The Potassium‐Argon Laser Experiment (KArLE): In Situ Geochronology for Planetary Robotic Missions

Geochronology is a fundamental measurement for planetary samples, providing global and solar system context for the conditions prevailing on the planet at the time of major geological events. The potassium (K)‐Argon (Ar) laser experiment (KArLE) will make in situ noble gas geochronology measurements aboard planetary robotic missions such as rovers and landers. Laser‐induced breakdown spectroscopy (LIBS) is used to measure the K abundance in a sample and to release its noble gases; the evolved Ar is measured by mass spectrometry, and relative K content is related to absolute Ar abundance by sample mass, determined by optical measurement of the ablated volume. This approach allows K and Ar to be measured on identical volumes multiple times to create an isochron, which improves the age determination and reveals irregularities in the rock if they exist. The KArLE technique measures a whole‐rock K‐Ar age with 10% uncertainty or better for rocks 2 Ga or older, sufficient to resolve the absolute age of many planetary samples. The LIBS–mass spectrometry approach is attractive because the analytical components have been flight‐proven, do not require further technical development and provide essential measurements (complete elemental abundance, evolved volatile analysis, micro‐imaging) as well as in situ geochronology.     

Non‐Matrix‐Matched Calibration for the Multi‐Element Analysis of Geological and Environmental Samples Using 200 nm Femtosecond LA‐ICP‐MS: A Comparison with Nanosecond Lasers

LA‐ICP‐MS is one of the most promising techniques for in situ analysis of geological and environmental samples. However, there are some limitations with respect to measurement accuracy, in particular for volatile and siderophile/chalcophile elements, when using non‐matrix‐matched calibration. We therefore investigated matrix‐related effects with a new 200 nm femtosecond (fs) laser ablation system (NWRFemto200) using reference materials with different matrices and spot sizes from 10 to 55 μm. We also performed similar experiments with two nanosecond (ns) lasers, a 193 nm excimer (ESI NWR 193) and a 213 nm Nd:YAG (NWR UP‐213) laser. The ion intensity of the 200 nm fs laser ablation was much lower than that of the 213 nm Nd:YAG laser, because the ablation rate was a factor of about 30 lower. Our experiments did not show significant matrix dependency with the 200 nm fs laser. Therefore, a non‐matrix‐matched calibration for the multi‐element analysis of quite different matrices could be performed. This is demonstrated with analytical results from twenty‐two international synthetic silicate glass, geological glass, mineral, phosphate and carbonate reference materials. Calibration was performed with the certified NIST SRM 610 glass, exclusively. Within overall analytical uncertainties, the 200 nm fs LA‐ICP‐MS data agreed with available reference values.     

Instrumentation Development for In Situ 40Ar/39Ar Planetary Geochronology

The chronology of the Solar System, particularly the timing of formation of extra‐terrestrial bodies and their features, is an outstanding problem in planetary science. Although various chronological methods for in situ geochronology have been proposed (e.g., Rb‐Sr, K‐Ar), and even applied (K‐Ar), the reliability, accuracy, and applicability of the ⁴⁰Ar/³⁹Ar method makes it by far the most desirable chronometer for dating extra‐terrestrial bodies. The method however relies on the neutron irradiation of samples, and thus a neutron source. Herein, we discuss the challenges and feasibility of deploying a passive neutron source to planetary surfaces for the in situ application of the ⁴⁰Ar/³⁹Ar chronometer. Requirements in generating and shielding neutrons, as well as analysing samples are described, along with an exploration of limitations such as mass, power and cost. Two potential solutions for the in situ extra‐terrestrial deployment of the ⁴⁰Ar/³⁹Ar method are presented. Although this represents a challenging task, developing the technology to apply the ⁴⁰Ar/³⁹Ar method on planetary surfaces would represent a major advance towards constraining the timescale of solar system formation and evolution.     

Testing Nano-Powder and Fused-Glass Mineral Reference Materials for In Situ Rb-Sr Dating of Glauconite,Phlogopite, Biotite and Feldspar via LA-ICP-MS/MS

Reference materials (RMs) with well-characterised composition are necessary for reliable quantification and quality control of isotopic analyses of geological samples. For in situ Rb-Sr analysis of silicate minerals via laser ablation inductively coupled plasma tandem mass spectrometry (LA-ICP-MS/MS) with a collision/reaction cell, there is a general lack of mineral-specific and matrix-matched RMs, which limits wider application of this new laser-based dating technique to certain minerals. In this work, pressed nano-powder pellets (NP) of four RMs, GL-O (glauconite), Mica-Mg (phlogopite), Mica-Fe (biotite) and FK-N (K-feldspar), were analysed and tested for in situ Rb-Sr dating, complemented by isotope dilution (ID) MC-ICP-MS Rb-Sr analyses of GL-O and Mica-Mg. In addition, we attempted to develop alternative flux-free and fused ‘mineral glasses’ from the above RMs for in situ Rb-Sr dating applications. Overall, the results of this study showed that among the above RMs only two NP (Mica-Mg-NP and GL-O-NP) were suitable and robust for in situ dating applications. These two nano-powder reference materials, Mica-Mg-NP and GL-O-NP, were thus used as primary RMs to normalise and determine Rb-Sr ages for three natural minerals: MDC phlogopite and GL-O glauconite grains, and also Mica-Fe-NP (biotite). Our in situ analyses of the above RMs yielded Rb-Sr ages that are in good agreement (within 8%) of published ages, which suggests that both Mica-Mg-NP and GL-O-NP are suitable RMs for in situ Rb-Sr dating of phlogopite, glauconite and biotite. However, using secondary RMs is recommended to monitor the quality of the obtained ages.     

Natural Titanite Reference Materials for In Situ U‐Pb and Sm‐Nd Isotopic Measurements by LA‐(MC)‐ICP‐MS

Titanite is a common accessory mineral that preferentially incorporates considerable amounts of U and light rare earth elements in its structure, making it a versatile mineral for in situ U‐Pb dating and Sm‐Nd isotopic measurement. Here, we present in situ U‐Pb ages and Sm‐Nd isotope measurement results for four well‐known titanite reference materials (Khan, BLR‐1, OLT1 and MKED1) and eight titanite crystals that could be considered potential reference material candidates (Ontario, YQ‐82, T3, T4, TLS‐36, NW‐IOA, Pakistan and C253), with ages ranging from ~ 20 Ma to ~ 1840 Ma. Results indicate that BLR‐1, OLT1, Ontario, MKED1 and T3 titanite have relatively homogeneous Sm‐Nd isotopes and low common Pb and thus can serve as primary reference materials for U‐Pb and Sm‐Nd microanalysis. YQ‐82 and T4 titanite can be used as secondary reference materials for in situ U‐Pb analysis because of their low common Pb. However, internal structures and mineral inclusions in YQ‐82 will require careful selection of suitable target domains. Pakistan titanite is almost concordant with an age of 21 Ma and can be used as a reference material when dating Cenozoic titanite samples.     

High‐Precision Fe and Mg Isotope Ratios of Silicate Reference Glasses Determined In Situ by Femtosecond LA‐MC‐ICP‐MS and by Solution Nebulisation MC‐ICP‐MS

In this study, a technique for high precision in situ Fe and Mg isotope determinations by femtosecond‐laser ablation‐multi collector‐ICP‐MS (fs‐LA‐MC‐ICP‐MS) was developed. This technique was employed to determine reference values for a series of common reference glasses that may be used for external standardisation of in situ Fe and Mg isotope determinations in silicates. The analysed glasses are part of the MPI‐DING and United States Geological Survey (USGS) reference glass series, consisting of basaltic (BIR‐1G, BCR‐2G, BHVO‐2G, KL2‐G, ML3B‐G) and komatiitic (GOR128‐G and GOR132‐G) compositions. Their Fe and Mg isotope compositions were determined by in situ fs‐LA‐MC‐ICP‐MS and by conventional solution nebulisation multi‐collector ICP‐MS. We determined δ⁵⁶Fe values for these glasses ranging between ‐0.04‰ and 0.10‰ (relative to IRMM‐014) and δ²⁶Mg values ranging between ‐0.40‰ and ‐0.15‰ (relative to DSM‐3). Our fs‐LA‐MC‐ICP‐MS results for both Fe and Mg isotope compositions agreed with solution nebulisation analyses within analytical uncertainties. Furthermore, the results of three USGS reference glasses (BIR‐1G, BHVO‐2G and BCR‐2G) agreed with previous results for powdered and dissolved aliquots of the same reference materials. Measurement reproducibilities of the in situ determinations of δ⁵⁶Fe and δ²⁶Mg values were usually better than 0.12‰ and 0.13‰ (2s), respectively. We further demonstrate that our technique is a suitable tool to resolve isotopic zoning in chemically‐zoned olivine crystals. It may be used for a variety of different applications on isotopically‐zoned minerals, e.g., in magmatic or metamorphic rocks or meteorites, to unravel their formation or cooling rates.     

Laser Ablation In Situ Silicon Stable Isotope Analysis of Phytoliths

Silicon is a beneficial element for many plants and is deposited in plant tissue as amorphous bio‐opal called phytoliths. The biochemical processes of silicon uptake and precipitation induce isotope fractionation: the mass‐dependent shift in the relative abundances of the stable isotopes of silicon. At the bulk scale, δ³⁰Si ratios span from ?2 to +6‰. To further constrain these variations in situ, at the scale of individual phytolith fragments, we used femtosecond laser ablation multi‐collector inductively coupled plasma‐mass spectrometry (fsLA‐MC‐ICP‐MS). A variety of phytoliths from grasses, trees and ferns were prepared from plant tissue or extracted from soil. Good agreement between phytolith δ³⁰Si ratios obtained by bulk solution MC‐ICP‐MS analysis and in situ isotope ratios from fsLA‐MC‐ICP‐MS validates the method. Bulk solution analyses result in at least twofold better precision for δ³⁰Si (2s on reference materials ≤ 0.11‰) over that found for the means of in situ analyses (2s typically ≤ 0.24‰). We find that bushgrass, common reed and horsetail show large internal variations up to 2‰ in δ³⁰Si, reflecting the various pathways of silicon from soil to deposition. Femtosecond laser ablation provides a means to identify the underlying processes involved in the formation of phytoliths using silicon isotope ratios.     

Iron Distribution in Size‐Resolved Aerosols Generated by UV‐Femtosecond Laser Ablation: Influence of Cell Geometry and Implications for In Situ Isotopic Determination by LA‐MC‐ICP‐MS

The influence of ablation cell geometry (Frames single‐ and HelEx two‐volume cells) and laser wavelength (198 and 266 nm) on aerosols produced by femtosecond laser ablation (fs‐LA) were evaluated. Morphologies, iron mass distribution (IMD) and ⁵⁶Fe/⁵⁴Fe ratios of particles generated from magnetite, pyrite, haematite and siderite were studied. The following two morphologies were identified: spherules (10–200 nm) and agglomerates (5–10 nm). Similarity in IMD and ablation rate at 198 and 266 nm indicates similar ablation mechanisms. ⁵⁶Fe/⁵⁴Fe ratios increased with aerodynamic particle size as a result of kinetic fractionation during laser plasma plume expansion, cooling and aerosol condensation. The HelEx cell produces smaller particles with a larger range of ⁵⁶Fe/⁵⁴Fe ratios (1.85‰) than particles from the Frames cell (1.16‰), but the bulk aerosol matches the bulk substrate for both cells, demonstrating stoichiometric fs‐LA sampling. IMD differences are the result of faster wash out of the HelEx cell allowing less time for agglomeration of small, low‐δ ⁵⁶Fe particles with larger, high‐δ ⁵⁶Fe particles in the cell. Even with a shorter ablation time, half the total Fe ion intensity, and half the ablation volume, the HelEx cell produced Fe isotope determinations for magnetite that were as precise as the Frames cell, even when the latter included an aerosol‐homogenising mixing chamber. The HelEx cell delivered a more constant stream of small particles to the ICP, producing a more stable Fe ion signal (0.7% vs. 1.5% RSE for ⁵⁶Fe in a forty‐cycle single analysis), constant instrumental mass bias and thus a more precise measurement.     

Characterisation of Apatites as Potential Uranium Reference Materials for Fission‐track Dating by LA‐ICP‐MS

We report homogeneity tests on large natural apatite crystals to evaluate their potential as U reference materials for apatite fission‐track (AFT) thermochronology by laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS). The homogeneity tests include the measurements of major element concentrations by electron probe microanalysis (EPMA), whereas for U concentration, isotope dilution (ID) ICP‐MS and laser ablation (LA) ICP‐MS were employed. Two apatite crystals are potential reference materials for LA‐ICP‐MS analysis: a 1 cm³ fraction of a Durango crystal (7.5 μg g^?1 U) and a 1 cm³ Mud Tank crystal (6.9 μg g^?1 U). The relative standard deviation (1 RSD) of the U concentration determined by ID‐ICP‐MS of both apatite crystals was ≤ 1.5%, whereas 1 RSD for the LA‐ICP‐MS results was better than 4%, providing sufficient homogeneity for fission‐track dating. The results on the U homogeneity for two different apatite samples are an important step towards establishing in situ dating routines for AFT analysis by LA‐ICP‐MS.     

In Situ Determination of First‐Row Transition Metal,Ga and Ge Abundances in Geological Materials via Medium‐Resolution LA‐ICP‐MS

An in situ, medium‐resolution LA‐ICP‐MS method was developed to measure the abundances of the first‐row transition metals, Ga and Ge in a suite of geological materials, namely the MPI‐DING reference glasses. The analytical protocol established here hinged on maximising the ablation rate of the ultraviolet (UV) laser system and the sensitivity of the ICP‐MS, as well minimising the production of diatomic oxides and argides, which serve as the dominant sources of isobaric interferences. Non‐spectral matrix effects were accounted for by using multiple external calibrators, including NIST SRM 610 and the USGS basaltic glasses BHVO‐2G, BIR‐1G and BCR‐2G, and utilising ⁴³Ca as an internal standard. Analyses of the MPI‐DING reference glasses, which represent geological matrices ranging from basaltic to rhyolitic in composition, included measurements of concentrations as low as < 10⁰ μg g^?1 and as high as > 10⁴ μg g^?1. The new data reported here were found to statistically correlate with the ‘preferred’ reference values for these materials at the 95% confidence level, though with significantly better precision, typically on the order of ≤ 3% (2s_m). This analytical method may be extended to any matrix‐matched geological sample, particularly oceanic basalts, silicate minerals and meteoritic materials.     

Defining the Potential of Nanoscale Re‐Os Isotope Systematics Using Atom Probe Microscopy

Atom probe microscopy (APM) is a relatively new in situ tool for measuring isotope fractions from nanoscale volumes (< 0.01 μm³). We calculate the theoretical detectable difference of an isotope ratio measurement result from APM using counting statistics of a hypothetical data set to be ± 4δ or 0.4% (2s). However, challenges associated with APM measurements (e.g., peak ranging, hydride formation and isobaric interferences), result in larger uncertainties if not properly accounted for. We evaluate these factors for Re‐Os isotope ratio measurements by comparing APM and negative thermal ionisation mass spectrometry (N‐TIMS) measurement results of pure Os, pure Re, and two synthetic Re‐Os‐bearing alloys from Schwander et al. (2015, Meteoritics and Planetary Science, 50, 893) [the original metal alloy (HSE) and alloys produced by heating HSE within silicate liquid (SYN)]. From this, we propose a current best practice for APM Re‐Os isotope ratio measurements. Using this refined approach, mean APM and N‐TIMS ¹⁸⁷Os/¹⁸⁹Os measurement results agree within 0.05% and 2s (pure Os), 0.6–2% and 2s (SYN) and 5–10% (HSE). The good agreement of N‐TIMS and APM ¹⁸⁷Os/¹⁸⁹Os measurements confirms that APM can extract robust isotope ratios. Therefore, this approach permits nanoscale isotope measurements of Os‐bearing alloys using the Re‐Os geochronometer that could not be measured by conventional measurement principles.     

Cretaceous evolution of a metamorphic core complex,the Veporic unit,Western Carpathians (Slovakia): P–T conditions and in situ40Ar/39Ar UV laser probe dating of metapelites

Alpine metamorphism, related to the development of a metamorphic core complex during Cretaceous orogenic events, has been recognized in the Veporic unit, Western Carpathians (Slovakia). Three metamorphic zones have been distinguished in the metapelites: 1, chloritoid + chlorite + garnet; 2, garnet + staurolite + chlorite; 3, staurolite + biotite + kyanite. The isograds separating the metamorphic zones have been modelled by discontinuous reactions in the system K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O (KFMASH). The isograds are roughly parallel to the north‐east‐dipping foliation related to extensional updoming along low‐angle normal faults. Thermobarometric data document increasing P–T conditions from c. 500 °C and 7–8 kbar to c. 620 °C and 9–10 kbar, reflecting a coherent metamorphic field gradient from greenschist to middle amphibolite facies. ⁴⁰Ar/³⁹Ar data obtained by high spatial resolution in situ ultraviolet (UV) laser ablation of white micas from the rock slabs constrain the timing of cooling and exhumation in the Late Cretaceous. Mean dates are between 77 and 72 Ma; however, individual white mica grains record a range of apparent ⁴⁰Ar/³⁹Ar ages indicating that cooling below the blocking temperature for argon diffusion was not instantaneous. The reconstructed metamorphic P–T–t path is ‘clockwise’, reflecting post‐burial decompression and cooling during a single Alpine orogenic cycle. The presented data suggest that the Veporic unit evolved as a metamorphic core complex during the Cretaceous growth of the Western Carpathian orogenic wedge. Metamorphism was related to collisional crustal shortening and stacking, following closure of the Meliata Ocean. Exhumation was accomplished by synorogenic (orogen‐parallel) extension and unroofing in an overall compressive regime.     

Dating palaeo‐seismic faulting in the Taiwan Mountain Belt

In‐situ ⁴⁰Ar/³⁹Ar laser microprobe dating was carried out on the Hoping pseudotachylite from a mylonite‐fault zone in the metamorphosed basement complex of the active Taiwan Mountain Belt to determine the timing of the responsible earthquake(s). The dating results, distributed from 3.2 to 1.6 Ma with errors ranging from 0.2 to 1.1 Ma, were derived from a combination of two Ar isotopic system end‐members with inverse isochron ages of 1.55 ± 0.05 and 2.87 ± 0.07 Ma, respectively. Petrographical observations reveal fault melt containing ultracataclasites, therefore the older inverse isochron end‐member may be attributed to the relic wall rock Ar isotopic system contained in micro‐breccia. Without significant Ar loss expected, the ~1.6 Ma for the young end‐member defines the exact time of the pseudotachylite formation. Seismic faulting therefore occurred during basement rock exhumation in the Taiwanese hinterland.     

U‐Th Zircon Dating by Laser Ablation Single Collector Inductively Coupled Plasma‐Mass Spectrometry (LA‐ICP‐MS)

Zircon crystals in the age range of ca. 10–300 ka can be dated by ²³⁰Th/²³⁸U (U‐Th) disequilibrium methods because of the strong fractionation between Th and U during crystallisation of zircon from melts. Laser ablation inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) analysis of nine commonly used reference zircons (at secular equilibrium) and a synthetic zircon indicates that corrections for abundance sensitivity and dizirconium trioxide molecular ions (Zr₂O₃⁺) are critical for reliable determination of ²³⁰Th abundances in zircon. When corrected for abundance sensitivity and interferences, mean activity ratios of (²³⁰Th)/(²³⁸U) for nine reference zircons analysed on five different days averaged 0.995 ± 0.023 (95% confidence weighted by data‐point uncertainty only, MSWD = 1.6; n = 9), consistent with their U‐Pb ages > 4 Ma that imply equilibrium for all intermediate daughter isotopes (including ²³⁰Th) within the ²³⁸U decay chain. U‐Th zircon ages generated by LA‐ICP‐MS without mitigating (e.g., by high mass resolution) or correcting for abundance sensitivity and molecular interferences on ²³⁰Th are potentially unreliable. To validate the applicability of LA‐ICP‐MS to this dating method, we acquired data from three late Quaternary volcanic units: the 41 ka Campanian Ignimbrite (plutonic clasts), the 161 ka Kos Plateau Tuff (juvenile clasts) and the 12 ka Puy de Dôme trachyte lava (all eruption ages by Ar/Ar, with zircon U‐Th ages being of equal or slightly older). A comparison of the corrected LA‐ICP‐MS results with previously published secondary ion mass spectrometry (SIMS) data for these rocks shows comparable ages with equivalent precision for LA‐ICP‐MS and SIMS, but much shorter analysis durations (~ 2 min vs. ~ 15 min) per spot with LA‐ICP‐MS and much simpler sample preparation. Previously undated zircons from the Yali eruption (Kos‐Nisyros volcanic centre, Greece) were analysed using this method. This yielded a large age spread (~ 45 to > 300 ka), suggesting significant antecryst recycling. The youngest zircon age (~ 45 ± 10 ka) provides a reasonable maximum estimate for the eruption age, in agreement with the previously published age using oxygen isotope stratigraphy (~ 31 ka).     

The tectono‐metamorphic evolution of the very low‐grade hangingwall constrains two‐stage gneiss dome formation in the Montagne Noire (Southern France)

The Montagne Noire in the southernmost French Massif Central is made of an ENE‐elongated gneiss dome flanked by Palaeozoic sedimentary rocks. The tectonic evolution of the gneiss dome has generated controversy for more than half a century. As a result, a multitude of models have been proposed that invoke various tectonic regimes and exhumation mechanisms. Most of these models are based on data from the gneiss dome itself. Here, new constraints on the dome evolution are provided based on a combination of very low‐grade petrology, K–Ar geochronology, field mapping and structural analysis of the Palaeozoic western Mont Peyroux and Faugères units, which constitute part of the southern hangingwall of the dome. It is shown that southward‐directed Variscan nappe‐thrusting (D₁) and a related medium‐P metamorphism (M₁) are only preserved in the area furthest away from the gneiss dome. The regionally dominant pervasive tectono‐metamorphic event D₂/M₂ largely transposes D₁ structures, comprises a higher metamorphic thermal gradient than M₁ (transition low‐P and medium‐P metamorphic facies series) and affected the rocks between c. 309 and 300 Ma, post‐dating D₁/M₁ by more than 20 Ma. D₂‐related fabrics are refolded by D₃, which in its turn, is followed by dextral‐normal shearing along the basal shear zone of both units at c. 297 Ma. In the western Mont Peyroux and Faugères units, D₂/M₂ is largely synchronous with shearing along the southern dome margin between c. 311 and 303 Ma, facilitating the emplacement of the gneiss dome into the upper crust. D₂/M₂ also overlaps in time with granitic magmatism and migmatization in the Zone Axiale between c. 314 and 306 Ma, and a related low‐P/high‐T metamorphism at c. 308 Ma. The shearing that accompanied the exhumation of the dome therefore was synchronous with a peak in temperature expressed by migmatization and intrusion of melts within the dome, and also with the peak of metamorphism in the hangingwall. Both, the intensity of D₂ fabrics and the M₂ metamorphic grade within the hangingwall, decrease away from the gneiss dome, with grades ranging from the anchizone–epizone boundary to the diagenetic zone. The related zonation of the pre‐D₃ metamorphic field gradients paralleled the dome. These observations indicate that D₂/M₂ is controlled by the exhumation of the Zone Axiale, and suggest a coherent kinematic between the different crustal levels at some time during D₂/M₂. Based on integration of these findings with regional geological constraints, a two‐stage exhumation of the gneiss dome is proposed: during a first stage between c. 316 and 300 Ma dome emplacement into the upper crust was controlled by dextral shear zones arranged in a pull‐apart‐like geometry. The second stage from 300 Ma onwards was characterized by northeast to northward extension, with exhumation accommodated by north‐dipping detachments and hangingwall basin formation along the northeastern dome margin.     

Amphibolite facies retrograde metamorphism of the Zhujiachong eclogite,SE Dabieshan: 40Ar/39Ar age constraints from argon extraction using UV‐laser microprobe,in vacuo crushing and stepwise heating

The Zhujiachong eclogite in the south‐eastern Dabieshan ultra‐high‐P terrane has been overprinted during retrograde metamorphism, with the development of garnet‐amphibolite mineral assemblages in most rocks in the outcrop. This study is focused on providing age constraints for the retrograde amphibolite facies and greenschist facies mineralogy by ⁴⁰Ar/³⁹Ar dating. By applying a novel approach of combining three different techniques for extracting argon: laser stepwise heating of single grains and small separates, a spot fusion technique by UV‐laser ablation microprobe on polished sections and an in vacuo crushing technique for liberating radiogenic argon from fluid inclusions, it is demonstrated that an internally consistent thermal history can be derived. The ⁴⁰Ar/³⁹Ar ages indicate that phengite formed before 265 Ma, probably during the ultra‐high‐P event. Ages associated with amphibolite facies retrograde metamorphism range from 242 to 217 Ma by the analyses of amphibole. Ages of c. 230 Ma were found for the symplectite matrix that formed during retrogression from eclogite pyroxene. Late stage hydrothermal activity leading to the formation of coarse‐grained paragonite and fluid inclusions in vein amphibole was dated at c. 200 Ma. These age results agree well with the mineral crystallization sequence observed from thin‐sections of the retrograded eclogite: phengite → paragonite and amphibole in matrix → amphibole in the corona.     

Chemical Characterisation of Natural Ilmenite: A Possible New Reference Material

Seven ilmenite (FeTiO₃) megacrysts derived from alnöite pipes (Island of Malaita, Solomon Islands) were characterised for their major and trace element compositions in relation to their potential use as secondary reference materials for in situ microanalysis. Abundances of thirteen trace elements obtained by laser ablation ICP‐MS analyses (using the NIST SRM 610 glass reference material) were compared with those determined by solution‐mode ICP‐MS measurements, and these indicated good agreement for most elements. The accuracy of the LA‐ICP‐MS protocol employed here was also assessed by repeated analysis of MPI‐DING international glass reference materials ML3B‐G and KL2‐G. Several of the Malaitan ilmenite megacrysts exhibited discrepancies between laser ablation and solution‐mode ICP‐MS analyses, primarily attributed to the presence of a titano‐magnetite exsolution phase (at the grain boundaries), which were incorporated solely in the solution‐mode runs. Element abundances obtained by LA‐ICP‐MS for three of the ilmenite megacrysts (CRN63E, CRN63H and CRN63K) investigated here had RSD (2s) values of < 20% and therefore can be considered as working values for reference purposes during routine LA‐ICP‐MS analyses of ilmenite.     

Precise and Accurate In Situ Determination of Lead Isotope Ratios in NIST,USGS, MPI‐DING and CGSG Glass Reference Materials using Femtosecond Laser Ablation MC‐ICP‐MS

Lead isotope ratio data were obtained with good precision and accuracy using a 266 nm femtosecond laser ablation (fLA) system connected to a multi‐collector ICP‐MS (MC‐ICP‐MS) and through careful control of analytical procedures. The mass fractionation coefficient induced by 266 nm femtosecond laser ablation was approximately 28% lower than that by 193 nm excimer laser ablation (eLA) with helium carrier gas. The exponential law correction method for Tl normalisation with optimum adjusted Tl ratio was utilised to obtain Pb isotopic data with good precision and accuracy. The Pb isotopic ratios of the glass reference materials NIST SRM 610, 612, 614; USGS BHVO‐2G, BCR‐2G, GSD‐1G, BIR‐1G; and MPI‐DING GOR132‐G, KL2‐G, T1‐G, StHs60/80‐G, ATHO‐G and ML3B‐G were determined using fLA‐MC‐ICP‐MS. The measured Pb isotopic ratios were in good agreement with the reference or published values within 2s measurement uncertainties. We also present the first high‐precision Pb isotopic data for GSE‐1G, GSC‐1G, GSA‐1G and CGSG‐1, CGSG‐2, CGSG‐4 and CGSG‐5 glass reference materials obtained using the femtosecond laser ablation MC‐ICP‐MS analysis technique.     

NanoSr – A New Carbonate Microanalytical Reference Material for In Situ Strontium Isotope Analysis

The in situ measurement of Sr isotopes in carbonates by MC‐ICP‐MS is limited by the availability of suitable microanalytical reference materials (RMs), which match the samples of interest. Whereas several well‐characterised carbonate reference materials for Sr mass fractions > 1000 µg g^?1 are available, there is a lack of well‐characterised carbonate microanalytical RMs with lower Sr mass fractions. Here, we present a new synthetic carbonate nanopowder RM with a Sr mass fraction of ca. 500 µg g^?1 suitable for microanalytical Sr isotope research (‘NanoSr’). NanoSr was analysed by both solution‐based and in situ techniques. Element mass fractions were determined using EPMA (Ca mass fraction), as well as laser ablation and solution ICP‐MS in different laboratories. The ⁸⁷Sr/⁸⁶Sr ratio was determined by well‐established bulk methods for Sr isotope measurements and is 0.70756 ± 0.00003 (2s). The Sr isotope microhomogeneity of the material was determined by LA‐MC‐ICP‐MS, which resulted in ⁸⁷Sr/⁸⁶Sr ratios of 0.70753 ± 0.00007 (2s) and 0.70757 ± 0.00006 (2s), respectively, in agreement with the solution data within uncertainties. Thus, this new reference material is well suited to monitor and correct microanalytical Sr isotope measurements of low‐Sr, low‐REE carbonate samples. NanoSr is available from the corresponding author.     

Reappraisal of the GL‐O Reference Material for K‐Ar Dating: New Insight from Microanalysis,Single‐Grain and Milligram Ar Measurements

The homogeneity and Ar‐dating suitability of the GL‐O reference material were re‐evaluated to determine whether this material is sufficiently homogeneous to be suitable for the calibration of modern high sensitivity instruments. Based on new micro‐analyses and noble gas determinations, our contribution reveals several kinds of inhomogeneity at the grain scale: disparity in the glauconitisation among and within the pellets, variable occurrence of a phosphatic component within pellets (1% m/m on average), and rare occurrences of calcite and detrital grains. Measurements on test portions of ≤ 1 mg reflect such heterogeneity with variability in ⁴⁰Ar* content that exceeds analytical uncertainty, including a few highly anomalous values. The lesser evolved glauconite population yielded ⁴⁰Ar* contents ~ 15% lower than the value of 24.8 nl g^?1 recommended by Odin et al. (1982, Numerical dating in stratigraphy. Wiley (Chichester, UK), 123–148). But the measured concentrations of ⁴⁰Ar* converge towards the aforementioned value as test portion mass increased to > 3 mg. A few rare 3 mg experiments still yielded ⁴⁰Ar* contents lower than the recommended value (down to 24.0 nl g^?1), and we recommend using more conservative minimum masses of 5–10 mg. A further purification step for GL‐O or the intercalibration of its powder version could be considered to diminish the size of the test portions and the intensity of the measured signals.