Oxalic acid was used for several purposes. Firstly, it was used for the acidification of the biogas digester samples. Acidification of samples is an important strategy to ensure protonation of SCFA before their separation on a polar column. Previous study showed that protonated SCFA were better extracted from complex matrix than ionized SCFA [13]. This is most likely due to ionized SCFA have higher interaction with the constituents of the complex matrix than the protonated SCFA. Theoretical consideration shows that pH less than 3 of the matrix provides a complete protonation of the SCFA due to the studied SCFA have a pKa of roughly 4.8. In the present study, the added oxalic acid brought the samples matrix to about pH 2.The second purpose was to reduce column contamination due to its volatile nature opposed to the non-volatile inorganic acids such as hydrochloric and phosphoric acids employed in the previous studies [4,19]. Thirdly, it was used to improve peak sharp ness and reduce peak tailing due to the liberated formic acid in the injector. In the previous study, formic acid was added to saturate the polar column that reduces adsorption of SCFA on the column and ultimately provides the above mentioned benefits [22]. Moreover, the liberated formic acid from oxalic acid was used for the purpose of cleaning unwanted residues of SCFA from the polar column. Previous studies showed that after the injection of formic acid, ghost peaks did not appear in a chromatogram [13,20]. Our results also showed that ghost peaks were not observed even after several injections of underivatized analytes into GC/MS system.