In situ analysis of major and trace elements of anhydrous minerals by LA-ICP-MS without applying an internal standard

Abstract Here we describe an internal standard-independent calibration strategy for LA-ICP-MS analysis of anhydrous minerals and glasses. Based on the normalization of the sum of all metal oxides to 100 wt.%, the ablation yield correction factor (AYCF) was used to correct the matrix-dependent absolute amount of materials ablated during each run. A Y C F = 100 ∑ j = 1 N ( c p s sam j × l j ) , l j = C rm j / c p s rm j , where cpssamj and cpsrmj are net count rates of analyte element j of the sample and reference material for calibration, Crmj is concentration of element j in the reference material, N is the number of elements that can be determined by LA-ICP-MS. When multiple reference materials were used for calibration, l value can be calculated with regression statistics according to the used reference materials. Applying an AYCF and using the USGS reference glasses BCR-2G, BHVO-2G and BIR-1G as reference materials for external calibration, analyses of MPI-DING reference glasses generally agree with recommended values within 5% for major elements (relative standard deviation (RSD) = 0.3–3.9% except for P2O5, n = 11), and 5–10% for trace elements. Analyses of anhydrous silicate minerals (clinopyroxene, orthopyroxene, olivine, plagioclase and garnet) and spinel generally agree with the results of electron microprobe analysis within 0.2–7% for SiO2, Fe2O3, MgO and CaO. RSD are generally  0.1 wt.%. The results indicate that, by applying an AYCF and using USGS reference glasses as multiple reference materials for calibration, elements of these anhydrous minerals can be precisely analyzed in situ by LA-ICP-MS without applying internal standardization. The different element fractionations between the NIST glasses and those glasses with natural compositions indicate that NIST SRM 610 is a less than ideal reference material for external calibration of analyses of natural silicates.

[1]  W. White,et al.  Sources of error in external calibration ICP-MS analysis of geological samples and an improved non-linear drift correction procedure , 1993 .

[2]  P. Potts Microprobe techniques in the earth sciences , 1995 .

[3]  S. Eggins,et al.  A simple method for the precise determination of ≥ 40 trace elements in geological samples by ICPMS using enriched isotope internal standardisation , 1997 .

[4]  S. Jackson,et al.  A Compilation of New and Published Major and Trace Element Data for NIST SRM 610 and NIST SRM 612 Glass Reference Materials , 1997 .

[5]  S. Eggins,et al.  Compositional heterogeneity in NIST SRM 610-617 glasses , 2002 .

[6]  D. Günther,et al.  Preliminary Characterisation of New Glass Reference Materials (GSA‐1G, GSC‐1G, GSD‐1G and GSE‐1G) by Laser Ablation‐Inductively Coupled Plasma‐Mass Spectrometry Using 193 nm, 213 nm and 266 nm Wavelengths , 2005 .

[7]  D. Günther,et al.  Determination of Forty Two Major and Trace Elements in USGS and NIST SRM Glasses by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry , 2002 .

[8]  Z. Zajacz,et al.  LA-ICPMS analyses of silicate melt inclusions in co-precipitated minerals: Quantification, data analysis and mineral/melt partitioning , 2007 .

[9]  Shenghong Hu,et al.  Volume-optional and low-memory (VOLM) chamber for laser ablation-ICP-MS: application to fiber analyses , 2007 .

[10]  R. Hinton NIST SRM 610, 611 and SRM 612, 613 Multi‐Element Glasses: Constraints from Element Abundance Ratios Measured by Microprobe Techniques , 1999 .

[11]  P. Besson,et al.  Redox state, microstructure and viscosity of a partially crystallized basalt melt , 2004 .

[12]  P. Hoppe,et al.  The Preparation and Preliminary Characterisation of Eight Geological MPI‐DING Reference Glasses for In‐Situ Microanalysis , 2000 .

[13]  D. Günther,et al.  Accurate U‐Pb Age and Trace Element Determinations of Zircon by Laser Ablation‐Inductively Coupled Plasma‐Mass Spectrometry , 2004 .

[14]  D. Günther,et al.  Quantitative element mapping of Mg alloys by laser ablation ICP-MS and EPMA , 2005 .

[15]  Jean Susini,et al.  Redox state of iron in peralkaline rhyolitic glass/melt: X-ray absorption micro-spectroscopy experiments at high temperature , 2006 .

[16]  S. Eggins,et al.  Deposition and element fractionation processes during atmospheric pressure laser sampling for analysis by ICP-MS , 1998 .

[17]  N. Jakubowski,et al.  Optimisation of a laser ablation cell for detection of hetero-elements in proteins blotted onto membranes by use of inductively coupled plasma mass spectrometry , 2006 .

[18]  A. Rocholl Major and Trace Element Composition and Homogeneity of Microbeam Reference Material: Basalt Glass USGS BCR-2G , 1998 .

[19]  J. Yáñez,et al.  A rapid approach for assessment of arsenic exposure by elemental analysis of single strand of hair using laser ablation-inductively coupled plasma-mass spectrometry , 2007 .

[20]  D. Günther,et al.  The uncertainty budget of the multi-element analysis of glasses using LA-ICP-MS , 2007 .

[21]  A. Simionovici,et al.  Iron oxidation states in silicate glass fragments and glass inclusions with a XANES micro-probe , 2001 .

[22]  C. Butt,et al.  Sub-surface charging, a source of error in microprobe analysis , 1984 .

[23]  H. Longerich,et al.  Ultra‐Trace Element Analysis of NIST SRM 616 and 614 using Laser Ablation Microprobe‐Inductively Coupled Plasma‐Mass Spectrometry (LAM‐ICP‐MS): a Comparison with Secondary Ion Mass Spectrometry (SIMS) , 1997 .

[24]  R. Frischknecht,et al.  Capabilities of an Argon Fluoride 193 nm Excimer Laser for LaserAblation Inductively Coupled Plasma Mass Spectometry Microanalysis ofGeological Materials , 1997 .

[25]  Heinrich,et al.  Formation of a magmatic-hydrothermal ore deposit: insights with LA-ICP-MS analysis of fluid inclusions , 1998, Science.

[26]  Y. Lahaye,et al.  Ultraviolet Laser Sampling and High Resolution Inductively Coupled Plasma‐Mass Spectrometry of NIST and BCR‐2G Glass Reference Materials , 1997 .

[27]  R. Frischknecht,et al.  Quantitative analysis of major, minor and trace elements in fluid inclusions using laser ablation–inductively coupled plasmamass spectrometry , 1998 .

[28]  Jean-Michel Mermet,et al.  Determination of elements in polymers by laser ablation inductively coupled plasma atomic emission spectrometry: effect of the laser beam wavelength, energy and masking on the ablation threshold and efficiency , 1996 .

[29]  A. Figueiredo,et al.  Platinum-Group Elements and Gold Determination in NiS Fire Assay Buttons by UV Laser Ablation ICP-MS , 1998 .

[30]  K. Jochum,et al.  Chemical Characterisation of the USGS Reference Glasses GSA‐1G, GSC‐1G, GSD‐1G, GSE‐1G, BCR‐2G, BHVO‐2G and BIR‐1G Using EPMA, ID‐TIMS, ID‐ICP‐MS and LA‐ICP‐MS , 2005 .

[31]  K. Simon,et al.  Chemical Characterisation of NIST Silicate Glass Certified Reference Material SRM 610 by ICP‐MS, TIMS, LIMS, SSMS, INAA, AAS and PIXE , 1997 .

[32]  D. Günther,et al.  Timing of normal faulting along the Indus Suture in Pakistan Himalaya and a case of major 231 Pa/ 235 U initial disequilibrium in zircon , 2001 .

[33]  A. Woodland,et al.  Ferric iron in orogenic lherzolite massifs and controls of oxygen fugacity in the upper mantle , 2006 .

[34]  A. Kent,et al.  Production of barium and light rare earth element oxides during LA-ICP-MS microanalysis , 2005 .

[35]  G. Jenner,et al.  Determination of Zr and Hf in a Flux-Free Fusion of Whole Rock Samples using Laser Ablation Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) with Isotope Dilution Calibration , 1999 .

[36]  D. Günther,et al.  Enhanced sensitivity in laser ablation-ICP mass spectrometry using helium-argon mixtures as aerosol carrier , 1999 .

[37]  D. Günther,et al.  Elemental fractionation in laser ablation-inductively coupled plasma-mass spectrometry: evidence for mass load induced matrix effects in the ICP during ablation of a silicate glass , 2007 .

[38]  R. Vannucci,et al.  Determination of Incompatible Trace Elements in Mantle Clinopyroxenes by LA‐ICP‐MS: A Comparison of Analytical Performance with Established Techniques , 1999 .

[39]  W. McDonough,et al.  The composition of peridotites and their minerals: a laser-ablation ICP–MS study , 1998 .

[40]  D. Günther,et al.  Inter-laboratory note. Laser ablation inductively coupled plasma mass spectrometric transient signal data acquisition and analyte concentration calculation , 1996 .

[41]  G. Hieftje,et al.  Identification of alloys using single shot laser ablation inductively coupled plasma time-of-flight mass spectrometry , 2002 .

[42]  C. Butt,et al.  Rapid increase of sodium count rates during the electron microprobe analysis of sepiolite. The role of zeolitic water , 1977 .

[43]  K. Herwig,et al.  MPI‐DING reference glasses for in situ microanalysis: New reference values for element concentrations and isotope ratios , 2006 .

[44]  D. Draper,et al.  Constraints on the origin of the oxidation state of mantle overlying subduction zones: An example from Simcoe, Washington, USA , 1996 .

[45]  P. Sylvester Trends in Analytical Developments and Earth Science Applications in LA‐ICP‐MS and LA‐MC‐ICP‐MS for 2004 and 2005 , 2006 .

[46]  W. Griffin,et al.  Quantitative analysis of trace element abundances in glasses and minerals: a comparison of laser ablation inductively coupled plasma mass spectrometry, solution inductively coupled plasma mass spectrometry, proton microprobe and electron microprobe data , 1998 .

[47]  Gary M. Hieftje,et al.  Methods for shot-to-shot normalization in laser ablation with an inductively coupled plasma time-of-flight mass spectrometer , 2000 .

[48]  D. Günther,et al.  Quantitative analysis of silicates using LA-ICP-MS with liquid calibration , 2004 .

[49]  H. Longerich,et al.  The design, operation and role of the laser-ablation microprobe coupled with an inductively coupled plasma-mass spectrometer (LAM- ICP-MS) in the Earth sciences , 1995 .

[50]  Detlef Günther,et al.  Quantitative multi-element analysis of minerals, fluid and melt inclusions by laser-ablation inductively-coupled-plasma mass-spectrometry , 2003 .

[51]  Detlef Günther,et al.  Solid sample analysis using laser ablation inductively coupled plasma mass spectrometry , 2005 .

[52]  K. Sasa,et al.  Trace Element Analysis of Fused Whole‐Rock Glasses by Laser Ablation‐ICP‐MS and PIXE , 2006 .

[53]  L. Strnad,et al.  Laser Ablation and Solution ICP‐MS Determination of Rare Earth Elements in USGS BIR‐1G, BHVO‐2G and BCR‐2G Glass Reference Materials , 2005 .

[54]  Detlef Günther,et al.  Wavelength dependant ablation rates for metals and silicate glasses using homogenized laser beam profiles — implications for LA-ICP-MS , 2001 .

[55]  S. Eggins Laser Ablation ICP-MS Analysis of Geological materials prepared as Lithium Borate Glasses , 2003 .

[56]  A. Ghazi,et al.  Trace element determination of single fluid inclusions in quartz by laser ablation ICP-MS , 1997 .

[57]  A. Williams-Jones,et al.  COMPOSITIONAL HETEROGENEITY IN FLUORITE AND THE GENESIS OF FLUORITE DEPOSITS: INSIGHTS FROM LA-ICP-MS ANALYSIS , 2003 .

[58]  I. Butler,et al.  UV Laser Ablation ICP-MS: Some Applications in the Earth Sciences , 1997 .

[59]  K. Jochum,et al.  Reference Materials in Geoanalytical Research ‐Review for 2004 and 2005 , 2006 .

[60]  D. Günther,et al.  Laser ablation-ICP-MS: particle size dependent elemental composition studies on filter-collected and online measured aerosols from glass , 2004 .

[61]  K. Jochum,et al.  Validation of LA-ICP-MS trace element analysis of geological glasses using a new solid-state 193 nm Nd : YAG laser and matrix-matched calibration , 2007 .