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.     

内蒙古阿拉善左旗巴音诺尔公花岗岩体TIMS锆石U-Pb年龄

内蒙古自治区阿拉善东南部的巴音诺尔公花岗岩体,地处华北陆块西北缘,霍尔森-查干楚鲁构造带以南的雅布赖-巴音诺尔公构造带内。岩体整体上受NEE向构造控制,主要由中-细粒黑云母花岗岩和中-粗粒似斑状黑云母花岗岩2种岩石类型组成。采用TIMS锆石U-Pb定年法,测得巴音诺尔公岩体不同位置中-细粒黑云母花岗岩和中-粗粒似斑状黑云母花岗岩样品年龄分别为304.7±2.8Ma和289.0±3.8Ma,属于晚石炭世—早二叠世。结合前人资料,提出巴音诺尔公岩体至少存在2期岩浆活动,分别为晚石炭世(304Ma)和早二叠世(289~272Ma)。     

内蒙古阿拉善地区沙拉扎山花岗岩体TIMS锆石U-Pb年龄

内蒙古阿拉善地区的沙拉扎山处于华北板块、塔里木板块和天山-兴蒙造山带接触部位,恩格尔乌苏蛇绿岩带与查干础鲁蛇绿岩带之间。沙拉扎山内出露一套巨大花岗质岩基,为了认识其岩浆活动期次,对沙拉扎山岩体不同部位花岗质岩石样品进行了TIMS锆石U-Pb测年。结果表明,沙拉套尔汗花岗闪长岩年龄为233.1±5.8Ma,乌力吉花岗岩2个样品年龄分别为228.1±0.4Ma和207.7±0.8Ma。对比分析前人对该区岩体年龄的研究成果,认为沙拉扎山出露的花岗岩由早二叠世晚期(273~274Ma)、早三叠世(248~252Ma)、晚三叠世早期(228~236Ma)和晚三叠世末期(207Ma)4期岩浆活动叠加而成,同时发育在沙拉扎山的4期岩浆活动在巴音—诺尔公地区也有相应的岩浆记录。     

Determination of Platinum‐Group Elements and Re‐Os Isotopes using ID‐ICP‐MS and N‐TIMS from a Single Digestion after Two‐Stage Column Separation

We report an improved procedure for the determination of the platinum‐group elements (PGE) and Re, and Os isotopes from a single sample aliquot by isotope dilution (ID) using inductively coupled plasma‐mass spectrometry (ICP‐MS) and negative thermal ionisation mass spectrometry (N‐TIMS), respectively. A two‐stage column method was used to purify PGE‐Re from their sample matrix and interfering elements (e.g., Mo, Zr and Hf) after Os had been separated by CCl₄ solvent extraction. The first column separation step used cation exchange resin (AG50W‐X8) to concentrate PGE‐Re and some potential interfering elements (e.g., Mo, Zr and Hf). In the second step, N‐benzoyl‐N‐phenylhydroxylamine (BPHA) extraction resin was used to separate PGE‐Re from the remaining interfering elements, which all remained strongly absorbed to the resin. The method was used to determine the PGE and rhenium, and Os isotope ratios in a range of geochemical reference materials (TDB‐1, WGB‐1, BHVO‐2 and UB‐N). The obtained results agree well with those previously published. This new method enables PGE‐Re abundances and Os isotopic ratios to be determined on the same sample digestion, and circumvents the problems created by sample heterogeneity when comparing PGE and Re‐Os isotope data.     

内蒙古中部商都县库伦图地区晚三叠世花岗岩的地球化学特征及构造意义

内蒙古商都县位于中朝陆块北部、华北地台北缘,区内岩浆岩分布广泛.对商都县库伦图地区的铜顶山二长花岗岩和和眭村--民主村正长花岗岩进行了锆石TIMS U-Pb定年,结果表明两岩体分别形成于(236.5±4.2)Ma和(231.8±1.1)Ma.岩石学和地球化学研究表明二长花岗岩和正长花岗岩均属于高硅、准铝一过铝质高钾钙碱...     

Isotopic climate record in a Holocene stalagmite from Ursilor Cave (Romania)

The PU‐2 stalagmite from Ursilor Cave provides the first dated Romanian isotope record for the Holocene. The overall growth rate of the speleothem was 3.5 cm kyr^?1, corresponding to a temporal resolution of 142 y between each isotope analysis. The ‘Hendy’ tests indicate that isotopic equilibrium conditions occurred during the formation of PU‐2, and hence that it is suitable for palaeoclimatic studies. The relationship between δ¹⁸O and temperature was found to be positive. This can be interpreted either as rain‐out with distance from the west‐northwest ocean source of evaporation or shifts in air mass source with changing North Atlantic Oscillation indices. Applying five U–Th thermal ionisation mass spectrometric (TIMS) dates to a 17.5 cm isotope profile (δ¹⁸O and δ¹³C) along the stalagmite growth axis enabled a tentative interpretation of the palaeoclimate signal over the past 7.1 kyr. Spikes of depleted isotopic δ¹⁸O values are centred near ca. 7, ca. 5.2 and ca. 4 ka, reflecting cool conditions. The record shows two warm intervals between ca. 3.8 and ca. 3.2 ka (the maximum warmth) and from ca. 2 to ca. 1.4 ka, when the δ¹⁸O values were less negative than present. The ‘Holocene Climate Optimum’ spanning the time interval from ca. 6.8 to ca. 4.4 ka is not well expressed in the PU‐2 stalagmite. Individual spikes of lighter δ¹³C are interpreted as indicative of periods of heavy rainfall, at ca. 7, ca. 5.5, and ca. 3.5 ka. The overall trend to lighter δ¹³C in the PU‐2 stalagmite may reflect a gradual decrease in water–rock interaction. The results demonstrate that the effect of North Atlantic oceanic changes extended to the investigated area. Nevertheless, some differences in temporal correlation and intensity of stable isotopic response to these climatic events have been found, but the exact nature of these differences and the underlying mechanism is yet to be determined. Copyright © 2002 John Wiley & Sons, Ltd.     

陨石中铼锇同位素化学分离过程的几个重要影响因素

本文针对陨石中铼锇同位素比值高精度测定,选取6块不同类型的普通球粒陨石（吉林陨石、信阳陨石、武安陨石、肇东陨石、河北陨石、荷叶塘陨石）和两块铁陨石（南丹铁陨石和T-5）进行预处理和化学过程的一些条件实验。实验结果表明,陨石金属表面的锈迹清洗使用1M的HCl效果更佳;对于样品溶解,逆王水溶解效果比浓硝酸好,高温溶样熔解彻底,常温状态下仅能溶解出约30%的陨石样品中的Os;微蒸馏二次纯化可提高Os测定信号的稳定性和精度;稀释剂的浓度及加入量应与样品匹配,且达到平衡状态是高精度和高准确度的保障;普通球粒陨石取样范围在0.1g-0.3g (即样品中Os的绝对含量为100ng)即可获取最佳信号强度和精度;本次实验全流程空白Os可控制至0.5~81pg,Re可控制至4～77pg采用同位素稀释法,当187Os/188Os比值的精度最小可至4ppm（n=120,2se）。     

高精度热电离质谱（TIMS）在南极陨石研究中的应用前景

热电离质谱（TIMS）是同位素地球化学研究中传统、可靠、分析精度高的主要测试仪器之一,尤其对于微量样品的高精度同位素比值测定,以其高精度和高灵敏度获得广泛的认可,这一特征在天体化学微量样品同位素研究中具有广阔的应用前景。目前,新型TRITON TIMS质谱仪已实现了Re–Os,Cr,Sr,Nd,Pb等同位素的高精度测定。采用TIMS测定Sr同位素比值的Sr含量范围可由10pg—100ng以上,87Sr/88Sr比值测定精度可达到5‰—5ppm;LaJolla Nd同位素标样测试结果为：143Nd/144Nd=0.511842±0.000005（2SE,n=28）,143Nd/144Nd比值测定精度最佳可达2ppm;207Pb–204Pb双稀释剂法对Pb含量为5—20ng样品测定,外部精度206Pb/204Pb、207Pb/204Pb和208Pb/204Pb分别达到±0.0034、±0.0046和±0.0100（2SE,n=28）;负离子状态（NTIMS）下对Os含量低至几—几十pg的样品测定187Os/188Os比值精度可达0.2‰以内,对Os含量为ng级的样品,187Os/188Os比值精度好于20ppm;Cr同位素比值50Cr/52Cr,53Cr/52Cr,54Cr/52Cr的分析精度分别可达到1ppm,2ppm,2ppm（2SD）以内。这些方法涵盖了亲石元素、亲铁元素,长寿命放射性同位素和短寿命灭绝核素的同位素研究,为我国南极陨石的深入研究提供了有力技术保障。     

TIMS测定铀矿石样品中^234U/^238U、^230Th/^232Th、^228Ra/^226Ra的方法研究

研究了TIMS测定铀矿石样品中234U/238U、230Th/232Th、228Ra/226Ra的方法。建立了铀矿石密闭混酸一次溶样的方法和采用阴离子、阳离子和Sr特效树脂逐级离子交换分离纯化U、Th和Ra的流程,满足了TIMS测量要求。测定结果表明：100～1000 ng的天然铀中234U/238U,其测量精密度从静态多接收的2.34%提高到动态多接收的0.47%;对230Th与232Th丰度接近、质量为1μg左右的钍,采用三带点样技术和法拉第多接收技术测定230Th/232Th,其内精度平均值为0.0048%,外精度为0.028%;采用单带加钽发射剂,ETP跳峰测定50～100 fg镭-228稀释剂中的228Ra/226Ra,其内精度小于0.10%,外精度小于0.20%。比较TIMS和HR-ICP-MS、α能谱法测定234U/238U、230Th/232Th、228Ra/226Ra结果,三者结果相吻合。TIMS测量法样品用量少、快速、准确、精密度高,是U、Th、Ra同位素比值测定方法的又一补充。     

第四纪年龄测定的新技术──热电高质谱铀系法的发展近况

近10年来国际上用热电离质谱代替α谱仪测定不平衡铀系样品的年龄，在造礁珊瑚、洞穴堆积物、年轻火山岩和湖泊沉积物等领域已取得了显著的成果。该技术有明显的优点，如样品用量少，测试时间短，测量精度高，测年范围宽，是中更新世至全新世以来有效的测年方法之一，可为全球变化研究提供高精度和高灵敏度的年龄谱，展示了热电离质谱技术如同加速器质谱技术一样，有广阔的应用前景。我们曾用MAT－262质谱仪对国内石笋标样(GBW04412，GBW04413)和国际珊瑚标样(RKM－4)进行过测试，取得了与标准值一致的结果。