Trace Cu(II) as an Efficient Electron-Transfer Shuttle for Reductive Deiodination of Refractory Iodinated Contrast Media Compounds.

Iodinated contrast media compounds (ICMs) are intensively applied in medical diagnostic radiology and have received wide environmental concerns due to formation potential of iodinated disinfection byproducts. Conventional water/wastewater treatment processes cannot effectively remove ICMs; reducing their total organic iodine concentration is even more difficult. The source control or elimination of ICMs thus becomes necessary. We report here that the refractory ICMs (5 µM) can be efficiently deiodinated by ascorbate/ascorbic acid (AA) (200 µM) coupled with a trace amount of Cu(II) (5 µM) through catalytic reduction but not oxidation, contrary to the conventional concept of AA/Cu(II) coupling, which produces reactive oxygen species. Taking diatrizoate (DTZ, a refractory ICM) as an example, the coupling completely deiodinated DTZ without destroying its molecular structure. High-performance liquid chromatography inductively coupled plasma mass spectrometry analysis revealed that ternary complexes form between Cu(II), ascorbate, and the anilide moiety of DTZ. Cu(II) in the ternary complex works as an efficient electron-transfer shuttle to convey electrons from ascorbate to the target compound, inducing sequential and complete deiodination. Both DTZ and the nonionic ICMs can be effectively deiodinated even in human urine. Thus, AA coupled with trace Cu(II) could be potentially useful for the source elimination of organic iodine of ICMs.

Effects of a simulated maritime shift schedule on vigilance, sleep, and sleepiness.

Shift work is associated with circadian misalignment, which causes sleep loss, impairs performance, and increases the risk of accidents. Shorter, more frequently shifting watch schedules, widely used in industries such as maritime operation, defense, and mining, may mitigate these risks by reducing shift length and providing sleep opportunities for all workers across the biological night. However, the effects of frequently shifting work on sleep and performance still need to be clarified. The current study investigated the vigilance, sleepiness, and sleep patterns of fifteen participants who lived in a controlled and confined laboratory that mimicked a maritime environment for 14 d following a simulating frequent shift schedule. The results of psychomotor vigilance tasks (PVT) suggest that this shift schedule may lead to an accumulation of vigilance detrimental across watch days, with both reaction speed impairment and error growth. Furthermore, the circadian phase significantly affects PVT performance, with the afternoon shift section showing relatively better performance. Overall, more working hours per day resulted in poorer PVT performance. As the shift progressed, total sleep duration reduced slightly, and wake after sleep onset (WASO) increased. Sleep during the biological night was generally longer than sleep in the daytime. Less on-watch time was linked to longer overall sleep duration. Additionally, although the subjective sleepiness obtained by the Karolinska Sleepiness Scale (KSS) varied insignificantly across days, the KSS score was negatively correlated with PVT performance. This research can serve as a foundation for developing countermeasures to mitigate frequently shifting schedules' potentially detrimental effects and safety risks.

Trace Cu(II)-Mediated Selective Oxidation of Benzothiazole: The Predominance of Sequential Cu(II)-Cu(I)-Cu(III) Valence Transition and Dissolved Oxygen.

Trace Cu(II), which inherently exists in soil and some water/wastewater, can trigger persulfate oxidation of some pollutants, but the oxidation capability and mechanism are not well understood, especially toward refractory pollutants. We report in this research that benzothiazole (BTH), a universal refractory pollutant typically originating from tire leachates and various industrial wastewater, can be facilely and selectively removed by peroxydisulfate (PDS) with an equimolar BTH/PDS stoichiometry in the presence of environmental-relevant contents of Cu(II) (below several micromoles). Comprehensive scavenging tests, electron spin resonance analysis, spectroscopy characterization, and electrochemical analysis, revealed that PDS first reduces the BTH-coordinated Cu(II) to Cu(I) and then oxidizes Cu(I) to high-valent Cu(III), which accounts for the BTH degradation. Moreover, once the reaction is initiated, the superoxide radical is probably produced in the presence of dissolved oxygen, which subsequently dominates the reduction of Cu(II) to Cu(I). This facile oxidation process is also effective in removing a series of BTH derivatives (BTHs) that are of environmental concern, thus can be used for their source control. The results highlight the sequential Cu(II)-Cu(I)-Cu(III) transition during PDS activation and the crucial role of contaminant coordination with Cu(II) in oxidative transformation.

Modification Mechanism of Polyamide Reverse Osmosis Membrane by Persulfate: Roles of Hydroxyl and Sulfate Radicals.

Oxidative modification is a facile method to improve the desalination performance of thin-film composite membranes. In this study, we comparatively investigated the modification mechanisms induced by sulfate radical (SO4• -) and hydroxyl radical (HO•) for polyamide reverse osmosis (RO) membrane. The SO4• -- and HO•-based membrane modifications were manipulated by simply adjusting the pH of the thermal-activated persulfate solution. Although both of them improved the water permeability of the RO membrane under certain conditions, the SO4• --modified membrane notably prevailed over the HO•-modified one due to higher permeability, more consistent salt rejection rates over wide pH and salinity ranges, and better stability when exposed to high doses of chlorine. The differences of the membranes modified by the two radical species probably can be related to their distinct surface properties in terms of morphology, hydrophilicity, surface charge, and chemical composition. Further identification of the transformation products of a model polyamide monomer using high-resolution mass spectrometry demonstrated that SO4• - initiated polymerization reactions and produced hydroquinone/benzoquinone and polyaromatic structures; whereas the amide group of the monomer was degraded by HO•, generating hydroxyl, carboxyl, and nitro groups. The results will enlighten effective ways for practical modification of polyamide RO membranes to improve desalination performances and the development of sustainable oxidation-combined membrane processes.

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.

Effective activation of peroxymonosulfate with natural manganese-containing minerals through a nonradical pathway and the application for the removal of bisphenols.

Synthetic manganese oxides had been widely investigated to activate peroxymonosulfate (PMS) for contaminant removal in recent years. The generation of reactive oxygen species (ROS, e.g., radicals) was believed to be the primary PMS activation pathways. In this work, we report that natural manganese-containing minerals (NMMs) were also effective for PMS activation to degrade bisphenols in water. Moreover, a nonradical pathway different from literatures, was confirmed according to scavenging tests, electron paramagnetic resonance (EPR) characterization, chemical probing, solvent exchange, and Raman and electrochemical analysis. It was verified that PMS complexed with the mineral surface via inner-sphere interaction. This surface interaction improved its reactivity towards the probe compounds, bisphenols. Taking bisphenol AF (BPAF) as an example, its degradation rate was related to surface area and dosages of the mineral. Water constituents such as Cl-, HCO3-, and NOM had negligible impact on BPAF removal. The activity of the mineral was kept in an 80-hour continuous flow test. The PMS/NMM coupled oxidation degraded BPAF through direct electron transfer, and the degradation intermediates further underwent hydroxylation, bond cleavage, H-atom substitution, aromatic ring-opening, and decarboxylation. Consequently, eco-toxicity of BPAF can be reduced during the oxidation.

A Review on Additives-assisted Ultrasound for Organic Pollutants Degradation.

In the past 2 decades, considerable attentions have been paid to the sonochemical advanced oxidation processes (SAOPs) in the fields of pollutants removal. SAOPs are powerful methods for refractory pollutants degradation due to the free radicals (e.g., •OH and •H) generated by water pyrolysis and extremely high temperature and pressure in and around cavitation bubbles. Reports on various additives for the improvement of sonochemical pollutants degradation including oxidants, inorganic anions, etc. have been made. This paper presents a comprehensive review on the ultrasound (US) alone and sono-hybrid systems for various pollutants degradation. In this paper, the degradation efficiency of various pollutants in sono-hybrid systems are elucidated in detail, and particular emphasis is placed on the reaction mechanism of additives in US for the enhancement of pollutants degradation. The problems on the applications of the current sono-hybrid systems are identified and discussed, and the outlooks for further in-depth studies on the challenges and some research needs for the applications of SAOPs for the removal of organic pollutants from aquatic systems are made at the end.

Nonradical Oxidation of Pollutants with Single-Atom-Fe(III)-Activated Persulfate: Fe(V) Being the Possible Intermediate Oxidant.

When applied for the remediation of polluted water/soil, peroxydisulfate (PDS) usually needs to be effectively activated to generate sulfate radical as the working oxidant. However, a significant part of the oxidation capacity of PDS is lost in this way because sulfate radical unselectively reacts with most of the substances in water/soil. PDS activation without generating radicals is preferred to maximize its oxidation capacity for targeted pollutants. Here, we report that single-atom Fe(III)- and nitrogen-doped carbon (Fe-N-C) can efficiently activate PDS to selectively remove some organic pollutants following an unreported nonradical pathway. The single-atom Fe(III) coordinated with pyridinic N atoms was confirmed to be the active site for the catalytic decomposition of PDS. However, the PDS decomposition did not produce radicals or reactive oxygen species. It is very likely that the coordinated Fe(III) is readily converted to Fe(V) through two-electron abstraction by PDS, and Fe(V) is responsible for the selective degradation of organic pollutants. The PDS/Fe-N-C-coupled process utilizes more oxidation capacity of PDS than both radical oxidation and other reported nonradical oxidation like PDS/CuO under the same experimental conditions. This process provides a new approach to selectively degrade some organic pollutants through PDS activation.

Trace Cupric Species Triggered Decomposition of Peroxymonosulfate and Degradation of Organic Pollutants: Cu(III) Being the Primary and Selective Intermediate Oxidant.

Activation of persulfates to degrade refractory organic pollutants is currently a hot topic of advanced oxidation. Developing simple and effective activation approaches is crucial for the practical application of persulfates. We report in this research that trace cupric species (Cu(II) in several µM) can efficiently trigger peroxymonosulfate (PMS) oxidation of various organic pollutants under slightly alkaline conditions. The intermediate oxidant dominating this process was investigated with electron paramagnetic resonance (EPR), chemical probing, and in situ Raman spectroscopy. Unlike conventional PMS activation, which generates sulfate radical, hydroxyl radical, or singlet oxygen as major oxidants, Cu(III) was confirmed to be the primary and selective intermediate oxidant during the Cu(II)/PMS oxidation. Hydroxyl radical is the secondary intermediate oxidant formed from the reaction of Cu(III) with OH-. Hybrid oxidation by the two oxidants imparts Cu(II)/PMS with high efficiency in the degradation of a series of pollutants. The results of this work suggest that, with no need of introducing complex catalysts, trace Cu(II) inherent in or artificially introduced to some water or wastewater can effectively trigger PMS oxidation of organic pollutants.

Sonolytic degradation of bisphenol S: Effect of dissolved oxygen and peroxydisulfate, oxidation products and acute toxicity.

In this paper, the kinetics of bisphenol S (BPS) degradation in the presence of peroxydisulfate (PDS) or dissolved oxygen (DO) in ultrasound (US) system were investigated. For PDS (US/PDS), increased PDS concentration result in faster BPS degradation, but the enhancement was not remarkable with multiplying PDS dosages. Therefore, heterogeneous PDS activation model based on a Langmuir-type adsorption mechanism was proposed to explain the trait of BPS abatement. The equilibrium constant of PDS (KPDS) was calculated to be 2.91 × 10-4/µM, which was much lower than that of BPS, suggesting that PDS was hard to adsorb on the gas-liquid interface of the cavitation bubble following by activation. Besides, the formation of •OH and SO4•- in US/PDS system was reinvestigated. The result showed that SO4•- rather than •OH was the predominant radical, which was quite different from previous study. Dissolved oxygen largely improve the degradation of BPS in US system and •OH rather than O2•- was proved to be the main reactive oxygen species (ROS). The improvement of •OH generation possibly caused by the reaction of DO with •H so that it cannot recombine with •OH. The transformation of the BPS in US system mainly included BPS radical polymerization, hydroxylation and hydrolysis. Frustratingly, the acute toxicity assay of Vibrio fischeri suggests that the degradation products of BPS are more toxic. These results will improve the understanding on the activation mechanisms of PDS and the role of dissolved oxygen play in US. Further investigations may need to explore other treatment ways of BPS and evaluate the acute toxicity of degradation products.

Enhanced mineralization of atrazine by surface induced hydroxyl radicals over light-weight granular mixed-quartz sands with ozone.

A light-weight granular mixed-quartz sand (denoted as L-GQS) combined with stirring-assisted bubble column reactor was firstly applied in catalytic ozonation of atrazine. The L-GQS, with a density of 2.36 g cm-3 and average diameter of ca. of 4 mm, was readily churned up and uniformly distributed within the solution in the reactor. The introduction of L-GQS was found to exhibit enhanced catalytic ozonation of atrazine, with the increase in degradation rate and the dissolved organic carbon (DOC) removal being more than 2-fold for the catalytic process (L-GQS dosage = 5 g L-1, [atrazine]0 = 50 µM, [O3] = 25 mg L-1, gas flow = 0.2 L min-1, at pH 7.0 and 293 K). The L-GQS settled at the bottom of the reactor after experimentation, allowing its easy separation from the solution. A complete characterization of the material (XRD, XPS, FTIR, FE-SEM/EDS, BET and pHpzc) revealed that L-GQS consisted of α-quartz, ß-cristobalite, anorthoclase and small amount of iron oxy-hydroxides. Hydroxyl groups, Bronsted acid sites and Lewis acid sites on the surface of L-GQS all contributed to the atrazine adsorption, ozone decomposition and ·OH generation. The L-GQS catalyzed ozonation exhibited superior atrazine degradation and mineralization rates in a wide range of pH (3.0-9.0) and reaction temperatures (278 K-293 K). Also, an enhancement of DOC abatement was observed both in presence of natural organic matter isolates and natural water matrices (river water) when L-GQS was used. Finally, the degradation mechanism was proposed, based on the intermediates and by-products formation analyzed by LC-QTOF-MS/MS and ionic chromatography. Our results indicate that the L-GQS combined with stirring-assisted bubble column reactor could be utilized as an enhancement of ozone-based advanced oxidation processes.

Morphology Control Studies of MnTiO3 Nanostructures with Exposed {0001} Facets as a High-Performance Catalyst for Water Purification.

Novel single-crystal hexagonal MnTiO3 nanosheets with exposed {0001} facets have been synthesized via a simple one-pot hydrothermal method using NaOH as a mineralizer and tetraethylammonium hydroxide (TEAH) as a morphology controller. The intermediate morphologies of MnTiO3 nanostructures such as nanoparticles, nanowires, nanorods, and nanodiscs are trapped kinetically by adjusting the synthesis conditions. This approach enables us to elucidate the growth mechanisms of MnTiO3 nanosheets based on the tetraethylammonium cation adsorption abilities on different MnTiO3 crystal facets combined with density functional theory calculations. Dissolution and recrystallization processes are involved during the MnTiO3 crystallization. The surface-controlled MnTiO3 has been found to be effective as a catalyst for ozonation in the degradation of 4-chlorophenol (4-CP). Within typical experimental conditions (catalyst dosage = 0.3 g L-1, [4-CP]0 = 50 mg L-1, [O3] = 20 mg L-1, gas flow = 0.1 L min-1, pH 6.8, and T = 293 K), the total organic carbon (TOC) removal efficiency of 4-CP in catalytic ozonation with well-structured MnTiO3 (MnTiO3-180-10 sample) was 76.3% after 60 min, compared with only 22.1 and 38.5% TOC removal in the absence of catalyst and with uncontrolled MnTiO3 (MnTiO3-no TEAH sample), respectively. Benefiting from the high exposure percentage of {0001} facet, mixed-valences of manganese, surface hydroxyl groups, and the enrichment Lewis acid sites provided by Mn and Ti, the morphology-controlled MnTiO3 nanosheets can be applied as heterogeneous catalytic ozonation catalysts which exhibit excellent pollutant degradation. We anticipate that MnTiO3 can be a promising candidate material for the application in remediation of organic pollutants in water.

[Feasibility of 3BER-S Process for the Deep Denitrification in Synch with the Removal of PAEs from Reclaimed Water].

In order to investigate the feasibility of deep denitrification and simultaneous removing phthalate esters (PAEs) in the process of reclaimed water treatment uses three-dimensional biofilm-electrode reactor coupled with sulfur autotrophic deep denitrification technology (3BER-S), the technological characteristics and mechanisms were analyzed based on determining the static adsorption capacity of biofilm cultured active carbon fillers in 3BER-S reactor together with the operation results of dynamic denitrification and simultaneous PAEs removing. The results showed that the average adsorption rates of DBP, DEHP were 85.84% and 97.12% in the biofilm cultured active carbon fillers, the equilibrium adsorption capacities were 0.1426 mg x g(-1) and 0.162 mg(-1) and the time spans of reaching adsorption saturation were 120 min and 60 min, respectively; The existence of PAEs had no obvious effect on denitrification, the reactor effluent concentration of TN was in range of 1-2 mg x L(-1) before and after the addition of PAEs, and the average removal rate of TN reached above 94%; 3BER-S denitrification system showed significant ability in removing PAEs, leading to effluent concentrations of DBP and DEHP of no more than 6 microg x L(-1) with removal rates of above 96%; this was due to the synergistic effect of absorption, biodegradation and electrochemistry. After treatment with 3BER-S technology, DBP and DEHP in simulative municipal secondary effluent met the regulated limitation of The Reuse of Urban Recycling Water Quality Standard for Groundwater Recharge (GB/T 19772-2005).