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激光剥蚀-电感耦合等离子体质谱法对白钨矿中稀土元素的原位测定

In-situ Determination of Rare Earth Elements in Scheelite by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry

  • 摘要: 白钨矿的稀土元素含量及标准化配分模式图可以作为判断矿床成因的重要依据,其原位分析更有利于在单个矿物层面剖析成矿流体演化等特征。本文采用配备193 nm ArF准分子激光器的GeoLasPro剥蚀系统(LA)和电感耦合等离子体质谱仪(ICP-MS)对云南大坪金矿含金石英脉白钨矿中的稀土元素进行LA-ICP-MS原位分析。分析结果表明,选用玻璃标准参考物质NIST 610作为外标,Ca作为内标元素,可以对稀土元素进行较为精准的测量。阴极发光图显示,大坪金矿含金石英脉中的白钨矿晶体内部成分分布较为均匀,其稀土元素球粒陨石标准化曲线特征一致,为明显的中稀土富集型,稀土总量(ΣREEs)很高,介于918.00~2094.97 μg/g之间,δEu为1.17~1.95,有较明显的Eu正异常,无明显的Ce异常,但各元素含量在一定范围内有变动,体现出其稀土元素含量分布不完全均一的特征。首次对同一白钨矿样品的LA-ICP-MS原位分析和ICP-MS溶液分析结果进行对比研究,用实验数据论证了LA-ICP-MS原位分析方法的准确可靠性。事实证明,样品溶液ICP-MS分析所得的结果只能代表所溶样品的平均含量,而采用LA-ICP-MS可以在较高空间分辨率条件下( < 40 μm)对白钨矿稀土元素进行快速、原位分析,这对稀土元素含量分布不均匀的白钨矿样品测试有着更为重要的意义。

     

    Abstract: Rare earth elements (REEs) composition and chondrite-normalized REEs patterns of scheelites can be used as an important basis to determine the genesis of deposits. In-situ determination is more conducive to analysis of ore-forming fluid evolution characteristics in terms of single minerals. REEs compositions in scheelite from auriferous quartz veins in Daping gold deposit were analyzed in-situ by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) coupled with 193 nm ArF excimer GeoLasPro laser ablation system and are reported in this paper. The results show that analysis of scheelite can yield precise and accurate data for REEs by using NIST 610 as the external standard and Ca as the internal standard. The cathode luminescence images show that the crystal composition of scheelite is relatively homogeneous. The experimental results show that they have very similar MREEs-enriched patterns with chondrite-normalized, which have very high ΣREEs(918.00-2094.97 μg/g), obvious positive anomaly of δEu(1.17-1.95), and no anomaly of Ce.However, the content of each element changes within a certain range, which reflects that the REEs distributions are not exactly homogeneous. Comparing the analysis results of in-situ Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry(LA-ICP-MS) and solution nebulization ICP-MS, the accuracy and reliability of the in-situ LA-ICP-MS method is demonstrated for the first time. Based on all the results, routine digestion and ICP-MS analytical method provide the average contents of a bulk sample. By comparison, LA-ICP-MS has the advantages of being a rapid method with high spatial resolution ( < 40 μm) and in-situ analysis, which is more important for scheelites which host an inhomogeneous rare earth elements distribution.

     

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