High-Efficiency Microwave-Assisted Digestion Combined to in Situ Ultraviolet Radiation for the Determination of Rare Earth Elements by Ultrasonic Nebulization ICPMS in Crude Oils

摘要

A method for heavy and extraheavy crude oil digestion based on microwave-assisted wet digestion (MW-AD) and ultraviolet (UV) radiation using diluted HNO_3 was applied for the determination of rare earth elements (REE) by inductively coupled plasma mass spectrometry (ICPMS) with an ultrasonic nebulizer (USN). Even using pressurized systems conventional acid digestion is not feasible for efficient crude oil digestion, especially for heavy and extraheavy crude oils that generally present high amounts of asphaltenes and resins. In the proposed system, UV radiation is generated in situ by immersed electrodeless Cd discharge lamps positioned inside quartz vessels. The use of diluted solutions (1-14.4 mol L~(-1) HNO_3 and 1-4 mol L~(-1) H_2O_2) were evaluated for heavy and extraheavy crude oil digestion (API density of 11.1-19.0). With the proposed method the residual carbon content was lower than 13 mg C/100 mg of sample, and it was possible to digest sample masses up to 500 mg using 4 mol L~(-1) HNO_3 and 4 mol L~(-1) H_2O_2. Interferences caused by excessive acid concentration and carbon content in digests were minimized allowing limits of quantification for REEs as low as 0.3 ng g~(-1). Samples were also digested using MW-AD in pressurized systems with concentrated HNO_3, but even using 280 ℃, 80 bar, and concentrated HNO_3, MW-AD method was not suitable for REE determination due to interferences in ICPMS determination. The combination of microwave heating with UV was considered a suitable and effective way to digest crude oil allowing further determination of low concentrations of REE by ICPMS.