EXAFS study on the cause of enrichment of heavy REEs on bacterial cell surfaces

Takahashi, Yoshio*; Yamamoto, Mika*; Yamamoto, Yuhei; Tanaka, Kazuya  

Among various natural samples, rare earth element (REE) pattern of bacteria exhibits anomalous enrichment at heavy REE (HREE) part, which can be a signature of bacteria-related materials. In this study, REE binding site on the cell surface of a Gram-positive bacterium (Bacillus subtilis) responsible for the HREE enrichment has been identified by extended X-ray absorption fine structure (EXAFS) coupled with the variation of REE distribution pattern. EXAFS showed that (1) HREE is bound to multiple phosphate site at lower REE-bacteria ratio (=[REE]/[bac]), but the fraction coordinated to carboxylate increased as the increase in the ratio and (2) the binding sites of light and middle REE change from phosphate with lesser coordination number to carboxylate site as the [REE]/[bac] ratio increases. On the other hand, the enrichment of HREE in the REE distribution patterns of bacteria was less marked as the increase in the [REE]/[bac] ratio. This result is consistent with the EXAFS results, since REE pattern of multiple phosphate site exhibits monotonous increase for HREE, while phosphate with lesser coordination number and carboxylate site have maxima around Sm. Based on these results, it was clear that phosphate site is more stable than carboxylate site as the binding site for REE. The average bond lengths between REE and oxygen were compared among various REE sorbed on bacteria, showing that the bond length was much shorter for HREE than those extrapolated from the trend between La and Dy due to the selective binding of HREE to the multiple phosphate site. Based on the results, it is thought that materials having such phosphate site can induce anomalous HREE enrichment in natural systems. Compared with other possible host phases of REE such as metal oxides and humic substances, the multiple phosphate site is unique to bacteria and bacteria-related materials such as biofilm and microbial mats, which leads to the potential of REE pattern as a biomarker in natural samples.