Arsine (AsH3) and phosphine (PH3) in industrial emissions in the purification of liquefied petroleum gas (LPG) in two petrochemical plants, one in Colombia, the other in Spain—were the focus of this research. The study shows the challenges and contributions to environmental sciences in quantifying the magnitude of the environmental impact of these pollutants. AsH3 and PH3 were determined and quantified in industrial emissions, thereby demonstrating the source of their formation. Prior to this research, evaluations of these contaminants were not available either to the scientific community or to the public. The focus was on two stages of the LPG purification process: the deethanizer, where the most volatile compounds are separated from the LPG, and the splitter, where propylene is removed from propane. Monitoring was extremely complex because of strict safety requirements at each point. It was carried out over a period of one year, with 432 samples taken at different times to evaluate the stability and magnitude of possible environmental impacts. To overcome the analytical barrier of contaminating compounds at trace or ultra-trace levels, and their probable variability in pressure and temperature at the point of exit from each column, a new methodology was developed coupling a variable pressure sampler (VPS) to a gas chromatograph with a mass spectrometer. The analytical method employed a zeolite-packed prototype column which was validated and employed on an industrial scale, to mitigate the environmental impact of AsH3 and PH3 in the atmosphere. For the validation of each prototype, AsH3 and PH3 standards of 1.0, 0.1, 0.05, 0.01 and 0.005 ppm were used. The removal efficiencies varied between 97.97 and 99.91%. The RSD varied between 2.7 and 9.1% and the t-test of students of paired data showed P values greater than 0.05 at a significance level of 95%. In the affluents of the deethanizer, the highest levels of AsH3 and PH3 in the Colombian plant were 0.21 and 0.31 ppm respectively; in Spain they were 0.23 and 0.25 ppm. These values are higher than those established by OSHA, NIOSH and those quantified in the atmosphere by other studies. The concentration levels were identified at 40 TM h−1, which was the highest operating rate for the deethanizer and the splitter. For the splitter affluents, the highest values of AsH3 and PH3, both in Colombia and Spain, were 0.009 ppm. The installation of columns filled with zeolite at the exit points in these two plants, permitted obtaining effluents with a percentage removal greater than 99.95%, demonstrating the selectivity of the catalytic system as well as the effort to mitigate environmental impact.