as inclusions in garnet, from phase relations in the Cu-Fe-S and Fe-Ti-O-S systems, and from phase rule considerations for the multi-component system. The sulfur fugacity estimated for pelites and basites containing pyrrhotite, pyrite and rutile increased with increasing metamorphic grade; the oxygen fugacity in these schists was less than 10^–27.6 bars at 400° C, 10 kb and 10^–22.3 bars at 500° C, 11 kb. Among the other components of the metamorphic fluid in pelites, H₂O was major, CH₄, CO₂ and H₂S minor, and H₂, CO, COS and SO₂ rare. The fluid composition altered with advancing metamorphic grade, such that H₂O decreased while CO₂, CH₄ and H₂S increased, and this change was linked to concurrent massive decarbonization in the rock matrices.     

Manganiferous phyllosilicate assemblages: occurrences,compositions and phase relations in metamorphosed Mn deposits

Mn-rich members of the pyrosmalite-family [(Mn, Fe)₈Si₆O₁₅(OH, Cl)₁₀], friedelite and schallerite have been identified as rock-forming minerals together with caryopilite, in several metamorphosed carbonate Mn-deposits. The phase assemblages and mineral compositions are described for eight of these localities each of which represents a distinct geologic situation. Friedelite is always Cl-bearing and occurs both as a prograde phase in low-grade metamorphic rocks (Pyrenees, Haute-Maurienne) and as a secondary phase formed by retrogressive replacement of primary anhydrous phases in higher-grade rocks. Schallerite, an Asbearing relative of friedelite, occurs in the greenschist metamorphic deposit of the Ködnitztal (Austria) together with other As-minerals. In these deposits, caryopilite is typically formed during retrograde metamorphism by alteration of, generally anhydrous, Mn-silicates. Based upon these occurrences, a qualitative petrogenetic grid for the system MnO-SiO₂-CO₂-H₂O with the phases friedelite, caryopilite, pyroxmangite/rhodonite, tephroite, rhodochrosite, quartz, CO₂, and H₂O is proposed. The phase relations imply that Cl- (or As-) free friedelite is not stable in hydrous systems with respect to caryopilite. From the mineral assemblages containing hydrous Mn silicates, waterrich fluids are inferred during the retrograde metamorphic evolution of the investigated deposits. Chemical data for Mn-rich chlorites, which are basically members of the clinochlore-pennantite series which coexist with the pyrosmalite minerals, show the absence of intermediate Mn/Mg ratios. This supports the existence of a miscibility gap as previously hypothesized by other authors.     

Lead incorporation during crystal growth and the misinterpretation of geochronological data from low-238U/204Pb metamorphic minerals

The isotopic composition of lead available for incorporation during metamorphic reactions is heterogeneous, depends on the reaction history of the metamorphic rock, and is commonly not accessible for measurement as the precursor minerals have been consumed during the growth of the metamorphic phases. The initial lead composition has a significant effect on the age of low-²³⁸U/²⁰⁴Pb metamorphic phases (e.g. garnet, rutile, titanite, staurolite, vesuvianite and ilmenite). Using a distinct value (e.g. leached K-feldspar Pb, model Pb) rather than a geologically reasonably constrained range may result in apparently precise, yet inaccurate ages. Since age data from metamorphic minerals are widely used to unravel the P–T–t–d evolution of orogens, inaccurate ages result in: (1) incorrect timing (duration) of P–T loops and associated with it the heat budget and mass transfer in orogens; (2) arbitrary rates (based on the age difference between core and rim) for mineral growth, P–T evolution and deformation; and (3) apparent sequences of isotopic closure for the U–Pb system of contrasting minerals.     

A tomographic imagery segmentation methodology for three-phase geomaterials based on simultaneous region growing

X-ray computed tomography is a powerful non-destructive technique used in many domains to obtain the three-dimensional representation of objects, starting from the reconstitution of two-dimensional images of radiographic scanning. This technique is now able to analyze objects within a few micron resolutions. Consequently, X-ray microcomputed tomography opens perspectives for the analysis of the fabric of multiphase geomaterials such as soils, concretes, rocks and ceramics. To be able to characterize the spatial distribution of the different phases in such complex and disordered materials, automated phase recognition has to be implemented through image segmentation. A crucial difficulty in segmenting images lies in the presence of noise in the obtained tomographic representation, making it difficult to assign a specific phase to each voxel of the image. In the present study, simultaneous region growing is used to reconstitute the three-dimensional segmented image of granular materials. First, based on a set of expected phases in the image, regions where specific phases are sure to be present are identified, leaving uncertain regions of the image unidentified. Subsequently, the identified regions are grown until growing phases meet each other with vanishing unidentified regions. The method requires a limited number of manual parameters that are easily determined. The developed method is illustrated based on three applications on granular materials, comparing the phase volume fractions obtained by segmentation with macroscopic data. It is demonstrated that the algorithm rapidly converges and fills the image after a few iterations.