The San Miguel lignite deposit (late Eocene, lower Jackson Group) of south Texas consists of four or more thin (generally < 1 m thick) lignite benches that are separated by claystone and mudstone partings. The partings are composed of altered volcanic air-fall ash that has been reworked by tidal or channel processes associated with a back-barrier depositional environment. The purpose of this study is to examine the relationship between the ash yield and the petrographic and geochemical characteristics of the San Miguel lignite as mined. Particular attention is given to 12 of the environmentally sensitive trace elements (As, Be, Cd, Cr, Co, Hg, Mn, Ni, Pb, Sb, Se, and U) that have been identified as possible hazardous air pollutants (HAPs) by the United States Clean Air Act Amendments of 1990. A total of 29 rock and lignite samples were collected and characterized by geochemical and petrographic methods. The major conclusions of the study are as follows: (1) The distribution of Mn is inversely related to the ash yield of the lignite samples. This indicates an organic affinity, or an association with finely disseminated minerals in the lignite that contain this element. (2) On a whole-coal basis, the concentration of the HAPs' element Pb is positively related to ash yield in lignite samples. This indicates an inorganic affinity for Pb. (3) Average whole-coal concentrations of As, Be, Sb, and U in the San Miguel samples are greater than published averages for these elements in other U.S. lignites. (4) The upper and lower lignite benches of the San Miguel deposit are both ash- and algal-rich, indicating that these intervals were probably deposited in wetter conditions than those in which the middle intervals formed. (5) The dominance of the eugelinite maceral subgroup over the huminite subgroup indicates that the San Miguel lignites were subjected to peat-forming conditions (either biogenic or chemical) that enabled degradation of wood cellular material into matrix gels, or that the plants that formed these lignite benches were less woody and more prone to formation of matrix gels. (6) An inertinite-rich layer (top of the B bed) might have formed from widespread oxidation of the San Miguel peat as a result of a volcanic ash fall which was subsequently reworked.