Degradation of benzoic acid in an advanced oxidation process: The effects of reducing agents.

Fenton reaction is widely used for hazardous pollutant degradation. Reducing agents (RAs) have been proven to be efficient in promoting the generation of HO• in Fenton reaction by accelerating the redox cycle of Fe3+/Fe2+. However, the roles of different RAs in Fenton reaction remain unrevealed. In this work, the catalytic activity of three RAs, i.e., hydroxylamine (NH2OH), ascorbic acid (AA) and cysteine (Cys), on the degradation of benzoic acid (BA) and the hydroxyl radical formation in the Fenton-RAs system were investigated. Results show the catalytic performance of RAs in BA degradation by Fenton reaction followed an order of NH2OH > AA > Cys. Compared with the conventional Fenton system, the effective pH range in the Fenton-NH2OH system extended from 3.0 to 5.0, while the optimal pH in the Fenton-AA and Fenton-Cys systems ranged from 3.0 to 4.0. The Fenton-AA system exhibited a two-stage reaction toward BA degradation, which was different from the Fenton-NH2OH and Fenton-Cys systems. Furthermore, the dosing manner of AA was found to be a key factor governing its role in the Fenton-AA system. This observation suggests the different mechanisms behind the enhancement of the three RAs in Fenton system. Different from NH2OH and Cys, AA would inhibit the generation of HO•, especially at the fast stage of degradation process, where Fe3+ has not accumulated yet. In addition, the economic analysis using the electrical energy per order indicates Fenton-NH2OH system was economically feasible with the lowest energy input, compared to Fenton-AA and Fenton-Cys systems. These results are useful to better understand the roles of RAs in Fenton system, and also provide guidance about the selection and dosing manner of suitable RAs in the advanced oxidation processes.

Optimizing sludge dewatering with a combined conditioner of Fenton's reagent and cationic surfactant.

Enhancing sludge dewatering is of importance in reducing environmental burden and disposal costs. In this work, a cationic surfactant, cetyl trimethyl ammonium bromide (CTAB), was combined with Fenton's reagent for sludge dewatering. Results show that the Fenton-CTAB conditioning significantly promotes the sludge dewatering. Using combined techniques of response surface methodology and uniform design, dosages of Fe2+, H2O2, and CTAB for water content response were optimized to be 89, 276, and 233 mg/g dry solids (DS), respectively. The water content of sludge decreased from 79.0% to 66.8% under the optimal conditions. Compared with cationic polyacrylamide, the Fenton-CTAB system exhibited superior sludge dewatering performance. To gain insights into the mechanisms involved in sludge dewatering, the effects of Fenton-CTAB conditioning on the composition of extracellular polymeric substances (EPS) and the morphology of the sludge flocs were investigated. The decomposition of EPS into some dissolved organics and the release of proteins in tightly bound EPS facilitated the conversion of bound water to free water and further reduced the water content of sludge cake. After conditioning, morphology of sludge showed aggregation. Overall, the enhanced sludge dewatering by Fenton-CTAB treatment provides an efficient way for management of sewage sludge.

Changing profiles of bound water content and distribution in the activated sludge treatment by NaCl addition and pH modification.

Currently the dewatering of activated sludge from wastewater treatment plants is a problem not well solved. Extracellular polymeric substances (EPS), including loosely bound EPS (LB-EPS) and tightly bound EPS (TB-EPS), are highly hydrated biopolymers and play important roles in sludge dewatering. In the present work, two types of treatments, i.e., salt addition and pH modification, were proposed to evaluate the effects of bound water content and its distribution on the dewatering performance of activated sludge. Results show that the bound water content in activated sludge was deeply related to the floc structures and EPS compositions. Both salt addition and acid treatment altered the flocculated matrix and increased the contents of LB-EPS, resulting in the release of trapped water and reduction in sludge volume. In addition, the chemical treatments also affected the distribution of bound water. The internal water content increased upon the dose of NaCl, leading to a decreased water content trapped in EPS. Hence, salt addition caused a slower filtration rate, but did not effectively decrease the total water content, although the EPS were decomposed. Under acidic conditions, cell lysis helped to release the intracellular water and further enhance the sludge dewatering performance. In contrast, conditioning with low-dosage alkali increased the bound water content and deteriorated the sludge dewaterability. Therefore, an in-depth investigation into the mechanisms is useful to optimize the activated sludge dewatering process.

Enhanced dewatering of excess activated sludge through decomposing its extracellular polymeric substances by a Fe@Fe2O3-based composite conditioner.

Efficient sludge dewatering methods are highly desired by municipal wastewater treatment plants. In this study, Fe@Fe2O3 nanomaterial, combined with polydiallyldimethylammonium chloride (PDMDAAC) and H2SO4, was used for sludge dewatering. This composite conditioner exhibited an excellent dewatering capability. By using uniform design, the optimized dosages of Fe@Fe2O3, H2SO4 and PDMDAAC were determined to be 40, 136 and 4.8mg/gDS (dry solids), respectively. The moisture content of sludge cake decreased from 78.1% to 64.8%, and the capillary suction time from 56 to 21s. The sludge extracellular polymeric substances (EPS) were decomposed, resulting in greater conversion of the bound water into free water and the release of free water. The electron spin resonance results show that the molecular oxygen activation process induced by Fe@Fe2O3 produced hydroxyl radicals, which were mainly responsible for the EPS decomposition. In this way, an efficient composite conditioner for enhancing sludge dewatering was developed.

Probing the roles of Ca(2+) and Mg(2+) in humic acids-induced ultrafiltration membrane fouling using an integrated approach.

Membrane fouling induced by natural organic matter (NOM) negatively affects the performance of ultrafiltration (UF) technology in producing drinking water. Divalent cation is found to be an important factor that affects the NOM-induced membrane fouling process. In this work, attenuated total reflection-Fourier transformation infrared spectroscopy (ATR-FTIR) coupled with quartz crystal microbalance (QCM), assisted by isothermal titration calorimetry (ITC), is used to explore the contribution of Mg(2+) and Ca(2+), the two abundant divalent cations in natural water, to the UF membrane fouling caused by humic acid (HA) at a molecular level. The results show that Ca(2+) exhibited superior performance in accelerating fouling compared to Mg(2+). The hydrophobic polyethersulfone (PES) membrane exhibited greater complexation with HA in the presence of Mg(2+) and Ca(2+), compared to the hydrophilic cellulose membrane, as evidenced by the more intense polysaccharide C-O, aromatic C=C and carboxylic C=O bands in the FTIR spectra. The QCM and ITC measurements provide quantitative evidence to support that Ca(2+) was more effective than Mg(2+) in binding with HA and accumulating foulants on the membrane surfaces. The higher charge neutralization capacity and more favorable binding ability of Ca(2+) were found to be responsible for its greater contribution to the NOM-induced membrane fouling than Mg(2+). This work offers a new insight into the mechanism of cation-mediated NOM-induced membrane fouling process, and demonstrates that such an integrated ATR-FTIR/QCM/ITC approach could be a useful tool to explore other complicated interaction processes in natural and engineered environments.

Copper release from copper nanoparticles in the presence of natural organic matter.

Copper nanoparticles (CuNPs) are widely used and inevitably released into aqueous environments, causing ecological and health risks. Ubiquitous natural organic matter (NOM) might affect the copper release behaviors from CuNPs and their toxicity. This work aims to elucidate how NOM affects copper release from CuNPs, with a focus on the impacts of NOM properties and the NOM-CuNPs interaction mechanism. The copper release kinetics and different copper fractions induced by representative NOMs were characterized. The presence of NOM led to a more dispersive state of CuNPs clusters. Copper release mainly resulted from complexation reactions between CuNPs and functional groups of NOM. Humic substances were more effective in releasing copper than sodium alginate and bovine serum albumin, due to a higher amount of functional groups and lower molecular weight, which facilitated the contact and complexion reactions. Chlorination treatment of NOM significantly decelerated copper release due to the destruction of functional groups and less attachment of NOM. However, the copper releasing ability of humic acid was not substantially affected by Ca²âº-induced coagulation. This study provides better understanding about the persistence and transformation of CuNPs in aquatic environments.