Metamorphic evolution of a subduction complex, South Shetland Islands, Antarctica

A subduction complex composed of ocean floor material mixed with arc-derived metasediments crops out in the Elephant Island group and at Smith Island, South Shetland Islands, Antarctica, with metamorphic ages of 120-80 Ma and 58-47 Ma? respectively. Seven metamorphic zones (I-VII) mapped on Elephant Island delineate a gradual increase in metamorphic grade from the pumpellyite-actinolite facies, through the crossite-epidote blueschist facies, to the lower amphibolite facies. Geothermometry in garnet-amphibole and garnet-biotite pairs yields temperatures of about 350 degrees C in zone III to about 525 degrees C in zone VII. Pressures were estimated on the basis of Si content in white mica, Al2O3 content in alkali amphibole, Na-M4/Al-IV in sodic-calcic and calcic amphibole, Al-VI/Si in calcic amphibole, and jadeite content in clinopyroxene. Mean values vary from about 6-7.5 kbar in zone II to about 5 kbar in zone VII. Results from the other islands of the Elephant Island group are comparable to those from the main island; Smith Island yielded slightly higher pressures, up to 8 kbar, with temperatures estimated between 300 and 350 degrees C. Zoned minerals and other textural indications locally enable inference of P-T-t trajectories, all with a clockwise evolution. A reconstruction in space and time of these P-T-t paths allows an estimate of the thermal structure in the upper crust during the two ductile deformation phases (D-1 & D-2) that affected the area. This thermal structure is in good agreement with the one expected for a subduction zone. The arrival and collision of thickened oceanic crust may have caused the accretion and preservation of the subduction complex. In this model, D-1 represents the subduction movements expressed by the first vector of the clockwise P-T-t path, D-2 reflects the collision corresponding to the second vector with increasing temperature and decreasing pressure, and D-3 corresponds to isostatic uplift accompanied by erosion, under circumstances of decreasing temperature and pressure.

The Palu Metamorphic Complex, NW Sulawesi, Indonesia: Origin and evolution of a young metamorphic terrane with links to Gondwana and Sundaland

The Palu Metamorphic Complex (PMC) is exposed in a late Cenozoic orogenic belt in NW Sulawesi, Indonesia. It is a composite terrane comprising a gneiss unit of Gondwana origin, a schist unit composed of meta-sediments deposited along the SE Sundaland margin in the Late Cretaceous and Early Tertiary, and one or more slivers of amphibolite with oceanic crust characteristics. The gneiss unit forms part of the West Sulawesi block underlying the northern and central sections of the Western Sulawesi Province. The presence of Late Triassic granitoids and recycled Proterozoic zircons in this unit combined with its isotopic signature suggests that the West Sulawesi block has its origin in the New Guinea margin from which it rifted in the late Mesozoic. It docked with Sundaland sometime during the Late Cretaceous. U–Th–Pb dating results for monazite suggest that another continental fragment may have collided with the Sundaland margin in the earliest Miocene. High-pressure (HP) and ultrahigh-pressure (UHP) rocks (granulite, peridotite, eclogite) are found as tectonic slices within the PMC, mostly along the Palu–Koro Fault Zone, a major strike-slip fault that cuts the complex. Mineralogical and textural features suggest that some of these rocks resided at depths of 60–120 km during a part of their histories. Thermochronological data (U–Th–Pb zircon and 40Ar/39Ar) from the metamorphic rocks indicate a latest Miocene to mid-Pliocene metamorphic event, which was accompanied by widespread granitoid magmatism and took place in an extensional tectonic setting. It caused recrystallization of, and new overgrowths on, pre-existing zircon crystals, and produced andalusite–cordierite–sillimanite–staurolite assemblages in pelitic protoliths, indicating HT–LP (Buchan-type) metamorphism. The PMC was exhumed as a core complex at moderate rates (c. 0.7–1.0 mm/yr) accompanied by rapid cooling in the Plio-Pleistocene. Some of the UHP rocks were transported to the surface at significantly higher rates (⩾16 mm/yr). The results of our study do not support recent plate tectonic reconstructions that propose a NW Australia margin origin for the West Sulawesi block (e.g. Hall et al., 2009).

A structural and metamorphic study of the southern Menderes Massif (Western Turkey)

P-T conditions, paragenetic studies and the relation between mineral growth, deformation and - when possible- isograd minerals have been used to describe the type of metamorphism involved within lower units of the southern Menderes Massif of the Anatolide Belt in western Turkey. The study areas mainly consist of Proterozoic orthogneiss and surrounding schists of presumed Paleozoic age. Both units are seen as nappes in the southern study area, the Çine and the Selimiye nappe, on the whole corresponding to Proterozoic orthogneiss and surrounding schists, respectively. The Çine and Selimiye nappes are part of a complex geological structure within the core series of the Menderes Massif. Their emplacement under lower greenschist facies conditions, would result from closure of the northern Neo-Thethys branch during the Eocene. These two nappes are separated by a major tectonic structure, the Selimiye shear zone, which records top-to-the-S shearing under greenschist facies conditions. Amphibolite to upper amphibolite facies metamorphism is widely developed within the metasedimentary rocks of the Çine nappe whereas no metamorphism exceeding lower amphibolite facies has been observed in the Selimiye nappe. In the southern margin of the Çine Massif, around Selimiye and Millas villages, detailed sampling has been undertaken in order to map mineral isograds within the Selimiye nappe and to specify P-T conditions in this area. The data collected in this area reveals a global prograde normal erosion field gradient from south to north and toward the orthogneiss. The mineralogical parageneses and P-T estimates are correlated with Barrovian-type metamorphism. A jump of P-T conditions across the Selimiye shear zone has been identified and estimated c. 2 kbar and 100 °C which evidences the presence of amphibolite facies metasedimentary rocks near the orthogneiss. Metasedimentary rocks from the overlying Selimiye nappe have maximum P-T conditions of c. 4-5 kbar and c. 525 °C near the base of the nappe. Metasedimentary rocks from the Çine nappe underneath the Selimiye shear zone record maximum P-T conditions of about 7 kbar and >550 °C. Kinematic indicators in both nappes consistently show a top-S shear sense. Metamorphic grade in the Selimiye nappe decreases structurally upwards as indicated by mineral isograds defining the garnet-chlorite zone at the base, the chloritoid-biotite zone and the biotite-chlorite zone at the top of the nappe. The mineral isograds in the Selimiye nappe run parallel to the regional SR foliation. 40Ar/39Ar mica ages indicate an Eocene age of metamorphism in the Selimiye nappe and underneath the Çine nappe in this area. Metasedimentary rocks of the Çine nappe 20-30 km north of the Selimiye shear zone record maximum P-T conditions of 8-11 kbar and 600-650 °C. Kinematic indicators show mainly top-N shear sense associated with prograde amphibolite facies metamorphism. An age of about 550 Ma could be indicated for amphibolite facies metamorphism and associated top-N shear in the orthogneiss and metasedimentary rocks of the Çine nappe. However, there is no evidence for polymetamorphism in the 6 metasedimentary rocks of the Çine nappe, making tectonic interpretations about late Neoproterozoic to Cambrian and Tertiary metamorphic events speculative. In the western margin of the Çine Massif metamorphic mineral parageneses and pressure– temperature conditions lead to similar conclusion regarding the erosion field gradient, prograde normal toward the orthogneiss. The contact between orthogneiss and surrounding metasedimentary rocks is mylonitic and syn-metamorphism. P-T estimates are those already observed within the Selimiye nappe and correlated with lower amphibolite facies parageneses. Finally additional data in the eastern part and a general paragenetic study within the Menderes Massif lower units, the Çine and the Selimiye nappes, strongly suggest a single Barrovian-type metamorphism predating Eocene emplacement of the high pressure–low temperature Lycean and Cycladic blueschist nappes. Metamorphic mineral parageneses and pressure–temperature conditions do not support the recently proposed model of high pressure–low temperature metamorphic overprinting, which implies burial of the lower units of the Menderes Massif up to depth of 30 km, as a result of closure of the Neo-Tethys. According to the geochronological problem outlined during this thesis, there are two possible schemes: either Barrovian-type metamorphism is Proterozoic in age and part of the sediments from Selimiye nappe (lower amphibolite facies) has to be proterozoic of age too, or Barrovian-type metamorphism in Eocene of age. In the first case the structure observed now in the core series would correspond to simple exhumation of Proterozoic basement. In the latter case a possible correlation with closure of Neo-Tethys (sensu stricto, southern branch) is envisaged.

Neotethys closure history of Anatolia: insights from 40Ar–39Ar geochronology and P–T estimation in high pressure metasedimentary rocks

The multiple high-pressure (HP), low-temperature (LT) metamorphic units of Western and Central Anatolia offer a great opportunity to investigate the subduction- and continental accretion-related evolution of the eastern limb of the long-lived Aegean subduction system. Recent reports of the HP–LT index mineral Fe-Mg-carpholite in three metasedimentary units of the Gondwana-derived Anatolide–Tauride continental block (namely the Afyon Zone, the Ören Unit and the southern Menderes Massif) suggest a more complicated scenario than the single-continental accretion model generally put forward in previous studies. This study presents the first isotopic dates (white mica 40Ar–39Ar geochronology), and where possible are combined with P–T estimates (chlorite thermometry, phengite barometry, multi-equilibrium thermobarometry), on carpholite-bearing rocks from these three HP–LT metasedimentary units. It is shown that, in the Afyon Zone, carpholite-bearing assemblages were retrogressed through greenschist-facies conditions at c. 67–62 Ma. Early retrograde stages in the Ören Unit are dated to 63–59 Ma. In the Kurudere–Nebiler Unit (HP Mesozoic cover of the southern Menderes Massif), HP retrograde stages are dated to c. 45 Ma, and post-collisional cooling to c. 26 Ma. These new results support that the Ören Unit represents the westernmost continuation of the Afyon Zone, whereas the Kurudere–Nebiler Unit correlates with the Cycladic Blueschist Unit of the Aegean Domain. In Western Anatolia, three successive HP–LT metamorphic belts thus formed: the northernmost Tavşanlı Zone (c. 88–82 Ma), the Ören–Afyon Zone (between 70 and 65 Ma), and the Kurudere–Nebiler Unit (c. 52–45 Ma). The southward younging trend of the HP–LT metamorphism from the upper and internal to the deeper and more external structural units, as in the Aegean Domain, points to the persistence of subduction in Western Anatolia between 93–90 and c. 35 Ma. After the accretion of the Menderes–Tauride terrane, in Eocene times, subduction stopped, leading to continental collision and associated Barrovian-type metamorphism. Because, by contrast, the Aegean subduction did remain active due to slab roll-back and trench migration, the eastern limb (below Southwestern Anatolia) of the Hellenic slab was dramatically curved and consequently teared. It therefore is suggested that the possibility for subduction to continue after the accretion of buoyant (e.g. continental) terranes probably depends much on palaeogeography.

Mesoproterozoic Deposition, Regional Metamorphism and Deformation in North-Central New Mexico: Evidence from Metamorphic Monazite and Detrital Zircon Geochronology in the Picuris Mountains

Detrital zircon and metamorphic monazite ages from the Picuris Mountains, north central New Mexico, were used to confirm the depositional age of the Marquenas Formation, to document the depositional age of the Vadito Group, and to constrain the timing of metamorphism and deformation in the region. Detrital zircon 207Pb/206Pb ages were obtained with the LA-MC-ICPMS from quartzites collected from the type locality of the Marquenas Formation exposed at Cerro de las Marquenas, and from the lower Vadito Group in the southern and eastern Picuris Mountains. The Marquenas Formation sample yields 113 concordant ages including a Mesoproterozoic age population with four grains ca. 1470 Ga, a broad Paleoproterozoic age peak at 1695 Ma, and minor Archean age populations. Data confirm recent findings of Mesoproterozoic detrital zircons reported by Jones et al. (2011), and show that the Marquenas Formation is the youngest lithostratigraphic unit in the Picuris Mountains. Paleoproterozoic and Archean detrital grains in the Marquenas Formation are likely derived from local recycled Vadito Group rocks and ca. 1.75 Ga plutonic complexes, and ca. 1.46 detrital zircons were most likely derived from exposed Mesoproterozoic plutons south of the Picuris. Ninety-five concordant grains from each of two Vadito Group quartzites yield relatively identical unimodal Paleoproterozoic age distributions, with peaks at 1713-1707 Ma. Eastern exposures of quartzite mapped as Marquenas Formation yield detrital zircon age patterns and metamorphic mineral assemblages that are nearly identical to the Vadito Group. On this basis, I tentatively assigned the easternmost quartzite to the Vadito Group. Zircon grains in all samples show low U/Th ratios, welldeveloped concentric zoning, and no evidence of metamorphic overgrowth events, consistent with an igneous origin. North-directed paleocurrent indicators, such as tangential crossbeds (Soegaard & Eriksson, 1986) and other primary sedimentary structures, are preserved in the Marquenas Formation quartzite. Together with pebble-toboulder metaconglomerates in the Marquenas, these observations suggest that this formation was deposited in a braided alluvial plain environment in response to syntectonic uplift to the south of the Picuris Mountains. Metamorphic monazite from two Vadito Group quartzite samples were analyzed with an electron microprobe (EMP). Elemental compositional variation with respect to Th and Y define core and rim domains in monazite grains, and show lower concentrations of Th (1.46-1.52 wt%) and Y (0.67 wt%) in the cores, and higher concentrations of Th (1.98 wt%) and Y (1.06 wt%) in the rims. Results show that Mesoproterozoic core and rim ages from five grains overlap within uncertainty, ranging from 1395-1469 Ma with an average age of 1444 Ma. This 1.44 Ga average age is the dominant timing of metamorphic monazite growth in the region, and represents the timing of metamorphism experienced by the region. An older 1630 Ma core observed in sample CD10-12 may be interpreted as a result of low temperature metamorphism in lower Vadito Group rocks due to heat from ca. 1.65 Ga granitic intrusions. Core ages ca. 1.5 Ga are likely due to a mixing age of two different age domains during analyses. Confirmed sedimentation at 1.48-1.45 Ga and documented mid-crustal regional metamorphism in northern New Mexico ca. 1.44-1.40 are likely associated with a Mesoproterozoic orogenic event.

Metamorphic and geochronogical study of the Triassic El Oro metamorphic complex, Ecuador: Implications for high-temperature metamorphism in a forearc zone

In the forearc of the Andean active margin in southwest Ecuador, the El Oro metamorphic complex exhibits a well exposed tilted forearc section partially migmatized. We used Raman spectroscopy on carbonaceous matter (RSCM) thermometry and pseudosections coupled with mineralogical and textural studies to constrain the pressure–temperature (P–T) evolution of the El Oro metamorphic complex during Triassic times. Our results show that anatexis of the continental crust occurred by white-mica and biotite dehydration melting along a 10 km thick crustal domain (from 4.5 to 8 kbar) with increasing temperature from 650 to 700 °C. In the biotite dehydration melting zone, temperature was buffered at 750–820 °C in a 5 km thick layer. The estimated average thermal gradient during peak metamorphism is of 30 °C/km within the migmatitic domain can be partitioned into two apparent gradients parts. The upper part from surface to 7 km depth records a 40–45 °C/km gradient. The lower part records a quasi-adiabatic geotherm with a 10 °C/km gradient consistent with an isothermal melting zone. Migmatites U–Th–Pb geochronology yielded zircon and monazite ages of 229.3 ± 2.1 Ma and 224.5 ± 2.3 Ma, respectively. This thermal event generated S-type magmatism (the Marcabeli granitoid) and was immediately followed by underplating of the high-pressure low-temperature (HP-LT) Arenillas–Panupalí unit at 225.8 ± 1.8 Ma. The association of high-temperature low-pressure (HT-LP) migmatites with HP-LT unit constitutes a new example of a paired metamorphic belt along the South American margin. We propose that in addition to crustal thinning, underplating of the Piedras gabbroic unit before 230 Ma provided the heat source necessary to foster crustal anatexis. Furthermore, its MORB signature shows that the asthenosphere was involved as the source of the heat anomaly. S-type felsic magmatism is widespread during this time and suggests that a large-scale thermal anomaly affected a large part of the South American margin during the late Triassic. We propose that crustal anatexis is related to an anomaly that arose during subduction of the Panthalassa ocean under the South American margin. Slab verticalization or slab break-off can be invoked as the origin of the upwelling of the asthenosphere.

The igneous charnockite—high-K alkali-calcic I-type granite—incipient charnockite association in Trivandrum Block, southern India

The Pan-African (640 Ma) Chengannoor granite intrudes the NW margin of the Neoproterozoic high-grade metamorphic terrain of the Trivandrum Block (TB), southern India, and is spatially associated with the Cardamom hills igneous charnockite massif (CM). Geochemical features characterize the Chengannoor granite as high-K alkali-calcic I-type granite. Within the constraints imposed by the high temperature, anhydrous, K-rich nature of the magmas, comparison with recent experimental studies on various granitold source compositions, and trace- and rare-earth-element modelling, the distinctive features of the Chengannoor granite reflect a source rock of igneous charnockitic nature. A petrogenetic model is proposed whereby there was a period of basaltic underplating; the partial melting of this basaltic lower crust formed the CM charnockites. The Chengannoor granite was produced by the partial melting of the charnoenderbites from the CM, with subsequent fractionation dominated by feldspars. In a regional context, the Chengannoor I-type granite is considered as a possible heat source for the near-UHT nature of metamorphism in the northern part of the TB. This is different from previous studies, which favoured CM charnockite as the major heat source. The Occurrence of incipient charnockites (both large scale as well as small scale) adjacent to the granite as well as pegmatites (which contain CO2, CO2-H2O, F and other volatiles), suggests that the fluids expelled from the alkaline magma upon solidification generated incipient charnockites through fluid-induced lowering of water activity. Thus the granite and associated alkaline pegmatites acted as conduits for the transfer of heat and volatiles in the Achankovil Shear Zone area, causing pervasive as well as patchy charnockite formation. The transport Of CO2 by felsic melts through the southern Indian middle crust is suggested to be part of a crustal-scale fluid system that linked mantle heat and CO2 input with upward migration of crustally derived felsic melts and incipient charnockite formation, resulting in an igneous charnockite - I-type granite - incipient charnockite association.

Vibrational spectroscopy of phthalocyanine and naphthalocyanine in sandwich-type (na)phthalocyaninato and porphyrinato rare earth complexes : (Part 10) The infrared and Raman characteristics of phthalocyanine in heteroleptic bis(phthalocyaninato) rare earth complexes with decreased molecular symmetry

The infrared (IR) spectroscopic data for a series of eleven heteroleptic bis(phthalocyaninato) rare earth complexes MIII(Pc)[Pc(α-OC5H11)4] (M = Sm–Lu, Y) [H2Pc = unsubstituted phthalocyanine, H2Pc(α-OC5H11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyanine] have been collected with 2 cm−1 resolution. Raman spectroscopic properties in the range of 500–1800 cm−1 for these double-decker molecules have also been comparatively studied using laser excitation sources emitting at 632.8 and 785 nm. Both the IR and Raman spectra for M(Pc)[Pc(α-OC5H11)4] are more complicated than those of homoleptic bis(phthalocyaninato) rare earth analogues due to the decreased molecular symmetry of these double-decker compounds, namely C4. For this series, the IR Pc√− marker band appears as an intense absorption at 1309–1317 cm−1, attributed to the pyrrole stretching. With laser excitation at 632.8 nm, Raman vibrations derived from isoindole ring and aza stretchings in the range of 1300–1600 cm−1 are selectively intensified. In contrast, when excited with laser radiation of 785 nm, the ring radial vibrations of isoindole moieties and dihedral plane deformations between 500 and 1000 cm−1 for M(Pc)[Pc(α-OC5H11)4] intensify to become the strongest scatterings. Both techniques reveal that the frequencies of pyrrole stretching, isoindole breathing, isoindole stretchings, aza stretchings and coupling of pyrrole and aza stretchings depend on the rare earth ionic size, shifting to higher energy along with the lanthanide contraction due to the increased ring-ring interaction across the series. The assignments of the vibrational bands for these compounds have been made and discussed in relation to other unsubstituted and substituted bis(phthalocyaninato) rare earth analogues, such as M(Pc)2 and M(OOPc)2 [H2OOPc = 2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyanine].

Vibrational spectroscopy of phthalocyanine and naphthalocyanine in sandwich-type (na)phthalocyaninato and porphyrinato rare earth complexes: Part 14. The infrared and Raman characteristics of phthalocyanine in “pinwheel-like” homoleptic bis[1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninato] rare earth(III) double-decker complexes

The infrared (IR) spectroscopic data and Raman spectroscopic properties for a series of 13 “pinwheel-like” homoleptic bis(phthalocyaninato) rare earth complexes M[Pc(α-OC5H11)4]2 [M = Y and Pr–Lu except Pm; H2Pc(α-OC5H11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyanine] have been collected and comparatively studied. Both the IR and Raman spectra for M[Pc(α-OC5H11)4]2 are more complicated than those of homoleptic bis(phthalocyaninato) rare earth analogues, namely M(Pc)2 and M[Pc(OC8H17)8]2, but resemble (for IR) or are a bit more complicated (for Raman) than those of heteroleptic counterparts M(Pc)[Pc(α-OC5H11)4], revealing the decreased molecular symmetry of these double-decker compounds, namely S8. Except for the obvious splitting of the isoindole breathing band at 1110–1123 cm−1, the IR spectra of M[Pc(α-OC5H11)4]2 are quite similar to those of corresponding M(Pc)[Pc(α-OC5H11)4] and therefore are similarly assigned. With laser excitation at 633 nm, Raman bands derived from isoindole ring and aza stretchings in the range of 1300–1600 cm−1 are selectively intensified. The IR spectra reveal that the frequencies of pyrrole stretching and pyrrole stretching coupled with the symmetrical CH bending of –CH3 groups are sensitive to the rare earth ionic size, while the Raman technique shows that the bands due to the isoindole stretchings and the coupled pyrrole and aza stretchings are similarly affected. Nevertheless, the phthalocyanine monoanion radical Pc′− IR marker band of bis(phthalocyaninato) complexes involving the same rare earth ion is found to shift to lower energy in the order M(Pc)2 > M(Pc)[Pc(α-OC5H11)4] > M[Pc(α-OC5H11)4]2, revealing the weakened π–π interaction between the two phthalocyanine rings in the same order.

Raman spectroscopic characteristics of phthalocyanine and naphthalocyanine in sandwich-type phthalocyaninato and porphyrinato rare earth complexes Part 5. – Raman spectroscopic characteristics of naphthalocyanine in mixed [tetrakis(4-tert-butylphenyl)porphyrinato]-(naphthalocyaninato) rare earth double-deckers

Raman spectra were recorded in the range 400–1800 cm−1 for a series of 15 mixed \[tetrakis(4-tert-butylphenyl)porphyrinato](2,3-naphthalocyaninato) rare earth double-deckers M(TBPP)(Nc) (M = Y; La–Lu except Pm) using laser excitation at 632.8 and 785 nm. Comparisons with bis(naphthalocyaninato) rare earth counterparts reveal that the vibrations of the metallonaphthalocyanine M(Nc) fragment dominate the Raman features of M(TBPP)(Nc). When excited with radiation of 632.8 nm, the most intense vibration appears at about 1595 cm−1, due to the naphthalene stretching. These complexes exhibit the marker Raman band for Nc•− as a medium-intense band in the range 1496–1507 cm−1, attributed to the coupling of pyrrole and aza stretching, while the marker Raman band of Nc2− in intermediate-valence Ce(TBPP)(Nc) appears as a strong band at 1493 cm−1 and is due to the isoindole stretchings. By contrast, when excited with radiation of 785 nm that is in close resonance with the main Q absorption band of the naphthalocyanine ligand, the ring radial vibrations at ca 680 and 735 cm−1 for MIII(TBPP)(Nc) are selectively intensified and are the most intense bands. For the cerium double-decker, the most intense vibration also acting as the marker Raman band of Nc2− appears at 1497 cm−1 with contributions from both pyrrole CC and aza CN stretches. The same vibrational modes show weak to medium intensity scattering at 1506–1509 cm−1 for MIII(TBPP)(Nc) and this is the marker Raman band of Nc•− when thus excited. The scatterings due to the Nc breathings, ring radial vibration, aza group stretchings, naphthalene stretchings, benzoisoindole stretchings and the coupling of pyrrole CC and aza CN stretchings in MIII(TBPP)(Nc) are all slightly blue shifted along with the decrease in rare earth ionic radius, confirming the effects of increased ring–ring interactions on the Raman characteristics of naphthalocyanine in the mixed ring double-deckers.