Efficient treatment of secondary treated refinery wastewater using sand biofiltration: Removal of hazardous organic pollutants.

This study explored the potential of sand biofiltration for tertiary treatment of real refinery wastewater. The biofilter (2 cm (I.D.) x 15 cm (L)) operated on secondary treated refinery wastewater at flow rate of 1 mL/min had empty bed contact time (EBCT) of 47.12 min for one circulation. Maximum reduction in COD after 4, 8 and 12 times recirculation was 25 %, 52 % and 56 %; while the TOC reduction was 33 %, 43 % and 51 %, respectively, after biofilm development over 30 days. Quantification using two dimensional gas chromatography - time of flight mass spectrometry (GCxGC-TOF MS) revealed that several of the identified target compounds could not be detected in the wastewater after 12 recirculations. After 8 times recirculation, most of the compounds showed very high removal efficiency. For biofiltration over the flow rate range 2-10 mL/min, the reduction in COD and NH4+-N ranged from 62-73 % and 78-86 %, respectively, after 8 times recirculation. The nitrite concentration first increased and subsequently decreased, while the nitrate concentration continuously increased with increase in the number of recirculations. Solid phase micro-extraction (SPME) analysis of the aqueous phase using GCxGC-TOF MS and a semi-quantitative approach indicated that the removal of predominant classes of compounds was greater than 95 % after 8 times recirculation, with maximum reduction occurring in the first pass through the biofilter. Assimilable organic carbon (AOC) reduction was 98 % after 8 times recirculation. Metagenomic analysis revealed that Proteobacteria was the most dominant phylum in the biofilter. Many known polynuclear aromatic hydrocarbon (PAH) degraders, such as Sphingomonadales, Burkholderiales, Rhodobacterales and Rhodospirillales, were found in the biofilter leading to high removal efficiency of hazardous organic pollutants.

Essential oil mediated synthesis and application of highly stable copper nanoparticles as coatings on textiles and surfaces for rapid and sustained disinfection of microorganisms.

Rampant pathogenesis induced by communicable microbes has necessitated development of technologies for rapid and sustained disinfection of surfaces. Copper nanoparticles (CuNPs) have been widely reported for their antimicrobial properties. However, nanostructured copper is prone to oxidative dissolution in the oil phase limiting its sustained use on surfaces and coatings. The current study reports a systematic investigation of a simple synthesis protocol using fatty acid stabilizers (particularly essential oils) for synthesis of copper nanoparticles in the oil phase. Of the various formulations synthesized, rosemary oil stabilized copper nanoparticles (RMO CuNPs) were noted to have the best inactivation kinetics and were also most stable. Upon morphological characterization by TEM and EELS, these were found to be monodispersed (φ5-8 nm) with copper coexisting in all three oxidation states on the surface of the nanoparticles. The nanoparticles were drop cast on woven fabric of around 500 threads per inch and exposed to gram positive bacteria (Staphylococcus aureus), gram negative bacteria (Escherichia coliandPseudomonas aeruginosa), enveloped RNA virus (phi6), non-enveloped RNA virus (MS2) and non-enveloped DNA virus (T4) to encompass the commonly encountered groups of pathogens. It was possible to completely disinfect 107copies of all microorganisms within 40 min of exposure. Further, this formulation was incorporated with polyurethane as thinners and used to coat non-woven fabrics. These also exhibited antimicrobial properties. Sustained disinfection with less than 9% cumulative copper loss for upto 14 washes with soap water was observed while the antioxidant activity was also preserved. Based on the studies conducted, RMO CuNP in oil phase was found to have excellent potential of integration on surface coatings, paints and polymers for rapid and sustained disinfection of microbes on surfaces.

A portable EIS-based biosensor for the detection of microcystin-LR residues in environmental water bodies and simulated body fluids.

Due to the eutrophication of water bodies around the world, there is a drastic increase in harmful cyanobacterial blooms leading to contamination of water bodies with cyanotoxins. Chronic exposure to cyanotoxins such as microcystin leads to oxidative stress, inflammation, and liver damage, and potentially to liver cancer. We developed a novel and easy-to-use electrochemical impedance spectroscopy-based immunosensor by fabricating stencil-printed conductive carbon-based interdigitated microelectrodes and immobilising them with cysteamine-capped gold nanoparticles embedded in polyaniline. It has been also coupled with a custom handheld device enabling regular on-site assessment, especially in resource-constrained situations encountered in developing countries. The sensor is able to detect microcystin-LR up to 0.1 µg L-1, having a linear response between 0.1 and 100 µg L-1 in lake and river water and in serum and urine samples. In addition to being inexpensive, easy to fabricate, and sensitive, it also has very good selectivity.

Fate, detection technologies and toxicity of heterocyclic PAHs in the aquatic and soil environments.

Heterocyclic polynuclear aromatic hydrocarbons (PAH) are characterized by higher aqueous solubility and enhanced bioavailability due to presence of nitrogen, sulfur or oxygen heteroatoms in their chemical structure and are referred to as nitrogen (PANH), sulfur (PASH) and oxygen (PAOH) heterocyclic PAHs, respectively. Inspite of their significant ecotoxicity and human health impacts, these compounds have not yet been included in the U.S. EPA's list of "priority PAH". The current paper presents a comprehensive review of the environmental fate, various detection techniques and toxicity of heterocyclic PAH compounds, highlighting their significant environmental impacts. Heterocyclic PAHs have been detected at 0.03 to 11,000 ng/L in various aquatic bodies and at 0.1 to 3210 ng/g in contaminated land. PANHs are the most polar heterocyclic PAHs, having aqueous solubility at least 10 to 10,000 times higher than PAH, PASH, and PAOH compounds, which make them more bioavailable. Aquatic fate of heterocyclic PAHs is dominated by volatilization and biodegradation processes for low molecular weight (MW) compounds and photochemical oxidation for high MW compounds. Sorption of heterocyclic PAHs on soil is governed by partitioning to soil organic carbon, cation exchange, and surface complexation mechanisms for PANHs and non-specific interactions, such as van der Waals forces with soil organic carbon for PASHs and PAOHs. Various chromatographic and spectroscopic techniques, such as HPLC and GC, NMR, and TLC have been employed to elucidate their distribution and fate in the environment. PANHs are also the most acutely toxic heterocyclic PAHs with EC50 values ranging from 0.001 to 1100 mg/L in various species of bacteria, algae, yeast, invertebrate, and fish. Heterocyclic PAHs also induce mutagenicity, genotoxicity, carcinogenicity, teratogenicity, and phototoxicity in various aquatic and benthic organisms and terrestrial animals. Compounds, such as 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) and some acridine derivatives are proven human carcinogens and several other heterocyclic PAHs are suspected human carcinogens.

Photodegradation of a mixture of five pharmaceuticals commonly found in wastewater: Experimental and computational analysis.

Photochemical transformation of pharmaceuticals plays an important role in their natural attenuation, especially in lagoon-based wastewater treatment plants and surface waters receiving substantial sunlight. In this study, the photodegradation of five important pharmaceuticals was studied in samples obtained from a wastewater treatment plant and surface water sources. Batch photodegradation studies for a mixture of pharmaceuticals (diclofenac, sulfamethoxazole, acetaminophen, carbamazepine and gemfibrozil) were carried out in a photochemical reactor. Multiple aliquots of samples removed from the reactor during the experiment were analyzed through high-performance liquid chromatography (HPLC) coupled to a photodiode array (PDA) detector. Intermediate products formed due to photodegradation were identified by ultra-high-performance liquid chromatography coupled with a time-of-flight mass spectrometry (UHPLC-MS/MS). Diclofenac and sulfamethoxazole were found to undergo direct photodegradation due to strong light absorption, whereas the indirect route of photosensitized degradation in the presence of dissolved organic matter (DOM) and model humic acid was significant for acetaminophen, carbamazepine, and gemfibrozil. The reactive radicals such as hydroxyl (OH•), singlet oxygen (1O2) and excited states of DOM (*DOM) were predominantly responsible for the indirect photodegradation of acetaminophen, gemfibrozil and carbamazepine, respectively. Computational analysis revealed that chlorine and carbon atoms belonging to the benzene ring of diclofenac were more reactive to radical attack. Sulfamethoxazole photodegradation occurred through oxidation of the NH2 group. Acetaminophen was more susceptible to electrophilic radical attack at the O-11, and N-7 positions and carbon atoms ortho to the phenolic oxygen and the amine group. The double bonds between C-7, C-8 and C-13 were the most reactive sites for carbamazepine that participated in the phototransformation pathway. Organic matter plays a critical role in the photodegradation of emerging contaminants. The coupling of DFT calculations with UHPLC-MS/MS analysis provided insights on key functional groups participating in the phototransformation pathway. Thus, both parent pharmaceuticals and the photodegradation intermediates should be considered during wastewater treatment.

Slurry phase biodegradation of heavy oily sludge and evidence of asphaltene biotransformation.

Oily sludge management is a global environmental concern due to its hazardous nature. Oily sludge obtained from a refinery in India had 19-21% oil content. The oil was highly enriched in the asphaltene fraction. Slurry phase biodegradation of this oily sludge in presence of a 3-membered bacterial consortium was optimized in presence of Triton X-100 to increase the bioavailability of hydrocarbons. Triton X-100 at 4 times the critical micelle concentration (CMC) showed the highest degradation where oil removal of 53.1% was achieved from a 10% sludge slurry over 90 days. GCxGC analysis of n-alkanes present in the oily sludge after the biodegradation study showed an increase in the lower n-alkanes, i.e., dodecane and tridecane over the first 30 days, whereas the higher n-alkanes were removed to a much higher extent. Heptadecane showed the maximum extent of degradation with 94.9% removal in 90 days and an initial degradation rate of 0.079 day-1. The, maximum rate of degradation was observed for pentacosane (0.083 day-1) with 93.7% removal in 90 days. The increase in the lower n-alkanes may be attributed to biotic transformation of the asphaltene fraction which was also confirmed through FTIR and pyrolysis GCxGC analysis. Biodegradation was found to cause changes in the pyrolysis product of asphaltenes where four and three-ring pyrolysis products decreased while the one and two-ring pyrolysis products increased. In presence of the consortium asphaltene removal over 90 days was 12% whereas only 0.4% removal was obtained in the abiotic controls.

Photocatalytic activity of graphene oxide-TiO2 nanocomposite on dichlorvos and malathion and assessment of toxicity changes due to photodegradation.

Heterogeneous photocatalysis was used for the removal of two widely used organophosphorus pesticides, dichlorvos, and malathion from water. Graphene oxide-TiO2 nanocomposite (GOT) was synthesized and used as a photocatalyst for the removal of these pesticides. Batch studies for optimizing photocatalytic degradation and mineralization of pesticides over 80 min were conducted by varying the pH (2-10), catalyst dose (20 mg/L-200 mg/L), and initial pesticide concentration (0.5 mg/L-20 mg/L), and the irradiation source (125 W UV and visible lamp). Degradation kinetics for the pesticides were evaluated. Ellman assay was used to estimate the toxic effect of pesticides and evaluate toxicity reduction due to treatment. The highest degradation and mineralization of dichlorvos and malathion was observed at pH 6 and the optimum catalyst dose was 60 mg/L. Under UV irradiation, 80% and 90% degradation were observed for dichlorvos and malathion, respectively for 0.5 mg/L initial pesticide concentration. The photocatalytic degradation reaction followed Langmuir-Hinshelwood kinetics. A high degree of mineralization was achieved for both the pesticides. Analysis of the results revealed that the residual toxic effect after photocatalysis was primarily due to the residual parent compound. A comparative study revealed that GOT yielded better pesticide degradation compared to commercially available TiO2 under both UV and visible irradiation.

Performance of treatment schemes comprising chromium-hydrogen peroxide-based advanced oxidation process for textile wastewater.

The present study investigated the performance of a chromium-based advanced oxidation process using chromium (as Cr3+ or Cr6+) and H2O2 for the treatment of synthetic and simulated textile wastewaters. With the Cr3+/H2O2 system, the maximum total organic carbon (TOC) and color removals from the synthetic dye wastewater (Remazol Brilliant Violet 5R dye concentration = 100 mg/L) were 75% and 99%, respectively, within 30 min duration ([Cr3+]:[H2O2] = 1:30, stoichiometric H2O2 dose = 2.01 ml/L and pH = 7). Whereas the same catalyst and oxidant combination resulted in chemical oxygen demand (COD) and color removals of ~ 46%, and 84%, respectively, after 3 h of reaction at the optimized reaction conditions (i.e., [Cr3+]:[H2O2] = 1:50, stoichiometric H2O2 dose = 11.6 ml/L and pH = 7) from the simulated textile wastewater (initial pH = 10.2, and COD = 1820 mg/L). Further, the addition of stoichiometric H2O2 dose to the pretreated wastewater and pH adjustment increased the overall COD removal to 77%. Both oxidation and precipitation reactions were found responsible for organics removal from the wastewater. The other alternative involving activated carbon adsorption as second step, was not found as effective as the above scheme. The data on COD removal from simulated textile wastewater could be fit adequately in the retarded first-order kinetic model. Based on the COD and color removal results and preliminary cost analysis, this can be suggested that the Cr3+/H2O2 oxidation process followed by pH adjustment and further H2O2 treatment was the best option for the removal of COD and color from the simulated combined textile wastewater.

Characterization and biodegradability assessment of water-soluble fraction of oily sludge using stir bar sorptive extraction and GCxGC-TOF MS.

Percolation of water through oily sludge during storage and handling of the sludge can cause soil and groundwater contamination. In this study, oily sludge from a refinery was equilibrated with water to obtain the water-soluble fraction (WSF) of oily sludge. The WSF had dissolved organic carbon (DOC) of 166 mg/L. Human cell line-based toxicity assay revealed IC50 of 41 mg/L indicating its toxic nature. The predominant compounds in WSF of oily sludge included isomers of methyl, dimethyl and trimethyl quinolines and naphthalenes along with phenol derivatives and other polynuclear aromatic hydrocarbons (PAHs). Biodegradation of WSF of oily sludge was studied using a consortium of Rhodococcus ruber, Bacillus sp. and Bacillus cereus isolated from the refinery sludge. The consortium of the three strains resulted in 70% degradation over 15 days with a first-order degradation rate of 0.161 day-1. Further analysis of the WSF was performed using the stir-bar sorptive extraction (SBSE) followed by GCxGC-TOF MS employing a PDMS Twister. The GCxGC analysis showed that Bacillus cereus was capable of degrading the quinoline, phenol and naphthalene derivatives in WSF of oily sludge at a faster rate compared to pyridine and benzoquinoline derivatives. Quinoline, phenol, biphenyl, naphthalene, pyridine and benzoquinolines derivatives in the WSF of oily sludge were reduced by 87%, 92%, 88%, 77%, 40% and 62%, respectively with respect to the controls. The WSF of oily sludge contained, n-alkanes, ranging from n-C12 to n-C18 which were removed within 2 days of biodegradation.

Polyphenol stabilized copper nanoparticle formulations for rapid disinfection of bacteria and virus on diverse surfaces.

Rapid and sustained disinfection of surfaces is necessary to check the spread of pathogenic microbes. The current study proposes a method of synthesis and use of copper nanoparticles (CuNPs) for contact disinfection of pathogenic microorganisms. Polyphenol stabilized CuNPs were synthesized by successive reductive disassembly and reassembly of copper phenolic complexes. Morphological and compositional characterization by transmission electron microscope (TEM), selected area diffraction and electron energy loss spectroscopy revealed monodispersed spherical (ϕ5-8 nm) CuNPs with coexisting Cu, Cu(I) and Cu (II) phases. Various commercial grade porous and non-porous substrates, such as, glass, stainless steel, cloth, plastic and silk were coated with the nanoparticles. Complete disinfection of 107copies of surrogate enveloped and non-enveloped viruses: bacteriophage MS2, SUSP2, phi6; and gram negative as well as gram positive bacteria:Escherichia coliandStaphylococcus aureuswas achieved on most substrates within minutes. Structural cell damage was further analytically confirmed by TEM. The formulation was well retained on woven cloth surfaces even after repeated washing, thereby revealing its promising potential for use in biosafe clothing. In the face of the current pandemic, the nanomaterials developed are also of commercial utility as an eco-friendly, mass producible alternative to bleach and alcohol based public space sanitizers used today.

Environmental contamination by heterocyclic Polynuclear aromatic hydrocarbons and their microbial degradation.

Heterocyclic polynuclear aromatic hydrocarbons (PAHs) have been detected in all environmental matrices at few ppb to several ppm concentrations and they are characterized by high polarity. Some heterocyclic PAHs are mutagenic and carcinogenic to humans and various organisms. Despite being potent environmental pollutants, these compounds have received less attention. This paper focuses on the sources and occurrence of these compounds and their microbial degradation using diverse species of bacteria, fungi, and algae. Complete removal of 1.8 to 2614 mg/L of nitrogen heterocyclic PAH (PANH), 0.27 to 184 mg/L of sulfur heterocyclic PAH (PASH), and 0.6 to 120 mg/L of oxygen heterocyclic PAH (PAOH) compounds by various microbial species was observed between 3 h and 18 days, 8 h to 6 days, and 4 h to 250 h, respectively under aerobic condition. Strategies for enhancing the removal of heterocyclic PAHs from aquatic systems are also discussed along with the challenges.

Elucidation of substrate interaction effects in multicomponent systems containing 3-ring homocyclic and heterocyclic polynuclear aromatic hydrocarbons.

Bacterial growth and degradation experiments were conducted on carbazole (CBZ), fluorene (FLU) and dibenzothiophene (DBT) individually and in various mixture combinations using an efficient polynuclear aromatic hydrocarbon (PAH) degrading bacterial strain, Pseudomonas aeruginosa RS1. In single component systems, bacterial growth on CBZ (specific growth rate, µ = 0.99 day-1) was much higher compared to that on FLU (µ = 0.38 day-1) and DBT (µ = 0.33 day-1) and bacterial growth was inhibited in the presence of FLU and DBT in binary (µ = 0.64 day-1) and ternary (µ = 0.75 day-1) mixtures. Multisubstrate additive modelling indicated growth inhibition in all the systems. The degradation of the compounds was significantly inhibited in binary mixtures. While the degradation of the compounds in binary mixtures varied from 35 ± 4% to 73 ± 3%, their degradation varied from 61 ± 5% to 91 ± 4%, when applied as sole substrates and from 77 ± 3% to 96 ± 3%, when applied in a ternary mixture. Degradation experiments were also conducted in ternary mixtures using a 23 full factorial design and the results were examined using analysis of variance (ANOVA) and Tukey's honest significant difference (HSD) tests. At a low concentration of the heterocyclics, CBZ and DBT (5 mg L-1 each), the degradation of the PAH, FLU, was significantly enhanced (from 81 ± 1% to 93 ± 0.3%) when its concentration was increased from 5 to 30 mg L-1. The full factorial design can provide valuable insights into substrate interaction effects in mixtures.

Development and evaluation of DEAE silica gel columns for simultaneous concentration of coliphages and rotavirus from natural water samples.

Enteric viruses are commonly present in water bodies in regions with poor sanitation. Although the occurrence of these viruses poses a health risk they are difficult to quantify due to their low concentration and they may remain undetected in the absence of adequate preconcentration. The present study reports the synthesis and utilization of DEAE silica gel (DSiG) as an adsorbent for virus concentration. Two coliphages, MS2 and SUSP2, and an enteric virus, rotavirus A (RVA) were chosen for examining the preconcentration efficiency of DSiG columns. Studies conducted at a low flow rate of 5 mL/min yielded good removal of viruses through adsorption. Studies at a higher flow rate of 50 mL/min followed by elution with optimized eluents yielded a high recovery of MS2 and RVA even when they were present at low concentration (0.01 copy/mL). The eluent Na(1.5 M)-Tw(2%)-G3X (glycine 3X broth, 1.5 M NaCl, 2% Tween, pH 10.2) showed maximum elution of RVA and MS2. Optimal SUSP2 recovery was observed on employing an eluent composed of 1.5 M NaCl, 3% Tween, 0.05 M KH2PO4 at pH 9.2. Subsequently, both the eluents were successively applied for elution of the adsorbed viruses. This method was applied for virus preconcentration from lake water in the monsoon and winter seasons. The DSiG column could achieve adequate preconcentration for all the three viruses, i.e., SUSP2, MS2, and RVA, even when they were present at very low concentration and the recovery achieved was comparable to that achieved with ultracentrifugation while the processing time required for handling large volumes of water was considerably lower.

Photocatalysis of dichlorvos using graphene oxide-TiO2nanocomposite under visible irradiation: process optimization using response surface methodology.

Graphene oxide-TiO2nanocomposite (GOT) was used for degradation and mineralization of dichlorvos, an organophosphorus pesticide, from aqueous solution under visible irradiation. The nanocomposite was characterized by scanning electron microscopy, transmission electron microscopy, UV-DRS, Fourier-transform infrared spectroscopy, Raman spectroscopy, and x-ray photoelectron spectroscopy. Anatase phase TiO2nanoparticles (10-20 nm in diameter) were present in the nanocomposite. The nanoparticles were uniformly distributed on reduced GO sheets. A three-factor face-centered central composite design with response surface methodology was used for modeling and optimization of various variables that may potentially affect photodegradation, i.e. pH, catalyst loading, and initial dichlorvos concentration. A quadratic model was built to predict degradation, mineralization efficiency, and reaction rate constant. The experimental and predicted values depicted a good correlation and the utility of the models was confirmed by the highF-values observed for the degradation and mineralization models. High coefficient of determination (R2) was obtained for the degradation (R2 = 0.95) and mineralization (R2 = 0.93) models. Pareto analysis was carried out to determine the effect of each variable on photocatalytic degradation and mineralization. The predicted results suggested that the optimum conditions for obtaining maximum degradation (69%) and mineralization (64%) were: initial dichlorvos concentration of 0.5 mg l-1with a catalyst dose of 110 mg l-1at pH 6.5. The main effect plots also suggested a significant influence of the variables used in the photocatalysis of dichlorvos by GOT.

Seasonal variation in fluorescence characteristics of dissolved organic matter in wastewater and identification of proteins through HRLC-MS/MS.

In the present study, wastewater samples acquired from five wastewater treatment plants (WWTPs), located in western India were characterized using fluorescence spectroscopy, and resin-based fractionation was conducted to fractionate DOM into hydrophobic and hydrophilic base, acid, and neutral fractions. Among several fractions, the hydrophilic acid (HIA) and hydrophilic neutral (HIN) fractions were present in higher abundance (more than 50% of DOC) compared to the hydrophilic base (HIB) fraction in both influent and effluent wastewater stream obtained from WWTPs. Tryptophan-like and tyrosine-like substances were also abundant in the influent and effluent stream of WWTPs. Further, LC-MS/MS analysis could identify 235 and 288 DOM proteins in the influent and effluent stream of WWTP-1, respectively. These proteins revealed varying percentage of tryptophan and tyrosine residues. The tryptophan residues primarily contributed to protein-like fluorescence in wastewater. The proteins were further classified based on their role in biological processes, location in the cell, and molecular function. Among several proteins, Alzheimer's and Huntington disease biomarkers were identified at WWTP-1. Their presence in the surface water can serve as an early warning system for wastewater-based epidemiology.

Growth kinetics of Pseudomonas aeruginosa RS1 on fluorene and dibenzothiophene, concomitant degradation kinetics and uptake mechanism.

The current study illustrates the growth kinetics of an efficient PAH and heterocyclic PAH degrading bacterial strain, Pseudomonas aeruginosa RS1 on fluorene (FLU) and dibenzothiophene (DBT) over the concentration 25-500 mg L-1 and their concomitant degradation kinetics. The specific growth rate (µ) was found to lie within the range of 0.32-0.57 day-1 for FLU and 0.24-0.45 day-1 for DBT. The specific substrate utilization rate (q) of FLU and DBT over the log growth phase was between 0.01 and 0.14 mg FLU mg VSS-1 day-1 for FLU and between 0.01 and 0.18 mg DBT mg VSS-1 day-1 for DBT, respectively. The µ and q values varied within a narrow range for both FLU and DBT and they did not follow any specific trend. Dissolution together with direct interfacial uptake was the possible uptake mechanism for both FLU and DBT. The q values over the log growth phase depicts the specific substrate transformation rates. Kirby-Bauer disc diffusion studies performed using an E. coli strain indicated accumulation of some toxic intermediates of FLU and DBT during their degradation. Decrease in TOC and toxicity towards the end of the degradation experiments indicates further utilization of the intermediates. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s13205-021-02742-7.

Efficacy and reusability of mixed-phase TiO2-ZnO nanocomposites for the removal of estrogenic effects of 17ß-Estradiol and 17α-Ethinylestradiol from water.

Photocatalytic removal of estrogenic compounds (ECs), 17ß-estradiol (E2), and 17α-ethinylestradiol (EE2) were assessed using a TiO2-ZnO nanocomposite (NC) over a range of initial EC concentration (Co; 10 mg/L - 0.05 mg/L). Photocatalytic removal was evaluated under UV and visible irradiation using 10 mg/L NC over 240 min duration. After 240 min, analysis using GCxGC TOF MS revealed 100% transformation at Co ≤ 1 mg/L and ≥25% transformation at Co ≤ 10 mg/L under visible irradiation. Degradation was accompanied by breakdown of the fused ring structure of E2, generating smaller molecular weight by-products which were subsequently mineralized as revealed through TOC removal. With UV photocatalysis, ~30% and ~20% mineralization was attained for E2 and EE2, respectively, for Co of 10 mg/L. Under visible irradiation, ~25% and ~10% mineralization was achieved for E2 and EE2, respectively. Estrogenicity variation was estimated using the E-screen assay conducted with estrogen receptor-positive MCF-7 breast cancer cells. Complete removal of estrogenicity of ECs was confirmed after 240 min of photocatalysis under UV and visible irradiation. FTIR spectroscopy-based analysis of the NC after E2 photocatalysis revealed the presence of sorbed organics. Desorption, followed by GC × GC TOF-MS analysis revealed these organics as by-products of photocatalysis. Desorption of sorbed organics followed by recalcination at 600 °C for 1 h regenerated the active sites on the NC, enabling its efficient reuse for 3 cycles under visible irradiation without loss in activity.

Antiviral application of colloidal and immobilized silver nanoparticles.

This study explored the application of colloidal and immobilized silver nanoparticles (AgNPs) for inactivation of bacteriophages. Coliphages that are commonly used as indicators for enteric viruses, were used in this study. Colloidal AgNPs were synthesized via a chemical reduction approach using sodium borohydride as reducing agent and trisodium citrate as stabilizing agent. AgNP-immobilized glass substrate was prepared by immobilizing AgNPs on amine-functionalized glass substrate by post-immobilization method. The AgNP-immobilized glass substrate was also tested so as to minimize the release of AgNPs in the treated water. The characterization of AgNPs and the AgNP-immobilized glass surface was done using field emission gun-transmission electron microscopy and scanning electron microscopy. Studies conducted with varying concentrations of colloidal AgNPs displayed good antiviral activity for MS2 and T4 bacteriophage. Colloidal AgNPs at a dose of 60 µg ml-1 could completely inactivate MS2 and T4 bacteriophage within 30 and 50 min with an initial concentration of 103 PFU ml-1. Contaminated water (100 ml) in an unstirred batch reactor with an initial bacteriophage concentration of 103 PFU ml-1 could be inactivated by the AgNP-immobilized glass substrate (1 cm × 1 cm, containing 3.7 µg cm-2 silver) suspended centrally in the batch reactor. Complete 3-Log bacteriophage inactivation was achieved within 70 and 80 min for MS2 and T4 bacteriophage, respectively, while the aqueous silver concentration was less than 25 µg l-1. This is significantly lower than the recommended standard for silver in drinking water (i.e. 100 µg l-1, US EPA). Thus, AgNP-immobilized glass may have good potential for generating virus-free drinking water.

Evanescent Wave Optical Fiber Sensors Using Enzymatic Hydrolysis on Nanostructured Polyaniline for Detection of ß-Lactam Antibiotics in Food and Environment.

ß-Lactam antibiotics such as penicillins and cephalosporins are extensively used for human infection therapy. Consistent unintended exposure to these antibiotics via food and water is known to promote antibiotic-resistant bacterial pathogenesis with high morbidity and mortality in humans. An optical enzymatic biosensor for rapid and point-of-use detection of these antibiotics in food and water has been developed and tested. Enzymatic hydrolysis of ß-lactams, on the electroactive polyaniline nanofibers, altered the polymeric backbone of the nanofibers, from emeraldine base form to emeraldine salt, which was measured as an increase in evanescent wave absorbance at 435 nm. The sensors were calibrated by spiking antibiotic-free milk with ceftazidime (as a model ß-lactam analyte) in a linear range of 0.36-3600 nM (R2 = 0.98). The calibration was further validated for packaged milk, local cow milk, and buffalo milk. A similar calibration was devised for chicken meat samples in a linear range of 9-1800 nM (R2 = 0.982) and tap water in a linear range of 0.18-180 nM (R2 = 0.99). Interestingly, it was possible to use the same calibration for the determination of other ß-lactam antibiotics (ampicillin, amoxicillin, and cefotaxime), which reflects the usefulness of the sensor for wide-scale deployment. The sensor performance was validated with a wastewater sample, from a wastewater treatment plant (WWTP), qualitatively analyzed by high-resolution liquid chromatography coupled with mass spectroscopy for detection of ß-lactams. The sensor scheme developed and tested is of grassroot relevance as a quick solution for measurement of ß-lactam residues in food and environment.