An on-tine procedure for the determination of traces of total mercury in environmental and biological samples is described. The present methodolog combines cold vapor generation associated to atomic absorption spectrometry (CV-AAS) with preconcentration of the analyte on a minicolumn packed with activated carbon. The retained analyte was quantitatively eluted from the minicolumn with nitric acid. After that, volatile specie of mercury was generated by merging the acidified sample and sodium tetrahydroborate(III) in a continuous flow system. The gaseous analyte was subsequently introduced via a stream of At carrier into the atomizer device. Optimizations of both, preconcentration and mercury volatile specie generation variables were carried out using two level full factorial design (2(3)) with 3 replicates of the central point. Considering a sample consumption of 25 mL, an enrichment factor of 13-fold was obtained. The detection limit (3 sigma) was 10 ng L-1 and the precision (relative standard deviation) was 3.1% (n = 10) at the 5 mu g L-1 level. The calibration curve using the preconcentration system for mercury was linear with a correlation coefficient of 0.9995 at levels near the detection limit up to at least 1000 Rg L-1. Satisfactory results were obtained for the analysis of mercury in tap water and hair samples. (c) 2006 Elsevier B.V. All rights reserved.