Experimental and modeling of tetracycline degradation in water in a flow-through enzymatic monolithic reactor.

In this work, the laccase from Trametes versicolor was immobilized in highly porous silica monoliths (0.6-cm diameter, 0.5-cm length). These monoliths feature a unique homogeneous network of interconnected macropores (20 µm) with mesopores (20 nm) in the skeleton and a high specific surface area (330 m2/g). The enzymatic monoliths were applied to degrade tetracycline (TC) in model aqueous solutions (20 ppm). For this purpose, a tubular flow-through reactor (FTR) configuration with recycling was built. The TC degradation was improved with oxygen saturation, presence of degradation products, and recirculation rate. The TC depletion reaches 50% in the FTR and 90% in a stirred tank reactor (CSTR) using crushed monoliths. These results indicate the importance of maintaining a high co-substrate concentration near active sites. A model coupling mass transfers with a Michaelis-Menten kinetics was applied to simulate the TC degradation in real wastewaters at actual TC concentration (2.8 10-4 ppm). Simulation results show that industrial scale FTR reactor should be suitable to degrade 90% of TC in 5 h at a flow rate of 1 mL/min in a single passage flow configuration. Nevertheless, the process could certainly be further optimized in terms of laccase activity, oxygen supply near active sites, and contact time.

A novel process for the covalent immobilization of laccases on silica gel and its application for the elimination of pharmaceutical micropollutants.

In the present work, pharmaceutical micropollutant degradation by laccase immobilized on silica through an innovative process is proposed. The influence of different parameters on the immobilization conditions was evaluated by a 23 full factorial design, and parameters leading to the highest activity were identified. Under these conditions, laccase activity reached 14 ± 2 U g-1 of silica with a protein immobilization yield of 35%. The biocatalyst characterization did not show any change in pH and thermal stabilities but enhanced the long-term storage of laccases. Immobilized T. versicolor laccases were then tested to remove four pharmaceutical micropollutants (amoxicillin, ciprofloxacin, carbamazepine, and sulfamethoxazole) in the presence of redox mediators (syringaldehyde, p-coumaric acid, and ABTS). High removal yields (50-100% according to the pollutant) were obtained within 4 h of treatment due to the synergistic effect of laccase-mediator biotransformation and adsorption on the support. Overall, the pharmaceuticals' removal efficiency was highly influenced by their physicochemical properties; however, the presence of redox mediators impacted not only the oxidation mechanism but also the interactions between the biocatalyst and micropollutants. Finally, the reusability of the biocatalyst was proved during 7 degradation cycles.

Concentration of 1,3-dimethyl-2-imidazolidinone in Aqueous Solutions by Sweeping Gas Membrane Distillation: From Bench to Industrial Scale.

Sweeping gas membrane distillation (SGMD) is a useful option for dehydration of aqueous solvent solutions. This study investigated the technical viability and competitiveness of the use of SGMD to concentrate aqueous solutions of 1,3-dimethyl-2-imidazolidinone (DMI), a dipolar aprotic solvent. The concentration from 30% to 50% of aqueous DMI solutions was attained in a bench installation with Liqui-Cel SuperPhobic® hollow-fiber membranes. The selected membranes resulted in low vapor flux (below 0.15 kg/h·m2) but were also effective for minimization of DMI losses through the membranes, since these losses were maintained below 1% of the evaporated water flux. This fact implied that more than 99.2% of the DMI fed to the system was recovered in the produced concentrated solution. The influence of temperature and flowrate of the feed and sweep gas streams was analyzed to develop simple empirical models that represented the vapor permeation and DMI losses through the hollow-fiber membranes. The proposed models were successfully applied to the scaling-up of the process with a preliminary multi-objective optimization of the process based on the simultaneous minimization of the total membrane area, the heat requirement and the air consumption. Maximal feed temperature and air flowrate (and the corresponding high operation costs) were optimal conditions, but the excessive membrane area required implied an uncompetitive alternative for direct industrial application.

New porous monolithic membranes based on supported ionic liquid-like phases for oil/water separation and homogenous catalyst immobilisation.

Porous monolithic advanced functional materials based on supported ionic liquid-like phase (SILLP) systems were used for the preparation of oleophilic and hydrophobic cylindrical membranes and successfully tested as eco-friendly and safe systems for oil/water separation and for the continuous integration of catalytic and separation processes in an aqueous-organic biphasic reaction system.

Potentialities of active membranes with immobilized laccase for Bisphenol A degradation.

Herein, we report the development of immobilized laccase based membrane bioreactor as a novel bio-catalytic system for the degradation of emerging endocrine disruptor i.e., Bisphenol A. Two laccase forms i.e. (1) in-house isolated and purified from an indigenous white-rot fungi Pycnoporus sanguineus (CS43) and (2) Trametes versicolor (commercial laccase from Sigma-Aldrich®) were immobilized on a multi-channel ceramic membrane (1.4µm in diameter) using 4% glutaraldehyde as a cross-linking agent. The immobilization yield and bisphenol A degradation activities of immobilized laccases were recorded at various pH levels. The surface topographies of immobilized-laccase membranes were accessed by scanning electron microscopy. In this study, 100% degradation of bisphenol A (20mg/L) was achieved in less than 24h in the presence of laccase from P. sanguineus (CS43) (620.55±14.85U/L) and T. versicolor (620.55±14.85U/L). The enzymes showed an optimal activity at pH 5 and 5.4 with a degradation rate of 204.8±1.8 and 79.0±0.1µmol/min/U for P. sanguineus (CS43) and T. versicolor, respectively. In conclusion, the highest immobilization of unit per square centimeter and efficient degradation potentiality strongly recommend the newly developed immobilized laccase based membrane bioreactor as a novel tool to tackle emerging contaminants degradation issues.

Removal of antibiotics in wastewater by enzymatic treatment with fungal laccase - Degradation of compounds does not always eliminate toxicity.

In this study, the performance of immobilised laccase (Trametes versicolor) was investigated in combination with the mediator syringaldehyde (SYR) in removing a mixture of 38 antibiotics in an enzymatic membrane reactor (EMR). Antibiotics were spiked in osmosed water at concentrations of 10µg·L(-1) each. Laccase without mediator did not reduce the load of antibiotics significantly. The addition of SYR enhanced the removal: out of the 38 antibiotics, 32 were degraded by >50% after 24h. In addition to chemical analysis, the samples' toxicity was evaluated in two bioassays (a growth inhibition assay and the Microtox assay). Here, the addition of SYR resulted in a time-dependent increase of toxicity in both bioassays. In cooperation with SYR, laccase effectively removes a broad range of antibiotics. However, this enhanced degradation induces unspecific toxicity. If this issue is resolved, enzymatic treatment may be a valuable addition to existing water treatment technologies.

Membrane bioprocesses for pharmaceutical micropollutant removal from waters.

The purpose of this review work is to give an overview of the research reported on bioprocesses for the treatment of domestic or industrial wastewaters (WW) containing pharmaceuticals. Conventional WW treatment technologies are not efficient enough to completely remove all pharmaceuticals from water. Indeed, these compounds are becoming an actual public health problem, because they are more and more present in underground and even in potable waters. Different types of bioprocesses are described in this work: from classical activated sludge systems, which allow the depletion of pharmaceuticals by bio-degradation and adsorption, to enzymatic reactions, which are more focused on the treatment of WW containing a relatively high content of pharmaceuticals and less organic carbon pollution than classical WW. Different aspects concerning the advantages of membrane bioreactors for pharmaceuticals removal are discussed, as well as the more recent studies on enzymatic membrane reactors to the depletion of these recalcitrant compounds.