Unveiling the oxidation mechanism of persistent organic contaminants via visible light-induced dye-sensitized reaction by red mud suspension with peroxymonosulfate.

A dye-sensitized photocatalysis system was developed for degrading persistent organic contaminants using solid waste (i.e., red mud, RM) and peroxymonosulfate (PMS) under visible light. Complete degradation of acid orange 7 (AO7) was achieved in RM suspension with PMS, where the co-existence of amorphous FeO(OH)/α-Fe2O3 was the key factor for PMS activation. The experimental results obtained from photochemical and electrochemical observations confirmed the enhanced PMS activation due to the Fe-OH phase in RM. DFT calculations verified the acceleration of PMS activation due to the high adsorption energy of PMS on FeO(OH) and low energy barrier for generating reactive radicals. Compared to the control experiment without AO7 showing almost no degradation of other organic contaminants (phenol, bisphenol A, 4-chlorophenol, 4-nitrophenol, and benzoic acid), photo-sensitized AO7* enhanced electron transfer in the FeIII/FeII cycle, dramatically enhancing the degradation of organic contaminants via radical (•OH, SO4•-, and O2•-) and non-radical (dye*+ and 1O2) pathways. Therefore, the novel finding of this study can provide new insights for unique PMS activation by heterogeneous Fe(III) containing solid wastes and highlight the importance of sensitized dye on the interaction of PMS with Fe charge carrier for the photo-oxidation of organic contaminants under visible light.

Unveiling the positive effect of mineral induced natural organic matter (NOM) on catalyst properties and catalytic dechlorination performance: An experiment and DFT study.

Herein, we report the significant effects of natural organic matter contained in natural zeolite (Z-NOM) on the physicochemical characteristics of a Ni/Fe@natural zeolite (NF@NZ) catalyst and its decontamination performance toward the dechlorination of trichloroethylene (TCE). Z-NOM predominantly consists of humic-like substances and has demonstrable utility in the synthesis of bimetallic catalysts. Compared to NF@NZ600C (devoid of Z-NOM), NF@NZ had increased dispersibility and mobility and showed significant enhancement in the catalytic dechlorination of TCE owing to the encapsulation of Ni0/Fe0 nanoparticles by Z-NOM. The results of corrosion experiments, spectroscopic analyses, and H2 production experiments confirmed that Ni0 acted as an efficient cocatalyst with Fe0 to enhance the dechlorination of TCE to ethane, and Z-NOM-capped Ni0 showed improved adsorption of TCE and atomic hydrogen on their reactive sites and oxidation resistance. The density functional theory (DFT) studies have substantiated the improved adsorption of TCE due to the presence of NOM (especially by COOH structure) and the enhanced charge density at the Ni site in the Ni/Fe bimetal alloy for the stronger adsorption of hydrogen atoms that ultimately enhanced the TCE reduction reaction. These findings illustrate the efficiency of NOM containing natural minerals toward the synthesis of bimetallic catalysts for practical applications.

The role of Fe dissolution in olivine-hydroxylamine-induced Fenton reaction for enhanced oxidative degradation of organic pollutant.

In this study, a dye pollutant (methyl orange, MO) was effectively oxidized in a hydroxylamine (HA)-assisted Fenton system using various Al/Si/Fe- and Fe-containing minerals. The fastest degradation kinetics of MO were observed in the olivine-HA Fenton system, whereas other Al/Si/Fe and Fe-rich minerals (magnetite and lepidocrocite) demonstrated much slower degradation kinetics. The degradation rate constants were proportional to dissolved Fe(II) quantities in mineral suspensions (R2 = 0.98), indicating the crucial role of dissolved Fe(II) quantity in HA-assisted Fenton reactions. Radical scavenging and electron spin resonance results revealed that MO was dominantly oxidized by ·HO produced in the olivine-HA Fenton system. The continuous production of aqueous Fe(II) via direct Fe(II) dissolution at a pH of 3 and further Fe dissolution from the reductive dissolution of surface Fe(III) by HA was the main driving force for efficient MO degradation. Furthermore, lowering the pH by the addition of hydroxylamine hydrochloride resulted in the effective removal of MO under various pH conditions (3-9), indicating the additional advantage of HA use in Fenton reactions. Liquid chromatography-mass spectroscopy analysis revealed that the cleavage of C-N and C-C bonds, demethylation, hydroxylation, and dehydroxylation were the main processes for MO oxidation in the olivine-HA Fenton system.

The enhanced reduction of bromate by highly reactive and dispersive green nano-zerovalent iron (G-NZVI) synthesized with onion peel extract.

In this study, novel green nano-zerovalent iron (G-NZVI) is synthesized for the first time using onion peel extract for the prevention of rapid surface oxidation and the enhancement of particle dispersibility with a high reductive capacity. The results from various surface analyses revealed that the spherical shape of G-NZVI was fully covered by the onion peel extract composed of polyphenolic compounds with C[double bond, length as m-dash]C-C[double bond, length as m-dash]C unsaturated carbon, C[double bond, length as m-dash]C, C-O, and O-H bonds, resulting in high mobility during column chromatography. Furthermore, the obtained G-NZVI showed the complete removal of 50 mg L-1 of bromate (BrO3 -) in 2 min under both aerobic (k = 4.42 min-1) and anaerobic conditions (k = 4.50 min-1), showing that G-NZVI had outstanding oxidation resistance compared to that of bare NZVI. Moreover, the observed performance of G-NZVI showed that it was much more reactive than other well-known reductants (e.g., Fe and Co metal organic frameworks), regardless of whether aerobic or anaerobic conditions were used. The effects of G-NZVI loading, the BrO3 - concentration, and pH on the BrO3 - removal kinetics using G-NZVI were also investigated in this study. The results provide the novel insight that organic onion peel waste can be reused to synthesize highly reactive anti-oxidative nanoparticles for the treatment of inorganic chemical species and heavy metals in water and wastewater.

Characterization of rare earth elements present in coal ash by sequential extraction.

Although it has recently been reported that notable amounts of rare earth elements (REEs) are present in the residual coal ash, little is currently known regarding the association of these elements with the coal ash matrix, thereby limiting the potential for extraction of REEs from coal ash. In this study, we analyzed the binding characteristics of REEs within coal ash via sequential extraction and examined REE recovery during a coal ash recycling process. Major components of coal ash were found to be mineral oxides, mainly composed of Si, Fe, Al, and Ca, and residual carbons. Bottom and fly ashes were found to contain 185.8 mg/kg and 179.2 mg/kg of REEs, respectively. Tessier sequential extraction confirmed that 85 % of REEs are included in the residual fraction of both bottom and fly ashes. Furthermore, BCR sequential extraction revealed that 60-70 % of REEs are contained within the residual fraction, thereby indicating that REEs are strongly bound in both bottom and fly ashes and the use of very strong acids is required for the thorough extraction of REEs from coal ash. Additionally, it was found that 46.3 % of REEs can be recovered from the wastewaters produced during the process of coal ash-derived zeolite synthesis.

Red mud-activated peroxymonosulfate process for the removal of fluoroquinolones in hospital wastewater.

In this study, a novel peroxymonosulfate (PMS) activation method, which combines a solid waste (i.e., red mud, RM) and a reducing agent (i.e., hydroxylamine, HA), for the oxidative degradation of fluoroquinolones (FQs; i.e., flumequine (FLU) and ciprofloxacin (CIP)) in hospital wastewater (HW) was developed. The addition of HA into the PMS/RM suspension significantly enhanced FLU removal, owing to its ability to enhance the Fe(III)/Fe(II) cycle on the RM surface. The results of the quenching experiments suggested the predominance of SO4•- over •OH in the PMS/RM/HA system. Moreover, owing to the greater reactivity between CIP and SO4•-, CIP removal was more effective than FLU removal. Additionally, the liquid chromatography-mass spectroscopy (LC-MS) analysis revealed that the oxidation of CIP and FLU by PMS/RM/HA occurred via sequential and separate processes, involving ring cleavage, hydroxylation, decarbonylation, and defluorination. Surprisingly, the wastewater components exhibited contrasting effects on FLU removal in HW. Natural organic matter, nitrate and sulfate showed a slight impact on the removal performance of FLU, whereas chloride improved the oxidation extent. However, phosphate significantly inhibited the FLU removal because of its competitive binding at the RM surface and its scavenging effect towards SO4•-. This inhibitory effect was overcome by increasing the PMS concentration and its sequential addition, thus guaranteeing successful mineralization of FLU in HW. These results show that the RM/HA system can be utilized to activate PMS for the removal of antibiotics in wastewater.

Effect of groundwater ions (Ca2+, Na+, and HCO3-) on removal of hexavalent chromium by Fe(II)-phosphate mineral.

A systematic study was conducted to investigate the effect of major groundwater ions (i.e., Ca2+, Na+, and HCO3-) on removal of hexavalent chromium (Cr(VI)) by an Fe(II)-phosphate mineral (i.e., vivianite). The batch experiments revealed that the second-order rate constant for Cr(VI) removal by vivianite with Ca2+ + CO32- (0.076-1.90 mM) and Na+ + HCO3- (0.26-6.50 mM) was 1.5-5.2 times lower than that without these ions. The removal kinetics of Cr(VI) by vivianite was abruptly slowed down with the increased ion concentration, which showed their inhibitory effect on the reaction. The results of the geochemical modeling and density functional theory calculations showed that the presence of Ca2+ + HCO3- and Na+ + HCO3- can form less favorable Cr(VI) species (i.e., CaCrO4(aq) and NaCrO4-) on the Fe-B site of vivianite surface, leading to the inhibitory effect observed in this study. Finally, the X-ray absorption spectroscopy results showed that reductive immobilization of Cr(VI) to Cr(III) occurred by structural Fe(II) oxidation of vivianite to amorphous mixed-valence Fe-phosphate via an inner-sphere complexation. The results suggest that the presence of Ca2+, Na+, and HCO3- in phosphorous-enriched iron-reducing environments may lower the remedial efficiency of Cr(VI) removal.

Prussian blue immobilized cellulosic filter for the removal of aqueous cesium.

Cesium is a typical radioisotope that has a long half-life and is dangerous and can be emitted in the event of a nuclear accident. Prussian blue (PB), which is known to effectively adsorb cesium, is difficult to separate when it is dissolved in an aqueous system. In this study, PB was immobilized on a filter type support media, cellulose filter (CF), for use as a selective material for cesium adsorption. The commercially available CF was functionalized by the addition of acrylic acid (AA) (i.e., CF-AA) to enhance the PB immobilization, which increased both PB loading and binding strength. The AA functionalization changed the major functional groups from hydroxyl to carboxylic, as confirmed by Fourier-transform infrared spectroscopy. As a result of the surface modification, the PB immobilization increased 1.5 times and reduced detachment of PB during washing. The prepared adsorbent, CF-AA-PB, was tested for its cesium adsorption capability. Cesium adsorption equilibrated within 3 h, and the maximum cesium adsorption capacity was 16.66 mg/g. The observed decrease in the solution pH during cesium adsorption inhibited the overall cesium uptake; however, this was minimized by buffering. The prepared CF-AA-PB was used as a filter material and its potential use as a countermeasure for removing radioactive cesium from a contaminated water stream was demonstrated.

Novel synthesis of nanoscale zerovalent iron from coal fly ash and its application in oxidative degradation of methyl orange by Fenton reaction.

We firstly developed a novel synthesis method of nanoscale zerovalent iron (NZVI) using Fe sources in coal fly ash (CFA) for the oxidative degradation of methyl orange by Fenton reaction. Hydrochloric acid (HCl) and methyl isobutyl ketone (MIBK) were used for Fe dissolution from CFA and selective Fe(III) chelation, respectively. Among varied HCl concentrations, 7 N HCl showed the best performance for the oxidation of aqueous Fe(II) to Fe(III) and efficient chelation of Fe(III) with MIBK. The NZVI-CFA was synthesized by adding NaBH4 to a solution of Fe(III)-chelated MIBK, yielding NZVI transformation >95% from Fe(III) in HCl. Various surface analyses were performed to characterize the NZVI-CFA, which was almost identical to typical NZVI-Bare. HCl and MIBK could be reused several times, indicating potential reusability of chemicals used in the synthesis. Remarkable >96% decolorization of methyl orange was obtained by the NZVI-CFA-induced Fenton reaction at pH 3, with a ∼22% decrease in total organic carbon in 7 min. The heterogeneous Fenton reaction initiated by NZVI-CFA with H2O2 showed reactivity similar to that of the homogeneous Fenton reaction (i.e., aqueous Fe(II) with H2O2), indicating the importance of homogeneous reaction for the oxidative degradation of methyl orange.

Molecular Identification of Cr(VI) Removal Mechanism on Vivianite Surface.

Experimental and theoretical studies were conducted to identify the molecular-scale reaction mechanism for Cr(VI) removal by a ferrous phosphate mineral, vivianite. The surface-normalized rate constant for Cr(VI) removal in a vivianite suspension at pH 7 was higher than those obtained for other Fe(II)-containing minerals (i.e., magnetite and pyrite). The highest rate constant was obtained at pH 5, which was 35- and 264-times higher than those obtained at pH 7 and 9, respectively, indicating the dramatic acceleration of removal kinetics with decreasing pH of suspension. The X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES) spectroscopy revealed that Cr(VI) removal involved reduction of Cr(VI) to Cr(III) coupled with oxidation of Fe(II) to Fe(III) on the vivianite surface. In addition, the density functional theory (DFT)-optimized structure of the Cr(VI)-vivianite complex was consistent with that obtained from extended X-ray absorption fine structure (EXAFS) spectroscopy and revealed the transformation of vivianite to amorphous Fe(III) phosphate. We also demonstrated that both Cr(VI) species, HCrO4̅ and CrO42-, can effectively bind to the vivianite surface, particularly on the Fe sites having 6 neighboring Fe molecules with 4 H2O and 2 PO4 moieties. Our results show that Cr(VI) is readily reduced to Cr(III) by vivianite via adsorption and inner-sphere complexation, suggesting that in anoxic iron-phosphate-enriched environments, vivianite may significantly influence the fate and transport of Cr(VI).