title: Kinetic and mechanism investigation on the gamma irradiation induced degradation of endosulfan sulfate.
abstract: 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.
authors.affiliation: Institute of Chemical Sciences, University of Swat, Swat 19130, Pakistan; Radiation Chemistry Laboratory, National Centre of Excellence in Physical Chemistry, University of Peshawar, Peshawar 25120, Pakistan. Electronic address: samadchemistry@gmail.com.
authors.forename: Noor S
authors.initials: NS
authors.lastname: Shah
authors.affiliation: Radiation Chemistry Laboratory, National Centre of Excellence in Physical Chemistry, University of Peshawar, Peshawar 25120, Pakistan.
authors.forename: Javed Ali
authors.initials: JA
authors.lastname: Khan
authors.affiliation: Radiation Chemistry Laboratory, National Centre of Excellence in Physical Chemistry, University of Peshawar, Peshawar 25120, Pakistan.
authors.forename: Shah
authors.initials: S
authors.lastname: Nawaz
authors.affiliation: Radiation Chemistry Laboratory, National Centre of Excellence in Physical Chemistry, University of Peshawar, Peshawar 25120, Pakistan.
authors.forename: M
authors.initials: M
authors.lastname: Ismail
authors.affiliation: Department of Environmental and Conservation Sciences, University of Swat, Swat 19130, Pakistan.
authors.forename: Kifayatullah
authors.initials: K
authors.lastname: Khan
authors.affiliation: Radiation Chemistry Laboratory, National Centre of Excellence in Physical Chemistry, University of Peshawar, Peshawar 25120, Pakistan.
authors.forename: Hasan M
authors.initials: HM
authors.lastname: Khan
mesh_terms: D000838:Anions; D004726:Endosulfan / Q000031:analogs & derivatives* / Q000032:analysis / Q000528:radiation effects; D005720:Gamma Rays; D006812:Humic Substances / Q000032:analysis; D017665:Hydroxyl Radical / Q000737:chemistry; D007700:Kinetics; D010084:Oxidation-Reduction; D014874:Water Pollutants, Chemical / Q000032:analysis* / Q000528:radiation effects; D018508:Water Purification / Q000379:methods*
chemical_list: D000838:Anions; D006812:Humic Substances; D014874:Water Pollutants, Chemical; D017665:Hydroxyl Radical; C544689:endosulfan sulfate; D004726:Endosulfan
keywords: Advanced oxidation and reduction processes (AORPs); Co-60 source; Endosulfan sulfate; Gamma irradiation; Pesticides; Water treatment