Rare earth elements detoxification mechanism in the hyperaccumulator Dicranopteris linearis: [silicon-pectin] matrix fixation.

Dicranopteris linearis is the best-known hyperaccumulator species of rare earth elements (REEs) and silicon (Si), capable of dealing with toxic level of REEs. Hence, this study aimed to clarify how D. linearis leaves cope with excessive REE stress, and whether Si plays a role in REE detoxification. The results show that lanthanum (La - as a representative of the REEs) stress led to decreased biomass and an increase of metabolism related to leaf cell wall synthesis and modification. However, the La stress-induced responses, especially the increase of pectin-related gene expression level, pectin polysaccharides concentration, and methylesterase activity, could be mitigated by Si supply. Approximately 70% of the Si in D. linearis leaves interacted with the cell walls to form organosilicon Si-O-C linkages. The Si-modified cell walls contained more hydroxyl groups, leading to a more efficient REE retention compared to the Si-free ones. Moreover, this [Si-cell wall] matrix increased the pectin-La accumulation capacity by 64%, with no effect on hemicellulose-La and cellulose-La accumulation capacity. These results suggest that [Si-pectin] matrix fixation is key in REE detoxification in D. linearis, laying the foundation for the development of phytotechnological applications (e.g., REE phytomining) using this species in REE-contaminated sites.

Selective recovery of rare earth elements and value-added chemicals from the Dicranopteris linearis bio-ore produced by agromining using green fractionation.

The increasing demand for Rare Earth Elements (REEs) and the depletion of mineral resources motivate sustainable strategies for REE recovery from alternative unconventional sources, such as REE hyperaccumulator. The greatest impediment to REE agromining is the difficulty in the separation of REEs and other elements from the harvested biomass (bio-ore). Here, we develop a sulfuric acid assisted ethanol fractionation method for processing D. linearis bio-ore to produce the pure REE compounds and value-added chemicals. The results show that 94.5% of REEs and 87.4% of Ca remained in the solid phase, and most of the impurities (Al, Fe, Mg, and Mn) transferred to the liquid phase. Density functional theory calculations show that the water-cation bonds of REEs and Ca cations were broken more easily than the bonds of the cations of key impurities, causing lower solubility of REEs and Ca compounds. Subsequent separation and purification led to a REE-oxide (REO) product with a purity of 97.1% and a final recovery of 88.9%. In addition, lignin and phenols were obtained during organosolv fractionation coupled with a fast pyrolysis process. This new approach opens up the possibility for simultaneous selective recovery of REEs and to produce value-added chemicals from REE bio-ore refining.