AbstractThe combination of a flow injection analysis system‐hydride generation (FIAS HG) and transversely heated graphite atomizer–atomic absorption spectrometry (THGA AAS) has been applied for the sensitive detection of organolead compounds [e.g. detection limit of trimethyl‐lead species (TriML): 32 ng l−1for a 0.5 ml sample loop] in the presence of inorganic lead. A mixture of hydrochloric acid and ethylenediaminetetra‐acetic acid (EDTA) as a carrier solution in the flow injection system suppressed interferences of inorganic lead. Calibration with various organolead compounds in the range 0.25–8 μg l−1was carried out in the presence of 10 mg l−1Pb2+without any interferences. Additionally, statistical aspects of the determination of trimethyl‐lead have been studied. Different parameters, e.g. working range, detection limit, recovery function etc., were calculated with respect to quality assurance i