Atom Probe Tomography: Development and Application to the Geosciences

Atom probe tomography (APT) is an analytical technique that provides quantitative three‐dimensional elemental and isotopic analyses at sub‐nanometre resolution across the whole periodic table. Although developed and mostly used in the materials science and semiconductor fields, recent years have seen increasing development and application in the geoscience and planetary science disciplines. Atom probe studies demonstrate compositional complexity at the nanoscale and provide fundamental new insights into the atom‐scale mechanisms taking place in minerals over geological time. Here, we provide an overview of APT, including the historical development and technical aspects of the instrumentation, and the fundamentals of data acquisition, data processing and data reconstruction. We also review previous studies and highlight the potential future applications of nanoscale geochemical studies of natural materials.     

Concurrent Determination of U‐Pb Age and REE Mass Fractions of Zircon by High Mass Resolution SIMS

A combined geochronological and geochemical investigation for the same domain of zircon provides valuable information on timing and genesis, particularly in the case of multi‐growth metamorphic zircon. A high spatial resolution concurrent analytical method for zircon U‐Pb age and rare earth element content was successfully achieved in this study, using a multi‐collector secondary ion mass spectrometer (SIMS) at a ~ 8 μm diameter scale. Special instrument parameters were employed, including a high mass resolution of approximately 15000 applied to replace the previous energy filter method, and a dynamic multi‐collector mode used to reduce the measurement time to 18 min per analysis. Six zircon reference materials yielded precise and accurate ²⁰⁶Pb/²³⁸U ages, which are comparable to those obtained by the ordinary mono‐collector method, but with 2–3 times higher spatial resolution. All zircon grains measured in this study showed enriched heavy‐REE (HREE) contents consistent with previously reported values determined by LA and solution ICP‐MS methods. The light‐REE (LREE) mass fractions measured using both SIMS and LA‐ICP‐MS methods in this study, although with quite different volume, show consistent results within uncertainties.     

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).     

Organic Geochemical Microanalysis by Time‐of‐Flight Secondary Ion Mass Spectrometry (ToF‐SIMS)

Time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) is a powerful method for the chemical analysis of solid surfaces. In this paper, the capabilities and limitations of this technique and the potential for its use in geochemical research are outlined. Using ToF‐SIMS, the chemical composition of sample structures down to 10–100 μm can be determined, without the need for pre‐selection or labelling of the analysed substances. In addition, the lateral distribution of organic and inorganic compounds can be mapped in geochemical samples at a resolution in the micrometre range. The capabilities of the technique in geochemistry are illustrated by two examples. In the first example, it is shown that ToF‐SIMS can be used to detect biomarkers in oil samples, making it a promising method for the analysis of biomarkers in fluid inclusions. In the second example, a number of specific lipid biomarkers were identified and mapped on the surface of a microbial mat cryosection surface. Post‐measurement optical microscopy correlated the localisation of the lipids with the presence of methanotrophic archaea in the microbial mat.     

Measurement of the Isotopic Composition of Molybdenum in Geological Samples by MC‐ICP‐MS using a Novel Chromatographic Extraction Technique

A novel preconcentration method is presented for the determination of Mo isotope ratios by multi‐collector inductively coupled plasma‐mass spectrometry (MC‐ICP‐MS) in geological samples. The method is based on the separation of Mo by extraction chromatography using N‐benzoyl‐N‐phenylhydroxylamine (BPHA) supported on a microporous acrylic ester polymeric resin (Amberlite CG‐71). By optimising the procedure, Mo could be simply and effectively separated from virtually all matrix elements with a single pass through a small volume of BPHA resin (0.5 ml). This technique for separation and enrichment of Mo is characterised by high selectivity, column efficiency and recovery (~ 100%), and low total procedural blank (~ 0.18 ng). A ¹⁰⁰Mo‐⁹⁷Mo double spike was mixed with samples before digestion and column separation, which enabled natural mass‐dependent isotopic fractionation to be determined with a measurement reproducibility of  < 0.09‰ (δ^98/95Mo, 2s) by MC‐ICP‐MS. The mean δ^98/95Mo_{SRM 3134} (NIST SRM 3134 Mo reference material; Lot No. 891307) composition of the IAPSO seawater reference material measured in this study was 2.00 ± 0.03‰ (2s, n = 3), which is consistent with previously published values. The described procedure facilitated efficient and rapid Mo isotopic determination in various types of geological samples.     

GGR Biennial Critical Review: Analytical Developments Since 2014

This GGR biennial critical review covers developments and innovations in key analytical methods published since January 2014, relevant to the chemical, isotopic and crystallographic characterisation of geological and environmental materials. In nine selected analytical fields, publications considered to be of wide significance are summarised, background information is provided and their importance evaluated. In addition to instrumental technologies, this review also presents a summary of new developments in the preparation and characterisation of rock, microanalytical and isotopic reference materials, including a précis of recent changes and revisions to ISO guidelines for reference material characterisation and reporting. Selected reports are provided of isotope ratio determinations by both solution nebulisation MC‐ICP‐MS and laser ablation‐ICP‐MS, as well as of radioactive isotope geochronology by LA‐ICP‐MS. Most of the analytical techniques elaborated continue to provide new applications for geochemical analysis; however, it is noted that instrumental neutron activation analysis has become less popular in recent years, mostly due to the reduced availability of nuclear reactors to act as a neutron source. Many of the newer applications reported here provide analysis at increasingly finer resolution. Examples include atom probe tomography, a very sensitive method providing atomic scale information, nanoscale SIMS, for isotopic imaging of geological and biological samples, and micro‐XRF, which has a spatial resolution many orders of magnitude smaller than conventional XRF.     

Refinement of the Micro‐Distillation Technique for Isotopic Analysis of Geological Samples with pg‐Level Osmium Contents

In recent years, the ¹⁸⁷Re–¹⁸⁷Os isotope system has been increasingly used to study samples containing very small quantities of Os. For such samples, optimisation of measurement procedures is essential to minimise the loss of Os before mass spectrometric measurements. Micro‐distillation is a necessary purification step that is applied after the main Os chemical separation procedure, prior to Os isotope ratio measurements by negative‐thermal ionisation mass spectrometry (N‐TIMS). However, unlike the other separation steps, this procedure has not yet been optimised for small samples. In this study, we present a refined micro‐distillation method that achieved higher yields and allowed high‐precision R(¹⁸⁷Os/¹⁸⁸Os) expressed as ¹⁸⁷Os/¹⁸⁸Os measurements for small‐sized geological samples that contain only a few pg Os. The Os recovery in the micro‐distillation step was tested by changing the operating conditions including heating time and temperature, and amounts of oxidant and reductant. Recoveries were measured by the isotope dilution ICP‐MS method after the addition of ¹⁹⁰Os‐enriched spike solution. We found that the most critical factor controlling the chemical yield of Os during micro‐distillation is the extent of dilution of the reductant (HBr) by H₂O evaporated from the oxidant. A refined micro‐distillation method, in which the amount of oxidant solution is reduced from the conventional method, achieved an improved chemical yield of Os (~ 90%). This refined method was applied to the measurement of ¹⁸⁷Os/¹⁸⁸Os by N‐TIMS of varying test portions of the geological reference material BIR‐1a. The resulting ¹⁸⁷Os/¹⁸⁸Os ratios of BIR‐1a matched the literature data, with propagated uncertainties of 0.2, 1.1 and 11% digested sample quantities containing 150, 10 and 1 pg of Os, respectively.     

A Microscopic and Nanoscale Understanding of the Formation of Gold Geochemical Provinces

Gold geochemical provinces in China were delineated through stream sediment or catchment sediment sampling in this study. Each gold geochemical province delineated by a threshold value of 2.5 ng/g covers an area of thousands of kilometers. It is a dilemma that geochemists traditionally thought that gold could not migrate for a long distance in rivers or streams to form a large-scale geochemical anomaly due to its chemical inertness and high specific density. The quantitative spectroscopic analysis and observations under a scanning electron microscope(SEM) indicate the presence of submicroscopic gold particles(5 μm in diameter) in large quantities, and observations under a Transmission Electron Microscopy(TEM) further suggest the presence of nanoscale gold particles(several tens of nanometre in diameter) in ores, rocks, soils and stream sediments. Particularly, submicroscopic and nanoscale gold particles less than 5 μm were only found in samples having a low gold content(10ng/g). This result shows that geochemical provinces, delineated by a threshold value of 2.5 ng/g, are formed by long-distance transport of ultrafine gold in streams. The findings may provide direct microscopic evidence for gold migration to form geochemical provinces.     

A Potential (U‐Th)/He Zircon Reference Material from Penglai Zircon Megacrysts

In this study (U‐Th)/He dating of the Penglai zircons, which occur as abundant megacrysts in Neogene alkaline basalts in northern Hainan Province, south‐eastern China, was undertaken. A weighted mean age of 4.06 ± 0.35 Ma (2s) with a mean square weighted deviation (MSWD) of 1.79 was obtained from eighteen fragments of four zircon megacrysts using single‐crystal laser fusion He determinations and the U‐Th isotope dilution (ID) method. The (U‐Th)/He ages are consistent, homogeneous and systematically slightly younger than the preferred ²⁰⁶Pb/²³⁸U age of 4.4 ± 0.1 Ma (95% confidence interval) determined by ID‐TIMS and subsequently published U‐Pb results. The U‐Pb isotopic system in zircon has a high closure temperature of ~ 900 °C, and the preferred U‐Pb age may record both the time since eruption and the zircon residence time in the magma chamber. In contrast, the closure temperature of the zircon (U‐Th)/He system is ~ 190 °C and the zircon megacrysts were brought quickly to the surface by the host basaltic magma. Thus, the (U‐Th)/He age represents the timing of the eruption. Based on the unlimited quantity, large grain size, mostly weak broad zoning, rapid cooling and homogenous (U‐Th)/He ages, we consider the Penglai zircons suitable for use as a reference material in (U‐Th)/He isotope geochronology.     

Lacustrine sedimentological and geochemical records for the last 170 years of climate and environmental changes in southeastern China

Reconstruction of modern climate and environmental changes in east Asia using inland natural climate archives can provide valuable insights on decadal–multidecadal climate and environmental patterns that are probably related to both natural and anthropogenic forcing. Here we investigated an 89‐cm‐long sediment core (TH1) from Tian Lake, southeastern China, for sedimentological, physical and geochemical parameters in order to understand climate and environmental changes for the latest two centuries. ¹³⁷Cs‐ and ²¹⁰Pb‐based age models show that the fine sand–coarse silt‐dominated core contains ~170 years (c. AD 1842–2011) of continuous sedimentation. Sediments with fine sands, low MS values, high water content, high TOC content and a high C:N ratio from c. AD 1842 to 1897 suggest intense hydrological conditions and strong runoff in the catchment, probably because of a humid climate. From AD 1897 to 1990, sediments with very fine sand and coarse silt, high MS values, low water content and unchanged TOC and C:N ratios indicate normal hydrological conditions and in‐lake algae‐derived organic matter. During this interval, the chemical weathering indicators show stronger weathering conditions compared with sediments deposited during AD 1842–1897, supporting the dominance of weathered surface soil input in the earlier interval and physical erosion dominance in the later period, respectively. Since AD 1990, the continuous decrease of geochemical proxies suggests human‐interacted Earth surface processes in the catchment of Tian Lake. A PCA revealed four dominant geochemical controlling factors – detrital input, trophic status, grain size and early diagenesis –, accounting for 26, 20, 18 and 16% of total variance, respectively. This study for the first time provides lacustrine geochemical evidence for the most recent two centuries of climate and environmental changes in coastal southeastern China, a region that is currently undergoing an inversion of critical zone, i.e. an overturning of its soil profile, owing to swift modernization.     

Rapid U‐Pb Geochronology by Laser Ablation Multi‐Collector ICP‐MS

Detrital zircon (DZ) U‐Pb laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) has revolutionised the way geologists approach many Earth science questions. Although recent research has focused on rapid sample throughput, acquisition rates are limited to 100–300 analyses h^?1. We present a method to acquire zircon U‐Pb dates at rates of 120, 300, 600 and 1200 analyses h^?1 (30, 12, 6 and 3 s per analysis) by multi‐collector LA‐ICP‐MS. We demonstrate the efficacy of this method by analysing twelve zircon reference materials with dates from ~ 3465 to ~ 28 Ma. Mean offset from high‐precision dates increases with faster rates from 0.9% to 1.1%; mean random 1s uncertainty increases from 0.6% to 1.3%. We tested this new method on a sandstone sample previously characterised by large‐n DZ geochronology. Quantitative comparison shows increased correspondence among age distributions comprising > 300 dates. This new method holds promise for DZ geochronology because (a) it requires no major changes to hardware, but rather modifications to software; (b) it yields robust age distributions well‐suited for quantitative analysis and maximum depositional age calculations; (c) there is only a minor sacrifice of accuracy and measurement uncertainty; and (d) there is less burden to researchers in terms of time investment and analytical cost.     

A Practical Approach for Collecting Large‐n Detrital Zircon U‐Pb Data sets by Quadrupole LA‐ICP‐MS

A measurement procedure for the rapid acquisition of U‐Pb dates for detrital zircons by quadrupole LA‐ICP‐MS was developed. The procedure achieves a threefold increase in measurement efficiency compared with the most commonly used methods. Utilising reduced background counting times and a shortened ablation period, a throughput of ~ 130 measurements/h can be achieved. The measurement procedure was characterised and validated using data from thirty‐nine sessions acquired over a twelve‐month period. Systematic measurement error in ²⁰⁶Pb/²³⁸U dates for reference materials used for quality control with ages between 28.2 and 2672 Ma was < 1.5%. Average measurement uncertainty, including both random and systematic components, was 1–4% (2s). Interrogation of time‐resolved calculated dates and signal intensities for each measurement allows for the detection and elimination of portions of measurements exhibiting age heterogeneities, zoning, lead loss and contamination by common lead. The measurement procedure diminishes the need to acquire cathodoluminescence imagery for routine detrital zircon applications further increasing throughput and reducing cost. The utility of the measurement procedure is demonstrated by the measurement of samples previously characterised by LA‐MC‐ICP‐MS.     

Whole-rock geochemistry and U-Pb ages of Devonian bimodal-type rhyolites from the Rudny Altai,Russia: Petrogenesis and tectonic settings

The paper presents new original data on the Devonian felsic volcanism of the NW Rudny Altai (Russia) in the west of Central Asian Orogenic Belt (CAOB) – the front part of the Altai convergent margin of the Siberian continent. Two geochemical types of subvolcanic rhyolites were emplaced synchronously with the bimodal rhyolite-basalt association, which began to form in the end-Emsian, and clearly manifested on the border of the Givetian and the Frasnian. The rhyolites yield zircon U-Pb ages of ca. 390 Ma (R1-type) and 380 Ma (R2- and R3-types), reflecting two peaks of the volcanic activity. Most of these rocks have extreme petrochemical characteristics of high SiO₂ contents and have contrast Na/K ratios. Their compositions are transition between calc-alkaline and tholeiite series: (La/Yb)_n ~ 2–7, Zr/Y ~ 4 (Zr < 350 ppm) and La/Sm ~ 0.55–1. Rhyolites bear the distinctive geochemical signature of A-type felsic magma, such as enrichments in Zr, Nb, Y and Ce (>350 ppm), Zr (>250 ppm), and high Ga/Al (>2.6) values. The island-arc-like R1-rhyolite formed immediately after the beginning of rifting due to widespread crustal melting under reduced conditions. The generation of rift-like R2- and R3-rhyolites took place under non-equilibrium conditions, synchronously with the rise in the upper crust of Givetian-Frasnian basic magmas, as a result of the active lithospheric extension and high thermal input from the underlying hot mantle. We propose an extension regime in the transition area between the island-arc and back-arc basin for the origin of rhyolites. The study of the Devonian volcanism of the Rudny Altai gives important information about the processes that occurred at the initial stage of the formation of the Altai convergent margin.     

The Design of Re‐usable Carius Tubes for the Determination of Rhenium,Osmium and Platinum‐Group Elements in Geological Samples

The traditional Carius tube technique is cumbersome and requires skilful work to seal the Carius tube, which can be used only once. We describe a modification to the technique that does not require the use of a high‐temperature welding torch to melt the Carius tube to seal it. The newly designed Carius tube consists of a main body with a 3 mm‐thick glass wall, a neck and head with walls 4 mm in thickness, and an efficient screw‐thread stopper. These new features allowed the tube to be used repeatedly. We demonstrate relatively low procedural blanks derived for Re and Os, and platinum‐group elements (PGEs), using the redesigned tube. A temperature of 220 °C could be reached for about 5 ml of HNO₃ for a 47 ml tube and for 32 ml of inverse aqua regia for a 200 ml tube. This digestion technique can be used for routine analysis of Re and PGEs in geological samples.     

Optimisation of Lithium Chromatography for Isotopic Analysis in Geological Reference Materials by MC‐ICP‐MS

The lithium isotope system can be an important tracer for various geological processes, especially tracing continental weathering. The key to this application is the accurate and precise determination of lithium isotopic composition. However, some of the previously established column separation methods are not well behaved when applied to chemically diverse materials, due to the significant variations in matrix/lithium ratios in some materials. Here, we report a new dual‐column system for lithium purification to achieve accurate and precise analysis of lithium isotopic compositions using a multi‐collector inductively coupled plasma‐mass spectrometer (MC‐ICP‐MS). Compared with single‐column systems, our dual‐column system yielded a consistent elution range of the lithium‐bearing fraction (7–16 ml) for samples with a large range of lithium loads and matrix compositions, so that column re‐calibration is not required. In addition, this method achieved complete lithium recovery and low matrix interference (e.g., Na/Li ≤ 1) with a short elution time (~ 6 h, excluding evaporation), with the entire procedure completed in 1.5 days. We report high precision Li isotopic compositions in twelve chemically diverse materials including seawater, silicates, carbonates, manganese nodules and clays. New recommended Li isotopic values and associated uncertainties are presented as reference values for quality control and inter‐laboratory calibration for future research and were consistent with previously published data. However, significant lithium isotopic variances (~ 1‰) in BHVO‐2 from different batches suggest Li isotopic heterogeneity in this reference material and that Li isotopic studies using this reference material should be treated with caution.     

Electron Microprobe/SIMS Determinations of Al in Olivine: Applications to Solar Wind,Pallasites and Trace Element Measurements

Electron probe microanalyser measurements of trace elements with high accuracy are challenging. Accurate Al measurements in olivine are required to calibrate SIMS implant reference materials for measurement of Al in the solar wind. We adopt a combined EPMA/SIMS approach that is useful for producing SIMS reference materials as well as for EPMA at the ~ 100 µg g^?1 level. Even for mounts not polished with alumina photoelectron spectroscopy shows high levels of Al surface contamination. In order to minimise electron beam current density, a rastered 50 × 100 µm electron beam was adequate and minimised sensitivity to small Al‐rich contaminants. Reproducible analyses of eleven SIMS‐cleaned spots on San Carlos olivine agreed at 69.3 ± 1.0 µg g^?1. The known Al mass fraction was used to calibrate an Al implant into San Carlos. Accurate measurements of Al were made for olivines in the pallasites: Imilac, Eagle Station and Springwater. Our focus was on Al in olivine, but our technique could be refined to give accurate electron probe measurements for other contamination‐sensitive trace elements. For solar wind, it is projected that the Al/Mg abundance ratio can be determined to 6%, a factor of 2 more precise than the solar spectroscopic ratio.     

Determination of U–Pb Ages for Young Zircons using Laser Ablation‐ICP‐Mass Spectrometry Coupled with an Ion Detection Attenuator Device

We have developed new analytical procedures to measure precise and accurate ²³⁸U–²⁰⁶Pb and ²³⁵U–²⁰⁷Pb ages for young (~ 1 Ma) zircons using laser ablation‐ICP‐mass spectrometry. For young zircons, both careful correction for the background counts and analysis of very small Pb/U ratios (i.e., ²⁰⁶Pb/²³⁸U < 0.00016 and ²⁰⁷Pb/²³⁵U < 0.0001 for 1 Ma zircons) are highly desired. For the correction of the background, the contribution of the background signal intensities for the analytes, especially for the residual signal intensities for ²⁰⁶Pb and ²⁰⁷Pb, was defined through laser ablation of synthesised zircons (ablation blank) containing negligible Pb. The measured signal intensities for ²⁰²Hg, ²⁰⁶Pb and ²⁰⁷Pb signals obtained by the ablation blank were slightly higher than those obtained by data acquisition without laser ablation (gas blank). For the wider dynamic range measurements on Pb/U ratios, an attenuator device for the ion detection system was employed to extend the capability to monitor high‐intensity signals (i.e., > 3 Mcps). Through the attenuator device, the ion currents were reduced to 1/450 of the signal intensity without the attenuator. Because the switching time for the attenuator was shorter than 1 ms, signal intensities for only specific isotopes could be reduced. With attenuation of the ²³⁸U signal, counting statistics on ²⁰⁶Pb and ²⁰⁷Pb isotopes could be improved and counting loss on the ²³⁸U signal could be minimised. To demonstrate the reliability of this new analytical technique, ²³⁸U–²⁰⁶Pb and ²³⁵U–²⁰⁷Pb ages for three young zircon samples (collected from Osaka Group Pink Volcanic Ash, Kirigamine and Bishop Tuff) were measured. The data presented here demonstrate clearly that the present technique could become a major analytical tool for in situ U–Pb age determination of young zircons (~ 1 Ma).     

On the Lu-Hf Isotope Geochemistry of Silicate Rocks

This paper reviews the history (TIMS, hot‐SIMS, MC‐ICP‐MS), significance, geochemical behaviour and current uncertainties (λ¹⁷⁶ Lu, Hf‐Nd Bulk Silicate Earth) surrounding the Lu‐Hf isotope system, and thus marks two decades of its application to geochemical problems. An appendix further presents (a) improvements to the original chemistry protocol of Blichert‐Toft et al. (1997) for application to Mg‐rich samples and (b) a compilation of previously published and new Hf isotope determinations by MC‐ICP‐MS for a set of international rock reference materials. Prior to the advent of multiple‐collector plasma source mass spectrometry (MC‐ICP‐MS), routine analysis of the Lu‐Hf isotope system developed only slowly because of the extreme difficulty of measuring Hf isotope compositions with thermal ionisation mass spectrometry, caused by the very high first ionisation potential of Hf. However, Hf isotope compositions can be measured relatively easily using MC‐ICP‐MS and this new technique now provides reproducible measurements at high precision regardless of the matrix from which Hf is separated. Of the commonly used long‐lived radiogenic isotope systems, only the Sm‐Nd and Lu‐Hf isotope systems are unaffected by parent/daughter fractionations related to volatile nebular processes and core formation. While other systems (Rb‐Sr, U‐Th‐Pb, Re‐Os) may also be used to investigate the chemical evolution of the Earth, Moon, Mars and parent bodies of differentiated meteorites, the larger uncertainties in their bulk chemical and isotopic values limit their application to determine geochemical budgets and assess planetary mantle‐crust evolution. In the study of garnet‐bearing rocks, both for dating purposes and as an isotopic tracer for source provenance and mantle processes, the Lu‐Hf isotope system likewise is of major interest because of the high partition coefficient of Lu compared to Hf for garnet with respect to other minerals. Furthermore, the larger Lu/Hf fractionation compared to Sm/Nd during melting beneath ridges produces proportionally higher Lu/Hf in the residue and faster in‐growth of a radiogenic Hf isotopic signature (compared to Nd), which may help shed light on the dynamics of mantle melting. While the chemistry protocol and mass spectrometric technique for high‐precision Lu‐Hf isotope analysis have been resolved in satisfactory ways over the past five years, more accurate determination of the decay constant for ¹⁷⁶ Lu, at present known with a precision of only about 4%, still needs to be completed and a consensus reached on which value to use for future Lu‐Hf isotope studies. Although the current combined Lu‐Hf and Sm‐Nd Bulk Silicate Earth parameters are plagued by possible incompatibilities in chondrite selection and potential interlaboratory biases, a more accurate set of values may not be readily established owing to heterogeneities in the isotopic composition of chondrites that far exceed present analytical accuracy.     

Chemical weathering over the last 1200 years recorded in the sediments of Gonghai Lake,Lvliang Mountains,North China: a high‐resolution proxy of past climate

Increasing interest in global climate change has led to attempts to understand and quantify the relationship between chemical weathering processes and environmental conditions, especially climate. This interest necessitates the identification of new climate proxies for the reconstruction of two important Earth surface processes: physical erosion and chemical weathering. In this study, an AMS ¹⁴C‐dated 2.8‐m‐long sediment core, GH09B1, from Lake Gonghai in north‐central China was subjected to detailed geochemical analyses to evaluate the intensity of chemical weathering conditions in the catchment. Multivariate statistical analysis of major and trace elemental data of 139 subsamples revealed that the first principal component axis PCA1 explained ～53% of the variance in the assemblage of elements/oxides with significant positive correlations between PCA1 scores and the separation of mobile and soluble elements/oxides from the immobile and resistant elements/oxides, which is thus able to indicate the chemical weathering in the catchment. These results are supported by the down‐core trends of other major and trace elemental ratios of chemical weathering intensity as well as by pollen data from the same core. Variations in PCA1, chemical index of alteration (CIA), Rb/Sr ratio and other oxides ratios indicate stronger chemical weathering due to a wet climate during the Medieval Warm Period (MWP). However, the MWP was interrupted by an interval of relatively weaker chemical weathering conditions from AD 940–1070. Weak chemical weathering under a dry climate occurred during the Little Ice Age (LIA), and increased chemical weathering intensity during the Current Warm Period (CWP). Our proxy records of chemical weathering over the last millennium correlate well with the available proxy records of precipitation from Gonghai Lake as well as with the speleothem oxygen isotope record from Wanxiang Cave, but do not show a significant correlation with the temperature record in N China, suggesting that the chemical weathering intensity in the study area was mainly controlled by the amount of rainfall rather than by temperature. We conclude that high resolution lacustrine sediment geochemical parameters can be used as reliable proxies for climate variations at centennial‐decadal time scales.     

Sulfur Concentration in Geochemical Reference Materials by Solution Inductively Coupled Plasma‐Mass Spectrometry

With implications for the origin of ore deposits, redox state of the atmosphere, and effects of volcanic outgassing, understanding the sulfur cycle is vital to our investigation of Earth processes. However, the paucity of sulfur concentration measurements in silicate rocks and the lack of well‐calibrated reference materials with concentrations relevant to the rocks of interest have hindered such investigations. To aid in this endeavour, this study details a new method to determine sulfur concentration via high mass resolution solution inductively coupled plasma‐mass spectrometry (ICP‐MS). The method is based on an aqua regia leach, involving relatively rapid sample preparation and analysis, and uses small test portion masses (< 50 mg). We utilised two independently prepared standard solutions to calibrate the analyses, resulting in 4% accuracy, and applied the method to eight geochemical reference materials. Measurements were reproducible to within ~ 10%. Sulfur concentrations and isotopes of six reference materials were measured additionally by elemental analyser‐combustion‐isotope ratio mass spectrometry to independently evaluate the accuracy of the ICP‐MS method. Reference materials that yielded reproducible measurements identical to published values from other laboratories (JGb‐1, JGb‐2 and MAG‐1) are considered useful materials for the measurement of sulfur. Reference materials that varied between studies but were reproducible for a given test portion perhaps suffer from sample heterogeneity and are not recommended as sulfur reference materials.