Johannes C. Hunziker

The evolution of illite to muscovite: mineralogical and isotopic data from the Glarus Alps, Switzerland

Thirty-five illite and muscovite concentrates were extracted from Triassic and Permian claystones, shales, slates and phyllites along a cross-section from the diagenetic Alpine foreland (Tabular Jura and borehole samples beneath the Molasse Basin) to the anchi- and epimetamorphic Helvetic Zone of the Central Alps. Concentrates and thin sections were investigated by microscopic, X-ray, infrared, Mössbauer, thermal (DTA and TG), wet chemical, electron microprobe, K-Ar, Rb-Sr, 40Ar/39Ar and stable isotope methods.With increasing metamorphic grade based on illite “crystallinity” data (XRD and IR) the following continuous changes are observed: (i) the 1Md→2M1 polymorph transformation is completed in the higher grade anchizone; (ii) K2O increases from 6–8 wt. % (diagenetic zone) to 8.5–10% (anchizone) to 10–11.5% (epizone), reflecting an increase in the total negative layer charge from 1.2 to 2.0; (iii) a decrease of the chemical variation of the mica population with detrital muscovite surviving up to the anchizone/ epizone boundary; iv) a shift of an endothermic peak in differential thermal curves from 500 to 750° C; (v) K-Ar and Rb-Sr apparent ages of the fraction <2 μm decrease from the diagenetic zone to the epizone, K-Ar ages being generally lower than Rb-Sr ages. The critical temperature for total Ar resetting is estimated to be 260±30° C. K-Ar and Rb-Sr ages become concordant when the anchizone/ epizone boundary is approached. The stable isotope data, on the other hand, show no change with metamorphic grade but are dependent on stratigraphic age.These results suggest that the prograde evolution from 1 Md illite to 2M1 muscovite involves a continuous lattice restructuration without rupture of the tetrahedral and octahedral bonds and change of the hydroxyl radicals, however this is not a recrystallization process. This restructuration is completed approximately at the anchizone/epizone boundary. The isotopic data indicate significant diffusive loss of 40Ar and 87Sr prior to any observable lattice reorganization. The restructuration progressively introduces a consistent repartition of Ar and K in the mineral lattices and is outlined by the 40Ar/39Ar age spectra.Concordant K-Ar and Rb-Sr ages of around 35-30 Ma. with concomitant concordant 40Ar/39Ar release spectra are representative for the main phase of Alpine metamorphism (Calanda phase) in the Glarus Alps. A second age group between 25 and 20 Ma. can probably be attributed to movements along the Glarus thrust (Ruchi phase), while values down to 9 Ma., in regions with higher metamorphic conditions, suggest thermal conditions persisting at least until the middle Tortonian.

Dating of deformation phases using K-Ar and 40Ar/39Ar techniques: results from the Northern Apennines

Paleozoic to Oligocene metasedimentary rocks present in the Alpi Apuane region of the Northern Apennines, Italy, have been sequentially deformed during a Tertiary progressive deformation. In an attempt to date the individual deformation episodes, over 50 conventional K-Ar and 1140 Ar/39Ar incremental gas release analyses have been carried out on fine grained white micas separated from samples whose structural settings were well known. Mineralogy, X-ray diffractometry, and thin-section analyses indicate that the constituent muscovite and phengite formed under metamorphic conditions of 3–4 kbars and 300–400°C during all deformational phases. Pre-existing micas were variably crenulated during each subsequent deformational phase. Both K-Ar and 40Ar/39Ar analyses were carried out on 0.6-2μm, 2–6 μm and 6–20 μm size separates of the phengitic white mica. Although the K-Ar apparent ages range from 11 to 27 Ma and are consistent with available stratigraphic constraints, the 40Ar/39Ar age spectra display variable internal discordancy. These isotopic data indicate that: (1) both the K-Ar and 40Ar/39Ar total-gas ages decrease as the degree of crenulation increases; (2) the K-Ar and 40Ar/39Ar total-gas ages decrease as grain size decreases; (3) for each sample, characteristics of the 40Ar/39Ar age spectra depend upon grain size, with fine sizes yielding discordant patterns which systematically increase in apparent age from low to high temperature and (4) phengitic micas associated with earliest structures yield generally older ages than micas associated with later structures. The isotopic results are interpreted to indicate that the major deformation phase (D1) occurred at approximately 27 Ma with subsequent pulses ending by c. 10 Ma. These results may be combined with finite strain data to suggest that the region was deformed at strain rates between 10−15 and 10−14 s−1. A 27 Ma age indicates Mid-Oligocene initiation of plate tectonic activity in the Western Mediterranean and concomitant deformation in the Northern Apennines.

Equilibrium-disequilibrium relations in the Monte Rosa Granite, Western Alps: Petrological, Rb-Sr and stable isotope data

AbstractNine samples from the Monte Rosa Granite have been investigated by microscopic, X-ray, wet chemical, electron microprobe, stable isotope and Rb-Sr and K-Ar methods. Two mineral assemblages have been distinguished by optical methods and dated as Permian and mid-Tertiary by means of Rb-Sr age determinations. The Permian assemblage comprises quartz, orthoclase, oligoclase, biotite, and muscovite whereas the Alpine assemblage comprises quartz, microcline, albite+epidote or oligoclase, biotite, and phengite. Disequilibrium between the Permian and Alpine mineral assemblages is documented by the following facts: (i) Two texturally distinguishable generations of white K-mica are 2 M muscovite (Si=3.1–3.2) and 2 M or 3 T phengite (Si=3.3–3.4). Five muscovites show Permian Rb-Sr ages and oxygen isotope fractionations indicating temperatures between 520 and 560 ° C; however, K-Ar ages are mixed or rejuvenated. Phengite always shows mid-Tertiary Rb-Sr ages, (ii) Two biotite generations can be recognized, although textural evidence is often ambiguous. Three out of four texturally old biotites show mid-Tertiary Rb-Sr cooling ages while the oxygen isotopic fractionations point to Permian, mixed or Alpine temperatures, (iii) Comparison of radiogenic and stable isotope relations indicates that the radiogenic isotopes in the interlayer positions of the micas were mobilized during Alpine time without recrystallization, that is, without breaking Al-O or Si-O bonds. High Ti contents in young muscovites and biotites also indicate that the octahedral (and tetrahedral) sites remained undisturbed during rejuvenation. (iv) “Isotopic reversals” in the order of O18 enrichment between K-feldspar and albite exist. Arguments for equilibrium during Permian time are meagre because of Alpine overprinting effects. Texturally old muscovites show high temperatures and Permian Rb-Sr ages in concordancy with Rb-Sr whole rock ages. For the tectonically least affected samples, excellent concordance between quartz-muscovite and quartz-biotite “Permian temperatures” implies oxygen isotope equilibrium in Permian time which was undisturbed during Alpine metamorphism. Arguments for equilibrium during the mid-Tertiary metamorphism are as follows: (i) Mid-Tertiary Rb-Sr mineral isochrons of up to six minerals exist, (ii) Oxygen isotope temperatures of coexisting Alpine phengites and biotites are concordant.The major factor for the adjustment of the Permian assemblages to Alpine conditions was the degree of Alpine tectonic overprinting rather than the maximum temperatures reached during the mid-Tertiary Alpine metamorphism. The lack of exchange with externally introduced fluid phases in the samples least affected by tectonism indicates that the Monte Rosa Granite “stewed in its own juices”. This seems to be the major cause for the persistence of Permian ages and corresponding temperatures.

A Nd and Sr isotopic study of the Ivrea zone, Southern Alps, N-Italy

The Ivrea zone represents a tilted cross section through deep continental crust. Sm-Nd isotopic data for peridotites from Baldissero and Balmuccia and for a suite of gabbros from the mafic formation adjacent to the Balmuccia peridotite provide evidence for an event of partial melting 607±19 Ma ago in an extended mantle source with ɛ607Nd=+0.4±0.3. The peridotites are interpreted as the corresponding melt residue, the lower part of the mafic formation as the complementary melts which underwent further differentiation immediately after extraction. The Finero body represents a complex with layers of phlogopite peridotite, hornblende peridotite, and amphibole-rich gabbro. The isotopic signatures fall into two groups: (1) highly radiogenic Nd and low-radiogenic Sr characterize the phlogopite-free, amphibole-rich rocks, whereas (2) low-radiogenic Nd and highly radiogenic Sr is found in ultramafics affected by “phlogopite metasomatism”. Phlogopite metasomatism in the Ivrea zone is dated by a Rb-Sr whole rock isochron yielding 293±13 Ma. It was fed by K-rich fluids which were probably derived from metasediments. The high initial ɛ293Ndvalue of about +7.5 for phlogopite-free samples indicates a high time-integrated Sm/Nd ratio in the Finero protolith 293 Ma ago. Sm-Nd analyses of metapelites from the paragneiss series yield Proterozoic “crustal residence ages” of 1.2 to 1.8 Ga. Internal Sm-Nd isochrons for three garnetiferous rocks show that closure of garnet at temperatures around 600° C or even lower occurred about 250 Ma ago.

K--Ar and Rb--Sr Dating of Blue Amphiboles, Micas, and Associated Minerals from the Western Alps

The results of 63 new radiometric K-Ar and Rb-Sr measurements on metamorphic minerals from the internal units of the Western Alps show Hercynian, Permian, as well as three Alpine age groups. The first of the Alpine ages cover the period between 78 and 100 m.y. and refer to high pressure parageneses. The second group comprises K-Ar 39 to 50 m.y. ages; these values are affected by some inherited argon, as indicated by Rb-Sr measurements which point to 35–36±4–5 m.y., i.e. similar to the culmination of the Lepontine crystallization. The final group includes 15 to 30 m.y. ages. It is not yet clear which geologic processes have led to this isotope re-equilibration. Large amounts of inherited argon have been found in Alpine metamorphic minerals of the basement rocks.

Regional distribution of white K-mica polymorphs and their phengite content in the Central Alps

Some 150 white K-micas from the Central Alps were analysed for their polymorph and phengite content.Pre-Alpine white K-micas and those belonging to the Meso-Alpine Lepontine Metamorphic “High” show exclusively the 2M1 polymorph. The 3T structural form, on the other hand, has been found in one third of the white K-micas formed during the Alpine regional metamorphism. In most cases this trigonal structure coexists with varying amounts of the 2M1 form. The 3T distribution pattern suggests that this polymorph originated during the Eo-Alpine high-pressure/“low temperature” metamorphism. Provided this interpretation is correct, the sporadic occurrence of this polymorph within the Meso-Alpine staurolite zone may be used as a tracer for the Eo-Alpine metamorphism.The following improved correlation between the (060, 331) reflections of 2M1 white K-micas and the RM-content (= 2Fe2O3+FeO+MgO in molar proportions), based on 24 micas from granitoid rocks, is presented: d(060, 331)= 1.498+0.082 RM.The phengite content of Alpine white K-micas belonging to the assemblage muscovite-biotite-K-feldspar-quartz was estimated from RM values or derived from chemical analyses and was found to be clearly related to metamorphic grade. Phengite-rich micas were formed during the Eo-Alpine high-P/“ low-T” metamorphism while aluminous muscovite was found within the Meso-Alpine thermal high of the Lepontine gneiss area. White K-micas from areas which underwent both the Eo-Alpine and the Meso-Alpine metamorphism display variable phengite contents. Although these micas show Tertiary Rb-Sr and K-Ar ages, the variable phengite content presumably reflects conditions during the Eo-Alpine high-P/“low-T” metamorphism. This interpretation implies that the cations occupying the interlayer positions are more easily equilibrated than those in octahedral and tetrahedral structural sites.A compilation of 3T white K-mica occurrences described in the literature is given in the appendix.

Progressive niedriggradige Metamorphose glaukonitführender Horizonte in den helvetischen Alpen der Ostschweiz

Glauconite-bearing formations of Cretaceous and Tertiary age in the Helvetic zone of the Glarus Alps have been investigated by microscopic, X-ray, wet chemical, electron microprobe, Mössbauer spectroscopic, and K-Ar dating methods. 3 different metamorphic zones with increasing grade can be distinguished (Fig. 3). Original, unmetamorphosed sediments containing glauconite-calcite-quartz±chlorite comprise zone I. The glauconite is very rich in potassium (8–9 wt.%) and the chlorite is Fe-rich. In zone II green stilpnomelane forms by the reaction: glauconite±chlorite + quartz = stilpnomelane + k-feldspar + H2O + O2. The green stilpnomelane contains as much as ten times the amount of K found in brown stilpnomelane, which is believed to be a weathering feature. In zone III biotite appears by the reaction: chlorite + k-feldspar = biotite + stilpnomelane + quartz + H2O. Riebeckite is a possible additional phase in all three zones. Generally, zones I–III are arranged nearly parallel to the Alpine border with metamorphic grade increasing to the south. In the Glarnisch Massif, however, the transition from zone I to zone II is clearly controlled by the overburden of the nappe pile (Fig. 6). The beginning of zone II also seems to coincide with the middle of the anchizone, as defined by illite-crystallinity measurements in adjoining marly shales and slates; this corresponds approximately to the transition from the zeolite facies to the prehnitepumpellyite facies.K-Ar-ages on glauconites regularly decrease when approaching the zone I/II-transition. Field evidence and combined K-Ar age determinations on glauconites, stilpnomelanes and riebeckites point to a peak of the metamorphism during Lower to Middle Oligocene, shortly after the main orogenic phase in this part of the Helvetic Alps.