A Rapid Method for Determining Boron Concentration (ID‐ICP‐MS) and δ11B (MC‐ICP‐MS) in Vegetation Samples after Microwave Digestion and Cation Exchange Chemical Purification

We present in this article a rapid method for B extraction, purification and accurate B concentration and δ¹¹B measurements by ID‐ICP‐MS and MC‐ICP‐MS, respectively, in different vegetation samples (bark, wood and tree leaves). We developed a rapid three‐step procedure including (1) microwave digestion, (2) cation exchange chromatography and (3) microsublimation. The entire procedure can be performed in a single working day and has shown to allow full B recovery yield and a measurement repeatability as low as 0.36‰ (± 2s) for isotope ratios. Uncertainties mostly originate from the cation exchange step but are independent of the nature of the vegetation sample. For δ¹¹B determination by MC‐ICP‐MS, the effect of chemical impurities in the loading sample solution has shown to be critical if the dissolved load exceeds 5 μg g^?1 of total salts or 25 μg g^?1 of DOC. Our results also demonstrate that the acid concentration in the sample loading solution can also induce critical isotopic bias by MC‐ICP‐MS if chemistry of the rinsing‐, bracketing calibrator‐ and sample solutions is not thoroughly adjusted. We applied this method to provide a series of δ¹¹B values of vegetal reference materials (NIST SRM 1570a = 25.74 ± 0.21‰; NIST 1547 = 40.12 ± 0.21‰; B2273 = 4.56 ± 0.15‰; BCR 060 = ?8.72 ± 0.16‰; NCS DC73349 = 16.43 ± 0.12‰).     

Improved Inter‐calibration of Faraday Cup and Ion Counting for In Situ Pb Isotope Measurements Using LA‐MC‐ICP‐MS: Application to the Study of the Origin of the Fangshan Pluton,North China

A laser ablation multi‐collector inductively coupled plasma‐mass spectrometry (LA‐MC‐ICP‐MS) method was developed to obtain precise and accurate Pb isotopic ratio measurements in low‐Pb materials (< 10 μg g^?1) using a combination of Faraday cups and ion counters (FC–IC). The low abundance ²⁰⁴Pb (~ 1.4%) was collected using an IC. A NBS 981 standard solution was used to cross‐calculate the FC–IC gain and to investigate the signal response characteristics of the IC. A significant, continuous and linear decrease in the FC–IC gain was observed within 1 hr, but this drift could be corrected using the calibrator‐sample‐calibrator bracketing method. In addition, a non‐linear response of the IC used in this study was observed and corrected by a non‐linear correction algorithm, which was established by measuring a series of gravimetrically prepared NBS 981 standard solutions (NIST SRM 981). Compared with the conventional arrangement, the use of the newly designed X skimmer cone and Jet sample cone improved the signal intensities from Pb isotopes by a factor of 1.9. Compared with only Faraday cups, using a combination FC–IC array was found to enhance the measurement repeatability (RSD) of ^20xPb/²⁰⁴Pb by approximately one order of magnitude when the ²⁰⁴Pb intensity was < 8 mV. Eight natural glasses and the NIST SRM 612 reference material glass (as a calibration material) were measured to evaluate the new protocol for Pb isotope determination. The analytical results were in agreement with the reference values within 2s measurement uncertainties. For MPI‐DING ATHO‐G (5.67 μg g^?1 total Pb), KL2‐G (2.07 μg g^?1 total Pb) and ML3B‐G (1.38 μg g^?1 total Pb), the typical accuracies of ^20xPb/²⁰⁴Pb were 0.09% of preferred values with precisions of < 0.33% (2RSD). The Pb isotope ratios in feldspars from granodiorite and within mafic microgranular enclaves (MMEs) from the Fangshan pluton, North China, were measured using the present method. The Pb isotopic compositions of feldspars from the whole host granodiorite show that that are radiogenic in the margin zone and gradually become less radiogenic. For the MMEs, the Pb isotopic compositions of feldspars are highly variable and overlap with those of the whole host granodiorite. For single‐grain feldspar, the strong rim‐core‐rim variations of the Pb isotopic compositions and trace elements are interpreted to have been generated via magma mixing. These results suggest that the Fangshan pluton underwent magma mixing of mantle‐derived mafic magmas with felsic magmas, and the proportion of the mafic magma influx decreased over time.     

西昆仑慕士塔格-公格尔印支期侵入岩岩石与锆石地球化学特征及研究意义

西昆仑造山带南侧的麻扎-康西瓦缝合带,是古特提斯洋闭合的位置。慕士塔格-公格尔作为昆仑山的主峰,紧邻该缝合带的东北侧分布,主要岩性为花岗闪长岩和黑云母二长花岗岩。作者系统研究了两种岩性的地球化学及年代学特征,探讨了岩石成因,反演了古特提斯洋的构造演化历史。岩体岩浆锆石LA-ICP-MS U-Pb测年结果显示,花岗闪长岩和黑云母二长花岗岩的成岩年龄分别为(213.0±0.5)~(215.4±0.9)Ma和(220.6±0.5)~(222.1±0.4)Ma,是晚三叠世岩浆活动的产物。两种岩性均为高硅(w(SiO2)65%)、富碱(w(K2O+Na2O)6%)、钙碱性-高钾钙碱性、准铝质(A/CNK1),富集大离子亲石元素(LILE)和轻稀土元素(LREE),亏损高场强元素(HFSE)和重稀土(HREE)。微量元素组成特征、低锆石饱和温度及高分异指数显示慕士塔格-公格尔花岗岩体为高分异I型花岗岩。岩体锆石的εHf(t)值变化范围较小,为-4.46~-0.17,指示岩浆以壳源为主。综合研究表明,慕士塔格-公格尔花岗岩体可能是同碰撞造山环境下,老的下地壳受地幔热源影响部分熔融,形成的长英质壳源岩浆侵入地壳内部而冷却结晶形成。     

New ICP‐MS Results for Trace Elements in Five Iron‐Formation Reference Materials

Iron formations (IFs) typically contain low mass fractions of most trace elements, including the rare earth elements (REE), and few publications describe analytical methods dedicated to this matrix. In this study, we used bomb and table‐top acid dissolution procedures and ICP‐MS to determine the mass fractions of trace elements in IF reference materials FER‐1, FER‐2, FER‐3, FER‐4 and IF‐G. The full digestion of the IF samples with the bomb procedure required the addition of a small amount of water together with the acids. The results obtained by this method mostly agreed statistically with published values. The most remarkable exception was the higher values obtained for the heavy REE in FER‐3. The recoveries of the REE obtained with the table‐top procedure were slightly higher than those of the bomb digestion, except for the values of the heavy REE in FER‐3 and FER‐4, which were up to 30% lower than published values. Sintering of the samples with sodium peroxide was performed to determine the REE, but the results tended to be lower than those derived following acid digestion. On the whole, the recoveries showed dependence on the conditions of digestion, but subtle differences in trace mineral composition between samples also exerted influence on the analytical results for trace elements.     

Combined Separation of Cu,Fe and Zn from Rock Matrices and Improved Analytical Protocols for Stable Isotope Determination

Isotope ratios of heavy elements vary on the 1/10000 level in high temperature materials, providing a fingerprint of the processes behind their origin. Ensuring that the measured isotope ratio is precise and accurate depends on employing an efficient chemical purification technique and optimised analytical protocols. Exploiting the disparate speciation of Cu, Fe and Zn in HCl and HNO₃, an anion exchange chromatography procedure using AG1‐×8 (200–400 mesh) and 0.4 × 7 cm Teflon columns was developed to separate them from each other and matrix elements in felsic rocks, basalts, peridotites and meteorites. It required only one pass through the resin to produce a quantitative and pure isolate, minimising preparation time, reagent consumption and total analytical blanks. A ThermoFinnigan Neptune Plus MC‐ICP‐MS with calibrator‐sample bracketing and an external element spike was used to correct for mass bias. Nickel was the external element in Cu and Fe measurements, while Cu corrected Zn isotopes. These corrections were made assuming that the mass bias for the spike and analyte element was identical, and it is shown that this did not introduce any artificial bias. Measurement reproducibilities were ± 0.03‰, ± 0.04‰ and ± 0.06‰ (2s) for δ⁵⁷Fe, δ⁶⁵Cu and δ⁶⁶Zn, respectively.     

Bias in the Determination of Zr,Y and Rare Earth Element Concentrations in Selected Silicate Rocks by ICP‐MS when Using Some Routine Acid Dissolution Procedures: Evidence from the GeoPT Proficiency Testing Programme

The analytical results for the modified river sediment, SdAR‐1 circulated in Round 31 of the GeoPT proficiency testing programme, revealed unexpected discrepancies for Zr, Y and most higher atomic number rare earth elements, in determinations made by ICP‐MS using acid attack digestion methods. This investigation compares these ICP‐MS results with those obtained for SdAR‐1 by three other methods: (a) ICP‐MS using fusion/sintering for sample digestion, (b) XRF analysis and (c) INAA. The distribution of results for the elements Rb, Sr, Ce, Y, Yb and Zr is examined and compared with those of the test material for Round 25 of GeoPT, Paraná basalt, HTB‐1. A substantial proportion (though not all) of Y, Yb and Zr determinations in SdAR‐1 by ICP‐MS/acid attack was variably low (sometimes very low) compared with other methods. A detailed evaluation of the procedures used to determine these results indicated that successful determinations by ICP‐MS/acid attack could be made if digestions were made at 180 °C for 48 hr using at least 2 ml HF per 100 mg of sample. We suggest that the more benign conditions (used by many laboratories) resulted in incomplete digestion of resistant minerals, such as zircon.     

IsoSpike: Improved Double‐Spike Inversion Software

The double‐spike approach for correction of instrumental mass bias in mass spectrometry data is well established. However, there is very little consistency within the scientific community in terms of double‐spike data reduction. Double‐spike solutions require computer calculation, using either geometric or algebraic approaches, and are often performed using spreadsheet calculations that vary from group to group and between isotope systems. Here, we present IsoSpike, a generalised computer procedure for the processing of double‐spike mass spectrometry data, built as an add‐on for the Iolite data‐reduction package ( www.iolite.org.au ). Use of this software permits visualisation of mass spectrometry data in a time window, and rigorous treatment and screening of data. Additionally, IsoSpike uses an integration‐by‐integration approach where the double‐spike calculations are performed on every integration within an analysis, providing straightforward quantification of uncertainties on double‐spike‐corrected isotope ratios. The advantages of this approach over traditional methods are discussed here. Platinum stable isotope data are presented as an example data set, although the procedure is applicable to any double‐spike system. IsoSpike is freely available from www.isospike.org .     

融合反射强度图像的地铁隧道点云自动配准

针对地铁隧道点云数据特征点少、在大视角点云数据间配准拼接时出现精度差、效率低等问题,本文以提高配准效率及精度作为出发点,以目前主流的ICP算法为基础,首先将激光点云按中心投影方式生成反射强度图像并以此作为配准源,采用规则格网分割提取匹配,建立均匀分布的同名点;然后利用反射强度图像上的同名点与点云之间的一一对应关系,完成视角点云间的初配准;最后在初次配准的基础上,采用KD树改进算法进行点云数据的精细配准。试验结果表明,本文在实现点云数据自动配准的同时,提高了地铁隧道点云数据的配准效率及精度。     

基于Delaunay三角剖分的ICP算法研究与实现

针对ICP迭代点云配准算法,利用MATLAB中封装的三角剖分函数,迅速搜索迭代过程中的最近点,简化ICP配准算法的实现,并设计一种模拟实验的方法验证算法的有效性。实验表明,利用基于三角剖分的ICP迭代算法可以达到较好的配准精度。     

基于特征点法向量的点云配准算法

在传统的迭代最近点算法（ICP）中,需要两片点云具有良好的初始位置,否则在配准时容易陷入局部最优。针对该问题,本文提出了一种基于特征点提取与配对的粗配准方法,以调整两片点云重叠部分的初始位置。首先,利用SIFT算法提取两片点云公共部分的特征点;其次,根据特征点法向量之间的欧氏距离将两片点云的特征点两两配对;然后,利用法向量的夹角对特征点对进行提纯;最后,通过单位四元数法,求解出旋转及平移矩阵,完成粗配准。试验表明,本文基于特征点法向量的粗配准方法可为精配准提供良好的初始位置,在一定程度上避免配准时陷入局部最优的现象。