Direct Mass Spectrometric Analysis of Hydrogen Sulfide in Complex Oil Samples

Due to the high viscosity and bulk complexity of crude oil samples, it poses a grand challenge to determine hydrogen sulfide (H2S) in them. Although many methods have been developed for the analysis of H2S in complex systems, these methods generally have complex processes, large analysis error and low sensitivity. In the study, based on the reaction between triazine and H2S by generating thiadiazine, a small volume of complex crude oil sample was introduced directly into a triazine solution using acetonitrile as solvent for transferring H2S into detectable species by organic mass spectrometry. The experimental parameters of solution composition, acetic acid content, reaction time and reaction temperature were optimized, and the method of paper spray ionization-mass spectrometry (PSI-MS) was established for rapid analysis of H2S in complex crude oil samples. An optimal performance was achieved when the reaction of triazine and H2S was carried out at 30 ℃ for 2 h with acetonitrile containing 0.1% acetic acid as solvent. The standard curve for the quantitative analysis of H2S was constructed according to the linear relationship between MS signal intensity of resulting thiadiazine and the concentration of H2S, which was applied for actual crude oil samples from different sources. The results showed that the linear range and the limit of detection (LOD) were 0.1-1 000 μg/L and 0.041 μg/L with intra-day precision of 3.04% and inter-day precision of 3.18%, respectively. The PSI-MS was also employed to determine H2S in different actual crude oil samples, and the spiked recovery was 91.7%-103.5% with relative standard deviation (RSD) of 1.2%-4.5%. This method has the advantages of easy operation, low cost, high sensitivity and less contamination to mass spectrometer, which is promising for the direct and fast analysis of H2S in complex crude oil samples.