Photoacoustic spectroscopic (PAS) detection of infrared absorption often produces spectra with enhanced intensities for weaker peaks, enabling the detection of features due to overtones and combinations, as well as less-abundant isotopic species. To illustrate this phenomenon, we present and discuss PAS infrared spectra of calcite (CaCO<sub>3</sub>). We use linearization of rapid-scan spectra, as well as comparing step-scan and rapid-scan spectra, to demonstrate that saturation is not the driving force behind these enhanced intensities. Our results point to a new knowledge gap, since a theoretical basis for the enhancement of these weak bands has not yet been developed.