Fractionation of sulphur relative to iron during laser ablation-ICP-MS analyses of sulphide minerals: implications for quantification

Gilbert, Sarah; Danyushevsky, Leonid V.; Goemann, Karsten; Death, David L.

doi:10.1039/c4ja00012a

Cited by 48 publications

(34 citation statements)

References 42 publications

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“…The Se/Fe, Co/Fe, Ni/Fe and Ge/Fe ratios keep reasonably constant, whereas the Se/S, Co/S, Ni/S and Ge/S ratios are readily affected by changes in carrier gas flow. Results (Figure 2) clearly show that Fe is a much more suitable choice as internal element standard compared with S. As observed by Gilbert et al [22], significant fractionation of S relative to Fe occurs in all sulfides during LA-ICP-MS. The underlying mechanisms explaining this phenomenon are not clear at present, but are possibly linked to decomposition of pyrite during laser ablation [23].…”

Section: Precise Determination Of Trace Elements Using Fe or S Normalsupporting

confidence: 56%

“…Paul et al [20] suggest to spatially register the element map with principal component analysis, segment the phases, normalize them with different internal standards and generate the map through iterative calculations. In previous quantitative spot trace element studies, both S or Fe have been used as an internal element standard [13,21,22]. However, one recent study [23] identified decomposition of pyrite during laser ablation into at least two phases, and subsequent disproportionate transport of materials to the mass spectrometer, leading us to re-evaluate which element, Fe or S, is the better choice as an internal standard element.…”

Section: Introductionmentioning

confidence: 99%

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Mapping of Sulfur Isotopes and Trace Elements in Sulfides by LA-(MC)-ICP-MS: Potential Analytical Problems, Improvements and Implications

et al. 2016

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Abstract:Constraints on accurate quantitative trace element and sulfur (S) isotope analysis of sulfide minerals, especially pyrite, by laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) remain imperfectly understood at the present time. Mapping of S isotope distributions within a complex sample containing several minerals requires an evaluation of the matrix effects and accuracy. Here, we apply LA-Q(quadrupole)-ICP-MS and LA-MC(multiple collector)-ICP-MS methods to analyze trace elements and S isotopes in sulfides. Spot analysis of S isotopes was conducted to evaluate the influence of matrix effects. The matrix effects from siderite and magnetite are deemed to be negligible in mapping analysis at the precision of this study. Both Fe and S were used as internal standard elements to normalize trace element concentrations in pyrite. Fe proved to be the better choice because the normalized counts per second ratio of trace elements with Fe is much more stable than if using S. A case study of a sulfide sample from the Chengmenshan Cu deposit, Jiangxi Province, South China, demonstrates the potential of combined S isotope and trace element mapping by LA-(MC)-ICP-MS. The results suggest that this deposit underwent multi-stage ore formation. Elements, including Au and Ag, were hosted in early-stage pyrite but were re-concentrated into multi-component sulfide assemblages during a late-stage hydrothermal event, which also led to crosscutting veins containing pyrite largely devoid of trace elements, except Se. Combining in situ S isotope and trace element analysis on the same sample represents a powerful tool for understanding ore-forming processes.

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Section: Precise Determination Of Trace Elements Using Fe or S Normalsupporting

confidence: 56%

Section: Introductionmentioning

confidence: 99%

Mapping of Sulfur Isotopes and Trace Elements in Sulfides by LA-(MC)-ICP-MS: Potential Analytical Problems, Improvements and Implications

et al. 2016

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“…An additional topic of concern is the potential for fractionation during transport of ablated material from sample to plasma to mass spectrometer, e.g., between iron and sulfur [24]. Fractionation can be caused at various stages, including chemical reaction processes (mineral decomposition, etc.)…”

Section: Melts Aerosols Vapours and Mineral Decompositionmentioning

confidence: 99%

Trace Element Analysis of Minerals in Magmatic-Hydrothermal Ores by Laser Ablation Inductively-Coupled Plasma Mass Spectrometry: Approaches and Opportunities

et al. 2016

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Laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) has rapidly established itself as the method of choice for generation of multi-element datasets for specific minerals, with broad applications in Earth science. Variation in absolute concentrations of different trace elements within common, widely distributed phases, such as pyrite, iron-oxides (magnetite and hematite), and key accessory minerals, such as apatite and titanite, can be particularly valuable for understanding processes of ore formation, and when trace element distributions vary systematically within a mineral system, for a vector approach in mineral exploration. LA-ICP-MS trace element data can assist in element deportment and geometallurgical studies, providing proof of which minerals host key elements of economic relevance, or elements that are deleterious to various metallurgical processes. This contribution reviews recent advances in LA-ICP-MS methodology, reference standards, the application of the method to new mineral matrices, outstanding analytical uncertainties that impact on the quality and usefulness of trace element data, and future applications of the technique. We illustrate how data interpretation is highly dependent on an adequate understanding of prevailing mineral textures, geological history, and in some cases, crystal structure.

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“…Most elements of interest show similar trends in changing yield with increasing laser fluence; however, for simplicity only Mg, Ca, Mn and Fe have been shown in Figure 5 as these elements are the most homogeneous in the P‐Cal sample and span a range of element volatilities; previously linked to element fractionation in LA‐ICP‐MS (Hirata 1997, Gilbert et al . 2014). Based on the observations in Figure 5, the ideal fluence for the laser ablation system used in this study would be 3.5 J cm −2 .…”

Section: Resultsmentioning

confidence: 99%

Use of Non‐Matrix Matched Reference Materials for the Accurate Analysis of Calcium Carbonate by LA‐ICP‐MS

Thompson

Goemann

et al. 2021

Geostandard Geoanalytic Res

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Advances in laser ablation inductively coupled plasma‐mass spectrometry have improved analytical precision for mineral analysis, expanding geological interpretations from LA‐ICP‐MS results. However, with improvements in analytical precision, systematic errors from calibration can become more obvious and affect data quality. To improve the accuracy of the LA‐ICP‐MS technique, a fully quantified method is presented for the analysis of minerals with a CaCO3 matrix. An in‐house calcite sample (P‐Cal) was developed with an independently constrained composition and compared with measurement results from LA‐ICP‐MS analysis, generated using multiple spot sizes, laser fluences and calibration methods. For many elements, calibration against NIST SRM 612 as a calibration reference material and USGS GSD‐1G and USGS BCR‐2G as secondary reference materials (calibration B) provided the best accuracy for CaCO3 analysis. Ablation rates and element yield (ICP‐MS signal intensity in counts per second for a given isotope relative to the mass fraction of the respective element) in calcium carbonate closely resembles NIST SRM 612; however, the down‐hole fractionation curves of USGS BCR‐2G (basaltic glass matrix) are a better fit for carbonate. Variations in accuracy for measurements at different spot sizes are negligible compared with the other effects discussed. Additionally, ablation characteristics for powdered crystals versus large fragments produce a negligible effect on the accuracy of the results for calcium carbonate.

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Fractionation of sulphur relative to iron during laser ablation-ICP-MS analyses of sulphide minerals: implications for quantification

Abstract: In this study we investigate the effect that the mineral composition has on the quantification of sulphur by Laser Ablation ICP-MS (LA-ICP-MS) between a range of sulphide minerals: pyrite, pyrrhotite, bornite, chalcopyrite, sphalerite, pentlandite and tetrahedrite.

Cited by 48 publications

References 42 publications

Mapping of Sulfur Isotopes and Trace Elements in Sulfides by LA-(MC)-ICP-MS: Potential Analytical Problems, Improvements and Implications

Mapping of Sulfur Isotopes and Trace Elements in Sulfides by LA-(MC)-ICP-MS: Potential Analytical Problems, Improvements and Implications

Trace Element Analysis of Minerals in Magmatic-Hydrothermal Ores by Laser Ablation Inductively-Coupled Plasma Mass Spectrometry: Approaches and Opportunities

Use of Non‐Matrix Matched Reference Materials for the Accurate Analysis of Calcium Carbonate by LA‐ICP‐MS

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