Search Results (70)

Orange processing generates large amounts of waste orange peels (WOPs), which are a valuable source of bioactive polyphenols. This study investigated the use of mild (urea) and strong (sodium hydroxide) alkaline catalysts to enhance polyphenol extraction via an ethanol-based organosolv process. First, the two catalysts were evaluated in terms of process performance, extraction kinetics, and treatment severity. Subsequently, response surface methodology was applied to optimize the conditions, and the obtained extracts were characterized for their polyphenolic profile and antioxidant activity. The sodium hydroxide (SoHy)-catalyzed treatment, using 70% ethanol as solvent, was the most effective, yielding 33.4 ± 1.7 mg of total polyphenols (as gallic acid equivalents) per gram of dry mass. For both catalysts tested, the yield followed a severity-dependent linear model. Liquid chromatography–mass spectrometry of extracts produced under optimized conditions showed that hesperidin was the predominant polyphenolic constituent, but the SoHy-catalyzed treatment resulted in the generation of three novel compounds, tentatively identified as ethyl esters of p-coumaric, ferulic and sinapic acids. Such an effect was not observed in the extracts produced with the urea (Ur)-catalyzed treatment. This compositional modification was reflected on both the antiradical activity and ferric-reducing power, which were found to be significantly enhanced in the extracts produced via the SoHy-catalyzed treatment. These findings highlight how treatment conditions can be tuned to modify the polyphenolic composition of WOP extracts and reinforce antioxidant activity. Such insights could support the development of WOP valorization strategies within integrated biorefineries. Full article

In this study, we investigated the impact of varying iron (Fe) and aluminum (Al) contents on the adsorption of phosphonates to activated sludge. Phosphonates originating from household applications account for up to 40% of the non-reactive dissolved phosphorus in domestic sewage treatment plants and thus can contribute to the eutrophication of water bodies. Although these substances are not readily degradable, substantial quantities, ranging from 40% to more than 90%, are removed by sludge adsorption. The results demonstrate a strong correlation between the adsorption of aminophosphonates and the Fe³⁺ content of the sludge. The maximum phosphonate loadings were 5.94 mmol g⁻¹ Fe³⁺ for ATMP, 4.94 mmol g⁻¹ Fe³⁺ for EDTMP, 4.74 mmol g⁻¹ Fe³⁺ for DTPMP, and 2.25 mmol g⁻¹ Fe³⁺ for glyphosate. In contrast to pure ferric hydride flocs, the adsorption of phosphonates was approximately threefold higher when the hydroxides were located within activated sludge flocs. It is concluded that native sludge flocs provide larger iron surfaces than ferric hydroxide alone. Based on the weight of the adsorbents, aluminum salts were four times less efficient than ferric salts. In sludge without ferric or aluminum hydroxides, phosphonate adsorption was negligible. Full article

The limited availability of high-quality ore deposits and the environmental hazards of metallurgical wastes highlight the importance of developing resource-efficient metal recovery technologies. Zinc kiln slag (ZKS), also known as Waelz slag, a by-product material enriched in non-ferrous metals, was processed through oxidative HCl leaching with H₂O₂ as an oxidant. Thermodynamic simulation and laboratory experiments were applied to determine optimal leaching conditions to dissolve copper, zinc, and iron. Optimal leaching efficiency was achieved with consumptions of 0.8 g HCl and 0.1 g H₂O₂ per gram of ZKS, a liquid-to-solid (L/S) ratio of 5 mL/g, a temperature of 70 °C, and a duration of 180 min, which resulted in recoveries of 96.3% Cu, 93.6% Fe, and 76.8% Zn. The solid residue with 43.5 wt.% C is promising for reuse as a reductant material in pyrometallurgical processes. Copper and arsenic were separated from the leachate via cementation with iron powder, achieving recovery rates of 98.9% and 91.2%, respectively. A subsequent two-step iron precipitation produced ferric hydroxide with 52.2 wt.% Fe and low levels of impurities. As a result, the developed novel hydrochloric acid oxidative leaching and metal precipitation route for ZKS recycling provides an efficient and sustainable alternative to conventional treatment methods. Full article

In this study, we investigate the effects of adding varying proportions of fulvic acid during the digestion of pyrite on the iron concentration in both dissolved and diluted sodium aluminate solutions. Based on the occurrence characteristics of iron in the solutions, oxygen was introduced into the diluted solution to examine its iron removal efficiency, and the influence of organic compounds in the solution on iron removal through oxidation was investigated. The results indicate that, during high-pressure digestion, organic compounds forms complexes with iron, disrupting the hydrophilic iron (or ferrous) hydroxide film formed on the pyrite surface, thereby accelerating its dissolution and leading to a sharp increase in sulfur and iron content in the leachate. After cooling and dilution (100 °C, Na₂O_k 170 g/L), the iron content in the sodium aluminate solution continued to be influenced by organic compounds, showing a significant positive correlation. Oxygenation experiments for iron removal were performed using the diluted solution. Under conditions of an oxygen flow rate of 60 mL/min and an oxidation duration of 2 h (95 °C, oxygen partial pressure was 0.05 Mpa), the iron content (calculated as Fe₂O₃) decreased from 0.078 g/L to 0.021 g/L. Characterization and analysis of the iron removal precipitates revealed that the iron-containing minerals were primarily trivalent iron phases, such as goethite and hematite, with minimal ferrous iron content. Additionally, organic carbon also precipitated together with iron, which confirms the synergistic removal of iron and organic compounds. These findings demonstrate that the oxidation of reducing sodium aluminate solutions containing organic compounds, sulfur, and iron with atmospheric oxygen during the Bayer process sedimentation stage can effectively oxidize predominantly ferrous iron into less soluble ferric iron, thereby achieving iron removal. Full article

It has been demonstrated that iron-reducing bacteria (IRB) Acidiphilium cryptum JF-5 (Alphaproteobacteria) could release arsenic from secondary iron oxyhydroxides in mine areas. This study used injecting IRB technology to carry out arsenic sequestration experiments aimed at alleviating arsenic pollution. Temperature and acetate were found to enhance arsenic release from amorphous arsenic-containing hydroxides. A suitable temperature (35 °C) increased the release of arsenic(III) and arsenic(V) by more than 1.9–2.5 and 1.1–1.3 times, respectively. The addition of acetate increased arsenic(III) and arsenic(V) release by more than 2.8–6.1 and 1.1–1.3 times, respectively, compared to the control group. After injecting IRB into amorphous arsenic-containing hydroxide sediment, arsenic associated with particles/colloid was reductively released with aqueous arsenic(III) and arsenic(V), which account for 4%–334% of aqueous arsenic(III) and 6%–332% of aqueous arsenic(V), respectively. Results from the suspension solid also showed that the average values for the lower and upper sites are 131 mg/L and 118 mg/L, respectively. These suspension solids contain rich iron. The effectiveness of this IRB-assisted arsenic release technology became better under suitable temperature (35 °C) than at low temperature (8 °C) due to biological activity. These results suggest that microbially assisted reduction using iron-reducing bacteria may effectively release arsenic by sequestrating arsenic as aqueous and particle/colloidal phases. Full article

The solution microstructure during the ferric sulfate-assisted precipitation of calcium fluoride was systematically investigated using molecular dynamics simulations and DFT methods. The microscopic behavior of various ions in a calcium fluoride box in the presence of ferric sulfate was simulated using MD. The corresponding hydrated cluster structures were extracted from the MD trajectory; then, the structure was optimized and the frequency was calculated at the B3LYP/6–311++G(d, p) level. The results show that no hydrated clusters had imaginary frequencies. Based on the topology, interaction region indicator, and surface electrostatic potential and binding energy analysis of the hydrated clusters, it was revealed that ferric ions are easily hydrolyzed to form hydrated clusters of ferric hydroxide at higher pH levels. The most stable of these structures is [Fe(OH)₃·(H₂O)₂], which has the lowest binding energy. During the ferric sulfate coagulation process, calcium fluoride clusters and ferric hydroxide clusters could form binuclear clusters through electrostatic interaction. The two metal centers in the binuclear cluster, Ca and Fe, are connected by hydroxide ions. Full article

The High-Density Sludge (HDS) process is widely used for the treatment of acid mine water as it produces a sludge of high density. The aim of this study was the development of a process where iron in mine water can be removed as magnetite, to assist with rapid settling of sludge. It was concluded that Fe²⁺ can be removed as Fe₃O₄ (magnetite) by forming Fe(OH)₂ and Fe(OH)₃ in the mole ratio of 1:2. Magnetite can form in the absence or presence of gypsum. The settling rate of magnetite-rich sludge is substantially faster than that of ferric hydroxide-rich sludge. It is recommended that further studies be carried out on the separation of magnetite gypsum through magnetic separation. Full article

Microwave-based reactions have gained traction in recent years due to their ability to enhance reaction rates and yield while reducing energy consumption. Also, according to the conception of ‘waste to materials’, various waste feeds are intensively sought to be tested. The experimental setup of this study involved varying pH levels, oxidation agents, and precipitation agents to optimize the synthesis process of iron red based on waste iron sulfate. The selection of oxidation and precipitation agents was found to significantly influence the pigment synthesis process. Various oxidizing agents, including hydrogen peroxide and atmospheric air, were evaluated for their effectiveness in promoting the oxidation of ferrous ions to ferric ions, essential for pigment formation. Additionally, different precipitation agents such as sodium hydroxide and ammonia solution were assessed for their ability to precipitate iron hydroxides and facilitate pigment particle formation. The characterization of synthesized pigments revealed promising results in terms of quality and color properties. Helium Ion Microscopy (HIM) analysis confirmed the formation of well-defined pigment particles with controlled morphology. X-ray diffraction (XRD) studies provided insights into the crystalline structure of the pigments, indicating the presence of characteristic iron oxide phases. By improving this technology, waste iron sulfate can be efficiently transformed into valuable iron pigments, offering a sustainable solution for waste management while meeting the growing demand for high-quality pigments. Full article

Transition-metal-based oxygen evolution reaction (OER) catalysts have attracted widespread attention due to their inexpensive prices, unique layered structures, and rich active sites. Currently, designing low-cost, sustainable, and simple synthesis methods is essential for the application of transition-metal-based catalysts. Here, magnetic field (MF)-assisted chemical corrosion, as a novel technology, is adopted to construct superior OER electrocatalysts. The produced Ni(Fe)(OH)₂-Fe₂O₃ electrode exhibits an overpotential of 272 mV at a current density of 100 mA cm⁻², presenting a 64 mV reduction compared to the electrode without an MF. The experimental results indicate that an MF can induce the directional growth of Fe₂O₃ rods and reduce their accumulation. In addition, an external MF is beneficial for the lattice dislocation of the obtained catalysts, which can increase the surface free energy, thus reducing the activation energy and accelerating the electrochemical reaction kinetics. This work effectively combines a magnetic field with chemical corrosion and electrochemical energy, which offers a novel strategy for the large-scale development of environmentally friendly and superior electrocatalysts. Full article

This study presents findings regarding the kinetics of ferrous iron oxidation in solution mediated by Acidithiobacillus ferrooxidans bacteria within a continuous-flow bioreactor employing diverse types of immobilizers. The objective is to augment the rate of ferrous iron oxidation in solutions utilizing an immobilizer for Acidithiobacillus ferrooxidans strains. Immobilization represents a promising avenue for enhancing the efficiency of Fe²⁺ oxidation via acidophilic ferrooxidizing bacteria, leading to a several-fold increase in oxidation rate. A comparative analysis was conducted to evaluate the efficacy of different types of immobilizer in facilitating iron oxidation within a continuous-flow bioreactor, including the application of wood chips coated with Fe(OH)₃. The results indicate that wood chips coated with iron hydroxide serve as effective type of immobilizer, facilitating the robust attachment of Acidithiobacillus ferrooxidans via electrostatic interactions between negatively charged bacteria and positively charged surfaces. Experimental investigations were conducted using novel immobilization matrices in pilot-scale tests simulating the underground borehole leaching (UBL) of uranium. The bioactivation of leaching solutions enhances the efficiency and environmental compatibility of UBL compared to conventional chemical oxidation methods. The relationships between redox potential and ferric iron content in bioactivated solutions during the UBL of uranium were delineated. The significance of this study lies in its elucidating the pivotal role of Fe²⁺ oxidation in uranium extraction processes, particularly in the context of UBL. By employing bioactivation mediated by Acidithiobacillus ferrooxidans, the study demonstrates not only enhanced uranium extraction efficiency, but also markedly improved environmental sustainability compared to traditional chemical oxidation methods. The findings reveal crucial correlations between redox potential and ferric iron concentration in bioactivated solutions. Full article

The employment of granular ferric iron-(oxy)hydroxides, a well-known economic and effective method, lowers arsenic concentrations in different water types. However, for direct application in polluted groundwaters, there is a need to develop new injectable adsorbents for aquifers that could also neutralize acidic media. In this context, a granular ferric hydroxide-calcite (GFH-C) adsorbent was size-reduced to 0.4–50 µm by sonication with the aim of improving (i) the adsorption of As(III) and As(V) at different pHs and (ii) the pH control through the dissolution of calcite. Batch experiments were conducted to determine As(III) and As(V) adsorption isotherms and kinetics, as well as calcite dissolution kinetics, using GFH-C of two sizes (granular and sonicated). Results showed that the arsenic binding capacity of sonicated adsorbents did not improve significantly. On the contrary, the As(III) and As(V) adsorption kinetics improved with the sonication, as in the case of calcite dissolution kinetics. The dissolution of calcite from the adsorbent made the water pH increase to around 9.2–9.4. The sonicated adsorbent offers an advantage in depolluting As-containing groundwater due to its smaller size, which is linked with faster arsenic adsorption and effective acidic water neutralization. Full article

Stormwater runoff from expressways generally has high concentrations of heavy metals. However, the heavy metal removal of conventional sand filters is low, so a better alternative is required. In this study, several inexpensive materials were tested for their heavy metal adsorption, and the performances of the selected materials were evaluated via field tests. The results of laboratory experiments showed that the Cu adsorption capacity followed the order of Na-zeolite > zeolite > biochar > granular ferric hydroxide > sand ≥ orchid stone. The performance of a pilot-scale dual-media filter filled with Na-zeolite and mortar granules was monitored for four rainfall events at an expressway site, and was compared to that of a sand filter. Both filters showed similar event mean concentration (EMC) removal for BOD, COD, TOC, and T-N, without a notable decrease in hydraulic conductivity. However, the removal of T-P, Cu, Zn, Cr, Ni, and Fe by the dual-media filter was 37.6–74.8%, 59.1–90.1%, 84.9–99.7%, 100.0%, 100.0%, and 78.7–94.4%, respectively, which was up to 4.5 times of that of the sand filter. In addition, it was stable regardless of the influent EMCs. Overall, we showed that the dual-media filter is excellent in heavy metal removal from stormwater runoff, with negligible clogging. Full article

The development of multifunctional biomimetic nanozymes with high catalytic activity and sensitive response is rapidly advancing. The hollow nanostructures, including metal hydroxides, metal-organic frameworks, and metallic oxides, possess excellent loading capacity and a high surface area-to-mass ratio. This characteristic allows for the exposure of more active sites and reaction channels, resulting in enhanced catalytic activity of nanozymes. In this work, based on the coordinating etching principle, a facile template-assisted strategy for synthesizing Fe(OH)₃ nanocages by using Cu₂O nanocubes as the precursors was proposed. The unique three-dimensional structure of Fe(OH)₃ nanocages endows it with excellent catalytic activity. Herein, in the light of Fe(OH)₃-induced biomimetic nanozyme catalyzed reactions, a self-tuning dual-mode fluorescence and colorimetric immunoassay was successfully constructed for ochratoxin A (OTA) detection. For the colorimetric signal, 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) can be oxidized by Fe(OH)₃ nanocages to form a color response that can be preliminarily identified by the human eye. For the fluorescence signal, the fluorescence intensity of 4-chloro-1-naphthol (4-CN) can be quantitatively quenched by the valence transition of Ferric ion in Fe(OH)₃ nanocages. Due to the significant self-calibration, the performance of the self-tuning strategy for OTA detection was substantially enhanced. Under the optimized conditions, the developed dual-mode platform accomplishes a wide range of 1 ng/L to 5 μg/L with a detection limit of 0.68 ng/L (S/N = 3). This work not only develops a facile strategy for the synthesis of highly active peroxidase-like nanozyme but also achieves promising sensing platform for OTA detection in actual samples. Full article

Recovering iron from the bauxite residue (BR) is one of the long-standing challenges in the mining industry. However, there is a substantial lack of information in the literature regarding sample properties and iron extraction by reducing hydrogen. The present study aims at reducing a Greek BR using hydrogen, its characterization, and separating iron by magnetic separation processes. To this end, the reduced sample was characterized using X-ray diffractometry analysis (XRD), X-ray fluorescence spectrometer analysis (XRF), thermomagnetic analysis (TMA), automated mineralogy (AM), and scanning electron microscopy (SEM) coupled with energy dispersive spectroscopy (EDS). The effect of particle size (−200 + 100 µm, −100 + 75 µm, and <75 µm) was investigated through a medium-intensity magnetic separation (MIMS, Davis Tube) at 1000–2500 Gauss and a Slon^® magnetic separator (1000 G). The effects of solid content (3% and 10% w/w) in a wet low-intensity magnetic separation (WLIMS, 350 G) and a two-stage MIMS followed by WLIMS were investigated. It was revealed that through reduction at 500 °C and 2 h with 20 wt% NaOH under 5 vol.% H₂ + 95 vol.% N₂, iron oxides and ferric oxyhydroxide (Fe₂O₃ and FeOOH) were converted into magnetite (Fe₃O₄), whereas aluminum (oxy)hydroxides (Al(OOH), Al(OH)₃) were reacted with Na⁺ towards sodium aluminates (NaAlO₂). The AM observations indicated that only 3% of iron was in the phase of liberated magnetite, and the remaining was associated with Na, Al, and Ti phases with different intensities. The dissemination of iron throughout the matrix of the sample was recognized as the principal challenge in the physical separation processes. It was found that increasing magnetic intensity from 1000 G to 2500 G resulted in improved recovery for all studied particle size fractions in Davis Tube tests. The particle range of −106 + 74 µm was chosen as the most appropriate size to achieve the maximum Fe content of 41%. The results of WLIMS (350 G) showed the maximum Fe grade but revealed less recovery of 52% and 27% at 10% and 3% solid contents, respectively, compared to the Davis Tube trials. Full article

Nanoparticles, by virtue of their amorphous nature and high specific surface area, exhibit ideal pozzolanic activity which leads to the formation of additional C-S-H gel by reacting with calcium hydroxide, resulting in a denser matrix. The proportions of ferric oxide (Fe₂O₃), silicon dioxide (SiO₂), and aluminum oxide (Al₂O₃) in the clay, which interact chemically with the calcium oxide (CaO) during the clinkering reactions, influence the final properties of the cement and, therefore, of the concrete. Through the phases of this article, a refined trigonometric shear deformation theory (RTSDT), taking into account transverse shear deformation effects, is presented for the thermoelastic bending analysis of concrete slabs reinforced with ferric oxide (Fe₂O₃) nanoparticles. Thermoelastic properties are generated using Eshelby’s model in order to determine the equivalent Young’s modulus and thermal expansion of the nano-reinforced concrete slab. For an extended use of this study, the concrete plate is subjected to various mechanical and thermal loads. The governing equations of equilibrium are obtained using the principle of virtual work and solved using Navier’s technique for simply supported plates. Numerical results are presented considering the effect of different variations such as volume percent of Fe₂O₃ nanoparticles, mechanical loads, thermal loads, and geometrical parameters on the thermoelastic bending of the plate. According to the results, the transverse displacement of concrete slabs subjected to mechanical loading and containing 30% nano-Fe₂O₃ was almost 45% lower than that of a slab without reinforcement, while the transverse displacement under thermal loadings increased by 10%. Full article