The toxicity of Al to Desulfovibrio desulfuricans G20 was assessed over a period of 8 weeks in a modified lactate C medium buffered at four initial pHs (5.0, 6.5, 7.2, and 8.3) and treated with five levels of added Al (0, 0.01, 0.1, 1.0, and 10 mM). At pH 5, cell population densities decreased significantly and any effect of Al was negligible compared to that of the pH. At pHs 6.5 and 7.2, the cell population densities increased by 30-fold during the first few days and then remained stable for soluble-Al concentrations of <5 ؋ 10 ؊5 M. In treatments having total-Al concentrations of >1 mM, soluble-Al concentrations exceeded 5 ؋ 10 ؊5 M and limited cell population growth substantially and proportionally. At pH 8.3, soluble-Al concentrations were below the 5 ؋ 10 ؊5 M toxicity threshold and cell population density increases of 20-to 40-fold were observed. An apparent cell population response to added Al at pH 8.3 was attributed to the presence of large, spirilloidal bacteria (accounting for as much as 80% of the cells at the 10 mM added Al level). Calculations of soluble-Al speciation for the pH 6.5 and 7.2 treatments that showed Al toxicity suggested the possible presence of the Al 13 O 4 (OH) 24 (H 2 O) 12 7؉ "tridecamer" cation and an inverse correlation of the tridecamer concentration and the cell population density. Analysis by 27 Al nuclear magnetic resonance spectroscopy, however, yielded no evidence of this species in freshly prepared samples or those taken 800 days after inoculation. Exclusion of the tridecamer species from the aqueous speciation calculations at pHs 6.5 and 7.2 yielded inverse correlations of the neutral Al(OH) 3 and anionic Al(OH) 4 ؊ monomeric species with cell population density, suggesting that one or both of these ions bear primary responsibility for the toxicity observed.Aluminum, the most abundant metal and the third most abundant element in the earth's crust (37), finds surprisingly little use in biological systems. Although the inherent chemistry of Al certainly is a factor, the chemical conditions existing on the earth at the time the earliest organisms were developing may also have played a role (42, 43). These conditions, which include neutral pH and the absence of oxygen, were such that the solubility of Al was minimal relative to that of divalent metals such as Mg, Ca, and Fe(II). Even if availability were not limiting, however, several other chemical properties of Al strongly militate against its use in cellular metabolism (5). The inherently slow rate of inner-sphere ligand exchange for Al 3ϩ (10 5 to 10 8 times slower than for Mg 2ϩ , Ca 2ϩ , or Fe 2ϩ [41]) makes its complexes relatively inert. Further inertness stems from the lack of any electron transfer chemistry. Moreover, Al 3ϩ forms complexes with greater thermodynamic stability than that of those formed by the divalent metals because of its smaller size and higher valence. Thus, the ability of Al to form strong, relatively inert complexes not only prevents its use by the cyclic feedback-regulated processes in cellu...