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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)

Microplastic accumulation in agricultural soils can stress plants and affects quality of the products. Current research on the effects of microplastics on plants is not consistent and the underlying mechanisms are yet unknown. Here, the molecular mechanisms of the stress response were investigated via metabolomic and transcriptomic analyses of rice Oryza sativa L. II Y900 and XS123 under the exposure of polystyrene microplastics (PS-MPs) in a field study. Distinct responses were obtained in these two rice subspecies, showing decreased head rice yield by 10.62% in Y900 and increase by 6.35% in XS123. The metabolomics results showed that PS-MPs exposure inhibited 29.63% of the substance accumulation-related metabolic pathways and 43.25% of the energy expenditure-related metabolic pathways in the Y900 grains; however, these related pathways were promoted in the XS123 grains. The transcriptomics results indicated that the expression of genes encoding proteins involved in the tricarboxylic acid cycle in the Y900 grains was inhibited, but it was enhanced in the XS123 grains. The XS123 subspecies could response against microplastic exposure stress through the metabolite accumulation and energy expenditure pathways, while the Y900 could not. The results provide insight into the perturbation of rice grains in farmlands with microplastics contamination.

The electrogeneration of H

A hybrid sludge conditioning strategy with electrooxidation and Fe(II) addition was used for heavy metal removal from sewage sludge and industrial sludge, with simultaneous sludge dewatering and stabilization. With the addition of 82 mg/g DS Fe(II) and treatment time of 4.5 h, heavy metal removals of 72.95% and 78.49% for Cu, 66.29% and 84.26% for Zn, and 36.52% and 36.99% for Pb were achieved from sewage sludge and industrial sludge samples respectively. The system pH decreased to 2.33 and 2.98 and the oxidation–reduction potential (ORP) values increased to 435.90 mV and 480.60 mV in sewage sludge and industrial sludge samples, respectively, which was conducive to the desorption and dissolution of heavy metals from sludge structures and the degradation of the organic compounds that complexed with heavy metals. In addition, the hybrid conditioning process demonstrated excellent dewatering performance due to the efficient electrochemical disintegration of sludge flocs together with the coagulation of sludge particles by Fe(III) generated via electrooxidation. The strong acidic and oxidative environment produced by the enhanced electrooxidation process was also responsible for pathogen inactivation.

The electrogeneration of H2O2 and electro-regeneration of ferrous are conflicting matters in electro-Fenton system. In this research, the degradation of Rhodamine B, methyl orange (MO) and 4-chlorophenol (4-CP) was investigated using a novel dual-cathode microbial fuel cell (MFC) electro-Fenton (EF) hybrid system. An air-cathode of an EF system was used for H2O2 electrogeneration and a carbon felt cathode of a MFC was used to accelerate Fe2+ regeneration. Synergistic improvement of MFC power generation and the degradation of the above refractory organics through EF reaction was achieved. The EF air-cathode was fabricated by adopting activated carbon/graphite powder mixture and PVDF binder, which showed higher H2O2 generation but slower Fe3+ reduction rate than MFC carbon felt cathode. The Rhodamine B removal rate constant and mineralization current efficiency of the MFC coupled EF were 64% and 42% higher than that of uncoupled EF, respectively. The MFC-EF coupled system also exhibited significantly higher removal efficiency for MO and 4-CP than that of un-coupled EF system. Moreover, the power density of MFC was greatly enhanced by coupling EF due to higher Fe3+/Fe2+ redox potential than oxygen reduction.

Redox metal ions play the crucial role in versatile advanced oxidation technologies, in which controlling the active species formation through catalyst design is one of the key challenges in oxidant utilization. This work describes an example of different active species formations in CuO-mediated degradation just because of supporting material differences. Although three CuO catalysts were prepared by similar procedures, it was found that CuO-MgO catalyst demonstrated high efficiency in phenol degradation with bicarbonate activated H2O2, in which the superoxide radical is crucial, while hydroxyl radical and singlet oxygen are ignorable. For the CuO-MgO-Al2O3 and CuO-Al2O3 catalysts, the degradation proceeds by popular hydroxyl radical based process, however, the efficiency was poor. The EPR experiments also confirmed the absence of hydroxyl radical in CuO-MgO system but its presence in CuO-MgO-Al2O3 and CuO-Al2O3 system. The high catalytic efficiency with ignorable hydroxyl radical in the CuO-MgO system leads us to propose that an alternative Cu(III) species dominates the degradation. The basic MgO support may facilitate the formation of the Cu(III) species, whereas the neutral MgO-Al2O3 and acidic Al2O3 supports are unable to stabilize the high valent Cu(III) species, leading to the common hydroxyl radical mechanism with low efficiency of H2O2 in alkaline conditions.

In this study, the long-term stability of Cr(VI) in the FeSO4 and H2SO4 (FeSO4-H2SO4) treated chromite ore processing residue (COPR) after 400 curing days and the stabilization mechanisms were investigated. FeSO4-H2SO4 treatment significantly reduced toxicity characteristic leaching procedure (TCLP) and synthetic precipitation leaching procedure (SPLP) Cr(VI) concentrations to lower than the regulatory limit of 1.5mgL-1 (HJ/T 301-2007, China EPA) even for the samples curing 400days, achieving an outstanding long-term stability. Our independent leaching tests revealed that H+ and SO42- have synergistic effect on promoting the release of Cr(VI), which would make Cr(VI) easier accessed by Fe(II) during stabilization. The contributions of H+ and SO42- to Cr(VI) release ratio were 25%-44% and 19%-38%, respectively, as 5mol H2SO4 per kg COPR was used. X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and alkaline digestion analyses were also employed to interpret the possible stabilization mechanism. Cr(VI) released from COPR solid was reduced to Cr(III) by Fe(II), and then formed stable FexCr(1-x)(OH)3 precipitate. This study provides a facile and reliable scheme for COPR stabilization, and verifies the excellent long-term stability of the FeSO4-H2SO4 treated COPR.

The novel catalyst LaCu

The novel catalyst LaCu0.5Fe0.5O3-δ with oxygen vacancies (OVs) was prepared and demonstrated excellent stability and activity for the degradation of bisphenol A. The removal rate of 92.1 % and H2O2 utilization efficiency of 70.4 % were obtained due to the efficient hydroxyl radical generation mediated by OVs. The density functional theory calculation showed that the substitution of Cu and formation of OVs significantly increases the charge density near the active sites. Bader charge analysis revealed that the charge offset accelerated the reduction of Fe. The elevation of electron transfer efficiency also promotes the valence transition of copper and iron atoms. The reversible electronic transition between Fe2+ ⇆ Fe3+, Cu+ ⇆ Cu2+ and Cu2+ ⇆ Fe2+ involved in this reaction were considered to be enhanced and the homolytic bond clearage of H2O2 was simultaneously promoted, facilitated by the electron-rich region combined with OVs on the surface of LaCu0.5Fe0.5O3-δ.

Conditioning sewage sludge with Fenton's reagent and skeleton builders has been proved to be an effective mean to achieve deep dewatering. This work aimed to give a comprehensive insight into the mechanism involved. The results show that significant synergistic effect existed between Fenton's reagent and skeleton builders. With the optimum dosage, water content of dewatered sludge cake could be reduced to 49.5±0.5%. Furthermore, raw sludge existed in the form of zoogloea and its flocs surface was plate-like. After Fenton oxidation, partial of extracellular polymeric substances (EPS) was destroyed and the amounts of protein and polysaccharide dissolved in filtrate increased. Meanwhile, sludge flocs turned into smaller ones. After adding skeleton builders, constantly-changing environment promoted senescence and death of microorganism. A large area of plate-like structure disappeared, instead of which were holes. Irregular non-living things inlayed or pierced microbial cells, promoting the conversion from bound water to free water as well as further reduction of the sludge particle size. Additionally, these irregular substances could form a rigid porous structure under high pressure, which could transmit the stresses to the sludge internal parts and provide outflow channels for free water. Consequently, conditioned sludge was suitable for high pressure deep dewatering.

A sustainable method, with minimal pollution and low energy cost in comparison with the conventional smelting methods, is proposed for treating components of spent lead-acid battery pastes in aqueous organic acid(s). In this study, PbO, PbO2, and PbSO4, the three major components in a spent lead paste, were individually reacted with a mixture of aqueous sodium citrate and acetic acid solution. Pure lead citrate precursor of Pb3(C6H5O7)2 · 3H2O is the only product crystallized in each leaching experiment. Conditions were optimized for individual lead compounds which were then used as the basis for leaching real industrial spent paste. In this work, efficient leaching process is achieved and raw material cost is reduced by using aqueous sodium citrate and acetic acid, instead of aqueous sodium citrate and citric acid as reported in a pioneering hydrometallurgical method earlier. Acetic acid is not only cheaper than citric acid but is also more effective in aiding dissolution of the lead compounds thus speeding up the leaching process in comparison with citric acid. Lead citrate is readily crystallized from the aqueous solution due to its low solubility and can be combusted to directly produce leady oxide as a precursor for making new battery pastes.

In this study, the long-term stability of Cr(VI) in the FeSO

In this research, Bayer red mud (RM) was pretreated through alkali-thermal activation process, and prepared as an one-part geopolymer precursor, which could be used as geopolymeric solidification/stabilization (S/S) reagent for municipal solid waste incineration fly ash (MSWI FA). Compressive strength test, modified TCLP leaching test and sequential extraction test were conducted to evaluate the effectiveness of the RM-based geopolymeric S/S reagent. The results show that the S/S effects for heavy metals of RM-based geopolymer exhibit the following order: Pb>Cu>Zn>Cr. Most of the Zn, Pb and Cu in the MSWI FA transform from the leachable fractions into the inactive fractions difficult or unavailable to leach out. In the geopolymeric S/S solid, the active aluminosilicates in MSWI FA are dissolved in the alkaline environment formed by pretreated RM and then participate in the geopolymerization, which increases the SiO2/Al2O3 ratio and enhances the structural stability of geopolymeric S/S solid. MSWI FA offsets the strength deterioration of RM based one-part geopolymer and improves the immobilization efficiency for heavy metals in the geopolymer structure.

Chemical conditioners are often used to enhance sewage sludge dewaterability through altering sludge properties and flocs structure, both affect odorous compounds emissions not only during sludge conditioning but also in subsequent sludge disposal. This study was to investigate emission characteristics of ammonia (NH 3 ), sulfur dioxide (SO 2 ), hydrogen sulfide (H 2 S) and carbonyl sulfide (COS) generated from sewage sludge conditioned by three representative conditioners, i.e., organic polymers, iron salts and skeleton builders, F-S (Fenton's reagent and skeleton builders) composite conditioner. The results demonstrate that polyacrylamide (PAM) has an insignificant effect on emission characteristics of nitrogen- and sulfur-containing odorous compounds, because the properties, sulfur and nitrogen speciations are similar in PAM-conditioned sludge and raw sludge (RS). Significant increases of SO 2 and H 2 S emissions in the H 2 SO 4 conditioning process were observed due to the accelerated decomposition of sulfur-containing amino acids in acidic environment. Fenton peroxidation facilitates the formation of COS. CaO can reduce sulfur-containing gases emission via generation of calcium sulfate. However, under strong alkaline conditions, free ammonia or protonated amine in sludge can be easily converted to volatile ammonia, resulting in a significant release of NH 3 .

Leaching copper from shredded particles of waste printed circuit boards (PCBs) was carried out in sulfuric acid solution using hydrogen peroxide as an oxidant at room temperature. The influence of system variables on copper recovery by leaching was investigated, such as sulfuric concentration, amount of hydrogen peroxide addition, waste PBCs particle size, presence of cupric ion, temperature and time. The results shown that the optimum addition amount was 100 mL 15 (wt%) sulfuric acid solution and 10 mL of 30% hydrogen peroxide for leaching 10 g waste PCBs powder with a solid/liquid ratio of 1/10 for 3 h at room temperature (∼23 °C). Moreover leaching temperature and initial copper ion concentration had insignificant effect on the leaching recovery of copper. The effect of different particle size of shredded waste PCBs on leaching of copper was investigated under the optimum leaching condition. The results revealed that shredding pieces of waste PCBs smaller than 1 mm was efficient and suitable for copper leaching. Then the leaching solution was concentrated to crystallize CuSO 4 ·5H 2 O, and crystal liquor was reused for the next cycles.

As part of contribution for developing a green recycling process of spent lead acid battery, a nanostructural lead oxide was prepared under the present investigation in low temperature calcination of lead citrate powder. The lead citrate, the precursor for preparation of this lead oxide, was synthesized through leaching of spent lead acid battery paste in citric acid solution. Both lead citrate and oxide products were characterized by means of thermogravimetric-differential thermal analysis (TG-DTA), X-ray diffraction (XRD), and scanning electron microscope (SEM). The results showed that the lead citrate was sheet-shape crystal of Pb(C6H6O7)·H2O. When the citrate was calcined in N2 gas, β-PbO in the orthorhombic phase was the main product containing small amount of Pb and C and it formed as spherical particles of 50–60 nm in diameter. On combusting the citrate in air at 370 °C (for 20 min), a mixture of orthorhombic β-PbO, tetragonal α-PbO and Pb with the particle size of 100–200 nm was obtained, with β-PbO as the major product. The property of the nanostructural lead oxide was investigated by electrochemical technique, such as cyclic voltammetry (CV). The CV measurements presented the electrochemical redox potentials, with reversibility and cycle stability over 15 cycles.

Red mud is a solid waste produced in the process of alumina extraction from bauxite. In this paper, recovery iron from Bayer red mud was studied with direct reduction roasting process followed by magnetic separation, and then building materials were prepared from alumosilicate residues. After analysis of chemical composition and crystalline phase, the effects of different parameters on recovery efficiency of iron were carried out. The optimum reaction parameters were proposed as the following: ratio of carbon powder: red mud at 18:100, ratio of additives: red mud at 6:100, roasting at 1300 degrees C for 110min. With these optimum parameters, total content of iron in concentrated materials was 88.77%, metallization ratio of 97.69% and recovery ratio of 81.40%. Then brick specimens were prepared with alumosilicate residues and hydrated lime. Mean compressive strength of specimens was 24.10MPa. It was indicated that main mineral phase transformed from nepheline (NaAlSiO4) in alumosilicate residues to gehlenite (Ca2Al2SiO7) in brick specimens through X-ray diffraction (XRD) technology. The feasibility of this transformation under the experimental conditions was proved by thermodynamics calculation analysis. Combined the recovery of iron with the reuse of alumosilicate residues, it can realize zero-discharge of red mud from Bayer process.