Titanite Growth Research Articles

Mineral chemistry and in-situ U-Pb geochronology of altered pegmatite from the vicinity of the Strashimir Pb-Zn vein deposit

The current study presents new mineralogical, geochemical and geochronological data for a pegmatite body hosted in gneisses and marbles from the vicinity of the Strashimir Pb-Zn vein deposit, Madan ore district, South Bulgaria. The mineral composition of the studied pegmatite is represented by oligoclase–andesine (An10.1–33.2) and albite (An0–7.6), which prevail over K-feldspar (Or87.9–92.4), and quartz. The established accessory minerals are allanite-(Ce), titanite, apatite and zircon. The pegmatite/marble contact is affected by later hydrothermal silicate-carbonate alteration without detected ore mineralization, despite the spatial proximity with the Strashimir Pb-Zn vein deposit. Epidote-group minerals in pegmatite are defined as members of the clinozoisite–epidote series. As a major constituent of the hydrothermal alteration zone, they are manifested in two well-distinguished generations along with chlorite, quartz and carbonates. The calculated temperature of chlorite mineralization yields T° of crystallization in the range of 223–266 °C. As a result of the hydrothermal fluid circulation, the accessory allanite-(Ce) is transformed to REE-rich epidote-clinozoisite, marked by depletion of REE and Fe and enrichment of Si, Al, and Ca. Due to the limited mobility of REE in fluids, after leaching these elements are incorporated in nearby crystallized epidotes. According to the occurrence, mineral association and chemical properties, three titanite populations are distinguished in the pegmatite. Two of them were in-situ dated by the LA-ICP-MS U-Pb method and reveal overlapping ages of 39.9±2.1 Ma and 39.5±2.2 Ma (39.3±1.2 Ma combining all titanite analyses). The ages are interpreted as titanite growth in a pegmatite body related to granitic melts in the Late Alpine high-metamorphic units (Madan Unit) of the Central Rhodopes. Hydrothermal fluids either did not affect the U-Pb isotope system of the titanites or were derived from the same fluid-rich melt.

Making sense of shear zone fabrics that record multiple episodes of deformation: Electron backscatter diffraction–derived and crystallographic vorticity axis–enhanced petrochronology

Abstract We present a new method of linking microstructures, electron backscatter diffraction (EBSD)–derived crystallographic vorticity axis (CVA) analysis, and titanite petrochronology to directly link fabric development to specific deformation events in shear zone rocks with complex histories. This approach is particularly useful where overprinting is incomplete, such that it is unknown which fabric is being dated by the petrochronometer. Here, we compared single-phase CVA patterns of fabric-forming minerals with those of synkinematic petrochronometers (e.g., titanite) to associate the timing of fabric development with deformational events in the middle crust of the George Sound shear zone, Fiordland, New Zealand. The host rocks to the George Sound shear zone include the Carboniferous Large Pluton, where titanite petrochronology demonstrates an unequivocally Cretaceous age of metamorphic titanite growth within mylonitic foliation. However, the host rocks show two distinct CVA patterns: a transtensional deformation event recorded by quartz and plagioclase, and a pure-shear–dominated transpressional deformation event recorded by biotite and titanite. Therefore, the transpressional CVA pattern of the titanite, coupled with its Cretaceous age, shows that it cannot be used to date the quartz and plagioclase fabric developed in response to an older transtensional deformation event. These results demonstrate the necessity of combining EBSD and CVA analysis with petrochronology to demonstrate that synkinematic accessory phase petrochronometers show the same kinematic deformation geometry (i.e., CVA pattern) as the fabric being dated.

Zircon as a Recorder of Trace Element Changes during High-Grade Metamorphism of Neoarchean Lower Crust, Shevaroy Block, Eastern Dharwar Craton, India

AbstractSystematic changes in whole-rock chemistry, mineralogy, mineral textures, and mineral chemistry are seen along a ca. 95-km traverse of late Archean granitoid orthogneisses in the Shevaroy Block, Eastern Dharwar Craton, southern India. The traverse passes from amphibolite-grade gneisses in the north to granulite-grade rocks (charnockite) in the south. Changes include whole-rock depletion of Rb, Cs, Th, and U in the granulite grade rocks as relative to the amphibolite grade gneisses, and oxidation trends regionally from highly oxidised granulite-facies rocks near the magnetite–haematite buffer to relatively reduced amphibolite-facies rocks below the fayalite-magnetite-quartz. Rare earth elements show limited mobility and are hosted a variety of minerals whose presence is dependent on the metamorphic grade ranging from titanite and allanite in the amphibolite-facies rocks to monazite in the vicinity of the orthopyroxene-in isograd to apatite in the granulite-grade charnockite. Cathodoluminescence and back-scattered electron sub-grain imaging and sensitive high-resolution ion microprobe analysis of zircon from 29 samples of dioritic, tonalitic, and granitic orthogneiss from the traverse reveals magmatic zircon cores that record the emplacement of the granitoid protoliths mostly about 2580 to 2550 Ma, along with a few older mid to late Archean tonalites. Protolith zircon was modified during metamorphism by overgrowth and/or replacement. Relative to igneous cores, U-enriched metamorphic zircon, dominant in the amphibolite-grade gneisses, formed at ca. 2530 Ma, predating retrograde titanite growth at ca. 2500 Ma. Uranium-depleted mantles grew on zircon between 2530 and 2500 Ma in granulite-grade samples south of the orthopyroxene-in isograd. In some of these samples, the U-depleted metamorphic zircon is preceded by mantles of U-undepleted zircon, indicating a progression of metamorphic zircon growth with increasingly depleted compositions between 2530 and 2500 Ma. With increasing metamorphic grade (from amphibolite to granulite) and oxidation state, allanite and monazite disappear from the assemblage and zircon became depleted in U and Th. Whole-rock U-Th compositions became decoupled from relict magmatic zircon compositions, reflecting the development of U-depleted metamorphic zircon and indicating that whole-rock chemical differences along the traverse were produced during metamorphism, rather than just reflecting differences in dioritic vs granitic protoliths. Although in situ anatexis and melt extraction may have played a role, whole-rock and zircon depletion of trace elements can be explained by the action of externally derived, oxidising, low-H2O activity hypersaline fluids migrating up through the mid to lower crust. Fluids and element migration during metamorphism may be the end result of subduction related processes that cumulated in the collision and concatenation of island arcs and continental blocks. These tectonic processes assembled the Dharwar Craton at the end of the Archean.

Titanite geochemistry and textures: Implications for magmatic and post-magmatic processes in the Notch Peak and Little Cottonwood granitic intrusions, Utah

Abstract Textural and compositional variations in titanite constrain the roles of magma mixing and hydrothermal alteration in two plutons in central Utah: the Jurassic Notch Peak and the Oligocene Little Cottonwood stocks. In the Notch Peak intrusion, magmatic titanite grains usually have oscillatory zones combined with BSE-bright sector zones, in some cases surrounding simple unzoned cores. These grains are frequently overprinted by hydrothermal titanite with low concentrations of high field strength elements (HFSE). Magmatic titanite has an average δ18O of 6.0‰ and post-magmatic titanite is 6.2‰, as analyzed by SIMS. Average Zr-in-titanite temperatures are also similar, with 718 °C for magmatic and 711 °C for hydrothermal titanite. These observations indicate simple magmatic growth, followed by hydrothermal alteration by magmatic fluids. Titanite in aplite dikes and sills has lower concentrations of all trace elements except F. Many titanite grains in the aplites have late overgrowths of high-Fe titanite. This high-Fe titanite has δ18O of 6‰ and an average Zr-in-titanite temperature of 718 °C and likely precipitated from a last flush of exsolved magmatic water enriched in Cl and Fe. Titanite in the Little Cottonwood stock typically has distinct patchy cores with rounded and embayed ilmenite inclusions. Mafic enclaves have abundant titanite that is similar in texture and δ18O (5.1‰) to titanite in the host (δ18O = 4.9‰), but it has a slightly higher average Zr-in-titanite temperature (731 vs. 717 °C). The patchy cores in the enclaves have the highest average Zr-in-titanite temperature (759 °C) and distinctive REE patterns. The textural and compositional data indicate that a hotter, more reduced, ilmenite-bearing mafic magma mixed into an oxidized felsic magma, destabilizing existing ilmenite and allowing crystallization of titanite. In the granodiorite and in the enclaves, hydrothermal growth of titanite is evidenced by distinct narrow rims as well as anhedral titanite that grew between sheets of chloritized biotite. Secondary hydrothermal titanite typically has lower concentrations of most HFSE, but is relatively enriched in F, Mg, Mo, and U, and it has higher Nb/Ta and lower Th/U ratios. Post-magmatic titanite also has strikingly different REE patterns than magmatic titanite, including the absence of pronounced Eu anomalies and lower REE abundances. These chemical features are controlled by element solubilities in aqueous fluids. In most cases, hydrothermal titanite has δ18O values similar to magmatic titanite, indicating alteration and recrystallization from exsolved magmatic fluids. The involvement of meteoric water with low δ18O is evident locally; individual spots have δ18O as low as 1.7‰ in the Little Cottonwood stock. Titanite compositions and textures provide important insights into the origins of granitic rocks and can be used to distinguish separate batches of magma, gauge the evolution of magmatic rocks, assess mixing processes, and infer compositions of mixing components. Because titanite also forms hydrothermally, it retains hints about the composition, temperature, and oxygen fugacity of the hydrothermal fluids and reveals details about titanite-forming reactions. However, the Al-in-titanite geobarometer does not yield realistic pressures of crystallization and the use of titanite as a geochronometer is compromised by the development of U-rich hydrothermal titanite.

EPMA geochemistry and LA-ICPMS dating of allanite, epidote, monazite, florencite and titanite from the Jaduguda uranium deposit, Singhbhum Shear Zone, eastern India: Implications for REE mineralization vis-à-vis tectonothermal events in the Proterozoic Mobile Belt

The Singhbhum shear zone (SSZ), eastern India, located close to the boundary between the Proterozoic North Singhbhum Mobile Belt and the Archaean Singhbhum craton, is the best known uranium province and one of the most important copper districts in India. The uranium ores and associated rocks are enriched in rare earth elements (REEs). This study integrates texture, composition and in situ LA-ICPMS dating of allanite, epidote, monazite, florencite and titanite from the Jaduguda uranium deposit in the SSZ. The earliest LREE-rich allanite (Allanite-Ce) formed at 1883 ± 14 Ma and was subsequently replaced and overgrown respectively by LREE-depleted allanite and epidote at 1637 ± 11 Ma and 1107 ± 18 Ma. The earliest monazite (Monazite-Ce) formed at ca. 1809 ± 9 Ma, while a new generation of monazite and florencite are dated at 952.2 ± 7.9 Ma and 959 ± 83 Ma respectively. Titanite, discordant to the pervasive foliation, records ancient Pb-loss and probably new titanite growth at 978 ± 17 Ma.The SSZ witnessed protracted evolutionary history with accompanying multi-stages REE mineralization and mobilization, spanning over ca. 900 Ma. The Paleoproterozoic LREE-mineralization occurred in two different pulses at ca. 1.88 Ga and ca. 1.80 Ga predating the known ages of metamorphism. It is envisaged that extension-related faults developed at the present location of the SSZ acted as fluid conduits and localized the earliest ca. 1.88 Ga hydrothermal REE mineralization. It is unclear whether the ca 1.80 event is the continuation of the ca 1.88 Ga event or represents a separate and discrete pulse of mineralization in the same locale under different geotectonic environment. The ca. 1.64 Ga event associated with LREE-removal is related to either reactivation of the existing faults or partial closure of the mobile belt with concomitant shear deformation and metamorphism in the shear zone when the rocks in the northern mobile belt were thrust southwards along existing mineralized faults. The status of the ca. 1.11 Ga event is ambiguous. The 950 ± 50 Ma event, which primarily redistributed REEs from existing mineralization is related to the final closure of the mobile belt and reactivation of the SSZ associated with the formation of the greater Indian land mass in Peninsular India.

Deconstructing Earth's oldest ichnofossil record from the Pilbara Craton, West Australia: Implications for seeking life in the Archean subseafloor.

Microtextures of titanite (CaTiSiO5 ) in exceptionally preserved Archean pillow lavas have been proposed as the earliest examples of microbial ichnofossils. An origin from microbial tunneling of seafloor volcanic glass that is subsequently chloritized and the tunnels infilled by titanite has been argued to record the activities of subseafloor microbes. We investigate the evidence in pillow lavas of the 3.35Ga Euro Basalt from the Pilbara Craton, Western Australia, to evaluate the biogenicity of the microtextures. We employ a combination of light microscopy and chlorite mineral chemical analysis by EPMA (electron probe micro-analysis) to document the environment of formation and analyze their ultrastructure using FIB-TEM (focussed ion beam combined with transmission electron microscopy) to investigate their mode of growth. Petrographic study of the original and re-collected material identified an expanded range of titanite morphotypes along with early anatase growth forming chains and aggregates of coalesced crystallites in a sub-greenschist facies assemblage. High-sensitivity mapping of FIB lamellae cut across the microtextures confirm that they are discontinuous chains of coalesced crystallites that are highly variable in cross section and contain abundant chlorite inclusions, excluding an origin from the mineralization of previously hollow microtunnels. Comparison of chlorite mineral compositions to DSDP/IODP data reveals that the Euro Basalt chlorites are similar to recent seafloor chlorites. We advance an abiotic origin for the Euro Basalt microtextures formed by spontaneous nucleation and growth of titanite and/anatase during seafloor-hydrothermal metamorphism. Our findings reveal that the Euro Basalt microtextures are not comparable to microbial ichnofossils from the recent oceanic crust, and we question the evidence for life in these Archean lavas. The metamorphic reactions that give rise to the growth of the Euro Basalt microtextures could be commonplace in Archean pillow lavas and need to be excluded when seeking traces of life in the subseafloor on the early Earth.

Titanite petrochronology linked to phase equilibrium modelling constrains tectono-thermal events in the Akia Terrane, West Greenland

The Mesoarchean Akia Terrane in West Greenland contains a detailed magmatic and metamorphic mineral growth record from 3.2 Ga to at least c. 2.5 Ga. This time span makes this region an important case study in the quest to track secular changes in geodynamic style which may ultimately inform on the development of plate tectonics as a globally linked system of lateral rigid plate motions. The common accessory mineral titanite has recently become recognised as a powerful high temperature geochronometer whose chemistry may chart the thermal conditions of its growth. Furthermore, titanite offers the potential to record the time-temperature history of mafic lithologies, which may lack zircon. Although titanite suffers from higher levels of common Pb than many other UPb chronometers, we show how measurement of 207Pb/206Pb in texturally coeval biotite may assist in the characterization of the appropriate common Pb composition in titanite. Titanite extracted from two samples of mafic gneisses from the Akia Terrane both yield UPb ages of c. 2.54 Ga. Although coeval, their chemistry implies growth under two distinctly different processes. In one case, the titanite has elevated total REE, high Th/U and grew from an in-situ partial melt, consistent with an identical date to granite dyke zircon. In contrast, the second titanite sample contains greater common Pb, lower total REE, lower Th/U, and grew from dominantly hydrothermal fluids. Zr-in-titanite thermometry for partial melt-derived titanite, with activities constrained by phase equilibrium modelling, indicates maxima of c. 690 °C. Elsewhere in the Akia Terrane, coeval metamorphism linked to growth of hydrothermal titanite is estimated at temperatures of c. 670 °C. These new results when coupled with existing findings indicate punctuated, repeated metamorphic events in the Akia Terrane, in which high temperature conditions (re)occurred at least three times between 3.0 and 2.5 Ga, but crucially changed in style across a c. 3.0 Ga change point. We interpret this change in metamorphism as reflecting a fundamental shift in geodynamic style in West Greenland at 3.0 Ga, consistent with other estimates for the onset of widespread plate tectonic-type processes.

Titanite Mineralization of Microbial Bioalteration Textures in Jurassic Volcanic Glass, Coast Range Ophiolite, California

Volcanic glasses are rarely preserved in the rock record, and the quality of preservation generally declines with increasing age. Records preserved in ancient basaltic glasses therefore provide important links between processes operating in the distant past, and those that are active on the Earth today. Microbial colonization has been linked to the formation of characteristic structures in basaltic glass, including tubules and granule-filled tubules, which are thought to be produced by microbially mediated glass dissolution. Structures of similar occurrence and morphology but filled almost entirely with fine-grained titanite have been documented in some ancient metabasalts. It has been suggested that the ancient titanite-mineralized structures are mineralized equivalents of hollow tubules in modern glassy basaltic rocks, but a direct link has not been firmly established. We report the discovery of tubular bioalteration structures in fresh and minimally altered basaltic glasses of middle Jurassic (164 Ma) age from the Stonyford Volcanic Complex (SFVC), Coast Range Ophiolite, California. Tubular structures hosted in unaltered basaltic glass are typically hollow, whilst those in zones of zeolitic alteration are mineralized by titanite. Tubules are continuous across zeolite-glass interfaces, which mark an abrupt change from titanite-filled to hollow tubules, demonstrating that titanite growth occurs preferentially within pre-existing tubular structures. Titanite mineralization in the SFVC represent a link between tubular structures in modern basaltic glass and titanite-mineralized features of similar morphology and spatial distribution in ancient metabasalts. Our observations support a link between textures in modern glassy basaltic rocks and some of the oldest-known putative ichnofossils.

Paleocene metamorphism along the Pennine\u2013Austroalpine suture constrained by U\u2013Pb dating of titanite and rutile (Malenco, Alps)

We present in situ rutile and titanite U–Pb geochronology for three samples from the Ur breccia, which forms the boundary between the Malenco unit and the Margna nappe (Eastern Central Alps) near Pass d’Ur in southeast Switzerland. These sampled both oceanic brecciated material and a blackwall reaction zone in contact with a micaschist and serpentinized peridotite. Peak temperatures during Alpine metamorphism in these units were ~ 460 ± 30 °C. Textural observations combined with new geochronological data indicate that rutile and titanite both grew below their closure temperatures during Alpine metamorphism. We present a technique to calculate the most precise and accurate ages possible using a two-dimensional U–Pb isochron on a Wetherill concordia. Rutile from two samples gave a U–Pb isochron age of 63.0 ± 3.0 Ma. This age conflicts with previous 39Ar–40Ar data on heterogeneous amphiboles from which an age of 90–80 Ma was inferred for the high pressure part of the Alpine evolution, but is consistent with K–Ar ages and Ar–Ar ages on phengitic white mica. Titanite from three samples gave a U–Pb isochron age of 54.7 ± 4.1 Ma. This age is consistent with Rb–Sr isochron ages on mylonites along and in the footwall of the Lunghin–Mortirolo movement zone, a major boundary that separates ductile deformation in the footwall from mostly localized and brittle deformation in the hangingwall. Our ages indicate a Paleocene rather than upper Cretaceous metamorphism of the Pennine–Austroalpine boundary and permit at most ~ 15 Myr, and possibly much less, between the growth of rutile and titanite.

Temporal and spatial variations in magmatism and transpression in a Cretaceous arc, Median Batholith, Fiordland, New Zealand

AbstractWe investigated the interplay between deformation and pluton emplacement with the goal of providing insights into the role of transpression and arc magmatism in forming and modifying continental arc crust. We present 39 new laser-ablation–split-stream–inductively coupled plasma–mass spectrometry (LASS-ICP-MS) and secondary ion mass spectrometry (SIMS) 206Pb/238U zircon and titanite dates, together with titanite geochemistry and temperatures from the lower and middle crust of the Mesozoic Median Batholith, New Zealand, to (1) constrain the timing of Cretaceous arc magmatism in the Separation Point Suite, (2) document the timing of titanite growth in low- and high-strain deformational fabrics, and (3) link spatial and temporal patterns of lithospheric-scale transpressional shear zone development to the Cretaceous arc flare-up event. Our zircon results reveal that Separation Point Suite plutonism lasted from ca. 129 Ma to ca. 110 Ma in the middle crust of eastern and central Fiordland. Deformation during this time was focused into a 20-km-wide, arc-parallel zone of deformation that includes previously unreported segments of a complex shear zone that we term the Grebe shear zone. Early deformation in the Grebe shear zone involved development of low-strain fabrics with shallowly plunging mineral stretching lineations from ca. 129 to 125 Ma. Titanites in these rocks are euhedral, are generally aligned with weak subsolidus fabrics, and give rock-average temperatures ranging from 675 °C to 700 °C. We interpret them as relict magmatic titanites that grew prior to low-strain fabric development. In contrast, deformation from ca. 125 to 116 Ma involved movement along subvertical, mylonitic shear zones with moderately to steeply plunging mineral stretching lineations. Titanites in these shear zones are anhedral grains/aggregates that are aligned within mylonitic fabrics and have rock-average temperatures ranging from ∼610 °C to 700 °C. These titanites are most consistent with (re)crystallization in response to deformation and/or metamorphic reactions during amphibolite-facies metamorphism. At the orogen scale, spatial and temporal patterns indicate that the Separation Point Suite flare-up commenced during low-strain deformation in the middle crust (ca. 129–125 Ma) and peaked during high-strain, transpressional deformation (ca. 125–116 Ma), during which time the magmatic arc axis widened to 70 km or more. We suggest that transpressional deformation during the arc flare-up event was an important process in linking melt storage regions and controlling the distribution and geometry of plutons at mid-crustal levels.

Trace elements in titanite: A potential tool to constrain polygenetic growth processes and timing

The petrological information preserved in the trace element signature of titanite is a valuable complement to in situ U/Pb geochronology, and can be used to refine interpretations on the growth of this mineral. We present trace element and U/Pb isotopic compositions of titanite grains in five amphibolite- to granulite-facies samples from the east Albany-Fraser Orogen of Western Australia. Chondrite-normalised rare earth element (REE) abundance patterns discriminate between titanite populations and correlate with backscatter electron (BSE) zonation. In two samples, titanite REE composition correlates with proximity to garnet, and in one sample titanite composition correlates with gneissic compositional banding.The Dy/Yb ratio can be used as a geochemical indicator to link titanite growth to garnet growth. Titanite that crystallised in a garnet-bearing assemblage is HREE-depleted with Dy/Yb > 2, whereas titanite that crystallised in a garnet-free assemblage typically has flat HREE patterns with Dy/Yb < 2. The titanite grains investigated in this study have a wide range of Eu and LREE signatures, with no obvious correlation to mineralogy, lithology, or growth environment. Furthermore, the Th/U ratio is not uniquely diagnostic of metamorphic or magmatic titanite. For the five samples reported here, Eu, LREE and Th/U are useful to discriminate between titanite populations, but not necessarily as growth process indicators.By integrating the REE signatures with U/Pb data, the five new titanite U/Pb ages can be linked to a range of processes: magmatic titanite crystallisation, metamorphic titanite growth, garnet growth, and/or cooling through the closure temperature for Pb diffusion in titanite.

Anticlockwise metamorphic pressure–temperature paths and nappe stacking in the Reisa Nappe Complex in the Scandinavian Caledonides, northern Norway: evidence for weakening of lower continental crust before and during continental collision

Abstract. This study investigates the tectonostratigraphy and metamorphic and tectonic evolution of the Caledonian Reisa Nappe Complex (RNC; from bottom to top: Vaddas, Kåfjord, and Nordmannvik nappes) in northern Troms, Norway. Structural data, phase equilibrium modelling, and U-Pb zircon and titanite geochronology are used to constrain the timing and pressure–temperature (P–T) conditions of deformation and metamorphism during nappe stacking that facilitated crustal thickening during continental collision. Five samples taken from different parts of the RNC reveal an anticlockwise P–T path attributed to the effects of early Silurian heating (D1) followed by thrusting (D2). At ca. 439 Ma during D1 the Nordmannvik Nappe reached the highest metamorphic conditions at ca. 780 ∘C and ∼9–11 kbar inducing kyanite-grade partial melting. At the same time the Kåfjord Nappe was at higher, colder, levels of the crust ca. 600 ∘C, 6–7 kbar and the Vaddas Nappe was intruded by gabbro at &gt; 650 ∘C and ca. 6–9 kbar. The subsequent D2 shearing occurred at increasing pressure and decreasing temperatures ca. 700 ∘C and 9–11 kbar in the partially molten Nordmannvik Nappe, ca. 600 ∘C and 9–10 kbar in the Kåfjord Nappe, and ca. 640 ∘C and 12–13 kbar in the Vaddas Nappe. Multistage titanite growth in the Nordmannvik Nappe records this evolution through D1 and D2 between ca. 440 and 427 Ma, while titanite growth along the lower RNC boundary records D2 shearing at 432±6 Ma. It emerges that early Silurian heating (ca. 440 Ma) probably resulted from large-scale magma underplating and initiated partial melting that weakened the lower crust, which facilitated dismembering of the crust into individual thrust slices (nappe units). This tectonic style contrasts with subduction of mechanically strong continental crust to great depths as seen in, for example, the Western Gneiss Region further south.

Age and temperature-time evolution of retrogressed eclogite-facies rocks in the Paleoproterozoic Nagssugtoqidian Orogen, South-East Greenland: Constrained from U-Pb dating of zircon, monazite, titanite and rutile

LA-ICP-MS U-Pb dating of zircon, monazite, titanite and rutile was carried out to investigate the temperature-time evolution of eclogite-facies rocks in the Kuummiut Terrane of the Paleoproterozoic Nagssugtoqidian Orogen in South-East Greenland. The terrane is dominated by Archean TTG gneiss and a variety of supracrustal rocks; basic dykes intruded the gneiss during Paleoproterozoic deformation. Detrital zircon in garnet-kyanite schist gives Archean to Paleoproterozoic dates and confines the maximum deposition of the metasediment precursor to 2107 ± 21 Ma. Intrusion of the metabasic dykes occurred at 2146 ± 63 and 2092 ± 22 Ma, within error of the detrital zircon date, possibly indicating near-contemporaneous dyke emplacement and sedimentation. About 200 m.y. after dyke emplacement, the Kuummiut Terrane underwent a clockwise PT-evolution, involving eclogite-facies metamorphism and subsequent exhumation into the mid crust. The majority of zircon, monazite and titanite give metamorphic dates between 1891 ± 10 and 1882 ± 3 Ma. Although the REE patterns in metamorphic zircon reflect growth at eclogite-facies conditions, the zircons are associated with retrograde mineral assemblages and their dates are indistinguishable from amphibolite-facies titanite. This may be interpreted to indicate that the timing of eclogite- and high-pressure amphibolite-facies metamorphism overlap within error, consistent with rapid and tectonically-controlled exhumation. However, previous studies have shown that the REE and U-Pb systematics in zircon may be decoupled during retrograde metamorphism, and the range in dates is thus best interpreted to reflect mineral growth and recrystallization during high-pressure amphibolite-facies retrogression. Monazite and titanite dates between 1872 ± 70 and 1821 ± 31 Ma reflect regional medium-pressure amphibolite-facies metamorphism and mark the final stages of compressional deformation in the Kuummiut Terrane. The subsequent thermal evolution was associated with titanite growth until 1738 ± 61 Ma, a time where the majority of rutile cooled below its closure temperature. The youngest rutile dates at 1645 ± 63 and 1617 ± 91 Ma correlate with the emplacement of post-tectonic intrusive complexes. Collectively, the data show that after an initial tectonically-controlled exhumation, the Kuummiut Terrane experienced relatively slow, erosion-controlled cooling with only minor thermal perturbations during the waning stages of metamorphic and magmatic activity.

The early exhumation history of the Western TianshanUHPmetamorphic belt, China: New constraints from titanite U–Pb geochronology and thermobarometry

AbstractThe Chinese Western Tianshan terrane is a well‐known ultrahigh‐pressure (UHP) metamorphic belt that mainly consists of subducted oceanic crustal materials. While two uplift stages have been recognized, the early exhumation history has not been fully constrained. We conducted U–Th–Pb and trace element microanalysis of titanite as well as zircon fromUHPeclogites. Apart from several inclusions in garnet, three types of retrograde titanite have been identified based on their petrographic occurrences: (a) in matrix enclosing relict rutile; (b) as coarse‐grained coronas around garnet; and (c) in veins coexisting with epidote and/or apatite. The three types of titanite are homogeneous in chemical composition, low in Al, enriched in middle rare earth elements (REEs), and depleted in lightREEs and heavyREEs, suggesting their growth during retrograde decompression. Sensitive high‐resolution ion microprobe (SHRIMP) andLA‐ICP‐MSU–Pb dating of titanite from four samples, regardless of their textural occurrences, gave consistent ages ofc. 306 Ma. Phase equilibria modelling and Zr‐in‐titanite thermometry indicate that titanite replaced rutile at ~14 kbar and ~570°C, following a nearly isothermal decompression from theUHPpeak conditions of 30 kbar and 550–570°C.SHRIMPzircon U–Pb dating yields two age groups:c. 320 Ma andc. 305 Ma. The former is generally interpreted to be the age ofUHPstage. The latter, overlapping the titanite ages, represents the timing of titanite growth during exhumation. Thus, we estimate that the near‐isothermal exhumation from theUHPpeak conditions to the epidote–amphibolite facies retrogression (14 kbar) lastedc. 15 Ma, corresponding to an average exhumation rate of 3.4 ± 2.5 mm/yr (2σ). This exhumation rate lies within the range of oceanicLT‐HPbelts in the absence of continental subduction, suggesting a similar slab exhumation mechanism that operates in theUHPregime. The consistent retrograde metamorphic ages recorded by titanite from different localities, and the general agreement amongP–Tpaths in the adjacent area, suggest that theUHPunit of Western Tianshan metamorphic belt was likely exhumed as a coherent unit.

Titanite-bearing calc-silicate rocks constrain timing, duration and magnitude of metamorphic CO2 degassing in the Himalayan belt

The pressure, temperature, and timing (P-T-t) conditions at which CO2 was produced during the Himalayan prograde metamorphism have been constrained, focusing on the most abundant calc-silicate rock type in the Himalaya. A detailed petrological modeling of a clinopyroxene+scapolite+K-feldspar+plagioclase+quartz±calcite calc-silicate rock allowed the identification and full characterization – for the first time – of different metamorphic reactions leading to the simultaneous growth of titanite and CO2 production. The results of thermometric determinations (Zr-in-Ttn thermometry) and U-Pb geochronological analyses suggest that, in the studied lithology, most titanite grains grew during two nearly consecutive episodes of titanite formation: a near-peak event at 730–740°C, 10kbar, 30–26Ma, and a peak event at 740–765°C, 10.5kbar, 25–20Ma. Both episodes of titanite growth are correlated with specific CO2-producing reactions and constrain the timing, duration and P-T conditions of the main CO2-producing events, as well as the amounts of CO2 produced (1.4–1.8wt% of CO2). A first-order extrapolation of such CO2 amounts to the orogen scale provides metamorphic CO2 fluxes ranging between 1.4 and 19.4Mt/yr; these values are of the same order of magnitude as the present-day CO2 fluxes degassed from spring waters located along the Main Central Thrust. We suggest that these metamorphic CO2 fluxes should be considered in any future attempts of estimating the global budget of non-volcanic carbon fluxes from the lithosphere.

Apatite and titanite from the Karrat Group, Greenland; implications for charting the thermal evolution of crust from the U-Pb geochronology of common Pb bearing phases

Titanite and apatite have Pb closure temperatures of ∼700°C and 450–550°C, respectively, allowing different points on a cooling trajectory to be determined. However, both phases typically accommodate moderate to significant quantities of common Pb. Understanding the thermal diffusivity of a specific isotopic system in different minerals along with their apparent U-Pb age allows modelling of regional cooling trends. Such cooling trends may provide key evidence for correct interpretation of the measured geochronometer. Specifically, thermal history reconstruction may address questions related to the interpretation of an isotopic date as the time of crystallization versus cooling, or alternatively, as a resetting age. In this work, a case study from metavolcanic rocks of the Karrat Group, West Greenland, is used to inform the U-Pb geochronology of common Pb bearing phases, thermal modelling, and also the regional geology. Magmatic apatite yields a reset U-Pb age of 1826±9Ma, whereas titanite yields a mean U-Pb age of 1768±8Ma. The apatite age is interpreted as the time of total resetting during a >485°C event. In contrast, the titanite age is interpreted as the time of metamorphic crystallization, consistent with its REE chemistry. Thermal modelling indicates this metamorphic event did not exceed 452°C. The resetting of the U-Pb system in magmatic apatite is interpreted as a response to the collision between the Rae Craton and the Superior Craton during the Trans-Hudson Orogeny. However, subsequent metamorphic titanite growth is interpreted as distal evidence of an event shared with the Nagssugtoqidian Orogen. The modelled thermal history implies over 100 million years of communal tectonic history between the Nagssugtoqidian and Rinkian Orogens. Of great significance is the fact that both apatite and titanite show distinctly different common Pb compositions. Apatite retains common Pb with a composition similar to ancient common Pb, whereas titanite retains common Pb with a lower 207Pb/206Pb ratio implying it was influenced also by Pb from recrystallized precursor U bearing minerals. The common Pb signature in minerals may assist in interpretation of the growth mechanism of the dated phase.

Petrogenetic relations among titanium‐rich minerals in an anatectic high‐P mafic granulite

AbstractThe petrogenetic relations among Ti‐rich minerals in high‐grade metabasites is illuminated here through a detailed petrological investigation of an anatectic garnet–clinopyroxene granulite from the Grenville Province, Ontario, Canada containing rutile, titanite and ilmenite in distinct microtextural settings. Garnet porphyroblasts exhibit zoned Ti concentrations (up to 0.15 wt% TiO2 in their cores), as well as a variety of rutile inclusion types, including clusters of small, variably elongate grains and thin (≤1 μm) oriented needles. Calcite inclusions in garnet, commonly observed surrounding garnet cores containing quartz and clinozoisite, indicate the presence of evolving C–O–H fluids during garnet growth and suggest that the rutile clusters may have formed from subsequent Ti diffusion and rutile precipitation within existing fluid inclusions. Titanite forms large subhedral crystals and typically occurs where the primary garnet–clinopyroxene assemblage is in contact with leucosome containing megacrystic hornblende, silvialitic scapolite and calcic plagioclase. Many titanite crystals exhibit marginal subgrains that correspond with sharp changes in their major and trace element composition, likely related to a dissolution–precipitation or recrystallization process following primary crystallization. Clinopyroxene–ilmenite symplectite coronas surround titanite in most locations, likely forming from reaction with the hornblende‐plagioclase matrix (±fluids/melt). Integration of multi‐equilibria thermobarometry and Zr thermometry in rutile and titanite with phase equilibrium modelling allows definition of a clockwise P–T path evolving to peak pressures of ~1.5 GPa at ~750°C during garnet and rutile growth, followed by peak temperature conditions of ~1.2 GPa and ~820–880°C associated with melt‐present titanite growth, and finally cooling and decompression to regional amphibolite facies conditions (~1.0 GPa and ~750°C) associated with the formation of clinopyroxene–ilmenite symplectites surrounding titanite. P–T pseudosections calculated for the pristine (leucosome‐ and titanite ‐free) metabasite bulk composition reproduce much of the prograde phase relations, but predict rutile as the stable Ti‐rich mineral at the peak thermal conditions associated with melt‐present titanite growth. The P–M(CaO) and T–M(CaO) models show that bulk CaO concentrations have a significant effect on the stability ranges of titanite and rutile. Increased bulk CaO tends to stabilize titanite to higher pressure and temperature at the expense of rutile, with a ≥15% increase in CaO producing the observed titanite‐bearing assemblage at high‐P granulite facies conditions. Thus, the model results are consistent with the textural observations, which suggest that titanite stability is associated with a chemical exchange between the host metabasite and a Ca‐rich melt.

Age and tectonic setting of the Udokan sediment-hosted copper-silver deposit, Transbaikalia, Russia

The Udokan Cu–Ag deposit in Transbaikalian Russia is one of the largest individual examples of the sediment-hosted stratiform type. Mineralization is hosted by the Udokan Complex, a ~12,000-m-thick metasedimentary sequence deposited between ~2.2 and 2.06Ga in a large intra- to peri-cratonic basin constructed over Archean basement of the Siberian craton. The basin was inverted and metamorphosed to dominantly greenschist facies at ~1.9Ga, as a consequence of the collision between the Aldan and Stanovoi domains.Titanite is a common constituent of the greenschist metamorphic assemblages of the Udokan Complex as well as being an integral part of the stratiform disseminated and associated veinlet Cu sulfide mineralization at Udokan. Titanite crystals were separated from a sample collected in the Medny area of the deposit where typical, high-grade, disseminated and veinlet chalcocite-bornite mineralization is well exposed. Titanite crystals from the disseminated and veinlet fractions were separately dated by the ID-TIMS U–Pb method, with the disseminated fraction returning a concordia age of 1895.3±9.7Ma and the veinlet fraction a concordia age of 1896.7±7.8Ma. Combination of both titanite fractions produced a concordia age of 1896.2±6.2Ma.The titanite age effectively dates the associated Cu sulfide mineralization. Since there is no evidence that titanite growth is appreciably younger than either the mineralization in the Medny area or the Udokan deposit as a whole, a ~1.9-Ga age for the stratiform Cu mineralization is considered likely. This age is undistinguishable from that of regional metamorphism during the collisional orogeny that led to final amalgamation of the Siberian craton and its incorporation into Columbia. The age also confirms Udokan as the world's oldest sediment-hosted Cu deposit and that its formation coincided with a continental-scale orogeny rather than with diagenesis and extensional basin development ~150m.y. earlier.

Thermochronology of extensional orogenic collapse in the deep crust of Zealandia

The exhumed Fiordland sector of Zealandia offers a deep-crustal view into the life cycle of a Cordilleran-type orogen from final magmatic construction to extensional orogenic collapse. We integrate U-Pb thermochronologic data from metamorphic zircon and titanite with structural observations from >2000 km 2 of central Fiordland to document the tempo and thermal evolution of the lower crust during the tectonic transition from arc construction and crustal thickening to crustal thinning and extensional collapse. Data reveal that garnet granulite facies metamorphism and partial melting in the lower crust partially overlapped with crustal thickening and batholith construction during emplacement of the Western Fiordland Orthogneiss (WFO) from 118 to 115 Ma. Metamorphic zircons in metasedimentary rocks yield 206 Pb/ 238 U (sensitive high-resolution ion microprobe–reverse geometry) dates of 116.3–112.0 Ma. Titanite laser ablation split stream inductively coupled plasma–mass spectrometry chronology from the same rocks yielded complex results, with relict Paleozoic 206 Pb/ 238 U dates preserved at the margins of the WFO. Within extensional shear zones that developed in the thermal aureole of the WFO, titanite dates range from 116.2 to 107.6 Ma and have zirconium-in-titanite temperatures of ∼900–750 °C. A minor population of metamorphic zircon rims and titanites in the Doubtful Sound region yield younger dates of 105.6–102.3 Ma with corresponding temperatures of 740–730 °C. Many samples record Cretaceous overdispersed dates with 5–10 m.y. ranges. Core-rim traverses and grain maps show complex chemical and temporal variations that cannot easily be attributed to thermally activated volume diffusion or simple core-rim crystallization. We interpret these Cretaceous titanites not as cooling ages, but rather as recording protracted growth and/or crystallization or recrystallization in response to fluid flow, deformation, and/or metamorphic reactions during the transition from garnet granulite to upper amphibolite facies metamorphism. We propose a thermotectonic model that integrates our results with structural observations. Our data reveal a clear tectonic break at 108–106 Ma that marks a change in processes deep within the arc. Prior to this break, arc construction processes dominated and involved (1) emplacement of mafic to intermediate magmas of the Malaspina and Misty plutons from 118 to 115 Ma, (2) contractional deformation at the roof of the Misty pluton in the Caswell Sound fold-thrust belt from 117 to 113 Ma, and (3) eclogite to garnet granulite facies metamorphism and partial melting over >8 m.y. from 116 to 108 Ma. These processes were accompanied by complex patterns of lower crustal flow involving both horizontal and vertical displacements. After this interval, extensional orogenic collapse initiated along upper amphibolite facies shear zones in the Doubtful Sound shear zone at 108–106 Ma. Zircon and titanite growth and/or crystallization or recrystallization at this time clearly link upper amphibolite facies metamorphism to mylonitic fabrics in shear zones. Our observations are significant in that they reveal the persistence of a hot and weak lower crust for ≥15 m.y. following arc magmatism in central Fiordland. We propose that the existence of a thermally weakened lower crust within the Median Batholith was a key factor in controlling the transition from crustal thickening to crustal thinning and extensional orogenic collapse of the Zealandia Cordillera.

Extreme Nb/Ta fractionation in metamorphic titanite from ultrahigh-pressure metagranite

Extremely high Nb/Ta ratios (up to 239) occur in metamorphic titanite from ultrahigh-pressure metagranite in the Sulu orogen. This indicates significant Nb/Ta fractionation in subduction-zone fluids. By means of U–Pb dating and trace element analysis of titanite, we distinguish the metamorphic domains from the anatectic domains. Titanite U–Pb dating yields lower intercept ages of 215±12Ma to 222±27Ma for the metagranite samples, with regardless of the compositional differences between the two types of titanite domains. This indicates the two generations of titanite growth during exhumation of deeply subducted continental crust. The metamorphic titanite shows significantly elevated Nb but decreased Ta and thus higher Nb/Ta ratios than the anatectic titanite. The increase of Nb/Ta ratios for the metamorphic titanite is associated more with a decrease of Ta than an increase of Nb, suggesting the control of fluid composition on the titanite Nb/Ta ratios. Because the metamorphic titanite grew during the exhumation of deeply subducted continental crust, its unusually high Nb/Ta ratios are ascribed to the breakdown of hydrous minerals such as phengite and biotite that host much more Nb than Ta. This implies that the composition of subduction-zone fluids is primarily dictated by the geochemical property of hydrous minerals that break down during dehydration reaction at high-pressure to ultrahigh-pressure conditions. Therefore, significant Nb/Ta fractionation in Ti-rich accessory minerals such as titanite and rutile, at least on the mineral scale, during subduction-zone processes is possibly much more common than previously thought.