Determination of Platinum‐Group Elements and Re‐Os Isotopes using ID‐ICP‐MS and N‐TIMS from a Single Digestion after Two‐Stage Column Separation

We report an improved procedure for the determination of the platinum‐group elements (PGE) and Re, and Os isotopes from a single sample aliquot by isotope dilution (ID) using inductively coupled plasma‐mass spectrometry (ICP‐MS) and negative thermal ionisation mass spectrometry (N‐TIMS), respectively. A two‐stage column method was used to purify PGE‐Re from their sample matrix and interfering elements (e.g., Mo, Zr and Hf) after Os had been separated by CCl₄ solvent extraction. The first column separation step used cation exchange resin (AG50W‐X8) to concentrate PGE‐Re and some potential interfering elements (e.g., Mo, Zr and Hf). In the second step, N‐benzoyl‐N‐phenylhydroxylamine (BPHA) extraction resin was used to separate PGE‐Re from the remaining interfering elements, which all remained strongly absorbed to the resin. The method was used to determine the PGE and rhenium, and Os isotope ratios in a range of geochemical reference materials (TDB‐1, WGB‐1, BHVO‐2 and UB‐N). The obtained results agree well with those previously published. This new method enables PGE‐Re abundances and Os isotopic ratios to be determined on the same sample digestion, and circumvents the problems created by sample heterogeneity when comparing PGE and Re‐Os isotope data.     

Accurate and High‐Precision Determination of Boron Isotopic Ratios at Low Concentration by MC‐ICP‐MS (Neptune)

We report an approach for the accurate and reproducible measurement of boron isotope ratios in natural waters using an MC‐ICP‐MS (Neptune) after wet chemistry sample purification. The sample matrix can induce a drastic shift in the isotopic ratio by changing the mass bias. It is shown that, if no purification is carried out, the direct measurement of a seawater diluted one hundred times will induce an offset of ?7‰ in the isotopic ratio, and that, for the same concentration, the greater the atomic mass of the matrix element, the greater the bias induced. Whatever the sample, it is thus necessary to remove the matrix. We propose a method adapted to water samples allowing purification of 100 ng of boron with a direct recovery of boron in 2 ml of 3% v/v HNO₃, which was our working solution. Boron from the International Atomic Energy Agency IAEA‐B1 seawater reference material and from the two groundwater reference materials IAEA‐B2 and IAEA‐B3, was chemically purified, as well as boron from the certified reference material NIST SRM 951 as a test. The reproducibility of the whole procedure (wet chemistry and MC‐ICP‐MS measurement) was ± 0.4‰ (2s). Accuracy was verified by comparison with positive‐TIMS values and with recommended values. Seawater, being homogeneous for boron isotope ratios, is presently the only natural water material that is commonly analysed for testing accuracy worldwide. We propose that the three IAEA natural waters could be used as reference samples for boron isotopes, allowing a better knowledge of their isotopic ratios, thus contributing to the certification of methods and improving the quality of the boron isotopic ratio measurements for all laboratories.     

ICP法测定化探矿样中的微量元素

介绍在ＰＡＮ－铜试剂－柠檬酸体系中分离富集、ＩＣＰ－１００型仪器同时测定化探样品中微量铜、铅、锌、镉、钴、镍６元素的新方法     

Chemical Characterization of Carbonated Natural Mineral Waters Produced in Turkey: Compliance with European Water Quality Standards

In this study, a total of 100 samples from 25 brands of carbonated natural mineral waters (CNMWs) produced in Turkey were analyzed for a total of 36 water quality constituents to determine their suitability for human consumption. Parameters examined include pH, electrical conductivity, ammonia, nitrate, nitrite, sulfate, sulfite, orthophosphate, chloride, fluoride, bicarbonate, and 25 major/trace elements analyzed by inductively coupled plasma‐mass spectrometry (ICP‐MS). The presence of these constituents in this type of water was investigated considering recent concerns about their quality and the lack of trace element information on the manufacturer labels. The analytical results obtained in this study were compared to the European Union (EU) norms, labeled values on bottles, as well as values from the literature. Results of this study have shown that Turkish CNMWs may contain high concentrations of sulfite, which is a known allergen, especially for chronic asthmatic population. CNMWs surveyed in this study have also appreciable amounts of fluoride (>1.5 mg L^?1) that may have detrimental effects on health of children. The EU standards for As, Ba, Mn, and Ni were exceeded in seven CNMWs classified as “high mineral”. Compared to similar type of bottled waters from Europe and North America, CNMWs from Turkey generally contained higher elemental concentrations.     

Natural Obsidian Glass as an External Accuracy Reference Material in Laser Ablation‐Inductively Coupled Plasma‐Mass Spectrometry

Compared with solution ICP‐MS, LA‐ICP‐MS studies have thus far reported comparatively few external reference data for accuracy estimates of experiments. This is largely the result of a paucity of available reference materials of natural composition. Here, we report an evaluation of natural glass (obsidian) as an inexpensive and widely available external reference material. The homogeneity of over forty elements in six different obsidian samples was assessed by LA‐ICP‐MS. Accuracy was tested with two obsidian samples that were fully characterised by electron probe microanalysis and solution ICP‐MS. Laser ablation experiments were performed with a variety of ablation parameters (fluence, spot sizes, ablation repetition rates) and calibration approaches (natural vs. synthetic reference materials, and different internal standard elements) to determine the best practice for obsidian analysis. Furthermore, the samples were analysed using two different laser wavelengths (193 nm and 213 nm) to compare the effect of potential ablation‐related phenomena (e.g., fractionation). Our data indicate that ablation with fluences larger than 6 J cm^?2 and repetition rates of 5 or 10 Hz resulted in the most accurate results. Furthermore, synthetic NIST SRM 611 and 612 glasses worked better as reference materials compared with lower SiO₂ content reference materials (e.g., BHVO‐2G or GOR128‐G). The very similar SiO₂ content of the NIST SRM glasses and obsidian (i.e., matrix and compositional match) seems to be the first‐order control on the ablation behaviour and, hence, the accuracy of the data. The use of different internal standard elements for the quantification of the obsidian data showed that Si and Na yielded accurate results for most elements. Nevertheless, for the analysis of samples with high SiO₂ concentrations, it is recommended to use Si as the internal standard because it can be more precisely determined by electron probe microanalysis. At the scale of typical LA analyses, the six obsidian samples proved to be surprisingly homogenous. Analyses with a spot size of 80 μm resulted in relative standard deviations (% RSD) better than 8% for all but the most depleted elements (e.g., Sc, V, Ni, Cr, Cu, Cd) in these evolved glasses. The combined characteristics render obsidian a suitable, inexpensive and widely available, external quality‐control material in LA‐ICP‐MS analysis for many applications. Moreover, obsidian glass is suited for tuning purposes, and well‐characterised obsidian could even be used as a matrix‐matched reference material for a considerable number of elements in studies of samples with high SiO₂ contents.     

The Design of Re‐usable Carius Tubes for the Determination of Rhenium,Osmium and Platinum‐Group Elements in Geological Samples

The traditional Carius tube technique is cumbersome and requires skilful work to seal the Carius tube, which can be used only once. We describe a modification to the technique that does not require the use of a high‐temperature welding torch to melt the Carius tube to seal it. The newly designed Carius tube consists of a main body with a 3 mm‐thick glass wall, a neck and head with walls 4 mm in thickness, and an efficient screw‐thread stopper. These new features allowed the tube to be used repeatedly. We demonstrate relatively low procedural blanks derived for Re and Os, and platinum‐group elements (PGEs), using the redesigned tube. A temperature of 220 °C could be reached for about 5 ml of HNO₃ for a 47 ml tube and for 32 ml of inverse aqua regia for a 200 ml tube. This digestion technique can be used for routine analysis of Re and PGEs in geological samples.     

In Situ Quantitative Measurement of Rare Earth Elements in Uranium Oxides by Laser Ablation‐Inductively Coupled Plasma‐Mass Spectrometry

Advances in the quantification of rare earth elements (REE) at the micrometric scale in uranium oxides by laser ablation‐inductively coupled plasma‐mass spectrometry are described. The determination of the best analytical conditions was tested using a uranium oxide (Mistamisk) the concentrations of REE in which were previously estimated by other techniques. Comparison between the use of U or Pb as an internal standard clearly showed a diameter‐dependent fractionation effect related to Pb at small crater diameters (16 and 24 μm), which was not found for U. The quantification of REE contents in uranium oxide samples using both matrix‐matched (uranium oxide) and non‐matrix‐matched (NIST SRM 610 certified glass) external calibrators displayed no significant difference, demonstrating a limited matrix effect for REE determination by LA‐ICP‐MS. Moreover, no major interferences on REEs were detected. The proposed methodology (NIST SRM 610 as external calibrator and U as internal standard) was applied to samples from uranium deposits from around the world. The results showed that LA‐ICP‐MS is a suitable analytical technique to determine REE down to the μg g^?1 level in uranium oxides at the micrometre scale and that this technique can provide significant insights into uranium metallogeny.     

Towards 3D lidar point cloud registration improvement using optimal neighborhood knowledge

Automatic 3D point cloud registration is a main issue in computer vision and remote sensing. One of the most commonly adopted solution is the well-known Iterative Closest Point (ICP) algorithm. This standard approach performs a fine registration of two overlapping point clouds by iteratively estimating the transformation parameters, assuming good a priori alignment is provided. A large body of literature has proposed many variations in order to improve each step of the process (namely selecting, matching, rejecting, weighting and minimizing). The aim of this paper is to demonstrate how the knowledge of the shape that best fits the local geometry of each 3D point neighborhood can improve the speed and the accuracy of each of these steps. First we present the geometrical features that form the basis of this work. These low-level attributes indeed describe the neighborhood shape around each 3D point. They allow to retrieve the optimal size to analyze the neighborhoods at various scales as well as the privileged local dimension (linear, planar, or volumetric). Several variations of each step of the ICP process are then proposed and analyzed by introducing these features. Such variants are compared on real datasets with the original algorithm in order to retrieve the most efficient algorithm for the whole process. Therefore, the method is successfully applied to various 3D lidar point clouds from airborne, terrestrial, and mobile mapping systems. Improvement for two ICP steps has been noted, and we conclude that our features may not be relevant for very dissimilar object samplings.     

U–Pb zircon age from the radiolarian‐bearing Hitoegane Formation in the Hida Gaien Belt,Japan

The dating of radiolarian biostratigraphic zones from the Silurian to Devonian is only partially understood. Dating the zircons in radiolarian‐bearing tuffaceous rocks has enabled us to ascribe practical ages to the radiolarian zones. To extend knowledge in this area, radiometric dating of magmatic zircons within the radiolarian‐bearing Hitoegane Formation, Japan, was undertaken. The Hitoegane Formation is mainly composed of alternating beds of tuffaceous sandstones, tuffaceous mudstones and felsic tuff. The felsic tuff and tuffaceous mudstone yield well‐preserved radiolarian fossils. Zircon grains showing a U–Pb laser ablation–inductively coupled plasma–mass spectrometry age of 426.6 ± 3.7 Ma were collected from four horizons of the Hitoegane Formation, which is the boundary between the Pseudospongoprunum tauversi to Futobari solidus–Zadrappolus tenuis radiolarian assemblage zones. This fact strongly suggests that the boundary of these assemblage zones is around the Ludlowian to Pridolian. The last occurrence of F. solidus is considered to be Pragian based on the reinterpretation of a U–Pb sensitive high mass‐resolution ion microprobe (SHRIMP) zircon age of 408.9 ± 7.6 Ma for a felsic tuff of the Kurosegawa belt, Southwest Japan. Thus the F. solidus–Z. tenuis assemblage can be assigned to the Ludlowian or Pridolian to Pragian. The present data also contribute to establishing overall stratigraphy of the Paleozoic rocks of the Fukuji–Hitoegane area. According to the Ordovician to Carboniferous stratigraphy in this area, Ordovician to Silurian volcanism was gradually reduced to change the sedimentary environment into a tropical lagoon in the early Devonian. And the quiet Carboniferous environment was subsequently interrupted, throwing it once more into the volcanic conditions in the Middle Permian.     

The San Gregorio Magno lacustrine basin (Campania,southern Italy): improved characterization of the tephrostratigraphic markers based on trace elements and isotopic data

Central–southern Italy is one of the most suitable areas in the world for tephrostratigraphic studies, owing to the numerous volcanic sources with explosive activity during the Pleistocene. This work presents a systematic investigation of the chemical (trace elements) and isotopic (Sr and Nd) compositions of the main tephra markers within lacustrine sediments of the San Gregorio Magno Basin (Campania, southern Italy). This study: (i) provides full geochemical (trace elements and isotopes) characterization of eight significant Upper Pleistocene marker layers (X‐6, X‐5, C‐22, MEGT/Y‐7, CI/Y‐5, C‐10, Y‐3, NYT/C2) widely dispersed over the Mediterranean area; (ii) proposes a new tephra marker for Marine Isotope Stage 7, dated to 240 ka; and (iii) refines the correlations of tephra levels belonging to the investigated sequence. This study highlights that in most cases the Nd isotope composition of the glass and Sr isotope composition of the coexisting minerals are more reliable than ⁸⁷Sr/⁸⁶Sr of the glass, and hence is more helpful as a further tool for tephrostratigraphic correlations, as recently proposed in the literature. Moreover, this study is a first step towards the construction of a complete geochemical database for future tephra investigations in the Mediterranean area. Copyright © 2019 John Wiley & Sons, Ltd.