Layer-by-layer assembled graphitic carbon nitride membranes for water treatment.

Meeting societal demand for potable water supply remains one of the prioritized challenges faced in the modern era. The anthropogenic intervention has led to a dire situation threatening ecological balance and human health. There is an inevitable need for the development of new technologies and innovations in existing technologies for water treatment. Photocatalytic Membrane technology, encompassing the merits of membrane filtration and photocatalytic degradation has evolved as a potential and reliable technology for sustainable water treatment. Innovations in photocatalytic materials and membrane fabrication techniques can lead to the goal of commercialization of membrane water treatment technology. Herein, we demonstrate the potential of graphitic carbon nitride (g-C3N4) and its functionalized analog as photocatalytic membranes for sustainable water treatment. g-C3N4 and Tetracarboxyphenylporphyrin sensitized g-C3N4 (g-C3N4/TCPP) was introduced onto commercial nylon membrane surface via a layer-by-layer (LBL) assembly method using chitosan and sodium salt of polystyrene sulphonic acid as polyelectrolytes. The fabricated membranes were characterized to ensure the integration of the photocatalysts. The performance of the membranes for water treatment was assessed by selecting some common dyes as model pollutants. The modified membranes exhibited excellent flux recovery and could afford high rejection rates upon irradiation indicating the prospects for sustainable filtration.

Occurrence and distribution of steroid hormones (estrogen) and other contaminants of emerging concern in a south indian water body.

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 ß 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.

Human exposure to methyl and butyl parabens and their transformation products in settled dust collected from urban, semi-urban, rural, and tribal settlements in a tropical environment.

The present study involved monitoring the distribution of two widely consumed parabens (methyl paraben (MeP) and butyl paraben (BuP)) and their transformation products in indoor dust from different categories of settlement (urban, semi-urban, rural, and tribal homes). The results revealed a prevalent occurrence of parabens in all the settlement categories. A non-normal distribution pattern for MeP and BuP levels across the sampling sites was noted. While comparing the residence time of parabens in dust samples, it was found that the half-lives of the analytes were greater in the dust from urban (MeP t1/2: 47.510 h; BuP t1/2: 22.354 h) and rural (MeP t1/2: 27.725 h and BuP t1/2: 31.500 h) areas. The presence of paraben metabolites, such as hydroxy methylparaben (OH-MeP), para hydroxy benzoic acid (p-HBA), and benzoic acid (BA) in dust samples supports their transformation within indoor spaces. The average daily intake of parabens through dust ingestion and dermal absorption by children was higher than adults. BuP was the prime contributor (>85%) to the total estradiol equivalency quotient (tEEQ) in all the settlement categories.

Organic micropollutant removal and phosphate recovery by polyelectrolyte multilayer membranes: Impact of buildup interactions.

Polyelectrolyte multilayer (PEM) deposition conditions can favorably or adversely affect the membrane filtration performance of various pollutants. Although pH and ionic strength have been proven to alter the characteristics of PEM, their role in determining the buildup interactions that control filtration efficacy has not yet been conclusively proved. A PEM constructed using electrostatic or non-electrostatic interactions from controlled deposition of a weak polyelectrolyte could retain both charged and uncharged pollutants from water. The fundamental relationship between polyelectrolyte charge density, PEM buildup interaction, and filtration performance was explored using a weak-strong electrolyte pair consisting of branching poly (ethyleneimine) and poly (styrene sulfonate) (PSS) across pH ranges of 4-10 and NaCl concentrations of 0 M-0.5 M. PEI/PSS multilayers at acidic pH were dominated by electrostatic interactions, which favored the selective removal of a charged solute, phosphate over chloride, while at alkaline pH, non-electrostatic interactions dominated, which favored the removal of oxybenzone (OXY), a neutral hydrophobic solute. The key factor determining these interactions was the charge density of PEI, which is controlled by pH and ionic strength of the deposition solutions. These findings indicate that the control of buildup interactions can largely influence the physico-chemical and transport characteristics of PEM membranes.

Degradation studies of bisphenol S by ultrasound activated persulfate in aqueous medium.

The degradation of recalcitrant organic pollutants by sulphate radical (SO4•-) represents one of the most recent developments in oxidation-based water treatment. In most cases, persulfate (PS) acts as a precursor of sulphate radicals. This study employed ultrasound-activated PS to generate reactive species, facilitating the degradation of bisphenol S (BPS), a well-known contaminant of emerging concern (CECs). An ultrasound with a frequency of 620 kHz and 80 W power was utilised for the degradation studies. The applied oxidation system successfully resulted in the complete degradation of BPS in both pure and real environmental water samples. Additionally, the Chemical oxygen demand (COD) was reduced to an acceptable limit in both matrices, with a reduction of 85 % in pure water and 73 % in river water. The degradation was monitored by varying chemical parameters such as pH, inorganic ions, and organics concentration. The results indicate that under specific pH conditions, the degradation efficiency followed the order of pH 3 > 4 > 7 > 11. The presence of coexisting matrices suppressed the efficiency by scavenging the reactive species. Utilizing high-resolution mass spectrometry (HRMS) analysis, this study identified seven intermediate products during identified during the degradation of BPS. Furthermore, a comprehensive mechanism has been deduced for the transformation and degradation process. All the results presented in this study underscore the applicability of the US/PS system in the removal of CECs.

Singlet oxygen in the removal of organic pollutants: An updated review on the degradation pathways based on mass spectrometry and DFT calculations.

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.

Delineating the cascade of molecular events in protein aggregation triggered by Glyphosate, aminomethylphosphonic acid, and Roundup in serum albumins.

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 ß-sheet fractions at the expense of α-helix. The highest percentage, 24.6%, of antiparallel ß-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.

Spectro-kinetic investigations on the release mechanism of lysozyme from layer-by-layer reservoirs.

The investigations of protein adsorption and release on interfaces aid in the elucidation of the protein-surface interaction mechanism, which has several applications in the biomedical area. The spectro-kinetic and morphological analysis of the release of lysozyme (Lyz) from chitosan/polystyrene sulphonate (CHI/PSS) multilayer immobilized at pHs 10.6, 8.8 and 5.0 shows that the extent of release strongly depends on the pH of Lyz loading and the ionic strength of the desorbing solution. When compared to pH 8.8, the release for pH 10.6 achieves equilibrium more rapidly. At loading pH 10.6, the release is surface-mediated, at pH 8.8, it is both surface- and bulk-mediated, while at pH 5.0 it is bulk mediated with minimal release. Lyz released for loading pH 10.6 retains its native secondary structure. Kinetic fitting suggests that high loading pH 8.8-10.6 and high release ionic strength (0.5-1.0 M NaCl) lead to burst release of Lyz from CHI/PSS multilayer. Surface morphology changes of multilayer interface upon Lyz loading and release are highlighted by SEM topography and AFM height distribution analysis. The present work indicates that CHI/PSS multilayer system can function as a reservoir for burst as well as controlled release of lysozyme by selecting the loading pH and ionic strength.

Bio-physical and computational studies on serum albumin / target protein binding of a potential anti-cancer agent.

The successful evolution of an effective drug depends on its pharmacokinetics, efficiency and safety and these in turn depend on the drug-target/drug-carrier protein binding. This work, deals with the interaction of a pyridine derivative, 2-hydroxy-5-(4-methoxyphenyl)-6-phenylpyridine 3-carbonitrile (HDN) with serum albumins at physiological conditions utilizing the steady state and time-resolved fluorescence techniques by probing the emission behavior of Trp in BSA and HSA. In-silico studies revealed a combined static and dynamic quenching mechanism for the interactions. The binding studies suggests a spontaneous binding between HDN and the albumins with a moderate binding affinity (Kb ∼ 10-5 M-1) with a single class of binding site. The FRET mediated emission from HDN indicates preferential binding of HDN in subdomain IIA of the albumins with Trp residue in close proximity. Circular dichroism results indicate HDN induced conformational changes for BSA and HSA, but the α-helical secondary structure was well preserved even up to a concentration of 10 µM HDN. Moderate binding affinity of HDN with BSA and HSA and the unaltered secondary structure of proteins on binding propose the potential application of HDN as an efficient drug. The application of docking method on the affinity of HDN towards the proposed target/receptor is discussed.

Identification of micropollutants from graywater of different complexity and remediation using multilayered membranes.

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.

ATR-FTIR and LC-Q-ToF-MS analysis of indoor dust from different micro-environments located in a tropical metropolitan area.

Indoor dust is an important matrix that exposes humans to a broad spectrum of chemicals. The information on the occurrence of contaminants of emerging concern (CECs), their metabolites, and re-emerging contaminants in indoor dust is rather limited. As the indoor environment is exposed to various chemicals from personal care products, furniture, building materials, machineries and cooking/cleaning products, there is a high chance of the presence of hazardous contaminants in indoor dust. In the present study, dust samples were collected from four different micro indoor environments (photocopying centres, residential houses, classrooms, and ATM cabins) located in an urban environment located in India's southwestern part. The collected samples were subjected to ATR - FTIR and LC-Q-ToF-MS analyses. The ATR - FTIR analysis indicated the presence of aldehydes, anhydrides, carboxylic acids, esters, sulphonic acids, and asbestos - a re-emerging contaminant. A total of 19 compounds were identified from the LC-Q-ToF-MS analysis. These compounds belonged to various classes such as plasticisers, plasticiser metabolites, photoinitiators, personal care products, pharmaceutical intermediates, surfactants, and pesticides. To the best of our knowledge, this is the first report regarding the presence of CECs in indoor environments in Kerala and also the suspected occurrence of pesticides (metaldehyde and ethofumesate) in classroom dust in India. Another important highlight of this work is the demonstration of ATR-FTIR as a complementary technique for LC-Q-ToF-MS in the analysis of indoor pollution while dealing with totally unknown pollutants. These results further highlight the occurrence of probable chemically modified metabolites in the tropical climatic conditions in a microenvironment.

Alcohol ethoxysulfates (AES) in environmental matrices.

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.

Potential involvement of environmental triggers in protein aggregation with mercuric chloride as a model.

Heavy metal based toxicity has a direct relation with the perturbation of protein structure. We have investigated the progressive unfolding of ovalbumin, in the presence of increasing concentration mercury (0-6.25 µM) using different spectroscopic techniques. Formation of amorphous aggregate has been observed at the physiological pH. Initial addition of HgCl2 resulted in the association of monomers to oligomers that proceeded to non-fibrillar aggregates on further addition. The sigmoidal curve obtained from the Stern-Volmer plot clearly divided into three stage transition. A strong lag phase is observed indicating the time dependence for the association of competent monomers. The second stage was resolved into non-cooperative binding. These results match very well with the data from atomic force microscopy and the free energy change observed in the regions. Raman spectroscopic studies indicated toxic antiparallel ß-sheets structure. Time dependent atomic force microscopy study revealed the off-pathway nature of amorphous aggregates. At molten globular state, similar quenching behaviour is observed. The atomic force microscopy images clearly indicate at pH 2.2 the initiation of fibril formation occurs at lower concentration of HgCl2 itself. Our results revealed the conformation switch of ovalbumin upon the contact of an environmental toxin and its possible way of toxicity.

Probing the Role of Cu(II) Ions on Protein Aggregation Using Two Model Proteins.

Copper is an essential trace element for human biology where its metal dyshomeostasis accounts for an increased level of serum copper, which accelerates protein aggregation. Protein aggregation is a notable feature for many neurodegenerative disorders. Herein, we report an experimental study using two model proteins, bovine serum albumin (BSA) and human serum albumin (HSA), to elucidate the mechanistic pathway by which serum albumins get converted from a fully folded globular protein to a fibril and an amorphous aggregate upon interaction with copper. Steady-state fluorescence, time-resolved fluorescence studies, and Raman spectroscopy were used to monitor the unfolding of serum albumin with increasing copper concentrations. Steady-state fluorescence studies have revealed that the fluorescence quenching of BSA/HSA by Cu(II) has occurred through a static quenching mechanism, and we have evaluated both the quenching constants individually. The binding constants of BSA-Cu(II) and HSA-Cu(II) were found to be 2.42 × 104 and 0.05 × 104 M-1, respectively. Further nanoscale morphological changes of BSA mediated by oligomers to fibril and HSA to amorphous aggregate formation were studied using atomic force microscopy. This aggregation process correlates with the Stern-Volmer plots in the absence of discernible lag phase. Raman spectroscopy results obtained are in good agreement with the increase in antiparallel ß-sheet structures formed during the aggregation of BSA in the presence of Cu(II) ions. However, an increase in α-helical fractions is observed for the amorphous aggregate formed from HSA.

Occurrence, distribution and removal of organic micro-pollutants in a low saline water body.

A low saline backwater canal, mainly utilized for domestic and agricultural purposes, has been analyzed for the possible presence of organic micropollutants (OMP) and their potential removal was explored by multilayered microfiltration membranes. The qualitative as well as quantitative analysis were carried out for a span of one year using the technique of liquid chromatography connected with high resolution mass spectrometry (LC-Q-TOF-MS). The identification of the formally unknown compounds was initially done using non-target analysis based on the mass accuracy, isotopic pattern and MS/MS spectral interpretation. Results of the non target screening revealed the presence of 11 OMPs. Five of these OMPs were confirmed using standards; these include chlorophene (CHP), oxybenzone (OXY), N, N-diethyl-meta-toluamide (DEET), N, N-diethyl-benzamide (DEB) and dibutyl phthalate (DBP). Among the confirmed OMPs, the highest concentration was observed for DBP (244.61 ng l-1). The most frequently observed OMP in the study area was DBP while the least was DEB which is an insect repellent as well as a degradation product of DEET. The ecological risk associated with the target compounds has also been analyzed by calculating the risk quotient (RQ) and the results revealed that at the detected levels, these compounds are capable of causing low to medium risk. Low pressure (<0.3 bar) filtrations of the compounds were attempted using microfiltration (MF) and, poly(ethyleneimine)/poly(styrene sulfonate) (PEI/PSS) multi-layered MF membrane for spiked ultrapure water and also for natural water from the back-water canal. The batch mode illustrates nearly complete removal of CHP and OXY in spiked solutions and a good removal efficiency from natural water. The effect of coexisting ions and surfactants in feed is also illustrated. The high efficiency of the removal of both CHP and OXY, in such a complex medium highlights the potential application of the present method for the removal of similar OMPs in natural waters.

Sonochemical degradation of benzenesulfonic acid in aqueous medium.

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 (Ia-c) and two di (IIa&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 (k2 = (7.16 ± 0.04) × 109 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.

Unravelling the fibrillation mechanism of ovalbumin in the presence of mercury at its isoelectric pH.

The intriguing resemblances of amyloid fibrils and spider silk in protein aggregation diseases have instigated the exploration of identical structural features if any in their oligomeric pathways. The serpin group protein, ovalbumin, on defolding in HgCl2 shares commonness to the micellar pathway of spidroins for their aggregation in response to a pH trigger. The structural feature changes from monomer to worm like fibril with a shift in the primary protein pH to slightly acidic pH (4.5), and then proceeds through a secondary nucleation pathway to 'hillock' and 'hydra' like protofibrils rich in ß-sheet and random coil conformers upon exposure to mercury. The findings are backed by atomic force microscopy, confocal Raman spectroscopy and fluorescence measurements. Unlocking such structural features can favorably assist in the design of therapeutics.

Low - cost multilayered green fiber for the treatment of textile industry waste water.

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.

Effect of inorganic ions on the ultrasound initiated degradation and product formation of triphenylmethane dyes.

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.

Screening and quantification of emerging contaminants in Periyar River, Kerala (India) by using high-resolution mass spectrometry (LC-Q-ToF-MS).

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.