Quartz‐in‐garnet and Ti‐in‐quartz thermobarometry: Methodology and first application to a quartzofeldspathic gneiss from eastern Papua New Guinea

Mineral inclusions are ubiquitous in metamorphic rocks and elastic models for host‐inclusion pairs have become frequently used tools for investigating pressure–temperature (P–T) conditions of mineral entrapment. Inclusions can retain remnant pressures () that are relatable to their entrapment P–T conditions using an isotropic elastic model and P–T–V equations of state for host and inclusion minerals. Elastic models are used to constrain P–T curves, known as isomekes, which represent the possible inclusion entrapment conditions. However, isomekes require a temperature estimate for use as a thermobarometer. Previous studies obtained temperature estimates from thermometric methods external of the host‐inclusion system. In this study, we present the first P–T estimates of quartz inclusion entrapment by integrating the quartz‐in‐garnet elastic model with titanium concentration measurements of inclusions and a Ti‐in‐quartz solubility model (QuiG‐TiQ). QuiG‐TiQ was used to determine entrapment P–T conditions of quartz inclusions in garnet from a quartzofeldspathic gneiss from Goodenough Island, part of the (ultra)high‐pressure terrane of Papua New Guinea. Raman spectroscopic measurements of the 128, 206, and 464 cm^?1 bands of quartz were used to calculate inclusion pressures using hydrostatic pressure calibrations (), a volume strain calculation (), and elastic tensor calculation (), that account for deviatoric stress. values calculated from the 128, 206, and 464 cm^?1 bands’ hydrostatic calibrations are significantly different from one another with values of 1.8 ± 0.1, 2.0 ± 0.1, and 2.5 ± 0.1 kbar, respectively. We quantified elastic anisotropy using the 128, 206 and 464 cm^?1 Raman band frequencies of quartz inclusions and stRAinMAN software (Angel, Murri, Mihailova, & Alvaro, 2019,  234 :129–140). The amount of elastic anisotropy in quartz inclusions varied by ~230%. A subset of inclusions with nearly isotropic strains gives an average and of 2.5 ± 0.2 and 2.6 ± 0.2 kbar, respectively. Depending on the sign and magnitude, inclusions with large anisotropic strains respectively overestimate or underestimate inclusion pressures and are significantly different (<3.8 kbar) from the inclusions that have nearly isotropic strains. Titanium concentrations were measured in quartz inclusions exposed at the surface of the garnet. The average Ti‐in‐quartz isopleth (19 ± 1 ppm [2σ]) intersects the average QuiG isomeke at 10.2 ± 0.3 kbar and 601 ± 6°C, which are interpreted as the P–T conditions of quartzofeldspathic gneiss garnet growth and entrapment of quartz inclusions. The P–T intersection point of QuiG and Ti‐in‐quartz univariant curves represents mechanical and chemical equilibrium during crystallization of garnet, quartz, and rutile. These three minerals are common in many bulk rock compositions that crystallize over a wide range of P–T conditions thus permitting application of QuiG‐TiQ to many metamorphic rocks.     

Activity–composition relations for the calculation of partial melting equilibria in metabasic rocks

A set of thermodynamic models is presented that, for the first time, allows partial melting equilibria to be calculated for metabasic rocks. The models consist of new activity–composition relations combined with end‐member thermodynamic properties from the Holland & Powell dataset, version 6. They allow for forward modelling in the system NaO–CaO–KO–FeO–MgO–AlO–SiO–HO–TiO–FeO. In particular, new activity–composition relations are presented for silicate melt of broadly trondhjemitic–tonalitic composition, and for augitic clinopyroxene with Si–Al mixing on the tetrahedral sites, while existing activity–composition relations for hornblende are extended to include KO and TiO. Calibration of the activity–composition relations was carried out with the aim of reproducing major experimental phase‐in/phase‐out boundaries that define the amphibolite–granulite transition, across a range of bulk compositions, at ≤13 kbar.     

Evolution of metamorphic fluid recorded in granulite facies metacarbonate rocks from the middle segment of the Mogok metamorphic belt in central Myanmar

The Mogok metamorphic belt of Palaeogene age, which records subduction‐ and collision‐related events between the Indian and Eurasian plates, lies along the western margin of the Shan plateau in central Myanmar and continues northwards to the eastern Himalayan syntaxis. Reaction textures of clinohumite‐ and scapolite‐bearing assemblages in Mogok granulite facies metacarbonate rocks provide insights into the drastic change in fluid composition during exhumation of the collision zone. Characteristic high‐grade assemblages of marble and calcsilicate rock are clinohumite+forsterite+spinel+phlogopite+pargasite/edenite+calcite+dolomite, and scapolite+diopside+anorthite+quartz+calcite respectively. Calculated petrogenetic grids in CaO–MgO–Al₂O₃–SiO₂–H₂O–CO₂ and subsets of this system were employed to deduce the pressure–temperature–fluid evolution of the clinohumite‐ and scapolite‐bearing assemblages. These assemblages suggest higher temperature (>780–810°C) and [=CO₂/(CO₂+H₂O) >0.17–0.60] values in the metamorphic fluid for the peak granulite facies stage, assuming a pressure of 0.8 GPa. Calcite grains commonly show exsolution textures with dolomite particles, and their reintegrated compositions yield temperatures of 720–880°C. Retrograde reactions are mainly characterized by a reaction zone consisting of a dolomite layer and a symplectitic aggregate of tremolite and dolomite grown between clinohumite and calcite in marble, and a replacement texture of scapolite by clinozoisite in calcsilicate rock. These textures indicate that the retrograde reactions developed under lower temperature (<620°C) and (<0.08–0.16) conditions, assuming a pressure of 0.5 GPa. The metacarbonate rocks share metamorphic temperatures similar to the Mogok paragneiss at the peak granulite facies stage. The values of the metacarbonate rock at peak metamorphic stage are, however, distinctly higher than those previously deduced from carbonate mineral‐free paragneiss. Primary clinohumite, phlogopite and pargasite/edenite in marble have F‐rich compositions, and scapolite in calcsilicate rock contains Cl, suggesting a contrast in the halogen compositions of the metamorphic fluids between these two lithologies. The metamorphic fluid compositions were probably buffered within each lithology, and the effective migration of metamorphic fluid, which would have extensively changed the fluid compositions, did not occur during the prograde granulite facies stage throughout the Mogok metamorphic belt. The lower conditions of the Mogok metacarbonate rocks during the retrograde stage distinctly contrast with higher conditions recorded in metacarbonate rocks from other metamorphic belts of granulite facies. The characteristic low conditions were probably due to far‐ranging infiltration of H₂O‐dominant fluid throughout the middle segment of the Mogok metamorphic belt under low‐amphibolite facies conditions during the exhumation and hydration stage.     

Iterative thermodynamic modelling—Part 1: A theoretical scoring technique and a computer program (Bingo-Antidote)

This paper introduces the software solution Bingo-Antidote for thermodynamic calculations at equilibrium based on iterative thermodynamic models. It describes a hybrid strategy combining the strength of Gibbs energy minimization (GEM) and inverse thermobarometry models based on the comparison between the modelled and observed mineral assemblage, modes and compositions. The overall technique relies on quantitative compositional maps acquired by electron probe micro-analyser for obtaining a mutually consistent set of observed data such as bulk rock and mineral compositions. Thus it offers the opportunity to investigate metamorphic rocks on a microscale. The scoring part Bingo integrates three statistical model quality factors for the assemblage, for the mineral modes, for the mineral compositions combined in a global evaluation criterion that quantifies how the model reproduces the observations for the investigated volume. The input parameters of GEM affecting the model quality such as pressure, temperature and eventually some components of the bulk composition (e.g. the molar amount of hydrogen, carbon or oxygen) or activity variables of fluids and gases (e.g. , , f(O₂)) can be optimized by inversion in Antidote using several mapping stages followed by a direct search optimization. Examples of iterative models based on compositional maps processed with Bingo-Antidote demonstrate the utility of the program. In contrast to the qualitative interpretation of phase diagrams, the inversion maximizes the benefits of GEM and permits the derivation of statistically ‘optimal’ pressure–temperature conditions for well-equilibrated samples. In addition, Bingo-Antidote opens new avenues for petrological investigations such as the generation of chemical potential landscape maps.     

Metamorphic imprint of accretion and ridge subduction in the Pan‐African Damara Belt,Namibia

Ridge subduction is an inescapable plate tectonic process, but has only been documented in modern circum‐Pacific environments and not yet been recognized from suture zones associated with supercontinent assembly, likely because its imprint is obliterated by later collision. The formation of the Pan‐African Damara Belt of central Namibia involved northward subduction of the Khomas Sea underneath the Congo Craton, prior to final suturing of the Congo and Kalahari Cratons. The accretionary history of the Belt is preserved in the Southern and Southern Marginal Zones, which consist of turbiditic metasedimentary and intercalcated mafic rocks with MORB affinity. Two localities in the Kuiseb and Gaub canyons reveal that aluminous metapelites contain a fabric‐defining assemblage of fine‐grained muscovite, chlorite, biotite, quartz and graphite that is overprinted by randomly oriented porphyroblasts and poikiloblasts of garnet, staurolite, kyanite and biotite. Associated metamafic rocks consist of hornblende, chlorite, epidote, rutile and quartz, with actinolite cores preserved in amphibole porphyroblasts. Metamorphic conditions for the fabric‐defining assemblage are estimated at ～10 kbar and 540–560 C, whereas peak metamorphism likely occurred at 10–10.5 kbar and 600 C. Consequently, these rocks preserve a two‐stage prograde metamorphic history, where initial tectonic burial was followed by relatively rapid, near‐isobaric heating without attendant deformation to peak metamorphic conditions. We propose that initial burial occurred through subduction and underplating to the accretionary prism, before ridge subduction and opening of a slab window heated the rocks to peak metamorphic conditions. The exceptional preservation of the tectono‐thermal imprint of the accretionary orogenic stage is due to the relatively soft, largely aborted collision that characterized the Damara orogeny, which can be attributed to the confined extent of the Khomas Sea.     

Phase equilibria for graphitic metapelite including solution of CO2 in melt and cordierite: implications for dehydration,partial melting and graphite precipitation

When graphite is present, carbon‐bearing species dissolve in the C‐O‐H fluid and lower the activity of water (). Accordingly, metamorphic reactions that involve water, namely dehydration and partial melting reactions, adjust their P–T positions to accommodate the change of . In this modelling study, pseudosections are calculated for graphite‐bearing systems that are either closed or that progressively lose fluid and/or melt. The diagrams incorporate a new model of CO₂ solubility in felsic melts that we derived to be compatible with a recently published melt model. As the result of the lowered in the carbon‐bearing systems, the temperature displacements of the solidus can be as large as 50 °C at low pressures in cordierite‐bearing zones (<4 kbar), but are smaller than 15 °C at mid‐pressure P–T conditions (4–9 kbar). In the supersolidus region, the phase relations among silicate minerals + melt are very close to those in carbon‐free systems. The fluid CO₂ content increases as temperature increases in the supersolidus assemblages. The CO₂‐rich fluid can be stable in granulite facies conditions in an oxidized system. In graphitic systems, melt and/or cordierite dominate the CO₂ budget of high‐grade rocks. During cooling, the fluid that exsolves from such crystalizing melt is CO₂‐rich. In addition to the phase relations, the pseudosections presented in this study enable researchers to quantitatively investigate the evolution of phase modes, including graphite, along specific metamorphic P–T paths. At low pressures in the cordierite stability field, graphite is predicted to precipitate as the pressure increases or temperature decreases in the subsolidus assemblages, or temperature increases in the region of melt + fluid coexistence. On the other hand, the graphite abundance remains nearly constant along the mid‐pressure P–T series, but the graphite mode in the supersolidus region may increase due to residual enrichment if the melt is extracted. The modelling results show that metamorphic processes in closed systems lead to only small changes in graphite mode (a few tenths of a per cent). This strongly suggests that open‐system behaviours are required for large amounts of graphite deposition, including fluid infiltration and mixing or residual enrichment processes in high‐grade rocks. In addition to P–T pseudosections, P/T–X_O diagrams (X_O = O/(H + O) in the fluid) illustrate the thermodynamic features of internal buffering from another perspective, and explore the dependence of phase relations on the externally imposed redox state. If the system is equilibrated with CO₂ or CH₄‐rich infiltrating fluid, the temperature displacements of metamorphic reactions can be larger than 50 °C, compared with carbon‐free systems.     

Mineralogy,Fluid Inclusions,and Sulfur Isotopes of the Huanzala Deposits,Peru: Early Skarn and Late Polymetallic Replacement Style Mineralizations

Carbonate‐replacement polymetallic mineralization at the Huanzala deposits (9°51′S, 77°00′W) was conducted in two contrasting stages that occurred in almost the same location. Early‐stage mineralization has a relation with a granodiorite porphyry stock, whereas the late‐stage mineralization is genetically associated with quartz porphyry sills. The early stage involved low to intermediate sulfidation Cu–Zn–(Pb) mineralization associated with metasomatic skarn, and the late stage involved high to intermediate sulfidation Cu–Zn–Pb–(Mn) mineralization associated with hydrothermal alteration characterized by paragonitic sericitization. The orebodies are hosted by steeply dipping (approximately 60°NE) Lower Cretaceous carbonate rocks in a relatively narrow range of approximately 4 km in horizontal extent and less than 1 km in depth. The pathway of the early‐stage brine‐derived fluids (300–>400°C, >33 wt% NaCl equivalent) along a plot of log against 1000/T is best explained by the progressive dual decline of the value and the temperature under rock‐buffering conditions; this decline saw the pathway progress through the stability field of pyrrhotite to reach that of pyrite and promoted a decrease in FeS from 14.5 to 1.6 mol% in the sphalerite. In contrast, an explanation for the pathway of the late‐stage fluids (140–290°C, 3–13 wt% NaCl equivalent) is given by an almost isothermal decline at approximately 270°C, with passing through the stability field of pyrite–bornite to reach that of chalcopyrite, promoting an increase in FeS from 0.1 to 1.6 mol% in the sphalerite, suggesting gas‐buffering conditions. The ore formation pressure records in the fluid inclusions illustrate an approximately 2‐km erosion during the roughly 2‐Myr total lifetime of the hydrothermal system.     

The origin of chloritoid – 3‐mica pseudomorph growth in staurolite–muscovite schist,Bangriposi (Eastern India)

At Bangriposi, variable stages in replacement of staurolite by chloritoid – Na–K–Ca mica shimmer aggregates in muscovite schists provides insight into the complex interplay between fluid flow, mass transfer, and dissolution–precipitation during pseudomorph growth. Idioblastic chloritoid growing into mica caps without causing visible deformation, and monomineralic chloritoid veins (up to 300 μm wide) within shimmer aggregates replacing staurolite attest to chloritoid nucleation in fluid‐filled conduits along staurolite grain boundaries and crystallographic planes. The growth of shimmer aggregates initiated along staurolite margins, and advanced inwards into decomposing staurolite along networks of crystallographically controlled fluid‐filled conduits. Coalescence among alteration zones adjacent to channel fills led to dismemberment and the eventual demise of staurolite. Mass balance calculation within a volume‐fixed, silica‐conserved reference frame indicate the shimmer aggregates grew via precipitation from fluids in response to mass transport that led to the addition of H₂O, K₂O, Na₂O and CaO in the reaction zone, and Al₂O₃ was transported outward from the inward‐retreating margin of decomposing staurolite. This aided precipitation of chloritoid in veins and in the outer collars, and as disseminated grains in the shimmer aggregates at mid‐crustal condition (~520 ± 20 °C, 5.5 ± 2.0 kbar). Computation using one‐dimensional transport equation suggests that staurolite decomposition involved advection dominating over diffusive transport; the permeation of externally derived H₂O caused flattening of chemical potential gradients in H₂O and aqueous species, for example, and , computed using the Gibbs method. This suggests that staurolite decomposition was promoted by the infiltration of a large volume of H₂O that flattened existing chemical potential gradients. In the initial stages of replacement, chloritoid super‐saturation in fluid caused preferential nucleation and growth of chloritoid at staurolite grain boundaries and in crystallographic planes. As reaction progressed, further chloritoid nucleation was halted, but chloritoid continued to grow as the 3‐mica aggregates continued to replace the remaining staurolite in situ, while the chloritoid‐compatible elements were transported in the water‐rich phase facilitating continued growth of the existing chloritoid grains.     

Discrete element method analysis of non‐coaxial flow under rotational shear

This study focuses on non‐coaxial flow behavior of cohesionless soil undergoing cyclic rotational shear, with a special interest in the effects of particle‐scale characteristics. To this end, we perform a series of 2D discrete element simulations with various particle shapes, inter‐particle coefficient of friction, initial density, and stress ratios. The validity and efficacy of the numerical model is established by systematically comparing numerical simulation results with existing laboratory testing results. Such comparison shows that the numerical simulations are capable of capturing mechanical behavior observed in laboratory testing under rotational shear. We further demonstrate and quantify a strong yet simple relationship between the deviatoric part of the normalized strain increment and the non‐coaxial angle, denoted by and ψ, respectively. This quantitative correlation between ψ and is independent of applied stress ratio, initial and current void ratio, and the number of cycles applied, but dependent on the principal stress orientation and particle‐scale characteristics. At the same , specimens with higher inter‐particle friction angle or smaller particle aspect ratio show greater non‐coaxial angles. A simple model is able to fit this ψ‐ relationship well, which provides a useful relationship that can be exploited in developing constitutive models for rotational shearing. Copyright © 2014 John Wiley & Sons, Ltd.     

Observations on the extended Matsuoka–Nakai failure criterion

The equivalent Mohr–Coulomb (M‐C) friction angle ? (J. Geotech. Eng. 1990; 116 (6):986–999) of the extended Matsuoka–Nakai (E‐M‐N) criterion has been examined under all possible stress paths. It is shown that ? depends only on the ratio of cohesion to confining stress c^′/σ and the frictional angle ?, where ? is the friction angle measured in triaxial compression (or extension) to which the E‐M‐N surface is fitted. It is also shown that ? is independent of c^′, when σ=0 and of σ when c^′=0, with the former representing an upper bound and the latter a lower bound of ? for any particular stress path. The closest point projection method has also been implemented successfully with the E‐M‐N criterion, and plane strain and axisymmetric element tests performed to verify some theoretical predictions relating to failure and post‐yielding behavior. Finally, a bearing capacity problem was analyzed using both E‐M‐N and M‐C, highlighting the conservative nature of M‐C for different friction angles. Copyright © 2009 John Wiley & Sons, Ltd.     

Mineral equilibrium constraints on the feasibility of diffusive H2O-fluxed melting in the continental crust

Generation of granitic melt is believed to occur predominantly by melting through the breakdown of hydrous minerals. However, melting due to the influx of H₂O has been recognized in anatectic amphibolite facies tonalitic grey gneisses, metagreywackes and low-P metapelites, and has consequently been proposed as an alternative mechanism for the generation of granitic melt. Melting induced by H₂O addition is recognized from voluminous melt production at relatively low temperature, where hydrous minerals are stable and anhydrous minerals are preferentially consumed during melting. Mineral equilibrium modelling to determine the P–T conditions, melt volumes, melting reactions and viable H₂O sources reveals that the process is not restricted to specific compositions or P–T conditions, although lower pressure and lithologies with a low hydrous mineral content are more favourable. Melting reactions in all lithologies primarily consume quartz and feldspars to yield 5–6 mol.% melt for each mol.% of H₂O added. remains constant at ~0.70 to 0.77 during progressive melting as long as alkali feldspar is present. Once alkali feldspar is exhausted, plagioclase becomes the main reactant, producing more tonalitic melt compositions with gradually higher . Our results demonstrate that, at the site of melting, melting is driven by diffusion of H₂O into the target rock along chemical potential gradients, rather than the advective flow of a mechanically distinct water-rich fluid phase. Melting will initiate and proceed as long as a gradient exists between the H₂O source and target lithology. Our calculations show that an ordinary magma, such as an I-type magma with typical H₂O content, has a high enough to be a viable H₂O source, allowing diffusive H₂O-fluxed melting to produce melt proportions and fertility comparable to that of dehydration melting. However, high degrees of partial melting require a considerable amount of H₂O, which necessitates a continuously advecting H₂O source such as a magma conduit or melt-bearing shear zone. A magmatic H₂O source at emplacement level will undergo a similar amount of crystallization as the melt fraction produced in the target rock such that there will be no net melt production. Considering that shear-zone hosted magma conduits are localized features, diffusive H₂O-fluxed melting is likely to only be viable in a small fraction of the anatectic orogenic crust. Although it may play an important role in locally raising melt volumes and modifying magma chemistry through mingling and hybridization, it does not appear to, of itself, be able to generate significant volumes of granitic melt.     

Autogenic incision‐backfilling cycles and lobe formation during the growth of alluvial fans with supercritical distributaries

Autogenic cycles of channelization, terminal deposit formation, channel backfilling and channel abandonment have been observed in the formation of fans and deltas. In subcritical flow, these terminal deposits are characterized as mouth bars that lead to flow bifurcation, backwater and eventual channel backfilling. Similar, although less well characterized, cycles also take place on supercritical subaerial and submarine fans. This study investigates the hydraulics and morphodynamics of autogenic incision and backfilling cycles associated with supercritical distributive channel flow in alluvial fans. The research questions of the study are: (i) how are supercritical autogenic cycles on alluvial fans different from the subcritical cycles; (ii) what are the hydraulic and sediment transport characteristics at the various stages of autogenic feedback cycles; and (iii) what role do the cycles play in the overall fan evolution? These questions are investigated in the laboratory, and emphasis is placed on measuring the hydraulic and topographic evolution of the systems during the cycles. The cycles arise quasi‐periodically under constant water and sediment discharge. Periods of sheet‐like flow are competent to move sediment () but not competent enough to carry the full imposed load. The net result is preferential deposition near the inlet, resulting in fan steepening and an increase in flow competency with time. At a sediment supply to capacity ratio of , the sheet‐like flow is unstable to small erosional events near the inlet, resulting in the collapse of the distributed flow to a strong channelized state. During channelization, a graded () supercritical (Fr > 1) channel develops and transports eroded and fed sediment up to and through the fan front – extending the fan, initiating a lobe shaped deposit and reducing the local slope. The slopes defined by a sheet‐like flow with and channelized flow with set the maximum and minimum slopes on the fan, respectively. Once formed, graded channels act as bypass conduits linking the inlet with the terminal deposit. On average, deposits are up to six channel depths in thickness and have volumes approximately five times that of the excavated channel. The main distinctive characteristics of the supercritical cycles relate to how the flow interacts with the terminal deposit. At the channel to deposit transition, the flow undergoes a weak hydraulic jump, resulting in rapid sedimentation, dechannelization and lateral expansion of the flow, and deposition of any remaining sediment on top of the channel fill and floodplain. This process often caps the channel as the deposit propagates up channel erasing memory of the excavated channel.     

Mineralogy,nucleation and growth of dolomite in the laboratory and sedimentary environment: A review

Dolomite [CaMg(CO₃)₂] forms in numerous geological settings, usually as a diagenetic replacement of limestone, and is an important component of petroleum reservoir rocks, rocks hosting base metal deposits and fresh water aquifers. Dolomite is a rhombohedral carbonate with a structure consisting of an ordered arrangement of alternating layers of Ca²⁺ and Mg²⁺ cations interspersed with anion layers normal to the c‐axis. Dolomite has symmetry, lower than the (CaCO₃) symmetry of calcite primarily due to Ca–Mg ordering. High‐magnesium calcite also has symmetry and differs from dolomite in that Ca²⁺ and Mg²⁺ ions are not ordered. High‐magnesium calcite with near‐dolomite stoichiometry (≈50 mol% MgCO₃) has been observed both in nature and in laboratory products and is referred to in the literature as protodolomite or very high‐magnesium calcite. Many dolomites display some degree of cation disorder (Ca²⁺ on Mg²⁺ sites and vice versa), which is detectable using transmission electron microscopy and X‐ray diffractometry. Laboratory syntheses at high temperature and pressure, as well as studies of natural dolomites show that factors affecting dolomite ordering, stoichiometry, nucleation and growth include temperature, alkalinity, pH, concentration of Mg and Ca, Mg to Ca ratio, fluid to rock ratio, mineralogy of the carbonate being replaced, and surface area available for nucleation. In spite of numerous attempts, dolomite has not been synthesized in the laboratory under near‐surface conditions. Examination of published X‐ray diffraction data demonstrates that assertions of dolomite synthesis in the laboratory under near‐ambient conditions by microbial mediation are unsubstantiated. These laboratory products show no evidence of cation ordering and appear to be very high‐magnesium calcite. Elevated‐temperature and elevated‐pressure experiments demonstrate that dolomite nucleation and growth always are preceded by very high‐magnesium calcite formation. It remains to be demonstrated whether microbial‐mediated growth of very high‐magnesium calcite in nature provides a precursor to dolomite nucleation and growth analogous to reaction paths in high‐temperature experiments.     

Improved rotational hardening rule for cohesive soils and definition of inherent anisotropy

Improved, microfabric‐inspired rotational hardening rules for the plastic potential and bounding surfaces associated with the generalized bounding surface model for cohesive soils are presented. These hardening rules include 2 new functions, f_η and , that improve the simulation of anisotropically consolidated cohesive soils. Three model parameters are associated with the improved hardening rules. A detailed procedure for obtaining suitable values for these parameters is presented. The first 2 parameters affect the simulation of constant stress ratio loading where, because of the presence of f_η, the third parameter is inactive. The second new function, , accelerates the rotation of the plastic potential and bounding surfaces during shearing, which is particularly important for overconsolidated soils tested in extension. This paper also describes the proper manner in which to define the inherent anisotropy. This seemingly straightforward test has rarely been discussed in sufficient detail.     

Temperature,fluid content and rheology of localized ductile shear zones in subsolidus cooling plutons

Temperature and fluid content are critical parameters that control rock rheology and strain localization in the continental crust. Here, we determine by thermodynamic modelling the of localized ductile shearing during cooling of three different granitoid plutons: the Rieserferner and the Adamello plutons in the Italian Alps, and the Lake Edison pluton in the Sierra Nevada—USA. Shear zones exploited precursor joints, associated veins and alteration zones. and P−T phase diagram sections were computed with Perple_X in the system MnO−Na₂O−CaO −K₂O−FeO−MgO−Al₂O₃−SiO₂−H₂O−Fe₂O₃. The phase diagram sections show that the nucleation of the brittle precursors (joints, veins) occurred at T» 450°C at fluid-saturated conditions. Localized ductile shearing likely occurred at temperature ranging between 420 and 460°C evolving from initially fluid-saturated to fluid-undersaturated conditions in a closed system. In this temperature range, granitoid rocks are potentially subject to a series of retrograde metamorphic reactions replacing the load-bearing feldspars with weaker phyllosilicates. Metamorphic reactions occurred in spatial association with the precursory structures, leading to localized shearing. Decreasing temperature and fluid-undersaturated conditions likely hampered progressive strain accommodation in shear zones by slowing down metamorphic reactions, thermally activated dislocation creep processes, fluid-mediated deformation mechanisms and weakening mechanisms. Polyphase granitoid ultramylonite and mylonitic quartz veins have been affected differently by the fluid-undersaturated conditions of the system, as consequence of different dominant deformation mechanisms and syn-kinematic paragenesis during localized shearing. Localized ductile shearing in cooling plutons effectively occurs in a limited temperature range (420–460°C) in which the strain accommodation capacity of the shear zone is controlled by the negative feedback between the cooling rate, the kinetics of metamorphic reactions and deformation mechanisms, and the consumption of the limited amount of available fluids.     

A statistical analysis of the distribution of cordierite and biotite in hornfels from the Bugaboo contact aureole: implications for the kinetics of porphyroblast crystallization

The three‐dimensional disposition of cordierite and biotite crystals in a hornfels from the contact aureole of the Bugaboo Batholith is quantified using high‐resolution X‐ray micro‐computed tomography and global as well as scale‐dependent pattern statistics. The results demonstrate a random distribution of cordierite and biotite crystal sizes for all scales across the entire rock volume studied indicative of interface‐controlled prograde metamorphic reaction kinetics. The reaction considered responsible for the mineral assemblage and the formation of cordierite and biotite in the hornfels is Ms + Chl + Qtz = Crd + And + Bt + . Rock‐specific phase equilibria point to metamorphic conditions of ~520 –550 °C and 3 kbar for this reaction. The common approach to approximate the shape of crystals as spherical underestimates the influence of the Strauss hard‐core process on rock texture and may be misinterpreted to reflect ordering of crystal sizes by inhibition of nucleation and growth commonly associated with diffusion‐controlled reaction kinetics. According to our findings, Strauss hard‐core ordering develops at length scales equal to and less than the average major axis of the crystal population. This is significantly larger than what is obtained if a spherical crystal geometry would be assumed, and increases with deviation from sphericity. For the cordierite and biotite populations investigated in this research, Strauss hard‐core ordering developed at length scales of up to ～2.2 and 1.25 mm, respectively, which is almost 1 mm longer than the scales that would be obtained if a spherical geometry would have been assumed. Our results highlight the importance of a critical assessment of the geometrical model assumptions commonly applied in the three‐dimensional analysis of crystal size distributions, and underline the need for a quantitative understanding of interface processes in order to appreciate their role in the kinetics of contact metamorphic reactions and rock texture formation.     

Jadeite–garnet glaucophane schists in the Bizan area,Sambagawa metamorphic belt,eastern Shikoku,Japan: significance and extent of eclogite facies metamorphism

Eclogite facies metamorphic rocks have been discovered from the Bizan area of eastern Shikoku, Sambagawa metamorphic belt. The eclogitic jadeite–garnet glaucophane schists occur as lenticular or sheet‐like bodies in the pelitic schist matrix, with the peak mineral assemblage of garnet + glaucophane + jadeite + phengite + quartz. The jadeitic clinopyroxene (X_Jd 0.46–0.75) is found exclusively as inclusions in porphyroblastic garnet. The eclogite metamorphism is characterized by prograde development from epidote–blueschist to eclogite facies. Metamorphic P–T conditions estimated using pseudosection modelling are 580–600 °C and 18–20 kbar for eclogite facies. Compared with common mafic eclogites, the jadeite–garnet glaucophane schists have low CaO (4.4–4.5 wt%) and MgO (2.1–2.3 wt%) bulk‐rock compositions. The P–T– pseudosections show that low X_Ca bulk‐rock compositions favour the appearance of jadeite instead of omphacite under eclogite facies conditions. This is a unique example of low X_Ca bulk‐rock composition triggered to form jadeite at eclogite facies conditions. Two significant types of eclogitic metamorphism have been distinguished in the Sambagawa metamorphic belt, that is, a low‐T type and subsequent high‐T type eclogitic metamorphic events. The jadeite–garnet glaucophane schists experienced low‐T type eclogite facies metamorphism, and the P–T path is similar to lawsonite‐bearing eclogites recently reported from the Kotsu area in eastern Shikoku. During subduction of the oceanic plate (Izanagi plate), the hangingwall cooled gradually, and the geothermal gradient along the subduction zone progressively decreased and formed low‐T type eclogitic metamorphic rocks. A subsequent warm subduction event associated with an approaching spreading ridge caused the high‐T type eclogitic metamorphism within a single subduction zone.     

Geochemical evidence of microbial activity within ooids

Ooid formation remains elusive despite their importance as palaeoclimatic indicators and important contributors to global carbonate budget. Based on stable isotopes, nutrient and elemental analyses on solid components and ooidal leachates, this study supports the notion of microbial involvement in the development of ooids from Great Bahama Bank. Carbon and nitrogen isotopic analyses on organic fractions identified geochemical signatures of microbial activity. The δ¹³C values for organic carbon in the bulk (?11·9 to ?16·9‰); intercrystalline/intracrystalline (?11·9 to 16·7‰); and intracrystalline phases (?12·4 to ?17·7‰) were similar and, except for the more enriched values of ooids from Butterfly Beach, were within the range of photosynthesisers. The δ¹⁵N values for the bulk (+0·5 to ?0·2‰); intercrystalline/intracrystalline (?0·3‰ to ?0·7‰) and intracrystalline organic matter (?0·3 to ?1·7‰) showed a narrow range consistent with nitrogen fixation. While positive δ¹⁵N and δ¹⁸O values of the leached from the ooids provided evidence of denitrification, the carbonate associated sulphate δ³⁴S_CAS of the bulk sediments (+19·2 to +19·6‰) and δ³⁴S of the leachates (+16·6 to +18·3‰) provided weak indication of sulphate reduction, suggesting either that high concentrations of isotopically enriched S are overriding bio‐signatures of sulphate reduction or that microbes are preferentially using as an electron acceptor. In contrast, the elevated sulphate concentrations of the leachates suggest the occurrence of microbial sulphide oxidation within ooids. The high Mg/Ca of the leachates and scanning electron microscope analyses provide putative evidence of amorphous calcium carbonate and a formative role in CaCO₃ precipitation. Together, these findings indicate that a redox dependent microbial consortium may influence CaCO₃ precipitation in the form of ooid accretion, cementation and micritization. It is also inferred that ooid deposits are not suitable indicators of palaeoclimate because ooids are affected throughout their life by a complex chain of abiotic and biological processes which can lead to large geochemical offsets.     

A comment on diffusion and the displacement of atoms in metamorphic transformations

Experimental data on diffusion in olivine , are used to define certain terms – diffusion coefficient, jump frequency, characteristic distance, random walk – that are useful in a discussion of atom displacements under natural conditions. Examples of atom displacements in two metamorphic terranes of the Canadian Precambrian Shield are then examined, as follows. (i) In a high‐grade metamorphic terrane in the Mid‐Proterozoic Grenville Province (Otter Lake Area), Mg concentration gradients about dolomite microcrystals in calcite and Na gradients about albite microcrystals in K‐feldspar are viewed as stranded Mg–Ca and Na–K interdiffusion gradients, formed by exsolution during slow cooling from ~700 to ~400 °C. (ii) In the Archean Slave Province (Yellowknife area), the crystallization of sillimanite, near andalusite but within crystals of quartz, possibly occurred by coupled Al–Si and oxygen–vacancy interdiffusion in quartz at ~550 °C. And the crystallization of garnet from chlorite occurred by the two‐way crystal‐boundary diffusion of several kinds of atoms across distances ranging to 3 mm. (iii) In the Otter Lake area, the crystallization of orthopyroxene–hornblende–spinel reaction zones at boundaries between crystals of olivine and plagioclase in metagabbro, evidently occurred by the mechanism of interstitial diffusion, that transported Mg, Fe, Mn and O atoms across the reaction zone from olivine to the plagioclase–(hornblende+spinel) boundary, and Si, Al, Ca and Na atoms from plagioclase to the olivine–orthopyroxene boundary, accompanied by NaSi–CaAl interdiffusion in plagioclase, and the addition of hydrogen and minor Ti, Zn, F, Cl and K from beyond the reaction zone. Also, centimetric reaction zones, with abundant biotite and plagioclase, at boundaries between K‐feldspar gneiss and deformed amphibolite dykes, evidently formed by the reaction, strained hornblende (in amphibolite) + K‐feldspar (in gneiss)→biotite (in amphibolite) + plagioclase (in gneiss), with crystal‐boundary diffusion of (Na + Ca) atoms and of K atoms across the reaction zone.     

UHT metamorphism on Seram,eastern Indonesia: reaction microstructures and P–T evolution of spinel‐bearing garnet–sillimanite granulites from the Kobipoto Complex

The island of Seram, part of the northern limb of the Banda Arc in eastern Indonesia, exposes an extensive Mio‐Pliocene granulite facies migmatite complex (the Kobipoto Complex) comprising voluminous leucosome‐rich diatexites and scarcer Al–Fe‐rich residual granulites. The migmatites are intimately associated with ultramafic rocks of predominantly lherzolitic composition that were exhumed by substantial lithospheric extension beneath low‐angle detachment faults; heat supplied by the lherzolites was evidently a major driver for the granulite facies metamorphism and accompanying anatexis. Residual garnet–sillimanite granulites sampled from the Kobipoto Mountains, central Seram, contain scarce garnet‐hosted inclusions of hercynite spinel (~1.5 wt% ZnO) + quartz (± ilmenite) in direct grain‐boundary contact – an assemblage potentially indicative of metamorphism under ultrahigh‐temperature (UHT) conditions. thermocalc ‘Average P–T’ reactions and melanosome‐specific thermocalc , T–M_O, and P–T pseudosections in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃ (NCKFMASHTO) chemical system, supported by Ti‐in‐garnet thermobarometry, are permissive of the rock having experienced a clockwise P–T path peaking at 925 °C and 9 kbar – thus narrowly reaching UHT conditions – before undergoing near‐isothermal decompression to ~750 °C and ~4 kbar. Spinel + quartz assemblages are interpreted to have formed at or just after the metamorphic peak from localized reactions between sillimanite, ilmenite and surrounding garnet. Further decompression of the rock resulted in the formation of complex reaction microstructures comprising cordierite ± plagioclase coronae around garnet, and symplectic intergrowths of cordierite + spinel + ilmenite around sillimanite. Small grains of sapphirine + corundum developed subsequently within spinel by localized quartz‐absent reactions. The post‐peak evolution of the granulites may be related to previously published U–Pb zircon and ⁴⁰Ar/³⁹Ar ages of c. 16 Ma, further substantiating the claim for the Kobipoto Complex granulites having recorded Earth's youngest‐identified episode of UHT metamorphism, albeit at slightly lower temperature and higher pressure than previously inferred. The Kobipoto Complex granulites demonstrate how UHT conditions may be achieved in the ‘modern’ Earth by extreme lithospheric extension, which, in this instance, was driven by slab rollback of the Banda Arc.