Lanthanide humic substances complexation. I. Experimental evidence for a lanthanide contraction effect

International audience; The interaction of the lanthanides (Ln) with humic substances (HS) was investigated with a novel chemical speciation tool, Capillary Electrophoresis-Inductively Coupled Plasma Mass Spectrometry (CE-ICP-MS). By using an EDTA ligand competition method, a bi-modal species distribution of LnEDTA and LnHS is attained, separated by CE, and detected online by sector field ICP-MS. We quantified the binding of all 14 rare earth elements (REEs), Sc and Y with Suwannee river fulvic acid, Leonardite coal humic acid, and Elliot soil humic acid under environmental conditions (pH 6 9, 0.001 0.1 mol L?1 NaNO3, 1 1000 nmol L?1 Ln, 10 20 mg L?1 HS). Conditional binding constants for REE HS interaction (Kc) ranged from 8.9 < log Kc < 16.5 under all experimental conditions, and display a lanthanide contraction effect, ?LKc: a gradual increase in Kc from La to Lu by 2 3 orders of magnitude as a function of decreasing ionic radius. HS polyelectrolyte effects cause Kc to increase with increasing pH and decreasing ionic strength. ?LKc increases significantly with increasing pH, and likely with decreasing ionic strength. Based on a strong correlation between ?LKc values and denticity for organic acids, we suggest that HS form a range of tri- to tetra-dentate complexes under environmental conditions. These results confirm HS to be a strong complexing agent for Ln, and show rigorous experimental evidence for potential REE fractionation by HS complexation.