In this work, analytical bias arising from the gas chromatographic determination of sulfur compounds was evaluated by the application of direct loop injection method to the GC/PFPD detection of four sulfur compounds including H$_{2}$S, CH$_{3}$SH, DMS, and DMDS. For the proper evaluation of analytical uncertainties involved in GC calibration, we employed two comparative techniques of calibration at fxed concentration injection (CFCI) vs calibration at fixed volume injection (CFVI) method. The results of our study indicate that CFCI method exhibits very poor sensitivity due to the matrix effect with varying injection volumes. On the other hand, as CFVI method overcomes such limitation, it can be used to obtain very accurate quantification of S compounds at their high concentration levels above a few to a few tens ppb.