An effective pre-treatment method for the determination of short-chain fatty acids in a complex matrix by derivatization coupled with headspace single-drop microextraction

• An improved sample pre-treatment method for the analysis of SCFAs in RICO products.
• Combine the HS-SDME with derivatization method for quantitative analysis of SCFAs in complex matrices.
• This method allows detection of the studied analytes at low concentrations in aqueous phases.

We have developed a sample preparation method involving derivatization combined with headspace single-drop microextraction (HS-SDME) for the determination of short-chain fatty acids (SCFAs) in complex matrices. The derivatization of SCFAs was conducted using the BF3/ethanol method prior to HS-SDME. The HS-SDME extraction conditions for the derivatization products (ethyl esters) of SCFAs were optimized using 1.0 μL of dibutylphthalate (DBP), 1000 rpm stirring speed, 30% (w/v) NaCl, 20 min extraction time, and 7 mL of sample solution in a 12 mL vial. Quantitative determination of ethyl esters was performed using gas chromatography (GC). Linear calibration curves and excellent reproducibility were obtained using these optimized extraction conditions. Compared with our previous work, the significantly lower detection limits (0.11, 0.017, 0.0060, and 0.0024 μg/mL for C2 to C5 SCFAs, respectively) indicate that this new method is suitable for quantitative analysis of SCFAs in complex matrices, such as the RuO4 oxidation products of kerogen or asphaltene.