Optimised Ferrozine Micro‐Method for the Determination of Ferrous and Ferric Iron in Rocks and Minerals

The ferrozine wet chemical method was optimised for the determination of the total iron content and speciation in small geological samples. The ferrozine micro‐method involves dissolution by a mixture of HF and H₂SO₄ followed by spectrophotometric analysis using the complexing agent ferrozine. The method was tested for twenty‐one replicates of eight rock RMs using test portions of 5–14 mg and containing 0.37–5.45 mg total Fe and more than 0.29 mg Fe(II). The optimised ferrozine method was accurate to within 0.23% m/m FeO and 0.34% m/m total Fe, which compares favourably to other wet chemical methods.     

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.     

Rapid Determination of Trace and Ultra Trace Level Elements in Diverse Silicate Rocks in Pressed Powder Pellet Targets by LA‐ICP‐MS using a Matrix‐Independent Protocol

A simple, single sample preparation involving pressed rock powder pellets was utilised to determine the trace and ultra trace abundances of petrogenetically important elements including high field‐strength elements and REEs by laser ablation‐ICP‐MS. One of the elements predetermined by XRF spectrometry served as an internal standard. The influence of sample preparation parameters (grain size, pellet compactness and amount of binding media) on analytical performance was also investigated, including sample homogeneity issues at the laser sampling scale. Line scanning with a high repetition frequency (20 Hz) and large beam diameter (200 μm) ensured ablation from a larger sample surface area, eliminating issues related to sample heterogeneity. A median grain size of about 10 μm for silicate rock powders was found to be sufficiently representative at this scale of laser sampling. Granitic rocks or samples containing resistant minerals such as zircon needed extra grinding to achieve grain sizes down to < 5 μm for better precision for elements that are concentrated in these phases. Using ¹³⁷Ba as an internal standard, reasonable accuracies within 15–20% for most of the high mass trace elements were achieved; in the case of low mass elements, it may deviate up to 40%. Precision of measurements rarely exceeded 15% RSD.     

An Assessment of Performance in the Routine Analysis of Silicate Rocks Based on an Analysis of Data Submitted to the GeoPT Proficiency Testing Programme for Geochemical Laboratories (2001–2011)

Data reported by laboratories contributing to the GeoPT proficiency testing programme for geochemical laboratories over the period from 2001 to 2011 have been assessed to identify the elements and concentration ranges over which analytical performance can be considered satisfactory. Criteria developed in the paper indicated that performance in the content determination of the elements/constituents SiO₂, Al₂O₃, MnO, Cs, Dy, Er, Eu, Ga, Hf, Ho, Lu, Nd, Pr, Sm, Sr, Tb, Tl, Tm, U, Y, Yb and Zn was satisfactory over the full concentration range assessed. The elements/constituents TiO₂, Fe₂O₃(T), MgO, CaO, Na₂O, K₂O, P₂O₅, Ba, Be, Cd, Ce, Co, Gd, La, Li, Nb, Rb, Sb, Sc, Sn, Ta, Th, V and Zr showed some degradation in performance at lower concentration levels (approaching the detection limit of some techniques). Performance in determining LOI, As, Bi, Cr, Cu, Ge, Mo, Ni, Pb and W was in general unsatisfactory over the full concentration range assessed. Other elements (especially Fe(II)O, H₂O⁺, CO₂, Ag, Au, B, Br, Cl, F, Hg, I, In, Ir, N, Os, Pd, Pt, Re, Rh, S, Se, Te) could not be evaluated as they were not routinely reported by laboratories participating in the GeoPT programme, often because they are present in silicate rocks at sufficiently low concentrations to require a pre‐concentration stage. Some suggestions are made for the causes of unsatisfactory performance, but further progress will require a detailed assessment of the methods used by participating laboratories, which will form the subject of a further paper.     

Classical and New Procedures of Whole Rock Dissolution for Trace Element Determination by ICP‐MS

Sample digestion is a critical stage in the process of chemical analysis of geological materials by ICP‐MS. We present a new HF/HNO₃ procedure to dissolve silicate rock samples using a high pressure asher system. The formation of insoluble AlF₃ was the major obstacle in achieving full recoveries. This was overcome by setting an appropriate digestion temperature and adding Mg to the samples before digestion. Sodium peroxide sintering was also investigated and the inclusion of a heating step to the alkaline sinter solution improved the recoveries of thirteen elements other than the lanthanides. The results of these procedures were compared with data sets generated by common acid decomposition techniques. Forty‐one trace elements were determined using an ICP‐QMS equipped with a collision cell. Under optimum conditions of gas flow and kinetic energy discrimination, polyatomic interferences were eliminated or attenuated. The measurement bias obtained for eight reference materials (BCR‐2, BHVO‐2, BIR‐1, BRP‐1, OU‐6, GSP‐2, GSR‐1 and RGM‐1) and intermediate precision (RSD) were generally better than ± 5%. The expanded measurement uncertainties estimated for two certified reference materials were mostly between 7 and 15%. New data sets for the reference materials are provided, including constituents with previously unavailable values and also for the USGS candidate reference material G‐3.     

An Evaluation of the Inter‐Method Discrepancies in Ferromanganese Nodule Proficiency Test GeoPT 23A

Round 23 of the GeoPT international proficiency testing scheme included the ferromanganese nodule powder FeMn‐1 which was distributed as an additional sample (23A). The aim of this initiative was to assess overall analytical performance for such a challenging oxide matrix with a view to the possible certification of such a material in accordance with ISO Guide requirements. To investigate inter‐method discrepancies, precision data and the method means for the most frequently used analytical methods (XRF, ICP‐MS and ICP‐AES) and sample preparation techniques were calculated and then compared using statistical tests of equivalence. For most major elements, XRF and ICP‐AES data dominated and these were found to give equivalent results. In contrast, for most trace elements significant discrepancies were detected between data obtained by different analytical methods. Possible causes are discussed with a view to attributing their origin to calibration strategy, sensitivity or interferences. It is assumed that the unusual oxide matrix generated unexpected interferences and thus method bias. Discrepancies observed between data from different analytical methods provide valuable information for the participating analysts, helping them to avoid systematic errors and thus minimising bias. They also suggest actions necessary to improve results for any future certification of such a material.     

A Practical Method for Accurate Measurement of Trace Level Fluorine in Mg‐ and Fe‐Bearing Minerals and Glasses Using Electron Probe Microanalysis

Fluorine plays an important role in magmatic and hydrothermal processes, but due to its low abundance in geological samples determining F is difficult by electron probe microanalysis. By using a W‐Si multi‐layered pseudocrystal as the diffraction crystal instead of thallium acid phthalate (TAP), count rates were considerably higher, which however introduced spectral interferences between FKα and FeLα and MgKβ lines when normal integral mode is applied. In this study, we developed a protocol using a W‐Si multi‐layered pseudocrystal for measuring accurately trace level F in both minerals and glasses. First, we used differential mode with an optimised PHA (pulse height analysis) setting in signal processing, instead of normal integral mode, which completely eliminated the second‐order MgKβ line. Second, the overlap of the first‐order FeLα on FKα peak, which cannot be filtered by modifying the PHA setting, was calibrated quantitatively using F‐free minerals and silicate glasses. Applying this two‐step method, F was determined in a number of reference glasses, as well as in glasses synthesised from powders of the rock reference materials AC‐E, GS‐N and DR‐N. Our data are consistent within error with F concentrations determined by other methods, demonstrating the reliability of this method.     

Use of Hydrofluoric Acid Desilicification in the Determination of Highly Siderophile Element Abundances and Re‐Pt‐Os Isotope Systematics in Mafic‐Ultramafic Rocks

Properly combining highly siderophile element (HSE: Re, Pd, Pt, Ru, Ir, Os) abundance data, obtained by isotope dilution, with corresponding ¹⁸⁷Os/¹⁸⁸Os and ¹⁸⁶Os/¹⁸⁸Os measurements of rocks requires efficient digestion of finely‐ground powders and complete spike‐sample equilibration. Yet, because of the nature of commonly used methods for separating Os from a rock matrix, hydrofluoric acid (HF) is typically not used in such digestions. Consequently, some silicates are not completely dissolved, and HSE residing within these silicates may not be fully accessed. Consistent with this, some recent studies of basaltic reference materials (RMs) have concluded that an HF‐desilicification procedure is required to fully access the HSE (Ishikawa et al. (2014) Chemical Geology, 384, 27–46; Li et al. (2015) Geostandards and Geoanalytical Research, 39, 17–30). Highly siderophile element abundance and Os isotope studies of intraplate basalts typically target samples with a range of MgO contents (< 8 to > 18% m/m, or as mass fractions, < 8 to > 18 g per 100 g), in contrast to the lower MgO mass fractions (< 10 g per 100 g) of basalt and diabase RMs (i.e., BIR‐1, BHVO‐2, TDB‐1). To investigate the effect of HF‐desilicification on intraplate basalts, experiments were performed on finely ground Azores basalts (8.1–17 g per 100 g MgO) using a ‘standard acid digestion’ (2:1 mixture of concentrated HNO₃ and HCl), and a standard acid digestion, followed by HF‐desilicification. No systematic trends in HSE abundances were observed between data obtained by standard acid digestion and HF‐desilicification. Desilicification procedures using HF do not improve liberation of the HSE from Azores basalts, or some RMs (e.g., WPR‐1). We conclude that HF‐desilicification procedures are useful for obtaining total HSE contents of some young lavas, but this type of procedure is not recommended for studies where Re‐Pt‐Os chronological information is desired. The collateral effect of a standard acid digestion to liberate Os, followed by HF‐desilicification to obtain Re and Pt abundances in samples, is that the measured Re/Os and Pt/Os may not correspond with measured ¹⁸⁷Os/¹⁸⁸Os or ¹⁸⁶Os/¹⁸⁸Os.     

Comparison of Two Sample Preparation Methods for X‐Ray Fluorescence Spectrometry in the Determination of Ni and Cr

Pressed powder pellets and fused beads or glass disks are routinely used in X‐ray fluorescence spectrometry for the determination of major and trace elements, respectively, in geological materials. In order to evaluate the performance of these two sample preparation methods, we determined Ni and Cr concentrations of fourteen RMs from Japan, France and South Africa, and eighty‐five igneous and three sedimentary rock samples from Mexico in both powder pellets and glass beads. We also computed new values of statistical parameters for RMs from an outlier‐based multiple‐test method and compared them with the literature mean and confidence limit values. The results showed that the multiple‐test method provided more reliable central tendency and dispersion parameters for RMs than those obtained previously from the two or three standard deviation method, or from robust methods. The powder pellet and fused bead sample preparation methods provided consistent results for Ni and Cr at concentration levels > 50 μg g^?1 in this application; for lower concentration levels, however, these methods showed somewhat greater differences. For quantitative comparisons, both ordinary and weighted least‐squares linear regression models were used to show that the two sample preparation methods provided generally unbiased results.     

An Investigation of the Reliability of HF Acid Mixtures in the Bomb Digestion of Silicate Rocks for the Determination of Trace Elements by ICP‐MS

The influence of the mixtures HF‐HNO₃ and HF‐NH₄F‐HNO₃ in bomb digestion for trace element determination from different rock types was studied using ICP‐MS. It is shown that the HF concentration, not the ratio of reagents in the decomposing mixture, controls the digestion process of a rock. Data for Zr in the granite G‐2 as a function of HF concentration gave the same results as reaction mixtures of various compositions. A complete digestion in 50‐mg sample bombs was achieved by 1.0 ml of HF alone, or with a mixture of other acids at a HF concentration of at least 35% m/m at 196 °C over 18 h. The results of the analysis of basalts BCR‐1, BIR‐1, mica schist SDC‐1, shale SBC‐1, granites G‐2, SG‐1A, garnet‐biotite plagiogneiss GBPg‐1, rhyolite RGM‐1, granodiorite GSP‐1, trachyandesite MTA‐1 and rhyolite MRh‐1 are given and compared against available data. The reproducibility of the element determinations by ICP‐MS and XRF as an independent non‐destructive analysis for a quality check in the range of concentrations typical for routine rock samples is given.     

A Method for Rapid Determination of Re and Os Isotope Compositions Using ID‐MC‐ICP‐MS Combined with the Sparging Method

A simple, rapid method for the determination of Re and Os concentrations and isotope compositions using isotope dilution multi‐collector inductively coupled plasma‐mass spectrometry (ID‐MC‐ICP‐MS) combined with Carius tube digestion and sparging introduction of Os was developed. For Os measurement, four channeltron ion counters to detect different Os isotopes were used simultaneously, which led to a drastic reduction in the measurement time. Rhenium isotopes were measured by means of eight Faraday cups with solution nebulisation and an ultrasonic membrane desolvator. The representative ¹⁸⁸Os count rate of an Os standard solution containing 50 pg of total Os was approximately 110000–120000 cps at the onset of measurement; the Re intensity of our in‐house 10 pg g^?1 standard solution reached 1820 V/μg g^?1 with a sample uptake rate of 95–99 μl min^?1. These values indicate that the sensitivity of the method was sufficient even for samples with low Re and Os concentrations, such as chert. As the temporal variations of the amplification efficiency of the ion counters differed from one another, we adopted a sample‐calibrator bracketing method to correct the measured Re and Os isotope ratios. The Re and Os concentrations via the isotope dilution method and the ¹⁸⁷Os/¹⁸⁸Os ratios of two sedimentary rock reference materials (JMS‐2 and JCh‐1) on the basis of the isotope ratios determined by the MC‐ICP‐MS and by negative thermal ionisation mass spectrometry (N‐TIMS) were comparable within their ranges. Based on Os isotope measurement of the IAG reference material [Durham Romil Os (DROsS)], the average difference from the recommended value and precision of Os isotope measurements by the sparging method in combination with multi‐ion‐counters were 0.72% and 0.76% [1RSD (%), n = 29], respectively. The precisions in the ¹⁸⁷Os/¹⁸⁸Os ratios [1RSD (%)] of JMS‐2, JCh‐1 and DROsS were 0.35–0.71, 1.56–3.31 and 0.99–1.28%, respectively, which depended on their Os ion intensities. No systematic difference was observed between the Re and Os geochemical compositions of JCh‐1 and JMS‐2 obtained by means of digestion with inverse aqua regia and CrO₃‐H₂SO₄ solutions, suggesting that either acid solution can be used for the sparging method of sedimentary rock samples. As CrO₃‐H₂SO₄ solution is believed to liberate predominantly the hydrogenous Re and Os fraction from organic‐rich sediment, the sparging method combined with CrO₃‐H₂SO₄ digestion and multi‐ion‐counters in the mass spectrometry is expected to be a powerful tool for reconstructing the secular change in marine Os isotope compositions with high sample throughput.