A procedure for chromium (Cr) determination in pharmaceutical grade barium sulfate by direct solid sampling electrothermal atomic absorption spectrometry (DSS-ET AAS) with Zeeman-effect background correction was developed. Operational conditions for the proposed procedure and the use of citric acid, ammonium phosphate, palladium and magnesium nitrate as chemical modifiers were evaluated. Pyrolysis and atomization temperatures were set at 1500 and 2400 degrees C, respectively and the use of matrix modifiers did not improve these conditions. Graphite platform presented high degradation rate, but minima changes were observed in the sensitivity or signal profile. Samples (0.3-1 mg) were weighted and introduced into the furnace using a manual solid sampling system. The linear concentration range of the calibration curve was from 100 to 1800 pg (R(2)>0.995). The characteristic mass was 7.7 pg and the limit of detection was 2.4 pg. Chromium concentration in commercial samples ranged from 0.45 to 1.06 microg g(-1) and these results were confirmed by standard addition method. The mean reproducibility was 12% (n=20 in a 3-day period) and repeatability was less than 9%. Results obtained using inductively coupled plasma optical emission spectrometry and conventional electrothermal atomic absorption spectrometry after extraction with HNO3 were around 20% lower than those obtained by the proposed procedure. It was assumed that the low results were due to incomplete extraction even using hard conditions related to temperature and pressure. The proposed procedure by DSS-ET AAS provided some advantages related to recommended pharmacopoeias methodology, as lower risks of contamination and analyte losses, higher specificity, accuracy and sensitivity, no toxic or unstable reagents are required, and calibration with aqueous standards was feasible.