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Abstract: In this study, changes in the abundance and distribution of diamondoids in petroleum with thermal maturity were investigated by a simulation oil cracking experiment. Highly sensitive and selective gas chromatography–triple quadrupole mass spectrometry (GC–MS–MS) was employed to quantify diamondoids at ppm and sub-ppm levels. The results indicate that diamondoids were generated primarily within the maturity range 1.0–2.1% EasyRo and destroyed at high thermal maturity (>2.1% EasyRo). Hence, the occurrence of high concentrations of diamondoids probably corresponds to the maturity range from the wet gas to the early dry gas stage (i.e., 1.5–2.5% EasyRo). Good correlations were observed between a few ratios of diamondoids (i.e., EAI, DMAI-1, DMDI-1 and TMAI-1) and EasyRo. This finding indicates that these parameters may be useful maturity indices for organic matter from the late oil window to the dry gas window. [Copyright &y& Elsevier]

Abstract: In this study, a simple solvent dilution followed by highly selective and sensitive gas chromatography–triple quadrupole mass spectrometry (GC–MS–MS) detection was employed to quantify diamondoids in crude oils. Runtime parameters, i.e., parent and daughter ions, collision energy (CE) and scan time, were optimized to obtain maximum selectivity and sensitivity for target analytes. Under optimum conditions, the reproducibility and accuracy of the method were tested and found to be satisfactory. Comparison of GC–MS–MS and GC–MS methods for the determination of diamondoids indicates that GC–MS–MS yields higher sensitivity (method quantitation limits of 0.08–0.37μg/goil) and better selectivity than GC–MS (method quantitation limits of 0.78–8.44μg/goil) due to the elimination of matrix ion interferences using the selected reaction monitoring (SRM) mode. In addition, quantitative data confirm that group separation has a considerable effect on the quantification of diamondoids and the effect appears to depend on multiple factors. Two crude oils (TZ261 and TD2) from the Tarim Basin, China were used to evaluate the GC–MS–MS method. The results prove that the GC–MS–MS method is a promising tool for quantitative analysis of diamondoids in crude oils, especially for oil samples with low diamondoid concentrations. [Copyright &y& Elsevier]

Abstract: In this study, headspace single-drop microextraction (HS-SDME) coupled with gas chromatography–isotope ratio mass spectrometry (GC–IRMS), was employed to determine compound specific carbon isotopic values (δ13C) of gasoline range hydrocarbons. The reproducibility of the method was found to be satisfactory. By comparison with the δ13C values of the twelve target compounds determined using direct injection of their n-C16 solution, no obvious isotopic fractionation was observed during the HS-SDME procedures. Some parameters that could affect the carbon isotopic fractionation, such as ionic strength of working solutions and inlet split ratio, were examined. The results also suggest that these factors had no significant effect on the carbon isotopic determination of gasoline range hydrocarbons. The application of HS-SDME to a crude oil sample proved that this method could be a promising tool for the determination of carbon isotopic values of gasoline range hydrocarbons in oils or aqueous samples. [Copyright &y& Elsevier]