The autoignition of spatially non-homogeneous hydrogen-air mixtures in 2-D random turbulence and mixture fraction fields is studied using the Direct Numerical Simulation (DNS) approach coupled with detailed kinetics. The coupling between chemistry and the unsteady scalar dissipation rate field is investigated over a wide range of different autoignition scenarios. The simulations show that autoignition is initiated at discrete spatially localized sites, referred to as kernels, by radical build-up in high-temperature, fuel-lean mixtures, and at relatively low dissipation rates. Detailed analysis of the dominant chemistry and the relative roles of reaction and diffusion is implemented by tracking the evolution of four representative kernels that characterize the range of ignition behaviors observed in the simulation. This evolution yields different autoignition delay scenarios as well as extinction at the different sites based on the local dissipation rates and their temporal histories. Where significant autoignition delay and extinction are observed, a shift in the relative roles of dominant reactions that contribute to radical production and consumption during this induction phase is observed. This shift is particularly characterized by an increased role of termination reactions during the intermediate stages of the induction period, which results in extinction in approximately two thirds of the ignition kernels in the computational domain. The fate of the different kernels is associated with: (1) the dissipation of heat that contributes to a slowdown in chemical reactions and a shift in the balance between chain-branching and chain-termination reactions; (2) the dissipation of mass that keeps the radical pool growth in check, and that is promoted by slower reaction rates; and (3) counter to the effects of dissipation of heat and intermediate species, the preferential diffusion of H-2 relative to both heat and its diluent, N-2, that promotes ignition. Ultimately, the balance between radical production and dissipation determines the success or failure of a given kernel to ignite. A new criterion for unsteady ignition is presented based on the instantaneous balance between radical production and dissipation. A Damkohler number, so defined, must remain above a critical value of unity at all times during the induction period if the kernel is to eventually ignite. Inherent in a multi-step kinetic description of ignition phenomena is the disparate time scales associated with different elementary reactions that, coupled with the characteristic scales of heat and mass dissipation, may yield different dominant chemistries at different stages of the induction process for a given kernel. To capture the strong history effects associated with radical build-up, new ignition progress variables based on key radical species are investigated. (C) 2003 The Combustion Institute. All rights reserved.