Hasan M. 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.

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.

Natural gamma-emiting radionuclides in Pakistani Portland cement

Studies of the natural gamma-emitting radionuclides in Portland cement manufactured in the North West Frontier Province (NWFP) of Pakistan and the various raw materials which compose the product have been carried out using gamma-spectrometric techniques. For data acquisition a high-purity germanium detector (HPGe) was used. The range of the total specific activity (minimum and maximum values) due to all the three radionuclides (40K, 226Ra and 232Th) were found to be 187.8+/-63.5-573.2+/-73.1 Bq kg(-1) (Portland cement); 54.5+/-16.1-183.9+/-31.4 Bq kg(-1) (limestone); 87.1+/-30.7-297.1+/-64.4 Bq kg(-1) (gypsum); 696.4+/-79.1-1043.9+/-85.0 Bq kg(-1) (slate); and 490.9+/-54.5-570.2+/-59.8 Bq kg(-1) (latrite). The average specific activities due to 40K in Portland cement and all the raw materials were found to be higher when compared with 226Ra and 232Th. Such materials do not pose any excess radiological health problem.

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.

Detection of radiation treatment of spices and herbs of Asian origin using thermoluminescence of mineral contaminants

Abstract Eight types of spices and herbs or their mixtures of Asian origin have been investigated for detection of irradiation treatment using thermoluminescence (TL) of insoluble mineral contaminants adhering to the samples. These samples were irradiated by 60Co γ-rays (at absorbed doses 1, 5 and 10 kGy) as well as by 10-MeV electrons using an accelerator (at a dose of 5.4 kGy). The integrated TL intensities of glow curves from the irradiated samples were found to be much higher than those from unirradiated samples. These results were normalized by administering a re-irradiation γ-ray dose of 1 kGy and calculating the ratio of the integral of the first glow curve (of unirradiated or irradiated samples) to that of the second glow curve (after re-irradiation). This ratio is less than 0.02 for all unirradiated samples and more than 0.3 for all irradiated samples (more than 1 for samples irradiated to 5 kGy or at higher doses), thereby making discrimination between irradiated and unirradiated samples possible. If one also compares the different temperature regions of the glow-curve maxima of unirradiated and irradiated samples, unequivocal discrimination is achieved for those previously irradiated to doses equal to or greater than 1 kGy.

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.

Norm and associated radiation hazards in bricks fabricated in various localities of the North-West Frontier Province (Pakistan)

The activity concentrations of natural gamma-emitting radionuclides and associated radiation hazards due to 40K, 226Ra and 232Th have been measured in baked brick samples, collected from six highly populated areas of the North-West Frontier Province (NWFP) of Pakistan. For the detection, analysis and data acquisition, a high purity germanium (HPGe) detector coupled with a high resolution multichannel analyser (MCA) was used. The range of the average values of the activity concentrations due to 40K, 226Ra and 232Th were found to be 680.3 +/- 22.2-784.4 +/- 30.7 Bq kg(-1), 36.9 +/- 3.5-51.9 +/- 3.3 Bq kg(-1) and 52.5 +/- 3.6-67.6 +/- 3.1 Bq kg(-1), respectively. Radium equivalent (Ra(eq)) activities and various hazard indices were also calculated to assess the radiation hazards. All the brick samples showed Ra, activities within the limit (370 Bq kg(-1)) set by the Organization for Economic Cooperation and Development (OECD) countries. The results of different criterion formulae also complemented each other in this study. The derived data have been compared with the reported values for other countries of the world.

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.

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.