Isotope Ratio Determination in the Earth and Environmental Sciences: Developments and Applications in 2006–2007

This review documents developments and applications in the field of isotope ratio determination, as reflected in the literature for the Earth and Environmental Sciences for the years 2006 and 2007. The emphasis is predominantly on applications, reflecting the enormous diversity of problems to which isotopic analysis can now be applied, but viewed in the context of rapid uptake of new analytical technologies and significant new drivers of research output.     

GGR Critical Review of Analytical Developments in 2006–2007

In 2005 the Geostandards and Geoanalytical Research editorial team, in the true spirit of scientific endeavour, embarked on an experiment of our own. We decided to trial a new kind of review, somewhat different from those more typically observed in journals, and one that would provide readers with a summary of analytical developments across a broad range of topics appropriate to the Earth sciences. The first contribution of this kind appeared in 2005, and reported on developments in 2003 (Hergt et al. 2005). The second, this time a biennial review, was published in 2006 and reported on highlights of the 2004 and 2005 literature (Hergt et al. 2006). Based on reprint requests, positive remarks at conferences and strong citations we consider the experiment a resounding success and proudly present here the third in this series. This comprises six individual review sections that cover the main analytical technologies and topical application fields in geoanalysis and geochemistry, including geological and environmental reference materials, ICP‐thermal and secondary ionisation‐mass spectrometry, as well as neutron activation analysis, X‐ray fluorescence and atomic absorption spectrometry.     

结合图像信息的快速点云拼接算法

现有三维激光扫描设备通常配有一个同轴相机,它可以对扫描场景进行拍摄。针对带有同轴相机的激光扫描设备,本文提出了一种结合图像信息的快速点云拼接算法。与传统拼接算法同时计算点云间的旋转和平移变换不同,本文对这两种变换分别进行求解。其中,不同扫描点云间的旋转变换是利用视觉几何知识由同轴相机在不同扫描站点下拍摄的图像直接获得,而平移变换是由本文提出的改进ICP算法得到。在改进的ICP算法中,只有平移变换的3个未知量被迭代计算,其输入是去除旋转变换后的点云。试验结果表明利用图像获得的点云旋转变换具有很高的准确性;并且由于本文算法中迭代过程只针对平移变换的3个变量进行计算,因此与需要迭代计算6个变量的传统ICP算法相比,本文算法计算复杂度大幅降低,同时更易收敛于全局最优值且收敛速度有所提高。     

U‐Th Zircon Dating by Laser Ablation Single Collector Inductively Coupled Plasma‐Mass Spectrometry (LA‐ICP‐MS)

Zircon crystals in the age range of ca. 10–300 ka can be dated by ²³⁰Th/²³⁸U (U‐Th) disequilibrium methods because of the strong fractionation between Th and U during crystallisation of zircon from melts. Laser ablation inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) analysis of nine commonly used reference zircons (at secular equilibrium) and a synthetic zircon indicates that corrections for abundance sensitivity and dizirconium trioxide molecular ions (Zr₂O₃⁺) are critical for reliable determination of ²³⁰Th abundances in zircon. When corrected for abundance sensitivity and interferences, mean activity ratios of (²³⁰Th)/(²³⁸U) for nine reference zircons analysed on five different days averaged 0.995 ± 0.023 (95% confidence weighted by data‐point uncertainty only, MSWD = 1.6; n = 9), consistent with their U‐Pb ages > 4 Ma that imply equilibrium for all intermediate daughter isotopes (including ²³⁰Th) within the ²³⁸U decay chain. U‐Th zircon ages generated by LA‐ICP‐MS without mitigating (e.g., by high mass resolution) or correcting for abundance sensitivity and molecular interferences on ²³⁰Th are potentially unreliable. To validate the applicability of LA‐ICP‐MS to this dating method, we acquired data from three late Quaternary volcanic units: the 41 ka Campanian Ignimbrite (plutonic clasts), the 161 ka Kos Plateau Tuff (juvenile clasts) and the 12 ka Puy de Dôme trachyte lava (all eruption ages by Ar/Ar, with zircon U‐Th ages being of equal or slightly older). A comparison of the corrected LA‐ICP‐MS results with previously published secondary ion mass spectrometry (SIMS) data for these rocks shows comparable ages with equivalent precision for LA‐ICP‐MS and SIMS, but much shorter analysis durations (~ 2 min vs. ~ 15 min) per spot with LA‐ICP‐MS and much simpler sample preparation. Previously undated zircons from the Yali eruption (Kos‐Nisyros volcanic centre, Greece) were analysed using this method. This yielded a large age spread (~ 45 to > 300 ka), suggesting significant antecryst recycling. The youngest zircon age (~ 45 ± 10 ka) provides a reasonable maximum estimate for the eruption age, in agreement with the previously published age using oxygen isotope stratigraphy (~ 31 ka).     

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.     

High‐Precision Mass‐Dependent Molybdenum Isotope Variations in Magmatic Rocks Determined by Double‐Spike MC‐ICP‐MS

Small mass‐dependent variations of molybdenum isotope ratios in oceanic and island arc rocks are expected as a result of recycling altered oceanic crust and sediments into the mantle at convergent plate margins over geological timescales. However, the determination of molybdenum isotope data precise and accurate enough to identify these subtle isotopic differences remains challenging. Large sample sizes – in excess of 200 mg – need to be chemically processed to isolate enough molybdenum in order to allow sufficiently high‐precision isotope analyses using double‐spike MC‐ICP‐MS techniques. Established methods are either unable to process such large amounts of silicate material or require several distinct chemical processing steps, making the analyses very time‐consuming. Here, we present a new and efficient single‐pass chromatographic exchange technique for the chemical isolation of molybdenum from silicate and metal matrices. To test our new method, we analysed USGS reference materials BHVO‐2 and BIR‐1. Our new data are consistent with those derived from more involved and time‐consuming methods for these two reference materials previously published. We also provide the first molybdenum isotope data for USGS reference materials AGV‐2, the GSJ reference material JB‐2 as well as metal NIST SRM 361.     

Determination of Gold in e‐Waste Dust Samples and Geological Matrices by ICP‐MS after Extraction by an HClO4‐HBr‐HI‐Aqua Regia Mixture

This study describes two methods (Procedures‐1 and ‐2) for the direct extraction of Au by an inorganic acid mixture (HClO₄‐HBr‐HI‐aqua regia) from complex sample matrices. Standard PTFE jars at 200 °C were used to decompose test portions of 0.5–1 g, with subsequent precise and accurate analysis by ICP‐MS without any other preconcentration or separation. Procedure‐1 decomposed samples effectively without the necessity of leaching with HF and was developed for dust samples from e‐waste (electronic waste) processing; however, testing on geological reference materials showed very good results. The analyses of replicate decompositions (n = 5) from both procedures yielded very good precision (< 5% RSD) for most of the reference materials. The accuracy achieved was better than ± 10%, with the exception of NIST SRM 2782 data from Procedure‐1. Two unknown samples of dust from e‐waste processing (P‐1 and VM‐1) exhibited elevated concentrations of Au (21.31–61.64 μg g^?1) with precision better than 10% (n = 5). The proposed techniques are simple, sensitive and sparing in the use of chemicals, and are designed for a variety of e‐waste dust samples. No significant influences were observed for the predicted spectral interferences on mass ¹⁹⁷Au.     

Barium Isotopic Compositions of Geological Reference Materials

The interest in variations of barium (Ba) stable isotope amount ratios in low and high temperature environments has increased over the past several years. Characterisation of Ba isotope ratios of widely available reference materials is now required to validate analytical procedures and to allow comparison of data obtained by different laboratories. We present new Ba isotope amount ratio data for twelve geological reference materials with silicate (AGV‐1, G‐2, BHVO‐1, QLO‐1, BIR‐1, JG‐1a, JB‐1a, JR‐1 and JA‐1), carbonate (IAEA‐CO‐9) and sulfate matrices (IAEA‐SO‐5 and IAEA‐SO‐6) relative to NIST SRM 3104a. In addition, two artificially fractionated in‐house reference materials BaBe12 and BaBe27 (δ^137/134Ba = ?1.161 ± 0.049‰ and ?0.616 ± 0.050‰, respectively) are used as quality control solutions for the negative δ‐range. Accuracy of our data was assessed by interlaboratory comparison between the University of Bern and the United States Geological Survey (USGS). Data were measured by MC‐ICP‐MS (Bern) and TIMS (USGS) using two different double spikes for mass bias correction (¹³⁰Ba–¹³⁵Ba and ¹³²Ba–¹³⁶Ba, respectively). MC‐ICP‐MS measurements were further tested for isobaric and non‐spectral matrix effects by a number of common matrix elements. The results are in excellent agreement and suggest data accuracy.     

电感耦合等离子体质谱仪测定可可西里冰芯样品中超痕量Cd和Pb

介绍了利用电感耦合等离子体质谱仪(ICPMS)直接测定冰芯样品中超痕量重金属Cd和Pb的实验和分析方法,用国家一级标准溶液进行分析过程中的质量控制.仪器对测定浓度在20～100ng·L^-1之间Pb的分析精度<10%,对浓度在5～100ng·L^-1Cd的分析精度<10%,标准加入回收率在85%～107%之间.Cd和Pb的检测下限分别为0.62ng·L^-1和0.15ng·L^-1.初步探索了冰芯外部被污染部分的去除方法,给出了实验结果,并利用此方法对青藏高原马兰冰川的一根22m深冰芯进行了处理,分析了其中的Cd和Pb的浓度。     

LA‐ICP‐MS Zircon U‐Pb Dating of Intermediate‐Acidic Intrusive Rocks and Molybdenite Re‐Os Dating from the Bangpu Mo (Cu) Deposit,Tibet and its Geological Implication

The multi-stage intrusions of intermediate-acid magma occur in the Bangpu mining district, the petrogenic ages of which have been identified. The times and sequences of their emplacement have been collated and stipulated in detail in this paper by using the laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) zircon U-Pb dating method. The ages of biotite monzogranite that were formed before mineralization in the southwest of this mining district are 70±1?Ma (mean square of weighted deviates (MSWD) =9.5, n=8) and 60.60±0.31?Ma (MSWD=3.8, n=16), which belong to the late Cretaceous–early Paleocene in age. That means, they are products of an early tectonic-magmatic event of the collision between the Indian and Asian continentals. The ages of ore-bearing monzogranite porphyry and ore-bearing diorite porphyrite are 16.23±0.19?Ma (MSWD=2.0, n=26) and 15.16±0.09?Ma (MSWD=3.9, n=5) separately, which belong to the middle Miocene in age; namely, they are products of the Gangdese post-collision extensional stage when crust-mantle materials melted and mixed as well as magmatic intrusion simultaneously occurred. Some zircons with ages of 203.6±2.2?Ma (MSWD=1.18, n=7) were captured in the ore-bearing diorite porphyrite, which shows that there had been tectono-magmatic events in the late Triassic–early Jurassic. Molybdenum (copper) ore-bodies produced in the monzogranite porphyry and copper (molybdenum) ore-bodies produced in the diorite porphyrite are the main ore types in this ore deposit. The model ages of Re-Os isotopic dating for the 11 molybdenite are 13.97–15.84?Ma, while isochron ages are 14.09±0.49?Ma (MSWD=26). The isochron ages of seven molybdenite from molybdenum (copper) ore with monzogranite porphyry type are 14.11±0.31?Ma (MSWD=5.2). There is great error in the isochron ages of four molybdenite from copper (molybdenum) ore with diorite porphyrite type, and their weighted average model ages of 14.6±1.2?Ma (MSWD=41), which generally represent the mineralization age. The results about the Re-Os isotopic dating of molybdenite in the ore of different types have limited exactly that, the minerlazation age of this ore deposits is about 14.09?Ma, which belongs to the middle Miocene mineralization. The Bangpu deposit has a uniform metallogenic dynamics background with the porphyry type and skarn-type deposits such as Jiama, Qulong and others.