LA-ICP-MS U–Pb dating of detrital rutile and zircon from the Reynolds Range: A window into the Palaeoproterozoic tectonosedimentary evolution of the North Australian Craton
Abstract The Palaeoproterozoic Reynolds Range of the Arunta Region, central Australia, comprises a series of shallow marine clastic sediments (Reynolds Range Group) which overlies deeper water sequences of turbidites (Lander Rock Formation) and minor sandstones (“unnamed sandstone”). U–Pb age data collected from detrital rutile and zircon in these rocks indicates these sequences contain very similar age spectra, although with a notable and important shift to younger ages within the stratigraphically younger Reynolds Range Group. Detrital zircons from the “unnamed sandstone” directly underlying the unconformity with the Reynolds Range Group contain a major age component at ca. 1860 Ma, toget…
Indo-Antarctic derived detritus on the northern margin of Gondwana: evidence for continental-scale sediment transport
Provenance studies from Cambro-Ordovician sediments of the North Gondwana passive margin typically ascribe a North African source, a conclusion that cannot be reconciled with all observations. We present new U-Pb ages from detrital rutile and zircon from Late Ordovician sediments from Saxo-Thuringia, Germany. Detrital zircons yield age populations of 500–800 Ma, 900–1050 Ma and 1800–2600 Ma. The detrital rutile age spectra are unimodal with ages between 500 and 650 Ma and likely represent, together with the 500–800 Ma and 1800–2600 Ma zircon populations, detritus sourced predominantly from North Africa. In contrast, the c. 950 Ma zircons, which are persistently found in Cambro-Ordovician se…
A New LA ‐ ICP ‐ MS Method for Ti in Quartz: Implications and Application to High Pressure Rutile‐Quartz Veins from the Czech Erzgebirge
Experimental determination of the pressure and temperature controls on Ti solubility in quartz provides a calibration of the Ti-in-quartz (TitaniQ) geothermometer applicable to geological conditions up to ~ 20 kbar. We present a new method for determining 48Ti mass fractions in quartz by LA-ICP-MS at the 1 μg g−1 level, relevant to quartz in HP-LT terranes. We suggest that natural quartz such as the low-CL rims of the Bishop Tuff quartz (determined by EPMA; 41 ± 2 μg g−1 Ti, 2s) is more suitable than NIST reference glasses as a reference material for low Ti mass fractions because matrix effects are limited, Ca isobaric interferences are avoided, and polyatomic interferences at mass 48 are i…
High-sensitivity U–Pb rutile dating by secondary ion mass spectrometry (SIMS) with an O2+ primary beam
Abstract We present a secondary ionization mass spectrometry (SIMS) technique for U–Pb geochronology of rutile at high spatial resolution and sensitivity using an O2+ primary ion beam coupled with surficial O2 gas deposition (O2 flooding). The O2+ beam is ~ 10 × more intense than conventionally applied O− or O2− beams at the same lateral resolution. Natural and synthetic rutile was determined to be conductive under O2+ bombardment, permitting higher excavation (sputter) rates than conventional SIMS using negatively charged O-beams without detrimental effects of sample charging. The main advantage of O2+ is rapid sputtering at shallow primary ion penetration depths. This minimizes the contri…
Freshening of the Alaska Coastal Current recorded by coralline algal Ba/Ca ratios
Arctic Ocean freshening can exert a controlling influence on global climate, triggering strong feedbacks on ocean‐atmospheric processes and affecting the global cycling of the world’s oceans. Glacier‐fed ocean currents such as the Alaska Coastal Current are important sources of freshwater for the Bering Sea shelf, and may also influence the Arctic Ocean freshwater budget. Instrumental data indicate a multiyear freshening episode of the Alaska Coastal Current in the early 21st century. It is uncertain whether this freshening is part of natural multidecadal climate variability or a unique feature of anthropogenically induced warming. In order to answer this, a better understanding of past var…
MPI-DING reference glasses for in situ microanalysis: New reference values for element concentrations and isotope ratios
We present new analytical data of major and trace elements for the geological MPI-DING glasses KL2-G, ML3B-G, StHs6/80-G, GOR128-G, GOR132-G, BM90/21-G, T1-G, and ATHO-G. Different analytical methods were used to obtain a large spectrum of major and trace element data, in particular, EPMA, SIMS, LA-ICPMS, and isotope dilution by TIMS and ICPMS. Altogether, more than 60 qualified geochemical laboratories worldwide contributed to the analyses, allowing us to present new reference and information values and their uncertainties (at 95% confidence level) for up to 74 elements. We complied with the recommendations for the certification of geological reference materials by the International Associ…
Assessment of Five Monazite Reference Materials for U-Th/Pb Dating Using Laser-Ablation ICP-MS
Monazite is a common accessory phosphate mineral that occurs under a wide range of pressure and temperature conditions in sedimentary, metamorphic and igneous rocks. Monazite contains high amounts of Th and U, rendering single monazite grains suitable for in-situ U-Th/Pb dating using laser ablation inductively-coupled mass spectrometry (LA-ICP-MS). Two key aspects of monazite dating that are critical for accurate age data with maximum precision are (i) optimized instrumental conditions to minimize analytical scatter and (ii) a well characterized reference material to ensure the accuracy of the obtained aged. Here, we analyzed five monazite reference materials (USGS 44069, 94-222, MAdel, Moa…
Rutile crystals as potential trace element and isotope mineral standards for microanalysis
Abstract The present paper reports trace element concentrations of 15 elements (V, Cr, Fe, Zr, Nb, Mo, Sn, Sb, Hf, Ta, W, Lu, Pb, Th and U) as well as Pb and Hf isotope data for four relatively homogeneous and large (centimeter size) rutile grains. Methods employed are SIMS, EMP, LA-ICP-MS, ID-MC-ICP-MS and TIMS. For most elements homogeneity is usually within ± 10% and occasionally variations are even narrower (± 5%), particularly in the core of two of the studied grains. The trace element concentrations of the grains span a broad compositional range (e.g., Zr concentrations are ca. 4, 100, 300 and 800 ppm). Provisional concentration values, calculated based on the homogeneity of the eleme…
ASSESSING TRACE ELEMENT (DIS)EQUILIBRIUM AND THE APPLICATION OF SINGLE ELEMENT THERMOMETERS IN METAMORPHIC ROCKS
Abstract Empirical and experimental calibration of single element solubility thermometers, such as Zr-in-rutile, Zr-in-titanite, Ti-in-zircon, and Ti-in-quartz, within the past 13 years has greatly expanded our ability to assess the pressure and temperature conditions of individual minerals associated with specific textures in metamorphic rocks. Combined with advances in in situ techniques for analyzing trace concentrations, this has led to an increase in the combined use of single element thermometers, geochronometers, and isotope ratios, often simultaneously, in metamorphic minerals. Here we review the calibration and application of single element thermometers at the pressure and temperat…
The volatile inventory (F, Cl, Br, S, C) of magmatic apatite: An integrated analytical approach
Abstract Apatite is ubiquitous in a wide range of magmatic rocks and its F–Cl–Br–S systematics can be used to decipher e.g., mixing processes within a magmatic complex and may give insights into fluid un-mixing and degassing processes during the emplacement and cooling of plutonic rocks. In this study, we analyzed a F-apatite (Durango, Mexico), a Cl-apatite (Odegarden, Norway) and apatites from five plutonic samples from the alkaline Mt. Saint Hilaire Complex (Canada) by means of Electron Microprobe Analysis (EPMA), Laser Ablation ICP-MS (LA-ICP-MS), Secondary Ion Mass Spectrometry (SIMS), pyrohydrolysis combined with ion chromatography, Fourier Transformed Infrared Spectroscopy (FTIR), Ins…
The fate of subducted oceanic slabs in the shallow mantle: Insights from boron isotopes and light element composition of metasomatized blueschists from the Mariana forearc.
Abstract Serpentine muds from South Chamorro Seamount (SCS), drilled during ODP Leg 195 at Site 1200 contain metamafic clasts that experienced blueschist-facies metamorphism (including the critical mineral assemblage pumpellyite – Na-amphibole – epidote). These schists represent fragments from the actual slab–mantle interface at ~ 27 km depth. Their heterogeneous lithology with a metasomatic character indicates significant mobility of major elements in the Mariana forearc, a region of melange formation as it can also be observed in onland exposures such as the Catalina Schist. As the Mariana forearc blueschists show no late stage alteration they permit the direct study of material transfer …
Carboniferous high-potassium I-type granitoid magmatism in the Eastern Pontides: The Gümüşhane pluton (NE Turkey)
The Gumushane pluton, a high-K calc-alkaline I-type granodionte/granite complex, forms an important component of the pre-Liassic basement of the Eastern Pontides (NE Turkey) In its eastern part, the pluton shows a compositional zonation ranging from biotite-hornblende granodiorite in the NW through biotite-hornblende granite to leucogranite/granophyre in the SE Numerous mafic microgranular enclaves (up to similar to 40 cm in diameter) suggest the former presence of globules of mafic melt during crystallization Emplacement of the pluton occurred during the latest Early Carboniferous, as shown by the 320 +/- 4 Ma Ar-40-Ar-39 bionte/homblende and 324 +/- 6 Ma LA-ICP-MS U-Pb zircon ages. In Har…
Combined thermodynamic and rare earth element modelling of garnet growth during subduction: Examples from ultrahigh-pressure eclogite of the Western Gneiss Region, Norway
Abstract Major and trace element zonation patterns were determined in ultrahigh-pressure eclogite garnets from the Western Gneiss Region (Norway). All investigated garnets show multiple growth zones and preserve complex growth zonation patterns with respect to both major and rare earth elements (REE). Due to chemical differences of the host rocks two types of major element compositional zonation patterns occur: (1) abrupt, step-like compositional changes corresponding with the growth zones and (2) compositionally homogeneous interiors, independent of growth zones, followed by abrupt chemical changes towards the rims. Despite differences in major element zonation, the REE patterns are almost…
Post-collisional adakite-like magmatism in the Ağvanis Massif and implications for the evolution of the Eocene magmatism in the Eastern Pontides (NE Turkey)
In the Anatolia, the Caucasus and northwest Iran, the Eocene epoch is characterized by widespread basic to acidic magmatism, whose temporal and spatial evolutions and origin are poorly understood. In this paper, we provide geochronological and geochemical data on a suite of Early Eocene intrusions from northeast Turkey and discuss their origin within a regional tectonic framework. Post to late-collisional, moderate to small bodies of quartz diorite and leucogranodiorite as well as later dacite porphyries intrude Permo-Triassic low-grade metamorphic rocks in the southern part of the Eastern Pontides very close to the Neo-Tethyan Izmir-Ankara-Erzincan suture. In places, the intrusives display…
A recipe for the use of rutile in sedimentary provenance analysis
Abstract Rutile has received considerable attention in the last decade as a valuable petrogenetic indicator mineral. Based on both new and previously published data, we carve out advantages and pitfalls regarding TiO 2 -minerals in sedimentary provenance analysis. This results in a recipe for the use of rutile in provenance studies. The main points are: Rutile geochemistry from different grain size fractions does not differ systematically, and hence rutiles should be extracted from the fraction containing the most rutile grains (usually 63–200 μm). Similarly, different magnetic susceptibility of rutile does not systematically imply different trace element composition. Before interpretation …
Fluid migration above a subducted slab - Thermodynamic and trace element modelling of fluid-rock interaction in partially overprinted eclogite-facies rocks (Sesia Zone, Western Alps)
Abstract The amount and composition of subduction zone fluids and the effect of fluid–rock interaction at a slab–mantle interface have been constrained by thermodynamic and trace element modelling of partially overprinted blueschist-facies rocks from the Sesia Zone (Western Alps). Deformation-induced differences in fluid flux led to a partial preservation of pristine mineral cores in weakly deformed samples that were used to quantify Li, B, Sr and Pb distribution during mineral growth, -breakdown and modification induced by fluid–rock interaction. Our results show that Li and B budgets are fluid-controlled, thus acting as tracers for fluid–rock interaction processes, whereas Sr and Pb budge…
Polymetamorphism in the mainland Lewisian complex, NW Scotland - phase equilibria and geochronological constraints from the Cnoc an t’Sidhean suite
The metamorphic evolution of rocks cropping out near Stoer, within the Assynt terrane of the central region of the mainland Lewisian complex of NW Scotland, is investigated using phase equilibria modelling in the NCKFMASHTO and MnNCKFMASHTO model systems. The focus is on the Cnoc an t’Sidhean suite, garnet-bearing biotite-rich rocks (brown gneiss) with rare layers of white mica gneiss, which have been interpreted as sedimentary in origin. The results show that these rocks are polymetamorphic and experienced granulite facies peak metamorphism (Badcallian) followed by retrograde fluid-driven metamorphism (Inverian) under amphibolite facies conditions. The brown gneisses are inferred to have c…
Age, Nd–Hf isotopes, and geochemistry of the Vijayan Complex of eastern and southern Sri Lanka: A Grenville-age magmatic arc of unknown derivation
Abstract The ca. 1.0–1.1 Ga Vijayan Complex (VC) of eastern and southeastern Sri Lanka is one of three high-grade metamorphic terranes making up the basement of the island and is in tectonic contact with the adjacent, older Highland Complex. It consists predominantly of granitoid gneisses ranging in composition from diorite to leucogranite, with a distinct calc-alkaline geochemical signature, and is interpreted as a magmatic arc. Strong ductile deformation has obliterated almost all original intrusive relationships. High-grade metamorphism during the Pan-African event at ca. 610–520 Ma has produced widespread granulite-facies assemblages that are now largely retrogressed and were affected b…
Characterisation of Apatites as Potential Uranium Reference Materials for Fission-track Dating by LA-ICP-MS
We report homogeneity tests on large natural apatite crystals to evaluate their potential as U reference materials for apatite fission-track (AFT) thermochronology by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). The homogeneity tests include the measurements of major element concentrations by electron probe microanalysis (EPMA), whereas for U concentration, isotope dilution (ID) ICP-MS and laser ablation (LA) ICP-MS were employed. Two apatite crystals are potential reference materials for LA-ICP-MS analysis: a 1 cm3 fraction of a Durango crystal (7.5 μg g−1 U) and a 1 cm3 Mud Tank crystal (6.9 μg g−1 U). The relative standard deviation (1 RSD) of the U concentrat…
Coralline algal growth-increment widths archive North Atlantic climate variability
Over the past decade coralline algae have increasingly been used as archives of paleoclimate information. Encrusting coralline algae, which deposit annual growth increments in a high Mg-calcite skeleton, are amongst the longest-lived shallow marine organisms. In fact, a live-collected plant has recently been shown to have lived for at least 850 years based on radiometric dating. While a number of investigations have successfully used geochemical information of coralline algal skeletons to reconstruct sea surface temperatures, less attention has been paid to employ growth increment widths as a temperature proxy. Here we explore the relationship between growth and environmental parameters in …
Direct dating of gold by radiogenic helium: Testing the method on gold from Diamantina, Minas Gerais, Brazil
New analytical developments have made radiogenic helium ( 4 He) applicable to archeological gold artifacts for age determinations. Here we report the application of the U/Th– 4 He method to the direct dating of gold from the historically important gold deposit in Diamantina, Minas Gerais, Brazil. The U/Th– 4 He age of 515 ± 55 Ma for the Diamantina gold is corroborated by a new U/Pb age of 524 ± 16 Ma for rutile recovered from auriferous pockets. These ages tie the Diamantina gold mineralization to the Brasiliano orogenic event, in the context of the Gondwana amalgamation. Our results indicate that U/Th– 4 He dating of gold is possible, opening new perspectives for the dating of gold deposi…
Zircon ages for a felsic volcanic rock and arc-related early Palaeozoic sediments on the margin of the Baydrag microcontinent, central Asian orogenic belt, Mongolia
Abstract Magmatic zircons from the basal part of an arc terrane in the accretionary complex NE of the Baydrag microcontinental block in central Mongolia were dated at 544 ± 7 Ma and reflect arc magmatism at the Ediacaran/Cambrian boundary. Detrital zircon ages for clastic metasediments of the adjacent Dzag zone suggest a depositional age
Sinistral transport along the Trans-European Suture Zone: detrital zircon–rutile geochronology and sandstone petrography from the Carboniferous flysch of the Pontides
AbstractThe Lower Carboniferous flysch of the Istanbul Zone in Turkey is an over 1500 m thick turbiditic sandstone–shale sequence marking the onset of the Variscan deformation in the Pontides. It overlies Lower Carboniferous black cherts and is unconformably overlain by Lower Triassic continental sandstones and conglomerates. The petrography of the Carboniferous sandstones and the geochronology and geochemistry of the detrital zircons and rutiles were studied to establish the provenance of the clastic rocks. The sandstones are feldspathic to lithic greywackes and subgreywackes with approximately equal amounts of quartz, feldspar and lithic clasts. The amount of quartz and lithic fragments d…
Fluid Migration above a Subducted Slab-Constraints on Amount, Pathways and Major Element Mobility from Partially Overprinted Eclogite-facies Rocks (Sesia Zone, Western Alps)
The Western Alpine Sesia-Lanzo Zone (SLZ) is a sliver of eclogite-facies continental crust exhumed from mantle depths in the hanging wall of a subducted oceanic slab. Eclogite-facies felsic and basic rocks sampled across the internal SLZ show different degrees of retrograde metamorphic overprint associated with fluid influx. The weakly deformed samples preserve relict eclogite-facies mineral assemblages that show partial fluid-induced compositional re-equilibration along grain boundaries, brittle fractures and other fluid pathways. Multiple fluid influx stages are indicated by replacement of primary omphacite by phengite, albitic plagioclase and epidote as well as partial re-equilibration a…
Evidence for boron incorporation into the serpentine crystal structure
Serpentinite mud volcanoes from the Mariana forearc comprise B-rich mantle wedge peridotites serpentinized by slab fluids. The major component of these rocks are serpentine group minerals [Mg 3 Si 2 O 5 (OH) 4 ], showing highly variable textural and geochemical features. Micro-Raman spectroscopy reveals that the serpentine minerals are well-crystallized lizardite and chrysotile. In situ SIMS spot analyses and element mapping via ToF-SIMS show that B is evenly distributed across serpentine grains, suggesting that serpentine, both lizardite and chrysotile in different textural regions, can host significant amounts of B (up to ~200 μg/g) into its crystal structure. As such structurally bound B…
Metamorphic reaction rates at ∼650–800°C from diffusion of niobium in rutile
Abstract The ability to quantify the rates at which metamorphic reactions occur is critical to assessing the extent to which equilibrium is achieved and maintained in a variety of dynamic settings. Here we investigate the kinetics of rutile replacement by titanite during amphibolite-facies overprinting of eclogite, garnet amphibolite and anorthosite from Catalina Island, CA, the Tromso Nappe, Norway, the North Qaidam terrane, China, and the Guichicovi Complex, Mexico. Trace element concentration profiles across rutile rimmed by titanite, as determined by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), reveal Nb zoning in rutile that we interpret as the result of Nb …
Mg/Ca ratios in coralline algae record northwest Atlantic temperature variations and North Atlantic Oscillation relationships
Climate variability in the North Atlantic has been linked in part to the North Atlantic Oscillation (NAO). The NAO influences marine ecosystems in the northwestern Atlantic and transport variability of the cold Labrador Current. Understanding historic patterns of NAO variability requires long‐term and high‐resolution climate records that are not available from instrumental data. Here we present the first century‐scale proxy record of sea surface temperature (SST) variability from the Newfoundland shelf, a region from which other annual‐resolution shallow marine proxies are unavailable. The 116 year record was obtained from three sites along the eastern Newfoundland shelf using laser ablatio…
High-resolution analysis of trace elements in crustose coralline algae from the North Atlantic and North Pacific by laser ablation ICP-MS
We have investigated the trace elemental composition in the skeleta of two specimens of attached-living coralline algae of the species Clathromorphum compactum from the North Atlantic (Newfoundland) and Clathromorphum nereostratum from the North Pacific/Bering Sea region (Amchitka Island, Aleutians). Samples were analyzed using Laser Ablation-Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) yielding for the first time continuous individual trace elemental records of up to 69 years in length. The resulting algal Mg/Ca, Sr/Ca, U/Ca, and Ba/Ca ratios are reproducible within individual sample specimens. Algal Mg/Ca ratios were additionally validated by electron microprobe analyses (Amch…
The geochemistry of Tl and its isotopes during magmatic and hydrothermal processes: The peralkaline Ilimaussaq complex, southwest Greenland
Abstract We use thallium (Tl) concentrations, K/Rb, K/Tl and Rb/Tl ratios and Tl isotopes in minerals from the alkaline to peralkaline Ilimaussaq complex (South Greenland) to trace magmatic differentiation, crustal assimilation, magmatic degassing, ore precipitation and hydrothermal metasomatism. Closed-system magmatic differentiation is marked by a coherent decrease of K/Tl- and K/Rb-ratios, whereas crustal assimilation results in a strong Tl-enrichment, causing low K/Tl-ratios compared to K/Rb-ratios. Thallium isotopes show only slight changes during orthomagmatic differentiation and the assimilation of crustal material cannot be traced, since the isotopic composition of the average crust…
Jurassic Ophiolite Formation And Emplacement As Backstop To A Subduction-Accretion Complex In Northeast Turkey, The Refahiye Ophiolite, And Relation To The Balkan Ophiolites
International audience; The eastern Mediterranean region within the Tethyan realm shows a high concentration of ophiolites with contrasting times of formation and emplacement along the belt: In the Balkans, the ophiolites formed during the early to medial Jurassic, and were obducted during the late Jurassic, whereas in Turkey and farther east, structurally intact Jurassic ophiolites are rare and Jurassic ophiolite obduction is unknown. Here we report a structurally intact, large ophiolite body of early Jurassic age from NE Turkey, the Refahiye ophiolite, located close to the suture zone between the Eastern Pontides and the Menderes-Taurus block. The Refahiye ophiolite forms an outcrop belt,…
Coralline algal Barium as indicator for 20th century northwestern North Atlantic surface ocean freshwater variability
During the past decades climate and freshwater dynamics in the northwestern North Atlantic have undergone major changes. Large-scale freshening episodes, related to polar freshwater pulses, have had a strong influence on ocean variability in this climatically important region. However, little is known about variability before 1950, mainly due to the lack of long-term high-resolution marine proxy archives. Here we present the first multidecadal-length records of annually resolved Ba/Ca variations from Northwest Atlantic coralline algae. We observe positive relationships between algal Ba/Ca ratios from two Newfoundland sites and salinity observations back to 1950. Both records capture episodi…