Thermal 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.

Evidence of glass bead‐making in the early Islamic Iberian Peninsula

AbstractGlass beads from two Islamic archaeological sites in the Tagus valley in central Spain were selected and analysed by laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS), and a subset of samples (n = 6) was analysed for Pb isotopes by multicollector thermal ionization mass spectrometry (MC‐TIMS). The analytical and isotopic data of the beads from Ciudad de Vascos (Toledo) and Albalat (Cáceres) demonstrate beyond reasonable doubt that glass beads were produced in the Iberian Peninsula during the Islamic period using local Pb‐silica and soda‐rich plant‐ash glass. The bead workshops in al‐Andalus were evidently part of an efficient system of glass collection and recycling, and used only relatively simple bead‐making techniques such as winding and folding. At present it is unclear to what extent the Islamic bead‐makers in the Iberian Peninsula were involved in the international trade in glass beads or whether their products were mainly destined for a regional market. Despite local production, some samples show compositional and typological features that suggest the import of finished glass beads, perhaps from Central Asia.

Platinum-rhenium-osmium isotope systematics of chromitite and native osmium from the Guli Massif (Maimecha-Kotui Province, Russia)

To gain insight into the source of ore material, this study presents the first Re-Os and Pt-Os isotopic and highly siderophile element (HSE) abundance data for chromitite and osmium minerals from the Guli massif of ultramafic, alkaline rocks and carbonatites located in the Maimecha-Kotui province, Polar Siberia. The study utilized a number of analytical techniques, including electron microprobe analysis, negative thermal ionization mass spectrometry (N-TIMS) and high pressure asher digestion and an isotope dilution-inductively coupled plasma-mass spectrometry. The HSE concentrations in chromitite samples range from 191 to 866 ppb with a predominance of Ir-group platinum-group elements (PGE) (Os, Ir and Ru) over Pt-group PGE (Rh, Pt and Pd) and Re, which is consistent with their platinum-group mineral control (i. e., Os-Ir alloys and laurite, RuS2) within the chromitite. The Re-Os and Pt-Os isotope data indicate that the HSE budget of the chromitite and osmium minerals from the Guli massif was largely controlled by that of the mantle source, which evolved with long-term near-chondritic Re/Os and Pt/Os ratios; this source is within the range of those for the majority of komatiite and abyssal peridotite sources.

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

Photochemical degradation of antibiotics: real-time investigation by aerodynamic thermal breakup droplet ionization mass spectrometry.

A method is proposed for studying photochemical reactions in solution in real time using aerodynamic/thermal breakup droplet ionization mass spectrometry. Capabilities of the method were demonstrated by analyses of photodegradation processes of three antibiotics (thiamphenicol, ciprofloxacin, and ofloxacin) by means of aqueous solutions. The method rapidly provided information about photochemical changes for understanding the photochemical processes.

Precise Determination of Cd Isotope Ratios at 3-10 ng Level by Thermal Ionization Mass Spectrometry Using a Molybdenum Silicide Emitter.

Thermal ionization mass spectrometry (TIMS) combined with the double spike technique has excellent analytical precision for Cd isotopic ratio analysis. However, because of the low ionization efficiency of Cd by TIMS, it is still not possible to obtain high precision Cd isotope ratios for small sample size (<100 ng) due to the lack of a highly sensitive emitter for Cd. A new loading method using molybdenum silicide (MoSi2) emitter has been developed for Cd isotope ratio measurements. This emitter produces a significant enhancement in the ionization efficiency of Cd and thus significantly reduces the required sample size to the 3-10 ng level. Analyses of δ114/110Cd for the NIST SRM 3108 using 108Cd-116Cd double spike method show excellent reproducibility (2 SD) that reaches ±0.032‰, ±0.042‰, and ±0.051‰ for 10, 5, and 3 ng of Cd, respectively. This method was further verified with a suite of geological reference materials. Replicate digestions and analyses (n = 8, 2 SD) of δ114/110Cd for NIST SRM 2711a, NOD A-1, and GBW08401 demonstrated good external reproducibility with results of 0.596 ± 0.024‰ for NIST SRM 2711a, 0.150 ± 0.036‰ for NOD A-1, and -0.665 ± 0.084‰ for GBW08401. These data clearly indicate that MoSi2 is an excellent alternative for traditional silica gel to Cd isotopic measurements, especially for samples with a low content of Cd.

Ages and structural relationships in the Ganderian central Cape Breton Highlands, Nova Scotia, Canada

Structural complexity of the Cape Breton Highlands is a key problem in reconstructing tectonic events in the northern Appalachian orogen. A new U–Pb thermal ionization mass spectrometry age of 428.53 ± 0.16 Ma for metarhyolite in the Calumruadh Brook Formation shows that volcanic and sedimentary rocks were deposited before collision of the Aspy and Bras d'Or terranes along the Eastern Highlands shear zone. A new U–Pb laser ablation zircon age of 394 +6/−4 Ma confirms that peak metamorphism in the Middle River complex continued during convergence linked to late stages of the Acadian orogeny. The compressive tectonic environment evolved into a transpressional system after initial collision in the late Silurian and caused a repeated pattern of imbrication of units in the Aspy terrane in the hanging wall in the collision. The shear zones bounding the geological units are curvilinear and have south-directed kinematics, imbricating units and transporting higher grade rocks over lower grade rocks, and moving plutons upward relative to their host rocks during and shortly after intrusion. The vergence of imbrication is parallel to the direction of transpressional movement on the main Eastern Highlands shear zone. This geometry is present in Ordovician–Silurian rocks and repeated in Devonian plutonic rocks, indicating that the overall transpressional tectonic setting was a long-lived feature of the orogen. The shear zones localized late syn- to post-deformational plutons that intruded at ca. 375–370 Ma. By the latest Devonian, emplacement of the ca. 363 Ma Margaree and related plutons marked the beginning of extension in the central Cape Breton Highlands.

The leaky chronometer: Evidence for systematic cryptic Pb loss in laser ablation U‐Pb dating of zircon relative to CA‐TIMS

AbstractU–Pb dating of zircon via laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) has become a primary method for determining the age of crystalline rocks and the provenance and maximum depositional age of (meta)sedimentary rocks. Although chemical abrasion has become a standard approach for mitigating Pb loss in zircon dated via high‐resolution thermal ionization mass spectrometry (CA‐TIMS), laser ablation dating is rarely accompanied by chemical abrasion. We evaluate the accuracy of U–Pb dates acquired via LA‐ICP‐MS relative to CA‐TIMS through analysis of a large database of paired analyses from the same zircon crystals. We show that laser ablation 206Pb/238U dates are systematically younger than their CA‐TIMS counterparts, with a greater shift in detrital zircon (−2.0%) versus igneous or metamorphic zircon (−0.9%). Although systematic biases related to “matrix effects” may be a contributing factor, our analysis suggests that unmitigated cryptic Pb loss is likely widespread in laser ablation U–Pb datasets.

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.

Updating the Upper Cretaceous (Campanian) Two Medicine Formation of Montana: Lithostratigraphic revisions, new CA-ID-TIMS U-Pb ages, and a calibrated framework for dinosaur occurrences

The Campanian Two Medicine Formation of northwestern Montana, USA, is richly fossiliferous, and discoveries made within the unit over the past century have greatly advanced our appreciation of dinosaur paleobiology and evolution. Previously undifferentiated from a lithostratigraphic perspective, the formation is now subdivided into four new members that include (from base to top) (1) the Rock City Member, (2) the Shields Crossing Member, (3) the Hagans Crossing Member, and (4) the Flag Butte Member. These new formal units and their associated fossil occurrences are also now included in an age model founded on eight high-resolution chemical abrasion−isotope dilution−thermal ionization mass spectrometry (CA-ID-TIMS) U-Pb ages. New age data confirm that the Two Medicine Formation accumulated during much of the Campanian, with deposition spanning ca. 82.4 Ma to 74.4 Ma. New age data further indicate that a major reorganization of depositional systems, marked by a shift from predominantly lacustrine to alluvial facies and accompanied by a dramatic increase in accommodation, transpired near the base of the new Flag Butte Member at ca. 76.3 Ma. This change in depositional regime correlates in age with the Judith River−Belly River discontinuity, which marks the contact between the McClelland Ferry and Coal Ridge Members in the Judith River Formation and coincides with the onset of the Bearpaw transgression in north-central Montana. The new lithostratigraphic and chronostratigraphic framework for the Two Medicine Formation serves to contextualize and calibrate the formation’s rich dinosaur fossil record, which can now be interrogated with increased clarity and precision. These results also provide ground truth for numerical models that explore the structure of the fossil record in relation to alluvial architecture and terrestrial sequence stratigraphy.

Effect of chemical abrasion of zircon on SIMS U–Pb, δ18O, trace element, and LA-ICPMS trace element and Lu–Hf isotopic analyses

Abstract. This study assesses the effect of chemical abrasion on in situ mass spectrometric isotopic and elemental analyses in zircon. Chemical abrasion improves the U–Pb systematics of SIMS (secondary ion mass spectrometry) analyses of reference zircons, while leaving other isotopic systems largely unchanged. SIMS 206Pb/238U ages of chemically abraded reference materials TEMORA-2, 91500, QGNG, and OG1 are precise to within 0.25 % to 0.4 % and are within uncertainty of chemically abraded TIMS (thermal ionization mass spectrometry) reference ages, while SIMS 206Pb/238U ages of untreated zircons are within uncertainty of TIMS reference ages where chemical abrasion was not used. Chemically abraded and untreated zircons appear to cross-calibrate within uncertainty using all but one possible permutation of reference materials, provided that the corresponding chemically abraded or untreated reference age is used for the appropriate material. In the case of reference zircons QGNG and OG1, which are slightly discordant, the SIMS U–Pb ages of chemically abraded and untreated material differ beyond their respective 95 % confidence intervals. SIMS U–Pb analysis of chemically abraded zircon with multiple growth stages is more difficult to interpret. Treated igneous rims on zircon crystals from the S-type Mount Painter Volcanics are much lower in common Pb than the rims on untreated zircon grains. However, the analyses of chemically abraded material show excess scatter. Chemical abrasion also changes the relative abundance of the ages of zircon cores inherited from the sedimentary protolith, presumably due to some populations being more likely to survive the chemical abrasion process than others. We consider these results from inherited S-type zircon cores to be indicative of results for detrital zircon grains from unmelted sediments. Trace element, δ18O, and εHf analyses were also performed on these zircons. None of these systems showed substantial changes as a result of chemical abrasion. The most discordant reference material, OG1, showed a loss of OH as a result of chemical abrasion, presumably due to dissolution of hydrous metamict domains or thermal dehydration during the annealing step of chemical abrasion. In no case did zircon gain fluorine due to exchange of lattice-bound substituted OH or other anions with fluorine during the HF partial dissolution phase of the chemical abrasion process. As the OG1, QGNG, and TEMORA-2 zircon samples are known to be compositionally inhomogeneous in trace element composition, spot-to-spot differences dominated the trace element results. Even the 91500 megacrystic zircon pieces exhibited substantial chip-to-chip variation. The light rare earth elements (LREEs) in chemically abraded OG1 and TEMORA-2 were lower than in the untreated samples. Ti concentration and phosphorus saturation ((Y + REE) / P) were generally unchanged in all samples.

Comparative evaluation of uranium isotope ratios by peak-jumping and static multi-collector measurements in thermal ionization mass spectrometry

The 235U/238U isotope ratios of uranium standard reference materials and an environmental uranium sample recovered from seawater were measured by thermal ionization mass spectrometry using the single-collector peak-jumping and static multi-collection modes. All the 235U/238U isotope ratios measured in the peak-jumping mode were systematically lower than the values obtained in the static measurements. The lowering of the measured isotope ratios became more remarkable with the decrease in the 235U isotopic abundance, resulting in the maximum 2.2‰-lower value comparable to isotope mass fractionation. The lowering of isotope ratios is not due to the apparent loss of 235U ion currents caused by the time constant of the Faraday amplifier used but attributable to the actual decrease of ion currents by ion-beam changes in the mass switching step of peak-jumping mode. Furthermore, the proper collection of ion beams to the Faraday cup was achieved by allowing sufficient delay time for eliminating the effect of ion-beam changes, which was significantly longer than the time needed for the response of the amplifiers.

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.

Micro-sample Nd isotopic measurement on reference rock powders via the thermal ionization mass spectrometer Nd+ mode

The Sm–Nd isotopic system has been broadly utilized for dating and tracing in earth and planetary sciences. However, low Nd+ ionization efficiency permanently hinders precise and accurate measurements on small amounts of Nd samples. So far, isotopic measurement of micro-amount Nd sample via thermal ionization mass spectrometry (TIMS) Nd+ mode was mostly performed on Nd reference solutions, but less on natural rock or mineral samples. In the present study, analytical procedures to measure isotopic composition via the TIMS Nd+ mode were designed for natural rock powders by using 1–5 ng pure Nd. The analytical technique was refined through low-blank sample digestion, small-column chemistry for Nd extraction from matrix elements, loading Nd using purified H3PO4 solution, and careful heating of filaments before data acquisition. Measurements on small Nd amounts (1 ng–5 ng) of either the JNdi-1 reference solution or four reference rock powders yielded satisfactory results of 143Nd/144Nd value with respect to precision and accuracy. The analytical results agree well with the recommendation values of the reference materials within analytical errors and the internal precision is better than ±0.005 % (2RSE). When using 1 ng or 2 ng Nd amounts, 144Nd ion flow can remain stable in a signal intensity of >100 mV, and without the assistance of an additional ionization enhancer. Therefore, the analytical procedure, featured by low procedural blank (about 10–22 pg), high Nd+ ionization efficiency, and easy operation, has broad prospects for the application of Nd isotope in single-grain minerals or micro-samples.

Extracting very small amounts of potassium from iron meteorites for the analysis of potassium isotope ratios

The isotope abundance of cosmogenic K, especially the ratios of cosmogenic 40K/41K, can be used to determine reliable cosmic-ray exposure (CRE) ages for iron meteorites. Despite this potential, there are only very few studies and essentially no new data since the pioneering work by H. Voshage more than 40 years ago. This shortfall is likely due to the immense analytical difficulties encountered when extracting cosmogenic K from iron meteorites with typical concentrations in the range of a few ppb or below. Chemical extraction procedures are very challenging, resulting in large blank contributions that must be subtracted, and do have low yields preventing an efficient separation of K from the Fe matrix. The K extracted from iron meteorites is dominated by native K (non-cosmogenic K from the sample), includes K from terrestrial contamination, and only a tiny amount is of cosmogenic origin. In order to separate K from iron meteorites a physical extraction technique was developed that involves extraction of K from molten iron meteorites. In this set-up, terrestrial and native K can be partly separated from cosmogenic K by sophisticated pre-heating and extraction techniques. Sample K is ion-optically collected on a rhenium filament. The filaments are then used as evaporation filaments in a double filament set-up of a Triton Plus Thermal-Ionization Mass Spectrometer (TIMS). Though, cosmogenic K is detectable in all samples, the measured isotope ratios are always close to terrestrial, indicating that the majority of the measured 39K and 41K is from K with almost terrestrial isotope composition. The measured 40K signal is dominantly of cosmogenic origin. The K background is either native K from the sample or terrestrial contamination. The measurements are compromised by unstable signals, i.e., by large fluctuations of the ion currents and/or large variations in the isotope ratios during the course of a single run, sometimes even with fractionation reversals. Such difficulties are likely due to the fact that the K ions are implanted into the filament rather than deposited onto the surface. In addition, parts of the filaments are covered with condensed iron, also affecting the signal stability. Despite these analytical challenges, clear cosmogenic signals were detected in almost all studied iron meteorites and cosmogenic 40K/41K ratios could be determined. However, the data quality is not yet sufficient for precise K isotope studies and for calculating reliable 40K/41K CRE ages for iron meteorites.

Application of ATONA Amplifiers to the Measurement of Uranium Isotopic Ratios by Thermal Ionization Mass Spectrometry.

Uranium isotopic composition can provide valuable information about the history and provenance of a nuclear material; therefore, uranium isotopic analyses are frequently made in the nuclear forensics, safeguards, and environmental monitoring communities. These measurements have always presented challenges due to the extreme variability in the relative abundance between the major (235U, 238U) and minor (233U, 234U, 236U) isotopes of uranium. The recently developed ATONA (Atto- to Nano-Amp) amplification system paired with Faraday cup detectors has a large dynamic range and low noise floor making it ideal for measuring uranium isotopic ratios in materials of both natural and anthropogenic origin. A wide variety of certified reference materials were analyzed to investigate the utility of the ATONA amplification system for determining uranium isotopic composition in samples ranging from depleted to highly enriched. The ATONA amplifiers provide nearly an order of magnitude improvement in external reproducibility over 1011 Ω amplifiers when measuring the minor 234U/238U ratio in isotopically natural and depleted samples and when paired with a secondary electron multiplier can measure very low relative abundance uranium isotopes (i.e., 236U).

Rapid Characterization of Undeclared Pharmaceuticals in Herbal Preparations by Ambient Ionization Mass Spectrometry for Emergency Care.

In Asia, some herbal preparations have been found to be adulterated with undeclared synthetic medicines to increase their therapeutic efficiency. Many of these adulterants were found to be toxic when overdosed and have been documented to bring about severe, even life-threatening acute poisoning events. The objective of this study is to develop a rapid and sensitive ambient ionization mass spectrometric platform to characterize the undeclared toxic adulterated ingredients in herbal preparations. Several common adulterants were spiked into different herbal preparations and human sera to simulate the clinical conditions of acute poisoning. They were then sampled with a metallic probe and analyzed by the thermal desorption-electrospray ionization mass spectrometry. The experimental parameters including sensitivity, specificity, accuracy, and turnaround time were prudently optimized in this study. Since tedious and time-consuming pretreatment of the sample is unnecessary, the toxic adulterants could be characterized within 60 s. The results can help emergency physicians to make clinical judgments and prescribe appropriate antidotes or supportive treatment in a time-sensitive manner.

U–Pb LA-ICP-MS and Re–Os dating of wolframite and molybdenite: Constraints on multiple mineralization and cooling history (40Ar/39Ar) for the magmatic–hydrothermal system at Borralha, northern Portugal

The Borralha area (Iberian Massif, Portugal) reflects a long-lived and multiphase magmatism (ca. 316 to 300 Ma), characterized by three types of granite emplacement during two different extensional events (E1 and E2) and one compressional event (C3) within the Variscan orogeny. The W (Cu) mineralization styles correspond to veinlets and quartz veins (i.e., São António and Santa Helena), and disseminations in the Santa Helena breccia pipe. Molybdenite coexists with an Fe-bearing wolframite–quartz assemblage in the Venise breccia pipe and quartz veins (i.e., São José and São Paulo).The geochemistry and geochronology of wolframite and molybdenite samples were studied by electron probe microanalysis (EPMA), in-situ U–Pb laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) and Re–Os thermal ionization mass spectrometry (TIMS). The wolframite yields a U–Pb age (sample WBV1) of 315.2 ± 4.7 Ma (2σ), representing the first recognized episode of W deposition in the Iberian Massif. Wolframite samples (WBV1, WB1, and WB4) have a ferberite composition with a hübnerite/ferberite ratio of < 29. High amounts of Nb (up to 3703 ppm) with low Ta (up to 123 ppm) and REEs (up to 11.4 ppm) and conversely, low amounts of Nb (up to 471 ppm) with high Ta (up to 190 ppm) and REEs (up to 53.7 ppm) were measured in wolframite samples. The REEs normalized patterns of the wolframite samples record a mixed signature. Large and positive Eu/Eu* and Er/Er* anomalies were identified (sample WBV1), whereas negative Ce/Ce* and Nd/Nd* anomalies were observed in samples WB1 and WB4.Molybdenite Re–Os dating yields absolute ages ranging from 305.1 to 303.8 ± 2.2 Ma (2σ), which are coeval with the emplacement of E2 biotite granite (Penedos; I-type; <305 Ma). Low amounts of Re (<1 ppm), W, Co, Ni, As, Cu, Bi, Fe, Mn V and Se (<0.005 wt%) were detected in the molybdenite structure.Constraints between the timing of W- and Mo-deposition and a protracted cooling history of the host rocks are confirmed by 40Ar/39Ar white mica dating. The 40Ar/39Ar ages obtained for secondary white micas collected from Mo veins (Venise breccia pipe; 277 ± 3 and 287 ± 4 Ma 2σ) and W (Cu) dissemination (Santa Helena breccia pipe; 287 ± 2 and 279.0 ± 6 Ma 2σ) record the isotopic resetting by later hydrothermal overprints and cooling /exhumation history after E2 Gerês biotitic granite emplacement.The W-ore deposition did occurred during the final E1 extensional tectonic stage (315 Ma) and E2 extensional tectonic stage for Mo-ore deposition, where a temporal offset was needed for the adjustment of tectonic conditions after the C3 compressional and E2 extensional stage started.

High-Precision Measurement of the 238Pu/239Pu Isotope Ratio by TIMS.

With an aim to improve the precision of isotopic standards of special nuclear materials like uranium and plutonium, National Bureau of Standards (NBS) undertook the recertification of isotopic standards prepared between 1960 and 1970. In a recent initiative, Lawrence Livermore National Laboratory (LLNL) in collaboration with New Brunswick Laboratory Program Office (NBL PO) undertaken efforts to recertify SRM 946, SRM 947, and SRM 948. The primary goal of this drive is to lower the uncertainties associated with the isotopic compositions of plutonium standards. The drive is also aims to minimize the uncertainty associated with measurement of the 238Pu content from 2% to ∼0.3%. In this connection, our laboratory at the Fuel Chemistry Division, Bhabha Atomic Research Centre, proposes a novel indicator "minima in the (RMO254/(i+16))/(RM238/i) curve" (where i = m/z 233 or 235 amu), which is the ratio of the isotope ratio of metal oxides (238M16O/iM16O) to that of metal ions (238M/iM) of uranium in determining the accurate 238Pu content by thermal ionization mass spectrometry. Various enriched uranium spikes have been employed to study the efficacy of the minima in the (RMO(254)/(i+16))/(RM238/i) curve. With the combination of monitoring the minima in the (RMO(254)/(i+16))/(RM238/i) curve and the application of the 233U spike (with an isotope abundance of 238U ∼ 0.05%), an external precision of 0.2% has been achieved in the determination of the 238Pu/239Pu isotope ratio for isotopic standard SRM 947.

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.