Recent Developments in the Immobilization of Laccase on Carbonaceous Supports for Environmental Applications - A Critical Review.

Τhe ligninolytic enzyme laccase has proved its potential for environmental applications. However, there is no documented industrial application of free laccase due to low stability, poor reusability, and high costs. Immobilization has been considered as a powerful technique to enhance laccase's industrial potential. In this technology, appropriate support selection for laccase immobilization is a crucial step since the support could broadly affect the properties of the resulting catalyst system. Through the last decades, a large variety of inorganic, organic, and composite materials have been used in laccase immobilization. Among them, carbon-based materials have been explored as a support candidate for immobilization, due to their properties such as high porosity, high surface area, the existence of functional groups, and their highly aromatic structure. Carbon-based materials have also been used in culture media as supports, sources of nutrients, and inducers, for laccase production. This study aims to review the recent trends in laccase production, immobilization techniques, and essential support properties for enzyme immobilization. More specifically, this review analyzes and presents the significant benefits of carbon-based materials for their key role in laccase production and immobilization.

Evaluation of bio-fenton oxidation approach for the remediation of trichloroethylene from aqueous solutions.

In the present study, a Bio-Fenton oxidation approach for the removal of trichloroethylene (TCE) was developed through the optimization of enzyme-based hydrogen peroxide (H2O2) production from glucose. Glucose oxidase (GOD) was evaluated for the production of H2O2 and the optimized parameters were found to be the oxidation of 60 mM glucose by 1 mg mL-1 of GOD which yielded a conversion of 88.4% of glucose for subsequent utilization in the Bio-Fenton process. The biologically produced H2O2 was further used for the removal of TCE from groundwater samples by addition of ferrous ion to the reaction mixture. To determine the efficiency of hydroxyl radicals generated in Fenton reactions to remove TCE in a cost-efficient way, preliminary experiments such as classical Fenton and pseudo Bio-Fenton were carried out in aqueous solutions containing TCE in order to obtain the optimum conditions and then the efficiency of bio-Fenton was tested in groundwater. Based on these results, almost 97% of TCE was removed from aqueous solution within 30 min of classical Fenton under low pH condition (pH 3.0). While performing pseudo bio-Fenton experiments, the optimum conditions were determined to be pH 7.0 and 30 ppm H2O2 which yielded 61% removal of TCE in 30 min. Although a comparatively lower removal (30.2%) in groundwater containing TCE was achieved using Bio-Fenton process, it was at a neutral pH. The process was further enhanced by the addition of hydrogen peroxide after 3 h of reaction and a maximum of 48.4% removal of TCE was observed. Thus, this process will help to prevent the scavenging of the unstable H2O2 and can be employed in-situ.

Adsorptive immobilization of agro-industrially produced crude laccase on various micro-biochars and degradation of diclofenac.

Although enzymes are gifted with unique and unprecedented catalytic activity and selectivity over a wide range of pollutants, still their stability related issues often hinder their application in real environmental conditions. In this study, agro-industrially produced crude laccase was concentrated using ultrafiltration. Crude laccase was immobilized on pine wood (BC-PW), pig manure (BC-PM) and almond shell (BC-AS) biochar microparticles. Immobilization of laccase was investigated at various laccase activities on micro-biochars and the release (desorption) of the enzyme has been studied. It was observed that for all the biochars, as the initial concentration of laccase increased in the crude solution, the binding capacity and as result immobilization efficiency also increased. BC-PM was found to be the most effective (31.4 ±â€¯3.1 U g-1) at 10 U mL-1 of enzyme activity followed by BC-AS (24.3 ±â€¯4.8 U g-1) and BC-PW (14.58 ±â€¯3.3 U g-1). In addition, the biochars were functionalized with citric acid for possible surface modifications and the effect of biochars for the adsorption of enzymes has been investigated. Isotherm studies of enzyme loading onto biochar established homogeneous monolayer adsorption as the major mechanism. The desorption of laccase from all biochars followed pseudo-second-order model. Immobilized laccase exhibited superior storage ability and shelf-life which were three times higher than free laccase. Finally, the immobilized laccase was used for the degradation of micropollutant, DCF and near 100% removal was obtained within 5 h at an environmentally relevant concentration (500 µg L-1).

Impact of biochar amendment in agricultural soils on the sorption, desorption, and degradation of pesticides: A review.

Extensive and inefficient use of pesticides over the last several decades resulted in serious soil and water contamination by imposing severe toxic effects on living organisms. Soil remediation using environment-friendly amendments to counteract the presence of pesticides in soil seems to be one suitable approach to solve this problem. Biochar has emerged as a promising material for adsorbing and thus decreasing the bioavailability of pesticides in polluted soils, due to its high porosity, surface area, pH, abundant functional groups, and highly aromatic structure, mainly depending on the feedstock and pyrolysis temperature. However, biochar effects and mechanisms on the sorption and desorption of pesticides in the soil are poorly understood. Either high or low pyrolysis temperature has both positive and negative effects on sorption of pesticides in soil, one by larger surface area and the other by a large number of functional groups. Therefore, a clear understanding of these effects and mechanisms are necessary to engineer biochar production with desirable properties. This review critically evaluates the role of biochar in sorption, desorption, and degradation of pesticides in the soil, along with dominant properties of biochar including porosity and surface area, pH, surface functional groups, carbon content and aromatic structure, and mineralogical composition. Moreover, an insight into future research directions has been provided by evaluating the bioavailability of pesticide residues in the soil, effect of other contaminants on pesticide removal by biochar in soils, effect of pesticide properties on its behavior in biochar-amended soils, combined effect of biochar and soil microorganisms on pesticide degradation, and large-scale application of biochar in agricultural soils for multifunction.

An insight into the adsorption of diclofenac on different biochars: Mechanisms, surface chemistry, and thermodynamics.

Biochars were prepared from feedstocks pinewood and pig manure. Biochar microparticles obtained through grinding were evaluated for the removal of emerging contaminant diclofenac (DCF) and the underlying mechanism were thoroughly studied. Characterization of biochar was carried out using particle size analyzer, SEM, BET, FT-IR, XRD, XPS and zeta potential instrument. Pig manure biochar (BC-PM) exhibited excellent removal efficiency (99.6%) over pine wood biochar (BC-PW) at 500 µg L-1 of DCF (environmentally significant concentration). Intraparticle diffusion was found to be the major process facilitated the adsorption. BC-PW followed pseudo first-order kinetics whereas BC-PM followed pseudo second-order kinetics. Pine wood biochar was largely affected by pH variations whereas for pig manure biochar, pH effects were minimal owing to its surface functional groups and DCF hydrophobicity. Thermodynamics, presence of co-existing ions, initial adsorbate concentration and particles size played substantial role in adsorption. Various isotherms models were also studied and results are presented.

Adsorption of diclofenac onto different biochar microparticles: Dataset - Characterization and dosage of biochar.

Due to its wide occurrence in water resources and toxicity, pharmaceuticals and personal care products are becoming an emerging concern throughout the world. Application of residual/waste materials for water remediation can be a good strategy in waste management as well as in waste valorization. Herein, this dataset provides information on biochar application for the removal of emerging contaminant, diclofenac from water matrices. The data presented here is an extension of the research article explaining the mechanisms of adsorption diclofenac on biochars (Lonappan et al., 2017 [1]). This data article provides general information on the surface features of pine wood and pig manure biochar with the help of SEM and FTIR data. This dataset also provides information on XRD profiles of pine wood and pig manure biochars. In addition, different amounts of biochars were used to study the removal of a fixed concentration of diclofenac and the data is provided with this data set.

Diclofenac and its transformation products: Environmental occurrence and toxicity - A review.

Diclofenac (DCF) is a prevalent anti-inflammatory drug used throughout the world. Intensive researches carried out in the past few decades have confirmed the global ubiquity of DCF in various environmental compartments. Its frequent occurrence in freshwater environments and its potential toxicity towards several organisms such as fish and mussels makes DCF an emerging environmental contaminant. At typical detected environmental concentrations, the drug does not exhibit toxic effects towards living organisms, albeit chronic exposure may lead to severe effects. For DCF, about 30-70% removal has been obtained through the conventional treatment system in wastewater treatment plant being the major primary sink. Thus, the untreated DCF will pass to surface water. DCF can interact with other inorganic contaminants in the environment particularly in wastewater treatment plant, such as metals, organic contaminants and even with DCF metabolites. This process may lead to the creation of another possible emerging contaminant. In the present context, environmental fate of DCF in different compartments such as soil and water has been addressed with an overview of current treatment methods. In addition, the toxicity concerns regarding DCF in aquatic as well as terrestrial environment along with an introduction to the metabolites of DCF through consumption as well as abiotic degradation routes are also discussed. Further studies are required to better assess the fate and toxicological effects of DCF and its metabolites and must consider the possible interaction of DCF with other contaminants to develop an effective treatment method for DCF and its traces.

Adsorption of methylene blue on biochar microparticles derived from different waste materials.

Biochar microparticles were prepared from three different types of biochar, derived from waste materials, such as pine wood (BC-PW), pig manure (BC-PM) and cardboard (BC-PD) under various pyrolysis conditions. The microparticles were prepared by dry grinding and sequential sieving through various ASTM sieves. Particle size and specific surface area were analyzed using laser particle size analyzer. The particles were further characterized using scanning electron microscope (SEM). The adsorption capacity of each class of adsorbent was determined by methylene blue adsorption tests in comparison with commercially available activated carbon. Experimental results showed that dye adsorption increased with initial concentration of the adsorbate and biochar dosage. Biochar microparticles prepared from different sources exhibited improvement in adsorption capacity (7.8±0.5 mg g(-1) to 25±1.3 mg g(-1)) in comparison with raw biochar and commercially available activated carbon. The adsorption capacity varied with source material and method of production of biochar. The maximum adsorption capacity was 25 mg g(-1) for BC-PM microparticles at 25°C for an adsorbate concentration of 500 mg L(-1) in comparison with 48.30±3.6 mg g(-1) for activated carbon. The equilibrium adsorption data were best described by Langmuir model for BC-PM and BC-PD and Freundlich model for BC-PW.

Diclofenac in municipal wastewater treatment plant: quantification using laser diode thermal desorption--atmospheric pressure chemical ionization--tandem mass spectrometry approach in comparison with an established liquid chromatography-electrospray ionization-tandem mass spectrometry method.

Diclofenac (DCF), a prevalent non-steroidal anti-inflammatory drug (NSAID) is often detected in wastewater and surface water. Analysis of the pharmaceuticals in complex matrices is often laden with challenges. In this study a reliable, rapid and sensitive method based on laser diode thermal desorption/atmospheric pressure chemical ionization (LDTD/APCI) coupled with tandem mass spectrometry (MS/MS) has been developed for the quantification of DCF in wastewater and wastewater sludge. An established conventional LC-ESI-MS/MS (liquid chromatography-electrospray ionization-tandem mass spectrometry) method was compared with LDTD-APCI-MS/MS approach. The newly developed LDTD-APCI-MS/MS method reduced the analysis time to 12s in lieu of 12 min for LC-ESI-MS/MS method. The method detection limits for LDTD-APCI-MS/MS method were found to be 270 ng L(-1) (LOD) and 1000 ng L(-1) (LOQ). Furthermore, two extraction procedures, ultrasonic assisted extraction (USE) and accelerated solvent extraction (ASE) for the extraction of DCF from wastewater sludge were compared and ASE with 95.6 ± 7% recovery was effective over USE with 86 ± 4% recovery. The fate and partitioning of DCF in wastewater (WW) and wastewater sludge (WWS) in wastewater treatment plant was also monitored at various stages of treatment in Quebec Urban community wastewater treatment plant. DCF exhibited affinity towards WW than WWS with a presence about 60% of DCF in WW in contrary with theoretical prediction (LogKow=4.51).