Murtaza Sayed

Advanced oxidation for the treatment of chlorpyrifos in aqueous solution

Chlorpyrifos is an organophosphate pesticide and is significant because of its extensive use, persistence in the environment, wide distribution, and its toxicity may lead to lung and central nervous system damage, developmental and autoimmune disorders and vomiting. In the present study, the irradiation of chlorpyrifos in aqueous solution by (60)Co γ-rays was conducted on a laboratory scale and the removal efficiency of chlorpyrifos was investigated. The SPME-GC-ECD method was used for analysis of chlorpyrifos. Aqueous solutions of different concentrations of target compound (200-1000 μg L(-1)) were irradiated through 30-575 Gy. Gamma irradiation showed 100% degradation for a 500 μg L(-1) solution at an absorbed dose of 575 Gy (the dose rate was 300 Gy h(-1)). The radiolysis of chlorpyrifos was pseudo-first order (decay) with respect to dose. The dose constants determined in this study ranged from 8.2×10(-3) to 2.6×10(-2) Gy(-1), and decreased with an increase in the initial concentration of chlorpyrifos, while the radiation chemical yield (G-value) for the loss of chlorpyrifos was found to decrease with increasing absorbed dose. The effect of saturated solutions of N2 and N2O, and radical scavengers tert-butanol, iso-propanol, H2O2, NaNO3 and NaNO2 on the degradation of chlorpyrifos were also studied. The results showed that the oxidative OH was the most important in the degradation of chlorpyrifos, while the reductive radicals, aqueous electron and H, were of less importance for the degradation of chlorpyrifos. The inorganic by-products Cl(-), SO4(2-) and PO4(3-) were quantitatively determined by IC.

Degradation of ciprofloxacin in water by advanced oxidation process: kinetics study, influencing parameters and degradation pathways

ABSTRACT Gamma-radiation-induced degradation of ciprofloxacin (CIP) in aqueous solution and the factors affecting the degradation process have been investigated. The results showed that CIP (4.6 mg/L) was almost completely degraded at an absorbed dose of 870 Gy. The kinetic studies of aqueous solutions containing 4.6, 10, 15 and 17.9 mg/L indicated that the decomposition of CIP by gamma irradiation followed pseudo-first-order kinetics and the decay constant (k) decreased from 5.9  ×  10−3 to 1.6  ×  10−3 Gy−1 with an increase in CIP initial concentration from 4.6 to 17.9 mg/L. The effect of saturation of CIP solution with N2, N2O or air on radiation-induced degradation of CIP was also investigated. The effects of radical scavengers, such as t-BuOH and i-PrOH, showed the role of reactive radicals towards degradation of CIP in the order of . The apparent second-order rate constant of with CIP was calculated to be 2.64 × 109 M−1 s−1. The effects of solution pH as well as natural water contaminants, such as , , and , on CIP degradation by gamma-irradiation were also investigated. Major degradation products, including organic acids, were identified using UPLC-MS/MS and IC, and degradation pathways have been proposed.

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.

VUV-Photocatalytic Degradation of Bezafibrate by Hydrothermally Synthesized Enhanced {001} Facets TiO2/Ti Film

In the present study, a novel TiO2/Ti film with enhanced {001} facets was synthesized by the hydrothermal technique followed by calcination for studying the removal of bezafibrate (BZF), from an aqueous environment. The synthesized photocatalyst was characterized by FE-SEM, XRD, HR-TEM, and PL-technique. The second-order rate constant of (•)OH with BZF was found to be 5.66 × 10(9) M(-1) s(-1). The steady state [(•)OH] was measured as 1.16 × 10(-11) M, on the basis of oxidation of terephthalic acid. The photocatalytic degradation of BZF followed pseudo-first-order kinetics according to the Langmuir-Hinshelwood model (k1 = 2.617 mg L(-1) min(-1) and k2 = 0.0796 (mg L(-1))(-1)). The effects of concentration and the nature of various additives including inorganic anions (NO3(-), NO2(-), HCO3(-), CO3(2-), Cl(-)) and organic species (fulvic acid) and initial solution pHs (2, 4, 6, 9) on photocatalytic degradation of BZF were investigated. It was found that the nature and concentration of studied additives significantly affected the photocatalytic degradation of BZF. The efficiency of the photocatalytic degradation process in terms of electrical energy per order was estimated. Degradation schemes were proposed on the basis of the identified degradation byproducts by ultraperformance liquid chromatography.

Effect of Isopropanol on Microstructure and Activity of TiO2 Films with Dominant {001} Facets for Photocatalytic Degradation of Bezafibrate

Titanium dioxide (TiO2) films with dominant {001} facets coated on a titanium sheet (Ti) were synthesized with the simple hydrothermal method by using Ti as the precursor and substrate. The effect of addition of isopropanol into the hydrothermal solution on the structure, photocatalytic activity, and stability of as-synthesized TiO2 films was investigated. The presence of isopropanol obviously influenced the microstructure of as-synthesized TiO2 films, which was converted from microspheres into irregular close stack of truncated tetrahedrons. And the percentage of exposed {001} facets calculated from the Raman spectra increased from 48.2% to 57%. Accordingly, the TiO2 films prepared with addition of isopropanol showed high and stable photocatalytic activity, which is nearly 2.6 times as that of the conventional P25 TiO2 coated on Ti-substrate. In addition, the photocatalytic activity of as-synthesized TiO2 films was greatly enhanced after calcination treatment at 600°C, which can be attributed to removal of fluoride ions and organic residuals adsorbed on the surface of the catalyst. Photoluminescence (PL) technique was used for the detection of produced hydroxyl radicals (•OH) on the surface of UV-illuminated TiO2 using terephthalic acid as probe molecule. The photocatalytic degradation intermediates of bezafibrate were analyzed by an ultraperformance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), and accordingly the degradation pathways were proposed.

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.

The interaction of a model active pharmaceutical with cationic surfactant and the subsequent design of drug based ionic liquid surfactants

Interactions of active pharmaceutical ingredients (API) with surfactants remain an important research area due to the need to improve drug delivery systems. In this study, UV-Visible spectrophotometry was used to investigate the interactions between a model low molecular weight hydrophilic drug sodium valproate (SV) and cationic surfactant cetyltrimethylammonium bromide (CTAB). Changes in the spectra of SV were observed in pre- and post-micellar concentrations of CTAB. The binding constant (Kb) values and the number of drug molecules encapsulated per micelle were calculated, which posed the possibility of mixed micelle formation and strong complexation between SV and CTAB. These results were compared to those of a novel room temperature surface active ionic liquid, which was synthesized by the removal of inorganic counterions from a 1:1 mixture of CTAB and SV. In this new compound the drug now constitutes a building block of the carrier and, as such, has considerably different surfactant properties to its building blocks. In addition, enhanced solubility in a range of solvents, including simulated gastric fluid, was observed. The study provides valuable experimental evidence concerning the performance of drug based surfactant ionic liquids and how their chemical manipulation, without altering the architecture of the API, leads to control of surfactant behavior and physicochemical properties. In turn, this should feed through to improved and controlled drug release rates and delivery mechanisms, and the prevention of precipitation or formation of polymorphs typical of crystalline form APIs.

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.

Ag-loaded thermo-sensitive composite microgels for enhanced catalytic reduction of methylene blue

In this work, we report the synthesis of composite system pNAC, composed of silver nanoparticles embedded in pure thermo-sensitive crosslinked polymer network of poly(N-isopropylacrylamide-co-acrylamide) (pNA), using as a catalyst for the reduction of methylene blue (MB) dye by sodium borohydride (NaBH4). The pNA was prepared by conventional free radical polymerization technique using sodium dodecyl sulfate as stabilizing agent, followed by in situ reduction of AgNO3 inside the polymer network by NaBH4 for the synthesis of composite systems pNACs. The synthesized pNA and pNACs were characterized by FTIR, dynamic light scattering, thermo-gravimetric analysis, scanning electron microscopy and UV–visible spectroscopy techniques. The materials were found sensitive toward temperature change of the medium. The entrapment ability of pNA toward different amounts of AgNO3 solution was studied, and effect of metal content on particle size of pNACs was analyzed. The pNACs were applied as a catalyst for the reduction of MB in which they exhibit high catalytic activity and reusability toward the reaction.

Uptake of heavy metal ions from aqueous media by hydrogels and their conversion to nanoparticles for generation of a catalyst system: two-fold application study

Poly(methacrylic acid) (P(MAA)), poly(acrylamide) (P(AAm)) and poly(3-acrylamidopropyltrimethyl ammonium chloride) (P(APTMACl)) were synthesized as anionic, neutral and cationic hydrogels, respectively. The synthesized hydrogels have the ability to be used as absorbents for the removal of selected heavy metal ions such as Cu2+, Co2+, Ni2+ and Zn2+ from aqueous media. Absorption studies revealed that the absorption of metal ions by the hydrogels followed the order Cu2+ > Ni2+ > Co2+ > Zn2+. For the mechanism of absorption, both Freundlich and Langmuir absorption isotherms were applied. Metal ion entrapped hydrogels were treated using an in situ chemical reduction method in order to convert the metal ions into metal nanoparticles for the synthesis of hybrid hydrogels. The synthesis and morphology were confirmed using FT-IR and SEM, while the absorbed metal amounts were measured using TGA and AAS. The hybrid hydrogels were further used as catalysts for the reduction of macro (methylene blue, methyl orange and congo red) and micro (4-nitrophenol and nitrobenzene) pollutants from the aqueous environment. The catalytic performance and re-usability of the hybrid hydrogels were successfully investigated.