高压密闭消解-电感耦合等离子体质谱法测定锰矿石中的稀土元素前处理方法研究

高压密闭消解因称样量小、用酸量少、空白低等优点成为测定稀土元素前处理的主要方法。但锰矿石组分复杂,锰含量差别较大且具有多种不同价态,常含有伴(共)生金属和其他杂质,该方法采用常规酸溶体系很难将其消解完全,造成ICP-MS测试结果不准确。本文从样品前处理消解效果出发,选择锰矿石标准物质GBW07261、GBW07263、GBW07266和一个锰矿石样品,试验了三种酸溶前处理方法对锰矿石稀土元素测试的影响。结果表明:方法一(氢氟酸-硝酸密闭消解,硝酸复溶提取)不能将锰矿石样品完全消解,测定值偏低0. 28%～61. 31%;方法二(氢氟酸-硝酸-双氧水密闭消解,硝酸-双氧水复溶,硝酸提取)和方法三(氢氟酸-硝酸密闭消解,盐酸复溶,硝酸提取)均可将锰矿石样品消解完全,用ICP-MS测定稀土元素的数据较为接近,与传统的过氧化钠熔融ICP-MS法测定值吻合。但实验过程中发现对于锰含量较高的样品,方法三需多次重复加入盐酸复溶后方可将样品消解完全,而方法二复溶一次即可。因此,方法二对锰矿石样品的消解效率更高,精密度好(0. 96%～2. 68%),加标回收率在95. 0%～107. 0%之间,更适用于锰矿石中稀土元素的分析。     

电感耦合等离子体质谱法测定灌木枝叶中微量元素的样品预处理方法研究

利用电感耦合等离子体质谱法(ICP-MS)测定植物样品中微量元素的关键技术是消除植物样品的有机基体效应,本文通过预处理方法中的酸消解体系、称样量和消解方式消除其影响。以国家标准物质灌木枝叶组合样(GBW07603)为材料进行研究,对比分析了硝酸-过氧化氢、硝酸-氢氟酸、硝酸-氢氟酸-过氧化氢3种酸溶体系的消解效果,以确定最佳酸溶体系,进而定量研究2种称样量(50 mg和100 mg)和3种消解方式(密封高压二次消解、密封高压一次消解、微波消解)的消解效果,并以In作为内标采用ICP-MS测定微量元素含量。结果表明:硝酸-氢氟酸-过氧化氢酸溶体系的消解效果最好;50 mg的测定值更接近于参考值;微波消解法的测定值明显偏低,而密封高压二次消解法是灌木枝叶样品预处理的有效方法。     

电感耦合等离子体质谱测定灌木枝叶中微量元素的样品预处理方法研究

利用电感耦合等离子体质谱法(ICP-MS)测定植物样品中微量元素的关键技术是消除植物样品的有机基体效应,本文通过预处理方法中的酸消解体系、称样量和消解方式消除其影响。以国家标准物质灌木枝叶组合样(GBW07603)为材料进行研究,对比分析了硝酸-过氧化氢、硝酸-氢氟酸、硝酸-氢氟酸-过氧化氢3种酸溶体系的消解效果,以确定最佳酸溶体系,进而定量研究2种称样量(50 mg和100 mg)和3种消解方式(密封高压二次消解、密封高压一次消解、微波消解)的消解效果,并以In作为内标采用ICP-MS测定微量元素含量。结果表明:硝酸-氢氟酸-过氧化氢酸溶体系的消解效果最好;50 mg的测定值更接近于参考值;微波消解法的测定值明显偏低,而密封高压二次消解法是灌木枝叶样品预处理的有效方法。     

混合酸敞开或高压密闭溶样-ICPMS测定地质样品中稀土元素

测定地质样品中的稀土元素时,用碱熔法处理样品过程繁琐,混合酸敞开酸溶法的酸种类多,用量较大,而微波消解法批次处理样品少,效率不高。本文比较了7种混合酸敞开酸溶体系、硝酸-氢氟酸高压密闭体系对样品溶样的效果,采用电感耦合等离子体质谱测定15个稀土元素的含量,建立了一套样品前处理体系简单、酸用量少、相对快捷的测定地质样品中稀土元素的方法。通过对59件国家标准物质的测试分析,结果表明硫酸-氢氟酸敞开酸溶和硝酸-氢氟酸高压密闭溶样两套体系的方法检出限、精密度、准确度均能达到地质行业相关标准测试要求。硫酸-氢氟酸敞开酸溶体系对于样品中钡含量较高,或样品量较少时适用;硝酸-氢氟酸高压密闭溶样体系的检出限更低,适用于大批量样品的分析测试。两套体系均不需要进行数学干扰校正,且酸用量少（最多6 mL）,分析效率高（平均每日分析测试300件）,有较大的推广应用价值。     

密闭酸溶-电感耦合等离子体发射光谱/质谱法测定花岗伟晶岩中32种微量元素

花岗伟晶岩富集锂铍铷铯铌钽等稀有金属元素,准确测定其中的大离子亲石元素、高场强元素和稀土等微量元素,可用于判断成矿流体物质来源、成岩构造环境。目前的测试方法研究主要集中在锂铍铷铯铌钽等少数元素,样品消解方法有四酸敞开法、五酸敞开法、密闭酸溶法等,存在难溶矿物分解不完全、锆铪钍铀和稀土等元素回收率偏低等问题。本文对比了盐酸-硝酸-氢氟酸-高氯酸敞开消解法、盐酸-硝酸-氢氟酸-高氯酸-硫酸敞开消解法、硝酸-氢氟酸密闭消解法三种方法的分解效果。结果表明：四酸消解法中,铌钽锆铪钨和重稀土元素结果严重偏低;五酸消解法由于采用硫酸-氢氟酸-过氧化氢体系提取,有效地防止了铌钽的水解,铌钽钨等元素测定结果准确,但锆铪钡铅和轻稀土元素测定结果偏低。硝酸-氢氟酸密闭消解法使用王水代替硝酸进行残渣复溶,促进了铌钽锆铪和稀土等元素的复溶,采用电感耦合等离子体发射光谱和质谱法(ICP-OES/MS)可以准确测定花岗伟晶岩中稀有金属、稀土元素等32种元素,方法检出限为0.004～2.50μg/g,精密度(RSD,n=12)为1.0%～8.3%。将该方法应用于8种花岗岩、伟晶岩及稀有金属矿标准物质和三种类型实际样品...     

硼酸溶液敞口酸溶-电感耦合等离子体质谱法测定萤石中稀土元素

萤石中稀土元素的研究对揭示成矿物质来源、成矿流体的性质和矿床成因均具有十分重要的意义。传统的过氧化钠碱熔-电感耦合等离子体质谱(ICP-MS)分析方法可以解决萤石中稀土元素的测定问题,但过氧化钠提纯难度高,过程繁杂,不宜大量样品的处理,且待测溶液总盐度大易产生基体干扰等;常规的酸溶法因使用的试剂一般为硝酸和氢氟酸,这些酸均不与萤石的主要成分氟化钙发生反应而很少应用。本文基于氟化钙能溶于硫酸和硼酸,采用硼酸溶液(10%硫酸和25%盐酸介质)和氢氟酸处理样品,硝酸提取,引入103Rh和185Re双内标,建立了硼酸溶液敞口酸溶ICP-MS测定萤石中稀土元素的分析方法。相比于传统的过氧化钠碱熔方法,本方法采用的试剂纯度高,可以有效地降低空白,方法检出限为0.002~0.016μg/g,低于过氧化钠碱熔方法的检出限(0.006~0.058μg/g),回收率在94.0%~107.6%之间,方法精密度(RSD)为0.7%~2.7%。本方法配制的硼酸溶液能够有效地与萤石反应,可充分分解萤石样品,简化了样品处理流程,有效地控制了稀土元素的损失,数据可靠性高,适用于大量萤石样品的稀土元素分析。     

电感耦合等离子体发射光谱法测定稀土矿石中15种稀土元素——四种前处理方法的比较

稀土元素在矿石中有多种不同的赋存形式,主要有离子吸附型和矿物晶格型,稀土不同赋存形态对其本身准确分析测定有很大的影响。本文从稀土元素在矿石中不同赋存形态的角度出发,探讨了不同前处理方法对稀土准确测试结果的影响,采用盐酸-硝酸-氢氟酸-高氯酸(四酸)敞开酸溶、盐酸-硝酸-氢氟酸-高氯酸-硫酸(五酸)敞开酸溶、氢氟酸-硝酸封闭压力酸溶、氢氧化钠-过氧化钠碱熔四种方法对离子吸附型和矿物晶格型两类赋存类型的稀土矿石样品进行前处理,电感耦合等离子体发射光谱法测定其中的15种稀土元素。结果表明:对于离子吸附型的稀土矿石标准物质(GBW 07161、GBW 07188),四酸敞开酸溶法测定的结果明显偏低,15种稀土元素大都偏低10%~20%,五酸敞开酸溶法、封闭压力酸溶法和碱熔法的测定值与标准值吻合;而对于稀土以离子化合物及类质同象置换的形式赋存于矿物晶格中的白云鄂博轻稀土矿石样品,三种酸溶法结果较碱熔法均偏低,其中四酸敞开酸溶法偏低最多,约偏低20%左右,五酸敞开酸溶法和封闭压力酸溶法偏低5%~15%。本文提出,对于离子吸附型稀土矿,五酸敞开酸溶法和封闭压力酸溶法可以代替传统操作复杂的碱熔法,但对于稀土以离子形式赋存于矿物晶格型的稀土矿,目前最合适的前处理法是传统的碱熔法。     

常压酸溶-电感耦合等离子体质谱法测定地球化学勘查样品中的铌钽

常压酸溶法因溶矿效率高、成本低、检出限低,在地质实验室被广泛应用,但采用常用的氢氟酸-硝酸-盐酸-高氯酸四酸法处理样品,铌钽溶出率低,铌钽在容器壁发生水解和聚合反应导致其部分吸附或沉降,从而使测试结果偏低。因此,应用常压酸溶-电感耦合等离子体质谱(ICP-MS)分析地球化学勘查样品中的铌钽,需要解决的两个关键问题是铌钽的溶出率和试液中铌钽的水解。针对溶出率的不足,本方法在酸体系中引入硫酸,即氢氟酸-硝酸-盐酸-高氯酸-硫酸可以完全将铌钽溶出;针对水解,采用5%氢氟酸-5%硫酸-5%过氧化氢为提取剂,并采取与样品前处理相同分析流程的标准物质制作曲线,这两个方法相结合能有效抑制样品溶液中铌钽的水解,同时标准物质制作曲线法降低了ICP-MS分析中的样品溶液与标准溶液基体不一致引起的误差。本方法经国家标准物质验证,相对误差小于±7%,相对标准偏差在3.11%~6.27%之间(n=11),铌钽的检出限分别为0.04μg/g和0.03μg/g,相比于碱熔法检出限0.33μg/g具有明显优势,可以准确测定地球化学勘查样品中的铌钽。     

高压密闭消解-电感耦合等离子体质谱法测定和田玉中15种稀土元素

和田玉的稀土元素丰富,准确测定稀土元素含量对于揭示和田玉成矿物质来源、成矿流体的性质和矿床成因具有重要的意义。本文通过比较硝酸-氢氟酸、四硼酸锂-偏硼酸锂碱熔两种前处理方法,确定了使用硝酸-氢氟酸溶样,再采用电感耦合等离子体质谱法（ICP-MS）测定和田玉中钇镧铈镨钕钐铕钆铽镝钬铒铥镱镥15种稀土元素的含量。为降低基体效应,以¹⁰³Rh和⁴⁹In作内标补偿基体效应和校正灵敏度漂移,样品检出限为0.0008~0.0091μg/L,回收率为101.0%~120.0%,精密度（RSD）为0.55%~1.83%（n=11）。本方法的用酸量少,空白值低,应用于不同地区和田玉的分析,其稀土元素的配分模式特征为右倾型轻稀土富集,初步探讨的稀土元素丰度特征可为研究主产区宝玉石的矿床成因提供依据。     

常压密闭微波消解-电感耦合等离子体质谱法测定磷矿石中的稀土元素

磷矿石中的稀土元素测定方法主要使用电感耦合等离子体质谱法（ICP-MS）,样品处理方式主要采用敞口混合酸溶和碱熔。传统的酸溶和碱熔处理矿石样品时间较长,试剂加入量大,操作过程较为繁琐,且易造成环境污染。微波消解直接向样品释放能量,工作效率高,且易挥发元素被保留在消化溶液中,防止挥发造成结果偏差及环境污染。本文采用微波消解对磷矿石进行处理,并在二次消解过程中加入饱和硼酸络合溶矿过程中产生的不溶物氟化钙,在线加入铑和铼双内标的方式,建立了ICP-MS测定磷矿石中15种稀土元素的方法。结果表明：二次消解过程中加入饱和硼酸能有效地络合沉淀,彻底溶解样品,经上机测定后15种稀土元素的相对标准偏差（RSD）在0.68%～4.52%之间,回收率在93.1%～106.6%之间,方法检出限为0.003～0.029μg/g。选取两个磷矿石样品,用本方法与混合酸（盐酸-硝酸-氢氟酸-硫酸）酸溶方法进行对比试验,相对标准偏差在-5.82%～5.99%之间,表明本方法测定稀土元素是有效可行的。对于样品的前处理方法,酸溶、碱熔和微波消解都有各自的特点,微波密封消解能避免一些能形成易挥发组分的损失并且外源性污染少。...     

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