High-precision Pb isotope analysis by multicollector-ICP-mass-spectrometry using 205Tl/203Tl normalization: Optimization and calibration of the method for the studies of Pb isotope variations

The development of the MC-ICP-MS method, which was launched about one decade ago and was largely stimulated by the need to solve geological problems, has opened a new avenue in isotope mass spectrometry. One of the advantages of this method is the possibility of applying a newly developed approach to the correction of analytical results for the effect of mass discrimination by normalizing the measured isotope ratios of an element to a reference (standard) isotope ratio of another element. This makes it possible to overcome the main disadvantage of conventional thermal ionization mass spectrometry (TIMS), in which the effect of mass discrimination cannot be fully taken into account during isotope analysis, and thus to implement a highly accurate method for the analysis of Pb-isotope composition. In application to the capability of the NEPTUNE MC-ICP mass spectrometer, we optimized and calibrated a method for high-accuracy Pb isotope analysis in solutions spiked with Tl, with all currently measured Pb-isotope ratios normalized to the standard ²⁰⁵Tl/²⁰³Tl ratio (TLN-MC-ICP-MS). The factors affecting the random and systematic analytical errors were examined, and the optimal operating regime and analytical conditions were determined. Much attention was paid to the correlation of the measurement results and the mass discrimination effect determined from the ²⁰⁵Tl/²⁰³Tl ratio. The value of the ²⁰⁵Tl/²⁰³Tl normalizing ratio was analytically determined through isotope analyses of the NIST SRM 981, and SRM 982 standard samples of Pb-isotope composition. The data obtained for two mixtures Tl + Pb (SRM 982) and Tl + Pb (SRM 981) in ten replicate analyses were 2.38898 ± 12 and 2.38883 ± 20, respectively. These results are in good mutual agreement, and their general mean ²⁰⁵Tl/²⁰³Tl = 2.3889 ± 1 coincides (within the error) with the recently published values of 2.3887 ± 7 [Collerson et al., 2002] and 2.3889 ± 1 [Thirlwall, 2002]. The precision of the method (±2SD), which was assayed by the long-term reproducibility of the results of replicate analyses of SRM 981 and seven galena samples (90 analyses) was 0.016–0.018% for the ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb ratios and 0.005 and 0.009% for the ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb ratios, respectively. The precision of the isotope analysis of common Pb was significantly improved (by factors of 6–10 for various isotope ratios) compared with the precision of TIMS techniques acceptable in isotope studies during three decades. The described method was applied to examine the Pb-isotope composition of approximately 250 samples of galena, scheelite, and pyrite from a number of well known (including large) gold, sulfied, and base-metal deposits. The precision of the method (0.01–0.02%) makes it possible to study small inter-and intra-phase differences in Pb-isotope ratios in hydrothermal and magmatic rocks, to assay the scale of regional and variations in the isotope composition of ore Pb, and to correlate the Pb-isotope composition of rocks and ores and reveal its evolutionary trends.     

电感耦合等离子体质谱法测定磷矿石中的碘

建立了电感耦合等离子体质谱法测定磷矿石中碘的方法。试样经磷酸、高氯酸分解,用氨水调至弱碱性,直接用电感耦合等离子体质谱法测定,方法检出限为0.33μg/g,加标回收率为95.0%~97.4%,精密度(RSD,n=12)为2.77%~3.17%。经磷矿石国家一级标准物质(GBW 07210和GBW 07211)验证,结果满意。     

A stable isotope-based approach to tropical dendroclimatology

We describe a strategy for development of chronological control in tropical trees lacking demonstrably annual ring formation, using high resolution δ¹⁸O measurements in tropical wood. The approach applies existing models of the oxygen isotopic composition of alpha-cellulose (Roden et al., 2000), a rapid method for cellulose extraction from raw wood (Brendel et al., 2000), and continuous flow isotope ratio mass spectrometry (Brenna et al., 1998) to develop proxy chronological, rainfall and growth rate estimates from tropical trees lacking visible annual ring structure. Consistent with model predictions, pilot datasets from the temperate US and Costa Rica having independent chronological control suggest that observed cyclic isotopic signatures of several permil (SMOW) represent the annual cycle of local rainfall and relative humidity. Additional data from a plantation tree of known age from ENSO-sensitive northwestern coastal Peru suggests that the 1997-8 ENSO warm phase event was recorded as an 8‰ anomaly in the δ¹⁸O of α-cellulose. The results demonstrate reproducibility of the stable isotopic chronometer over decades, two different climatic zones, and three tropical tree genera, and point to future applications in paleoclimatology.     

位场反演计算的场比值法及在宽城地区磁异常解释中的应用

在磁异常的反演计算中, 为了避免由于选错了磁性体的形状而产生很大的误差, 前人已研究了多种所谓自动反演的计算方法。与传统的方法不同, 用这些方法, 可以同时确定磁性体的几何形状和埋藏深度等参数。但是前人研究的方法需要计算磁异常的三阶导数, 因此所受高频噪声干扰十分严重, 以至于影响到计算结果的可靠性。因此很难用到实际资料处理中。 本文提出的场比值法可以同时确定磁性体的形状和埋藏深度。场比值法通过场比值field-ratio来确定磁性体的形状, field-ratio的物理含义与Euler反褶积公式中的形状因子类似。场比值法的优点是在反演计算中只需要计算磁异常的一、二阶导数, 因此比前人的方法受高频随机干扰小, 可以用于实际资料的处理中。模型实验证明了场比值法的正确性, 在河北省宽城地区用场比值法对磁异常反演计算, 展示了方法的实用性。 关键词: 磁异常; 自动反演; 磁性体形状的判别     

GGR Critical Review of Analytical Developments in 2004–2005

In 2005 Geostandards and Geoanalytical Research embarked upon a new initiative for its readers. Key researchers in various fields of geoanalytical technique development and their application were identified and invited to provide reviews pertinent to their expertise. As noted in the first of these publications "…instead of revisiting the historical context or decades of development in each analytical technique, the goal here has been to capture a snapshot of "hot topics" across a range of fields as represented in the… literature" (Hergt et al . 2005). Rather than prepare an annual review, a decision was taken earlier this year to provide a biennial summary of progress and accomplishments, in this case for the years 2004–2005. The principal techniques employed in Earth and environmental sciences are covered here, and include laser ablation and multicollector ICP-MS, ICP-AES, thermal ionisation and secondary ion mass spectrometry, as well as neutron activation analysis, X-ray fluorescence and atomic absorption spectrometry. A comprehensive review of the development of reference materials, often essential to these techniques, is also provided. The contributions assembled serve both to keep readers informed of advances they may be unfamiliar with, but also as a means of showcasing examples of the breadth and depth of work being conducted in these fields.     

U/Th dating by SHRIMP RG ion-microprobe mass spectrometry using single ion-exchange beads

We present a new analytical method for U-series isotopes using the SHRIMP RG (Sensitive High mass Resolution Ion MicroProbe) mass spectrometer that utilizes the preconcentration of the U-series isotopes from a sample onto a single ion-exchange bead. Ion-microprobe mass spectrometry is capable of producing Th ionization efficiencies in excess of 2%. Analytical precision is typically better than alpha spectroscopy, but not as good as thermal ionization mass spectroscopy (TIMS) and inductively coupled plasma multicollector mass spectrometry (ICP-MS). Like TIMS and ICP-MS the method allows analysis of small samples sizes, but also adds the advantage of rapidity of analysis. A major advantage of ion-microprobe analysis is that U and Th isotopes are analyzed in the same bead, simplifying the process of chemical separation. Analytical time on the instrument is ∼60 min per sample, and a single instrument-loading can accommodate 15-20 samples to be analyzed in a 24-h day. An additional advantage is that the method allows multiple reanalyses of the same bead and that samples can be archived for reanalysis at a later time. Because the ion beam excavates a pit only a few μm deep, the mount can later be repolished and reanalyzed numerous times. The method described of preconcentrating a low concentration sample onto a small conductive substrate to allow ion-microprobe mass spectrometry is potentially applicable to many other systems.     

浙江省东阳晚白垩世早期新的翼龙足迹

本文报道了浙江东阳发现的中国第2个翼龙足迹化石点, 也是亚洲发现的第8个翼龙足迹化石点。化石足迹产于晚白垩世早期方岩组的紫红色泥质粉砂岩中。发现有3个手的印迹和1个右足印。手的印迹的长宽分别为6.5 cm 和4cm. 非对称具有3个指的印迹。足迹9 cm长和1.5 cm宽。该足迹不同于以前发现的, 可能代表一新的类型。除了翼龙足迹外, 还发现鸟类、小型兽脚类、鸟脚类及蜥脚类脚印, 形成一个丰富的动物群, 它的发现为研究该地区的古生态环境及古地理具有重要意义。同时为以后在该地区发现这些造迹动物的骨骼化石提供了重要依据。     

密闭溶样-电感耦合等离子体质谱法测定煅烧高岭土中微量重金属元素

建立了密闭溶样-电感耦合等离子体质谱法同时测定煅烧高岭土中铜、铅、锌、铬、镉和锰等6个微量重金属元素的有效方法。实验中对仪器的最佳工作参数进行了优化,选择适当的同位素,并用铑作内标元素,有效地抑制了分析信号的漂移以及分子和多原子离子的质谱干扰;探讨了混合酸消解体系、消解液用量、密闭溶样的时间对测定结果的影响。以硝酸-氢氟酸作为消化试剂,在180℃下溶解4 h能完全消解样品。在选定的实验条件下,对煅烧高岭土样品进行了精密度和回收率试验,方法相对标准偏差(RSD,n=9)为0.96%~2.22%,加标回收率为98.0%~101.5%。     

Applications of magnetic sector ICP-MS in geochemistry

Inductively coupled plasma mass spectrometry (ICP-MS) is a technique that provides rapid and sensitive multielement and isotope analysis of various environmental materials. This technique has developed into a valuable tool for data acquisition in geochemistry. Quadrupole and magnetic sector mass analysers are the most important types of mass filters that are commercially available with these instruments. Magnetic sector instruments are more expensive than quadrupole-based instruments, but provide enhanced sensitivity and higher mass resolution. This paper reviews applications of single- and multiple-collector magnetic sector ICP-MS in different fields of geochemistry and shows where the use of magnetic sector ICP-MS is advantageous.     

电感耦合等离子体质谱法(ICP-MS)测定水系沉积物中的铌钽锆铪

建立电感耦合等离子体质谱法(ICP-MS)测定水系沉积物中铌、钽、锆、铪四种元素的分析方法。将样品与氢氧化钠、过氧化钠混合物放入高温炉中,熔融分解完全,用热水提取,过滤后弃去滤液,将滤纸及沉淀用酒石酸-盐酸溶液溶解,稀释至刻度测定。方法检出限(3s)为:LD(Nb)=0.08μg/g,LD(Ta)=0.04μg/g,LD(Zr)=0.5μg/g,LD(Hf)=0.04μg/g,精密度(RSD%,n=6)为:0.84%~4.21%。该测定方法具有灵敏度高、精密度好、分析速度快、线性范围宽、操作性强等优势。采用该方法对国家一级标准物质进行测定表明,其结果与标准值吻合。此方法已在实际地质调查样品分析中得到应用。     

Diamond in Oceanic Peridotites and Chromitites: Evidence for Deep Recycled Mantle in the Global Ophiolite Record

Diamonds have been discovered in mantle peridotites and chromitites of six ophiolitic massifs along the 1300 km‐long Yarlung‐Zangbo suture (Bai et al., 1993; Yang et al., 2014; Xu et al., 2015), and in the Dongqiao and Dingqing mantle peridotites of the Bangong‐Nujiang suture in the eastern Tethyan zone (Robinson et al., 2004; Xiong et al., 2018). Recently, in‐situ diamond, coesite and other UHP mineral have also been reported in the Nidar ophiolite of the western Yarlung‐Zangbo suture (Das et al., 2015, 2017). The above‐mentioned diamond‐bearing ophiolites represent remnants of the eastern Mesozoic Tethyan oceanic lithosphere. New publications show that diamonds also occur in chromitites in the Pozanti‐Karsanti ophiolite of Turkey, and in the Mirdita ophiolite of Albania in the western Tethyan zone (Lian et al., 2017; Xiong et al., 2017; Wu et al., 2018). Similar diamonds and associated minerals have also reported from Paleozoic ophiolitic chromitites of Central Asian Orogenic Belt of China and the Ray‐Iz ophiolite in the Polar Urals, Russia (Yang et al., 2015a, b; Tian et al., 2015; Huang et al, 2015). Importantly, in‐situ diamonds have been recovered in chromitites of both the Luobusa ophiolite in Tbet and the Ray‐Iz ophiolite in Russia (Yang et al., 2014, 2015a). The extensive occurrences of such ultra‐high pressure (UHP) minerals in many ophiolites suggest formation by similar geological events in different oceans and orogenic belts of different ages. Compared to diamonds from kimberlites and UHP metamorphic belts, micro‐diamonds from ophiolites present a new occurrence of diamond that requires significantly different physical and chemical conditions of formation in Earth's mantle. The forms of chromite and qingsongites (BN) indicate that ophiolitic chromitite may form at depths of >150‐380 km or even deeper in the mantle (Yang et al., 2007; Dobrthinetskaya et al., 2009). The very light C isotope composition (δ13C ‐18 to ‐28‰) of these ophiolitic diamonds and their Mn‐bearing mineral inclusions, as well as coesite and clinopyroxene lamallae in chromite grains all indicate recycling of ancient continental or oceanic crustal materials into the deep mantle (>300 km) or down to the mantle transition zone via subduction (Yang et al., 2014, 2015a; Robinson et al., 2015; Moe et al., 2018). These new observations and new data strongly suggest that micro‐diamonds and their host podiform chromitite may have formed near the transition zone in the deep mantle, and that they were then transported upward into shallow mantle depths by convection processes. The in‐situ occurrence of micro‐diamonds has been well‐demonstrated by different groups of international researchers, along with other UHP minerals in podiform chromitites and ophiolitic peridotites clearly indicate their deep mantle origin and effectively address questions of possible contamination during sample processing and analytical work. The widespread occurrence of ophiolite‐hosted diamonds and associated UHP mineral groups suggests that they may be a common feature of in‐situ oceanic mantle. The fundamental scientific question to address here is how and where these micro‐diamonds and UHP minerals first crystallized, how they were incorporated into ophiolitic chromitites and peridotites and how they were preserved during transport to the surface. Thus, diamonds and UHP minerals in ophiolites have raised new scientific problems and opened a new window for geologists to study recycling from crust to deep mantle and back to the surface.     

锍镍试金富集-等离子体质谱法测定煌斑岩中铂族元素

试金配料中适量加入铁粉,控制硫化铁在锍扣中的含量在20%~40%,获得的锍扣直接用水浸泡粉化后加盐酸分解,分解结束后趁热过滤,沉淀用1mL王水溶解,定容后上机测定,Cs作内标。改进后的方法空白水平进一步降低,检出限得到显著改善,分析流程简化。采用改进后的锍镍试金富集-等离子体质谱法测定了云南哀牢山金矿带煌斑岩和国家一级标准物质GBW 07288(GPt-1)、GBW 07290(GPt-3)中的铂族元素(PGEs)含量,方法检出限为0.001~0.01ng/g,精密度(RSD,n=5)为7.49%~16.6%。     

Effects of Subduction of Pacific Plate on the Great Xing’an Range: Constriants from Geochronology and Geochemistry of the Shaxilate Granite Porphyry

As a widely‐developed mineral in various types of rocks, pyrite features important geological information such as temperature and pressure during its formation and evolution (An et al., 2014; An et al., 2018). It is an important geological formation for studying the origins of rocks, mineralization, and deposits (Xue et al., 2014; An et al., 2016). The study of the genesis of gold deposits is a research hotspot in current geology and mineral deposits not only because of high economic value, but also because of important practical significance (An et al., 2017; Yang et al., 2014). Shandong Zhaoyuan, as the third largest gold production area in the world, has important research significance of the origin and generation of gold‐bearing minerals (Xue et al., 2014; Wen et al., 2014). In this study, pyrite from augen granite (figure 1a), syenite (figure 1b), basite (figure 1c) and gold ore (figure 1d) at Zhaoyuan gold deposit Shandong Province, was selected as the research object. The morphological and structural micro‐fabrics were analysed by polarized light microscopy (PLM) and Raman spectroscopy to reveal the source and process of gold further.     

APPLICATION OF THE ICP-MS TECHNIQUE TO TRACE ELEMENT ANALYSIS OF PERIDOTITES AND THEIR MINERALS

Inductively coupled plasma mass spectrometry (ICP-MS) has been applied to the determination of Rb, Sr, Ba, Zr, Hf, Nb, Ta, Th, U, Pb, Sc and 14 REE in peridotites and their constituent minerals: garnet, clinopyroxene, orthopyroxene and olivine. Determination limits for most elements are 1–10 ppb (in the solid sample), with accuracy and precision comparable to those of thermal ionisation and spark-source mass spectrometry. New data on international standards PCC-1, DTS-1, UB-N and JP-1 are reported.     

电感耦合等离子体质谱联用技术在元素形态分析中的应用进展

电感耦合等离子体质谱(ICP-MS)作为一种高灵敏度的分析技术在痕量超痕量无机元素分析方面已被广泛应用,其与色谱分离技术相结合为元素形态分析提供了强有力的检测工具.本文阐述了近年来利用不同ICP-MS联用技术进行元素形态分析的研究进展,主要包括:①气相色谱-电感耦合等离子体质谱联用技术(GC-ICP-MS);②毛细管电...     

Comments on the paper “The nature of “Svecofennian” zircon in the Belomorian Mobile Belt and some geological implications” by A.A. Shchipanskii and A.I. Slabunov

Eclogites were relatively recently found in the Belomorian Mobile Belt (BMB) (Volodichev et al., 2004; Shchipanskii et al., 2005; Konilov et al., 2004). The very first isotopic dates (Volodichev et al., 2004; Mints et al., 2010) were obtained for these rocks in the northwestern (in the Salma and Kuru-Vaara areas) and central (Gridino area) portions of BMB and corresponded to the Archean: approximately 2.72–2.87 Ga. Because no crustal eclogites older that 2.0 Ga (Möller et al., 1995) had been known before these dates were obtained, these eclogites were regarded as unique. It is commonly believed that no crustal eclogites could be formed in the Archean because the crust was then relatively thin (Kröner, 2010), and hence, the find of crustal eclogites of Archean age in BMB called for a fundamental revision of geodynamic reconstructions of the crustal evolution and was one of the main arguments invoked to support the hypothesis that currently operating geodynamic mechanisms of plate tectonic can be extrapolated to the Early Precambrian (Rozen et al., 2008). However, these finds were practically immediately followed by serious doubts that the primary estimates of the timing of the eclogite metamorphism in the Belomorian Belt may be incorrect (Mitrofanov et al., 2009; and others).     

ICP-MS在新疆、青海区调样品测定中的应用

本文以敞开式四酸溶样,电感耦合等离子体质谱测定了新疆、青海区调样品中的Co、Mo、W、Pb等元素,并把ICP-MS、ICP-AES和XRF三个大型仪器对新疆卡克-色帕巴衣地区样品的测定结果进行了比较,确定了区调样品元素分析方法的配套方案,并对溶样过程进行了一系列的优化,其方法检出限和精密度均符合DZ0130.4-2006及补充说明中1﹕5万化探样品标准要求。经国家标准物质验证,结果与标准值相符。优化的分析方法快速灵敏度高,能用于地球化学填图计划中分析测试任务, 同时也用于日常大规模多元素分析。     

辽西建昌县玲珑塔含翼龙和带羽毛恐龙化石地层层序和时代归属

最近辽西建昌地区报道发现了一系列带羽毛恐龙和翼龙化石, 其赋存化石的地层层位时代一直富有争议。我们结合前人资料对玲珑塔含化石地层剖面进行了野外调查和实测, 厘定了含化石地层沉积层序和时代归属。剖面顶底岩石组合特征主要以溢流相中性熔岩和近火山口相火山碎屑岩为主, 中间层位为河流相-湖泊相碎屑岩。该剖面产有大量叶肢介、介形类、双壳类、昆虫、鱼类、植物化石和大量脊椎动物化石。上述化石指示含恐龙化石地层时代为中侏罗世。通过区域对比认为含恐龙化石地层与区域上髫髻山组地层层序和岩石组合相似, 因此认为含恐龙化石地层为中侏罗世髫髻山组(火山岩同位素年代学年龄范围为152~165 Ma)。     

Analysis of High Density Regional Geochemical Soil Samples at the Council for Geoscience (South Africa): The Importance of Quality Control Measures

The Council for Geoscience (CGS, South Africa) has a statutory mandate to carry out regional geochemical mapping in South Africa that needs to be rapidly and accurately analysed. Both simultaneous X-ray fluorescence spectrometry (S-XRF) and a newly developed method using inductively coupled plasma-mass spectrometry (ICP-MS) were employed. Various trace elements that could not previously be analysed by S-XRF can now be analysed by ICP-MS for the regional geochemical mapping programme, e.g., Cd, Mo, Te and Li. Using both techniques, the CGS aims to report element distributions for some fifty elements. To ensure that element concentration levels correlate over map boundaries, quality control measures in the sampling, sample preparation and analyses were of critical importance. This paper aims to discuss the sample preparation and quality control measures as applied to the ∼5500 samples of the Giyani and Tzaneen 1:100000 scale map sheets sampled at a density of one soil sample per km². ICP-MS batch- and instrumental drift-correction procedures will be discussed. As a final step, geochemical data were overlain over simplified geological maps using geographical information system software. These maps complement existing geological information of South Africa, help in the identification of exploration targets, test exploration models and initiate further geological research.