Insight into the Efficient Selective Reduction of Cr(VI) in Sulfite/UV Process under Near-Neutral Conditions: The Critical Role of In Situ-Generated Sulfite Radical.

Efficient removal of contaminants in complex water matrices under mild conditions is highly desirable but still challenging. In this study, we unraveled the overlooked but crucial role of sulfite radical (SO3·-) in the efficient selective reduction of toxic Cr(VI) under near-neutral conditions. Fast removal of Cr(VI) at around pH 7 in sulfite/UV was found to be attributable to high reactivity of SO3·- toward HCrO4- (∼5.3 × 106 M-1 s-1). Furthermore, SO3·- was fast generated in situ via one-electron oxidation of S(IV) by transient reactive protonated Cr(V) and Cr(IV) intermediates. Therefore, the specific reactivity of SO3·- and its in situ generation together resulted in the surprisingly positive effect of nitrate and the efficient reduction of Cr(VI) in authentic surface water and industrial wastewater. A mathematical model was developed to simulate Cr(VI) removal in the process, and thus quantitatively demonstrated the roles of reactive species, i.e., SO3·- contributed to ∼93% of Cr(VI) reduction in surface water. Overall, this study provides an insight into the pivotal role of SO3·- in Cr(VI) reduction, and underscores its significance in selective reduction and detoxification of contaminants.

Thiourea Dioxide Coupled with Trace Cu(II): An Effective Process for the Reductive Degradation of Diatrizoate.

Diatrizoate, a refractory ionic iodinated X-ray contrast media (ICM) compound, cannot be efficiently degraded in a complex wastewater matrix even by advanced oxidation processes. We report in this research that a homogeneous process, thiourea dioxide (TDO) coupled with trace Cu(II) (several micromoles, ubiquitous in some wastewater), is effective for reductive deiodination and degradation of diatrizoate at neutral pH values. Specifically, the molar ratio of iodide released to TDO consumed reached 2 under ideal experimental conditions. TDO eventually decomposed into urea and sulfite/sulfate. Based on the results of diatrizoate degradation, TDO decomposition, and Cu(I) generation and consumption during the TDO-Cu(II) reaction, we confirmed that Cu(I) is responsible for diatrizoate degradation. However, free Cu(I) alone did not work. It was proposed that Cu(I) complexes are actual reactive species toward diatrizoate. Inorganic anions and effluent organic matter negatively influence diatrizoate degradation, but by increasing the TDO dosage, as well as extending the reaction time, its degradation efficiency can still be guaranteed for real hospital wastewater. This reduction reaction could be potentially useful for in situ deiodination and degradation of diatrizoate in hospital wastewater before discharge into municipal sewage networks.

Overlooked Role of Peroxides as Free Radical Precursors in Advanced Oxidation Processes.

Research efforts on advanced oxidation processes (AOPs) have long been focused on the fundamental chemistry of activation processes and free radical reactions. Little attention has been paid to the chemistry of the precursor oxidants. Herein, we found that the precursor oxidants could lead to quite different outcomes. A counterintuitive result was observed in the photoreduction of bromate/iodate: the combination of H2O2 and UV enhanced the reduction of bromate/iodate, whereas the addition of persulfate to the UV system led to an inhibitory effect. Thermodynamic and kinetic evidence suggests that the reduction of bromate in UV/H2O2 was attributable to the direct reaction between HOBr and H2O2. Both experimental determination and kinetic simulation demonstrate that the reaction between HOBr and H2O2 dominated over the •OH-mediated reactions. These results suggest that H2O2 possesses some particular redox properties that distinguish it from other peroxides. The prototypical UV/H2O2 process is not always an AOP: it can also be an enhanced reduction process for chemicals with intermediates that are reducible by H2O2. Considering the increasing interest in persulfate-based AOPs, the results of this study identify some novel advantages of the classical H2O2-based AOPs.

Autocatalytic Decomplexation of Cu(II)-EDTA and Simultaneous Removal of Aqueous Cu(II) by UV/Chlorine.

Traditional processes usually cannot enable efficient water decontamination from toxic heavy metals complexed with organic ligands. Herein, we first reported the removal of Cu(II)-EDTA by a UV/chlorine process, where the Cu(II)-EDTA degradation obeyed autocatalytic two-stage kinetics, and Cu(II) was simultaneously removed as CuO precipitate. The scavenging experiments and EPR analysis indicated that Cl• accounted for the Cu(II)-EDTA degradation at diffusion-controlled rate (∼1010 M-1 s-1). Mechanism study with mass spectrometry evidence of 11 key intermediates revealed that the Cu(II)-EDTA degradation by UV/chlorine was an autocatalytic successive decarboxylation process mediated by the Cu(II)/Cu(I) redox cycle. Under UV irradiation, Cu(I) was generated during the photolysis of the Cl•-attacked complexed Cu(II) via ligand-to-metal charge transfer (LMCT). Both free and organic ligand-complexed Cu(I) could form binary/ternary complexes with ClO-, which were oxidized back to Cu(II) via metal-to-ligand charge transfer (MLCT) with simultaneous production of Cl•, resulting in the autocatalytic effect on Cu(II)-EDTA removal. Effects of chlorine dosage and pH were examined, and the technological practicability was validated with authentic electroplating wastewater and other Cu(II)-organic complexes. This study shed light on a new mechanism of decomplexation by Cl• and broadened the applicability of the promising UV/chlorine process in water treatment.

Chlorate Formation Mechanism in the Presence of Sulfate Radical, Chloride, Bromide and Natural Organic Matter.

Halides and natural organic matter (NOM) are inevitable in aquatic environment and influence the degradation of contaminants in sulfate radical (SO4•-)-based advanced oxidation processes. This study investigated the formation of chlorate in the coexposure of SO4•-, chloride (Cl-), bromide (Br-) and/or NOM in UV/persulfate (UV/PDS) and cobalt(II)/peroxymonosulfate (Co/PMS) systems. The formation of chlorate increased with increasing Cl- concentration in the UV/PDS system, however, in the Co/PMS system, it initially increased and then decreased. The chlorate formation involved the formation of hypochlorous acid/hypochlorite (HOCl/OCl-) as an intermediate in both systems. The formation was primarily attributable to SO4•- in the UV/PDS system, whereas Co(III) played a significant role in the oxidation of Cl- to HOCl/OCl- and SO4•- was important for the oxidation of HOCl/OCl- to chlorate in the Co/PMS system. The pseudo-first-order rate constants ( k') of the transformation from Cl- to HOCl/OCl- were 3.32 × 10-6 s-1 and 9.23 × 10-3 s-1 in UV/PDS and Co/PMS, respectively. Meanwhile, k' of HOCl/OCl- to chlorate in UV/PDS and Co/PMS were 2.43 × 10-3 s-1 and 2.70 × 10-4 s-1, respectively. Br- completely inhibited the chlorate formation in UV/PDS, but inhibited it by 45.2% in Co/PMS. The k' of SO4•- reacting with Br- to form hypobromous acid/hypobromite (HOBr/OBr-) was calculated to be 378 times higher than that of Cl- to HOCl/OCl-, but the k' of Co(III) reacting with Br- to form HOBr/OBr- was comparable to that of Cl- to HOCl/OCl-. NOM also significantly inhibited the chlorate formation, due to the consumption of SO4•- and reactive chlorine species (RCS, such as Cl·, ClO· and HOCl/OCl-). This study demonstrated the formation of chlorate in SO4•--based AOPs, which should to be considered in their application in water treatment.

Enhanced debromination of 4-bromophenol by the UV/sulfite process: Efficiency and mechanism.

Halogenated aromatic compounds have attracted increasing concerns due to their toxicity and persistency in the environment, and dehalogenation is one of the promising treatment and detoxification methods. Herein, we systematically studied the debromination efficiency and mechanism of para-bromophenol (4-BP) by a recently developed UV/sulfite process. 4-BP underwent rapid degradation with the kinetics accelerated with the increasing sulfite concentration, pH (6.1-10) and temperature, whereas inhibited by dissolved oxygen and organic solvents. The apparent activation energy was estimated to be 27.8kJ/mol. The degradation mechanism and pathways of 4-BP were explored by employing N2O and nitrate as the electron scavengers and liquid chromatography/mass spectrometry to identify the intermediates. 4-BP degradation proceeded via at least two pathways including direct photolysis and hydrated electron-induced debromination. The contributions of both pathways were distinguished by quantifying the quantum yields of 4-BP via direct photolysis and hydrated electron production in the system. 4-BP could be readily completely debrominated with all the substituted Br released as Br-, and the degradation pathways were also proposed. This study would shed new light on the efficient dehalogenation of brominated aromatics by using the UV/sulfite process.

Production of Hydroxyl Radical via the Activation of Hydrogen Peroxide by Hydroxylamine.

The production of the hydroxyl radical (HO·) is important in environmental chemistry. This study reports a new source of HO· generated solely from hydrogen peroxide (H2O2) activated by hydroxylamine (HA). Electron paramagnetic resonance analysis and the oxidation of a HO· probe, benzoic acid, were used to confirm the production of HO·. The production of HO· increased with increasing concentrations of either HA or H2O2 as well as decreasing pH. The second-order rate constant for the reaction was (2.2 ± 0.2) × 10(-4) M(-1) s(-1). HO· was probably produced in two steps: the activation of H2O2 by protonated HA and then reaction between the H2O2 and the intermediate protonated aminoxyl radical generated in the first step. Such a two-step oxidation can possibly be ascribed to the ionizable hydroxyl moiety in the molecular structure of HA, as is suggested by comparing the reactivity of a series of HA derivatives in HO· production. The results shed light on a previously unknown source of HO· formation, which broadens the understanding of its role in environmental processes.

Intramolecular generation of endogenous Cu(III) for selectively self-catalytic degradation of Cu(II)-EDTA from wastewater by UV/peroxymonosulfate.

HO•/SO4•--based advanced oxidation processes for the decomplexation of heavy metal-organic complexes usually encounter poor efficiency in real scenarios. Herein, we reported an interesting self-catalyzed degradation of Cu(II)-EDTA with high selectivity in UV/peroxymonosulfate (PMS). Chemical probing experiments and competitive kinetic analysis quantitatively revealed the crucial role of in situ formed Cu(III). The Cu(III) species not only oxidized Cu(II)-EDTA rapidly at ∼3 × 107 M-1 s-1, but also exhibited 2-3 orders of magnitude higher steady-state concentration than HO•/SO4•-, leading to highly efficient and selective degradation of Cu(II)-EDTA even in complex matrices. The ternary Cu(II)-OOSO3- complexes derived from Cu(II)-EDTA decomposition could generate Cu(III) in situ via the Cu(II)-Cu(I)-Cu(III)-Cu(II) cycle involving intramolecular electron transfer. This method was also applicable to various Cu(II) complexes in real electroplating wastewater, demonstrating higher energy efficiency than commonly studied UV-based AOPs. This study provids a proof of concept for efficient decomplexation through activating complexed heavy metals into endogenous reactive species.

Dry deposition fluxes and inhalation risks of toxic elements in total suspended particles in the Bohai Rim region: Long-term trends and potential sources.

Long-term changes in dry deposition fluxes (DDF) and health risks for toxic elements (TE) in total suspended particles (TSP) in the Bohai Rim region are important for assessing control effects of pollution sources. Thus, we investigated the trends in DDF and concentrations for TSP and TE and health risks of TE in eight cities in the region from 2011-2020. TSP concentration and DDF showed general downward trends. Compared to the before Clear Air Action Plan (BCAAP, 2011-2012) period, concentration and DDF of TE over the Clear Air Action Plan (CAAP, 2013-2017) period substantially decreased, with the highest decrease rates in Zn, Cd, and Cr. During the study period, non-carcinogenic (HI) and total carcinogenic (TCR) risks for children and adults were 0.09 and 0.04, and 1.54 × 10-5 and 2.65 × 10-5, respectively, with Cr6+ and As being dominant contributors. Compared to the BCAAP period, HI and TCR over the CAAP period decreased by 36.8 % and 32.4 %, respectively. However, their risks increased over the Blue Sky Protection Campaign (BSPC, 2018-2020) period. Potential source contribution function suggested substantial changes in potential risk areas over different control periods, with the BSPC primarily being on land and the Yellow Sea.

Optimizing Paclitaxel Oral Absorption and Bioavailability: TPGS Co-Coating via Supercritical Anti-Solvent Fluidized Bed Technology.

Supercritical anti-solvent fluidized bed (SAS-FB) coating technology has the advantages of reducing particle size, preventing high surface energy particle aggregation, improving the dissolution performance and bioavailability of insoluble drugs. The poor solubility of Biopharmaceutics Classification System (BCS) class IV drugs poses challenges in achieving optimal bioavailability. Numerous anti-cancer drugs including paclitaxel (PTX) belong to the BCS class IV, hindering their therapeutic efficacy. To address this concern, our study explored SAS-FB technology to coat PTX with D-α-tocopherol polyethylene glycol 1000 succinate (TPGS) onto lactose. Under our optimized conditions, we achieved a PTX coating efficiency of 96.8%. Further characterization confirmed the crystalline state of PTX in the lactose surface coating by scanning electron microscopy and X-ray powder diffraction. Dissolution studies indicated that SAS-FB processed samples release over 95% of the drug within 1 min. Moreover, cell transmembrane transport assays demonstrated that SAS-FB processed PTX samples co-coated with TPGS had an enhanced PTX internalization into cells and a higher permeability coefficient compared to those without TPGS. Finally, compared to unprocessed PTX, SAS-FB (TPGS) and SAS-FB processed samples showed a 2.66- and 1.49-fold increase in oral bioavailability in vivo, respectively. Our study highlights the efficacy of SAS-FB co-coating for PTX and TPGS as a promising strategy to overcome bioavailability challenges inherent in BCS class IV drugs. Our approach holds broader implications for enhancing the performance of similarly classified medications.

Comparison of permanganate preoxidation and preozonation on algae containing water: cell integrity, characteristics, and chlorinated disinfection byproduct formation.

Aqueous suspensions of Microcystis aeruginosa were preoxidized with either ozone or permanganate and then subjected to chlorination under conditions simulating drinking water purification. The impacts of the two oxidants on the algal cells and on the subsequent production of dissolved organic matter and disinfection byproducts were investigated. Preozonation dramatically increased disinfection byproduct formation during chlorination, especially the formation of haloaldehydes, haloacetonitriles, and halonitromethanes. Preoxidation with permanganate had much less effect on disinfection byproduct formation. Preozonation destroyed algal cell walls and cell membranes to release intracellular organic matter (IOM), and less than 2.0% integrated cells were left after preozonation with the dosage as low as 0.4 mg/L. Preoxidation with permanganate mainly released organic matter adsorbed on the cells' surface without causing any damage to the cells' integrity, so the increase in byproduct formation was much less. More organic nitrogen and lower molecular weight precursors were produced in a dissolved phase after preozonation than permanganate preoxidation, which contributes to the significant increase of disinfection byproducts after preozonation. The results suggest that permanganate is a better choice than ozone for controlling algae derived pollutants and disinfection byproducts.

Rapid acceleration of ferrous iron/peroxymonosulfate oxidation of organic pollutants by promoting Fe(III)/Fe(II) cycle with hydroxylamine.

The reaction between ferrous iron (Fe(II)) with peroxymonosulfate (PMS) generates reactive oxidants capable of degrading refractory organic contaminants. However, the slow transformation from ferric iron (Fe(III)) back to Fe(II) limits its widespread application. Here, we added hydroxylamine (HA), a common reducing agent, into Fe(II)/PMS process to accelerate the transformation from Fe(III) to Fe(II). With benzoic acid (BA) as probe compound, the addition of HA into Fe(II)/PMS process accelerated the degradation of BA rapidly in the pH range of 2.0-6.0 by accelerating the key reactions, including the redox cycle of Fe(III)/Fe(II) and the generation of reactive oxidants. Both sulfate radicals and hydroxyl radicals were considered as the primary reactive oxidants for the degradation of BA in HA/Fe(II)/PMS process with the experiments of electron spin resonance and alcohols quenching. Moreover, HA was gradually degraded to N2, N2O, NO2 (−), and NO3 (−), while the environmentally friendly gas of N2 was considered as its major end product in the process. The present study might provide a promising idea based on Fe(II)/PMS process for the rapid degradation of refractory organic contaminants in water treatment.

Multiple roles of UV/KMnO4 in cyanobacteria containing water treatment: Cell inactivation & removal, and microcystin degradation.

Cyanobacterial blooms present great challenges to drinking water treatment and human health. The novel combination of potassium permanganate (KMnO4) and ultraviolet (UV) radiation is engaged as a promising advanced oxidation process in water purification. This study investigated the treatment of a typical cyanobacteria, Microcystis aeruginosa by UV/KMnO4. Cell inactivation was significantly improved by UV/KMnO4 treatment, compared to UV alone or KMnO4 alone, and cells were completely inactivated within 35 min by UV/KMnO4 in natural water. Moreover, effective degradation of associated microcystins was simultaneously achieved at UV fluence rate of 0.88 mW cm-2 and KMnO4 dosages of 3-5 mg L-1. The significant synergistic effect is possibly attributable to the highly oxidative species produced during UV photolysis of KMnO4. In addition, the cell removal efficiency via self-settling reached 87.9 % after UV/KMnO4 treatment, without additional coagulants. The fast in situ generated manganese dioxide was responsible for the enhancement of M. aeruginosa cell removal. This study firstly reports multiple roles of UV/KMnO4 process in cyanobacterial cell inactivation and removal, as well as simultaneous microcystin degradation under practical conditions.

MOF-derived CeO2/Co3O4-Fe2O3@CC nanocomposites as highly sensitive electrochemical sensor for bisphenol A detection.

A novel CeO2/Co3O4-Fe2O3@CC electrode derived from CeCo-MOFs was developed for detecting the endocrine disruptor bisphenol A (BPA). Firstly, bimetallic CeCo-MOFs were prepared by hydrothermal method, and obtained material was calcined to form metal oxides after doping Fe element. The results suggested that hydrophilic carbon cloth (CC) modified with CeO2/Co3O4-Fe2O3 had good conductivity and high electrocatalytic activity. By the analyses of cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), the introduction of Fe increased the current response and conductivity of the sensor, greatly increasing the effective active area of the electrode. Significantly, electrochemical test proves that the prepared CeO2/Co3O4-Fe2O3@CC had excellent electrochemical response to BPA with a low detection limit of 8.7 nM, an excellent sensitivity of 20.489 µA/µM·cm2, a linear range of 0.5-30 µM, and strong selectivity. In addition, the CeO2/Co3O4-Fe2O3@CC sensor had a high recovery rate for the detection of BPA in real tap water, lake water, soil eluent, seawater, and PET bottle samples, which showed its potential in practical applications. To sum up, the CeO2/Co3O4-Fe2O3@CC sensor prepared in this work had excellent sensing performance, good stability and selectivity for BPA, which can be well used for the detection of BPA.

Generation mechanism of singlet oxygen from the interaction of peroxymonosulfate and chloride in aqueous systems.

Peroxymonosulfate (PMS, HSO5-) is a widely-used disinfectant and oxidant in environmental remediation. It was deemed that PMS reacted with chloride (Cl-) to form free chlorine during water purification. Here, we demonstrated that singlet oxygen (1O2) was efficiently generated from PMS and Cl- interaction. Mechanism of 1O2 formation was uniquely verified by the reaction of HSO5- and chlorine molecule (Cl2) and the oxygen atoms in 1O2 deriving from the peroxide group of HSO5- were revealed. Density functional theory calculations determined that the reaction of HSO5- and Cl2 was thermodynamically favorable and exergonic at 37.8 kcal/mol. Quite intriguingly, 1O2 was generated at a higher yield (1.5 × 105 M - 1 s - 1) than in the well-known reaction of H2O2 with Cl2 (35 M - 1 s - 1). Besides chlorine, 1O2 formed in PMS-Cl- interaction dominated the degradation of micropollutants, also it substantially enhanced the damage of deoxynucleoside in DNA, which were beneficial to micropollutant oxidation and pathogen disinfection. The contribution of 1O2 for carbamazepine degradation was enhanced at higher Cl- level and lower pH, and reached 96.3% at pH 4.1 and 5 min. Natural organic matter (NOM) was a sink for chlorine, thereby impeding 1O2 formation to retard carbamazepine degradation. 1O2 also played important roles (48.3 - 63.5%) on the abatement of deoxyguanosine and deoxythymidine at pH 4.1 and 10 min in PMS/Cl-. On the other hand, this discovery also alerted the harm of 1O2 for human health as it can be formed during the interaction of residual PMS in drinking water/swimming pools and the high-level Cl- in human bodies.

Efficient reductive dechlorination of monochloroacetic acid by sulfite/UV process.

Most halogenated organic compounds (HOCs) are toxic and persistent, and their efficient destruction is currently a challenge. Here, we proposed a sulfite/UV (253.7 nm) process to eliminate HOCs. Monochloroacetic acid (MCAA) was selected as the target compound and was degraded rapidly in the sulfite/UV process. The degradation kinetics were accelerated proportionally to the increased sulfite concentration, while the significant enhancement by increasing pH only occurred in a pH range of 6.0-8.7. The degradation proceeded via a reductive dechlorination mechanism induced by hydrated electron (e(aq)(-)), and complete dechlorination was readily achieved with almost all the chlorine atoms in MCAA released as chloride ions. Mass balance (C and Cl) studies showed that acetate, succinate, sulfoacetate, and chloride ions were the major products, and a degradation pathway was proposed. The dual roles of pH were not only to regulate the S(IV) species distribution but also to control the interconversion between e(aq)(-) and H(•). Effective quantum efficiency (Φ) for the formation of e(aq)(-) in the process was determined to be 0.116 ± 0.002 mol/einstein. The present study may provide a promising alternative for complete dehalogenation of most HOCs and reductive detoxification of numerous toxicants.

A newly-designed free-standing NiCo2O4 nanosheet array as effective mediator to activate peroxymonosulfate for rapid degradation of emerging organic pollutant with high concentration.

Nowadays effective treatment of high concentration organic wastewater is still a formidable task facing human beings. Herein, for the first time, a well-defined ZIF-67-derived NiCo2O4 nanosheet array was successfully prepared by a feasible method. In comparison with ordinary NiCo2O4 nanosphere, the formation of nanosheet structure could offer more opportunities to exposure internal active sites of NiCo2O4, thereby resulting in smaller interface resistance and higher charge transfer efficiency. As expected, ZIF-67-derived NiCo2O4 nanosheet array displayed great performance in peroxymonosulfate (PMS) activation. More importantly, recyclable redox couples of Co3+/Co2+ and Ni3+/Ni2+ endowed the stable catalytic activity of NiCo2O4 nanosheet. Interestingly, developed NiCo2O4-1/PMS oxidation system could achieve the effective degradation of antibiotics with high concentration in a short time. Both radical and nonradical pathways were involved into PMS activation, wherein SO4-, OH, O2- and 1O2 were major reactive oxygen species. The formation paths of reactive oxygen species and effects of inorganic anions were also investigated. Electrochemical analyses revealed that NiCo2O4-1 with nanosheet structure mediated the electron transfer between PMS and tetracycline (TC), which played a vital role in TC degradation. Furthermore, developed NiCo2O4-1/PMS oxidation system displayed great removal ability towards TC in actual water samples, and degradation products were low toxicity or no toxicity. In short, current work not only developed an effective oxidation system for completing the rapid degradation of antibiotic with high concentration, but also shared some novel insights into the activation mechanism of SR-AOPs.

Fabrication of 3D self-supported MoS2-Co-P/nickel foam electrode for adsorption-electrochemical removal of Cr(â ¥).

Electrochemistry is considered to be one of the most efficient and environment-friendly methods for removing highly toxic Cr (Ⅵ). In this study, a 3D self-supported MoS2-Co-P/nickel foam (NF) electrode was prepared via a calcination-hydrothermal process to remove the Cr (Ⅵ) in aqueous medium. Scanning electron microscope (SEM) analysis indicated that the pine-needle-like Co2P nanoneedle and flower-like MoS2 nanosheets were successfully loaded on the three-dimensional (3D) framework of NF, which provided abundant active sites. The electrode modified by Co, P and MoS2 exhibited high removal efficiency of Cr (Ⅵ) (96.9%) at pH 3.0, current of 0.128 mA and voltage of 2.5 V. Co, P and MoS2 have the synergistic promotion on the catalytic performance of electrodes, and the reduction efficiency of Cr (Ⅵ) was greatly improved by 127.5 times relative to pure NF. The enhanced removal of Cr (Ⅵ) was related to the coupling effect of adsorption and electrocatalytic reduction. The mechanism study indicated that electron (e-) is the active species of Cr (Ⅵ) reduction. The Cr (Ⅵ) removal rate was maintained at 90 ± 1% after five successive cycle experiments, demonstrating good stability and potential industrial applications of MoS2-Co-P/NF.

Efficient removal of Cr(VI) at alkaline pHs by sulfite/iodide/UV: Mechanism and modeling.

Efficient removal of toxic hexavalent chromium (Cr(VI)) under alkaline conditions is still a challenge due to the relatively low reactivity of CrO42-. This study proposed a new sulfite/iodide/UV process to remove Cr(VI). The removal of Cr(VI) followed pseudo-zero-order kinetics at alkaline pHs, and was enhanced by sulfite and iodide with synergy. Compared with sulfite/UV, iodide in sulfite/iodide/UV showed about 40 times higher concentration-normalized enhancement for Cr(VI) removal, and reduced the requirement of sulfite ([S(IV)]0/[Cr(VI)]0 of about 2.1:1) by more than 90%. The Cr(VI) removal was accelerated by decreasing pH and by increasing temperature, and was slightly influenced by dissolved oxygen, carbonate, and humic acid. The process was still effective in real surface water and industrial wastewater. Mechanism and pathways of Cr(VI) removal were revealed by quenching experiments, competition kinetic analysis, product identification and quantification, and mass and electron balance. Both eaq- and SO3•- were responsible for Cr(VI) removal, making contributions of about 75% and 25%, respectively. When eaq- mainly reacted with Cr(VI), SO3•- participated in reduction of Cr(V) and Cr(IV) intermediates, with Cr(III), S2O62-, and SO42- as the final products. A model was developed to predict removal kinetics of Cr(VI), and well interpreted the roles of S(IV) and iodide in the process. This study sheds light on mechanism of Cr(VI) removal at alkaline pHs by kinetic modeling, and thus advances the applicability of this promising process for water decontamination.