Thirteen pure volatile, semi-volatile and non-volatile chlorinated organic compounds of molecular weights ranging from trichloroethylene (MW = 131.39 g mole -¹) to hexachlorobenzene (MW = 284.78 g mole-¹) were determined in aqueous matrices by GC-ECD. After 10% salt addition, different extraction tests were performed using fibres whose adsorbing phase was based on microsphere carbon particles characterized by a constant size. Five experimental parameters were optimized: extraction temperature and time, position of the fibre in the GC injector port, desorption temperature and time. The optimized analytical protocol was employed to determine the efficiency of a real activated carbon adsorption plant to remove organic chlorinated pollutants from an industrial wastewater at ng l-¹ levels.