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Practical and effective strategies for the detoxification of aflatoxins are critically needed. We have shown that a phyllosilicate clay (HSCAS): i) tightly binds aflatoxins in aqueous solutions, including milk; ii) markedly decreases the bioavailability of radiolabeled aflatoxins; iii) greatly diminishes aflatoxicosis in young animals, i.e., rats, chickens, turkeys, lambs, and pigs; and iv) reduces the level of aflatoxin M1 in the milk from lactating dairy cattle and goats. In further studies, ligands with one or more of the functional groups in common with aflatoxin were reacted with HSCAS in vitro in an attempt to elucidate the specificity and mechanism of tight binding (or chemisorption). A chemisorption index (C alpha) was developed, allowing for direct comparison of various clay and zeolitic minerals with HSCAS. Chemisorption indices were determined by HPLC analysis of extracts of the supernatants and sorbed pellets (exhaustively extracted with methanol and chloroform). The beta-dicarbonyl system of aflatoxin was found to be essential for tight binding by HSCAS. Comparison of the chemisorption indices from various classes of compounds with spectral data (DRIFTS) indicated that the molecular mechanism of aflatoxin binding may involve the chelation of metal ions in HSCAS with the beta-dicarbonyl moiety in aflatoxin. Computer modeling was utilized to provide additional information. Preliminary evidence suggests that aflatoxin B1 may react at surfaces and within the interlayers of HSCAS particles. With knowledge of the mechanism involved, it has been possible to further enhance the propensity of HSCAS for aflatoxins.