上扬子西南缘早三叠世嘉陵江组物源分析和构造环境:沉积学、重矿物电子探针和U- Pb年龄的限定

上扬子西南缘地区广泛分布峨眉山玄武岩,受其影响在中带金阳和外带荥经地区嘉陵江组发育滨岸和潮坪环境沉积物。本文在交错层理恢复的物源方向基础上,根据重矿物组成、重矿物电子探针和碎屑锆石测年结果,综合分析不同区域嘉陵江组物源区,进而探讨嘉陵江组形成的构造环境。嘉陵江组砂岩碎屑重矿物锆石、磷灰石、铬尖晶石等指示物源主要来自于岩浆岩,且自中带至外带基性岩浆岩所占比重逐渐减少。电气石电子探针分析显示,二者物源主要来自于贫锂花岗岩和变质砂岩、板岩。铬尖晶石显示,金阳地区物源来自峨眉山玄武岩和洋岛岩浆岩类岩石,荥经物源主要来自洋岛岩浆岩类岩石,个别为峨眉山玄武岩。碎屑锆石表明,嘉陵江组物源主要来自于新元古代岩浆岩和晚二叠世峨眉山玄武岩,前者经历再搬运。综合物源分析表明,嘉陵江组物源主要来自康滇古陆,岩石类型主要为峨眉山玄武岩和砂岩等。沉积序列和物源分析表明,嘉陵江组反映了沉积物蚀顶过程。结合地震资料、大火成岩省的分析成果表明,嘉陵江组形成于火山型裂谷边缘。     

‘Box‐Profile’ Ion Implants as Geochemical Reference Materials for Electron Probe Microanalysis and Secondary Ion Mass Spectrometry

Although electron probe microanalysis and secondary ion mass spectrometry are widely used analytical techniques for geochemical and mineralogical applications, metrologically rigorous quantification remains a major challenge for these methods. Secondary ion mass spectrometry (SIMS) in particular is a matrix‐sensitive method, and the use of matrix‐matched reference materials (RMs) is essential to avoid significant analytical bias. A major problem is that the number of available RMs for SIMS is extremely small compared with the needs of analysts. One approach for the production of matrix‐specific RMs is the use of high‐energy ion implantation that introduces a known amount of a selected isotope into a material. We chose the more elaborate way of implanting a so‐called ‘box‐profile’ to generate a quasi‐homogeneous concentration of the implanted isotope in three dimensions, which allows RMs not only to be used for ion beam analysis but also makes them suitable for EPMA. For proof of concept, we used the thoroughly studied mineralogically and chemically ‘simple’ SiO₂ system. We implanted either ⁴⁷Ti or ⁴⁸Ti into synthetic, ultra‐high‐purity silica glass. Several ‘box‐profiles’ with mass fractions between 10 and 1000 μg g^?1 Ti and maximum depths of homogeneous Ti distribution between 200 nm and 3 μm were produced at the Institute of Ion Beam Physics and Materials Research of Helmholtz‐Zentrum Dresden‐Rossendorf. Multiple implantation steps using varying ion energies and ion doses were simulated with Stopping and Range of Ions in Matter (SRIM) software, optimising for the target concentrations, implantation depths and technical limits of the implanter. We characterised several implant test samples having different concentrations and maximum implantation depths by means of SIMS and other analytical techniques. The results show that the implant samples are suitable for use as reference materials for SIMS measurements. The multi‐energy ion implantation technique also appears to be a promising procedure for the production of EPMA‐suitable reference materials.     

Effects of the peat acid digestion protocol on geochemically and morphologically diverse tephra deposits

Tephra shards for electron probe microanalysis are most efficiently extracted from peat using acid digestion, which removes organic material that hinders density separation methods. However, strong acids are known to alter glass chemical compositions, and several studies have examined how acid digestion affects rhyolitic volcanic glass. The focus on rhyolitic tephra in these studies leaves considerable uncertainty, as the dissolution rates of natural glasses (including tephra) are determined by the chemical composition and surface area/volume ratio, both of which vary in tephra deposits. Here, we use duplicate samples of basaltic, trachydacitic and rhyolitic tephra to examine physical and geochemical alteration following acid digestion. Scanning electron microscope imagery reveals no discernible degradation of glass surfaces, and electron probe microanalysis results from duplicate samples are statistically indistinguishable. These findings suggest the acid digestion protocol for organic peats does not significantly alter glass geochemistry regardless of shard morphologies or geochemical compositions.     

华北克拉通南缘石炭系本溪组铁-铝黏土矿物质来源: 以河南三门峡大安铝黏土矿床为例*

华北克拉通在中奥陶世至晚石炭世期间一直出露地表,经历了长期的风化作用,形成大规模的铁-铝黏土矿,其成矿物源一直是研究的热点,尤其是本溪组底部铁矿和铁质黏土矿与上部铝黏土矿是否为同一来源尚未查清。本研究选取克拉通南缘大安铝黏土矿床作为研究对象,展开微区矿物及元素地球化学组成分析,进一步探讨铁-铝黏土矿物质来源。大安矿床内含矿岩系自下而上包括铁质黏土岩、铝土矿、铝质黏土矿;局部喀斯特高地缺失铝土矿,铝质黏土矿直接覆盖于铁质黏土岩之上。铁质黏土岩在洼地以菱铁矿、黄铁矿和伊利石为主,在隆起区以赤铁矿、伊利石和高岭石为主。铝土矿以硬水铝石、伊利石和锐钛矿为主;铝质黏土矿主要矿物为伊利石。矿物微区分析在黏土矿底部发现大量的碳化硅和少量自然硅、硅铁矿、铬铁矿;区域对比揭示北秦岭造山带内商丹缝合带和二郎坪群中的蛇绿岩为铝黏土矿形成提供了成矿物质。本溪组底部铁质黏土与上部铝黏土矿稳定元素比率(例如Zr/TiO₂、Hf/TiO₂、Nb/TiO₂、Ta/TiO₂)存在明显差异,揭示二者为不同来源: 底部铁质黏土岩和铁矿层为底板碳酸盐岩原地风化的产物;而上部铝黏土矿是异地搬运物,北秦岭造山带在晚石炭世的整体抬升为华北铝黏土矿形成提供了重要的成矿物质。     

Electron Probe Microanalysis of Bromine in Minerals and Glasses with Correction for Spectral Interference from Aluminium,and Comparison with Microbeam Synchrotron X‐Ray Fluorescence Spectrometry

The strong spectral interference between Br‐ and Al‐induced X‐ray lines hampers the utilisation of electron probe microanalysis (EPMA) for measuring Br mass fractions in Al‐bearing minerals and glasses. Through measuring Br‐free Al‐bearing materials, we established an EPMA method to quantify the overlap from AlKα on BrLβ, which can be expressed as a linear function of the Al₂O₃ content. The count rate of the BrLβ peak signal was enhanced by high beam currents and long measurement times. Application of this EPMA method to Al‐ and Br‐bearing materials, such as sodalite and scapolite, and to five experimental glasses yielded Br mass fractions (in the range of 250–4000 μg g^?1) that are consistent with those measured by microbeam synchrotron X‐ray fluorescence (μ‐SXRF) spectrometry. The EPMA method has an estimated detection limit of ~ 100–300 μg g^?1. We propose that this method is useful for measuring Br mass fractions (hundreds to thousands of μg g^?1) in Al‐bearing minerals and glasses, including those produced in Br‐doped experiments. In addition, the natural marialitic scapolite (ON70) from Mpwapwa (Tanzania) containing homogeneously distributed high mass fractions of Br (2058 ± 56 μg g^?1) and Cl (1.98 ± 0.03% m/m) is an ideal reference material for future in situ analyses.     

Tephrostratigraphy of the last 170 ka in sedimentary successions from the Adriatic Sea

In this study are discussed new SEM-EDS analyses performed on glass shards from five cores collected in the Central Adriatic Sea and two cores recovered from the South Adriatic Sea. A total of 26 tephra layers have been characterized and compared with the geochemical features of terrestrial deposits and other tephra archives in the area (South Adriatic Sea and Lago Grande di Monticchio, Vulture volcano). The compositions are compatible with either a Campanian or a Roman provenance. The cores, located on the Central Adriatic inner and outer shelf, recorded tephra referred to explosive events described in the literature: AP3 (sub-Plinian activity of the Somma-Vesuvius, 2710 ± 60 ¹⁴C years BP); Avellino eruption (Somma–Vesuvius, 3548 ± 129 ¹⁴C years BP); Agnano Monte Spina (Phlegrean Fields, 4100 ± 400 years BP); Mercato eruption (Somma–Vesuvius, 8010 ± 35 ¹⁴C years BP; Agnano Pomici Principali eruption (Phlegrean Fields, 10,320 ± 50 ¹⁴C years BP); Neapolitan Yellow Tuff (Phlegrean Fields, 12,100 ± 170 ¹⁴C years BP). Some of these layers were also observed in the South Adriatic core IN68-9 in addition to younger (AP2, sub-Plinian eruption, Somma–Vesuvius, 3225 ± 140 ¹⁴C years BP), and older layers (Pomici di Base eruption, Somma–Vesuvius, 18,300 ± 150 ¹⁴C years BP). Significant is the tephra record of core RF95-7 that, for the first time in the Adriatic Sea, reports the occurrence of tephra layers older than 60 ka: the well known Mediterranean tephra layers X2 (ca. 70 ka), W1 (ca. 140 ka) and V2 (Roman origin, ca. 170 ka) as well as other tephra layers attributed, on the basis of geochemistry and biostratigraphy, to explosive eruptions occurred at Vico (138 ± 2 and 151 ± 3 ka BP) and Ischia (147–140 ka BP).     

皖南花山锑金矿床硫化物电子探针分析及其指示意义

花山锑金矿床位于皖南东至县境内, 是皖南地区代表性金-多金属矿床之一。 本次工作对花山锑金矿床开展了野外地质、岩相学特征观察以及金属硫化物电子探针分析, 得到以下结论：1） 花山锑金矿床主要成矿阶段可分为毒砂-黄铁矿（PyⅠ）阶段、黄铜矿-黄铁矿 （PyⅡ）阶段和方解石-辉锑矿阶段。 2） 金在不同阶段硫化物中均有赋存, 其矿化伴随整个热液成矿过程, 且以毒砂-PyⅠ阶段和黄铜矿-PyⅡ阶段为主。 毒砂-PyⅠ阶段和黄铜矿-PyⅡ阶段发育金矿化, 无锑矿化, 方解石-辉锑矿阶段发育锑、金共生矿化。 3） 早阶段即毒砂 -PyⅠ阶段和黄铜矿-PyⅡ阶段载金矿物为黄铁矿、毒砂及黄铜矿, 成矿物质来源以地层为 主;晚阶段即方解石-辉锑矿阶段载金矿物为辉锑矿, 成矿物质来源以燕山期岩浆岩为主。 本次工作对东至及皖南地区金矿床的寻找勘探具有重要的指示意义。     

GGR Biennial Critical Review: Analytical Developments Since 2014

This GGR biennial critical review covers developments and innovations in key analytical methods published since January 2014, relevant to the chemical, isotopic and crystallographic characterisation of geological and environmental materials. In nine selected analytical fields, publications considered to be of wide significance are summarised, background information is provided and their importance evaluated. In addition to instrumental technologies, this review also presents a summary of new developments in the preparation and characterisation of rock, microanalytical and isotopic reference materials, including a précis of recent changes and revisions to ISO guidelines for reference material characterisation and reporting. Selected reports are provided of isotope ratio determinations by both solution nebulisation MC‐ICP‐MS and laser ablation‐ICP‐MS, as well as of radioactive isotope geochronology by LA‐ICP‐MS. Most of the analytical techniques elaborated continue to provide new applications for geochemical analysis; however, it is noted that instrumental neutron activation analysis has become less popular in recent years, mostly due to the reduced availability of nuclear reactors to act as a neutron source. Many of the newer applications reported here provide analysis at increasingly finer resolution. Examples include atom probe tomography, a very sensitive method providing atomic scale information, nanoscale SIMS, for isotopic imaging of geological and biological samples, and micro‐XRF, which has a spatial resolution many orders of magnitude smaller than conventional XRF.     

粤西庙山铜多金属矿床硫化物微量元素LA-ICP-MS原位测定及S同位素对矿床成因的制约

庙山铜多金属矿床是在粤西阳春盆地内新近发现的一处铜多金属矿床。矿体主要呈似层状和透镜状产于泥盆系的陆源碎屑岩和含泥质的碳酸盐岩中。本文以矿石矿物黄铁矿和闪锌矿为研究对象,采用LA-ICP-MS原位微区分析新技术对其微量元素特征进行研究。结果表明,庙山铜多金属矿床中黄铁矿以富Se、Te和As,贫Ni元素为特征,其Co/Ni和S/Se比值特征指示其成因与岩浆热液型矿床密切相关;闪锌矿的微量元素组成指示其主要形成于中高温环境,以富Mn、In、Se,贫Ga、Ge、Tl等元素为特征,总体与国外一些典型的矽卡岩型矿床（如Baita Bihor、Majdanpek、Ocna de Fier和Valea Seaca）相似。同时,闪锌矿的部分微量元素比值（如Zn/Cd、Ga/In等）以及相关的微量元素图解（如Ge-In, Ge-Se等）均表明庙山矿床的成因类型与矽卡岩型矿床一致。硫同位素测试结果表明,矿石的δ34S值较为集中（-0.4‰ ~ +2‰）,平均0.69‰,具有较为明显的塔式分布特征,反映成矿物质具有岩浆来源的特征。以地质现象为基础,结合硫化物原位微区分析和硫同位素数据,我们认为庙山铜多金属矿床属于与岩浆热液有关的矽卡岩型矿床。     

Biomass Burning in Southern Africa: Individual Particle Characterization of Atmospheric Aerosols and Savanna Fire Samples

Ambient atmospheric aerosols and savanna fireparticulate emission samples from southern Africa werecharacterised in terms of particle classes and theirnumber abundance by electron probe X-ray microanalysis(EPXMA). About ten particle classes were identifiedfor each sample. The major classes werealuminosilicates and sea salts for ambient coarse(2–10 m equivalent aerodynamic diameter (EAD))samples, and K-S and S-only particles for ambient fine(<2 m EAD) samples. The K-S particles are oneof the major products of biomass burning. The EPXMAresults were found to be consistent with the resultsfrom bulk analyses on a sample by sample basis. Forsavanna fire fine samples, quantitative EPXMA revealedthat many particles had a composition of simple saltssuch as KCl. Some particles had a deviatingcomposition in the sense that more ionic species wereinvolved in sustaining the balance between cations andanions, and they were composite or mixed salts.Because of extensive processing during the atmospherictransport, the composition of the K-S particles in theambient samples was different from K₂SO₄,and such particles were enriched with S. The finepyrogenic KCl particles and the fine sea-saltparticles were much depleted in chlorine.