Efficient adsorption and photocatalytic degradation of water emerging contaminants through nanoarchitectonics of pore sizes and optical properties of zirconium-based MOFs.

Over the past decades, the presence of pharmaceutical emerging contaminants in water bodies is receiving increasing attention due to the high concentration detected from wastewater effluent. Water systems contain a wide range of components coexisting together, which increases the difficulty of removing pollutants from the water. In order to achieve selective photodegradation and to enhance the photocatalytic activity of the photocatalyst on emerging contaminants, a Zr-based metal-organic framework (MOF), termed VNU-1 (VNU represents Vietnam National University) constructed with ditopic linker 1,4-bis(2-[4-carboxyphenyl]ethynyl)benzene (H2CPEB), with enlarged pore size and ameliorated optical properties, was synthesized and applied in this study. When compared to UiO-66 MOFs, which only had 30% photodegradation of sulfamethoxazole, VNU-1 had 7.5 times higher adsorption and reached 100% photodegradation in 10 min. The tailored pore size of VNU-1 resulted in size-selective properties between small-molecule antibiotics and big-molecule humic acid, and VNU-1 maintained high photodegradation performance after 5 cycles. Based on the toxicity test and the scavenger test, the products after photodegradation had no toxic effect on V. fischeri bacteria, and the superoxide radical (·O2-) and holes (h+) generated from VNU-1 dominated the photodegradation reaction. These results demonstrate that VNU-1 is a promising photocatalyst and provide a new insight for developing MOF photocatalyst to remove emerging contaminants in the wastewater systems.

Interfacial nanoarchitectonics for ZIF-8 membranes with enhanced gas separation.

Metal-organic framework (MOF) membranes are potentially useful in gas separation applications. Conventional methods of MOF membrane preparation require multiple steps and high-pressure conditions. In this study, a reliable one-step interfacial synthesis method under atmospheric pressure has been developed to prepare zeolitic imidazolate framework-8 (ZIF-8) membranes supported on porous α-Al2O3 disks. To obtain optimal ZIF-8 membranes, three reaction parameters were investigated, namely, reaction temperature, reaction time, and concentration of the organic linker (i.e., 2-methylimidazole). The growth of ZIF-8 membranes under various parameters was evaluated by field-emission scanning electron microscopy, and the optimal synthesis conditions were determined (i.e., 80 °C for 12 h in 50 mM of 2-methylimidazole). The as-synthesized ZIF-8 membranes were then applied to CO2/N2 gas separation, which exhibited a maximum separation factor of 5.49 and CO2 gas permeance of 0.47 × 10-7 mol·m-2·s-1·Pa-1.

Diels-Alder Conversion of Acrylic Acid and 2,5-Dimethylfuran to para-Xylene Over Heterogeneous Bi-BTC Metal-Organic Framework Catalysts Under Mild Conditions.

The heterogeneous metal-organic framework Bi-BTC successfully catalyzed the synthesis of para-xylene from bio-based 2,5-dimethylfuran and acrylic acid in a promising yield (92 %), under relatively mild conditions (160 °C, 10 bar), and with a low reaction-energy barrier (47.3 kJ mol-1 ). The proposed reaction strategy also demonstrates a remarkable versatility for furan derivatives such as furan and 2-methylfuran.

Synthesis of MOF525/PEDOT Composites as Microelectrodes for Electrochemical Sensing of Dopamine.

Dopamine (DA) is an important neurotransmitter responsible for the functions and activities of multiple systems in human. Electrochemical detection of DA has the advantages of fast analysis and cost-effectiveness, while a regular electrode probe is restricted to laboratory use because the probe size is too large to be suitable for an in vivo or in vitro analysis. In this study, we have developed porphyrin-based metal organic framework (MOF525) and poly(3,4-ethylenedioxythiophene) (PEDOT)-based composites to modify microelectrode for DA detection. Two types of PEDOT monomers with different functional groups were investigated in this study. By varying the monomer ratios, electrolyte concentrations, and electropolymerization temperature, it was found that the PEDOT monomer containing carboxylic group facilitated the formation of regular morphology during the electropolymerization process. The uniform morphology of the PEDOT promoted the electron transmission efficiency in the same direction, while the MOF525 provided a large reactive surface area for electrocatalysis of DA. Thus, the MOF525/PEDOT composite improved the sensitivity-to-noise ratio of DA signaling, where the sensitivity reached 11 nA/µM in a good linear range of 4-100 µM. In addition, porphyrin-based MOF could also increase the selectivity to DA against other common clinical interferences, such as ascorbic acid and uric acid. The as-synthesized microelectrode modified with MOF525/PEDOT in this study exhibited great potential in real time analysis.

Assessment of agricultural waste-derived activated carbon in multiple applications.

To minimize waste production and reduce reliance on fossil fuels, agricultural waste such as rice straw has been actively used in biochemical production. In Taiwan, cellulosic waste has been used in anaerobic digestion for bioethanol production. This process produces a large amount of biomass-associated sludge that may become a serious environmental issue. Therefore, in this study, the anaerobic digestion sludge was recycled for the production of activated carbon via pyrolysis and activation by KOH. Surface characterization showed increased surface area and development of microporous structure upon activation. The FTIR image showed that high temperature activation eliminated most functional groups in the activated carbon, except for CO and C-O groups. The results showed that the activated carbon could be used for pollutant adsorbents such as molecular dyes (methylene blue: 217 mg g-1) and metal ions (copper: 169 mg g-1) from aqueous solution. In addition, the as-synthesized activated carbon can be used for CO2 capture and capacitor. Instead of focusing on one single application, we proposed that centralized production of activated carbon could be used in various applications, while further modification could be adopted depending on the need of its specific application.

Effect of N2 flow rate on kinetic investigation of lignin pyrolysis.

Fast pyrolysis of lignin can obtain valuable products such as bio-oil, bio-chemical, syngas, and biochar. In this study, two types of lignin known as brown solid from the byproduct of cellulosic ethanol fermentation and commercial dealkaline lignin from the papermaking process were used for pyrolysis in a 3-L batch reactor at 300-450 °C. The product composition in the liquid and gas phases were analyzed by using gas chromatography-mass spectrometry/Flame-ionization detector/thermal conductivity detector (GC-MS/FID/TCD). Increasing the N2 flow rate to 150 mL/min was sufficient to increase the production of bio-oil/bio-organics up to 15% for brown solid pyrolysis. In contrast, the biochemical production during dealkaline lignin pyrolysis was not sensitive to the change of the N2 flow rate. The amount of biochar produced in the pyrolysis (~60%) slightly changed at various pyrolysis temperature and gas flow rate, which could be due to the relatively low pyrolysis temperature that was insufficient to decompose the lignin. The GC-MS analysis also revealed that C7-C8 compounds, which represented the phenolic compounds, were the most abundant in the liquid products. Kinetic models of the pyrolysis were established based on the thermogravimetric analysis.

De Novo synthesis of platinum-nanoparticle-encapsulated UiO-66-NH2 for photocatalytic thin film fabrication with enhanced performance of phenol degradation.

The structural and chemical stability of UiO-66-NH2 and its simulated solar irradiation responsive characteristic make it a suitable metal-organic framework (MOF) candidate as photocatalytic material. Platinum nanoparticles (Pt NPs) are typically immobilized in MOF to enhance the photocatalytic efficiency. However, introducing high metal content in MOF with high dispersion is still challenging using conventional methods. In this paper, we present de novo synthesis of Pt@UiO-66-NH2, which can reach a highest metal content of 16 wt% with an average nanoparticle size of around 2 nm as confirmed by ICP-MS analysis and TEM images. The presence of benzoic acid plays multiple important roles in Pt@UiO-66-NH2 formation, including binding formation with Zr clusters, facilitating Pt dispersion, and being a modulator in MOF construction. In addition, the Pt@UiO-66-NH2 is fabricated on the α-Al2O3 substrate as a photocatalytic membrane reactor (PMR) for phenol degradation, which shows over 70 % removal efficiency under light irradiation and H2O2 addition. The recycle test shows that the PMR can maintain high catalytic efficiency. The facile de novo synthesis method proposed in this study enables effective immobilization of high metal content in MOF, and construction of membrane-based photocatalyst for scale-up application.

Waste-derived compost and biochar amendments for stormwater treatment in bioretention column: Co-transport of metals and colloids.

Bioretention systems, as one of the most practical management operations for low impact development of water recovery, utilize different soil amendments to remove contaminants from stormwater. For the sake of urban sustainability, the utilization of amendments derived from waste materials has a potential to reduce waste disposal at landfill while improving the quality of stormwater discharge. This study investigated the efficiency of food waste compost and wood waste biochar for metal removal from synthetic stormwater runoff under intermittent flow and co-presence of colloids. Throughout intermittent infiltration of 84 pore volumes of stormwater, columns amended with compost and biochar removed more than 50-70% of influent metals, whereas iron-oxide coated sand was much less effective. Only a small portion of metals adsorbed on the compost (< 0.74%) was reactivated during the drainage of urban pipelines that do not flow frequently, owing to abundant oxygen-containing functional groups in compost. In comparison, co-existing kaolinite enhanced metal removal by biochar owing to the abundance of active sites, whereas co-existing humic acid facilitated mobilization via metal-humate complexation. The results suggest that both waste-derived compost and biochar show promising potential for stormwater harvesting, while biochar is expected to be more recalcitrant and desirable in field-scale bioretention systems.

Soil amendments for immobilization of potentially toxic elements in contaminated soils: A critical review.

Soil contamination by potentially toxic elements (PTEs) has led to adverse environmental impacts. In this review, we discussed remediation of PTEs contaminated soils through immobilization techniques using different soil amendments with respect to type of element, soil, and amendment, immobilization efficiency, underlying mechanisms, and field applicability. Soil amendments such as manure, compost, biochar, clay minerals, phosphate compounds, coal fly ash, and liming materials are widely used as immobilizing agents for PTEs. Among these soil amendments, biochar has attracted increased interest over the past few years because of its promising surface properties. Integrated application of appropriate amendments is also recommended to maximize their use efficiency. These amendments can reduce PTE bioavailability in soils through diverse mechanisms such as precipitation, complexation, redox reactions, ion exchange, and electrostatic interaction. However, soil properties such as soil pH, and clay, sesquioxides and organic matter content, and processes, such as sorption/desorption and redox processes, are the key factors governing the amendments' efficacy for PTEs immobilization in soils. Selecting proper immobilizing agents can yield cost-effective remediation techniques and fulfill green and sustainable remediation principles. Furthermore, long-term stability of immobilized PTE compounds and the environmental impacts and cost effectiveness of the amendments should be considered before application.

Advances in lignin valorization towards bio-based chemicals and fuels: Lignin biorefinery.

Lignin is one of the most promising renewable sources for aromatic hydrocarbons, while effective depolymerization towards its constituent monomers is a particular challenge because of the structural complexity and stability. Intensive research efforts have been directed towards exploiting effective valorization of lignin for the production of bio-based platform chemicals and fuels. The present contribution aims to provide a critical review of key advances in the identification of exact lignin structure subjected to various fractionation technologies and demonstrate the key roles of lignin structures in depolymerization for unique functionalized products. Various technologies (e.g., thermocatalytic approaches, photocatalytic conversion, and mechanochemical depolymerization) are reviewed and evaluated in terms of feasibility and potential for further upgrading. Overall, advances in pristine lignin structure analysis and conversion technologies can facilitate recovery and subsequent utilization of lignin towards tailored commodity chemicals and fungible fuels.

Sorption, mobility, and bioavailability of PBDEs in the agricultural soils: Roles of co-existing metals, dissolved organic matter, and fertilizers.

Polybrominated diphenyl ethers (PBDEs) are common pollutants released from electronic waste (e-waste) dismantling and recycling activities. Our city-wide survey of agricultural soils in Qingyuan (40 sampling sites), where e-waste recycling has been active, observed exceedance of PBDEs above background levels (average of 251.9ngg-1, 87 times the regional baseline concentration) together with elevated levels of metals/metalloids at the contamination hotspots, such as As (180.4mgkg-1), Cu (100.7mgkg-1), Zn (93.4mgkg-1), Pb (37.8mgkg-1), Cr (15.1mgkg-1), and Cd (0.3mgkg-1). Hence, a twenty-cycle batch sorption test on composite soil samples from the e-waste site was conducted to study the fate of BDE-28 (2,4,4'-tribromodiphenyl ether) and BDE-99 (2,2',4,4',5-pentabromodiphenyl ether) under the influence of co-existing trace elements (TEs) (Cu, Pb, Zn, and Cd, which exceeded Chinese Environmental Quality Standard for Soils), dissolved organic matter (extracted from local peat), and locally available commercial fertilizer. The results showed that the presence of TEs barely affected the sorption of BDEs, probably because the low concentration of BDEs in the environment resulted in nearly complete sorption onto the soil. In contrast, metals sorption onto soil was promoted by the presence of BDEs. The mobility of BDE-28 was higher than BDE-99 in water leaching tests, while the leaching concentration of BDE-99 was further reduced in simulated acid rain possibly due to protonation of π-accepting sites in soil organic matter. In the freshly spiked soil, BDEs of greater hydrophobicity and larger molecular size exhibited higher bioavailability (due to greater affinity to Tenax extraction), which was contrary to the field contaminated soil. Similarly, the co-occurrence of metals and fertilizer increased the bioavailability of newly sorbed BDE-99 more than BDE-28 in the soil. These results illustrate the need to holistically assess the fate and interactions of co-existing organic and inorganic pollutants in the agricultural soils.

Production of 5-hydroxymethylfurfural from starch-rich food waste catalyzed by sulfonated biochar.

Sulfonated biochar derived from forestry wood waste was employed for the catalytic conversion of starch-rich food waste (e.g., bread) into 5-hydroxymethylfurfural (HMF). Chemical and physical properties of catalyst were characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) surface area, and elemental analysis. The conversion of HMF was investigated via controlling the reaction parameters such as catalyst loading, temperature, and reaction time. Under the optimum reaction conditions the HMF yield of 30.4 Cmol% (i.e., 22 wt% of bread waste) was achieved in the mixture of dimethylsulfoxide (DMSO)/deionized-water (DIW) at 180 °C in 20 min. The effectiveness of sulfonated biochar catalyst was positively correlated to the density of strong/weak Brønsted acidity (SO3H, COOH, and OH groups) and inversely correlated to humins content on the surface. With regeneration process, sulfonated biochar catalyst displayed excellent recyclability for comparable HMF yield from bread waste over five cycles.

Removal of chlorinated organic solvents from hydraulic fracturing wastewater by bare and entrapped nanoscale zero-valent iron.

With the increasing application of hydraulic fracturing, it is urgent to develop an effective and economically feasible method to treat the large volumes of fracturing wastewater. In this study, bare and entrapped nanoscale zero-valent iron (nZVI) were introduced for the removal of carbon tetrachloride (CT) and 1,1,2-trichloroethane (TCA) in model high-salinity fracturing wastewater. With increasing ionic strength (I) from Day-1 (I = 0.35 M) to Day-90 (I = 4.10 M) wastewaters, bare nZVI presented significantly lower removal efficiency of CT (from 53.5% to 38.7%) and 1,1,2-TCA (from 71.1% to 21.7%) and underwent more serious Fe dissolution from 1.31 ±â€¯1.19% in Day-1 to 5.79 ±â€¯0.32% in Day-90 wastewater. Particle aggregation induced by high ionic strength was primarily responsible for the lowered performance of nZVI due to less available reactive sites on nZVI surface. The immobilization of nZVI in alginate with/without polyvinyl alcohol provided resistance to particle aggregation and contributed to the superior performance of entrapped nZVI in Day-90 wastewater for 1,1,2-TCA removal (62.6-72.3%), which also mitigated Fe dissolution (4.00-4.69%). Both adsorption (by polymer matrix) and reduction (by immobilized nZVI) were involved in the 1,1,2-TCA removal by entrapped nZVI. However, after 1-month immersion in synthetic fracturing wastewater, a marked drop in the reactivity of entrapped nZVI for 1,1,2-TCA removal from Day-90 wastewater was observed with significant release of Na and total organic carbon. In summary, bare nZVI was sensitive to the nature of the fracturing wastewater, while the use of environmentally benign entrapped nZVI was more promising for wastewater treatment.

Valorization of lignocellulosic fibres of paper waste into levulinic acid using solid and aqueous Brønsted acid.

This study aims to produce levulinic acid (LA) from paper towel waste in environment-friendly and economically feasible conditions, and evaluate the difference using solid and aqueous Brønsted acids. Direct dehydration of glucose to LA required sufficiently strong Brønsted acidity, where Amberlyst 36 demonstrated rapid production of approximately 30Cmol% of LA in 20min. However, the maximum yield of LA was limited by mass transfer. In contrast, the yield of LA gradually increased to over 40Cmol% in 1M H2SO4 at 150°C in 60min. The SEM images revealed the conversion in dilute acids under microwave at 150°C resulting in swelling structures of cellulose, which were similar to the pre-treatment process with concentrated acids. Further increase in reaction temperature to 200°C significantly shortened the reaction time from 60 to 2.5min, which saved the energy cost as revealed in preliminary cost analysis.

Aging effects on chemical transformation and metal(loid) removal by entrapped nanoscale zero-valent iron for hydraulic fracturing wastewater treatment.

In this study, alginate and polyvinyl alcohol (PVA)-alginate entrapped nanoscale zero-valent iron (nZVI) was tested for structural evolution, chemical transformation, and metals/metalloids removal (Cu(II), Cr(VI), Zn(II), and As(V)) after 1-2month passivation in model saline wastewaters from hydraulic fracturing. X-ray diffraction analysis confirmed successful prevention of Fe0 corrosion by polymeric entrapment. Increasing ionic strength (I) from 0 to 4.10M (deionized water to Day-90 fracturing wastewater (FWW)) with prolonged aging time induced chemical instability of alginate due to dissociation of carboxyl groups and competition for hydrogen bonding with nZVI, which caused high Na (7.17%) and total organic carbon (24.6%) dissolution from PVA-alginate entrapped nZVI after 2-month immersion in Day-90 FWW. Compared to freshly-made beads, 2-month aging of PVA-alginate entrapped nZVI in Day-90 FWW promoted Cu(II) and Cr(VI) uptake in terms of the highest removal efficiency (84.2% and 70.8%), pseudo-second-order surface area-normalized rate coefficient ksa (2.09×10-1Lm-2h-1 and 1.84×10-1Lm-2h-1), and Fe dissolution after 8-h reaction (13.9% and 8.45%). However, the same conditions inhibited Zn(II) and As(V) sequestration in terms of the lowest removal efficiency (31.2% and 39.8%) by PVA-alginate nZVI and ksa (4.74×10-2Lm-2h-1 and 6.15×10-2Lm-2h-1) by alginate nZVI. The X-ray spectroscopic analysis and chemical speciation modelling demonstrated that the difference in metals/metalloids removal by entrapped nZVI after aging was attributed to distinctive removal mechanisms: (i) enhanced Cu(II) and Cr(VI) removal by nZVI reduction with accelerated electron transfer after pronounced dissolution of non-conductive polymeric immobilization matrix; (ii) suppressed Zn(II) and As(V) removal by nZVI adsorption due to restrained mass transfer after blockage of surface-active micropores. Entrapped nZVI was chemically fragile and should be properly stored and regularly replaced for good performance.

Polar aprotic solvent-water mixture as the medium for catalytic production of hydroxymethylfurfural (HMF) from bread waste.

Valorisation of bread waste for hydroxymethylfurfural (HMF) synthesis was examined in dimethyl sulfoxide (DMSO)-, tetrahydrofuran (THF)-, acetonitrile (ACN)-, and acetone-water (1:1v/v), under heating at 140°C with SnCl4 as the catalyst. The overall rate of the process was the fastest in ACN/H2O and acetone/H2O, followed by DMSO/H2O and THF/H2O due to the rate-limiting glucose isomerisation. However, the formation of levulinic acid (via rehydration) and humins (via polymerisation) was more significant in ACN/H2O and acetone/H2O. The constant HMF maxima (26-27mol%) in ACN/H2O, acetone/H2O, and DMSO/H2O indicated that the rates of desirable reactions (starch hydrolysis, glucose isomerisation, and fructose dehydration) relative to undesirable pathways (HMF rehydration and polymerisation) were comparable among these mediums. They also demonstrated higher selectivity towards HMF production over the side reactions than THF/H2O. This study differentiated the effects of polar aprotic solvent-water mediums on simultaneous pathways during biomass conversion.

A critical review on sustainable biochar system through gasification: Energy and environmental applications.

This review lays great emphasis on production and characteristics of biochar through gasification. Specifically, the physicochemical properties and yield of biochar through the diverse gasification conditions associated with various types of biomass were extensively evaluated. In addition, potential application scenarios of biochar through gasification were explored and their environmental implications were discussed. To qualitatively evaluate biochar sustainability through the gasification process, all gasification products (i.e., syngas and biochar) were evaluated via life cycle assessment (LCA). A concept of balancing syngas and biochar production for an economically and environmentally feasible gasification system was proposed and relevant challenges and solutions were suggested in this review.

Valorization of starchy, cellulosic, and sugary food waste into hydroxymethylfurfural by one-pot catalysis.

This study aimed to produce a high-value platform chemical, hydroxymethylfurfural (HMF), from food waste and evaluate the catalytic performance of trivalent and tetravalent metals such as AlCl3, CrCl3, FeCl3, Zr(O)Cl2, and SnCl4 for one-pot conversion. Starchy food waste, e.g., cooked rice and penne produced 4.0-8.1 wt% HMF and 46.0-64.8 wt% glucose over SnCl4 after microwave heating at 140 °C for 20 min. This indicated that starch hydrolysis was effectively catalyzed but subsequent glucose isomerization was rate-limited during food waste valorization, which could be enhanced by 40-min reaction to achieve 22.7 wt% HMF from cooked rice. Sugary food waste, e.g., kiwifruit and watermelon, yielded up to 13 wt% HMF over Sn catalyst, which mainly resulted from naturally present fructose. Yet, organic acids in fruits may hinder Fe-catalyzed dehydration by competing for the Lewis sites. In contrast, conversion of raw mixed vegetables as cellulosic food waste was limited by marginal hydrolysis at the studied conditions (120-160 °C and 20-40 min). It is interesting to note that tetravalent metals enabled HMF production at a lower temperature and shorter time, while trivalent metals could achieve a higher HMF selectivity at an elevated temperature. Further studies on kinetics, thermodynamics, and reaction pathways of food waste valorization are recommended.

Enhancing anti-microbial properties of wood-plastic composites produced from timber and plastic wastes.

Considering the resource waste and environmental burden for timber and plastic materials ending up at landfills, this study proposed upcycling wood and plastic waste into value-added wood-plastic composites (WPCs), complying with the standard requirements of flexural strength, thickness swelling, water absorption and thermal insulation. Biological deterioration is a major concern of WPCs. Bacterial survival, fungal attack and algal growth of bactericide-treated WPCs were holistically analysed. Melamine resin was adopted for impregnating anti-microbial agents on the surface. All the agents showed excellent bactericidal rate (Escherichia coli), yet poly-diallyl-dimethyl-ammonium chloride (PolyDADMAC) and silver had the lowest minimum inhibitory concentrations. In terms of weight loss and strength reduction due to fungal decay (Coriolus versicolor), PolyDADMAC, silver and cetyltrimethylammonium bromide (CTAB) imparted the highest resistance on the WPCs. Moreover, PolyDADMAC and copper provided the most protection against algal growth (Chlorella vulgaris), and the former presented durable inhibitory effect. This study presents a value-added solution to wood/plastic waste recycling.

Nanoscale zero-valent iron for metal/metalloid removal from model hydraulic fracturing wastewater.

Nanoscale zero-valent iron (nZVI) was tested for the removal of Cu(II), Zn(II), Cr(VI), and As(V) in model saline wastewaters from hydraulic fracturing. Increasing ionic strength (I) from 0.35 to 4.10 M (Day-1 to Day-90 wastewaters) increased Cu(II) removal (25.4-80.0%), inhibited Zn(II) removal (58.7-42.9%), slightly increased and then reduced Cr(VI) removal (65.7-44.1%), and almost unaffected As(V) removal (66.7-75.1%) by 8-h reaction with nZVI at 1-2 g L-1. The removal kinetics conformed to pseudo-second-order model, and increasing I decreased the surface area-normalized rate coefficient (ksa) of Cu(II) and Cr(VI), probably because agglomeration of nZVI in saline wastewaters restricted diffusion of metal(loid)s to active surface sites. Increasing I induced severe Fe dissolution from 0.37 to 0.77% in DIW to 4.87-13.0% in Day-90 wastewater; and Fe dissolution showed a significant positive correlation with Cu(II) removal. With surface stabilization by alginate and polyvinyl alcohol, the performance of entrapped nZVI in Day-90 wastewater was improved for Zn(II) and Cr(VI), and Fe dissolution was restrained (3.20-7.36%). The X-ray spectroscopic analysis and chemical speciation modelling demonstrated that the difference in removal trends from Day-1 to Day-90 wastewaters was attributed to: (i) distinctive removal mechanisms of Cu(II) and Cr(VI) (adsorption, (co-)precipitation, and reduction), compared to Zn(II) (adsorption) and As(V) (bidentate inner-sphere complexation); and (ii) changes in solution speciation (e.g., from Zn2+ to ZnCl3- and ZnCl42-; from CrO42- to CaCrO4 complex). Bare nZVI was susceptible to variations in wastewater chemistry while entrapped nZVI was more stable and environmentally benign, which could be used to remove metals/metalloids before subsequent treatment for reuse/disposal.