Trace Element Analysis of Fused Whole‐Rock Glasses by Laser Ablation‐ICP‐MS and PIXE

Abstract

The concentrations of fifty trace elements, including relatively volatile elements and transition metal elements, in fused glasses of Geological Survey of Japan rock reference materials GSJ JR‐2, JA‐1, JA‐2, JB‐1a, JB‐3, JGb‐1 and JF‐1 were determined by particle (proton) induced X‐ray emission (PIXE) and laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS). The fused glasses were prepared by rapid fusion and subsequent quenching in welded platinum capsules and were found to be homogeneous for major elements and for trace elements with concentrations of more than 1 μg g‐1 within the observed precision (± 10% mean) on a 70 μm sampling scale. The values obtained by PIXE and LA‐ICP‐MS for the transition elements (Cr, Mn, Fe, Ni and Cu), the relatively volatile elements (Zn, Ga, Rb and Pb) and the refractory elements (Y, Zr, Nb and Th) with concentrations greater than a few μg g‐1 showed good agreement (within 10 % relative difference). The values for almost all the elements detected at concentrations higher than 1 μg g‐1 as determined by LA‐ICP‐MS also agreed well with the reference values (mean relative difference < ± 10%), except for B and Cu. The good agreement confirmed the appropriateness of the NIST SRM 600 series glass calibration reference material for LA‐ICP‐MS analysis of glasses with variable major‐element compositions for almost all elements. The concentrations of Cu in all the samples were lower than the reference values, which was attributed to adsorption of the transition metals onto the platinum capsule during preparation.

Calibration and correction of LA-ICP-MS and LA-MC-ICP-MS analyses for element contents and isotopic ratios

“…The lack of matrix-matched calibration standards is recognized to be the biggest hindrance in the analysis of multielements by LA-ICP-MS (Durrant and Ward, 2005;Miliszkiewicz et al, 2015). Reference materials preparation techniques including (1) pressed-powder pellets with (Jarvis and Williams, 1993;O'Connor et al, 2007) and without (Arroyo et al, 2009;Garbe-Sch€ onberg and Müller, 2014) binders; (2) fused glasses with (Becker and Dietze, 1999;Eggins, 2003;Perkins et al, 1993) and without flux agent (Fedorowich et al, 1993;He et al, 2016;Jochum et al, 2000;Kurosawa et al, 2006;Nehring et al, 2008;Norman et al, 1996;Reid et al, 1999;Stoll et al, 2008;Zhu et al, 2013). Solution-based calibration method (Becker, 2002;Dressler et al, 2010;Günther et al, 1997;Kovacs et al, 2009;Leach et al, 1999;Thompson et al, 1989;Yang et al, 2010) can be applied in the absence of suitable solid reference materials.…”

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

“…Pb) [22,25]. To minimize the volatilization of elements during high-temperature melting, the sample can be melted in a sealed platinum capsule, although this method is inherently expensive and not suitable for routine analysis [131] or in a BN crucible, which may result in metal segregation caused by the reduction of BN and result in the loss of Cr, Ni and Cu [23]. The loss of volatile elements could be suppressed through the use of a sandwich-like heater with a double-filament [139].…”

“…Based on the sample preparation technique, LA-ICP-MS methods have been applied to the bulk analysis of various samples, including (1) the direct analysis of a rock slice [24,126], (2) the analysis of pressed-powder pellets both with binders [1, 26,127] and without binders [128], and (3) the analysis of fused glasses fused both with a flux agent [6, 129,130] and without a flux agent [22,23,25,61,[131][132][133][134].…”

Sample Preparation for Determination of Rare Earth Elements in Geological Samples by ICP-MS: A Critical Review

“…The LA-ICP-MS has been applied to direct analysis of the sample surface (Li et al 2010;Himmler et al 2010;Severs et al 2009;Pereira et al 2001) or to the analysis of solid samples as a fine-grained powder, prepared as pressed pellets (Arroyo et al 2009;Ito et al 2009;Lee, Chang, and Jiang 2003) or fused as glasses (Leite et al 2011;Kurosawa et al 2006;Eggins et al 2003). Direct LA-ICP-MS analysis of bulk solid samples can avoid tedious sample preparations, allows the analysis of the sample spatial homogeneity and incrustation characterization.…”