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New potential barite reference materials for LA-MC-ICP-MS sulfur isotope analysis with application to hydrothermal barite in the huayangchuan deposit， western China

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Journal of Earth Science 2024年

作者： Jiali Fu Xinqian He zhaochu hu Shuo Yin Jian Ma Kaiyun Chen Wen Zhang National Key Laboratory of Prospecting， Mining and Remote Sense Detecting on Uranium Resources， East China University of Technology State Key Laboratory of Nuclear Resources and Environment， East China University of Technology School of Earth Sciences， East China University of Technology State Key Laboratory of Geological Processes and Mineral Resources， China University of Geosciences Wuhan State Key Laboratory of Continental Dynamics， Department of Geo logy， Northwest University

Sulfur isotopes of S-bearing materials are powerful tools to trace various geological processes and sulfur sources in earth sciences， especially in ore deposits where sulfide-sulfate pair coprecipitates widely. However， in-situ S isotope determination of barite is challenging without natural matrix-matched reference material. In this study， we present two natural barite reference materials （1-YS and 294-YS） for in-situ sulfur isotopic analysis. Independent LA-MC-ICP-MS laboratories were utilized to test the δ34S micron-scale homogeneity of 1-YS and 294-YS barites that have 2s repeatabilities of better than ±0.45 ‰ and ±0.41 ‰， respectively. Meanwhile， the in-situ analysis results are consistent with the results of the bulk analysis by GS-IRMS within uncertainty. The grand mean δ34S values of 1-YS （13.37‰ ± 0.42 ‰， 2s） and 294-YS （14.38‰ ± 0.44 ‰， 2s） are the final recommended values obtained from four independent laboratories. All the results confirm the suitability of 1-YS and 294-YS barite used as calibration materials with respect to in-situ S isotopic analysis. Moreover， the new developed barite reference materials were used as matrix-matched standard to calibrate the barite samples from the huayangchuan carbonatite-hosted U-polymetallic deposit （Qinling orogenic belt， western China） to obtain δ34S values. Utilizing the temperature-dependent δ34S fractionation of barite-pyrite pair， we calculate the formation temperature of barite （i.e.， 506 to 537 ℃） and the δ34S value of mineralizing fluid （i.e.， -7.11‰ to -7.59 ‰） in the huayangchuan deposit. The results indicate an involvement of sedimentary sulfur， presumably acting as a potential uranium source （e.g.， upper crustal materials） for the giant huayangchuan deposit.

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Destruction of the Northern Margin of the North China Craton in Mid-Late Triassic: Evidence from Asthenosphere-derived Mafic Enclaves in the Jiefangyingzi Granitic Pluton from the Chifeng Area, Southern Inner Mongolia

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Acta Geologica Sinica(English Edition) 2020年第4期94卷 1071-1092页

作者： LIU Jianfeng LI Jinyi CHI Xiaoguo ZHENG Peixi hu zhaochu ZHANG Xiaowei Key Laboratory of Deep-Earth Dynamics of Ministry of Natural Resources Institute of GeologyChinese Academy of Geological SciencesBeijing 100037China Institute of Geology Chinese Academy of Geological SciencesBeijing 100037China Key Laboratory of Mineral Resources Evaluation in Northeast Asia Ministry of Land and ResourcesChangchun 130061China College of Earth Science Jilin UniversityChangchun 130061China State Key Laboratory of Geological Processes and Mineral Resources China University of GeosciencesWuhan 430074China

The petrology, geochronology and geochemistry of the mafic enclaves in the Mid-Late Triassic Jiefangyingzi pluton from Chifeng area, southern Inner Mongolia, in China are studied to reveal their petrogenetic relationship with the host pluton. Furthermore, the coeval magmatic assemblage and its petrogenesis on the northern margin of the North China craton(NCC) are studied synthetically to elucidate their tectonic setting and the implications for the destruction of the NCC. Zircon U-Pb dating reveals that the mafic enclaves formed at 230.4 ± 2.2 Ma, which is similar to the age of the host pluton. The most basic mafic enclaves belong to weak alkaline rocks, and they display rare earth element(REE) and trace element normalized patterns and trace element compositions similar to those of ocean island basalt(OIB). In addition, they have positive εNd(t) values(+3.84 to +4.94) similar to those of the Cenozoic basalts on the northern margin of the NCC. All of these geochemical characteristics suggest that the basic mafic rocks originated from the asthenosphere. Petrological and geochemical studies suggest that the Jiefangyingzi pluton and the intermediate mafic enclaves were formed by the mixing of the asthenosphere-derived and crust-derived magmas in different degrees. The Mid-Late Triassic magmatic rocks on the northern margin of the NCC could be classified into three assemblages according to their geochemical compositions: alkaline series, weak alkaline–sub-alkaline series and sub-alkaline series rocks. Petrogenetic analyses suggest that the upwelling of the asthenosphere played an important role in the formation of these Mid-Late Triassic magmatic rocks. Basing on an analysis of regional geological data, we suggest that the northern margin of the NCC underwent destruction due to the upwelling of the asthenosphere during the Mid-Late Triassic, which was induced by the delamination of the root of the collisional orogeny between Sino-Korean and Siberian paleoplates in Late P

关键词： mafic enclave craton destruction asthenosphere Mid-Late Triassic North China craton

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Simultaneous in-situ determination of U-Pb age and trace elements in zircon by LA-ICP-MS in 20 μm spot size

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Chinese Science Bulletin 2007年第9期52卷 1257-1264页

作者： LIU XiaoMing GAO Shan DIWU ChunRong YUAN HongLin hu zhaochu National Key Laboratory of Geological Processes and Mineral Resources Faculty of Earth Sciences China University of Geosciences Wuhan 430074 China National Key Laboratory of Continental Dynamics Department of Geology Northwest University Xi'an 710069 China

Simultaneous in-situ determination of U-Pb ages and 20 trace elements of three international zircon standards(91500,GJ1 and TEMORA 1) and one laboratory zircon standard(SK10-2) separated from Cenozoic fine-grained gabbro was carried out on quadrupole ICP-MS equipped with 193 nm excimer laser in 20 μm spot size. The weighted mean 206Pb/238U ages of 91500,GJ1 and TEMORA 1 are 1064.4±4.8 Ma(2σ ),603.2±2.4 Ma(2σ ) and 418.2±2.4 Ma(2σ ),respectively. The relative standard de-viations(RSDs) of 206Pb/238U ages(2σ ) are less than 2.2% for single measurements and 0.6% for weighted means. The obtained weighted mean 206Pb/238U ages of three standard zircons agree with the recommended values within 2σ error. The weighted mean 206Pb/238U age of SK10-2 is 31.42±0.25 Ma(2σ ) and the RSDs of 206Pb/238U ages(2σ ) are between 2.4% and 5.7% for single measurements and less than 0.8% for weighted mean. The obtained weighted mean 206Pb/238U age is in good agreement with the age obtained by Yuan(2004). Trace element concentrations of NIST612 and NIST614 obtained under the same LA-ICP-MS operating conditions agree with the recommended values within analytical error. The results indicate that it is possible to measure U-Pb age and trace elements simultaneously by LA-ICP-MS in a small spot size of 20 μm.

关键词：锆石测年痕量元素 LA-ICP-MS 源尺寸焦斑同步现场测定

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Applications of LA-ICP-MS in the elemental analyses of geological samples

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Chinese Science Bulletin 2013年第32期58卷 3863-3878页

作者： LIU YongSheng hu zhaochu LI Ming GAO Shan State Key Laboratory of Geological Processes and Mineral Resources China University of Geosciences

Laser ablation-inductively coupled plasma-mass spectrometry(LA-ICP-MS),which is a rapidly developing analytical technique for the analyses of trace elements and isotopes,plays an important role in advancing the study of Earth science,especially with respect to *** article reviews the application of LA-ICP-MS in the elemental analysis of solid geological *** LA-ICP-MS has been widely used in the spatial resolution analysis of element compositions and rapid bulk analysis of whole-rock and soil samples,the analysis accuracy is restricted by numerous factors,including the instrumental conditions,the elemental fractionation and matrix effects,the lack of sufficient matrix-matched reference materials,and the strategies for quantitative calibration and sensitivity drift *** to the type of samples and the analyte elements,the analysis accuracy can be improved through the optimization of instrument conditions and the adoption of suitable correction strategies and reference materials.

关键词： LA-ICP-MS 痕量元素分析应用地质样品电感耦合等离子体质谱基质效应校正策略分析精度

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Review on in situ Isotopic Analysis by LA-MC-ICP-MS

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Journal of Earth Science 2023年第6期34卷 1663-1691页

作者： Jie Lin Ao Yang Ran Lin Ji Mao zhaochu hu Yongsheng Liu State Key Laboratory of Geological Processes and Mineral Resources China University of GeosciencesWuhan 430074China Faculty of Materials Science and Chemistry China University of GeosciencesWuhan 430078China

The method of LA-MC-ICP-MS has become one choice for the analysis of many isotopic systems due to its relatively low cost,high analysis speed,high spatial resolution,and low matrix ***,there are still many challenges in the accuracy,precision,and spatial resolution of in situ isotopic composition determination by LA-MC-ICP-MS,which mainly include:(1)how to improve instrument sensitivity,further improve the spatial resolution,and achieve simultaneous determination of isotopes,multiple isotopes,or isotopes with trace elements in low-content samples?(2)how to deduct and correct interference to improve the accuracy of isotopic determination?(3)how to correct isotope fractionation?(4)how to reduce the matrix effect of isotopes?how to develop matrix-matched reference materials?and(5)how to achieve non-matrix-matched correction of isotopes?The high-sensitivity cone combinations,gas mixture,shield torch,and reasonable detector array can be applied to improve the elemental *** interferences include the background interference and the interferences from the matrix elements(the isobaric interference,the polyatomic interference,and doubly charged ions interference).To reduce or even eliminate the interference,commonly used methods including interference elimination,background correction,and interference correction by evaluating with an interference-free *** fractionation correction mainly involves external standard calibration and internal and pseudo-internal standard *** non-matrix matched calibration,many methods can be applied,such as the femtosecond laser,line scan,low laser energy,wet plasma condition,optical setup below the sample surface,and matching the intensity of the sample and *** this review,we systematically summarized the above challenges and solutions to promote the study and application of LA-MC-ICP-MS in isotopic determination.

关键词： LA-MC-ICP-MS isotopic determination interference isotopic fractionation matrix ef-fect reference materials isotopes geochemistry

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Review of High-Precision Sr Isotope Analyses of Low-Sr Geological Samples

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Journal of Earth Science 2015年第5期26卷 763-774页

作者： Jie Lin Yongsheng Liu Haihong Chen Lian Zhou zhaochu hu Shan Gao State Key Laboratory of Geological Processes and Mineral Resources China University of Geosciences

Isotope plays an important role in both tracing and dating in earth science, especially 87Rb-86 Sr system. With the development of earth science, whole-rock analysis can＇t sufficiently meet the requirements for scientific research and the micro-analysis becomes more and more significant. Laser ablation multi-collector inductively-coupled plasma mass-spectrometry（LA-MC-ICP-MS） has been extensively applied in micro-zone analysis due to its low sample-consumption, high accuracy, in situ and low requirements on matrix, but it is still difficult to accurately measure Sr isotope compositions especially for the samples with high Rb/Sr ratios and low Sr contents as it is restricted by severe quality discrimination and various types of mass spectrum interferences. Consequently, thermal ionization mass-spectrometry（TIMS）, as the most accurate and precise method to analyze isotopic ratios, is still the most popular method of analyzing Sr ratios, especially for the samples with low Sr contents. This paper makes a systematic review on the high-precision Sr isotope analyses of low-Sr geological samples, including the micro-sampling technique, ultra-low procedural blank chemical method and TIMS measurement technique. The combination of ultra-low procedural blank and TIMS can be used to perform high-precision micro-analysis of the samples with ng magnitude, which will be undoubtedly an important direction for Rb-Sr geochronology, geochemistry and environmental studies.

关键词： Sr isotope compositions Ultra-low procedural blank TIMS Micro-sampling Sr-specific resin Micro-ion exchange column

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Geochemical Characteristics and Geological Significance of Early Permian Baya'ertuhushuo Gabbro in South Great Xing'an Range

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Acta Geologica Sinica(English Edition) 2011年第1期85卷 116-129页

作者： LIU Jianfeng CHI Xiaoguo ZHAO Zhi ZHANG Xingzhou MA Zhihong WANG Tiefu hu zhaochu College of Earth Sciences Jilin University Changchun 130061 China Institute of Geology Chinese Academy of Geological Sciences Beijing 100037 China The Center of Test and Science Experiment Jilin University Changchun 130026 China State Key Laboratory of Geological Processes and Mineral Resources China University of Geosciences Wuhan 430074 China

Field geological investigation and geochemical analysis are carried out on Baya＇ertuhushuo Gabbro in South Great Xing＇an Range. Field investigation reveals that the gabbro is a magmatic intrusion rather than a component of an ophiolite suite as previously thought. Zircon laser ablation inductively coupled plasma mass spectroscopy （LA-ICP-MS） U-Pb dating indicates the gabbro was formed in 274-275 Ma, just as the widespread volcanic rocks of Dashizhai Formation （P1d）, monzogranites and miarolitic alkali-feldspar granites in the study area. The gabbro has SiO2 content between 47.23 wt% and 50.17 wt%, high MgO and FeOT contents of 6.95-11.29 wt% and 7.32- 12.24wt%, respectively, and it belongs to low-K tholeiitic series in the SiO2-K2O diagram. The Chondrite-normalized rare earth element （REE） patterns and primitive mantle-normalized spider diagrams of the gabbro are similar to those of Normal Mid-Ocean Ridge Basalt （N-MORB） except for the enrichment of large ion lithophfle elements （LILE）, such as Rb, Ba and K. In trace element tectonic discriminative diagrams, the samples are mainly plotted in the N-MORB field, and Zircon in situ Lu-Hf isotopic analysis also indicates the gabbro originated from depleted mantle. Through synthetic studies of the geochemical characteristics and petrogenesis of Baya＇ertuhushuo gabbro, volcanic rocks of Dashizhai Formation and granitoids in the area, it is suggested that the early Permian magmatism in the Xilinhot-Xiwuqi area formed in the tectonic setting of asthenosphere upwelling, which was caused by breaking-off of the subducted Paleo-Asian Ocean slab.

关键词： gabbro geochemistry early Permian zircon U-Pb age south Great Xing'an Range

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Non-matrix-matched analysis of U-Th-Pb geochronology of bastn?site by laser ablation inductively coupled plasma mass spectrometry

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Science China Earth Sciences 2021年第4期64卷 667-676页

作者： Tao LUO He ZHAO Wen ZHANG Jingliang GUO Keqing ZONG Yongsheng LIU Junfeng ZHANG zhaochu hu State Key Laboratory of Geological Processes and Mineral Resources China University of GeosciencesWuhan 430074China

Bastn?site is widespread in alkali granite, carbonatite and REE ore deposits. The U-Th-Pb ages of bastn?site can constrain the mineralization age. Currently, the lack of suitable in situ analysis reference material is the major obstacle of bastn?site U-Th-Pb geochronology. In this study, the matrix effects of U-Pb and Th-Pb age determination in bastn?site using glass NIST 610 as the external calibration reference were evaluated with the 193-nm excimer LA-ICP-MS analysis in normal and additional gases laser ablation modes. The obtained U-Th-Pb ages of bastn?site were approximately 7–11% lower than their reference values in the normal analytical mode(without additional gas). Fortunately, the determined systematic age biases in UTh-Pb dating were significantly reduced(less than 1–2%) with the addition of water vapor within the ablation chamber. This reduction may be attributed to the observed significant suppression of206 Pb/238 U and208 Pb/232 Th downhole fractionation in both NIST 610 glass and bastn?site by introducing a small quantity of water vapor in the ablation chamber. In addition, the obtained206 Pb/238 U and208 Pb/232 Th ages of bastn?site K-9, LZ1384, and MAD809 showed great consistency with their corresponding recommended values. The obtained results show that accurate and precise U-Th-Pb ages of bastn?site can be simultaneously obtained by using glass NIST 610 as the primary calibration standard in 193-nm LA-ICP-MS with the water vapor-assisted method. This simple and effective water vapor-assisted non-matrix-matched laser ablation method helps to promote the geological application of bastn?site U-Th-Pb geochronology.

关键词： LA-ICP-MS U-Th-Pb ages Non-matrix-matched method Bastn?site

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Accurate Determination of Zr Isotopic Ratio in Zircons by Femtosecond Laser Ablation MC-ICP-MS with “Wet” Plasma Technique

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Journal of Earth Science 2022年第1期33卷 67-75页

作者： Wen Zhang zhaochu hu Lanping Feng Zaicong Wang Yongsheng Liu Yantong Feng Hong Liu State Key Laboratory of Geological Processes and Mineral Resources School of Earth SciencesChina University of GeosciencesWuhan 430074China

This work evaluates the use of femtosecond laser ablation multiple collector inductively coupled plasma mass spectrometry(fs-LA-MC-ICP-MS) for Zr isotopic analysis in zircons. The mass fractionation caused by instrumental mass discrimination was corrected by a combination of internal correction using Sr as an internal standard(coming from a NIST SRM 987 standard solution) and external correction using a matrix-matched standard. Several important instrument parameters were investigated, such as the effect of the addition of N;and "wet" plasma condition, the mass fractionation behaviors between Zr isotopes and Sr isotopes, the position effect in laser ablation cell and the effect of laser ablation parameters(laser spot size and energy density). The Zr isotope compositions of seven zircons(GJ-1, 91500, Ple?ovice, Rak-17, Paki, Aus and Mala) were determined by the developed fs-LAMC-ICP-MS and thermal ionization mass spectrometry(TIMS). Our fs-LA-MC-ICP-MS results for Zr isotope compositions agreed with TIMS analyses within analytical uncertainties, indicating the presented method is a suitable tool to resolve isotopic zoning in natural zircons. The results also suggest that GJ-1, 91500, Ple?ovice, Paki, Aus and Mala had the homogenous Zr isotope composition and could be considered as the potential candidates for the Zr isotope analysis in zircons, except Rak-17 which presented the large Zr isotope variation.

关键词： Zr isotope analysis zircon LA-MC-ICP-MS reference materials

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An Effective Oxide Interference Correction on Sc and REE for Routine Analyses of Geological Samples by Inductively Coupled Plasma-Mass Spectrometry

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Journal of Earth Science 2019年第6期30卷 1302-1310页

作者： Wei Zhao Keqing Zong Yongsheng Liu zhaochu hu Haihong Chen Ming Li State Key L aboratory of Geological Processes and Mineral Resources China University of GeosciencesWuhan 430074China State Key Laboratory of Desert and Oasis Ecology Xinjiang Institute of Ecology and GeographyChinese Academy of SciencesUrumqi 830011China Xinjiang Research Center for Mineral Resources Xinjiang Institute of Ecology and GeographyChinese Academy of SciencesUrumqi 830011China

Oxide interference correction plays a vital role in the accurate determination of trace element compositions of geological samples by inductively coupled plasma-mass spectrometry(ICP-MS).In this study,we found that the oxide production is mainly controlled by the gas flow of the ICP-MS and a constant oxide correction factor(OCF)can be measured during a routine ***,we can obtain the oxide production by just investigating the gas flow for a fixed ICP-MS system with monitoring of ***,Ba and LREE oxide interferences on the Sc,Eu and Gd of four geological standard samples GSP-2,JP-1,GBW03112 and GBW03113 were corrected by such method and the results were in good agreement with the recommended ***,the present study provides a simple and fast correction method for the oxide interferences of the geological samples during the routine ***,a Microsoft Excel spreadsheet template integrating the correction equations was developed in an in-house software(ICPMSData Cal)for effective calibration.

关键词： oxide interference ICP-MS Sc REE geological samples

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