Trace element systematics in granulite facies rutile: implications for Zr geothermometry and provenance studies

Metamorphic rutile from granulite facies metapelitic rocks of the Archean Pikwitonei Granulite Domain (PGD; Manitoba, Canada) provides constraints on the systematics of trace elements in rutile during high‐temperature conditions and subsequent slow cooling. Compositional profiles and maps of the Zr concentrations in rutile grains (120–600 μm) from three metapelitic gneisses were acquired by electron probe micro‐analysis, using a spatial resolution of down to 2 μm. Simultaneously, profiles were analysed for Nb, Cr and V, which have significantly different diffusion characteristics in rutile. The profiles of all elements show relatively homogeneous concentrations within most grains, but significant inter‐grain differences even within a single thin section. Some rutile grains display a slight concentration decrease from a neighbouring garnet towards the matrix for all measured elements. The lack of diffusion profiles for all analysed elements shows that these are highly immobile in rutile and that distributions of these elements are primary and preserve prograde information. The Nb and Cr concentrations overlap with ranges that are ascribed to different provenances indicating that source discrimination based on these elements is not possible in all cases. High retentiveness for Zr implies that the Zr‐in‐rutile geothermometer is highly robust to diffusive re‐equilibration, even during very slow cooling (<2 °C Ma^?1) from granulite facies conditions. Most grains have high Zr contents (3000–4600 ppm). Differences between high Zr contents suggest that during growth under vapour‐absent conditions there may not be saturation of Zr in rutile, even if zircon is present. Therefore, several rutile grains need to be analysed in a sample to obtain a useful minimum peak temperature. The highest Zr concentrations correspond to ～900 °C. This is significantly higher than previous peak temperature estimates of 820 °C based on two‐feldspar thermometry. On a regional scale this implies that part of the PGD was affected by ultra‐high temperature (UHT) metamorphism. It also implies that rutile is able to preserve primary compositions even to UHT conditions. This study shows that, if combined with textural information, Zr‐in‐rutile has the potential to be a very useful tool for estimating rutile crystallization temperatures and peak metamorphic conditions. For granulite facies rocks, Zr‐in‐rutile yields more reliable peak metamorphic temperatures than most other exchange geothermometers, which tend to partially re‐equilibrate by diffusion during cooling.     

The robustness of the Zr-in-rutile and Ti-in-zircon thermometers during high-temperature metamorphism (Ivrea-Verbano Zone, northern Italy)

This study investigates the behaviour of the Zr-in-rutile and Ti-in-zircon thermometers in granulite facies metapelites from the Ivrea-Verbano Zone lower crustal section. U–Pb ages of zircon constrain the timing of regional amphibolite–granulite facies metamorphism to 316 ± 3 Ma and record zircon recrystallisation and resetting of U–Pb ages at 276 ± 4 Ma and 258 ± 3 Ma. Zr-in-rutile thermometry records peak contact metamorphic temperatures related to intrusion of mafic magmatic rocks and gives peak temperatures between 900–930 °C and 1,000–1,020 °C that are consistent with the geological settings of the samples. Ti-in-zircon temperatures of 700–800 °C and 810–870 °C record growth or re-equilibration of zircon after cooling from peak temperatures. Ti-in-quartz thermometry for one sample records both peak and retrograde temperatures. Some rutiles in all samples record resetting of Zr-in-rutile temperatures at ~750–800 °C. Electron microprobe profiles across individual rutiles demonstrate that Zr expulsion occurred by recrystallisation rather than by diffusive exchange. Exsolution of small needles of baddelyite or zircon from rutile is an important method of Zr redistribution, but results in no net Zr loss from the grain. The demonstration that Zr-in-rutile thermometry can robustly record peak temperatures that are not recorded by any other thermometer emphasises the relevance of this technique to investigating the evolution of high-grade metamorphic terranes, such as those that characterise the lower crust.     

Testing the fidelity of thermometers at ultrahigh temperatures

A highly residual granulite facies rock (sample RG07‐21) from Lunnyj Island in the Rauer Group, East Antarctica, presents an opportunity to compare different approaches to constraining peak temperature in high‐grade metamorphic rocks. Sample RG07‐21 is a coarse‐grained pelitic migmatite composed of abundant garnet and orthopyroxene along with quartz, biotite, cordierite, and plagioclase with accessory rutile, ilmenite, zircon, and monazite. The inferred sequence of mineral growth is consistent with a clockwise pressure–temperature (P–T) evolution when compared with a forward model (P–T pseudosection) for the whole‐rock chemical composition. Peak metamorphic conditions are estimated at 9 ± 0.5 kbar and 910 ± 50°C based on conventional Al‐in‐orthopyroxene thermobarometry, Zr‐in‐rutile thermometry, and calculated compositional isopleths. U–Pb ages from zircon rims and neocrystallized monazite grains yield ages of c. 514 Ma, suggesting that crystallization of both minerals occurred towards the end of the youngest pervasive metamorphic episode in the region known as the Prydz Tectonic Event. The rare earth element compositions of zircon and garnet are consistent with equilibrium growth of these minerals in the presence of melt. When comparing the thermometry methods used in this study, it is apparent that the Al‐in‐orthopyroxene thermobarometer provides the most reliable estimate of peak conditions. There is a strong textural correlation between the temperatures obtained using the Zr‐in‐rutile thermometer––maximum temperatures are recorded by a single rutile grain included within orthopyroxene, whereas other grains included in garnet, orthopyroxene, quartz, and biotite yield a range of temperatures down to 820°C. Ti‐in‐zircon thermometry returns significantly lower temperature estimates of 678–841°C. Estimates at the upper end of this range are consistent with growth of zircon from crystallizing melt at temperatures close to the elevated (H₂O undersaturated) solidus. Those estimates, significantly lower than the calculated temperature of this residual solidus, may reflect isolation of rutile from the effective equilibration volume leading to an activity of TiO₂ that is lower than the assumed value of unity.     

Polygenetic titanite records the composition of metamorphic fluids during the exhumation of ultrahigh‐pressure metagranite in the Sulu orogen

An integrated study of U–Pb ages and trace elements was carried out for titanite and zircon from ultrahigh‐pressure (UHP) metagranites in the Sulu orogen, east‐central China. The results provide constraints on the composition of metamorphic fluids during the exhumation of deeply subducted continental crust. Titanite has two domain types based on REE patterns and trace element variations, Ttn‐I and Ttn‐II respectively. These two domains show indistinguishable U–Pb ages of 232 ± 14 to 220 ± 8 Ma, in general agreement with anatectic zircon U–Pb ages of 223 ± 4 to 219 ± 2 Ma for the partial melting event during early exhumation. The Ttn‐I domains have significantly higher REE, Th, Ta and Sr, and higher Th/U ratios than the Ttn‐II domains, indicating that the two domains have grown from metamorphic fluids with different compositions. For the Ttn‐I domains, Zr‐in‐titanite thermometry yields high temperatures of 773–851 °C at 2.5 GPa, and petrographic observations reveal the presence of melt pseudomorphs. Thus, they are interpreted to have grown from hydrous melts in the early exhumation stage. In contrast, the Ttn‐II domains were texturally equilibrated with amphibolite facies minerals such as biotite and plagioclase and contain inclusions of plagioclase and quartz. The Zr‐in‐titanite thermometry yields lower temperatures of 627–685 °C at 1.0 GPa. In combination with their REE patterns, they are interpreted to have grown from aqueous solutions at amphibolite facies metamorphic conditions during further exhumation. The differences in Th and Sr contents are prominent between the Ttn‐I and Ttn‐II domains, signifying the compositional difference between the hydrous melts and aqueous solutions. Therefore, the polygenetic titanite in the UHP metamorphic rocks provides insights into the geochemical property of metamorphic fluids during the continental subduction‐zone processes.     

麻粒岩相金红石微量元素体系

麻粒岩是研究地壳演化最重要的变质岩类,金红石作为麻粒岩中常见的副矿物之一,深入探究其微量元素体系特点,可为大陆地壳演化研究提供新的视角.根据麻粒岩金红石的基础数据（显微结构、微量元素、离子替换方式）以及地壳常见造岩矿物的微量元素特点,初步探讨了麻粒岩变质过程中微量元素行为和扩散效应.麻粒岩金红石Zr含量可记录不同阶段的变质温度,但次生锆石和钛铁矿可对其Zr含量有较大影响,作为孤立体系（不与锆石和石英平衡）的金红石不能用于温度计算;金红石Nb、Ta、Cr和V不仅受全岩成分控制,还与变质过程中黑云母、钛铁矿、蓝晶石等矿物的形成和分解紧密相关;金红石与富Fe矿物之间有强烈的Fe扩散效应.深入理解麻粒岩变质过程中金红石微量元素行为,可为限定大陆地壳变质演化和动力学过程提供重要的矿物学信息.      

A high precision U–Pb age of metamorphic rutile in coesite-bearing eclogite from the Dabie Mountains in central China: a new constraint on the cooling history

This paper first reports a high precision U–Pb age of 218±1.2 Ma for rutile in coesite-bearing eclogite from Jinheqiao in the Dabie Mounteins, east–central China. This work shows that the U–Pb mineral (rutile+omphacite) isochron age of 218±2.5 Ma and conventional rutile U–Pb concordia age of 218±1.2 Ma obtained by common Pb correction based on the Pb isotopic composition of omphacite in the same eclogite sample are consistent, proving that the omphacite with low U/Pb ratio (μ=2.8) can be used for common Pb correction in U–Pb dating of rutile. Oxygen isotope analysis of rutile aliquots gave the consistent δ¹⁸O values of −6.1±0.1%, demonstrating oxygen isotope homogenization in the rutile of different grains as inclusion in garnet and grain in matrix. Oxygen isotope thermometry yields temperatures of 695±35 and 460±15 °C for quartz–garnet and quartz–rutile pairs, respectively. These oxygen isotopic observations suggest that the diffusion of oxygen in rutile as inclusion in garnet is not controlled by garnet. According to field-based thermochronological studies of rutile, an estimate of the T_c of about 460 °C for U–Pb system in rutile under rapid cooling conditions (20 °C/Ma) was advised. Based on this U–Pb age as well as the reported chronological data with their corresponding metamorphic and/or closure temperature, an improved T–t path has been constructed. The T–t path confirms that the UHPM rocks in South Dabie experienced a rapid cooling following the peak metamorphism before 220 Ma and a long isothermal stage from 213 to 180 Ma around 425 °C.     

Early Carboniferous HP metamorphism in the Hida Gaien Belt,Japan: Implications for the Palaeozoic tectonic history of proto‐Japan

We report two new eclogite localities (at Kanayamadani and Shinadani) in the high‐P (HP) metamorphic rocks of the Omi area in the western most region of Niigata Prefecture, Japan, which form part of the Hida Gaien Belt, and determine metamorphic conditions and pressure–temperature (P–T) paths. The metamorphic evolution of the eclogites is characterized by a tight hairpin‐shaped P–T path from prograde epidote–blueschist facies to peak eclogite facies and then retrograde blueschist facies. The prograde metamorphic stage is characterized by various amphibole (winchite, barroisite, glaucophane) inclusions in garnet, whereas the peak eclogite facies assemblage is characterized by omphacite, garnet, phengite and rutile. Peak P–T conditions of the eclogites were estimated to be ~600°C and up to 2.0 GPa by conventional cation‐exchange thermobarometry, Ti‐in‐zircon thermometry and quartz inclusion Raman barometry respectively. However, the Raman spectra of carbonaceous material thermometry of metapelites associated with the eclogites gave lower peak temperatures, possibly due to metamorphism at different conditions before being brought together during exhumation. The blueschist facies overprint following the peak of metamorphism is recognized by the abundance of glaucophane in the matrix. Zircon grains in blueschist facies metasedimentary samples from two localities adjacent to the eclogites have distinct oscillatory‐zoned cores and overgrowth rims. Laser ablation inductively coupled plasma mass spectrometry U–Pb ages of the detrital cores yield a wide range between 3,200 and 400 Ma, with a peak at 600–400 Ma. In the early Palaeozoic, proto‐Japan was located along the continental margin of the South China craton, providing the source of the older population of detrital zircon grains (3,200–600 Ma) deposited in the trench‐fill sediments. In addition, subduction‐related magmatism c. 500–400 Ma is recorded in the crust below proto‐Japan, which might have been the source for the younger detrital zircon grains. The peak metamorphic age was constrained by SHRIMP dating of the overgrowth rims, yielding Tournaisian ages of 347 ± 4 Ma, suggesting subduction in the early Carboniferous. Our results provide clear constraints on the initiation of subduction, accretion and the development of an arc‐trench system along the active continental margin of the South China craton and help to unravel the Palaeozoic tectonic history of proto‐Japan.     

Integrated garnet and zircon–titanite geochronology constrains the evolution of ultra‐high–pressure terranes: An example from the Sulu orogen

Dating ultra‐high–pressure (UHP) metamorphic rocks provides important timing constraints on deep subduction zone processes. Eclogites, deeply subducted rocks now exposed at the surface, undergo a wide range of metamorphic conditions (i.e. deep subduction and exhumation) and their mineralogy can preserve a detailed record of chronologic information of these dynamic processes. Here, we present an approach that integrates multiple radiogenic isotope systems in the same sample to provide a more complete timeline for the subduction–collision–exhumation processes, based on eclogites from the Dabie–Sulu orogenic belt in eastern China, one of the largest UHP terranes on Earth. In this study, we integrate garnet Lu–Hf and Sm–Nd ages with zircon and titanite U–Pb ages for three eclogite samples from the Sulu UHP terrane. We combine this age information with Zr‐in‐rutile temperature estimates, and relate these multiple chronometers to different P–T conditions. Two types of rutile, one present as inclusions in garnet and the other in the matrix, record the temperatures of UHP conditions and a hotter stage, subsequent to the peak pressure (‘hot exhumation') respectively. Garnet Lu–Hf ages (c. 238–235 Ma) record the initial prograde growth of garnet, while coupled Sm–Nd ages (c. 219–213 Ma) reflect cooling following hot exhumation. The maximum duration of UHP conditions is constrained by the age difference of these two systems in garnet (c. 235–220 Ma). Complementary zircon and titanite U–Pb ages of c. 235–230 Ma and c. 216–206 Ma provide further constraints on the timing of prograde metamorphism and the ‘cold exhumation' respectively. We demonstrate that timing of various metamorphic stages can thus be determined by employing complementary chronometers from the same samples. These age results, combined with published data from adjacent areas, show lateral diachroneity in the Dabie–Sulu orogeny. Three sub‐blocks are thus defined by progressively younger garnet ages: western Dabie (243–238 Ma), eastern Dabie–northern Sulu (238–235 Ma) and southern Sulu terranes (225–220 Ma), which possibly correlate to different crustal slices in the recently proposed subduction channel model. These observed lateral chronologic variations in a large UHP terrane can possibly be extended to other suture zones.     

Zircon growth during subduction and exhumation metamorphism of mafic rocks,Aktyuz terrain,North Tiahshan,Kyrgyzstan

The interpretation of whether a dated metamorphic zircon generation grew during the prograde, peak or retrograde stage of a metamorphic cycle is critical to geological interpretation. This study documents a case at Aktyuz metamorphic terrain, in the southern of Kokchetav‐North Tianshan belt, involving progressive metamorphic recrystallization of mafic rock to eclogite and associated behavior of zircon. Zircons in eclogites are mainly fine grains (5 to 20 μm), and preferentially concentrated with rutile/ilmenite. They also occur as individual grains or clusters in amphibole coronas of garnet. A few larger grains commonly preserve inherited cores and evidence of dissolution and metamorphic outgrowths. Zircon grains separated from amphibolites show inherited zircons with typically magmatic feature, although this become progressively blurred in response to resorption and recrystallization. Mineral inclusions represent epidote‐amphibolite facies in the prograde metamorphism, and the embayed boundary between recrystallized domains and inherited zircons suggest fluid/melt participation. The metamorphic domains are mainly simple overgrowth around the inherited cores or recrystallization domains. The absence of peak metamorphic mineral inclusions and steep pattern of MREE‐HREE indicate no sufficient garnet formed before the metamorphic zircon overgrowth. A tiny rim with homogeneously bright CL image can be distinguished in most zircons. Amphibole inclusions have similar compositions to those in the coronas of garnets, suggesting a retrograde metamorphic origin. The inherited zircon crystallized at 880‐730 Ma, revealing similar age range to the gneiss in Aktyuz area, whereas metamorphic zircon dates prograde metamorphism at 497.9 ±1.4 Ma. In this case, the bulk Zr budget in rocks will become locked into Zr‐bearing minerals during the mafic magma intrusion, when the inherited zircon melting and resorption. The texture shows that metamorphic zircon grew both in the prograde and retrograde stage, and Zr‐bearing magmatic minerals and rutile/ilmenite are by far the main source of Zr for the two stages, respectively.     

Behaviour of geochronometers and timing of metamorphic reactions during deformation at lower crustal conditions: phase equilibrium modelling and U–Pb dating of zircon,monazite, rutile and titanite from the Kalak Nappe Complex,northern Norway

This study investigates the behaviour of the geochronometers zircon, monazite, rutile and titanite in polyphase lower crustal rocks of the Kalak Nappe Complex, northern Norway. A pressure–temperature–time–deformation path is constructed by combining microstructural observations with P–T conditions derived from phase equilibrium modelling and U–Pb dating. The following tectonometamorphic evolution is deduced: A subvertical S1 fabric formed at ~730–775 °C and ~6.3–9.8 kbar, above the wet solidus in the sillimanite and kyanite stability fields. The event is dated at 702 ± 5 Ma by high‐U zircon in a leucosome. Monazite grains that grew in the S1 fabric show surprisingly little variation in chemical composition compared to a large spread in (concordant) U–Pb dates from c. 800 to 600 Ma. This age spread could either represent protracted growth of monazite during high‐grade metamorphism, or represent partially reset ages due to high‐T diffusion. Both cases imply that elevated temperatures of >600 °C persisted for over c. 200 Ma, indicating relatively static conditions at lower crustal levels for most of the Neoproterozoic. The S1 fabric was overprinted by a subhorizontal S2 fabric, which formed at ~600–660 °C and ~10–12 kbar. Rutile that originally grew during the S1‐forming event lost its Zr‐in‐rutile and U–Pb signatures during the S2‐forming event. It records Zr‐in‐rutile temperatures of 550–660 °C and Caledonian ages of 440–420 Ma. Titanite grew at the expense of rutile at slightly lower temperatures of ~550 °C during ongoing S2 deformation; U–Pb ages of c. 440–430 Ma date its crystallization, giving a minimum estimate for the age of Caledonian metamorphism and the duration of Caledonian shearing. This study shows that (i) monazite can have a large spread in U–Pb dates despite a homogeneous composition; (ii) rutile may lose its Zr‐in‐rutile and U–Pb signature during an amphibolite facies overprint; and (iii) titanite may record crystallization ages during retrograde shearing. Therefore, in order to correctly interpret U–Pb ages from different geochronometers in a polyphase deformation and reaction history, they are ideally combined with microstructural observations and phase equilibrium modelling to derive a complete P–T–t–d path.     

金红石Zr温度计在苏鲁-大别榴辉岩研究中的应用：问题讨论

金红石Zr含量温度计在苏鲁-大别超高压榴辉岩中的应用普遍得出了比峰期变质温度明显偏低的温度值。通过对比国内外的研究,并结合岩相学的分析,认为除了超高压可能使金红石对Zr的容纳度降低外,较强的退变质和流体作用下的扩散丢失是造成金红石Zr含量降低的主要原因。同一样品不同金红石颗粒之间Zr含量和温度的显著差别说明金红石与共存锆石和石英之间的Zr配分平衡已受到退变质作用的破坏且未能达到再平衡,金红石Zr含量温度代表的是每个颗粒受不同程度退变质和扩散影响后的某个缓冲状态,其平均温度的地质意义很难界定。只有将金红石的赋存状态、岩相学分析等研究与数据本身的均匀性分析结合起来进行综合判断,才有可能对金红石Zr温度计给出合理解释。     

碎屑金红石:沉积物源的一种指针

近年来,碎屑金红石的研究已成为沉积物源区分析的一个新前沿。金红石的地球化学组成,尤其是Cr,Nb,Zr等微量元素的含量,对其母岩的形成条件和所经历的地质过程都具有重要的指示意义,同时,碎屑金红石在沉积、成岩过程中表现出极高的稳定性,因而是物源分析的理想指针矿物。首先介绍金红石的矿物学和地球化学基本性质,分析不同来源的金红石典型特征,重点阐述碎屑金红石在物源分析中运用的5个方面:①金红石重矿物比值;②金红石矿物化学成分Cr-Nb判别图解;③金红石Zr含量温度计;④金红石的U-Pb和(U-Th)/He定年;⑤金红石Lu-Hf同位素。综合上述5个方面的物源分析研究,可以获取金红石的母岩类型、形成温度及后期所经历的热演化史等信息。碎屑金红石的物源研究处于起步和探索阶段,仍存在一些亟需解决的问题。     

Peak metamorphic temperatures from cation diffusion zoning in garnet

A model that relates the characteristic diffusion length and average cooling rate to peak temperature was developed for chemical diffusion in spherical geometries on the basis of geospeedometry principles and diffusion theory. The model is quantitatively evaluated for cation diffusion profiles in garnet. Important model parameters were calibrated empirically using diffusion zoning of Ca in garnet from the Pikwitonei Granulite Domain, a terrane for which the thermal history has been well characterized. The results are used: (i) to empirically test diffusion parameters for Mg and Fe(II) and (ii) to develop a tool that uses the diffusion zoning of these cations in garnet to constrain peak temperature conditions for garnet‐bearing rocks. The thermometric approach was externally tested by applying it to garnet crystals from various metamorphic terranes worldwide and comparing the results to published peak temperature estimates. The results overlap within uncertainties in all cases, but result that are based on Fe(II) and Mg chemical‐diffusion profiles are up to three times more precise than those acquired by conventional methods. The remarkable consistency of the results implies that the model is robust and provides a reliable means of estimating peak temperatures for different types of high‐grade metamorphic rock. The tool could be of particular advantage in rocks where critical assemblages for conventional thermometry do not occur or have been replaced during retrogression.     

Petrology,geochemistry and P–T–t path of lawsonite‐bearing retrograded eclogites in the Changning–Menglian orogenic belt,southeast Tibetan Plateau

The Changning–Menglian orogenic belt (CMOB) in the southeastern Tibetan Plateau, is considered as the main suture zone marking the closure of the Palaeo‐Tethys Ocean between the Indochina and Sibumasu blocks. Here, we investigate the recently discovered retrograded eclogites from this suture zone in terms of their petrological, geochemical and geochronological features, with the aim of constraining the metamorphic evolution and protolith signature. Two types of metabasites are identified: retrograded eclogites and mafic schists. The igneous precursors of the retrograded eclogites exhibit rare earth element distribution patterns and trace element abundance similar to those of ocean island basalts, and are inferred to have been derived from a basaltic seamount in an intra‐oceanic tectonic setting. In contrast, the mafic schists show geochemical affinity to arc‐related volcanics with the enrichment of Rb, Th and U, and depletion of Nb, Ta, Zr, Hf and Ti, and their protoliths possibly formed at an active continental margin tectonic setting. Retrograded eclogites are characterized by peak metamorphic mineral assemblages of garnet, omphacite, white mica, lawsonite and rutile, and underwent five‐stage metamorphic evolution, including pre‐peak prograde stage (M₁) at 18–19 kbar and 400–420°C, peak lawsonite‐eclogite facies (M₂) at 24–26 kbar and 520–530°C, post‐peak epidote–eclogite facies decompression stage (M₃) at 13–18 kbar and 530–560°C, subsequent amphibolite facies retrogressive stage (M₄) at 8–10 kbar and 530–600°C, and late greenschist facies cooling stage (M₅) at 5–8 kbar and 480–490°C. Laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) U–Pb spot analyses of zircon show two distinct age groups. The magmatic zircon from both the retrograded eclogite and mafic schist yielded protolith ages of 451 ± 3 Ma, which is consistent with the ages of Early Palaeozoic ophiolitic complexes and ocean island sequences in the CMOB reported in previous studies. In contrast, metamorphic zircon from the retrograded eclogite samples yielded consistent Triassic metamorphic ages of 246 ± 2 and 245 ± 2 Ma, which can be interpreted as the timing of closure of the Palaeo‐Tethys Ocean. The compatible peak metamorphic mineral assemblages, P–T–t paths and metamorphic ages, as well as the similar protolith signatures for the eclogites in the CMOB and Longmu Co–Shuanghu suture (LCSS) suggest that the two belts formed part of a cold oceanic subduction system in the Triassic. The main suture zone of the Palaeo‐Tethyan domain extends at least 1,500 km in length from the CMOB to the LCSS in the Tibetan Plateau. The identification of lawsonite‐bearing retrograded eclogites in the CMOB provides important insights into the tectonic framework and complex geological evolution of the Palaeo‐Tethys.     

Rutile occurrence and trace element behavior in medium-grade metasedimentary rocks: example from the Erzgebirge, Germany

Metamorphic textures in medium-grade (~500–550°C) metasedimentary rocks from the Erzgebirge give evidence of prograde rutile crystallization from ilmenite. Newly-crystallized grains occur as rutile-rich polycrystalline aggregates that pseudomorph the shape of the ilmenites. In-situ trace element data (EMP and SIMS) show that rutiles from the higher-grade samples record large scatter in Nb content and have Nb/Ti ratios higher than coexisting ilmenite. This behavior can be predicted using prograde rutile crystallization from ilmenite and indicates that rutiles are reequilibrating their chemistry with remaining ilmenites. On the contrary, rutiles from the lowest grade samples (~480°C) have Nb/Ti ratios that are similar to the ones in ilmenite. Hence, rutiles from these samples did not equilibrate their chemistry with remaining ilmenites. Our data suggest that temperature may be one of the main factors determining whether or not the elements are able to diffuse between the phases and, therefore, reequilibrate. Newly-crystallized rutiles yield temperatures (from ~500 to 630°C, Zr-in-rutile thermometry) that are in agreement with the metamorphic conditions previously determined for the studied rocks. In quartzites from the medium-grade domain (~530°C), inherited detrital rutile grains are detected. They are identified by their distinct chemical composition (high Zr and Nb contents) and textures (single grains surrounded by fine grained ilmenites). Preliminary calculation, based on grain size distribution of rutile in medium-grade metapelites and quartzites that occur in the studied area, show that rutiles derived from quartzites can be anticipated to dominate the detrital rutile population, even if quartzites are a minor component of the exposure.     

Rutile R632 – A New Natural Reference Material for U‐Pb and Zr Determination

A new natural rutile reference material is presented, suitable for U‐Pb dating and Zr‐in‐rutile thermometry by microbeam methods. U‐Pb dating of rutile R632 using laser ablation ICP‐MS with both magnetic sector field and quadrupole instruments as well as isotope dilution‐thermal ionisation mass spectrometry yielded a concordia age of 496 ± 2 Ma. The high U content (> 300 μg g^?1) enabled measurement of high‐precision U‐Pb ages despite its young age. The sample was found to have a Zr content of 4294 ± 196 μg g^?1, which makes it an excellent complementary reference material for Zr‐in‐rutile thermometry. Individual rutile grains have homogeneous compositions of a number of other trace elements including V, Cr, Fe, Nb, Mo, Sn, Sb, Hf, Ta and W. This newly characterised material significantly expands the range of available rutile reference materials relevant for age and temperature determinations.     

Zr-in-rutile thermometry of eclogites from the Karakaya Complex in NW Turkey: Implications for rutile growth during subduction zone metamorphism

Eclogites occur as a tectonic slice within a metabasite-phyllite-marble unit of the Karakaya Complex in northwest Turkey. The high-pressure mineral assemblage in eclogite is mainly composed of garnet + omphacite + glaucophane + epidote + quartz. Trace element characteristics of rutile and Zr-in-rutile temperatures were determined for eclogites from the Karakaya Complex. Core-rim analyses of rutile grains yield remarkable trace element zoning with lower contents of Zr, Nb and Ta in the core than in the rim. The variations in Zr, Nb and Ta can be ascribed to growth zoning rather than diffusion effects. The Nb/Ta and Zr/Hf ratios increase with a decrease in Ta and Hf contents, which could be ascribed to the effect of metamorphic dehydration in subduction zones on rutile Nb/Ta differentiation. The rutile grains from eclogites in the Karakaya Complex are dominated by subchondritic Nb/Ta and Zr/Hf ratios. It can be noted that subchondritic Nb/Ta may record rutile growth from local sinks of aqueous fluids from metamorphic dehydration.The Zr contents of all rutile grains range between 81 and 160 ppm with an average of 123 ppm. The Zr-in-rutile thermometry yields temperatures of 559–604 °C with an average temperature of 585 °C for eclogites from the Karakaya Complex. This average temperature suggests growth temperature of rutile before peak pressure during the subduction. However, some rutile grains have higher Zr contents in the outermost rims compared to the core. Zr-in-rutile temperatures of the rims are about 20 °C higher than those of the cores. This suggests that the outermost rims would have grown from a distinct fluid at higher temperatures than that of the cores. Moreover, Zr contents and calculated temperatures in both inclusion rutile and matrix rutile from eclogites are identical, which suggests that eclogites within the Karakaya Complex belong to the same tectonic slice and underwent similar metamorphic evolution.     

Microstructurally controlled trace element (Zr,U–Pb) concentrations in metamorphic rutile: An example from the amphibolites of the Bergen Arcs

As a common constituent of metamorphic assemblages, rutile provides constraints on the timing and conditions of rock transformation at high resolution. However, very little is known about the links between trace element mobility and rutile microstructures that result from synmetamorphic deformation. To address this issue, here we combine in situ LA-ICP-MS and sensitive high-resolution ion microprobe trace element data with electron back-scatter diffraction microstructural analyses to investigate the links between rutile lattice distortions and Zr and U–Pb systematics. Furthermore, we apply this integrated approach to constrain further the temperature and timing of amphibolite facies metamorphism and deformation in the Bergen Arcs of southwestern Norway. In outcrop, the formation of porphyroblastic rutile in dynamically hydrated leucocratic domains of otherwise rutile-poor statically hydrated amphibolite provides key contextual information on both the ambient conditions of hydration and deformation and the composition of the reactive fluid. Rutile in amphibolite recorded ambient metamorphic temperatures of ~590–730°C during static hydration of the granulitic precursor. By contrast, rutile from leucocratic domains in the directly adjacent shear zone indicates that deformation was accompanied by a localized increase in temperature. These higher temperatures are recorded in strain-free rutile (~600–860°C) and by Zr concentration measurements on low-angle boundaries and shear bands (620–820°C). In addition, we also observe slight depletions of Zr and U along rutile low-angle boundaries relative to strain-free areas in deformed grains from the shear zone. This indicates that crystal–plastic deformation facilitated the compositional re-equilibration of rutile upon cooling to slightly below the peak temperature of deformation. Cessation of deformation at mid-crustal conditions near ~600°C is recorded by late stage growth of small (<150 µm) rutile in the high-strain zones. U–Pb age data obtained from the strain-free and distorted rutile grains cluster in distinct populations of 437.4 ± 2.7 Ma and c. 405–410 Ma, respectively. These different ages are interpreted to reflect the difference in closure for thermally induced Pb diffusion between undeformed and deformed rutile during post-deformation exhumation and cooling. Thus, our results provide a reconstruction of the thermochronological history of the amphibolite facies rocks of the Lindås Nappe and highlight the importance of integration of microstructural data during application of thermometers and geochronometers.     

北大别的高温超高压变质作用与多阶段折返

近期的变质岩石学、地球化学及同位素年代学研究表明,北大别整体经历了高温超高压变质作用和多阶段折返历史,因而表现为广泛发育的多期减压结构和极少保留早期的超高压变质记录。北大别榴辉岩以高温变质作用以及折返期间因麻粒岩相和角闪岩相退变质变质作用而形成的多期后成合晶为显著特征。石榴子石中伴有放射状胀裂纹的单晶和多晶石英包体指示早期柯石英的转变结果,这已被锆石中发现的柯石英残晶所证实。结合北大别北部榴辉岩和片麻岩中发现的金刚石等超高压证据以及三叠纪变质记录,由此证明北大别整体经历过深俯冲和印支期超高压变质作用。北大别榴辉岩的多阶段高温条件主要来自石榴子石-绿辉石矿物对温度计、单斜辉石中紫苏辉石+石英针状矿物出熔体以及金红石中较高的Zr含量和变质锆石中较高的Ti含量等得出的温度证据。此外,多期后成合晶以及石榴子石和单斜辉石等矿物中成分分带的存在,证明该区榴辉岩经历了一个多阶段、快速折返过程;而不同变质阶段的温度、压力和形成时代,却反映该区榴辉岩经历了长时间的高温变质演化与缓慢冷却过程。长时间的高温变质作用与缓慢冷却过程也许正是北大别长期难以发现柯石英和有关超高压记录的重要原因。因此,这些成果为大别山三个不同超高压岩片的差异折返模型的建立提供了新的证据。     

Age and duration of ultrahigh-temperature metamorphism in the Anápolis–Itauçu Complex, Southern Brasília Belt, central Brazil – constraints from U–Pb geochronology, mineral rare earth element chemistry and trace-element thermometry

Integrated petrographic and chemical analysis of zircon, garnet and rutile from ultrahigh‐temperature (UHT) granulites in the Anápolis–Itauçu Complex, Brazil, is used to constrain the significance of zircon ID‐TIMS U–Pb geochronological data. Chondrite‐normalized rare earth element (REE) profiles of zircon cores have positive‐sloping heavy‐REE patterns, commonly inferred to be magmatic, whereas unambiguous metamorphic grains and overgrowths have flat to slightly negatively sloping heavy‐REE patterns. However, in one sample, a core of zircon interpreted as having formed prior to garnet crystallization and a metamorphic zircon formed within microstructures involving garnet breakdown both display elevated heavy‐REE (and Y) with positive‐sloping patterns. D_REE(zrc/grt) partition coefficients suggest an approximation to equilibrium between zircon and garnet cores, although progressive enrichment in heavy REE towards garnet rims occurs in two of the samples investigated. Titanium‐in‐zircon thermometry indicates zircon growth during both the prograde and post‐peak evolution, but not at peak temperatures of the UHT metamorphism. By contrast, zirconium‐in‐rutile thermometry of inclusions armoured by garnet records crystallization temperatures, based on the upper end of the interquartile range of the data, of ～890 to 870 °C and maximum temperature around 980 °C, indicating prograde and retrograde growth close to and after peak conditions. Rutile located in retrograde microstructures records crystallization temperatures of 850 to 820 °C. Rutile intergrown with ilmenite and included within orthopyroxene, which is associated with exsolved zircon, records temperatures ～760 °C, consistent with Ti‐in‐zircon crystallization temperatures. ID‐TIMS U–Pb geochronological data from two of the four samples investigated define upper intercept ages of 641.3 ± 8.4 Ma (MSWD 0.91) and 638.8 ± 2.5 Ma (MSWD 1.03) that correlate with periods of zircon growth along the prograde segment of the P–T path. Individual zircon U–Pb dates retrieved from all samples range from 649 to 634 Ma, indicating a maximum duration of c. 15 Myr for the UHT event. This period is interpreted as recording modest thickening of hot backarc lithosphere located behind the Arenópolis Arc at the edge of the São Francisco Craton consequent upon terminal collision of the Parána Block with the arc during the amalgamation of West Gondwana.