Preparation of multiwalled carbon nanotubes/hydroxyl-terminated silicone oil fiber and its application to analysis of crude oils.

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.

Determination of diamondoids in crude oils using gas purge microsyringe extraction with comprehensive two dimensional gas chromatography-time-of-flight mass spectrometry.

Based on a homemade device, gas purge microsyringe extraction (GP-MSE) of crude oil samples was developed for the first time. As a simple, fast, low-cost, sensitive and solvent-saving technique, GP-MSE provides some outstanding advantages over the widely used sample preparation methods for crude oils such as column chromatography (ASTM D2549). Several parameters affecting extraction efficiency were optimized, including extraction temperature, extraction time, extraction solvent, condensing temperature and purge gas flow rate. With the optimized GP-MSE conditions, several real crude oil samples were extracted, and trace diamondoids were determined using comprehensive two dimensional gas chromatography-time-of-flight mass spectrometry (GC×GC-TOFMS). In total, more than 100 diamondoids were detected and 27 marker compounds were identified and quantified accurately. The limits of detection (LODs, S/N=3) were less than 0.08µg/L for all diamondoids. The relative standard deviation (RSD) was below 8%, ranging from 1.1 to 7.6%. The linearity of the developed method was in the range of 0.5-100.0µg/L with correlation coefficients (R2) more than 0.996. The recoveries obtained at spiking 50µg/L were between 81 and 108% for diamondoids in crude oil samples. The developed method can also be extended to the analysis of other components in crude oils and other complex matrices.

[Recent advances in analysis of petroleum geological samples by comprehensive two-dimensional gas chromatography].

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.

[Characterization of compounds in crude oils by gas purge micro-syringe extraction coupled to comprehensive two-dimensional gas chromatography].

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.