A hydride generation (HG) procedure has been described for determination of Pb by ICP-MS using potassium hexacyanomanganate(III), K3Mn(CN)(6), as an additive to facilitate the generation of plumbane (PbH4). Potassium hexacyanomanganate(III) was prepared in acidic medium as it was unstable in water. The stability of hexacyanomanganate(III) was examined in dilute solutions of HCl, HNO3 and H2SO4. The solutions prepared in 1% v/v H2SO4 were found to be stable for over a period of 24 h. The least suitable medium was 1% v/v HNO3. For generation of plumbane, acidic hexacyanomanganate(III) and sample solutions were mixed on-line along a 5-cm long tygon tubing (1.14 mm i.d.) and then reacted with 2% m/v sodium borohydride (NaBH4). A concentration of 0.5% m/v K3Mn(CN)(6) facilitated the generation of PbH4 remarkably. In comparison to H2SO4, HCl provided broader working range for which optimum concentration was 1% v/v. No significant interferences were noted from transition metals and hydride forming elements, up to 0.5 mu g mL(-1) levels, except Cu which depressed the signals severely. The depressive effects in the presence of 0.1 mu g mL(-1) Cu were alleviated by increasing the concentration of K3Mn(CN)(6) to 2% m/v. Under these conditions, the sensitivity was enhanced by a factor of at least 42 to 48. The detection limit (3 s) was 0.008 mu g L-1 for Pb-208 isotope. Average signal-to-noise ratio (S/N) ranged between 18 and 20 for 1.0 mu g mL(-1) Pb solution. The accuracy of the method was verified by analysis of several certified reference materials, including Nearshore seawater (CASS-4), Bone ash (SRM 1400), and Mussel tissue (SRM 2976). The procedure was also successfully applied to the determination of Pb in coastal seawater samples by ICP-MS. (C) 2012 Elsevier B.V. All rights reserved.