Trace element determination in crude oil and its fractions by inductively coupled plasma mass spectrometry using ultrasonic nebulization of toluene solutions

A method was developed for the determination of trace elements in crude oil by inductively coupled plasma mass spectrometry (ICP-MS) after sample dissolution in toluene and subsequent ultrasonic nebulization (USN). Carbon build-up at the interface and ion lenses was minimized by optimization of the argon to oxygen ratio in the plasma and by the desolvating action of the USN. The analyte addition technique, combined with internal standardization (¹¹⁵In), was the only calibration procedure capable to correct properly for signal suppression, especially observed in solutions with higher concentrations of asphaltenes. Analytical curves with good linearity (r²>0.99), and solution detection limits (LOD–3σ) of 0.1 μg l^?1 for V, Ni, Co, Y, Mo, Cd, Ba and La, and in the range of 0.1–1 μg l^?1 for Al, Ti, Fe, Zn, Sr, Ag, Sn and Pb were obtained. Method validation was performed by analyzing two certified reference materials. For National Institute for Standards and Technology (NIST) 1634c (V, Ni, Co), accuracy was approximately 10%, similar as observed for other 12 elements in NIST 1084a. Asphaltenes were separated from the oil bulk of crude oil samples from the Potiguar Basin (Brazil) using precipitation in heptane. The heptane-soluble fraction (maltenes) was separated by elution chromatography into three sub-fractions: (1) saturated and low molecular mass (MM) aromatics, (2) aromatics and low MM polar compounds, and (3) high MM polar compounds (resins). Trace elements were determined in these fractions after dissolution in toluene, by USN–ICP-MS. Mass balance calculations showed a significant increase of most elements (10–30 times) in the asphaltenic fraction, and in minor proportions in fraction 3, compared to the crude oil samples. Comparison with microwave-assisted acid decomposition showed good agreement, validating the proposed methodology and emphasizing its applicability for routine analysis of crude oil and other toluene soluble petroleum products.