Rutile Grains Research Articles

Al and Si diffusion in rutile

Abstract Diffusion of Al and Si has been measured in synthetic and natural rutile under anhydrous conditions. Experiments used Al2O3 or Al2O3-TiO2 powder mixtures for Al diffusant sources, and SiO2-TiO2 powder mixtures or quartz-rutile diffusion couples for Si. Experiments were run in air in crimped Pt capsules, or in sealed silica glass ampoules with solid buffers (to buffer at NNO or IW). Al profiles were measured with Nuclear Reaction Analysis (NRA) using the reaction 27Al(p,γ)28Si. Rutherford Backscattering spectrometry (RBS) was used to measure Si diffusion profiles, with RBS also used in measurements of Al to complement NRA profiles. We determine the following Arrhenius relations from these measurements: For Al diffusion parallel to c, for experiments buffered at NNO, over the temperature range 1100–1400 °C: D Al = 1.21 × 10 − 2 exp ⁡ ( − 531 ± 27 kJ/ mol − 1 / RT ) m 2 s − 1 . For Si diffusion parallel to c, for both unbuffered and NNO-buffered experiments, over the temperature range 1100–1450 °C: D Si = 8.53 × 10 − 13 exp ⁡ ( − 254 ± 31 kJ/ mol − 1 / RT ) m 2 s − 1 . Diffusion normal to (100) is similar to diffusion normal to (001) for both Al and Si, indicating little diffusional anisotropy for these elements. Diffusivities measured for synthetic and natural rutile are in good agreement, indicating that these diffusion parameters can be applied in evaluating diffusivities in rutile in natural systems Diffusivities of Al and Si for experiments buffered at IW are faster (by a half to three-quarters of a log unit) than those buffered at NNO. Si and Al are among the slowest-diffusing species in rutile measured thus far. Diffusivities of Al and Si are significantly slower than the diffusion of Pb and slower than the diffusion of tetravalent Zr and Hf and pentavalent Nb and Ta. These data indicate that Al compositional information will be strongly retained in rutile, providing evidence for the robustness of the recently developed Al in rutile thermobarometer. For example, at 900 °C, Al compositional information would be preserved over ~3 Gyr in the center of 250 μm radius rutile grains, but Zr compositional information would be preserved for only about 300 000 yr at this temperature. Al-in-rutile compositions will also be much better preserved during subsolidus thermal events subsequent to crystallization than those for Ti-in-quartz and Zr-in-titanite crystallization thermometers.

Zirconium in rutile thermometry of the Himalayan ultrahigh-pressure eclogites and their retrogressed counterparts, Kaghan Valley, Pakistan

This study reports zirconium-in-rutile thermometry data from the Himalayan ultrahigh-pressure eclogites and their retrogressed counterparts. The Zr contents of three textural varieties of rutile i.e. matrix rutile, inclusion phase, and overgrown by ilmenite/titanite from coesite-bearing eclogites, slightly retrogressed eclogites, highly retrogressed eclogites, and amphibolites were analyzed for Zr contents using the electron probe micro-analyser. Majority of the rutile grains exhibited homogeneous chemical compositions in all the aforementioned textural varieties; however, some of grains were relatively heterogeneous. Average temperature values of 729 °C, 727 °C, and 706 °C were obtained for the matrix, inclusion, and overgrown rutiles from UHP eclogites and of 705 °C, 699 °C, and 707 °C for those from HP eclogites, respectively. Slightly retrogressed eclogites yielded similar average T values of 703 °C, 706 °C, and 706 °C, respectively, whereas highly retrogressed eclogites resulted in relatively low average temperatures, ca. 690 °C, 691 °C, and 679 °C, respectively. When compared with these eclogites, lower average T values of 672 °C, 630 °C, and 656 °C were obtained from garnetites, and of 665 °C, 658 °C, and 640 °C from garnet amphibolites, respectively. The relatively homogeneous Zr contents and higher temperature values from the matrix rutile in HP and UHP eclogites suggest peak or near-peak metamorphic crystallization, whereas grains with low Zr contents, yielding low temperature values, were likely to be affected by the late-stage retrogression.

Oxidation‐led decomposition of hexagonal boron nitride coatings on alloy substrates at 900 °C: Ti‐6Al‐4V

AbstractHexagonal boron nitride (h‐BN) coatings on Ti‐6Al‐4V substrates undergo complete decomposition in air at 900 °C. This fate is similar to that of this ceramic material on chromia‐former alloys, and unlike that of a mass of powder treated in isolation. As the ceramic and alloy oxidize concurrently, outwardly diffusing aluminum (III) ions but not the predominant titanium (IV) ions react with the boron trioxide that forms around the h‐BN basal plane peripheries. Resultant aluminum borate is incorporated into the growing scale and the boron trioxide diffusion barrier is depleted. By this mechanism, the oxidation of h‐BN is maintained at an enhanced rate, until both this material and its oxide completely decompose. Liberated nitrogen from the oxidation of h‐BN can enter the underlying scale as a randomly distributed solute in rutile solid solution. The post‐coating oxide‐atmosphere interface comprises elongated aluminum borate crystallites protruding through at the boundaries between 3–5 at% nitrogen‐doped rutile grains. It differs significantly from that of oxidized, uncoated Ti‐6Al‐4V, which is occupied by a thin α‐alumina layer atop rutile. This interface does not change with an additional 72 h of heat‐treatment.

Growth Kinetics of Microarc Oxidation TiO2 Ceramic Film on Ti6Al4V Alloy in Tetraborate Electrolyte

The growth kinetics of microarc oxidation TiO2 ceramic film on Ti6Al4V alloy in 0.1 M Na2B4O7·10H2O electrolyte were studied using scanning electron microscopy, transmission electron microscope, atomic force microscope, X-ray diffraction, and potentiodynamic polarization. It was found that the discharge sizes increased gradually from anodic oxidation, spark discharge, and microarc to arc discharges in the microarc oxidation process, and reached the maximum value without anymore increases. The microarc oxidation coating was mainly composed of nanocrystalline rutile TiO2 grains with very little amorphous titanium dioxide, and was made up of three layers, namely an inner dense thin layer, a middle dense thick layer, and a porous outer layer. The content of the rutile phase increased with the increasing discharge size, and when the discharge size reached a maximum, the increase rate decreased slightly. The surface roughness, Rv, and corrosion resistance of the coating increased with the increasing discharge size until the discharge size reached a maximum. It was concluded that the thickness of two dense layers depended on the discharge size, with any changes in it revealing the growth kinetics of the coating. A new method was developed to obtain the effective thickness of the coatings by measuring the thickness of the two dense layers. The results demonstrated that the growth kinetics of the two dense layers are linear during spark and microarc discharges, of which the growth trend is the same as that of the voltage. A linear relationship for the voltage and thickness of the two dense layers was obtained.

Benefits of a Multiproxy Approach to Detrital Mineral Provenance Analysis: An Example from the Merrimack River, New England, USA

AbstractThe advantages in provenance research of U‐Pb dating different detrital minerals along with simultaneously analyzing trace elements is demonstrated in a study of sand from the mouth of the Merrimack River in New England, USA. Zircon ages record episodes of magmatism in the Early Paleozoic, peaking in the Early Devonian, followed by quiescence through the remainder of the Paleozoic and additional magmatic episodes in the Jurassic and Cretaceous. Simultaneous measurement of trace elements in zircons reveals a shift from arc magmatism to crustal melting associated with terrane collision in the Early Devonian, while many Jurassic grains are clearly derived from A‐type granites. Detrital monazites and rutiles have Devonian and Permian ages. Many of the older monazites have trace element characteristics suggestive of igneous origin, while Permian monazites are clearly metamorphic and record orogenesis that is absent from the detrital zircon record. Rutile grains have trace element chemistry indicative of mostly metasedimentary source rocks, and Zr thermometry indicates growth under amphibolite facies conditions. Age offsets between monazite and rutile populations provide information about the region's cooling history. Titanite grains have trace element chemistry mostly consistent with igneous origin and U‐Pb ages lining up with minor zircon age populations in the Ordovician‐Silurian and the Middle Devonian, suggesting that these magmatic episodes produced metaluminous compositions. These results show that combining trace element fingerprinting with dating and analyzing multiple detrital mineral species provide a more complete portrait of the geologic history of the sediment source region than U‐Pb dating of zircon alone.

Badanie wpływu zawartości minerałów ciężkich na naturalną promieniotwórczość skał miocenu zapadliska przedkarpackiego

In the Miocene rocks of the Carpathian Foredeep, the occurrence of overestimating the measurements of natural radioactivity logs for mudstones was noticed. This phenomenon causes problems with recognition on the basis of natural radioactivity profiling of these rocks from claystones, characterized by inferior petrophysical parameters. In this study, another possible source of increased radioactivity of mudstone rocks, i.e. the content of heavy minerals that tend to accumulate radioactive elements - uranium and thorium - was investigated. Heavy minerals, belonging to the accessory minerals, such as zircon, apatite, monazite, rutile, garnet and titanite, are characterized by increased radioactivity due to substitutions of U and Th in the crystal lattice. Natural radioactivity of the test samples was measured using the gamma spectrometry method with the RT-50 device from the Georadis company. The heavy minerals were then removed from the rock samples using a heavy liquid, previously separating the samples into grain fractions to facilitate the separation of the heavy fraction. The individual grain fractions deprived of heavy minerals were put back together and the uranium, thorium (and potassium) content was re-measured. Microscopic observations were also made to qualitatively analyze the mineralogical structure of the separated heavy fraction. In the tested samples, among others: zircon, tourmaline, garnet, rutile, apatite, chlorite or titanite grains were identified. The results of the measurements of natural radioactivity, before and after the separation of heavy minerals, do not give a clear answer to the problem of excessive indications of the gamma logs. It is necessary to increase the number of analyzed samples. The trend of decreasing amounts of U and Th in the samples from which the heavy fraction was isolated was observed. However, changes in radioactivity are so small that they do not allow to draw final conclusions. Additional analyzes are needed to assess the impact of other sources of uranium and thorium in analyzed rocks, such as the content of organic matter or Th content in clays.

Low-temperature impedance spectroscopic analyses of ceramic electrodes based on Mo and Co co-doped SnO2

Low resistive electrodes based on Co and Mo co-doped SnO2 were prepared by the conventional solid-state reaction and sintered at 1250?C for 2 h. Concentration of Co2O3 precursor was unchanged (1mol%), while MoO3 was varied (0.25, 0.50 to 0.75mol%) to promote conductivity. The structural and microstructural characterization revealed that the samples have a rutile-type structure without secondary phases and large rutile grains with low porosity. Electrical measurements on DC mode have shown a semiconductor behaviour of the SnO2 samples doped with 0.25 and 0.75 at.% of Mo at temperatures below 50K, indicating their suitability for low-temperature electronic applications. Impedance measurements indicate reduced energy barriers of less than 1meV formed between highly conductive crystallites for the SnO2 samples doped with 0.25 and 0.75 at.% of Mo. The sample with Mo content of 0.50 at.% presented a higher energy barrier at a few hundredths of eV, with space charges at the crystallite boundaries.

Characterization and Photocatalytic Performance of Potassium-Doped Titanium Oxide Nanostructures Prepared via Wet Corrosion of Titanium Microspheres.

Potassium doped titanium oxide (KTiOx) nanowires were prepared by the wet corrosion process (WCP) and their photocatalytic effects were systematically characterized. For the synthesis of KTiOx, the potassium hydroxide concentration of the WCP was varied in order to obtain nanostructures with different surface area and surface charge. Structural and crystalline properties of KTiOx were studied by means of X-ray diffraction, scanning and transmission electron microscopy. Chemical composition was determined by X-ray fluorescence and energy-dispersive X-ray analysis. Photocatalytic performance was investigated as a function of the surface area, pH, and crystalline structures by studying the degradation of methylene blue, cardiogreen, and azorubine red dyes upon UV irradiation. The negatively charged crystalline KTiOx nanostructures with high surface area showed significantly higher photocatalytic degradation compared to their TiOx counterpart. They also showed high efficiency for recovery and re-use. Annealing KTiOx nanostructures improved structural properties leading to well-ordered layered structures and improved photocatalysis. However, annealing at temperatures higher than 600 °C yielded formation of rutile grains at the surface of nanowires, significantly affecting the photocatalytic performance. We believe that KTiOx nanostructures produced by WCP are very promising for photocatalysis, especially due to their high photocatalytic efficiency as well as their potential for re-use and durability.

Metamorphic pressure–temperature conditions of the Lützow–Holm Complex of East Antarctica deduced from Zr–in–rutile geothermometer and Al<sub>2</sub>SiO<sub>5</sub> minerals enclosed in garnet

The metamorphic pressure–temperature (P–T) conditions of high–grade pelitic gneisses from Akarui Point, Skarvsnes, Skallen, and Rundvågshetta in the Lützow–Holm Complex (LHC), East Antarctica are re–examined by applying the Zr–in–rutile geothermometer to rutile inclusions in garnet enclosing Al2SiO5 minerals and to matrix rutile grains. By utilizing the P zoning of garnet to indicate isochronous surface, samples from Akarui Point, Skarvsnes, and Skallen were shown to have experienced almost the same P–T conditions around the kyanite/sillimanite transition boundary (~ 830–850 °C/~ 11 kbar). From Rundvågshetta, higher–T condition (850 ± 15 °C/0.1 kbar to 927 ± 16 °C/12.5 kbar) was confirmed from rutile inclusions in garnet enclosing sillimanite. Matrix rutile yielded similar temperature as inclusion rutile for Akarui Point, Skarvsnes, and Skallen samples. Therefore, the traditional metamorphic zone mapping based on matrix mineral assemblages, which classified Akarui Point as belonging to the transitional zone between the upper–amphibolite and the granulite facies zones, does not reflect the highest metamorphic conditions attained. The P–T–t evolution of the LHC needs to be re–evaluated utilizing detailed petrochronological approaches.

Dynamics of ketamine-related resting state functional connectivity changes in healthy controls

It has been shown that certain host minerals can robustly shield mineral inclusions and prevent loss of petrochronological information during subsequent thermal events. Rutile inclusions in garnet may crystallize under a wide range of metamorphic conditions and thus rutile is expected to be a useful geochronometer for constraining different stages of a metamorphic P-T path. Hence, it is important to ascertain whether rutile inclusions shielded by garnet retain the original crystallization age information despite later retrograde cooling or subsequent new thermal events. In this study, we test the “shielding effect” of garnet on rutile inclusions from the Baizhangya eclogite in the North Dabie Zone (China), which underwent a multi-stage thermal evolution. Secondary ion mass spectrometry (SIMS) UPb dating of inherited zircon core domains constrains a Neoproterozoic formation age (~770 Ma) of the eclogite protolith. SIMS UPb dating of metamorphic zircon and complementary thermal-ionization mass spectrometry (TIMS) SmNd isochron dating of garnet revealed Triassic eclogite-facies metamorphic ages (245–210 Ma). An Early Cretaceous SIMS UPb age of ca. 130 Ma, yielded by matrix rutile grains and rutile inclusions, suggests significant isotopic alteration since crystallization. This indicates that shielding was ineffective, since the UPb ages derived from the rutile inclusions, although hermetically armored by garnet, were influenced by a subsequent Early Cretaceous tectono-thermal event. Further transmission electron microscope (TEM) analysis revealed the presence of hematite microlites along the garnet-rutile boundaries, which may have acted as a potential reservoir to store the expelled radiogenic Pb from rutile. This study suggests that newly formed minerals located along mineral boundaries seem to be crucial for understanding the shielding effect.

Evidence for a 200 km thick diamond-bearing root beneath the Central Mackenzie Valley, Northwest Territories, Canada? Diamond indicator mineral geochemistry from the Horn Plateau and Trout Lake regions

The Central Mackenzie Valley (CMV) area of Northwest Territories is underlain by Precambrian basement belonging to the North American Craton. The potential of this area to host kimberlitic diamond deposits is relatively high judging from the seismologically-defined lithospheric thickness, age of basement rocks (2.2–1.7 Ga) and presence of kimberlite indicator minerals (KIMs) in Quaternary sediments. This study presents data for a large collection of KIMs recovered from stream sediments and till samples from two study areas in the CMV, the Horn Plateau and Trout Lake. In the processed samples, peridotitic garnets dominate the KIM grain count for both regions (> 25% each) while eclogitic garnet is almost absent in both regions (< 1% each). KIM chemistry for the Horn Plateau indicates significant diamond potential, with a strong similarity to KIM systematics from the Central and Western Slave Craton. The most significant issue to resolve in assessing the local diamond potential is the degree to which KIM chemistry reflects local and/or distal kimberlite bodies. Radiogenic isotope analysis of detrital kimberlite-related CMV ilmenite and rutile grains requires at least two broad age groups for eroded source kimberlites. Statistical analysis of the data suggests that it is probable that some of these KIMs were derived from primary and/or secondary sources within the CMV area, while others may have been transported to the area from the east-northeast by Pleistocene glacial and/or glaciofluvial systems. At this stage, KIM chemistry does not allow the exact location of the kimberlitic source(s) to be constrained.

Interpretation and significance of combined trace element and U–Pb isotopic data of detrital rutile: a case study from late Ordovician sedimentary rocks of Saxo-Thuringia, Germany

The U–Pb age and trace element composition of detrital rutile provide information about the metamorphic history of the source region that cannot be constrained by traditional U–Pb dating of detrital zircon. Previous provenance investigations focussed on only one of these methods. Based on a large LA-ICP-MS trace element and U–Pb isotopic dataset of detrital rutile and U–Pb isotopic data of detrital zircon from late Ordovician sedimentary rocks of Saxo-Thuringia, Germany, this paper discusses the application and significance of combining these methods in provenance investigations. U–Pb age spectra from the detrital zircons analysed show multiple age components (multimodal age spectra) in all samples. This is in contrast with the detrital rutile data, as only one sample yielded a multimodal U–Pb age distribution. Multimodal age spectra of detrital rutile are most likely preserved in sediments from (large) catchment areas with complex geological histories. They may also be related to specific sedimentation events, such as glacial washout during the retreat of large ice shields (e.g. the Hirnantian glaciation of Gondwana). Unimodal age spectra are however not restricted to small catchment areas, if the provenance region is characterized by a pervasive thermal overprint such as the Pan-African orogeny throughout Gondwana. Unimodal age distributions may further consist of overlapping age cluster detectable by different trace element composition of the detrital rutile grains. The combined U–Pb age and trace element data from detrital rutile grains demonstrate that rutile sourced from metapelitic rocks yield reliable and precise U–Pb ages. In contrast, detrital rutile classified to be of metamafic origin generally has too low uranium concentrations to be dated reliably by LA-ICP-MS. Detrital rutile records low- to medium-grade metamorphic events in the source region and therefore has the potential to better constrain the maximum depositional age of sedimentary rocks in comparison to U–Pb dating of detrital zircon.

Tracking the prograde P\u2013T path of Precambrian eclogite using Ti-in-quartz and Zr-in-rutile geothermobarometry

A Fe–Ti-rich garnet, clinopyroxene, and quartz eclogite sample from the 1.0 Ga Sveconorwegian orogen, SW Sweden, contains abundant quartz, rutile, and zircon in distinct micro-textural sites: garnet core, garnet rim, and matrix, constituting an ideal case for investigation of the behavior of Zr-in-rutile and Ti-in-quartz at high-pressure and temperature. A P–T path, peaking at 16.5–19 kbar and 850–900 °C, has been constrained independently for the same rock by pseudosection modelling; input pressures from this model were used for trace element geothermometry of each garnet micro-textural domain. Trace element thermo(baro)metry, based on in situ Secondary Ion Mass Spectrometry analyses of Ti contents in quartz and Zr contents in rutile, yields P–T estimates of progressive crystallization of quartz and rutile along the prograde metamorphic path. For inclusions in the garnet cores, Zr-in-rutile geothermometry yields 700–715 °C and Ti-in-quartz 620–640 °C at 7 kbar. For inclusions in the garnet rims, temperature estimates are 760–790 °C (Zr-in-rutile) and 740–920 °C (Ti-in-quartz) at 12–18 kbar. Finally, matrix rutile records 775–800 °C and locally ~ 900 °C, and quartz records temperatures up to 900 °C at 18 kbar. Ti-in-quartz estimates for the metamorphic peak (inclusions in the garnet rims and matrix) conform to the pseudosection, but appear too low for the early prograde stage (garnet cores), possibly due to lack of equilibrium at T < 700 °C. The pseudosection shows that rutile was produced by continuous ilmenite breakdown during the early stages of prograde metamorphism, a reaction that was completed at ~ 730 °C. Rutile grains in the garnet rims and the matrix grew subsequently larger by recrystallization of previously produced rutile. However, recrystallized rutile does not predominantly record peak temperatures, but instead yield 745–840 °C between 12 and 18 kbar. In the pseudosection, this temperature range broadly coincides with a stage during which (Ti-bearing) hornblende was consumed and clinopyroxene produced (i.e., dehydration); the Zr contents thus appear to reflect the last stage of efficient rutile recrystallization, catalysed by fluids released by the dehydration of hornblende preceding the metamorphic peak. Concurrently, combination of the isopleths for Ti content in quartz and Zr content in rutile (i.e. independent from pseudosection modelling) yields pressure and temperature conditions in almost perfect agreement with the P–T path as deduced from the pseudosection. The variation in Ti concentration in quartz is small regardless of crystal size, and the Ti-in-quartz geothermometer provides both precise and accurate peak temperatures of 875–920 °C, without a significant diffusional reequilibration. The lack of significant Ti diffusion in quartz is consistent with an inferred short residence time at high temperature. This study illustrates that Zr-in-rutile and Ti-in-quartz geothermobarometry can robustly constrain prograde P–T conditions and yield further insights into recrystallization processes at high temperature. The combination of these methods and integration of the results with pseudosection modelling is a versatile tool for investigating the petrologic history of high-grade rocks.

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 (&gt; 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.

Peculiarities of Diamonds in Eclogitic Xenoliths from the Komsomolskaya Kimberlite Pipe, Yakutia

The first studies of diamonds in eclogitic xenoliths from the Komsomolskaya kimberlite pipe are described. Among round and oval-shaped xenoliths with diamond ingrowths, samples with a garnet content of 40–90% of the xenolith volume dominate. Two eclogite samples contain grains of accessory rutile; a kyanite sample is also revealed. Certain samples contain two or more crystals of diamonds. Diamonds with an octahedral habit and crystals with transitional habits, which belong to an octahedral-rhombic dodecahedral row, dominate in eclogites; there are many variety VIII aggregates. A high concentration of structural nitrogen, commonly in the A form, was registered in most of the crystals. Diamonds with a small content of nitrogen impurities, 40–67% in the B1 form, are present in a number of xenoliths. The calculated temperatures of the formation of eclogitic xenoliths is 1100–1300°C. Diversity in the impurity compositions of diamonds in the same xenolith shows that these diamonds were formed at various times and in different settings. The diamond position in xenoliths, the various level of nitrogen aggregation in the diamonds, and a number of other factors point to the later formation of the diamonds, as compared to minerals of eclogites, from fluid or fluid-melts in the process of metasomatosis.

A window into the lower crust: Trace element systematics and the occurrence of inclusions/intergrowths in granulite-facies rutile

Rutile occurs as an accessory mineral in many high-temperature metamorphic assemblages and has the potential to identify and investigate UHT metamorphic terranes. Whilst the use of Zr-in-rutile geothermometry to identify ultrahigh-temperature terranes is appealing, its application to granulites can be difficult owing to diffusional resetting of Zr concentrations during cooling and decompression. In order to provide constraints on P-T conditions and trace element systematics during ultrahigh-temperature metamorphism, metamorphic rutile in granulites from the Archean Napier Complex and the Palaeozoic Rauer Group, Antarctica have been investigated for trace element composition and mineral inclusions/intergrowths. Textural observations and Zr-in-rutile temperatures show that unlike the large proportion of rutiles grains in the matrix, rutile grains that are shielded by phases with low Zr-diffusivities (e.g. orthopyroxene) and/or are in chemical isolation from zircon, have the potential to retain Zr concentrations that correspond to ultrahigh-temperatures. Principal Component Analysis reveals that V, Cr, Nb, Mo, Ta and W are significantly enriched in rutile from Archean and Proterozoic ultrahigh-temperature terranes. High concentrations of elements such as Cr and V indicate a spinel-rich source, demonstrating the effect of protolith bulk chemical composition on rutile trace element signatures. Rutile is shown to contain inclusions and intergrowths of aluminium silicate, quartz, corundum and feldspar, including the first reported occurrence of prograde kyanite, which provides direct evidence that the Napier Complex experienced a typical clockwise P-T evolution.

The origin and geochemical characteristics of rutile in eluvial and fluvial-alluvial placers and quartz veins of the Menderes Massif from the Neoproterozoic Pan-African Belt, Western Turkey

Rutile occur in important amounts within Quaternary detrital sediments, and quartz veins which cut down the Paleozoic aged Eşme formation in the Menderes Massif on the Neoproterozoic Pan-Afrikan Belt in the west of Turkey. As a result of erosion, transport and accumulation of rutile-bearing quartz veins in the mica schists of the Eşme formation outcropped between Eşme (Uşak) and Kula (Manisa), the placer rutile occurrences occur in terraces, fluvial-alluvial and eluvial deposits. This study investigates the element content of rutile, oxygen isotope ratios of rutile and quartz, and formation temperature of rutile related to titanium source rock.Field observations show that rutiles are located in quartz veins that cut the schists. After these veins were fragmented and eroded, blocks of quartz with rutile and rutile grains are transported into clastic sediments in slope debris (eluvial), terraces and recent fluvial-alluvial deposits. Whereas quartz, rutile, ilmenite, and albite are found in the paragenesis of the rutile-bearing quartz vein fragments, the placers forming the terraces and current fluvial-alluvial deposits contain quartz, albite, muscovite, orthoclase, kaolinite, rutile, dravite, ilmenite, and zircon. The rutile grains in the examined placers and quartz vein fragments have grain sizes ranging from mm fractions to 5–6 cm.The major oxide compositions of the rutile grains have average values of 94 wt.% TiO2, 1.5 wt.% Fe2O3, 0.5 wt.% SiO2, and 0.3 wt.% Al2O3. The rutile samples have average values Nb of 1424 ppm, V of 980 ppm, W of 192 ppm, Ta of 94 ppm, and Zr of 73 ppm. The rutiles in the study area are defined as iron-rich rutile “nigrine” due to high iron content. Quartz veins are host rocks of rutile grains in the terrace and fluvial-aluvial sediments.The rutile-bearing quartz veins may be sourced from the Lower-Middle Miocene aged granites which are intruded the rocks in the Menderes Massif. Based on the analysis results of the methods of Zr thermometer from Zr values containing rutile and quartz-rutile geothermometer from oxygen isotope results (13.5‰ and 6‰) of quartz and rutile samples, the formation temperature of the rutile-bearing quartz veins were found to be at temperatures of 537 °C and 561 °C, respectively. These temperatures indicate that the rutile-bearing quartz veins may be in a temperature range between pegmatitic and/or hydrothermal stages.

Rutile alteration and authigenic growth in metasandstones of the Moeda Formation, Minas Gerais, Brazil – A result of Transamazonian fluid–rock interaction

Microstructures, trace elements and U–Pb ages of rutile grains are reported from two metasandstone samples of the Moeda Formation, which is the basal unit of the Minas Supergroup in the Quadrilátero Ferrífero, Minas Gerais, Brazil. The Moeda metasandstones, deposited between 2.68 and 2.65 Ga, are intercalated with Witwatersrand-like, pyritiferous and auriferous metaconglomerate layers. Rutile from both samples shows unusually high contents of Th (1–142 ppm) and rare-earth elements (ΣREE = 1–132 ppm), with chondrite-normalized middle REE humps, and reveals post-depositional U–Pb ages of ≤2.25 Ga; only three grains yielded significantly older ages of up to 2.72 Ga, pointing to a detrital origin. The combined data set suggests that rutile formation and alteration at 2.25 Ga was caused by distinct fluid-mediated processes, which erased nearly all provenance information. Detrital, rounded rutile grains in sample A were altered by a coupled dissolution–reprecipitation process (type 1), resulting in highly porous grains. These show variable contents of rutile-compatible and -incompatible trace elements: Th (1–48 ppm), Zr (25–796 ppm), U (12–167 ppm), Pb (9–52 ppm), Cr (900–12,878 ppm), W (143–3939 ppm), Nb (1148–6168 ppm), Sb (6–63 ppm), as well as variable ratios of Zr/Hf, Y/Ho and Th/U. Rutile grains in sample B are mostly authigenic (type 2), and formed after dissolution of pre-existing detrital rutile grains and subsequent transport and homogenization of trace elements. This interpretation is supported by the anhedral shape of some grains and the finding of numerous, randomly oriented muscovite laths. The authigenic population has significantly lower, and less variable contents of trace elements compared to type-1 rutile: Th (0.5–16 ppm), Zr (21–67 ppm), U (5.8–24 ppm), Pb (6-18 ppm), Cr (1379–3153 ppm), W (9.4–70 ppm), Nb (921–3058 ppm), Sb (3.3–10 ppm), and distinctively lower ratios of Zr/Hf (7.9) and Th/U (0.2), but variable Y/Ho ratios. Significant contents of Th and REE are explained by co-precipitation with TiO2 aggregates prior to structural ripening. The close association of rutile with muscovite, the rutile MREEN humps and the results of Zr-in-rutile thermometry suggest that rutile formation and alteration in the investigated sandstones was mediated by K(Na)–Si–P-bearing aqueous fluids at temperatures of about 490 °C. The rutile MREEN humps are interpreted to result from the tetrad effect during leaching of spatially associated detrital zircon grains. Uranium–Pb ages of ≤2.25 Ga indicate that the fluid overprint started at the onset of the Transamazonian orogeny, perhaps related to the opening of the Sabará foreland basin.

Mineralogy and spectroscopy of Owen Group sandstones, Australia: implications for the provenance, diagenesis, and origin of coloration

Mineralogical studies were conducted on sandstones of Late Cambrian-Early Ordovician Owen Group, southern West Coast Range, Tasmania, Australia. Several samples were analysed using conventional thin section and point counting techniques, while others were further analysed under a Scanning Electron Microscope with back scattering and Energy Dispersive X-ray Spectroscopy capabilities. The result of petrographic analyses includes provenance, possible sources and controls over coloration in sandstone samples. The sandstones are mainly comprised of quartz, mica, lithic grains (volcanic, metamorphic and sedimentary), clays, zircon, tourmaline, leucoxene, rutile, and chert grains. These were derived from a Proterozoic Tyennan metamorphic and a Middle Cambrian Mount Read Volcanic provenance. Following deposition, sediments underwent severe diagenesis including quartz overgrowth, iron coatings, haematite, chlorite and sericite alterations, linings and cements. Multi-phase haematite-related diagenesis is present and late stage hydrothermal fluid alterations assemblages have severely altered and colored the sediments.

Xenoliths of Eclogites with Diamonds from the Yubileinaya Kimberlite Pipe, Yakutia

The first results of study of minerals and diamonds of diamond-bearing eclogites from kimberlites of the Yubileinaya pipe with a variable percent amount of clinopyroxene and garnet are presented. Samples with a garnet content from 30 to 90% of the xenolith volume are dominant among the round to oval xenoliths with diamonds. Five eclogite samples contain grains of accessory rutile, as well as corundum and kyanite. Some samples host two or more diamond crystals.