Photoluminescence (PL) spectra of freshly etched and ambient-aged porous silicon specimens have been measured and analyzed to extract spectral contributions due to quantum confinement (QC) and non-QC effects. It is shown that all spectra can be deconvolved into five Gaussian bands with typical peak energies 1.59, 1.76, 1.84, 1.94, and 2.07 eV. Ambient aging induces similar to0.1 eV blueshift in each of the three highest energy peaks, which is attributed to QC effects. In contrast, the two lowest energy peaks remain unshifted as expected for non-QC effects. Because size of the porous silicon nanoparticles is deduced from the magnitude of blueshift, it is imperative to correctly identify the spectral components associated solely with QC. The three closely spaced Gaussian bands are summed and the resulting single Gaussian band is analyzed with the model of Islam and Kumar [J. Appl. Phys. 93, 1753 (2003)]. Results show that peak energy of the freshly etched sample is 1.86 eV with average nanoparticle size L-0=3.90 nm and dispersion sigma=0.065 nm. Ambient aging for 40 days causes this peak to blueshift to 2.07 eV and reduces the nanoparticle size to L-0=3.37 nm with dispersion sigma=0.088 nm. The reduction in particle size (DeltaL=0.53 nm) is attributed to oxidation of the nanocrystalline surface, and corresponds to approximately 2 monolayers of oxide growth. (C) 2004 American Institute of Physics.