Formation mechanism of persistent free radicals during pyrolysis of Fenton-conditioned sewage sludge: Influence of NOM and iron.

The present study provided an innovative insight into the formation mechanism of persistent free radicals (PFRs) during the pyrolysis of Fenton-conditioned sludge. Fenton conditioners simultaneously improve the dewatering performance of sewage sludge and catalyze the pyrolysis of sewage sludge for the formation of PFRs. In this process, PFRs with a total number of spins of 9.533×1019 spins/g DS could be generated by pyrolysis of Fenton-conditioned sludge at 400°C. The direct thermal decomposition of natural organic matter (NOM) fractions contributed to the formation of carbon-centered radicals, while the Maillard reaction produced phenols precursors. Additionally, the reaction between aromatic proteins and iron played a crucial role in the formation of phenoxyl or semiquinone-type radicals. Kinetics analysis using discrete distributed activation energy model (DAEM) demonstrated that the average activation energy for pyrolysis was reduced from 178.28 kJ/mol for raw sludge to 164.53 KJ/mol for Fenton conditioned sludge. The reaction factor (fi) indicated that the primary reaction in Fenton-conditioned sludge comprised of 27 parallel first-order reactions, resulting from pyrolysis cleavage of the NOM fractions, the Maillard reaction, and iron catalysis. These findings are significant for understanding the formation process of PFRs from NOM in Fenton-conditioned sludge and provide valuable insight for controlling PFRs formation in practical applications.

Peroxymonosulfate activation by trace iron(III) porphyrin for facile degradation of organic pollutants via nonradical oxidation.

Nonradical species with great resistance to interference have shown great advantages in complex wastewater treatment. Herein, a novel system constructed by biodegradable tetrakis-(4-carboxyphenyl)-porphyrinatoiron(III) (FeIII-TCPP) and peroxymonosulfate (PMS) was proposed for facile decontamination. Nonradical pathway is observed in FeIII-TCPP/PMS, where 1O2 and high-valent iron-oxo species play dominant roles. The genres and valence of high-valent iron-oxo species, including iron(IV)-oxo porphyrin radical-cationic species [OFeIV-TCPP•+] and iron(IV)-hydroxide species [FeIV-TCPP(OH)], are ascertained, along with their generation mechanism. The axial ligand on the iron axial site affects the ground spin state of FeIII-TCPP, further influencing the thermodynamic reaction pathway of active species. With trace catalyst in micromoles, FeIII-TCPP exhibits high efficiency by degrading bisphenol S (BPS) completely within 5 min, while Co2+/PMS can only achieve a maximum of 26.2% under identical condition. Beneficial from nonradical pathways, FeIII-TCPP/PMS demonstrates a wide pH range of 3-10 and exhibits minimal sensitivity to interference of concomitant materials. BPS is primarily eliminated through ß-scission and hydroxylation. Specifically, 1O2 electrophilically attacks the C-S bond of BPS, while high-valent iron-oxo species interacts with BPS through an oxygen-bound mechanism. This study provides novel insights into efficient activation of PMS by iron porphyrin, enabling the removal of refractory pollutants through nonradical pathway.

Molecular mechanisms and physiological responses of rice leaves co-exposed to submicron-plastics and cadmium: Implication for food quality and security.

The effects of co-exposure to aged submicron particles (aSMPs) and Cd as model contaminants on rice leaves via the foliar route were investigated. Thirty-day-old rice seedlings grown in soil were exposed to Cd (nitrate) through foliar spraying at concentrations of 1, 10, 50, 100, and 500 µM, with or without aSMP at a rate of 30 µg d-1. It was observed that Cd translocated from leaves to roots via stems even without co-exposure to SMP. Co-exposure can reduce cadmium levels in leaves. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis confirmed a significant reduction (29.3 - 77.9%) in Cadmium accumulation in the leaves of rice plants during co-exposure. Exposure to Cd resulted in physiological, transcriptomic, and metabolomic changes in rice leaves, disrupting 28 metabolism pathways, and impacting crop yield and quality. Exposure to both Cd and aSMPs can interfere with the Cd distribution in plants. Rice leaves exposed solely to Cd exhibit higher toxicity and Cd accumulation, compared to those co-exposed to Cd and aSMPs. The accumulation of Cd in plant leaves is enhanced with aSMPs, which may lead to more pronounced gene expression regulation and changes in metabolic pathways, compared to Cd exposure. Our study found that the independent Cd exposure group had higher Cd accumulation and toxicity in rice leaves compared to the combined exposure of Cd and aSMPs. We hypothesize that aged negatively charged SMPs can capture Cd and reduce its exposure in the free state while jointly inhibiting Cd-induced oxidative and chloroplast damage, thereby reducing the potential risk of Cd exposure in rice plants.

Sludge-derived iron-carbon material enhancing the removal of refractory organics in landfill leachate: Characteristics optimization, removal mechanism, and molecular-level investigation.

Mature landfill leachate is a refractory organic wastewater, and needs physical and chemical pretreatments contemporaneously, e.g. iron-carbon micro-electrolysis (IC-ME). In this study, a novel iron-carbon (Fe-C) material was synthesized from waste activated sludge to be utilized in IC-ME for landfill leachate treatment. The pyrolysis temperature, mass ratio of iron to carbon, and solid-liquid ratio in leachate treatment were optimized as 900 °C with 1.59 and 34.7 g/L. Under these optimal conditions, the chemical oxygen demand (COD) removal efficiency reached 79.44 %, which was 2.6 times higher than that of commercial Fe-C material (30.1%). This excellent COD removal performance was indicated to a better mesoporous structure, and uniform distribution of zero-valent iron in novel Fe-C material derived from sludge. The contribution order of COD removal in IC-ME treatment for landfill leachate was proven as coagulation, adsorption, and redox effects by a contrast experiment. The removal of COD includes synthetic organic compounds, e.g. carcinogens, pharmaceuticals and personal care products. The contents of CHO, CHON, and CHOS compounds of dissolved organic matter (DOM) in the leachate were decreased, and both the molecular weight and unsaturation of lipids, lignin, and tannic acids concentration were also reduced. Some newly generated small molecular DOM in the treated leachate further confirmed the existence of the redox effect to degrade DOM in leachate. The total cost of sludge-derived Fe-C material was only USD$ 152.8/t, which could save 76% of total compared with that of commercial Fe-C materials. This study expands the prominent source of Fe-C materials with excellent performance, and deepens the understanding of its application for leachate treatment.

Novel PbO@C composite material directly derived from spent lead-acid batteries by one-step spray pyrolysis process.

A one-step spray pyrolysis process is investigated for the first time in the field of spent lead-acid batteries (LABs) recycling. The spent lead paste that derived from spent LAB is desulfurized and then leached to generate the lead acetate (Pb(Ac)2) solution, which is then sprayed directly into a tube furnace to prepare the lead oxide (PbO) product by pyrolysis. The low-impurity lead oxide product (9 mg/kg Fe and 1 mg/kg Ba) is obtained under the optimized conditions (the temperature of 700 °C, the pumping rate of 50 L/h, and the spray rate of 0.5 mL/min). The major crystalline phases of the synthesized products are identified to be α-PbO and ß-PbO. In the spray pyrolysis process, Pb(Ac)2 droplets are sequentially transformed into various intermediate products: H2O(g)@Pb(Ac)2 solution, Pb(Ac)2 crystals@PbO, and the final PbO@C product. Owning its carbon skeleton structure, the recovered PbO@C product (carbon content of 0.14%) shows better performance than the commercial ball-milled lead oxide powder in battery tests, with higher initial capacity and better cycling stability. This study could provide a strategy for the short-route recovery of spent LABs.

Peroxymonosulfate activated by natural porphyrin derivatives for rapid degradation of organic pollutants via singlet oxygen and high-valent iron-oxo species.

The activation of peroxymonosulfate (PMS) by sodium ferric chlorophyllin (SFC), a natural porphyrin derivative extracted from chlorophyll-rich substances, was systematically investigated for facile degradation of bisphenol A (BPA). SFC/PMS is capable of degrading 97.5% of BPA in the first 10 min with the initial BPA concentration of 20 mg/L and pH = 3, whereas conventional Fe2+/PMS could only remove 22.6% of BPA under identical conditions. It demonstrates a prominent flexibility to a broad pH range of 3-11 with complete pollutant degradation. A remarkable tolerance toward concomitant high concentration of inorganic anions (100 mM) was also observed, among which (bi)carbonates can even accelerate the degradation. The nonradical oxidation species, including high-valent iron-oxo porphyrin species and 1O2, are identified as dominant species. Particularly, the generation and participation of 1O2 in the reaction is evidenced by experimental and theoretical methods, which is vastly different from the previous study. The specific activation mechanism is unveiled by density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations. The results shed light on effective PMS activation by iron (III) porphyrin and the proposed natural porphyrin derivative would be a promising candidate for efficient abatement of recalcitrant pollutants toward complicated aqueous media in wastewater treatment.

Generation of high-valent iron-oxo porphyrin cation radicals on hemin loaded carbon nanotubes for efficient degradation of sulfathiazole.

Hemin has attracted considerable interest as an efficient catalyst recently, however, its direct application is inefficient due to severe molecular aggregation. Immobilizing hemin on various supports is a feasible approach to address this issue. In this work, a CNTs-hemin catalyst was prepared by loading hemin onto multiwalled carbon nanotubes (CNTs) through ball milling. Compared with hemin, CNTs-hemin demonstrates remarkably enhanced performance in the peroxymonosulfate system, with a 650-fold improvement of apparent rate constant, reaching 97.8% degradation of sulfathiazole in 5 min. High-valent iron-oxo porphyrin cation ((Porp)+•FeIV=O) radicals are proposed as the dominant reactive species in the CNTs-hemin/peroxymonosulfate system instead of sulfate radicals (SO4•-), hydroxyl radicals (•OH), superoxide radicals (O2•-) and singlet oxygen (1O2). More in-depth mechanisms reveal that the strong electron transfer between CNTs and hemin promotes the generation of (Porp)+•FeIV=O radicals through a heterolysis pathway. This research enriches the understanding of the catalytic mechanism of supported biomimetic catalysts for PMS activation and provides a perspective on the role of support materials for catalytic activity.

Iron-calcium reinforced solidification of arsenic alkali residue in geopolymer composite: Wide pH stabilization and its mechanism.

Arsenic-alkali residue (AAR) from antimony production can pose significant health and environmental hazards due to the risk of arsenic (As) leaching. In this study, geopolymer composite synthesized from fly ash (FA) was investigated for efficient stabilization of high-arsenic-containing AAR (As2O3 of 22.74 wt%). Two industrial wastes, e.g., granulated blast furnace slag (GBFS) with active calcium composition and water-quenched slag (WQS) from lead-zinc smelting with active iron composition, were investigated for the reinforcement of AAR geopolymer solidification. A wide pH stabilization (from pH = 3-pH = 12) of AAR with the geopolymer composite was successfully achieved, and As leaching concentration of geopolymer with the addition of 5 wt% AAR was significantly reduced from 2343.73 mg/L (AAR) to that below 0.18 mg/L, which successfully meet the regulatory limit of Chinese domestic waste landfill (GB, 18598-2019, 1.2 mg/L) and hazardous waste landfill (GB16889-2008, 0.3 mg/L). Johnbaumite (Ca5(AsO4)3(OH)) was formed in geopolymer composite and leached samples with initial pH from 2.6 to 6 (final pH from 5.54 to 13.15). Magnetite and iron hydroxide phases with strong adsorption and/or As co-precipitation capability were also observed. As stabilization was also achieved with iron oxidation from As(III) to As(V). This study solves the problem of unstable As leaching at different pH for the solidification of arsenic-bearing solid waste, and provides a promising and practical strategy for efficient solidification/stabilization of AAR as well as other similar arsenic-bearing solid wastes with geopolymer composite.

Iron porphyrin-TiO2 modulated peroxymonosulfate activation for efficient degradation of 2,4,6-trichlorophenol with high-valent iron-oxo species.

Developing efficient catalysts with low cost and environmental friendliness for peroxymonosulfate (PMS) activation attracts broad interest. In this study, TiO2-hemin was prepared by immobilizing hemin on TiO2 using a ball milling method, demonstrating 126.9-fold enhanced catalytic degradation efficiency compared with unsupported hemin in the PMS activation system, with 92.9% of 2,4,6-trichlorophenol (2,4,6-TCP) removed in 10 min. The superior performance is attributed to the strong interaction between TiO2 and hemin, which induces the redistribution of the electron density of hemin molecules. In the TiO2-hemin/PMS system, sulfate radicals (SO4•-), hydroxyl radicals (•OH), singlet oxygen (1O2), and superoxide radicals (O2•-) were identified, which only played a minor role in the elimination of 2,4,6-TCP. Instead, high-valent iron-oxo species were proposed and identified as the primary active species. This study provides a facile strategy to enhance the activity of the biomimetic catalyst and offers insight into the catalytic mechanism of iron porphyrin with PMS activation.

Cooperation of multiple active species generated in hydrogen peroxide activation by iron porphyrin for phenolic pollutants degradation.

The narrow acid pH range and the nonselectivity of the dominant •OH limit the Fenton systems to remediate the organic wastewater. Inspired by the role of heme in physiological processes, we employed iron porphyrin as a novel homogeneous catalyst to address this issue. Multiple active species are identified during the activation of H2O2, including high-valent iron porphyrin ((por)Fe(IV)) species ((por)Fe(IV)-OH, (por)+•Fe(IV)=O) and oxygen-centered radicals (•OH, HO2•/•O2-), as well as atomic hydrogen (*H) and carbon-centered radicals. With the cooperation of these active species, the degradation of pollutants could be resistant to the interference of concomitant ions and proceed over a wide pH range. This cooperative behavior is further verified by intermediates identified from bisphenol A degradation. Specifically, the presence of *H could facilitate the cleavage of the C-C bond and the addition of unsaturated or aromatic molecules. (Por)+•Fe(IV)=O could hydroxylate substrates with an oxygen rebound mechanism. Hydrogen atom abstraction of contaminants could be performed by (por)Fe(IV)-OH to form desaturated products by attacking oxygen-centered radicals. The ecotoxicity of bisphenol A could be significantly decreased through degradation. This study would provide a new approach to wastewater treatment and shed light on the interaction between metalloporphyrin and peroxide in an aqueous solution.

Changes of phosphorus species during (hydro) thermal treatments of iron-rich sludge and their solubilization mediated by a phosphate solubilizing microorganism.

This study systematically evaluated phosphorus (P) solubilization from pyrochar and hydrochar derived from both raw sludge and iron-rich sludge. The data indicated, that an increase in thermal treatment temperature and the presence of iron promoted the accumulation of P in both pyrochar (derived at 300, 500, and 800 °C) and hydrochar (derived at 100, 200, and 280 °C). After incubating pyrochar and hydrochar with a phosphate solubilizing microorganism (PSM) (Pseudomonas aeruginosa) for 30 days, PSM significantly promoted the solubilization of P in pyrochar and hydrochar synthesized at low temperatures rather than those at high temperatures, with a 59 % increase for the pyrolysis of raw sludge at 300 °C than that pyrolyzed at 800 °C and a 62 % increase for the hydrothermal treatment of raw sludge at 100 °C than that treated at 280 °C. And the phenomena were more obvious on the char samples derived from iron-rich sludge. The mass balance of different P species in the solid and liquid phases indicated that after incubating with PSM for 30 days, NaOH-P was the main P solubilized from the solid phase of pyrochar and HCl-P was the main P solubilized from the solid phase of hydrochar. Considering P availability to plants, the preliminary economic analysis indicated that the hydrothermal treatment of iron-rich sludge at 100 °C showed the highest economic benefits for P recovery, with the net cost of 28.79 USD/ton wet sludge. This study was useful in giving novel insights into the reuse of char samples as P fertilizer, and also suggested the importance of Pseudomonas aeruginosa and other bacteria in sludge application, particularly in terms of P solubilization.

Pretreatment of sludge with sodium iron chlorophyllin-H2O2 for enhanced biogas production during anaerobic digestion.

This study investigated a novel sodium iron chlorophyllin-H2O2 (SIC-H2O2) sludge pretreatment strategy before anaerobic digestion to enhance methane production. The efficiencies and mechanism of the proposed strategy to enhance sludge biodegradability were explored. The SIC-H2O2 pretreatment could enhance the oxidation performance for sludge floc disintegration to dissociate TB-EPS into S-EPS increased SCOD to 521.38 mg/L. The increase of solubilization and release of EPS with the pretreatment facilitate the biogas production at 702 L kg-1 VS, which was 3-folds of the control and significantly higher than other pretreatments. The result of excitation-emission matrix and parallel factor (EEM-PARAFAC) analysis showed that the SIC-H2O2 pretreatment enhanced the dissociation of TB-EPS fractions, especially the protein-like and soluble microbial by-product-like substances. Electron paramagnetic resonance (EPR) results provided evidence for homolytic catalysis H2O2 for the generation OH and the production of high-valent (Por)FeIV(O) intermediates. Synergistic effects of reactive oxygen species (OH, H2O2 and /HO2) and (Por)FeIV(O) enhanced the EPS disintegration during SIC-H2O2 pretreatment. The mixed-acid type fermentation provided continuous VFAs supply under the enrichment of Chloroflexi and Actinobacteria and multiplication Methanosaeta also promoted methane production. This research provides a feasible pretreatment strategy increase sludge biodegradability and enhance biogas production in the anaerobic digestion process.

Sludge-derived biochar with multivalent iron as an efficient Fenton catalyst for degradation of 4-Chlorophenol.

Fe-rich biochar with multivalent iron compounds (Fe0, Fe0.95C0.05, Fe3O4, and FeAl2O4) pyrolyzed from sludge cake conditioned with Fenton's reagent and red mud was utilized as an efficient Fenton catalyst for the degradation of 4-chlorophenol (4-CP). Effects of pyrolysis temperature and sludge conditioner composition on the transformation of iron compounds were studied. Both homogeneous Fenton reaction initiated by Fe2+ leached from both low-valent Fe0 and Fe0.95C0.05, and heterogeneous Fenton reaction initiated by solid iron phases of Fe3O4 and FeAl2O4 were revealed to contribute to the degradation of 4-CP. The removal efficiency of 4-CP remained 100% after five successive degradation rounds. The homogeneous Fenton reaction mainly works in the first degradation round, and the heterogeneous Fenton reaction dominates in subsequent degradation rounds. The findings of this study suggest that sewage sludge derived Fe-rich biochar could be utilized as an efficient Fenton catalyst for recalcitrant organics degradation.

Phosphorus recovery from the liquid phase of anaerobic digestate using biochar derived from iron-rich sludge: A potential phosphorus fertilizer.

A novel technique for phosphorus recovery from the liquid phase of anaerobic digestate was developed using biochar derived from iron-rich sludge (dewatered sludge conditioned with Fenton's reagent). The biochar pyrolyzed from iron-rich sludge at a low temperature of 300 °C (referred to as Fe-300 biochar) showed a better phosphorus (P) adsorption capacity (most of orthophosphate and pyrophosphate) than biochars pyrolyzed at other higher temperatures of 500-900 °C, with the maximum P adsorption capacity of up to 1.843 mg g-1 for the liquid phase of anaerobic digestate. Adsorption isotherms study indicated that 70% P was precipitated through chemical reaction with Fe elements, i.e., Fe(II) and Fe(III) existed on the surface of the Fe-300 biochar, and other 30% was through surface physical adsorption as simulated by a dual Langmuir-Langmuir model using the potassium dihydrogen orthophosphate (KH2PO4) as a model solution. The seed germination rate was increased up to 92% with the addition of Fe-300 biochar after adsorbing most of P, compared with 66% without the addition of biochar. Moreover, P adsorbed by the chemical reaction in form of iron hydrogen phosphate can be solubilized by a phosphate-solubilizing microorganism of Pseudomonas aeruginosa, with the total solubilized P amount of 3.045 mg g-1 at the end of an incubation of 20 days. This study indicated that the iron-rich sludge-derived biochar could be used as a novel and beneficial functional material for P recovery from the liquid phase of anaerobic digestate. The recovered P with biochar can be re-utilized in garden soil as an efficient P-fertilizer, thus increasing the added values of both the liquid phase of anaerobic digestate and the iron-rich sludge.

Biogas and phosphorus recovery from waste activated sludge with protocatechuic acid enhanced Fenton pretreatment, anaerobic digestion and microbial electrolysis cell.

Biogas and phosphorus recovery from waste activated sludge (WAS) with sequential homogeneous protocatechuic acid (PCA) enhanced Fenton pretreatment, anaerobic digestion (AD) and microbial electrolysis cell (MEC) were investigated. The cumulation of biogas production of WAS-Fenton-AD was 330.4 mL/g VS, which was 2.05-fold of the control without pretreatment (WAS-AD) during anaerobic digestion. Biogas production of 178 mL/L/d from WAS-Fenton-AD-MEC was achieved, which was 5.23-fold of the WAS-MEC, 2.28-fold of WAS-Fenton-MEC and 1.46-fold of WAS-AD-MEC, respectively. Enhanced phosphorus recovery in form of struvite reached 1.72 g/g TS (18.03% of total P) with a purity of 74.4%. Microbial community richness and diversity analysis revealed that the pretreatment process under circumneutral condition improved the diversity of microbial community, which was consisted of Bacteroidetes (33.90%), Proteobacteria (33.14%), and Chloroflexi (10.14%), compared to a majority of Firmicutes (70.81%) in WAS-AD. This study provides a feasible strategy for the recovery of biogas combined with phosphorus from WAS.

A micromilled microgrid sensor with delaminated MXene-bismuth nanocomposite assembly for simultaneous electrochemical detection of lead(II), cadmium(II) and zinc(II).

A delaminated MXene-bismuth (Bi@d-Ti3C2) nanocomposite was synthesized for the construction of a microgrid electrochemical sensor via mechanical milling. The Bi@d-Ti3C2 nanocomposite was synthesized by accumulation of Bi(III) on the surface of delaminated Ti3C2 nanosheets through electrostatic attraction and subsequent in-situ growth of bismuth nanorods. Under optimized experimental conditions, the sensor exhibits (a) linear responses to Pb(II), Cd(II) and Zn(II) in the concentration range from 1 to 20 µg L-1, (b) well separated peak potentials at -0.54 V, -0.76 V and - 1.15 V vs. Ag/AgCl, (c) sensitivities of 0.98, 0.84 and 0.60 µA L µg-1, and (d) detection limits of 0.2, 0.4 and 0.5 µg L-1, respectively. This performance is attributed to the uniform dispersion of Bi nanorods on electrically conductive delaminated Ti3C2 MXene, and to the enhanced diffusion due to the microgrid structure. Graphical abstractSchematic representation of a microgrid sensor based on delaminated MXene-bismuth (Bi@d-Ti3C2) nanocomposite for the simultaneous electrochemical determination of Pb(II), Cd(II) and Zn(II).

Unraveling oxidation behaviors for intracellular and extracellular from different oxidants (HOCl vs. H2O2) catalyzed by ferrous iron in waste activated sludge dewatering.

Cell lysis in sludge pretreatment by advanced oxidation process (AOP) has a great effect on sludge dewaterability. Cell lysis caused by reactive radicals (e.g. hydroxyl radical) was dependent on the reaction site of AOP. However, little is known about the accurate radical generation site of AOP in sludge pretreatment. In this study, two kinds of oxidation behaviors from different oxidants (HOCl vs. H2O2) catalyzed by ferrous iron were comparatively investigated. Higher amount of living cells (84.3%) and hydroxyl radicals (9.86 × 10-5 M), and more fragmentized sludge flocs (particle sizes of D50 was 50.1 vs. 57.3 µm of RS) were detected in sludge conditioned by Fe2+/H2O2, which implied that Fenton reaction mainly happened at surface and outside of sludge flocs (such as EPS layer and liquid phase). Thus, it could be regarded as "extracellular oxidation". Fewer living cells (undetectable), fewer amount of hydroxyl radicals (undetectable in sludge), and more integrated sludge flocs (particle size of D50 was 56.1 vs. 57.3 µm of RS) were determined in sludge conditioned by Fe2+/Ca(ClO)2. Hence, it could be regarded as "Intracellular oxidation". In addition, sludge pretreatment based on Fe2+/Ca(ClO)2 could achieve simultaneous deep-dewatering performance and total coliforms inactivation. Based on response surface methodology, the optimal dosages of Fe2+ and Ca(ClO)2 were proposed as 106.1 and 234.5 mg/g volatile solids respectively, without any acidification of sludge. Under these optimal dosages, the water content of dewatered sludge cake was 51.9 ±â€¯0.1 wt% and the pH of the final filtrate was 5.8 ±â€¯0.2. Total coliforms of sludge could be inactivated in 10 s after Fe2+/Ca(ClO)2 addition.

Simulation on flow field and gas hold-up of a pilot-scale oxidation ditch by using liquid-gas CFD model.

A liquid-gas two-phase computational fluid dynamics (CFD) model was developed to simulate flow field and gas hold-up in a pilot-scale oxidation ditch (OD). The volume of fluid (VOF) model and the mass flow inlet boundary condition for gas injection were introduced in this model. The simulated values of the flow velocities and the gas hold-up were verified by experimental measurements in the pilot-scale OD. The results showed that the gas hold-up at test-site 3, immediately downstream of the surface aerator, was the highest among all three test-sites. Most of the gas existed in the upper portion of the ditch and was close to the inner side of the channel. Based on the liquid-gas two-phase CFD model, three operating conditions with different setting height ratios of the submerged impellers were simulated. The simulated results suggested that the setting heights of the submerged impellers have significant impacts on the flow velocity distribution. Lowering the setting height could increase the flow velocity in the pilot-scale OD. An optimal setting height ratio of 0.273 was proposed, which would be beneficial for minimizing sludge sedimentation, especially near the inner side of the curve bend.

In situ generation of zero valent iron for enhanced hydroxyl radical oxidation in an electrooxidation system for sewage sludge dewatering.

A hybrid electrochemical conditioning strategy for enhanced sewage sludge dewatering was proposed. A water content of 47.2 wt.% for the dewatered sludge cake was achieved at an applied voltage of 20 V for 30 min, which was significantly lower than previously reported results. The capillary suction time (CST) and specific resistance to filtration (SRF) were decreased by 75.6% and 90.9%, respectively. Four simultaneous processes, including electrooxidation, the electro-Fenton process, molecular oxygen activation via zero valent iron (ZVI) and Fe(III) flocculation, had synergetic effects on the degradation of extracellular polymeric substances (EPS) to enhance sludge dewaterability. The in situ generation of ZVI on the cathode electrode facilitated the reduction of Fe(III) to Fe(II) via activation of molecular oxygen. The sludge pH decreased spontaneously and remained acidic due to the competitive reaction of ZVI generation to hydrogen evolution as well as the Fe(III) flocculation process, which further guaranteed the high efficiency of hydroxyl radical generation. Changes in the physiochemical properties of the sludge (particle size distribution, zeta potential, viscosity and EPS characteristics) induced by the hybrid conditioning process were further explored. In addition, the economic potential of the hybrid system was preliminarily assessed (USD$ 127.6/ton dry sludge).