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.

Lead (Pb) sorption to hydrophobic and hydrophilic zeolites in the presence and absence of MTBE.

The co-contamination of the environment by metals and organic pollutants is a significant concern, and one such example is lead (Pb) and methyl tert-butyl ether (MTBE) due to their historic use as fuel additives. Clinoptilolite is an abundant and efficient zeolite for metal removal, but the potential interference of co-existing organic pollutants on metal removal, such as MTBE, have rarely been discussed. In this study, a combination of batch sorption tests and synchrotron-based X-ray absorption spectroscopic analyses were employed to investigate Pb sorption mechanism(s) onto clinoptilolite in the presence and absence of MTBE. A comparison was made to synthetic ZSM-5 zeolite to gain insights into differences in Pb binding mechanisms between hydrophilic (clinoptilolite) and hydrophobic (ZSM-5) zeolites. Site occupancy and surface precipitation contributed equally to Pb removal by clinoptilolite, while surface precipitation was the main Pb removal mechanism for ZSM-5 followed by site occupancy. Despite the negligible effect of 100 mg/L MTBE on observed Pb removal from solution by both zeolites, a surface-embedded Pb removal mechanism, through the Mg site on clinoptilolite surface, arises when MTBE is present. This study provides an understanding of atomic-level Pb uptake mechanisms on zeolites, with and without co-contaminating MTBE, which aids in their application in water treatment at co-contaminated sites.

Reusable magnetite nanoparticles-biochar composites for the efficient removal of chromate from water.

Biochar (BC) and magnetite (Fe3O4) nanoparticles (MNP) have both received considerable recent attention in part due to their potential use in water treatment. While both are effective independently in the removal of a range of anionic metals from aqueous solution, the efficacy of these materials is reduced considerably at neutral pH due to decreased metal adsorption and MNP aggregation. In addition to synthetic metal oxide-biochar composites for use in treatment and remediation technologies, aggregates may also occur in nature when pyrolytic carbon is deposited in soils. In this study, we tested whether magnetite synthesized in the presence of biochar leads to increased removal efficiency of hexavalent chromium, Cr(VI), at the mildly acidic to neutral pH values characteristic of most natural and contaminated aqueous environments. To do so, magnetite nanoparticles and biochar produced from ground willow were synthesized to form composites (MNP-BC). Batch studies showed that MNP-BC markedly enhanced both adsorption and reduction of Cr(VI) from aqueous solution at acidic to neutral pH as compared to MNP and BC separately, suggesting a strong synergetic effect of hybridizing Fe3O4 with BC. Mechanistically, the Cr(VI) removal processes occurred through both adsorption and intraparticle diffusion followed by reduction to Cr(III). Synchrotron-based X-ray absorption spectroscopy analyses confirmed that Cr(VI) was reduced at the surface of MNP-BC, with electrons derived directly from both biochar and magnetite at low pH, while at near-neutral pH, biochar increased Cr(VI) reduction by inhibiting MNP aggregation. Extended X-ray absorption fine structure fitting results confirmed that the Cr(III) precipitates consist of Cr(OH)3 and chromite (Cr2FeO4) nanoparticles. Our results demonstrate that MNP-BC composites have great potential as a material for the treatment of chromate-containing aqueous solutions across a wide range of pH values, and provide information valuable broadly relevant to soils and sediments that contain biochar.

Inhibition of naphthalene leaching from municipal carbonaceous waste by a magnetic organophilic clay.

Municipal solid waste conversion into biofuels via gasification is one of the latest technologies to divert waste from landfills. The byproduct of the process is a carbonaceous material, which is often tainted with polycyclic aromatic hydrocarbons (PAH) such as naphthalene that can leach into the environment and have toxic effects on aquatic organisms. In this paper, we present a novel method to address the issue of leachable naphthalene in a carbonaceous waste produced from a gasification process, using a magnetic sorbent. The sorbent was fabricated by the coprecipitation of iron oxide nanoparticles on an organophilic clay under atmospheric conditions. The characterization results show that the intercalated nanoparticles are predominantly magnetite with a diameter of 15-20 nm, and increase the clay specific surface area from 0.4 to 17 m2 g-1. Toxicity characteristic leaching procedure results indicate that the magnetic composite has a high naphthalene inhibition efficiency comparable to that of the original clay. As opposed to the clay alone, the magnetic hybrid can be separated from the carbonaceous waste with a magnet, regenerated by heat treatment, and reused without compromising its naphthalene removal efficiency. Thus, these composites may provide a cost-effective method to curtail leaching of PAH from contaminated carbonaceous waste.

Mechanisms of the Removal of U(VI) from Aqueous Solution Using Biochar: A Combined Spectroscopic and Modeling Approach.

Biochar has been touted as a promising sorbent for the removal of inorganic contaminants, such as uranium (U), from water. However, the molecular-scale mechanisms of aqueous U(VI) species adsorption to biochar remain poorly understood. In this study, two approaches, grounded in equilibrium thermodynamics, were employed to investigate the U(VI) adsorption mechanisms: (1) batch U(VI) adsorption experiments coupled to surface complexation modeling (SCM) and (2) isothermal titration calorimetry (ITC), supported by synchrotron-based X-ray absorption spectroscopy (XAS) analyses. The biochars tested have considerable proton buffering capacity and most strongly adsorb U(VI) between approximately pH 4 and 6. FT-IR and XPS studies, along with XAS analyses, show that U(VI) adsorption occurs primarily at the proton-active carboxyl (-COOH) and phenolic hydroxyl (-OH) functional groups on the biochar surface. The SCM approach is able to predict U(VI) adsorption behavior across a wide range of pH and at varying initial U(VI) and biochar concentrations, and U adsorption is strongly influenced by aqueous U(VI) speciation. Supporting ITC measurements indicate that the calculated enthalpies of protonation reactions of the studied biochar, as well as the adsorption of U(VI), are consistent with anionic oxygen ligands and are indicative of both inner- and outer-sphere complexation. Our results provide new insights into the modes of U(VI) adsorption by biochar and more generally improve our understanding of its potential to remove radionuclides from contaminated waters.

Removal of hexavalent chromium in aqueous solutions using biochar: Chemical and spectroscopic investigations.

Biochar is an emerging low-cost sorbent used for removing trace metals from water. In this study, we evaluated the removal potential of aqueous hexavalent chromium (Cr(VI)) by biochars produced from soybean (Glycinemax L.) and burcucumber (Sicyos angulatus L.) residues. The highest Cr(VI) removal from solution occurred at low pH values (pH2-5), and adsorption decreased approximately tenfold when the pH increased from 2 to 10. Synchrotron-based X-ray absorption spectroscopy (XAS) investigations showed that Cr(VI) species were reduced to trivalent chromium (Cr(III)) at the biochar surface following Cr(VI) adsorption. Linear combination fitting (LCF) of X-ray absorption near edge structure (XANES) data indicated that approximately 90% of the total Cr(VI) (962µM) was reduced to Cr(III). Extended X-ray absorption fine structure (EXAFS) fitting results yielded interatomic chromium (CrCr) distances consistent with the formation of Cr(III) precipitates as Cr(OH)3. Trivalent chromium is far less soluble than Cr(VI) and typically precipitates as amorphous Cr(III) solids. Thus, biochars produced by soybean and burcucumber residues are a promising technique for both adsorbing and reductively immobilizing Cr(VI) from aqueous solutions.

Thermodynamic Analysis of Nickel(II) and Zinc(II) Adsorption to Biochar.

While numerous studies have investigated metal uptake from solution by biochar, few of these have developed a mechanistic understanding of the adsorption reactions that occur at the biochar surface. In this study, we explore a combined modeling and spectroscopic approach for the first time to describe the molecular level adsorption of Ni(II) and Zn(II) to five types of biochar. Following thorough characterization, potentiometric titrations were carried out to measure the proton (H+) reactivity of each biochar, and the data was used to develop protonation models. Surface complexation modeling (SCM) supported by synchrotron-based extended X-ray absorption fine structure (EXAFS) was then used to gain insights into the molecular scale metal-biochar surface reactions. The SCM approach was combined with isothermal titration calorimetry (ITC) data to determine the thermodynamic driving forces of metal adsorption. Our results show that the reactivity of biochar toward Ni(II) and Zn(II) directly relates to the site densities of biochar. EXAFS along with FT-IR analyses, suggest that Ni(II) and Zn(II) adsorption occurred primarily through proton-active carboxyl (-COOH) and hydroxyl (-OH) functional groups on the biochar surface. SCM-ITC analyses revealed that the enthalpies of protonation are exothermic and Ni(II) and Zn(II) complexes with biochar surface are slightly exothermic to slightly endothermic. The results obtained from these combined approaches contribute to the better understanding of molecular scale metal adsorption onto the biochar surface, and will facilitate the further development of thermodynamics-based, predictive approaches to biochar removal of metals from contaminated water.

Modified sequential extraction for biochar and petroleum coke: Metal release potential and its environmental implications.

A modified Community Bureau of Reference (CBR) sequential extraction method was tested to assess the composition of untreated pyrogenic carbon (biochar) and oil sands petroleum coke. Wood biochar samples were found to contain lower concentrations of metals, but had higher fractions of easily mobilized alkaline earth and transition metals. Sewage sludge biochar was determined to be less recalcitrant and had higher total metal concentrations, with most of the metals found in the more resilient extraction fractions (oxidizable, residual). Petroleum coke was the most stable material, with a similar metal distribution pattern as the sewage sludge biochar. The applied sequential extraction method represents a suitable technique to recover metals from these materials, and is a valuable tool in understanding the metal retaining and leaching capability of various biochar types and carbonaceous petroleum coke samples.

Uranium release from sediment to groundwater: influence of water chemistry and insights into release mechanisms.

Uranium (U) contamination in groundwater often results from natural geochemical processes such as mineral dissolution and desorption of adsorbed U from mineral surface. Although U adsorption and U mineral dissolution have been extensively studied, current knowledge of minerals and water chemistry conditions that control U release in uncontaminated soil and aquifers is still limited. Identification of these minerals and the knowledge of how water chemistry conditions influence U release is critical to better understand, predict, and manage geogenic U contamination in soil and groundwater. The objective of this study is to determine the extent and mechanisms of U release from a heterogeneous natural sediment under water chemistry conditions relevant to natural soil water and groundwater. A sediment sample was collected and characterized by XRD, SEM-EDX and extraction methods, and examined using laboratory leaching experiments. Our results show that Fe-Mn (oxy)hydroxides and silicate minerals are the major U hosting minerals, and a substantial fraction of U exists as adsorbed ions on minerals. We also found that U release is controlled by a number of interactive processes including dissolution of U-bearing minerals, U desorption from mineral surface, formation of aqueous U complexes, and reductive precipitation of U. Results from this study shed light on the important geochemical reactions that need be considered for developing a conceptual model that predicts U contamination in subsurface environment.