Powdered Hierarchically Porous Silica Monoliths for the Selective Extraction of Scandium.

Scandium (Sc) is a high value Critical Material that is most commonly used in advanced alloys. Due to current and potential supply limitations, there has been an international effort to find new and improved ways to extract Sc from existing and novel resources. Solid-phase extraction (SPE) is one promising approach for Sc recovery, particularly for use with low-grade feedstocks. Here, unfunctionalized, powdered hierarchically porous silica monoliths from DPS Inc. (DPS) are used for Sc extraction in batch and semicontinuous flow systems at model conditions. The sorbent exhibits excellent mass transfer properties, much like the whole monoliths, which should permit Sc to be rapidly recovered from large volumes of feedstock. The Sc adsorption capacity of the material is ∼142.7 mg/g at pH 6, dropping to ∼12.0 mg/g at pH 3, and adsorption is furthermore highly selective for Sc compared with the other rare earth elements (REEs). Under semicontinuous flow conditions, recovery efficiency is limited by a kinetic process. The primary mechanism responsible for the system's slow approach to equilibrium is the Sc adsorption reaction kinetics rather than inter- or intraparticle diffusion. Overall, this unmodified hierarchically porous silica powder from DPS shows great promise for the selective extraction of Sc from various feedstocks.

A perspective on developing solid-phase extraction technologies for industrial-scale critical materials recovery.

Critical materials (CMs) are a group of elements that have been determined to be important for the modern economy, but which may face current or potential supply limitations. Some examples of metals that have received the CM designation include the rare earth elements, indium, gallium, and lithium. The last decade has seen a major push for the development of new and improved technologies for the recovery and purification of CMs from various traditional and non-traditional resources in an effort to diversify supply. Solid-phase extraction (SPE) is one broad category of these experimental extraction technologies. SPE involves the application of a solid material to preferentially retain in the solid phase one or more specific components of an aqueous solution, leaving the other components behind in the aqueous phase. A wide range of different sorbents has been used for SPE, and many offer significant potential advantages, including low cost, low environmental impact, and high customizability. Hierarchically porous silica monoliths are one example of a cutting-edge sorbent that provides a durable, high surface area foundation that can be functionalized with a variety of targeted ligands for the selective extraction of specific CMs. Despite impressive recent advances in SPE, there remain areas for improvement that are common across the discipline. To demonstrate the practical viability of these innovative CM recovery systems, future SPE studies would benefit from devoting additional focus to the scalability of their material, as well as from focusing on real-world feedstocks and conducting techno-economic analyses and environmental impact studies.

Electronic waste as a source of rare earth element pollution: Leaching, transport in porous media, and the effects of nanoparticles.

Rare earth elements (REEs) are an emerging pollutant whose increasing use in various technological applications causes increasing risk of environmental contamination. Electronic waste (E-waste) could be one major source of REE pollution, as E-waste typically contains elevated REE concentrations and is often handled in unsafe and environmentally hazardous ways. Here, a series of leaching assays revealed that <1% of REEs available in a representative E-waste were released except at acidic conditions (pH 2) rarely observed in nature. If REEs are leached from E-waste, the extent of their spread in the environment will depend, in large part, on their mobility through porous media. Measurements of REE transport through saturated sand demonstrated extremely limited mobility except at acidic conditions (pH 2), though significant REE retention by the substrate still occurs at this low pH. Similar experiments in a natural soil found REE mobility to be even lower in that substrate, with complete REE retention even after the passage of up to 215 pore volumes of a 500 ppb REE solution. Aqueous REEs are therefore not expected to be highly mobile in the environment. The presence of natural or anthropogenic nanoparticles may affect REE behavior during leaching and/or transport. Measurements indicated that silica nanoparticles can increase the concentration of fluid-mobile REEs during E-waste leaching, but both plastic and silica nanoparticles have a negligible effect on REE transport. Ultimately, the experiments and analysis presented here suggest that the threat of REE pollution from E-waste is minimal except at specific sites with unusual environmental conditions.

Magnesium isotope fractionation during microbially enhanced forsterite dissolution.

Bacillus subtilis endospore-mediated forsterite dissolution experiments were performed to assess the effects of cell surface reactivity on Mg isotope fractionation during chemical weathering. Endospores present a unique opportunity to study the isolated impact of cell surface reactivity because they exhibit extremely low metabolic activity. In abiotic control assays, 24 Mg was preferentially released into solution during forsterite dissolution, producing an isotopically light liquid phase (δ26 Mg = -0.39 ± 0.06 to -0.26 ± 0.09‰) relative to the initial mineral composition (δ26 Mg = -0.24 ± 0.03‰). The presence of endospores did not have an apparent effect on Mg isotope fractionation associated with the release of Mg from the solid into the aqueous phase. However, the endospore surfaces preferentially adsorbed 24 Mg from the dissolution products, which resulted in relatively heavy aqueous Mg isotope compositions. These aqueous Mg isotope compositions increased proportional to the fraction of dissolved Mg that was adsorbed, with the highest measured δ26 Mg (-0.08 ± 0.07‰) corresponding to the highest degree of adsorption (~76%). The Mg isotope composition of the adsorbed fraction was correspondingly light, at an average δ26 Mg of -0.49‰. Secondary mineral precipitation and Mg adsorption onto secondary minerals had a minimal effect on Mg isotopes at these experimental conditions. Results demonstrate the isolated effects of cell surface reactivity on Mg isotope fractionation separate from other common biological processes, such as metabolism and organic acid production. With further study, Mg isotopes could be used to elucidate the role of the biosphere on Mg cycling in the environment.

Microbe Encapsulation for Selective Rare-Earth Recovery from Electronic Waste Leachates.

Rare earth elements (REEs) are indispensable components of many green technologies and of increasing demand globally. However, refining REEs from raw materials using current technologies is energy intensive and enviromentally damaging. Here, we describe the development of a novel biosorption-based flow-through process for selective REE recovery from electronic wastes. An Escherichia coli strain previously engineered to display lanthanide-binding tags on the cell surface was encapsulated within a permeable polyethylene glycol diacrylate (PEGDA) hydrogel at high cell density using an emulsion process. This microbe bead adsorbent contained a homogenous distribution of cells whose surface functional groups remained accessible and effective for selective REE adsorption. The microbe beads were packed into fixed-bed columns, and breakthrough experiments demonstrated effective Nd extraction at a flow velocity of up to 3 m/h at pH 4-6. The microbe bead columns were stable for reuse, retaining 85% of the adsorption capacity after nine consecutive adsorption/desorption cycles. A bench-scale breakthrough curve with a NdFeB magnet leachate revealed a two-bed volume increase in breakthrough points for REEs compared to non-REE impurities and 97% REE purity of the adsorbed fraction upon breakthrough. These results demonstrate that the microbe beads are capable of repeatedly separating REEs from non-REE metals in a column system, paving the way for a biomass-based REE recovery system.

Recovery of Rare Earth Elements from Geothermal Fluids through Bacterial Cell Surface Adsorption.

The increasing demand for rare earth elements (REEs) in the modern economy motivates the development of novel strategies for cost-effective REE recovery from nontraditional feedstocks. We previously engineered E. coli to express lanthanide binding tags on the cell surface, which increased the REE biosorption capacity and selectivity. Here we examined how REE adsorption by the engineered E. coli is affected by various geochemical factors relevant to geothermal fluids, including total dissolved solids (TDS), temperature, pH, and the presence of specific competing metals. REE biosorption is robust to TDS, with high REE recovery efficiency and selectivity observed with TDS as high as 165,000 ppm. Among several metals tested, U, Al, and Pb were found to be the most competitive, causing >25% reduction in REE biosorption when present at concentrations ∼3- to 11-fold higher than the REEs. Optimal REE biosorption occurred between pH 5-6, and sorption capacity was reduced by ∼65% at pH 2. REE recovery efficiency and selectivity increased as a function of temperature up to ∼70 °C due to the thermodynamic properties of metal complexation on the bacterial surface. Together, these data define the optimal and boundary conditions for biosorption and demonstrate its potential utility for selective REE recovery from geofluids.

Recovery of Rare Earth Elements from Low-Grade Feedstock Leachates Using Engineered Bacteria.

The use of biomass for adsorption of rare earth elements (REEs) has been the subject of many recent investigations. However, REE adsorption by bioengineered systems has been scarcely documented, and rarely tested with complex natural feedstocks. Herein, we engineered E. coli cells for enhanced cell surface-mediated extraction of REEs by functionalizing the OmpA protein with 16 copies of a lanthanide binding tag (LBT). Through biosorption experiments conducted with leachates from metal-mine tailings and rare earth deposits, we show that functionalization of the cell surface with LBT yielded several notable advantages over the nonengineered control. First, the efficiency of REE adsorption from all leachates was enhanced as indicated by a 2-10-fold increase in distribution coefficients for individual REEs. Second, the relative affinity of the cell surface for REEs was increased over all non-REEs except Cu. Third, LBT-display systematically enhanced the affinity of the cell surface for REEs as a function of decreasing atomic radius, providing a means to separate high value heavy REEs from more common light REEs. Together, our results demonstrate that REE biosorption of high efficiency and selectivity from low-grade feedstocks can be achieved by engineering the native bacterial surface.

Vitamin E increases biomarkers of estrogen stimulation when taken with tamoxifen.

BACKGROUND: Vitamin E (alpha-tocopherol acetate, AT) diminishes the antiproliferative effect of tamoxifen on breast cancer cells in vitro. METHODS: A prospective study of seven women taking tamoxifen for adjuvant therapy of breast cancer. Four who were already taking AT supplements had random core biopsies of the normal breast and again 30 days after discontinuing AT. Three who were not on AT had biopsies before and after adding AT 400 mg for 30 days. Biopsies were stained for estrogen receptor (ER) and the mitogen-activated protein kinase p-ERK. Tissue extracts were assayed for p-ERK by enzyme-linked immunosorbent assay. Serum levels of alpha-tocopherol and tamoxifen were measured. RESULTS: Five out of seven patients had lower tamoxifen levels while taking AT, four of these went to subtherapeutic levels. Biopsies showed 23% of ductal cells were ER positive when patients were off AT and 70% on AT (P = 0.02). P-ERK staining was 21% off AT and 82% on AT. Five of seven patients had significantly higher tissue p-ERK when on AT. CONCLUSIONS: Biomarkers of estrogen-stimulation (ER, progesterone receptor, and p-ERK) were higher in breast biopsies of women taking vitamin E supplements while taking tamoxifen. Findings suggest that vitamin E supplements may interfere with the therapeutic effects of tamoxifen.