Degradation of carbofuran in water by solar photocatalysis in presence of photosensitizers

The effect of the presence of photosensitizers, methylene blue (MB) and rose Bengal (RB), on the degradation of carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate) in water in a solar photocatalytic system was investigated. It was found that as compared to MB, RB generally showed a stronger effect on the decomposition of carbofuran under comparable conditions. Among the conditions studied, adding 2 x 10(-6) M of RB, that corresponding to 2% of the initial concentration of carbofuran solution in the system, rendered the most effective degradation of carbofuran. As a result, a carbofuran removal percentage of 69.9%, a mineralization efficiency of 28.0%, and a microtoxicity reduction of 65.0% could be achieved. The degradation and mineralization of carbofuran was found to follow the pseudo-first order reaction kinetics. The decomposition mechanism of carbofuran was further investigated through identification of the intermediates to elaborate the influence of dye photosensitizer on the solar photocatalysis of carbofuran in water. On the basis of the intermediates identified, including carbofuran phenol, 3-hydroxy carbofuran phenol, and substituted alcohols (3-phenoxy 1-propanol, 2-ethyl 1-hexanol, 2-butoxyl ethanol), it appears that hydrolysis and hydroxylation were the two key mechanisms for decomposing carbofuran during the process of solar photocatalysis with the aid of dye photosensitizer.     

Photocatalytic oxidation of xenobiotics in water with immobilized TIO2 on agitator

Abstract

A novel photocatalytic oxidation reactor, using Degussa P‐25 T_iO₂ as a stationary phase with a thickness of 1.5–2.0 um on the blades of agitator, was developed to study the photocatalytic oxidation of xenobiotics. Particularly in this device, separation of photocatalyst from the purified water after oxidation reaction was not necessary, and no other aeration equipment was required to supply oxygen. To examine the efficiency of this device, photocatalytic degradation of xenobiotic organics such as carbofuran was studied as an example. Results indicated that carbofuran could be degraded completely with mineralization efficiency of 20 % after 6 hours of oxidation under the imposed conditions. The mineralization rate of carbofuran was found to follow the pseudo‐first order reaction kinetics. Moreover, the rate constant of mineralization was found to be proportional to T_iO₂ film area and the square root of UV light intensity. These results implied the mineralization efficiency of carbofuran could be improved through increasing T_iO₂ film area and UV light intensity. Accordingly, this novel device showed potential application for degrading xenobiotics in water.     

Solar photocatalysis for treatment of Acid Yellow-17 (AY-17) dye contaminated water using Ag@TiO2 core–shell structured nanoparticles

Wastewater released from textile industries causes water pollution, and it needs to be treated before discharge to the environment by cost effective technologies. Solar photocatalysis is a promising technology for the treatment of dye wastewater. The Ag@TiO₂ nanoparticles comprising of Ag core and TiO₂ shell (Ag@TiO₂) have unique photocatalytic property of inhibition of electron–hole recombination and visible light absorption, which makes it a promising photocatalyst for use in solar photocatalysis and with higher photocatalytic rate. Therefore, in the present work, the Ag@TiO₂ nanoparticles synthesized by one pot method with postcalcination step has been used for the degradation of Acid Yellow-17 (AY-17) dye under solar light irradiation. The Ag@TiO₂ nanoparticles were characterized using thermogravimetric–differential thermal analysis, X-ray diffraction, transmission electron microscopy, selected area electron diffraction, and energy dispersive X-ray analysis. The catalyst has been found to be very effective in solar photocatalysis of AY-17, as compared to other catalysts. The effects of pH, catalyst loading, initial dye concentration, and oxidants on photocatalysis were also studied. The optimized parameters for degradation of AY-17 using Ag@TiO₂ were found to be pH?3, dye/catalyst ratio of 1:10 (g/g), and 2 g/L of (NH₄)₂S₂O₈ as oxidant. Efficient decolorization and mineralization of AY-17 was achieved. The kinetics of color, total organic carbon, and chemical oxygen demand removal followed the Langmuir–Hinshelwood model. Ag@TiO₂ catalyst can be reused thrice without much decline in efficiency. The catalyst exhibited its potential as economic photocatalyst for treatment of dye wastewater.     

Kinetics of carbofuran insecticide conversion under methanogenic conditions

Abstract

This study reports on the kinetics of carbofiiran insecticide transformation under controlled aquatic methanogenic conditions. Attempts were also made to investigate the effects of culture acclimation on the kinetics of carbofiiran transformation.

The results indicate that in an anaerobic system carbofuran was hydrolyzed to carbofiiran phenol and monomethyl amine by hydrolysis. Analysis of the kinetic parameters showed that active anaerobic cultures (both acclimated and unnacclimated) do not enhance the rate of hydrolysis of carbofuran. The hydrolysis product, monomethyl amine, was further mineralized by the methanogenic culture. The major product of carbofuran hydrolysis, carbofiiran phenol, was resistant to further degradation.     

Solar light–driven photocatalytic degradation and mineralization of beta blockers propranolol and atenolol by carbon dot/TiO2 composite

Herein improved solar light–driven photocatalytic degradation and mineralization of two emerging pollutants as well as recalcitrant beta blockers propranolol (PR) and atenolol (AT) have been demonstrated by metal-free carbon dot/TiO₂ (CDT) composite. Hydrothermally synthesized TiO₂ has been decorated with electrochemically synthesized carbon dots (CDs) and was well characterized by various analytical techniques viz. XRD, FTIR, Raman, XPS, UV–visible DRS, FESEM, and TEM. The optimized CDT composite, 2CDT (2 mL carbon dot/TiO₂), showed?~?3.45- and?~?1.75-fold enhancement in the photodegradation rate as compared to pristine TiO₂ for PR and AT respectively in 1 hour of irradiation along with complete degradation of PR and AT after 3 hours of irradiation. 2CDT exhibited 76% and 80% mineralization of PR and AT in contrast with 62% and 47% observed by pristine TiO₂. Further, the major reaction intermediates formed after degradation have been identified by HPLC/MS analysis, confirming more than 99% reduction of the parent compound for both PR and AT. Reusability of the optimized catalyst also showed successful degradation up to 3 cycles, showing reduction abilities of 97%, 95%, and 94% for 1st, 2nd, and 3rd cycle respectively. The enhanced degradation and mineralization efficiency of the 2CDT composite could be attributed to the excellent photosensitizer and electron reservoir properties of the CD along with upconverted photoluminescence behavior. The present study unlocks the possibility of using metal-free, facile CDT composite for effective degradation and mineralization of widely used beta blockers and other pharmaceuticals.

     

A novel BiVO4-GO-TiO2-PANI composite for upgraded photocatalytic performance under visible light and its non-toxicity

A novel non-toxic hybrid BiVO₄-GO-TiO₂-polyaniline (PANI) (BVGT-PANI) composite with superior photocatalysis was successfully prepared via a one-pot hydrothermal reaction. The structural and morphological characterizations of the synthesized compounds were analyzed by a series of techniques. We found excellent photocatalytic efficiencies for methylene blue (MB) and phenol degradation under visible light irradiation after adhering the PANI to the photocatalyst. The degradation rates of MB and phenol reach up to approximately 85% and 80%, respectively, after 3 h of irradiation. For photodegradation MB, BVGTA exhibit the highest k_app rate constant of about 1.06?×?10^?2 min^?1, which is about 1.63-fold faster than BVG and 2.94-fold faster than BVGT. For photodegradation of phenol, BVGTA exhibits the highest k_app rate constant, of about 8.86?×?10^?3min^?1, which is about 1.2-fold faster than BVG and 1.96-fold faster than BVGT. Furthermore, vitro toxicity test against Bacillus subtilis and Staphylococcus aureus demonstrated that the nanophotocatalyst is non-toxic.

     

Comparison of various advanced oxidation processes for the degradation of phenylurea herbicides

Various types of advanced oxidation processes (AOPs), such as UV photolysis, ozonation, heterogeneous photocatalysis and their combinations were comparatively examined at the same energy input in a home-made reactor. The oxidative transformations of the phenylurea herbicides fenuron, monuron and diuron were investigated. The initial rates of transformation demonstrated that UV photolysis was highly efficient in the cases of diuron and monuron. Ozonation proved to be much more effective in the transformation of fenuron than in those of the chlorine containing monuron and diuron. In heterogeneous photocatalysis, the rate of decomposition decreased with increase of the number of chlorine atoms in the target molecule. Addition of ozone to UV-irradiated solutions and/or TiO₂-containing suspensions markedly increased the initial rates of degradation. Dehalogenation of monuron and diuron showed that each of these procedures is suitable for the simultaneous removal of chlorinated pesticides and their chlorinated intermediates. Heterogeneous photocatalysis was found to be effective in the mineralization.     

Phenol electrooxidation on Fe-Co3O4 thin film electrodes in alkaline medium

Fe-Co₃O₄ thin film with different amounts of Fe have been used for the electro-oxidation of phenol in alkaline medium at room temperature. The electrodes were prepared by coating stainless steel supports with successive layers of the oxides, obtained by thermal decomposition at 673 K. The electrolysis was carried out at constant potential and the phenol disappearance, during the electrolysis, was monitored by UV-Vis absorbance measurements between 250 and 500 nm. After 3 h of electrolysis, the intermediates were identified by comparing the HPLC data and UV-Vis spectra to those from pure standards. The results indicate that the same oxidation products are formed on the different prepared electrodes, namely the decomposition products of phenol such as benzoquinone, hydroquinone and cathecol in basic medium. Simulated results show clearly the decrease of the amount of phenolic species with the electrolysis time. An enhancement of the phenol removal is observed with the presence of iron in the oxide. Under the operating conditions, around 30% of the initial phenol has been removed at ca. 3 h and the complete degradation is obtained after 54 h of electrolysis, when Fe-Co₃O₄ thin film with 10% of Fe is used as anode.     

Vis/Co-TiO_2/KHSO_5体系Fenton-光催化协同降解苯酚

通过溶胶-凝胶法制备了同时具有可见光(Vis)光催化和Fenton催化双重活性的Co-TiO2催化剂。通过对比Vis/Co-TiO2/KHSO5、Co-TiO2/KHSO5和Vis/Co-TiO23种体系对苯酚的降解效果,Vis/Co-TiO2/KHSO5表现出明显的Fenton-光催化协同作用。进一步研究pH值、KHSO5与苯酚摩尔比(nKHSO5∶nC6H6O)和Co-TiO2投加量(mCo-TiO2)对Fenton-光催化协同降解苯酚效果的影响。结果表明,pH=6.9、nKHSO5∶nC6H6O=10∶1、mCo-TiO2=1.0 g/L时,降解率达100%。最后,结合XRD、XPS和UV-DRS等手段和催化活性实验数据分析了Vis/Co-TiO2/KHSO5体系的催化机理。     

Reductive transformation of 2,4-dichlorophenoxyacetic acid by nanoscale and microscale Fe3O4 particles

Reductive transformation of 2,4-dichlorophenoxyacetic acid (2,4-D) by nanoscale and microscale Fe₃O₄ was investigated and compared. Disappearance of the parent species and formation of reaction intermediates and products were kinetically analyzed. Results suggest that the transformation of 2,4-D followed a primary pathway of its complete reduction to phenol and a secondary pathway of sequential reductive hydrogenolysis to 2,4-dichlorophenol (2,4-DCP), chlorophenol (2-CP, 4-CP) and phenol. About 65% of 2,4-D with initial concentration of 50 μ M was transformed within 48 h in the presence of 300 mg L^?1 nanoscale Fe₃O₄, and the reaction rates increased with increasing dosage of nanoscale Fe₃O₄. The decomposition of 2,4-D proceeded rapidly at optimum pH 3.0. Chloride was identified as a reduction product for 2,4-D in the magnetite–water system. Reductive transformation of 2,4-D by microscale Fe₃O₄ was slower than that by nanoscale Fe₃O₄. The reactions apparently followed pseudo-first-order kinetics with respect to the 2,4-D transformation. The degradation rate of 2,4-D decreased with the increase of initial 2,4-D concentration. In addition, anions had a significant adverse impact on the degradation efficiency of 2,4-D.     

Evaluation of different electrochemical methods on the oxidation and degradation of Reactive Blue 4 in aqueous solution

The oxidation of a reactive dye, Reactive Blue 4, RB4, (C.I. 61205), widely used in the textile industries to color natural fibers, was studied by electrochemical techniques. The oxidation on glassy carbon electrode and reticulated vitreous carbon electrode occurs in only one step at 2.0 < pH < 12 involving a two-electron transfer to the amine group leading to the imide derivative. Dye solution was not decolorized effectively in this electrolysis process. Nevertheless, the oxidation of this dye on Ti/SnO2/SbO(x) (3% mol)/RuO2 (1% mol) electrode showed 100% of decolorization and 60% of total organic carbon removal in Na2SO4 0.2 M at pH 2.2 and potential of +2.4V. Experiments on degradation photoelectrocatalytic were also carried out for RB4 degradation in Na2SO4 0.1 M, pH 12, using a Ti/TiO2 photoanode biased at +1.0 V and UV light. After 1h of electrolysis the results indicated total color removal and 37% of mineralization.     

Degradation of rhodamine B by Fe(0)-based Fenton process with H2O2

Degradation of rhodamine B by Fe(0)-based Fenton process with H₂O₂ was investigated. The effects of H₂O₂ dose, Fe(0) dose, initial concentration of rhodamine B and initial pH value on the degradation of rhodamine B were examined. The results showed that the degradation and mineralization of rhodamine B occurred with low dose of H₂O₂ and Fe(0). The intermediates of rhodamine B were analyzed with UV-Vis spectrophotometry and ion chromatography and the mechanism of oxidative degradation of rhodamine B was also discussed. The reactive oxygen species (·OH) produced in Fe(0)-based Fenton process with H₂O₂ is the key to the degradation of rhodamine B by ways of N-de-ethylation, chromophore cleavage, ring-opening and mineralization.     

MnO2催化Fenton试剂降解苯酚废水

实验对MnO2催化Fenton试剂氧化高浓度苯酚废水的动力学特性和去除效果进行了研究。结果表明,MnO2可以提高Fenton试剂体系对苯酚的降解率以及COD的去除率;Fenton试剂以及MnO2催化Fenton试剂氧化苯酚废水体系中苯酚的降解都符合拟一级动力学模型。在MnO2催化Fenton试剂氧化体系中,苯酚的降解速率常数有明显提高,反应活化能也有所降低,说明MnO2的加入可以使反应容易进行。废水降解前后紫外可见吸收光谱和红外谱图表明,Fenton试剂法将苯酚可能降解为羧酸、烯烃等有机物中间体。     

Photocatalytic degradation of azo dyes by nitrogen-doped TiO2 nanocatalysts

This study examined the photocatalytic degradation of three azo dyes, acid orange 7 (AO7), procion red MX-5B (MX-5B) and reactive black 5 (RB5) using a new type of nitrogen-doped TiO2 nanocrystals. These newly developed doped titania nanocatalysts demonstrated high reactivity under visible light (lambda>390 nm), allowing more efficient usage of solar light. The doped titania were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Experiments were conducted to compare the photocatalytic activities of nitrogen-doped TiO2 nanocatalysts and commercially available Degussa P25 powder using both UV illumination and solar light. It is shown that nitrogen-doped TiO2 after calcination had the highest photocatalytic activity among all three catalysts tested, with 95% of AO7 decolorized in 1 h under UV illumination. The doped TiO2 also exhibited substantial photocatalytic activity under direct sunlight irradiation, with 70% of the dye color removed in 1h and complete decolorization within 3 h. Degussa P25 did not cause detectable dye decolorization under identical experimental conditions using solar light. The decrease of total organic carbon (TOC) and evolution of inorganic sulfate (SO4(2-)) ions in dye solutions were measured to monitor the dye mineralization process.     

Carbofuran degradation in soil profiles

Abstract

Two soils, Puyallup fine sandy loam from Puyallup, WA, and Ellzey fine sand from Hastings, FL, each with a prior history of carbofiiran exposure but with different pedological and climatological characteristics, were found to exhibit enhanced degradation toward carbofiiran in surface and subsurface soil layers. The treated Puyallup and Ellzey soils exhibited higher mineralization rates for both the carbonyl and the aromatic ring of carbofiiran when compared to untreated soils. Disappearance rates of [¹⁴C‐URL (uniformly ring labeled)] carbofiiran in the treated Ellzey soil was faster than in untreated soil, and also faster in surface soil than in subsurface soil. Initial degradation patterns in the treated Ellzey soil were also different from those in the untreated soil. The treated Ellzey soil degraded carbofuran mainly through biological hydrolysis, while untreated soil degraded carbofuran through both oxidative and hydrolytic processes.     

Photocatalytic degradation of phenol using Ag core-TiO<Subscript>2</Subscript> shell (Ag@TiO<Subscript>2</Subscript>) nanoparticles under UV light irradiation

Ag@TiO₂ nanoparticles were synthesized by one pot synthesis method with postcalcination. These nanoparticles were tested for their photocatalytic efficacies in degradation of phenol both in free and immobilized forms under UV light irradiation through batch experiments. Ag@TiO₂ nanoparticles were found to be the effective photocatalysts for degradation of phenol. The effects of factors such as pH, initial phenol concentration, and catalyst loading on phenol degradation were evaluated, and these factors were found to influence the process efficiency. The optimum values of these factors were determined to maximize the phenol degradation. The efficacy of the nanoparticles immobilized on cellulose acetate film was inferior to that of free nanoparticles in UV photocatalysis due to light penetration problem and diffusional limitations. The performance of fluidized bed photocatalytic reactor operated under batch with recycle mode was evaluated for UV photocatalysis with immobilized Ag@TiO₂ nanoparticles. In the fluidized bed reactor, the percentage degradation of phenol was found to increase with the increase in catalyst loading.     

Carbofuran degraded by iron-doped anatase: Weakening the cholinesterase inhibitory activity in the photoproducts mixture

Carbofuran is a toxic carbamate pesticide, and its use has increased in recent years. While marketing information indicates stability in different chemical media, carbofuran exhibits relative photolability. The aim of this research was to decompose carbofuran and to identify the photoproducts achieved when two different doped titania photocatalysts were employed under UV irradiation. The iron-doped TiO₂ materials were obtained (a) via a hydrothermal method and (b) by an ultrasound-assisted sol–gel method. The precursors were TiOSO₄?xH₂O and Fe₃(NO₃)·9H₂O. X-ray studies confirmed that the anatase phase of the iron-doped TiO₂ resulted from the two preparation methods. The photocatalytic performance of the prepared materials was monitored by LC/ESI-QTOF-MS, enabling the identification of photoproducts: oxo-carbamates, hydroxylated benzofuranes, a carboxamide, and one amine. By using the iron-doped TiO₂ materials, 2,2-dimethyl-2,3-dihydrobenzofuran-3,7-diol was the most abundant photoproduct, and N,2,2-trimethyl-2,3-dihydrobenzofuran-7-amine was the only compound that had not been previously reported in the photolysis and photocatalysis of carbofuran. The product 3-hydroxy carbofuran, a cholinesterase inhibitor, was quantified and was found to be transformed into compounds that lack this inhibitive property.     

Optimization of photo-Fenton process parameters on carbofuran degradation using central composite design

Carbofuran, one of the most toxic and biorefractory carbamate compounds, is widely used in insecticides in Taiwan (9-18% of total insecticides production per year). In the present study, a central composite design experiment was used to study the effect of photo-Fenton treatment on carbofuran solution and to optimize the process variables such as carbofuran concentration (1-100 mg L(-1)), H(2)O(2) dosage rate (0.25-6 mg L(-1) min(-1)) and Fe(3+) dosage (1-50 mg L(-1)), which influenced the efficiency of carbofuran degradation and mineralization. The results indicated that all the variables investigated in this study had significant roles in the degradation and mineralization of carbofuran in solution. The carbofuran degradation and mineralization efficiencies were increased with increase in H(2)O(2) dosage rate and Fe(3+) dosage, and with decrease in carbofuran concentration. Furthermore, optimum values of both H(2)O(2) dosage rate and Fe(3+) dosage were found to shift to higher values as carbofuran concentration increased. Based on the model obtained in this study, optimum H(2)O(2) dosage rate and Fe(3+) dosage were found to be 4 mg L(-1) min(-1) and 20 mg L(-1), respectively, for 51 mg L(-1) of carbofuran concentration. Under these conditions, carbofuran was completely removed within 30 min and coupled with 78% mineralization at the end of experiment.     

Photocatalytic ozonation of pesticides in a fixed bed flow through UVA-LED photoreactor

In this study, a fixed bed flow through UVA-LED photoreactor was used to compare the efficiency of ozone, photocatalysis and photocatalysis-ozone degradation, and mineralization of two pure pesticides, 2,4-dichlorophenoxyacetic acid (2,4-D) and 2-methyl-4-chlorophenoxyacetic acid (MCPA), and a commercial one, Killex®. For the degradation of the parent compounds, ozone-based processes were more effective. While for mineralization, photocatalytic processes were more effective. Photocatalytic ozonation was the most efficient process for both the degradation and mineralization of the parent compounds. The degradation rates and mineralization by photocatalytic ozonation were higher than the summation of the corresponding rates by ozonation and photocatalysis, indicating a symbiotic relationship.Overall, the photocatalytic ozonation process with the fixed bed TiO₂ reduces the time needed for the degradation and mineralization of the pesticides, reduces the costs of powder catalyst separation and overcomes the reduced efficiency of immobilized catalysts, which makes the process quite attractive for practical applications.     

Kinetics and mechanism of TNT degradation in TiO2 photocatalysis

The photocatalytic degradation of TNT in a circular photocatalytic reactor, using a UV lamp as a light source and TiO(2) as a photocatalyst, was investigated. The effects of various parameters such as the initial TNT concentration, and the initial pH on the TNT degradation rate of TiO(2) photocatalysis were examined. In the presence of both UV light illumination and TiO(2) catalyst, TNT was more effectively degraded than with either UV or TiO(2) alone. The reaction rate was found to obey pseudo first-order kinetics represented by the Langmuir-Hinshelwood model. In the mineralization study, TNT (30 mg/l) photocatalytic degradation resulted in an approximately 80% TOC decrease after 150 min, and 10% of acetate and 57% of formate were produced as the organic intermediates, and were further degraded. NO(-)(3) NO(-)(2), and NH(+)(4) were detected as the nitrogen byproducts from photocatalysis and photolysis, and more than 50% of the total nitrogen was converted mainly to NO(-)(3)in the photocatalysis. However, NO(-)(3) did not adsorbed on the TiO(2) surface. TNT showed higher photocatalytic degradation efficiency at neutral and basic pH.