A new technique has been developed to deconvolve and quantify the mass concentrations of hydrocarbon-like and oxygenated organic aerosols (HOA and OOA) using highly time-resolved organic mass spectra obtained with an Aerodyne Aerosol Mass Spectrometer (AMS). This technique involves a series of multivariate linear regressions that use mass-to-charge ratios (m/źs) 57 (mostly C4H9+) and 44 (mostly CO 2+)-the identified AMS mass spectral tracers for HOA and OOA, respectively-as the initial principal components. Two algorithms have been developed: algorithm 1 is based solely on m/z 44 and m/z57, and algorithm 2 is an iterative procedure expanded from algorithm 1. This technique was applied to the AMS organic aerosol data acquired at the EPA Pittsburgh Supersite during September 2002. The reconstructed organic concentrations (= HOA + OOA) agree well with the measured values (r2 = 0.997, slope = 0.998), and the reconstructed organic data matrix (size = 3199 time steps × 300 m/źs) explains 99% of the variance in the measured time series. In addition, the extracted mass spectrum of HOA shows high similarity to those of diesel exhaust, lubricating oil, and freshly emitted traffic aerosols observed in urban areas, while the spectrum of OOA closely resembles those of aged organic aerosols sampled in rural areas and also shows similarity with the spectrum of fulvic acid-a humic-like substance that is ubiquitous in the environment and has previously been used as ananalogueto represent polyacid components found in highly processed and oxidized atmospheric organic aerosols. There is evidence for the presence of a third component, although its contribution to the total organic signal appears to be small in this study. The most important result is that m/z 44 and m/z 57 are reliable AMS mass spectral "markers" that provide the "first guess" for algorithm 2 which allows the quantitative description of the organic aerosol concentration and mass spectra over a period of 16 days in a major urban area and allows the extraction of mass spectra of 00A and H0A that can be interpreted chemically. These findings indicate the potential of performing organic source apportionment on the basis of total particle mass, rather than on the basis of organic tracer compounds that contribute a small fraction of this mass. © 2005 American Chemical Society.