An experimental study was performed on the N2-induced quenching of He-induced intensity enhancement effect in reduced-pressure plasma emission produced by Nd-YAG irradiation on solid zircaloy and porous fossil samples. The spatial distributions and temporal variations in the emission intensities show pronounced intensity quenching effects on the He I 667.9 nm, H I 656.2 nm, and D I 656.1 nm emission lines in both samples when a tiny amount (5% by volume) of nitrogen was added to helium gas, while leaving the spatial and temporal intensity profiles of the heavier Zr and Ca atoms virtually unaffected. In both cases of different ambient gases, the spatial and temporal variations in the He, H, and D emission intensities exhibit distinct features and changes, which are clearly distinguishable from those observed on the Zr and Ca emission lines, which were mainly produced by the shock-wave induced thermal excitation process. The analysis of these data unambiguously revealed the presence of an additional and distinct “He-assisted” excitation mechanism in the He plasma, which was further suggested to be related to the He metastable excited state. The quenching effect was therefore explained as a consequence of energy depletion of the He metastable excited state triggered by the Penning ionization process induced by the presence of nitrogen. This also explains the relatively insensitive response of the Zr and Ca emission intensity profiles to nitrogen addition despite the increased plasma electron density resulting from the ionization process.