ALBERT

Notes: Abstract The reaction chloritoid (ctd)=almandine (alm)+diaspore+H2O (CAD) has been reversed using Fe3+-free synthetic chloritoid and almandine, under fO2 conditions of the solid oxygen buffer Fe/FeO (CADWI), and using partially oxidized synthetic minerals under fO2 conditions of the solid oxygen buffer Ni/NiO (CADNNO). Experiments have been conducted between 550 and 700°C, 25 and 45 kbar. The equilibrium pressure and temperature conditions are strongly dependent on the fO2 conditions (CADNNO lies some-what 50°C higher than CADWI). This can be explained by a decrease in aH2O for experiments conducted on the Fe/FeO buffer, and a decrease in actd and aalm (through incorporation of ferric iron preferentially in chloritoid) for experiments conducted on the Ni/NiO buffer. The H2O activity has been calculated using the MRK equation of state, and the values obtained checked against the shift of the equilibrium diaspore=corundum+H2O bracketed on the Fe/FeO buffer and under unbuffered fO2 conditions. For fO2 buffered by the assemblage Fe/FeO, aH2O increases with pressure from about 0.85 at 600°C, 12 kbar to about 0.9 at 605°C, 25 kbar and 1 above 28 kbar. For fO2 buffered by the assemblage Ni/NiO, aH2O=1. The aH2O decrease from Ni/NiO to Fe/FeO is, however, too small to be entirely responsible for the temperature shift between CADNNO and CADWI. In consequence, the amount of ferric iron in almandine and chloritoid growing in the CADNNO experiments must be significant and change along the CADNNO, precluding calculation of the thermodynamic properties of chloritoid from this reaction. Our experimental data obtained on the Fe/FeO buffer are combined, using a thermodynamic analysis, with Ganguly's (1969) reversal of the reaction chloritoid=almandine+corundum +H2O (CAC) on the same oxygen buffer. Experimental brackets are mutually consistent and allow extraction of the thermodynamic parameters H o f,ctd and S octd. Our thermodynamic data are compared with others, generally calculated using Ganguly's bracketing of CACNNO. The agreement between the different data sets is relatively good at low pressure, but becomes rapidly very poor toward high pressure conditions. Using our thermodynamic data for chloritoid and KD=(Fe3+/Al)ctd/(Fe3+/Al)alm estimated from natural assemblages, we have calculated the composition of chloritoid and almandine growing from CADNNO and CACNNO. The Fe3+ content in chloritoid and almandine increases with pressure, from less than 0.038 per FeAl2SiO5(OH)2 formula unit at 10 kbar to at least 0.2 per formula unit above 30 kbar. This implies that chloritoid and almandine do contain Fe3+ in most natural assemblages. The reliability of our results compared to natural systems and thermodynamic data for Mg-chloritoid is tested by comparing the equilibrium conditions for the reaction chloritoid+quartz=garnet (gt)+kyanite+H2O (CQGK), calculated for intermediate Fe−Mg chloritoid and garnet compositions, from the system FASH and from the system MASH. For 0.65〈(XFe)gt〈0.8, CQKG calculated from FASH and MASH overlap for KD=(Mg/Fe)ctd/(Mg/Fe)gt=2. This is in good agreement with the KD values reported from chloritoid+garnet+quartz+kyanite natural assemblages.

Notes: Abstract  Fluid inclusions and F, Cl concentration of hydrous minerals were analysed in the coesite-pyrope quartzite, the interlayered jadeite quartzite and their country-rock gneiss from the Dora-Maira massif using a combination of microthermometry, Raman spectrometry, synchrotron X-ray microfluorescence and electron microprobe analysis. Three populations of fluid inclusions were recognized texturally and can be related to distinct metamorphic stages. A low-salinity aqueous fluid occurs in the retrogressed country gneiss and as late secondary inclusions in jadeite quartzite and chloritized pyrope. An earlier secondary population is found in matrix quartz of the jadeite- and pyrope-quartzites. This population can be related to the early decompression and so to incipient breakdown of garnet into phlogopite-bearing assemblages. The inclusion fluid is highly saline (up to 84 wt% equivalent NaCl) and contains Na, Ca, Fe, Cu and Zn as major cations. In pyrope quartzite, additional K was found in these brines, which locally coexist with CO2-rich inclusions. The oldest fluid inclusions are preserved in kyanite grains included in fresh pyrope and in pyrope itself. In pyrope, all inclusions have decrepitated and contain magnesite, an Mg-phosphate, sheet-silicate(s), a chloride and an opaque phase, with no fluid preserved. In contrast, the kyanite inclusions in pyrope preserve primary H2O-CO2 low-salinity fluid inclusions, probably owing to the low compressibility of the kyanite inclusions and host garnet. In spite of in-situ re-equilibration, these inclusions can be interpreted as relics of the dehydration fluid that attended pyrope growth. These correlations between textural and chemical fluid inclusion data and metamorphic stages are consistent with the fluid composition calculated from the halogen content of different generations of phlogopite and biotite. The preservation of different fluid compositions, both in time and space, is evidence for local control and possibly origin of the fluids, in agreement with isotopic data. These results, in particular the absence of CO2 in the jadeite quartzite, are best interpreted in terms of a fluid-melt system evolution. With increasing metamorphism, partitioning of H2O, Na, Ca, Fe and heavy metals into melt (jadeite quartzite) and Mg, Na/K, F, CO2 and P(?) into a residual aqueous fluid can account for depletion in Na, Ca and Fe of the pyrope quartzite. During the retrograde path, a H2O rose as melt crystallized, generating the two populations of hypersaline and water-rich fluids that were highly reactive to pyrope. The process of fluid-melt interaction envisioned here coupled with models of melt extraction in subduction zones provides an attractive opportunity for the instantaneous (〈1 Ma) and selective transport of elements between a downgoing slab and the overlying mantle wedge.

Notes: Abstract The40Ar-39Ar method has been applied to high pressure (HP) white micas from the Gran Paradiso crystalline massif and from the overthrust Schistes Lustrés of its western slope. Preliminary petrographic and microanalytical investigation of the phengite micas showed that their celadonite-content decreases with time (from Si3.65 to Si3.05), and that less foliated samples are the most suitable for the metastable persistence of the high celadonite-content of the early HP stage during subsequent metamorphic evolution. Such samples were investigated together with one where mica is a pure retrogressive product. Two groups of plateau-ages have been found: (a) 60 to 75 Ma on HP phengites and early paragonites of unretrograded HP parageneses, thus dating the early HP metamorphic stage; (b) 38–40 Ma on HP phengites (most often in slightly retrograded HP parageneses) and on the purely retrogressive mica. For the HP phengites in (b), this age is considered to reflect the end of Ar readjustement during the later lowerP and/or higherT metamorphic stage, and not their crystallization. This disparity in plateau-ages for micas sampled within the same area shows that under the sameP-T conditions some systems were open while others remained closed. This can be closely related to the mineralogical behaviour: chemically active systems are isotopically active, whereby the reverse is not necessarily true. Thus, although temperature exceeded by far the usually assumed sealing-temperature of white micas, many systems have remained unaffected during the late Eocene event. Therefore, temperature cannot be the determining parameter for the opening of a system. Chemical reactivity, starting mineralogy and, primarily, pervasive deformation and the related fluid behaviour appear to be the effective controls. This implies that thermally activated diffusion processes (volume diffusion...) cannot be geologically significant. Consequently, the blocking temperature concept which rests on the opposite assumption now appears questionable. The fact that a mica does not necessarily behave as open above its “blocking temperature” necessitates at least a clear distinction between opening- and sealing-temperatures.

Notes: Abstract Ellenbergerite occurs as purple millimetre-size grains associated with talc, kyanite, clinochlore, rutile, and zircon in composite inclusions within decimetre-large pyrope crystals (90–98 mole percent end-member) in the quartzite layer of the Dora Maira massif, Western Alps, from which coesite has been recently reported (Chopin 1984). It is hexagonal, a=12.255(8), c=4.932(4) Å, Z=1, space group P63. Mohs hardness 6.5; Dmes 3.15, Dcal 3.10; no cleavage. Uniaxial negative and vividly pleochroic,ω colourless,ε colourless to deep lilac with colour zoning. The intensely coloured variety hasω 1.6789(5),ε 1.670(1); microprobe analysis yields SiO2 39.1, P2O5 0.45, Al2O3 25.1, TiO2 4.0, MgO 22.2, FeO 0.20, sum 99.05 wt.% including H2O 8.0 (coulometrically). The formula calculated on a O28(OH)10 basis (implying 7.5 wt.% H2O) is Mg6.71 Fe0.03 Ti0.61 Al6.00 Si7.92 P0.08 O28(OH)10 The colour zoning is due to nearly complete Ti⇌Zr substitution. In addition ellenbergerite may contain more than 8 wt.% P2O5 with strictly correlated changes of Si, Mg, Al and Ti+Zr contents, over 80% of which represent the SiAl⇌PMg substitution. The structure has been determined from 1049 observed independent reflections and refined to R=0.034, Rw=0.031, including six of ten protons. It consists of single chains of face-sharing octahedra with one third vacancies extending along the six-fold screw axes, and of pairs of fully occupied face-sharing octahedra linked by edge-sharing to form octahedral double chains parallel to the twofold screw axes, all interconnected by SiO4 tetrahedra. It may be compared with the dumortierite polymorph with space group P63mc derived hypothetically by Moore and Araki (1978). The structural formula is (Mg,Ti,Zr,□)2 Mg6(Al,Mg)6 (Si,P)2 Si6 O28(OH)10 Face-sharing octahedra are an unusual feature in silicates which results in a dense structure and reflects, considering the common bulk composition, the uncommon high-pressure formation conditions (about 25–30 kbar, 700–800° C). Ti4+-Fe2+ charge transfer between face-sharing octahedra on the six-fold screw axes most likely accounts for the absorption scheme.

Notes: Abstract Three meta-acidic rocks from the western Italian Alps, a magnesiochloritoid-bearing “metapelite” from the Monte Rosa massif, a coesite-pyrope-“quartzite” from the Dora Maira massif and the Monte Mucrone granite in the Sesia Zone, have been studied by U-Pb zircon, Rb-Sr on whole-rock, apatite and phengite and Sm-Nd wholerock methods. The mineral parageneses of the investigated rocks indicate high- to very-high-pressure and medium-to-high-temperature metamorphism. This combined isotopic study has enabled us to constrain the ages of magmatic and metamorphic events and also to compare the behaviour of U-Pb zircon systems in three intensely metamorphosed areas of the Pennine domain. The U-Pb zircon data have yielded a magmatic age for the Monte Mucrone granite at 286±2 Ma. This result confirms the occurence of late-Hercynian magmatism in the Sesia Zone, as in other Austro-Alpine units and in other areas of the European crystalline basement. In the Monte Rosa massif, a geologically meaningless lower intercept age of 192±2 Ma has been interpreted as an artefact due to a complex evolution of the U-Pb zircon system. The magmatic shape of the zircons implies a magmatic or volcano-sedimentary protolith for this rock, originally considered as a metasediment. The very-high-pressure metamorphism in the Dora Maira “quartzite” has produced an opening of the U-Pb zircon system at 121+12−29 Ma. The Rb-Sr data support the occurence of high-grade metamorphism during Cretaceous times. Phengites model ages are slightly younger than the U-Pb zircon lower intercept ages due to cooling phenomena or possible response of the phengites to a later deformation. The Nd model ages from the whole-rock samples, as well as the U-Pb upper intercept ages from zircons of all three investigated rocks, indicate the presence of Proterozoic crustal components inherited from the precursors of these meta-acidic rocks. The studied zircon populations and their U-Pb systems apparently showed open-system behaviour only when affected by extreme metamorphic conditions (700–750° C, 〉 28 kbar), whereas eclogite-facies conditions of 500–550° C and 14–16 kbar were not enough to disturb significantly the U-Pb zircon evolution. It is also probable that the sedimentary or magmatic origin of the protoliths of these meta-acidic rocks, which involved different characteristics such as grain-size and fluid phase concentration and composition, could be another important factor controlling the U-Pb zircon system behaviour during metamorphic events.

Notes: Abstract The polymorphic relations for Mg3(PO4)2 and Mg2PO4OH have been determined by reversed experiments in the temperature-pressure (T-P) range 500–1100 °C, 2–30 kbar. The phase transition between the low-pressure phase farringtonite and Mg3(PO4)2-II, the Mg analogue of sarcopside, is very pressure dependent and was tightly bracketed between 625 °C, 7 kbar and 850 °C, 9 kbar. The high-temperature, high-pressure polymorph, Mg3(PO4)2-III, is stable above 1050 °C at 10 kbar and above 900 °C at 30 kbar. The low-pressure stability of farringtonite is in keeping with its occurrence in meteorites. The presence of iron stabilizes the sarcopside-type phase towards lower P. From the five Mg2PO4OH polymorphs only althausite, holtedahlite, β-Mg2PO4OH (the hydroxyl analogue of wagnerite) and ɛ-Mg2PO4OH were encountered. Relatively speaking, holtedahlite is the low-temperature phase (〈600 °C), ɛ-Mg2PO4OH the high-temperature, low-pressure phase and β-Mg2PO4OH the high-temperature, high-pressure phase, with an intervening stability field for althausite which extends from about 3 kbar at 500 °C to about 12 kbar at 800 °C. Althausite and holtedahlite are to be expected in F-free natural systems under most geological conditions; however, wagnerite is the most common Mg-phosphate mineral, implying that fluorine has a major effect in stabilizing the wagnerite structure. Coexisting althausite and holtedahlite from Modum, S. Norway, show that minor fluorine is strongly partitioned into althausite (KD F/OH≈ 4) and that holtedahlite may incorporate up to 4 wt% SiO2. Synthetic phosphoellenbergerite has a composition close to (Mg0.9□0.1)2Mg12P8O38H8.4. It is a high-pressure phase, which breaks down to Mg2PO4OH + Mg3(PO4)2 + H2O below 8.5 kbar at 650 °C, 22.5 kbar at 900 °C and 30 kbar at 975 °C. The stability field of the phosphate end-member of the ellenbergerite series extends therefore to much lower P and higher T than that of the silicate end-members (stable above 27 kbar and below ca. 725 °C). Thus the Si/P ratio of intermediate members of the series has a great barometric potential, especially in the Si-buffering assemblage with clinochlore + talc + kyanite + rutile + H2O. Application to zoned ellenbergerite crystals included in the Dora-Maira pyrope megablasts, western Alps, reveals that growth zoning is preserved at T as high as 700–725 °C. However, the record of attainment of the highest T and/or of decreasing P through P-rich rims (1 to 2 Si pfu) is only possible in the presence of an additional phosphate phase (OH-bearing or even OH-dominant wagnerite in these rocks), otherwise the trace amounts of P in the system remain sequestered in the core of Si-rich crystals (5 to 8 Si pfu) and can no longer react.

Notes: Abstract Magnesiocarpholite has been synthesized on its own composition between 15 and 25 kb water pressure and 415°–600° C. Best conditions are 25 kb-550° C, starting from a mixture of oxides and synthetic cordierite. Within the MgO-Al2O3-SiO2-H2O system, possible substitutions appear to be very limited in magnesiocarpholite. Cell-parameters are a=13.706(3), b= 20.075(3), c=5.107(l) Å, space group Ccca. The larger cell, as compared with the most magnesian natural carpholites, is tentatively ascribed to structural disorder. Preliminary stability data confirm the low-temperature character of this mineral which is shown to be a high-pressure equivalent of sudoite+quartz.

Notes: Abstract A phengite-talc-chloritoid-chlorite-kyanite-quartz assemblage is reported from a nearly undeformed quartz-rich metapelite found in the Monte Rosa massif (Western Alps). Chloritoid contains up to 74 mol % of the Mg end member and is the most magnesian ever reported. Textural relationships and mineral compositions suggest equilibrium and therefore a low-variance assemblage which represents the high-pressure stability limit of chlorite+quartz according to the terminal reaction $${\text{chlorite + quartz }} \rightleftarrows {\text{ talc + chloritoid + kyanite + H}}_{\text{2}} {\text{O}}{\text{.}}$$ Mineral compositions combined with new experimental data on the stability of the Mg-chloritoid end member lead, for a temperature close to 500° C, to a pressure estimate of 16 kbar and a water activity of 0.6 which is supported by fluid inclusions study. Chloritoid composition is in fact a fine metamorphic indicator which opens new ways for barometry in high-grade blueschists. It demonstrates here the existence of a high-pressure metamorphism in the Monte Rosa massif. The assemblage remained mineralogically unaffected during the subsequent lower-pressure evolution. Two size fractions of the single phengite generation were analysed by the 39Ar-40Ar incremental release method. Both spectra are identical with a plateau at 110±3 Ma representing over 96% of the 39Ar degassed. The ages of the first heating steps are discordant and increase with increasing temperature from values near 70 Ma to the plateau age. Isotope correlation diagrams show two 36Ar components, one released at high temperature and correlated with 40Ar and 39Ar, the other released at low temperature in a mixture of atmospheric argon and of a loosely held argon of 70 Ma apparent age. The 110 Ma plateau age may reflect the presence of homogeneously incorporated excess argon, the 70 Ma value might then be a true age. However we favour the alternative hypothesis that the 110 Ma plateau age is a true age, implying that the internal crystalline massifs of the Western Alps have endured high-pressure metamorphism as early as mid-Cretaceous. Whatever the interpretation chosen, the preserved high-pressure mineral assemblage remained isotopically unaffected during the low-pressure mid-Tertiary event which is recorded by the 37 Ma plateau age of phengite from a foliated, recrystallised quartzite collected in the same, westernmost part of the massif. The contrasting behaviour of the two samples shows that even at temperatures as high as 400–450° C deformation and recrystallisation are also major controlling factors of isotope mobility.

Notes: Abstract 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.