Chemical Abrasion Isotope Dilution Thermal Ionization Mass Spectrometry Research Articles

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.

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.

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 >500 km into the continental interior during the Ottawan and Rigolet phases of the Grenvillian Orogeny.

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.

HIGH-PRECISION CA-ID-TIMS AGE CONSTRAINTS ON THE NIBLACK Cu-Zn-Au-Ag DEPOSITS: A NEOPROTEROZOIC VOLCANIC-HOSTED MASSIVE SULFIDE DEPOSIT IN THE NORTH AMERICAN CORDILLERA

Abstract The Neoproterozoic-Cambrian Wales Group and Ordovician-early Silurian Moira Sound unit of Prince of Wales Island, Alaska, USA, host numerous volcanic-hosted massive sulfide (VHMS) deposits and occurrences, including the Niblack VHMS deposits. Previous attempts to determine the age of the felsic volcanic host rocks in the Niblack area have resulted in conflicting results and interpretations. We have utilized chemical abrasion-isotope dilution-thermal ionization mass spectrometry (CA-ID-TIMS) U-Pb zircon geochronology to acquire highly precise crystallization and maximum depositional ages for a total of six samples of felsic volcanic and intrusive rocks from Niblack. This study establishes age constraints for the Niblack felsic succession of (1) crystallization ages of 565.1 ± 0.9 and 564.8 ± 1.0 Ma for coherent rhyolite flows, (2) maximum depositional ages of 565.3 ± 0.9 and 565.2 ± 0.9 Ma for felsic volcaniclastic rocks, (3) a crystallization age of 565.2 ± 0.9 Ma for a quartz-feldspar-phyric subvolcanic sill, and (4) a crystallization age of 564.8 ± 1.0 Ma for a felsic dike that crosscuts the Niblack felsic succession. These results indicate that the ~200-m-thick Niblack felsic succession and VHMS deposits formed during one episode of felsic volcanism at ca. 565.1 ± 0.9 Ma and are thus confirmed as part of the Neoproterozoic Wales Group. Results of this study provide the first chronostratigraphic framework for felsic volcanism associated with VHMS deposit formation at Niblack and have implications for mineral exploration on Prince of Wales Island and elsewhere in the Alexander terrane.

High-precision U-Pb age constraints on the Permian floral turnovers, paleoclimate change, and tectonics of the North China block

Abstract The Permian marine-terrestrial system of the North China block provides an exceptional window into the evolution of northern temperate ecosystems during the critical transition from icehouse to greenhouse following the late Paleozoic ice age (LPIA). Despite many studies on its rich hydrocarbon reserves and climate-sensitive fossil flora, uncertain temporal constraints and correlations have hampered a thorough understanding of the records of geologic, biologic, and climatic change from the North China block. We present a new chronostratigraphy based on high-precision U-Pb chemical abrasion–isotope dilution–thermal ionization mass spectrometry (CA-ID-TIMS) geochronology of tuffs from a near-complete latest Carboniferous–Permian succession in North China. The results indicate that the predominance of continental red beds, climate aridification, and the disappearance of coals and characteristic tropical flora were well under way during the Cisuralian (Early Permian) in the North China block, significantly earlier than previously thought. A nearly 20 m.y. hiatus spanning the early Kungurian to the mid-Guadalupian (or later) is revealed in the northern North China block to have close temporal and spatial associations with the closure and/or subduction of the Paleo-Asian Ocean and its related tectonic convergence. This long hiatus was concomitant with the prominent loss of the highly diverse and abundant Cathaysian floras and the widespread invasion of the monotonous Angaran floras under arid climate conditions in the North China block. Similarities in the floral and climate shift histories between Euramerica and North China suggest that aside from the regional tectonic controls and continental movement, extensive volcanism during the Cisuralian may have played a major role in the global warming and aridification in the aftermath of the LPIA.

High-latitude ice and climate control on sediment supply across SW Gondwana during the late Carboniferous and early Permian

Abstract The response of sediment routing to climatic changes across icehouse-to-greenhouse turnovers is not well documented in Earth's pre-Cenozoic sedimentary record. Southwest Gondwana hosts one of the thickest and most laterally extensive records of Earth's penultimate icehouse, the late Paleozoic ice age. We present the first high-resolution U-Pb zircon chemical abrasion–isotope dilution–thermal ionization mass spectrometry (CA-ID-TIMS) analysis of late Paleozoic ice age deposits in the Kalahari Basin of southern Africa, which, coupled with existing CA-ID-TIMS zircon records from the Paraná and Karoo Basins, we used to refine the late Paleozoic ice age glacial history of SW Gondwana. Key findings from this work suggest that subglacial evidence in the Kalahari region is restricted to the Carboniferous (older than 300 Ma), with glacially influenced deposits culminating in this region by the earliest Permian (296 Ma). The U-Pb detrital zircon geochronologic records from the Paraná Basin of South America, which was located downstream of the Kalahari Basin in the latest Carboniferous and Permian, indicate that large-scale changes in sediment supplied to the Paraná were contemporaneous with shifts in the SW Gondwana ice record. Gondwanan deglaciation events were associated with the delivery of far-field, African-sourced sediments into the Paraná Basin. In contrast, Gondwanan glacial periods were associated with the restriction of African-sourced sediments into the basin. We interpret the influx of far-field sediments into the Paraná Basin as an expansion of the catchment area for the Paraná Basin during the deglaciation events, which occurred in the latest Carboniferous (300–299 Ma), early Permian (296 Ma), and late early Permian (<284 Ma). The coupled ice and detrital zircon records for this region of Gondwana present opportunities to investigate climate feedbacks associated with changes in freshwater and nutrient delivery to late Paleozoic ocean basins across the turnover from icehouse to greenhouse conditions.

Age and Paleoenvironmental Significance of the Frazer Beach Member—A New Lithostratigraphic Unit Overlying the End-Permian Extinction Horizon in the Sydney Basin, Australia

The newly defined Frazer Beach Member of the Moon Island Beach Formation is identified widely across the Sydney Basin in both outcrop and exploration wells. This thin unit was deposited immediately after extinction of the Glossopteris flora (defining the terrestrial end-Permian extinction event). The unit rests conformably on the uppermost Permian coal seam in most places. A distinctive granule-microbreccia bed is locally represented at the base of the member. The unit otherwise consists of dark gray to black siltstone, shale, mudstone and, locally, thin lenses of fine-grained sandstone and tuff. The member represents the topmost unit of the Newcastle Coal Measures and is overlain gradationally by the Dooralong Shale or with a scoured (disconformable) contact by coarse-grained sandstones to conglomerates of the Coal Cliff Sandstone, Munmorah Conglomerate and laterally equivalent units. The member is characterized by a palynological “dead zone” represented by a high proportion of degraded wood fragments, charcoal, amorphous organic matter and fungal spores. Abundant freshwater algal remains and the initial stages of a terrestrial vascular plant recovery flora are represented by low-diversity spore-pollen suites in the upper part of the unit in some areas. These assemblages are referable to the Playfordiaspora crenulata Palynozone interpreted as latest Permian in age on the basis of high precision Chemical Abrasion Isotope Dilution Thermal Ionization Mass Spectrometry (CA-IDTIMS) dating of thin volcanic ash beds within and stratigraphically bracketing the unit. Plant macrofossils recovered from the upper Frazer Beach Member and immediately succeeding strata are dominated by Lepidopteris (Peltaspermaceae) and Voltziopsis (Voltziales) with subsidiary pleuromeian lycopsids, sphenophytes, and ferns. Sparse vertebrate and invertebrate ichnofossils are also represented in the Frazer Beach Member or in beds immediately overlying this unit. The Frazer Beach Member is correlative, in part, with a thin interval of organic-rich mudrocks, commonly known as the “marker mudstone” capping the Permian succession further to the north in the Bowen, Galilee and Cooper basins. The broad geographic distribution of this generally <5-m-thick mudrock unit highlights the development in eastern Gondwana of extensive, short-lived, shallow lacustrine systems with impoverished biotas in alluvial plain settings in the immediate aftermath of the end-Permian biotic crisis.

High-precision ID-TIMS cassiterite U–Pb systematics using a low-contamination hydrothermal decomposition: implications for LA-ICP-MS and ore deposit geochronology

Abstract. Cassiterite (SnO2) is the most common ore phase of Sn. Typically containing 1–100 µg g−1 of uranium and relatively low concentrations of common Pb, cassiterite has been increasingly targeted for U–Pb geochronology, principally via microbeam methods, to understand the timing and durations of granite-related magmatic–hydrothermal systems throughout geological time. However, due to the extreme resistance of cassiterite to most forms of acid digestion, there has been no published method permitting the complete, closed-system decomposition of cassiterite under conditions in which the basic necessities of measurement by isotope dilution can be met, leading to a paucity of reference and validation materials. To address this a new low blank (< 1 pg Pb) method for the complete acid decomposition of cassiterite utilising HBr in the presence of a mixed U–Pb tracer, U and Pb purification, and thermal ionisation mass spectrometry (TIMS) analyses has been developed. Decomposition rates have been experimentally evaluated under a range of conditions. A careful balance of time and temperature is required due to competing effects (e.g. HBr oxidation), yet the decomposition of 500 µm diameter fragments of cassiterite is readily achievable over periods comparable to zircon decomposition. Its acid-resistant nature can be turned into an advantage by leaching common Pb-bearing phases (e.g. sulfides, silicates) without disturbing the U–Pb systematics of the cassiterite lattice. The archetypal Sn–W greisen deposit of Cligga Head, SW England, is used to define accuracy relative to chemical abrasion–isotope dilution–thermal ionisation mass spectrometry (CA-ID-TIMS) zircon U–Pb ages and demonstrates the potential of this new method for resolving high-resolution timescales (<0.1 %) of magmatic–hydrothermal systems. However, data also indicate that the isotopic composition of initial common Pb varies significantly, both between crystals and within a single crystal. This is attributed to significant fluid–rock interactions and the highly F-rich acidic nature of the hydrothermal system. At microbeam precision levels, this issue is largely unresolvable and can result in significant inaccuracy in interpreted ages. The ID-TIMS U–Pb method described herein can, for the first time, be used to properly characterise suitable reference materials for microbeam cassiterite U–Pb analyses, thus improving the accuracy of the U–Pb cassiterite chronometer as a whole.

Climate forcing of terrestrial carbon sink during the Middle Jurassic greenhouse climate: Chronostratigraphic analysis of the Yan’an Formation, Ordos Basin, North China

Abstract Exploring the relationship between coal deposits as an important terrestrial carbon sink and orbital forcing of climate is critical for understanding the global carbon cycle and climate change. The Jurassic greenhouse period, characterized by extensive coal reserves widely distributed in the mid-latitude terrestrial basins, marks a significant coal-forming interval in Earth's history. However, understanding of the processes that controlled the formation and distribution of coal at this time is inadequate. The Yan’an Formation of the Ordos Basin in north central China is among the largest and most extensively studied Jurassic coal reservoirs of the world. Here we establish a high-resolution age framework for the Yan’an Formation derived from integrated, high-precision U-Pb zircon geochronology using chemical abrasion-isotope dilution-thermal ionization mass spectrometry (CA-ID-TIMS) on interstratified ash beds and cyclostratigraphy based on centimeter-scale magnetic susceptibility. Accordingly, the main coal-forming interval of the Yan’an Formation spanned ca. 174.0 Ma to <171.7 Ma, which coincided with the onset of the Middle Jurassic. The spectral analyses of the Yan’an Formation coal seams demonstrate a strong correlation to minima in the 405 k.y. orbital eccentricity cycles, suggesting a strong climate control on lake level fluctuations and clastic sediment input. Finally, we explore the cyclicity of a large set of published marine carbon isotope data from western Tethys and its phase relationship to cyclic coal deposition in the Ordos Basin. Our resutls underscore the role of terrestrial organic carbon burial in the global carbon cycle during the Middle Jurassic.

The Global Stratotype Section and Point (GSSP) for the base- Sakmarian Stage (Cisuralian, Lower Permian)

The Sakmarian Stage represents a critical time interval because the Late Paleozoic Ice Age reached its acme during this time. After extensive studies, we herein use the First Appearance Datum (FAD) of the conodont Mesogondolella monstra within the lineage from M. uralensis -> M. monstra -> M. manifesta at Bed 26/3 of the Usolka section in the southern Urals, Russia, as the primary signal for the base-Sakmarian GSSP. The first occurrence of the conodont Sweetognathus binodosus within the lineage from Sw. off. merrilli -> Sw. binodosus is used as an auxiliary marker for the base of the Sakmarian Stage. An extrapolated age for this GSSP is 293.52 +/- 0.17 Ma produced by a Monte Carlo simulation based on two ash beds dated by chemical abrasion isotope dilution thermal ionization mass spectrometry (CA-ID-TIMS). The Sr-87/Sr-86 isotopic value based on conodont apatite for the base of the Sakmarian Stage is approximately 0.70787. Two minor negative excursions in delta(13)C(carb )are present at the boundary levels and the upper one is consistent with the GSSP level. The documentation of fusulinaceans, ammonoids, brachiopods and palynology also aid intercontinental and marine-terrestrial correlation. The Usolka section meets the requirements for the GSSP and a monument has been established; correlation with sections in North America and South China is also well documented.

Re-assessing the Upper Permian Stratigraphic Succession of the Northern Sydney Basin, Australia, by CA-IDTIMS

High precision Chemical abrasion-isotope dilution thermal ionisation mass spectrometry (CA-IDTIMS) U-Pb zircon results from tuff marker beds that are interstratified within the Upper Permian deposits of the northern Sydney Basin add constraints on the timing of sediment deposition, and afford a better understanding of the regional stratigraphy. The results indicate a magmatic influence during the deposition of the sediments, with episodic events spanning at least from 255.65 ± 0.08 to 255.08 ± 0.09 Ma. The zircon data suggest that the studied sedimentary rocks and tuffs have accumulated simultaneously over a short time interval, which contrasts with current stratigraphic models that suggest a much greater period of deposition and stratigraphic thickness. Therefore, an updated stratigraphic correlation of the basin is suggested, which combines the presently defined Lambton, Adamstown, and Boolaroo sub-groups into a single Lambton sub-group. This updated correlation framework is stratigraphically and geochronologically constrained and provides a more precise exploration model for the northern Sydney Basin. This case study highlights the valuable contribution of the CA-IDTIMS method in intrabasinal correlations of sedimentary successions, when integrated with a robust sedimentological framework, to minimize the stratigraphic uncertainties.

Provenance, stratigraphic and precise depositional age constraints for an outlier of the 1.9 to 1.8 Ga Nonacho Group, Rae craton, Northwest Territories, Canada

The Nonacho Group comprises six formations of continental clastic rocks that were deposited between 1.91 and 1.83 Ga. The Nonacho Group is part of a broader assemblage of conglomerate and sandstone that was deposited atop the Rae craton in response to the amalgamation of Laurentia and supercontinent Nuna, but the details of its tectonic setting are contentious. This paper documents an outlier of Nonacho Group rocks ∼50 km east of the main Nonacho basin. Field observations and LA-ICPMS (laser ablation inductively coupled plasma mass spectrometry) U-Pb detrital zircon geochronology are integrated with previous studies of the main basin to better understand the group’s depositional history, provenance and tectonic setting. The lithology and detrital zircon age spectra of the outlier allow for its correlation to the upper two formations of the Nonacho Group. CA-ID-TIMS (chemical abrasion isotope dilution thermal ionization mass spectrometry) analyses of two fragments of the youngest detrital zircon provide a maximum depositional age of 1901.0 ± 0.9 Ma. A felsic volcanic cobble dated at ca. 2.38 Ga provides evidence of volcanism during the Arrowsmith orogeny. Detrital zircon dates recovered from the outlier (ca. 3.4–3.0, 2.7, 2.5–2.3 and 2.0–1.9 Ga) are consistent with derivation from topography of the Taltson and/or Thelon orogens on the western margin of the Rae craton. Taltson-Thelon (2.0 to 1.9 Ga) aged detritus is only abundant in the upper two formations of the Nonacho Group, marking a change in provenance from the lower formations. This change in provenance may have coincided with a period of renewed uplift and the unroofing of Taltson-Thelon plutons. The detrital zircon provenance and depositional age of the Nonacho Group is consistent with models that link its deposition to the Taltson and/or Thelon orogens. However, tectonism associated with the 1.9 to 1.8 Ga Snowbird and Trans-Hudson orogens to the east could also have affected basin formation or the change in provenance from the lower to upper Nonacho Group. This study highlights the importance of CA-ID-TIMS in establishing accurate and precise maximum depositional ages for sedimentary successions.

Late Silurian zircon U–Pb ages from the Ludlow and Downton bone beds, Welsh Basin, UK

The Ludlow Bone Bed (Welsh Basin) is a critical stratigraphic horizon and contains a rich assemblage of fish scales. Units above provide insights into the early evolution of animal and plant life. The bed has not yet been radioisotopically dated. Here, we report 207 secondary ion mass spectrometry (SIMS) ages from 102 zircon (ZrSiO 4 ) grains from the Ludlow ( n = 2) and stratigraphically higher Downton ( n = 1) bone beds. SIMS ages are middle Ordovician (471.6 ± 20.7 Ma) to late Devonian (375.7 ± 14.6 Ma, 238 U– 206 Pb, ±1σ analytical uncertainty). Cathodoluminescence images show that the youngest ages appear affected by alteration. Chemical abrasion isotope dilution thermal ionization mass spectrometry (CA-ID-TIMS) U–Pb geochronology was utilized to improve precision. Detrital zircon grains from Downton yield 424.91 ± 0.34/0.42/0.63 Ma and from Ludlow 424.85 ± 0.32/0.41/0.62 Ma ( n = 5 each, 238 U– 206 Pb, ±2σ analytical, tracer or systematic uncertainty). These ages provide a maximum deposition age. Results overlap the basal Přídolí age (423.0 ± 2.3 Ma) in its stratotype (Požáry Section, Reporyje, Prague, Czech Republic). The Ludlow Bone Bed marks the base of the local Downton Group, which has previously been correlated with the base of the Přídolí Series. The CA-ID-TIMS ages are older than those for other land arthropod-bearing sediments, such as the Cowie Harbour Fish Bed and Rhynie Chert. Supplementary material: An Excel file containing detailed information on the SIMS analyses, a figure showing calibration curves for AS3 standards sputtered over sessions 1 and 2, and a figure showing CA-ID-TIMS U–Pb age data (concordia and weighted mean plots) are available at https://doi.org/10.6084/m9.figshare.c.5087031

The Central Sudetic Ophiolite (European Variscan Belt): precise U–Pb zircon dating and geotectonic implications

AbstractPrecise U–Pb zircon dating using the chemical abrasion – isotope dilution – thermal ionization mass spectrometry (CA-ID-TIMS) method constrains the age of the Central Sudetic Ophiolite (CSO) in the Variscan Belt of Europe. A felsic gabbro from the Ślęża Massif contains zircon xenocrysts dated at 404.8 ± 0.3 Ma and younger crystals dated at 402.6 ± 0.2 Ma that determine the final crystallization age of the gabbro. An identical age of 402.7 ± 0.3 Ma was determined for plagiogranite from the Nowa Ruda–Słupiec Massif, and plagiogranite from the Braszowice–Brzeźnica Massif yields a similar, but less reliable, age of > 401.2 Ma. The different massifs in the CSO are therefore considered as tectonically dismembered fragments of a single oceanic domain formed atc.402.6–402.7 Ma (Early Devonian – Emsian). The magmatic activity recorded in the CSO was contemporaneous with the high-temperature/high-pressure metamorphism of granulites and peridotites in the Góry Sowie Massif, separating dismembered parts of the CSO. This suggests geodynamic coupling between the continental subduction recorded in the Góry Sowie and the oceanic spreading recorded in the CSO. Regional geological data indicate that the CSO was obducted beforec.383 Ma, less than 20 Ma after its formation at an oceanic spreading centre. The CSO is shown to be one of the oldest and first obducted among the Devonian ophiolites of the Variscan Belt. The CSO probably originated in an evolved back-arc basin in which the influence of subduction-related fluids and melts increased with time, from negligible during the formation of predominant mid-ocean-ridge-type magmatic rocks to strong at later stages, when rodingites, epidosites and other minor lithologies formed.

Radioisotopic and biostratigraphic constraints on the classical Middle–Upper Permian succession and tetrapod fauna of the Moscow syneclise, Russia

Abstract The East European Platform and the PreUrals are the regions where the Permian System was first established, but the provincialism of fossils and lack of radioisotopic age control have prevented the use there of the regional Permian subdivisions used outside of the region. We report the first U-Pb zircon chemical abrasion–isotope dilution–thermal ionization mass spectrometry (CA-ID-TIMS) age of 253.95 ± 0.06 Ma for a volcanic tuff from the terrestrial upper part of the lower Vyatkian Regional Stage in the Moscow syneclise (Russia). This age greatly improves the correlation of the East European Platform and the PreUrals with the international geologic time scale, and contributes to our understanding of sedimentation within the Permian-Triassic transition in the studied region. The new radioisotopic age integrated within the regional chronostratigraphic framework reveals the synchrony in extinction of faunas of the Dinocephalian superassemblage in the studied region with that in South Africa.

U-Pb zircon age constraints on the earliest eruptions of the Deccan Large Igneous Province, Malwa Plateau, India

Climate instability driven by emission of volatiles during emplacement of large igneous provinces (LIPs) is frequently invoked as a potential cause of mass extinctions. However, documenting this process in the geologic record requires a holistic understanding of eruption rates, the location of eruptive centers, and potential sources of climate-changing volatiles. We present new chemical abrasion–isotope dilution–thermal ionization mass spectrometry (CA-ID-TIMS) U-Pb zircon geochronology from Malwa Plateau basalts on the northern margin of the Deccan LIP, India. These basalts have been previously interpreted as either an extension of the province's main volcanic stratigraphy or as an independent eruptive center active up to millions of years prior to the main eruptive phase. Our data instead demonstrate that the lower Malwa Plateau basalts are temporally correlative with the first pulse of Deccan volcanism and provide new constraints on its initiation and duration. Paleomagnetic data further indicate that upper Malwa Plateau basalts may be age-equivalent to the second, third, and fourth pulses of Deccan volcanism. The relative thicknesses of age-equivalent packages of basalt are consistent with eruption of the Deccan LIP from a southward-migrating eruptive center. The first eruptive pulse is coeval with a ∼200 kyr Late Maastrichtian warming event preserved globally in contemporaneous stratigraphic sections. We propose that the first pulse of Deccan magmatism was more voluminous in the north, where it erupted through organic-rich sedimentary rocks of the Narmada-Tapti rift basin. Thermal metamorphism of these sediments could have been a source of sufficient CO2 to drive the Late Maastrichtian warming event, which if true would reconcile the apparent dampened warming signals associated with later Deccan eruptive pulses.

U-Pb and Re-Os geochronology tracks stratigraphic condensation in the Sturtian snowball Earth aftermath

AbstractThe snowball Earth hypothesis predicts a strong hysteresis resulting in discrete multi-million-year glaciations followed by globally synchronous deglaciation. Here we present new U-Pb zircon and Re-Os sedimentary rock geochronology and Os isotope chemostratigraphy from post-Sturtian sequences in south China to test the synchroneity of deglaciation. High-precision chemical abrasion–isotope dilution–thermal ionization mass spectrometry (CA-ID-TIMS) U-Pb zircon dates refine the minimum age of deglaciation to 660.98 ± 0.74 Ma, which is ∼2 m.y. older than previously reported. We also provide a new maximum age constraint on the onset of the Marinoan glaciation of 657.17 ± 0.78 Ma. A global compilation of new Os isotope chemostratigraphy reveals a large and systematic trend to unradiogenic values over <1 m of stratigraphy. Together, these data indicate that the Mn-carbonates in south China are not cap carbonates that formed as a response to post-snowball alkalinity, but are authigenic carbonates that formed millions of years after deglaciation. Sturtian cap carbonates tend to be absent or more condensed than their younger Marinoan counterparts. We suggest that this reflects a combination of enhanced accommodation space in early Cryogenian underfilled rift basins, stronger hysteresis, larger ice volume, and/or higher CO2 levels needed for deglaciation of the longer Sturtian glaciation. Further, our findings indicate that the apparent diachroneity of deglaciation can be explained readily as a consequence of stratigraphic condensation, itself due to the large post-Sturtian glacioeustatic transgressive sequence that outpaced shallow-water carbonate deposition.

Dating multiply overprinted granites: The effect of protracted magmatism and fluid flow on dating systems (zircon U-Pb: SHRIMP/SIMS, LA-ICP-MS, CA-ID-TIMS; and Rb–Sr, Ar–Ar) – Granites from the Western Erzgebirge (Bohemian Massif, Germany)

The Variscan granites from the Western Erzgebirge were repeatedly dated by various methods, but no consensus has been reached about their exact intrusion ages. This study presents a multi-dating approach for the four largest intrusions from the Western Erzgebirge (Aue-Schwarzenberg, Bergen, Eibenstock, Kirchberg). We analysed several samples from each pluton/suite with zircon U–Pb CA-ID-TIMS (chemical abrasion-isotope dilution-thermal ionization mass spectrometry) to obtain robust temporal information on their age and tempo of intrusion. These data enable us for the first time to define three intrusive episodes of 1–2 Ma each, separated by quiet periods of several Ma. The Aue-Schwarzenberg suite represents the oldest granites that intruded at ~323–322 Ma followed by the granites from Bergen and Kirchberg 2–4 Ma later. The highly evolved ore-bearing granites from the Eibenstock pluton intruded after a time lag of ~5 Ma at ~315–314 Ma. The new data show that there is a resolvable age difference between the two known granite groups. Granite group 2 (also assigned as younger igneous complex, represented by the Eibenstock pluton) is ≥5 Ma younger than granite group 1 (assigned as older igneous complex, represented by granites from Aue-Schwarzenberg, Bergen and Kirchberg).Protracted magmatism and late-/post-magmatic fluid flow partly reset the U–Pb system of these granites to variable degrees, making a precise and accurate dating of their intrusion ages challenging. Pb loss in zircons is often combined with high common Pb (Pbc). SHRIMP/SIMS (sensitive high mass resolution ion microprobe/secondary ion mass spectrometry) and LA-ICP-MS (laser ablation-inductively coupled plasma-mass spectrometry) on non-CA zircons document that Pb loss and high Pbc is quite variable within zircon grains and may be located in micro-fractures. We demonstrate that chemical abrasion (CA) clearly minimizes or removes both Pb loss and Pbc. Results from prior LA-ICP-MS and SHRIMP dating on non-CA zircons from the same samples considerably helped the interpretation of the CA-ID-TIMS data when Pb loss was not completely erased by CA. In such cases we often had to choose the oldest analyses for mean age calculation in contrast to the common practice of the CA-ID-TIMS community to choose the youngest dates.Rb–Sr and Ar–Ar dating systems revealed age differences between the older group and the younger ore-bearing granites albeit with diverging absolute ages. Most Ar–Ar ages are identical with CA-ID-TIMS ages and would imply rapid cooling. However, samples from the older group have excess Ar that could have led to too old ages. In contrast, Rb–Sr ages for the older granites are 0–7 Ma younger than their intrusions. Fluid induced alteration led to the formation of Li-mica, fluorite and cassiterite (greisenization). For the youngest granite (Eibenstock), Li-mica was used to date the first greisenization. Samples without visible hydrothermal overprint yielded identical Ar–Ar and Rb–Sr ages as severely greisenized samples. This implies re-equilibration due to the hydrothermal overprint for all Ar–Ar and Rb–Sr ages from the Eibenstock pluton. According to Ar–Ar dating, the first ore formation (~315 Ma) is coeval with the CA-ID-TIMS intrusion age of the Eibenstock granite while it is delayed by ~6 (±3) Ma according to Rb–Sr dating (308 ± 3 Ma).