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.     

Lithium Isotope Composition of Ultramafic Geological Reference Materials JP‐1 and DTS‐2

An organic solvent‐free two‐step column procedure is presented that provided robust, high yield and super clean separation of Li from silicate rock sample matrices. The measured δ⁷Li value for BHVO‐2 of +4.29 ± 0.23‰ (1s) is comparable with the reported values. The δ⁷Li values for GSJ JP‐1 (+3.14 ± 0.41‰, 1s) and USGS DTS‐2 (+4.91 ± 0.34‰, 1s) presented here provide new reference values for ultramafic rock reference materials.     

La fabrique magnétique du flysch dauphinois (Alpes francaises) : origine et application quantitative

Résumé

Les propriétés magnétiques des schistes, grès et calcaires du flysch eocène de la zone dauphinoise ont été étudiées en relation avec la minéralogie et la structure de ces roches. La susceptibilité magnétique en champ faible est principalement due au paramagnétisme des phyllosilicates (illite et chlorite).

L’anisotropie de susceptibilité correspond à un ellipsoïde aplati qui présente les caractéristiques suivantes : un axe minimal perpendiculaire à la schistosité et un axe maximal parallèle soit à une linéation d’intersection soit à la direction d’étirement maximal.

On présente un modèle mathématique simple permettant d’utiliser le taux d’anisotropie magnétique pour quantifier l’orientation préférentielle des phyllosilicates. Ce modèle testé sur les niveaux les plus phylliteux du flysch donne des résultats en bon accord avec ceux de la goniometrie de texture. Les possibilités et les avantages de cette méthode structure-logique quantitative sont discutés.     

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.     

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.     

Âges KAr des roches magmatiques du fossé de Garoua (Cameroun) : leur place dans le cadre de la « Ligne du Cameroun »

KAr analyses on whole rock and minerals are reported for the Kokoumi anorogenic pluton and alkaline volcanics of the Benue valley, west of Garoua (northern Cameroon), which belong to the northern part of the ‘Cameroon Line’. The two formations yield similar ages of 39 and 37 Ma, respectively. These values likely correspond to the time of emplacement. They are in agreement with the interpretation considering the ‘Cameroon Line’ as a huge lithospheric crack tapping a hot deep asthenospheric zone. To cite this article: R. Montigny et al., C. R. Geoscience 336 (2004).     

Eaux fortement minéralisées et circulations profondes dans le socle. Exemple des Alpes franco-italiennes

The presence in the French–Italian Alps of several springs characterized by a high sodium–chloride content, depleted in oxygen-18, tritium free and with low carbon-14 activity, is well known. The geological, hydrological, and geochemical studies in progress for the new high-speed railway tunnel crossing the French–Italian Alps, show, in the drilled boreholes at a mean elevation of 700 masl, the presence of brines. Brines appear to be the basis of the geological, structural, and hydrodynamic systems, and fill the largest faults and the main tectonic contacts. The brines squeezed by tectonic activity, are mobilised at depth by freshwaters from the surface. To cite this article: G.-M. Zuppi et al., C. R. Geoscience 336 (2004).     

Some characteristics of geomagnetic reversals inferred from detailed volcanic records

The transitional virtual geomagnetic poles (VGPs) of the five most detailed records lie within the longitudinal bands of America, western Europe and eastern Asia. This distribution does not support the hypothesis of a direct link with heterogeneities of the lower mantle underneath Americas and eastern Asia. A similar distribution of VGPs persists by adding less detailed records and show similarities with the distribution of maximum inclination anomalies predicted by time-averaged field models. However, the two databases are far too limited to infer any recurrence of non-dipole components during reversals. Clusters of VGPs are observed in most records at various geographical locations without preference for specific longitudes, which most likely result from intense volcanism during short time periods rather than from transitional dipolar states.     

Precise Determination of Sm and Nd Concentrations and Nd Isotopic Compositions in Highly Depleted Ultramafic Reference Materials

In this study, a high‐precision method for the determination of Sm and Nd concentrations and Nd isotopic composition in highly depleted ultramafic rocks without a preconcentration step is presented. The samples were first digested using the conventional HF + HNO₃ + HClO₄ method, followed by the complete digestion of chromite in the samples using HClO₄ at 190–200 °C and then complete dissolution of fluoride formed during the HF decomposition step using H₃BO₃. These steps ensured the complete digestion of the ultramafic rocks. The rare earth elements (REEs) were separated from the sample matrix using conventional cation‐exchange chromatography; subsequently, Sm and Nd were separated using the LN columns. Neodymium isotopes were determined as NdO⁺, whereas Sm isotopes were measured as Sm⁺, both with very high sensitivity using single W filaments with TaF₅ as an ion emitter. Several highly depleted ultramafic rock reference materials including USGS DTS‐1, DTS‐2, DTS‐2b, PCC‐1 and GSJ JP‐1, which contain extremely low amounts of Sm and Nd (down to sub ng g^?1 level), were analysed, and high‐precision Sm and Nd concentration and Nd isotope data were obtained. This is the first report of the Sm‐Nd isotopic compositions of these ultramafic rock reference materials except for PCC‐1.     

Suitability of Mn‐ and Fe‐Rich Reference Materials for Microanalytical Research

Manganese‐ and iron‐rich materials are of major geoscientific and economic interest, many of which contain microscopic features that provide valuable information. To obtain accurate results, a homogeneous microanalytical reference material for calibration is needed. Several researchers have used the Mn‐ and Fe‐rich RMs, JMn‐1, NOD‐A‐1, NOD‐P‐1 and FeMn‐1, for this purpose; therefore, they were tested in this study to determine their suitability for microanalysis. Their homogeneity was investigated by laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) with two different types of lasers (nano‐ and femtosecond), with spot and line scan analyses and with different operating parameters, such as spot size, pulse repetition rate and fluence. As the established manganese nodule RMs revealed inhomogeneities for picogram to microgram test portions, we also investigated the new synthetic Fe‐ and Mn‐rich RM, FeMnOx‐1. FeMnOx‐1 was found to be homogeneous for large (ø 40 μm: 2% RSD repeatability) and small (ø 8–10 μm: 10% RSD repeatability) spot sizes. This homogeneity is in the range of the homogeneous NIST SRM 610 and GSE‐1G reference glasses. Furthermore, FeMnOx‐1 revealed a large‐scale homogeneity within uncertainties of a few per cent, using test portions in the ng range, when measuring four individual mounts of this material.