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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 + , Ca 2+ , NH 4 + , Mg 2+ ), anions (NO 3 - , SO 4 2- , HCO 3 - , CO 3 2- , PO 4 3- ), 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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Steroid hormones (SHs) are among the important classes of Contaminants of Emerging Concern (CECs) whose detection in aquatic environments is vital due to their potential adverse health impacts. Their detection is challenging because of their lower stability in natural conditions and low concentrations. This study reports the presence of steroid hormones in a major river system, the Periyar River, in Kerala (India). Water samples were collected from thirty different river locations in the case of SHs and five locations within these in the case of other CECs. These were subjected to LC-MS/MS and LC-Q-ToF/MS analyses. Five SHs, estriol, estrone, 17 β estradiol, progesterone, and hydroxy progesterone, were separated and targeted using MS techniques. The studies of the water samples confirmed the presence of the first three estrogens in different sampling sites, with estrone present in all the sampling sites. The concentration of estrone was detected in the range from 2 to 15 ng/L. Estriol and estradiol concentrations ranged from 1.0 to 5 ng/L and 1-6 ng/L, respectively. The hormones at some selected sites were continuously monitored for seven months. The chosen areas include the feed water sites for the drinking water treatment plants across the river. The monthly data revealed that estrone is the only SHs detected in all the samples in the selected months. The highest concentration of SH was found in August. Twelve CECs belonging to pharmaceuticals and personal care products were identified and quantified. In addition, 31 other CECs were also identified using non-target analysis. A detailed study of the hormone mapping reported here is the first from any South Indian River., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Graywater reuse is one of the important concepts in attaining water sustainability. A major challenge in this area is to realize various components present in graywater. The present study involves the identification of the chemical components of graywater collected from three different environments and to investigate the efficiency of removal of some of these chemical components using ultrafiltration membranes (polyelectrolyte multilayer (PEM) membranes). The chemical components were analyzed using liquid chromatography connected with quadrupole time-of-flight (UPLC-Q-ToF-MS). A number of micropollutants including surfactants and certain contaminants of emerging concern (CECs) were identified from these samples. Out of 16 compounds identified, 13 were surfactants and the remaining were caffeine, oxybenzone, and benzophenone. These surfactants are mostly the ingredients of various detergents. Low-pressure filtration studies of the collected samples were carried out utilizing chitosan/polyacrylic acid (CHI/PAA) multilayer membranes. A 5.5 bilayer membrane showed more than 95% rejection of the identified compounds in the selected samples and significant improvement in the water quality parameters. This demonstrates that the membrane used in this work is effective in the removal of various chemicals from graywater as well as enhancing the water quality., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Extensive use of surfactants in numerous fields resulted in their discharge into various environmental compartments including soil, sediment, and water. Alcohol ethoxysulfates (AES) together with alcohol ethoxylates (AE), alkyl sulfates (AS), and linear alkyl benzene sulfonates (LAS) find wide variety of applications in consumer products including both domestic and industrial applications. Consequently, all these surfactants pose several concerns to both aquatic and human health. In the context of environmental impacts, AES has almost equal importance as that of LAS though the literature on this topic is only emerging. This review provides a detailed overview on the various aspects of the anionic surfactant, AES, such as toxicity of AES, its fate in the ecosystem, technical advancements in the area of identification and quantification, its occurrence and distribution in different environmental compartments spanning across the world, and finally a remark of its potential removal strategy from the environment., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Degradation of benzenesulfonic acid (BSA), the simplest aromatic sulfonic acid with extreme industrial importantance, by sonochemically generated hydroxyl radical (OH) have been thoroughly investigated. A reasonable reduction (∼50%) in the total organic carbon (TOC) was achieved only after prolonged irradiation (∼275 min, 350 kHz) of ultrasound, although a short irradiation of less than an hour is enough to degrade significant amount of BSA. The degradation efficiency of ultrasound has been reduced in lower and extremely higher frequencies, and upon increasing the pH. An irregular, but continuous, release of sulfate ions was also observed. Further, the release of protons upon the oxidation of BSA consistently reduces the experimental pH to nearly 2. High resolution mass spectrometric (HRMS) analyses reveals the formation of a number of aromatic intermediates, including three mono (I a-c ) and two di (II a&b ) hydroxylated BSA derivatives as the key products in the initial stages of the reaction. Pulse radiolysis studies revealed the generation of hydroxycyclohexadienyl-type radicals, characterized by absorption bands at 320 nm (k 2  = (7.16 ± 0.04) × 10 9  M -1  s -1 ) and 380 nm, as the immediate intermediates of the reaction. The mechanism(s) leading to the degradation of BSA under sonolytic irradiation conditions along with the effect of various factors, such as the ultrasound frequency and reaction pH, have been explained in detail. The valuable mechanistic aspects obtained from our pulse radiolysis and HRMS studies are essential for the proper implementation of sonochemical techniques into real water purification process and, thus, receives extreme environmental relevance., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The present study describes the monitoring of some of the major classes of surfactants in water. The separation, identification, and the quantitative estimation of the compounds were achieved using LC-Q-ToF-MS. The analyses revealed the presence of variety of surfactants including linear alkylbenzene sulfonate (LAS), alcohol ethoxysulfates (AES), and alcohol ethoxylates (AE). Further, emphasis was given to AES as they are one of the most produced and consumed surfactants in the world. And as far as India is concerned, the present study is one of the most significant attempt regarding the identification and quantification of AES. The data obtained during the analysis revealed that the average concentration of AES C12Ex varied from 0.7 to 13.6 μg L -1 while that of C14Ex ranged between 1.3 and 10.4 μg L -1 . The risk assessment revealed that higher chain AES are capable of posing medium level risk to the aquatic compartment. In addition, the study also included the physicochemical analysis of water from the selected area. Water was found to be acidic in nature and the salinity, TDS, and EC values were found to be high during the pre-monsoon season. The order of the levels of anionic constituents was of Cl - >SO 4 2- SO 4 2- >F - >NO 3 2- ≅ PO 4 2- while that of cations were Na +  > Mg 2+  > K +  > Ca 2+ . Results of correlation analysis showed that statistically negative correlation exists between AES homologs and pH while slight positive correlations were found between AES and other parameters including TDS and EC. The suitability of this water for domestic and agricultural purposes has been examined on the ground of basic quality indices such as the water quality index (WQI) and sodium adsorption ratio (SAR). The WQI measurements also revealed that the water quality of the region falls under the "very poor" category especially during the pre-monsoon season. The study could explore the cumulative share of these canals in the quality impairment of the receiving Vembanad Lake.

The presence of emerging contaminants (ECs) in different aquatic systems may contribute to hazardous effects on aquatic organisms and subsequently on human health. In the present work, liquid chromatography coupled to a quadrupole time of flight mass spectrometer (LC-Q-ToF-MS) was used to identify and quantify a series of ECs in Periyar River in Aluva region, Kerala, India. The water samples were pre concentrated using solid-phase extraction (SPE) prior to analysis. The compounds were probed in both positive and negative ionization mode using electro spray ionization (ESI). Method validations were performed for linearity, limit of detection (LOD), limit of quantification (LOQ), accuracy, and precision (intraday and inter day). The ECs were quantified using standard calibration curve. The identified nine ECs include pharmaceuticals, personal care products, steroids, surfactants, and phthalate. A relatively high concentration was observed in the case of 2-dodecyl benzene sulfonic acid (1012 ng/l) and low concentration was observed for lignocaine (4.3 ng/l; since this is below LOQ, the value is only approximate). In addition, we have identified another 28 organic compounds using the technique of non-target analysis out of which seven compounds fall in the category of surfactants. Being the first report on ECs in Periyar River, the data is very important as this river is one of the biggest and important rivers of Kerala having several purification units for drinking water in the province.

Ultrasound is known to degrade organic compounds by pyrolysis and by the reaction of free radicals. In this work, sonolytic degradation of an identified water pollutant, coomassie brilliant blue (CBB), has been carried out in pure water as well as in river water. In the case of pure water, 90 % degradation was obtained after 30 min of sonication (350 kHz frequency, 60 W power), whereas in river water, the same efficiency was achieved only after 90 min. The degradation was also performed in the presence of varying concentration of (10-100 mg L -1 ) inorganic ions such as chloride, sulfate, nitrate, bicarbonate, and carbonate ions which were detected in the river water sample. Higher concentration of chloride enhanced the degradation due to the salting out mechanism. The enhancement of degradation in the presence of nitrate is mainly due to the change in the surface potential at the interface of the cavitating bubble. Bicarbonate ion and carbonate ion enhanced the degradation due to the involvement of carbonate radicals. A possible degradation mechanism is proposed based on the product profile determined by LC-Q-ToF-MS. The low efficiency of degradation in river water compared to that in pure water is likely due to the increased rate of bubble dissolution or escape of bubbles (degassing effect), and the scavenging of • OH by the organic content (high chemical oxygen demand (COD)).

The study on the possible pathway of hydroxyl radicals mediated sonolytic degradation of paraben in water is reported. Methylparaben (MPB) which is the most utilized of paraben family is selected as a model emerging pollutant. The influence of common anions and some selected emerging contaminants that may coexist in typical water matrix on the degradation pattern is analyzed alongside. Among the anions, carbonate presents a negative influence which is attributed to the competition for OH radical. Some emerging contaminants also showed negative impact on degradation as was clear from HPLC data. The intermediates, analyzed by LC-Q-TOF-MS include hydroxylated and hydrolytic products. Three major steps (aromatic hydroxylation, hydroxylation at the ester chain and hydrolysis) are proposed to involve in the reaction of OH radical with MPB which ultimately leads to mineralization. The intensity of formation and decay of mono and dihydroxy products of MPB in the presence of additives have also been evaluated. COD analysis indicates a percentage reduction of 98% at 90 min of sonolysis and further increase in the degradation time resulted complete mineralization, which became evident from the mass spectrometric data. MTT assay revealed considerable decrease in the potential cytotoxicity., (Copyright © 2015 Elsevier B.V. All rights reserved.)

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 (200 kHz, 350 kHz, 620 kHz and 1 MHz) and power density (3.5 W mL(-1), 9.8 W mL(-1) and 19.6 W mL(-1)) on the degradation profile was evaluated. The optimum performance was obtained at 350 kHz and 19.6 W mL(-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(-4) M), hydrogen peroxide (1×10(-4) M), and peroxodisulphate (1×10(-4) M) 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., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Atenolol is a β-blocker drug and an identified emerging pollutant. Advanced oxidation processes (AOPs) utilise the reaction of a highly oxidising species (hydroxyl radicals, (•)OH) for the mineralisation of emerging pollutants since conventional treatment methodologies generally fail to degrade these compounds. In the present work, degradation of atenolol was carried out using ultrasound with frequencies ranging from 200 kHz to 1 MHz as a source of hydroxyl radical. The degradation was monitored by HPLC, total organic carbon (TOC) and chemical oxygen demand (COD) reduction and ion chromatography (IC). Nearly 90 % of degradation of atenolol was observed with ultrasound having 350 kHz. Both frequency and power of ultrasound affect the efficiency of degradation. Nearly 100 % degradation was obtained at a pH of 4. Presence of various additives such as sodium dodecyl sulphate, chloride, sulphate, nitrate, phosphate and bicarbonate was found to reduce the efficiency of degradation. Although nearly 100 % degradation of atenolol was observed under various experimental conditions, only about 62 % mineralisation (from TOC and COD measurements) was obtained. Nearly eight intermediate products were identified using high-resolution mass spectrometry (LC-Q-TOF). These products were understood as the results of hydroxyl radical addition to atenolol. The degradation studies were also carried out in river water which also showed a similar degradation profile. A mechanism of degradation and mineralisation is presented.

Oxidative degradation of fensulfothion, a model organophosphorus compound, has been investigated by pulse radiolysis and H2O2/UV photolysis. A nearly complete transformation of fensulfothion was observed within 4min of irradiation. Very little Total Organic Carbon (TOC) reduction was obtained at this time scale. When the product studies at this stage were conducted using LC-MS/MS analyses, nearly 20 transformation products were obtained. The entire products were identified as from the reaction of OH with fensulfothion or with some of its initially transformed products. Nearly 80% reduction in TOC was observed when photolysis was conducted using higher concentrations of H2O2 at longer time scale. A reaction rate constant (bimolecular) of 1.10×10(10)dm(3)mol(-1)s(-1) was obtained for the reaction of OH with fensulfothion using pulse radiolysis technique. The transient absorption spectrum obtained from the reaction of OH has a maximum at 280nm and a weak, broad maximum around 500nm along with a small shoulder around 340nm. The intermediate spectrum is assigned to the radical cation of fensulfothion (3) and the hydroxyl radical adducts (1 and 2). This assignment is supported by the intermediate spectrum (λmax at 280nm) from the reaction of sulfate radical anion (SO4(-)) (k2=3.20×10(9)dm(3)mol(-1)s(-1)) which is a one electron oxidant. It is thus demonstrated that the combination of both pulse radiolysis and the product estimation using LC-MS/MS is ideal in probing the complete mechanism which is very important in the mineralization reactions using Advanced Oxidation Processes., (Copyright © 2012 Elsevier Ltd. All rights reserved.)