高Rb/Sr岩石样品中Sr同位素多接收等离子体质谱分析校正方法研究

在利用多接收电感耦合等离子体质谱(MC-ICPMS)进行Sr同位素研究中,⁸⁷Rb对于⁸⁷Sr干扰严重。岩石样品经化学分离后,若Rb/Sr≤0.0005,可以采用传统的Rb干扰扣除方法对⁸⁷Sr/⁸⁶Sr测定值进行准确校正;但如果样品经化学分离后仍含有较高的Rb/Sr比,同量异位素的干扰不能完全消除,则无法准确校正⁸⁷Sr/⁸⁶Sr测定值,直接影响测试结果的准确度。本文针对Rb含量较高的地质样品设计两组实验,确定了⁸⁷Sr/⁸⁶Sr同位素比值与Rb/Sr元素含量比值的关系曲线,并在理论分析的基础上,提出包含同位素分馏校正在内的重叠干扰校正方法。通过实际地质样品验证,该校正方法在较高含量Rb元素共存(Rb/Sr<0.2)的Sr纯化液中,能够较为准确地测量⁸⁷Sr/⁸⁶Sr同位素比值,降低了MC-ICPMS分析地质样品中Sr同位素时对化学分离步骤的要求。而对于Rb/Sr>0.2的地质样品,因仪器分馏效应和记忆效应影响,测试精确度大大降低,无论采用何种校正方法均无法得到准确的Sr同位素组成。     

微波消解-电感耦合等离子体质谱法测定铁矿石中15个稀土元素

分析地质样品中稀土元素的含量,现有的方法都受到基体干扰和共存元素干扰,电感耦合等离子体质谱(ICP-MS)已在痕量元素分析中得到广泛应用,通过条件优化可准确测定稀土元素。本文建立了ICP-MS同时测定铁矿石中钇镧铈镨钕钐铕钆铽镝钬铒铥镱镥15个稀土元素的方法,样品用盐酸、硝酸和氢氟酸高温密闭消解,消解完全后转移定容,在线加入¹⁰³Rh、¹¹⁵In、¹⁸⁵Re内标液进行测定,方法回收率为95%~104%,精密度(RSD)≤3.5%。对12个国家24个代表性主产区进口的铁矿石样品进行检测,分析其稀土元素的配分模式特征为右倾型轻稀土富集,现阶段的进口铁矿粉多为多产区复合配矿。本方法较其他传统方法大幅降低能耗,提高了分析效率,初步探讨的稀土元素丰度特征可为研究主产区铁矿石的矿床成因、提高我国烧结球团矿的加工工艺提供依据。     

四种前处理方法对电感耦合等离子体质谱测定植物样品中27种微量元素的影响

采用HNO₃-HClO₄-HF常压消解、HNO₃-H₂O₂-HF高压密闭消解、HNO₃-H₂O₂微波消解,干法灰化后残渣用HNO₃-HF-HClO₄溶解等四种方法对植物样品进行前处理,使用电感耦合等离子体质谱(ICP-MS)对植物样品中的27种元素进行定量分析,探讨了不同前处理方法对ICP-MS测定植物样品中微量元素的影响。分析结果表明: HNO₃-HClO₄-HF常压消解使用大量试剂,污染环境,造成空白值高;在常压体系中HClO₄的加入能提高样品的消解效率,但赶酸不完全,会造成复合离子对钒和砷的干扰;干法灰化过程中某些元素(硼、汞等)会损失;常压消解和高压密闭消解中加入HF能有效地提高铍、稀土、钇、钛、锑、铀等元素的回收率,但在蒸干赶HF的过程中,会造成硼和汞的损失,并且钢套的生锈会造成铬、镍空白值高。尽管没有一种方法能适用于所有元素的分析,但相比较而言,HNO₃-H₂O₂微波消解体系操作简单,大部分元素(除铍、钛、锑、铋、稀土)能得到满意的结果,精密度(RSD)均小于10%(n=10),相对误差(RE)为-4.6%~13.6%。     

福建云霄石榴子石宝石矿物学特征

福建云霄是我国重要的宝石级石榴子石产地,然而该区石榴子石的致色机理不清,制约了对其形成机制的理解及后续开发利用。本文选取7件福建云霄橙黄-橙红色石榴子石样品,利用傅立叶红外光谱、紫外-可见光光谱和拉曼光谱分析其谱学特征,使用电子探针及激光剥蚀电感耦合等离子体质谱仪(LA-ICP-MS)分析限定其主量、微量元素组成。结果表明云霄石榴子石主要为锰铝榴石,其颜色主要与二价锰(Mn²⁺)和铁离子(Fe²⁺)对可见光的吸收有关,Mn²⁺导致其主体呈橙色,少量Fe²⁺控制其橙红色调,微量Ti⁴⁺使其呈褐色调。福建云霄石榴子石样品核部锰含量相对较低而铁、镁含量较高,锰元素含量由核部向边部逐渐升高,且具有重稀土元素富集、轻稀土元素亏损的左倾配分模式和Eu负异常,表明其形成于岩浆结晶作用晚期。     

风冷回流消解-电感耦合等离子体质谱法同时测定植物样品中46个元素

采用HNO3-H2O2体系对植物样品进行风冷回流消解,电感耦合等离子体质谱法(ICP-MS)同时测定植物样品中46个元素的含量。将称有样品的磨口锥形瓶加装风冷管后直接放在普通平板铝块电热板上,一次可对45个锥形瓶回流装置同时进行加热,不需要严格地规定消解时间,保证回流加热微沸消解至消解完全即可。植物标准物质(GBW 10012、GBW 10014和GBW 10019)的分析结果与标准值相一致,方法精密度(RSD,n=6)为0.44%～5.59%。与干法灰化消解和微波消解等样品处理方法相比较,操作简单快捷,试剂用量少,空白值较低,溶液盐度较小,有利于植物样品中多元素ICP-MS同时测定。采用调试液调节ICP-MS仪器测定的最佳化,确定了ICP-MS测定的最佳条件,同时探讨了元素之间的干扰关系,采用数学校正法有效地消除了测定的干扰。     

广东东莞地区中侏罗统塘厦组凝灰质沉积物的元素地球化学特征及构造背景

东莞地区中侏罗统塘厦组为富含凝灰质的湖泊沉积。对样品进行全岩分析和ICP-MS微量元素分析,并计算Sr/Ba、B/Ga和Ca/Mg比值,其比值变化与古盐度变化成正相关,特征显示塘厦组为咸水湖泊沉积,由下至上古盐度逐渐降低,水体深度也逐渐变浅。对样品进行ICP-MS稀土元素分析,计算各样品δCe值和(La/Yb)_N比值,δCe值介于0.83 ~ 1.31之间,(La/Yb)_N值均明显大于1或小于1,其特征反映湖泊沉积物沉积速率较低,只在塘厦组底部和上部出现相对高的沉积。元素P和Sr/Cu值反映其富集与迁移,受到气候的控制。元素P平均值在0.205×10^-2; Sr/Cu平均值大于4.0×10^-6,在中晚期出现最低值1.42×10^-6,这是塘厦组以干热气候为主,中晚期出现了短暂温湿气候所造成的。塘厦组为干热气候下缓慢沉积的咸水湖泊沉积。Zr-Th、La-Th-Sc判别图解、稀土元素特征及区域构造分析,显示中侏罗世东莞地区构造背景为活动大陆边缘的弧后盆地。受伸展作用影响,本区发育弧后裂谷型湖盆。泥岩La/Yb-∑REE源岩判别图解显示,源岩为玄武岩、花岗岩和沉积岩。     

磁铁矿中微量元素的激光剥蚀-电感耦合等离子体质谱分析方法探讨

微区原位分析提供了固体物质的元素及同位素组成的空间分布信息,有利于解决不同的地质问题、环境问题和工业方面的问题。磁铁矿中微量元素地球化学组成有助于研究成矿时的物理化学条件和示踪新的矿床。本文建立了利用激光剥蚀-电感耦合等离子体质谱(LA-ICP-MS)分析磁铁矿中微量元素的方法,探讨了选择必要的分析元素,选择合适的内标、外标,选择恰当的束斑大小等方法。以LA-ICP-MS分析澳大利亚Ernest Henry IOCG矿床磁铁矿中微量元素的方法为例,采用NIST SRM 610作为外标,Fe作为内标较为合理;正常情况下采用32~60 μm的激光束,但对于个别样品中磁铁矿颗粒较小,可以考虑使用较小的激光束(24 μm或16 μm);为消除质谱干扰,Ti选择测量⁴⁹Ti,Cu选择测量⁶⁵Cu,Sn选择测量¹¹⁸Sn。     

我国海洋地质分析测试技术

21世纪是海洋开发和利用的新世纪,随着国家对海洋地质调查工作的日益重视,海洋地质分析测试技术迎来了快速发展时期。本文对我国海洋地质分析测试技术的最新进展进行了简要评述:为满足海洋区域调查、海岸带地质调查的需要,建立了以大型分析仪器为主的多元素同时分析海洋地质样品的快速高效分析方法体系;针对新能源天然气水合物样品,开展了异常识别测试技术和应用测试技术研究,建立了用离子色谱法快速测定孔隙水中阴离子Cl^-、Br^-、SO₄^2-和阳离子Na⁺、NH₄⁺、K⁺、Ca²⁺、Mg²⁺ 的方法,开发出了以声学、电阻、时域反射(Time Domain Reflectometry, 简称为TDR)三种探测技术为主的适用于天然气水合物模拟实验的探测新技术;对于海洋沉积物中有机污染物样品,采用复合固相萃取净化柱,对海洋沉积物萃取液样品进行净化分离,依次选用正己烷和正己烷－二氯甲烷混合液淋洗固相萃取净化柱,可有效保留基体杂质,实现了海洋环境地质调查中基质复杂沉积物样品的同时净化、分离与测试,可显著提高实验效率;同时在大洋矿产样品分析技术、海洋地质标准物质研制、船载与原位化学探测技术等方面也取得了重要进展。本文还提出在海洋调查和监测的应用中,船载及原位测试技术将愈趋重要,加强海洋化学传感器的性能和检测集成化技术是今后的一个重要发展方向。     

一次溶矿多仪器联合测定铀矿地质样品中目标元素、伴生元素和主微量元素

为实现铀矿地质样品中的目标元素、伴生元素和主微量元素的一次溶矿、多仪器联合测定,样品采用逆王水预消解、四酸常压消解溶矿、低温蒸干和逆王水提取;消解得到的试样原液经ICP-OES测定主量元素,原液稀释后经ICP-MS测定目标元素（U、Th）、伴生元素（Mo、V、Ga、Ge、Re）和微量元素,原液经酸化和加入铁盐溶液后经AFS测定伴生元素Se;通过优化各仪器的测定条件和采取恰当的干扰消除方法,各元素得到准确测定。经试验测定,各元素的线性相关系数大于0.999,主量元素检出限为0.001%～0.03%,其他元素检出限为0.005～0.6μg/g;经国家标准物质验证,各元素的相对误差为-11.3%～12.1%,相对标准偏差（n=12）为2.1%～7.0%。文章中的研究方法实现了一次溶矿、多仪器联合测定的目的,测试结果满足地质矿产实验室测试质量规范的要求。     

微波消解-电感耦合等离子体质谱法测定煤中的硼

煤中硼的准确测定对于研究成煤的沉积环境具有重要意义。微波消解-电感耦合等离子体质谱(ICP-MS)可以有效地测定煤中的大部分微量元素,但由于硼易挥发等特殊的物理化学性质,致使硼的测定过程较为繁琐,测试结果不够准确。本文对微波消解ICP-MS测定煤中硼含量的分析方法进行了改进。样品中加入磷酸、硝酸和氢氟酸,用微波消解仪消解完全,置于电热板加热赶酸完毕后用硝酸提取。硼的卤化物易挥发,磷酸的加入使硼与磷酸结合生成难挥发的稳定络合物,起到了固硼的作用。ICP-MS测定中采用铍作为内标,通过在线加入的方式有效地补偿了基体效应产生的影响;用稀氨水冲洗进样系统,很好地降低了硼的记忆效应;选择高分辨率模式来测定,避免了12C和40Ar4+等质谱峰的干扰。方法的仪器检出限(0.22ng/mL)和方法检出限(0.34 ng/mL)较低,方法精密度(RSD)小于0.6%,灵敏度高,且测定标准样品的准确度良好。该方法简单快速,适用于批量分析煤样中硼的含量。     

The terrestrial fauna of the Late Triassic Pant-y-ffynnon Quarry fissures,South Wales,UK and a new species of Clevosaurus (Lepidosauria: Rhynchocephalia)

Pant-y-ffynnon Quarry in South Wales yielded a rich cache of fossils in the early 1950s, including articulated specimens of new species (the small sauropodomorph dinosaur Pantydraco caducus and the crocodylomorph Terrestrisuchus gracilis), but no substantial study of the wider fauna of the Pant-y-ffynnon fissure systems has been published. Here, our overview of existing specimens, a few described but mostly undescribed, as well as freshly processed material, provides a comprehensive picture of the Pant-y-ffynnon palaeo-island of the Late Triassic. This was an island with a relatively impoverished fauna dominated by small clevosaurs (rhynchocephalians), including a new species, Clevosaurus cambrica, described here from a partially articulated specimen and isolated bones. The new species has a dental morphology that is intermediate between the Late Triassic Clevosaurus hudsoni, from Cromhall Quarry to the east, and the younger C. convallis from Pant Quarry to the west, suggesting adaptive radiation of clevosaurs in the palaeo-archipelago. The larger reptiles on the palaeo-island do not exceed 1.5?m in length, including a small carnivorous crocodylomorph, Terrestrisuchus, and a possible example of insular dwarfism in the basal dinosaur Pantydraco.     

Définition d'une limite multicritère ; stratigraphie du passage Campanien–Maastrichtien du site géologique de Tercis (Landes,SW France)Definition of a multi-criteria boundary; stratigraphy of the Campanian–Maastrichtian interval of the geological site at Tercis (Landes,SW France)

Lithostratigraphy, physicochemical stratigraphy, biostratigraphy, and geochronology of the 77–70 Ma old series bracketing the Campanian–Maastrichtian boundary have been investigated by 70 experts. For the first time, direct relationships between macro- and microfossils have been established, as well as direct and indirect relationships between chemo-physical and biostratigraphical tools. A combination of criteria for selecting the boundary level, duration estimates, uncertainties on durations and on the location of biohorizons have been considered; new chronostratigraphic units are proposed. The geological site at Tercis is accepted by the Commission on Stratigraphy as the international reference for the stratigraphy of the studied interval. To cite this article: G.S. Odin, C. R. Geoscience 334 (2002) 409–414.     

The effect of water on accessory phase solubility in subaluminous and peralkaline granitic melts

The solubilities of columbite, tantalite, wolframite, rutile, zircon and hafnon were determined as a function of the water contents in peralkaline and subaluminous granite melts. All experiments were conducted at 1035 °C and 2 kbar and the water contents of the melts ranged from nominally dry to approximately 6 wt.% H₂O. Accessory phase solubilities are not affected by the water content of the peralkaline melt. By contrast, solubilities are affected by the water content of the subaluminous melt, where the solubilities of all the accessory phases examined increase with the water content of the melt, up to 2 wt.% H₂O. At higher water contents, solubilities are nearly constant. It can be concluded that water is not an important control of accessory phase solubility, although the water content will affect diffusivities of components in the melt, thus whether or not accessory phases will be present as restite material. The solubility behaviour in the subaluminous and peralkaline melts supports previous spectroscopic studies, which have observed differences in the coordination of high field strength elements in dry vs. wet subaluminous granitic glasses, but not for peralkaline granitic glasses. Lastly, the fact that wolframite solubility increases with increasing water content in the subaluminous melt suggests that tungsten dissolved as a hexavalent species.     

Late Wuchiapingian (Late Dzhulfian,early Late Permian) limestone olistolites within the Tertiary flysch of Glypia Unit (Mount Parnon,central–eastern Peloponnesus,Greece)

Some olistolites reworked in a Tertiary flysch of Mount Parnon (Peloponnesus, Greece) exhibit a Late Permian assemblage, dominated by Paradunbarula (Shindella) shindensis, Hemigordiopsis cf. luquensis and Colaniella aff. minima. This association corresponds to the Late Wuchiapingian (=Late Dzhulfian), a substage whose algae and foraminifera are generally little known. Contemporaneous limestones crop out in the middle part of the Episkopi Formation in Hydra, but they are rather commonly reworked in Mesozoic and Cainozoic sequences. The palaeobiogeographical affinities shared by the foraminiferal markers of Greece, southeastern Pamir, and southern China, are very strong (up to the specific level), and are congruent with the Pangea B reconstructions. To cite this article: E. Skourtsos et al., C. R. Geoscience 334 (2002) 925–931.     

PALEONTOLOGY

正20141596 Liu Yunhuan(School of Earth Sciences and Resources,Chang’an University,Xi’an 710054,China);Shao Tiequan Early Cambrian Quadrapyrgites Fossils of Xixiang Boita in Southern Shaanxi Province(Journal of Earth Sciences and Environment,ISSN1672-6561,CN61-1423/P,35(3),2013,p.39-43,3 illus.,20 refs.)     

GEOCHEMICAL EXPLORATION

正20141719 Chen Zhijun(State Key Laboratory of Geological Processes and Mineral Resources,China University of Geosciences,Wuhan 430074,China);Chen Jianguo Automated Batch Mapping Solution for Serial Maps:A Case Study of Exploration Geochemistry Maps(Journal of Geology,ISSN1674-3636,CN32-1796/P,37(3),2013,p.456-464,2 illus.,2 tables,10 refs.)     

MICROPALAEONTOLOGY

正20140962 Chen Fenning(Xi’an Institute of Geology and Mineral Resources,Xi’an710054,China);Chen Ruiming Late Miocene-Early Pleistocene Ostracoda Fauna of Gyirong Basin,Southern Tibet(Acta Geologica Sinica,ISSN0001-5717,CN11-1951/P,87(6),2013,p.872-886,6illus.,56refs.)     

PETROLOGY

正1.IGNEOUS PETROLOGY20142008Cai Jinhui(Wuhan Center,China Geological Survey,Wuhan 430205,China);Liu Wei Zircon U-Pb Geochronology and Mineralization Significance of Granodiorites from Fuzichong Pb-Zn Deposit,Guangxi,South China(Geology and Mineral Resources of South China,ISSN1007-3701,CN42-1417/P,29(4),2013,p.271-281,7illus.,     

ENVIRONMENTAL GEOLOGY

正20141205Cheng Weiming(State Key Laboratory of Resources and Environmental Information System,Institute of Geographic Sciences and Natural Resources Research,CAS,Beijing 100101,China);Xia Yao Regional Hazard Assessment of Disaster Environment for Debris Flows:Taking Jundu Mountain,Beijing as an     

PROSPECTING EXPLORATION

正20141266Fan Chaoyan(Guangdong Provincial Key Laboratory of Mineral Resources and Geological Processes,Guangzhou 510275,China);Wang Zhenghai On Error Analysis and Correction Method of Measured Strata Section with Wire Projection Method(Journal of