Michael A. Kruge, Earth and Environmental Studies Dept.
Montclair State University, Upper Montclair, NJ 07043 USA


Chemistry Of Fossil Charcoal In Cretaceous-Tertiary Boundary Strata, Arroyo El Mimbral, Mexico

Collaborators: J. C. Crelling (SIU-C), A. Montanari (Osservatorio Geologico di Coldigioco), B. A. Stankiewicz (Univ. of Bristol) and D. F. Bensley (Carbon Consultants International).



It is estimated that approximately 25% of terrestrial biomass was consumed in the catastrophic fire [1] following the bolide impact [2] now widely accepted to have ended the Cretaceous Period. Fossil organic matter (OM) in K/T boundary sediments should therefore be expected to show evidence of this event. Rocks from the K/T site at Arroyo el Mimbral (Taumalipas, Mexico) were reported to contain plant remains [3]. The Mimbral boundary unit consists of 3 m of coarse clastics, set incongruously in a sequence of pelagic marls, and is interpreted to be megawave deposits from the aftermath of the impact [3]. Upon acid digestion (HCl/HF) and floatation of 6 Mimbral samples, most yielded only traces of organic matter (OM). However, one was found to contain 0.2% OM by weight. This sample was studied in detail by organic petrographic and geochemical methods.

The Mimbral OM is 90% inertinite (fossil charcoal). The inertinite particles are large, approaching a millimeter in size in some cases, and show extraordinary preservation of fine botanical detail [4]. While most sedimentary OM assemblages contain a few percent of inertinite, it is most unusual to see inertinite as the predominant component. It is even more unusual to find such an occurrence within a pelagic sequence, as inertinite originates from charring of land plant material. (Instead, fossil marine algal or bacterial remains would be expected.) The remaining 10% is vitrinite (diagenetically-altered, but uncharred terrestrial plant remains).

Flash pyrolysis-gas chromatography/mass spectrometry (py-GC/MS) of the OM concentrate indicates a predominance of polyaromatic structures, often without alkylation. These chemical features are indicative of severe thermal alteration due to partial combustion and therefore consistent with the petrographic recognition of fossil charcoal. Among hydrocarbons (organic compounds containing only H and C), aromatics comprise 59% of the pyrolyzate, while aliphatics (long chain structures typically derived from fossil algae, bacteria and higher plant waxes) only account for 5%. Among heterocompounds (organic compounds which also contain O, N or S), which collectively account for 35% of the pyrolyzate, virtually all are aromatic.

Oxygenated compounds are abundant, comprising 24% of the pyrolyzate. Of these, about a third are phenolic. Phenols are characteristic pyrolysis products of vitrinite and are molecular markers for the structure inherited from the precursor lignin [5]. Thus, the phenols could be assumed to derive from the minor vitrinite in the Mimbral sample. However thermally-altered vitrinites (such as the Mimbral, which has a mean reflectance of 1.3%) have been shown to produce only minor amounts of phenols [6]. If, as suspected, the elevated reflectance of the Mimbral vitrinite is due to the brief, severe thermal pulse of the impact [4], chemical characteristics normally obliterated by slow, geothermal heating may still be present. The other major oxygenated compounds are the three-ring structures dibenzofuran and fluorene-9-one, together accounting for >7% of the pyrolyzate. The occurrence of both these compounds as major components of sedimentary OM, even one dominated by inertinite, is highly unusual. These may results from oxidation of highly aromatic material, such as inertinite, prior to deposition or during weathering at the outcrop. Alternatively, since the lignin of the original plant material was oxygen-rich, the oxygen in these compounds may be inherited directly from biomass.

Compounds containing both nitrogen and oxygen are surprisingly abundant, comprising >4% of the pyrolyzate. One compound, identified as an indole-dione, is similar to compounds produced during the flash pyrolysis of proteins [7] and thus could again represent direct inheritance from biomass. Another compound in this class, acridinone, has a larger, triaromatic structure, but is still likely derived from charred biomass. Dibenzothiophenes (triaromatic organosulfur compounds) are also abundant, accounting for 5% of the pyrolyzate. These likely result from the diagenetic incorporation of sulfur from sulfate in pore waters after deposition, rather than directly from biomass.

The unusually good preservation of botanical evidence, as observed by both petrographic and chemical methods, is consistent with rapid charring and deposition inferred from the scenario of impact-firestorm-megawave at the end of the Cretaceous Period.


References: [1] Ivany L.C. and Salawitch R. J. (1993) Geology, 21, 487-490. [2] Alvarez L. W. et al. (1980) Science, 208, 1095-1108. [3] Smit J. et al. (1992) Geology, 20, 99-103. [4] Kruge et al. (1994) Geochim. Cosmochim. Acta, 58, 1393-1397. [5] Hatcher P. G. (1990) Org. Geochem., 16, 959-968. [6] Kruge M. A. and Bensley D. F. (1994) In Vitrinite Reflectance as a Maturity Parameter; P. K. Mukhopadhyay and W. G. Dow, eds., Amer. Chem. Soc. Symp. Series 570, p. 136-148. [7] Boon J. J. and de Leeuw J. W. (1987) J. Anal. Appl. Pyro., 11, 313-327.


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Last updated: 2002.08.13