In situ analysis of major and trace elements of anhydrous minerals by LA-ICP-MS without applying an internal standard

We present new reference values for the NIST SRM 610–617 glasses following ISO guidelines and the International Association of Geoanalysts’ protocol. Uncertainties at the 95% confidence level (CL) have been determined for bulk- and micro-analytical purposes. In contrast to former compilation procedures, this approach delivers data that consider present-day requirements of data quality. New analytical data and the nearly complete data set of the GeoReM database were used for this study. Data quality was checked by the application of the Horwitz function and by a careful investigation of analytical procedures. We have determined quantitatively possible element inhomogeneities using different test portion masses of 1, 0.1 and 0.02 μg. Although avoiding the rim region of the glass wafers, we found moderate inhomogeneities of several chalcophile/siderophile elements and gross inhomogeneities of Ni, Se, Pd and Pt at small test portion masses. The extent of inhomogeneity was included in the determination of uncertainties. While the new reference values agree with the NIST certified values with the one exception of Mn in SRM 610, they typically differ by as much as 10% from the Pearce et al. (1997) values in current use. In a few cases (P, S, Cl, Ta, Re) the discrepancies are even higher.



Nous presentons des nouvelles valeurs de reference pour les verres NIST SRM 610–617 en suivant les recommandations de l’ISO et le protocole de l’IAG. Les incertitudes au niveau de confiance de 95% ont ete determinees a des fins d’analyse totale et de micro-analyse. Contrairement aux procedures de compilation precedentes, cette approche fournit des donnees qui tiennent compte des exigences actuelles dans la qualite des donnees. De nouvelles donnees analytiques et le jeu de donnees presque complet de la base de donnees GeoReM ont ete utilises pour cette etude. La qualite des donnees a ete verifiee par l’application de la fonction de Horwitz et par un examen minutieux des procedures analytiques. Nous avons determine quantitativement les possibles inhomogeneites d’element en utilisant des prises d’essai de masses differentes correspondant a 1, 0.1 et 0.02 μg. Bien que nous ayons evite les zones de bordure des disques de verre, nous avons trouve des inhomogeneites moderees pour plusieurs elements chalcophiles/siderophiles et des inhomogeneites flagrantes de Ni, Se, Pd et Pt pour les prises d’essai de petites masses. La mesure d’inhomogeneite a ete incluse dans la determination des incertitudes. Alors que les nouvelles valeurs de reference sont en accord avec les valeurs NIST certifiees a la seule exception du Mn dans SRM 610, elles sont generalement differentes, avec des ecarts de pres de 10%, des valeurs de Pearce et al. (1997) qui sont d’un usage courant. Dans quelques cas (P, S, Cl, Ta, Re), les ecarts sont encore plus eleves.

Determination of Reference Values for NIST SRM 610–617 Glasses Following ISO Guidelines

We have developed a new database named GeoReM (http://georem.mpch-mainz.gwdg.de) for reference materials and isotopic standards of geochemical and mineralogical interest. Reference samples include rock powders originating from the USGS, GSJ, GIT-IWG, synthetic and natural reference glasses originating from NIST, USGS, MPI-DING, as well as mineral (e.g., 91500 zircon), isotopic (e.g., La Jolla, E&A, NIST SRM 981), river water and seawater reference materials. GeoReM is a relational database, which strongly follows the concept of the three EARTHCHEM databases. It contains published analytical and compilation values (major and trace element concentrations, radiogenic and stable isotope ratios), important metadata about the analytical values, such as uncertainty, uncertainty type, method and laboratory. Sample information and references are also included. Three different ways of interrogating the database are possible: (1) sample names or material types, (2) chemical criteria and (3) bibliography. Some typical applications are described. GeoReM currently (October 2005) contains more than 750 geological reference materials, 6000 individual sets of results and references to 650 publications.

http://www.crpg.cnrs-nancy.fr/Geostandards/GGR_pdf.v29/ms820.pdf

GeoReM: A New Geochemical Database for Reference Materials and Isotopic Standards

[1] The abundances of 60 elements in 616 Ocean Floor Basaltic (OFB) glasses from the Abyssal Volcanic Glass Data File (AVGDF) of the Smithsonian Institution have been determined by laser-ablation (LA)-ICP-MS and electron microprobe analysis (EMPA). The elements analyzed include all 28 of the refractory lithophile elements, which provide the framework for establishing the geochemical behavior and source abundances of volatile, chalcophile and siderophile elements. In addition to the traditionally analyzed elements (rare earth elements (REE), high field strength elements (HFSE), large ion lithophile elements (LILE) and first row transition elements (FRTE)), we report analyses for lesser-analyzed elements (Li, Be, Ga, Ge, As, Se, Mo, Ag, Cd, In, Sn, Sb, W, Tl and Bi). The precision of the method for most elements is between 2 and 4%, one standard deviation, although ratios of elements determined simultaneously are more precise (e.g., REE, Zr/Hf). Subsets of 329 glasses were analyzed by electron microprobe for S and 154 glasses for Cl. The results define a representative trace element geochemistry of OFB, against which local variations resulting from differences in basalt petrogenesis in a range of tectonic settings or different styles of magmatic differentiation may be compared.

/pdf/analysis-of-60-elements-in-616-ocean-floor-basaltic-glasses-38xxpzk2y2.pdf

Analysis of 60 elements in 616 ocean floor basaltic glasses

The Indus–Yarlung Zangbo ophiolites from Nanga Parbat to Namche Barwa syntaxes, southern Tibet: First synthesis of petrology, geochemistry, and geochronology with incidences on geodynamic reconstructions of Neo-Tethys

We present new analytical data of major and trace elements for the geological MPI-DING glasses KL2-G, ML3B-G, StHs6/80-G, GOR128-G, GOR132-G, BM90/21-G, T1-G, and ATHO-G. Different analytical methods were used to obtain a large spectrum of major and trace element data, in particular, EPMA, SIMS, LA-ICPMS, and isotope dilution by TIMS and ICPMS. Altogether, more than 60 qualified geochemical laboratories worldwide contributed to the analyses, allowing us to present new reference and information values and their uncertainties (at 95% confidence level) for up to 74 elements. We complied with the recommendations for the certification of geological reference materials by the International Association of Geoanalysts (IAG). The reference values were derived from the results of 16 independent techniques, including definitive (isotope dilution) and comparative bulk (e.g., INAA, ICPMS, SSMS) and microanalytical (e.g., LA-ICPMS, SIMS, EPMA) methods. Agreement between two or more independent methods and the use of definitive methods provided traceability to the fullest extent possible. We also present new and recently published data for the isotopic compositions of H, B, Li, O, Ca, Sr, Nd, Hf, and Pb. The results were mainly obtained by high-precision bulk techniques, such as TIMS and MC-ICPMS. In addition, LA-ICPMS and SIMS isotope data of B, Li, and Pb are presented.

/pdf/mpi-ding-reference-glasses-for-in-situ-microanalysis-new-2gtmtexuej.pdf

Cees-Jan de Hoog

Papers

MPI-DING reference glasses for in situ microanalysis: New reference values for element concentrations and isotope ratios