AbstractThin‐film standards of lead and zinc were prepared by precipitating precise amounts of their insoluble salts directly on to polyamide film substrates for the calibration of the x‐ray spectrometer. Samples of different particle deposition characteristics were then prepared and analysed by XRF, atomic‐absorption and inductively coupled plasma atomic‐emission spectrometry. The optimum sizes of thin‐film specimens were selected to be the same as the area of the specimen plane where the average flux of the primary x‐ray beam is fairly uniform. No significant difference in response of the spectrometer to the Zn Kα and Pb Lβ between the samples and the standards were observed. The correlation of the XRF results with those obtained by the other two methods was found to be 1.008±0.029 for lead and 0.995±0.020 for zinc. The amount of metal present ranged from about 5 to 350 μg for lead and from 10 to