Dilution Thermal Ionization Mass Spectrometry Research Articles

High-resolution sedimentary cyclostratigraphy and astronomical signals in the Upper Ordovician of Southwest China

During the Late Ordovician, a series of significant biotic and geological events occurred globally and more specifically in South China. The development of a high-resolution orbital cyclostratigraphic framework and a precise radioisotope dating has greatly enhanced our understanding of the factors controlling these events. In this study, quantitative proxies for palaeo-water depths, derived from sedimentological analyses, serve as indicators for orbital cyclostratigraphic assessment.Relatively shallow-marine carbonates with well-developed shallowing-upward cycles were deposited in the western Yangtze Platform during the Late Ordovician. High-resolution geochronological data were obtained from high-precision isotope dilution thermal ionization mass spectrometry (ID-TIMS) zircon dating of K-bentonite beds at the studied section. This facilitated sedimentary facies and environmental analyses, as well as the recognition of sedimentary cycles. Based on mud content, bioclastic content, and laminations, four sedimentary facies, twelve sedimentary microfacies, and forty-eight shallowing-upward sedimentary cycles were identified in the Daduhe Formation.Through comparative time series analysis of depth rank, lime mudstone-calcareous mudstone binary data, non-carbonate content, and anhysteretic remanent magnetization (ARM), astronomical cycles and trends in sedimentation rates have been identified. This study confirms the reliability of radioisotope dating, establishing a 0.46 Myr duration for the Dicellograptus complexus graptolite biozone and a 0.96 Myr duration for the Paraorthograptus pacificus graptolite biozone, both with an empirical uncertainty of 0.1 Myr. This research proposes a reliable method for identifying astronomical cycles through high-precision sedimentary microfacies and cyclostratigraphy, in comparison with rock magnetic cyclostratigraphy studies.

Zircon U–Pb CA–ID–TIMS constraints on the chronology of the Late Carboniferous–early Permian continental Döhlen Basin and its correlation with the Thuringian Forest Basin (Central and Eastern Germany)

We present new zircon U–Pb chemical abrasion–isotope dilution–thermal ionization mass spectrometry (CA–ID–TIMS) ages of two Late Carboniferous–early Permian continental basins in Germany. Three volcanic rocks from the Döhlen Basin (Saxony), and two tuff samples of the Thuringian Forest Basin (Thuringia) were dated. Our data indicate that all four formations of the Döhlen Basin were deposited in the interval of approx. 300 Ma to 298 Ma. The tuff samples of the Thuringian Forest Basin provided ages that overlap with the Döhlen Basin data. The Niederhäslich Formation of the Döhlen Basin and the Manebach and Goldlauter formations of the Thuringian Forest Basin contain fossil-rich lacustrine horizons, which have been correlated to a variety of formations in other European basins through the use of insect, amphibian, or conchostracan assemblage zones. Our new data thus provide new absolute age constraints for different fossil assemblage zones. Furthermore, the data can be considered a strong indication for simultaneous large-scale volcanic activity between 300 and 298 Ma. A relation between volcanic and post-Variscan transtensional tectonic activity is proposed because both the Döhlen Basin and the Thuringian Forest Basin are bound to NW trending strike-slip faults.Graphical abstract

High-precision U-Pb zircon dating identifies a major magmatic event on the Moon at 4.338 Ga.

The Moon has had a complex history, with evidence of its primary crust formation obscured by later impacts. Existing U-Pb dates of >500 zircons from several locations on the lunar nearside reveal a pronounced age peak at 4.33 billion years (Ga), suggesting a major, potentially global magmatic event. However, the precision of existing geochronology is insufficient to determine whether this peak represents a brief event or a more protracted period of magmatism occurring over tens of millions of years. To improve the temporal resolution, we have analyzed Apollo 14, 15, and 17 zircons that were previously dated by ion microprobe at ~4.33 Ga using isotope dilution thermal ionization mass spectrometry. Concordant dates with sub-million-year uncertainty span ~4 million years from 4.338 to 4.334 Ga. Combined with Hf isotopic ratios and trace element concentrations, the data suggest zircon formation in a large impact melt sheet, possibly linked to the South Pole-Aitken basin.

Zircon Petrochronology of Au-Rich Porphyry and Epithermal Deposits in the Golden Quadrilateral (Apuseni Mountains, Romania)

Abstract The Golden Quadrilateral of the Apuseni Mountains (Romania) represents the richest Au(-Cu-Te) porphyry and epithermal district of Europe and the Western Tethyan metallogenic belt. The Au(-Cu-Te) mineralization is associated with Neogene calc-alkaline magmatism along graben structures growing during the late stages of the Alpine-Carpathian orogeny. We use zircon petrochronology to study the time-space distribution, sources, composition, and timescales of the Au(-Cu-Te)-mineralizing magmatism and explore its link to regional tectonics. Our own and published U-Pb zircon ages document ore-forming magmatic activity between ~13.61 and 7.24 Ma. In combination with available paleomagnetic data, the new zircon ages corroborate the hypothesis that the magmatism in the Golden Quadrilateral evolved in a tectonic environment dominated by major (up to 70°) crustal block rotation. Hafnium isotope composition of Neogene zircon (εHf between –2 and 10) supports the predominant origin of the magmas from a heterogeneous lithospheric mantle, which may have been fertilized during an earlier Cretaceous subduction event and possibly by concurrent Miocene subduction. Xenocrystic zircon shows involvement of crustal sources resembling European continental basement. Fertility indicators, including Eu/Eu* and oxygen fugacity based on zircon composition, show no systematic correlation with the mineralizing events and/or age. High-precision (isotope dilution-thermal ionization mass spectrometry) U-Pb zircon geochronology demonstrates that the magmatic systems exposed at district scale evolved over less than ~100 k.y. and that durations of hydrothermal mineralization pulses were even shorter.

Evaluating reference materials and common-Pb corrections for high-resolution apatite U[sbnd]Pb geochronology

We report isotope dilution thermal ionization mass spectrometry (ID-TIMS) and laser ablation split stream inductively coupled plasma mass spectrometry (LASS) UPb data for a suite of widely available reference apatites: Fish Canyon Tuff, Mount Dromedary, TEMORA 2, and Duluth Complex anorthosite. We apply different common-Pb correction strategies to the UPb data sets: (1) anchoring to a Stacey and Kramers (1975) model Pb composition; (2) unanchored 2-D 238U/206Pb-207Pb/206Pb isochron regressions; and (3) unanchored 3-D 238U/206Pb-207Pb/206Pb-204Pb/206Pb isochron regressions. The different common-Pb corrections yield consistent dates within each ID-TIMS and LASS data set, with 3-D regression method producing the highest precision isochrons. FCT apatite produces an ID-TIMS 3-D isochron age of 28.8 ± 3.7 Ma with (207Pb/206Pb)i = 0.851 ± 0.021. Mount Dromedary apatite yields an ID-TIMS 3-D isochron age of 98.4 ± 0.5 Ma with (207Pb/206Pb)i = 0.839 ± 0.003. TEMORA 2 apatite has an ID-TIMS 3-D isochron age of 402 ± 7 Ma and (207Pb/206Pb)i = 0.839 ± 0.008. Duluth Complex anorthosite apatite yields an ID-TIMS 3-D isochron age of 1077 ± 9 Ma with (207Pb/206Pb)i = 0.849 ± 0.046. The MSWDs associated with isochrons calculated from both the ID-TIMS and LASS data sets are larger than expected for a single age population, revealing complexities that are otherwise not captured by 2-D isochron methods. In the case of FCT apatite, the ID-TIMS data indicate significant heterogeneity in the initial Pb ratio ((207Pb/206Pb)i = 0.845–0.856), invalidating this sample as a viable reference apatite for high-precision geochronology. Additionally, the common-Pb compositions of TEMORA 2 and Duluth Complex anorthosite apatites calculated using the ID-TIMS data deviate from bulk Earth Pb evolution models beyond 2σ uncertainty. The data emphasize the utility of unanchored age regressions in generating the highest fidelity apatite UPb dates. Further, TEMORA 2 and Duluth Complex apatite ages are both younger than their corresponding zircon UPb ages, highlighting the need to independently verify the ages of prospective reference apatites.

Timing of Hydrothermal Alteration and Au-Sb-W Mineralization, Stibnite-Yellow Pine District, Idaho

Abstract The Stibnite-Yellow Pine district of central Idaho was mined from the early 1900s until the 1990s, extracting gold, antimony, tungsten, and mercury from veins and disseminated and replacement ores in mountainous terrain along the headwaters of the Salmon River. Mining during the two World Wars supplied critical antimony and tungsten to the war efforts. Recent exploration has delineated mineral resources of over 187 metric tons Au, 274 metric tons Ag, and 93,000 metric tons Sb. Mineralization is hosted in Cretaceous Idaho batholith granitic rocks and a sequence of Neoproterozoic to Paleozoic metasedimentary strata of carbonate and siliciclastic compositions. Historic studies outlined some of the complex paragenesis but debated the absolute age of mineralization. New petrographic and geochronologic work documents a sequence of five hydrothermal events in the Stibnite-Yellow Pine district. Event 1 is related to Cretaceous magmatic and hydrothermal activity and includes events ranging in age from 86 to 75 Ma, including sparse quartz-molybdenite veins dated at 86 Ma. Disseminated gold mineralization of Event 2 is associated with sericitic alteration and sulfidation of igneous biotite and replacement of plagioclase by potassium feldspar, largely in granodiorite. Gold is present in zoned arsenian pyrite in both disseminated ores and in crosscutting carbonate-quartz veins containing pyrite and arsenopyrite. The large Yellow Pine deposit, localized at a dilatant bend in the Meadow Creek fault, hosts such disseminated and vein gold. Event 2 is interpreted as the major gold-forming event; 40Ar/39Ar ages of sericite and potassium feldspar alteration range, respectively, from 70 to 59 and 66 to 56 Ma. The long span is interpreted to reflect the age of gold mineralization and local overprinting by Event 3. A narrower range from 66 to 61 Ma is interpreted to date the peak of gold mineralization and alteration. Event 3, tungsten mineralization with scheelite, is texturally later than Event 2 gold and localized along the Meadow Creek structure. Event 3 scheelite has been dated by isotope dilution-thermal ionization mass spectrometry (ID-TIMS) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) U-Pb methods at 57 Ma. Event 4, best developed in the West End area, includes gold-silver–bearing quartz-carbonate-pyrite veins and breccias with epithermal textures and potassium feldspar alteration envelopes. Adularia from Event 4 yields 40Ar/39Ar plateau ages of 52 to 51 Ma. Event 5 antimony and mercury mineralization consists of stibnite veins and breccia cements at the Yellow Pine and Hangar Flat deposits as well as cinnabar veins and replacements at the peripheral Fern and Hermes deposits; it is constrained by an LA-ICP-MS U-Pb date on scheelite (ca. 47 Ma) intergrown with stibnite. Minor propylitic and argillic alteration is evident in 47 Ma igneous dikes, which do not contain economic mineralization. The Au-Sb-W ores in the Stibnite-Yellow Pine mining district formed over an extended time period from about 70 to 45 Ma in multiple pulses that were localized along the Meadow Creek fault zone. Each event corresponds to episodes of magmatism and/or hydrothermal activity in the region. Insignificant Event 1 skarn and molybdenum mineralization is similar in age to the Thompson Creek porphyry molybdenum deposit in central Idaho. Event 2 gold mineralization occurred during a magmatic gap in central Idaho but was synchronous with magmatism in the Bitterroot lobe further north; Event 2 is similar in age to orogenic gold-arsenic mineralization at the Beartrack mine in eastern Idaho. Event 3 scheelite mineralization coincides with tungsten mineralization at the Quartz Creek deposit, late magmatism in the Bitterroot lobe, and rapid exhumation of the Atlanta lobe of the Idaho batholith. Event 4 gold mineralization is coincident with the onset of regional Challis magmatism and extension. Event 5 antimony and mercury mineralization is time-equivalent to epithermal gold mineralization in the nearby Thunder Mountain volcanic field and the peak of Challis magmatism.

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.

Modeling apparent Pb loss in zircon U–Pb geochronology

Abstract. The loss of radiogenic Pb from zircon is known to be a major factor that can cause inaccuracy in the U–Pb geochronological system; hence, there is a need to better characterize the distribution of Pb loss in natural samples. Treatment of zircon by chemical abrasion (CA) has become standard practice in isotope dilution–thermal ionization mass spectrometry (ID-TIMS), but CA is much less commonly employed prior to in situ analysis via laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) or secondary ionization mass spectrometry (SIMS). Differentiating the effects of low levels of Pb loss in Phanerozoic zircon with relatively low-precision in situ U–Pb dates, where the degree of Pb loss is insufficient to cause discernible discordance, is challenging. We show that U–Pb isotopic ratios that have been perturbed by Pb loss may be modeled by convolving a Gaussian distribution that represents random variations from the true isotopic value stemming from analytical uncertainty with a distribution that characterizes Pb loss. We apply this mathematical framework to model the distribution of apparent Pb loss in 10 igneous samples that have both non-CA LA-ICP-MS or SIMS U–Pb dates and an estimate of the crystallization age, either through CA U–Pb or 40Ar/39Ar geochronology. All but one sample showed negative age offsets that were unlikely to have been drawn from an unperturbed U–Pb date distribution. Modeling apparent Pb loss using the logit–normal distribution produced good fits with all 10 samples and showed two contrasting patterns in apparent Pb loss; samples where most zircon U–Pb dates undergo a bulk shift and samples where most zircon U–Pb dates exhibited a low age offset but fewer dates had more significant offset. Our modeling framework allows comparison of relative degrees of apparent Pb loss between samples of different age, with the first and second Wasserstein distances providing useful estimates of the total magnitude of apparent Pb loss. Given that the large majority of in situ U–Pb dates are acquired without the CA treatment, this study highlights a pressing need for improved characterization of apparent Pb-loss distributions in natural samples to aid in interpreting non-CA in situ U–Pb data and to guide future data collection strategies.

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.

Geochronological and geochemical effects of zircon chemical abrasion: insights from single-crystal stepwise dissolution experiments

Abstract. Chemical abrasion in hydrofluoric acid (HF) is routinely applied to zircon grains prior to U–Pb dating by isotope dilution thermal ionization mass spectrometry (ID-TIMS) to remove radiation-damaged portions of grains affected by Pb loss. Still, many chemically abraded datasets exhibit evidence of residual Pb loss. Here we test how the temperature and duration of chemical abrasion affect zircon U–Pb and trace element systematics in a series of 4 h, single-crystal stepwise dissolution experiments at 180 and 210 ∘C. Microtextural data for the zircon samples studied are presented in a companion paper by McKanna et al. (2023). We find that stepwise dissolution at 210 ∘C is more effective at eliminating material affected by open-system behavior and enriched in U, common Pb (Pbc), and light rare earth elements (LREEs); reduces the presence of leaching-induced artifacts that manifest as reverse discordance; and produces more consistent and concordant results in zircon from the three rocks studied. We estimate that stepwise dissolution in three 4 h steps is roughly equivalent to a single ∼ 8 h leaching step due to the insulating properties of the PTFE sleeve in the Parr pressure dissolution vessel, whereas traditionally labs utilize a single 12 h leaching step. We conclude that a single 8 h leaching step at 210 ∘C should remove Pb loss effects in the majority of zircon and that this can be used as an effective approach for routine analysis. Further, we calculate time-integrated alpha doses for leachates and residues from measured radionuclide concentrations to investigate (1) the alpha dose of the material dissolved under the two leaching conditions and (2) the apparent minimum alpha dose required for Pb loss susceptibility: ≥ 6×1017 α g−1.

An exploratory study of “large‐n” detrital zircon geochronology of the Book Cliffs, UT via rapid (3 s/analysis) U–Pb dating

AbstractDetrital zircon (DZ) U–Pb geochronology has improved the way geologists approach questions of sediment provenance and stratigraphic age. However, there is debate about what constitutes an appropriate sample size (i.e., the number of dates in a DZ sample, n), which depends on project objectives, sample complexity, and, critically, analytical budget. Additionally, there is ongoing concern about bias introduced by zircon grain size. We tested a recently developed rapid (3 s/analysis) data acquisition method by multicollector laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) that incorporates an automated selection routine and calculates two‐dimensional grain geometry from polished sample surfaces. Eleven samples were analysed from below and above the Late Cretaceous (Campanian) basal Castlegate unconformity of the Book Cliffs, Utah, in a down‐depositional‐dip transect including Price, Horse, Tusher, and Thompson canyons. 12,448 new concordant dates were generated during two measurement sessions. Results are consistent with recent studies suggesting there is no major provenance change and little time (1–2 Myr) represented across the unconformity. Grain size and sample size both exert a strong control on sample dissimilarity. Age distributions constructed from subsamples of large grains are systematically less similar to whole samples; age distributions composed of small grains are overall more similar to whole samples. As such, North American sediment sources that produce large grains such as the Grenville and Yavapi‐Mazatzal belts can bias age distributions if only large grains are analysed. A sample size of n = 100 is inadequate for characterizing age distributions as complex as those of the Book Cliffs, whereas a sample size of n = 300 provides good characterization. Sample size of n ≈ 1000 or more is unnecessary unless project objectives include scanning for subordinate age groups, such as when identifying the youngest grains for calculating a maximum depositional age (MDA). Dates used in MDA calculations acquired with rapid acquisition are best re‐analysed with longer LA‐ICP‐MS acquisition methods or isotope dilution thermal ionization mass spectrometry for increased accuracy and precision. We include new MATLAB code and open‐source software programs, DZpick and DZmda, for automated spot picking and calculating MDAs.

U–Pb zircon–rutile dating of the Llangynog Inlier, Wales: constraints on an Ediacaran shallow-marine fossil assemblage from East Avalonia

The Llangynog Inlier of south Wales contains an assemblage of Ediacaran macrofossils from a shallow-marine environment, including discoidal morphs of Aspidella and rare examples of Hiemalora , Palaeopascichnus and Yelovichnus . These are taxa found at other sites in the Avalonian microcontinent (e.g. Charnwood Forest and eastern Newfoundland) and in the younger White Sea Ediacaran assemblages. As the Charnwood fossils reflect a deep-water environment, and no macrofossils have been found in the Ediacaran rocks of the Long Mynd, the fossils of the Llangynog Inlier represent a unique glimpse of shallow-marine life in southern Britain (East Avalonia). However, the lack of absolute age constraints has hampered direct comparison with other assemblages. Here, we report in situ zircon and rutile U–Pb dates from a rhyolitic ash-flow layer of the Coed Cochion Volcaniclastic Member, Llangynog Inlier, which constrains the age of the fossiliferous strata. A weighted mean single grain zircon isotope dilution thermal ionization mass spectrometry U–Pb age of 564.09 ± 0.70 Ma is interpreted as the rhyolite's crystallization age. This age is consistent with in situ laser ablation inductively coupled plasma mass spectrometry zircon and rutile U–Pb dating. The Llangynog age temporally correlates these fossils to dated horizons within East Avalonia at the Beacon Hill Formation, Charnwood (565.22 ± 0.89 Ma) and the Stretton Shale Formation, Long Mynd (566.6 ± 2.9 Ma). Correlations to West Avalonia include the time-equivalent Fermeuse Formation, St John's Group, eastern Newfoundland (564.13 ± 0.65 Ma). The data presented here establish the biota of the Llangynog Inlier as a lateral equivalent to the similarly shallow-marine, tidally influenced ecosystem of the upper Fermeuse Formation. Intra-terrane depositional environmental variability also affects what is preserved in Avalonian fossil sites. Further, time-constrained geochemical data reinforce the Llangynog Inlier's classification within the Wrekin Terrane. Supplementary material : U–Pb data, reference material and figures showing sedimentary structures are available at https://doi.org/10.6084/m9.figshare.c.6965642

Direct quantification of femtogram per liter (fg L−1) level 90Sr in rainwater using thermal ionization mass spectrometry

This paper proposes the direct quantification of radioactive strontium-90 at femtogram per liter levels using isotope dilution-thermal ionization mass spectrometry with effective preconcentration of rainwater.

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.

Tracking the Eurydesma Fauna transgression across southwestern Gondwana

The cold water Eurydesma Fauna, consisting of bivalves, brachiopods, and scarce gastropods, has been associated in several basins of Gondwana with the terminal phase of the Late Paleozoic Ice Age (LPIA). The Eurydesma Fauna-bearing transgression has been identified in basins of South America and southern Africa. In western Karoo Basin of South Africa four phases of ice growth and decay have been proposed for the Dwyka Group on the basis of interstratified glaciogenic diamictites overlain by non-glaciogenic, ice rafted debris free mudstones. Each of these phases is assigned to deglaciation sequences (sensu Visser, 1997) and has been proposed to be incomplete, third order sequences made up of a basal lowstand systems tract (LST) followed by a transgressive systems tract (TST) or exclusively by a thick TST. The correlation of these deglaciation sequences has been extended to the adjacent Aranos-Kalahari basin and to the Paraná Basin (Itararé Group) in South America. Recent high-precision UPb ages on single crystal chemical abrasion, isotope dilution-thermal ionization mass spectrometry (CA-IDTIMS) have helped to refine the diachronous demise of the LPIA and the age of the Eurydesma transgression. Tentative correlations with the glaciogenic section (Sauce Grande Formation) in the Ventana Fold belt (VFB) and Malvinas/Falkland Islands (Fitzroy Tillite Formation) are supported by radiometric ages, and similar facies associations respectively. This interbasinal correlation of deglaciation sequences and radiometric ages allowed to constrain the occurrence of this fauna in southwestern Gondwana to the Asselian.The postglacial nature of the Eurydesma Fauna transgression in South American basins, particularly in the VFB-Claromecó Basin of Argentina, is in contrast with its interglacial character in the Southern African basins, where the Eurydesma transgression caps the deglaciation sequence 3 and underlies the deglaciation sequence 4.

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.

U–Pb age constraints on the Carboniferous–Permian transition in continental basins of eastern equatorial Pangaea (France): implications for the depositional history and correlations across the late Variscan Belt

Intramontane late Carboniferous–Permian basins of western Europe developed during the latest orogenic stages of the Variscan Mountain Belt in eastern Pangaea, at equatorial palaeolatitudes. Their stratigraphic framework is mainly based on continental subdivisions (e.g. Stephanian and Autunian continental stages), which can be contentious owing to biostratigraphic biases, resulting in long-distance diachronous subdivisions. To provide precise inter-basinal and global correlations to the internationally recognized chronostratigraphic marine stages, this study reports new U–Pb geochronology from the Aumance and Decize–La Machine basins, located in the northern French Massif Central. Zircon grains extracted from three volcanic ash-fall layers give weighted mean 206 Pb/ 238 U ages of 299.11 ± 0.35, 298.73 ± 0.36 and 298.59 ± 0.35 Ma (2 σ total propagated uncertainty) by the chemical abrasion isotope dilution thermal ionization mass spectrometry method, coinciding with the Carboniferous–Permian transition (Gzhelian and Asselian stages). These ages imply that the northern Massif Central basins developed synchronously in relatively short periods of time (<10 myr), reflecting substantial sedimentation rates. Finally, the new chronology of infilling of these basins confirms that they were connected during the late Carboniferous and early Permian periods, improving the knowledge on the late orogenic Variscan geodynamic setting in this area. Supplementary material: Operating conditions and complete analytical results are available at https://doi.org/10.6084/m9.figshare.c.6805228

A shifty Toba magma reservoir: Improved eruption chronology and petrochronological evidence for lateral growth of a giant magma body

Polycyclic caldera complexes hold clues to understanding why some magmatic systems develop into supersized magma bodies and how they can recover to produce several caldera-forming eruptions. However, the geologic records of the transitions between successive caldera events are very often inaccessible due to limited preservation of eruptive products of inter-caldera activity, prompting the search for alternative archives of magma evolution such as accessory minerals. Here we applied multiple geochemical tools to study one of the most active caldera centres of the Quaternary, the Toba caldera complex in Sumatra (Indonesia), which produced at least four caldera-forming eruptions in the last 1.6 My, including the iconic Youngest Toba Tuff at 74 ka. We combined feldspar 40Ar/39Ar and zircon U–Pb geochronology of proximal pyroclastic deposits with glass and mineral chemistry of both the tuffs and distal marine tephra to revise the eruption chronology of Toba, obtaining new eruption ages of 1417 -31/+14 ka (zircon) or 1339 ± 39/39 ka (plagioclase, internal/full external 2σ uncertainty) for the Haranggaol Dacite Tuff, 783.81 ± 0.85/1.32 ka (sanidine) for Oldest Toba Tuff, and 503.61 ± 1.36/1.50 ka (sanidine) for Middle Toba Tuff. Isotope dilution thermal ionisation mass spectrometry (ID-TIMS) U–Pb crystallisation ages, trace element contents and Hf isotopic ratios of zircons illuminate changes in the shallow magma reservoir which saw near-continuous zircon crystallisation over 1.6 My. Prolonged build-ups to each eruption with highly scattered zircon trace element compositions reflect a complex, heterogeneous character of the shallow reservoir, without a clear temporal trend or indications of the eruption trigger. In contrast, hafnium isotopes in zircon display a pronounced shift towards unradiogenic values immediately after the OTT caldera collapse, followed by a gradual recovery to a baseline value of εHf = -7 at the time of YTT eruption, interpreted as a reflection of the shift in magma reservoir position corresponding to change in the character of assimilated crust. We can show in unprecedented detail how a large caldera collapse affects magma geochemistry; however, identification of patterns in the behaviour of the Toba system and making geochemistry-based predictions about its future development remain a challenge.