The treatment of stabilized landfill leachate (SLL) by conventional biological treatment is often inefficient due to the presence of bio-recalcitrant substances. In this study, the feasibility of coagulation-flocculation coupled with the Fenton reaction in the treatment of SLL was evaluated. The efficiency of the selected treatment methods was evaluated through total organic carbon (TOC) removal from SLL. With ferric chloride as the coagulant, coagulation-flocculation was found to achieve the highest TOC removal of 71% at pH 6. Then, the pretreated SLL was subjected to the Fenton reaction. Nearly 50% of TOC removal was achieved when the reaction was carried out at pH 3, H2O2:Fe2+ ratio of 20:1, H2O2 dosage of 240 mM and 1 h of reaction time. By coupling the coagulation-flocculation with the Fenton reaction, the removal of TOC, COD (chemical oxygen demand) and turbidity of SLL were 85%, 84% and 100%, respectively. The ecotoxicity study performed using zebrafish revealed that 96 h LC50 for raw SLL was 1.40% (v/v). After coagulation-flocculation, the LC50 of the pretreated SLL was increased to 25.44%. However, after the Fenton reaction, the LC50 of the treated SLL was found to decrease to 10.96% due to the presence of H2O2 residue. In this study, H2O2 residue was removed using powdered activated charcoal. This method increased the LC50 of treated effluent to 34.48% and the removal of TOC and COD was further increased to 90%. This finding demonstrated that the combination of the selected treatment methods can be an efficient treatment method for SLL.
Microbial arsenite oxidation is an essential biogeochemical process whereby more toxic arsenite is oxidized to the less toxic arsenate. Thiomonas strains represent an important arsenite oxidizer found ubiquitous in acid mine drainage. In the present study, the arsenite oxidase gene (aioBA) was cloned from Thiomonas delicata DSM 16361, expressed heterologously in E. coli and purified to homogeneity. The purified recombinant Aio consisted of two subunits with the respective molecular weights of 91 and 21 kDa according to SDS-PAGE. Aio catalysis was optimum at pH 5.5 and 50-55 °C. Aio exhibited stability under acidic conditions (pH 2.5-6). The V max and K m values of the enzyme were found to be 4 µmol min(-1) mg(-1) and 14.2 µM, respectively. SDS and Triton X-100 were found to inhibit the enzyme activity. The homology model of Aio showed correlation with the acidophilic adaptation of the enzyme. This is the first characterization studies of Aio from a species belonging to the Thiomonas genus. The arsenite oxidase was found to be among the acid-tolerant Aio reported to date and has the potential to be used for biosensor and bioremediation applications in acidic environments.
The aim of this study was to determine hydrolytic stability [acid value (AV)] and oxidative stability [peroxide value (PV) and conjugated dienes (CD)] of selected blended oils during potato frying. The blended oils were prepared by blending palm oil with corn oil (POCO), sesame oil (POSO) and rice bran oil (PORBO). Blended vegetable oils were prepared in a ratio of 1 to 1 (v/v) and tested for 0, 10 and 20 times after frying potato. AV and PV were determined by titration method, while CD was determined using the spectrophotometric method. Increasing frequency of oil frying contributed to increased level of AV in all blended oils. PVs were increased in all samples, with most noticeable increment observed in POSO, followed by PORBO and POCO. CD levels of the blended oils were also increased after 20 times of potato frying compared with the unused oil and after 10 times of frying. POCO was the most stable oil in terms of hydrolytic and oxidative stabilities. It is most suitable for deep-fat frying of potato chips and industrial application.
Photocatalytic fuel cell (PFC) was employed to provide renewable power sources to photoelectro-Fenton (PEF) process to fabricate a double-chambered hybrid system for the treatment of azo dye, Amaranth. The PFC-PEF hybrid system was interconnected by a circuit attached to the electrodes in PFC and PEF. Circuit connection is the principal channel for the electron transfer and mobility between PFC and PEF. Thus, different circuit connections were evaluated in the hybrid system for their influences on the Amaranth dye degradation. The PFC-PEF system under the complete circuit connection condition attained the highest decolourization efficiency of Amaranth (PFC: 98.85%; PEF: 95.69%), which indicated that the complete circuit connection was crucial for in-situ formation of reactive species in dye degradation. Besides, the pivotal role of ultraviolet (UV) light irradiation in the PFC-PEF system for both dye degradation and electricity generation was revealed through various UV light-illuminating conditions applied for PFC and PEF. A remarkable influence of UV light irradiation on the production of hydrogen peroxide and generation and regeneration of Fe2+ in PEF was demonstrated. This study provided a comprehensive mechanistic insight into the dye degradation and electricity generation by the PFC-PEF system.
Azo dyes are the most varied class of synthetic chemicals with non-degradable characteristics. They are complex compounds made up of many different parts. It was primarily utilized for various application procedures in the dyeing industry. Therefore, it's crucial to develop an economical and environmentally friendly approach to treating azo dyes. Our present investigation is an integrated approach to the electrooxidation (EO) process of azo dyes using RuO2-IrO2-TiO2 (anode) and titanium mesh (cathode) electrodes, followed by the biodegradation process (BD) of the treated EO dyes. Chemical oxygen demand (COD) removal efficiency as follows MB (55%) ≥ MR (45%) ≥ TB (38%) ≥ CR (37%) correspondingly. The fragment generated during the degradation process which was identified with high-resolution mass spectrometry (HRMS) and its degradation mechanism pathway was proposed as demethylation reaction and N-N and C-N/C-S cleavage reaction occurs during EO. In biodegradation studies by Aeromonas hydrophila AR1, the EO treated dyes were completely mineralized aerobically which was evident by the COD removal efficiency as MB (98%) ≥ MR (92.9%) ≥ TB (88%) ≥ CR (87%) respectively. The EO process of dyes produced intermediate components with lower molecular weights, which was effectively utilized by the Aeromonas hydrophila AR1 and resulted in higher degradation efficiency 98%. We reported the significance of the enhanced approach of electrochemical oxidation with biodegradation studies in the effective removal of the pollutants in dye industrial effluent contaminated water environment.
10,11-Dihydro-10-hydroxy carbamazepine has been degraded in deionized water and wastewater samples using an electrochemical process. The anode used in the treatment process was graphite-PVC. Different factors such as initial concentration, NaCl amount, type of matrix, applied voltage, role of H2O2, and pH solution were investigated in the treatment of 10,11-dihydro-10-hydroxy carbamazepine. From the outcome of the results, it was noticed that the chemical oxidation of the compound followed a pseudo-first-order reaction. The rate constants were ranged between 22 × 10-4 and 483 × 10-4 min-1. After electrochemical degradation of the compound, several by-products were raised, and they were analyzed using an accurate instrument, liquid chromatography-time of flight-mass spectrometry (LC-TOF/MS). In the present study, the treatment of the compound was followed by high energy consumption under 10 V and 0.5 g NaCl, reaching up to 0.65 Wh mg-1 after 50 min. The inhibition of E. coli bacteria after incubation of the treated 10,11-dihydro-10-hydroxy carbamazepine sample was investigated in terms of toxicity.
Polycyclic aromatic hydrocharbons (PAHs) are a class of highly toxic pollutants that are highly detrimental to the ecosystem. Landfill leechate emanated from municipal solid waste are reported to constitute significant PAHs. In the present investigation, three Fenton proceses, namely conventional Fenton, photo-fenton and electro-fenton methods have been employed to treat landfill leehcate for removing PAHs from a waste dumpig yard. Response surface methodology (RSM) and artificial neural network (ANN) methodologies were adopted to optimize and validate the conditions for optimum oxidative removal of COD and PAHs. The statistical analysis results showed that all independent variables chosen in the study are reported to have significant influence of the removal effects with P-values <0.05. Sensitivity analysis by the developed ANN model showed that the pH had the highest significance of 1.89 in PAH removal when compared to the other parameters. However for COD removal, H2O2 had the highest relative importance of 1.15, followed by Fe2+ and pH. Under optimal treatment conditions, the photo-fenton and electro-fenton processes showed better removal of COD and PAH compared to the Fenton process. The photo-fenton and electro-fenton treatment processes removed 85.32% and 74.64% of COD and 93.25% and 81.65% of PAHs, respectively. Also the investigations revelaed the presence of 16 distinct PAH compunds and the removal percentage of each of these PAHs are also reported. The PAH treatment research studies are generally limited to the assay of removal of PAH and COD levels. In the present investigation, in addition to the treatment of landfill leachate, particle size distribution analysis and elemental characterization of the resultant iron sludge by FESEM and EDX are reported. It was revealed that elemental oxygen is present in highest percentage, followed by iron, sulphur, sodium, chlorine, carbon and potassium. However, iron percentage can be reduced by treating the Fenton-treated sample with NaOH.
In order to investigate the effects of the secondary coordination sphere in fine-tuning redox potentials (E°') of type 1 blue copper (T1Cu) in cupredoxins, we have introduced M13F, M44F, and G116F mutations both individually and in combination in the secondary coordination sphere of the T1Cu center of azurin (Az) from Pseudomonas aeruginosa. These variants were found to differentially influence the E°' of T1Cu, with M13F Az decreasing E°', M44F Az increasing E°', and G116F Az showing a negligible effect. In addition, combining the M13F and M44F mutations increases E°' by 26 mV relative to WT-Az, which is very close to the combined effect of E°' by each mutation. Furthermore, combining G116F with either M13F or M44F mutation resulted in negative and positive cooperative effects, respectively. Crystal structures of M13F/M44F-Az, M13F/G116F-Az, and M44F/G116F-Az combined with that of G116F-Az reveal these changes arise from steric effects and fine-tuning of hydrogen bond networks around the copper-binding His117 residue. The insights gained from this study would provide another step toward the development of redox-active proteins with tunable redox properties for many biological and biotechnological applications.
The combination of UV and water-soluble Fe(III) complexes is an effective method for generating Fe(II) in situ for activating advanced oxidation processes. This study explored the potential of Fe(III)-diethylenetriaminepentaacetic acid (Fe(III)-DTPA) and Fe(III)-ethylene glycol-bis(2-aminoethylether)-N,N,N',N'-tetraacetic acid (Fe(III)-EGTA) in activating the UV/persulfate (UV/PS) for sulfamethazine removal. The initial screening showed that Fe(III)-EGTA and Fe(III)-DTPA could significantly improve the rate of sulfamethazine removal. The optimum molar ratios of persulfate to Fe(III)-DTPA and Fe(III)-EGTA were 100:1 and 100:2.5. The predicted percentage of sulfamethazine removal under the optimized conditions, obtained using response surface methodology, was ~99% for both catalysts. The pH range of 6 to 8 did not significantly affect the performance of UV/PS in the removal of sulfamethazine. The percentage sulfamethazine removal in the selected water samples was ranged from 93.6% to 99.6%, agreeing with the predicted value. The performance of both catalysts in activating UV/PS is comparable with that of the frequently used Fe(III)-EDDS. PRACTITIONERS POINTS: The potential of Fe(III)-DTPA and Fe(III)-EGTA in activating UV/persulfate (UV/PS) was explored. Fe(III)-DTPA and Fe(III)-EGTA improved the performance of UV/PS in sulfamethazine removal. Fe(III)-DTPA and Fe(III)-EGTA are effective in catalyzing UV/PS under pH 6 to 8. The performance of Fe(III)-DTPA and Fe(III)-EGTA is comparable with well-studied Fe(III)-EDDS.
A systematic study of the electrochemical oxidation of 1,2-diarylalkenes was carried out with the focus on detailed product studies and variation of product type as a function of aromatic substitution. A reinvestigation of the electrochemical oxidation of 4,4'-dimethoxystilbene under various conditions was first carried out, and all products formed were fully characterized and quantitated. This was followed by a systematic investigation of the effect of aromatic substitution on the nature and distribution of the products. The aromatic substituents were found to fall into three main categories, viz., substrates in which the nature and position of the aromatic substituents gave rise to essentially the same products as 4,4'-dimethoxystilbene, for example, tetraaryltetrahydrofurans, dehydrotetralins, and aldehydes (p-MeO or p-NMe2 on one ring and X on the other ring, where X = o-MeO or p-alkyl, or m- or p-EWG; e.g., 4-methoxy-4'-trifluoromethylstilbene); those that gave rise to a mixture of indanyl (or tetralinyl) acetamides and dehydrotetralins (or pallidols) (both or one ring substituted by alkyl groups, e.g., 4,4'-dimethylstilbene); and those where strategic placement of donor groups, such as OMe and OH, led to the formation of ampelopsin F and pallidol-type carbon skeletons (e.g., 4,3',4'-trimethoxystilbene). Reaction pathways to rationalize the formation of the different products are presented.
This study assessed several common oxidative indices in subjects infected with intestinal parasites, as well as in colorectal cancer (CRC) patients both with and without intestinal parasites.
Accumulation of oxidized nucleic acids causes genomic instability leading to senescence, apoptosis, and tumorigenesis. Phytoagents are known to reduce the risk of cancer development; whether such effects are through regulating the extent of nucleic acid oxidation remains unclear. Here, we outlined the role of reactive oxygen species in nucleic acid oxidation as a driving force in cancer progression. The consequential relationship between genome instability and cancer progression highlights the importance of modulation of cellular redox level in cancer management. Current epidemiological and experimental evidence demonstrate the effects and modes of action of phytoagents in nucleic acid oxidation and provide rationales for the use of phytoagents as chemopreventive or therapeutic agents. Vitamins and various phytoagents antagonize carcinogen-triggered oxidative stress by scavenging free radicals and/or activating endogenous defence systems such as Nrf2-regulated antioxidant genes or pathways. Moreover, metal ion chelation by phytoagents helps to attenuate oxidative DNA damage caused by transition metal ions. Besides, the prooxidant effects of some phytoagents pose selective cytotoxicity on cancer cells and shed light on a new strategy of cancer therapy. The "double-edged sword" role of phytoagents as redox regulators in nucleic acid oxidation and their possible roles in cancer prevention or therapy are discussed in this review.
For many liver malignancies, major hepatectomy is the usual therapy. Although a normal liver has a tremendous capacity for regeneration, liver hepatectomy in humans is usually carried out on a diseased liver and, in such cases, liver regeneration takes place in a cirrhotic remnant. Mitochondrial function in cirrhotic livers shows a variety of changes compared to control livers. This study investigated how mitochondrial respiratory function and antioxidant capacity change following partial hepatectomy of cirrhotic livers, because liver regeneration requires greater energy demands and control of oxidative stress. Cirrhosis was induced in male Wistar-Furth rats by administration of thioacetamide. NADH-cytochrome c reductase activity, mitochondrial glutathione peroxidase activity and mitochondrial GSH levels were all significantly lowered in cirrhotic livers and in the cirrhotic remnants up to 72 h after 70% hepatectomy when compared to the corresponding controls. Lower respiratory control ratios with succinate as substrate were also observed from 6 to 48 h post-hepatectomy. At 24 h post-hepatectomy, higher levels of lipid peroxidation were observed. We conclude that, compared to the controls, cirrhotic livers have diminished oxidative phosphorylation capabilities due to changes in NADH and FADH(2)-linked respiration as well as impaired antioxidant defenses following partial hepatectomy. Both of these factors, if critical, could then impede liver regeneration.
The impact of microwave roasting on the thermooxidative degradation of perah seed oil (PSO) was evaluated during heating at a frying temperature (170°C). The roasting resulted significantly lower increment of the values of oxidative indices such as free acidity, peroxide value, p-anisidine, total oxidation (TOTOX), specific extinctions and thiobarbituric acid in oils during heating. The colour L* (lightness) value dropped gradually as the heating time increased up to 12 h, whereas a*(redness) and b* (yellowness) tended to increase. The viscosity and total polar compound in roasted PSO was lower as compared to that in unroasted one at each heating times. The tocol retention was also high in roasted samples throughout the heating period. The relative contents of polyunsaturated fatty acids (PUFAs) were decreased to 94.42% and saturated fatty acids (SFAs) were increased to 110.20% in unroasted sample, after 12 h of heating. On the other hand, in 3 min roasted samples, the relative contents of PUFAs were decreased to 98.08% and of SFAs were increased to 103.41% after 12 h of heating. Outcome from analyses showed that microwave roasting reduced the oxidative deteriorations of PSO during heating.
Silylated cellulose has been successfully synthesized using TEMPO-oxidized nanocellulose (TEMPO-NC) from oil palm empty fruit bunch and 3-aminopropyltriethoxysilane (APS) in an ethanol/water medium at a low curing temperature of 40 °C as compared to those reported in the literature of above 100 °C. Confirmation of the grafting process can be seen from the new FTIR peaks at 810 cm-1 and 749 cm-1 which are attributed to the SiC stretching and SiC, and new 13C NMR signals at 10.3, 21.7 and 42.7 ppm which are assigned to C7, C8, and C9 of the silylated TEMPO-NC. The decrease in the intensities of the cellulose peaks of C2, C3, C6 and C6' in the 13C NMR indicates that silylation not only occurs on the hydroxyls, but more importantly on the TEMPO-NC carboxylic moiety of C6', which is postulated as being the primary factor for this successful modification. This is further corroborated by the emergence of three signals at 43, 61, and 69 ppm in the 29Si NMR spectrum which corresponds to Si(OSi)(OR)2R', Si(OSi)2(OR)R', and Si(OSi)3R' units respectively. Additional evidence is provided by the EDX which shows an increase in Si weight percent of 1.94 after reaction. This silylated cellulose from OPEFB has the potentials to be used as bionanocomposite reinforcing elements.
In this study, the zinc oxide (ZnO) layer was synthesised on the surface of Zn plates by three different techniques, i.e. electrolysis, hydrogen peroxide and heat treatment. The synthesised ZnO layers were characterised using scanning electron microscopy, X-ray diffraction, UV-visible diffuse reflectance and photoluminescence spectroscopy. The photocatalytic activity of the ZnO layer was further assessed against methylene blue (MB) degradation under UV irradiation. The photocatalytic degradation of MB was achieved up to 84%, 79% and 65% within 1 h for ZnO layers synthesised by electrolysis, heat and hydrogen peroxide treatment, respectively. The reusability results show that electrolysis and heat-treated ZnO layers have considerable photocatalytic stability. Furthermore, the results confirmed that the photocatalytic efficiency of ZnO was directly associated with the thickness and enlarged surface area of the layer. Finally, this study proved that the ZnO layers synthesised by electrolysis and heat treatment had shown better operational stability and reusability.
Aging is characterized by progressive decline in physiological and body function due to increase in oxidative damage. Gelam honey has been accounted to have high phenolic and nonphenolic content to attenuate oxidative damage. This study was to determine the effect of local gelam honey on oxidative damage of aged rats. Twenty-four male Spraque-Dawley rats were divided into young (2 months) and aged (19 months) groups. Each group was further divided into control (fed with plain water) and supplemented with 2.5 mg/kg body weight of gelam honey for 8 months. DNA damage level was determined by comet assay and plasma malondialdehyde (MDA) by high performance liquid chromatography (HPLC). The activity of blood and cardiac antioxidant enzymes was determined by spectrophotometer. The DNA damage and MDA level were reduced in both gelam honey supplemented groups. Gelam honey increases erythrocytes CAT and cardiac SOD activities in young and cardiac CAT activity in young and aged groups. The DNA damage was increased in the aged group compared to young group, but reduced at the end of the study. The decline of oxidative damage in rats supplemented with gelam honey might be through the modulation of antioxidant enzyme activities.
Treatment of industrial waste water (e.g. textile waste water, phenol waste water, pharmaceutical etc) faces limitation in conventional treatment procedures. Advanced oxidation processes (AOPs) do not suffer from the limits of conventional treatment processes and consequently degrade toxic pollutants more efficiently. Complexity is faced in eradicating the restrictions of AOPs such as sludge formation, toxic intermediates formation and high requirement for oxidants. Increased mass-transfer in AOPs is an alternate solution to this problem. AOPs combined with Fluidized bed reactor (FBR) can be a potential choice compared to fixed bed or moving bed reactor, as AOP catalysts life-span last for only maximum of 5-10 cycles. Hence, FBR-AOPs require lesser operational and maintenance cost by reducing material resources. The time required for AOP can be minimized using FBR and also treatable working volume can be increased. FBR-AOP can process from 1 to 10 L of volume which is 10 times more than simple batch reaction. The mass transfer is higher thus the reaction time is lesser. For having increased mass transfer sludge production can be successfully avoided. The review study suggests that, optimum particle size, catalyst to reactor volume ratio, catalyst diameter and liquid or gas velocity is required for efficient FBR-AOP systems. However, FBR-AOPs are still under lab-scale investigation and for industrial application cost study is needed. Cost of FBR-AOPs highly depends on energy density needed and the mechanism of degradation of the pollutant. The cost of waste water treatment containing azo dyes was found to be US$ 50 to US$ 500 per 1000 gallons where, the cost for treating phenol water was US$ 50 to US$ 800 per 1000 gallons. The analysis for FBR-AOP costs has been found to depend on the targeted pollutant, degradation mechanism (zero order, 1st order and 2nd order) and energy consumptions by the AOPs.
In the present study, a comparison of central composite design (CCD) and Taguchi method was established for Fenton oxidation. [Dye]ini, Dye:Fe(+2), H2O2:Fe(+2), and pH were identified control variables while COD and decolorization efficiency were selected responses. L 9 orthogonal array and face-centered CCD were used for the experimental design. Maximum 99% decolorization and 80% COD removal efficiency were obtained under optimum conditions. R squared values of 0.97 and 0.95 for CCD and Taguchi method, respectively, indicate that both models are statistically significant and are in well agreement with each other. Furthermore, Prob > F less than 0.0500 and ANOVA results indicate the good fitting of selected model with experimental results. Nevertheless, possibility of ranking of input variables in terms of percent contribution to the response value has made Taguchi method a suitable approach for scrutinizing the operating parameters. For present case, pH with percent contribution of 87.62% and 66.2% was ranked as the most contributing and significant factor. This finding of Taguchi method was also verified by 3D contour plots of CCD. Therefore, from this comparative study, it is concluded that Taguchi method with 9 experimental runs and simple interaction plots is a suitable alternative to CCD for several chemical engineering applications.
During the process and operation of the dyes, the wastes produced were commonly found to contain organic and inorganic impurities leading to risks in the ecosystem and biodiversity with the resultant impact on the environment. Improper effluent disposal in aqueous ecosystems leads to reduction of sunlight penetration which in turn diminishes photosynthetic activity, resulting in acute toxic effects on the aquatic flora/fauna and dissolved oxygen concentration. Recently, photodegradation of various synthetic dyes has been studied in terms of their absorbance and the reduction of oxygen content by changes in the concentration of the dye. The advantages that make photocatalytic techniques superior to traditional methods are the ability to remove contaminates in the range of ppb, no generation of polycyclic compounds, higher speed, and lower cost. Semiconductor metal oxides, typically TiO2, ZnO, SnO, NiO, Cu2O, Fe3O4, and also CdS have been utilized as photocatalyst for their nontoxic nature, high photosensitivity, wide band gap and high stability. Various process parameters like photocatalyst dose, pH and initial dye concentrations have been varied and highlighted. Research focused on surface modification of semiconductors and mixed oxide semiconductors by doping them with noble metals (Pt, Pd, Au, and Ag) and organic matter (C, N, Cl, and F) showed enhanced dye degradation compared to corresponding native semiconductors. This paper reviews recent advances in heterogeneous photocatalytic decolorization for the removal of synthetic dyes from water and wastewater. Thus, the main core highlighted in this paper is the critical selection of semiconductors for photocatalysis based on the chemical, physical, and selective nature of the poisoning dyes.