Green Approach for Rare Earth Element (REE) Recovery from Coal Fly Ash.

Due to the growing demands of rare earth elements (REEs) and the vulnerability of REEs to potential supply disruption, there have been increasing interests in recovering REEs from waste streams such as coal fly ash (CFA). Meanwhile, CFA as a large industrial waste stream in the United States (U.S.) poses significant environmental and economic burdens. Recovery of REEs from CFA is a promising solution to the REE scarcity issue and also brings opportunities for CFA management. This study demonstrates a green system for REE recovery from Class F and C CFA that consists of three modules: REE leaching using citrate, REE separation and concentration using oxalate, and zeolite synthesis using secondary wastes from Modules I and II. In Module I, ∼10 and 60% REEs were leached from the Class F and C CFA samples, respectively, using citrate at pH 4. In Module II, the addition of oxalate selectively precipitated and concentrated REEs from the leachate via the formation of weddellite (CaC2O4·2H2O), while other trace metals remained in solution. In Module III, zeolite was synthesized using wastes from Modules I and II. This study is characterized by the successful recovery of REEs and upcycling of secondary wastes, which addresses both REE recovery and CFA management challenges.

Simultaneous oxidation of Mn(II) and As(III) on cupric oxide (CuO) promotes As(III) removal at circumneutral pH.

Oxidation of Mn(II) or As(III) by molecular oxygen is slow at pH < 9, while they can be catalytically oxidized in the presence of oxide minerals and then removed from contaminated water. However, the reaction mechanisms on simultaneous oxidation of Mn(II) and As(III) on oxide mineral surface and their accompanied removal efficiency remain unclear. This study compared Mn(II) oxidation on four common metal oxides (γ-Al2O3, CuO, α-Fe2O3 and ZnO) and investigated the simultaneous oxidation and removal of Mn(II) and As(III) through batch experiments and spectroscopic analyses. Among the tested oxides, CuO and α-Fe2O3 possess greater catalytic activity toward Mn(II) oxidation. Oxidation and removal kinetics of Mn(II) and As(III) on CuO indicate that O2 is the terminal electron acceptor for Mn(II) and As(III) oxidation on CuO, and Mn(II) acts as an electron shuttle to promote As(III) oxidation and removal. The main oxidized product of Mn(II) on CuO is high-valent MnOx species. This newly formed Mn(III) or Mn(IV) phases promote As(III) oxidation on CuO at circumneutral pH 8 and is reduced to Mn(II), which may be then released into solution. This study provides new insights into metal oxide-catalyzed oxidation of pollutants Mn(II) and As(III) and suggests that CuO should be considered as an efficient material to remediate Mn(II) and As(III) contamination.

Cancer cell-derived exosomal miR-425-3p induces white adipocyte atrophy.

White adipose tissue wasting plays a critical role in the development and progression of cancer cachexia. However, the mechanism behind the loss of adipose tissue remains ill-defined. In this study, we found that cancer cell-derived exosomes highly expressed miR-425-3p. Administration of cancer cell-derived exosomes significantly inhibited proliferation and differentiation of human preadipocytes-viscereal (HPA-v) cells. In mature adipocytes, cancer cell-derived exosomes activated cAMP/PKA signalling and lipophagy, leading to adipocyte lipolysis and browning of white adipocytes. These exosomes-induced alterations were almost abolished by endocytosis inhibitor cytochalasin D (CytoD) and antagomiR-425-3p, or reproduced by miR-425-3p mimics. In addition, bioinformatics analysis and luciferase reporter assay revealed that miR-425-3p directly targeted proliferation-related genes such as GATA2, IGFBP4, MMP15, differentiation-related gene CEBPA, and phosphodiesterase 4B gene (PDE4B). Depletion of PDE4B enhanced cAMP/PKA signalling and lipophagy, but had no effects on HPA-v proliferation and differentiation. Taken together, these results suggested that cancer cell-derived exosomal miR-425-3p inhibited preadipocyte proliferation and differentiation, increased adipocyte lipolysis, and promoted browning of white adipocytes, all of which might contribute to adipocyte atrophy and ultimately the loss of adipose tissue in cancer cachexia.Abbreviations: ADPN: adiponectin; aP2: adipocyte protein 2 or fatty acid binding protein 4 (FABP4); BCA: bicinchoninic acid assay; BFA: bafilomycin A1; BMI: body mass index; C/EBP: CCAAT/enhancer binding protein; CEBPA: CCAAT/enhancer-binding protein-alpha; C-Exo: cancer cell-derived exosomes; CNTL: control; CREB: cAMP-response element binding protein; CytoD: cytochalasin D; ECL: chemiluminescence; GATA2: GATA Binding Protein 2; HFD: high fat diet; HSL: hormone-sensitive lipase; IGFBP4: insulin like growth factor binding protein 4; IRS-1: insulin receptor substrate-1; ISO: isoproterenol hydrochloride; KD: knockdown; KO: knock out; LC3: microtubule-associated protein 1A/1B-light chain 3; LMF: lipid mobilizing factor; LPL: lipoprotein lipase; MMP15: matrix metallopeptidase 15; Mir-Inh-C-Exo: cancer cell-derived exosomes with miR-425-3p inhibition; mTOR: mammalian target of rapamycin; Mut: mutant; N-Exo: normal cell-derived exosomes; NSCLC: non-small cell lung cancer; PBS, phosphate buffered saline; PGC-1: peroxisome proliferator-activated receptor-gamma coactivator-1; PDEs: phosphodiesterases; PKI: PKA inhibitor; PKA: cAMP-dependent protein kinase; PLIN1: Perilipin 1; PTHRP: parathyroid hormone-related protein; PVDF: polyvinylidene difluoride; shRNA: short hairpin RNA; UCP1: uncoupling protein 1; WT: wild type.

Rethinking the biotic and abiotic remineralization of complex phosphate molecules in soils and sediments.

Phosphorus (P) is an essential macronutrient for all living organisms. Despite a diversity of P compounds in the environment, orthophosphate is the most bioavailable form of P. Remineralization of complex P molecules (e.g., organic P and phosphoanhydrides) into orthophosphate is traditionally considered to be carried out primarily by enzymes. Natural minerals are recently viewed to be abiotic catalysts (as compared to the organic phosphatases) to facilitate the cleavage of terminal P-O-C/P bonds and remineralization of complex P compounds. However, quantitative comparison between biotic and abiotic remineralization pathways of complex P molecules is still missing, impeding our capability to assess the importance and contribution of abiotic P remineralization in the environment. This study compares the hydrolysis rates of six organic phosphates and three inorganic phosphoanhydrides by representative enzymes (acid and alkaline phosphatases) and natural oxide minerals (hematite, birnessite, and boehmite). The results show that enzymes and minerals have different substrate preferences. Specifically, alkaline phosphatase hydrolyzes phosphate monoesters faster than phosphoanhydrides, whereas acid phosphatase and minerals show higher hydrolysis rates toward phosphoanhydrides than phosphate monoesters. Although the hydrolysis rates by enzymes (~µM hr-1) are orders of magnitude higher than those by minerals (~µM d-1), normalization of the rates by the natural abundance of enzymes and minerals leads to comparable contributions of both processes in soils and sediments. These results highlight the significance of natural minerals in the remineralization of complex P compounds, a process that was traditionally overlooked but with important implications for constraining P biogeochemical cycling in the environment.

Experimental Study on Diesel Engine Emission Characteristics Based on Different Exhaust Pipe Coating Schemes.

The thermal insulation performance of exhaust pipes coated with various materials (basalt and glass fiber materials) under different braiding forms (sleeve, winding and felt types) and the effects on the emission characteristics of diesel engines were experimentally studied through engine bench tests. The results indicated that the thermal insulation performance of basalt fiber was higher than that of glass fiber, and more notably advantageous at the early stage of the diesel engine idle cold phase. The average temperature drop during the first 600 s of the basalt felt (BF) pipe was 2.6 °C smaller than that of the glass fiber felt (GF) pipe. Comparing the different braiding forms, the temperature decrease in the felt-type braided material was 2.6 °C and 2.9 °C smaller than that in the sleeve- and winding-type braided materials, respectively. The basalt material was better than the glass fiber material regarding the gaseous pollutant emission reduction performance, especially in the idling cold phase of diesel engines. The NOx conversion rate of the BF pipe was 7.4% higher than that of the GF pipe, and the hydrocarbon (HC) conversion rate was 2.3% higher than that of the GF pipe, while the CO conversion rate during the first 100 s was 24.5% higher than that of the GF pipe. However, the particulate matter emissions were not notably different.

Multiprincipal Component P2-Na0.6(Ti0.2Mn0.2Co0.2Ni0.2Ru0.2)O2 as a High-Rate Cathode for Sodium-Ion Batteries.

Mixing transition metal cations in nearly equiatomic proportions in layered oxide cathode materials is a new strategy for improving the performances of Na-ion batteries. The mixing of cations not only offers entropic stabilization of the crystal structure but also benefits the diffusion of Na ions with tuned diffusion activation energy barriers. In light of this strategy, a high-rate Na0.6(Ti0.2Mn0.2Co0.2Ni0.2Ru0.2)O2 cathode was designed, synthesized, and investigated, combining graph-based deep learning calculations and complementary experimental characterizations. This new cathode material delivers high discharge capacities of 164 mA g-1 at 0.1 C and 68 mAh g-1 at a very high rate of 86 C, demonstrating an outstanding high rate capability. Ex situ and operando synchrotron X-ray diffraction were used to reveal the detailed structural evolution of the cathode upon cycling. Using the climbing-image nudged elastic-band calculation and Ab initio molecular dynamics simulations, we show that the optimal transition metal composition enables a percolating network of low barrier pathways for fast, macroscopic Na diffusion, resulting in the observed high rate performance.

Comparative assessment of pre- and inter-stage hydrothermal treatment of municipal sludge for increased methane production.

Hydrothermal treatment (HT) is a promising technology to enhance anaerobic digestion (AD) of municipal sludge. However, the capacity of pre- and inter-stage HT (i.e., HT-AD and AD-HT-AD, respectively) to enhance the digestibility of municipal sludge has not been sufficiently explored. This study compared the efficacy of pre- and inter-stage HT performed from 90 to 185°C to enhance methane production from a mixture of primary sludge and waste activated sludge using mesophilic (35°C) biochemical methane potential tests. In both configurations, sludge solubilization increased with HT temperature. HT-AD, and to a greater extent AD-HT-AD, increased the release of ammonium nitrogen. Even though HT at 185°C dramatically increased sludge solubilization, the overall specific methane yield with HT at 185°C was lower than or comparable to that at lower HT temperatures in the HT-AD and AD-HT-AD configurations, respectively. Up to 155°C HT, the overall specific methane yield with the HT-AD configuration was higher by 4.9%-8.3% compared to the AD-HT-AD configuration. However, when the HT energy was considered, compared to the control (i.e., AD of sludge without HT), the net energy gain (ΔE) decreased as the HT temperature increased, becoming negative at an HT of 185°C. The AD-HT-AD configuration resulted in a higher overall volatile solids destruction (by 8.1 to 20.1%). In conclusion, for municipal sludge with a relatively high ultimate digestibility, as was the case in this study, HT-AD is preferable as it has a smaller footprint and is easier to operate than the AD-HT-AD configuration. However, given the significantly higher volatile solids destruction in the AD-HT-AD configuration, compared to the HT-AD configuration, AD-HT-AD may be more beneficial considering post-AD sludge handling processes. PRACTITIONER POINTS: Hydrothermal treatment (HT) increased the rate and extent of methane production from municipal sludge mixture. 155°C was the optimal temperature for either pre- or inter-stage HT to increase biogas production. Pre- and inter-stage HT resulted in comparable ultimate methane production. Pre-stage HT is preferable to inter-stage HT (smaller footprint, easier to operate). AD-HT-AD resulted in significantly higher volatile solids destruction compared to the HT-AD configuration.

Transformation and Mobility of Cu, Zn, and Cr in Sewage Sludge during Anaerobic Digestion with Pre- or Interstage Hydrothermal Treatment.

Anaerobic digestion (AD) combined with hydrothermal treatment (HT) is an attractive technology for sewage sludge treatment and resource recovery. The fate and distribution of heavy metals in the sludge during combined HT/AD significantly affect the sludge final disposal/utilization options, yet such information is still lacking. This study systematically characterizes the transformation of important heavy metals Cu, Zn, and Cr in sewage sludge during AD with pre- or interstage HT (i.e., HT-AD or AD-HT-AD, respectively). Complementary sequential chemical extraction and X-ray absorption spectroscopy were used to characterize the speciation and mobility of metals. For the HT-AD system, both Cu and Zn predominantly occur as sulfides in HT hydrochars. Subsequent AD favors the formation of Cu2S and partial transformation of nano-ZnS to adsorbed and organo-complexed Zn species. HT favors the formation of Cr-bearing silicates in hydrochars, whereas Fe(III)-Cr(III)-hydroxide and Cr(III)-humic complex are the predominant Cr species in AD solids. Similar reaction pathways occur in the AD-HT-AD system with some minor differences in metal species and contents, as the first-stage AD changed the sludge matrix. These findings have important implications for understanding the fate and mobility of heavy metals in sludge-derived hydrochars and AD solids.

Thermochemistry of sulfur during pyrolysis and hydrothermal carbonization of sewage sludges.

Sulfur (S) is an abundant and redox-active element in urban wastewater systems and plays a critical role in both the wastewater and sludge treatment processes. This study comparatively characterized the transformation of S and several closely associated metals (Cu, Zn, and Fe) during pyrolysis (250 to 750 °C) and hydrothermal carbonization (HTC, 150 to 275 °C) treatments of sewage sludge. S, Fe, Zn, and Cu K-edge X-ray absorption spectroscopy was applied to quantitatively evaluate the fate of S and contribution of different S species in regulating metal speciation. During pyrolysis, aliphatic-S and sulfonate were preferentially degraded at low temperature (below 350 °C) and sulfate was thermochemically reduced at temperature above 450 °C, while metal sulfides (up to 27%) and thiophenes (up to 70%) were increasingly formed. Similar to the pyrolysis process, metal sulfides (up to 40% at temperature above 200 °C) and thiophenes were formed during HTC. The degradation of thiols and organic sulfide, as well as sulfate reduction, released sulfide and strongly affected metal speciation. For example, almost all Cu and half of Zn were transformed into Cu-Fe- or Zn-Fe-sulfides during HTC, whereas they were partially desulfidized during pyrolysis. High abundance of reduced S species (S-1 and S-2) in hydrochars may contribute to their strong reductive adsorption of Cr(VI). Results from this work reveal the thermochemical reactions driving the transformations of S and its associated metals during pyrolysis and HTC. The results provide fundamental knowledge for selecting thermochemical sludge treatment techniques for value-added applications of the products.

Coevolution of Iron, Phosphorus, and Sulfur Speciation during Anaerobic Digestion with Hydrothermal Pretreatment of Sewage Sludge.

Anaerobic digestion (AD) with hydrothermal (HT) pretreatment is an emerging technology for enhanced resource recovery from sewage sludge. This study investigates the speciation of Fe, P, and S during sequential HT-AD treatment of sewage sludge using sequential chemical extraction, X-ray diffraction, and X-ray absorption spectroscopy. Results suggest strong correlations between Fe and P species as well as Fe and S species, affecting the solubility and bioavailability of each other. For instance, much vivianite formed in the hydrochars after HT treatment at low temperature, while more strengite precipitated at higher HT temperature. During the subsequent AD process, microbial reduction of strengite and other Fe(III) species led to the formation of more vivianite, with concurrent P release into the solution and adsorption onto other minerals. HT pretreatment of sewage sludge had a weak effect on the sulfidation of Fe during the AD process. This work has important implications for understanding the nutrient speciation and availability in sludge-derived hydrochars and AD solids. It also provides fundamental knowledge for the selection and optimization of HT pretreatment conditions for enhanced resource recovery through sequential HT-AD process.

Redox Cycling Driven Transformation of Layered Manganese Oxides to Tunnel Structures.

Mn oxides are among the most ubiquitous minerals on Earth and play critical roles in numerous elemental cycles in biotic/abiotic loops as the key redox center. Yet, it has long puzzled geochemists why the laboratory synthesis of todorokite, a tunnel-structured Mn oxide, is extremely difficult while it is the dominant form over other tunneled phases in low-temperature natural environments. This study employs a novel electrochemical method to mimic the cyclic redox reactions occurring over long geological time scales in an accelerated manner. The results revealed that the kinetics and electron flux of the cyclic redox reaction are key to the layer-to-tunnel structure transformation of Mn oxides, provided new insights for natural biotic and abiotic redox reactions, and explained the dominance of todorokite in nature.

Energy and Nutrient Recovery from Sewage Sludge and Manure via Anaerobic Digestion with Hydrothermal Pretreatment.

Global expectation for sustainability has prompted the transition of practices in wastewater treatment plants toward not only waste management but also energy and nutrient recovery. It has been shown that low-temperature hydrotherm (HT) treatment can enhance downstream biogas production via anaerobic digestion (AD). Yet, because the application of combined HT and AD is still at an early stage, a systematic understanding of the dynamic speciation evolution of important elements is still lacking. This study investigates energy and nutrient recovery from sewage sludge and swine manure via combined HT-AD treatment. Bench-scale investigation was conducted to evaluate biogas production and understand the dynamic evolution of organic carbon (C) and phosphorus (P) speciation. C and P speciations were characterized using complementary chemical and spectroscopic techniques, including 13C nuclear magnetic resonance (NMR) spectroscopy, P X-ray absorption near edge structure (XANES) spectroscopy, and sequential chemical extraction. Results from this study suggest that low-temperature HT pretreatment can achieve enhanced biogas production for sludge compared to the minimal effect on the biogas production from manure. It also provides guidance for P recovery from liquid digestate and solid residue after the AD process.

Polyphosphate Adsorption and Hydrolysis on Aluminum Oxides.

The geochemical behaviors of phosphate-containing species at mineral-water interfaces are of fundamental importance for controlling phosphorus mobility, fate, and bioavailability. This study investigates the sorption and hydrolysis of polyphosphate (a group of important long-chained phosphate molecules) on aluminum oxides in the presence of divalent metal cations (Ca2+, Cu2+, Mg2+, Mn2+, and Zn2+) at pH 6-8. γ-Al2O3 with three particle sizes (5, 35, and 70 nm) was used as an analogue of natural aluminum oxides to investigate the particle size effect. All metal cations enhanced polyphosphate hydrolysis at different levels, with Ca2+ showing the most significant enhancement, and the difference in the enhancement might be due to the intrinsic affinity of metal cations to polyphosphate. In the presence of Ca2+, the hydrolysis rate decreased with increasing mineral particle size. Solid-state 31P nuclear magnetic resonance spectroscopy (NMR) revealed the main surface P species to be amorphous calcium phosphate precipitates, phosphate groups in polyphosphate that formed direct bonds with the mineral surface as inner-sphere complexes, and phosphate groups in polyphosphate that were not directly bonded to the mineral surfaces. Our results reveal the critical roles of mineral-water interface processes and divalent metal cations on controlling polyphosphate speciation and transformation and phosphorus cycling.

Lithium-Doping Stabilized High-Performance P2-Na0.66Li0.18Fe0.12Mn0.7O2 Cathode for Sodium Ion Batteries.

While sodium-ion batteries (SIBs) hold great promise for large-scale electric energy storage and low speed electric vehicles, the poor capacity retention of the cathode is one of the bottlenecks in the development of SIBs. Following a strategy of using lithium doping in the transition-metal layer to stabilize the desodiated structure, we have designed and successfully synthesized a novel layered oxide cathode P2-Na0.66Li0.18Fe0.12Mn0.7O2, which demonstrated a high  capacity of 190 mAh g-1 and a remarkably high capacity retention of ∼87% after 80 cycles within a wide voltage range of 1.5-4.5 V. The outstanding stability is attributed to the reversible migration of lithium during cycling and the elimination of the detrimental P2-O2 phase transition, revealed by ex situ and in situ X-ray diffraction and solid-state nuclear magnetic resonance spectroscopy.

Enhanced adsorption and slow release of phosphate by dolomite-alginate composite beads as potential fertilizer.

The recovery and reuse of phosphorus (P) from wastewater treatment process is a critical and viable target for sustainable P utilization. This study explores a novel approach of integrating ultrafine mineral particles into hydrogel matrixes for enhancing the capacity of phosphate adsorption. Dolomite-alginate (DA) hydrogel beads were prepared by integrating ball-milled, ultrafine dolomite powders into calcium cross-linked alginate hydrogel matrix. The adsorption isotherms followed a Langmuir-Freundlich adsorption model with higher specific adsorption capacity than those reported in literature. The kinetics of phosphate adsorption suggest that the adsorption is diffusion controlled. Investigation of adsorption capacity at different pH showed a maximum adsorption capacity in the pH range of 7-10. Lastly, we demonstrated that the DA beads are capable of slowly releasing most of the adsorbed phosphate, which is an important criterion for them to be an effective phosphorous fertilizer. This study, using DA composite hydrogel as an example, demonstrates a promising strategy of immobilizing ultrafine mineral adsorbents into biocompatible hydrogel matrix for effective recovery of phosphorous resource from wastewater. PRACTITIONER POINTS: Integration of dolomite and alginate hydrogel beads is demonstrated using ball milling. Ball milling process increases the specific adsorption capacity of dolomite on phosphorus. Adsorption isotherms, kinetics, and pH effects of the dolomite-alginate beads are investigated. The dolomite-alginate beads can be used as slow-release phosphorus fertilizer.

Preferential utilization of inorganic polyphosphate over other bioavailable phosphorus sources by the model diatoms Thalassiosira spp.

Polyphosphates and phosphomonoesters are dominant components of marine dissolved organic phosphorus (DOP). Collectively, DOP represents an important nutritional phosphorus (P) source for phytoplankton growth in the ocean, but the contribution of specific DOP sources to microbial community P demand is not fully understood. In a prior study, it was reported that inorganic polyphosphate was not bioavailable to the model diatoms Thalassiosira weissflogii and Thalassiosira pseudonana. However, in this study, we show that the previous finding was a misinterpretation based on a technical artefact of media preparation and that inorganic polyphosphate is actually widely bioavailable to Thalassiosira spp. In fact, orthophosphate, inorganic tripolyphosphate (3polyP), adenosine triphosphate (ATP) and adenosine monophosphate supported equivalent growth rates and final growth yields within each of four strains of Thalassiosira spp. However, enzyme activity assays revealed in all cultures that cell-associated hydrolysis rates of 3polyP were typically more than ~10-fold higher than degradation of ATP and the model phosphomonoester compound 4-methylumbelliferyl phosphate. These results build on prior work, which showed the preferential utilization of polyphosphates in the cell-free exudates of Thalassiosira spp., and suggest that inorganic polyphosphates may be a key bioavailable source of P for marine phytoplankton.

Biogeochemical fate of ferrihydrite-model organic compound complexes during anaerobic microbial reduction.

Associations of organic carbon (OC) with iron (Fe) oxide minerals play an important role in regulating the stability of OC in soil environments. Knowledge about the fate and stability of Fe-OC complexes is impaired by the heterogeneity of OC. Additional biogeochemical variables in soil environments, such as redox conditions and microbes, further increase complexity in understanding the stability of mineral-associated soil OC. This study investigated the fate and stability of model organic compounds, including glucose (GL), glucosamine (GN), tyrosine (TN), benzoquinone (BQ), amylose (AM), and alginate (AL), complexed with an Fe oxide mineral, ferrihydrite (Fh), during microbial reduction. During a 25-d anaerobic incubation with Shewanella putrefaciens CN32, the reduction of Fe followed the order of Fh-BQ > Fh-GL > Fh-GN > Fh-TN > Fh-AL > Fh-AM. In terms of OC released during the anaerobic incubation, Fh-GN complexes released the highest amount of OC while Fh-AM complexes released the lowest. Organic carbon regulated the reduction of Fe by acting as an electron shuttle, affecting microbial activities, and associating with Fh. Benzoquinone had the highest electron accepting capacity, but potentially can inhibit microbial activity. These findings provide insights into the roles of different organic functional groups in regulating Fe reduction and the stability of Fh-bound OC under anaerobic conditions.

Comprehensive Understandings of Rare Earth Element (REE) Speciation in Coal Fly Ashes and Implication for REE Extractability.

In recent years, recovery of rare earth elements (REEs) from coal fly ashes (CFAs) has been considered as a promising resource recovery option. Yet, quantitative information on REE speciation in CFAs and its correlation with REE extractability are not well established. This study systematically investigated the REE speciation-extractability relationship in four representative CFA samples by employing multiple analytical and spectroscopic techniques across the micro to bulk scale and in combination with thermodynamic calculations. A range of REE-bearing phases are identified, such as REE oxides, REE phosphates, apatite, zircon, and REE-bearing glass phase. REEs can occur as discrete particles, as particles encapsulated in the glass phase, or distribute throughout the glass phase. Although certain discrepancies exist on the REE speciation quantified by X-ray adsorption spectroscopy and acid leaching due to intrinsic limitations of each method, both approaches show significant fractions of REE oxides, REE phosphates, apatite, and REE-bearing Fe oxides. This study contributes to an in-depth understanding of the REE speciation-distribution-extractability relationship in CFAs and can help identify uncertainties associated with the quantification of REE speciation. It also provides a general methodology for future studies on REE speciation in complex environmental samples and a knowledge basis for the development of effective REE recovery techniques.

Formation of Zn-Al layered double hydroxides (LDH) during the interaction of ZnO nanoparticles (NPs) with γ-Al2O3.

Zinc and aluminum layered double hydroxides (Zn-Al LDH) are a common group of major Zn species in various Zn-contaminated soil/sediment environments, yet their formation pathways and underlying mechanisms under varied conditions are not well understood. This study investigated the formation of Zn-Al LDHs through the direct interaction of two solid substrates, ZnO nanoparticles (NPs) and a representative Al oxide, γ-Al2O3. Batch experiments and complementary microscopic and spectroscopic analyses were conducted to elucidate the reaction kinetics and mechanisms, as well as the morphologic and structural evolution of the products. Dissolved Zn and Al concentrations decreased significantly in a dual solid system compared to a single solid system. A bulk Zn-Al LDH phase was found to form under a wide pH range (6.5-9.5). Aside from Zn-Al LDH, γ-Al2O3 was the main remaining solid phase at pH 6.5, whereas ZnO NPs were the main residual solid phases at pH 9.5. Formation of amorphous Zn(OH)2 was also observed at both pH values, likely due to Zn2+ release at low pH and Al(OH)4- adsorption at high pH. It is proposed that the formation of Zn-Al LDH occurs via a dissolution-sorption-coprecipitation process, where the solubility of ZnO NPs or γ-Al2O3 solid phases determines the reaction pathways and kinetics under varied pH conditions. The results from this work revealed the transformation mechanisms for ZnO NPs under conditions from weakly acidic to alkaline pH with highly available Al particles and shed light on the environmental fate of ZnO NPs in Zn or ZnO NP contaminated environments.

Effect of Manganese Oxide Aging and Structure Transformation on the Kinetics of Thiol Oxidation.

The kinetics and mechanism of thiol oxidation by Mn oxides undergoing dynamic structural transformation under environmentally relevant conditions remain poorly understood. In this study, thiol/disulfide pair concentrations were simultaneously determined in situ using voltammetric microelectrodes during the interaction of four common thiols (cysteine, homocysteine, cysteamine, and glutathione) with fresh and aged δ-MnO2 at pH 7.0. The reaction kinetics was first order with respect to thiol and zero order with respect to Mn oxides. A transient intermediate sulfur surface species observed during the reaction provides evidence for a mechanism involving two successive one-electron transfer steps. The reaction kinetics of fresh and aged δ-MnO2 was investigated with cysteine and compared to that of manganite, a Mn(III) oxyhydroxide phase. The reactivity of aged δ-MnO2 decreased as a result of structural transformation to cryptomelane but remained higher than that of manganite, suggesting the potential roles of transient Mn(III) surface intermediate in promoting the reduction of Mn(IV) in δ-MnO2 and cryptomelane (compared to Mn(III) in manganite). This study demonstrates the importance of correlating Mn oxide mineral structure and redox reactivity and extends the potential for thiols commonly found in sedimentary environments to be utilized as electron shuttles during dissimilatory Mn reduction.