An Optimised 1,10‐Phenanthroline Method for the Determination of Ferrous and Ferric Oxides in Silicate Rocks,Soils and Minerals

A precise, accurate and rapid method for the sequential determination of FeO and Fe₂O₃ in rocks, soils and some non‐refractory minerals by 1,10‐phenanthroline spectrophotometry is described. Fe(II) and Fe(III) were leached from the sample (?200 mesh) using a mixture of NH₄HF₂ and H₂SO₄ at 40–80 °C for 10 min on a hot plate. Both Fe(II) and Fe(III) could be conveniently estimated sequentially from the same reaction mixture at the μg g^?1 to percentage level. The method is better than the existing wet chemical methods, including the commonly used Pratt's titrimetric redox method, for Fe(II) and Fe(III) determinations in rock and soil samples in terms of precision, accuracy and rapidity. The throughput of the method was very high; at least forty to fifty samples could be estimated easily in a day. The results obtained compare favourably with those obtained by Pratt's method, as well as for certified/recommended values of a set of eleven certified reference materials having FeO and Fe₂O₃ contents in the range 0.21–14.63% and 0.58–8.48%, respectively. The optimised 1,10 phenanthroline method was found to be accurate to within 0.21% m/m FeO and 0.30% m/m Fe₂O₃ compared with the literature values of the certified reference materials studied.     

Étude expérimentale des transformations de phase dans un gradient thermique : application au granite de Soultz-sous-Forêts,France

The circulation of an injected fluid in the deep granite of the Soultz-sous-Forêts HDR (‘Hot Dry Rock’) site causes important textural and mineralogical modifications. In order to determine the potential crystallization sequences along the fluid pathway, several experiments under thermal gradient were conducted at 600 bar (between 300 and 200 °C). After 40 days, the observed sequences of the newly formed products along the thermal gradient are always as follows, from high to low temperatures: quartz, feldspars, and finally interstratified clays, this implying a significant mobility of aluminium in the solution. To cite this article: A. Baldeyrou et al., C. R. Geoscience 335 (2003).     

Strontium,SO42−/Cl− and Mg2+/Ca2+ ratios as tracers for the evolution of seawater into coastal aquifers: the example of Castell de Ferro aquifer (SE Spain)

The strontium content and the SO₄^2?/Cl^? and Mg²⁺/Ca²⁺ ratios were used as natural tracers of the residence time of seawater intrusion into the Castell de Ferro aquifer. Analysis of these parameters indicated the existence of two principal flowpaths in the aquifer. The first flows through the eastern part of the aquifer, through the karstified Castell de Ferro massif; it accommodates a larger and more rapid flow, so that the residence time is shorter, leading to lower SO₄²⁺/Cl^? ratios, lower Sr²⁺ content and higher Mg²⁺/Ca²⁺ ratios. The second flowpath is in the western sector, and flows exclusively through alluvial deposits; the flow here is slower, particularly that flowing towards the sea. Thus the residence time of the water here will be longer and there is scant flushing of the intruded seawater; this is manifested in the high Sr²⁺ content, high SO₄²⁺/Cl^? and low Mg²⁺/Ca²⁺ ratios. To cite this article: P. Pulido-Leboeuf et al., C. R. Geoscience 335 (2003).     

The GeoPT Proficiency Testing Scheme for Laboratories Routinely Analysing Silicate Rocks: A Review of the Operating Protocol and Proposals for its Modification

The GeoPT proficiency testing programme for geochemical laboratories has been operating for nearly 20 years. This review, based on an analysis of accumulated data and extensive experience, examines whether the protocol followed during this period continues to be appropriate. Possible changes that might be considered for future implementation are examined, in particular the procedures for calculating assigned values, target values, z‐scores and the applicability of dual fitness‐for‐purpose criteria. We conclude that the existing protocol remains largely appropriate and effective, but propose that a single fitness‐for‐purpose criterion be adopted, with an option for laboratories to recalculate their z‐scores if the criterion is inappropriate for their requirements.     

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.     

Zinc Isotopic Compositions of NIST SRM 683 and Whole‐Rock Reference Materials

In this study the homogeneity of the zinc isotopic composition in the NIST SRM 683 reference material was examined by measuring the Zn isotopic signature in microdrilled sample powders from two metal nuggets. Zinc was purified using AG MP‐1M resin and then measured by MC‐ICP‐MS. Instrumental mass bias was corrected using the “sample‐standard bracketing” method and empirical external normalisation with Cu doping. After evaluating the potential effects of varying acid mass fractions and different matrices, high‐precision Zn isotope data were obtained with an intermediate measurement precision better than ± 0.05‰ (δ⁶⁶Zn, 2s) over a period of 5 months. The δ⁶⁶Zn_JMC‐Lyon mean values of eighty‐four and fourteen drilled powders from two nuggets were 0.11 ± 0.02‰ and 0.12 ± 0.02‰, respectively, indicating that NIST SRM 683 is a good isotopic reference material with homogeneous Zn isotopes. The Zn isotopic compositions of seventeen rock reference materials were also determined, and their δ⁶⁶Zn values were in agreement with most previously published data within 2s. The δ⁶⁶Zn values of most of the rock reference materials analysed were in the range 0.22–0.36‰, except for GSP‐2 (1.07 ± 0.06‰, n = 12), NOD‐A‐1 (0.96 ± 0.03‰, n = 6) and NOD‐P‐1 (0.78 ± 0.03‰, n = 6). These comprehensive data should serve as reference values for quality assurance and interlaboratory calibration exercises.     

Direct Quantitative Determination of Trace Elements in Fine‐Grained Whole Rocks by Laser Ablation‐Inductively Coupled Plasma‐Mass Spectrometry

Previous laser ablation‐ICP‐MS bulk analyses have been confined to volcanic glasses and glass disks or powder pellets similar to those used for XRF analysis. This study proposes a method to determine twenty trace elements (fourteen rare earth elements, Sc, Y, Zr, Nb, Hf and Ta) by LA‐ICP‐MS directly from polished thick sections and rock slabs of six fine‐grained crystalline and aphanitic rocks (five volcanic rocks and one pelitic tillite). Laser scanning of eight to ten 20 mm long linear tracks using a spot size of 160 μm, with a total ablated area of 26–32 mm², was performed. Quantification was carried out by (a) internal standardisation using Si and (b) without applying internal standardisation. In the latter method, external determination of one element in conventional LA‐ICP‐MS quantification is no longer needed. Although the fine‐grained rocks studied contained variable amounts of volatiles (up to 4%), this method gave results that agree within 10% relative with those obtained by internal standardisation using Si. Two USGS basalt glass reference materials (BCR‐2G and BHVO‐2G) were used for external calibration. The results and the associated trace element patterns and ratios of elemental pairs obtained from both methods of quantification showed good agreement with the results from solution nebulisation ICP‐MS within 20% (mostly within 10%) relative. Fine‐grained rocks are common and include volcanic, sedimentary and low‐grade metamorphic rocks (e.g., basalt, andesite, rhyolite, shale, mudstone, tillite, loess, pelite and slate) and their trace element contents and associated ratios are important geochemical tracers in studies focusing on the composition and evolution of the crust and mantle. Our method provides a simple and quantitative way to determine trace elements in fine‐grained rocks even with those displaying complex textures.     

天山羊背石上冰蚀痕迹分布与冰底过程的初步研究

本文根据羊背石上的冰蚀痕迹的资料,着重探讨了其冰蚀痕迹分布规律和冰底动力过程。羊背石迎冰面顶部的擦痕多、多度大且平直,而属部多为新月型裂纹、新月型凿口、颤痕、凿口和较短的钉头状探痕。羊背石的背冰面受拔蚀作用强,裂隙的密度、宽度、深度大。背冰面的横剖面,从上向下可分为强烈挤压破碎带、强烈剪切破碎带和微弱挤压－剪切破碎带,而从中到两则分别是破碎带、裂隙探痕带和控痕带。     

Reference Values Following ISO Guidelines for Frequently Requested Rock Reference Materials

We present new reference values for nineteen USGS, GSJ and GIT‐IWG rock reference materials that belong to the most accessed samples of the GeoReM database. The determination of the reference values and their uncertainties at the 95% confidence level follows as closely as possible ISO guidelines and the Certification Protocol of the International Association of Geoanalysts. We used analytical data obtained by the state‐of‐the‐art techniques published mainly in the last 20 years and available in GeoReM. The data are grouped into four categories of different levels of metrological confidence, starting with isotope dilution mass spectrometry as a primary method. Data quality was checked by careful investigation of analytical procedures and by the application of the Horwitz function. As a result, we assign a new and more reliable set of reference values and respective uncertainties for major, minor and a large group of trace elements of the nineteen investigated rock reference materials.