Analysis of nano-mineral chemistry with single particle ICP-Time-of-Flight-MS; a novel approach to discriminate between geological environments

IF 3.6 2区地球科学 Q1 GEOCHEMISTRY & GEOPHYSICS

Chemical Geology Pub Date : 2024-11-13 DOI:10.1016/j.chemgeo.2024.122498

Aaron J. Goodman , Hark Karkee , Shiqiang Huang , Katharina Pfaff , Yvette D. Kuiper , Zhaoshan Chang , Alexander Gundlach-Graham , James F. Ranville

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引用次数: 0

Abstract

Studies of indicator minerals and mineral chemistry are widely used in geochemistry and are particularly useful in mineral exploration. Due to the low abundance of indicator mineral grains, large field samples and extensive laboratory processing are required for these studies. However, nano- and submicron-scale mineral particles (NPs, diameter < 1 μm) are highly abundant in geochemical sample media, containing millions to billions of particles per gram of soil or sediment. In this study, we analyze mineral NPs using single particle inductively coupled plasma time-of-flight mass spectrometry (spICP-TOFMS), a recently developed technique for high throughput elemental characterization of NPs. We investigate the limitations of the technique that arise from the working range of the ICP-TOFMS instrument and the analytical uncertainty of measured element masses in single particles. Despite these limitations, spICP-TOFMS can be used to determine accurate element mass ratios in NPs, which we validated through analysis of mineral specimens. Elemental mass ratios obtained from spICP-TOFMS in the mineral specimens were supported by SEM-EDS. We analyzed the mineral chemistry of two pairs of elements, ZrHf and NbTa in geochemical samples (sediments, soils, and mine waste) adjacent to a carbonatite and a lithium‑cesium‑tantalum-type pegmatite. Hundreds to thousands of NPs were detected in only 30–80 min of spICP-TOFMS analysis, indicating that these particle types are highly abundant. Pegmatite-associated samples contained Hf and Ta-rich NPs, compared to carbonatite-associated samples that displayed the chondritic or crustal abundance mass ratios in single particles. Zr:Hf mass ratios measured in NPs by spICP-TOFMS were supported by LA-ICP-MS analysis of zircons from selected samples. Diagnostic nano-mineral compositions including Nb-Ta-Bi-Sb (large grains of which are rarely found) were abundant in pegmatite-associated samples, but virtually absent in carbonatite-associated samples. In this study, we demonstrate that the chemistry of mineral nanoparticles can be used to discriminate between geological environments, and for the first time, we show that spICP-TOFMS is an effective tool for this type of analysis.

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利用单颗粒 ICP-Time-of-Flight-MS 分析纳米矿物化学；区分地质环境的新方法

指示矿物和矿物化学研究在地球化学中应用广泛，在矿物勘探中尤其有用。由于指示矿物颗粒的丰度较低，这些研究需要大量的野外样本和广泛的实验室处理。然而，纳米级和亚微米级矿物颗粒（NPs，直径 < 1 μm）在地球化学样品介质中含量极高，每克土壤或沉积物中含有数百万至数十亿颗粒。在本研究中，我们使用单颗粒电感耦合等离子体飞行时间质谱（spICP-TOFMS）分析矿物 NPs，这是最近开发的一种用于高通量 NPs 元素表征的技术。我们研究了该技术的局限性，这些局限性来自于 ICP-TOFMS 仪器的工作范围和单颗粒中测量元素质量的分析不确定性。尽管存在这些局限性，我们还是利用 spICP-TOFMS 测定了 NPs 中的精确元素质量比，并通过对矿物标本的分析进行了验证。矿物样本中通过 spICP-TOFMS 获得的元素质量比得到了 SEM-EDS 的支持。我们分析了邻近碳酸盐岩和锂铯钽型伟晶岩的地球化学样本（沉积物、土壤和矿山废料）中两对元素 ZrHf 和 NbTa 的矿物化学性质。仅在 30-80 分钟的 spICP-TOFMS 分析时间内，就检测到了数百至数千个 NPs，表明这些颗粒类型非常丰富。伟晶岩相关样本中含有富含 Hf 和 Ta 的 NPs，而碳酸盐岩相关样本中的单一颗粒则显示出软玉或地壳丰度质量比。通过 spICP-TOFMS 测得的 NPs 中 Zr:Hf 的质量比得到了来自选定样品的锆石的 LA-ICP-MS 分析的支持。在伟晶岩相关样本中，包括 Nb-Ta-Bi-Sb（很少发现大颗粒的 Nb-Ta-Bi-Sb）在内的诊断性纳米矿物成分非常丰富，但在碳酸盐岩相关样本中却几乎没有。在这项研究中，我们证明了矿物纳米颗粒的化学成分可用于区分不同的地质环境，并首次证明了 spICP-TOFMS 是进行此类分析的有效工具。

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来源期刊

Chemical Geology 地学-地球化学与地球物理

CiteScore

7.20

自引率

10.30%

发文量

374

审稿时长

3.6 months

期刊介绍： Chemical Geology is an international journal that publishes original research papers on isotopic and elemental geochemistry, geochronology and cosmochemistry. The Journal focuses on chemical processes in igneous, metamorphic, and sedimentary petrology, low- and high-temperature aqueous solutions, biogeochemistry, the environment and cosmochemistry. Papers that are field, experimentally, or computationally based are appropriate if they are of broad international interest. The Journal generally does not publish papers that are primarily of regional or local interest, or which are primarily focused on remediation and applied geochemistry. The Journal also welcomes innovative papers dealing with significant analytical advances that are of wide interest in the community and extend significantly beyond the scope of what would be included in the methods section of a standard research paper.