A series of basaltic compositions and compositions within the simple system CaO-MgO-FeO-Al2O3-SiO2 have been crystallized to garnetclinopyroxene bearing mineral assemblages in the range 24–30 kb pressure, 750°–1,300° C temperature. Microprobe analyses of coexisting garnet and clinopyroxene show that K
D(Fe2+/MgG+/Fe2+/MgCpx) for the Fe-Mg exchange reaction between coexisting garnet and clinopyroxene is obviously dependent upon the Ca-content and apparently independent of the Mg/(Mg+Fe) content of the clinopyroxene and garnet. The Ca-effect is believed to be due to a combination of non-ideal Ca-Mg substitutions in the garnet and clinopyroxene. Our data and interpretation reconciles previous inconsistencies in the temperature dependence of K
D
− values determined in experimental studies of simple systems, complex basalt, grospydite and garnet peridotite compositions. Previous differences between the effect of pressure upon K
Das predicted from simple system theory (Banno, 1970), and that observed in experiments on multicomponent natural rock compositions (Raheim and Green, 1974a) can now be resolved. We have determined K
Das a function of P, T, and X

 Gt
 Ca
 (grossular) and derived the empirical relation 
$$T\left( {^\circ {\text{K}}} \right) = \frac{{3104X_{{\text{Ca}}}^{{\text{Gt}}} + 3030 + 10.86P\left( {{\text{kb}}} \right)}}{{\ln K_{\text{D}} + 1.9034}}$$

 . This empirical relationship has been applied to garnet-clinopyroxene bearing rocks from a wide range of geological environments. The geothermometer yields similar estimates for garnet-clinopyroxene equilibration for neighbouring rocks of different composition and different K
Dvalues. In addition, temperature estimates using the above relationship are more consistent with independent temperature estimates based on other geothermometers than previous estimates which did not correct for the Ca-effect. An alternative approach to the above empirical geothermometer was attempted using regular solution models to derive Margules parameters for various solid solutions in garnets and clinopyroxenes. The derived Margules parameters are broadly consistent with those determined from binary solution studies, but caution must be exercised in interpreting them in terms of actual thermodynamic properties of the relevant crystalline solid solutions because of the assumptions which necessarily have to be made in this approach.

An experimental study of the effect of Ca upon garnet-clinopyroxene Fe-Mg exchange equilibria

A pyrope-quartzite originally described by Vialon (1966) from the Dora Maira massif was resampled and reinvestigated. Garnet (up to 25 cm in size), phengite, kyanite, talc and rutile are in textural equilibrium in an undeformed matrix of polygonal quartz. The garnet is a pyrope-almandine solid solution with 90 to 98 mol % Mg end-member. It contains inclusions of coesite which has partially inverted to quartz, resulting in a typical radial cracking of the host garnet around the inclusions. Several lines of evidence show that coesite crystallised under nearly static pressure conditions and that the whole matrix has once been coesite. The formidable pressures of formation implied (≧28 kbar) are independently indicated by i) the coexistence of nearly pure pyrope with free silica and talc, ii) the coexistence of jadeite with kyanite, iii) the high Si content of phengite. Water activity must have been low. The stability of talc-phengite and the presence of rare glaucophane inclusions in pyrope point to low formation temperatures (about 700 °C) and to a probable Alpine age for the assemblage. This is evidence that low temperature gradients, how essentially transient they are, may nevertheless persist to considerable depths. Moreover, the upper crustal (evaporite-related?) origin of the quartzite and its interbedding within a continental unit implies that continental crust may also be subducted to depths of 90 km or more. The return back to the surface is problematic; the retrograde assemblages observed show that it must be tectonic. If the rocks remain at depth, new perspectives open for the genesis of intermediate to acidic magmas. Eventually, the role of continental crust in geodynamics may have to be reconsidered.

Coesite and pure pyrope in high-grade blueschists of the Western Alps: a first record and some consequences

Coesite is reported for the first time from the Caledonide orogen. It occurs as inclusions in clinopyroxene in the dolomite-eclogite at Grytting, Norway, and provides valuable new evidence to support the hypothesis of extremely high pressure (≥30 kbar) in certain Norwegian eclogites. This finding has implications for the geodynamics and kinetics of the concepts of microscale intracrystalline tectonic overpressure and of macroscale local or regional tectonic overpressure, and for the hypotheses of subduction and obduction involving a more than 100km vertical component of transport.

Coesite in clinopyroxene in the Caledonides and its implications for geodynamics

[1] We present new experimentally determined trace element partition coefficients for nine garnet/melt and two clinopyroxene/melt pairs at 2.9–3.1 GPa and 1325°–1390°C, applicable to anhydrous partial melting of MORB-like eclogite in the upper mantle. Phase compositions are similar to those documented in partial melting experiments of eclogite at these conditions: garnets with 16–25% grossular component and 0.4–2.0 wt % TiO2 coexist with siliceous partial melts having 52.4–57.1 wt % SiO2 and 1.1–6.7 wt % TiO2. Observed garnet/melt partitioning depends on TiO2 concentrations in garnet. Among the high-TiO2 garnets (1.4–2.0 wt % TiO2), partition coefficients (Dgt/melt) increase with increasing grossular content of garnet (16–24%), but for the low-TiO2 garnets (0.4–0.6 wt % TiO2) there is no difference in partitioning behavior at 19–24% grossular. In general, partition coefficients for the low-TiO2 garnets tend to be higher than for the high-TiO2 garnets. DZr and DHf increase with higher grossular content, as does DZr/DHf, but DZr and DHf always remain smaller than unity, and TiO2 in garnet appears to have little effect on DZr/DHf. DTh and DU have average values of 0.0012 and 0.0111 for the high-TiO2 garnets and 0.0074 and 0.0376 for the low-TiO2 garnets (DU/DTh of 9.1 and 5.1, respectively), affirming that partial melting of eclogite in the upper mantle can produce liquids with significant (230Th)/(238U) excess. D values of highly charged cations (Nb, Ta, Th, U) are lower in high-TiO2 garnets. This is likely because Ti4+ occupying the garnet Y site requires charge balance by 2+ cations in Y or 3+ cations in Z, thereby limiting the availability of these charge-balancing substitutions to accommodate other highly charged cations. The overall range of our new garnet/melt partition coefficients, regardless of Ti and grossular content, is similar to literature garnet/melt partitioning data applicable to garnet peridotite melting, and therefore bulk partition coefficients for eclogite and peridotite depend largely on mineral modes and choice of partitioning data for clinopyroxene. Using our new data and previously published data from the literature, we calculate bulk partition coefficients appropriate for two MORB-like eclogites (82% clinopyroxene + 18% garnet and 75% clinopyroxene + 25% garnet) and a garnet peridotite (60% olivine + 17% orthopyroxene + 13% clinopyroxene + 10% garnet). Bulk partition coefficients are generally much higher for MORB-like eclogite when compared to garnet peridotite, with the exception of Th and U. However, the ratios of bulk partition coefficients of eclogite and garnet peridotite are similar for pairs such as DSm/DYb, DZr/DHf and DU/DTh, indicating that both lithologies can induce similar trace element fractionations during partial melting in the presence of garnet.

https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1029/2003GC000638

Experimental determination of trace element partitioning between garnet and silica-rich liquid during anhydrous partial melting of MORB-like eclogite

We review experimental phase equilibria associated with partial melting of mafic lithologies ( pyroxenites) at high pressures to reveal systematic relationships between bulk compositions of pyroxenite and their melting relations. An important aspect of pyroxenite phase equilibria is the existence of the garnet–pyroxene thermal divide, defined by the enstatite–Ca-Tschermaks pyroxene–diopside plane in CaO–MgO–Al2O3–SiO2 projections. This divide appears at pressures above 2 GPa in the natural system where garnet and pyroxenes are the principal residual phases in pyroxenites. Bulk compositions that reside on either side of the divide have distinct phase assemblages from subsolidus to liquidus and produce distinct types of partial melt ranging from strongly nepheline-normative to quartz-normative compositions. Solidus and liquidus locations are little affected by the location of natural pyroxenite compositions relative to the thermal divide and are instead controlled chiefly by bulk alkali contents and Mg-numbers. Changes in phase volumes of residual minerals also influence partial melt compositions. If olivine is absent during partial melting, expansion of the phase volume of garnet relative to clinopyroxene with increasing pressure produces liquids with high Ca/Al and low MgO compared with garnet peridotite-derived partial melts.

High-pressure Partial Melting of Mafic Lithologies in the Mantle

http://ruby.colorado.edu/~smyth/Research/Papers/Coesite.pdf

C.J. Hatton

Papers

A coesite-sanidine grospydite from the Roberts Victor kimberlite