硼同位素分析测试技术研究进展

硼(B)是一个质量较轻的流体活动性元素。它有2个稳定同位素：¹⁰B和¹¹B,两者之间相对质量差较大,导致自然界显著的硼同位素分馏。因此,硼同位素作为强有力的非传统稳定同位素示踪工具,在化学、环境、生物、地球及行星科学等研究领域具有广泛的应用。近二十年来,国内外硼同位素分析测试技术不断改进并取得了诸多重要进展。然而,获取高质量硼同位素数据,在样品消解、分离纯化以及质谱测试三个主要环节中仍然存在很多挑战。因为硼具有易挥发性及其在不同pH值环境中因配位不同导致同位素分馏,样品消解和分离纯化对硼同位素准确测量有很大影响。样品消解法主要有高温水解法、酸溶法、碱熔法和灰化法,其中酸溶法与碱熔法是最常用的方法。分离纯化法主要包括离子交换法、硼酸甲酯蒸馏法和微升华法。这些样品前处理方法各有利弊。质谱测试方法主要有两类：一类是溶液法,即热电离质谱法(TIMS)或多接收电感耦合等离子体质谱法(MC-ICP-MS);另一类是微区原位分析法,即二次离子质谱法(SIMS)或激光剥蚀法(LA)-MC-ICP-MS。不同的测试方法对样品前处理要求不同：溶液法要求去除基质;...     

有孔虫中硼的分离及其同位素组成测定的初步研究

本文初步建立了一种用硼特效树脂和阴、阳混和离子交换树脂相结合进行有孔虫中硼的分离和同位素测定的方法。该方法适用低硼含量 (纳克级 )的微体古生物中的硼的分离和同位素测定 ,分离过程不产生同位素分馏 ,满足了正热电离质谱法测定硼同位素的要求。     

清江盆地洋湖凹陷岩盐矿床A1孔泥岩段硼同位素组成特征研究

近年来,硼同位素研究在指示沉积环境及物源方面取得了良好进展。通过开展清江盆地盐岩矿床泥岩段矿物组成、硼含量及XRD衍射实验、热电离质谱法测量硼同位素等实验手段,研究δ11B值变化与物源、沉积环境和气候作用的关系,分析影响清江盆地盐岩矿床硼同位素分馏因素,发现多源性可能成为δ11B发生变化的原因之一,粘土矿物优先吸附10B从而导致δ11B值降低,同时盐矿物序列变化和伊利石的减少表明该时期整体气候变化为干冷向温湿改变,可能伴随有河流改道而导致物源发生变化,从而影响δ11B值的变化。     

负热电离质谱法测试硼同位素与大气pCO2的重建

海洋有孔虫的硼同位素能够反映海水酸碱度值的变化,为研究大气CO2浓度在长时间尺度上的变化提供了一种新的手段,甚至可能超出冰芯所能企及的范围.天然样品中硼同位素的测定方法最为常用的是热电离质谱法,分为正热电离质谱法与负热电离质谱法.目前海洋有孔虫硼同位素分析主要应用负热电离质谱法,该方法最大的优点是所需要的样品量比较小(<1ng B),实验精度却相对比较高(0.6‰～2.0‰;2s.d.).近年来,基于常规负热电离质谱法发展的全蒸发负热电离质谱法通过分析完所有样品而有效降低分析过程中所发生的分馏效应所带来的影响,并使样品的信号最大化,该方法精度能够达到0.7‰(2s.d.).本文详细介绍了常规负热电离质谱法和全蒸发负热电离质谱法的各个分析步骤,包括样品前处理、涂样、质谱分析、同质异位素干扰以及实验分析精度等方面.随着实验分析技术的进展,海洋有孔虫硼同位索已被用来重建长时间尺度(百万年和千万年)和短时间尺度(冰期-间冰期)的大气CO2浓度变化.现有的研究证实利用海洋浮游有孔虫硼同位素重建的大气CO2浓度变化与Vostok冰芯记录的大气CO2浓度变化吻合地很好.     

硼同位素在矿床学中的应用研究

硼在自然界有两种稳定同位素11B和10B,常采用δ(11B)/10-3来表示不同地质体的同位素组成。由于硼同位素在不同地质体中的分馏作用大,在较大温度范围内岩浆-热液流体中的高活动性和化学性质稳定等方面的优势,使硼同位素在地球科学研究中的作用越来越广泛。控制硼同位素分馏的主要因素是硼源。一般情况下,非海相的硼酸盐矿物和与之相关的电气石的δ(11B)值为负值,而在某些盐湖卤水和与海相环境有关的硼酸盐矿物的δ(11B)值则为正值。目前,硼同位素示踪主要应用于块状硫化物矿床、与花岗岩有关的热液矿床以及盐湖矿床的研究。随着硼同位素分馏机制及其在不同环境地质样品中分布特征的深入研究,硼同位素在解决矿床的成矿物质来源、矿床成因和成矿作用等方面将发挥更大的作用。     

湘南高温热液矿床中硼同位素组成及分馏作用研究

根据湘南高温地热区硼同位素研究，总结了硼同位素的分馏特征。湘南高温热液交代矿床硼酸盐矿物的σ^11B值均为负值（－1．34％～－13．28％）；不同蒸馏阶段获得样品的σ^11B值有较大差异，早期蒸馏硼产晚期蒸馏硼酸有较高的σ^11B值，晚期蒸发阶段样品的σ^11B值较早期阶段的σ^11B值低近40％，表明在热液交代过程中^11B较^10B活跃，优先进人流体相或蒸汽相；水岩作用中硼同位素分馏与硅化交代强度成正相关关系，并且是硅置换^11B，造成岩石亏损^11B，而呈现低的σ^11B值；水化反应中硼被吸入，并优先吸入^11B，导致蚀变岩中σ^11B升高。研究认为，硼同位素分馏特征可以用于分析成矿流体演化及水岩作用性质，而不限于分析成矿物质来源。     

俯冲-碰撞带硼循环

俯冲带控制着地球内部和表层的物质与能量交换.硼(B)是一个质量轻的流体活动性元素.B及其同位素体系是理解俯冲-碰撞带流/熔体活动和物质循环的重要工具.本文综述了俯冲板块中各储库的硼含量和同位素组成以及主导硼分配的关键矿物.介绍了目前对大洋俯冲带弧前、弧下和弧后深度下硼循环的主要认识;简要介绍了刚起步的大陆俯冲-碰撞带硼循环研究.阐述了含电气石(超)高压变质岩在俯冲带硼迁移研究中的重要性.指出今后需深化含水矿物在不同地温梯度下脱水/熔融过程中硼同位素分馏研究,加强流/熔体包裹体硼同位素分析技术及应用研究.由于B及同位素可有效区分大洋地壳和大陆地壳物质,未来将在造山带演化和地球深部物质循环研究中扮演更重要的角色.     

硼同位素及其地质应用研究

硼的两个稳定同位素（10B 和11B）相对质量差较大,因此,硼同位 素分馏较显著。由于分析测量技术方面的改进和创新, 硼同位素地球化学近年来有了长足 的发展。业已查明,自然界中δ11B值变化为 －37‰～+58‰。其中,较负的 δ11B值见于非海相蒸发硼酸盐矿物和某些电气石,而较正的δ11B值见 于某些盐湖卤水和蒸发海水。现代大洋水的δ11B值十分恒定 (+39,5‰)。原始 地幔的δ11B值估测为－10‰±2‰。陨石的δ11B值很不均一,变化 可达90‰。而月岩的δ11B值变化较小（－6‰～+4‰）。由于硼同位素存在大的 分馏和不同地质体中截然不同的δ11B值,硼同位素地质应用范围十分广泛。目 前,硼同位素在研究星云形成过程和宇宙事件,壳-幔演化和板块俯冲作用过程,判别沉积 环境,研究矿床成因,示踪古海洋和古气候条件,和判断环境污染源区等方面的研究中成效显著。     

理论计算阳离子对水体中B(OH)_3和B(OH)_4~-间硼同位素平衡分馏的影响

采用密度泛函方法模拟了阳离子对水体中B(OH)3和B(OH)4-的影响,计算海水的硼同位素平衡分馏参数。模拟海水环境时,选择基于分子簇模型的"水滴"法,以最多12个水分子环绕兴趣分子的方式构建"水滴"。对海水环境的计算结果显示,B(OH)3和B(OH)4-的硼同位素平衡分馏系数在25?C时为1.031,与纯水环境下的该分馏值并无明显差别。研究表明前人对B(OH)3和B(OH)4-间硼同位素平衡分馏参数的实验测定可能存在问题。研究结果为精进硼同位素古环境重建工作和硼同位素平衡分馏测定提供了理论制约。     

负热电离质谱法测试硼同位素与大气pCO2的重建

海洋有孔虫的硼同位素能够反映海水酸碱度值的变化,为研究大气CO₂浓度在长时间尺度上的变化提供了一种新的手段,甚至可能超出冰芯所能企及的范围。天然样品中硼同位素的测定方法最为常用的是热电离质谱法,分为正热电离质谱法与负热电离质谱法。目前海洋有孔虫硼同位素分析主要应用负热电离质谱法,该方法最大的优点是所需要的样品量比较小（＜1ng B),实验精度却相对比较高(0.6‰～2.0‰;  2sd.)。近年来,基于常规负热电离质谱法发展的全蒸发负热电离质谱法通过分析完所有样品而有效降低分析过程中所发生的分馏效应所带来的影响,并使样品的信号最大化,该方法精度能够达到0.7‰(2s.d.)。本文详细介绍了常规负热电离质谱法和全蒸发负热电离质谱法的各个分析步骤,包括样品前处理、涂样、质谱分析、同质异位素干扰以及实验分析精度等方面。随着实验分析技术的进展,海洋有孔虫硼同位素已被用来重建长时间尺度(百万年和千万年)和短时间尺度(冰期-间冰期)的大气CO₂浓度变化。现有的研究证实利用海洋浮游有孔虫硼同位素重建的大气CO₂浓度变化与Vostok冰芯记录的大气CO₂浓度变化吻合地很好。     

Composition-Induced Variations in SIMS Instrumental Mass Fractionation during Boron Isotope Ratio Measurements of Silicate Glasses

An analytical artefact is reported here related to differences in instrumental mass fractionation between NIST SRM glasses and natural geological glasses during SIMS boron isotope determinations. The data presented demonstrated an average 3.4‰ difference between the NIST glasses and natural basaltic to rhyolitic glasses mainly in terms of their sputtering-induced fractionation of boron isotopes. As no matrix effect was found among basaltic to rhyolitic glasses, instrumental mass fractionation of most natural glass samples can be corrected by using appropriate glass reference materials. In order to confirm the existence of the compositionally induced variations in boron SIMS instrumental mass bias, the observed offset in SIMS instrumental mass bias has been independently reproduced in two laboratories and the phenomenon has been found to be stable over a period of more than one year. This study highlights the need for a close match between the chemical composition of the reference material and the samples being investigated.     

Boron and Oxygen Isotope Composition of Certified Reference Materials NIST SRM 610/612 and Reference Materials JB-2 and JR-2

We present data on the concentration, the isotope composition and the homogeneity of boron in NIST silicate glass reference materials SRM 610 and SRM 612, and in powders and glasses of geological reference materials JB-2 (basalt) and JR-2 (rhyolite). Our data are intended to serve as references for both microanalytical and wet-chemical techniques. The δ¹¹ B compositions determined by N-TIMS and P-TIMS agree within 0.5% and compare with SIMS data within 2.5%. SIMS profiles demonstrate boron isotope homogeneity to better than δ¹¹ B = 2% for both NIST glasses, however a slight boron depletion was detected towards the outermost 200 μm of the rim of each sample wafer. The boron isotope compositions of SRM 610 and SRM 612 were indistinguishable. Glasses produced in this study by fusing JB-2 and JR-2 powder also showed good boron isotope homogeneity, both within and between different glass fragments. Their major element abundance as well as boron isotope compositions and concentrations were identical to those of the starting composition. Hence, reference materials (glasses) for the in situ measurement of boron isotopes can be produced from already well-studied volcanic samples without significant isotope fractionation. Oxygen isotope ratios, both within and between wafers, of NIST reference glasses SRM 610 and SRM 612 are uniform. In contrast to boron, significant differences in oxygen isotope compositions were found between the two glasses, which may be due to the different amounts of trace element oxides added at ten-fold different concentration levels to the silicate matrix.     

An optimized procedure for boron separation and mass spectrometry analysis for river samples

An optimized procedure for the separation of boron from natural river samples and an improved mass spectrometry determination of boron isotopic ratio are presented. The chemical procedure, based on the use of the boron-specific resin Amberlite IRA 743, is especially efficient in separating boron from natural organic matter-rich samples like river waters.The properties of Amberlite IRA 743 have been investigated. The two factors important in determining the boron affinity for the resin are: the pH value and the ionic strength of the solution from which B is to be extracted. A logarithmic relationship between B partition coefficients and pH values is found. High ionic strength significantly lowers the fixation of B onto the Amberlite resin.The knowledge of the factors controlling the affinity of the resin Amberlite IRA 743 for boron enables us to design a simple and miniaturized chemical separation procedure characterized by (i) three chromatographic steps using, respectively, 50, 10 and 3 μl of resin, (ii) no evaporation step between each column, and (iii) final separation of boron from residual organic matter by sublimation of boric acid at 75 °C.Boron isotopic ratios are measured using an improved cesium metaborate technique, with graphite and mannitol. Adequate loading conditions enable us to obtain typical signal intensities of 5×10⁻¹² A for 250 ng of boron. No in-run isotopic fractionation is observed, the external reproducibility for standards processed through the entire chemical procedure, as well as for samples, corresponds to 0.35‰ (±2σ). According to this precision, a slight, but reproducible isotopic fractionation of 0.4‰ is observed for standards processed through the entire chemical procedure whose origin is discussed, but is still unclear.     

A Common Reference Material for Cadmium Isotope Studies – NIST SRM 3108

Research into natural mass‐dependent stable isotope fractionation of cadmium has rapidly expanded in the past few years. Methodologies are diverse with MC‐ICP‐MS favoured by all but one laboratory, which uses thermal ionisation mass spectrometry (TIMS). To quantify the isotope fractionation and correct for instrumental mass bias, double‐spike techniques, sample‐calibrator bracketing or element doping has been used. However, easy comparison between data sets has been hampered by the multitude of in‐house Cd solutions used as zero‐delta reference in different laboratories. The lack of a suitable isotopic reference material for Cd is detrimental for progress in the long term. We have conducted a comprehensive round‐robin assay of NIST SRM 3108 and the Cd isotope offsets to commonly used in‐house reference materials. Here, we advocate NIST SRM 3108 both as an isotope standard and the isotopic reference point for Cd and encourage its use as ‘zero‐delta’ in future studies. The purity of NIST SRM 3108 was evaluated regarding isobaric and polyatomic molecular interferences, and the levels of Zn, Pd and Sn found were not significant. The isotope ratio ¹¹⁴Cd/¹¹⁰Cd for NIST SRM 3108 lies within ～ 10 ppm Da^?1 of best estimates for the Bulk Silicate Earth and is validated for all measurement technologies currently in use.     

Lead Isotope Homogeneity of NIST SRM 610 and 612 Glass Reference Materials: Constraints from Laser Ablation Multicollector ICP-MS (LA-MC-ICP-MS) Analysis

This contribution presents data for laser ablation multicollector ICP‐MS (LA‐MC‐ICP‐MS) analyses of NIST SRM 610 and 612 glasses with the express purpose of examining the Pb isotope homogeneity of these glasses at the ～ 100 μm spatial scale, relevant to in situ analysis. Investigation of homogeneity at these scales is important as these glasses are widely used as calibrators for in situ measurements of Pb isotope composition. Results showed that at the levels of analytical uncertainty obtained, there was no discernable heterogeneity in Pb isotope composition of NIST SRM 610 and also most probably for NIST SRM 612. Traverses across the ～ 1.5 mm glass wafers supplied by NIST, consisting of between 75 and 133 individual measurements, showed no compositional outliers at the two standard deviation level beyond those expected from population statistics. Overall, the measured Pb isotope ratios from individual traverses across NIST SRM 610 and 612 wafers closely approximate single normally‐distributed populations, with standard deviations similar to the average internal uncertainty for individual measurement blocks. Further, Pb isotope ratios do not correlate with Tl/Pb ratios measured during the analysis, suggesting that regions of volatile element depletion (marked by low Tl/Pb) in these glasses are not associated with changes in Pb isotope composition. For NIST SRM 610 there also appeared to be no variation in Pb isotope composition related to incomplete mixing of glass base and trace element spike during manufacture. For NIST SRM 612 there was some dispersion of measured ratios, including some in a direction parallel to the expected mixing line for base‐spike mixing. However, there was no significant correlation parallel to the mixing line. At this time this cannot be unequivocally demonstrated to result from glass heterogeneity, but it is suggested that NIST SRM 610 be preferred for standardising in situ Pb isotope measurements. Data from this study also showed significantly better accuracy and somewhat better precision for ratios corrected for mass bias by external normalisation to Pb isotope ratios measured in bracketing calibrators compared to mass bias corrected via internal normalisation to measured ²⁰⁵Tl/²⁰³Tl, although the Tl isotopic composition of both glasses appears to be homogeneous.     

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.     

AG-MP-1M阴离子交换树脂分离-表面热电质谱法测定沉积物中的铅同位素组成

利用新型阴离子交换树脂分离沉积物中的重金属Pb,采用表面热电离质谱法(TIMS)测定了沉积物样品中的Pb同位素组成。新型树脂为大孔径阴离子树脂AG-MP-1M,淋洗液采用低浓度的盐酸,避免了使用难以纯化的氢溴酸,可有效地降低试剂空白。通过对铅同位素标准物质NIST NBS-981的重复测试,方法的精密度(<0.5%,2s)和准确度均达到了应用研究的要求。对5个实际沉积物样品中的铅同位素组成进行测定,获得了理想的分析效果。     

古海水pH值代用指标——海洋碳酸盐硼同位素研究进展

仪器测量的海水pH记录太短，无法评估海水pH自然变化的频率和幅度,并预测未来大气CO₂急剧增加后海水酸度的响应。海相碳酸盐的硼同位素是目前恢复古海洋pH的有效途径，倍受古气候—环境学家的重视。评述了近年来海洋碳酸盐的硼同位素的最新研究成果和研究现状，重点探讨了海相碳酸盐的硼同位素的测定方法、硼同位素—pH模型和古海水pH恢复等前沿内容，旨在提供一个系统的海洋碳酸盐硼同位素—pH系统的基本概念及研究思路，以利于气候学、地质学界了解这一交叉领域的发展动态。     

Nickel Isotope Variations in Terrestrial Silicate Rocks and Geological Reference Materials Measured by MC‐ICP‐MS

Although initial studies have demonstrated the applicability of Ni isotopes for cosmochemistry and as a potential biosignature, the Ni isotope composition of terrestrial igneous and sedimentary rocks, and ore deposits remains poorly known. Our contribution is fourfold: (a) to detail an analytical procedure for Ni isotope determination, (b) to determine the Ni isotope composition of various geological reference materials, (c) to assess the isotope composition of the Bulk Silicate Earth relative to the Ni isotope reference material NIST SRM 986 and (d) to report the range of mass‐dependent Ni isotope fractionations in magmatic rocks and ore deposits. After purification through a two‐stage chromatography procedure, Ni isotope ratios were measured by MC‐ICP‐MS and were corrected for instrumental mass bias using a double‐spike correction method. Measurement precision (two standard error of the mean) was between 0.02 and 0.04‰, and intermediate measurement precision for NIST SRM 986 was 0.05‰ (2s). Igneous‐ and mantle‐derived rocks displayed a restricted range of δ^60/58Ni values between ?0.13 and +0.16‰, suggesting an average BSE composition of +0.05‰. Manganese nodules (Nod A1; P1), shale (SDO‐1), coal (CLB‐1) and a metal‐contaminated soil (NIST SRM 2711) showed positive values ranging between +0.14 and +1.06‰, whereas komatiite‐hosted Ni‐rich sulfides varied from ?0.10 to ?1.03‰.     

Precise and accurate in situ Pb-Pb dating of apatite, monazite, and sphene by laser ablation multiple-collector ICP-MS

To evaluate in situ Pb dating by laser ablation multiple-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS), we analysed apatite, sphene, and monazite from Paleoproterozoic metamorphic rocks from West Greenland. Pb isotope ratios were also determined in the National Institute of Standards and Technology (NIST) 610 glass standard and were corrected for mass fractionation by reference to the measured thallium isotope ratio. The NIST 610 glass was used to monitor Pb isotope mass fractionation in the low Tl/Pb accessory minerals. Replicate analyses of the glass (1 to 2 min) yielded ratios with an external reproducibility comparable to conventional analyses of standard reference material 981 by thermal ionisation mass spectrometry (TIMS). Mineral grains were generally analysed with a 100-μm laser beam, although some monazite crystals were analysed at smaller spot sizes (10 and 25 μm). The common Pb isotope ratios required for age calculations were either measured on coexisting plagioclase by LA-MC-ICP-MS or could be ignored, as individual crystals exhibit sufficient Pb isotopic heterogeneity to perform isochron calculations on replicate analyses of single crystals. Mean mineral ages with the ²⁰⁴Pb ion beam measured in the multiplier were as follows: apatite, 1715 ± 23 m.y.; sphene, 1789 ± 11 m.y.; and monazite, 1783 to 1888 m.y., with relative uncertainties on individual monazite ages of <0.2% but highly reproducible age determinations on single monazite crystals (?1%). Isochron ages calculated from several mineral analyses without assumption of common Pb also yield precise age determinations. Apatite and monazite Pb ages determined by in situ Pb isotope analysis are identical to those determined by conventional TIMS analysis of bulk mineral separates, and the analytical uncertainties of these short laser analyses with no prior mechanical or chemical separation are comparable to those obtained by TIMS. Detailed examination of the sphene in situ age data does, however, show a small discrepancy between the LA-MC-ICP-MS and TIMS ages (∼1% younger). High-resolution mass scans of the sphene during ablation clearly showed several small and as yet unidentified isobaric interferences that overlap with the ²⁰⁷Pb peak at the resolution conditions for measurement of isotope ratios. These might account for the age discrepancy between the LA-MC-ICP-MS and TIMS sphene ages. LA-MC-ICP-MS is a rapid, accurate, and precise method for in situ determination of Pb isotope ratios that can be used for geochronological studies in a manner similar to an ion microprobe, albeit currently at a somewhat degraded spatial resolution. Further modifications to the LA-MC-ICP-MS system, such as improved sensitivity, ion transmission, and LA methodology, may lead to this type of instrument becoming the method of choice for many types of in situ Pb isotope dating.