Information on chemical partitioning and associated risk of airborne metals, particularly during a haze-fog episode, is limited. Fine particulate matter (PM2.5) was collected during a severe haze-fog event in winter and non-haze-fog periods in summer and fall from an urban region of a typical Chinese mega-city, Nanjing. The particulate-bound metals (Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Mo, Na, Ni, Pb, Sr, Ti, V, and Zn) were chemically fractionated in a four-step sequential extraction procedure and human health risk was assessed. During the haze-fog episode, PM2.5 was extremely elevated with a mean concentration of 281 mu g/m(3) (range: 77-431 mu g/m(3)), whereas the mean PM2,5 concentrations in summer and fall periods were 86 mu g/m(3) (range: 66-111 mu g/m(3)) and 77 mu g/m(3) (range: 42-131 mu g/m(3)), respectively. All elements had significantly higher concentrations and many metals exceeded relevant limits on haze-fog days. K, Na, Sr, Zn, Mo, Ca, Cd, Mg, Mn, Cu, Ba, Cr and As all showed relatively high proportions of the soluble and exchangeable fraction and strong bio-accessible potential. High temperature and humidity may increase the bio-accessible fraction of many airborne metals. The hazard index for potential toxic metals was 0.115, which was lower than the safe limit (1). However, the combined carcinogenic risk was 1.32 x 10(-6) for children and 5.29 x 10(-6) for adults, with both values being higher than the precautionary criterion (10(-6)). Results of this study provide information for the behavior and risk mitigation of airborne metals. (C) 2016 Elsevier B.V. All rights reserved.