The development of analytical techniques for on-site real-time data analysis has received attention in recent years in terms of their potential utilization for industrial and environmental requirements. The sample pretreatment stage is generally the weak link of the entire analytical procedure. Therefore, efforts are directed towards the development of efficient and safe automated sample pretreatment techniques, based on flow-injection analysis (FIA). This study is focused on simplifying the procedures of sample preparation and detection for industrial hygiene applications, and the exploration of field-suited methods. Conceivably, a particular ligand could be utilized to enhance detections limits, with the use if specific complexation ions and analysis for improved capabilities. Hence, nine kinds of ligands that include: 2-mercaptonicotinic acid, thetrahexylammonium bromide, 1,5-diphenylcarbazide, 8-hydroxyquinoline, 1-aspartyl-L-phenylalanine, flavone, 1,10-phenanthroline, 2-(5-bromo-2-pyridylazo)-5-(diethylamino)phenol and 1-penicillamine were evaluated regarding the extraction efficiency and specific selective chelation of toxic metals such as chromium or arsenic in representative reference materials such as paint chips, fly ash and dust.