Wastewater Treatment Using Membrane Bioreactor Technologies: Removal of Phenolic Contaminants from Oil and Coal Refineries and Pharmaceutical Industries.

Huge amounts of noxious chemicals from coal and petrochemical refineries and pharmaceutical industries are released into water bodies. These chemicals are highly toxic and cause adverse effects on both aquatic and terrestrial life. The removal of hazardous contaminants from industrial effluents is expensive and environmentally driven. The majority of the technologies applied nowadays for the removal of phenols and other contaminants are based on physio-chemical processes such as solvent extraction, chemical precipitation, and adsorption. The removal efficiency of toxic chemicals, especially phenols, is low with these technologies when the concentrations are very low. Furthermore, the major drawbacks of these technologies are the high operation costs and inadequate selectivity. To overcome these limitations, researchers are applying biological and membrane technologies together, which are gaining more attention because of their ease of use, high selectivity, and effectiveness. In the present review, the microbial degradation of phenolics in combination with intensified membrane bioreactors (MBRs) has been discussed. Important factors, including the origin and mode of phenols' biodegradation as well as the characteristics of the membrane bioreactors for the optimal removal of phenolic contaminants from industrial effluents are considered. The modifications of MBRs for the removal of phenols from various wastewater sources have also been addressed in this review article. The economic analysis on the cost and benefits of MBR technology compared with conventional wastewater treatments is discussed extensively.

Fabrication and Characterization of Functional Biobased Membranes from Postconsumer Cotton Fabrics and Palm Waste for the Removal of Dyes.

Textile industries currently face vast challenges for the active removal of colored wastewater. Indeed, sustainable, recyclable, and green approaches are still lacking to achieve this aim. Thus, the present study explored the utilization of highly functional, green, recyclable, fully bio-based, and cost-effective composite membranes from post-consumer cotton fabrics and palm waste for wastewater treatment purposes. Highly functional cellulose nanofibers (CNF) were produced from waste cotton fabrics and filter paper using an acid hydrolysis technique. The yield of nanofibers extracted from waste cotton fabrics and filter paper was 76.74 and 54.50%, respectively. The physical, chemical, and structural properties of nanofibers were studied using various advanced analytical techniques. The properties of isolated nanofibers were almost similar and comparable to those of commercial nanofibers. The surface charge densities were -94.0, -80.7, and -90.6 mV for the nanofibers of palm waste, cotton fibers, and filter paper, respectively. After membrane fabrication using vacuum and hot-pressing techniques, the characteristics of the membrane were analyzed. The results showed that the average pore size of the palm-waste membrane was 1.185 nm, while it was 1.875 nm for membrane from waste cotton fibers and filter paper. Congo red and methylene blue dyes were used as model solutions to understand the behavior of available functional groups and the surface ζ-potential of the membrane frameworks' interaction. The membrane made from palm waste had the highest dye removal efficiency, and it was 23% for Congo red and 44% for methylene blue. This study provides insights into the challenges associated with the use of postconsumer textile and agricultural waste, which can be potentially used in high-performance liquid filtration devices for a more sustainable society.

Chemo-enzymatic functionalized sustainable cellulosic membranes: Impact of regional selectivity on ions capture and antifouling behavior.

Most of the polymeric membranes synthesized for decentralization of polluted water use fossil-based components. Thus, there is an urgent need to create robust and tunable nano/micro materials for confidently designing efficient and selective polymeric water filters with guaranteed sustainability. We have chosen a robust high-grade microfibrillated cellulose (MFC) as the functional material and selectively tuned it via enzymatic catalysis, which led to the attachment of phosphate group at the C6 position, followed by esterification (fatty acid attachment at C2 and C3 carbon), which led to the increase in its antifouling properties. We have demonstrated the robustness of the functionalization by measuring the separation of various metal ions, and the antifouling properties by adding foulants, such as Bovine Serum Albumin (BSA) and cancerous cells to the test solutions. These prototype affinity MFC membranes represent the most promising type of next-generation high-performance filtration devices for a more sustainable society.

Poly(lactic acid)/poly(butylene succinate) dual-layer membranes with cellulose nanowhisker for heavy metal ion separation.

In this study, poly(lactic acid) (PLA)/poly(butylene succinate) (PBS) dual-layer membranes filled with 0-3 wt% cellulose nanowhisker (CNWs) were fabricated with aim to remove metal ions from wastewater. An integrated method was employed in the membrane fabrication process by combining water vapor-induced and crystallization-induced phase inversions. The membrane thickness was measured in between 11 and 13 µm, which did not pose significant flux deviation during filtration process. The 3% CNW filled membrane showed prominent and well-laminated two layers structure. Meanwhile, the increase in CNWs from 0 to 3% loadings could improve the membrane porosity (43-74%) but reducing pore size (2.45-0.54 µm). The heat resistance of neat membrane enhanced by 1% CNW but decreased with loadings of 2-3% CNWs due to flaming behavior of sulphated nanocellulose. Membrane with 3% CNW displayed the tensile strength (23.5 MPa), elongation at break (7.1%), and Young's modulus (0.75 GPa) as compared to other samples. For wastewater filtration performance, the continuous operation test showed that 3% CNW filled membrane exhibited the highest removal efficiency for both cobalt and nickel metal ions reaching to 83% and 84%, respectively. We concluded that CNWs filled dual-layer membranes have potential for future development in the removal of heavy metal ions from wastewater streams.

CelluPhot: Hybrid Cellulose-Bismuth Oxybromide Membrane for Pollutant Removal.

The simultaneous removal of organic and inorganic pollutants from wastewater is a complex challenge and requires usually several sequential processes. Here, we demonstrate the fabrication of a hybrid material that can fulfill both tasks: (i) the adsorption of metal ions due to the negative surface charge, and (ii) photocatalytic decomposition of organic compounds. The bioinorganic hybrid membrane consists of cellulose fibers to ensure mechanical stability and of Bi4O5Br2/BiOBr nanosheets. The composite is synthesized at low temperature of 115 °C directly on the cellulose membrane (CM) in order to maintain the carboxylic and hydroxyl groups on the surface that are responsible for the adsorption of metal ions. The composite can adsorb both Co(II) and Ni(II) ions and the kinetic study confirmed a good agreement of experimental data with the pseudo-second-order equation kinetic model. CM/Bi4O5Br2/BiOBr showed higher affinity to Co(II) ions than to Ni(II) ions from diluted aqueous solutions. The bioinorganic composite demonstrates a synergistic effect in the photocatalytic degradation of rhodamine B (RhB) by exceeding the removal efficiency of single components. The fabrication of the biologic-inorganic interface was confirmed by various analytical techniques including scanning electron microscopy (SEM), scanning transmission electron microscopy with energy dispersive X-ray spectroscopy (STEM EDX) mapping, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The presented approach for controlled formation of the bioinorganic interface between natural material (cellulose) and nanoscopic inorganic materials of tailored morphology (Bi-O-Br system) enables the significant enhancement of materials functionality.

Morphological, Physiochemical and Thermal Properties of Microcrystalline Cellulose (MCC) Extracted from Bamboo Fiber.

Bamboo fibers are utilized for the production of various structures, building materials, etc. and is of great significance all over the world especially in southeast Asia. In this study, the extraction of microcrystalline cellulose (MCC) was performed using bamboo fibers through acid hydrolysis and subsequently different characterizations were carried out using various advanced techniques. Fourier transform infrared (FTIR) spectroscopy analysis has indicated the removal of lignin from MCC extracted from bamboo pulp. Scanning Electron Microscopy (SEM) revealed rough surface and minor agglomeration of the MCC. Pure MCC, albeit with small quantities of impurities and residues, was obtained, as revealed by Energy Dispersive X-ray (EDX) analysis. X-ray diffraction (XRD) indicates the increase in crystallinity from 62.5% to 82.6%. Furthermore, the isolated MCC has slightly higher crystallinity compared to commercial available MCC (74%). The results of thermal gravimetric analysis (TGA) demonstrate better thermal stability of isolated MCC compared to its starting material (Bamboo fibers). Thus, the isolated MCC might be used as a reinforcing element for the production of green composites and it can also be utilized as a starting material for the production of crystalline nanocellulose in future.

Role of functional groups in the production of self-assembled microfibrillated cellulose hybrid frameworks and influence on separation mechanisms of dye from aqueous medium.

In this article, the role of surface ζ-potential, surface charge density of functional groups and available surface functional groups (-OH and -COO-) of microfibrillated cellulose (MFC) was explored in the production of self-assembled dimensional frameworks. Furthermore, 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) oxidation of MFC and in situ TEMPO functionalization of produced frameworks were performed. The effect of increased charge density of carboxylic groups (-COO-) and decrease in surface ζ-potential on binding of titanium dioxide (TiO2) and horseradish peroxidase (HRP) was investigated further. High binding of TiO2 and HRP was reported due to high density of carboxylic group (-COO-) on produced functional frameworks. Thereafter, a model water of Irgalite Violet NZ dye was targeted to understand the behavior of available functional groups and introduced surface ζ-potential of frameworks towards adsorption of dye. Possible size-exclusion of dye aggregates was also explored using neat-MFC frameworks. Photo-oxidation (TiO2) and enzymatic catalysis (HRP) were studied further and highly effective system towards dye degradation was reported. Lastly, this study has shown a well deliberated quantitative understanding of functional groups/their density responsible for the production of frameworks and separation of dye.

Processing-Structure-Property Correlation Understanding of Microfibrillated Cellulose Based Dimensional Structures for Ferric Ions Removal.

In this research article, wood based microfibrillated cellulose (MFC) was studied to gain a better understanding of the process of dependent network formation. Networking potential and obtained properties of the produced dimensional structures could be controlled using opted processing routes. The fabricated dimensional structure, using freeze-drying (FD) is a highly open and porous network (98% porosity) compared to slightly tight, dense and less porous network produced after pressing at 200kN (96% porosity), followed by vacuum-filtered (VF) networks (33% porosity). The porosity (17%) was further decreased when the casting (CS) method was used, further producing a highly dense and compressed network. High water flux (180.8 ± 11 L/m2h) of pressed freeze-dried (PFD) followed by vacuum-filtered (VF) (11.4 ± 1.9 L/m2h) and casting CS (0.7 ± 0.01 L/m2h) were calculated using device. Furthermore, increased water flux (1.4 fold) of Experimental Paper Machine (XPM) based structures was reported in comparison with CS structures. Pore-sized distribution and surface area were measured using Hg porosimetry; they showed an average pore size of 16.5 µm for FD, followed by PFD (8.2 µm) structures. A 27-fold decrease in average pore-size was observed for CS structure in comparison with the FD structures. Highest tensile strength (87 ± 21 MPa) was recorded for CS structures, indicating a more highly compacted network formation compared to VF (82 ± 19 MPa) and PFD (1.6 ± 0.06 MPa). Furthermore, an attempt was made to upscale the VF structures using traditional paper making approach on XMP. Improved tensile strength (73 ± 11 MPa) in machine produced structures is due to alignment of fibers towards machine direction compared to cross directional (43 ± 9 MPa) fractured structures as shown in our Scanning Electron Microscopy (SEM) analysis. Surface functionalization of MFC using enzyme (hexokinase) was performed to increase the adsorption efficiency towards ferric ions removal. All fabricated structures were further evaluated for Fe(iii) removal and it was summarized that charge densities of functional groups, produced ζ-potential and networking potential were dominating influential factors for adsorption fluctuation of ferric ions.

Isolation and characterization of nanocrystalline cellulose from roselle-derived microcrystalline cellulose.

Roselle fiber is a renewable and sustainable agricultural waste enriched with cellulose polysaccharides. The isolation of Nanocrystalline cellulose (NCC) from roselle-derived microcrystalline cellulose (MCC) is an alternative approach to recover the agricultural roselle plant residue. In the present study, acid hydrolysis with different reaction time was carried out to degrade the roselle-derived MCC to form NCC. The characterizations of isolated NCC were conducted through Fourier Transform Infrared Ray (FTIR), Transmission Electron Microscopy (TEM), Field Emission Scanning Electron Microscopy (FESEM), Atomic Force Microscopy (AFM), Dynamic Light Scattering (DLS), Energy Dispersive Spectroscopy (EDS), X-ray Diffraction (XRD), Thermogravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC). As evaluated from the performed morphological investigations, the needle-like shape NCC nanostructures were observed under TEM and AFM microscopy studies, while irregular rod-like shape of NCC was observed under FESEM analysis. With 60min hydrolysis time, XRD analysis demonstrated the highest NCC crystallinity degree with 79.5%. In thermal analysis by TGA and DSC, the shorter hydrolysis time tended to produce NCC with higher thermal stability. Thus, the isolated NCC from roselle-derived MCC has high potential to be used in application of pharmaceutical and biomedical fields for nanocomposite fabrication.

Necessity of enzymatic hydrolysis for production and functionalization of nanocelluloses.

Nanocellulose (NC) from cellulosic biomass has recently gained attention owing to their biodegradable nature, low density, high mechanical properties, economic value and renewability. They still suffer, however, some drawbacks. The challenges are the exploration of raw materials, scaling, recovery of chemicals utilized for the production or functionalization and most important is toxic behavior that hinders them from implementing in medical/pharmaceutical field. This review emphasizes the structural behavior of cellulosic biomass and biological barriers for enzyme interactions, which are pertinent to understand the enzymatic hydrolysis of cellulose for the production of NCs. Additionally, the enzymatic catalysis for the modification of solid and NC is discussed. The utility of various classes of enzymes for introducing desired functional groups on the surface of NC has been further examined. Thereafter, a green mechanistic approach is applied for understanding at molecular level.

Immobilization of horseradish peroxidase on ß-cyclodextrin-capped silver nanoparticles: Its future aspects in biosensor application.

This study aimed to work out a simple and high-yield procedure for the immobilization of horseradish peroxidase on silver nanoparticle. Ultraviolet-visible (UV-vis) and Fourier-transform infrared spectroscopy and transmission electron microscopy were used to characterize silver nanoparticles. Horseradish peroxidase was immobilized on ß-cyclodextrin-capped silver nanoparticles via glutaraldehyde cross-linking. Single-cell gel electrophoresis (Comet assay) was also performed to confirm the genotoxicity of silver nanoparticles. To decrease toxicity, silver nanoparticles were capped with ß-cyclodextrin. A comparative stability study of soluble and immobilized enzyme preparations was investigated against pH, temperature, and chaotropic agent, urea. The results showed that the cross-linked peroxidase was significantly more stable as compared to the soluble counterpart. The immobilized enzyme exhibited stable enzyme activities after repeated uses.

Nanoporous membranes with cellulose nanocrystals as functional entity in chitosan: removal of dyes from water.

Fully biobased composite membranes for water purification were fabricated with cellulose nanocrystals (CNCs) as functional entities in chitosan matrix via freeze-drying process followed by compacting. The chitosan (10 wt%) bound the CNCs in a stable and nanoporous membrane structure with thickness of 250-270 µm, which was further stabilized by cross-linking with gluteraldehyde vapors. Scanning electron microscopy (SEM) studies revealed well-individualized CNCs embedded in a matrix of chitosan. Brunauer, Emmett and Teller (BET) measurements showed that the membranes were nanoporous with pores in the range of 13-10nm. In spite of the low water flux (64 Lm(-2) h(-1)), the membranes successfully removed 98%, 84% and 70% respectively of positively charged dyes like Victoria Blue 2B, Methyl Violet 2B and Rhodamine 6G, after a contact time of 24h. The removal of dyes was expected to be driven by the electrostatic attraction between negatively charged CNCs and the positively charged dyes.

Low concentration of silver nanoparticles not only enhances the activity of horseradish peroxidase but alter the structure also.

Chemical synthesis of Ag-NPs was carried out using reduction method. The reduction mechanistic approach of silver ions was found to be a basic clue for the formation of the Ag-NPs. The nanoparticles were characterized by UV-vis, FT-IR and TEM analysis. We had designed some experiments in support of our hypothesis, "low concentrations of novel nanoparticles (silver and gold) increases the activity of plant peroxidases and alter their structure also", we had used Ag-NPs and HRP as models. The immobilization/interaction experiment had demonstrated the specific concentration range of the Ag-NPs and within this range, an increase in HRP activity was reported. At 0.08 mM concentration of Ag-NPs, 50% increase in the activity yield was found. The U.V-vis spectra had demonstrated the increase in the absorbance of HRP within the reported concentration range (0.06-0.12 mM). Above and below this concentration range there was a decrease in the activity of HRP. The results that we had found from the fluorescence spectra were also in favor of our hypothesis. There was a maximum increase in ellipticity and α-helix contents in the presence of 0.08 mM concentration of Ag-NPs, demonstrated by circular dichroism (CD) spectra. Finally, incubation of a plant peroxidase, HRP with Ag-NPs, within the reported concentration range not only enhances the activity but also alter the structure.

Removal of benzidine from polluted water by soluble and immobilized peroxidase in batch processes and continuous horizontal bed reactor.

Bitter gourd peroxidase entrapped on calcium-alginate-starch beads was employed for the treatment of water, polluted with benzidine, in a batch process as well as in a continuous reactor. The immobilized enzyme had the same pH and temperature optima as the soluble enzyme. The immobilized enzyme could effectively remove more than 70% of benzidine in a stirred batch process after three hours. After its sixth repeated use, the immobilized enzyme was able to oxidatively degrade and polymerize 58% of benzidine. The horizontal bed reactor, containing the peroxidase entrapped on calcium-alginate-starch beads, retained more than 40% benzidine removal efficiency after one month of its continuous operation. The absorption spectra of the treated benzidine exhibited a marked difference in the absorption at various wavelengths, compared with untreated compound. The horizontal bed reactor containing immobilized peroxidase would be significantly successful for the large-scale treatment of water polluted with aromatic compounds.

Application of fly ash adsorbed peroxidase for the removal of bisphenol A in batch process and continuous reactor: assessment of genotoxicity of its product.

In the present study peroxidase has been immobilized simply by adsorption on fly ash. On fly ash adsorbed nearly 1113 U of peroxidase activity per g. Comparative degradation of endocrine disrupter, bisphenol A has been performed by soluble and immobilized enzyme. Soluble and immobilized enzyme removed maximum bisphenol A in the presence of 0.3mM guaiacol, a redox mediator, 0.75 mM H(2)O(2) in sodium phosphate buffer, pH 7.0 at 40 °C. Degradation of bisphenol A in batch process was 61%, 100% and 100% at 20, 40 and 60 °C, respectively. Fly ash adsorbed peroxidase was more effective in the degradation of bisphenol A as compared to its free form. Immobilized enzyme catalyzed complete degradation of bisphenol A at 40 °C within 3.5h. The oxidative degradation and polymerization of bisphenol A was also evaluated in the continuous bed-reactors at different flow rates. The removal of this compound was maximum at a flow rate of 20 mL h(-1). HPLC analysis showed two clear peaks, one related to bisphenol A and other related to its degradation product, 4-isopropenylphenol. Plasmid nicking and comet assays demonstrated that the product, 4-isopropenylphenol was significantly nontoxic.