Chemical Abrasion Isotope Dilution Thermal Ionization Mass Spectrometry Research Articles

Discriminating Superimposed Alteration Associated with Epigenetic Base and Precious Metal Vein Systems in the Rouyn-Noranda Mining District, Quebec; Implications for Exploration in Ancient Volcanic Districts

Abstract The Rouyn-Noranda mining district of Quebec contains 20 Cu-Zn (±Au ±Ag) volcanogenic massive sulfide (VMS) deposits, including the giant and gold-rich Quemont and Horne deposits. Mineralized epigenetic veins are also present, but their origin and relative timing remain enigmatic. The nature and extent of their alteration signatures and the effect of their superposition on district-scale alteration patterns is unknown. The VMS-related quartz-sulfide Cu-Zn-Ag veins have δ18Oquartz values of 8.5 ± 0.8‰, reflecting δ18Ofluid compositions of –0.4 to 3.1‰ (250°–350°C) that are typical of Archean seawater. They are associated with a proximal Fe-rich chlorite alteration and marginal spotted sericite-chlorite alteration with whole-rock δ18O values of 2.9 to 5.9‰ and are interpreted to have formed within the structurally controlled discordant upflow zones of a VMS hydrothermal system. Younger gold-bearing quartz-carbonate veins were emplaced along mechanical anisotropies created by mafic dikes during north-south compression and the formation of regional E-trending faults, folds, and cleavage. They are characterized by δ18Oquartz values of 11.3 ± 0.8‰, reflecting δ18Ofluid compositions of 2.4 to 5.9‰ (250°–350°C), typical of a metamorphic fluid, possibly mixed with a lower δ18O upper crustal fluid. They are associated with ankerite, calcite, muscovite, chlorite, albite, and quartz ± hematite alteration with whole-rock δ18O values of 5.8 to 10.3‰. Chemical abrasion-isotope dilution-thermal ionization mass spectrometry (CA-ID-TIMS) U-Pb zircon ages for two tonalite intrusions constrain the maximum age of the Cu-Zn-Ag veins to 2697.6 ± 0.7 Ma and the minimum age to 2695.3 ± 1.0 Ma, which is also the maximum age of the gold quartz-carbonate veins. Superposition of alteration related to the gold quartz-carbonate veins on previously chlorite- and sericite-altered rocks has resulted in mixed alteration signals with whole-rock δ18O values of ~6 to 8‰ that have perturbed and masked regional alteration patterns related to older VMS mineralization, such as those found in the Quemont and Horne deposits. These results indicate that defining alteration vectors in camps that have superimposed hydrothermal systems requires full consideration of the hydrothermal history of the camp, and if such constraints are lacking, whole-rock δ18O values should not be used as a stand-alone exploration method.

Geochronological constraints on the Hangenberg Event of the latest Devonian in South China

The Hangenberg Event was one of the most significant mass extinctions accompanied by large-scale climate changes at the end of the Devonian period. Lack of precise and accurate geochronological constraints in the eastern Paleotethys has hindered a high-resolution global correlation of the Hangenberg Event. Here, we report the U–Pb dates of zircons from the bentonite samples intercalated with strata recording the Hangenberg Event in the Muhua region, Guizhou, South China, using both sensitive high-resolution ion microprobe (SHRIMP) and chemical abrasion - isotope dilution - thermal ionization mass spectrometry (CA-ID-TIMS) methods. A bentonite within the Hangenberg Event strata in the Muhua area was dated at 360.47 ± 0.68 Ma by CA-ID-TIMS, which is more precise than the results obtained by SHRIMP methods (361.5 ± 2.9 Ma and 359.8 ± 1.5 Ma). Thus, we propose that the Hangenberg Event took place at 360.47 ± 0.68 Ma in South China, based on the first precise CA-ID-TIMS zircon age from the Daposhang section. The age obtained from South China for the Devonian–Carboniferous boundary overlaps with that in Geologic Time Scale 2020, within the total uncertainties.

Tephra zircon U-Pb geochronology of kimberlite maar sedimentary fills in subarctic Canada: Implications for Eocene paleoclimate and Late Cretaceous paleogeography

The Wombat and Giraffe kimberlite pipes in the Lac de Gras kimberlite field (64°N, 110°W) of the Northwest Territories, Canada, preserve unique post-eruptive lacustrine and paludal sedimentary records that offer rare insight into high-latitude continental paleoclimate. However, depositional timing—a key datum for atmospheric CO2 and paleoclimatic proxy reconstructions—of these maar infills remains ambiguous and requires refinement because of the large range in the age of kimberlites within the Lac de Gras kimberlite field. Existing constraints for the Giraffe pipe post-eruptive lacustrine and paludal maar sedimentary facies include a maximum Rb-Sr age of ca. 48 Ma (Ypresian, Eocene) based on kimberlitic phlogopite and a glass fission-track age of ca. 38 Ma (Bartonian, Eocene). The age of the Wombat pipe lacustrine maar sediments remains unclear, with unpublished pollen-based biostratigraphy suggesting deposition in the Paleocene (66−56 Ma). In this study, we examine distal rhyolitic tephra beds recovered from exploration drill cores intersecting the Wombat and Giraffe maar facies. We integrate zircon U-Pb laser ablation−inductively coupled plasma−mass spectrometry (LA-ICP-MS) and chemical abrasion−isotope dilution−thermal ionization mass spectrometry (CA-ID-TIMS) geochronology, glass fission-track dating, palynology, and tephra glass geochemistry to refine chronological frameworks for these sedimentary deposits. The Giraffe maar CA-ID-TIMS tephra zircon U-Pb dating yielded a Bayesian model age of 47.995 ± 0.082|0.087 Ma (Ypresian) for the upper portion of the lacustrine sediments, while a single zircon grain from tephra in the lowermost lacustrine sediments had an age of 48.72 ± 0.29|0.30 Ma. The revised geochronology for the Giraffe maar provides a working age model for the ∼50 m record of lacustrine silt and indicates an age ∼10 m.y. older than previously thought. The Wombat maar LA-ICP-MS zircon U-Pb dating yielded an age of 80.9 ± 1.0 Ma (Campanian), which indicates deposition during the Late Cretaceous. This first radiometric age for the Wombat maar deposits is substantially older than earlier biostratigraphic inferences of a Paleocene age. This new age suggests that the Wombat maar sediments preserve evidence of some of the oldest known freshwater diatoms and synurophytes and provide key constraints for the paleogeography of the Western Interior Seaway during the Late Cretaceous.

Late Kungurian Radioisotope Age of the Boundary Between the Balakhonka and Kolchugino Groups in the Kuznetsk Basin (Western Siberia, Russia) – Additional Evidence for the Validity of the Ufimian Stage of the East European Permian

This article discusses the Late Kungurian radioisotopic age (276.9 ± 0.4 Ma) of the middle part of the Starokuznetsk Formation (Kuznetsk Subgroup, Kolchugino Group) of the Kuznetsk Basin determined by chemical abrasion–isotope dilution–thermal ionization mass spectrometry (CA-ID-TIMS). The analysis of the biostratigraphic data confirms that the layer dated belongs to the interval in which the Balakhonka Flora (cordaitoid) was replaced by the Kolchugino Flora (fern-pteridosperm-cordaitoid). This indicates that the change from the Balakhonka Flora to the Kolchugino Flora in the low latitudes of Angaraland took place during the Late Kungurian. The data obtained were used for direct correlation of the lower part of the Kolchugino Group with the Upper Kungurian of the International Chronostratigraphic Chart. Similar sequences of non-marine bivalve assemblages in the Permian successions of Angaraland (giant Prokopievskia, Khosedaella-Redikorella-Palaeomutela, and dominant Palaeomutela) and Eastern Europe (giant Sinomya, Palaeomutela-Khosedaella-Redikorella, and dominant Palaeomutela) further support the validity of the correlation of the Kuznetsk Subgroup with the Ufimian Stage. The placement of the lower boundary of the Kolchugino Group in the upper part of the Kungurian Stage of the International Chronostratigraphic Scale raises the question of the continuation of the Ufimian Stage as an independent straton in the East European Stratigraphic Scale. Its lower boundary coincides with the beginning of the change in the Balakhonka and Kolchugino Flora in the low latitudes of Angaraland, as well as with the faunal exchanges between the Euramerican and Angarian non-marine bivalve assemblages.

MULTIPULSED MAGMATISM AND DURATION OF THE HYDROTHERMAL SYSTEM OF THE GIANT JIAMA PORPHYRY Cu SYSTEM, TIBET, CHINA

Abstract Jiama is the largest porphyry-skarn ore system in the Gangdese metallogenic belt, Tibet. It is composed of porphyry Cu-Mo, Cu-polymetallic skarn, Cu-Pb-Zn manto, and distal vein Au orebodies with associated Ag, W, and Bi. However, the precise timing of the magmatism and hydrothermal events at Jiama remains obscure. Here, using high-precision chemical abrasion-isotope dilution-thermal ionization mass spectrometry (CA-ID-TIMS) U-Pb zircon dating of ore-bearing and post-ore intrusions, we accurately constrain the lifespan of magmatism and hydrothermal mineralization. Monzogranite porphyry dikes are cut by Cu-Mo vein mineralization in the deeper part of the system, indicating that they were emplaced pre-ore, and yield a crystallization age of 15.534 ± 0.007 Ma (mean square of weighted deviates [MSWD] = 0.99, n = 6). A granodiorite porphyry that cuts the monzogranite porphyry and hosts vein and disseminated chalcopyrite and molybdenite is considered synchronous with ore and yields a crystallization age of 15.368 ± 0.007 Ma (MSWD = 1.01, n = 5). These two phases of intrusions are cut by quartz-diorite porphyry bodies, which yield a crystallization age of 15.076 ± 0.006 Ma (MSWD = 0.13, n = 6) and contain weak, subeconomic Cu and almost no molybdenum mineralization. A post-ore barren quartz monzonite porphyry yields a crystallization age of 14.925 ± 0.006 Ma (MSWD = 1.12, n = 6). The lifespan of magmatism at Jiama is thus about 0.61 m.y. The difference with previous molybdenite Re-Os isochron ages from the porphyry (14.7 ± 0.3 Ma), hornfel (14.7 ± 0.4 Ma), and skarn (15.4 ± 0.2 Ma) suggests that high-precision chronology is required to decipher accurate timing of mineralization in porphyry systems such as Jiama. The 40Ar/39Ar ages of hydrothermal biotite coexisting with molybdenite in monzogranite porphyry and hornfels are 15.25 ± 0.17 Ma (MSWD = 1.6) and 15.25 ± 0.24 Ma (MSWD = 0.14), respectively, slightly younger than the granodiorite porphyry and older than weakly mineralized quartz diorite porphyry, which represents the time of the ore-forming hydrothermal event. Thus, Jiama is the product of pulsed magmatism during which a short-lived hydrothermal event formed the giant Cu polymetallic system.

Punctuated, episodic magmatism and mineralization of the Rogozna skarn-hosted Au-Zn-Pb-Cu deposits revealed through high-precision U-Pb zircon geochronology

The subvolcanic regions of magmatic centers are commonly associated with alteration, mineralization, and economic ore deposits, however the duration and frequency of mineralizing pulses within the overall lifespan of these centers can be poorly defined. Therefore, models for the formation of mineral systems require more high-precision geochronology data to refine their evolutionary models. Rogozna Mountain and its eponymous magmatic complex, located in SW Serbia, hosts multiple base metal deposits associated with variable rock types and structural expressions and serves as a natural laboratory to test the span and periodicity of mineralizing events. Unlike many deposits within the Rogozna magmatic complex (RMC) and elsewhere within the broader Serbo-Macedonian magmatic and metallogenic belt represented by Pb-dominated base metal sulfides, the Rogozna mining project (composed of the Gradina, Medenovac, Copper Canyon and Šanac deposits) also hosts Au-Cu mineralization. Based on previous isotope geochemistry, a single magmatic source was responsible for the sulfide crystallization associated with Au-Cu mineralization at the Copper Canyon deposit. Therefore, a detailed determination of igneous events and their temporal relationship remains crucial for understanding the formation of the Rogozna mineralized system and its multiple deposits.High-precision chemical abrasion-isotope dilution-thermal ionization mass spectrometry (CA-ID-TIMS) U-Pb zircon geochronology of six representative samples revealed the first phase of oxidized Au-Zn mineralization at the Medenovac deposit occurred prior to 28.833 ± 0.154 Ma, based on the inclusion of mineralized skarn clasts in breccia supported by an igneous-matrix. This age indicates that mineralization and skarn formation began over 1 Myr prior to reduced Au-Cu mineralization at the Copper Canyon deposit, which occurred over a period from approximately 27.76–27.61 Ma associated with a series of texturally diverse but compositionally similar quartz latite intrusions. Trachyandesitic dykes emplaced at 25.384 ± 0.068 Ma represent the youngest igneous event in the RMC. Previous models of the formation of the Rogozna mineralized system are likely flawed by inaccurate unit classification and incomplete sampling of intrusions associated with the deposits, resulting in an unrealistically simplistic evolutionary model for mineralization, rather than a protracted history of episodic alteration and mineralization. Therefore, a reinterpreted temporal hierarchy of the RMC is proposed based on new compositional and geochronological data, defining multiple mineralization events. This work highlights the necessity of combining a robust suite of textural analyses, field relationships, and high-precision geochronology to make accurate interpretations of deposit formation.

High-precision zircon age spectra record the dynamics and evolution of large open-system silicic magma reservoirs

The emplacement history and thermal evolution of subvolcanic magma reservoirs determine their longevity, size, and ability to feed volcanic eruptions. As zircon saturation is dependent on melt temperature and composition, quantitative analysis of zircon age distributions provides insight into the timing and magnitude of intensive parameter variations during the lifetime of a magma reservoir. Here we present chemical abrasion-isotope dilution-thermal ionization mass spectrometry (CA-ID-TIMS) U-Pb zircon crystallization ages and in-situ zircon trace-element geochemistry for a suite of caldera-related, coeval plutonic and volcanic units of the Permian Sesia Magmatic System (northern Italy). This dataset documents the protracted growth and evolution (∼1 Myr) of a voluminous (>1000 km3), upper crustal (3.5–2.0 kbar) silicic magma reservoir. Systematic changes in zircon composition with time reveal episodic intrusions of new magma into a single, progressively differentiating reservoir which was dominantly kept at high crystallinity conditions (>60 vol.%). The volcanic and plutonic units both show dispersed and heterogeneous CA-ID-TIMS age distributions. A stochastic, thermodynamics-based zircon saturation model accounting for fractional crystallization, recharge and thermal rejuvenation effects on zircon growth and stability in a rhyolitic magma body reproduces the observed distributions of zircon U-Pb ages. Model results suggest that zircon compositional variability and crystallization age heterogeneity, characteristic of the Sesia and other large silicic systems, distinguish open- and closed-system magmatic processes. Specifically, an increase of the mass of crystallized zircons over time is the hallmark of thermally and chemically mature magma reservoirs, capable of producing voluminous eruptions upon changes in the thermal and mechanical state of the system. Conversely, a decrease in crystallized zircon mass over time characterizes systems where crystallization dominates over magma mobility, hindering substantial mass release during eruptive events. We suggest that quantitative analyses of dispersed zircon crystallization age distributions obtained with high-precision techniques can be applied to the plutonic and volcanic record to identify mature silicic magma reservoirs whose properties and storage conditions allowed for catastrophic caldera-forming eruptions. This work provides the petrologic community with a new tool to investigate the genesis and evolution of zircon-bearing intermediate to silicic intrusive magmatism and caldera-forming volcanism through time and across tectonic settings.

Tithonian mafic intrusions in north-central Newfoundland: link to Atlantic rifting?

The small volume, Mesozoic alkali gabbro intrusions of the Budgell Harbour and Dildo Pond stocks and associated alkaline lamprophyre dykes in Notre Dame Bay in Newfoundland are an example of onshore magmatism that may be associated with North Atlantic Ocean opening. Chemical abrasion isotope dilution thermal ionization mass spectrometry U–Pb dating of zircon from Budgell Harbour Stock drill core samples yielded a weighted average 206Pb/238U age of 147.9 ± 0.5 Ma (95% confidence interval, mean square weighted deviation = 0.10). Five 40Ar/39Ar laser step-heating, single phlogopite grain analyses from the Budgell Harbour and Dildo Pond stocks, plus a lamprophyre dyke, yielded ages ranging from 146.3 ± 0.2 to 149.5 ± 0.5 Ma. The data demonstrate a ca. 148 Ma (Jurassic and Tithonian) alkaline magmatic event in Newfoundland, contemporaneous with rifting and offshore basin formation. These new age data and published determinations from magmatic rocks on conjugate margins and adjacent regions reveal long-lived episodic magmatism in the embryonic North Atlantic rift environment. We propose a new model whereby magmatism occurred in Notre Dame Bay at the convergence of older crustal-scale faults and localized Moho depth variations that may have triggered lithospheric mantle melting through isothermal, distal, and edge-driven upwelling related to regional extension.

How old is the Ordovician–Silurian boundary at Dob’s Linn, Scotland? Integrating LA-ICP-MS and CA-ID-TIMS U-Pb zircon dates

AbstractSedimentary rocks exposed at Dob’s Linn, Scotland, have significantly influenced our understanding of how life evolved over the Ordovician to Early Silurian. The current interpreted chronostratigraphic boundary between the Ordovician and Silurian periods is a Global Boundary Stratotype Section and Point (GSSP), calibrated to 443.8 ± 1.5 Ma (Hirnatian–Rhuddanian age), based on biostratigraphic markers, radioisotopic dates and statistical modelling. However, challenges arise due to tectonic disturbances, complex correlation issues and the lack of systematic dating in Ordovician–Silurian stratigraphic sections. Here, hundreds of zircon grains from three metabentonite ash horizons were dated using Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). A subset of the grains were re-analyzed using Chemical Abrasion Isotope Dilution Thermal Ionization Mass Spectrometry (CA-ID-TIMS). We present a high-precision CA-ID-TIMS 238U-206Pb weighted mean date of 440.44 ± 0.55/0.56/0.72 Ma (±analytical/with tracer/with U-decay constant) for the Coronagraptus cyphus biozone. However, the study reports younger, and in certain cases, older LA-ICP-MS zircon dates within the Coronagraptus cyphus, Akidograptus ascensus and Dicellograptus anceps zones, suspected as being influenced by Pb loss and LA-ICP-MS matrix mismatch. The study reports concerns about the suitability of Dob’s Linn as a GSSP section and examines various LA-ICP-MS maximum depositional age (MDA) approaches, suggesting the use of the TuffZirc date and the youngest mode weighted mean (YMWM) as suitable MDA calculations consistent with CA-ID-TIMS results.

Precise U-Pb age models refine Neoproterozoic western Laurentian rift initiation, correlation, and Earth system changes

The upper Tonian ChUMP (Chuar-Uinta Mountains-Pahrump) strata of the southwestern U.S.A. are hypothesized to be regional correlatives and to record a time of rift basin evolution commencing at ca. 770 Ma in western Laurentia (modern-day coordinates). We test this correlation using U-Pb chemical abrasion-isotope dilution-thermal ionization mass spectrometry (CA-ID-TIMS) on detrital zircon grains from basal units within these successions. ChUMP units yield CA-ID-TIMS maximum depositional ages (MDA) between 775 and 766 Ma: the Chuar Group of AZ has an MDA of 770.1 ± 0.5 Ma (n = 1) and an additional young zircon mode at 775.7 ± 0.3 Ma (n = 11); the Uinta Mountain Group of northern UT has an MDA of 766.3 ± 0.5 Ma (n = 5) and contains a second young mode at 775.1 ± 0.7 Ma (n = 3); and the basal Horse Thief Springs Formation of the middle Pahrump Group CA has an MDA of 775.4 ± 0.7 Ma (n = 3). The ca. 775 and 770 Ma grains are interpreted to be from zircon-bearing mafic sources related to the 770–778 Ma Gunbarrel Large Igneous Province of Yukon and NW U.S.A. The 766 Ma population was either derived from the Mt Rogers complex of eastern Laurentia or could have come from conjugate margins that were in the process of rifting away, such as Tasmania.The CA-ID-TIMS dates on the Chuar Group in Grand Canyon anchor a Bayesian age model for evaluating late Tonian Earth systems. Faster sediment accumulation rates (80 + 150/-44 m/My) in the lower Chuar Group are consistent with the inception of an extensional basin related to Rodinia breakup; slower rates in the upper Chuar Group (25 + 12/-5 m/My) record are associated with relatively deeper water sedimentation and concomitant organic carbon burial during marine transgression. The model also constrains the timing of several biological events recorded in the Chuar Group, including eukaryovorous predation (>767 Ma), the first appearance of vase-shaped microfossils (∼741 Ma), and the ranges of Cerebrosphaera globosa (=C. buickii; 800–743 Ma) and Lanulatisphaera laufeldii.(766–740 Ma), both proposed as possible marine index fossils for late Tonian time. Finally, the model can also be used to search for stratigraphic evidence of a purported glaciation at ca. 751 Ma.

Evidence for large disturbances of the Ediacaran geomagnetic field from West Africa

Constraining the paleogeography of the Ediacaran is crucial for understanding the extensive tectonic, biological and geochemical changes that occurred during that epoch. Paleomagnetism is an essential tool for reconstructing the Ediacaran paleogeography but it is complicated because the paleomagnetic data of that age display unusually fast and large directional oscillations. Two main competing hypotheses have been proposed: the occurrence of very fast True Polar Wander (TPW) episodes, which correspond to the motion of the planetary spin axis relative to the solid Earth, or strong geomagnetic field disturbances that could potentially be dominated by an equatorial dipole field. Their implications for paleogeographic reconstructions are radically different as TPW would result in a major latitudinal shift of continents of up to ∼ 90°. In this study, we focus on one rapid paleomagnetic change recorded in pyroclastic rocks of the Ouarzazate Group in the Anti-Atlas Belt (Morocco) that has been interpreted to reflect an exceptionally fast episode of True Polar Wander between ∼ 575 and 565 Ma. To further test this hypothesis, tight constraints on the rate of the paleomagnetic directional change are needed, as TPW is speed-limited by mantle viscosity. Here, we present high-resolution Chemical Abrasion Isotope-Dilution Thermal Ionization Mass Spectrometry (CA-ID-TIMS) U-Pb dates on zircons from seven pyroclastic levels distributed stratigraphically below, in between and above the horizons where the large paleomagnetic change is observed. Based on these new data, we estimate the associated lower bound rate of the apparent polar motion related to this abrupt paleomagnetic change to be 11.6°/Myrs [5.5 – 17.9]. This value is much higher than the TPW speed limit estimated from numerical simulations, suggesting that this large paleomagnetic change cannot be explained by TPW. It could rather be associated with intense perturbations of the Ediacaran geomagnetic field potentially oscillating from an axial to an equatorial dipole. The paleomagnetic pole that we interpret as referring to the axial dipole field would imply that West Africa was located at high latitude during the mid-Ediacaran.

Первые радиометрические датировки тонштейнов из угленосных отложений Кузнецкого бассейна: U-Pb-геохронология тайлуганской свиты

Tonsteins, predominantly solid kaolinite clay interbeds, are widespread in the coals of the Kuznetsk Basin and usually contain idiomorphic zircon grains of magmatic origin in quantities suitable for uranium-lead (U-Pb) radiometric dating. For the first time, tonstein zircons from coal seam 78 of the Tailugan Formation (Fm) are dated by two methods: Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) and Chemical Abrasion Isotope-Dilution Thermal Ionization Mass Spectrometry (CA-ID-TIMS). The CA-ID-TIMS datings of 257.0 ± 1.3 Ma and 256.6 ± 0.4 Ma determine the age of the lower boundary of the Tailugan Fm and the Tailuganian Regional Stage at 257.0 Ma. We estimate the duration of the Tailuganian to be around 4.22 million years. The dating results make it possible to directly correlate the Tailuganian of the Kuzbass with the upper half of the Wuchiapingian and with most of the Changhsingian of the International Chronostratigraphic Scale. The accumulation rate of total sediments of the Tailugan Fm, calculated without considering the compaction index, is approximately 0.13–0.18 mm/year, and the rate of coal accumulation is 0.024 mm/year. Such values are comparable to the accumulation rates of the Late Paleozoic coal-bearing strata of the Donetsk Basin and Western Australia. The rate of peat accumulation during the Tailuganian, calculated at a compaction index of 10:1, has been estimated at 0.24 mm/year. This value is comparable to the rates of peat accumulation in the Holocene bogs of the Kuznetsk Alatau in Siberia and the European part of Russia. The presence of tonsteins in the coal seams of the Tailugan Fm suggests that the upper surface of the peat at the time of its accumulation was below the water level, serving as a protective screen for the thin volcanic deposits and preventing its erosion. The assemblages of macroflora, ostracods, conchostracans and bivalves considerably vary through the section of the Tailugan Fm. This variation makes it possible to identify in Kuzbass the stratigraphic level that corresponds to the boundary between the Wuchiapingian and Changhsingian stages in the future.

Improving the chronostratigraphic framework of the Transvaal Supergroup (South Africa) through in-situ and high-precision U-Pb geochronology

The Transvaal Supergroup, on the Kaapvaal Craton in South Africa, is widely accepted as one of the best-preserved sedimentary archives to constrain planetary-scale environmental changes during the late Archean and early Proterozoic, yet the sedimentation age for certain stratigraphic intervals remains poorly constrained. To improve the temporal control on some of the first-order global changes recorded in these rocks, we carried out U-Pb analyses of detrital zircon populations from several clastic and volcano-clastic sedimentary units of the Transvaal Supergroup. We applied the Chemical Abrasion-Isotope Dilution-Thermal Ionization Mass Spectrometry (CA-ID-TIMS) technique on detrital and volcanic zircon populations that had been previously screened using the Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) technique. We report new maximum depositional age estimates for the Pannetjie (2456.6 ± 7.0 Ma), the Heynskop (2451.5 ± 2.5 Ma), the Makganyene (2423.1 ± 1.0 Ma) and the Hekpoort formations (2248.0 ± 1.1 Ma).A ca. 2.25 Ga-old cluster of LA-ICP-MS analyses in the Makganyene Formation was identified to be spurious, since it was completely removed during the chemical abrasion. Thus, we speculate that circulation of hydrothermal fluids and associated Pb-loss from a radiation-damaged lattice during the emplacement of the much younger Hekpoort Formation or possibly the Ophthalmia Orogeny, recorded in Western Australia, may have reset the U-Pb system of this zircon population. This implies that the accurate maximum depositional age of the Makganyene Formation is ca. 2.42 Ga instead, which denotes the age of the oldest glacial event of global extent during the Paleoproterozoic. Therefore, we suggest that the combination of both dating techniques is essential to ensure accurate maximum depositional age constraints for ancient detrital sedimentary rocks. Additionally, our data provides temporal constraints on a period characterized by major fluctuations in atmospheric oxygen. Finally, and supporting the complex nature of the Paleoproterozoic, linkages between widespread glaciations and atmospheric oxygen fluctuations remain to be explored.

To sink, or not to sink: The thermal and density structure of the modern northern Andean arc constrained by xenolith petrology

Abstract The thermal and compositional structure of arcs influence magmatic differentiation and lower-crustal foundering, two key processes impacting the evolution of the continental crust. Although many studies have proposed time scales of lithospheric recycling based on convective downwelling calculations, these models depend on the composition, density (ρ), and thermal structure of the lower crust and mantle, which are difficult to quantify in active continental arcs. Here, we constrained these properties for the Andean Northern Volcanic Zone using direct petrologic observations from a unique suite of lower-crust and mantle xenoliths from Mercaderes, Colombia. Chemical abrasion–isotope dilution–thermal ionization mass spectrometry (CA-ID-TIMS) U-Pb dates for zircons within the host tuff indicate the xenoliths erupted no earlier than 238 (±19) ka and thus capture a recent snapshot of the arc and subarc mantle. Equilibrium pressure-temperature (P-T) estimates for 81 xenoliths define three distinct thermal domains, interpreted as (1) a steep conductive geothermal gradient in the lower arc crust; (2) a convecting mantle wedge; and (3) cooled mantle in proximity to the subducting slab. Our results indicate the presence of an ~10–14-km-thick, high-density lithospheric root that is ~0.1 g/cm3 denser than the underlying mantle. Unlike records from exhumed paleoarcs, Rayleigh-Taylor instability calculations using our P-T-ρ constraints are unrealistically short for the northern Andes. We suggest the presence of partial melts in this hot arc root as a potential source of buoyancy preventing or significantly slowing down foundering.

Characterisation of Three Sri Lankan Zircon Megacrysts as Potential Reference Materials for Microbeam U‐Pb Geochronology and Hf‐O‐Zr Isotope Measurements

In situ U‐Pb geochronology and hafnium, oxygen and zirconium isotope measurements in zircons using laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) and ion microprobe techniques can provide essential isotopic data to constrain geological evolutionary histories. Developing reliable zircon reference materials is the cornerstone for in situ zircon chronology and isotopic studies. In this study, the homogeneity of U‐Pb ages and Hf‐O‐Zr isotope ratios in three Sri Lankan zircon megacrysts (SLZA, SLZB and SLZC) were investigated using multiple analytical methods. The obtained U, Th, Pb and Hf mass fractions of the SLZA zircon were 839 ± 56 μg g‐1 (1s), 151 ± 15 μg g‐1 (1s), 198 ± 28 μg g‐1 (1s) and 8635 ± 286 μg g‐1 (1s), respectively. The mass fractions of U, Th, Pb and Hf in the SLZB zircon were 1106 ± 106 μg g‐1 (1s), 331 ± 61 μg g‐1 (1s), 376 ± 57 μg g‐1 (1s) and 9673 ± 976 μg g‐1 (1s), respectively. The U, Th, Pb and Hf mass fractions determined in the SLZC zircon were 551 ± 35 μg g‐1 (1s), 111 ± 8 μg g‐1 (1s), 129 ± 18 μg g‐1 (1s) and 7881 ± 393 μg g‐1 (1s), respectively. The chemical abrasion isotope dilution thermal ionisation mass‐spectrometry (CA‐ID‐TIMS) method yielded a Th‐corrected weighted mean 206Pb/238U age of 556.94 ± 1.29 Ma (95% conf., n = 5) for the SLZA zircon, 552.90 ± 1.29 Ma (95% conf., n = 7) for the SLZB zircon and 560.83 ± 1.29 Ma (95% conf., n = 7) for the SLZC zircon. The obtained Hf isotopic compositions of the SLZA, SLZB and SLZC zircons determined with the solution MC‐ICP‐MS method were 0.281651 ± 0.000014 (2s, n = 10), 0.281704 ± 0.000008 (2s, n = 10) and 0.281676 ± 0.000006 (2s, n = 10), respectively. The obtained O isotopes of the SLZA and SLZB zircons measured with the laser fluorination method were 12.14 ± 0.56‰ (2s, n = 4) and 11.91 ± 0.30‰ (2s, n = 4), respectively. The Zr isotopes of the SLZA, SLZB and SLZC zircons determined with double spike TIMS analysis yielded mean δ94/90ZrSRM3169 values of ‐0.03 ± 0.06‰ (2s, n = 10), ‐0.03 ± 0.04‰ (2s, n = 10) and 0.00 ± 0.07‰ (2s, n = 8), respectively. The SLZA zircon can be used as a primary reference or quality control material for microbeam U‐Pb, Hf and Zr isotope measurements because of its slight heterogeneity. The U‐Pb, Hf and Zr isotopic compositions of the SLZB and SLZC megacrysts were homogeneous. The O isotopic compositions in the SLZA and SLZB zircon were slightly dispersed, indicating that these two megacrysts can only serve as secondary reference materials for microbeam O isotope measurements.

Tectonomagmatic evolution of southwestern Laurentia: Insights from zircon U-Pb geochronology and hafnium isotopic composition of the Red Bluff Granite Suite, west Texas, USA

AbstractWe provide laser ablation–multicollector–inductively coupled plasma–mass spectrometry (LA-MC-ICP-MS) and high-precision chemical abrasion–isotope dilution–thermal ionization mass spectrometry (CA-ID-TIMS) U-Pb ages and Hf isotopic compositions of zircons from the Red Bluff Granite Suite and mafic dikes in the Franklin Mountains of El Paso, Texas, USA. Granitoids exposed in the Franklin Mountains were previously divided into five magmatic stages based on cross-cutting relationships. Major and trace element compositions showed that these granitoids are ferroan, alkaline, and A2 type. Homogeneity in the whole-rock geochemistry suggests that the granite stages are genetically related and share similar petrogenetic histories. Weighted mean zircon 206Pb/238U dates from the older magmatic stage 1 alkali-feldspar quartz syenite and stage 2 alkali-feldspar granite are 1112.36 ± 0.35 and 1112.46 ± 0.37 Ma, respectively. The weighted mean εHf(t) values varying from +5.3 to +7.2 are similar to those of other regional ca. 1.1 Ga magmatic rocks throughout southwestern Laurentia. Geochemical characteristics, petrological modeling, and enriched Hf isotopic composition suggest fractional crystallization of a basaltic magma that was produced by melting of an enriched mantle reservoir. However, zircon inheritance ages of ca. 1.3 Ga and 1.26–1.15 Ga are consistent with a minor contribution from felsic crustal basement. Our data and regional geology are consistent with a post-collisional slab break-off that facilitated asthenospheric upwelling and partial melting of the enriched mantle, possibly subcontinental lithospheric mantle, extending from Llano Uplift, Texas, in the southeast to California to the northwest. Magma thus generated upon differentiation produced ferroan and A-type granitoids.

Precise U–Pb zircon dates from silicic super-eruptions during late Ediacaran extension in the Avalonian Caledonia terrane of southern New Brunswick, Canada

The Coldbrook Group and related plutons in the Caledonian Highlands of southern New Brunswick contain voluminous late Ediacaran silicic rocks formed in a magmatic event not recognized in other parts of Avalonia in the northern Appalachian orogen. To better constrain the age and origin of these rocks, we used U–Pb zircon dating by laser ablation inductively coupled plasma mass spectrometry to check for older inherited zircon and obtain trace element data, followed by chemical abrasion isotope dilution thermal ionization mass spectrometry (CA-TIMS) to obtain precise dates. Four silicic samples were dated from the Coldbrook Group, one from the Bonnell Brook pluton, and, for comparison, a felsic lithic-crystal tuff sample from the older arc-related Broad River Group. Overlapping CA-TIMS dates of 551.57 ± 0.23, 551.38 ± 0.24, and 551.70 ± 0.20 Ma for samples from the lower, middle, and upper Coldbrook Group, respectively, and 551.71 ± 0.19 Ma for granite from the Bonnell Brook pluton show that these units crystallized in 760 000 years or less, consistent with a super-eruption event. Rhyolite from the uppermost unit of the Coldbrook Group yielded a younger date of 549.18 ± 0.09 Ma, but the large extent of that unit is consistent with the possibility of a second younger super-eruption. The felsic lithic-crystal tuff sample from the Broad River Group yielded a date of 615.48 ± 0.16 Ma, consistent with previously published dates from that group and associated plutons. Differences in zircon chemistry between the Broad River Group sample and the late Ediacaran samples are consistent with the contrasting subduction-related vs within-plate extensional tectonic settings as suggested by previous studies of whole-rock petrological characteristics of the two age groups.

Precise zircon U-Pb dating of the Mesoproterozoic Gawler large igneous province, South Australia

The Mesoproterozoic Gawler Range Volcanics and Benagerie Volcanic Suite of the Gawler Craton and Curnamona Province, South Australia, together with associated intrusive magmatism, define an intracontinental, subaerial large igneous province (LIP) preserving an estimated 110 000 km3 of volcanic rock, which hosts one of the world's largest orebodies, the Fe oxide-Cu-Au-U deposit at Olympic Dam, and numerous other related Cu-Au deposits. New high-precision Chemical Abrasion Isotope Dilution Thermal Ionization Mass Spectrometry (CA-TIMS) U-Pb dates on volcanic zircons allow for regional correlations between stratigraphic units of the GRV and BVS, and an understanding of how magmatic styles, temperatures, composition and mantle source input evolve over the duration of the LIP. The new dates indicate that the entire volcanic province erupted over a geologically short time interval of less than 10 million years, from c. 1595 to 1586 Ma, culminating in a widespread, voluminous flood rhyolite province that erupted in less than 1.5 million years, and most likely in 260,000 years or less. This follows a pattern of volcanism that is similar in duration and volume to mafic and bimodal continental LIPs, of which the mafic-dominated Phanerozoic continental flood basalt provinces are the more common end member.

High-Precision Geochronology of the Xiaojiayingzi Mo Skarn Deposit: Implications for Prolonged and Episodic Hydrothermal Pulses

Abstract The timescales and duration of ore-forming processes in skarn systems are not well constrained. To better understand this, we present high-precision chemical abrasion-isotope dilution-thermal ionization mass spectrometry (CA-ID-TIMS) U-Pb zircon and isotope dilution-negative-thermal ionization mass spectrometry (ID-N-TIMS) Re-Os molybdenite geochronology of the Xiaojiayingzi Mo skarn deposit (0.13 Mt Mo at 0.22 wt %), northeastern China. The Xiaojiayingzi deposit is related to an intrusive complex composed of gabbroic diorite, monzodiorite, and granite porphyry. Molybdenite mineralization occurred in two ore blocks, Xiaojiayingzi (0.11 Mt Mo) and Kangzhangzi (0.02 Mt Mo). In the Kangzhangzi ore block, Mo mineralization is concentrated in skarn adjacent to a deep-seated granite porphyry, with minor disseminated and quartz veinlet mineralization within the granite porphyry. In contrast, economic Mo mineralization in the Xiaojiayingzi ore block is concentrated in skarns located between the contact of steeply dipping monzodiorite and the Mesoproterozoic Wumishan Formation, with minor Mo mineralization found in quartz and endoskarn veins hosted in the monzodiorite. Skarn mineralization in both ore blocks converges downward into the mineralized granite porphyry. In the Kangzhangzi ore block, skarn is zoned from deep proximal dark red-brown garnet to shallow distal dark-green pyroxene. In the Xiaojiayingzi ore block, proximal skarn is garnet rich, whereas pyroxene increases away from the monzodiorite-Wumishan Formation contact. In addition, pyroxene becomes more Fe and Mn rich with distance from the intrusions; Pb, Zn, and Ag increase toward the top of the system; and Mo and Fe increase with depth. High-precision CA-ID-TIMS U-Pb zircon geochronology indicates the gabbroic diorite crystallized at 165.359 ± 0.028/0.052/0.18 Ma (uncertainties presented as analytical/+ tracer/+ decay constant uncertainties), with subsequent crystallization of the monzodiorite and granite porphyry at 165.361 ± 0.040/0.059/0.19 and 165.099 ± 0.026/0.051/0.18 Ma, respectively. High-precision ID-N-TIMS Re-Os molybdenite geochronology indicates molybdenite mineralization at Xiaojiayingzi occurred in at least three discrete magmatic-hydrothermal pulses (nominally between 165.48 ± 0.09–165.03 ± 0.13, 163.73 ± 0.09, and 163.11 ± 0.11 Ma). The first episode of molybdenite mineralization formed in exoskarns, endoskarns, and quartz veins and had a minimum duration of 450 ± 40 k.y., between 165.48 ± 0.09/0.68/0.85 and 165.03 ± 0.13/0.67/0.85 Ma. It is likely that skarn ore represents a composite series of mineralization events, more than the three events capable of identification within analytical uncertainty of these high-precision data. Finally, Re-Os dating of quartz Mo veins cutting the monzodiorite and granite porphyry indicates that some mineralization postdated the observed intrusions, between 163.73 ± 0.09/0.70/0.86 and 163.11 ± 0.11/0.70/0.86 Ma, interpreted to be the result of deeper, unobserved intrusions. Collectively, these ages indicate that protracted, pulsed Mo mineralization at the Xiaojiayingzi deposit occurred over a period of at least 2.4 m.y. These data suggest that individual magmatic and/or skarn garnet ages may significantly underestimate the full duration of mineralization. In addition, this study highlights that systematically identifying skarn deposits associated with multiphase intrusive systems may reveal targets for future exploration, as it may point to previously undiscovered mineral resources.

Reassessing the intrusive tempo and magma genesis of the late Variscan Aar batholith: U–Pb geochronology, trace element and initial Hf isotope composition of zircon

The Variscan orogeny was responsible for the formation of a significant volume of igneous basement throughout present-day Europe. Detailed understanding of these rocks has, however, been obfuscated by significant overprinting during younger geologic events. In order to better understand the formation of this basement, we present U–Pb dates, trace element concentrations and Hf isotope compositions of zircon from 17 intrusions of the Variscan Aar batholith, located in the Aar Massif, Central Alps, Switzerland. Laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) was used to generate a large set of U–Pb dates, trace element and Hf isotope compositions on untreated zircon, as well as zircon pretreated by chemical abrasion. Furthermore, a subset of samples was also analyzed for high-precision U–Pb geochronology using chemical abrasion, isotope dilution, thermal ionization mass spectrometry (CA-ID-TIMS). The U–Pb dates of both dating techniques are significantly dispersed, indicating that they are influenced by multiple forms of complexity, including inheritance, domains of secondary alteration likely related to Alpine overprint or growth, decay damage related Pb-loss, and potentially protracted magmatic growth. Decay-damage related Pb-loss is likely a subordinate source of age scatter within the data, therefore chemical abrasion pretreatment is not capable of completely mitigating the observed analytical scatter. After rejection of outliers, the remaining data still exhibit excess scatter of several percent among 206Pb/238U dates in individual samples, however it is possible to interpret reasonable geologic ages from these data. These new U–Pb zircon age interpretations indicate the Aar batholith grew incrementally through four major magmatic pulses, which occurred at approximately 348, 333, 309 and 298 Ma. Based on the trace element and Hf isotope geochemistry, the melt source(s) of the Aar batholith evolved throughout the duration of batholith formation and growth. The transitioning from (i) melting of depleted mantle at 348 Ma during a stage of active continental arc magmatism (εHf = + 12 to + 10), (ii) melting of metasomatically enriched lithospheric mantle, possibly contaminated by crust during the 333 Ma pulse (εHf = − 10 to − 3), followed by (iii) an increasing incorporation of a juvenile mantle components during the 309 and 298 Ma pulses (εHf = − 3 to + 6). Finally, these new U–Pb ages yield a more detailed understanding of the Variscan Aar batholith by integrating the new detailed mapping of Aar Massif for the Geological Atlas of Switzerland, allowing for more accurate characterization and categorization of variably deformed heterogeneous intrusive bodies.