Low-Temperature, Low-Pressure Metamorphism of Mn-rich Rocks in the Lienne Syncline, Venn--Stavelot Massif (Belgian Ardennes), and the Role of Carpholite

Low-grade Mn-rich metamorphic rocks of the Lienne syncline (westernpart of the Venn–Stavelot Massif, Belgian Ardennes) havebeen re-examined to evaluate the petrological significance ofcarpholite proper, Mn^2$ Al₂[Si₂O₆](OH)₄. Metamorphic P–Tconditions of these rocks are estimated to be {small tilde}300C1–2 kbar, which is in accordance with the exclusive occurrenceof carpholite in low-P rocks such as hydrothermal environmentselsewhere. Carpholite of the Lienne syncline exclusively occursin quartz-rich segregations. Its composition is close to end-member.Thermodynamic calculations confirm that carpholite is a stablephase at low-pressure–low-temperature conditions, in contrastto ferro- and magnesiocarpholite, which are high-pressure minerals.No information is available on the high-P behaviour of carpholite.The occurrence of carpholite is partly closely associated withspessartine-bearing country rocks, or carpholite is alteredto assemblages with spessartine, sudoite, chlorite, muscoviteand paragonite. Spessartine in these rocks contains minor amountsof hydrogarnet component {(H/4)/[Si$(H/4)] = 0.03–0.06}.The presence of carpholite-spessartine assemblages in theselow-P rocks is in contrast to high-pressure metamorphic rocksfrom other areas, where parageneses such as fem/magnesiocarpholite–chloritoidor magnesiocarpholite–chlorite–kyanite occur. Theappearance of carpholite–garnet assemblages in low-P Mn-richrocks can be explained by contrasting phase relations becauseof a high Mn–Mg partition coefficient between the mineralsunder consideration. In rhodo-chrosite-bearing veins in theLienne syncline, nearly complete replacement of carpholite byspessartine and chlorite is due to the continuous reaction carpholite$ rhodochrosite $ quartz = spessartine $ chlorite $ H₂O $ CO₂,which defines a very low X_co, in the temperature range underconsideration. It is suggested that spessartine (possibly containingsome hydrogarnet component), during prograde metamorphism atlow pressure, becomes stable at a temperature of {small tilde}300C KEY WORDS: carpholite; spessartine; sudoite; Venn–Stavelot Massif; Ardemes ^*Corresponding author. Fax: x49/531/3918131. e-mail: t.theye{at}tu.bs.de     

A counter-clockwise P–T path for the Voltri Massif eclogites (Ligurian Alps, Italy)

Integrated petrological and structural investigations of eclogites from the eclogite zone of the Voltri Massif (Ligurian Alps) have been used to reconstruct a complete Alpine P–T deformation path from burial by subduction to subsequent exhumation. The early metamorphic evolution of the eclogites has been unravelled by correlating garnet zonation trends with the chemical variations in inclusions found in the different garnet domains. Garnet in massive eclogites displays typical growth zoning, whereas garnet in foliated eclogites shows rim‐ward resorption, likely related to re‐equilibration during retrogressive evolution. Garnet inclusions are distinctly different from core to rim, consisting primarily of Ca‐, Na/Ca‐amphibole, epidote, paragonite and talc in garnet cores and of clinopyroxene ± talc in the outer garnet domains. Quantitative thermobarometry on the inclusion assemblages in the garnet cores defines an initial greenschist‐to‐amphibolite facies metamorphic stage (M1 stage) at c. 450–500 °C and 5–8 kbar. Coexistence of omphacite + talc + katophorite inclusion assemblage in the outer garnet domains indicate c. 550 °C and 20 kbar, conditions which were considered as minimum P–T estimates for the M2 eclogitic stage. The early phase of retrograde reactions is polyphase and equilibrated under epidote–blueschist facies (M3 stage), characterized by the development of composite reaction textures (garnet necklaces and fluid‐assisted Na‐amphibole‐bearing symplectites) produced at the expense of the primary M2 garnet‐clinopyroxene assemblage. The blueschist retrogression is contemporaneous with the development of a penetrative deformation (D3) that resulted in a non‐coaxial fabric, with dominant top‐to‐the‐N sense of shear during rock exhumation. All of that is overprinted by a texturally late amphibolite/greenschist facies assemblages (M4 & M5 stages), which are not associated with a penetrative structural fabric. The combined P–T deformation data are consistent with an overall counter‐clockwise path, from the greenschist/amphibolite, through the eclogite, the blueschist to the greenschist facies. These new results provide insights into the dynamic evolution of the Tertiary oceanic subduction processes leading to the building up of the Alpine orogen and the mechanisms involved in the exhumation of its high‐pressure roots.     

The assemblage diaspore+quartz in metamorphic rocks: a petrological, experimental and thermodynamic study

The upper pressure limit of pyrophyllite is given by the equilibria (i) pyrophyllite=diaspore+quartz and (ii) pyrophyllite=diaspore+coesite. High- P experimental investigations carried out to locate equilibrium (i) yield brackets between 497 °C/24.8  kbar and 535 °C/25.1  kbar, and between 500 °C/23  kbar and 540 °C/23  kbar. Equilibrium (ii) was bracketed at 550 °C between 26.0 and 28.3  kbar. In the experimental P–T  range, equilibria (i) and (ii) are metastable with respect to kyanite. A stable P–T  grid is calculated using thermodynamic data derived under consideration of the present experimental results. According to these data, the lower pressure limit of the assemblage diaspore+quartz according to equilibrium (i) range from about 12  kbar/300 °C to 20  kbar/430 °C (in the presence of pure water). The upper stability of diaspore+quartz is limited by the reaction diaspore+quartz=kyanite+H₂O at about 450 °C (nearly independent of pressure) and, to higher pressure, by the quartz=coesite transition. Equilibrium (ii) is metastable over the whole P–T  range.
Natural occurrences600.S of the diaspore–quartz assemblage in metamorphic rocks in Sulawesi, New Caledonia, Amorgos and the Vanoise are characterized by minerals indicative of high- P such as ferro-magnesiocarpholite, glaucophane, sodic pyroxene and lawsonite. The metamorphic P–T  conditions of these rocks are estimated to be in the range 300–400 °C, >8  kbar. These data are compatible with the derived P–T  stability field of the diaspore+quartz assemblage. We conclude that, in metamorphic rocks, diaspore+quartz is, as ferrocarpholite, an indicator for unusual low- T  /very high- P settings.     

Experimental study of the stability of sudoite and magnesiocarpholite and calculation of a new petrogenetic grid for the system FeO–MgO–Al2O3–SiO2–H2O

The solid-solid reaction magnesiocarpholite = sudoite + quartz has been bracketed between 350 and 500°C, 6.3 and 7.8 kbar. Because it is impossible to synthesize end-member sudoite, all experiments were carried out using natural minerals as starting materials. Although mineral compositions were very close to those of the end-members, the effect of the fluorine content in carpholite was significant. Particularly in those experiments where sudoite grows at the expense of carpholite, electron microprobe analysis of the run products shows that a more stable F-rich carpholite crystallizes too, and consumes the fluorine released in solution by the breakdown of the original carpholite.
Our experimental results are combined, through a thermodynamic analysis, with a previous data set and with previous experimental data concerning the relative stability of chlorite, talc and magnesiocarpholite with excess of quartz and water as a function of P–T and AlAl(SiMg)_-1 substitutions in phyllosilicates. This allows us to constrain the feasible thermodynamic parameters (H°_f, sud; S ° sud) and (H°_f,car; S °_car) for the Mg end-members. Using the partition coefficients calculated from natural parageneses, we have computed a petrogenetic grid for the system FeO–MgO–Al₂O₃–SiO₂–H₂O. It demonstrates that parageneses involving sudoite and carpholite can be used as indicators of P–T conditions, up to 600° C, 8 kbar for sudoite, and at higher pressure for carpholite.