This paper reports steady-state dissolution rates of synthetic low-substitution Al-goethites (mol % Al < 10) at pH 5 in the presence of the trihydroxamate siderophore, desferrioxamine B (DFO-B), and the common biological ligand, oxalate. The siderophore-promoted Fe release rate increased both with the level of Al substitution and with DFO-B concentration up to about 100 microM, after which a plateau occurred, suggesting a saturation effect from DFO-B adsorption as a precursor to dissolution. At concentrations above 200 microM, oxalate also enhanced the Fe release rate, which however was not influenced by Al substitution. For Al-goethites with mol % Al < 4, the Fe release rate in the presence of 40 microM DFO-B together with varying concentrations of oxalate was typically greater than the corresponding sum of dissolution rates in the presence of the two ligands alone. This synergism may be the combined result of the ability of oxalate to adsorb strongly at the goethite surface, thus promoting Fe release, and of the high selectivity of DFO for Fe(III). Ferric oxalate complexes formed during dissolution will likely lose Fe3+ by ligand substitution with DFO-B, leading to the production of Fe(HDFO-B)+ and uncomplexed oxalate, the latter of which, in turn, could adsorb to the goethite surface again. For Al-goethites with mol % Al > 4, synergism was not apparent, which may signal the effect of a decreased surface density of Fe-OH sites associated with Al for Fe substitution. The oxalate-promoted release rates of Al did not scale with those of Fe, indicating incongruent dissolution. However, Al release rates in the presence of DFO-B did scale approximately with those of Fe but were not affected by the concentration of siderophore. These results are consistent with the presence of Al(OH)3 inclusions in Al-goethite.