A New LA‐ICP‐MS Method for Ti in Quartz: Implications and Application to High Pressure Rutile‐Quartz Veins from the Czech Erzgebirge

Experimental determination of the pressure and temperature controls on Ti solubility in quartz provides a calibration of the Ti‐in‐quartz (TitaniQ) geothermometer applicable to geological conditions up to ~ 20 kbar. We present a new method for determining ⁴⁸Ti mass fractions in quartz by LA‐ICP‐MS at the 1 μg g^?1 level, relevant to quartz in HP‐LT terranes. We suggest that natural quartz such as the low‐CL rims of the Bishop Tuff quartz (determined by EPMA; 41 ± 2 μg g^?1 Ti, 2s) is more suitable than NIST reference glasses as a reference material for low Ti mass fractions because matrix effects are limited, Ca isobaric interferences are avoided, and polyatomic interferences at mass 48 are insignificant, thus allowing for the use of ⁴⁸Ti as a normalising mass. Average titanium mass fraction from thirty‐three analyses of low temperature quartz from the Czech Erzgebirge is 0.9 ± 0.2 μg g^?1 (2s) using ⁴⁸Ti as a normalising mass and Bishop Tuff quartz rims as a reference material. The 2s average analytical uncertainty for individual analyses of ⁴⁸Ti is 8% for 50 μm spots and 7% for 100 μm spots, which offers much greater accuracy than the 21–41% uncertainty (2s) incurred from using ⁴⁹Ti as an analyte.     

Characterisation of a Natural Quartz Crystal as a Reference Material for Microanalytical Determination of Ti,Al, Li,Fe, Mn,Ga and Ge

A natural smoky quartz crystal from Shandong province, China, was characterised by laser ablation ICP‐MS, electron probe microanalysis (EPMA) and solution ICP‐MS to determine the concentration of twenty‐four trace and ultra trace elements. Our main focus was on Ti quantification because of the increased use of this element for titanium‐in‐quartz (TitaniQ) thermobarometry. Pieces of a uniform growth zone of 9 mm thickness within the quartz crystal were analysed in four different LA‐ICP‐MS laboratories, three EPMA laboratories and one solution‐ICP‐MS laboratory. The results reveal reproducible concentrations of Ti (57 ± 4 μg g^?1), Al (154 ± 15 μg g^?1), Li (30 ± 2 μg g^?1), Fe (2.2 ± 0.3 μg g^?1), Mn (0.34 ± 0.04 μg g^?1), Ge (1.7 ± 0.2 μg g^?1) and Ga (0.020 ± 0.002 μg g^?1) and detectable, but less reproducible, concentrations of Be, B, Na, Cu, Zr, Sn and Pb. Concentrations of K, Ca, Sr, Mo, Ag, Sb, Ba and Au were below the limits of detection of all three techniques. The uncertainties on the average concentration determinations by multiple techniques and laboratories for Ti, Al, Li, Fe, Mn, Ga and Ge are low; hence, this quartz can serve as a reference material or a secondary reference material for microanalytical applications involving the quantification of trace elements in quartz.     

The Preparation and Preliminary Characterisation of Three Synthetic Andesite Reference Glass Materials (ARM‐1, ARM‐2, ARM‐3) for In Situ Microanalysis

Three synthetic reference glasses were prepared by directly fusing and stirring 3.8 kg of high‐purity oxide powders to provide reference materials for microanalytical work. These glasses have andesitic major compositions and are doped with fifty‐four trace elements in nearly identical abundance (500, 50, 5 µg g^?1) using oxide powders or element solutions, and are named ARM‐1, 2 and 3, respectively. We further document that sector‐field (SF) ICP‐MS (Element 2 or Element XR) is capable of sweeping seventy‐seven isotopes (from ⁷Li to ²³⁸U, a total of sixty‐eight elements) in 1 s and, thus, is able to quantify up to sixty‐eight elements by laser sampling. Micro‐ and bulk analyses indicate that the glasses are homogeneous with respect to major and trace elements. This paper provides preliminary data for the ARM glasses using a variety of analytical techniques (EPMA, XRF, ICP‐OES, ICP‐MS, LA‐Q‐ICP‐MS and LA‐SF‐ICP‐MS) performed in ten laboratories. Discrepancies in the data of V, Cr, Ni and Tl exist, mainly caused by analytical limitations. Preliminary reference and information values for fifty‐six elements were calculated with uncertainties [2 relative standard error (RSE)] estimated in the range of 1–20%.     

Determination of Sm‐Nd Isotopic Compositions in Fifteen Geological Materials Using Laser Ablation MC‐ICP‐MS and Application to Monazite Geochronology of Metasedimentary Rock in the North China Craton

In this study, we report both ¹⁴³Nd/¹⁴⁴Nd and ¹⁴⁷Sm/¹⁴⁴Nd values in twelve minerals (apatite, titanite, monazite and eudialyte) based on analyses over 4 years using LA‐MC‐ICP‐MS. The positive correlation between the measured β_Sm and β_Nd (r² = 0.9981) over this time in our laboratory demonstrates the excellent long‐term stability of the method. Compared with the normal method, Sm and Nd signal intensities were improved by a factor of 2.9 with the use of X skimmer and Jet sample cones in combination with the addition of nitrogen at 3–6 ml min^?1 to the central gas flow. The enhancement of signal intensity benefits the accurate in situ determination of the Sm‐Nd isotopes of samples poor in these elements. ¹⁴³Nd/¹⁴⁴Nd values were also determined in two manganese nodules and GSMC Co‐rich crust with low mass fractions of Nd (94–293 μg g^?1). Generally, most of the obtained Sm‐Nd isotopic compositions in these geological materials are consistent with published values. ‘External reproducibility’ (2s) of ¹⁴³Nd/¹⁴⁴Nd and ¹⁴⁷Sm/¹⁴⁴Nd was typically better than 0.06‰ and 2.5‰, respectively, demonstrating that the Durango, Otter Lake, NW‐1 and MAD apatites, the Khan, and OLT‐1 titanites, MGMH#117531 monazite and LV01 eudialyte are promising candidate reference materials for in situ Sm‐Nd isotopic determinations. The Trebilcock, Mae Klang and 44069 monazites are only suitable for in situ Nd isotopic determinations because of their heterogeneous Sm/Nd compositions. The heterogeneous Sm‐Nd composition of titanite BLR‐1 demonstrates that it is not a suitable reference material for in situ Sm‐Nd isotopic determinations. Deep‐sea samples (NOD‐A‐1 and NOD‐P‐1 manganese nodule, GSMC Co‐rich crust) with low mass fractions of Nd also show homogenous Nd isotopic compositions. Sm‐Nd isotopic ratios of a monazite (MQG‐22) from the North China Craton were measured as a case study and gave a ¹⁴⁷Sm‐¹⁴³Nd isochron age of 1792 ± 35 Ma (MSWD = 3.2) consistent with the published metamorphic age of the host metasedimentary rocks. The results for both candidate reference materials and geological samples demonstrate that the in situ LA‐MC‐ICP‐MS analytical protocol described is feasible and robust for research in geological evolution.     

Investigating the Influence of Non‐Spectral Matrix Effects in the Determination of Twenty‐Two Trace Elements in Rock Samples by ICP‐QMS

The influence of non‐spectral matrix effects on the determination of twenty‐two trace elements (Rb, Sr, Y, Cs, Ba, lanthanides, Pb, Th and U) in rock samples using ICP‐MS was investigated. Three types of multi‐element solutions were synthesised containing the twenty‐two trace elements, In, Tl and ten major rock‐forming elements with varying mass fractions mimicking the compositions of basalt, peridotite and dolomite. The synthetic solutions were conditioned to have dilution factors (DF) of 1000–10000. The extent of sensitivity suppression relative to the DF = 10000 solution became more significant for smaller DF solutions, which was not constant across different elements in a single solution but displayed general dependence on m/z. This indicates that at least two internal standards (e.g., In and Tl) are required for the correction of sensitivity variation. On the basis of the results, a new isotope dilution‐internal standardisation method for the determination of twenty‐two trace elements with ICP‐MS was developed, in which the sensitivity variation was corrected by monitoring two enriched isotopes, ¹¹³In and ²⁰³Tl. This method, coupled with the quantitative correction of interference from oxides and hydroxides, achieved precise determination of twenty‐two trace elements in some rock reference materials with reproducibilities of ±2% for basaltic to andesitic samples.     

Improved Inter‐calibration of Faraday Cup and Ion Counting for In Situ Pb Isotope Measurements Using LA‐MC‐ICP‐MS: Application to the Study of the Origin of the Fangshan Pluton,North China

A laser ablation multi‐collector inductively coupled plasma‐mass spectrometry (LA‐MC‐ICP‐MS) method was developed to obtain precise and accurate Pb isotopic ratio measurements in low‐Pb materials (< 10 μg g^?1) using a combination of Faraday cups and ion counters (FC–IC). The low abundance ²⁰⁴Pb (~ 1.4%) was collected using an IC. A NBS 981 standard solution was used to cross‐calculate the FC–IC gain and to investigate the signal response characteristics of the IC. A significant, continuous and linear decrease in the FC–IC gain was observed within 1 hr, but this drift could be corrected using the calibrator‐sample‐calibrator bracketing method. In addition, a non‐linear response of the IC used in this study was observed and corrected by a non‐linear correction algorithm, which was established by measuring a series of gravimetrically prepared NBS 981 standard solutions (NIST SRM 981). Compared with the conventional arrangement, the use of the newly designed X skimmer cone and Jet sample cone improved the signal intensities from Pb isotopes by a factor of 1.9. Compared with only Faraday cups, using a combination FC–IC array was found to enhance the measurement repeatability (RSD) of ^20xPb/²⁰⁴Pb by approximately one order of magnitude when the ²⁰⁴Pb intensity was < 8 mV. Eight natural glasses and the NIST SRM 612 reference material glass (as a calibration material) were measured to evaluate the new protocol for Pb isotope determination. The analytical results were in agreement with the reference values within 2s measurement uncertainties. For MPI‐DING ATHO‐G (5.67 μg g^?1 total Pb), KL2‐G (2.07 μg g^?1 total Pb) and ML3B‐G (1.38 μg g^?1 total Pb), the typical accuracies of ^20xPb/²⁰⁴Pb were 0.09% of preferred values with precisions of < 0.33% (2RSD). The Pb isotope ratios in feldspars from granodiorite and within mafic microgranular enclaves (MMEs) from the Fangshan pluton, North China, were measured using the present method. The Pb isotopic compositions of feldspars from the whole host granodiorite show that that are radiogenic in the margin zone and gradually become less radiogenic. For the MMEs, the Pb isotopic compositions of feldspars are highly variable and overlap with those of the whole host granodiorite. For single‐grain feldspar, the strong rim‐core‐rim variations of the Pb isotopic compositions and trace elements are interpreted to have been generated via magma mixing. These results suggest that the Fangshan pluton underwent magma mixing of mantle‐derived mafic magmas with felsic magmas, and the proportion of the mafic magma influx decreased over time.     

辽宁四道沟热液金矿床中石英的稀土元素的特征及意义

本文用ＩＣＰ－ＭＳ测定了辽宁四道沟金矿矿脉中石英及其中流体包裹体中的稀土元素含量,发现石英的稀土元素配分模式类似于其中流体包裹体的稀土元素配分模式,推断石英中的稀土元素主要赋存于注流体包裹体中,流体包裹体中的稀土元素了石英的稀土元素配分模式,原生包裹中的流体是和石英同源的,其稀土元素指示的是石英形成过程中流体的信息。而次生包裹体中的流体是石英形成后的流体活动产物,其稀土元素指示的是后期流体活动的信     

Determination of Trace Element Mass Fractions in Ultramafic Rocks by HR‐ICP‐MS: A Combined Approach Using a Direct Digestion/Dilution Method and Preconcentration by Coprecipitation

A procedure is described for the determination of thirty‐seven minor and trace elements (LILE, REE, HFSE, U, Th, Pb, transition elements and Ga) in ultramafic rocks. After Tm addition and acid sample digestion, compositions were determined both following a direct digestion/dilution method (without element separation) and after a preconcentration procedure using a double coprecipitation process. Four ultramafic reference materials were investigated to test and validate our procedure (UB‐N, MGL‐GAS [GeoPT12], JP‐1 and DTS‐2B). Results obtained following the preconcentration procedure are in good agreement with previously published work on REE, HFSE, U, Th, Pb and some of the transition elements (Sc, Ti, V). This procedure has two major advantages: (a) it avoids any matrix effect resulting from the high Mg content of peridotite, and (b) it allows the preconcentration of a larger trace element set than with previous methods. Other elements (LILE, other transition elements Cr, Mn, Co, Ni, Cu, Zn, as well as Ga) were not fully coprecipitated with the preconcentration method and could only be accurately determined through the direct digestion/dilution method.     

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.     

A Comparison of In Situ Analytical Methods for Trace Element Measurement in Gold Samples from Various South African Gold Deposits

Trace element concentrations in gold grains from various geological units in South Africa were measured in situ by field emission‐electron probe microanalysis (FE‐EPMA), laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) and synchrotron micro X‐ray fluorescence spectroscopy (SR‐μ‐XRF). This study assesses the accuracy, precision and detection limits of these mostly non‐destructive analytical methods using certified reference materials and discusses their application in natural sample measurement. FE‐EPMA point analyses yielded reproducible and discernible concentrations for Au and trace concentrations of S, Cu, Ti, Hg, Fe and Ni, with detection limits well below the actual concentrations in the gold. LA‐ICP‐MS analyses required larger gold particles (> 60 μm) to avoid contamination during measurement. Elements that measured above detection limits included Ag, Cu, Ti, Fe, Pt, Pd, Mn, Cr, Ni, Sn, Hg, Pb, As and Te, which can be used for geochemical characterisation and gold fingerprinting. Although LA‐ICP‐MS measurements had lower detection limits, precision was lower than FE‐EPMA and SR‐μ‐XRF. The higher variability in absolute values measured by LA‐ICP‐MS, possibly due to micro‐inclusions, had to be critically assessed. Non‐destructive point analyses of gold alloys by SR‐μ‐XRF revealed Ag, Fe, Cu, Ni, Pb, Ti, Sb, U, Cr, Co, As, Y and Zr in the various gold samples. Detection limits were mostly lower than those for elements measured by FE‐EPMA, but higher than those for elements measured by LA‐ICP‐MS.     

An Isotope Dilution ICP‐MS Method for the Determination of Mg/Ca and Sr/Ca Ratios in Calcium Carbonate

Mg/Ca and Sr/Ca ratios in calcium carbonate are important components of many palaeoclimate studies. We present an isotope dilution method relying on a single mixed spike containing ²⁵Mg, ⁴³Ca and ⁸⁷Sr. Dozens of samples per day, as small as 10 μg of carbonate, could be dissolved, spiked and run in an ICP‐MS with a precision of 0.8% (2 RSD). Two instruments types, a sector field and a quadrupole ICP‐MS, were compared. The best long term precision found was 0.4% (2 RSD), although this increased by up to a factor of two when samples of very different Mg or Sr content were run together in the same sequence. Long term averages for the two instruments concurred. No matrix effects were detected for a range of Ca concentrations between 0.2 and 2 mmol l^‐1. Accuracy, tested by measuring synthetic standard solutions, was 0.8% with some systematic trends. We demonstrate the strength of this isotope dilution method for (a) obtaining accurate results for sample sets that present a broad Mg and Sr range and (b) testing solid carbonates as candidate reference materials for interlaboratory consistency. Mg/Ca and Sr/Ca results for reference materials were in good agreement with values from the literature.     

Evaluation of Major to Ultra Trace Element Bulk Rock Chemical Analysis of Nanoparticulate Pressed Powder Pellets by LA‐ICP‐MS

An efficient, clean procedure for the measurement of element mass fractions in bulk rock nanoparticulate pressed powder pellets (PPPs) by 193 nm laser ablation ICP‐MS is presented. Samples were pulverised by wet milling and pelletised with microcrystalline cellulose as a binder, allowing non‐cohesive materials such as quartz or ceramics to be processed. The LA‐ICP‐MS PPP analytical procedure was optimised and evaluated using six different geological reference materials (JP‐1, UB‐N, BCR‐2, GSP‐2, OKUM and MUH‐1), with rigorous procedural blank quantification employing synthetic quartz. Measurement trueness of the procedure was equivalent to that achieved by solution ICP‐MS and LA‐ICP‐MS analysis of glass. The measurement repeatability was as low as 0.5–2% (1s, n = 6) and, accordingly, PPP homogeneity could be demonstrated. Calibration based on the reference glasses NIST SRM 610, NIST SRM 612, BCR‐2G and GSD‐1G revealed matrix effects for glass and PPP measurement with NIST SRM 61×; using basalt glasses eliminated this problem. Most significantly, trace elements not commonly measured (flux elements Li, B; chalcophile elements As, Sb, Tl, In, Bi) could be quantified. The PPP‐LA‐ICP‐MS method overcomes common problems and limitations in analytical geochemistry and thus represents an efficient and accurate alternative for bulk rock analysis.     

Textural and Chemical Evolution of Unidirectional Solidification Textures in Highly Differentiated Granitic Rocks at Kharaatyagaan,Central Mongolia

Unidirectional solidification texture (UST) in an aplite body is recognized in the Neoproterozoic highly differentiated granitic rocks at Kharaatyagaan, central Mongolia. On the basis of crystal morphology, two main types of UST were identified in the aplite body: (i) thin crenulate UST layers; and (ii) thick intergrowth UST layers. Bulk geochemistry indicates that the Kharaatyagaan UST‐bearing aplite and aplite dike are alkaline, and are enriched in light rare‐earth elements. Scanning electron microscopy and cathadoluminescence imaging of UST quartz from Kharaatyagaan show four types of quartz: euhedral quartz phenocrysts with well‐developed concentric growth zoning (Qa1) in the aplite; euhedral quartz with weak growth zoning in the aplite (Qa2); UST quartz exhibiting distinct growth zones (Qu1); and UST quartz showing mosaic texture (Qu2). Crystallization temperatures determined by the Ti‐in‐quartz geothermometer of Qa1 and Qu1 quartz range between around 500°C and 780°C and Qa2 and Qu2 range between about 490° and 630°C. The cathodoluminescence textures of quartz are predominantly caused by variations in the trace elements contents of quartz. The Qa1 and Qu1 quartz crystals are characterized by high Ti and Al concentrations in the quartz lattice, and are observed in the bottom of the Kharaatyagaan hill, which formed in the early, less evolved magmatic stage. The Qa2 and Qu2 UST quartz characterized by low Ti and variable Al concentrations are found at the top. The UST layers crystallized along the upper part of the magma chamber in the presence of fluid phases exsolved from felsic magma.     

MC‐ICP‐MS Isotope Measurements with Direct Injection Nebulisation (d‐DIHEN): Optimisation and Application to Boron in Seawater and Carbonate Samples

We report here an optimisation of the demountable direct injection high efficiency nebuliser (d‐DIHEN) for isotopic measurements with a Neptune (ThermoFisher Scientific, Bremen, Germany) multi‐collector inductively coupled plasma‐mass spectrometer (MC‐ICP‐MS) and describe a method for boron isotopic ratio determination. With direct injection nebulisation 100% of the analyte was introduced into the ICP‐MS plasma and wash times were drastically reduced for elements such as boron and thorium. Compared to the classical stable introduction system (SIS: double Scott/cyclonic spray chamber), sensitivity for boron was 2–5 times higher with d‐DIHEN and wash times up to ten times shorter. Repeatability of ¹¹B/¹⁰B sample‐calibrator bracketing measurements reached 0.25‰ (2s) for seawater and coral samples. Method accuracy and reproducibility were tested on mixed reference solutions having δ¹¹B values in the ranges ?90 to +40‰ and ?2 to +2.5‰, demonstrating our ability to distinguish δ¹¹B values with differences of only 0.25‰. The international seawater reference material NRCC NASS‐5 (National Research Council, Ottawa, Canada), analysed in different sessions over a 10‐month period, yielded an average δ¹¹B value of +39.89 ± 0.25‰, in the upper range of previously published seawater values. A comparison between δ¹¹B determined by d‐DIHEN MC‐ICP‐MS and positive‐TIMS (P‐TIMS) for four modern corals showed an excellent agreement (with bias of less than 0.4‰).     

Quartz‐in‐garnet and Ti‐in‐quartz thermobarometry: Methodology and first application to a quartzofeldspathic gneiss from eastern Papua New Guinea

Mineral inclusions are ubiquitous in metamorphic rocks and elastic models for host‐inclusion pairs have become frequently used tools for investigating pressure–temperature (P–T) conditions of mineral entrapment. Inclusions can retain remnant pressures () that are relatable to their entrapment P–T conditions using an isotropic elastic model and P–T–V equations of state for host and inclusion minerals. Elastic models are used to constrain P–T curves, known as isomekes, which represent the possible inclusion entrapment conditions. However, isomekes require a temperature estimate for use as a thermobarometer. Previous studies obtained temperature estimates from thermometric methods external of the host‐inclusion system. In this study, we present the first P–T estimates of quartz inclusion entrapment by integrating the quartz‐in‐garnet elastic model with titanium concentration measurements of inclusions and a Ti‐in‐quartz solubility model (QuiG‐TiQ). QuiG‐TiQ was used to determine entrapment P–T conditions of quartz inclusions in garnet from a quartzofeldspathic gneiss from Goodenough Island, part of the (ultra)high‐pressure terrane of Papua New Guinea. Raman spectroscopic measurements of the 128, 206, and 464 cm^?1 bands of quartz were used to calculate inclusion pressures using hydrostatic pressure calibrations (), a volume strain calculation (), and elastic tensor calculation (), that account for deviatoric stress. values calculated from the 128, 206, and 464 cm^?1 bands’ hydrostatic calibrations are significantly different from one another with values of 1.8 ± 0.1, 2.0 ± 0.1, and 2.5 ± 0.1 kbar, respectively. We quantified elastic anisotropy using the 128, 206 and 464 cm^?1 Raman band frequencies of quartz inclusions and stRAinMAN software (Angel, Murri, Mihailova, & Alvaro, 2019,  234 :129–140). The amount of elastic anisotropy in quartz inclusions varied by ~230%. A subset of inclusions with nearly isotropic strains gives an average and of 2.5 ± 0.2 and 2.6 ± 0.2 kbar, respectively. Depending on the sign and magnitude, inclusions with large anisotropic strains respectively overestimate or underestimate inclusion pressures and are significantly different (<3.8 kbar) from the inclusions that have nearly isotropic strains. Titanium concentrations were measured in quartz inclusions exposed at the surface of the garnet. The average Ti‐in‐quartz isopleth (19 ± 1 ppm [2σ]) intersects the average QuiG isomeke at 10.2 ± 0.3 kbar and 601 ± 6°C, which are interpreted as the P–T conditions of quartzofeldspathic gneiss garnet growth and entrapment of quartz inclusions. The P–T intersection point of QuiG and Ti‐in‐quartz univariant curves represents mechanical and chemical equilibrium during crystallization of garnet, quartz, and rutile. These three minerals are common in many bulk rock compositions that crystallize over a wide range of P–T conditions thus permitting application of QuiG‐TiQ to many metamorphic rocks.     

Determination of Rare Earth Elements and Thorium at Nanogram Levels in Ultramafic Samples by Inductively Coupled Plasma‐Mass Spectrometry Combined with Chemical Separation and Pre‐concentration

A method was developed for the determination of low‐level rare earth elements (REEs) and thorium in ultramafic samples by inductively coupled plasma‐mass spectrometry. The conventional method for the digestion of ultramafic rocks using HNO₃ and HF results in considerable amounts of insoluble fluorides because of the high contents of Mg (generally up to 24% m/m) in these rocks. In this study, we used H₃BO₃ as a complexing agent to break down the insoluble fluorides, and then separated the REEs from Fe and Mg major and Ba, Ca, Cr minor matrices by anion exchange and co‐precipitation, respectively. The whole procedural blanks estimated from sample‐free analyses ranged from 0.232 ng for Ce to 0.006 ng for Tm and Lu. Limits of detection for this method, defined as three times the standard deviation of these blank analyses, varied from 0.51 ng g^?1 for Ce to 0.03 ng g^?1 for Lu. The recovery of REEs using this technique, as determined using the standard addition method, ranged from 92.9% for Y to 102.0% for Er with 3% (RSD) variation. The method was validated using GAS (GeoPT‐12), JP‐1 and PCC‐1, and the results were comparable to literature values, elucidating the applicability to the determination of ultra trace REEs in ultramafic rocks.     

LA‐ICP‐MS Analysis of Small Samples: Carbonate Reference Materials and Larval Fish Otoliths

This article proposes a methodology to analyse the composition of very small carbonate samples such as larval fish otoliths. The chemical composition of otoliths, which are carbonate structures in the inner ear, is often used to explore population dynamics in fishes. Recent advances in laser ablation‐inductively coupled plasma‐mass spectrometry have suggested its potential application to this field. In this study, analyses were performed using a 193 nm ArF Resonetics LA system, coupled to an Agilent 7700X‐ICP‐MS, with the following ablation parameters: a beam diameter of 5 μm, energy of 3 mJ, 2.7 J cm^?2, laser repetition rate of 10 Hz and translation speed of 2.5 μm s^?1. NIST SRM 610 glass was used as the primary calibration material. Performing this protocol, characterisation of a USGS GP‐4 reference material was achieved with suitable precision and accuracy, but the USGS MACS‐3 reference material appeared more heterogeneous under the ablation conditions tested. Calibration was performed using two different beam diameters (5 and 11 μm). Capelin (Mallotus villosus) otoliths measuring between 10 and 20 μm in diameter were tested. Even though a smaller beam diameter and lower energy were used compared with those normally employed to analyse larger otoliths, the method was successful.     

A Flux‐Free Fusion Technique for Rapid Determination of Major and Trace Elements in Silicate Rocks by LA‐ICP‐MS

A simple flux‐free fusion technique was developed to analyse major and trace element compositions of silicate rocks. The sample powders were melted in a molybdenum capsule sealed in a graphite tube to make a homogenous glass in a temperature‐controlled one‐atmosphere furnace. The glass was then measured for both major and trace element concentrations by LA‐ICP‐MS using a calibration strategy of total metal‐oxide normalisation. The optimum conditions (i.e., temperature and duration) to make homogeneous glasses were obtained by performing melting experiments using a series of USGS reference materials including BCR‐2, BIR‐1, BHVO‐2, AGV‐1, AGV‐2, RGM‐1, W‐2 and GSP‐2 with SiO₂ contents from 47 to 73% m/m. Analytical results of the USGS reference materials using our method were generally consistent with the recommended values within a discrepancy of 5–10% for most elements. The routine precision of our method was generally better than 5–10% RSD. Compared with previous methods of LA‐ICP‐MS whole‐rock analyses, our flux‐free fusion method is convenient and efficient in making silicate powder into homogeneous glass. Furthermore, it limits contamination and loss of volatile elements during heating. Therefore, our new method has great potential to provide reliable and rapid determinations of major and trace element compositions for silicate rocks.     

Development of a Matrix‐Matched Sphalerite Reference Material (MUL‐ZnS‐1) for Calibration of In Situ Trace Element Measurements by Laser Ablation‐Inductively Coupled Plasma‐Mass Spectrometry

Sphalerite (ZnS) is an abundant ore mineral and an important carrier of elements such as Ge, Ga and In used in high‐technology applications. In situ measurements of trace elements in natural sphalerite samples using LA‐ICP‐MS are hampered by a lack of homogenous matrix‐matched sulfide reference materials available for calibration. The preparation of the MUL‐ZnS1 calibration material containing the trace elements V, Cr, Mn, Co, Ni, Cu, Ga, Ge, As, Se, Mo, Ag, Cd, In, Sn, Sb, Tl and Pb besides Zn, Fe and S is reported. Commercially available ZnS, FeS, CdS products were used as the major components, whereas the trace elements were added by doping with single‐element ICP‐MS standard solutions and natural mineral powders. The resulting powder mixture was pressed to pellets and sintered at 400 °C for 100 h using argon as an inert gas. To confirm the homogeneity of major and trace element distributions within the MUL‐ZnS1 calibration material, measurements were performed using EPMA, solution ICP‐MS, ICP‐OES and LA‐ICP‐MS. The results show that MUL‐ZnS‐1 is an appropriate material for calibrating trace element determination in sphalerite using LA‐ICP‐MS.     

Determination of In and Sn Mass Fractions in Sixteen Geological Reference Materials by Isotope Dilution MC‐ICP‐MS

Mass fractions of Sn and In were determined in sixteen geological reference materials including basaltic/mafic (BCR‐2, BE‐N, BHVO‐1, BHVO‐2, BIR‐1, OKUM, W‐2, WS‐E), ultramafic (DTS‐2b, MUH‐1, PCC‐1, UB‐N) and felsic/sedimentary reference materials (AGV‐2, JA‐1, SdAR‐M2, SdAR‐H1). Extensive digestion and ion exchange separation tests were carried out in order to provide high yields (> 90% for Sn, > 85% for In), low total procedural blanks (~ 1 ng for Sn, < 3 pg for In) and low analytical uncertainties for the elements of interest in a variety of silicate sample matrices. Replicate analyses (n = 2–13) of Sn–In mass fractions gave combined measurement uncertainties (2u) that were generally < 3% and in agreement with literature data, where available. We present the first high‐precision In data for reference materials OKUM (32.1 ± 1.5 ng g^?1), DTS‐2b (2.03 ± 0.25 ng g^?1), MUH‐1 (6.44 ± 0.30 ng g^?1) and PCC‐1 (3.55 ± 0.35 ng g^?1) as well as the first Sn data for MUH‐1 (0.057 ± 0.010 μg g^?1) and DTS‐2b (0.623 ± 0.018 μg g^?1).