Method development for the determination of cadmium, copper, lead, selenium and thallium in sediments by slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry and isotopic dilution calibration

Abstract

A procedure for the determination of Cd, Cu, Pb, Se and Tl by slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) with calibration by isotopic dilution is proposed. The slurry is prepared by mixing the sample with diluted nitric and hydrofluoric acids in an ultrasonic bath and then in a water bath at 60 °C for 120 min. The slurries were let to stand at least for 12 h, manually shaken before poured into the autosampler cups and homogenized by passing through an argon flow, just before pipetting it into the furnace. The analytes were determined in two groups, according to their thermal behaviors. The furnace temperature program was optimized and the selected compromised pyrolysis temperatures were: 400 °C for Cd, Se and Tl and 700 °C for Cu and Pb. The vaporization temperature was 2300 °C. The analyses were carried out without modifier as no significant effect was observed for different tested modifiers. Different sample particle sizes did not affect the sensitivity significantly, then a particle size ≤50 μm was adopted. The accuracy was checked by analyzing five certified reference sediments, with analytes concentrations from sub-μg g −1 to a few hundreds μg g −1. The great majority of the obtained concentrations were in agreement with the certified values. The detection limits, determined for the MESS-2 certified sediment, were, in μg g −1: 0.01 for Cd; 0.8 for Cu; 0.4 for Pb; 0.4 for Se and 0.06 for Tl. The precision was adequate with relative standard deviations lower than 12%. Isotopic dilution showed to be an efficient calibration technique for slurry, as the extraction of the analyte to the liquid phase of the slurry and the reactions in the vaporizer must help the equilibration between the added isotope and the isotope in the sample.