Effects of Heating on the Binding of Rare Earth Elements to Humic Acids

In deep underground environments, temperature is one of the key factors affecting the geochemistry behaviors of rare earth elements (REE) in organic-rich fluid. However, the influence of temperature on the interaction between humic acids (HA) and REE is not well known. In the present study, the influence of temperature on the HA–REE-binding behavior was evaluated based on heating experiments of REE-doped HA solution. Lignite-extracted HA and REE-binding experiments were conducted over a temperature range of 20 to 200 °C to quantify HA–REE complexation and the influence of temperature on HA binding sites. Results showed that increasing temperature and decreasing [REE]/[HA] ratio cause an increase of K d value (the partition coefficient of REE between HA and aqueous solution). During heating K d REE K d REE patterns gradually change from middle REE-enriched-type (M-type) at 20 °C to light and middle REE-enriched-type (L-M-type) at 50 and 100 °C, and to light REE-enriched-type (L-type) at 150 °C and 200 °C. The increase of REE bonded with HA and modifications of K d REE patterns during the thermal treatment may be attributed to the increase of REE-binding sites, especially carboxylic sites, as a consequent of HA decomposition. This study provides a glimpse into the HA–REE-binding behaviors in the deep underground environment, which may shed light on the geochemical characteristics of REE in some organic-bearing rocks, and their changes during the coalification process.