RESUMO
A simple and efficient method to analyze the volatile and semivolatile organic compounds in crude oils has been developed based on direct immersion solid-phase microextraction coupled to comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (DI-SPME-GC × GC/TOFMS). A novel fiber, multiwalled carbon nanotubes/hydroxyl-terminated silicone oil (MWNTs-TSO-OH), was prepared by sol-gel technology. Using standard solutions, the extraction conditions were optimized such as extraction mode, extraction temperature, extraction time, and salts effect. With the optimized conditions, a real crude oil sample was extracted and then analyzed in detail. It shows that the proposed method is very effective in simultaneously analyzing the normal and branched alkanes, cycloalkanes, aromatic hydrocarbons, and biomarkers of crude oil such as steranes and terpanes. Furthermore, the method showed good linearity (r > 0.999), precision (RSD < 8%), and detection limits ranging from 0.2 to 1.6 ng/L.
Assuntos
Técnicas de Química Analítica/métodos , Nanotubos de Carbono/química , Petróleo/análise , Óleos de Silicone/química , Cromatografia Gasosa-Espectrometria de Massas/métodosRESUMO
Abundant geochemical information can be acquired by analyzing the chemical compositions of petroleum geological samples. The information obtained from the analysis provides scientifical evidences for petroleum exploration. However, these samples are complicated and can be easily influenced by physical (e. g. evaporation, emulsification, natural dispersion, dissolution and sorption), chemical (photodegradation) and biological (mainly microbial degradation) weathering processes. Therefore, it is very difficult to analyze the petroleum geological samples and they cannot be effectively separated by traditional gas chromatography/mass spectrometry. A newly developed separation technique, comprehensive two-dimensional gas chromatography (GC x GC), has unique advantages in complex sample analysis, and recently it has been applied to petroleum geological samples. This article mainly reviews the research progres- ses in the last five years, the main problems and the future research about GC x GC applied in the area of petroleum geology.
RESUMO
A novel sample pretreatment method, gas purge micro-syringe extraction (GP- MSE), coupled to comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (GC x GC/TOFMS) has been developed for the characterization of volatile and semi-volatile compounds in crude oils. In the sample pretreatment process, the analytes were carried to the microsyringe barrel by inert gas, and at the same time, trapped by an organic solvent. The whole process of extraction takes less than 10 min, and only 20 µL of organic solvent was needed. Using two custom standard solutions containing alkanes and polycyclic aromatic hydrocarbons (PAHs), the influences of the extraction conditions were investigated. The optimized conditions were as follows: 5 mg crude oil, 20 µL hexane (extraction solvent), extraction for 3 min at 300 °C, condensation temperature set at -2 °C, gas flow rate set at 2 mL/min. Under the optimized conditions, a real crude oil sample was extracted and then analyzed in detail. It showed that the proposed method was very effective in simultaneously analyzing the normal and branched alkanes, cycloalkanes, aromatic hydrocarbons, and biomarkers of crude oil such as steranes and terpanes. The recoveries obtained ranged from 82.0% to 107.3% and the detection limits ranged from 34 to 93 µg/L. The correlation coefficients (R2) were more than 0.99. The relative standard deviations (RSDs, n = 5) for all the analytes were below 10%. The results indicate that the proposed method is suitable for the characterization of volatile and semi-volatile compounds in crude oils with easy operation, high sensitivity and efficiency.