This work focuses on the remediation of polycyclic aromatic hydrocarbon (PAH)-contaminated soil using modified Fenton (MF) treatment coupled with a novel chelating agent (CA), a more effective technique among currently available technologies. The performance of MF treatment to promote PAH oxidation in artificially contaminated soil was investigated in a packed column with a hydrogen peroxide (H(2)O(2)) delivery system simulating in-situ soil flushing which is more representative of field conditions. The effectiveness of process parameters H(2)O(2)/soil, Fe(3+)/soil, CA/soil weight ratios and reaction time were studied using a 2(4) three level factorial design experiments. An optimised operating condition of the MF treatment was observed at H(2)O(2)/soil 0.05, Fe(3+)/soil 0.025, CA/soil 0.04 and 3h reaction time with 79.42% and 68.08% PAH removals attainable for the upper and lower parts of the soil column respectively. The effects of natural attenuation and biostimulation process as post-treatment in the remediation of the PAH-contaminated soil were also studied. In all cases, 3-aromatic ring PAH (phenanthrene) was more readily degraded than 4-aromatic ring PAH (fluoranthene) regardless of the bioremediation approach. The results revealed that both natural attenuation and biostimulation could offer remarkable enhancement of up to 6.34% and 9.38% in PAH removals respectively after 8 weeks of incubation period. Overall, the results demonstrated that combined inorganic CA-enhanced MF treatment and bioremediation serves as a suitable strategy to enhance soil quality particularly to remediate soils heavily contaminated with mixtures of PAHs.
Ferulic acid (FA) groups esterified to the arabinan side chains of pectic polysaccharides can be oxidatively cross-linked in vitro by horseradish peroxidase (HRP) catalysis in the presence of hydrogen peroxide (H(2)O(2)) to form ferulic acid dehydrodimers (diFAs). The present work investigated whether the kinetics of HRP catalyzed cross-linking of FA esterified to α-(1,5)-linked arabinans are affected by the length of the arabinan chains carrying the feruloyl substitutions. The kinetics of the HRP-catalyzed cross-linking of four sets of arabinan samples from sugar beet pulp, having different molecular weights and hence different degrees of polymerization, were monitored by the disappearance of FA absorbance at 316 nm. MALDI-TOF/TOF-MS analysis confirmed that the sugar beet arabinans were feruloyl-substituted, and HPLC analysis verified that the amounts of diFAs increased when FA levels decreased as a result of the enzymatic oxidation treatment with HRP and H(2)O(2). At equimolar levels of FA (0.0025-0.05 mM) in the arabinan samples, the initial rates of the HRP-catalyzed cross-linking of the longer chain arabinans were slower than those of the shorter chain arabinans. The lower initial rates may be the result of the slower movement of larger molecules coupled with steric phenomena, making the required initial reaction of two FAs on longer chain arabinans slower than on shorter arabinans.
Advanced oxidation processes (AOPs) such as Fenton, electro-Fenton and photo-Fenton have been applied effectively to remove refractory organics from landfill leachate. The Fenton reaction is based on the addition of hydrogen peroxide to the wastewater or leachate in the presence of ferrous salt as a catalyst. The use of this technique has proved to be one of the best compromises for landfill leachate treatment because of its environmental and economical advantages. Fenton process has been used successfully to mineralize wide range of organic constituents present in landfill leachate particularly those recalcitrant to biological degradation. The present study reviews the use of Fenton and related processes in terms of their increased application to landfill leachate. The effects of various operating parameters and their optimum ranges for maximum COD and color removal are reviewed with the conclusion that the Fenton and related processes are effective and competitive with other technologies for degradation of both raw and pre-treated landfill leachate.
Oxidation of sulfide in aqueous solution by hydrogen peroxide was investigated in the presence of hydrated ferric oxide catalyst. The ferric oxide catalyst was synthesized by sol gel technique from ferric chloride and ammonia. The synthesized catalyst was characterized by Fourier transform infrared spectroscopy, X-Ray diffraction analysis, scanning electrom microscope and energy dispersive X-ray analysis. The catalyst was quite effective in oxidizing the sulfide by hydrogen peroxide. The effects of sulfide concentration, catalyst loading, H2O2 dosing and temperature on the kinetics of sulfide oxidation were investigated. Kinetic equations and activation energies for the catalytic oxidation reaction were calculated based on the experimental results.
Decolorization of reactive azo dye, reactive black 5 (RB5), was conducted using Fe(III) immobilized on Montmorillonite K10 (MK10) as a catalyst in the presence of H(2)O(2) using Fenton-like oxidation process. The effect of different parameters such as iron ions loading on supported catalyst, catalyst dosage, initial pH of dye solution, initial concentration of H(2)O(2) and dye and reaction temperature on the decolorization efficiency of the process were studied. The results indicated that by using 12 mM of H(2)O(2) and 3.50 g L(-1) of the 0.11 wt.% Fe(III) oxide on MK10 catalyst at pH of 2.5, 99% of decolorization efficiency was achieved within 150 min in a batch process.
The decolorization of Acid Red 1 (AR1) in aqueous solution was investigated by Fenton-like process. The effect of different reaction parameters such as different iron ions loading on rice husk ash (RHA), dosage of catalyst, initial pH, the initial hydrogen peroxide concentration ([H(2)O(2)](o)), the initial concentration of AR1 ([AR1](o)) and the reaction temperature on the decolorization of AR1 was studied. The optimal reacting conditions were found to be 0.070 wt.% of iron (III) oxide loading on RHA, dosage of catalyst=5.0 g L(-1), initial pH=2.0, [H(2)O(2)](o)=8 mM, [AR1](o)=50 mg L(-1) at temperature 30 degrees C. Under optimal condition, 96% decolorization efficiency of AR1 was achieved within 120 min of reaction.
The effect of initial dissolved oxygen concentration (IDOC) on Fenton's reagent degradation of a dyestuff, Reactive Black 5 was explored in this study. The study was designed, conducted and analysed based on Central Composite Rotatable Design using a 3-1 lab-scale reactor. The participation of O2 in the process was experimentally observed and appears to be affected by the dosage of the reagents used in the study. The IDOC was found to have a significant influence on the process. Reducing the IDOC from 7.5 mg l(-1) to 2.5 mg l(-1) increased the removal of TOC by an average of about 10%. Reduction of IDOC from 10 mg l(-1) to 0 mg l(-1) enhanced the TOC removal by about 30%. The negative influence of IDOC is likely to be caused by the competition between the O2 and the reagents for the organoradicals. A model describing the relationship between initial TOC removal, reagent dosage and IDOC has also been developed.
Herein, an efficient epoxidation of 1-nonene is described. In a simple epoxidation system, commercially available Novozym 435, an immobilized Candida antarctica lipase B, and hydrogen peroxide (H(2)O(2)) were utilized to facilitate the in situ oxidation of phenylacetic acid to the corresponding peroxy acid which then reacted with 1-nonene to give 1-nonene oxide with high yield and selectivity. The aliphatic terminal alkene was epoxidised efficiently in chloroform to give an excellent yield (97%-99%) under the optimum reaction conditions, including temperature (35 °C), initial H(2)O(2) concentration (30%), H(2)O(2) amount (4.4 mmol), H(2)O(2) addition rate (one step), acid amount (8.8 mmol), and stirring speed (250 rpm). Interestingly, the enzyme was stable under the single-step addition of H(2)O(2) with a catalytic activity of 190.0 Ug-1. The entire epoxidation process was carried out within 12 h using a conventional water bath shaker.
Leachate pollution is one of the main problems in landfilling. Researchers have yet to find an effective solution to this problem. The technology that can be used may differ based on the type of leachate produced. Coliform bacteria were recently reported as one of the most problematic pollutants in semi-aerobic (stabilized) leachate. In the present study, the performance of the Electro-Fenton process in removing coliform from leachate was investigated. The study focused on two types of leachate: Palau Borung landfill leachate with low Coliform content (200 MPN/100 m/L) and Ampang Jajar landfill leachate with high coliform content (>24 × 10(4)MPN/100 m/L). Optimal conditions for the Electro-Fenton treatment process were applied on both types of leachate. Then, the coliform was examined before and after treatment using the Most Probable Number (MPN) technique. Accordingly, 100% removal of coliform was obtained at low initial coliform content, whereas 99.9% removal was obtained at high initial coliform content. The study revealed that Electro-Fenton is an efficient process in removing high concentrations of pathogenic microorganisms from stabilized leachate.
The objective of this study was to investigate the performance of employing Fenton's reagent in the advanced oxidation of ozone to treat stabilized landfill leachate in an ozone reactor. A central composite design (CCD) with response surface methodology (RSM) was applied to evaluate the relationships between operating variables, such as ozone and Fenton dosage, pH, and reaction time, to identify the optimum operating conditions. Quadratic models for the following four responses proved to be significant with very low probabilities (<0.0001): chemical oxygen demand (COD), color, NH-N, and ozone consumption (OC). The obtained optimum conditions included a reaction time of 90 min, 30 g/m³ ozone, 0.01 mol/L₂H₂O,0.02 mol/L Fe²⁺, and pH 5. COD, color, and NH₃-N removal rates of 79%, 100%, and 20%, respectively, and 0.18 kg O₃/kg COD OC were obtained. The predictions correspond well with experimental results (COD, color, and NH-N removal rates of 78%, 98.5%, and 19%, respectively, and 0.29 kg O₃/kg COD OC). This method reduces the treatment time and improves the treatment efficiency relative to a previously published method that used Fenton's reagent prior to ozonation.
In this study, the catalase-like activity of monomeric tau protein was reported in the presence of of zinc (Zn(II)) ions at low pH value. Monomeric tau protein contains two SH groups that are a target of disulfide bond formation. However these SH groups are able to interact with Zn(II) ion at pH 7.2 which creates a thiol bond as a mimetic model of chloroperoxidase active site which performs catalase like activity at low pH. Zn(II)/tau protein complex decomposed H2O2 with a high rate (Vm) as well as an efficient turn oven number (kcat) at pH 3. This remarkable catalase like activity is may be attributed to the conformational reorientation of protein at low pH. Circular dichroism (CD) studies did not demonstrate any secondary structural changes of tau protein after addition of Zn(II) ions at pH 7.2. In addition, tau protein shows identical CD bands at pH 7.2 and 3. Moreover, fluorescence quenching of tau by Zn(II) at pH 7.2 was initiated by complex formation rather than by dynamic collision. A significant red shift (6nm) was observed in the emission maximum of the fluorescence spectra when the protein was dissolved at pH 3 compared to pH 7.2. This conformational change can provide information regarding the rearrangements of the protein structure and exposure of Cys-Zn(II) group to the solvent which induces easy access of active site to H2O2 molecules and corresponding enhanced catalytic activity of Zn(II)/tau protein complex. This study introduces tau protein as a bio-inspired high performing scaffold for transition metal encapsulation and introducing an engineered apoprotein-induced biomimetic enzyme.
The objective of this study was to investigate the performance of employing H2O2 reagent in persulfate activation to treat stabilized landfill leachate. A central composite design (CCD) with response surface methodology (RSM) was applied to evaluate the relationships between operating variables, such as persulfate and H2O2 dosages, pH, and reaction time, to identify the optimum operating conditions. Quadratic models for the following two responses proved to be significant with very low probabilities (<0.0001): chemical oxygen demand (COD) and NH3-N removal. The obtained optimum conditions included a reaction time of 116 min, 4.97 g S2O8(2-), 7.29 g H2O2 dosage and pH 11. The experimental results were corresponding well with predicted models (COD and NH3-N removal rates of 81% and 83%, respectively). The results obtained in the stabilized leachate treatment were compared with those from other treatment processes, such as persulfate only and H2O2 only, to evaluate its effectiveness. The combined method (i.e., /S2O8(2-)/H2O2) achieved higher removal efficiencies for COD and NH3-N compared with other studied applications.
Hydrogen peroxide and UV radiation have been used in the photochemical degradation of isoprene in aqueous solutions. A kinetic study is carried out taking into account the contribution of the UV radiation reaction and the combined reaction with hydrogen peroxide. An empirical reaction rate expression, which considers the two reactions taking place in parallel, is suggested. Pseudo-first order rate constants are obtained from batch reactor data. As the molar ratio of H(2)O(2):isoprene increases, the rate of reaction increases linearly while the concentration of H(2)O(2) is observed to be nearly constant throughout the reaction; suggesting that the H(2)O(2) acts as a pseudo-catalyst. Nearly complete oxidation of isoprene is achieved. These results indicate that the H(2)O(2)/UV process appears to be a competitive alternative destructive treatment for removing isoprene from water present at low levels.
Protein oxidation of beef patties stored in high oxygen modified atmosphere packaging for 9 days was investigated. Meat was either stored in the dark, under light, or in the dark with addition of FeCl2/H2O2/myoglobin (forced oxidation). SDS-PAGE analysis showed high degree of protein polymerization for meat exposed to light, compared to the other samples. Light exposure induced reducible (disulfide) and non-reducible cross-links, while mainly disulfides were formed in meat stored in the dark. Light exposure was responsible for 58% loss of free thiols (Cys residues). No significant loss of other amino acid residues was observed and none of the most common oxidation products of tryptophan, tyrosine, and phenylalanine were detected. Intrinsic fluorescence measurements of tryptophan showed 27% loss in samples exposed to light, which was ascribed to loss of protein solubility via protein polymerization rather than tryptophan oxidation. Protein carbonyls were mainly detected in forced oxidized samples at Day 0.
The current research is focused on studying the biological efficacy of flexirubin, a pigment extracted from Chryseobacterium artocarpi CECT 8497.Different methods such as DPPH, H2O2, NO•, O2•-, •OH, lipid peroxidation inhibition by FTC and TBA, ferric reducing and ferrous chelating activity were carried out to evaluate the antioxidant activity of flexirubin. Molecular docking was also carried out, seeking the molecular interactions of flexirubin and a standard antioxidant compound with SOD enzyme to figure out the possible flexirubin activity mechanism. The new findings revealed that the highest level of flexirubin exhibited similar antioxidant activity as that of the standard compound according to the H2O2, •OH, O2•-, FTC and TBA methods. On the other hand, flexirubin at the highest level has shown lower antioxidant activity than the positive control according to the DPPH and NO• and even much lower when measured by the FRAP method. Molecular docking showed that the interaction of flexirubin was in the binding cavity of the SOD enzyme and did not affect its metal-binding site. These results revealed that flexirubin has antioxidant properties and can be a useful therapeutic compound in preventing or treating free radical-related diseases.
Effective regulation of p-phenylenediamine (PPD), a widely used precursor of hair dye that is harmful to human health in large concentration, relies upon an accurate yet simple detection of PPD. In this context, amperometric electrode sensor based on perovskite oxide becomes attractive given its portability, low cost, high sensitivity, and rapid processing time. This work reports the systematic characterization of a series of Sr-doped PrCoO3-δ perovskite oxides with composition of Pr1-xSrxCoO3-δ(x = 0, 0.2, 0.4, 0.6, 0.8, and 1) for PPD detection in an alkaline solution. PSC82 deposited onto glassy carbon electrode (PSC82/GCE) generates the highest redox currents which correlates with the highest hydrogen peroxide intermediates (HO2-) yield and the σ*-orbital (eg) filling of Co that is closest to unity for PSC82. PSC82/GCE provides the highest sensitivities of 655 and 308 μA mM-1 cm-2 in PPD concentration range of 0.5-2,900 and 2,900-10,400 μM, respectively, with a limit of detection of 0.17 μM. PSC82/GCE additionally demonstrates high selectivity to PPD and long term stability during 50 consecutive cyclic voltammetry scans and over 1-month storage period. The potential applicability of PSC82/GCE was also demonstrated by confirming the presence of very low concentration of PPD of below 0.5% in real hair dyes.
Activated carbons have been reported to be useful for adsorptive removal of the volatile anaesthetic sevoflurane from a vapour stream. The surface functionalities on activated carbons could be modified through aqueous oxidation using oxidising solutions to enhance the sevoflurane adsorption. In this study, an attempt to oxidise the surface of a commercial activated carbon to improve its adsorption capacity for sevoflurane was conducted using 6 mol/L nitric acid, 2 mol/L ammonium persulfate, and 30 wt per cent (wt%) of hydrogen peroxide (H2O2). The adsorption tests at fixed conditions (bed depth: 10 cm, inlet concentration: 528 mg/L, and flow rate: 3 L/min) revealed that H2O2 oxidation gave desirable sevoflurane adsorption (0.510 ± 0.005 mg/m2). A parametric study was conducted with H2O2 to investigate the effect of oxidation conditions to the changes in surface oxygen functionalities by varying the concentration, oxidation duration, and temperature, and the Conductor-like Screening Model for Real Solvents (COSMO-RS) was applied to predict the interactions between oxygen functionalities and sevoflurane. The H2O2 oxidation incorporated varying degrees of both surface oxygen functionalities with hydrogen bond (HB) acceptor and HB donor characters under the studied conditions. Oxidised samples with enriched oxygen functionalities with HB acceptor character and fewer HB donor character exhibited better adsorption capacity for sevoflurane. The presence of a high amount of oxygen functional groups with HB donor character adversely affected the sevoflurane adsorption despite the enrichment of oxygen functional groups with HB acceptor character that have a higher tendency to adsorb sevoflurane.
In this study aliphatic polyacids were synthesized using palm acid oil (PAO) and sunflower oil (SFO) via addition reaction technique. The synthesized materials were characterized using Fourier-transform infra-red (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-ToF-MS) and thermo-gravimetric analysis (TGA). Mixing formic acid and hydrogen peroxide with PAO or SFO at the ratio 3:10:1 produced the lowest iodine value of 10.57 and 9.24 respectively, indicating the increase in epoxidization of both oils. Adding adipic acid to the epoxidized oils at a ratio of 1:10 increases the acid values of SFO and PAO to 11.22 and 6.73 respectively. The existence of multi-acid groups present in synthesized polyacid was confirmed by MALD-ToF-MS. This feature indicates a possible value to the biomaterials development.
In the present study, microcrystalline cellulose (MCC) was isolated from oil palm fronds (OPF) using chemo-mechanical process. Wherein, alkaline hydrogen peroxide (AHP) was utilized to extract OPF fibre at different AHP concentrations. The OPF pulp fibre was then bleached with acidified sodium chlorite solution followed by the acid hydrolysis using hydrochloric acid. Several analytical methods were conducted to determine the influence of AHP concentration on thermal properties, morphological properties, microscopic and crystalline behaviour of isolated MCC. Results showed that the MCC extracted from OPF fibres had fibre diameters of 7.55-9.11nm. X-ray diffraction (XRD) analyses revealed that the obtained microcrystalline fibre had both celluloses I and cellulose II polymorphs structure, depending on the AHP concentrations. The Fourier transmission infrared (FTIR) analyses showed that the AHP pre-hydrolysis was successfully removed hemicelluloses and lignin from the OPF fibre. The crystallinity of the MCC was increased with the AHP concentrations. The degradation temperature of MCC was about 300°C. The finding of the present study showed that pre-treatment process potentially influenced the quality of the isolation of MCC from oil palm fronds.
Dicofol, a recommended Stockholm convention persistent organic pollutants (POPs) candidate is well known for its endocrine disruptive properties and has been extensively used as an organochlorine pesticide worldwide. The hydrodynamic cavitation (HC) treatment of Dicofol in aqueous media induced by a liquid whistle hydrodynamic cavitaion reactor (LWHCR) has been investigated while considering important parameters such as inlet pressure, initial concentration of Dicofol, solution temperature, pH, addition of H2O2 and radical scavenger for the extent of degradation. The pseudo-first-order degradation rate constant (k) was determined to be 0.073 min-1 with a cavitational yield of 1.26 × 10-5 mg/J at optimum operating conditions and a complete removal of Dicofol was achieved within 1 h of treatment. Considering the removal rate and energy efficiency, the optimal inlet pressure was found to be 7 bar, resulting in a cavitation number of 0.17. High performance liquid chromatography (HPLC) and Gas chromatography mass spectroscopy (GC-MS) analyses indicated a sharp decline in the concentration of Dicofol with treatment time and indicated the presence of degraded products. An 85% total organic carbon (TOC) removal was achieved within 1 h of treatment time, demonstrating successful mineralization of Dicofol. The obtained results suggest that the degradation of Dicofol followed thermal decomposition and successive recombination reactions at bubble-vapor interface. Overall, the attempted hydrodynamic cavitation demonstrated successful and rapid removal of endocrine disruptive chemicals such as Dicofol and is expected to provide efficient solution for wastewater treatment.