利用ICP-AES快速检测碳酸盐金属元素的方法研究

本实验采用湿法消解碳酸盐岩矿石样品,利用电感耦合等离子体发射光谱仪(ICP-AES),采用内标法和基体匹配法相结合测定了碳酸盐岩标准物质(GBW10035a)中高达54%的氧化钙主量元素含量及其它常微量元素的含量;对实际样品中微量元素进行样品加标回收率实验,对主量和常量元素采用稀释法验证。实验结果表明,样品加标回收率在94%~108%之间,稀释比率在99.4%~100.2%,标准物质测定值与标准值吻合,6次平行样测定的稳定性4%;该方法一次溶样,径向测定主量和常量元素,轴向测定微量元素含量,操作简单,快速,该方法适用于盐湖碳酸盐样品,以及其他含有碳酸盐的各类样品的分析测试。     

铼-锇同位素的等离子体质谱法测定及其在辉钼矿测年中的应用

研究了用ICPMS法测定地质样品Re-Os同位素的条件。通过选用Meinhard同心雾化器进样对Os(Ⅷ)水溶液进行测定,可使Os的测定灵敏度提高50倍。讨论了质量歧视效应校正中的有关问题。采用氧化剂清洗,克服了Os在进样系统中的严重记忆效应。用同位素稀释法测定了辉钼矿中Re和~(187)Os的含量,计算了成矿年龄。     

水平式ICP—AES分析岩石中痕量稀土元素（照相换线法）

本文对我室十年来用水平式TCP—AES照相换线法,分析岩石中痕量稀土元素的一些经验如试样分解、分离富集、标准配制、摄谱选线等条件,进行总结。现本法可同时测定Sc,Y等16个稀土元素。分析范围达5个故量级,即10~(-9)～10~(-5),采用水冷式加热雾室去溶,能防止雾化器堵塞;其检出限最低、准确度高、相对标准偏差均小于5%。     

A Synthetic Haematite Reference Material for LA‐ICP‐MS U‐Pb Geochronology and Application to Iron Oxide‐Cu‐Au Systems

In both nature and synthetic experiments, the common iron oxide haematite (α‐Fe₂O₃) can incorporate significant amounts of U into its crystal structure and retain radiogenic Pb over geological time. Haematite is a ubiquitous component of many ore deposit types and, therefore, represents a valuable hydrothermal mineral geochronometer, allowing direct constraints to be placed on the timing of ore formation and upgrading. However, to date, no suitable natural haematite reference material has been identified. Here, a synthetic haematite U‐Pb reference material (MR‐HFO) is characterised using LA‐ICP‐MS and ID‐TIMS. Centimetre‐scale ‘chips’ of synthesised α‐Fe₂O₃ were randomly microsampled via laser ablation‐extraction and analysed using ID‐TIMS. Reproducible U/Pb and Pb/Pb measurements were obtained across four separate chips (n = 13). Subsequently, an evaluation of the suitability MR‐HFO in constraining U‐Pb data via LA‐ICP‐MS is presented using a selection of natural samples ranging from Cenozoic to Proterozoic in age. The MR‐HFO normalised U‐Pb ratios are more concordant and ages more accurate versus the same LA‐ICP‐MS spot analyses normalised to zircon reference material, when compared with independently acquired ID‐TIMS data from the same natural haematite grains. Results establish MR‐HFO as a suitable reference material for LA‐ICP‐MS haematite U‐Pb geochronology.     

GHR1 Zircon – A New Eocene Natural Reference Material for Microbeam U‐Pb Geochronology and Hf Isotopic Analysis of Zircon

We present multitechnique U‐Pb geochronology and Hf isotopic data from zircon separated from rapakivi biotite granite within the Eocene Golden Horn batholith in Washington, USA. A weighted mean of twenty‐five Th‐corrected ²⁰⁶Pb/²³⁸U zircon dates produced at two independent laboratories using chemical abrasion‐isotope dilution‐thermal ionisation mass spectrometry (CA‐ID‐TIMS) is 48.106 ± 0.023 Ma (2s analytical including tracer uncertainties, MSWD = 1.53) and is our recommended date for GHR1 zircon. Microbeam ²⁰⁶Pb/²³⁸U dates from laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) and secondary ion mass spectrometry (SIMS) laboratories are reproducible and in agreement with the CA‐ID‐TIMS date to within < 1.5%. Solution multi‐collector ICP‐MS (MC‐ICP‐MS) measurements of Hf isotopes from chemically purified aliquots of GHR1 yield a mean ¹⁷⁶Hf/¹⁷⁷Hf of 0.283050 ± 17 (2s, n = 10), corresponding to a εHf₀ of +9.3. Hafnium isotopic measurements from two LA‐ICP‐MS laboratories are in agreement with the solution MC‐ICP‐MS value. The reproducibility of ²⁰⁶Pb/²³⁸U and ¹⁷⁶Hf/¹⁷⁷Hf ratios from GHR1 zircon across a variety of measurement techniques demonstrates their homogeneity in most grains. Additionally, the effectively limitless reserves of GHR1 material from an accessible exposure suggest that GHR1 can provide a useful reference material for U‐Pb geochronology of Cenozoic zircon and Hf isotopic measurements of zircon with radiogenic ¹⁷⁶Hf/¹⁷⁷Hf.     

Rapid Determination of Trace Element Compositions in Peridotites by LA‐ICP‐MS Using an Albite Fusion Method

A rapid sample preparation procedure is described to determine trace element compositions of peridotites using LA‐ICP‐MS. Peridotite powders were fused with albite in a molybdenum–graphite assembly to obtain homogeneous glasses. Best conditions for the fusion procedure (heating at 1500–1550 °C for 10–15 min with a sample‐to‐flux ratio of 1:2) were constrained with melting experiments on two USGS reference materials, PCC‐1 and DTS‐2B. Mass fractions of first series transition elements, Ba and Pb, in quenched glasses of PCC‐1 and DTS‐2B are consistent with published data within 10% RSD. Three spinel peridotite xenoliths from eastern China were analysed following both our method and conventional solution ICP‐MS. Compared with solution ICP‐MS, the relative deviations of our method for most elements were within 10%, while for the REE, Ta, Pb, Th and U, the relative deviations were within 20%. In particular, volatile elements (e.g., Pb and Zn) are retained in the glass. Compared with conventional wet chemistry digestion, our method is faster. Additional advantages are complete sample fusion, especially useful for samples with acid‐resistant minerals (spinel and rutile), and long‐term conservation of glasses allowing unlimited repeated measurements with microbeam techniques. The same approach can be used for analyses of other mantle rocks, such as eclogites and pyroxenites.     

Assessment of Dissolution of Silicate Rock Reference Materials with Ammonium Bifluoride and Nitric Acid in a Microwave Oven

The complete dissolution of representative test portions of powdered rock samples for the determination of the mass fractions of trace elements by ICP‐MS relies either on aggressive and time‐consuming acid digestions or fusion/sintering with appropriate fluxes. Here, we evaluate a microwave oven dissolution method that employs a solution of NH₄HF₂ and HNO₃. The entire procedure occurs in a closed vessel system and takes up to 4 h. In hundreds of digestions, the precipitation of fluorides was never observed. Replicate decomposition of 100 mg of twenty‐one international reference materials (RMs) of igneous rocks, and also one of a shale presented mostly satisfactory recoveries of forty‐one trace elements. Important exceptions were Zr and Hf in G‐2 and GSP‐2 (mean recoveries of ca. 70%), although for four other felsic rock RMs, the digestion was complete. For ultramafic rock RMs, we present Cr results that indicate quantitative dissolution of Cr‐bearing phases. We discuss the findings and conclude that advances in sample preparation of geological materials for instrumental analysis would benefit from a better understanding of how specific characteristics, such as composition and crystallinity of certain minerals, may affect their reactivity.     

Natural Titanite Reference Materials for In Situ U‐Pb and Sm‐Nd Isotopic Measurements by LA‐(MC)‐ICP‐MS

Titanite is a common accessory mineral that preferentially incorporates considerable amounts of U and light rare earth elements in its structure, making it a versatile mineral for in situ U‐Pb dating and Sm‐Nd isotopic measurement. Here, we present in situ U‐Pb ages and Sm‐Nd isotope measurement results for four well‐known titanite reference materials (Khan, BLR‐1, OLT1 and MKED1) and eight titanite crystals that could be considered potential reference material candidates (Ontario, YQ‐82, T3, T4, TLS‐36, NW‐IOA, Pakistan and C253), with ages ranging from ~ 20 Ma to ~ 1840 Ma. Results indicate that BLR‐1, OLT1, Ontario, MKED1 and T3 titanite have relatively homogeneous Sm‐Nd isotopes and low common Pb and thus can serve as primary reference materials for U‐Pb and Sm‐Nd microanalysis. YQ‐82 and T4 titanite can be used as secondary reference materials for in situ U‐Pb analysis because of their low common Pb. However, internal structures and mineral inclusions in YQ‐82 will require careful selection of suitable target domains. Pakistan titanite is almost concordant with an age of 21 Ma and can be used as a reference material when dating Cenozoic titanite samples.     

Denudation history of the Kiso Range,central Japan,and its tectonic implications: Constraints from low‐temperature thermochronology

Fission‐track (FT) and (U–Th–Sm)/He (He) analyses are used to constrain the denudation pattern and history of the Kiso Range, a Japanese fault‐block mountain range which has been uplifted since ca 0.8 Ma. We obtained nine zircon FT ages ranging 59.3–42.1 Ma, 18 apatite FT ages ranging 81.9–2.3 Ma, and 13 apatite He ages ranging 36.7–2.2 Ma. The apatite FT and He ages are divided into an older group comparable to the zircon FT age range and a younger group of <18 Ma. The younger ages are interpreted as a reflection of uplift of the Kiso Range because they were obtained only to the east of the Seinaiji‐touge Fault, and the event age estimated from apatite FT data is consistent with the timing of the onset of the Kiso Range uplift. On the basis of the distribution of the younger ages, we propose westward tilting uplift of the Kiso Range between the boundary fault of the Inadani Fault Zone and Seinaiji‐touge Fault, which implies a model of bedrock uplift that is intermediate between two existing models: a pop‐up model in which the Kiso Range is squeezed upward between the two faults and a tilted uplift model which assumes that the Kiso Range is uplifted and tilted to the west by the Inadani Fault Zone. The original land surface before the onset of uplift/denudation of the Kiso Range is estimated to have been uplifted to an elevation of 2700–4900 m. We estimated denudation rates at 1.3–4.0 mm/y and maximum bedrock uplift rates at 3.4–6.1 mm/y since ca 0.8 Ma. The Seinaiji‐touge fault is interpreted as a back thrust of the west‐dipping Inadani Fault Zone. The older group of apatite FT and He ages is interpreted to reflect long‐term peneplanation with a probable denudation rate of <0.1 mm/y.     

A multi‐geochronological study of the Hakusan volcano,central Japan

The Hakusan volcano, central Japan, is located in a region where two subducting plates (the Pacific Plate and the Philippine Sea Plate) overlap near the junction of four plates adjacent to the Japanese Islands (the Pacific Plate, the Philippine Sea Plate, the Eurasia Plate, and the North American Plate). The Hakusan volcano consists of products from four major volcanic episodes: Kagamuro, Ko‐hakusan, and Shin‐Hakusan I and II. To date the eruption events of the Hakusan volcano we applied thermoluminescence and fission track methods. ²³⁸U(²³⁴U)–²³⁰Th disequilibrium and ²⁰⁶Pb/²³⁸U methods were applied to date the zircon crystallization ages for estimating the magma residence time before the eruptions. The eruption ages we obtained are ca 250 ka for Kagamuro, ca 100 ka and ca 60 ka for Ko‐Hakusan, ca 50 ka for Shin‐Hakusan I, and <10 ka for Shin‐Hakusan II. They are concordant with previous reports based on K–Ar dating. Some of the pyroclastic rocks, possibly originating from Shin‐Hakusan II activities, are dated to be ca 36 ka or 50 ka, and belong to the Shin‐Hakusan I activity. The zircon crystallization ages show several clusters prior to eruption. The magma residence time was estimated for each volcanic activity by comparing the major crystallization events and eruption ages, and we found a gradual decrease from ca. 500 ky for the Kagamuro activity to ca. 5 ky for the Shin‐Hakusan II activity. This decrease in residence time may be responsible for the decrease in volume of erupted material estimated from the current topography of the region. The scale of volcanic activity, which was deduced from the number of crystallized zircons, is more or less constant throughout the Hakusan volcanic activity. Therefore, the decrease in magma residence time is most likely the result of stress field change.