Linson Lonappan

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).

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.

Biological synthesis of metallic nanoparticles: plants, animals and microbial aspects

The green synthesis (GS) of different metallic nanoparticles (MNPs) has re-evaluated plants, animals and microorganisms for their natural potential to reduce metallic ions into neutral atoms at no expense of toxic and hazardous chemicals. Contrary to chemically synthesized MNPs, GS offers advantages of enhanced biocompatibility and thus has better scope for biomedical applications. Plant, animals and microorganisms belonging to lower and higher taxonomic groups have been experimented for GS of MNPs, such as gold (Au), silver (Ag), copper oxide (CuO), zinc oxide (ZnO), iron (Fe2O3), palladium (Pd), platinum (Pt), nickel oxide (NiO) and magnesium oxide (MgO). Among the different plant groups used for GS, angiosperms and algae have been explored the most with great success. GS with animal-derived biomaterials, such as chitin, silk (sericin, fibroin and spider silk) or cell extract of invertebrates have also been reported. Gram positive and gram negative bacteria, different fungal species and virus particles have also shown their abilities in the reduction of metal ions. However, not a thumb rule, most of the reducing agents sourced from living world also act as capping agents and render MNPs less toxic or more biocompatible. The most unexplored area so far in GS is the mechanism studies for different natural reducing agents expect for few of them, such as tea and neem plants. This review encompasses the recent advances in the GS of MNPs using plants, animals and microorganisms and analyzes the key points and further discusses the pros and cons of GS in respect of chemical synthesis.

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.

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 ± 3.1 U g-1) at 10 U mL-1 of enzyme activity followed by BC-AS (24.3 ± 4.8 U g-1) and BC-PW (14.58 ± 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).

Bio-conversion of apple pomace into fumaric acid in a rotating drum type solid-state bench scale fermenter and study of the different underlying mechanisms

Utilization of apple industry solid waste, apple pomace (AP) for the production of fumaric acid (FA) using a rotating drum type solid-state bench scale fermenter was studied under optimized conditions and different mechanisms underlying the conversion were investigated. The filamentous fungal strain, Rhizopus oryzae 1526 was used in the study. The solid-state fermentation was carried out in continuous rotation, intermittent rotation and static mode of the fermenter operations for a maximum of 21 days. Two different moisture contents (70% and 50%, w/w) of AP were applied for each batch. The highest FA concentration (138 ± 9.11 g per kg dry weight of AP) was achieved at 50% moisture content and under continuous rotation after 14 days. Viability checking of the fungus showed maintenance of a high cell count (2.74 × 108 spores per g dry apple pomace) during fermentation. Analysis of AP fibre composition confirmed the conversion of insoluble dietary fibers into soluble dietary fibers and utilization of the dietary fibres for FA production. Total phenolic content of AP was considerably increased (by around 86%) from 185 ± 10.5 to 345 ± 8.5 mg per g lyophilizate after 18 days. LC/MS/MS analysis confirmed the consumption of sugars (glucose fructose and sucrose) present in AP by the fungus during fermentation. The presence of different phenolic compounds and changes in their content after fermentation was also confirmed by LC/MS/MS analysis. Two other operating conditions produced 82 ± 6.8 and 58 ± 8.5 g of FA per kg dry weight of AP, respectively after 18 days of fermentation.

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.

Environmental issues of Polybrominated Diphenyl Ethers.

ABSTRACT Polybrominated diphenyl ethers (PBDEs) are among the emerging contaminants that have been traced in almost all environmental compartments for the past 30 years. Their continued application as flame-retardant additives, persistence in nature due to fluorine groups, global atmospheric transport, and analytical challenges due to interferences and different properties of congeners indicate the urgent need of finding solutions to their use. The increasing level of PBDEs in the environment and especially human tissues is alarming due to their potential neurological effects, cancer proliferation, and thyroid hormone imbalance. Therefore, strict regulations need to be applied in all countries to control the PBDEs production consumption and disposal into the environment. Studies have shown that conventional wastewater treatment plants are unable to degrade PBDEs resulting in the transport of 60–90% of PBDEs to soil through biosolids application. On the other hand, advanced treatment processes, such as ultraviolet light, advanced oxidation, and photocatalytic degradation showed promising potential for removing PBDEs from wastewater (70–100% degradation efficiency). PBDEs can be replaced by natural flame retardants, such as nanoclay or new polymers, such as bishydroxydeoxybenzoin which have no environmental or health problems compared to PBDEs.