Obsidian nodules (marekanites or “Apache tears”) weathered out of volcanic units west of Chihuahua were utilized by the precontact native population for the manufacture of small stone implements. We subjected 77 specimens, including both unworked nodules and bipolar percussion debitage, collected in a 16,000sqkm area, to standard ICP–AES, XRF glass bead and C-H-N combustion analyses. The chemical compositions of the samples form four groups related to differing fractional crystallization histories which developed in four discrete magma chambers. K2O and Nb/Y versus SiO2diagrams define the volcanics as high-potassium, calc-alkalic rhyolites, similar to a regionally extensive sequence of rhyolites related to Farallon Plate subduction, and erupted between 36 and 27 Ma. Harker and ratio diagrams indicate that amphibole crystallization was a major control on the chemistries of the northern, southern and western volcanic sequences. The geochemical signature of the central area volcanic rocks was mainly the result of plagioclase and K-feldspar crystallization in the magma chamber. Attributing variance in the data set to differing fractional crystallization histories allows elements and element ratios to be selected for grouping techniques which maximize the effectiveness of these techniques. In this study, Sr/Y versus Ba/Zr is the best choice, reflecting the crystallization histories of plagioclase, amphibole, K-feldspar and possibly sphene, apatite and zircon.Some 90% of samples were collected in the area which matches their geochemistry. In the southern area the ratio plot is capable of distinguishing between the geochemical signatures of individual sites, which indicates that most procurement was within approximately 1km of where the nodule was worked. Of 10 anomalous, apparently exotic, samples, six were probably transported a minimum of 25km by humans, and the means of transport of four is unclear. The northern area had no exotic fragments, though a small sample size (N=11) makes this finding only suggestive.