Pilot-scale study on an advanced Fe-Cu process for refractory wastewater pretreatment.

The extreme pH, high color, and poor biodegradability of refractory wastewater have severe impacts on its biological treatment. To address this issue, an advanced Fe-Cu process with redox reaction and spontaneous coagulation was investigated and applied for pilot-scale (wastewater flow rate of 2000 m3·day-1) pretreatment of separately discharged acidic chemicals and alkaline dyeing wastewater. The advanced Fe-Cu process had five functions: (1) increasing the pH of chemical wastewater to 5.0 and above, with an influent pH of approximately 2.0; (2) transforming refractory organics of chemical wastewater with 10.0% chemical oxygen demand (COD) and 30.8% color removal, thereby enhancing the ratio of biological oxygen demand after five days (BOD5) to COD (B/C) from 0.21 to 0.38; (3) neutralizing the pH of the pretreated chemical wastewater for coagulation application with alkaline dyeing wastewater to avoid adding alkaline chemical; (4) achieving average nascent Fe(II) concentrations of 925.6 mg∙L-1 using Fe-Cu internal electrolysis for mixed wastewater coagulation, resulting in an average of 70.3% color removal and 49.5% COD removal; (5) providing more efficient COD removal and B/C enhancement than FeSO4∙7 H2O coagulation while avoiding secondary pollution. The green process offers an effective, easy-implemented solution for the pretreatment of separately discharged acidic and alkaline refractory wastewater.

Advanced treatment of industrial wastewater by ozonation with iron-based monolithic catalyst packing: From mechanism to application.

An Fe-based catalyst was prepared by oxidising waste Fe shavings directly in a solution. In engineering applications, Fe shavings were compressed and modified to form Fe-based monolithic catalyst packing. Both of which exhibited excellent catalytic activity in catalytic ozonation industrial wastewater after biochemical treatment. Fe-based monolithic catalyst packing has irregular channels, large porosity, small pore diameter, and the effective specific surface area (SSA) up to 3500 m2/m3, these characteristics are conducive to mass transfer, and promote the effective utilisation of •OH in the catalyst "action zone". A tower reactor (<3000 m3/d) and reinforced concrete construction reactor (>5000 m3/d) were designed according to the wastewater flow. Regression analysis showed that hydraulic residence time (HRT) and O3/CODin are important parameters in engineering design and operation. In addition, strategies for the application of Fe-based monolithic catalyst packing to wastewater with high salinity and high inorganic carbon concentration have been proposed. Fe-based monolithic catalyst packing catalytic ozonation is a relatively cost-effective and eco-friendly process with extremely broad application prospects in the advanced treatment of industrial wastewater.

FeS combined ozonation to remove p-aminobenzenesulfonamide from water: Density functional theory insights into the mechanism.

The applicability and performance of FeS in ozonation process to remove p-aminobenzenesulfonamide (SN) from water was assessed, and the working mechanism of FeS was comprehensively explored by both experimental means and density functional theory (DFT) simulation. FeS combined ozonation achieved 74% of SN removal in 60 min under the optimal condition, which was 37% higher than by ozonation alone, and 12% higher than FeO combined ozonation. Highly active species of •OH, •SO4-, 1O2 and •O2- were detected in the FeS combined ozonation system, the evolution pathway of the involved species was expounded with the aid of DFT calculation. The results revealed that •O2-, H2O2 and SO42- were originally formed via interface reactions on FeS surface, then gradually transformed into •OH, 1O2 and •SO4- through subsequent chain reactions. Moreover, FeS had a lower energy barrier of 0.16 eV than FeO with a value of 0.83 eV for the transformation of ozone to active atomic oxygen. The presented study provided a significant insight into the role of Fe-based materials in ozonation, and was of great importance to guide the route for ozonation process improvement.

Strategies to enhance the reactivity of zero-valent iron for environmental remediation: A review.

Application of zero-valent iron (ZVI) has become one of the most promising innovative technologies for the remediation of environmental pollutants. However, ZVI may suffer from the low intrinsic reactivity toward refractory pollutants, which seriously restricts its practical application in fields. Therefore, strategies have been developing to enhance the reactivity of ZVI. Until now, the most commonly used strategies include pretreatment of ZVI, synthesis of highly-active ZVI-based materials and additional auxiliary measures. In this review, a systematic and comprehensive summary of these commonly used strategies has been conducted for the following purposes: (1) to understand the fundamental mechanisms of the selected approaches; (2) to point out their advantages and shortcomings; (3) to illustrate the main problems of their large-scale application; (4) to forecast the future trend of developing ZVI technologies. Overall, this review is devoted to providing a fundamental understanding on the mechanism for enhancing the reactivity of ZVI and facilitating the practical application of ZVI technologies in fields.

Plausible 3D Face Wrinkle Generation Using Variational Autoencoders.

Realistic 3D facial modeling and animation have been increasingly used in many graphics, animation, and virtual reality applications. However, generating realistic fine-scale wrinkles on 3D faces, in particular, on animated 3D faces, is still a challenging problem that is far away from being resolved. In this article we propose an end-to-end system to automatically augment coarse-scale 3D faces with synthesized fine-scale geometric wrinkles. By formulating the wrinkle generation problem as a supervised generation task, we implicitly model the continuous space of face wrinkles via a compact generative model, such that plausible face wrinkles can be generated through effective sampling and interpolation in the space. We also introduce a complete pipeline to transfer the synthesized wrinkles between faces with different shapes and topologies. Through many experiments, we demonstrate our method can robustly synthesize plausible fine-scale wrinkles on a variety of coarse-scale 3D faces with different shapes and expressions.

Ozonation catalysed by ferrosilicon for the degradation of ibuprofen in water.

The search for optimal catalysts to improve the working efficiency of ozonation has always been an important issue in the research field of advanced oxidation processes. In this study, a novel catalyst, ferrosilicon, was selected as the catalyst in heterogeneous catalytic ozonation to degrade ibuprofen (IBP) in water and treat real pharmaceutical wastewater. During the procedure, 45#ferrosilicon exhibited the best catalytic activity. Under the optimized experimental conditions, the IBP removal reached 75%, which was a great improvement compared to the 37% removal by ozone alone. The 45#-ferrosilicon-catalysed ozonation also achieved 68% TOC removal for real pharmaceutical wastewater, which was 31% higher than that by ozone alone. The degradation pathway of IBP was proposed using GC/MS. The EPR test proved that the main active species in the system were free active radicals •OH, and the measured accumulative •OH amount was 102 µmol. The characterization results show that the nascent metallic oxides, hydroxides, and hydroxyoxides on the ferrosilicon surface facilitated the decomposition of ozone molecules and generation of free active radicals. The removal of target organic contaminants in the water was mainly attributed to the oxidization of these highly active species.

Iron foam combined ozonation for enhanced treatment of pharmaceutical wastewater.

In this study, iron foam combined ozonation was employed as an advanced oxidation process to treat the organic contaminants in real pharmaceutical wastewater. It was found that this procedure worked well in a wide range of pH, the existence of iron foam in ozonation system markedly elevated the mineralization level of organic contaminants. Within the reaction time of 120 min, iron foam combined ozonation achieved 53% of DOC removal percentage, which was 21% higher than that of ozone alone. Meanwhile, the biodegradability of the pharmaceutical wastewater was improved, a large part of the organic pollutants containing benzene rings and amino groups were effectively degraded, and a certain amount of phosphate and nitrogen also get removed. In iron foam combined ozonation, zero valent iron played the role as an activator. It was oxidized into iron oxides and oxyhydroxides, the electrons transferring among different valences of iron stimulated the decomposition of ozone and the generation of hydroxyl radicals, which accounted for most of the organic contaminants degradation.

Formation and transformation of schwertmannite in the classic Fenton process.

The massive amount of sludge generated by the classic Fenton process, which has often been hypothesized to consist of ferric hydroxide, remains a major obstacle to its large-scale application. Therefore, reutilization of Fenton sludge has recently gained more attention. Understanding the formation, transformation, and properties of Fenton sludge combined with the stages of the Fenton reaction is pivotal, but not well illustrated yet. In this study, SEM-EDS, FT-IR, XRD, and XPS were applied to study the morphology, crystallinity, elemental composition, and valence state of Fenton sludge. The authors report that schwertmannite and 2-line ferrihydrite were generated and transformed in the oxidation phase and the neutralization phase of the Fenton process. SO42- in the solution decreased by 8.7%-26.0% at different molar ratios of Fe(II) to H2O2; meanwhile, iron ion precipitated completely at pH 3.70 with the formation of schwertmannite containing sulfate groups in the Fenton sludge. The structural sulfate (Fe-SO4) in schwertmannite was released from the precipitate with the addition of OH-, and the production of Fenton sludge decreased with increasing pH when pH > 3.70. Goethite was found to form when the final pH was adjusted to 12 or at a reaction temperature of 80°C. Moreover, the possible thermal transformation to goethite and hematite indicated that Fenton sludge can be reused as a raw material for synthesizing more stable iron (hydro)oxides. The results provide useful insights into the formation and transformation of Fenton sludge, with implications for regulating the crystal type of Fenton sludge for further reuse.

Intersession Reliability and Within-Session Stability of a Novel Perception-Action Coupling Task.

BACKGROUND: The perception-action coupling task (PACT) was designed as a more ecologically valid measure of alertness/reaction times compared to currently used measures by aerospace researchers. The purpose of this study was to assess the reliability, within-subject variability, and systematic bias associated with the PACT.METHODS: There were 16 subjects (men/women = 9 / 7; age = 27.8 ± 3.6 yr) who completed 4 identical testing sessions. The PACT requires subjects to make judgements on whether a virtual ball could fit into an aperture. For each session, subjects completed nine cycles of the PACT, with each cycle lasting 5 min. Judgement accuracy and reaction time parameters were calculated for each cycle. Systematic bias was assessed with repeated-measures ANOVA, reliability with intraclass correlation coefficients (ICC), and within-subject variability with coefficients of variation (CVTE).RESULTS: Initiation time (Mean = 0.1065 s) showed the largest systematic bias, requiring the elimination of three cycles to reduce bias, with all other variables requiring, at the most, one. All variables showed acceptable reliability (ICC > 0.70) and within-subject variability (CVTE < 20%) with only one cycle after elimination of the first three cycles.CONCLUSIONS: With a three-cycle familiarization period, the PACT was found to be reliable and stable.Connaboy C, Johnson CD, LaGoy AD, Pepping G-J, Simpson RJ, Deng Z, Ma L, Bower JL, Eagle SR, Flanagan SD, Alfano CA. Intersession reliability and within-session stability of a novel perception-action coupling task. Aerosp Med Hum Perform. 2019; 90(2):77-83.

Pilot-scale study on catalytic ozonation of bio-treated dyeing and finishing wastewater using recycled waste iron shavings as a catalyst.

A pilot scale reactor with an effective volume of 2.93 m3 was built in-situ and run in both batch and continuous modes to investigate the removal for organic pollutants in bio-treated dyeing and finishing wastewater by heterogeneous catalytic ozonation under neutral pH with waste iron shavings as a catalyst. Experimental results showed that both running modes were able to reduce the chemical oxygen demand (COD) from 132-148 mg/L to a level below the discharge criteria (<80 mg/L) within 15-30 mins under several conditions. Specifically, significantly organic removal was observed with COD, soluble COD (sCOD) and dissolved organic carbon (DOC) decreased from the initial 165, 93 and 76 mg/L to 54, 28 and 16 mg/L respectively, when treated by 10.2 g-O3/min of ozone dosage at a hydraulic retention time of 30 mins under continuous mode. 80% proteins and 85% polysaccharides were removed with a decrease in their contribution to sCOD from 69% to 43%. Mineralization as well as conversion of high molecular organic compounds was observed through Gas Chromatography-Mass Spectrometer (GC-MS) & Liquid Chromatography-Mass Spectrometer (LC-MS) analysis, which led to a decrease of inhibitory effect from 29% to 25%, suggesting a reduction in the acute toxicity.

Industrial wastewater advanced treatment via catalytic ozonation with an Fe-based catalyst.

An Fe-based catalyst was used as a heterogeneous catalyst for the ozonation of industrial wastewater, and key operational parameters (pH and catalyst dosage) were studied. The results indicated that the Fe-based catalyst significantly improved the mineralization of organic pollutants in wastewater. TOC (total organic carbon) removal was high, at 78.7%, with a catalyst concentration of 200 g/L, but only 31.6% with ozonation alone. The Fe-based catalyst significantly promoted ozone decomposition by 70% in aqueous solution. Hydroxyl radicals (·OH) were confirmed to be existed directly via EPR (electron paramagnetic resonance) experiments, and ·OH were verified to account for about 34.4% of TOC removal with NaHCO3 as a radical scavenger. Through characterization by SEM-EDS (field emission scanning electron microscope with energy-dispersive spectrometer), XRD (X-ray powder diffraction) and XPS (X-ray photoelectron spectroscopy), it was deduced that FeOOH on the surface of the catalyst was the dominant contributor to the catalytic efficiency. The catalyst was certified as having good stability and excellent reusability based on 50 successive operations and could be used as a filler simultaneously. Thereby, it is a promising catalyst for practical industrial wastewater advanced treatment.

Microbial nitrate removal by waste iron shavings from the biological and catalytic ozonation treated dyeing and finishing wastewater.

The concentration of total nitrogen (TN) (between 40 and 60 mg/L, mainly nitrate) in the biological and catalytic ozonation treated dyeing and finishing wastewater needs to be reduced before discharge. The present study investigated the feasibility of using waste iron shavings as electron donor for nitrogen removal by biological denitrification. Two anoxic sequencing batch reactors (AnSBR) were continuously operated for more than 100 days. The results showed that the TN removal efficiency increased from 12% in the control reactor (AnSBR-C) to 20% in the reactor with waste iron shavings (AnSBR-Fe). The TN removal was mainly achieved by the reduction of nitrate by heterotrophic denitrification and autotrophic denitrification for AnSBR-Fe. The residual COD (38.4 mg/L) in the effluent of AnSBR-Fe was higher than that (22 mg/L) in the effluent of AnSBR-C, which could be due to that the bacteria preferred to use iron instead of the recalcitrant organics that present in the wastewater. Furthermore, 3DEEM, UHPLC-QTOF and GC-MS analysis were used to characterize the organics in the wastewater, and the results showed that the addition of waste iron shavings affected the degradation of organics during the biological denitrification process.

Copper-catalyzed activation of molecular oxygen for oxidative destruction of acetaminophen: The mechanism and superoxide-mediated cycling of copper species.

In this study, the commercial zero-valent copper (ZVC) was investigated to activate the molecular oxygen (O2) for the degradation of acetaminophen (ACT). 50 mg/L ACT could be completely decomposed within 4 h in the ZVC/air system at initial pH 3.0. The H2O2, hydroxyl radical (OH) and superoxide anion radical (O2-) were identified as the main reactive oxygen species (ROSs) generated in the above reaction; however, only OH caused the decomposition and mineralization of ACT in the copper-catalyzed O2 activation process. In addition, the in-situ generated Cu+ from ZVC dissolution not only activated O2 to produce H2O2, but also initiated the decomposition of H2O2 to generate OH. Meanwhile, the H2O2 could also be partly decomposed into O2-, which served as a mediator for copper cycling by reduction of Cu2+ to Cu+ in the ZVC/air system. Therefore, OH could be continuously generated; and then ACT was effectively degraded. Additionally, the effect of solution pH and the dosage of ZVC were also investigated. As a result, this study indicated the key behavior of the O2- during Cu-catalyzed activation of O2, which further improved the understanding of O2 activation mechanism by zero-valent metals.

The removal of organic precursors of DBPs during three advanced water treatment processes including ultrafiltration, biofiltration, and ozonation.

The removal efficiency of organic matter, the formation potential of trihalomethanes (THMFP), and the formation potential of haloacetic acids (HAAFP) in each unit of three advanced treatment processes were investigated in this paper. The molecular weight distribution and the components of organic matter in water samples were also determined to study the transformation of organic matter during these advanced treatments. Low-molecular-weight matter was the predominant fraction in raw water, and it could not be removed effectively by ultrafiltration and biofiltration. The dominant species of disinfection by-product formation potential (DBPFP) in raw water were chloroform and monochloroacetic acid (MCAA), with average concentrations of 107.3 and 125.9 µg/L, respectively. However, the formation potential of chloroform and MCAA decreased to 36.2 and 11.5 µg/L after ultrafiltration. Similarly, biological pretreatment obtained high removal efficiency for DBPFP. The total THMFP decreased from 173.8 to 81.8 µg/L, and the total HAAFP decreased from 211.9 to 84.2 µg/L. Separate ozonation had an adverse effect on DBPFP, especially for chlorinated HAAFP. Numerous low-molecular-weight compounds such as aldehydes, ketones, and alcohols were generated during the ozonation, which have been proven to be important precursors of HAAs. However, the ozonation/biological activated carbon (BAC) combined process had a better removal efficiency for DBPFP. The total DBPFP decreased remarkably from 338.7 to 113.3 µg/L after the O3/BAC process, far below the separated BAC of process B (189.1 µg/L).

Oxalate-assisted oxidative degradation of 4-chlorophenol in a bimetallic, zero-valent iron-aluminum/air/water system.

The reaction of zero-valent iron and aluminum with oxygen produced reactive oxidants that can oxidize 4-chlorophenol (4-CP). However, oxidant yield without metal surface cleaning to dissolve the native oxide layer or in the absence of ligands was too low for practical applications. The addition of oxalate (ox) to dissolved oxygen-saturated solution of Fe(0)-Al(0) significantly increased oxidant yield because of the dissolution, pH buffer, and complexing characteristics of ox. Ox-enhanced reactive oxidant generation was affected by ox concentration and solution pH. The critical effect of ox dosing was confirmed with the reactive species of [Fe(II)(ox)0] and [Fe(II)(ox)2 (2-)]. Systematic studies on the effect of the initial and in situ solution pH revealed that 4-CP oxidation was controlled by the continuous release of dissolved Fe(2+) and Al(3+), their fate, and the activation mechanisms of O2 reduction. The degradation pathway of 4-CP in ox-enhanced Fe(0)-Al(0)/O2 may follow the 4-chlorocatechol pathway. The robustness of the ox-enhanced Al(0)-Fe(0)-O2 process was determined with one-time dosing of ox. Therefore, ox is an ideal additive to enhancing the Fe(0)-Al(0)/O2 system for the oxidative degradation of aqueous organic pollutants.

Catalytic ozonation of organic pollutants from bio-treated dyeing and finishing wastewater using recycled waste iron shavings as a catalyst: Removal and pathways.

Catalytic ozonation of organic pollutants from actual bio-treated dyeing and finishing wastewater (BDFW) with iron shavings was investigated. Catalytic ozonation effectively removed organic pollutants at initial pH values of 7.18-7.52, and the chemical oxygen demand (COD) level decreased from 142 to 70 mg·L(-1) with a discharge limitation of 80 mg·L(-1). A total of 100% and 42% of the proteins and polysaccharides, respectively, were removed with a decrease in their contribution to the soluble COD from 76% to 41%. Among the 218 organic species detected by liquid chromatography-mass spectrometry, 58, 77, 79 and 4 species were completely removed, partially removed, increased and newly generated, respectively. Species including textile auxiliaries and dye intermediates were detected by gas chromatography-mass spectrometry. The inhibitory effect decreased from 51% to 33%, suggesting a reduction in the acute toxicity. The enhanced effect was due to hydroxyl radical (OH) oxidation, co-precipitation and oxidation by other oxidants. The proteins were removed by OH oxidation (6%), by direct ozonation, co-precipitation and oxidation by other oxidants (94%). The corresponding values for polysaccharides were 21% and 21%, respectively. In addition, the iron shavings behaved well in successive runs. These results indicated that the process was favorable for engineering applications for removal of organic pollutants from BDFW.

Novel iron metal matrix composite reinforced by quartz sand for the effective dechlorination of aqueous 2-chlorophenol.

In this work, we tested a novel iron metal matrix composite (MMC) synthesized by mechanically introducing quartz sand (SiO2) into an iron matrix (denoted as SiO2-Fe MMC). The pseudo-first-order reaction rate constant of the SiO2-Fe MMC (initial pH 5.0) for 20 mg/L of 2-chlorophenol (2-CP) was 0.051 × 10(-3) L/m(2)/min, which was even higher than that of some reported Pd/Fe bimetals. This extraordinary high activity was promoted by the quick iron dissolution rate, which was caused by the formation of Fe-C internal electrolysis from carbonization of process control agent (PCA) and the active reinforcement/metal interfaces during the milling process. In addition, pH has slight effect on the dechlorination rate. The SiO2-Fe MMC retained relatively stable activity, still achieving 71% removal efficiency for 2-CP after six consecutive cycles. The decrease in dechlorination efficiency can be attributed to the rapid consumption of Fe(0). A dechlorination mechanism using the SiO2-Fe MMC was proposed by a direct electron transfer from Fe(0) to 2-CP at the quartz sand/iron interface.

Event mean concentration and first flush effect from different drainage systems and functional areas during storms.

This study aimed to investigate the characteristics of the event mean concentration (EMC) and first flush effect (FFE) during typical rainfall events in outfalls from different drainage systems and functional areas. Stormwater outfall quality data were collected from five outfalls throughout Fuzhou City (China) during 2011-2012. Samples were analyzed for water quality parameters, such as COD, NH3-N, TP, and SS. Analysis of values indicated that the order of the event mean concentrations (EMCs) in outfalls was intercepting combined system > direct emission combined system > separated system. Most of the rainfall events showed the FFE in all outfalls. The order of strength of the FFE was residential area of direct emission combined system > commercial area of separated system > residential area of intercepting combined system > office area of separated system > residential area of separated system. Results will serve as guide in managing water quality to reduce pollution from drainage systems.

Effect of continuously dosing Cu(II) on pollutant removal and soluble microbial products in a sequencing batch reactor.

The effects of synthetic wastewater that contained 20 mg/L Cu(II) on the removal of organic pollutants in a sequencing batch reactor were investigated. Results of continuous 20 mg/L Cu(II) exposure for 120 days demonstrated that the chemical oxygen demand (COD) removal efficiency decreased to 42% initially, followed by a subsequent gradual recovery, which peaked at 78% by day 97. Effluent volatile fatty acid (VFA) concentration contributed 67 to 89% of the influent COD in the experimental reactor, which indicated that the degradation of the organic substances ceased at the VFA production step. Meanwhile, the varieties of soluble microbial products (SMP) content and main components (protein, polysaccharide, and DNA) were discussed to reveal the response of activated sludge to the toxicity of 20 mg/L Cu(II). The determination of Cu(II) concentrations in extracellular polymeric substances (EPS) and SMP throughout the experiment indicated an inverse relationship between extracellular Cu(II) concentration and COD removal efficiency.