The interpretation of UV-visible twilight absorption measurements of atmospheric chemical constituents is dependent on how well the optical path, or air mass factor, of light collected by the spectrometer is understood. A simple single scattering model and a Monte Carlo radiative transfer scheme have been developed to study the effects of multiple scattering, aerosol scattering, surface albedo and refraction on air mass factors for scattered light observations. At fairly short visible wavelengths (less than about 450 nm), stratospheric air mass factors are found to be relatively insensitive to multiple scattering, surface albedo and refraction, as well as aerosol scattering by background aerosols. Longer wavelengths display greater sensitivity to refraction and aerosol scattering. Tropospheric air mass factors are found to be highly dependent on aerosol scattering, surface albedo and, at long visible wavelengths (about 650 nm), refraction. Absorption measurements of NO2 and O4 are shown to support these conclusions.