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.

Enhanced removal of Pb(II) from acid mine drainage using green reduced graphene oxide/silver nanoparticles.

Mining activities can potentially release high levels of Pb(II) in acid mine drainage (AMD), which thereafter poses a significant threat to ecological security. In this study, green reduced graphene oxide/silver nanoparticles (rGO/Ag NPs) were successfully synthesized via a one-step approach using a green tea extract and subsequently used as a cost-effective absorbent to remove Pb(II) from AMD. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy indicated that organic functional groups in the green tea extracts, such as C=O-C, CO, and CC, acted both as reductants and stabilizers in the synthesis of rGO/Ag NPs. In addition, the removal efficiency of Pb(II) by rGO/Ag NPs (84.2 %) was much better than either rGO (75.4 %) or Ag NPs (12.3 %) alone. Also, in real AMD, the distribution coefficient (Kd) of Pb(II) (4528 mL/g), was much higher than other heavy metal indicating the adsorbent had a high selective affinity for Pb(II). Interestingly, after five cycles of use, the removal efficiency of Pb(II) by rGO/Ag NPs from AMD actually increased from 46.4 to 65.2 % due to iron oxides (i.e., Fe2O3 and Fe3O4) being generated when rGO/Ag NPs was exposed to AMD. The removal of Pb(II) via adsorption on the rGO/Ag NPs surface involved formation of hexagonal rod-like precipitates. This work demonstrated the potential of rGO/Ag NPs to be continuously used for the removal of Pb(II) from AMD.

Probing the geochemical characteristics of rare earth elements in the weathering profile of yttrium-rich heavy rare earth mine.

Understanding the complex geochemical characteristics of rare earth elements (REEs) in the weathering profile of ion-adsorbed rare earth ore is a crucial issue for establishing the best leaching agent dosage during in-situ leaching processes. This study focuses on soil samples collected from nine drill holes located at three hillslopes of a mining area in southwest Fujian. Analyzing the geochemical features of REEs revealed that the ore predominantly comprises Y, La, Ce, and Nd, with Y being the most abundant, constituting 20.24 %-33.64 % of total rare earth elements (TREEs) in each weathering profile. This categorizes the ore as an yttrium-rich heavy rare earth ion-adsorbed mine. Notably, REEs exhibit a concentration in the middle layer of the weathering profile, with content increasing first and then declining with deeper depth from the surface to the bottom. The ratio of light rare earth elements (LREEs) to heavy rare earth elements (HREEs) diminishes noticeably from shallow soil to middle soil, while deep soil reveals a slightly higher ratio than middle soil. These findings offer valuable insights into the scientific mining of this area and similar ion-adsorbed rare earth mines concerning their economic potential.

Intensive ammonium fertilizer addition activates iron and carbon conversion coupled cadmium redistribution in a paddy soil under gradient redox conditions.

While over-fertilization and nitrogen deposition can lead to the enrichment of nitrogen in soil, its effects on heavy metal fractions under gradient moisture conditions remains unclear. Here, the effect of intensive ammonium (NH4+) addition on the conversion and interaction of cadmium (Cd), iron (Fe) and carbon (C) was studied. At relatively low (30-80 %) water hold capacity (WHC) NH4+ application increased the carbonate bound Cd fraction (F2Cd), while at relatively high (80-100 %) WHC NH4+ application increased the organic matter bound Cd fraction (F4Cd). Iron­manganese oxide bound Cd fractions (F3Cd) and oxalate-Fe decreased, but DCB-Fe increased in NH4+ treatments, indicating that amorphous Fe was the main carrier of F3Cd. The variations in F1Cd and F4Cd observed under the 100-30-100 % WHC treatment were similar to those observed under low moisture conditions (30-60 % WHC). The C=O/C-H ratio of organic matter in soil decreased under the 30-60 % WHC treatment, but increased under the 80-100 % WHC treatment, which was the dominant factor influencing F4Cd changes. The conversion of NH4+ declined with increasing soil moisture content, and the impact on oxalate-Fe was greater at 30-60 % WHC than at 80-100 % WHC. Correspondingly, genetic analysis showed the effect of NH4+ on Fe and C metabolism at 30-60 % WHC was greater than at 80-100 % WHC. Specifically, NH4+ treatment enhanced the expression of genes encoding extracellular Fe complexation (siderophore) at 30-80 % WHC, while inhibiting genes encoding Fe transmembrane transport at 30-60 % WHC, indicating that siderophores simultaneously facilitated Cd detoxification and Fe complexation. Furthermore, biosynthesis of sesquiterpenoid, steroid, butirosin and neomycin was significantly correlated with F4Cd, while glycosaminoglycan degradation metabolism and assimilatory nitrate reduction was significantly correlated with F2Cd. Overall, this study gives a more comprehensive insight into the effect of NH4+ on activated Fe and C conversion on soil Cd redistribution under gradient moisture conditions.

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.

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.

Ferrous sulfide nanoparticles can be biosynthesized by sulfate-reducing bacteria: Synthesis, characterization and removal of heavy metals from acid mine drainage.

Ferrous sulfide nanoparticles (nFeS) have proven to be effective in removing heavy metals (HMs) from wastewater. One such approach, which has garnered much attention as a sustainable technology, is via the in situ microbial synthesis of nFeS. Here, a sulfate-reducing bacteria (SRB) strain, Geobacter sulfurreducens, was used to initially biosynthesize ferrous sulfide nanoparticles (SRB-nFeS) and thereafter remove HMs from acid mine drainage (AMD). SRB-nFeS was characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) coupled to an energy dispersive spectrometer (EDS), three-dimensional excitation-emission matrix (3D-EEM) spectroscopy, Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). Such characterization showed that SRB mediated the reduction of SO42- to S2- to form nFeS, where the metabolized substances functioned as complexing agents which coordinated with nFeS to form biofunctional SRB-nFeS with improved stability. One advantage of this synthetic route was that the attachment of nFeS to the bacterial surface protected SRB cells from HM toxicity. Furthermore, due to a synergistic effect between nFeS and SRB, HM removal from both solution and AMD by SRB-nFeS was enhanced relative to the constituent components. Thus, after 5 consecutive cycles of HM removal, SRB-nFeS removed, Pb(Ⅱ) (92.6%), Cd(Ⅱ) (78.7%), Cu(Ⅱ) (76.0%), Ni(Ⅱ) (62.5%), Mn(Ⅱ) (62.2%), and Zn(Ⅱ) (88.5%) from AMD This study thus provides new insights into the biosynthesis of SRB-nFeS and its subsequent practical application in the removal of HMs from AMD.

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.

Biocomposite based on graphene oxide immobilized Pseudomonas psychrotolerans for the recovery of Y(III) in acid mine drainage.

Rare earth elements (REEs) recovery is a critical issue concerning both resource recovery and wastewater utilization. In this study, a new bio-composite was fabricated using graphene oxide immobilized Pseudomonas psychrotolerans (PP@GO), which was isolated from the soil of REEs mine. Results showed that 99.6% Y(III) was removed in 48 h and various characterization confirmed that S-S, -NH2, HPO42-, -OH and -COOH from extracellular polymeric substances (EPS) secreted by microorganisms formed complexation with Y(III). As well, the Y(III) adsorption best followed Freundlich isotherm and non-linear pseudo-second-order kinetic model having R2 of 0.985 and 0.996, respectively, demonstrating that the adsorption was governed by multilayered chemisorption. Additionally, the effectiveness of PP@GO was not limited to Y(III), where 27.9% of this substance was removed in acid mine drainage (AMD), also exhibited great adsorption for other REEs, such as Er (45.0%) and Ho (43.8%). Furthermore, the adsorption efficiency of Y(III) remained high (70.0%) after a 5th cycle, emphasizing the consistent stability of PP@GO. Finally, REEs adsorbed could be greatly desorbed by KNO3, like Sm (80.1%) and La (80.0%), which revealed that PP@GO has great potential to recover REEs in AMD. Overall, this study offers a promising strategy for the green and sustainable REEs recovery and wastewater treatment.

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.

Improved recovery selectivity of rare earth elements from mining wastewater utilizing phytosynthesized iron nanoparticles.

While rare earth elements (REEs) play key roles in many modern technologies, the selectivity of recovering of REEs from mining wastewater remains a critical problem. In this study, iron nanoparticles (FeNPs) synthesized from euphorbia cochinchinensis extracts were successfully used for selective recovery of REEs from real mining wastewater with removal efficiencies of 89.4% for Y(III), 79.8% for Ce(III) and only 6.15% for Zn(Ⅱ). FTIR and XPS analysis suggested that the high selective removal efficiency of Y(III) and Ce(III) relative to Zn(Ⅱ) on FeNPs was due to a combination of selective REEs adsorption via complexing with O or N, ion exchange with H+ present in functional groups contained within the capping layer and electrostatic interactions. Adsorptions of Y(III) and Ce(III) on FeNPs conformed to pseudo second-order kinetics and the Langmuir isotherm model with maximum adsorption capacities of 5.10 and 0.695 mg∙g-1, respectively. The desorption efficiencies of Y(III) and Ce(III) were, respectively, 95.0 and 97.9% in 0.05 M acetic acid, where desorption involved competitive ion exchange between Y(III), Ce(III) and Zn(Ⅱ) with H+ contained in acetic acid and intraparticle diffusion. After four consecutive adsorption-desorption cycles, adsorption efficiencies for Y(III) and Ce(III) remained relatively high at 52.7% and 50.1%, respectively, while desorption efficiencies of Y(III) and Ce(III) were > 80.0% and 95.0%, respectively. Overall, excellent reusability suggests that FeNPs can practically serve as a potential high-quality selectivity material for recovering REEs from mining wastewaters.

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.

Interface coupling effect in biomass-derived iron sulfide nanomaterials triggering efficient hydrogen peroxide activation.

Slow electron migration in iron sulfide nanoparticles (C-FeS NPs) synthesized by co-precipitation severely limits the activation performance of hydrogen peroxide (H2O2). Herein, a biofunctional FeS NPs (P-FeS NPs) derived from Pinus massoniana Lamb biomass, with interface coupling effect, was used for enhanced H2O2 activation and norfloxacin (NOR) degradation. It was discovered that P-FeS NPs exhibited superior catalytic activity (100%) compared to C-FeS NPs (53.1%). Fe atoms of FeS NPs and hydroxyl groups (-OH) of Pinus massoniana Lamb biomass were mutually coupled to produce Fe-OH interfacial sites, which significantly increased the generation of multi-reactive species by accelerating the transfer of electrons across interfaces. Additionally, radical quenching tests elucidated that singlet oxygen (1O2) (66.6%) played a leading role, while hydroxyl radicals (•OH) (14.5%) and superoxide radicals (•O2-) (18.9%) were secondary oxidants. Finally, P-FeS NPs showed a high tolerance to a wide range of pH conditions and could remove 96.4% NOR from wastewater. Overall, this work generates important insights into understanding how green sustainable interfacial catalysts can accelerate catalytic 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.

Predicting the effect of silver nanoparticles on soil enzyme activity using the machine learning method: type, size, dose and exposure time.

In this study, machine learning models predicted the impact of silver nanoparticles (AgNPs) on soil enzymes. Artificial neural network (ANN) optimized with genetic algorithm (GA) (MAE = 0.1174) was more suitable for simulating overall trends, while the gradient boosting machine (GBM) and random forest (RF) were ideal for small-scale analysis. According to partial dependency profile (PDP) analysis, polyvinylpyrrolidone coated AgNPs (PVP-AgNPs) had the most inhibitory effect (average of 49.5%) on soil enzyme activity among the three types of AgNPs at the same dose (0.02-50 mg/kg). The ANN model predicted that enzyme activity first declined and then rose when AgNPs increased in size. Based on predictions from the ANN and RF models, when exposed to uncoated AgNPs, soil enzyme activities continued to decrease before 30 d, but gradually rose from 30 to 90 d, and fell slightly after 90 d. The ANN model indicated the importance order of four factors: dose > type > size > exposure time. The RF model suggested the enzyme was more sensitive when experiments were conducted at doses, sizes, and exposure times of 0.01-1 mg/kg, 50-100 nm, and 30-90 d, respectively. This study presents new insights on the regularity of soil enzyme responses to AgNPs.

One-step simultaneous biomass synthesis of iron nanoparticles using tea extracts for the removal of metal(loid)s in acid mine drainage.

Acid Mine Drainage (AMD) contains various metal/metalloid ions such as Fe, Cu, and As, which all impact seriously on mine ecosystems. Currently, the commonly used chemical methods for treating AMD may cause secondary pollution to appear in the environment. In this study, one-step simultaneous biomass synthesis of iron nanoparticles (Fe NPs) using tea extracts for the removal of heavy metals/metalloids in AMD is proposed. Characterizations revealed that the Fe NPs presented severely agglomerated particles with an average particle size of 119.80 ± 4.94 nm, on which various AMD-derived metal(loid)s, including As, Cu, and Ni, were uniformly dispersed. The biomolecules participating in the reaction in the tea extract were identified as polyphenols, organic acids, and sugars, which acted as complexing agents, reducing agents, covering/stabilizing agents, and promoted electron transfer. Meanwhile, the best reaction conditions (reaction time = 3.0 h, volume ratio of AMD and tea extract = 1.0:1.5, concentration of extract = 60 g/L, and T = 303 K) were obtained. Finally, the simultaneous formation of Fe NPs and their removal of heavy metals/metalloids from AMD was proposed, mainly involving the formation of Fe NPs and adsorption, co-precipitation, and reduction processes of heavy metals/metalloids.

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.

Impact of coexisting components in acid mine drainage on Sb(â ¢) oxidation by biosynthesized iron nanoparticles.

Despite the oxidation mechanism of antimonite (Sb(Ⅲ)) by biosynthesized iron nanoparticles (Fe NPs) has been reported, the impact of coexisting components in acid mine drainage (AMD) on the Sb(III) oxidation by Fe NPs is unknown. Herein, how the coexisting components in AMD affect Sb(Ⅲ) oxidation by Fe NPs was investigated. Firstly, Fe NPs achieved complete oxidation of Sb(Ⅲ) (100%), while only 65.0% of Sb(Ⅲ) was oxidized when As(Ⅲ) was added, due to competitive oxidation between As(Ⅲ) and Sb(Ⅲ), which was verified by characterization analysis. Secondly, the decline in solution pH improved Sb(Ⅲ) oxidation from 69.5% (pH 4) to 100% (pH 2), which could be attributed to the rise of Fe3+ in solution promoting the electron transfer between Sb(Ⅲ) and Fe NPs. Thirdly, the oxidation efficiencies of Sb(Ⅲ) fell by 14.9 and 44.2% following the addition of oxalic and citric acid, respectively, resulting from the fact that these two acids reduced the redox potential of Fe NPs, thereby inhibiting Sb(Ⅲ) oxidation by Fe NPs. Finally, the interference effect of coexisting ions was studied, where PO43- significantly reduced Sb(Ⅲ) oxidation efficiency due to the occupation of the surface-active sites on Fe NPs. Overall, this study has significant implications for the prevention of Sb contamination in AMD.

Removal of As(III) using a microorganism sustained secrete laccase-straw oxidation system.

While laccase oxidation is a novel and promising method for treating arsenite-containing wastewater, the high cost and unsustainability of commercially available enzymes indicate a need to investigate more cost-effective viable alternatives. Here, a microorganism sustained secrete laccase-straw oxidation system (MLOS) was established and subsequently evaluated for the removal of As(III). MLOS showed efficient biological As(III) oxidation, with an As(III) removal efficiency reaching 99.9% at an initial As(III) concentration of 1.0 mg·L-1. IC-AFS and XPS analysis showed that As(III) was partially oxidized to As(V), and partially As(III) adsorbed on the surface of rice straw. FTIR analysis revealed that hydroxyl, amine and amide groups were all involved in the As(III) removal process. SEM-EDS demonstrated that the surface structure of rice straw was destroyed following Comamonas testosteroni FJ17 (C. testosteroni FJ17) treatment, and the metal ions binding sites of rice straw were increased resulting in elemental arsenic being detected on the material surface. Molecular docking revealed the interaction between key residues of laccase and As(III). Laccase activity was negatively correlated with Cu(II) concentration in the As(III) oxidation. EEM showed that humic-like acids were also involved in the interaction with As(III). Overall, a MLOS derived from biomass waste has a significant potential to be developed as a green and sustainable technology for the treatment of wastewater containing As(III).