Methods are described for detecting and quantifying occult blood in a biological sample using laser desorption mass spectrometry (LD MS). Biological samples that can be analyzed using various embodiments of the present invention include stool (fecal occult blood, FOB), and any bodily fluid including urine, cerebrospinal fluid and other bodily fluids. If the heme or heme metabolite is bound to protein, the sample is treated with acid before analysis to release the porphyrin. Some of the methods use LD MS with a time of flight analyzer (TOF) to detect and measure unbound heme, other hemoglobin metabolites and other molecules that have a porphyrin-based structure, e.g., bilirubin, biliverdin, protoporphyrin IX, and Zinc protoporphyrin in the biological sample. In other methods, matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) is used to detect and quantify the individual .alpha.- and .beta.-polypeptide chains of hemoglobin.