Accurate Determination of Elemental Contents in Carbonate Minerals with Laser Ablation Inductively Coupled Plasma-Mass Spectrometry

BACKGROUNDTrace element information in carbonates provides key constraints for investigating ancient environments, paleoclimate evolution, shell-mantle interactions, diagenesis and mineralization processes. The accurate determination of trace element content in carbonate minerals have always been a...

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Main Authors: Tao LUO, Liyuan QING, Jinyu LIU, Wen ZHANG, Tao HE, Zhaochu HU
Format: Article
Language:English
Published: Science Press, PR China 2023-10-01
Series:Yankuang ceshi
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Online Access:http://www.ykcs.ac.cn/article/doi/10.15898/j.ykcs.202308020117
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author Tao LUO
Liyuan QING
Jinyu LIU
Wen ZHANG
Tao HE
Zhaochu HU
author_facet Tao LUO
Liyuan QING
Jinyu LIU
Wen ZHANG
Tao HE
Zhaochu HU
author_sort Tao LUO
collection DOAJ
description BACKGROUNDTrace element information in carbonates provides key constraints for investigating ancient environments, paleoclimate evolution, shell-mantle interactions, diagenesis and mineralization processes. The accurate determination of trace element content in carbonate minerals have always been a primary focus. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) can provide detailed information on trace element content in carbonate minerals. However, the elemental concentrations in carbonate minerals are usually extremely low (from hundreds of pg/g to tens of ng/g). A large spot size (from 44 to 100μm) is often used for trace element measurements in carbonate minerals. Therefore, the detection capability of low-content elements in carbonate minerals and the spatial resolution of LA determination still need to be improved.OBJECTIVESTo develop a new analytical method for determination of low-content trace elements in carbonate minerals with LA-ICP-MS.METHODSA new local aerosol extraction ablation cell was proposed in this study. Laser ablation was performed using high-repetition rates with the new designed ablation cell. The elemental contents in carbonate reference materials MACS-3, CGSP-A, CGSP-B, CGSP-C, and CGSP-D were determined with both ns and fs LA-Q-ICP-MS with a spot size of 32μm. Here, NIST 610 glass was used as an external calibration material and Ca was used as an internal standard.RESULTSThe obtained peak height of a single laser shot was enhanced by a factor of 13 with the local aerosol extraction ablation cell because of the rapid washout time. The signal intensities were increased by 1.5 times under high-repetition rate laser ablation mode. Therefore, the detection limits of trace elements in carbonate minerals obtained from nanosecond laser ablation at high repetition rates (20Hz) were reduced by 5-8 times compared to conventional analysis (6Hz). The detection limits of trace elements were reduced by 5-10 times with the frequency of femtosecond laser ablation increased from 10Hz to 100Hz. The elemental contents in carbonate reference materials were measured with both ns and fs LA-Q-ICP-MS with a spot size of 32μm. The obtained results of lithophile elements (e.g., Sc, Sr, Y, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Th) in carbonate CGSP series and carbonate MACS-3 showed good agreement with their reference values. However, the measured results of siderophile and chalcophile elements (e.g., Ni, Cu, Zn, As, Cd, Sn, Sb, and Pb) showed systematic bias (>20%), which may be related to the “downhole” fractionation effect caused by the high-repetition rate laser ablation used in this study.CONCLUSIONSThe new designed local aerosol extraction ablation cell combined with high-repetition rate laser ablation mode significantly improved the spital resolution and determination ability of low-content elements in carbonate minerals. The obtained results of lithophile elements in carbonate CGSP series and carbonate MACS-3 showed good agreement with their reference values using ns- and fs-LA-Q-ICP-MS with a spot size of 32µm. It is worth noting that the spatial resolution and the detection capability of ultra-low-content elements in carbonate minerals could be further improved with the proposed LA method combined with high-sensitivity magnetic sector mass spectrometry.
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spelling doaj-art-76d2615515ec4a9ab1bacdebf7aca6452025-08-20T02:59:23ZengScience Press, PR ChinaYankuang ceshi0254-53572023-10-01425996100610.15898/j.ykcs.202308020117yk202308020117Accurate Determination of Elemental Contents in Carbonate Minerals with Laser Ablation Inductively Coupled Plasma-Mass SpectrometryTao LUO0Liyuan QING1Jinyu LIU2Wen ZHANG3Tao HE4Zhaochu HU5State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences (Wuhan), Wuhan 430074, ChinaState Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences (Wuhan), Wuhan 430074, ChinaState Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences (Wuhan), Wuhan 430074, ChinaState Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences (Wuhan), Wuhan 430074, ChinaState Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences (Wuhan), Wuhan 430074, ChinaState Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences (Wuhan), Wuhan 430074, ChinaBACKGROUNDTrace element information in carbonates provides key constraints for investigating ancient environments, paleoclimate evolution, shell-mantle interactions, diagenesis and mineralization processes. The accurate determination of trace element content in carbonate minerals have always been a primary focus. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) can provide detailed information on trace element content in carbonate minerals. However, the elemental concentrations in carbonate minerals are usually extremely low (from hundreds of pg/g to tens of ng/g). A large spot size (from 44 to 100μm) is often used for trace element measurements in carbonate minerals. Therefore, the detection capability of low-content elements in carbonate minerals and the spatial resolution of LA determination still need to be improved.OBJECTIVESTo develop a new analytical method for determination of low-content trace elements in carbonate minerals with LA-ICP-MS.METHODSA new local aerosol extraction ablation cell was proposed in this study. Laser ablation was performed using high-repetition rates with the new designed ablation cell. The elemental contents in carbonate reference materials MACS-3, CGSP-A, CGSP-B, CGSP-C, and CGSP-D were determined with both ns and fs LA-Q-ICP-MS with a spot size of 32μm. Here, NIST 610 glass was used as an external calibration material and Ca was used as an internal standard.RESULTSThe obtained peak height of a single laser shot was enhanced by a factor of 13 with the local aerosol extraction ablation cell because of the rapid washout time. The signal intensities were increased by 1.5 times under high-repetition rate laser ablation mode. Therefore, the detection limits of trace elements in carbonate minerals obtained from nanosecond laser ablation at high repetition rates (20Hz) were reduced by 5-8 times compared to conventional analysis (6Hz). The detection limits of trace elements were reduced by 5-10 times with the frequency of femtosecond laser ablation increased from 10Hz to 100Hz. The elemental contents in carbonate reference materials were measured with both ns and fs LA-Q-ICP-MS with a spot size of 32μm. The obtained results of lithophile elements (e.g., Sc, Sr, Y, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Th) in carbonate CGSP series and carbonate MACS-3 showed good agreement with their reference values. However, the measured results of siderophile and chalcophile elements (e.g., Ni, Cu, Zn, As, Cd, Sn, Sb, and Pb) showed systematic bias (>20%), which may be related to the “downhole” fractionation effect caused by the high-repetition rate laser ablation used in this study.CONCLUSIONSThe new designed local aerosol extraction ablation cell combined with high-repetition rate laser ablation mode significantly improved the spital resolution and determination ability of low-content elements in carbonate minerals. The obtained results of lithophile elements in carbonate CGSP series and carbonate MACS-3 showed good agreement with their reference values using ns- and fs-LA-Q-ICP-MS with a spot size of 32µm. It is worth noting that the spatial resolution and the detection capability of ultra-low-content elements in carbonate minerals could be further improved with the proposed LA method combined with high-sensitivity magnetic sector mass spectrometry.http://www.ykcs.ac.cn/article/doi/10.15898/j.ykcs.202308020117la-icp-mscarbonate mineralstrace elementslocal aerosol extractionhigh-repetition rate laser ablation
spellingShingle Tao LUO
Liyuan QING
Jinyu LIU
Wen ZHANG
Tao HE
Zhaochu HU
Accurate Determination of Elemental Contents in Carbonate Minerals with Laser Ablation Inductively Coupled Plasma-Mass Spectrometry
Yankuang ceshi
la-icp-ms
carbonate minerals
trace elements
local aerosol extraction
high-repetition rate laser ablation
title Accurate Determination of Elemental Contents in Carbonate Minerals with Laser Ablation Inductively Coupled Plasma-Mass Spectrometry
title_full Accurate Determination of Elemental Contents in Carbonate Minerals with Laser Ablation Inductively Coupled Plasma-Mass Spectrometry
title_fullStr Accurate Determination of Elemental Contents in Carbonate Minerals with Laser Ablation Inductively Coupled Plasma-Mass Spectrometry
title_full_unstemmed Accurate Determination of Elemental Contents in Carbonate Minerals with Laser Ablation Inductively Coupled Plasma-Mass Spectrometry
title_short Accurate Determination of Elemental Contents in Carbonate Minerals with Laser Ablation Inductively Coupled Plasma-Mass Spectrometry
title_sort accurate determination of elemental contents in carbonate minerals with laser ablation inductively coupled plasma mass spectrometry
topic la-icp-ms
carbonate minerals
trace elements
local aerosol extraction
high-repetition rate laser ablation
url http://www.ykcs.ac.cn/article/doi/10.15898/j.ykcs.202308020117
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AT jinyuliu accuratedeterminationofelementalcontentsincarbonatemineralswithlaserablationinductivelycoupledplasmamassspectrometry
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