Chemical Analysis of Iron Meteorites Using a Hand‐Held X‐Ray Fluorescence Spectrometer

We evaluate the performance of a hand‐held XRF (HHXRF) spectrometer for the bulk analysis of iron meteorites. Analytical precision and accuracy were tested on metal alloy certified reference materials and iron meteorites of known chemical composition. With minimal sample preparation (i.e., flat or roughly polished surfaces) HHXRF allowed the precise and accurate determination of most elements heavier than Mg, with concentrations > 0.01% m/m in metal alloy CRMs, and of major elements Fe and Ni and minor elements Co, P and S (generally ranging from 0.1 to 1% m/m) in iron meteorites. In addition, multiple HHXRF spot analyses could be used to determine the bulk chemical composition of iron meteorites, which are often characterised by sulfide and phosphide accessory minerals. In particular, it was possible to estimate the P and S bulk contents, which are of critical importance for the petrogenesis and evolution of Fe‐Ni‐rich liquids and iron meteorites. This study thus validates HHXRF as a valuable tool for use in meteoritics, allowing the rapid, non‐destructive (a) identification of the extraterrestrial origin of metallic objects (i.e., archaeological artefacts); (b) preliminary chemical classification of iron meteorites; (c) identification of mislabelled/unlabelled specimens in museums and private collections and (d) bulk analysis of iron meteorites.     

Determination of Trace Silver in Polymetallic Ore Samples by Flame Atomic Absorption Spectrometry after Solid‐Phase Extraction Using a Microcolumn Comprising Eggshell Membrane

A rapid and inexpensive method was developed for the determination of trace silver in polymetallic ore samples by use of eggshell membrane (ESM), a natural biomaterial, as the solid‐phase extraction (SPE) adsorbent coupled with flame atomic absorption spectrometry (FAAS). The ESM was used for the separation/pre‐concentration of silver, and the parameters affecting sensitivity, such as pH, sample flow rate, eluent volume and eluent flow rate, were carefully investigated. ESM was found to be an effective solid phase extractant for the adsorption of trace silver over a wide range of acidity from 0.02 to 0.50 mol l^?1 HNO₃. The sample solution in 0.4 mol l^?1 HNO₃ was pumped through an ESM microcolumn at the rate of 1.0 ml min^?1. Silver was absorbed, and then eluted with a solution of 1.0% m/v thiourea–0.5% v/v HCl. Under these optimal conditions, ESM exhibited a good enrichment efficiency for silver with a dynamic adsorption capacity of 1.7 mg g^?1. The proposed method was applied to the FAAS determination of trace silver in polymetallic ores and geological reference materials, GSO‐2, 3 and 5, and GSD‐11, GSD‐12, and the determined values were in good agreement with certified values.     

A Compilation of Silicon,Rare Earth Element and Twenty‐One other Trace Element Concentrations in the Natural River Water Reference Material SLRS‐5 (NRC‐CNRC)

The natural river water certified reference material SLRS‐5 (NRC‐CNRC) was routinely analysed in this study for major and trace elements by ten French laboratories. Most of the measurements were made using ICP‐MS. Because no certified values are assigned by NRC‐CNRC for silicon and 35 trace element concentrations (rare earth elements, Ag, B, Bi, Cs, Ga, Ge, Li, Nb, P, Rb, Rh, Re, S, Sc, Sn, Th, Ti, Tl, W, Y and Zr), or for isotopic ratios, we provide a compilation of the concentrations and related uncertainties obtained by the participating laboratories. Strontium isotopic ratios are also given.     

Diagenetic formation of gypsum and dolomite in a cold‐water coral mound in the Porcupine Seabight,off Ireland

Authigenic gypsum was found in a gravity core, retrieved from the top of Mound Perseverance, a giant cold‐water coral mound in the Porcupine Basin, off Ireland. The occurrence of gypsum in such an environment is intriguing, because gypsum, a classic evaporitic mineral, is undersaturated with respect to sea water. Sedimentological, petrographic and isotopic evidence point to diagenetic formation of the gypsum, tied to oxidation of sedimentary sulphide minerals (i.e. pyrite). This oxidation is attributed to a phase of increased bottom currents which caused erosion and enhanced inflow of oxidizing fluids into the mound sediments. The oxidation of pyrite produced acidity, causing carbonate dissolution and subsequently leading to pore‐water oversaturation with respect to gypsum and dolomite. Calculations based on the isotopic compositions of gypsum and pyrite reveal that between 21·6% and 28·6% of the sulphate incorporated into the gypsum derived from pyrite oxidation. The dissolution of carbonate increased the porosity in the affected sediment layer but promoted lithification of the sediments at the sediment‐water interface. Thus, authigenic gypsum can serve as a signature for diagenetic oxidation events in carbonate‐rich sediments. These observations demonstrate that fluid flow, steered by environmental factors, has an important effect on the diagenesis of coral mounds.     

Integration of ASTER and landsat TM remote sensing data for chromite prospecting and lithological mapping in Neyriz ophiolite zone,south Iran

Chromite deposits in Iran are located in the ophiolite complexes, which have mostly podiform types and irregular in their settings. Exploration for podiform chromite deposits associated with ophiolite complexes has been a challenge for the prospectors due to tectonic disturbance and their distribution patterns. Most of Iranian ophiolitic zones are located in mountainous and inaccessible regions. Remote sensing approach could be applicable tool for choromite prospecting in Iranian ophiolitic zones with intensely rugged topography, where systematic sampling and conventional geological mapping are limited. In this study, Landsat Thematic Mapper (TM) and Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) satellite data were used for chromite prospecting and lithological mapping in the Neyriz ophiolitic zone in the south of Iran. Image transformation techniques, namely decorrelation stretch, band ratio and principal component analysis (PCA) were applied to Landsat TM and ASTER data sets for lithological mapping at regional scale. The RGB decorrelated image of Landsat TM spectral bands 7, 5, and 4, and the principal components PC1, PC2 and PC3 image of ASTER SWIR spectral bands efficiently showed the occurrence of major lithological units in the study area at regional scale. The band ratios of 5/3, 5/1, 7/5 applied on ASTER VNIR‐SWIR bands were very useful for discriminating most of rock units in the study area and delineation of the transition zone and mantle harzburgite in the Neyriz ophiolitic complex. Spectral Angle Mapper (SAM) technique was implemented to ASTER VNIR‐SWIR spectral bands for detecting minerals of rock units and especially delineation of the transition zone and mantle harzburgite as potential zones with high chromite mineralization in the Neyriz ophiolitic complex. The integration of information extracted from the image processing algorithms used in this study mapped most of lithological units of the Neyriz ophiolitic complex and identified potential areas of high chromite mineralization (transition zone and mantle harzburgite) for chromite prospecting targets in the future. Furthermore, image processing results were verified by comprehensive fieldwork and laboratory analysis in the study area. Accordingly, result of this investigation indicate that the integration of information extracted from the image processing algorithms using Landsat TM and ASTER data sets could be broadly applicable tool for chromite prospecting and lithological mapping in mountainous and inaccessible regions such Iranian ophiolitic zones.     

Formation Process of Zircon Associated with REE‐Fluorocarbonate and Niobium Minerals in the Nechalacho REE Deposit,Thor Lake,Canada

The two drill holes, which penetrated sub‐horizontal rare earth element (REE) ore units at the Nechalacho REE in the Proterozoic Thor Lake syenite, Canada, were studied in order to clarify the enrichment mechanism of the high‐field‐strength elements (HFSE: Zr, Nb and REE). The REE ore units occur in the albitized and potassic altered miaskitic syenite. Zircon is the most common REE mineral in the REE ore units, and is divided into five types as follows: Type‐1 zircon occurs as discrete grains in phlogopite, and has a chemical character similar to igneous zircon. Type‐2 zircon consists of a porous HREE‐rich core and LREE–Nb–F‐rich rim. Enrichment of F in the rim of type‐2 zircon suggests that F was related to the enrichment of HFSE. The core of type‐2 zircon is regarded to be magmatic and the rim to be hydrothermal in origin. Type‐3 zircon is characterized by euhedral to anhedral crystals, which occur in a complex intergrowth with REE fluorocarbonates. Type‐3 zircon has high REE, Nb and F contents. Type‐4 zircon consists of porous‐core and ‐rim, but their chemical compositions are similar to each other. This zircon is a subhedral crystal rimmed by fergusonite. Type‐5 zircon is characterized by smaller, porous and subhedral to anhedral crystals. The interstices between small zircon grains are filled by fergusonite. Type‐4 and type‐5 zircon grains have low REE, Nb and F contents. Type‐1 zircon is only included in one unit, which is less hydrothermally altered and mineralized. Type‐2 and type‐3 zircon grains mainly occur in the shallow units, while those of type‐4 and type‐5 are found in the deep units. The deep units have high HFSE contents and strongly altered mineral textures (type‐4 and type‐5) compared to the shallow units. Occurrences of these five types of zircon are different according to the depth and degree of the hydrothermal alteration by solutions rich in F and CO₃, which permit a model for the evolution of the zircon crystallization in the Nechalacho REE deposit as follows: (i) type‐1 (discrete magmatic zircon) is formed in miaskitic syenite. (ii) LREE–Nb–F‐rich hydrothermal zircon formed around HREE‐rich magmatic zircon (type‐2). (iii) type‐3 zircon crystallized through the F and CO₃‐rich hydrothermal alteration of type‐2 zircon which formed the complex intergrowth with REE fluorocarbonates; (iv) the CO₃‐rich hydrothermal fluid corroded type‐3, forming REE–Nb‐poor zircon (type‐4). Niobium and REE were no longer stable in the zircon structure and crystallized as fergusonite around the REE–Nb‐leached zircon (type‐4); (v) type‐5 zircon is formed by the more CO₃‐rich hydrothermal alteration of type‐4 zircon, suggested by the fact that type‐4 and type‐5 zircon grains are often included in ankerite. Type‐3 to type‐5 zircon grains at the Nechalacho REE deposit were continuously formed by leaching and/or dissolution of type‐2 zircon in the presence of F‐ and/or CO₃‐rich hydrothermal fluid. These mineral associations indicate that three representative hydrothermal stages were present and related to HFSE enrichment in the Nechalacho REE deposit: (i) F‐rich hydrothermal stage caused the crystallization of REE–Nb‐rich zircon (type‐2 rim and type‐3), with abundant formation of phlogopite and fluorite; (ii) F‐ and CO₃‐rich hydrothermal stage led to the replacement of a part of REE–Nb–F‐rich zircon by REE fluorocarbonate; and (iii) CO₃‐rich hydrothermal stage resulted in crystallization of the REE–Nb–F‐poor zircon and fergusonite, with ankerite. REE and Nb in hydrothermal fluid at the Nechalacho REE deposit were finally concentrated into fergusonite by way of REE–Nb–F‐rich zircon in the hydrothermally altered units.     

Geological Characteristics and Zircon U‐Pb Dating of Volcanic Rocks from the Beizhan Iron Deposit in Western Tianshan Mountains,Xinjiang, NW China

The Beizhan large iron deposit located in the east part of the Awulale metallogenic belt in the western Tianshan Mountains is hosted in the Unit 2 of the Dahalajunshan Formation as lens, veinlets and stratoid, and both of the hanging wall and footwall are quartz-monzonite; the dip is to the north with thick and high-grade ore bodies downwards. Ore minerals are mainly magnetite with minor sulfides, such as pyrite, pyrrhotite, chalcopyrite and sphalerite. Skarnization is widespread around the ore bodies, and garnet, diopside, wollastonite, actinolite, epidote, uralite, tourmaline sericite and calcite are ubiquitous as gangues. Radiating outwards from the center of the ore body the deposit can be classified into skarn, calcite, serpentinite and marble zones. LA-ICP-MS zircon U-Pb dating of the rhyolite and dacite from the Dahalajunshan Formation indicates that they were formed at 301.3±0.8 Ma and 303.7±0.9 Ma, respectively, which might have been related to the continental arc magmatism during the late stage of subduction in the western Tianshan Mountains. Iron formation is genetically related with volcanic eruption during this interval. The Dahalajunshan Formation and the quartz-monzonite intrusion jointly control the distribution of ore bodies. Both ore textures and wall rock alteration indicate that the Beizhan iron deposit is probably skarn type.     

Chemical and Isotopic Characteristics of the Kuroko‐Forming Volcanism

The Miocene northeast Honshu magmatic arc, Japan, formed at a terrestrial continental margin via a stage of spreading in a back‐arc basin (23–17 Ma) followed by multiple stages of submarine rifting (19–13 Ma). The Kuroko deposits formed during this period, with most forming during the youngest rifting stage. The mode of magma eruption changed from submarine basalt lava flows during back‐arc basin spreading to submarine bimodal basalt lava flows and abundant rhyolitic effusive rocks during the rifting stage. The basalts produced during the stage of back‐arc basin spreading are geochemically similar to mid‐ocean ridge basalt, with a depleted Sr–Nd mantle source, whereas those produced during the rifting stage possess arc signatures with an enriched mantle source. The Nb/Zr ratios of the volcanic rocks show an increase over time, indicating a temporal increase in the fertility of the source. The Nb/Zr ratios are similar in basalts and rhyolites from a given rift zone, whereas the Nd isotopic compositions of the rhyolites are less radiogenic than those of the basalts. These data suggest that the rhyolites were derived from a basaltic magma via crystal fractionation and crustal assimilation. The rhyolites associated with the Kuroko deposits are aphyric and have higher concentrations of incompatible elements than do post‐Kuroko quartz‐phyric rhyolites. These observations suggest that the aphyric rhyolite magma was derived from a relatively deep magma chamber with strong fractional crystallization. Almost all of the Kuroko deposits formed in close temporal relation to the aphyric rhyolite indicating a genetic link between the Kuroko deposits and highly differentiated rhyolitic magma.     

Numerical Simulation of 3D Borehole‐to‐Surface Electrical Method

The anomaly response characteristics of the vertical line‐source 3D borehole‐to‐surface model are simulated by an adaptive finite element method. The calculation shows that the anomaly in the radial direction is pressed and the closer to the source, the more pronounced, the anomaly is stretched in the direction perpendicular to the radius. Adding a B pole in the Y direction can offset the effect of stretching to some extent. The anomaly that is closer to the source of the profile is clearer than the anomaly that is far from the source. The research results are of great significance for guiding the practical application of the borehole‐to‐surface electrical method.     

GGR Biennial Critical Review: Analytical Developments Since 2014

This GGR biennial critical review covers developments and innovations in key analytical methods published since January 2014, relevant to the chemical, isotopic and crystallographic characterisation of geological and environmental materials. In nine selected analytical fields, publications considered to be of wide significance are summarised, background information is provided and their importance evaluated. In addition to instrumental technologies, this review also presents a summary of new developments in the preparation and characterisation of rock, microanalytical and isotopic reference materials, including a précis of recent changes and revisions to ISO guidelines for reference material characterisation and reporting. Selected reports are provided of isotope ratio determinations by both solution nebulisation MC‐ICP‐MS and laser ablation‐ICP‐MS, as well as of radioactive isotope geochronology by LA‐ICP‐MS. Most of the analytical techniques elaborated continue to provide new applications for geochemical analysis; however, it is noted that instrumental neutron activation analysis has become less popular in recent years, mostly due to the reduced availability of nuclear reactors to act as a neutron source. Many of the newer applications reported here provide analysis at increasingly finer resolution. Examples include atom probe tomography, a very sensitive method providing atomic scale information, nanoscale SIMS, for isotopic imaging of geological and biological samples, and micro‐XRF, which has a spatial resolution many orders of magnitude smaller than conventional XRF.