Uncertainties In Decay Constants Research Articles

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.

Implications for Ediacaran biological evolution from the ca. 602 Ma Lantian biota in China

Abstract The morphologically differentiated benthic macrofossils of algae and putative animal affinities of the Lantian biota in China represents the oldest known Ediacaran macroscopic eukaryotic assemblage. Although the biota provides remarkable insights into the early evolution of complex macroeukaryotes in the Ediacaran, the uncertainty in its age has hampered any robust biological evaluation. We resolve this issue by applying a petrographic-guided rhenium-osmium (Re-Os) organic-bearing sedimentary unit study on the Lantian biota. This work confines a minimum age for the first appearance of the Lantian biota to 602 ± 7 Ma (2σ, including decay constant uncertainty). This new Re-Os date confirms that the Lantian biota is of early–mid Ediacaran age and temporally distinct from the typical Ediacaran macrobiotas. Our results indicate that the differentiation and radiation of macroscopic eukaryotes, and the evolution of the primitive, erect epibenthic ecosystem, occurred in the early–mid Ediacaran and were associated with highly fluctuating oceanic redox conditions. The radiogenic initial 187Os/188Os ratios derived from the Lantian (1.14 ± 0.02) and other Ediacaran shales invoke oxidative weathering of upper continental crust in the early–middle Ediacaran, which may have stimulated the evolution of life and oceanic-atmospheric oxygenation. Integrated with published Ediacaran chronological and geochemical data, our new Re-Os geochemical study of the Lantian black shale provides a refined, time-calibrated record of environment and eukaryote evolution during the Ediacaran.

U-Pb ID-TIMS reference ages and initial Pb isotope compositions for Durango and Wilberforce apatites

We present new Isotope Dilution Thermal Ionisation Mass Spectrometry (ID-TIMS) U-Pb reference ages for apatites from type locations Durango, Cerro de Mercado, Mexico and Wilberforce, Ontario, Canada. A weighted mean 206Pb/238U obtained from 14 Durango apatite fragments yields an age of 32.716 ± 0.061/0.063/0.072 Ma (2σ analytical uncertainty; analytical and tracer uncertainty combined; analytical, tracer, and decay constant uncertainties combined; MSWD = 0.81). Correction of excess 206Pb from Th-disequilibrium in Durango apatite, using a Th/Umelt of 3.5 ± 1, yields a weighted mean 206Pb/238U age of 32.29 ± 0.12/0.12/0.12 Ma. A concordia-constrained linear 3-D isochron yields an age of 32.683 ± 0.050 Ma for Durango apatites (ratio + error (%) + correlation coefficients; MSWD = 7.6; no propagation of decay constant and Pbc composition uncertainty, isoplot v. 4.15). A weighted mean 206Pb/238U obtained from 9 Wilberforce apatite fragments yield an age of 930.9 ± 8.0/8.0/8.1 Ma (MSWD = 0.65). Excess 206Pb correction for Wilberforce is negligible (<100kyr) relative to the uncertainty. A concordia-constrained linear 3-D isochron yields an age of 923 ± 14 Ma (ratio + error (%) + correlation coefficients; MSWD = 367; no propagation of decay constant and Pbc composition uncertainty, isoplot v. 4.15) for Wilberforce apatites. Initial Pb isotope compositions for these apatites were obtained by regression of the U-Pb data (3-D linear regression) and yielded a 206Pb/204Pb of 18.19 ± 0.12 and 207Pb/204Pb of 15.67 ± 0.10 for the Durango apatite reference material, and a 206Pb/204Pb of 17.06 ± 0.37 and 207Pb/204Pb of 15.33 ± 0.29 for the Wilberforce apatite reference material. Varying the assumed initial Pb composition can have significant effects on the calculated U-Pb age of apatites, which is highlighted with synthetic apatite data based on the composition of the Durango apatite reference material. For Durango apatites, the frequently used estimates of common Pb from two-stage Pb evolution models can artificially shift the U-Pb data and yield inaccurate dates, relative to the use of 3-D isochrons constructed using data obtained from Durango apatite. The use of 3-D isochrons to extract initial Pb isotope data should be restricted to samples/material with single U-Pb date population (closed system) and where estimates from Pb-bearing-U-free co-genetic mineral phases is unavailable and evaluated on a case-by-case basis.

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.

Metamorphic evolution for the Inyoni shear zone: Investigating the geodynamic evolution of a 3.20 Ga terrane boundary in the Barberton granitoid greenstone terrane, South Africa

Abstract The Inyoni shear zone represents an important tectonic boundary between (i) the ca. 3.45 Ga high-pressure amphibolite facies, granite-greenstone domain south of the Barberton greenstone belt, termed the Stolzburg terrane, and (ii) the ca. 3.29 to 3.23 Ga rocks of the trondhjemitic Badplaas pluton to the west. The Stolzburg terrane is separated from the greenschist facies rocks of the rest of the Barberton greenstone belt by the Komati fault, which records &amp;gt;10 km uplift of the Stolzburg terrane relative to the lower-grade rocks of the greenstone belt at ca. 3.23 Ga. A number of studies within the Stolzburg terrane have documented high-pressure amphibolite facies metamorphism that occurred concurrently with exhumation, with the lowest apparent geothermal gradients documented in the Inyoni shear zone, where strong constraints on the age of metamorphism are most limited. In addition, different studies on Inyoni metamorphism have produced significantly different temperature estimates. This study utilizes garnet Sm-Nd geochronology in combination with P-T modelling to directly date the metamorphism and re-evaluate the P-T conditions of the Inyoni shear zone. Two petrologically distinct samples produce similar P-T evolutions. A heterogeneous sample with both garnet-bearing and garnet-absent domains gives up-P evolutions reaching conditions of 550 to 675°C and 7 to 10 kbar, whereas a homogenous sample containing garnet and clinopyroxene produces a similar dominantly up-P evolution reaching peak conditions of 650°C and 8 to 10 kbar. Sm-Nd garnet ages of 3 201.6 ± 4.7 Ma (MSWD = 1.02) and 3 200.3 ± 5.3 Ma (MSWD = 0.44) were obtained from two samples of the homogenous garnet and clinopyroxene-bearing amphibolite. The Sm-Nd garnet geochronology provides accurate ages for the metamorphism of the Inyoni shear zone, with age results suggesting activity on the Inyoni shear zone may have continued after the regional metamorphism at ca. 3.23 Ga previously established by zircon U-Pb geochronology. However, 147Sm decay constant uncertainty leaves open the possibility that Inyoni garnet growth could have coincided with the previously recognized 3.23 Ga regional metamorphism.

New high precision U-Pb ages and Hf isotope data from the Karoo large igneous province; implications for pulsed magmatism and early Toarcian environmental perturbations

To better constrain the age and duration of the magmatism associated with the Karoo large igneous province (LIP), we present new U-Pb ID-TIMS dates and εHf values from baddeleyite and zircon grains from Karoo basin mafic sills and from felsic samples from the Lebombo and Mwenezi monoclines, together with an 40Ar/39Ar age database of Karoo rocks that has been filtered for true plateau ages with >70% of 39Ar released and in which all 40Ar/39Ar ages were recalculated using the current best estimates for the decay constants. Zircon and baddeleyite ages from three Karoo basin sills range from 183.36 ± 0.17/0.27 to 183.06 ± 0.07/0.21 Ma, where the two uncertainties reflect the analytical error and the additional error associated with decay constant uncertainty. Zircon from the Mutandawhe pluton are dated to 176.84 ± 0.06/0.20 Ma, which represents the first high-precision U-Pb age of the late stage Karoo-LIP magmatism in the northern Lebombo-Mwenezi region. Initial hafnium isotopes are close to chondritic for the Karoo basin and central Lebombo samples (εHf from −2 to +3), but more negative for zircon grains from the Mutandawhe pluton (−11.3 ± 1.1, 2SD). In combination with previous studies and in agreement with the updated 40Ar/39Ar ages, we show that the sill complex that intruded the Karoo basin was short-lived at ~320 ± 180 ka and that it pre-dated the magmatism of the Ferrar-LIP by around 460 ka, whereas the entire Karoo-LIP was emplaced over a period of ca. 6.5 Ma. Based on high-precision U-Pb geochronology, Karoo-LIP magmatism occurred after 183.36 ± 0.17 Ma and therefore postdated the extinction pulses of the late Pliensbachian and likely the Pliensbachian-Toarcian boundary. However, we support previous conclusions that the start of the Karoo-LIP activity agrees with the onset of the Toarcian oceanic anoxic event and the early Toarcian warming, indicating that these environmental changes were likely a response to the magmatic activity of the Karoo-LIP.

A Chronostratigraphic Framework for the Rise of the Ediacaran Macrobiota: New Constraints from Mistaken Point Ecological Reserve, Newfoundland

Abstract The Conception and St. John’s Groups of southeastern Newfoundland contain some of the oldest known fossils of the Ediacaran macrobiota. The Mistaken Point Ecological Reserve UNESCO World Heritage Site is an internationally recognized locality for such fossils and hosts early evidence for both total group metazoan body fossils and metazoan-style locomotion. The Mistaken Point Ecological Reserve sedimentary succession includes ∼1500 m of fossil-bearing strata containing numerous dateable volcanogenic horizons, and therefore offers a crucial window into the rise and diversification of early animals. Here we present six stratigraphically coherent radioisotopic ages derived from zircons from volcanic tuffites of the Conception and St. John’s Groups at Mistaken Point Ecological Reserve. The oldest architecturally complex macrofossils, from the upper Drook Formation, have an age of 574.17 ± 0.66 Ma (including tracer calibration and decay constant uncertainties). The youngest rangeomorph fossils from Mistaken Point Ecological Reserve, in the Fermeuse Formation, have a maximum age of 564.13 ± 0.65 Ma. Fossils of the famous “E” Surface are confirmed to be 565.00 ± 0.64 Ma, while exceptionally preserved specimens on the “Brasier” Surface in the Briscal Formation are dated at 567.63 ± 0.66 Ma. We use our new ages to construct an age-depth model for the sedimentary succession, constrain sedimentary accumulation rates, and convert stratigraphic fossil ranges into the time domain to facilitate integration with time-calibrated data from other successions. Combining this age model with compiled stratigraphic ranges for all named macrofossils within the Mistaken Point Ecological Reserve succession, spanning 76 discrete fossil-bearing horizons, enables recognition and interrogation of potential evolutionary signals. Peak taxonomic diversity is recognized within the Mistaken Point and Trepassey Formations, and uniterminal rangeomorphs with undisplayed branching architecture appear several million years before multiterminal, displayed forms. Together, our combined stratigraphic, paleontological, and geochronological approach offers a holistic, time-calibrated record of evolution during the mid–late Ediacaran Period and a framework within which to consider other geochemical, environmental, and evolutionary data sets.

Measurement uncertainty of rossi-alpha neutron experiments

Rossi-alpha neutron experiments are used to estimate the prompt neutron decay constant of a fissile assembly, a quantity of widespread interest in applications including in nuclear nonproliferation and criticality safety. This work develops a mathematical model to efficiently estimate measurement uncertainty of Rossi-alpha neutron experiments inferred from a two-exponential fit model with histogram binning. The derived uncertainty estimates were validated using repeated Rossi-alpha measurements of a subcritical, 4.5-kg sphere of weapons-grade, alpha-phase plutonium with nickel, copper, tungsten, and polyethylene reflectors. The estimates of uncertainty for the histogram data produced by the model were conservative and agree with the reference uncertainties within noise. The estimates of the prompt neutron decay constant uncertainty agreed with the reference uncertainties within one standard deviation. The proposed model will reduce total measurement times, ultimately reducing operational and procedural costs in application.

Data-Driven and Precursor-Group Uncertainty Propagation of Lattice Kinetic Parameters in UAM Benchmark

A new data-driven sampling-based framework was developed for uncertainty quantification (UQ) of the homogenized kinetic parameters calculated by lattice physics codes such as TRITON and Polaris. In this study, extension of the database for the delayed neutron data (DND) is performed by exploring more delayed neutron experiments and adding additional isotopes/actinides to the data libraries. Afterwards, the framework is utilized to obtain a deeper knowledge of the kinetic parameters’ sensitivity and uncertainty. The kinetic parameters include precursor-group-wise delayed neutron fraction (DNF) and decay constant. Input uncertainties include nuclear data (i.e., cross-sections) and DND (i.e., precursor group parameters and fractional delayed neutron yield). It is found that kinetic parameters, especially DNFs, have large uncertainties. The DNF uncertainty is driven by the cross-section uncertainties for LWR designs, while decay constant uncertainty is dominated by the DND uncertainties. The usage of correlated U-235 thermal DND in the UQ process significantly reduces the DND uncertainty contribution on the kinetic parameters. Large void fraction and presence of neutron absorber (e.g., control rod) increase the DNF uncertainty due to the hardening of neutron spectrum. High correlation between the DNF groups (β1,..,β6) is observed, while the decay constant groups (λ1,..,λ6) show weak correlation to each other and also to DNF groups. The DNF uncertainties of the dominant precursor group 4 for PWR, BWR, and VVER are about 7.5%, 9.4%, and 7.6%, respectively. The DNF uncertainty grows to larger values after fuel burnup. Kinetic parameters’ values and uncertainties provided here can be efficiently used in subsequent core calculations, point reactor kinetics, and other applications.

GZ7 and GZ8 - Two Zircon Reference Materials for SIMS U-Pb Geochronology.

Here, we document a detailed characterisation of two zircon gemstones, GZ7 and GZ8. Both stones had the same mass at 19.2 carats (3.84 g) each; both came from placer deposits in the Ratnapura district, Sri Lanka. The U‐Pb data are in both cases concordant within the uncertainties of decay constants and yield weighted mean 206Pb/238U ages (95% confidence uncertainty) of 530.26 Ma ± 0.05 Ma (GZ7) and 543.92 Ma ± 0.06 Ma (GZ8). Neither GZ7 nor GZ8 have been subjected to any gem enhancement by heating. Structure‐related parameters correspond well with the calculated alpha doses of 1.48 × 1018 g−1 (GZ7) and 2.53 × 1018 g−1 (GZ8), respectively, and the (U‐Th)/He ages of 438 Ma ± 3 Ma (2s) for GZ7 and 426 Ma ± 9 Ma (2s) for GZ8 are typical of unheated zircon from Sri Lanka. The mean U mass fractions are 680 μg g−1 (GZ7) and 1305 μg g−1 (GZ8). The two zircon samples are proposed as reference materials for SIMS (secondary ion mass spectrometry) U‐Pb geochronology. In addition, GZ7 (Ti mass fractions 25.08 μg g−1 ± 0.18 μg g−1; 95% confidence uncertainty) may prove useful as reference material for Ti‐in‐zircon temperature estimates.

Cyclic Magmatic-Hydrothermal Evolution in Porphyry Systems: High-Precision U-Pb and Re-Os Geochronology Constraints on the Tibetan Qulong Porphyry Cu-Mo Deposit*

We present high-precision chemical abrasion-isotope dilution-thermal ionization mass spectrometry (CA-IDTIMS) U-Pb zircon and isotope dilution-negative-thermal ionization mass spectrometry (ID-N-TIMS) Re-Os molybdenite geochronology of the world-class Tibetan Qulong porphyry Cu-Mo deposit. The data is used to constrain the timing, duration, and to yield implications for the ore-forming processes. The U-Pb data suggest that the preore Rongmucuola pluton crystallized at 17.142 ± 0.014/0.014/0.023 Ma (uncertainties presented as analytical/+ tracer/+ decay constant uncertainties), with emplacements of the synore P porphyry and postore quartz diorite occurring at 16.009 ± 0.016/0.017/0.024 and 15.166 ± 0.010/0.011/0.020 Ma, respectively. The Re-Os analysis of multiple independent molybdenite separations from single molybdenite-bearing quartz veins yields sub-‰ level analytical precision (<1‰), which is comparable with that of modern CA-ID-TIMS U-Pb zircon geochronology. The new Re-Os data indicate that the majority of the metals at Qulong were deposited over a minimum duration of 266 ± 13 k.y., between 16.126 ± 0.008/0.060/0.077 and 15.860 ± 0.010/0.058/0.075 Ma, with the main phase of mineralization being broadly synchronous with the emplacement of the P porphyry. However, our Re-Os data of molybdenite hosted within the Rongmucuola pluton imply that a portion of mineralization also predated the P porphyry and suggest that the P porphyry is an intermineral porphyry stock, although mineralization cut by P porphyry has not been previously documented or observed in this study. Correlating the Re-Os ages with vein types (A-B-D veins) demonstrates that the mineralization process was cyclical, with the presence of at least three short-lived (38 ± 11 to 59 ± 10 k.y.) mineralization pulses between 16.126 ± 0.008 and 16.050 ± 0.005, 16.040 ± 0.007 and 15.981 ± 0.007, and ~15.981 ± 0.007 and 15.860 ± 0.010 Ma. Coupling the Re-Os molybdenite ages and quartz (coprecipitated with the dated molybdenite) fluid inclusion data suggests that the cooling history was also cyclic, and implies a rapid cooling rate during the entire mineralization process (0.55° ± 0.11°C/k.y.), with much faster cooling rates (1.19° ± 0.82° to 1.27° ± 0.53°C/k.y.) for the individual mineralization pulses. The cyclic and rapid cooling process requires an additional cooling mechanism rather than the inefficient conduction, which we attribute to meteoric water circulation. The presence of mineralization predating the intermineral P porphyry stock and the absence of evidence of an early porphyry stock at Qulong suggest that mineralization potentially can take place without contemporaneous magmatism at mineralization levels. As a result, dating magmatic events may not necessarily bracket the entire mineralization duration of a porphyry system. This highlights the importance of dating ore minerals to reveal a comprehensive picture of the magma-hydrothermal process. In addition, the absence of contemporaneous magmatism during mineralization has broad implications for the classification of porphyry copper deposits and mineral exploration. The timescales of mineralization cycles constrained here via direct dating of ore minerals (tens of k.y.) are comparable with those recently proposed through high-precision U-Pb zircon dating, diffusion modeling, and numerical simulation. We propose that the cyclic mineralization pulses are linked with the periodic release of volatiles from the lower crustal magma chamber, which are common for porphyry copper systems worldwide. The episodic/cyclic metal enrichment process potentially is one of the controlling factors of porphyry copper ore formation and is the key to differentiate the formation of economic and subeconomic porphyry deposits. Finally, direct comparison of molybdenite Re-Os dates from different laboratories and with the zircon U-Pb system needs to account for the much larger uncertainties from tracer calibration and decay constants, respectively. As a result, we lose the necessary resolution to investigate the ore-forming process at the k.y. level. Therefore, to reduce these uncertainties, calibration between the two chronometers, using shared tracer solutions and a transparent data reduction platform within the community is required.

Neoproterozoic amorphous “ekanite” (Ca2Th0.9U0.1Si8O20) from Okkampitiya, Sri Lanka: A metamict gemstone with excellent lead-retention performance

A rare gemstone form of ekanite from Okkampitiya, eastern Sri Lanka, has a chemical composition of Ca2Th0.9U0.1Si8O20, corresponding to that of the tetragonal mineral ekanite. The Okkampitiya material, however, has undergone amorphization and is found in a fully metamict state, which is ascribed to the long-term accumulation of high levels of self-irradiation damage (1.38 x 10(20) alpha decay events per gram). The ekanite nevertheless does not show any post-growth chemical alteration, and the radiogenic Pb has been retained. The Okkampitiya ekanite yielded a Neoproterozoic Pb-207/Pb-206 age of 562.1 +/- 0.8 Ma (uncertainty quoted at the 95% confidence level) that is concordant within the uncertainties of decay constants. The remarkable Pb-retention performance of ekanite contradicts the common hypothesis that metamictization in minerals results in U-Pb discordance. The exceptional chemical durability of the heavily radiation-damaged geological material described here has also implications for materials-science research. High radiation resistance, a key criterion in the search for advanced nuclear waste forms, may not be a prerequisite for high aqueous durability of a solid.

LGC-1: A zircon reference material for in-situ (U-Th)/He dating

A pairwise in-situ (U-Th)/He dating method has been proposed for mitigating matrix-related bias in U and Th measurements using synthetic reference materials. This method requires a natural zircon reference material whose (U-Th)/He age should be homogeneous on the scale (~10–100μm) to be used in such dating experiments. A newly characterized zircon LGC-1 megacryst fulfils this requirement. This pale-yellowish, flawless Sri Lanka gem specimen is about 1.2∗0.8∗0.8cm in size. Optical microscopy, cathodoluminescence-imaging, X-ray elemental mapping, and Raman spectroscopy on a large number of random shards did not reveal any detectable textural and compositional heterogeneity. Laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) analyses on a large number of randomly selected fragments yield 266 measurements of U, Th and Pb concentrations, which are within the corresponding experimental uncertainties. The weighted mean U, Th and Pb concentrations are 357.7±1.8ppm, 740.9±5.0ppm, and 39.06±0.18ppm, respectively, with a weighted mean Th/U ratio of 2.07±0.01, indistinguishable from Isotope Dilution ICP-MS (ID-ICP-MS) and Thermal Ionization Mass Spectrometry (ID-TIMS) results. ID-TIMS U/Pb ages are concordant within uncertainties of decay constants, with a concordia age of 541.70±0.70Ma. Conventional (U-Th)/He dating on 28 random shards from the crystal in different laboratories gives a central age of 476.4±5.7Ma. Six in-situ (U-Th)/He analyses yield consistent 4He concentrations and ages with weighted mean values of 1248±46nmol/g and 462±21Ma, respectively. Fractions of this zircon have been shared with several laboratories in the Australia, China, UK and US, and are expected to serve as a reference for both in-situ and conventional (U-Th)/He analyses. The combination of analytical methods used to characterize LGC-1 zircon may be used as a template for future age reference calibration.

Zircon M127 – A Homogeneous Reference Material for SIMS U–Pb Geochronology Combined with Hafnium, Oxygen and, Potentially, Lithium Isotope Analysis

In this article, we document a detailed analytical characterisation of zircon M127, a homogeneous 12.7 carat gemstone from Ratnapura, Sri Lanka. Zircon M127 has TIMS‐determined mean U–Pb radiogenic isotopic ratios of 0.084743 ± 0.000027 for 206Pb/238U and 0.67676 ± 0.00023 for 207Pb/235U (weighted means, 2s uncertainties). Its 206Pb/238U age of 524.36 ± 0.16 Ma (95% confidence uncertainty) is concordant within the uncertainties of decay constants. The δ18O value (determined by laser fluorination) is 8.26 ± 0.06‰ VSMOW (2s), and the mean 176Hf/177Hf ratio (determined by solution ICP‐MS) is 0.282396 ± 0.000004 (2s). The SIMS‐determined δ7Li value is −0.6 ± 0.9‰ (2s), with a mean mass fraction of 1.0 ± 0.1 μg g−1 Li (2s). Zircon M127 contains ~ 923 μg g−1 U. The moderate degree of radiation damage corresponds well with the time‐integrated self‐irradiation dose of 1.82 × 1018 alpha events per gram. This observation, and the (U–Th)/He age of 426 ± 7 Ma (2s), which is typical of unheated Sri Lankan zircon, enable us to exclude any thermal treatment. Zircon M127 is proposed as a reference material for the determination of zircon U–Pb ages by means of SIMS in combination with hafnium and stable isotope (oxygen and potentially also lithium) determination.

Fluid inclusion characteristics and molybdenite Re-Os geochronology of the Qulong porphyry copper-molybdenum deposit, Tibet

The Qulong porphyry copper and molybdenum deposit is located at the southwest margin of the Lhasa Terrane and in the eastern region of the Gangdese magmatic belt. It represents China’s largest porphyry copper system, with ∼2200 million tonnes of ore comprising 0.5 % Cu and 0.03 % Mo. The mineralization is associated with Miocene granodiorite, monzogranite and quartz-diorite units, which intruded into Jurassic volcanic units in a post-collisional (Indian-Asian) tectonic setting. Field observations and core logging demonstrate the alteration and mineralization at Qulong are akin to typical porphyry copper systems in subduction settings, which comprise similar magmatic-hydrothermal, potassic, propylitic and phyllic alteration assemblages. Molybdenite Re-Os geochronology confirms the relative timeframe defined by field observations and core logging and indicates that the bulk copper and molybdenum at Qulong were deposited within 350,000 years: between 16.10 ± 0.06 [0.08] (without and with decay constant uncertainty) and 15.88 ± 0.06 [0.08] Ma. This duration for mineralization is in direct contrast to a long-lived intrusive episode associated with mineralization based on previous zircon U-Pb data. Our fluid inclusion study indicates that the ore-forming fluid was oxidized and contained Na, K, Ca, Fe, Cu, Mo, Cl and S. The magmatic-hydrothermal transition occurred at ∼425 °C under lithostatic pressure, while potassic, propylitic and phyllic alteration occurred at hydrostatic pressure with temperature progressively decreasing from 425 to 280 °C. The fluid inclusion data presented here suggests that there has been ∼2.3 km of erosion at Qulong after its formation, and this erosion may be related to regional uplift of the Lhasa Terrane.

Chemostratigraphic and U–Pb geochronologic constraints on carbon cycling across the Silurian–Devonian boundary

The Devonian Period hosts extraordinary changes to Earth's biosphere. Land plants began their rise to prominence, with early vascular vegetation beginning its colonization of near-shore environments in the latest Silurian. Across the Silurian–Devonian (Pridoli–Lochkovian) transition, carbon isotope analyses of bulk marine carbonates (δCcarb13) from Laurentian and Baltic successions reveal a positive δCcarb13 shift. Known as the Klonk Event, values reach +5.8‰, making it one of the largest carbon isotope excursions in the Phanerozoic. Assigning rates and durations to these significant events requires a robust, precise Devonian time scale. Here we present 675 micritic matrix and 357 fossil-specific δCcarb13 analyses from the lower Devonian Helderberg Group of New York and West Virginia that exhibit the very positive δCcarb13 values observed in other Silurian–Devonian basins. This chemostratigraphic dataset is coupled with 66 ID-TIMS U–Pb dates on single zircons from six ash falls intercalated within Helderberg sediments, including dates on the stratigraphically lowest Devonian ashes yet developed. In this work, we (a) demonstrate that matrix and fossil-specific δCcarb13 values track one another closely in the Helderberg Group, (b) estimate the Silurian–Devonian boundary age in New York to be 421.3±1.2 Ma (2σ; including decay constant uncertainties), and (c) calculate the time required to evolve from baseline to peak δCcarb13 values at the onset of the Klonk event to be 1.00±0.25 Myr. Under these constraints, a steady-state perturbation to the global carbon cycle can explain the observed excursion with modern fluxes, as long as DIC concentration in the Devonian ocean remained below ∼2× the modern value. Therefore, potential drivers, such as enhanced burial of organic carbon, need not rely on anomalously high total fluxes of carbon to explain the Klonk Event.

First U–Pb SHRIMP age for the Pilmatué Member (Agrio Formation) of the Neuquén Basin, Argentina: Implications for the Hauterivian lower boundary

Ammonite-based biostratigraphic schemes for the Lower Cretaceous are fairly well refined across the world, from the standard zonation in the West Mediterranean province to the Boreal and Austral provinces in the northern and southern hemispheres, respectively. However, the lack of radioisotopic ages associated to the fossil-rich, Lower Cretaceous marine successions has hindered the accurate establishment of the numerical ages for the lower boundaries of its several stages (from Berriasian to Albian). Geochronological dating by U–Pb SHRIMP of a tuff layer that occurs within beds belonging to the Holcoptychites neuquensis Zone in the Pilmatué Member of the Agrio Formation in the Austral province (Neuquén Basin, Argentina) has resulted in an absolute age of 130.0 ± 0.6 Ma (2 sigma internal errors only) or 130.0 ± 0.8 Ma (including calibration and decay constant uncertainties). This age is interpreted to represent the time of eruption and thus the timing of the pyroclastic deposit. The H. neuquensis Zone is the equivalent of the A. radiatus Zone in the West Mediterranean province. Therefore, the obtained age is the first numerical data that could help constrain the Hauterivian lower boundary. Indeed, there is reasonable agreement with the latest proposed lower boundary of the Hauterivian at ∼132.9 Ma. On the other hand, the duration recently established for this stage would be hard to reconcile with the stratigraphic record of the entire Hauterivian in the study region (northeastern Neuquén Basin). Therefore, the results of this contribution could also help to assess the extent of the Hauterivian and associated stages.

Inventory calculation and nuclear data uncertainty propagation on light water reactor fuel using ALEPH-2 and SCALE 6.2

Two fuel assemblies, one belonging to the Takahama-3 PWR and the other to the Fukushima-Daini-2 BWR, were modelled and the fuel irradiation was simulated with the TRITON module of SCALE 6.2 and with the ALEPH-2 code. Our results were compared to the experimental measurements of four samples: SF95-4 and SF96-4 were taken from the Takahama-3 reactor, while samples SF98-6 and SF99-6 belonged to the Fukushima-Daini-2.Then, we propagated the uncertainties coming from the nuclear data to the isotopic inventory of sample SF95-4. We used the ALEPH-2 adjoint procedure to propagate the decay constant uncertainties. The impact was inappreciable. The cross-section covariance information was propagated with the SAMPLER module of the beta3 version of SCALE 6.2. This contribution mostly affected the uncertainties of the actinides. Finally, the uncertainties of the fission yields were propagated both through ALEPH-2 and TRITON with a Monte Carlo sampling approach and appeared to have the largest impact on the uncertainties of the fission products. However, the lack of fission yield correlations results is a serious overestimation of the response uncertainties.

Depositional age of the early Paleoproterozoic Klipputs Member, Nelani Formation (Ghaap Group, Transvaal Supergroup, South Africa) and implications for low-level Re–Os geochronology and Paleoproterozoic global correlations

We present new Re–Os isotope data from the early Paleoproterozoic Klipputs Member (Nelani Formation, Ghaap Group, Transvaal Supergroup, South Africa) to further evaluate low-level Re–Os geochronology of organic-rich sedimentary rocks and improve global correlations of Paleoproterozoic sedimentary rocks. The Klipputs Member contains Re (0.3–0.8ppb), total Os (34–177ppt) and common Os (192Os; 10–66ppt) abundances that overlap upper crustal abundances of 0.2–2ppb, 30–50ppt, and 12–21ppt, respectively. Five samples yield a Model 1 Re–Os date of 2479±20Ma (±22Ma if the 187Re decay constant uncertainty is included, 2σ, Mean Square of Weighted Deviates [MSWD]=0.01) using the CrVI-H2SO4 digestion protocol. Dissolution of the same sample powders using inverse aqua regia yields a Model 3 Re–Os date of 2862±190Ma (2σ, MSWD=148). Comparison of Re–Os isotope data between the two methods reveals that inverse aqua regia liberated a component of radiogenic detrital Os whereas the CrVI-H2SO4 medium did not. The Re–Os date of 2479±22Ma for the Klipputs Member is consistent with published geochronological ages from underlying and overlying stratigraphic units, suggesting the CrVI-H2SO4 protocol yields accurate Re–Os depositional ages from ORS containing very low levels of hydrogenous Re and hydrogenous+radiogenic Os. Hence, there is potential for widespread application of low-level Re–Os ORS geochronology, including sedimentary successions deposited before the Great Oxidation Event. The initial 187Os/188Os (0.12±0.01) from the Klipputs Member CrVI-H2SO4 regression indicates that dissolved Os in the contemporaneous local seawater originated from hydrothermal alteration of unradiogenic oceanic crust and/or cosmic dust rather than oxidative weathering of the radiogenic upper crust. In light of the Re–Os depositional age for the Klipputs Member, we propose that the stratigraphic units in the upper Hamersley Group above the Brockman Iron Formation (Western Australia) are younger than the Ghaap Group. Diamictite from the Doradale Formation in the Ghaap Group is constrained to be older than 2479±22Ma and thus may not be correlative with glacial deposits assigned to the oldest Paleoproterozoic glaciation.

Earth's earliest global glaciation? Carbonate geochemistry and geochronology of the Polisarka Sedimentary Formation, Kola Peninsula, Russia

As part of the International Continental Scientific Drilling Program's Fennoscandian Arctic Russia–Drilling Early Earth Project (ICDP FAR–DEEP), Palaeoproterozoic diamictic and associated rocks were targeted and recovered in Hole 3A on the Kola Peninsula of NW Russia. In addition to the diamictites, carbonate sedimentary rocks and volcanic ash layers (all metamorphosed to greenschist grade) were encountered. Sedimentology and geochemistry suggest deposition of the diamictites in an open-marine aragonite-precipitating environment. Sampling of the core and of outcrops from the same geographical area yielded a number of zircons for analyses, the majority of which were inherited. However a tuff at 20.01m core depth yielded zircons dated at 2434±1.2Ma (±6.6Myr including decay constant uncertainties) that we interpret as a magmatic age. These data, combined with dates from underlying intrusions, indicate deposition of the Polisarka Sedimentary Formation diamictites and underlying carbonates during an interval of time from ca. 2430 to 2440Ma. The carbonate rocks, which likely originally included aragonitic limestones, were deposited mostly in a deep-water setting (i.e. at least below storm wave base) and occur below the diamictite. They record two inorganic carbon δ13C excursions, from values of ca. 0‰ to minima of ca. −5.4‰, as the contact with the overlying diamictite is approached. The older (stratigraphically lower) excursion occurs about 9m below the base of the diamictic units and the younger one at 1m below. Throughout that interval, Mg/Ca ratios correlate strongly with δ13C (n=38, r=0.85), and combined with petrographic observations, this indicates that the first (stratigraphically lower) excursion was modified by secondary alteration and the second is recorded in resedimented dolostone clasts. It is tempting to speculate that these dolostone clasts were deposited in penecontemporaneous shallow-marine waters, and that their low δ13C values might reflect input of oxidised atmospheric methane to the ocean surface (and therefore the cause of the glaciation); the dolostones were subsequently resedimented into the deeper marine settings. However this must be left as a hypothesis to be tested when further age-constrained contemporaneous pre-glacial carbonate sections are found.