Copper Speciation in a Collection of Geochemical Reference Materials Using Sequential Extraction and Evaluation of the Validity Using XANES Spectroscopy          下载免费PDF全文

Atsuyuki Ohta  Ran Kubota 《Geostandards and Geoanalytical Research》2016,40(1):117-134

Copper speciation in a collection of Japanese geochemical reference materials (JSO‐1, JLk‐1, JSd‐1, ‐2, ‐3 and ‐4, JMs‐1 and JMs‐2) was achieved by sequential extraction and characterised using X‐ray absorption near‐edge structure spectroscopy. In the first step of the extraction, referred to as the acid fraction, between 1% and 20% total Cu within the reference materials was extracted. Such a result is typically accounted for by absorption of Cu onto clay minerals. However, the presence of Cu sulfate (an oxidation product of chalcopyrite) was observed in some of the stream sediments affected by mining activity (JSd‐2 and JSd‐3) instead. Copper was extracted in the reducible fraction (targeting Fe hydroxide and Mn oxide) (2–49% total Cu). Between 2% and 51% Cu was extracted in the oxidised fraction (targeting sulfides and organic matter). X‐ray absorption near‐edge structure spectroscopy clarified that the reducible fraction consisted of Cu bound to Fe hydroxide, whereas the oxidised fraction was a mixture of Cu bound to humic acid (HA) and Cu sulfide. In the oxidisable fraction, chalcopyrite was the predominant species identified in JSd‐2, and Cu bound to HA was the major species identified in JSO‐1 (a soil sample).  相似文献   

High Precision Sr‐Nd‐Hf‐Pb Isotopic Compositions of USGS Reference Material BCR‐2          下载免费PDF全文

Jason Jweda  Louise Bolge  Cornelia Class  Steven L. Goldstein 《Geostandards and Geoanalytical Research》2016,40(1):101-115

The Lamont‐Doherty Earth Observatory radiogenic isotope group has been systematically measuring Sr‐Nd‐Pb‐Hf isotopes of USGS reference material BCR‐2 (Columbia River Basalt 2), as a chemical processing and instrumental quality control monitor for isotopic measurements. BCR‐2 is now a widely used geochemical inter‐laboratory reference material (RM), with its predecessor BCR‐1 no longer available. Recognising that precise and accurate data on RMs is important for ensuring analytical quality and for comparing data between different laboratories, we present a compilation of multiple digestions and analyses made on BCR‐2 during the first author's dissertation research. The best estimates of Sr, Nd and Hf isotope ratios and measurement reproducibilities, after filtering at the 2s level for outliers, were ⁸⁷Sr/⁸⁶Sr = 0.705000 ± 11 (2s, 16 ppm, n = 21, sixteen digestions, one outlier), ¹⁴³Nd/¹⁴⁴Nd = 0.512637 ± 13 (2s, 25 ppm, n = 27, thirteen digestions, one outlier) and ¹⁷⁶Hf/¹⁷⁷Hf = 0.282866 ± 11 (2s, 39 ppm, n = 25, thirteen digestions, no outliers). Mean Nd and Hf values were within error of those reported by Weis et al. (2006, 2007) in their studies of RMs; mean Sr values were just outside the 2s uncertainty range of both laboratories. Moreover, a survey of published Sr‐Nd‐Hf data shows that our results fall within the range of reported values, but with a smaller variability. Our Pb isotope results on acid leached BCR‐2 aliquots (n = 26, twelve digestions, two outliers) were ²⁰⁶Pb/²⁰⁴Pb = 18.8029 ± 10 (2s, 55 ppm), ²⁰⁷Pb/²⁰⁴Pb = 15.6239 ± 8 (2s, 52 ppm), ²⁰⁸Pb/²⁰⁴Pb = 38.8287 ± 25 (2s, 63 ppm). We confirm that unleached BCR‐2 powder is contaminated with Pb, and that sufficient leaching prior to digestion is required to achieve accurate values for the uncontaminated Pb isotopic compositions.  相似文献   

An Investigation of Digestion Methods for Trace Elements in Bauxite and Their Determination in Ten Bauxite Reference Materials Using Inductively Coupled Plasma‐Mass Spectrometry          下载免费PDF全文

Wen Zhang  Liang Qi  Zhaochu Hu  Cunjiang Zheng  Yongsheng Liu  Haihong Chen  Shan Gao  Shenghong Hu 《Geostandards and Geoanalytical Research》2016,40(2):195-216

Trace elements from samples of bauxite deposits can provide useful information relevant to the exploration of the ore‐forming process. Sample digestion is a fundamental and critical stage in the process of geochemical analysis, which enables the acquisition of accurate trace element data by ICP‐MS. However, the conventional bomb digestion method with HF/HNO₃ results in a significant loss of rare earth elements (REEs) due to the formation of insoluble AlF₃ precipitates during the digestion of bauxite samples. In this study, the digestion capability of the following methods was investigated: (a) ‘Mg‐addition’ bomb digestion, (b) NH₄HF₂ open vessel digestion and (c) NH₄F open vessel digestion. ‘Mg‐addition’ bomb digestion can effectively suppress the formation of AlF₃ and simultaneously ensure the complete decomposition of resistant minerals in bauxite samples. The addition of MgO to the bauxite samples resulted in (Mg + Ca)/Al ratios ≥ 1. However, adding a large amount of MgO leads to significant blank contamination for some transition elements (V, Cr, Ni and Zn). The NH₄HF₂ or NH₄F open vessel digestion methods can also completely digest resistant minerals in bauxite samples in a short period of time (5 hr). Unlike conventional bomb digestion with HF/HNO₃, the white precipitates and the semi‐transparent gels present in the NH₄HF₂ and NH₄F digestion methods could be efficiently dissolved by evaporation with HClO₄. Based on these three optimised digestion methods, thirty‐seven trace elements including REEs in ten bauxite reference materials (RMs) were determined by ICP‐MS. The data obtained showed excellent inter‐method reproducibility (agreement within 5% for REEs). The relative standard deviation (% RSD) for most elements was < 6%. The concentrations of trace elements in the ten bauxite RMs showed agreement with the limited certified (Li, V, Cr, Cu, Zn, Ga, Sr, Zr and Pb) and information values (Co, Ba, Ce and Hf) available. New trace element data for the ten RMs are provided, some of which for the first time.  相似文献   

Production and Certification of Synthetic Selenium Isotopic Reference Materials          下载免费PDF全文

Tongxiang Ren  Jun Wang  Hai Lu  Tao Zhou  Yuanjing Zhou 《Geostandards and Geoanalytical Research》2016,40(2):227-238

Due to intensive research into selenium isotopes in recent years, the increasing requirement for reliable and comparable measurement results has created a strong demand for selenium isotopic certified reference materials (iCRM) that were previously not available. To address this, eleven selenium iCRMs were developed, including ten synthetic iCRMs (GBW 04447–GBW 04456) and one natural iCRM (GBW 04457). The synthetic iCRMs were prepared with ⁷⁶Se, ⁷⁸Se, ⁸⁰Se and ⁸²Se solutions and a natural selenium solution; the natural iCRM was prepared with highly pure selenium material. The property values of isotope ratios in these iCRMs were certified by calibrated mass spectrometry with a collision cell multi‐collector ICP‐MS. The mass discrimination effect of the instrument was corrected with corresponding ⁷⁸Se/⁷⁶Se isotope mixtures and ⁸²Se/⁷⁶Se isotope mixtures, which were gravimetrically prepared with purified, isotopically enriched selenium materials. Homogeneity and stability tests were performed, and no significant influences were found. The uncertainty of the property values of the iCRMs was evaluated according to the Guide to the Expression of Uncertainty in Measurement (GUM) of ISO/BIPM and ISO Guide 35. The δ^82/76Se value of GBW 04457 relative to NIST SRM 3149 was also calculated. These iCRMs are intended for use in calibration of instruments and evaluation of methods for the determination of selenium isotope ratios.  相似文献   

Zircon M127 – A Homogeneous Reference Material for SIMS U–Pb Geochronology Combined with Hafnium,Oxygen and,Potentially, Lithium Isotope Analysis          下载免费PDF全文

Lutz Nasdala  Fernando Corfu  John W. Valley  Michael J. Spicuzza  Fu‐Yuan Wu  Qiu‐Li Li  Yue‐Heng Yang  Chris Fisher  Carsten Münker  Allen K. Kennedy  Peter W. Reiners  Andreas Kronz  Michael Wiedenbeck  Richard Wirth  Chutimun Chanmuang  Manuela Zeug  Tamás Váczi  Nicholas Norberg  Tobias Häger  Alfred Kröner  Wolfgang Hofmeister 《Geostandards and Geoanalytical Research》2016,40(4):457-475

In this article, we document a detailed analytical characterisation of zircon M127, a homogeneous 12.7 carat gemstone from Ratnapura, Sri Lanka. Zircon M127 has TIMS‐determined mean U–Pb radiogenic isotopic ratios of 0.084743 ± 0.000027 for ²⁰⁶Pb/²³⁸U and 0.67676 ± 0.00023 for ²⁰⁷Pb/²³⁵U (weighted means, 2s uncertainties). Its ²⁰⁶Pb/²³⁸U age of 524.36 ± 0.16 Ma (95% confidence uncertainty) is concordant within the uncertainties of decay constants. The δ¹⁸O value (determined by laser fluorination) is 8.26 ± 0.06‰ VSMOW (2s), and the mean ¹⁷⁶Hf/¹⁷⁷Hf ratio (determined by solution ICP‐MS) is 0.282396 ± 0.000004 (2s). The SIMS‐determined δ⁷Li value is ?0.6 ± 0.9‰ (2s), with a mean mass fraction of 1.0 ± 0.1 μg g^?1 Li (2s). Zircon M127 contains ~ 923 μg g^?1 U. The moderate degree of radiation damage corresponds well with the time‐integrated self‐irradiation dose of 1.82 × 10¹⁸ alpha events per gram. This observation, and the (U–Th)/He age of 426 ± 7 Ma (2s), which is typical of unheated Sri Lankan zircon, enable us to exclude any thermal treatment. Zircon M127 is proposed as a reference material for the determination of zircon U–Pb ages by means of SIMS in combination with hafnium and stable isotope (oxygen and potentially also lithium) determination.  相似文献   

渤海湾海岸带地区~(137)Cs参考剖面——意义、方法及初步结果     

王福  田立柱  姜兴钰  李建芬  杨彪  袁海帆  王宏 《地质通报》2016,35(10):1622-1629

海岸带地区近百年来的现代地质过程重建必须以精确的年代学研究为基础,~(137)Cs时标法和~(210)Pb_(exc)测年法是目前广泛应用的方法。由于易受到河流沉积物供给变化、潮位状况、极端天气事件等的影响,海岸带现代过程的定量研究一直是高分辨率研究的瓶颈。区域性参考剖面可以提升现代沉积物测年方法在海岸带应用中的可靠性。因此,建立区域性的~(210)Pb_(exc)和~(137)Cs比活度-深度参考剖面,将改善对海岸带及邻近海区实测数据的解释。以渤海湾海岸带为研究区,选取沉积环境相对稳定、水平搬运作用较小的地区,采用人工探坑、Eijkelkamp槽型取样器获取了2个柱状岩心,通过γ能谱仪对样品进行~(210)Pb、~(226)Ra及~(137)Cs比活度测试,绘制剖面图,结合研究区已有数据,总结出6类海岸带常见的~(210)Pb_(exc)和~(137)Cs比活度-深度剖面类型,并重建了渤海湾海岸带~(137)Cs区域性参考剖面。结果显示,~(137)Cs在渤海湾地区的最大峰值指示1963年,可以作为区域性主要参考时标。但是,最大峰值上部的次峰在不同区域指示不同的时标,S4和S5两个站位该峰值指示的并非1986年时标。  相似文献   

A New Reference Material for Tritium Organic Molecules in Sediment: Results of an International Intercomparison Exercise          下载免费PDF全文

Phillip E. Warwick  Ian W. Croudace  Richard M. Marsh  Nicolas Baglan  Sang Bog Kim 《Geostandards and Geoanalytical Research》2018,42(2):253-262

Solid matrix ³H reference materials are challenging to prepare given the volatile nature of ³H and are often unrepresentative of the range of ³H forms that may be encountered during routine analysis. As a result, few ³H reference materials are currently available, undermining verification of analytical techniques for environmental ³H measurement. To address this, an International Working Group on Organically‐Bound Tritium Analysis determined to produce a tritium natural matrix reference material (NMRM). The reference material comprises marine sediment blended with sewage sludge contaminated with ³H‐organic species arising from authorised discharges from a radiopharmaceutical manufacturing site. Previous studies have demonstrated that the ³H species have persisted in the environment over three decades providing valuable supporting data to underpin the characterisation of the NMRM. The preparation and characterisation of the NMRM are described along with the subsequent application of the reference material in an international intercomparison exercise involving nineteen laboratories from nine countries. A reference value of 168 ± 22 Bq kg^?1 was derived from the data arising from the proficiency test.  相似文献   

Rutile R632 – A New Natural Reference Material for U‐Pb and Zr Determination          下载免费PDF全文

Emelie Axelsson  Jonas Pape  Jasper Berndt  Fernando Corfu  Klaus Mezger  Michael M. Raith 《Geostandards and Geoanalytical Research》2018,42(3):319-338

A new natural rutile reference material is presented, suitable for U‐Pb dating and Zr‐in‐rutile thermometry by microbeam methods. U‐Pb dating of rutile R632 using laser ablation ICP‐MS with both magnetic sector field and quadrupole instruments as well as isotope dilution‐thermal ionisation mass spectrometry yielded a concordia age of 496 ± 2 Ma. The high U content (> 300 μg g^?1) enabled measurement of high‐precision U‐Pb ages despite its young age. The sample was found to have a Zr content of 4294 ± 196 μg g^?1, which makes it an excellent complementary reference material for Zr‐in‐rutile thermometry. Individual rutile grains have homogeneous compositions of a number of other trace elements including V, Cr, Fe, Nb, Mo, Sn, Sb, Hf, Ta and W. This newly characterised material significantly expands the range of available rutile reference materials relevant for age and temperature determinations.  相似文献   

基于不同邻近标签数选择的LANDMARC定位算法研究     

谢亚琴  王超 《南京气象学院学报》2019,11(5):621-624

对于基于射频识别的LANDMARC室内定位算法而言,该系统采用"k近邻"算法,通过选取k个与待测标签相邻且符合特定条件的参考标签,最后根据这些标签的位置结合权值估算出待测标签的坐标信息.但是在实际的操作过程中,最近邻参考标签数的选取无指导原则,具有一定的盲目性.针对这一问题,通过选取与待定位参考点最近邻的参考节点作为未知点,通过搜索法获得最优的邻近标签数k,在随后的未知节点的定位过程中,选取k个邻近标签进行定位.经过多次实验,最终得出结论,使用改进后的LANDMARC算法的性能要优于原来经典的LANDMARC算法,精确度提升了10%左右,同时避免了k值选取的盲目性.  相似文献   

台风Chanchu(0601)变性过程中的强度变化及环境场分析     

刘珍圆  王咏青  张秀年  周玉淑 《热带气象学报》2019,35(4):528-538

利用非静力中尺度WRF模式模拟的台风Chanchu(0601)的输出资料,探讨了Chanchu减弱变性过程的强度及结构变化。分析结果表明:在台风Chanchu北移过程中,高层的暖心被破坏,强度快速减弱,眼壁对流发展高度降低,眼壁对流由对称结构演变为非对称,内核对流减弱。此减弱变性过程与惯性稳定度减小、垂直风切变增强、低层锋生等环境要素有关。惯性稳定度与台风强度变化一致,随着惯性稳定度降低,最大切向风减弱并不断外扩,Rossby变形半径增大从而潜热释放不集中难以维持台风强度,台风减弱;同时,内核区的高层暖心更易径向频散,从而高层暖心难以维持;环境的垂直风切变增强使台风的斜压性增强,台风垂直结构的倾斜度增大,对流发展高度降低;低层冷空气侵入台风中心趋于填塞,也利于台风强度减弱;台风登陆以后冷暖空气对比导致的锋生使得不稳定能量释放从而重新加强了Chanchu环流内的中低层对流活动,但较台风最强时刻而言对流强度减弱。总体减少的对流和降低的对流高度,导致潜热能释放减小,其向心输送也减少,不足以维持强暖心结构,最终使得台风减弱并变性。   相似文献