Chemical Abrasion Isotope Dilution Thermal Ionization Mass 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.

The terrestrial end-Permian mass extinction in the paleotropics postdates the marine extinction.

The end-Permian mass extinction was the most severe ecological event during the Phanerozoic and has long been presumed contemporaneous across terrestrial and marine realms with global environmental deterioration triggered by the Siberian Traps Large Igneous Province. We present high-precision zircon U-Pb geochronology by the chemical abrasion-isotope dilution-thermal ionization mass spectrometry technique on tuffs from terrestrial to transitional coastal settings in Southwest China, which reveals a protracted collapse of the Cathaysian rainforest beginning after the onset of the end-Permian marine extinction. Integrated with high-resolution geochronology from coeval successions, our results suggest that the terrestrial extinction occurred diachronously with latitude, beginning at high latitudes during the late Changhsingian and progressing to the tropics by the early Induan, spanning a duration of nearly 1 million years. This latitudinal age gradient may have been related to variations in surface warming with more degraded environmental conditions at higher latitudes contributing to higher extinction rates.

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.

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.

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.

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.

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.

Age constraints of the Guttulapollenites hannonicus–Cladaitina veteadensis Biozone in Argentina reveal the first record of Early Triassic (Olenekian) palynofloras in Western Gondwana

The upper Palaeozoic basins of central-western Argentina include continuous fossiliferous successions spanning the Carboniferous-Permian interval. The palynostratigraphic biozones comprise Late Mississippian, Pennsylvanian and Cisuralian assemblages. Recently, new palynofloras of the La Veteada Formation were referred to the Lopingian (late Permian). However, they are characterized by spores and tetrads of Lundbladispora spp. and Densoisporites spp., pollen grains of Lunatisporites pellucidus, L. noviaulensis and Protohaploxypinus samoilovichii, and the alga Syndesmorion stellatum, that distinguish the post-Permian recovery floras worldwide. A new uranium-lead chemical abrasion-isotope dilution-thermal ionization mass spectrometry (U-Pb CA-ID-TIMS) age confirms the Olenekian age of this stratigraphic unit and allows the identification of the first Early Triassic palynofloras in this region of western Gondwana. Comparison and correlation with similar assemblages from the southern and northern hemispheres supports the Early Triassic turnover with an increase of lycopsid cavate spores associated with some diagnostic species of taeniate and non-taeniate bisaccate pollen.

U–Pb geochronology of Late Silurian (Wenlock to Pridoli) volcanic and sedimentary rocks, central Newfoundland Appalachians: targeting the timing of transient extension as a prelude to Devonian orogenic gold mineralization

Bimodal igneous suites and associated immature clastic sedimentary rocks are characteristic of many orogenic gold-mineralized, crustal-scale fault zones globally. In the central Newfoundland Appalachian orogen, the Rogerson Lake Conglomerate belt and Botwood basin are Late Silurian (Wenlock to Pridoli), fault-controlled sedimentary rock sequences and magmatic suites closely associated with orogenic gold mineralization; however, the spatio-temporal evolution of faulting and associated sedimentation and magmatism are not fully resolved. U–Pb zircon geochronological results were obtained by using an integrated approach employing LA-ICPMS (laser ablation-inductively coupled plasma mass spectrometry) followed by CA-ID-TIMS (chemical abrasion-isotope dilution-thermal ionization mass spectrometry) on the same detrital samples. Using this approach, a maximum depositional age for sedimentary rocks of the Rogerson Lake Conglomerate sequence is 421.9 ± 1.0 Ma (Pridoli), which confirms that they are younger than, and stratigraphically overlie, ca. 422–420 Ma igneous rocks exposed along the central Newfoundland gold belt. Towards the stratigraphic middle of the Botwood basin in north-central Newfoundland, a tuffite layer intercalated with graded siltstone produced a maximum depositional age of 427.9 ± 3.1 Ma (Wenlock; Homerian). The age of emplacement of an autobrecciated, flow-banded rhyolite dome of the Charles Lake volcanic belt along the northwestern Botwood basin is 429.3 ± 0.7 Ma (Wenlock; Homerian). The high-precision CA-ID-TIMS zircon data establish a clear link between Wenlock to Pridoli magmatism and sedimentation throughout central Newfoundland. Furthermore, these geochronological results are consistent with a structural model involving the southeastward (present-day coordinates) advancement of a transient extensional fault system across strike of the Exploits Subzone between ca. 429 and 418 Ma, with propagation along strike to the southwest (Rogerson Lake Conglomerate belt) between ca. 422 and 418 Ma. Extensional faulting may have contributed to basin formation, subsidence, and exhumation of pre-Late Silurian rocks of the Exploits Subzone. Time-transgressive, extension-related magmatism and clastic sedimentation appear to mark the transition between the Salinic and Acadian orogenic cycles along the central Newfoundland gold belt. Transient Wenlock to Pridoli lithospheric extension may have been important for increasing heat and fluid flow in the crust as a prelude to Devonian crustal thickening, fluid focussing, and orogenic gold mineralization.

Expanded deepwater euxinia recorded in the Ediacaran–Cambrian boundary interval in South China

• The Ediacaran-Cambrian boundary interval at Pingyin in South China records a deepwater euxinia. • Expanded deepwater euxinia occurred in the Nanhua Basin during the Ediacaran-Cambrian transition. • The expanded deepwater euxinia probably resulted in the extinction of Ediacaran fauna. Global anoxia of shallow seawater during the Ediacaran–Cambrian (EC) transition has been interpreted as being caused by the upwelling of H 2 S-bearing deep seawater. This hypothesis implies the possible widespread occurrence of H 2 S-rich deep seawater during the EC transition. However, due to a lack of detailed investigation of environmental information recorded across the EC boundary (ECB) at deep-water facies sections, the occurrence of widespread H 2 S-rich deep seawater in paleo-basins during the EC transition is uncertain. The Pingyin section in South China is a deep-water-facies section for which the position of the ECB has been constrained by high-precision zircon chemical abrasion–isotope dilution–thermal ionization mass spectrometry U–Pb ages. Therefore, this section is a favourable site for obtaining information about deep seawater during the EC transition. In this paper, we present redox sensitive element (RSE) concentrations and Fe speciation of cherts from this section to study the redox condition of deep seawater recorded in the ECB at Pingyin. The results show dramatic differences of redox proxies in the cherts in the ECB from those underlying ones. The enrichment factors of U, V and Mo of the underlying samples are 2.08–6.89, 0.82–1.52 and 3.36–7.32, much lower than those of cherts in the ECB which are 16.52, 3.65 and 48.60, respectively. The underlying samples have Th/U ratios of 0.69–2.29, much higher than the cherts in the ECB with Th/U ratios of <0.30. The V/(V + Ni) ratios of most of the samples below the ECB are <0.84, whereas those of the samples at the ECB are >0.84. The Ce/Ce* values of the chert samples show an upward-decreasing trend below the ECB, but change to an increasing tendency immediately above the boundary. Almost all of the chert samples from the topmost Liuchapo Formation have Fe HR /Fe T ratios of >0.38. The Fe PY /Fe HR ratios of the samples underlying the ECB are lower than 0.80, whereas those of the samples around the ECB are higher than 0.80. These various indicators show that the ECB at Pingyin records an ancient deep-water redox turnover from anoxic ferruginous to sulphidic conditions. Combining the new findings with previous data, we conclude that the ECB in South China records the extensification of euxinia in deep water of the investigated paleo-basin. This event, which may have been global in extent, could have had a profound influence on early marine life and was likely a major cause of Ediacaran faunal extinction.

Latest Silurian syntectonic sedimentation and magmatism and Early Devonian orogenic gold mineralization, central Newfoundland Appalachians, Canada: Setting, structure, lithogeochemistry, and high-precision U-Pb geochronology

Abstract The eastern Dunnage Zone of the central Newfoundland Appalachians hosts Paleozoic orogenic gold mineralization along a northeast-trending, crustal-scale fault corridor that extends for more than 200 km. This orogenic gold system is characterized by polyphase, structurally controlled, quartz vein systems that cut Neoproterozoic granitoid rocks and unconformably overlying syntectonic, polymict conglomerate and associated transitional to calc-alkaline bimodal igneous rocks. High-precision chemical abrasion–isotope dilution–thermal ionization mass spectrometry (CA-ID-TIMS) U-Pb geochronology confirms a widespread, latest Silurian magmatic pulse (422–420 Ma) that is attributed to a transient phase of lithospheric extension resulting from asthenospheric and crustal melting related to slab break-off. Syntectonic conglomerate was deposited as a basal unit during extension-related uplift and erosion that lasted until ca. 418 Ma in north-central Newfoundland. Orogenic gold mineralization associated with syntectonic sedimentation and magmatism is hosted within third-order shear vein systems that form offshoots within a triangle zone–like structural corridor between southeast- and northwest-dipping, second-order fault splays and shear zones. The southeast-dipping fault system formed during northwest migration of the Acadian thrust front, whereas the northwest-dipping faults and shear zones are Salinic structures that were reactivated in the Early Devonian. Primary hydrothermal rutile in the orogenic gold-mineralized quartz veins produced ages of ca. 410 Ma. These ages are consistent with quartz vein emplacement and orogenic gold mineralization as a result of hydrothermal fluid-pressure cycling related to far-field compression and thermal perturbations during the Early Devonian Acadian orogenic cycle. The setting and process evolution of the central Newfoundland gold district are remarkably similar to that of world-class orogenic gold systems of the Canadian Shield.

Final inversion of the Midcontinent Rift during the Rigolet Phase of the Grenvillian Orogeny

Abstract Despite being a prominent continental-scale feature, the late Mesoproterozoic North American Midcontinent Rift did not result in the break-up of Laurentia, and subsequently underwent structural inversion. The timing of inversion is critical for constraining far-field effects of orogenesis and processes associated with the rift's failure. The Keweenaw fault in northern Michigan (USA) is a major thrust structure associated with rift inversion; it places ca. 1093 Ma rift volcanic rocks atop the post-rift Jacobsville Formation, which is folded in its footwall. Previous detrital zircon (DZ) U-Pb geochronology conducted by laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) assigned a ca. 950 Ma maximum age to the Jacobsville Formation and led researchers to interpret its deposition and deformation as postdating the ca. 1090–980 Ma Grenvillian Orogeny. In this study, we reproduced similar DZ dates using LA-ICP-MS and then dated 19 of the youngest DZ grains using high-precision chemical abrasion–isotope dilution–thermal ionization mass spectrometry (CA-ID-TIMS). The youngest DZ dated by CA-ID-TIMS at 992.51 ± 0.64 Ma (2σ) redefines the maximum depositional age of the Jacobsville Formation and overlaps with a U-Pb LA-ICP-MS date of 985.5 ± 35.8 Ma (2σ) for late-kinematic calcite veins within the brecciated Keweenaw fault zone. Collectively, these data are interpreted to constrain deposition of the Jacobsville Formation and final rift inversion to have occurred during the 1010–980 Ma Rigolet Phase of the Grenvillian Orogeny, following an earlier phase of Ottawan inversion. Far-field deformation propagated &amp;gt;500 km into the continental interior during the Ottawan and Rigolet phases of the Grenvillian Orogeny.

U-Pb and Sm-Nd Evidence for Episodic Orogenic Gold Mineralization in the Kalgoorlie Gold Camp, Yilgarn Craton, Western Australia

Abstract Different genetic and timing models for gold mineralization in the Kalgoorlie gold camp (Yilgarn craton, Western Australia) suggest either broadly synchronous, late-stage mineralization related to metamorphic fluids at ca. 2640 Ma or a punctuated mineralization history from ca. 2675 to 2640 Ma with the involvement of early magmatic-hydrothermal systems (represented by the Fimiston, Hidden Secret, and Oroya gold-telluride lodes) and late metamorphic fluids (represented by the Mt. Charlotte gold stockwork veins). The results of U-Pb and Sm-Nd geochronological studies of zircon, apatite, and titanite from pre-ore dikes and syn-ore dikes constrain the absolute timing of mineralization and provide new evidence to this timing controversy. Emplacement ages constrained by U-Pb sensitive high-resolution ion microprobe (SHRIMP) zircon data are interpreted to be similar for both the pre-ore dikes (n = 10) and syn-ore dikes (n = 7) at ca. 2675 Ma. An inferred emplacement age of ca. 2675 Ma for the syn-ore dikes is supported by a Sm-Nd isochron age from apatite (laser ablation-inductively coupled plasma-mass spectrometry; LA-ICP-MS) of 2678 ± 15 Ma and by a U-Pb titanite age (LA-ICP-MS) of 2679 ± 6 Ma. The results of chemical abrasion-isotope dilution-thermal ionization mass spectrometry U-Pb zircon analysis from the pre- and syn-ore dikes are complicated by multistage Pb loss, reverse discordance, and potential inheritance. However, the data are compatible with the emplacement of Fimiston/Hidden Secret gold mineralization at ca. 2675 Ma and suggest a younger age for Oroya mineralization at ca. 2665 Ma. These results contrast with models for orogenic gold deposits that invoke broadly synchronous, late-stage mineralization related to metamorphic fluids at ca. 2640 Ma. The bulk of the Kalgoorlie gold camp’s estimated 2,300 t Au endowment was emplaced at ca. 2675 Ma as Fimiston/Hidden Secret Au mineralization. This early Au mineralization was deformed and overprinted twice by subordinate Au mineralization at ca. 2665 (Oroya mineralization) and ca. 2640 Ma (Mt. Charlotte mineralization). Gold mineralization in the Kalgoorlie gold camp was protracted in nature from ca. 2675 to 2640 Ma and reflects the interplay of early magmatic (Fimiston, Hidden Secret, Oroya) and late metamorphic (Mt. Charlotte) hydrothermal fluid systems in the formation of hybrid intrusion-related and metamorphic orebodies.

Mississippian southern Laurentia tuffs came from a northern Gondwana arc

Abstract A Paleozoic arc that formed by southward subduction of the Rheic oceanic plate beneath northern Gondwana has long been inferred, but its history and geochemical signatures remain poorly understood. New U-Pb ages, juvenile εHf signatures, and trace-element composition data of young zircons from tuffs at two southern Laurentia sites indicate their derivation from a continental arc that was active from ca. 328 to ca. 317 Ma and permit correlation of sedimentary sequences 800 km apart in southern Laurentia. These include the Stanley tuffs in the Ouachita Mountains of southeastern Oklahoma and southwestern Arkansas and the newly discovered Barnett tuff in the subsurface of the Midland Basin in west Texas (USA). The Barnett tuff has a zircon chemical abrasion–isotope dilution–thermal ionization mass spectrometry U-Pb date of 327.8 ± 0.8 Ma, similar to the oldest Stanley tuff in the Ouachita Mountains. Zircon Hf isotope depleted mantle model ages further suggest that the source was a continental arc on basement with both Grenville and Pan-African affinities, pointing to northern Gondwana or peri-Gondwana terranes. The new data link the tuffs to granitoids (326 Ma) of the Maya block in southern Mexico, which was part of northern Gondwana. Correlation of the Stanley-Barnett tuffs across southern Laurentia suggests the likely presence of Mississippian tuffs over a broad region in southern Laurentia, and their usefulness for constraining absolute ages of basin fills and characterizing the Gondwanan arc.

Coupled magmatic and host rock processes during the initiation of the Tuolumne Intrusive Complex, Sierra Nevada, California, USA: A transition from ephemeral sheets to long-lived, active magma mushes

Abstract The initiation of pluton formation is rarely preserved as the rock record is typically overprinted by younger intruding pulses. An exception is the 80 km2 Kuna Crest lobe, which marks the initiation of the 95–85 Ma, 1100 km2 Tuolumne Intrusive Complex in the Sierra Nevada, California, USA. We present a detailed map of the lithologies and structure of the Kuna Crest lobe, associated sheeted complex and satellite plutons, and their host rocks, using chemical abrasion–isotope dilution–thermal ionization mass spectrometry and laser ablation–inductively coupled plasma–mass spectrometry U-Pb zircon geochronology, element and isotope geochemistry, and Al-in-hornblende thermobarometry to conclude the following: (a) The 94.91 ± 0.53 Ma to 92.75 ± 0.11 Ma Kuna Crest lobe and its marginal sheeted complex preserved the oldest intrusive pulses and most mantle-like compositions of the entire Tuolumne Intrusive Complex. (b) Emplacement began with magma wedging of low volume magma pulses resulting in a sheeted complex that is compositionally heterogeneous at outcrop scales, but isotopically homogeneous. (c) These early magmas established a pre-heated pathway within just a few hundreds of thousands of years that gave way to the formation of the ~1.5 million-year-long active, compositionally more homogeneous but isotopically more heterogeneous magma mush across the Kuna Crest lobe. The host rocks and previously intruded magma were displaced largely vertically through downward flow. (d) The melt-interconnected mush zone in the lobe allowed for magma mixing and crystal-liquid separation at the emplacement level. We interpret this lobe to represent an upper- to mid-crustal, vertical magma transfer zone that likely fed shallower plutons and potentially volcanic eruptions. We propose a filter pressing mechanism driven by vertical magma transport through the lobe resulting in margin-parallel fabrics, plagioclase-rich crystal cumulates, inward draining and upward loss (of up to 40%) of interstitial melts. Some inward drained melts hybridized with later intruding Half Dome magmas at the transition to the main Tuolumne Intrusive Complex. Some of the lobe magmas, including fractionated melts, drained laterally into the strain shadow of the lobe to form the satellite plutons, further contributing to cumulate formation in the lobe. This study documents that within only a few hundreds of thousands of years, arc magma plumbing systems are capable of establishing a focused magma pathway to build up to increasingly larger magma bodies that are capable of undergoing magma differentiation and feeding shallower plutons and volcanic eruptions.

Karst bauxite formation during Miocene Climatic Optimum (central Dalmatia, Croatia): mineralogical, compositional and geochronological perspectives

The Miocene Climatic Optimum (MCO) represents a global warm period (approximately 17–14.7 Ma) interrupting a long-term period of Cenozoic cooling. To elucidate if bauxitization took place in southeastern European mid-latitude areas during the MCO, we studied a section of undated massive karst bauxite (Crveni Klanac, CK) in central Dalmatia, Croatia, hosted in Upper Cretaceous limestones and overlain by Miocene Sinj Basin lacustrine deposits. Integrated mineralogical, morphological and geochemical analyses indicate the predominant mineral phases of the homogenous bauxite matrix are authigenic, subhedral to euhedral kaolinite and gibbsite. The in-situ mineralization was a consequence of pedogenic processes, indicating the CK bauxites formed autochthonously. In situ U–Pb zircon ages of the lower, middle and upper parts of the CK bauxite are very similar, dominated by Miocene and Oligocene ages, indicating that they all share similar protolith(s). Subsequent high-precision chemical abrasion-isotope dilution-thermal ionization mass spectrometry (CA-ID-TIMS) analyses indicate a maximum depositional age (MDA) for the pre-bauxitic material of 16.9576 ± 0.021 Ma (2σ uncertainty, incorporating decay constant uncertainty). This MDA, a maximum age of autochthonous bauxitization, coincides with the onset of the MCO. Based on currently available geochronological constraints, the maximum timeframe for CK bauxitization was less than ~ 700 ka, which matches the records of the MCO in paleo-mid-latitude Europe. The potential imprint of pre-17 Ma bauxitization and contribution of older (i.e., Upper Paleogene) bauxite deposits resedimented to the CK profile, as well as degree of potential parautochthonous origin of the CK bauxites, is yet to be investigated. More than simply aligning with regional and local reconstructions of continental climatic conditions during the onset and the early stages of the MCO, the high degree of autochthony of the CK bauxites provide a precise climatic constraint. For in-situ bauxitization to occur in the southeastern parts of mid-latitude continental Europe, paleoclimatic and paleoenvironmental conditions must have had mean annual temperature greater than 17–22 °C and mean annual precipitation of more than 1100–1200 mm.