Energy dispersive x-ray microanalysis (EDX) is widely used for the quantitative determination of local composition in thin film specimens. Extraction of quantitative data is usually accomplished by relating the ratio of the number of atoms of two species A and B in the volume excited by the electron beam (nA/nB) to the corresponding ratio of detected characteristic photons (NA/NB) through the use of a k-factor. This leads to an expression of the form nA/nB = kAB NA/NB where kAB is a measure of the relative efficiency with which x-rays are generated and detected from the two species.Errors in thin film x-ray quantification can arise from uncertainties in both NA/NB and kAB. In addition to the inevitable statistical errors, particularly severe problems arise in accurately determining the former if (i) mass loss occurs during spectrum acquisition so that the composition changes as irradiation proceeds, (ii) the characteristic peak from one of the minority components of interest is overlapped by the much larger peak from a majority component, (iii) the measured ratio varies significantly with specimen thickness as a result of electron channeling, or (iv) varying absorption corrections are required due to photons generated at different points having to traverse different path lengths through specimens of irregular and unknown topography on their way to the detector.