Novel combination of bioleaching and persulfate for the removal of heavy metals from metallurgical industry sludge.

The objective of this study was to remove heavy metals from metallurgical industry sludge by bioleaching alone and bioleaching combined with persulfate (PDS). The results showed that the removal of Cu, Zn, Pb, and Mn reached 70%, 83.8%, 25.2%, and 76.9% by bioleaching alone after 18 days, respectively. The experiment of bioleaching combined with PDS was carried out in which the optimal additive dosage of K2S2O8, 8 g/L, was added to bioleaching after 6 d. After 1 h, the removal of four heavy metals reached 75.1, 84.3, 36.7, and 81.6%, respectively. Compared with bioleaching alone, although the increase in removal efficiency was only slightly increased, the treatment cycle was distinctly shortened from 18 to 6 days + 1 h. The scanning electron microscopy (SEM) results showed that the surface morphology of the sludge was changed significantly by the combined treatment. The content of heavy metals was significantly reduced after bioleaching combined with PDS by energy dispersive X-ray spectroscopy (EDX). Through electron paramagnetic resonance (EPR) and free radical quenching experiments, it was indicated that sulfate radicals [Formula: see text] plays a leading role in the combined treatment. The treated sludge mainly existed in a stable form, and the bioavailability was reduced with European Community Bureau of Reference (BCR) morphology analysis. This study proved that the combination of bioleaching and PDS could not only shorten the treatment cycle but also further improve the efficiency of heavy metal leaching. It provides a novel treatment method for the removal of heavy metals from metallurgical industry sludge.

Cattail fibers as source of cellulose to prepare a novel type of composite aerogel adsorbent for the removal of enrofloxacin in wastewater.

In this study, cattail was researched as a natural cellulose source to extract cellulose. Dewaxing, alkali and bleaching treatments were carried out for the cattail fibers (CFs). The FTIR, SEM and XRD results indicated that hemicellulose and lignin were successfully removed from the CFs, and the content of cattail cellulose increased from 41.66 ± 1.11% to 89.72 ± 1.07%. Subsequently, cellulose aerogel was prepared by the extracted cattail cellulose. The Zeolitic imidazolate framework-8 (ZIF-8) was uniformly loaded onto the surface of cellulose aerogel by the in situ growth, and ZIF-8 Cattail Cellulose Aerogel (ZCCA) was finally prepared. The SEM, FTIR, XRD and TGA results further confirmed the successful preparation of ZCCA. Additionally, the results of the adsorption experiment showed that ZCCA had excellent adsorption performance for enrofloxacin, and the maximum adsorption capacity of enrofloxacin reached 172.09 mg·g-1 while showing good reusability. The adsorption process followed the pseudo-second-order kinetic model and the Langmuir isotherm model. Thermodynamic studies showed that the adsorption of enrofloxacin was a spontaneous endothermic reaction and that the adsorption mechanism involves the interaction of hydrogen bonds, electrostatic and π-π stacking.

[One-step Preparation of Lanthanum-Magnesium Ferrite and Its Phosphate Adsorption Capacity in Aqueous Solutions].

Due to the shortage of phosphate and the eutrophication caused by phosphorus pollution, it is urgent to recover phosphate from wastewater. Given their high adsorption capacity and convenient separation from water to which a magnetic field is applied, ferrite composites have received increasing attention for phosphate recovery. In this study, Spinel La@MgFe2O4 was prepared using a one-step co-precipitation method. La3+ loading on grain boundary defects of MgFe2O4, and phosphorus absorption capacity were examined using X-ray diffraction (XRD), Fourier-transform infrared spectrometry (FTIR), X-ray photoelectron spectroscopy (XPS), and vibrating sample magnetometry (VSM). The structure of La@MgFe2O4 involved La3+ loading on grain boundary defects of MgFe2O4 in the form of La(OH)3. The addition of La changed the crystallinity and morphology of MgFe2O4, which greatly improved the capacity of MgFe2O4 for phosphorus adsorption. Saturation magnetization remained at 14 emu·g-1, which was easily separated from water using an external magnetic field. The maximum adsorption capacity was 143.156 mg·g-1 at pH 6 and 10℃, which was comparable to that achieved at 25℃. Kinetic observations showed that a low phosphorus concentration (10 mg·L-1) could result in extremely low phosphorus adsorption by La@MgFe2O4 after 30 min. The adsorption mechanism shows that phosphorus is removed through ligand exchange and the formation of inner spherical complexes. La@MgFe2O4 has highly selective adsorption with respect to phosphate, and the adsorbent can be reused many times after desorption. Based on addition of 1 g·L-1 of La@MgFe2O4 in the treatment of low temperature municipal wastewater in Northern China, phosphate concentrations could be reduced to less than 0.5 mg·L-1 an hour, offering a promising means of phosphate adsorption even in cold regions.

[Experiment on Recovery of Phosphorus from Aqueous Solution by Calcium Doped Fe3O4].

Adsorption is an economical and effective method for recovering phosphate from wastewater. In order to improve the adsorption capacity of Fe3O4 for phosphate and for easy separation from water under the action of an external magnetic field, CaO2 was used in this study as an oxidant to partially oxidize Fe2+. A phosphorus recovery adsorbent, Ca doped Fe3O4 (CMIO), was prepared and was characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF) and vibrating sample magnetometer (VSM) techniques. The results showed that CMIO had a Ca2+ doped Fe3O4 crystal structure with a saturation magnetization of 38.82 emu·g-1, which was easily separated from water by using an external magnetic field. The phosphorus adsorption capacity of the CMIO decreased with an increase of pH value. When pH=2 and T=25℃, the maximum adsorption capacity was 24.10 mg·g-1, which is almost five times the adsorption capacity of pure Fe3O4. The phosphorus adsorption of CMIO was in accord with the Langmuir isotherm adsorption model, and the adsorption process followed the pseudo-second order kinetic model. The complexation of phosphate occurred on the inner surface of the CMIO to form a ≡Fe-Ca-P ternary complex, which can adsorb phosphorus. Compared with other anions in the aqueous solution, CMIO had good adsorption selectivity to PO43-, and the adsorbed PO43- could be desorbed by NaOH solution.The quality loss of the CMIO was less than 4% once, and multiple recycling was possible.

Recovery of phosphate from aqueous solution by magnetically recycled modified polishing powder composites.

This study investigated a magnetically recycled modified polishing powder (CMIO@PP) as an adsorbent of phosphate; the CMIO@PP was synthesized by combining the modified La/Ce-containing waste polishing powder with CaO2-modified Fe3O4 (CMIO). Results indicate that the CMIO@PP nanocomposite presents a crystal structure comprising La (OH)3, Ce (OH)3, and Fe3O4, and that CMIO is uniformly dispersed in the modified polishing powder. The CMIO@PP (1:3) is a suitable choice considering its magnetism and adsorption capacity. The magnetic adsorbent exhibits a high adsorption capacity of 53.72 mg/g, a short equilibrium time of 60 min, and superior selectivity for phosphate. Moreover, the adsorbent strongly depends on the pH during the adsorption process and maintains a large adsorption capacity when the pH level is between 2 and 6. The adsorption of phosphate by the CMIO@PP (1:3) accords with the Langmuir isotherm model, and the adsorption process follows the pseudo-second order model. Meanwhile, adsorption-desorption experiments show that the adsorbent could be recycled a few times and that a high removal efficiency of phosphate from civil wastewater was achieved. Finally, mechanisms show that the adsorption of phosphate by the CMIO@PP (1:3) is mainly caused by electrostatic attraction and ligand exchange.

Highly efficient enhancement of municipal sludge dewaterability using persulfate activation with nZVI/HA.

This study presents a sulfate radical-based oxidation method for improving municipal sludge dewaterability by combining persulfate and nanoscale zero-valent iron supported on humic acid (nZVI/HA-PS). Sludge dewaterability using persulfate activation with nZVI/HA was assessed for specific resistance to filterability (SRF), time to filter (TTF), settling volume percentage (SV30) and water content (Wc). The influencing factors, such as mass ratios of nZVI to HA, initial pH, PS dosage and nZVI/HA nanocomposite dosage, were investigated. Experimental results indicated that the SRF reduction efficiency of the sludge reached 86.47% using initial concentrations of 1.2 mmol/gVSS PS and 300 mg/L nZVI/HA. The soluble chemical oxygen demand (SCOD) of sludge supernatants increased from 79 mg/L to 710 mg/L under optimum conditioning, indicating that sludge flocs were effectively decomposed. Economic analysis demonstrated that the nZVI/HA-PS conditioning process is a potential method for improving sludge dewaterability.

[Influencing Mechanism of Calcium Peroxide Pre-treatment on Dewatering Performance of Waste Activated Sludge].

The evolution of sludge filteration dewaterability, floc structure and hydrolytic kinetics with calcium peroxide oxidation pre-treatment was investigated in this study. The effect of sludge characteristics with combined process of ferrous ion and calcium peroxide was deeply analyzed and the result suggested that the sludge dewatering performance was improved first and then worsened after CaO2 addition. When the dosage was 20 mg·g-1, sludge reached its optimal dewaterability. At the same time, sludge was effectively dissolved and the floc structure became loose and broken with the increase of organic matters in the supernatant. Moreover, sludge solubilization process followed the pseudo-zero-order kinetic equation well and the reaction rate of sludge with CaO2 treatment was 15.2 mg·L-1·h-1. In addition, sludge floc lysis was enhanced by the treatment of ferrous ion and calcium peroxide oxidation, whilst sludge dewaterability was improved due to the reconstruction of sludge floc structure by the iron ions produced. This study provided theoretical basis for application of calcium peroxide pre-treatment and its combining technique in sludge treatment.

Enhancement of waste activated sludge dewaterability using calcium peroxide pre-oxidation and chemical re-flocculation.

The effects of combined calcium peroxide (CaO2) oxidation with chemical re-flocculation on dewatering performance and physicochemical properties of waste activated sludge was investigated in this study. The evolutions of extracellular polymeric substances (EPS) distribution, composition and morphological properties were analyzed to unravel the sludge conditioning mechanism. It was found that sludge filtration performance was enhanced by calcium peroxide oxidation with the optimal dosage of 20 mg/gTSS. However, this enhancement was not observed at lower dosages due to the absence of oxidation and the performance deteriorated at higher dosages because of the release of excess EPS, mainly as protein-like substances. The variation in soluble EPS (SEPS) component can be fitted well with pseudo-zero-order kinetic model under CaO2 treatment. At the same time, extractable EPS content (SEPS and loosely bound EPS (LB-EPS)) were dramatically increased, indicating sludge flocs were effectively broken and their structure became looser after CaO2 addition. The sludge floc structure was reconstructed and sludge dewaterability was significantly enhanced using chemical re-flocculation (polyaluminium chloride (PACl), ferric iron (FeCl3) and polyacrylamide (PAM)). The inorganic coagulants performed better in improving sludge filtration dewatering performance and reducing cake moisture content than organic polymer, since they could act as skeleton builders and decrease the sludge compressibility.

Enhancement of activated sludge dewatering performance by combined composite enzymatic lysis and chemical re-flocculation with inorganic coagulants: Kinetics of enzymatic reaction and re-flocculation morphology.

The feasibility of combined process of composite enzymatic treatment and chemical flocculation with inorganic salt coagulants was investigated in this study. The evolution of extracellular polymeric substances (EPS) distribution, composition and morphological properties were analyzed to unravel the sludge conditioning mechanism. It was found that sludge filtration performance was deteriorated due to release of a large amount of biopolymers after enzymatic treatment. The change in EPS followed the pseudo-first-order kinetic equation well under enzymatic treatment. The feeding modes of enzymes had a significant influence on sludge lysis efficiency under compound enzymes treatment. Alpha amylase + protease was more effective in solubilization than other two addition modes (protease + α-amylase or simultaneous addition). The sludge floc re-formed and macromolecule biopolymers were effectively removed through coagulation process. At the same time, both of filtration rate and cake solid content of sludge treated with enzymes were improved with increasing dosage of coagulants, and ferric iron (FeCl3) had better performance in sludge dewaterability enhancement than polyaluminium chloride (PACl). In addition, sludge filtration property was slightly deteriorated, while the cake moisture reduction was favored at the optimal dosage of inorganic coagulants.