Use of X-ray Absorption Spectroscopy and Esterification to Investigate Cr(III) and Ni(II) Ligands in Alfalf a Biomass.

Previously performed studies have shown that alfalfa shoot biomass can bind an appreciable amount of nickel(II) and chromium(III) ions from aqueous solution. Direct and indirect approaches were applied to study the possible mechanis ms involved in metal binding by the alfalfa biomass. The direct approach involves investigations of the metal-bound alfal fa shoot biomass by X-ray absorption spectroscopic analysis (XANES and EXAFS). Results from these studies suggest that ni ckel(II) and chromium(III) binding mostly occurs through coordination with oxygen ligands. Indirect approaches consist of chemical modification of carboxylate groups that have been shown to play an important role in metal binding to the alfal fa biomass. An appreciable decrease in metal binding resulted after acidic methanol esterification of the biomass, indica ting that carboxyl groups are entailed in the metal binding by the alfalfa biomass. In addition, base hydrolysis of the a lfalfa biomass increased the binding of these metals, which further indicates that carboxyl groups play an important role in the binding of these metal ions from solution. Therefore, by combining two different techniques, our results indicate that carboxylate groups are the major ligands responsible for the binding of nickel(II) and chromium(III) by alfalfa bio mass.