Javed Ali Khan

Efficient removal of endosulfan from aqueous solution by UV-C/peroxides: A comparative study

This study explored the efficiency of UV-C-based advanced oxidation processes (AOPs), i.e., UV/S2O8(2-), UV/HSO5(-), and UV/H2O2 for the degradation of endosulfan, an organochlorine insecticide and an emerging water pollutant. A significant removal, 91%, 86%, and 64%, of endosulfan, at an initial concentration of 2.45 μM and UV fluence of 480 mJ/cm(2), was achieved by UV/S2O8(2-), UV/HSO5(-), and UV/H2O2 processes, respectively, at a [peroxide]0/[endosulfan]0 molar ratio of 20. The efficiency of these processes was, however, inhibited in the presence of radical scavengers, such as alcohols (e.g., tertiary butyl alcohol and isopropyl alcohol) and natural organic matter (NOM). The inhibition was also influenced by common inorganic anions in the order of nitrite > bicarbonate > chloride > nitrate ≈ sulfate. The observed pseudo-first-order rate constant decreased while the degradation rate increased with increasing initial concentration of the target contaminant. The degradation mechanism of endosulfan by the AOPs was evaluated revealing the main by-product as endosulfan ether. Results of this study suggest that UV-C-based AOPs are potential methods for the removal of pesticides, such as endosulfan and its by-products, from contaminated water.

Role of aqueous electron and hydroxyl radical in the removal of endosulfan from aqueous solution using gamma irradiation

The removal of endosulfan, an emerging water pollutant, from water was investigated using gamma irradiation based advanced oxidation and reduction processes (AORPs). A significant removal, 97% of initially 1.0 μM endosulfan was achieved at an absorbed dose of 1020 Gy. The removal of endosulfan by gamma-rays irradiation was influenced by an absorbed dose and significantly increased in the presence of aqueous electron (eaq(-)). However, efficiency of the process was inhibited in the presence of eaq(-) scavengers, such as N2O, NO3(-), acid, and Fe(3+). The observed dose constant decreased while radiation yield (G-value) increased with increasing initial concentrations of the target contaminant and decreasing dose-rate. The removal efficiency of endosulfan II was lower than endosulfan I. The degradation mechanism of endosulfan by the AORPs was proposed showing that reductive pathways involving eaq(-) started at the chlorine attached to the ring while oxidative pathway was initiated due to attack of hydroxyl radical at the SO bond. The mass balance showed 95% loss of chloride from endosulfan at an absorbed dose of 1020 Gy. The formation of chloride and acetate suggest that gamma irradiation based AORPs are potential methods for the removal of endosulfan and its by-products from contaminated water.

Efficient Photocatalytic Degradation of Norfloxacin in Aqueous Media by Hydrothermally Synthesized Immobilized TiO2/Ti Films with Exposed {001} Facets

In this study, a novel immobilized TiO2/Ti film with exposed {001} facets was prepared via a facile one-pot hydrothermal route for the degradation of norfloxacin from aqueous media. The effects of various hydrothermal conditions (i.e., solution pH, hydrothermal time (HT) and HF concentration) on the growth of {001} faceted TiO2/Ti film were investigated. The maximum photocatalytic performance of {001} faceted TiO2/Ti film was observed when prepared at pH 2.62, HT of 3 h and at HF concentration of 0.02 M. The as-prepared {001} faceted TiO2/Ti films were fully characterized by field-emission scanning electron microscope (FE-SEM), X-ray diffraction (XRD), high resolution transmission electron microscope (HR-TEM), and X-ray photoelectron spectroscopy (XPS). More importantly, the as-prepared {001} faceted TiO2/Ti film exhibited excellent photocatalytic performance toward degradation of norfloxacin in various water matrices (Milli-Q water, tap water, river water and synthetic wastewater). The individual influence of various anions (SO42-, HCO3-, NO3-, Cl-) and cations (K+, Ca2+, Mg2+, Cu2+, Na+, Fe3+) usually present in the real water samples on the photocatalytic performance of as-prepared TiO2/Ti film with exposed {001} facet was investigated. The mechanistic studies revealed that •OH is mainly involved in the photocatalytic degradation of norfloxacin by {001} faceted TiO2/Ti film. In addition, norfloxacin degradation byproducts were investigated, on the basis of which degradation schemes were proposed.

Kinetic and mechanism investigation on the gamma irradiation induced degradation of endosulfan sulfate.

The gamma irradiation was investigated for potential removal of endosulfan sulfate, an emerging water pollutant and central nervous system disruptor. A removal efficiency of 99.5% of initially 1.30 μM endosulfan sulfate was observed at an absorbed dose of 1020 Gy. Aqueous electron (eaq(-)) was found to play primary role in the removal of endosulfan sulfate which was possibly due to greater reactivity of eaq(-) with endosulfan sulfate, considering the second-order rate constant of 8.1×10(9) and 3.4×10(10) M(-1) s(-1) for hydroxyl radical (·OH) and eaq(-), respectively, with endosulfan sulfate. The removal efficiency of endosulfan sulfate was affected by the pH of aqueous solution, with observed removal efficiency of 99.5%, 98.3% and 31.3% at pH 6.2, pH 10.0, and pH 2.6, respectively. The efficiency was also influenced by inorganic anions and humic acid in the order of nitrate>nitrite>bicarbonate>carbonate ≃ humic acid. The initial degradation rate increased while degradation constant decreased with increasing initial concentrations of endosulfan sulfate. The degradation pathways showed that oxidative pathway was initiated at the SO2 bond while reductive pathways at the chlorine attached to the ring of endosulfan sulfate. The mass balance showed removal of 98% chloride and 72% sulfate ions from endosulfan sulfate at an absorbed dose of 1020 Gy. The removal of endosulfan sulfate followed by subsequent loss of by-products under extended treatment showed that gamma irradiation is potential technique for the remediation of organic pollutants from a water environment.

Role of eaq−, OH and H in radiolytic degradation of atrazine: A kinetic and mechanistic approach

The degradation of atrazine was investigated in aqueous solution by gamma-ray irradiation. 8.11 μM initial atrazine concentration could be completely removed in N₂ saturated solution by applying 3500 Gy radiation dose at a dose rate of 296 Gy h(-1). Significant removal of atrazine (i.e., 39.4%) was observed at an absorbed dose of 1184 Gy in air saturated solution and the removal efficiency was promoted to 50.5 and 65.4% in the presence of N₂O and N₂ gases, respectively. The relative contributions of hydrated electron, hydroxyl radical and hydrogen radical toward atrazine degradation were determined as ratio of observed dose constant (kobs) and found to be 5: 3: 1 for keaq(-): k·OH: kH·, respectively. The degradation efficiency of atrazine was 69.5, 55.6 and 37.3% at pH 12.1, 1.7 and 5.7, respectively. A degradation mechanism was proposed based on the identified degradation by-products by gas chromatography-mass spectrometry. Taking the relative contributions of oxidative and reductive species to atrazine degradation into account, reductive pathway proved to be a better approach for the radiolytic treatment of atrazine contaminated water.

HYDROXYL RADICAL BASED DEGRADATION OF CIPROFLOXACIN IN AQUEOUS SOLUTION

This study reports the degradation of ciprofloxacin (CIP) by means of ionizing radiations. Kinetic studies with aqueous concentrations of 4.6, 10, 15, 17.9 mg/L reveals that degradation of CIP follows pseudo -first order kinetics and the decay constant increased with decrease in initial concentration of CIP. The removal efficiency, represented by G-value, decreased with increasing absorbed dose and increased with higher [CIP] 0 concentration at a given absorbed dose. The effects of bubbling CIP solution with N 2 , N 2 O or air on CIP degradation were also studied. The influence of various radical scavengers like tert -butanol, iso -propanol, HCO 3 - , CO 3 2- , NO 3 - and NO 2 - as radical scavengers in N 2 - saturated solutions of CIP indicated that •OH were more closely associated with the radiolytic decomposition of CIP than other radicals, such as e - aq or •H. The pH value of aqueous media played a crucial role in the degradation of CIP. It was observed that degradation efficiency was higher under acidic condition compared to degradation in natural or alkaline media. F - , CH 3 COO - and HCOO - were formed as a result of CIP degradation that were analyzed by ion-chromatography.

Gamma radiolytic decomposition of endosulfan in aerated solution: the role of carbonate radical

The present study elaborates the removal of endosulfan, an emerging water pollutant and potential carcinogenic, in aerated solution. The influence of Cl−, NO3−, NO2−, CO32−, HCO3−, SO32−, and humic acid was assessed on the radiolytic degradation of endosulfan. A strong inhibition on the radiolytic degradation of endosulfan was observed in the presence of NO3−, NO2−, and SO32−. Instead, a slight increase in the removal efficiency of endosulfan was observed at high concentrations of CO32− and HCO3−. The formation of CO3•− in radiolytic degradation of endosulfan in the presence of CO32− and HCO3− was demonstrated by adding SO32− that rapidly react with CO3•−. The results indicate that CO3•− formed from the reactions of CO32− and HCO3− and commonly found in natural water can play an important role in the degradation of endosulfan and other sulfur containing electron-rich compounds. The study showed faster degradation of endosulfan at lower concentration compared to high concentration and removal was found to follow pseudo-first-order kinetic. Endosulfan ether was found as the main degradation product and degradation pathway was found to be initiated at the S=O bond of endosulfan. The efficiency of gamma irradiation in the removal of endosulfan was examined in terms of formation of short chain organic acids and chloride ion accumulation.

REMOVAL OF CRYSTAL VIOLET DYE FROM AQUEOUS SOLUTION BY GAMMA IRRADIATION

In this study the radiation-induced degradation of crystal violet (CV) dye under various experimental conditions has been investigated. D0.5, D0.9 and D0.99 values suggests that lower doses are required for 50%, 90% and 99% removal of CV dye when the sample solution contains excessive amount of •OH radicals. The removal efficiency of CV dye in terms of G-values was also calculated under each reaction conditions. The results showed that •OH radicals are playing effective role in the degradation of CV dye as compared to eaq‒ and •H radicals. The gamma irradiation process effectively degraded CV dye at all pH values. The organic byproducts were examined and accordingly degradation pathway was proposed.

Degradation of Acetaminophen in Aqueous Media by H2O2 Assisted Gamma Irradiation Process

In the present study, degradation of acetaminophen (ACT) aqueous solution was investigated up to an absorbed γ-irradiation dose of 1000 Gy. The effects of various additives on the degradation efficiency of ACT were also studied. The results showed that ACT degradation was increased with the increase of an absorbed dose. Based on spectrophotometric analysis, 82.5% degradation of the initial ACT concentration (9.98 × 10−5 M) was easily achieved at an absorbed dose of 1000 Gy. The decay of ACT followed pseudo-first order reaction kinetics at different initial concentrations. The radiation chemical yield (G-value) decreased with the increase of an absorbed dose, however at a specific absorbed dose G-values increased with the increase of ACT initial concentration. The addition of H2O2 in the range of 0.1–0.7% was effective for degradation of ACT. The degradation of ACT was inhibited in both acidic and basic solutions while maximium degradation effiency was acheived at nearly neautral solution pH, 7.6. The degradation process was markedly enhanced under oxidative conditions while strongly restrained under reductive conditions, which suggests the key role of oxidative radicals ( ̇OH) in the degradation of ACT.

Degradation of Crystal Violet Dye by Fenton and Photo-Fenton Oxidation Processes

Abstract The oxidative degradation of CV dye in aqueous media has been evaluated using Fenton (Fe2+/H2O2) and photo-Fenton (Fe2+/H2O2/UV) processes. Various operational parameters like H2O2 dosages, Fe2+ dosages and [CV]0 were optimized of both Fenton and photo-Fenton processes for the removal of CV dye from aqueous media. Kinetic results indicated that photo-Fenton process (kobs=0.0097 min−1, t1/2=71.45 min) is more effective than Fenton process (kobs=0.0074 min−1, t1/2=93.66 min). Second order rate constant of ˙OH radical with CV dye was calculated to be 3.96×109 M−1s−1. De-methylated organic intermediates of CV dye detected by LC-MS and some other intermediates like CH3COO−, HCOO−, NH4+ and Cl− were identified by ion-chromatography.