The effects of calcination temperature on Pd/gamma-alumina catalysts were studied using a variety of techniques to measure particle sizes, surface species, and activity in methane combustion. Pd/Al2O3 catalysts were synthesized using a new impregnation-vortexing method. Three catalysts containing 3.3 wt.% Pd/Al2O3 were calcined at 150 degrees C, 250 degrees C, and 500 degrees C. The light-off temperature for methane combustion was 250-255 degrees C for all catalysts and 100% methane combustion was achieved at 275 degrees C in 20 min with the 3Pd/Al2O3 250 degrees C catalyst under lean methane conditions. X-ray photoelectron spectroscopy showed PdOx and PdO on the catalysts surface, and conversion of some PdOx to PdO and Pd-0 after reaction. Particle sizes and dispersions were different in the three fresh and spent catalysts as shown by scanning transmission electron microscopy (STEM) and CO pulse chemisorption. In situ and operando diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) showed that after high temperature calcination, dormant monodentate carbonates are formed at the interface of Pd and alumina on the 3 Pd/Al2O3 500 degrees C catalyst, which are absent on the 3Pd/Al2O3 250 degrees C catalyst during reaction. Temperature-responsive CO species were observed for both 3Pd/Al2O3 catalysts, evidencing restructuring of the 3Pd/Al2O3 250 degrees C catalyst upon heating in accordance with the STEM results. The results indicate a varying degree of strong metal-support interactions, resulting in different adsorbed species over the catalysts during methane oxidation reaction. We suggest that, over the 3Pd/Al2O3 250 degrees C catalyst, the desorption of carbonates frees OH groups at the Pd-Al2O3 interface, which can react (with other OH or H) and desorb as water, a step which can be rate limiting on methane oxidation over Pd/Al2O3 at low temperatures. This research study highlights the possibility of altering catalytic properties and surfaces through calcination at different temperatures.