In this study, we investigated the analytical techniques to quantify the ambient concentration of hydrogen sulfide (H$_2$S) in air at ppt concentration level. For this purpose, an on-line GC analytical system equipped with both pulsed-flame photometric detector (PFPD) and thermal desorption unit (TDU) was investigated by collecting ambient air samples. The results of our study generally indicated that calibration conditions of GC system is highly sensitive to affect the accuracy of the analytical technique. Most importantly. we found that the use of different matrices in the the preparation stage of working standards was sensitive to control the overall performance of this technique. The calibration of our analytical system was tested by the two types of working standard (prepared by mixing either with high purity $N_2$ or with the ambient air). According to this test, the latter represented more efficiently the detecting conditions of actual air samples. The peak occurrence patterns of both air samples and standards (prepared by mixing with ambient air) were altered in a similar manner as the function of the loaded volume; however, it was not the case for the $N_2$-mixed standards. Results of our study suggest that detection of H$_2$S is highly different from other sulfides and that its quantification requires minimiaing interfering effects of non -pure substance (like water vapor) and (either sorptive or destructive) loss effects.