The emergence of issues related to environment from ECs is a topic under serious discussions worldwide in recent years. Indian scenario is not an exception as it is tremendously growing in its rate ...of production and consumption of compounds belongs to ECs categories. However, a comprehensive documentation on the occurrence of ECs and consequent ARGs as well as their toxic effects on vertebrates on Indian context is still lacking. In the present study, an extensive literature survey was carried out to get an idea on the geographical distribution of ECs in various environmental matrices (water, air, soil, sediment and sludge) and biological samples by dividing the entire subcontinent into six zones based on climatic, geographical and cultural features. A comprehensive assessment of the toxicological effects of ECs and the consequent antibiotic resistant genes has been included. It is found that studies on the screening of ECs are scarce and concentrated in certain geological locations. A total of 166 individual compounds belonging to 36 categories have been reported so far. Pharmaceuticals and drugs occupy the major share in these compounds followed by PFASs, EDCs, PCPs, ASWs and flame retardants. This review throws light on the alarming situation in India where the highest ever reported values of concentrations of some of these compounds are from India. This necessitates a national level monitoring system for ECs in order to assess the magnitude of environmental risks posed by these compounds.
•A baseline data on the current status of Emerging Contaminants (ECs) in Indian Environmental matrices is presented.•A stepwise progress of Indian research on ECs is explored.•The country is categorized into six zones based on climatic, geographical and cultural factors.•The presence of ECs in various matrices, occurrence of antibiotic resistance bacteria/genes and the toxic effects are discussed in each zone.•The gap areas were identified and provided suitable recommendations for future research works.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
Advanced oxidation processes (AOPs) hold great promise in the removal of organic contaminants. Reactive oxygen species (ROS) produced in AOPs react with target pollutants to initially form several ...intermediate compounds that finally undergo complete mineralization. Such observations are reported, especially for laboratory-scale experiments performed in pure water. On the other hand, while considering real contaminated wastewater matrices, particularly industrial effluents, there are many co-existing ions. Carbonate ions are one of the major inorganic ions commonly existing in water resources. Hence, these ions have a significant impact on the respective water treatment processes. This review focused on the effect of carbonate ions on the degradation of pollutants in AOPs. In AOPs, carbonate radicals are formed by the scavenging reaction of the respective ions with ROS. The reactivity of these radicals towards the pollutant varies with respect to the structure and functionality. Therefore, depending on the functionalities of the contaminants, these ions show both positive and negative effects. Thus, this review aims to summarize the effects of carbonate species on the degradation of organic contaminants during AOPs and their environmental impacts. The carbonates enhanced the degradation of several emerging organic pollutants, including aniline, bisphenol A, rhodamine B, acid orange 7, naphthalene, and phenol derivatives. Carbonate presence was also revealed to have a positive contribution in cases of drug degradation, including sulfamethoxazole, propranolol, sulfamethazine, salbutamol, trimethoprim, azithromycin, naproxen, oxcarbazepine, and oxytetracycline.
Water pollution by pharmaceutically active compounds is an emerging issue. Toxicological studies reveal that pharmaceuticals are indeed toxic for living organisms. The lack of suitable treatment ...technology for the complete removal of pharmaceuticals is therefore a major challenge. Advanced oxidation processes are emerging removal techniques that have many advantages versus conventional technologies. Many studies indicate that advanced oxidation processes, either in single or in combination with other degradation techniques, can enhance the degradation of pharmaceuticals in aqueous solutions. Here, we review the degradation of pharmaceuticals by sonolysis, an oxidation processes using ultrasound. In this technique, hydroxyl radicals are generated by pyrolytic cleavage of water molecules. We review the influence of operational parameters, additives and hybrid techniques on the degradation of pharmaceuticals. The maximum degradation of organic compounds was observed in the frequency range of 100–1000 kHz, which is in the high-frequency medium-power ultrasound. Even though almost all the experiments presented more than 90 % removal and good biodegradability of the target compound, good mineralization and the toxicity removal were hardly achieved. The efficiency of the degradation varies with water matrixes and varying pH. Major pathways of degradation are hydroxylation, dehalogenation, demethylation, decarboxylation, deamination, etc. More hybrid techniques have to be developed to scale up the application of ultrasound.
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EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
•Sonochemical degradation of triphenylmethane dyes has been studied.•100% degradation and more than 90% COD reduction was observed.•OH is found to be the major reactive species for the ...degradation.•Degradation and byproduct formation was greatly influenced by the carbonate ions.•Carbonate radical induced the degradation via electron transfer.
Triphenylmethane (TPM) dyes are an important category of dyes with a variety of industrial applications and consequently, these are found in the aquatic environment at relatively higher concentrations. Here, we report the degradation of two important TPM dyes (para rosaniline (PRA) and ethyl violet (EV)) in an aqueous medium by ultrasound which is one among the Advanced Oxidation Processes (AOPs). The main objective of this work is to study the effect of various inorganic ions on the degradation and the product formation of TPM dyes from the sonochemical reactions. Using a typical concentration of 10 ppm dyes and an ultrasonic frequency of 350 kHz and power of 60 W, a complete degradation of EV and PRA was observed with a pseudo first order rate constant of 0.2339 min−1 and 0.1956 min−1, respectively. The product analyses using high-resolution mass spectrometry (LC-Q-TOF-MS) revealed the formation of hydroxylated, de-alkylated, and other collapsed conjugated structure destructed products. The evolution of these products in the presence of various inorganic ions (Cl−, SO42−, NO3−, and CO3−) showed that only carbonate ions had a significant impact on the product evolution. The carbonate ions facilitated the formation of conjugated structure destructed product for both the dyes. This is attributed to the reactivity of carbonate radical, which facilitated the formation of carbon-centered radicals. This carbon-centered radical further undergoes reaction to cause the destruction of conjugated structures. This is confirmed by the identification of the corresponding product peaks in the mass spectra. The scavenging effect of carbonate ions was also reflected in the product study where there is a reduction in the formation of most of the hydroxylated products. One of the major inorganic species in any wastewater is carbonate ions and therefore the present result is very relevant to the understanding of oxidation based treatment protocol.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
The molecular basis of protein unfolding on exposure to the widely used herbicide, Glyphosate (GLY), its metabolite aminomethylphosphonic acid (AMPA), and the commercial formulation Roundup have been ...probed using human and bovine serum albumins (HSA and BSA). Protein solutions were exposed to chemical stress at set experimental conditions. The study proceeds with spectroscopic and imaging tools. Steady-state and time-resolved fluorescence (TRF) measurements indicated polarity changes with the possibility of forming a ground-state complex. Atomic force microscopy imaging results revealed the formation of fibrils from BSA and dimer, trimer, and tetramer forms of oligomers from HSA under the chemical stress of GLY. In the presence of AMPA, serum albumins (SAs) form a compact network of oligomers. The compact network of oligomers was transformed into fibrils for HSA with increasing concentrations of AMPA. In contrast, Roundup triggered the formation of amorphous aggregates from SAs. Analysis of the Raman amide I band of all aggregates showed a significant increase in antiparallel β-sheet fractions at the expense of α-helix. The highest percentage, 24.6%, of antiparallel β-sheet fractions was present in amorphous aggregate formed from HSA under the influence of Roundup. These results demonstrated protein unfolding, which led to the formation of oligomers and fibrils.
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•Evaluated the molecular events related to the toxicological impact of GLY, AMPA, and Roundup.•BSA and HSA were the preferred model proteins for the study.•GLY, AMPA, and Roundup show different binding affinities to BSA and HSA.•Reported on binding dynamics, nanostructure evolution, and secondary structural reorganization for the first time.•The nanostructures that evolved from SAs were similar to those observed in protein aggregation disorders.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
The degradation of pollutants by a non-radical pathway involving singlet oxygen (1O2) is highly relevant in advanced oxidation processes. Photosensitizers, modified photocatalysts, and activated ...persulfates can generate highly selective 1O2 in the medium. The selective reaction of 1O2 with organic pollutants results in the evolution of different intermediate products. While these products can be identified using mass spectrometry (MS) techniques, predicting a proper degradation mechanism in a 1O2-based process is still challenging. Earlier studies utilized MS techniques in the identification of intermediate products and the mechanism was proposed with the support of theoretical calculations. Although some reviews have been reported on the generation of 1O2 and its environmental applications, a proper review of the degradation mechanism by 1O2 is not yet available. Hence, we reviewed the possible degradation pathways of organic contaminants in 1O2-mediated oxidation with the support of density functional theory (DFT). The Fukui function (FF, f-, f+, and f0), HOMO-LUMO energies, and Gibbs free energies obtained using DFT were used to identify the active site in the molecule and the degradation mechanism, respectively. Electrophilic addition, outer sphere type single electron transfer (SET), and addition to the hetero atoms are the key mechanisms involved in the degradation of organic contaminants by 1O2. Since environmental matrices contain several contaminants, it is difficult to experiment with all contaminants to identify their intermediate products. Therefore, the DFT studies are useful for predicting the intermediate compounds during the oxidative removal of the contaminants, especially for complex composition wastewater.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
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•Layer by Layer assembly demonstrated for the first time on coir fibre.•Effect of salt on adsorption of varieties of cationic and anionic dyes at acidic and alkaline loading ...pH.•60–99% color removal for all selected dyes at wide range of pH, salt concentration, and surfactants.•Demonstration of local textile mill effluent treatment.•Very efficient COD removal of 84% and color removal of 81% within 30 min.
Layer by layer (LbL) assembly can be regarded as an emerging technology for the separation of organic micro-pollutants from water. Direct assembly of polyelectrolytes (PEs) under LbL mode on natural support material is rare. Here we report the integration of LbL to one of the most resourceful support materials that might have an enduring impact on water treatment in color industry. A low-cost adsorbent is developed from chitosan (CHI) and polyacrylic acid (PAA) through LbL deposition on coir fiber (CF) by alternate exposure to their aqueous solutions. Their layer dependent formation is characterized by spectroscopic and microscopic techniques. CHI/PAA multilayer coated coir fiber or simply, layered coir fiber (LCF) showed high loading of cationic and anionic dyes both at acidic and alkaline loading pH. The loading was between 70% and 99% at the acidic pH 3 which is attributed to the binding between LCF and dye molecules by electrostatic and hydrophobic forces. The performance of LCF in presence of NaCl, Na2SO4 and sodium dodecyl sulfate (SDS) in dye solution is discussed. Textile industrial waste water showed significant reduction in dye (81%) content along with COD (84%) and TDS.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
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•Degradation of Coomassie Brilliant Blue induced by ultrasound is investigated.•Maximum degradation at a frequency of 350kHz and power density of 19.6WmL−1.•Enhancement of degradation ...in the presence of low concentrations of Fe2+, H2O2, S2O82−.•13 transformed products identified using LC-Q-TOF-MS analysis.
Coomassie Brilliant Blue (CBB), discharged mainly from textile industries, is an identified water pollutant. Ultrasound initiated degradation of organic pollutants is one among the promising techniques and forms part of the Advanced Oxidation Processes (AOPs). Ultrasonic degradation of CBB under different experimental conditions has been investigated in the present work. The effect of frequency (200kHz, 350kHz, 620kHz and 1MHz) and power density (3.5WmL−1, 9.8WmL−1 and 19.6WmL−1) on the degradation profile was evaluated. The optimum performance was obtained at 350kHz and 19.6WmL−1. Similar to other sonolytic degradation of organic pollutants, maximum degradation of CBB was observed under acidic pH. The degradation profile indicated a pseudo-first order kinetics. The addition of ferrous ion (1×10−4M), hydrogen peroxide (1×10−4M), and peroxodisulphate (1×10−4M) had a positive effect on the degradation efficiency. The influence of certain important NOM like SDS and humic acid on the sonolytic degradation of CBB was also investigated. Both the compounds suppress the degradation efficiency. LC-Q-TOF-MS was used to identify the stable intermediate products. Nearly 13 transformed products were identified during 10min of sonication using the optimized operational parameters. This product profile demonstrated that most of the products are formed mainly by the OH radical attack. On the basis of these results, a degradation mechanism is proposed.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
The natural phototransformation of organic pollutants in the environment depends on several water constituents, including inorganic ions, humic substances, and pH. However, the literature information ...concerning the influence of various water components on the amount of phototransformation and their impact on the development of various transformation products (TPs) is minimal. This study investigated the phototransformation of ofloxacin (OFL), a fluoroquinolone antibiotic, in the presence of various water components such as cations (K+, Na+, Ca2+, NH4+, Mg2+), anions (NO3−, SO42−, HCO3−, CO32−, PO43−), pH, and humic substances when exposed to natural sunlight. The study reveals that neutral pH levels (0.39374 min⁻1) enhance the phototransformation of OFL in aquatic environments. Carbonate, among anions, shows the highest rate constant (2.89966 min⁻1), significantly influencing OFL phototransformation, while all anions exhibit a notable impact. In aquatic environments, indirect phototransformation of OFL, driven by increased reactive oxygen species, expedites light-induced reactions, potentially enhancing OFL phototransformation. A clear difference was visible in the type of transformation products (TPs) formed during direct and indirect photolysis. The impact of indirect photolysis in the product profile was evaluated by examining the unique properties of TPs in direct and indirect photolysis. The primary transformation products were generated by oxidation and cleavage processes directed towards the ofloxacin piperazinyl, oxazine, and carboxyl groups. The toxicity assessment of TPs derived from OFL revealed that among the 26 identified TPs, TP3 (demethylated product), TP7 and TP8 (decarboxylated products), and TP15 (piperazine ring cleaved product) could potentially have some toxicological effects. These findings suggest that the phototransformation of OFL in the presence of various water components is necessary when assessing this antibiotic's environmental fate.
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•Environmental factors impact ofloxacin phototransformation.•The presence of nitrate, carbonate, and bicarbonate enhances the transformation.•The transformation product profiles in direct and indirect photolysis are different.•Indirect photolysis amplifies OFL transformation, yielding unique degradation products with .•OH.•Most products are environmentally benign.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
Oxidative reactions of the hydroxyl radical (·OH) with methimazole (MMI), an antithyroid drug, are crucial for understanding its fate in oxidizing environments. By synergistically integrating density ...functional theory and ultraperformance liquid chromatography–quadrupole time-of-flight tandem mass spectrometry (UPLC-Q-TOF MS/MS) techniques, we elucidated the transients and transformation products (TPs) arising from the ·OH–MMI reactions. We probed two hydrogen-atom abstraction (HA) reactions, three radical adduct formation reactions, and single electron transfer (SET) at the M06-2X/6-311++G(d,p)/SMD(water) level. All proposed reaction channels, except for HA from the methyl group and SET, were found to be barrier-free. SET is the dominant oxidation pathway, accounting for 44% of oxidations, as determined by branching ratio analysis. The selenium analogue, MSeI, exhibited minor reactivity differences compared to MMI, yet its overall patterns resembled those of ·OH–MMI reactions. TPs were generated experimentally by reacting MMI with ·OH produced by UV-photolysis of H2O2. Eight TPs were identified from an approximately 24% degradation of MMI using UPLC-Q-TOF MS/MS analysis, and an additional two TPs were identified from the approximately 52% degraded MMI sample. The exact identities of all of the TPs were established through their corresponding fragmentation patterns. This study elucidates the drug’s susceptibility to free radical species under physiologically relevant conditions.
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IJS, KILJ, NUK, PNG, UL, UM
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