Spinel ferrite nanoparticles as potential materials in chlorophenol removal from wastewater.

Persistent organic pollutants (POPs) including chlorophenols (CPs) are increasing in water effluents, creating serious problems for both aquatic and terrestrial lives. Several research attempts have considered the removal of CPs by functionalised nanomaterials as adsorbents and catalysts. Besides the unique crystal structure, spinel ferrite nanomaterials (SFNs) own interesting optical and magnetic properties that give them the potential to be utilised in the removal of different types of CPs. In this review, we highlighted the recent research work that focused on the application of SFNs in the removal of different CP substances based on the number of chlorine atom attached to the phenolic compound. We have also discussed the structure and properties of SFN along with their numerous characterisation tools. We demonstrated the importance of identifying the structure, surface area, porosity, optical properties, etc. in the efficiency of the SFN during the CP removal process. The reviewed research efforts applied photocatalysis, wet peroxide oxidation (WPO), persulfate activated oxidation and adsorption. The studies presented different paths of enhancing the SFN ability to remove the CPs including doping (ion substitution), oxide composite structure and polymer composite structure. Experimental parameters such as temperature, dosage of CPs and SFN structure have shown to have a major effect in the CP removal efficiency. More attention is needed to investigate the different properties of SFN that can be tailored through different techniques and expected to have major role in the removal mechanism of CPs.

Exploring the Limitations of Osmotically Assisted Reverse Osmosis: Membrane Fouling and the Limiting Flux.

Osmotically assisted reverse osmosis (OARO) has shown great potential for low-cost and energy-efficient brine management. However, its performance can be significantly limited by membrane fouling. Here, we performed for the first time a comprehensive study on OARO membrane fouling, explored the associated fouling mechanisms, and evaluated fouling reversibility via simple physical cleaning strategies. First, internal membrane fouling at the draw (permeate) side was shown to be insignificant. Flux behavior in short-term operation was correlated to both the evolution of fouling and the change of internal concentration polarization. In long-term operation, membrane fouling constrained the OARO water flux to a singular, common upper limit, in terms of limiting flux, which was demonstrated to be independent of operating pressures and membrane properties. Generally, once the limiting flux was exceeded, the OARO process performance could not be improved by higher-pressure operation or by utilizing more permeable and selective membranes. Instead, different cyclic cleaning strategies were shown to be more promising alternatives for improving performance. While both surface flushing and osmotic backwashing (OB) were found to be highly effective when using pure water, a full flux recovery could not be achieved when a nonpure solution was used during OB due to severe internal clogging during OB. All in all, the presented findings provided significant implications for OARO operation and fouling control.

Thermally induced oxygen related defects in eco-friendly ZnFe2O4 nanoparticles for enhanced wastewater treatment efficiencies.

Herein, a simple but highly effective strategy of thermal annealing to modulate oxygen vacancies related defects in ZnFe2O4 (ZFO) nanoparticles for obtaining enhanced wastewater treatment efficiencies is reported. The as-prepared nanoparticles were thermally annealed at three different temperatures (500 °C, 600 °C and 700 °C) and their phase purity was confirmed by X-ray diffraction (XRD). All samples were found to exhibit pure phases of ZFO with different crystallite sizes ranging from 10 nm to 25 nm. The transmission electron microscope (TEM) images showed well dispersed nanoparticles and a strong correlation of grain size growth with annealing temperature was established. The optical absorption and emission characteristics were estimated through UV-visible and Photoluminescence (PL) spectroscopy. Raman spectroscopy and X-ray Photoelectron Spectroscopy (XPS) confirmed the variation of oxygen vacancies in the synthesized samples' lattice. The photocatalytic activities of all samples were investigated and the highest efficiencies were recorded for the ZFO samples annealed at 500 °C. Under high salinity condition, the organic dye degradation efficiency of the same sample remained the highest among all. The excellent dye degradation abilities in ZFO samples can be attributed to the abundance of oxygen vacancies in the crystal lattice that slow down the recombination rate during the photocatalysis process. Moreover, cytotoxicity tests revealed that all prepared ZFO samples showed insignificant cell structure effects on Picochlorum sp microalgae, as verified by Fourier-transform infrared (FTIR) spectroscopy. On the other hand, no significant changes were detected on the viable cell concentration and Chlorophyll a content. This work presents a systematic way to finely tune the crystal sizes and to modulate oxygen related defects in ZFO through a highly effective annealing approach to signify their potential in industrial wastewater and seawater treatment processes.

Evaluation of concentration technologies in the design of biorefineries for the recovery of resources from vinasse.

This article reports a study of five designs of vinasse biorefineries that incorporate anaerobic bioreactors followed by a concentration technology such as evaporation, reverse osmosis, or forward osmosis. Different techniques of draw solution regeneration - evaporation, reverse osmosis, and membrane distillation - were also analyzed. Exergy analysis, a method that evaluates the resource conversion efficiency of systems, was used to compare the alternatives. The results indicated that among the alternatives analyzed, the combination of anaerobic digestion and reverse osmosis presented the highest exergy efficiency (62%). However, evaporators were the most feasible in terms of costs. Both alternatives are interesting and the final choice depends on the technology available and local economy. In any case, the treatment of 491.76 m3/h of vinasse (exergy rate of 60513.8 kW) to recover 70% of water could reduce external water requirement by 66% and generate 28% additional electricity for the sugarcane plant. In this case, the water recovery could represent an economy of 8,490,435.76 USD/year for the Brazilian alcohol industry.

Insight into the effect of organic and inorganic draw solutes on the flux stability and sludge characteristics in the osmotic membrane bioreactor.

In this study, chloride based (CaCl2 and MgCl2) and acetate based (NaOAc and MgOAc) salts in comparison with NaCl were investigated as draw solutions (DS) to evaluate their viability in the osmotic membrane bioreactor (OMBR). Membrane distillation was coupled with an OMBR setup to develop a hybrid OMBR-MD system, for the production of clean water and DS recovery. Results demonstrate that organic DS were able to mitigate the salinity buildup in the bioreactor as compared to inorganic salts. Prolonged filtration runs were observed with MgCl2 and MgOAc in contrast with other draw solutes at the same molar concentration. Significant membrane fouling was observed with NaOAc while rapid flux decline due to increased salinity build-up was witnessed with NaCl and CaCl2. Improved characteristics of mixed liquor in terms of sludge filterability, particle size, and biomass growth along with the degradation of soluble microbial products (SMP) were found with organic DS.

Removal of methylene blue by adsorption on aluminosilicate waste: equilibrium, kinetic and thermodynamic parameters.

An aluminosilicate waste (AW) was investigated as adsorbent for methylene blue (MB) dye. AW was characterized by petrography, X-ray diffractometry, X-ray fluorescence, scanning electron microscopy, thermogravimetry and zeta potential measurements. It was found that AW contains kaolinite, and other minor components such as quartz, muscovite, smectite, siderite, pyrite and organic compounds. The chemical composition of AW is mainly SiO2 (49%) and Al2O3 (23%) and it has negative superficial charge above pH 1.73. Adsorption of MB dye was studied in a batch system under different conditions of initial dye concentration, contact time and temperature. The isothermal data from batch experiments were fitted to Langmuir and Freundlich equations, with a better fit shown by the Langmuir isotherm equation. Also, pseudo-first-order, pseudo-second-order and intraparticle diffusion models were considered to evaluate the rate parameters. The experimental data fitted the pseudo-first-order kinetic model best. Thermodynamic parameters were calculated, showing the adsorption to be an endothermic yet spontaneous process, with the activation energy of +37.8 kJ mol-1. The results indicate that AW adsorbs MB efficiently, and can be employed as a low-cost alternative in wastewater treatment for the removal of cationic dyes.

High strength domestic wastewater treatment with submerged forward osmosis membrane bioreactor.

Forward osmosis membranes are less prone to fouling with high rejection of salts, and the osmotic membrane bioreactor (OMBR) can be considered as an innovative membrane technology for wastewater treatment. In this study, a submerged OMBR having a cellulose triacetate membrane, with the active layer facing the feed solution configuration, was operated at different organic loading rates (OLRs), i.e., 0.4, 1.2 and 2.0 kg-COD/(m(3)·d) with chemical oxygen demand (COD) concentrations of 200 mg/L, 600 mg/L and 1,000 mg/L, respectively, to evaluate the performance on varying wastewater strengths. High organic content with sufficient amount of nutrients enhanced the biomass growth. High OLR caused more extrapolymeric substances production and less dewaterability. However, no significant differences in fouling trends and flux rates were observed among different OLR operational conditions.

Membrane fouling and performance evaluation of conventional membrane bioreactor (MBR), moving biofilm MBR and oxic/anoxic MBR.

In this study, three laboratory scale submerged membrane bioreactors (MBRs) comprising a conventional MBR (C-MBR), moving bed MBR (MB-MBR) and anoxic-oxic MBR (A/O-MBR) were continuously operated with synthesized domestic wastewater (chemical oxygen demand, COD = 500 mg/L) for 150 days under similar operational and environmental conditions. Kaldnes(®) plastic media with 20% dry volume was used as a biofilm carrier in the MB-MBR and A/O-MBR. The treatment performance and fouling propensity of the MBRs were evaluated. The effect of cake layer formation in all three MBRs was almost the same. However, pore blocking caused a major difference in the resultant water flux. The A/O-MBR showed the highest total nitrogen and phosphorus (PO4-P) removal efficiencies of 83.2 and 69.7%, respectively. Due to the high removal of nitrogen, fewer protein contents were found in the soluble and bound extracellular polymeric substances (EPS) of the A/O-MBR. Fouling trends of the MBRs showed 12, 14 and 20 days filtration cycles for C-MBR, MB-MBR and A/O-MBR, respectively. A 25% reduction of the soluble EPS and a 37% reduction of the bound EPS concentrations in A/O-MBR compared with C-MBR was a major contributing factor for fouling retardation and the enhanced filtration capacity of the A/O-MBR.

Effect of chemical composition on the flocculation dynamics of latex-based synthetic activated sludge.

This study investigates the effect of calcium, alginate, fibrous cellulose, and pH on the flocculation dynamics and final properties of synthetic activated sludges. A laboratory-scale batch reactor, fed with standard synthetic sludges was used. The effects of varying calcium concentration (5-25 mM), alginate concentration (25-125 mg/L), fibrous cellulose concentration (0.2-0.8 g/L) and pH (3-9) on the sludge characteristics were studied by varying one parameter whilst keeping the others constant. The results from experiments indicated that the calcium, alginate, fibrous cellulose, and pH had the critical effect on the aggregation rate, flocs size, and made the improvement of the final properties of sludge. Dynamic measurements have established the optimum conditions for floc formation and can accurately reflect the state of formation of the synthetic activated sludge flocs. These correlate well with measurements of settleability and turbidity of the synthetic activated sludge. The results of this study support the bonding theory and indicate that formation of cations-polymer complexes and polymer gelation are important means of flocculation. The development of synthetic activated sludges is suggested also to be a possible surrogate for studying the final properties of activated sludge.