A vapour generation (VG) procedure has been described for determination of Cd by ICP-MS. Volatile species of Cd were generated on-line by interacting acidic sample solution containing potassium hexacyanochromate(m), K3Cr(CN)(6), with sodium borohydride (NaBH4). The hexacyanochromate(III) complex was generated on-line by reacting 0.04 mol L-1 chromium(III) nitrate and 0.16 mol L-1 potassium cyanide (KCN) solutions in water. The resulting suspension of chromium(III) hydroxide, Cr(OH)(3), was fed continuously to acidic stream of sample solution in the presence of excess KCN. The experimental conditions were optimized for effective generation of volatile species of Cd. Optimum signals were obtained from reaction of sample solutions in 4% v/v HCl with 2% m/v NaBH4 solution. The presence of K3Cr(CN)(6) improved the efficiency of Cd vapour generation substantially affording 15-fold higher sensitivity. This phenomenon was thought to occur through formation of reactive intermediates evolved from the interaction of [Cr(CN)(6)](3-) with NaBH4 that react with Cd(II) to increase the yield of volatile Cd species. Under the optimum conditions, no significant interferences were observed from the transition metals, including Cu and Ni, up to 1.0 mu g mL(-1) levels. Among the hydride forming elements, Bi, Pb, Sb and Sn depressed the signals above 0.1 mu g mL(-1). The detection limits (3 s) were 6.2 and 5.2 ng L-1 for Cd-110 and Cd-111 isotopes, respectively. The method was successfully applied for determination of Cd by ICP-MS in several certified reference materials, including Nearshore seawater (CASS-4), Bone ash (SRM 1400), Dogfish liver (DOLT-4) and Mussel tissue (SRM 2976).