Isotope Dilution Thermal Ionization Mass Spectrometry Research Articles

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.

Recommendations for the reporting and interpretation of isotope dilution U-Pb geochronological information

U-Pb geochronology by isotope dilution−thermal ionization mass spectrometry (ID-TIMS) has the potential to be the most precise and accurate of the deep time chronometers, especially when applied to high-U minerals such as zircon. Continued analytical improvements have made this technique capable of regularly achieving better than 0.1% precision and accuracy of dates from commonly occurring high-U minerals across a wide range of geological ages and settings. To help maximize the long-term utility of published results, we present and discuss some recommendations for reporting ID-TIMS U-Pb geochronological data and associated metadata in accordance with accepted principles of data management. Further, given that the accuracy of reported ages typically depends on the interpretation applied to a set of individual dates, we discuss strategies for data interpretation. We anticipate that this paper will serve as an instructive guide for geologists who are publishing ID-TIMS U-Pb data, for laboratories generating the data, the wider geoscience community who use such data, and also editors of journals who wish to be informed about community standards. Combined, our recommendations should increase the utility, veracity, versatility, and “half-life” of ID-TIMS U-Pb geochronological data.

Rb, Sr, Sm and Nd elemental concentrations and Sr and Nd isotopic ratios of 13 Chinese rock reference materials using isotope dilution TIMS and MC–ICP–MS

The suitability of 13 Chinese silicate rock certified reference materials for Sr and Nd isotope analyses was investigated. To indicate their homogeneity and to provide information values, we report Sr and Nd isotopic data and Rb, Sr, Sm and Nd concentrations for reference materials GBW07 103–105, 109–113 and 121–125 spanning a broad compositional range. Test portions were spiked with tracers enriched in 87Rb–84Sr and 149Sm–145,146,150Nd and digested using HF, HNO3, and HClO4 acid-dissolution procedures. Chemical purification involved cation-exchange and HEHEHP or Ln resins. Analyses involved different instruments at four laboratories, including thermal ionisation mass spectrometry (TIMS) and multicollector–inductively coupled plasma–mass spectrometry (MC–ICP–MS). This study provides a comprehensive report of the Rb–Sr and Sm–Nd isotopic compositions of the reference materials, and the results indicate that the materials are comparable to those of well-characterised and widely utilized reference materials from the US Geological Survey and the Geological Survey of Japan. This is the first report of the Sr and Nd isotopic composition of standards GBW07111, GBW07112, GBW07121, GBW07122, GBW07123, GBW07124 and GBW07125. Our results are useful for quality control and assurance between laboratories and provide a robust reference-rock dataset for future studies involving classical Sr and Nd isotopic geochemistry.

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.

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.

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.

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.

RKV01 Rutile – A New Potential Archaean Reference Material for Microbeam U‐Pb Dating

Rutile stands as a classical mineral within U‐Pb geochronology, offering insights into both magmatic and metamorphic events, and contributing to the understanding of provenance of detrital sedimentary rocks. Addressing the paucity of high‐quality Archaean rutile reference materials suitable for microbeam U‐Pb dating, we present a natural rutile (RKV01) sourced from the Kaap Valley pluton, South Africa, positing it as a potential Archaean reference material. Major element determination was executed via electron probe microanalysis, while trace element determination was conducted using laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS). The determination of U‐Pb ages involved the application of isotope dilution‐thermal ionisation mass spectrometry (ID‐TIMS), secondary ion mass spectrometry (SIMS) and LA‐ICP‐MS. The ID‐TIMS mean 207Pb/206Pb age is 3225.61 ± 0.64 Ma (2s, MSWD = 0.83), interpreted as the best estimate for the crystallisation age. The relatively high U mass fraction (~ 83 μg g‐1), extremely low Th mass fraction (~ 0.003 μg g‐1), negligible common Pb and isotopically homogeneous compositions collectively facilitated precise 207Pb/206Pb age determination via microbeam methods. Both LA‐ICP‐MS and SIMS 207Pb/206Pb ages are characterised by reproducibility and were consistent with the ID‐TIMS age within 2s analytical uncertainty. The results underscore the potential of RKV01 rutile as an Archaean reference material for microbeam U‐Pb dating.

U–Pb zircon ages from tuffaceous beds in the Terreneuvian to Cambrian Series 2 sections of Avalonian southern New Brunswick, Canada: new constraints on chronostratigraphic correlations and the Cambrian time scale

Abstract Avalonian sections in the Saint John area, southern New Brunswick, have long contributed to global understanding of Cambrian chronostratigraphy. A tuffaceous bed in the Ratcliffe Brook Formation (RBF) in the Somerset Street section dated at c. 531 Ma has traditionally been considered to post-date small shelly fossils attributed to the Watsonella crosbyi Zone in the Hanford Brook section. A fine-grained tuffaceous bed approximately 8 m stratigraphically lower in the Somerset Street section yields a chemical abrasion isotope dilution–thermal ionization mass spectrometry zircon age of 532.3 ± 0.3 Ma; a tuffaceous carbonate unit in the lower RBF in Hanford Brook gives an age of 531.5 ± 0.3 Ma. Crystal and crystal-lithic tuff beds near the top of the RBF yield ages of 520.3 ± 0.3 Ma (in Hanford Brook) and 519.1 ± 0.3 Ma (in Ratcliffe Brook). The new ages confirm the correlation between the Somerset Street and Hanford Brook sections based on acritarchs and make the association of small shelly fossils in the Hanford Brook section younger than 531 Ma. This result is relevant to ongoing discussions on the age of the base of undefined Cambrian Stage 2. The radiometric ages also support a young age for the upper part of the RBF, perhaps extending into Epoch 2.

U–Pb zircon ages from tuffaceous beds in the Terreneuvian to Cambrian Series 2 sections of Avalonian southern New Brunswick, Canada: new constraints on chronostratigraphic correlations and the Cambrian time scale

Abstract Avalonian sections in the Saint John area, southern New Brunswick, have long contributed to global understanding of Cambrian chronostratigraphy. A tuffaceous bed in the Ratcliffe Brook Formation (RBF) in the Somerset Street section dated at c. 531 Ma has traditionally been considered to post-date small shelly fossils attributed to the Watsonella crosbyi Zone in the Hanford Brook section. A fine-grained tuffaceous bed approximately 8 m stratigraphically lower in the Somerset Street section yields a chemical abrasion isotope dilution–thermal ionization mass spectrometry zircon age of 532.3 ± 0.3 Ma; a tuffaceous carbonate unit in the lower RBF in Hanford Brook gives an age of 531.5 ± 0.3 Ma. Crystal and crystal-lithic tuff beds near the top of the RBF yield ages of 520.3 ± 0.3 Ma (in Hanford Brook) and 519.1 ± 0.3 Ma (in Ratcliffe Brook). The new ages confirm the correlation between the Somerset Street and Hanford Brook sections based on acritarchs and make the association of small shelly fossils in the Hanford Brook section younger than 531 Ma. This result is relevant to ongoing discussions on the age of the base of undefined Cambrian Stage 2. The radiometric ages also support a young age for the upper part of the RBF, perhaps extending into Epoch 2.

MAP-2 apatite: A new young age reference material for U–Pb dating with LA-ICPMS analysis

Apatite is an essential mineral for geochronology and geochemistry. Precise and accurate U–Pb Laser ablation (LA)-inductively coupled plasma mass spectrometry (ICPMS) dating of apatite requires suitable matrix-matched reference materials (RMs), but young RMs (<30Ma) are lacking from existing apatite RMs. We provided a gem-quality apatite MAP-2 collected from Myanmar and subjected it to detailed chemical composition and U–Pb dating analyses to assess its homogeneity and suitability as a reference material for LA-ICPMS age determination. The results of comprehensive analyses of multiple methods show that the MAP-2 apatite is largely free of inclusions and is relatively homogenous in chemical and isotopic content. Notably, MAP-2 apatite could be the youngest apatite U–Pb dating reference material (about 22 Ma) with relatively high U contents range from 161 μg g−1 to 231 μg g−1 and an average of 210 μg g−1. The isotope dilution-thermal ionization mass spectrometry (ID-TIMS) U–Pb measurements yielded weighted mean isotopic ratio values of 0.00345 ± 0.00003 for 206Pb/238U, 0.0243 ± 0.0039 for 207Pb/235U, 0.0512 ± 0.0082 for 207Pb/206Pb and the weighted mean 206Pb/238U ages of 22.18 ± 0.22 Ma (2SD, MSWD = 0.01, n = 6) as the recommended reference value. LA-ICPMS analyses yielded 207Pb-corrected weighted mean 206Pb/238U age of 22.0 ± 0.1/0.2 Ma (2SD, MSWD = 4.2, n = 232) and the results are consistent with ID-TIMS data within the limits of the ID-TIMS analytical uncertainly, which indicates that MAP-2 apatite has the potential as a reference material for microbeam determination of U–Pb ages.

Temporal variability in seawater Sr/Ca ratios within a coral atoll as an indicator of marine calcifier community diversity

Coral reefs are marine environments where calcium carbonate production and dissolution along with photosynthesis and respiration can have a large impact on the daily biogeochemical cycles of seawater dissolved inorganic carbon (DIC), total alkalinity (TA), oxygen (O2), and major nutrients. Using seawater samples from Tetiaroa Atoll, French Polynesia, we apply isotope dilution thermal ionization mass spectrometry (ID-TIMS) to show that these daily cycles of variability extend to the dissolved seawater Sr/Ca ratio (Sr/Casw). Hourly measurements over a 27+ hour period indicate that Sr/Casw covaries with DIC and TA and exhibits up to a 2% relative difference compared to the regional Pacific Ocean source water Sr/Casw value of 8.53 mmol/mol. We hypothesize that the primary mechanism of hourly variability in Sr/Casw is carbonate precipitation/dissolution by corals and other marine calcifiers on the Tetiaroa reef, while sedimentary redox processes may significantly contribute to an apparent decoupling between net calcification rates estimated from TA compared to dissolved calcium [Ca]sw concentrations. Using a simple Rayleigh distillation model and a two-member mixing equation, we estimate the net partition coefficient of Sr (KD-Sr) for each hourly sample as a mixture of coral (aragonite; KD-Sr ∼ 1.06) and crustose coralline algae (high Mg-calcite; KD-Sr ∼ 0.39) contributions to the measured variability of [Ca]sw and Sr/Casw. As the high Mg-calcites of crustose coralline algae are (1) integral components to the structure and stability of the reef framework and (2) more soluble than aragonite under more acidic conditions, we propose that continued analyses of Sr/Casw within coral reef environments could be a useful tool for monitoring the ecological distribution and contributions of marine calcifiers on reefs as ocean warming and acidification intensify in response to anthropogenic climate change. Additionally, seasonal, interannual, and/or centennial-scale offsets between the Sr/Casw of open ocean source seawater and ambient reef seawater may have significant implications for interpreting past changes in sea surface temperatures derived from the coral Sr/Ca paleothermometer.

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

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

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

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

Monazite and xenotime petrochronologic constraints on four Proterozoic tectonic episodes and ca. 1705 Ma age of the Uncompahgre Formation, southwestern Colorado, USA

Abstract The Proterozoic tectonic evolution of the southwestern USA remains incompletely understood due to limited constraints on the timing and conditions of the tectono-metamorphic phases and depositional age of metasedimentary successions. We integrated multi-scale compositional mapping, petrologic modeling, and in situ geochronology to constrain pressure-temperature-time paths from samples of Paleoproterozoic basement gneisses and overlying quartzites in southwestern Colorado, USA. Basement gneiss from the western Needle Mountains records metamorphic conditions of 600 °C at 0.75 GPa at 1764 ± 9 Ma and ~575 °C at 1741 ± 10 Ma. Gneiss sampled from drill core near Pagosa Springs, Colorado, records conditions of 700 °C at 1748 ± 9 Ma, 800 °C at 1.1 GPa at 1650 ± 40 Ma, 540 °C at 1570 ± 36 Ma, and 440 °C at 1424 ± 12 Ma. The Uncompahgre Formation was deposited at ca. 1705 Ma, as constrained by detrital monazite (1707 ± 8 Ma) and xenotime (1692 ± 40, 1725 ± 50 Ma), metamorphic xenotime (1650 ± 10 Ma), and published 40Ar/39Ar and detrital zircon data. Compositions of ca. 1705 Ma detrital monazite and xenotime are consistent with derivation from a garnet-bearing source in the Yavapai orogenic hinterland. The Vallecito Conglomerate and Uncompahgre Formation record macroscopic folding and greenschist-facies metamorphism at 1650 ± 10 Ma and temperatures of 270 °C to &amp;gt;570 °C at 1470–1400 Ma. Laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) zircon geochronology yielded dates of 1775 ± 18 Ma from the Twilight Gneiss and 1696 ± 7 Ma from the Bakers Bridge Granite, supporting previous isotope dilution–thermal ionization mass spectrometry (ID-TIMS) dates. The Eolus Granite yielded a date of 1463 ± 6 Ma, which is older than previous 1.44–1.43 Ga ID-TIMS dates. The newly dated granite of Cataract Gulch is 1421 ± 12 Ma. In situ analysis of detrital and meta-morphic monazite and xenotime, igneous zircon, and quantitative thermobarometry, integrated with previously published constraints, indicate multiple tectonic episodes after the emplacement of 1800–1760 Ma arc-related rocks. The region experienced greenschist- to amphibolite-facies metamorphism (M1) from 1760 Ma to 1740 Ma, which was followed by the intrusion of granites at 1730–1695 Ma and deposition of the Uncompahgre Formation at ca. 1705 Ma, contemporaneous with the Yavapai orogeny. Metamorphism at 1680–1600 Ma was characterized by greenschist-facies conditions near Ouray, Colorado, and granulite-facies conditions near Pagosa Springs (M2) during the Mazatzal orogeny. From 1470 Ma to 1400 Ma, greenschist- to amphibolite-facies metamorphism (M3) and largely granitic plutonism occurred during the protracted Picuris orogeny. These results demonstrate the power of monazite and xenotime analyses to constrain depositional ages, provenance, and pressure-temperature-time (P-T-t) paths to resolve the compound orogenic history that is characteristic of most mountain belts.

The Mutare–Fingeren dyke swarm: the enigma of the Kalahari Craton's exit from supercontinent Rodinia

Abstract The Rodinia supercontinent broke apart during the Neoproterozoic. Rodinia break-up is associated with widespread intraplate magmatism on many cratons, including the c. 720–719 Ma Franklin large igneous province (LIP) of Laurentia. Coeval magmatism has also been identified recently in Siberia and South China. This extensive magmatism terminates ∼1 myr before the onset of the Sturtian Snowball Earth. However, LIP-scale magmatism and global glaciation are probably related. U–Pb isotope dilution–thermal ionization mass spectrometry (ID-TIMS) baddeleyite dating herein identifies remnants of a new c. 724–712 Ma LIP on the eastern Kalahari Craton in southern Africa and East Antarctica: the combined Mutare–Fingeren Dyke Swarm. This dyke swarm occurs in northeastern Zimbabwe (Mutare Dyke Swarm) and western Dronning Maud Land (Fingeren Dyke Swarm). It has incompatible element-enriched mid-ocean ridge basalt-like geochemistry, suggesting an asthenospheric mantle source for the LIP. The Mutare–Fingeren LIP probably formed during rifting. This rifting would have occurred almost ∼100 myr earlier than previous estimates in eastern Kalahari. The placement of Kalahari against southeastern Laurentia in Rodinia is also questioned. Proposed alternatives, invoking linking terranes between Kalahari and southwestern Laurentia or close to northwestern Laurentia, also present challenges with no discernible resolution. Nevertheless, LIP-scale magmatism being responsible for the Sturtian Snowball Earth significantly increases.