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

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

Constraining the P–T path of a MORB-type eclogite using pseudosections, garnet zoning and garnet-clinopyroxene thermometry: an example from the Bohemian Massif

A mid‐ocean ridge basalt (MORB)‐type eclogite from the Moldanubian domain in the Bohemian Massif retains evidence of its prograde path in the form of inclusions of hornblende, plagioclase, clinopyroxene, titanite, ilmenite and rutile preserved in zoned garnet. Prograde zoning involves a flat grossular core followed by a grossular spike and decrease at the rim, whereas Fe/(Fe + Mg) is also flat in the core and then decreases at the rim. In a pseudosection for H₂O‐saturated conditions, garnet with such a zoning grows along an isothermal burial path at c. 750 °C from 10 kbar in the assemblage plagioclase‐hornblende‐diopsidic clinopyroxene‐quartz, then in hornblende‐diopsidic clinopyroxene‐quartz, and ends its growth at 17–18 kbar. From this point, there is no pseudosection‐based information on further increase in pressure or temperature. Then, with garnet‐clinopyroxene thermometry, the focus is on the dependence on, and the uncertainties stemming from the unknown Fe³⁺ content in clinopyroxene. Assuming no Fe³⁺ in the clinopyroxene gives a serious and unwarranted upward bias to calculated temperatures. A Fe³⁺‐contributed uncertainty of ±40 °C combined with a calibration and other uncertainties gives a peak temperature of 760 ± 90 °C at 18 kbar, consistent with no further heating following burial to eclogite facies conditions. Further pseudosection modelling suggests that decompression to c. 12 kbar occurred essentially isothermally from the metamorphic peak under H₂O‐undersaturated conditions (c. 1.3 mol.% H₂O) that allowed the preservation of the majority of garnet with symplectitic as well as relict clinopyroxene. The modelling also shows that a MORB‐type eclogite decompressed to c. 8 kbar ends as an amphibolite if it is H₂O saturated, but if it is H₂O‐undersaturated it contains assemblages with orthopyroxene. Increasing H₂O undersaturation causes an earlier transition to SiO₂ undersaturation on decompression, leading to the appearance of spinel‐bearing assemblages. Granulite facies‐looking overprints of eclogites may develop at amphibolite facies conditions.     

Strain coupling between upper mantle and lower crust: natural example from the Běstvina granulite body, Bohemian Massif

Strain patterns within mantle rocks and surrounding coarse‐grained felsic granulites from the Kutná Hora Crystalline Complex in the Variscan Bohemian Massif have been studied in order to assess their strain coupling. The studied rock association occurs within low‐strain domains surrounded by fine‐grained granulite and migmatite. The Doubrava peridotite contains closely spaced and steeply dipping layers of garnet clinopyroxenite, which are parallel to the NE–SW‐striking, high‐temperature foliation in nearby granulites, while the Úhrov peridotite lacks such layering. The Spa?ice eclogite is not associated with peridotite and shows upright folds of alternating coarse‐ and fine‐grained varieties bearing NE–SW‐striking axial planes. Electron back‐scattered diffraction measurements revealed full strain coupling between clinopyroxenites and coarse‐grained granulites in the S₁ fabric that is superposed on the S₀ fabric preserved in peridotites. The B‐type olivine lattice preferred orientation (LPO) characterizes the S₀ fabric in peridotites and its reworking is strongly controlled by the presence of macroscopic clinopyroxenite layering. The S₁ in clinopyroxenites and coarse‐grained granulites is associated with the LS‐type clinopyroxene LPO and prism <c> slip in quartz respectively. While the S₁ fabric in these rock types is accompanied invariably by a sub‐vertical stretching lineation, the S₁ fabric developed in reworked Úhrov peridotite is associated with strongly planar axial (010) type of olivine LPO. The peridotites with the S₀ fabric are interpreted to be relicts of a fore‐arc mantle wedge hydrated to a various extent above the Saxothuringian subduction zone. The prograde metamorphism recorded in peridotites and eclogites occurred presumably during mantle wedge flow and was reaching UHP conditions. Strain coupling in the S₁ fabric between clinopyroxenites and granulites at Doubrava and upright folding of eclogites at Spa?ice document a link between tectonic and magmatic processes during orogenic thickening, coeval with intrusions of the arc‐related calcalkaline suites of the Central Bohemian Plutonic Complex (c. 360–345 Ma). Juxtaposition of peridotites and granulites could be explained by a rheological heterogeneity connected to the development of clinopyroxenite layering in the upper mantle and a previously published model of a lithospheric‐scale transpressional arc system. It invokes vertical shearing along NE–SW trending, sub‐vertical foliations in the upper mantle that could have led to an emplacement of mantle bodies into the granulitized, orogenic root in the sub‐arc region. Clearly, such a transpressional arc system could represent an important pathway for an emplacement of deep‐seated rocks in the orogenic lower crust.     

Role of chemical processes on shear zone formation: an example from the Grimsel metagranodiorite (Aar massif,Central Alps)

Alpine deformation in the Grimsel granodiorite (Aar massif, Central Alps) at greenschist facies conditions (6.5 ± 1 kbar for 450°C ± 25°C) is characterized by the development of a network of centimetre to decametre localized shear zones that surround lenses of undeformed granodiorite. Localization of deformation is assumed to be the result of a first stage of extreme localization on brittle precursors (nucleation stage) followed by a transition to ductile deformation and lateral propagation into the weakly deformed granodiorite (widening stage). A paradox of this model is that the development of the ductile shear zone is accompanied by the crystallization of large amounts of phyllosilicates (white mica and chlorite) that maintains a weak rheology in the localized shear zone relative to the host rock so that deformation is localized and prevents shear zone widening. We suggest that chemical processes, and more particularly, the metamorphic reactions and metasomatism occurring during re‐equilibration of the metastable magmatic assemblage induced shear zone widening at these P–T–X conditions. These processes (reactions and mass transfer) were driven by the chemical potential gradients that developed between the thermodynamically metastable magmatic assemblage at the edge of the shear zone and the stable white mica and chlorite rich ultramylonite formed during the first stage of shear zone due to localized fluid infiltration metasomatism. P–T and chemical potential projections and sections show that the process of equilibration of the wall rocks (μ–μ path) occurs via the reactions: kf + cz + ab + bio + MgO + H₂O = mu + q + CaO + Na₂O and cz + ab + bio + MgO + H₂O = chl + mu + q + CaO + Na₂O. Computed phase diagram and mass balance calculations predict that these reactions induce relative losses of CaO and Na₂O of ～100% and ～40% respectively, coupled with hydration and a gain of ～140% for MgO. Intermediate rocks within the strain gradient (ultramylonite, mylonite and orthogneiss) reflect various degrees of re‐equilibration and metasomatism. The softening reaction involved may have reduced the strength at the edge of the shear zone and therefore promoted shear zone widening. Chemical potential phase diagram sections also indicate that the re‐equilibration process has a strong influence on equilibrium mineral compositions. For instance, the decrease in Si‐content of phengite from 3.29 to 3.14 p.f.u, when white mica is in equilibrium with the chlorite‐bearing assemblage, may be misinterpreted as the result of decompression during shear zone development while it is due only to syn‐deformation metasomatism at the peak metamorphic condition. The results of this study suggest that it is critical to consider chemical processes in the formation of shear zones particularly when deformation affects metastable assemblages and mass transfer are involved.     

Details of the gabbro‐to‐eclogite transition determined from microtextures and calculated chemical potential relationships

Permian‐aged metagabbros from the eclogite type‐locality in the eastern European Alps were partially to completely transformed to eclogite during Eoalpine intracontinental subduction. Microtextures developed along a preserved fluid infiltration and reaction front in the gabbros record the incipient gabbro‐to‐eclogite transition, allowing the details of the eclogitization process to be investigated. Original, anorthite‐rich igneous plagioclase is pervasively replaced by fine‐grained intergrowths of clinozoisite, kyanite and Na‐rich plagioclase. Where plagioclase was in contact with igneous orthopyroxene, 100–200 μm thick bimineralic coronae of symplectic kyanite and diopsidic clinopyroxene form along the edges of the grains. The rims of igneous orthopyroxene develop a complementary bimineralic corona of diopsidic clinopyroxene and garnet. Igneous clinopyroxene does not show any breakdown textures; however, jadeite content gradually increases towards the rims. In addition, exsolution lamellae inherited from the igneous clinopyroxene become progressively more jadeitic as eclogitization proceeds. Given that the igneous plagioclase is pervasively replaced by clinozoisite, kyanite and Na‐rich plagioclase, whereas kyanite–diopside symplectites are confined to narrow rim zones, we suggest that the development of these textures was controlled by the (im)mobility of different elements on different length scales. The presence of hydrous minerals in the core of anhydrous plagioclase indicates that H₂O diffusivity occurred on a mm‐scale. By contrast, the size of the anhydrous diopside–kyanite and diopside–garnet symplectites indicate that Fe–Mg–Ca–Na diffusivity was limited to a 10s of μm scale. Chemical potential relations calculated in the idealized NCASH chemical system show that the clinozoisite–kyanite–albite intergrowths formed due to an increase of μH₂O to plagioclase, whereas all other elements remained effectively immobile on the scale of this texture. Fluid conditions indicated by this texture span from virtually dry conditions (0.15) to H₂O‐saturation, and therefore does not imply that the rocks were ever fluid‐saturated. Calculations in the CMAS and NCFMAS systems show that the gabbro‐to‐eclogite transition is characterized by the growth of garnet, diopsidic clinopyroxene and kyanite due to diffusion of Ca (+ Na) and Mg (+ Fe) along a μCaO (+ Na₂O)–μMgO (+ FeO) chemical potential gradient developed between orthopyroxene and plagioclase compositional domains. The anhydrous nature of the textures indicate that the gabbro‐to‐eclogite transition is not driven by hydration; however, increased μH₂O acts as a catalyst that increases diffusivity of all elements and rates of dissolution–precipitation, allowing the overstepped metamorphic reactions to occur. Our results show that crustal eclogite formation requires low H₂O content, confirming that true eclogites are dry rocks.