Bulk and surface plasmon excitations in amorphous carbon (a-C) films have been characterized by core-level loss spectroscopy. Atomically smooth a-C surfaces were used in their as-grown state, after UHV annealing and after covalent immobilization of dense molecular monolayers (2-4 x 10(14) cm(-2)), either perfluorinated or labelled with an ester functionality. X-ray photoelectron spectra reveal a sp(3)-rich hybridization of surface C atoms, with a sigma + pi plasmon loss distribution centred at 29.5 +/- 1 eV, characteristic of a high electron density value. For molecular grafted surfaces, the energy distribution of plasmon losses reveals new contributions in the range 15-25 eV (clearly separated from the energy distribution of the bulk sigma + pi plasmon loss of a-C) with an increasing loss probability observed at grazing photoemission angles. A simple parameterization method is presented to derive bulk and surface plasmon loss distributions from angular core level loss spectroscopy (XPS) data, without a priori assumptions on the shape of the loss energy distributions. (C) 2009 Elsevier B. V. All rights reserved.