Petroleum-geochemical analyses of carbonaceous regionally metamorphosed rocks, carbonaceous rocks from ore deposits, and alkalic plutonic rocks from diverse settings, demonstrated the presence of very low to moderately low concentrations of solvent-extractable organic matter, this observation in spite of the fact that some of these rocks were exposed to extremely high metamorphic temperatures. Biomarker and ??13C analyses established that the extractable organic matter originated as sedimentary-derived hydrocarbons. However, the chemistry of the extractable bitumen has been fundamentally transformed from that found in sediment bitumen and oils. Asphaltenes and resins, as defined in the normal petroleum-geochemical sense, are completely missing. The principal aromatic hydrocarbons present in oils and sediment bitumens (especially the methylated naphthalenes) are either in highly reduced concentrations or are missing altogether, Instead, aromatic hydrocarbons typical of sediment bitumens and oils are very minor, and a number of unidentified compounds and oxygen-bearing compounds are dominant. Relatively high concentrations of alkylated benzenes are typical. The polar "resin" fraction, eluted during column chromatography, is the principal compound group, by weight, being composed of six to eight dominant peaks present in all samples, despite the great geologic diversity of the samples. These, and other, observations suggest that a strong drive towards equilibrium exists in the "bitumen." Gas chromatograms of the saturated hydrocarbons commonly have a pronounced hump in both the n-paraffins and naphthenes, centered near the C19 to C26 carbon numbers, and a ubiquitos minimum in the n-paraffin distribution near n-C12 to n-C14. Multiple considerations dictate that the bitumen in the samples is indigenous and did not originate from either surficial field contamination or from laboratory procedures. Our observations are consistent with the hydrolytic disproportion of organic matter (HDOM), in which water and organic matter, including hydrocarbons, easily exchange hydrogen or oxygen with one another under certain conditions (Helgeson et al., 1993). The process appears to take place via well-known organic-chemical redox reaction pathways and is most evident in open-fluid systems. The conclusion that HDOM took place in the analyzed samples, thus producing the chemistry of the extractable bitumen, is supported by numerous previously published organic-geochemical studies of metamorphic, volcanic, plutonic, and ore-deposit-related rocks by other investigators. HDOM is suggested as an unrecognized geologic agent of fundamental importance. The process appears to control major chemical reactions in diverse geologic environments including, but not limited to, petroleum geology and geochemistry, regional metamorphism, and base- and precious-metal ore deposition. Copyright ?? 2001 Elsevier Science Ltd.