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.     

Thermochronological constraints of the exhumation and uplift of the Sierra de Pie de Palo,NW Argentina

The Sierra de Pie de Palo located between 67°30′–68°30′ W and 31°00′–32°00′ S in the Argentine Western Sierras Pampeanas in Argentina is a distinct basement range, which lacks thermochronological data deciphering its exhumation and uplift history below 200 °C. Integrated cooling histories constrained by apatite fission-track data as well as (U–Th)/He measurements of zircon and apatite reveal that the structural evolution of this mountain range commenced during the Late Paleozoic and was mainly controlled by tectonically triggered erosion. Following further erosional controlled exhumation in a more or less extensional regime during the Mesozoic, the modern topography was generated by denudation in the Paleogene during the early stage of the Andean deformation, whereupon deformation propagated towards the west since the Late Mesozoic to Paleogene. This evolution is characterised by a total of 3.7–4.2 km vertical rock uplift and by 1.7–2.2 km exhumation with a rate of 0.03–0.04 mm/a within the Sierra de Pie de Palo since ca. 60 Ma. Onset of uplift of peak level is also referred to that time resulting in a less Pliocene amount of uplift than previously assumed.     

Silicifications pédogénétiques dans les dépôts hamadiens du piémont de Boudenib (Maroc)

Résumé

— Le système de piémont atlasique du Sud marocain, d’âge tertiaire, est constitué dans le secteur de Boudenib de deux unités distinctes. La llamada de Boudenib forme l’unité inférieure et se caractérise par d’importants encroûtements carbonatés, riches en dolomite et attapulgite. L’unité supérieure de la llamada du Cuir marque une reprise de l’érosion et le dépôt de matériaux relativement peu altérés.

Des silicifications affectent les différents faciès de l’unité inférieure, ainsi que les grès crétacés sous-jacents, et jalonnent une surface d’érosion intra-fonnationnelle. Ces silicifications sont précoces, puisque remaniées dans les dépôts ultérieurs. Les illuviations d’opale et les accumulations gramdaires intercalées entre les concrétionnements successifs de silice attestent d’environnements pédologiques. La silicification plus forte vers la partie supérieure des coupes, ainsi que l’association fréquente des faciés silicifiés avec des niveaux hioturhés et altérés sont également à rapporter à des dispositions pédologiques. Ce sont des silcréles pédogénétiques.

L’étude micrographique montre que la silicification procède par épigénie des argiles et des carbonates, ainsi que par des cristallisations dans les vides. C’est à partir des vides existants (fentes, bioturbations et porosité intergranulaire) que se développe la silicification, montrant ainsi le rôle primordial des circulations. En particulier, l’épigénie des carbonates par la silice semble limitée par la diffusion de la silice à partir des vides, où le renouvellement des solutions est assuré. Les séquences de cristallisation des différentes formes de silice (allant de l’opale vers les quartz automorphes) peuvent être interprétées en terme d’évolution du milieu au cours de la silicification. Au fur et à mesure que des dépôts de silice se font sur les parois des vides, les solutions nourricières sont isolées de la roche encaissante, elles se chargent alors moins en cations étrangers, et la cristallisation de plus grands cristaux peut intervenir.

Les silicifications se développent pendant une période de stabilité tectonique et s’installent dans un paysage de glacis et sous des climats chauds à saisons alternées. Leur reconnaissance à l’échelle régionale peut constituer un repère lithostratigraphique précieux.     

A Method for Rapid Determination of Re and Os Isotope Compositions Using ID‐MC‐ICP‐MS Combined with the Sparging Method

A simple, rapid method for the determination of Re and Os concentrations and isotope compositions using isotope dilution multi‐collector inductively coupled plasma‐mass spectrometry (ID‐MC‐ICP‐MS) combined with Carius tube digestion and sparging introduction of Os was developed. For Os measurement, four channeltron ion counters to detect different Os isotopes were used simultaneously, which led to a drastic reduction in the measurement time. Rhenium isotopes were measured by means of eight Faraday cups with solution nebulisation and an ultrasonic membrane desolvator. The representative ¹⁸⁸Os count rate of an Os standard solution containing 50 pg of total Os was approximately 110000–120000 cps at the onset of measurement; the Re intensity of our in‐house 10 pg g^?1 standard solution reached 1820 V/μg g^?1 with a sample uptake rate of 95–99 μl min^?1. These values indicate that the sensitivity of the method was sufficient even for samples with low Re and Os concentrations, such as chert. As the temporal variations of the amplification efficiency of the ion counters differed from one another, we adopted a sample‐calibrator bracketing method to correct the measured Re and Os isotope ratios. The Re and Os concentrations via the isotope dilution method and the ¹⁸⁷Os/¹⁸⁸Os ratios of two sedimentary rock reference materials (JMS‐2 and JCh‐1) on the basis of the isotope ratios determined by the MC‐ICP‐MS and by negative thermal ionisation mass spectrometry (N‐TIMS) were comparable within their ranges. Based on Os isotope measurement of the IAG reference material [Durham Romil Os (DROsS)], the average difference from the recommended value and precision of Os isotope measurements by the sparging method in combination with multi‐ion‐counters were 0.72% and 0.76% [1RSD (%), n = 29], respectively. The precisions in the ¹⁸⁷Os/¹⁸⁸Os ratios [1RSD (%)] of JMS‐2, JCh‐1 and DROsS were 0.35–0.71, 1.56–3.31 and 0.99–1.28%, respectively, which depended on their Os ion intensities. No systematic difference was observed between the Re and Os geochemical compositions of JCh‐1 and JMS‐2 obtained by means of digestion with inverse aqua regia and CrO₃‐H₂SO₄ solutions, suggesting that either acid solution can be used for the sparging method of sedimentary rock samples. As CrO₃‐H₂SO₄ solution is believed to liberate predominantly the hydrogenous Re and Os fraction from organic‐rich sediment, the sparging method combined with CrO₃‐H₂SO₄ digestion and multi‐ion‐counters in the mass spectrometry is expected to be a powerful tool for reconstructing the secular change in marine Os isotope compositions with high sample throughput.     

VizualAge: A Novel Approach to Laser Ablation ICP‐MS U‐Pb Geochronology Data Reduction

VizualAge, a new computer software tool for analysing U‐Pb data obtained by laser ablation‐inductively coupled plasma‐mass spectrometry, was developed. It consists of a data reduction scheme (DRS) for Iolite (a general mass spectrometry data analysis tool) as well as visualisation routines. In addition to the U/Pb and Th/Pb ages calculated by Iolite’s U‐Pb geochronology DRS, VizualAge also calculates ²⁰⁷Pb/²⁰⁶Pb ages and common Pb corrections for each time‐slice of raw data. Importantly, VizualAge allows one to display a live concordia diagram for visualising data on such a diagram as an integration interval is being adjusted. This provides instantaneous feedback regarding discordance, uncertainty, error correlation and common Pb. Several zircon data sets were used to illustrate how the live concordia could be used as a powerful inspection tool, revealing a single analysis to consist of zones of concordance, metamict areas, as well as inherited cores or younger overgrowths. VizualAge also constructs histograms, conventional and Tera‐Wasserburg type concordia diagrams, as well as 3D U‐Th‐Pb and total U‐Pb concordia diagrams. The precision and accuracy of data reduced with VizualAge are demonstrated with examples of the Ple?ovice, Temora‐2 and Penglai zircon reference materials. Data for zircon from the Long Lake Batholith (Wyoming craton) were used to illustrate how VizualAge calculated common Pb corrections and helped to expose as yet unexplained difficulties with accurately determining ²⁰⁴Pb.     

Late Ordovician to early Silurian calc-alkaline magmatism in the Xiemisitai Mountains,northern West Junggar: a response to the subduction of the Junggar-Balkhash Ocean

Basement exposed in the Placer de Guadalupe–Plomosas uplift in northern Mexico provides important clues for the geologic evolution of the region. The stratigraphic units form stacked thrust sheets of psammitic and calcareous formations, interlayered with magmatic rock. The eastern calcareous and quartzite formations exhibit structures associated with ductile deformation, whereas the upper stratigraphic units only contain structures formed via younger brittle deformation. Porphyry interlayered in the upper Plomosas Formation has a U-Pb zircon age of 171 ± 1 Ma. This age is consistent with its stratigraphic position, interbedded quartzarenites with a maximum depositional age of ~168 Ma. Granite flakes within the Horquilla Formation are dated at 209 ± 3 Ma, and the La Viñata quartzite exhibits a maximum age of ~193 Ma. The Upper Plomosas Formation correlates well with the arc-related Middle Jurassic Nazas Formation of northeastern Mexico, constituting the first report of a Jurassic continental margin arc outcrop in the ‘Central Mexican Gap zone’. We document Late Norian to Bajocian ages for the stratigraphic units cropping out in the Placer de Guadalupe area. The Jurassic age cluster indicates that the Nazas Arc magmatism in the region occurred during the Late Triassic and ended in the Middle Jurassic times. Permian ages previously assigned to these rocks and the occurrence of a Permo–Triassic deformation event have to be dismissed.     

金川镍矿含矿岩体的稀土元素及微量元素地球化学特征

通过对采自金川镍矿I矿区露天矿的第二期侵入岩体中。样品的稀土元素、微量元素进行全岩等离子质谱（ICP－MS）测定发现第二期侵入的岩体具有明显的轻稀土元素富集和无明显铕异常的特征，是上地幔低比例平衡部分熔融和分离结晶共同作用的产物。岩体中镍黄铁矿、磁黄铁矿、黄铁矿成条带状出现，表明其形成时低氧逸度的成岩环境。     

甘肃大型变形构造及蛇绿构造混杂岩带特征

大型变形构造带是地球表层重要的构造现象,它们记载了地壳的构造变形（走滑错移、逆冲叠覆和伸展滑移）过程及其动力学机制。本文根据大型变形构造定义及其分类原则,将甘肃省大型变形构造划分为3大类10种类型,初步厘定出大型变形构造带23个,简要叙述了主要大型变形构造规模、产状、构造层次、物质组成、变形期次等基本特征,探讨了大型变形构造与蛇绿构造混杂岩带的关系,从全省北山造山带、祁连造山带、西秦岭造山带和鄂尔多斯盆地“三带一盆”的构造格局出发,探讨大型变形构造形成、演化历史。     

甘孜—理塘结合带锰结核的发现及其地质意义

在甘孜—理塘结合带内理塘县中木拉乡附近发现锰结核。通过地质填图和综合研究,该锰结核产于结合带内瓦能蛇绿混杂岩组中的黑色粉砂质板岩中。其沉积层序为玄武岩→硅质岩→含锰结核粉砂质板岩。锰结核主量元素具有高Mn、低Fe、Si、Ca的特点,其中Mn含量为42.19%,高出大洋锰结核平均值1.83倍,Mn/Fe值较高,达8.1。锰结核中除Cr高于大洋锰结核平均值2～7倍外,多数微量元素低于大洋锰结核平均值。稀土元素具有较明显的Ce正异常,稀土总量、轻重稀土分异程度、Eu异常特征与混杂岩中的砂岩、硅质岩近似,而与玄武岩差别较大。该锰结核产出于大陆边缘构造环境,火山活动微弱,代表甘孜—理塘洋扩张到最大程度时的沉积。其时甘孜—理塘洋规模仍是有限的。