Determination of chloride in crude oil using isotope dilution GC–MS: A comparative study

Abstract

Optimisation and validation of a novel isotope dilution gas chromatography mass spectrometry (GC–MS) method for determination of inorganic chloride (Cl−) in crude oils is presented. The use of stable isotope dilution calibration approach decreases losses and biases and it is considered a higher order measurement approach. Samples were diluted with a 1:1 blend of isopropyl alcohol : toluene with 5% water, mixed with 37Cl− internal standard, water extracted and derivatized with triethyloxonium tetrafluoroborate at room temperature. This reagent converted Cl− into stable ethyl chloride (EtCl) which was detected by headspace GC–MS. A limit of quantitation of 100 µg kg−1 and limit of detection of 30 µg kg−1 were observed in crude oil samples when initial dilution was not required. The performance of this novel method was compared with combustion ion chromatography, ion chromatography with conductivity detection after microwave-induced combustion, and ASTM D3230 method on a set of medium and heavy crude oil samples. Despite the challenges of the measurement, a reasonable level of agreement was observed among methods over the range of 0.38 ± 0.02 to 993 ± 103 mg kg−1 of Cl−. Presented headspace GC–MS method proved to be suitable for analysis of all types of crude oils samples with an excellent reproducibility (RSD < 6%) and high sample throughput (7 min GC–MS run time).