The proton conductivity of radiation-grafted ethylenetetrafluoroethylene-grafted-poly(styrene sulfonic) acid (ETFE-g-PSSA) and Nafion 117 membranes between 25 and -37 degrees C is reported. The freezing of water in the membranes, which strongly depends on the internal acid concentration, results in a 4-fold decrease in proton conductivity. The activation energies before and after the freezing of the membranes are approximately 0.15 and 0.4 eV, consistent with proton transport through liquid water and strongly bound water, respectively. Differential scanning calorimetry data show that up to 14 H(2)O molecules per H(+)/SO(3)(-) group remain unfrozen at subzero temperatures and are believed to be responsible for the low temperature conductivity that is observed. These results indicate that proton conductivity in membranes may be achieved via strongly bound and highly polarized water.