To further investigate the effect of dilute acid pretreatment (DAP) and steam explosion pretreatment (SE) on the change in cellulose accessibility, several techniques were applied including a Simons' stain (SS) technique along with several NMR methods (i.e., NMR cryoporometry, H-1 spin-lattice (T-1) and H-1 spin-spin (T-2) relaxometry, and diffusometry). These methods were utilized to probe biomass porosity and thus assess cellulose accessibility on untreated and pretreated Populus. In general, these techniques indicate that pretreated Populus has larger pore size distributions and specific surface area (SSA) when compared to an untreated sample. The SS method revealed that DAP is more effective than SE in terms of the SSA increase, and that DAP increases SSA as a function of pretreatment severity. Relaxometry and diffusion measurements also suggest pore expansion occurs primarily in the first 10 min of DAP. (c) 2013 Elsevier Ltd. All rights reserved.