Homogeneity of the Geochemical Reference Material BRP-1 (Paraná Basin Basalt) and Assessment of Minimum Mass

Reference materials (RM) are required for quantitative analyses and their successful use is associated with the degree of homogeneity, and the traceability and confidence limits of the values established by characterisation. During the production of a RM, the chemical characterisation can only commence after it has been demonstrated that the material has the required level of homogeneity. Here we describe the preparation of BRP-1, a proposed geochemical reference material, and the results of the tests to evaluate its degree of homogeneity between and within bottles. BRP-1 is the first of two geochemical RM being produced by Brazilian institutions in collaboration with the United States Geological Survey (USGS) and the International Association of Geoanalysts (IAG). Two test portions of twenty bottles of BRP-1 were analysed by wavelength dispersive-XRF spectrometry and major, minor and eighteen trace elements were determined. The results show that for most of the investigated elements, the units of BRP-1 were homogeneous at conditions approximately three times more rigorous than those strived for by the test of "sufficient homogeneity". Furthermore, the within bottle homogeneity of BRP-1 was evaluated using small beam (1 mm²) synchrotron radiation XRF spectrometry and, for comparison, the USGS reference materials BCR-2 and GSP-2 were also evaluated. From our data, it has been possible to assign representative minimum masses for some major constituents (1 mg) and for some trace elements (1-13 mg), except Zr in GSP-2, for which test portions of 74 mg are recommended.     

Rapid screening of Zr-containing particles from Chang’e-5 lunar soil samples for isotope geochronology: Technical roadmap for future study

New samples returned by China Chang’e-5 (CE-5) mission offer an opportunity for studying the lunar geologic longevity, space weathering, and regolith evolution. The age determination of the CE-5 samples was among the first scientific questions to be answered. However, the precious samples, most in the micrometer size range, challenge many traditional analyses on large single crystals of zircon developed for massive bulk samples. Here, we developed a non-destructive rapid screening of individual zirconium-containing particle for isotope geochronology based on a Micro X-ray fluorescence analysis (µXRF). The selected particles were verified via scanning electron microscopy (SEM), 3D X-ray microscopy (XRM), and focused ion beam scanning electron microscopy (FIB-SEM) techniques, which showed that zirconium-bearing minerals with several microns were precisely positioned and readily suitable for site-specific isotopic dating by second ion mass spectrometry (SIMS). Such protocol could be also applicable in non-destructively screening other types of particles for different scientific purposes. We therefore proposed a correlative workflow for comprehensively studying the CE-5 lunar samples from single particles on nanometer to atomic scales. Linking various microscopic and spectromicroscopic instruments together, this workflow consists of six steps: (1) single-particle selection with non-destructive µXRF technique, (2) 2D/3D morphological and structural characterization with a correlative submicron 3D XRM and nanoscale resolution FIB-SEM imaging methods, (3) SEM analysis of the surface morphology and chemistry of the selected particle, (4) a series of microscopic and microbeam analyses (e.g., SEM, electron probe microanalysis, and SIMS) on the cross-section of the selected particle to obtain structural, mineralogical, chemical, and isotopic features from the micron to nanometer scale, (5) advanced 2D/3D characterization and site-specific sample preparation of thin foil/tip specimens on a microregion of interest in the selected particle with FIB-SEM technique, and (6) comprehensive analyses on the FIB-milled specimens at nanometer to atomic scale with synchrotron-based scanning transmission X-ray microscopy, analytic transmission electron microscopy, and atom probe tomography. Following this technical roadmap, one can integrate multiple modalities into a uniform frame of multimodal and multiscale correlated datasets to acquire high-throughput information on the limited or precious terrestrial and extraterrestrial samples.     

Analysis of Sediments and Soils by X-Ray Fluorescence Spectrometry Using Matrix Corrections Based on Fundamental Parameters

Wavelength dispersive X-ray fluorescence spectrometry (WD-XRF) is widely used for the analysis of soils and sediments using well characterised procedures. However, difficulties can occur with samples such as unknowns containing small amounts of ore materials and samples collected from contaminated sites where trace elemental concentrations can exceed the concentration range for routine analysis. We studied the performance of a commercially available method, based on fundamental parameters (FP) to correct matrix effects. The spectrometer was originally calibrated with elemental or simple compound calibrants. Samples were analysed as pressed powder pellets. Eighteen sediment and soil reference materials, three of them with certified values for some of their constituents, were used to evaluate accuracy, by comparing results with recommended values and their standard deviations (RV ± 2s) or certified values and their confidence intervals (CV ± Cl). When results fell systematically outside these intervals, calibrations were refined with geochemical reference materials. The best agreement of results with recommended and certified values was obtained when the contents of H₂O and C in each sample were included as matrix constituents during calculations. The detection limits of trace elements tended to be relatively high, because the measuring conditions employed were not maximised for sensitivity. The main advantage of the method tested was that it enabled the analysis of samples with high concentrations of trace elements and the determination of elements such as F, Bi, Sb and W, which are not commonly included in quantitative XRF analysis of geological samples.     

基于?－SVR和GA的初始地应力场位移反分析方法研究

基于一种改进的支持向量机（?－SVR）和改进的遗传算法（GA）,提出一种初始地应力场位移反分析方法。该方法通过正交设计方法安排较少次数的正分析方案,用?－SVR对正分析中测点位移值与参数构成的样本集进行学习,建立参数取值与观测点测值的非线性隐式方程;采用确定性或随机反分析的思路确定反分析的优化目标函数,并利用GA搜索最优参数取值。采用?－SVR方法建立的参数取值与位移量测点测值的非线性隐式方程,能够以很高的精度拟合和预测不同参数取值时的观测点测值,因此,可以用该隐式方程代替正分析,减少计算量;采用改进的GA方法能够准确搜索到最优参数;搜索到的最优参数值与理论值相当吻合。算例表明,基于?－SVR和GA的初始地应力场位移反分析方法是一种行之有效的初始地应力场位移反分析方法,可以广泛用于初始地应力场确定性反分析和随机反分析。     

GGR Biennial Review: Atomic Absorption,Inductively Coupled Plasma-Atomic Emission Spectrometry,Neutron Activation Analysis and X-Ray Fluorescence Spectrometry Review for 2008–2009

This review describes developments major and in trace element determination using atomic absorption spectroscopy (AAS), inductively coupled plasma-atomic emission spectrometry (ICP-AES), instrumental neutron activation analysis (INAA), and X-ray fluorescence (XRF) spectrometry that were reported in 2008 and 2009. Publication levels were comparable to those of previous years, except for XRF which showed an increase in the number of articles published in the past 2 years. In terms of number of publications and impact, the most active field was AAS, while INAA was the least active. As expected for well-established and mature methods, novel developments for all four analytical techniques were relatively sparse. For AAS, the most notable publications concerned developments in sample introduction, particularly focussing on solid samples, increasing analyte sensitivity, and higher sample throughput. For ICP-AES, publication of developments in sample introduction, remediation of matrix effects and calibration continues. Compared with past years, there was a clear focus on sample preconcentration methods, but very few publications reporting new hyphenated speciation methods. For INAA, there were several publications exploring the accuracy and robustness of the method, as well as the requirements for INAA to meet criteria for a primary method of measurement. Two other related techniques, delayed neutron activation analysis, and prompt gamma activation analysis, were also described. Hyphenated XRF techniques showed interesting developments in enabling XRF and XRD analysis on the same spot, and further work characterising and calibrating three-dimensional micro-XRF shows promising results for investigating sample heterogeneity.     

Deciphering the depositional environment of the laminated Crato fossil beds (Early Cretaceous,Araripe Basin,North‐eastern Brazil)

The laminated limestones of the Early Cretaceous Crato Formation of the Araripe Basin (North‐eastern Brazil) are world‐famous for their exceptionally well‐preserved and taxonomically diverse fossil fauna and flora. Whereas the fossil biota has received considerable attention, only a few studies have focused on the sedimentary characteristics and palaeoenvironmental conditions which prevailed during formation of the Crato Fossil Lagerstätte. The Nova Olinda Member represents the lowermost and thickest unit (up to 10 m) of the Crato Formation and is characterized by a pronounced rhythmically bedded, pale to dark lamination. To obtain information on palaeoenvironmental conditions, sample slabs derived from three local stratigraphic sections within the Araripe Basin were studied using high‐resolution multiproxy techniques including detailed logging, petrography, μ‐XRF scanning and stable isotope geochemistry. Integration of lithological and petrographic evidence indicates that the bulk of the Nova Olinda limestone formed via authigenic precipitation of calcite from within the upper water column, most probably induced and/or mediated by phytoplankton and picoplankton activity. A significant contribution from a benthonic, carbonate‐secreting microbial mat community is not supported by these results. Deposition took place under anoxic and, at least during certain episodes, hypersaline bottom water conditions, as evidenced by the virtually undisturbed lamination pattern, the absence of a benthonic fauna and by the occurrence of halite pseudomorphs. Input of allochthonous, catchment‐derived siliciclastics to the basin during times of laminite formation was strongly reduced. The δ¹⁸O values of authigenic carbonate precipitates (between ?7·1 and ?5·1‰) point to a ¹⁸O‐poor meteoric water source and support a continental freshwater setting for the Nova Olinda Member. The δ¹³C values, which are comparatively rich in ¹³C (between ?0·1 and +1·9‰), are interpreted to reflect reduced throughflow of water in a restricted basin, promoting equilibration with atmospheric CO₂, probably in concert with stagnant conditions and low input of soil‐derived carbon. Integration of lithological and isotopic evidence indicates a shift from closed to semi‐closed conditions towards a more open lake system during the onset of laminite deposition in the Crato Formation.     

Characterisation of Two New Reference Materials: STL-1, the Stewart Lepidolite and ZA-1, the Zapot Amazonite

The analysis of granitic pegmatites still remains a challenge because suitable natural reference materials are scarce or not available. Two new reference materials were prepared at the Smithsonian Institution, to provide an avenue to pursue the geochemical analysis of micas and feldspars in granitic pegmatites: STL-1, the Stewart lepidolite (NMNH 174041) and ZA-1, the Zapot amazonite (NMNH 174042). STL-1 was prepared from lepidolite collected from the lithium-rich Stewart pegmatite, San Diego County, California (33°22'52'N, 117°03'41'W). ZA-1 was prepared from an amazonite from the topaz-bearing Zapot pegmatite, Mineral County, Nevada, (38° 41'N, 118 °33'W). The results of this study indicated that STL-1 and ZA-1 are homogeneous and could be used as reference materials that would allow the expansion of calibration curves in XRF analysis up to 16000 μg g⁻¹ for Rb, 2000 μg g⁻¹ for Cs and 100 μg g⁻¹ for Tl. STL-1 and ZA-1 also contain unusually high concentrations of Ga and Tl, and STL-1 of Nb.     

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.     

High‐Arctic climate conditions for the last 7000 years inferred from multi‐proxy analysis of the Bliss Lake record,North Greenland

The Arctic is more vulnerable to climate change than are mid latitudes. Therefore, palaeolimnological studies from the High Arctic are important in providing insights into the dynamics of the climate system. Here we present a multi‐proxy study from one of the world's northernmost lakes: Bliss Lake, Peary Land, Greenland. The early Holocene (10 850–10 480 cal. a BP) is characterized by increased erosion and gradually more marine conditions. Full marine conditions developed from 10 480 cal. a BP until the lake was isolated at 7220 cal. a BP. From its marine isolation at 7220 cal. a BP Bliss Lake becomes a lacustrine environment. Evidence from geochemical proxies (δ¹³C and total organic carbon) suggests that warmer conditions prevailed between 7220 and 6500 cal. a BP, corresponding to the Holocene thermal maximum, and from 3300 until 910 cal. a BP. From 850 to 500 cal. a BP colder climate conditions persisted. The transition from warmer to colder climate conditions taking place around 850 cal. a BP may be associated with the transition from the Medieval Warm Period to the Little Ice Age. Copyright © 2011 John Wiley & Sons, Ltd.     

Geochemistry and origin of elements in some UK coals

Twenty-four UK coals ranging in rank with 4.6%–37.6% volatile matter were analysed for 46 major and trace elements. The samples were obtained from the UK Coal Bank and are representative of the major UK coal fields. The major element distributions are interpreted in terms of the mineralogical variations—quartz and kaolinite are largely responsible for the Si and Al, carbonates for Ca and Mg and pyrite for Fe. Also exerting an influence in some samples are siderite, Al-phosphate minerals and illite. Based on statistical relationships with the major elements, Rb, Cr, Th, Ce, Zr, Y, Ga, La, Ta, Nb and V are thought to be mainly present in the clay minerals, and As, Mo, Sb, Tl, Se and Bi and Pb are probably present in pyrite. Strontium and Ba are concentrated in a restricted number of samples related to the phosphate minerals. Germanium is the only element for which a major organic association can be demonstrated. Elements with an indirect association with the organic matter are Na, Cl, and Br in porefluids and possibly Te. The ash content is controlled mainly by the detrital input and the trace elements related to the ash content are therefore those elements associated with the clay minerals. Variations with rank would appear to be mainly related to the moisture content (porefluids). The trace elements associated with the quartz and clay minerals are thought to be dominantly detrital in origin. The non-detrital elements, essentially those contained in pyrite, are thought to have been incorporated in the depositional environment from waters with enhanced salinities through seawater ingress, hence there are positive relationships between S and trace element concentrations.