Combined LA-ICP-MS microanalysis of iodine, bromine and chlorine in fluid inclusions†,Journal of Analytical Atomic Spectrometry

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Combined LA-ICP-MS microanalysis of iodine, bromine and chlorine in fluid inclusions†
Journal of Analytical Atomic Spectrometry ( IF 3.1 ) Pub Date : 2018-03-08 00:00:00 , DOI: 10.1039/c7ja00415j
Tobias Fusswinkel _{1,

2,

3,

4,

5} , Christopher Giehl _{6,

7,

8,

9,

10} , Oliver Beermann _{6,

7,

8,

9} , Johan R. Fredriksson _{1,

2,

3,

4} , Dieter Garbe-Schönberg _{6,

7,

8,

9} , Lea Scholten _{6,

7,

8,

9} , Thomas Wagner _{5,

9,

11,

12}

Affiliation

Halogens are excellent tracers of hydrothermal fluid sources in sedimentary, magmatic, metamorphic and ore-forming environments. In situ LA-ICP-MS analysis of Cl and Br in single fluid inclusions has provided fundamentally new insight into the processes leading to the formation of economic mineral deposits. Enrichment and depletion of Br relative to the dominant halogen Cl may be caused by several processes besides seawater evaporation and halite dissolution, which cannot be unequivocally resolved on the basis of Br/Cl ratios alone. Triple-halogen analysis (Cl, Br and I) would provide the required additional constraint permitting discrimination between possible alternative processes. We present the first iodine concentration data of fluid inclusions determined by LA-ICP-MS microanalysis, using the natural scapolite reference material Sca17 for external standardization. The robustness of the method is verified by LA-ICP-MS analysis of synthetic fluid inclusions, which were prepared at 600 °C, and 100 or 200 MPa in cold-seal pressure vessels from four starting solutions containing Na, Rb, Cs, Cl, Br and I. LA-ICP-MS analysis yielded average I concentrations in excellent agreement with the starting solutions. Average concentrations in inclusions synthesized from the solution with 27 μg g⁻¹ I were 27.3 ± 3.9 μg g⁻¹ I (14.3% RSD), and 77.6 ± 6.4 μg g⁻¹ I (8.3% RSD) for the solution with 78 μg g⁻¹ I. Chlorine and Br reference concentrations were reproduced to better than 10% and 20% RSD, respectively. The method was subsequently applied to a pilot study of natural fluid inclusion samples from three geological settings (Alpine metamorphic quartz veins, post-Variscan quartz-Pb–Zn veins, and calcite veins with Mn oxide and hematite mineralization). The data demonstrate significant differences between the samples, which can be interpreted in terms of Br and I enrichment due to reactions with organic matter and fluid mixing processes between evaporite brines and halite dissolution brines. This highlights the potential of triple-halogen LA-ICP-MS analysis in fluid inclusions for tracing the source of crustal fluids in a wide range of geological environments.

中文翻译：

流体夹杂物中碘，溴和氯的组合LA-ICP-MS微分析†

卤素是沉积，岩浆，变质和成矿环境中热液源的极好的示踪剂。原位LA-ICP-MS对单一流体包裹体中Cl和Br的分析从根本上为导致形成经济矿藏的过程提供了新的见解。相对于主要卤素Cl而言，Br的富集和耗竭可能是由海水蒸发和盐酸盐溶解以外的几种过程引起的，这仅凭Br / Cl的比例就无法明确解决。三重卤素分析（Cl，Br和I）将提供所需的其他限制条件，从而可以区分可能的替代方法。我们提供了通过LA-ICP-MS微分析确定的流体夹杂物的第一碘浓度数据，使用了天然方铅矿参考材料Sca17进行了外部标准化。该方法的鲁棒性通过合成流体包裹体的LA-ICP-MS分析得到验证，它们是在600°C和100或200 MPa的冷密封压力容器中从含有Na，Rb，Cs，Cl，Br和I的四种起始溶液制备的。LA-ICP-MS分析得出的平均I浓度与起始解决方案。从溶液中合成的夹杂物中的平均浓度为27μgg^-1我分别为27.3±3.9微克克^-1 I（14.3％RSD），和77.6±6.4微克克^-1 I（8.3％RSD），用于与78微克溶液克^-1I.氯和溴的参考浓度分别高于10％和20％RSD。该方法随后被用于来自三个地质环境（高山变质石英脉，Variscan后石英-Pb-Zn脉和具有Mn氧化物和赤铁矿矿化的方解石脉）的天然流体包裹体样品的初步研究。数据表明样品之间存在显着差异，这可以通过与有机物的反应以及蒸发盐溶液和盐酸盐溶解盐溶液之间的流体混合过程来实现Br和I富集来解释。这突出了流体包裹体中三卤素LA-ICP-MS分析在追踪各种地质环境中地壳流体来源方面的潜力。

更新日期：2018-03-08

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