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Abstract: In this study, headspace single-drop microextraction (HS-SDME) coupled with gas chromatography-flame ionization detection (GC-FID), was employed to determine short-chain fatty acids (SCFAs) in ruthenium tetroxide (RuO4) oxidation products of asphaltenes. Several significant parameters, such as drop solvent type, drop volume, sample solution ionic strength, agitation speed, extraction time, and ratio of headspace volume to sample volume were optimized. Under optimum extraction conditions (i.e., a 3-μL drop of 1-butanol, 20min exposure to the headspace of a 6mL aqueous sample placed in a 10mL vial, stirring at 1000rpm at room temperature, and 30% (w/v) NaCl content), the reproducibility and accuracy of the method have been tested and found to be satisfactory. The analysis of a real asphaltene sample using this method proved that HS-SDME can be a promising tool for the determination of volatile SCFAs in complex matrices. [Copyright &y& Elsevier]

• Deans-switch is used to avoid complex preparation and losses of trace samples. • Baseline separation of crocetane and phytane is achieved (R >1.5) by 2D-GC technique. • First accurate determination of δ13C of crocetane in natural samples by 2D-GC-IRMS. Compound-specific isotope analysis of crocetane in sediments can be used to determine its origin. However, the co-elution of crocetane with phytane and complex substrates hinders the accurate determination of its isotopic composition. A heart-cutting two-dimensional gas chromatography–isotope ratio mass spectrometry (2D-GC–IRMS) method was developed to determine δ13C values of crocetane. Full chromatographic separation of crocetane was achieved with a 30 m CycloSil-B chiral capillary first column and a 60 m Chiraldex B-pH capillary second column (two series-connected 30 m Chiraldex B-pH capillary columns). Analyses of standard mixtures confirmed that the new method has satisfactory accuracy (deviations from the authentic values <0.5‰) and precision (RSDs <5%) for carbon isotope analyses of crocetane and phytane. The application of the method to two sediment samples indicates that baseline resolution is achieved (R >1.5) for crocetane and phytane, with 13C-depleted crocetane (δ13C values of −119.5‰ and −111.5‰ in the two natural samples, respectively) being an indicator of anaerobic oxidation of methane in cold seep areas. The new 2D-GC–IRMS method allows simple and efficient determination of the compound-specific carbon isotopic compositions of crocetane. [ABSTRACT FROM AUTHOR]