共查询到19条相似文献，搜索用时 117 毫秒
1.
激光剥蚀等离子体质谱分析中激光剥蚀参数对信号响应的影响 总被引：5，自引：1，他引：5
探讨了激光剥蚀等离子体质谱固体微区分析中激光剥蚀参数对元素分析信号灵敏度及稳定性的影响。这些参数包括激光功率、脉冲频率、剥蚀孔经、散焦距离、剥蚀方式等。讨论了优化的激光剥蚀等离子体质谱信号采集及数据处理方式。在全质量范围内选用具有代表性的元素作为研究对象,建立了激光剥蚀的一般性特征规律和266nm紫外激光系统的最佳操作条件。在选定的激光剥蚀参数下,大多数被测元素的检出限为22.8~457ng/g,能够满足固体微区分析的要求。 相似文献
2.
石笋样品的微量元素含量及Mg/Ca、Sr/Ca比值为高分辨的古气候重建提供重要指标。针对现有溶液分析技术易混合多个石笋微层、误差大的缺点,本文利用激光剥蚀电感耦合等离子体质谱技术(LA-ICP-MS)原位线扫描和点剥蚀方式对比分析了石笋生长轴方向的Mg/Ca和Sr/Ca空间分布趋势,研究表明二者均展现出显著的周期性变化特征,且周期性变化一致,其中40 μm束斑线扫描更具有稳定性强、分辨率高、快速简便的优点。通过探讨碳酸盐标准样品MASC-3与玻璃标准样品NIST 610、NIST 612、KL2G、ATHO-G的相对灵敏度系数关系和元素分馏行为,确定基体效应是造成相对灵敏度系数变化的主要原因。同时建立了以MASC-3、NIST 610和NIST 612多外标结合内标Ca归一定量分析石笋中45种元素方法,针对石笋碳酸盐样品,将主量元素Ca、Mg变形为碳酸盐形式,与其他元素加和归一,不仅改变了国内外研究中需要预先采用其他分析技术来测定内标元素含量的计算方法,而且有效地避免了C元素无法准确检测的问题,能够实现与Ca内标法校正结果的吻合。 相似文献
3.
4.
激光剥蚀电感耦合等离子体质谱测定岩石样品中稀土元素 总被引：10，自引：0，他引：10
以NIST612玻璃标准为外标校正物质, 采用42Ca为内标校正灵敏度漂移、基体效应、剥蚀效率及进样量的变化.将LSX-2 0 0激光剥蚀进样系统与POEMSIII电感耦合等离子体质谱仪联用, 对国际标准物质BCR-2 (玄武岩) 及国内标准物质GSR-11 (花岗岩) 玻璃熔饼进行了稀土元素的测定, 建立了LA -ICP -MS整体分析岩石样品中稀土元素的方法.结果表明, 绝大多数稀土元素准确度优于15 %, 测定精度(RSD) 小于10 %.稀土元素的检出限(LOD) 在21.4×10-9~23 1.6×10-9之间, 样品分析速度为2 0样品/h.在Excel软件下用VBA语言编制宏, 实现了脱机数据处理的自动化, 极大提高了工作效率. 相似文献
5.
激光焦平面变化对LA-ICPMS锆石U-Pb定年准确度的影响 总被引：3，自引：0，他引：3
元素分馏是影响LA-ICPMS锆石U-Pb定年准确度的重要因素之一,通常利用标样进行校正。激光聚焦位置变化会引起剥蚀坑形貌及U-Pb分馏的改变,标样和样品聚焦条件不一致将导致标样难以准确校正样品,并最终影响定年结果的准确性,但影响的程度、机制及可容忍范围目前尚不清楚。为此,文章以91500为标样、GJ-1为样品,详细研究了聚焦偏离30μm范围内剥蚀标样与样品锆石的剥蚀坑形貌变化以及由此导致的U-Pb定年误差。实验表明,在距离锆石表面30μm范围内,标样和样品焦平面同步变化时,二者U-Pb分馏形式及程度基本一致,激光焦平面偏离所引起的样品年龄与TIMS推荐值的偏差小于1%;当二者聚焦不同步时,标样与样品的U-Pb分馏差别显著,年龄偏差最大可超过3%。激光聚焦不同步导致的标样与样品剥蚀坑纵横比差异是引起年龄误差的根本原因,激光焦平面偏离锆石表面超过15μm,剥蚀坑坑口明显变大,纵横比减小,U-Pb分馏形式及程度发生改变。通过预剥蚀锆石,观察剥蚀坑轮廓,使激光焦平面在距离锆石样品表面15μm范围内,可确保标样与样品剥蚀坑形貌及U-Pb分馏状态一致,提高LA-ICPMS定年的准确度。 相似文献
6.
193nm ArF准分子激光系统对LA-ICP-MS分析中不同基体的剥蚀行为和剥蚀速率探究 总被引：7，自引：6，他引：1
探究LA-ICP-MS分析中不同基体的剥蚀行为和剥蚀速率,可为激光参数设定、基体匹配选择、数据质量保证等方面提供重要参考。本文研究了193 nm ArF准分子激光系统对人工合成/地质样品玻璃、常见矿物和粉末压片的剥蚀行为,同时探究了激光参数(束斑直径、能量密度和剥蚀频率)对剥蚀速率的影响情况。从剥蚀坑形貌可知,193nm ArF激光对玻璃和绝大多数矿物的剥蚀行为良好,但对石英相对较差,这可能与石英内含有微观包裹体,剥蚀过程中局部受热不均有关。粉末压片的剥蚀行为呈现出不可控,可通过提高粉末压片的压制压力或降低粉末颗粒的粒径来改善剥蚀行为;当剥蚀深度大于1.5倍束斑直径时,剥蚀速率随剥蚀深度的增加而逐渐减小,剥蚀深度最多可达束斑直径的两倍左右(RESOlution M-50型号激光系统,3.0 J/cm2激光能量密度);剥蚀速率随激光能量密度的增加而增大,但基本不受剥蚀频率(2~20 Hz)影响。不同基体具有特征的剥蚀速率,本文报道了43种基体的剥蚀速率参数,总体而言,NIST系列玻璃的剥蚀速率大于地质样品玻璃,碳酸盐矿物和硫化物矿物大于硅酸岩矿物,粉末压片大于玻璃和常见矿物。 相似文献
7.
地幔流体及其成矿作用 总被引：8，自引：0，他引：8
高灵敏度、高精密度、低检出限、多元素同时检测并可提供同位素组成比值信息的等离子体质谱与高空间分辨率的紫外激光采样技术结合 ,可定量地测定单个流体包裹体中常、微量元素含量 ,为成矿流体的研究提供了一个新的研究手段。文中简要地介绍了激光剥蚀电感耦合等离子体质谱 (LA ICP MS)分析仪器的发展 ,结合实验室的研究工作 ,就激光剥蚀池的设计、单个流体包裹体的剥蚀方法、元素的分馏效率、定量校正技术及其在成矿成因物理化学机制研究中的应用等进行评述 ,并阐述单个流体包裹体元素组成的LA ICP MS分析技术存在的局限和发展趋势。 相似文献
8.
锆石铀-铅定年激光剥蚀-电感耦合等离子体质谱原位微区分析进展 总被引：11，自引：3，他引：8
激光剥蚀-电感耦合等离子体质谱(LA-ICP-MS)技术是目前最常用的锆石U-Pb同位素年龄测定方法之一。该方法能够对单颗粒锆石内部年龄差异实现快速、准确的原位微区分析。文章总结了近年来激光剥蚀系统、ICP-MS技术以及LA-ICP-MS锆石U-Pb定年方法、相关应用实例研究的进展和现状。系统评述了激光发生器,剥蚀池,剥蚀参数(激光波长、脉冲宽度、剥蚀气体、孔径大小)以及四极杆和扇形磁场质谱仪对锆石U-Pb年龄数据的精度和准确度的影响。详细介绍了基于锆石年龄标准样品、标准溶液及其他标样的外标定量校准方法,单个U/Pb比值计算方法,普通铅校正方法以及同位素年龄与微量元素同时测定的方法。目前LA-ICP-MS锆石U-Pb定年技术主要应用于碎屑锆石的沉积物源区示踪和岩浆事件的年代学约束研究。 相似文献
9.
微区Sr同位素体系相对于传统全岩Sr同位素研究,可以揭示样品自身存在的不均一性,更好地反映样品经历的地质过程,已被广泛应用于各种地质研究领域,如研究壳幔相互作用、岩浆起源和演化,岩浆体系开放性研究,沉积盆地物源示踪及气候环境研究。准确测定Rb-Sr同位素比值是应用该同位素体系的前提。微钻取样-热电离质谱/多接收电感耦合等离子体质谱(TIMS/MC-ICPMS)和激光剥蚀多接收电感耦合等离子体质谱(LA-MC-ICPMS)作为分析地质样品微区Sr同位素组成的有效手段,已经得到了较为广泛的应用。两种技术在样品制备、干扰校正和质谱测试等方面各具优势和不足。微钻取样-TIMS/MC-ICPMS的最大优势是可获得高精度的Sr同位素数据(外精度优于100×10-6,2SD);但由于需要进行化学处理,流程繁琐耗时(约10天),实验周期较长,同时需要严格控制化学流程空白,且取样直径(200~2000μm)和取样深度(100~2000μm)较大,空间分辨率较低,但是该方法可以对高Rb样品(如钾长石)进行有效分析。LA-MC-ICPMS的最大优势是样品制备简单,数小时即可完成,且分析效率高,根据样品Sr含量的大小激光束斑直径多在60~300μm之间变化,其空间分辨率较前一种方法高,可在短时间内对大量样品进行分析。但由于不能进行化学分离,分析过程中存在多种干扰(如Rb、Ca、Kr和REEs等),影响了测试的精度(约200×10-6,2SD)和准确度(约150×10-6)。该方法目前只能对高Sr低Rb的样品(如斜长石、磷灰石等)进行有效分析,而对于干扰元素含量较高的样品目前无法应用。本文认为,对于微钻取样法,应将改进化学流程作为重点研究方向,提高化学处理效率,同时改善微钻取样法的取样技术,减小取样直径和深度以提高空间分辨率;对于激光剥蚀法,重点突破Kr、Rb和二价REEs等干扰校正问题,提高干扰元素含量较高的样品的分析精度和准确度,同时需要提高仪器灵敏度以满足低Sr含量样品的分析要求。 相似文献
10.
激光能量密度对LA-ICP-MS分析数据质量的影响研究 总被引：3，自引：2，他引：1
LA-ICP-MS分析矿物元素含量时激光能量密度会影响样品的剥蚀速率,从而影响测试过程的信号强度。激光能量密度变化对测试数据精确度的影响,以及不同天然矿物对激光能量密度的响应尚需进一步明确。本文测定了不同莫氏硬度天然矿物可稳定剥蚀的最小激光能量密度,评估了193nm ArF准分子激光系统中能量密度对地质标准样品(NIST SRM614、USGS BCR-2G、USGS GSC-1G)和天然矿物测试数据质量的影响。研究结果表明:①稳定剥蚀石英和萤石所需的最小激光能量密度为4～5J/cm~2,低于前人的报道值(10J/cm~2),而稳定剥蚀其他矿物(如滑石、磷灰石、刚玉等)所需的最小能量密度一般在1～2J/cm~2;②不同激光能量密度剥蚀条件下,标准样品中大部分微量元素测试结果与推荐值的相对误差小于20%,相对标准偏差(RSD)小于10%,而天然矿物中含量1μg/g的大部分微量元素测试数据的RSD小于20%;③在一定范围内,激光能量密度越大,数据平均相对误差越小,整体质量更好。 相似文献
11.
Marcel Guillong Kathrin Hametner Eric Reusser Stephen A. Wilson Detlef Günther 《Geostandards and Geoanalytical Research》2005,29(3):315-331
New glass reference materials GSA-1G, GSC-1G, GSD-1G and GSE-1G have been characterised using a prototype solid state laser ablation system capable of producing wavelengths of 193 nm, 213 nm and 266 nm. This system allowed comparison of the effects of different laser wavelengths under nearly identical ablation and ICP operating conditions. The wavelengths 213 nm and 266 nm were also used at higher energy densities to evaluate the influence of energy density on quantitative analysis. In addition, the glass reference materials were analysed using commercially available 266 nm Nd:YAG and 193 nm ArF excimer lasers. Laser ablation analysis was carried out using both single spot and scanning mode ablation. Using laser ablation ICP-MS, concentrations of fifty-eight elements were determined with external calibration to the NIST SRM 610 glass reference material. Instead of applying the more common internal standardisation procedure, the total concentration of all element oxide concentrations was normalised to 100%. Major element concentrations were compared with those determined by electron microprobe. In addition to NIST SRM 610 for external calibration, USGS BCR-2G was used as a more closely matrix-matched reference material in order to compare the effect of matrix-matched and non matrix-matched calibration on quantitative analysis. The results show that the various laser wavelengths and energy densities applied produced similar results, with the exception of scanning mode ablation at 266 nm without matrix-matched calibration where deviations up to 60% from the average were found. However, results acquired using a scanning mode with a matrix-matched calibration agreed with results obtained by spot analysis. The increased abundance of large particles produced when using a scanning ablation mode with NIST SRM 610, is responsible for elemental fractionation effects caused by incomplete vaporisation of large particles in the ICP. 相似文献
12.
Klaus Peter Jochum Brigitte Stoll Ulrike Weis Dorrit E. Jacob Regina Mertz‐Kraus Meinrat O. Andreae 《Geostandards and Geoanalytical Research》2014,38(3):265-292
LA‐ICP‐MS is one of the most promising techniques for in situ analysis of geological and environmental samples. However, there are some limitations with respect to measurement accuracy, in particular for volatile and siderophile/chalcophile elements, when using non‐matrix‐matched calibration. We therefore investigated matrix‐related effects with a new 200 nm femtosecond (fs) laser ablation system (NWRFemto200) using reference materials with different matrices and spot sizes from 10 to 55 μm. We also performed similar experiments with two nanosecond (ns) lasers, a 193 nm excimer (ESI NWR 193) and a 213 nm Nd:YAG (NWR UP‐213) laser. The ion intensity of the 200 nm fs laser ablation was much lower than that of the 213 nm Nd:YAG laser, because the ablation rate was a factor of about 30 lower. Our experiments did not show significant matrix dependency with the 200 nm fs laser. Therefore, a non‐matrix‐matched calibration for the multi‐element analysis of quite different matrices could be performed. This is demonstrated with analytical results from twenty‐two international synthetic silicate glass, geological glass, mineral, phosphate and carbonate reference materials. Calibration was performed with the certified NIST SRM 610 glass, exclusively. Within overall analytical uncertainties, the 200 nm fs LA‐ICP‐MS data agreed with available reference values. 相似文献
13.
Keegan E. Alagna Maurizio Petrelli Diego Perugini Giampiero Poli 《Geostandards and Geoanalytical Research》2008,32(1):103-120
In this study we evaluated the capability of a 213 nm laser ablation system coupled to a quadrupole-based ICP-MS in delivering accurate and precise U-Pb ages on zircons and monazites. Four zircon samples ( ca. 50 Ma to ca. 600 Ma) and four monazite samples ( ca. 30 Ma to ca. 1390 Ma) of known ages were analysed utilising laser ablation pits with diameters of 20 μm and 60 μm. Instrument mass bias and laser induced time-dependent elemental fractionation were corrected for by calibration against a matrix-matched reference material. Tera-Wasserburg plots of the calculated U-Pb data were employed to assess, and correct for, common Pb contributions. The results indicated that the LA-ICP-MS technique employed in this study allowed precise and accurate U-Pb isotope dating of zircon and monazite on sample areas 20 μm in diameter. At this spot size, the precisions achieved for single spot 206 Pb/238 U ages, were better than 5% (2s) for monazites and zircons with ages down to 30 Ma and 50 Ma, respectively. The precisions reported are comparable to those generally reported in SIMS and LA-MC-ICP-MS U-Pb isotope determinations. 相似文献
14.
Laser Ablation and Solution ICP-MS Determination of Rare Earth Elements in USGS BIR-1G, BHVO-2G and BCR-2G Glass Reference Materials 总被引：2，自引：0，他引：2
Ladislav Strnad Martin Mihaljevic Ondrej Sebek 《Geostandards and Geoanalytical Research》2005,29(3):303-314
Data are reported for rare earth elements (REE) in three geological glass reference materials (BIR-1G, BHVO-2G and BCR-2G) using a UV (266 nm) laser ablation ICP-MS system and the classical (HF-HClO4 ) acid decomposition method, followed by conventional nebulisation ICP-MS. External calibration of laser ablation analyses was performed using NIST SRM reference materials with internal standardisation using 29 Si and 44 Ca. Replicate analyses of reference basaltic glasses yielded an analytical precision of 1-5% (RSD) for all the elements by solution ICP-MS and 1-8% (RSD) by laser ablation ICP-MS. The relative differences between the REE concentrations measured by solution and laser ablation ICP-MS compared with the reference values were generally less than 11 % for most elements. The largest deviations occurred for La determined by solution ICP-MS in BIR-1G. The results of both solution and laser ablation ICP-MS agreed well, generally better than 7%, with the exception of La, Pr and Sm in BIR-1G. The measured REE laser ablation data for BIR-1G, BHVO-2G and BCR-2G agreed with the previously published data on these basaltic reference glasses, within a range of 0-10% for most elements. No significant influences were observed for the predicted spectral interferences on some REE isotopes in the analysis of basaltic glasses. 相似文献
15.
William T. Perkins Nicholas J.G. Pearce John A. Westgate 《Geostandards and Geoanalytical Research》1997,21(2):175-190
This contribution presents a review of the recent developments in laser ablation inductively coupled plasma-mass spectrometry. We describe the important developments which have occurred in the laser systems used, leading to a spatial resolution of around 20 (im, and give an overview of the major instrument developments which have affected the geological applications of laser ablation ICP-MS. We describe the calibration of laser ablation for the analysis of trace elements in two different matrices: volcanic glass shards and sulfide minerals. We show how single glass shards can be analysed using the National Institute of Standards and Technology (NIST) glass certified reference materials for calibration and demonstrate the effect of using single spot analyses compared to rastering of the calibration sample. We show the importance of inter-shard variation and demonstrate that averaged single shard analyses produce data which compare well with bulk analyses. The calibration of the laser system for sulfide mineral analysis is discussed and two different strategies are proposed, one using spiked pressed powder pellets of sulfides and the other metal reference materials. We present conclusions and recommendations for the calibration of laser ablation ICP-MS instruments. 相似文献
16.
Maurizio Petrelli Luca Caricchi Peter Ulmer 《Geostandards and Geoanalytical Research》2007,31(1):13-25
In this contribution we evaluate the capabilities of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) using a 12 μm spot size. Precision, accuracy and detection limits were assessed on the USGS BCR-2G reference material. We demonstrate that the 12 μm LA-ICP-MS analyses of experimentally-grown amphibole and garnet are in excellent agreement with secondary ion mass spectrometry (SIMS) trace element determinations on the same crystals. The 12 μm spot size configuration was subsequently used to determine trace element crystal-melt partition coefficients (Dc/m ) for a wide range of trace elements in amphibole in equilibrium with a basanitic melt. The following strategy to determine accurately and evaluate Dc/m is proposed. One or more major elements determined previously by electron probe microanalysis (EPMA) was used to ensure consistency between EPMA and the composition of the aerosol produced by the laser ablation. Measured Dc/m values were successively evaluated using the lattice strain model. The use of this strategy significantly improved the precision and accuracy of Dc/m determination when a LA-ICP-MS configuration with a high spatial resolution was employed. 相似文献
17.
激光剥蚀-电感耦合等离子体质谱(LA-ICP-MS)作为一项实用的技术被广泛应用于原位微区分析。在学者们更为关注的元素空间分布问题上,LA-ICP-MS线扫描较单点剥蚀具有更大的优势。线扫描过程中元素的空间分辨率是影响分析结果准确程度的因素之一。每个脉冲间的信号如果严重叠加会导致较低的空间分辨率。文章通过LA-ICP-MS的单脉冲剥蚀实验,研究了合成硅酸盐玻璃标准样品CGSG中不同元素的信号时间结构,及其对线扫描的空间分辨率的影响。结果表明,当激光束斑40 μm时,应用LA-ICP-MS进行线扫描测量空间分辨率能够满足线扫描技术分析的需求。 相似文献
18.
Paul J. Sylvester 《Geostandards and Geoanalytical Research》2008,32(4):469-488
Research in 2006 and 2007 dealing with laser ablation‐(multicollector)‐inductively coupled plasma‐mass spectrometry, LA‐(MC)‐ICP‐MS, involved studies concerned with optimising the technique itself, as well as applying the method to a variety of problems in the Earth sciences. The causes of elemental and isotopic fractionation produced during laser ablation continues to be of considerable interest, with evidence mounting that processes occurring both at the ablation site and in the argon plasma of the ICP are culpable. There is growing excitement in the use of femtosecond lasers for LA‐(MC)‐ICP‐MS, with the hope that they reduce or eliminate melting and non‐congruent volatilisation at the ablation site and thus approach stoichiometric sampling. Ablation chamber design emerged as a serious concern, particularly with respect to achieving the rapid washout needed for fine‐scale compositional mapping of geological objects. LA‐MC‐ICP‐MS provided data for a wide range of isotopic systems, especially hafnium, but also B, S, Mg, Cu, Fe, Sr, Nd, Pb and U. Measurement uncertainties in LA‐ICP‐MS were discussed by several researchers, and are critically reviewed here ‐ total uncertainties for trace element concentration measurements of silicates including errors on the calibration values of common reference materials are ～10% (95% confidence limits), though the precision of individual spot measurements (50 to 100 μm) is much better, ～1% RSD, using a 193 nm laser and a sector field‐ICP‐MS. LA‐ICP‐MS U‐Pb ages for zircon and other U‐rich accessory phases are claimed by most geoanalysts to have 2s uncertainties of ～0.7 and 1.3% respectively but the actual accuracy of the method is probably only as good as ～2% (2s), when uncertainties associated with laser‐induced Pb/U fractionation are included. 相似文献
19.
Previous laser ablation‐ICP‐MS bulk analyses have been confined to volcanic glasses and glass disks or powder pellets similar to those used for XRF analysis. This study proposes a method to determine twenty trace elements (fourteen rare earth elements, Sc, Y, Zr, Nb, Hf and Ta) by LA‐ICP‐MS directly from polished thick sections and rock slabs of six fine‐grained crystalline and aphanitic rocks (five volcanic rocks and one pelitic tillite). Laser scanning of eight to ten 20 mm long linear tracks using a spot size of 160 μm, with a total ablated area of 26–32 mm2, was performed. Quantification was carried out by (a) internal standardisation using Si and (b) without applying internal standardisation. In the latter method, external determination of one element in conventional LA‐ICP‐MS quantification is no longer needed. Although the fine‐grained rocks studied contained variable amounts of volatiles (up to 4%), this method gave results that agree within 10% relative with those obtained by internal standardisation using Si. Two USGS basalt glass reference materials (BCR‐2G and BHVO‐2G) were used for external calibration. The results and the associated trace element patterns and ratios of elemental pairs obtained from both methods of quantification showed good agreement with the results from solution nebulisation ICP‐MS within 20% (mostly within 10%) relative. Fine‐grained rocks are common and include volcanic, sedimentary and low‐grade metamorphic rocks (e.g., basalt, andesite, rhyolite, shale, mudstone, tillite, loess, pelite and slate) and their trace element contents and associated ratios are important geochemical tracers in studies focusing on the composition and evolution of the crust and mantle. Our method provides a simple and quantitative way to determine trace elements in fine‐grained rocks even with those displaying complex textures. 相似文献