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.

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.

Pyrite-enhanced degradation of chloramphenicol by low concentrations of H2O2.

A pyrite-catalyzed reaction was used to degrade chloramphenicol. Chloramphenicol could be almost 100% removed within 60 minutes when 1 mM H2O2 and 0.1 g/L pyrite were added at an initial pH=3. During oxidation, intermediates such as nitrobenzaldehyde and dichloroacetamide were identified by gas chromatography/mass spectrometry (GC/MS). The •OH was identified by electron spin-resonance spectroscopy. Pyrite was digested to determine elements by ICP (inductive coupled plasma emission spectrometer). To understand the reaction mechanism and the role of natural pyrite in these processes, techniques including scanning electron microscopy and energy dispersive spectrometry were employed to characterize the solid sample. The results explain that pyrite acts as a 'bond' between Fe3+ and H2O2, and this pathway continues to form •OH and inhibit the quenching reaction. Therefore, pyrite-catalyzed reactions would proceed even in low concentrations of H2O2.

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.

Effects of Cu2+, Ag+, and Pd2+ on the reductive debromination of 2,5-dibromoaniline by the ferrous hydroxy complex.

The ferrous hydroxy complex (FHC), composed of structural FeⅡ, has been shown to reduce a range of organic and inorganic contaminants. This study focused on the catalytic effects of Cu2+, Ag+, or Pd2+ on the reactivity of FHC suspensions towards 2,5-debromination (2,5-DBA). It was found that the target compound (2,5-DBA, 50 mg/L) could hardly be debrominated by FHC alone. However, Cu2+, Ag+, or Pd2+ had a significant promotion effect on the catalytic reactivity of structural FeⅡ on 2,5-DBA reduction. Pd2+ exhibited the best catalytic activity followed by Ag+ and Cu2+ in this study and the reductive debromination by Pd/FHC and Ag/FHC followed the pseudo-first-order kinetic model. Products distribution was highly dependent on the metal ions used. A reaction pathway was proposed in which the by-products were produced by hydrogenolysis and the elution order of bromines depended on the metal ions used. The enhanced reduction of 2,5-DBA by FHC suspensions modified by metal ions may prove useful in the development of improved materials for the treatment of halogenated organic compounds.

Pyrite cinder as a cost-effective heterogeneous catalyst in heterogeneous Fenton reaction: decomposition of H(2)O(2) and degradation of Acid Red B.

Pyrite cinder (PyC) was employed as a heterogeneous Fenton-like catalyst, and its catalytic activity was evaluated in view of the effects of catalyst dosage, pH and leaching metal ions. PyC showed significant reactivity, and the pseudo-first-order kinetic rate constant for decomposition of H(2)O(2) and degradation of Acid Red B (ARB) were 3.4 and 14.89 (10⁻³ min⁻¹) respectively when pH = 5. When 20 g/L PyC was added into 10 mM H(2)O(2) solution in neutral pH, H(2)O(2) could be completely degraded within 4 h, and more than 90% ARB was removed. Leaching metal ions from PyC were found to have little effect on decomposition of H(2)O(2) or on degradation of ARB. PyC still had high catalytic activity after five successive runs. The decomposition mechanism of H(2)O(2) was analyzed and the Haber-Weiss mechanism was employed in this paper. The electron spin resonance image showed •OH was produced and increased between 3 and 5 min in the PyC catalyzing H(2)O(2) reaction, which demonstrated that PyC had a durable ability to produce •OH.

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.

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.

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.

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.

Occurrence and distribution of organochlorine pesticides (DDT and HCH) in sediments from the middle and lower reaches of the Yellow River, China.

Sediments used in this study were selected from 23 stations in the middle and lower reaches of the Yellow River and its tributaries in November 2005. The levels and distribution patterns of selected organochlorine pesticides (OCPs = p,p(')-DDT, o,p (')-DDT, p,p(')-DDE, p,p(')-DDD, alpha-, beta-, gamma-, and delta-HCH) in samples were investigated by analysis of gas chromatography coupled with micro-electronic capture detector. Concentration of OCPs in the sediments from the Yellow River ranged from 0.05 to 5.03 ng g(-1) (mean, 1.02 ng g(-1)) for summation operatorDDT, 0.09-12.89 ng g(-1) (mean, 1.08 ng g(-1)) for summation operatorHCH. The concentration distribution of summation operatorDDT and summation operatorHCH varied significantly with different sampling station, indicating their different contamination sources. Composition analyses demonstrated that residues of DDTs in sediments came from the previous inputs of organochlorine pesticides, while beta-HCH and gamma-HCH significantly dominated in the sediments for HCHs.

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.

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.

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.

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.

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.

Simultaneous nitrogen and phosphor removal in an aerobic submerged membrane bioreactor.

Simultaneous nitrification and denitrification (SND) effect and phosphor removal were investigated in a one-staged aerobic submerged membrane bioreactor on pilot-scale with mixed liquor suspended solids (MLSS) 19-20 g/L. The effects of DO concentration, sludge floc size distribution on SND were studied. Test results suggested that SND was successfully performed in the membrane bioreactor (MBR) and about 70% total nitrogen removal efficiency was achieved when DO concentration was set to 0.2-0.3 mg/L. The main mechanisms governing SND were the suitable sludge floc size and the low DO concentration which was caused by low oxygen transfer rate with such a high MLSS concentration in the MBR. In the meantime, phosphor removal was also studied with polymer ferric sulfate (PFS) addition and 14 mg/L dosage of PFS was proper for the MBR to remove phosphor. PFS addition also benefited the MBR operation owing to its reduction of extracellular polymer substances (EPS) of mixed liquor.