Rare Earth Element Adsorption to Clay Minerals: Mechanistic Insights and Implications for Recovery from Secondary Sources.

The energy transition will have significant mineral demands and there is growing interest in recovering critical metals, including rare earth elements (REE), from secondary sources in aqueous and sedimentary environments. However, the role of clays in REE transport and deposition in these settings remains understudied. This work investigated REE adsorption to the clay minerals illite and kaolinite through pH adsorption experiments and extended X-ray absorption fine structure (EXAFS). Clay type, pH, and ionic strength (IS) affected adsorption, with decreased adsorption under acidic pH and elevated IS. Illite had a higher adsorption capacity than kaolinite; however, >95% adsorption was achieved at pH ∼7.5 regardless of IS or clay. These results were used to develop a surface complexation model with the derived binding constants used to predict REE speciation in the presence of competing sorbents. This demonstrated that clays become increasingly important as pH increases, and EXAFS modeling showed that REE can exist as both inner- and outer-sphere complexes. Together, this indicated that clays can be an important control on the transport and enrichment of REE in sedimentary systems. These findings can be applied to identify settings to target for resource extraction or to predict REE transport and fate as a contaminant.

Pyrolyzed biomass-derived nanoparticles: a review of surface chemistry, contaminant mobility, and future research avenues to fill the gaps.

Nanoparticles are abundant in the subsurface, soil, streams, and water bodies, and are often a critical control on elemental speciation, transport and cycling in the natural environment. This review provides an overview of pyrolyzed biomass-derived nanoparticles (PBNPs), their surface properties and reactivity towards aqueous species. We focus specifically on biochar-derived nanoparticles and activated carbon-derived nanoparticles which fall under our classification of PBNPs. Activated carbon-iron (nano)composites are included in some instances where there are significant gaps in literature because of their environmental relevance. Increased use of activated carbon, along with a resurgence in the manufacture and application of biochar for water treatment and soil amendment, has generated significant concerns about the mobility and toxicity of PBNPs derived from the bulk material in environmental applications. Recent examples are discussed to highlight current progress in understanding the influence of PBNPs on contaminant transport, followed by a critical discussion of gaps and future research directions.