LA-ICP-MS Calibrations for Intact Rock Samples with Internal Standard and Modified Constant-Sum Methods

Abstract

Laser ablation coupled with inductively coupled plasma-mass spectrometry (LA-ICP-MS) calibration was conducted with multiple spot analyses on eleven intact rock samples using both an internal standard (IS) method and a modified constant-sum (MCS) method. Methods were then compared for reported bulk elemental composition of the rocks. The MCS method was based on the sum of eight major elements, which is spatially more stable than one single major ele-ment as used in the IS method, and is quite constant among different rock samples. Calibrations were performed with standard reference materials NIST SRM 610, 612, 614, and 616. Little difference was found between using a single standard and a set of standards, because of the good linearity shown by the reference materials. Comparison of the two calibration methods shows that the MCS method produced better and more stable results than the IS method for heterogeneous samples. With the MCS method, approximately 94% to 95% of the total measurements are within the range of ±100% relative deviation, compared with 82% to 86% with the IS method. The IS method resulted insubstantial overestimations for some rock samples (e.g., 648% for Basalt BCR-2 using NIST SRM 610 as the calibration standard), while the largest deviation with the MCS method was 216% for U in Eagle Ford shale #80 sample. For Quartz latite QLO-1, a relative homogeneous sample, the IS method generated slightly better results than the MCS method. Regardless of method, spatially heterogeneous distribution of elements in the intact rock at the scale of the laser spot is considered to be the main reason for the large relative deviations seen in our work compared to published results.