Ion Microprobe Research Articles

How long can the middle crust remain partially molten during orogeny?

Extensive partial melting of the middle to lower crustal parts of orogens, such as of the current Himalaya-Tibet orogen, significantly alters their rheology and imposes first-order control on their tectonic and topographic evolution. We interpret the late Proterozoic Aracuai orogen, formed by the collision between the Sao Francisco (Brazil) and Congo (Africa) cratons, as a deep section through such a hot orogen based on U-Pb sensitive high-resolution ion microprobe (SHRIMP) zircon ages and Ti-in-zircon and Zr-in-rutile temperatures from the Carlos Chagas anatectic domain. This domain is composed of peraluminous anatexites and leucogranites that typically exhibit interconnected networks of garnet-rich leucosomes or a magmatic foliation. Zirconium-in-rutile temperatures range from 745 to 820 °C, and the average Ti-in-zircon temperature ranges from 712 to 737 °C. The geochronologic and thermometry data suggest that from 597 to 572 Ma this domain was partially molten and remained so for at least 25 m.y., slowly crystallizing between temperatures of ∼815 and >700 °C. Significant crustal thickening must have occurred prior to 600 Ma, with initial continental collision likely before 620 Ma, a time period long enough to heat the crust to temperatures required for widespread partial melting at middle crustal levels and to favor a “channel flow” tectonic behavior.

Ion microprobe–measured stable isotope evidence for ammonite habitat and life mode during early ontogeny

AbstractAmmonites have disparate adult morphologies indicative of diverse ecological niches, but ammonite hatchlings are small (~1 mm diameter), which raises questions about the similarity of egg incubation and hatchling life mode in ammonites. ModernNautilusis sometimes used as a model organism for understanding ammonites, but despite their outward similarities, the groups are only distantly related. Trends in ammonite diversity and extinction vulnerability in the fossil record contrast starkly with those of nautilids, and embryonic shells from Late Cretaceous ammonites are two orders of magnitude smaller than nautilid embryonic shells. To investigate possible environmental changes experienced by ammonite hatchlings, we used secondary ion mass spectrometry to analyze the oxygen and carbon isotope composition of the embryonic shells and early postembryonic whorls of five juveniles ofHoploscaphites comprimusobtained from a single concretion in the Fox Hills Formation of South Dakota. Co-occurring bivalves and diagenetic calcite were also analyzed to provide a benthic baseline for comparison. The oxygen isotope ratios of embryonic shells are more like those of benthic bivalves, suggesting that ammonite eggs were laid on the bottom. Ammonite shell immediately after hatching has more negative δ18O, suggesting movement to more shallow water that is potentially warmer and/or fresher. After approximately one whorl of postembryonic growth, the values of δ18O become more positive in three of the five individuals, suggesting that these animals transitioned to a more demersal mode of life. Two other individuals transition to even lower δ18O values that could suggest movement to nearshore brackish water. These data suggest that ammonites, like many modern coleoids, may have spawned at different times of the year. Because scaphites were one of the short-term Cretaceous–Paleogene extinction survivors, it is possible that this characteristic allowed them to develop a broader geographic range and, consequently, a greater resistance to extinction.

U\u2013Th isotopic microanalysis of zircon reference materials and KBSI working standards

BackgroundThe 238U–230Th disequilibrium dating of the mineral zircon (ZrSiO4) provides an efficient tool for investigating the time scales of Quaternary magmatic processes. In situ mass spectrometric U–Th microanalysis of zircon requires careful calibration and correction of the measured isotope data, particularly for the instrumental fractionation of U and Th isotopes.FindingsFor the selection of suitable calibration materials for U–Th isotopic analysis using a laser ablation multiple collector inductively coupled plasma mass spectrometer (LA-MCICPMS), we estimated the homogeneity of four reference zircons (91500, TEMORA 2, FC1, and Plešovice) and two zircon working standards (LKZ-1 and BRZ-1) in terms of their 232Th/238U ratios, based on the Pb isotopic compositions measured by a sensitive high-resolution ion microprobe (SHRIMP). The measured LA-MCICPMS 232Th/238U ratios of the zircons were calibrated externally using the SHRIMP 208Pb/206Pb-based average value of the 91500 zircon, 232Th/238U = 0.351 ± 0.035 (error corresponds to 1 standard deviation). The molecular interference-corrected 230Th/232Th ratios of the zircons were calibrated based on the assumption that the Plešovice zircon is in 238U–230Th secular equilibrium. After the calibration and correction, the activity ratios of 230Th/232Th and 238U/232Th for all reference zircons and working standards were plotted on the equiline.ConclusionsThis study confirms that the 91500 zircon is relatively homogeneous in terms of U/Th ratios (relative standard deviation = ~ 10%) and does not support a recent claim that the Plešovice zircon is not in 238U–230Th radioactive equilibrium. The working standards LKZ-1 and BRZ-1 can be used to check the reliability of U–Th isotopic analyses for Quaternary zircons.

Experimental constraints on hydrogen diffusion in garnet

The incorporation mechanisms and diffusional loss of hydrogen in garnet have been experimentally investigated. A suite of gem-quality hydrous spessartine- and grossular-rich garnets were analysed by Fourier transform infrared spectroscopy (FTIR) and by ion microprobe (SHRIMP-SI) to determine the calibration coefficients for quantification of FTIR data. The excellent agreement between measured absorption and OH/O indicates that the same molar extinction coefficient can be used for spessartine and grossular. The coefficient of 14400 l mol− 1 cm− 2 proposed by Maldener et al. (Phys Chem Miner 30:337–344, 2003) seems the most appropriate for both minerals. A grossular with 6.4% andradite and 1.6% almandine containing 834 ppm H2O, and an almost pure spessartine with 282 ppm H2O, were selected for diffusion experiments. 1.5-mm cubes of garnets were heated between 12 h and 10 days at 1 atm under various temperature (750–1050 °C) and oxygen fugacity ( $${f_{{{\text{O}}_2}}}$$ ) conditions, (ΔQFM + 15.2 to − 3.0). Diffusion profiles were acquired from sections through the cubes using FTIR, with a deconvolution algorithm developed to assess peak-specific behaviour. Different families of peaks have been identified based on their diffusive behaviour, representing hydrogen incorporated in different H-bearing defects. A dominant, fast, strongly $${f_{{{\text{O}}_2}}}$$ -dependent oxidation-related diffusion mechanism is proposed $$\left( {\{ {{\text{M}}^{2+}}+{{\text{H}}^+}\} +\frac{1}{4}{{\text{O}}_2}={{\text{M}}^{3+}}+\frac{1}{2}{{\text{H}}_2}{\text{O}}} \right)$$ (M=Fe, Mn) with a relatively low activation energy (158 ± 19 kJ mol− 1). This diffusion mechanism is likely restricted by availability of ferrous iron in grossular. At low oxygen fugacity, this diffusion mechanism is shut off and the diffusivity decreased by more than three orders of magnitude. A second, slower hydrogen diffusion mechanism has been observed in minor bands, where charge balance might be maintained by diffusion of cation vacancies, with much higher activation energy (≈ 200–270 kJ mol− 1). Spessartine shows clear differences in peak retentivity suggesting that up to four different H sites might exist. This opens exciting opportunities to use hydrogen diffusion in garnet as speedometer. However, it is essential to constrain the main diffusion mechanisms and the oxygen fugacity in the rocks investigated to obtain timescales for metamorphic or igneous processes.

Thermal and impact histories of 25143 Itokawa recorded in Hayabusa particles

Understanding the origin and evolution of near-Earth asteroids (NEAs) is an issue of scientific interest and practical importance because NEAs are potentially hazardous to the Earth. However, when and how NEAs formed and their evolutionary history remain enigmas. Here, we report the U-Pb systematics of Itokawa particles for the first time. Ion microprobe analyses of seven phosphate grains from a single particle provide an isochron age of 4.64 ± 0.18 billion years (1σ). This ancient phosphate age is thought to represent the thermal metamorphism of Itokawa’s parent body, which is identical to that of typical LL chondrites. In addition, the incorporation of other particles suggests that a significant shock event might have occurred 1.51 ± 0.85 billion years ago (1σ), which is significantly different from the shock ages of 4.2 billion years of the majority of shocked LL chondrites and similar to that of the Chelyabinsk meteorite. Combining these data with recent Ar-Ar studies on particles from a different landing site, we conclude that a globally intense impact, possibly a catastrophic event, occurred ca. 1.4 Ga ago. This conclusion enables us to establish constraints on the timescale of asteroid disruption frequency, the validity of the crater chronology and the mean lifetime of small NEAs.

Geochronology, petrogenesis and geodynamic significance of the Visean igneous rocks in the Central Sudetes, northeastern Bohemian Massif

New sensitive high-resolution ion microprobe (SHRIMP) UPb zircon geochronologic data, whole-rock geochemical and Sr-Nd-Pb isotopic data, and zircon and quartz δ18O isotopic data from the Staré Město granitoids (SMG), Jawornik granitoids (JG), and Kłodzko-Złoty Stok granitoids (KZSG) and associated mafic and ultramafic rocks are examined. This study provides new insights into the processes of magma generation, transport and emplacement during the Variscan development of the contact zone of the Saxothuringia, Teplá-Barrandia and Brunovistulia in the Central European portion of the Variscan belt. The results of this study, combined with existing geochemical and isotopic data, imply that the parental magmas of these intrusions share a close affinity and suggest that these intrusions formed in a subduction-related tectonic setting. The SMG, JG and KZSG magmas represent hybrids that formed from the contamination of partial melts from the lower crust and/or subducted sediments with various proportions of enriched mantle-derived melts. These mainly sheeted plutons intruded along the main geological boundaries during the Visean and recorded the vertical and lateral displacements between the major tectono-stratigraphic units (microplates) in the NE Bohemian Massif. In the Central Sudetes, these granitoid magmas were first emplaced along the northern continuation of the Moldanubian Zone. The SHRIMP UPb dating of zircons indicates that the SMG intruded the reactivated suture zone between the Brunovistulia and Saxothuringia at 344–341 Ma. Sills of the JG were emplaced between c. 347 and c. 334 Ma. The composite Kłodzko-Złoty Stok Pluton, which includes the KZSG and accompanying mafic enclaves and pyroxenite and lamprophyre dykes, was mainly emplaced at 340–333 Ma. The magmas of the KZSG possibly facilitated the final amalgamation of the Sudetic counterparts of the Teplá-Barrandia and Saxothuringia microplates during the orogenic uplift of the latter. Petrologic and oxygen isotopic data further indicate partial post-magmatic hydrothermal and/or alteration processes. Our new data further stress the connection of magma transfer and active shear zones, which could manifest as crustal-scale magma-ascent conduits.

Novel Applications of Focused Ion Beam Technique for Planetary Sample Analyses

We are using innovative FIB techniques to prepare samples of planetary materials for different types of coordinated analyses using ion microprobes, synchrotron beamlines, and specialized transmission electron microscopy (TEM) techniques. In these cases, the FIB sample preparation is the critical step in enabling these specialized analyses. We discuss several examples below utilizing the FEI Quanta3D instrument at the NASA Johnson Space Center. Trace element analyses utilizing synchrotron x-ray fluorescence. The trace element content of mineral grains in comet dust provides important clues on their formation and processing in the early solar system. We preformed coordinated analyses of a comet dust particle that had been prepared using ultramicrotomy for TEM analysis. Following the TEM analyses, we extracted a 70 nm thick section from a region of the carbon (C) film of the TEM grid, for additional analyses. A carbon ring ~2-3 μm thick was deposited on top of the C film using the FIB. The C film on the outer rim of the ring was milled away using various patterns to uniformly release the stresses on the film, preventing rupture and collapse, and was attached to the micromanipulator needle. We then isolated the ring completely and transferred the section to a silicon sample holder for analysis using the HXN (hard X-ray nanoprobe) beamline at NSLSII at Brookhaven National Lab. Coordinated Analyses of Presolar Grains. Rare sub-m presolar grains that originate in evolved stars and supernovae, occur in primitive astromaterials and are identified by their exotic isotopic compositions. Coordinated analyses of these grains using NanoSIMS, TEM, and other techniques on the same grain is enabled by innovative FIB sample preparation. In order to obtain subsequent isotopic analyses of Mg and Fe, contributions from surrounding grains were minimized. We precisely deposited a protective cap of Pt on top of the grain to preserve the grain of interest and then milled away about 5 μm diameter of the surrounding material. Following the isotopic analyses, the spindle was extracted and thinned to electron transparency for TEM microstructural analyses. In situ heating TEM experiments on lunar samples. We extracted a FIB thin section from Apollo 17 lunar rock 76015. To avoid ion-beam damage, e-beam deposition was used to deposit the first 500 nm of the C strap, followed by ion beam-assisted deposition of ~3 μm carbon. We performed an ex situ lift-out of the section and placed the section on one of the elements of a microelectromechanical systems (MEMS) - specialized heating substrate and attached the section to the substrate by depositing small C straps with the FIB. The heating chips utilize silicon nitride windows to support the samples and provide uniform heating while enabling TEM imaging. The heating chip was loaded into a Hitachi “Blaze” heating holder and analyzed using a Hitachi HF5000 at the University of Arizona.

U-Pb SHRIMP-II ages of titanite and timing constraints on apatite-nepheline mineralization in the Khibiny and Lovozero alkaline massifs (Kola Peninsula)

Results of this study of titanite samples collected from silicate rocks and apatite-nepheline-(sphene) ores from Paleozoic polyphase alkaline nepheline syenite complexes of the Khibiny and Lovozero massifs revealed the possibility of their in-situ U-Pb dating using sensitive high-resolution ion microprobe SHRIMP-II with an accuracy of 1.0-1.5%, which is comparable with that of U-Pb zircon analysis. Employing different approaches to age determination of the formation of the U-Pb system of titanites, the combined isochrons and mixing lines were plotted from the data obtained from the differentiated complex samples (121 analyses of five Khibiny samples and 52 analyses of one Lovozero sample) and apatite-nepheline ores (120 analyses of five Khibiny samples and 88 analyses of three Lovozero samples). They indicate synchronous crystallization of titanite in silicate rocks throughout the complexes: 374.1 ± 3.7 Ma for the Khibiny massif and 380.9 ± 4.5 Ma for the Lovozero massif, and attest to the later formation of phosphate-rare-metal ores: 371.0 ± 4.2 and 361.4 ± 3.2 Ma, respectively. The relatively delayed ore mineralization specific to the Lovozero massif can be accounted for the significantly lower volumes of magmatic melt and ore fluid involved, different thermal conditions, and the pattern of the investigated mineralization. As such, the obtained U-Pb data from titanite make it possible to limit significantly the time interval (most likely, not exceeding 15-20 Ma) comprising the evolution and activity of the ore-magmatic system of major agpaitic complexes, which is probably associated with plume magmatism.

Comendite Melts of the Early Mesozoic Bimodal Sant Association (Central Mongolia) and Mechanisms of Their Formation

Based on the investigation of melt inclusions using electron and ion microprobe analysis, we estimated the composition, evolution, and formation conditions of magmas producing the the comendites of the Sant bimodal volcanic association (Central Mongolia). The mechanisms of the formation of melts were determined. The primary melt and coexisting crystalline inclusions in quartz from three samples of comendites collected from different parts of the volcanic section were studied. Among the crystalline inclusions, sanidine, zircon, and the REE diortosilicate–chevkinite were identified. The phenocrysts of the comendites were determined to crystallize at temperatures of 880–960°C. The homogeneous glasses of melt inclusions have both trachydacite and rhyolite compositions. They are characterized by high concentrations of Zr, Nb, Rb, Y, Th and REE. Significant differences were determined in concentrations of Li and volatile component (H2O and F) in the glasses: some of the melts are enriched in these components, whereas other are depleted in them.

Petrogenesis of Mesozoic granites at Garorim Bay, South Korea: evidence for an exotic block within the southwestern Gyeonggi massif?

We present data from the Mesozoic Keumkang, Palbong, and Baekhwa granites in Garorim Bay, in the southwestern part of the Gyeonggi massif, South Korea. Using major and trace element concentrations, Sr-Nd-Pb isotopic compositions, and sensitive high-resolution ion microprobe (SHRIMP) zircon U-Pb ages, we aim to constrain the petrogenesis of the granites and explain their origin within a broader regional geological context. SHRIMP U-Pb zircon ages of 232.8 ± 3.2, 175.9 ± 1.2, and 176.8 ± 9.8 Ma were obtained from the Keumkang, Palbong and Baekhwa granites, respectively. The Late Triassic Keumkang granites belong to the shoshonite series and show an overall enrichment in large ion lithophile elements (LILE), a depletion in high field strength elements (HFSE) relative to primitive mantle, compared with neighboring elements in the primitive mantle-normalized incompatible trace element diagram with notable high Ba and Sr contents, and negligible Eu anomalies. The Keumkang granites are typified by highly radiogenic Sr and unradiogenic Nd and Pb isotopic compositions: (87Sr/86Sr)i = 0.70931–0.70959, (143Nd/144Nd)i = 0.511472–0.511484 [(eNd)i =–17.0 to–16.7], and (206Pb/204Pb) = 17.26–17.27. The Middle Jurassic Palbong and Baekhwa granites belong to the medium- to high-K calc-alkaline series, and show LILE enrichment and HFSE depletion similar to the Keumkang granites, but exhibit significant negative anomalies in Ba, Sr, and Eu. Furthermore, they have elevated Y and Yb contents at any given SiO2 content compared with other Jurassic granitoids from the Gyeonggi massif. The Palbong and Baekhwa granites have slightly less radiogenic Sr and more radiogenic Nd and Pb isotopic compositions [(87Sr/86Sr)i = 0.70396–0.70908, (143Nd/144Nd)i = 0.511622–0.511660, (eNd)i =–15.4 to–14.7, (206Pb/204Pb) = 17.56–17.76] relative to the Keumkang granites. The Keumkang granites are considered to have formed in a post-collisional environment following the Permo-Triassic Songrim orogeny that records continent-continent collision between the North and South China blocks, and may have formed by fractional crystallization of metasomatized lithospheric mantle-derived mafic melts. The Palbong and Baekhwa granites may have been produced from a gabbroic assemblage at pressures of less than ~15 kbar, associated with subduction of the paleo-Pacific (Izanagi) plate at the Eurasian continental margin. Elevated eNd(t) values in the granitoids from the southwestern part of the Gyeonggi massif relative to those of the central and northern parts, together with the comparatively shallow depth of origin, imply the presence of an exotic block in the Korean lithosphere.

In Situ Oxygen Isotope Determination in Serpentine Minerals by Ion Microprobe: Reference Materials and Applications to Ultrahigh‐Pressure Serpentinites

We present the first investigation of in situ oxygen isotopes in serpentine minerals by sensitive high‐resolution ion microprobe (SHRIMP). Chemically homogeneous samples of antigorite (δ18O = 8.30 ± 0.12‰), chrysotile (δ18O = 4.37 ± 0.02‰) and lizardite (δ18O = 5.26 ± 0.20‰) analysed by laser fluorination are identified as potential reference materials. They were analysed by SHRIMP to assess their homogeneity compared with the San Carlos olivine, as well as for potential matrix bias and crystal orientation effects. The reproducibility achieved for all samples was ± 0.30–0.55‰ (95% confidence level). Matrix bias between antigorite/olivine and antigorite/lizardite was up to ~ +3‰ and −1‰, respectively. Crystal orientation effects were identified only in chrysotile, and no matrix bias was observed over the investigated compositional range within each serpentine mineral. The new reference materials were used to measure the oxygen isotope composition of serpentines in an ultrahigh‐pressure metamorphic belt from Tianshan (China). By combining oxygen isotopes and trace element microanalyses, several stages of serpentinisation were recognised: (a) seafloor alteration, (b) recycling of internal metamorphic fluids during isothermal decompression and (c) shallow interaction with meteoric water during exhumation. No interaction with fluids derived from the surrounding metapelites during subduction was identified.

Mineralogy and titanite geochronology of the Caojiaba W deposit, Xiangzhong metallogenic province, southern China: implications for a distal reduced skarn W formation

The Caojiaba tungsten deposit (19.03 Mt@ 0.37 wt% WO3) is hosted by skarn along the contact between clastic and carbonate rocks in the Xiangzhong Metallogenic Province of southern China. The deposit is characterized by an early prograde skarn containing low andraditic garnet (Ad0.7–21.9) and hedenbergitic pyroxene (Hd52.9–77.3) overprinted by a retrograde biotite–chlorite assemblage and then by quartz–scheelite veins, similar to well-studied reduced tungsten skarns worldwide. Scheelite has low MoO3 (0.01–0.16 wt%), and ore commonly contains up to 1.5 ppm Au and up to 0.33 wt% Sb. Sensitive high-resolution ion microprobe (SHRIMP) U–Pb analyses of hydrothermal titanite coexisting with scheelite in three skarn ore samples provide ages between 206 ± 5 Ma and 196 ± 3 Ma (2σ). Our new ages demonstrate that the tungsten mineralization took place at Caojiaba between 206 and 196 Ma, overlapping the 228–201 Ma emplacement age of granitic rocks in the Xiangzhong Metallogenic Province. Mineralogical and geochronological evidence collectively indicates that Caojiaba is a distal reduced W skarn deposit. The 226–196 Ma granite-related W mineralization recognized throughout the province has a possible link with the widespread Sb–Au mineralization in the region.

SHRIMPDB: a new geoanalytical database for U-Th-Pb geochronological data from SHRIMP measurements

This paper introduces a novel web-based database, SHRIMPDB, to support the efficient reutilization of U-Th-Pb geochronological data from sensitive high-resolution ion microprobe (SHRIMP) measurements. In order to provide complete data content that can be reutilized by Earth scientists, a new data model containing analytical data and relevant sample metadata is proposed according to analyses of measurement procedures and the data characteristics of SHRIMP. Vivid data visualization, real-time data query interfaces (including a novel and intuitive polygonal region search), and a pragmatic data management module are designed and implemented using web-based and cloud GIS-based technologies, which provide a platform for Earth scientists to efficiently curate and share SHRIMP data on the internet. An incentive that encourages geochronologists to contribute data is suggested through cooperation between SHRIMPDB and the Beijing SHRIMP center. The database is currently under evaluation at the Beijing SHRIMP center. SHRIMPDB is globally available online at http://202.198.17.27/shrimpdb/home .

Characterization of Xenotime From Datas (Brazil) as a Potential Reference Material for In Situ U‐Pb Geochronology

AbstractThis study investigates five megacrysts of xenotime (XN01, XN02, XN03, XN04, and XN05) as potential reference materials (RMs) for U‐Pb geochronology. These crystals belong to a 300 g xenotime assortment, collected from alluvial deposits in SE Brazil. Electron microprobe and Laser Ablation‐Inductively Coupled Plasma‐Mass Spectrometry (LA‐ICP‐MS) analyses show that the selected crystals are internally homogeneous for most rare earth element, (REE, except some light REE) but are relatively heterogeneous for U and Th. The xenotime REE patterns are consistent with an origin from hydrothermal quartz veins in the Datas area that cut greenschist‐facies metasediments and that locally contain other accessory phases such as rutile and monazite. High‐precision U‐Pb Isotope Dilution‐Thermal Ionization Mass Spectrometry (ID‐TIMS) analyses showed slight age heterogeneity for the XN01 crystal not observed in the XN02 sample. The two crystals have slightly different average 206Pb/238U ages of 513.4 ± 0.5 Ma (2 s) and 515.4 ± 0.2 Ma (2 s), respectively. In situ U‐Pb isotope data acquired via LA‐(Q,SF,MC)‐ICP‐MS are within the uncertainty of the ID‐TIMS data, showing homogeneity at the 1% precision of the laser ablation (and probably ion microprobe) technique. U‐Pb LA‐(MC, SF)‐ICP‐MS analyses, using XN01 as a primary RM, reproduced the ages of other established RMs within less than 1% deviation. Other Datas crystals (XN03‐05) also display a reproducibility in Pb/U dates better than 1% on LA‐ICP‐MS, making them good candidates for further testing by ID‐TIMS.

Petrology, geochemistry, and Sr, Nd isotopes of mantle xenolith in Nghia Dan alkaline basalt (West Nghe An): implications for lithospheric mantle characteristics beneath the region

Petrology, geochemistry, and Sr, Nd isotopes of mantle xenolith in Nghia Dan alkaline basalt (West Nghe An): implications for lithospheric mantle characteristics beneath the region

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.

Beryllium-boron relative sensitivity factors for melilitic glasses measured with a NanoSIMS ion microprobe

Beryllium-boron relative sensitivity factors for melilitic glasses measured with a NanoSIMS ion microprobe

U-Pb geochronology of monazite in Precambrian tuffs reveals depositional and metamorphic histories

Uranium-lead geochronology of zircon in felsic tuffs plays a key role in the development of chronostratigraphic frameworks for sedimentary successions. This is particularly true for Precambrian basins, where biostratigraphy is of limited use for age determination or stratigraphic correlation. Although zircon is widely used to date tuffs, it can yield null results due to the presence of xenocrystic populations or isotopic resetting. Other potential U-Pb chronometers, such as monazite, which also crystallize from felsic magmas, are largely unreported from felsic tuff layers. Consequently, there has been a lack of studies to evaluate the potential of monazite for U-Pb isotope geochronology of tuffs. We present results of in situ U-Pb ion microprobe dating of monazite that co-exists with zircon in felsic tuffs from two Precambrian basins: the Earaheedy Basin (Frere Formation) in Western Australia and the Bushveld Basin (Lephala Formation) in southern Africa. We show that 207Pb/206Pb ages from monazite in felsic tuffs from the Frere Formation (1891 ± 9 Ma) and the Lephala Formation (2307 ± 9 Ma) are identical to zircon ages from the respective tuffs. Also, monazite in the Bushveld tuff preserves additional information, including a chronological fingerprint of the volcanic source (2.4–2.5 Ga xenocrysts) and the timing of low-grade metamorphism (2.16 Ga overgrowths). The ca. 2.16 Ga low-grade metamorphism identified in the Bushveld Basin is reminiscent of that widely recorded in the Pilbara Craton, Western Australian, lending support to arguments for a connection between the Kaapvaal and Pilbara cratons. Igneous and low-grade metamorphic monazites are readily distinguished based on texture and chemistry. Our study demonstrates that monazite can be used to accurately date felsic tuffs, offering a powerful tool for constraining depositional and metamorphic histories of Precambrian sedimentary basins.

Multi-stage growth and fluid evolution of a hydrothermal sulphide chimney in the East Pacific Ridge 1–2° S hydrothermal field: constraints from in situ sulphur isotopes

AbstractSulphur isotopes can be used as a powerful tool to trace fluid evolution and explore the formation of chimneys. To clarify the in situ S isotopic variations of sulphides at the micro-scale, we analyzed a sulphide chimney collected from the hydrothermal field in the East Pacific Rise 1–2° S using a sensitive high-mass-resolution ion micro-probe for stable isotopes (SHRIMP SI). Three mineral zones can be identified in the chimney: an external outer wall of porous anhydrite and colloform pyrite, an internal middle zone of sub-euhedral pyrite and massive chalcopyrite, and an inner zone of massive pyrite. The δ34SV-CDT values of the sulphides fall within the range 1.83–7.51 ‰ (avg. 4.05 ‰, n = 16), and S isotopic values increase from the core (3.09 ‰, n = 3) to the middle (3.78 ‰, n = 11) to the edge (6.99 ‰, n = 2). These results illustrate mineral crystallization processes and the mixing between seawater-derived S and magmatic–hydrothermal fluids during the growth of the chimney. The zones from the edge to the core are characterized by crystal morphologies of colloform/anhedral pyrite to massive pyrite with decreasing δ34S values, revealing multi-stage mineral deposition and sulphur isotopic fractionation. In contrast to the increase in δ34S values from the core to the edge in one profile (profile A), anomalously low δ34S values in fine-grained pyrite relative to chalcopyrite in another profile (profile B) in the middle zone result from S isotopic exchange between seawater SO42− and fluid H2S due to different fluid–seawater mixing, possibly caused by variations in permeability and porosity across the chimney.

Evidence of Enriched, Hadean Mantle Reservoir from 4.2-4.0 Ga zircon xenocrysts from Paleoarchean TTGs of the Singhbhum Craton, Eastern India

Sensitive High-Resolution Ion Microprobe (SHRIMP) U-Pb analyses of zircons from Paleoarchean (~3.4 Ga) tonalite-gneiss called the Older Metamorphic Tonalitic Gneiss (OMTG) from the Champua area of the Singhbhum Craton, India, reveal 4.24-4.03 Ga xenocrystic zircons, suggesting that the OMTG records the hitherto unknown oldest precursor of Hadean age reported in India. Hf isotopic analyses of the Hadean xenocrysts yield unradiogenic 176Hf/177Hfinitial compositions (0.27995 ± 0.0009 to 0.28001 ± 0.0007; ɛHf[t] = −2.5 to −5.2) indicating that an enriched reservoir existed during Hadean eon in the Singhbhum cratonic mantle. Time integrated ɛHf[t] compositional array of the Hadean xenocrysts indicates a mafic protolith with 176Lu/177Hf ratio of ∼0.019 that was reworked during ∼4.2-4.0 Ga. This also suggests that separation of such an enriched reservoir from chondritic mantle took place at 4.5 ± 0.19 Ga. However, more radiogenic yet subchondritic compositions of ∼3.67 Ga (average 176Hf/177Hfinitial 0.28024 ± 0.00007) and ~3.4 Ga zircons (average 176Hf/177Hfinitial = 0.28053 ± 0.00003) from the same OMTG samples and two other Paleoarchean TTGs dated at ~3.4 Ga and ~3.3 Ga (average 176Hf/177Hfinitial is 0.28057 ± 0.00008 and 0.28060 ± 0.00003), respectively, corroborate that the enriched Hadean reservoir subsequently underwent mixing with mantle-derived juvenile magma during the Eo-Paleoarchean.