Enhanced solar light photocatalytic performance of Fe-ZnO in the presence of H2O2, S2O82−, and HSO5− for degradation of chlorpyrifos from agricultural wastes: Toxicities investigation

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 H2O2, peroxydisulfate (S2O82−) and peroxymonosulfate (HSO5−) with Fe-ZnO under solar irradiation promoted removal of CPY. The peroxides yielded hydroxyl ([rad]OH) and sulfate radical ([Formula presented]) 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, HSO5− 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

Competition Kinetics: An Experimental Approach

In this chapter, free radical kinetics with the help of competition kinetics and some experimental results calculated by competition kinetics to find out the rate constant of reactive species (●OH, eaq−, ●H) with target compound, which is used by radiation chemists is briefly discussed. The competition kinetics method is well validated by taking ciprofloxacin, norfloxacin and bezafibrate as example compounds. The bimolecular rate constants of hydroxyl radical, hydrate electron and hydrogen atom has been calculated for example solute species (ciprofloxacin, norfloxacin and bezafibrate)

Solar light responsive bismuth doped titania with Ti\u3csup\u3e3+\u3c/sup\u3e for efficient photocatalytic degradation of flumequine: Synergistic role of peroxymonosulfate

© 2019 Elsevier B.V. The present study is focused on the synthesis of a novel solar light responsive bismuth doped titania (Bi-TiO2) through a facile so-gel technique by applying various wt% of Bi. The as-synthesized Bi-TiO2 showed superior photocatalytic performance than un-doped TiO2 towards degradation of flumequine (FLU) under solar light irradiation. The as-synthesized material was thoroughly characterized to examine its structure, morphology and chemical states. The EPR analysis revealed the existence of Ti3+ ion and oxygen vacancy, which is created due to Bi-doping. The as-synthesized Bi-TiO2 with 5 wt% Bi (TBi5) showed excellent photocatalytic performance as compared to their counterparts. The photocatalytic activity of TBi5 was further improved when added with peroxymonosulfate (HSO5−) and increased with increasing [HSO5−]0. The mechanistic investigation and radical scavenging studies revealed that [rad]OH and SO4[rad]− are involved in the degradation of FLU by the as-synthesized material. The bimolecular rate constants of [rad]OH and SO4[rad]− were calculated to be 9.1 × 109 M−1s−1 and 8.5 × 109 M−1s−1, respectively. The photocatalytic performance of the as-synthesized TBi5 coupled with HSO5− under solar light irradiation towards degradation of FLU in Milli-Q water (MW), tape water (TW) and synthetic wastewater (SWW) was 92, 82 and 70% with kapp values of 0.093, 0.085 and 0.066 min−1, respectively. Furthermore, the degradation pathways of FLU were predicted on the basis of its degradation products (DPs). The high mineralization of FLU as well as the evaluation of non-toxic DPs suggests that solar light/TBi5/HSO5− is a promising advanced oxidation process for the future wastewater treatment applications

Catalytic degradation of carbamazepine by surface modified zerovalent copper via activation of peroxymonosulfate: Mechanism, degradation pathways and ecotoxicity.

ABSTRACTIn this research work, surface modified nano zerovalent copper (nZVC) was prepared using simple borohydride reduction method. The spectroscopic and crystallographic results revealed the successful synthesis of surface modified nano zerovalent copper (nZVC) using solvents i.e., ethanol (ETOH), ethylene glycol (EG) and tween80 (T80). The as-synthesized material was fully characterized for morphological surface and crystal structural properties. The results indicated that EG provides excellent synthesis environment to nZVC compared to ETOH and T80 in terms of good dispersion, high surface area and excellent catalytic properties. The catalytic efficiency of nZVC/EG was investigated alone as well as with the addition of peroxymonosulfate (PMS) in the absence of light. The degradation results demonstrated that the involvement of PMS synergistically boosted the catalytic efficiency of synthesized nZVC/EG material. Furthermore, the degradation products (DPs) of CBZ were determined by GC-MS and subsequently the degradation pathways were proposed. The ecotoxicity analysis of the DPs was also explored. The proposed (nZVC/EG/PMS) system is economical and efficient and thus could be applied for the degradation of CBZ from aquatic system after altering the degradation pathways in such a way that results in harmless products formation

Efficient removal of norfloxacin using nano zerovalent cerium composite biochar-catalyzed peroxydisulfate

Norfloxacin (NOR), an important antibiotic used for the treatment of different infections which is reportedly causing huge quantity of water pollution and severe environmental issues. In this study, biochar prepared from Phoenix dactylifera roots biomass (PB) and composited with mesoporous nano-zerovalent cerium (nZVCe) was used for treatment of NOR solutions. The various characterization and treatment studies showed successful formation of the nZVCe and PB composite. The nZVCe was found to improve physiological characteristics and catalytic efficiency of PB. The nZVCe/PB composite caused 52% removal of NOR as compared to 23% by the individual PB. The use of peroxydisulfate (PDS) with PB and nZVCe/PB showed further improvement in the removal of NOR and caused 58 and 84% removal efficiencies of NOR by PB/PDS and nZVCe/PB/PDS, respectively. The use of PDS with PB and nZVCe/PB was found to yield ●OH and SO4 ●– which improved degradation of NOR, however, addition of ●OH and SO4 ●– scavengers impeded NOR degradation. The PB was found to have several oxygen functional groups which decomposed PDS into ●OH and SO4 ●–. The nZVCe/PB showed high recovery, reusability, and stability and caused high removal of NOR even at fifth cycle of treatment both in the absence and presence of PDS. The treatment of NOR by nZVCe/PB-catalyzed PDS showed encouraging results under different pH, and varying concentrations of PDS, nZVCe/PB, and NOR as well as in real water samples which suggest potential practical applications of NOR contaminated water. Degradation of NOR resulted into several products and the resulting final product proved to be non-toxic

Potential degradation of norfloxacin using UV-C/Fe2+/peroxides-based oxidative pathways

The removal of norfloxacin (NOR), a widely used pharmaceutical and emerging water pollutant, was studied using UV-C and Fe2+ catalyzed peroxides-based oxidative processes (e.g., UV-C/Fe2+/H2O2, UV-C/Fe2+/S2O8 2− and UV-C/Fe2+/HSO5 −) and compared with UV-C and UV-C/Fe2+. The UV-C and UV-C/Fe2+ degraded NOR to 38 and 55%. However, use of peroxides, i.e., H2O2, S2O8 2−, HSO5 − with UV-C and UV-C/Fe2+ promoted NOR %degradation to 75, 83, and 90% using [peroxides]0 = 50 mg/L, [Fe2+]0 = 1 mg/L, and [NOR]0 = 10 mg/L, respectively. The significant impact of peroxides on NOR degradation was due to their decomposition into ●OH and SO4 ●− which showed high activity towards NOR degradation. The ●OH and SO4 ●− formation from peroxides decomposition and their contribution in NOR degradation was verified by different scavenger studies. Among the UV-C/Fe2+/peroxides processes, UV-C/Fe2+/HSO5 − showed better performance. The changing concentrations of peroxides, Fe2+, and NOR affected degradation of NOR. The use of different pH and inorganic anions also influenced NOR degradation. The degradation pathways of NOR were established and analyzed acute as well as chronic toxicities of NOR and its DPs

Development of zerovalent iron and titania (Fe0/TiO2) composite for oxidative degradation of dichlorophene in aqueous solution: synergistic role of peroxymonosulfate (HSO5−)

Abstract Binary composite of zerovalent iron and titanium dioxide (Fe0/TiO2) was synthesized for the catalytic removal of dichlorophene (DCP) in the presence of peroxymonosulfate (PMS). The as-prepared composite (Fe0/TiO2) exhibits synergistic effect and enhanced properties like improved catalytic activity of catalyst and greater magnetic property for facile recycling of catalyst. The results showed that without addition of PMS at reaction time of 50 min, the percent degradation of DCP by TiO2, Fe0, and Fe0/TiO2 was just 5%, 11%, and 12%, respectively. However, with the addition of 0.8 mM PMS, at 10 min of reaction time, the catalytic degradation performance of Fe0, TiO2, and Fe0/TiO2 was significantly improved to 82%, 18%, and 88%, respectively. The as-prepared catalyst was fully characterized to evaluate its structure, chemical states, and morphology. Scanning electron microscopy results showed that in composite TiO2 causes dispersion of agglomerated iron particles which enhances porosity and surface area of the composites and X-ray diffraction (XRD), energy dispersive X-ray (EDX), and Fourier-transform infrared (FTIR) results revealed successful incorporation of Fe0, and oxides of Fe and TiO2 in the composite. The adsorption–desorption analysis verifies that the surface area of Fe0/TiO2 is significantly larger than bare Fe0 and TiO2. Moreover, the surface area, particle size, and crystal size of Fe0/TiO2 was surface area = 85 m2 g−1, particle size = 0.35 μm, and crystal size = 0.16 nm as compared to TiO2 alone (surface area = 22 m2 g−1, particle size = 4.25 μm, and crystal size = 25.4 nm) and Fe0 alone (surface area = 65 m2 g−1, particle size = 0.9 μm, and crystal size = 7.87 nm). The as-synthesized material showed excellent degradation performance in synthesized wastewater as well. The degradation products and their toxicities were evaluated and the resulted degradation mechanism was proposed accordingly. The toxicity values decreased in order of DP1 \u3e DP5 \u3e DP2 \u3e DP3 \u3e DP4 and the LC50 values toward fish for 96-h duration decreased from 0.531 to 67.2. This suggests that the proposed technology is an excellent option for the treatment of antibiotic containing wastewater.Graphical abstrac

Toxicities, kinetics and degradation pathways investigation of ciprofloxacin degradation using iron-mediated H\u3csub\u3e2\u3c/sub\u3eO\u3csub\u3e2\u3c/sub\u3e based advanced oxidation processes

© 2018 Institution of Chemical Engineers Ciprofloxacin (CIP) is a widespread emerging water pollutant and thus its removal from aquatic environment is vital. The use of Fe3+/H2O2 and Fe2+/H2O2 resulted in 38 and 64% removal of CIP (8.0 ppm), respectively, within 80 min reaction time (pH 5.8, [H2O2]0 = 80 ppm, and [iron]0 = 20 ppm). Low pH, high temperature, high dose of H2O2 and Fe2+, and low CIP concentration facilitated removal of CIP. The radical scavenger studies proved in situ generated [rad]OH to be involved primarily in the removal of CIP. The effect of temperature was used to estimate enthalpy and activation energies of the removal of CIP. At 800 min reaction time, the Fe2+/H2O2 resulted in 54% mineralization of CIP using 16.0 ppm [CIP]0, 320.0 ppm [H2O2]0, and 40.0 ppm [Fe2+]0. The potential degradation pathways of CIP established from the degradation of CIP by [rad]OH and products evolved was found to be initiated at C6 through the loss of fluoride ion. The acute and chronic toxicities of CIP and its degradation products were estimated with the final product found to be non-toxic. The results suggest that Fe2+/H2O2-mediated AOPs have high potential for degradation as well as toxicity elimination of CIP and its degradation products

Bismuth-Doped Nano Zerovalent Iron: A Novel Catalyst for Chloramphenicol Degradation and Hydrogen Production

© In this study, we showed that doping bismuth (Bi) at the surface of Fe0 (Bi/Fe0, bimetallic iron system) - synthesized by a simple borohydride reduction method - can considerably accelerate the reductive degradation of chloramphenicol (CHP). At a reaction time of 12 min, 62, 68, 74, 95, and 82% degradation of CHP was achieved with Fe0, Bi/Fe0-1 [1% (w/w) of Bi], Bi/Fe0-3 [3% (w/w) of Bi], Bi/Fe0-5 [5% (w/w) of Bi], and Bi/Fe0-8 [8% (w/w) of Bi], respectively. Further improvements in the degradation efficiency of CHP were observed by combining the peroxymonosulfate (HSO5-) with Bi/Fe0-5 (i.e., 81% by Bi/Fe0-5 and 98% by the Bi/Fe0-5/HSO5- system at 8 min of treatment). Interestingly, both Fe0 and Bi/Fe0-5 showed effective H2 production under dark conditions that reached 544 and 712 μM by Fe0 and Bi/Fe0-5, respectively, in 70 mL of aqueous solution containing 0.07 g (i.e., at 1 g L-1 concentration) of the catalyst at ambient temperature