An improved description of the interactions between rare earth elements and humic acids by modeling: PHREEQC-Model VI coupling

摘要

The Humic Ion Binding Model VI (Model VI) - previously used to model the equilibrium binding of rare earth elements (REE) by humic acid (HA) - was modified to account for differences in the REE constant patterns of the HA carboxylic and phenolic groups, and introduced into PHREEQC to calculate the REE speciation on the HA binding sites. The modifications were shown to greatly improve the modeling. They allow for the first time to both satisfactorily and simultaneously model a large set of multi-REE experimental data with the same set of equations and parameters. The use of PHREEQC shows that the light rare earth elements (LREE) and heavy rare earth elements (HREE) do not bind to HA by the same functional groups. The LREE are preferentially bound to carboxylic groups, whereas the HREE are preferentially bound to carboxy-phenolic and phenolic groups. This binding differentiation might lead to a fractionation of REE-HA patterns when competition between REE and other metals occur during complexation. A survey of the available data shows that competition with Al3+ could lead to the development of HREE-depleted HA patterns. This new model should improve the hydrochemical modeling of the REE since PHREEQC takes into account chemical reactions such as mineral dissolution/precipitation equilibrium and redox reactions, but also models kinetically controlled reactions and one-dimensional transport.