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This paper presents an improved photon path length probability density function method that permits simultaneous retrievals of column-average greenhouse gas mole fractions and light path modifications through the atmosphere when processing high-resolution radiance spectra acquired from space. We primarily describe the methodology and retrieval setup and then apply them to the processing of spectra measured by the Greenhouse gases Observing SATellite (GOSAT). We have demonstrated substantial improvements of the data processing with simultaneous carbon dioxide and light path retrievals and reasonable agreement of the satellite-based retrievals against ground-based Fourier transform spectrometer measurements provided by the Total Carbon Column Observing Network (TCCON).