The shockwave generated alongside the plasma is an intimately linked, yet often neglected additional input for the characterization of solid samples by laser-induced breakdown spectroscopy (LIBS). The present work introduces a dual LIBS-acoustics sensor that takes advantage of the analysis of the acoustic spectrum yielded by shockwaves produced on different geological samples to enhance the discrimination power of LIBS in materials featuring similar optical emission spectra. Six iron-based minerals were tested at a distance of 2 m using 1064 nm laser light and under pressure values ranging from 7 to 1015 mbar. These experimental parameters were selected to assess the effects of pressure, one of the main factors conditioning the propagation of sound as well as a commonly investigated influence in LIBS experiments. Moreover, precise values for carrying out the analyses were set based on one of the most exciting scenarios in which LIBS data may be enhanced by laser-induced acoustics: space exploration. This is exemplified by the tasks performed by the Mars 2020 SuperCam instrument located onboard the Perseverance rover. Authors evaluated the use of acoustic signals both in the time-domain and frequency-domain in sensitive cases for the distinguishing of minerals exhibiting LIBS spectra featuring almost the same emission lines using PCA schemes for each pressure setting. Thus, we report herein the impact of the surrounding pressure level upon this diagnostic tool. Overall, this paper seeks to show how the analytical potential of simultaneous phenomena taking place during a laser-produced plasma event is subjected to the defined operational conditions.