ZIF-8 Used for the Selective Recovery of Heavy Rare Earth Elements from Mining Wastewater.

In this study, a sample of 2-methylimidazole zinc salt (ZIF-8) demonstrated high selectivity for the recovery of heavy rare earth elements (REEs) from real rare earth mining wastewater. Results show that the distribution coefficient values of Y3+ (4.02 × 104 mL·g-1), Gd3+ (7.8 × 104 mL·g-1), and Dy3+ (6.8 × 104 mL·g-1) are orders of magnitude higher than those of K+ (359.51 mL·g-1), Mn2+ (266.67 mL·g-1), Ca2+ (396.42 mL·g-1), and Mg2+ (239.48 mL·g-1). Moreover, the desorption efficiency of heavy REEs exceeded 40%. Advanced characterizations and density functional theory (DFT) calculations were utilized to elucidate that the heavy REEs were more likely to bind to the nitrogen atoms of imidazole groups on ZIF-8 compared to non-REEs. Furthermore, the adsorption and desorption of heavy REEs primarily depend on the chemical interaction confirmed by adsorption kinetics, isotherm model, and thermodynamic analysis, which involves the dissociation of water and the formation of REE-O bonds. Finally, the ZIF-8 exhibits a remarkable recovery efficiency of over 40% for heavy REEs in column tests conducted over 7h. The findings reported here provide new insights into the selective recovery of heavy REEs from real mining wastewater.

Green rGO/FeNPs nanocomposites activated peroxydisulfate for the removal of mixed 17ß-estradiol and estriol.

Reduced graphene oxide/iron nanoparticles (rGO/FeNPs) synthesized by the chemical method have been used in Fenton oxidation of organic contaminants, yet little is known about biosynthesized rGO/FeNPs using green tea extract (GT) as how to activate persulfate in sulfate radical-based advanced oxidation processes. In this study, rGO/FeNPs were used to activate peroxydisulfate (PDS) for 17ß-estradiol (ßE2) and estriol (E3) removal. The rGO/FeNPs-PDS system removed 83.6% of ßE2 and 62.5% of E3 within 240 min, which was confirmed by a combination of adsorption and degradation via both radical and non-radical pathways. Four main reactive species in ßE2 and E3 degradation were observed, i.e., hydroxyl radical (·OH), sulfate radical (SO4·-), singlet oxygen (1O2) and electron transfer, with the respective contributions of ·OH (32.9 and 34.7%), SO4·- (16.1 and 19.7%), 1O2 (12.2 and 14.1%) and electron transfer (8.0 and 7.2%). Analysis of X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR), Electron Paramagnetic Resonance (EPR) and electrochemical measurements all indicated that beside the well-known role of Fe, CO from rGO through the generation of ·OH, SO4·-, 1O2 and electron transfer, as well as GT through electron transfer also participated in the activation of PDS. Finally, the degradation pathways of ßE2/E3 were proposed. Overall, this study provides a new insight into the biosynthesis of rGO/FeNPs to activate PDS for the oxidation of mixed emerging contaminants.

Uptake and transport mechanisms of rare earth hyperaccumulators: A review.

Due to their use in a number of advanced electronic technologies, Rare earth elements (REEs) have recently emerged as a key strategic resource for many nations worldwide. The significant increase in demand for REEs has thus greatly increased the mining of these substances, but this industrial-scale expansion of mining activities also poses potential risks to the surrounding environment, flora, fauna, and humans. Hence efficient REE remediation is one potential remediation process involving in situ clean-up of contaminated soil which has gained much attention in recent years, due to its low cost and lack of secondary pollution. However, some crucial aspects of phytoremediation, such as the precise-mechanisms of absorption, transport, and tolerance of REEs by hyperaccumulators -are poorly understood. This review briefly discusses the environmental risks associated with excess REEs, the efficacy of phytoremediation technologies coupled with, appropriate hyperaccumulator species to migrate REEs exposure. While REEs hyperaccumulator species should ideally be large-biomass trees and shrubs suitable for cropping in subtropical regions areas, such species have not yet been found. Specifically, this review focuses on the factors affecting the bioavailability of REEs in plants, where organic acids are critical ligands promoting efficient transport and uptake. Thus the uptake, transport, and binding forms of REEs in the above-ground parts of hyperaccumulators, especially the transporters isolated from the heavy metal transporter families, are discussed in detail. Finally, having summarized the current state of research in this area, this review proceeds to discuss current knowledge gaps and research directions. With a focus on hyperaccumulators, this review serves as a basis for future phytoremediation strategies of rare earth mining-impacted environments and addresses ecosystem/environmental degradation issues resulting from such mining activity.

Burkholderia cepacia immobilized onto rGO as a biomaterial for the removal of naphthalene from wastewater.

As one of the polycyclic aromatic hydrocarbons (PAHs), naphthalene is of serious environmental concern due to its carcinogenicity, persistence and refractory degradation. In this study, a new functional biomaterial based on Burkholderia cepacia (BK) immobilized on reduced graphene oxide (rGO) was prepared, resulting in the removal of 99.0% naphthalene within 48 h. This was better than the 67.3% for free BK and 55.6% for rGO alone. Various characterizations indicated that reduced graphene oxide-Burkholderia cepacia (rGO-BK) was successfully synthesized and secreted non-toxic and degradable surfactants which participated in the degradation of naphthalene. The adsorption kinetics and degradation kinetics conformed best to non-linear pseudo-second-order and pseudo-first-order kinetic models, respectively. Demonstrated in this work is that removing naphthalene by rGO-BK involved both chemically dominated adsorption and biodegradation. As well, GC-MS analysis revealed two things: firstly, that the degraded products of naphthalene were dibutyl phthalate, diethyl phthalate, phthalic acid, and benzoic acid; and secondly, two potentially viable biodegradation pathways of naphthalene by rGO-BK could be proposed. Finally, for practical application experiment, the rGO-BK was exposed to river water samples and generated 99% removal efficiency of naphthalene, so this study offers new insights into biomaterials that can remove naphthalene.

Transport and distribution of residual nitrogen in ion-adsorption rare earth tailings.

A large amount of nitrogen remains in ion-absorption rare earth tailings with in-situ leaching technology, and it continually ends up in groundwater sources. However, the distribution and transport of ammonium nitrogen (NH4+-N) and nitrate nitrogen (NO3--N) across tailings with both depth and hill slopes is still unknown. In this study, the amount of NH4+-N and nitrate nitrogen (NO3--N) was determined in tailings, and a soil column leaching experiment, served to assess the transport and distribution following mine closure. Firstly, a high concentration of NH4+-N in the leachate at the initial leaching stage was detected, up to 2000 mg L-1, and the concentration of NH4+-N clearly diminished as time passed. Meanwhile, the NH4+-N contents remained relatively high in soil. Secondly, both the content of NH4+-N and NO3--N varied greatly according to vertical distribution after leaching lasting several years. The amounts of NH4+-N and NO3--N in surface soil were much smaller than those in deep soil, with 3-4 orders of magnitude variation with depth. Thirdly, when disturbed by NH4+-N, the pH not only diminished but also changed irregularly as depth increased. Fourthly, although the amount of NO3--N was smaller than that of NH4+-N, both their distribution trend was similar with depth. In fact, NH4+-N and NO3--N were significantly correlated but this declined from the knap to the piedmont. Based on these results, it is suggested that mining activity could cause nitrogen to be dominated by NH4+-N and acidification in a tailing even if leaching occurs over several years. NO3--N derived from NH4+-N transports easily and it becomes the main nitrogen pollutant with the potential to be a long-lasting threat to the environment around a mine.

Bionanocomposite based on immobilization of Burkholderia cepacian on GO/MOF and its removal of malachite green from river water.

Bio-nanocomposites have attracted increasing research attention because they are able to integrate bio- and nano-related functions, and subsequently demonstrate potentially beneficial environmental applications. Here, a functional bionanomaterial based on Burkholderia cepacian (FZ) immobilized on GO/ZIF-8 was developed and used to remove malachite green (MG), with functions based on both biodegradation and adsorption. XRD and FTIR results showed that in situ production of GO/ZIF-8 by combining Zn2+ in ZIF-8 with the carboxyl group on the GO surface, led to FZ immobilized in GO/ZIF-8 through covalent bonding. Zeta analysis showed that the surface of FZ and GO/ZIF-8 had different charges under pH = 9.12, suggesting immobilization also occurred via electrostatic action. BET results confirmed that the specific surface area of GO/ZIF-8 was much larger than that of GO and ZIF-8, but the reduced specific surface area of FZ@GO/ZIF-8 could be due to FZ loading on its surface. The efficiency of FZ@GO/ZIF-8 in the removal of MG reached 99% and furthermore retained good stability after five cycles. The efficiency in removing multiple ions in river water reached more than 80%, which is evidence strongly suggesting that FZ@GO/ZIF-8 is an environmental bionanomaterial with effective application potential.

Biosynthesis of bionanomaterials using Bacillus cereus for the recovery of rare earth elements from mine wastewater.

The growing demand for rare earth elements (REEs) increasingly requires secondary resources such as mine wastewater containing high concentrations of REEs, to be used as a source of REEs. The current challenge is how to efficiently recover REEs from this feed source. In this paper, a functional bionanomaterial (FeNPs-EPS) was biosynthesized using Bacillus cereus as a possible means of recovering REEs. This composite was composed of both synthesized iron nanoparticles (FeNPs) and extracellular polymeric substances (EPS). Synthesis of the FeNPs-EPS composite via a one-step biosynthesis was confirmed by materials characterization. The peak in the material's UV-Vis spectra at 511 nm demonstrates the formation of FeNPs-EPS, where 3D-EEM showed that FeNPs-EPS was wrapped predominantly with tryptophan protein-like and humic acid-like substances. In addition, while FTIR indicated that the functional groups present in EPS where virtually identical to those observed in FeNPs-EPS, XPS demonstrated that Fe and O were the major elemental present as both FeO and Fe2O3. Zeta potential measurements indicated that FeNPs-EPS had good stability under different pH conditions, where BET analysis supported multilayer adsorption. Finally, on exposure to high concentrations of Eu(III) and Tb(III) in mine wastewater, the synthesized FeNPs-EPS demonstrated strong potential to remove two cations from the wastewater and hence a potentially practical way to efficiently recover REEs from such waste streams.

The origins of potentially superior properties and multifunctionalities of carbon-nano zero-valent iron in the carbonization pyrolysis process.

Although carbon-nano zero-valent iron (C@nZVI) composites with unique properties have been used for environmental remediation, the origins of their superior properties and multifunctionalities of C@nZVI still need to be verified. Here, iron precursor nanoparticles (PML-Fe NPs) synthesized by Pinus massoniana Lamb and carbonized C@nZVI were systemically compared to reveal the origins of the structure and performance of C@nZVI composites. Characterizations showed that structure-modulated C@nZVI has favorable properties of good crystallinity, graphite carbon-rich structure but also defects when compared to PML-Fe NPs. The resultant carbon layer fundamentally improved its dispersion and anti-oxidation properties. Further experiments demonstrated that the evolution of material crystallinity, graphitization and defects affected the reaction pathway of hexavalent chromium (Cr(VI)), oxytetracycline hydrochloride (OTC), and 17ß-estradiol (ßE2). The multifunctionalities covered adsorption, reduction and catalytic oxidation. This study explains the origins of multifunctional C@nZVI by understanding the structure-property correlation in the carbonization process.

Biosynthesis of silver nanoparticles using three different fruit extracts: Characterization, formation mechanism and estrogen removal.

Plant-mediated synthesis of silver nanoparticles (Ag NPs) is a green and economically viable method, which can offer numerous benefits over traditional chemical and physical methods. In this paper, three fruit extracts (tomato, orange, and grapefruit) served simultaneously as stabilizing and reducing agents during the biosynthesis of Ag NPs. The formation of Ag NPs, were monitored using the UV-visible absorption spectra of Ag NPs which exhibited three distinct bands centered at 439, 413, and 410 nm. SEM and TEM analysis indicated that these bands corresponded to three distinct spherical-shaped Ag NPs having average particle sizes of 73, 24, and 31 nm, respectively. XRD and EDS spectral analyses were used to verify the degree of crystallinity, nanostructure, and presence of Ag NPs. Advanced analysis using XPS, FTIR, and GC-MS indicated that the Ag NPs were coated with a variety of organic compounds including acids, aldehydes, esters, and ketones, indicating that fruit derived phytochemicals had a significant role in synthesis, and subsequently a mechanism of Ag NPs formation was proposed. The fabricated nanoparticles were also successfully used in Fenton-like oxidation for the environmental remediation of estrone and estriol, with removal efficiencies of 52.1 and 35.9%, respectively.

Enhanced removal of oxytetracycline from wastewater using bimetallic Fe/Ni nanoparticles combined with ZIF-8 nanocomposites.

The integration of metal-organic frameworks with other functional materials has recently emerged as a promising approach for creating innovative materials for environmental remediation. Here, a nano-sized iron/nickel (Fe/Ni) functionalized zeolitic imidazolate framework-8 (ZIF-8-Fe/Ni) was fabricated for oxytetracycline (OTC) removal from wastewater. Cyclic voltammetry and amperometric I-t measurements indicated that OTC was degraded by ZIF-8-Fe/Ni. X-ray diffraction spectroscopy (XRD), transmission electron microscopy mapping (TEM-mapping) and X-ray photoelectron spectroscopy (XPS) indicated that Fe/Ni was evenly dispersed throughout ZIF-8 and partially oxidized after reaction with OTC. OTC adsorption isotherms and kinetics best fitted the Langmuir isotherm (R2 > 0.982) and pseudo-second-order model (R2 > 0.997), respectively. Reduction kinetics data followed the pseudo-first-order model (R2 > 0.905), where the apparent activation energy (Ea) was 22.9 kJ mol-1, demonstrating that OTC degradation was mainly via a chemical process. The practical removal efficiency of OTC from real wastewater by ZIF-8-Fe/Ni was 92.6%, where even after application of ZIF-8-Fe/Ni for 5 consecutive removal cycles, a high OTC removal of 74.9% was maintained. Thus ZIF-8-Fe/Ni exhibited both high removal efficiency and good recyclability.

Bimetallic Fe/Ni nanoparticles derived from green synthesis for the removal of arsenic (V) in mine wastewater.

Since the incidences of arsenicosis have significantly increased worldwide in the last decade, remediation of arsenic (As) pollution is now imperative. In this study, calcined green synthesized Fe/Ni nanoparticles (C-Fe/Ni NPs) were evaluated for their efficacy for As (V) removal from aqueous solution. Under optimal experimental conditions As (V) removal efficiency reached 87.3%. Analysis of changes in the surface properties of C-Fe/Ni NPs before and after interaction with As (Ⅴ) using a range of advanced characterization techniques including IC-AFS, SEM-EDS, XPS and XRD revealed that the As removal mechanism involved only adsorption. Adsorption kinetics followed a pseudo-second order rate model (R2 > 0.986) and adsorption best fit the Langmuir isotherm model (R2 > 0.958). Thermodynamic studies indicated that adsorption was a spontaneous endothermic process. On the basis of these results, a removal mechanism of As (Ⅴ) by C-Fe/Ni NPs was proposed. Finally, the efficacy of the material for practical remediation of As from aqueous solution was assessed, including the influence of coexisting anions. While Cl-, NO3- and SO42- had little influence on As (V) removal, both H2PO4- and HCO3- significantly negatively affected removal.

Removal of low Sb(V) concentrations from mining wastewater using zeolitic imidazolate framework-8.

Wastewater generated during mining remains a significant source of antimony pollution, because techniques to quickly and efficiently remove antimony from wastewater do not exist. In this study, zeolitic imidazolate framework-8 (ZIF-8), a specific type of Metal Organic Frameworks (MOFs), was successfully used to remove trace levels (1 mg L-1) of Sb(V) with a high removal efficiency when the ZIF-8 dose was 0.5 g L-1. Scanning electron microscopy-X-ray energy dispersive spectrometry (SEM-EDS) indicated that Sb(V) was adsorbed onto the ZIF-8surface. The powder X-ray diffraction (XRD) pattern of ZIF-8 before and after adsorption of Sb(V) indicated that ZIF-8 was successfully synthesized, and remained structurally stable after Sb(V) was adsorbed. Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) both suggested complexation of zinc on ZIF-8 with Sb(V), where removal of Sb(V) by ZIF-8 followed the Langmuir adsorption isotherm with pseudo second-order kinetics. Thus, a possible removal mechanism was proposed which involved Sb(V) complexing with the zinc hydroxyl groups on ZIF-8 (Zn-OH-Sb). Practically, ZIF-8, could remove 78.6% of Sb(V) from a mining wastewater containing 20 µg L-1 Sb(V). Furthermore, ZIF-8 could be remain active after repeated uses and could still remove and 42.3% of Sb(V) from wastewater containing 1 mg L-1) Sb(V) even when the ZIF-8 was reused five time. This indicated that ZIF-8 had potential for practical removal of Sb(V) from mining wastewaters.

A Diamine-Based Integrated Absorption-Mineralization Process for Carbon Capture and Sequestration: Energy Savings, Fast Kinetics, and High Stability.

The high energy requirement of amine regeneration and the uncertainty of safe disposal of the captured CO2 remain big challenges to the large-scale implementation of amine scrubbing process for CO2 capture. Mineral carbonation represents a safe and permanent route to capture and store CO2 with net energy production but typically proceeds at a slow reaction rate. Here, we present a new integrated absorption and mineralization (IAM) process that couples a diamine-based CO2 absorption with fly-ash-triggered amine regeneration. The technical feasibility of the IAM process using 3-diethylaminopropylamine (DEAPA) and CaO-containing materials such as CaO and coal fly ashes was verified, and the reaction mechanism involved was investigated. It was found that CaO and CaO-rich coal fly ash were effective to regenerate DEAPA via the decomposition of DEAPA carbamate species and the formation of calcium carbonate precipitates. Furthermore, the diamine-based IAM process displayed a fast kinetics and a high stability for CO2 sequestration and can reduce the leachability of some heavy metals in the fly ash. These process properties render this diamine-based IAM process a great potential for carbon capture and sequestration applications.

Insights into the Chemical Mechanism for CO2(aq) and H+ in Aqueous Diamine Solutions - An Experimental Stopped-Flow Kinetic and 1H/13C NMR Study of Aqueous Solutions of N,N-Dimethylethylenediamine for Postcombustion CO2 Capture.

In an effort to advance the understanding of multiamine based CO2 capture process absorbents, we report here the determination of the kinetic and equilibrium constants for a simple linear diamine N,N-dimethylethylenediamine (DMEDA) via stopped-flow spectrophotometric kinetic measurements and 1H/13C NMR titrations at 25.0 °C. From the kinetic data, the formation of monocarbamic acid (DMEDACOOH) from the reaction of DMEDA with CO2(aq) is the dominant reaction at high pH > 9.0 (k7 = 6.99 × 103 M-1·s-1). Below this pH, the formation of protonated monocarbamic acid (DMEDACOOH2) via the pathway involving DMEDAH+ and CO2(aq) becomes active and contributes to the kinetics despite the 107-fold decrease in the rate constant between the two pathways. 1H and 13C NMR spectra as a function of decreasing pH (increasing HCl concentration) at 25.0 °C have been evaluated here to confirm the protonation events in DMEDA. Calculations of the respective DMEDA nitrogen partial charges have also been undertaken to support the NMR protonation study. A comparison of the DMEDA kinetic constants with the corresponding data for piperazine (PZ) reveals that despite the larger basicity of DMEDA, the enhanced and superior kinetic performance of PZ with CO2(aq) above its predicted Bronsted reactivity is not observed in DMEDA.

Simultaneous removal of Cu(II) and Cr(VI) by Mg-Al-Cl layered double hydroxide and mechanism insight.

Mg-Al-Cl layered double hydroxide (Cl-LDH) was prepared to simultaneously remove Cu(II) and Cr(VI) from aqueous solution. The coexisting Cu(II) (20mg/L) and Cr(VI) (40mg/L) were completely removed within 30min by Cl-LDH in a dosage of 2.0g/L; the removal rate of Cu(II) was accelerated in the presence of Cr(VI). Moreover, compared with the adsorption of single Cu(II) or Cr(VI), the adsorption capacities of Cl-LDH for Cu(II) and Cr(VI) can be improved by 81.05% and 49.56%, respectively, in the case of coexisting Cu(II) (200mg/L) and Cr(VI) (400mg/L). The affecting factors (such as solution initial pH, adsorbent dosage, and contact time) have been systematically investigated. Besides, the changes of pH values and the concentrations of Mg2+ and Al3+ in relevant solutions were monitored. To get the underlying mechanism, the Cl-LDH samples before and after adsorption were thoroughly characterized by X-ray powder diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. On the basis of these analyses, a possible mechanism was proposed. The coadsorption process involves anion exchange of Cr(VI) with Cl- in Cl-LDH interlayer, isomorphic substitution of Mg2+ with Cu2+, formation of Cu2Cl(OH)3 precipitation, and the adsorption of Cr(VI) by Cu2Cl(OH)3. This work provides a new insight into simultaneous removal of heavy metal cations and anions from wastewater by Cl-LDH.

Environmental application and ecological significance of nano-zero valent iron.

Toxicity studies considering both the bare and stabilized forms of zero valent iron nanoparticles (nZVI) could be timely, given that ecological risks identified are minimized through modification or with substitution of approaches in the synthesis, development and environmental application of the nanoparticles before succeeding to volume production. This review is focused on the fate, transport and toxicological implications of the bare nZVI and surface modified particles used for environmental applications.

Burkholderia vietnamiensis C09V as the functional biomaterial used to remove crystal violet and Cu(II).

Burkholderia vietnamiensis C09V (B.V. C09V) was used to remove both crystal violet (CV) and Cu(II) because dye effluents often contain dyes and metal ions. Inhibiting the strain׳s growth through the biosorption of Cu(II) on B.V. C09V and promoting its growth by using CV as a carbon source led to the degradation of CV (30mg/L). It fell to 36.9 percent and the amount of Cu(II) (50mg/L) removed rose to 34.9 percent in the presence of both CV and Cu(II). This outcome is comparable to the single presence of CV and Cu(II). EDS analysis showed that Cu(II) was adsorbed onto the strain (the atomic percentage of Cu(II) was 1.9 percent), while kinetic studies indicated that firstly, the decolorization of CV fitted well to the pseudo first-order degradation kinetic model and secondly, the biosorption of Cu(II) fitted well to the pseudo second-order kinetic model. The degradation rate constants of CV were stable in the 0.101-0.0068/h range and R(2) was both higher than 0.981 when Cu(II) concentrations were present. Furthermore, the biosorption capacity of Cu(II) ranged from 38.8 to 20.3mg/g at the CV concentration of 30mg/L (both R(2)>0.96). This suggests that the strain has the potential to degrade CV and facilitate the biosorption of Cu(II) in dye effluent.

Deciphering silver nanoparticles perturbation effects and risks for soil enzymes worldwide: Insights from machine learning and soil property integration.

Globally extensive research into how silver nanoparticles (AgNPs) affect enzyme activity in soils with differing properties has been limited by cost-prohibitive sampling. In this study, customized machine learning (ML) was used to extract data patterns from complex research, with a hit rate of Random Forest > Multiple Imputation by Chained Equations > Decision Tree > K-Nearest Neighbors. Results showed that soil properties played a pivotal role in determining AgNPs' effect on soil enzymes, with the order being pH > organic matter (OM) > soil texture ≈ cation exchange capacity (CEC). Notably, soil enzyme activity was more sensitive to AgNPs in acidic soil (pH < 5.5), while elevated OM content (>1.9 %) attenuated AgNPs toxicity. Compared to soil acidification, reducing soil OM content is more detrimental in exacerbating AgNPs' toxicity and it emerged that clay particles were deemed effective in curbing their toxicity. Meanwhile sand particles played a very different role, and a sandy soil sample at > 40 % of the water holding capacity (WHC), amplified the toxicity of AgNPs. Perturbation mapping of how soil texture alters enzyme activity under AgNPs exposure was generated, where soils with sand (45-65 %), silt (< 22 %), and clay (35-55 %) exhibited even higher probability of positive effects of AgNPs. The average calculation results indicate the sandy clay loam (75.6 %), clay (74.8 %), silt clay (65.8 %), and sandy clay (55.9 %) texture soil demonstrate less AgNPs inhibition effect. The results herein advance the prediction of the effect of AgNPs on soil enzymes globally and determine the soil types that are more sensitive to AgNPs worldwide.

Recovery of rare earth elements from mine wastewater using alginate microspheres encapsulated with zeolitic imidazolate framework-8.

There is increasing demand and interest in efficient methods for the recovery of rare earth elements (REEs) from wastewater because of the growing concerns associated with the negative impacts of REEs-rich waste discharged on pristine ecosystems. Here, we designed a ZIF-8@ALG composite hydrogel by encapsulating zeolitic imidazolate frameworks-8 (ZIF-8) into sodium alginate and poly (vinyl alcohol) double cross-linked networks (ALG) for the recovery of REEs from mine wastewater. ZIF-8@ALG showed exceptional REEs adsorption performance with the most superior separation factor (Ho/Mn) of 597.5. For the REEs considered, the ZIF-8@ALG composite exhibited a preference for heavy REEs with high adsorption efficiencies (65.3 ∼ 97.2%) and distribution coefficients (2045.5 ∼ 28500.0 mL·g-1). Adsorption involved a combination of electrostatic attraction, complexation and ion exchange mechanisms. REEs adsorbed on ZIF-8@ALG could also be desorbed using sodium citrate via ion-exchange and complexation, thus achieving efficient REEs recovery. In addition, ZIF-8@ALG was stable and reusable, maintaining effective adsorption in wastewater over four consecutive cycles, where the optimal adsorption efficiency reached 80.0%. Overall, this study provided an effective and feasible method for the recovery of REEs in mine wastewater, and confirmed that ZIF-8-based materials have significant potential for REEs recovery applications in wastewater engineering treatment.

Reconstructing the electron and spin structures of nanoscale iron sulfide through a biosurfactant layer towards radical-nonradical co-dominant regime.

Radical-nonradical co-dominant pathways have become a hot topic in advanced oxidation, but achieving this on transition metal sulfides (TMS) remains challenging because their inherently higher electron and spin densities always induce radicals rather than nonradicals. Herein, a biosurfactant layer (BLR) was introduced to redistribute the electron and spin structure of nanoscale iron sulfide (FeS), which allowed both radical and nonradical to co-dominate the catalytic reaction. The resulting BLR-encased FeS hybrid (BLR@FeS) exhibited satisfactory removal efficiency (98.5 %) for hydrogen peroxide (H2O2) activation, outperforming both the constituent components [FeS (70.9 %) and BLR (86.2 %)]. Advanced characterizations showed that C, O, N-related sites (-CO and -NC) in BLR attracted electrons in FeS due to their strong electronegativity and electron-withdrawing capacity, which not only decreased electron density in FeS, but also resulted in a shift of the Fe/S sites from the high-spin to the medium-spin state. The reaction routes established by the BLR@FeS/H2O2 system maintained desirable stability against environmental interferences such as common inorganic anions, humic acid and changes in pH. Our study provides a state-of-the-art, molecule-level understanding of tunable co-dominant pathways and expands the targeted applications in the field of advanced oxidation.