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This study investigated iron-mediated oxidative processes for the photochemical degradation of endosulfan, a chlorinated insecticide and central nervous system disruptor. At UV fluence of 360 mJ/cm 2 , 52.4% and 32.0% removal of 2.45 μM initial endosulfan was observed by UV/Fe 3+ and UV/Fe 2+ processes, respectively, at an initial concentration of 17.8 μM iron. The degradation of endosulfan by UV/Fe 3+ or UV/Fe 2+ was dramatically enhanced by adding peroxide (i.e., H 2 O 2 , S 2 O 8 2− or HSO 5 − ). Among the UV/peroxide/Fe processes, the highest degradation efficiency of 99.0% at UV fluence of 360 mJ/cm 2 was observed by UV/HSO 5 − /Fe 2+ with 2.45 μM [endosulfan] 0 , 17.8 μM [Fe 2+ ] 0 , and 49.0 μM [HSO 5 − ] 0 . The observed degradation rate constant of endosulfan was promoted either by increasing [Fe 2+ ] 0 and/or [peroxide] 0 or by decreasing [endosulfan] 0 , while the initial degradation rate of endosulfan increased with increasing [Fe 2+ ] 0 , [peroxide] 0 , or [endosulfan] 0 . At UV fluence of 6000 mJ/cm 2 , 45.0% mineralization as represented by the decrease in total organic carbon content was observed by UV/HSO 5 − /Fe 2+ at 9.80 μM [endosulfan] 0 , 980 μM [HSO 5 − ] 0 , and 17.8 μM [Fe 2+ ] 0 . The major by-product of endosulfan was observed in all cases to be endosulfan ether which was further degraded with an extended reaction time. The results suggest that iron-mediated advanced oxidation processes (AOPs) have a high potential for the removal of endosulfan and its by-product from contaminated water. [ABSTRACT FROM AUTHOR]

Conventional titanium dioxide (TiO2) materials can be activated only by ultraviolet (UV) light, which is only 4-5% of the whole solar spectrum. As a result, visible light (vis)-active TiO2-based photocatalysts have recently received significant attention in the field of TiO2 photocatalytic treatment and purification of water and air. This study reports the preparation of UV-visible light-active phosphorous (P)-doped, fluorine (F)-doped, and PF-co-doped anatase TiO2 nanoparticles via an innovative sol-gel method. Prepared nanoparticles were characterized by UV-vis diffuse reflectance spectroscopy, X-ray diffraction analysis, Raman spectroscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy (FTIR), and porosimetry analysis. Synthesized materials exhibited improved structural properties, including high surface area, small crystallite size, reduced band gap energy, mesoporous structure, and high porosity. Due to doping with P and F, light absorption of TiO2 in the visible light region was efficiently enhanced with effective band gap energy of 2.70 eV. Brunauer-Emmett-Teller (BET) surface area for PF-co-doped, P-doped, F-doped, and reference TiO2 nanoparticles was 212.0, 175.0, 88.8, and 79.7 m2/g, respectively. PF-co-doped TiO2 showed the highest photocatalytic degradation of atrazine, which could be attributed to the beneficial effects including small crystallite size, high BET surface area, and light absorption in UV-visible region, induced by co-doping of TiO2 with P and F. Finally, reaction intermediates were determined, which confirms the photocatalytic degradation of atrazine using the synthesized catalysts under UV-visible light illumination. [ABSTRACT FROM AUTHOR]

The removal of brilliant green (BG), a toxic organic and cationic dye, has been examined by UV/S 2 O 8 2− (PS), UV/HSO 5 − (PMS) and UV/H 2 O 2 processes. BG showed insignificant direct photolysis at 254 nm (i.e., 8.6% after 30 min). However, enhanced BG degradation was observed in UV/PS, UV/PMS and UV/H 2 O 2 systems as revealed from 63.1, 47.0 and 34.8% BG degradation, respectively, at 30 min of reaction time, using 0.05 mM BG and 1.0 mM oxidant initial concentration. The bimolecular rate constants of OH and SO 4 − with BG were determined to be 2.35 × 10 9 and 2.21 × 10 9 M −1 s −1 , respectively. Electrical energy per order (EE/O) values for UV/PS, UV/PMS and UV/H 2 O 2 processes were calculated to be 5.4, 6.8, and 7.8 KWh/m 3 /order, respectively. The addition of humic acid (HA) and inorganic anions inhibited the degradation of BG by UV/PS in the order of NO 2 −  > HA > HCO 3 −  > Cl −   > NO 3 −  ≈ SO 4 2− . The results of frontier electron densities (FEDs) showed that C-atom holding the three rings (C7), and C-atoms at para positions to N-alkyl groups of the two rings (C4 and C14) are the predominant sites for radical addition. Furthermore, nine degradation products (DPs) of BG were detected experimentally using LC/MS/MS. [ABSTRACT FROM AUTHOR]

Carbamazepine (CBZ), a widely used antiepileptic drug, was removed by UV–254 nm based advanced oxidation processes. CBZ was found to be stable under sole UV, however, removal of CBZ was promoted using Fe3+ and Fe2+ with UV. Further, removal efficiency of CBZ was significantly enhanced by coupling H2O2 with UV and Fe3+/Fe2+. At 3600 mJ cm−2, 7.5, 60.2, 74.3 and 90.6% CBZ degradation was achieved in UV, UV/H2O2, UV/H2O2/Fe3+ and UV/H2O2/Fe2+, using CBZ, H2O2, Fe2+ and Fe3+ at 21.16, 1060.00, 17.91 and 17.91 μM, respectively. Higher CBZ degradation in the presence of H2O2 was attributed to HO whose second-order rate constant with CBZ was calculated to be (8.83 ± 0.27) × 109 M−1 s−1. Removal of CBZ by UV/H2O2/Fe2+ system was optimum at pH 3.0, as 80.8, 90.6 and 70.4% CBZ degradation was observed at pH 2.0, 3.0 and 6.5, respectively. The removal of CBZ by UV/H2O2/Fe2+ was retarded in the presence of Cl− and humic acid as revealed from 84.5 and 56.7% CBZ degradation in the presence of Cl− and humic acid, respectively, compared to 90.6% in their absence at 3600 mJ cm−2. The CBZ degradation products were found to be less toxic than the parent compound, suggesting important role of UV-assisted AOPs in efficient removal and toxicity reduction of CBZ and their degradation products. [ABSTRACT FROM AUTHOR]

Desethyl-atrazine (DEA) and desisopropyl-atrazine (DIA) are the two major degradation by-products of atrazine (a suspected human carcinogen and endocrine disrupting herbicide), and show an equal toxicity to their parent compound. This study investigated the degradation of DEA and DIA with OH and SO 4 − generated from the activation of peroxides, i.e., persulfate (S 2 O 8 2− ), peroxymonosulfate (HSO 5 − ) and hydrogen peroxide (H 2 O 2 ), by UV-254 nm radiation in the presence or absence of Fe 2+ . Quantum yields of DEA and DIA were independent of pH (3.0–11.0). The higher quantum yield of reactive radicals from UV/S 2 O 8 2− , i.e., 1.8 compared to 1.04 for UV/HSO 5 − and 1.0 for UV/H 2 O 2 , resulted in greater efficiency of UV/S 2 O 8 2− for both DEA and DIA degradation. The second-order rate constants of DEA and DIA with SO 4 − were calculated to be (6.42 ± 0.12) × 10 8 and (1.70 ± 0.30) × 10 9 M −1 s −1 , and that with OH were (1.14 ± 0.09) × 10 9 and (2.22 ± 0.44) × 10 9 M −1 s −1 , respectively, suggesting a strong impact of side chains toward radical reactions. Fe 2+ promoted slightly the activation of the examined peroxides at pH 7.4. Presence of organic matter and alkalinity in field water samples negatively influenced the efficiency of UV/S 2 O 8 2− . Based on the identified degradation by-products by GC–MS, potential degradation pathways were proposed for both compounds. The results obtained suggested that DEA and DIA can be efficiently removed from the contaminated water by OH and SO 4 − based-AOPs. [ABSTRACT FROM AUTHOR]

Highlights: [•] Degradation of atrazine was investigated in UV, UV/H2O2, UV/HSO5 − and UV/S2O8 2− AOPs. [•] UV/S2O8 2− process was found to be more efficient as well as more economical. [•] The pH affected UV/S2O8 2− but had no significant influence on UV, UV/H2O2 and UV/HSO5 −. [•] Second order rate constants of atrazine with SO4 − and OH were found to be comparable. [•] Degradation mechanism was investigated by GC–MS and LC–MS/MS analysis. [ABSTRACT FROM AUTHOR]

Abstract: The degradation of atrazine, a widely used endocrine disrupting, carcinogenic and persistent herbicide, was investigated by photo-Fenton and photo-Fenton-like advanced oxidation technologies (AOTs): UV/H2O2/Fe2+, UV//Fe2+ and UV//Fe2+. The study was carried out at two pH value conditions, i.e., pH 3.0 and pH 5.8. At pH 3.0, UV//Fe2+ was found to be the most efficient technology whereas UV//Fe2+ was observed to be the most effective at pH 5.8. The degradation of atrazine followed pseudo-first-order reaction with the highest observed rate constant of 2.00×10−2 cm2/mJ in UV//Fe2+ system at the initial concentrations of 4.64μM atrazine, 46.4μM (PMS) and 35.81μM Fe2+. The UV fluence required for the complete removal of 4.64μM atrazine at initially 92.80μM of oxidant and 8.95μM of Fe2+ concentrations at pH 3.0 was found to be 480, 720 and 960mJ/cm2 in UV//Fe2+, UV//Fe2+ and UV/H2O2/Fe2+ systems, respectively. Humic and fulvic acids were found to negatively impact the degradation of atrazine. The removal of TOC was not significant unless a high UV fluence was applied. At an initial concentration of 18.56μM atrazine, 1856.00μM oxidant and 17.91μM Fe2+, a 62.94%, 47.10% and 44.09% decrease in TOC was achieved at a UV fluence of 6000mJ/cm2 in UV/PS/Fe2+, UV/PMS/Fe2+ and UV/H2O2/Fe2+ systems, respectively. Nevertheless, it is suggested in this study that photo-Fenton and photo-Fenton-like technologies are capable of removing atrazine from water efficiently. [Copyright &y& Elsevier]

Organochlorine pesticides (OCPs) have been used extensively as insecticides and herbicides. This study investigates the occurrence of lindane in surface water from the Peshawar valley ( i.e. , Peshawar, Charsadda, Nowshera, Mardan and Swabi districts of Khyber Pakhtunkhwa, Pakistan). Out of 75 samples tested ( i.e. , 15 samples from each district), 13 samples (including 2 from Peshawar, 3 from Charsadda, 4 from Nowshera, 1 from Mardan, and 3 from Swabi) are found to be contaminated with lindane. Overall, the detection frequency is 17.3%. The maximum concentration of lindane is detected in a water sample from Nowshera and found to be 2.60 μg L -1 . Furthermore, the degradation of lindane in the water sample from Nowshera, containing the maximum concentration, is investigated by simulated solar-light/TiO 2 (solar/TiO 2 ), solar/H 2 O 2 /TiO 2 and solar/persulfate/TiO 2 photocatalysis. The degradation of lindane by solar/TiO 2 photocatalysis is 25.77% after 10 h of irradiation. The efficiency of the solar/TiO 2 process is significantly increased in the presence of 500 μM H 2 O 2 and 500 μM persulfate (PS) (separately), represented by 93.85 and 100.00% lindane removal, respectively. The degradation efficiency of lindane is lower in natural water samples as compared to Milli-Q water, attributed to water matrix effect. Moreover, the identification of degradation products (DPs) shows that lindane follows similar degradation pathways in natural water samples as the one in Milli-Q water. The results show that the occurrence of lindane in surface waters of Peshawar valley is a matter of great concern for human beings and the environment. Interestingly, H 2 O 2 and PS assisted solar/TiO 2 photocatalysis is an effective method for the removal of lindane from natural water., Competing Interests: There are no conflicts of interest to declare., (This journal is © The Royal Society of Chemistry.)

In this study, biochar was prepared from Sidr plant leaves and used for the treatment of ciprofloxacin (CIP)-contaminated water. CIP is important class of emerging water pollutants from pharmaceutical industries. The biochar showed 65% adsorption efficiency and 43.48 mg/g adsorption capacity of CIP. Adsorption efficiency as well as adsorption capacity were improved to 91% and 62.50 mg/g, respectively, by phosphoric acid (H 3 PO 4 ) modified biochar. Removal of CIP by the prepared biochar was due to different surface functional groups of CIP and biochar as revealed from the study of different characterization analyses. The presence of PO 4 group in modified biochar led to maximum binding of CIP. Also, the modified biochar showed higher reusability potential and less leaching of ions when compared to the raw biochar. Removal of CIP was affected by concentrations of CIP, the amount of biochar and different pH's; the maximum removal of CIP was achieved at pH 4. The Freundlich and 3- group in modified biochar led to maximum binding of CIP. Also, the modified biochar showed higher reusability potential and less leaching of ions when compared to the raw biochar. Removal of CIP was affected by concentrations of CIP, the amount of biochar and different pH's; the maximum removal of CIP was achieved at pH 4. The Freundlich and pseudo-first-order models best fitted the removal of CIP by modified biochar. Advanced characterization techniques were applied to investigate surface and physiological characteristics of the biochar and modified biochar. The modification showed high impact on the performance and stability of biochar. The study showed significant impacts of modification on the potential of the biochar for treatment of CIP-contaminated water.

This study reported Fe doped zinc oxide (Fe-ZnO) synthesis to degrade chlorpyrifos (CPY), a highly toxic organophosphate pesticide and important sources of agricultural wastes. Fourier transform infrared, X-ray diffraction, scanning electron microscope, and energy-dispersive X-ray spectroscopic analyses showed successful formation of the Fe-ZnO with highly crystalline and amorphous nature. Water collected from agricultural wastes were treated with Fe-ZnO and the results showed 67% degradation of CPY by Fe-ZnO versus 39% by ZnO at 140 min treatment time. Detail mechanism involving reactive oxygen species production from solar light activated Fe-ZnO and their role in degradation of CPY was assessed. Use of H 2 O 2 , peroxydisulfate (S 2 O 8 2- ) and peroxymonosulfate (HSO 5 - ) with Fe-ZnO under solar irradiation promoted removal of CPY. The peroxides yielded hydroxyl (OH) and sulfate radical () under solar irradiation mediated by Fe-ZnO. Effects of several parameters including concentration of pollutant and oxidants, pH, co-existing ions, and presence of natural organic matter on CPY degradation were studied. Among peroxides, HSO 5 - revealed to provide better performance. The prepared Fe-ZnO showed high reusability and greater mineralization of CPY. The GC-MS analysis showed degradation of CPY resulted into several transformation products (TPs). Toxicity analysis of CPY as well as its TPs was performed and the formation of non-toxic acetate imply greater capability of the treatment technology., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The removal of brilliant green (BG), a toxic organic and cationic dye, has been examined by UV/S 2 O 8 2- (PS), UV/HSO 5 - (PMS) and UV/H 2 O 2 processes. BG showed insignificant direct photolysis at 254 nm (i.e., 8.6% after 30 min). However, enhanced BG degradation was observed in UV/PS, UV/PMS and UV/H 2 O 2 systems as revealed from 63.1, 47.0 and 34.8% BG degradation, respectively, at 30 min of reaction time, using 0.05 mM BG and 1.0 mM oxidant initial concentration. The bimolecular rate constants of OH and SO 4 - s 9 and 2.21 × 10 9 M -1 s -1 , respectively. Electrical energy per order (EE/O) values for UV/PS, UV/PMS and UV/H 2 O 2 processes were calculated to be 5.4, 6.8, and 7.8 KWh/m 3 /order, respectively. The addition of humic acid (HA) and inorganic anions inhibited the degradation of BG by UV/PS in the order of NO 2 -  > HA > HCO 3 -  > Cl -   > NO 3 -  ≈ SO 4 2- . The results of frontier electron densities (FEDs) showed that C-atom holding the three rings (C7), and C-atoms at para positions to N-alkyl groups of the two rings (C4 and C14) are the predominant sites for radical addition. Furthermore, nine degradation products (DPs) of BG were detected experimentally using LC/MS/MS., (Copyright © 2018 Elsevier B.V. All rights reserved.)

In this study, a novel immobilized TiO 2 /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 (H T ) and HF concentration) on the growth of {001} faceted TiO 2 /Ti film were investigated. The maximum photocatalytic performance of {001} faceted TiO 2 /Ti film was observed when prepared at pH 2.62, H T of 3 h and at HF concentration of 0.02 M. The as-prepared {001} faceted TiO 2 /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 TiO 2 /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 (SO 4 2- , HCO 3 - , NO 3 - , Cl - ) and cations (K + , Ca 2+ , Mg 2+ , Cu 2+ , Na + , Fe 3+ ) usually present in the real water samples on the photocatalytic performance of as-prepared TiO 2 /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 TiO 2 /Ti film. In addition, norfloxacin degradation byproducts were investigated, on the basis of which degradation schemes were proposed.