Catalytic wet air oxidation removal of tetracycline by La2O3 immobilized on recycled polyethylene terephthalate using the response surface methodology.

This study investigated the removal of tetracycline from the aqueous solutions by lanthanum oxide nanoparticles covered with polyethylene terephthalate (PET) using a low-cost and facile co-precipitation method, via catalytic wet air oxidation process (CWAO) by response surface methodology (RSM). XRD, FTIR, SEM, and EDX-map techniques have been employed to investigate the crystal structure, functional groups on the surface, morphologic characteristics, and elemental composition, respectively. Under optimum conditions (pH= 9, initial TC concentration= 20 mg L-1, nanocomposite dosage= 1.5 g L-1, pressure= 4 bar, temperature= 70 °C, and time= 90 min), TC removal efficiency by La2O3-PET was achieved at about 99.9%. The environmental parameters were assessed to determine tetracycline catalytic wet air oxidation degradation rate, which included cleaning gases, hydrogen peroxide, type of organic compounds, anions, radical scavenger and reusability. The ANOVA results indicated that the polynomial model proves that the model is entirely meaningful (F-value> 0.001 and P-value< 0.0001) and has high coefficient values of adjusted R2 (0.7404) and predicted R2 (0.5940). The findings indicated that the variables of time, pH, temperature, dosage, and TC concentration have the greatest role in removing tetracycline, respectively. However, pressure as a factor does not have a considerable influence on the performance of the system. In general, due to the presence of the role of additional anionics, the effectiveness of this method for removing tetracycline from drinking water was 82.76%. The catalyst indicated pleasing stability and recycling power during eight testing cycles. Further, the estimated electrical energy per order consumption (EEO) for the CWAO/La2O3-PET system was calculated as 5.31 kWh m-3 with an operational cost (OC) utilization of 1.78 USD kg-1 and it has been shown that this process is feasible and economically comparable to other CWAO processes. The breakdown intermediate products of tetracycline in the CWAO were examined using gas chromatography/mass spectrometry (GC-MS) analysis. The toxicity analyses for the removal of TC were carried out using Daphnia magna and the CWAO process achieved a remarkable decrease in the presence of La2O3-PET nanocomposite (LC50 and toxicity unit (TU) 48 h equal to 0.634 and 157.72 vol percent).

Facile provision of CuO-Kaolin nanocomposite for boosted sonocatalytic removal of Cr(VI) from hydrous media.

Nowadays, nanoscale materials have been widely applied in the removal of contaminants from the water system. Reduction of Cr(VI) (as a poisonous species) to Cr(III) (as a slight toxic species) was performed using CuO-Kaolin with ultrasound (US) irradiation. The CuO-Kaolin nanocomposite was synthesized via a facile co-precipitation method. Then X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscope and Energy dispersive X-ray spectroscopy analyses were performed to identify the structural features of CuO-Kaolin. The role of influential parameters for the reduction of Cr(VI) was investigated in sonocatalytic advanced oxidation system. About 89.35% of Cr(VI) was removed via US/CuO-Kaolin process after 90 min at optimum conditions (pH = 3, sonocatalyst dosage = 1 g L-1 and [Cr (VI)]0 = 20 mg L-1). This outstanding result was due to the synergistic effect of the increased electron delivery to conduction band on CuO-Kaolin nanocomposite and the increased reactive surface region of nanoparticles by sonication. The presence of H2O2 as an amplifier improved the removal efficiency of Cr(VI) from 89.35% to 100% after 20 min. Kinetic experimental results were well described by a pseudo-first-order kinetic model. Desorption experiments showed excellent stability of sonocatalyst during the reaction and maintenance of the catalytic activity up to 10 sequential cycles.

Design and modeling of diazinon degradation in hydrous matrix by Ni-doped ZnO nanorods under ultrasonic irradiation: process optimization using RSM (CCD), kinetic study, reaction pathway, mineralization, and toxicity assessment.

In first, the Ni-doped ZnO nanorods used as an appeal sonocatalyst was synthesized through co-precipitation method. Afterwards, the crystalline structure, functional groups, surface morphology, and elemental composition were characterized by a set of analysis. Removal of diazinon ((DZ) as a renowned pesticide) was investigated using sonocatalytic performance of US/Ni-doped ZnO system. In this empirical study, response surface methodology (RSM) based central composite design (CCD) was applied for optimization of operational factors. Under the optimum conditions such as initial pH = 5, initial DZ concentration = 15 mg L-1, sonocatalyst dosage = 1 g L-1, and in the presence of organic compounds (oxalic acid, humic acid, and folic acid) = 3 mg L-1, the sonocatalytic degradation of DZ after 15 min was 82.29%. The F-value (6.64) and P-value (< 0.0001) for DZ degradation in the quadratic model imply the proposed model was significant. A-factor (pH) considers as a prominent factor owing to having the highest F-value. In addition, the sonocatalytic data in this study exhibited valid fitting for the first order kinetic model (R2 > 0.98). After six consecutive cycles, the Ni-doped ZnO nanorods could be recyclable for sonocatalytic degradation of DZ. The five main compounds produced during the US/Ni-doped ZnO embracing 2-isopropyl-6-methyl-4-pyrimidinol (IMP), diethyl phosphonate, diazoxon, hydroxyldiazinon, and diazinon methyl ketone are formed in the path of DZ degradation. OFAT style also revealed 99.99% of DZ degradation with 73.26% of mineralization rate in optimum status. The Ni-doped ZnO presented agreeable sonocatalytic facility in the refinement of real water and wastewater matrix. Finally, the results of toxicity evaluation (Daphnia magna) in the sonocatalytic degradation of DZ (by US/Ni-doped ZnO system) showed that the toxicity of the DZ solution lessened under US waves (LC50 and TU 48 h equal to 36.472 and 2.741 volume percent, respectively).

Synthesis of ZnO immobilized on recycled polyethylene terephtalate for sonocatalytic removal of Cr(VI) from synthetic, drinking waters and electroplating wastewater.

In this study, Cr(VI) was removed sonocatalytically by the zinc oxide nanoparticle coated with polyethylene terephthalate (PET) fabricated through a facile co-precipitation method. The crystal structure, functional groups on the surface, morphology, surface composition and oxidation states of the nanomaterials were investigated by XRD, FTIR, SEM, EDX and XPS techniques. Environmental parameters including solution pH, catalyst dose, hexavalent chromium concentration, H2O2 content, purging gases, organic compounds and type and anions strength on the sonotocatalytic removal of Cr(VI) were also investigated. Additionally, the contribution of each process, reusability, Cr(VI) reduction from actual water and electroplating wastewater were evaluated. Under the optimal conditions, [Cr(VI)]0=20 mg/L, nanocomposite loading=1.6 g/L and pH=5, 99.92% of Cr(VI) was removed within 60 min. By increaing, Cr(VI) concentration (5-50 mg/L), kobs decreased to values between 0.1498 and 0.0063 min-1 and the calculated electrical energy per order (EEo) increased from 148.68 to 3535.24 kWh.m-3, respectively. The presence of purging gases, organic compounds and ionic strength negatively affected Cr(VI) reduction. Examination of radical scavengers showed that the most active radicals in Cr(VI) removal were O2•- and h+. The removal of the Cr(VI) using the US/ZnO-PET method (99.92%) was higher than that of the US/ZnO method (70.78%). The catalyst activity was well maintained up to eight consecutive cycles. In addition, the removal efficiency was approximately 72.23 and 68.55% for drinking water and real electroplating wastewater samples, respectively. The results of toxicity in the sonotocatalytic removal of Cr(VI) by Daphnia magna showed LC50 and toxicity unit (TU) 48 h, which was equal to 81.46 and 1.227 vol percent.

Photocatalytic removal of bentazon by copper doped zinc oxide nanorods: Reaction pathways and toxicity studies.

In this study, bentazon herbicide was degraded photocatalytically by copper doped zinc oxide nanorods fabricated by using a facile co-precipitation method. The crystal structure, morphology, surface composition, functional groups on the surface and valence state of the nanorods were investigated by XRD, SEM-EDX, FTIR, and XPS material characterization techniques. Environmental parameters including solution pH, catalyst dose, bentazon concentration, purging gases, H2O2 content, organic compound type and reusability affecting the rate of photocatalytic degradation of bentazon were evaluated. Under the optimal conditions, [Bentazon]0 = 20 mg L-1, Cu-ZnO loading = 0.5 g L-1, H2O2 = 2 mM, pH = 7 and in the presence of oxygen gas, 100% of the herbicide was removed within 60 min. By raising bentazon concentration (10-50 mg L-1), kobs decreased to values between 0.14 and 0.006 min-1 and the calculated electrical energy per order (EEo) increased from 38.16 to 727.27 (kWh m-3), respectively. The degradation removal of the herbicide using the UV/Cu-ZnO method (98.28%) was higher than that of the UV/ZnO method (32.14%) process. Interestingly, the photocatalytic performances in the first and fifth reuse cycles during catalyst recyclability tests were found to be similar. Generally, the efficacy of the method in the decomposition of bentazon in drinking water (78.95%) and actual sewage (46.77%) declined because of the presence of other anions due to their role as a scavenger of photogenerated reactive species. Intermediate products in the photocatalytic degradation of bentazon identified by gas chromatography/mass spectrometry (GC/MS) analysis were 2-amino-N-isopropyl-benzamide, 2-amino-benzoic acid, N-isopropyl-2-nitro-benzamide, and acids such as pentenedioic acid, oxalic acid and propenoic acid. Furthermore, the main mechanism for the photocatalytic removal of bentazon was determined to be via attack by hydroxyl radicals (•OH). The results of toxicity in the photocatalytic removal of bentazon by D. magna showed LC50 and toxicity unit (TU) 48 h equal to 46.10 and 9.56 vol percent.

Application of ZnO nanorods doped with Cu for enhanced sonocatalytic removal of Cr(VI) from aqueous solutions.

The aim of this research was to develop a simple and inexpensive process for reduction of Cr(VI) to Cr(III). Zinc oxide nanoparticles were synthesized with an easy co-precipitation procedure, and the addition of Cu2+ doping agent effectively enhanced the Cr(VI) reduction in the presence of ultrasound (US). XRD, FT-IR, FE-SEM, EDX, VSM, and XPS were used to determine the structural specifications of the zinc oxide nanoparticles. Under optimal conditions such as pH 3, initial Cr(VI) content of 20 mg/L, and catalyst dosage of 0.8 g/L, the ultrasonic/Cu-ZnO process showed a higher sonocatalytic activity (96.83%) than ultrasonic/ZnO (67.36%) after 60 min. By increasing pH and Cr(VI) concentration, the removal efficacy of Cr(VI) declined. The experimental data was well described with the first-order kinetic model. When initial Cr(VI) concentration increased from 10 to 50 mg/L, the first-order rate constant declined from 0.2326 to 0.0019 min-1 and electrical energy per order (EEO) enhanced from 19.81 to 2425.26 kWh/m3. Also, the ultrasonic/Cu-ZnO system exhibited considerable sonocatalytic performance in Cr(VI) reduction in the presence of hydrogen peroxide and citric acid, and complete removal was achieved within 60 min. The presence of anions negatively affected Cr(VI) reduction. Complete reduction was attained when ultrasound was applied at a power of 100 W. The catalyst activity was well maintained up to six consecutive cycles. In addition, the removal efficiency was approximately 62 and 65% for field water and real electroplating wastewater samples, respectively.

Application of Scallop shell-Fe3O4 nanoparticles for the removal of Cr(VI) from aqueous solutions.

In this study, removal of Cr(VI) by Scallop shell-Fe3O4 nanoparticles was investigated with variation of pH, adsorbent dosage, initial Cr(VI) concentration, ionic strength and temperature. Coating of Fe3O4 nanoparticles onto Scallop shell was identified by Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy and energy dispersive X-ray analysis. The maximum adsorption was observed at pH 3. Removal efficiency of Cr(VI) was increased with increasing adsorbent dosage, but was decreased with increasing initial Cr(VI) concentration and temperature. Removal efficiency of Cr(VI) was decreased in the presence of sulfate and carbonate ions. Adsorption kinetic study revealed that a pseudo-second order model better described the removal data than a pseudo-first order model and an intra-particle diffusion model. Maximum adsorption capacity was estimated to be 34.48 mg/g. Thermodynamic studies indicated that adsorption of Cr(VI) onto Scallop shell-Fe3O4 nanoparticles occurred via an exothermic (ΔH = -320.88 KJ mol-1) process. Adsorption efficiency of Cr(VI) by Scallop shell-Fe3O4 nanoparticles was maintained even after eight successive cycles.

Enhancement of photocatalytic activity of Cu-doped ZnO nanorods for the degradation of an insecticide: Kinetics and reaction pathways.

The photocatalytic degradation of organophosphorus pesticide such as diazinon was investigated by Cu-doped ZnO nanorods. Cu-doped ZnO nanorods were synthesized via a facile co-precipitation method. The catalyst was characterized by XRD, FESEM, EDX, VSM, XPS, and pHzpc techniques. The effects of some operational parameters such as solution pH, Cu-doped ZnO nanorods dosage, initial diazinon concentration, oxygen and nitrogen gases, H2O2 concentration, and type of organic compounds on the degradation efficiency were discussed through the photocatalytic experiments using the Cu-doped ZnO nanorods. Neutral pH was selected as an optimal pH condition due to a photo-corrosion of ZnO in acidic and basic conditions. As the Cu-doped ZnO nanorods dosage increased up to 0.2 g/L, degradation efficiency of diazinon was continuously enhanced. Pseudo-first-order rate constant (kobs) was decreased from 0.051 to 0.0052 min-1 and electrical energy per order (EEo) was increased from 94.12 to 923.08 (kWh/m3) by increasing diazinon concentration from 10 to 50 mg/L, respectively. The efficiency of the UV/Cu-doped ZnO for diazinon removal was approximately 96.97%, which was more effective than the UV/ZnO process (58.52%). Photocatalytic activity was maintained even after five successive cycles.

Intrinsic kinetics for fixed bed bioreactor in hospital wastewater treatment.

Variation in hospital wastewater (HWW) pollutants and differences with municipal wastewater (MWW), make the use of biokinetic coefficients obtained from activated sludge in the MWW treatment unprofitable for designing, modeling and evaluation of biological processes for HWW treatment. Since this study was conducted to evaluate the performance and biokinetic coefficients of a fixed bed bioreactor (FBBR) using rice husks as fixed media in HWW treatment, a new modified method was also proposed for biokinetic estimation in FBBR processes. For these purposes, five hydraulic retention times along with five sludge retention times were introduced to a pilot setup and the required data were attained. The performance process for chemical oxygen demand (COD) removal was significant (87.8-97.5%) in different conditions. The values of biokinetic coefficients k, Ks, Y and Kd were obtained as 2.42 (day-1), 55.5 (mgCOD/L), 0.2929 (mgBiomass/mgCOD) and 0.0164 (day-1), respectively. The rice husks with high surface area and high affinity for biomass accumulation on its surface are promising media for a green and environmentally friendly FBBR process. The kinetics parameters values are utilizable for modeling of FBBR using rice husks as fixed media in HWW treatment.

Polycyclic aromatic hydrocarbons (PAHs) in coastal sediments from urban and industrial areas of Asaluyeh Harbor, Iran: distribution, potential source and ecological risk assessment.

The distribution and toxicity levels of 16 EPA priority pollutant polycyclic aromatic hydrocarbons (PAHs) in the sediments of Asaluyeh shore, Iran were investigated. The total concentrations of the PAHs in surface sediments ranged from 1,054 to 17,448 ng/g dry weights with a mean concentration of 8,067 ng/g. The spatial distribution of PAHs showed that PAH levels are much higher in the industrial areas in comparison with urban areas. Based on diagnostic ratios, pyrogenic activities were dominant sources of PAHs pollution in sediments comparing petroleum sources. The toxic equivalent concentrations (TEQ Carc) of PAHs ranged from 172 to 2,235 ng TEQ/g with mean value of 997.9. Toxicity levels were evaluated using sediment quality guidelines (SQGs) and toxic equivalent factors. Samples were collected from industrial and urban stations in Asaluyeh shores. According to SQGs, ΣPAHs concentrations in sediments of urban areas were below the ERL (effects range low), but the industrial samples had ΣPAHs concentrations between ERL and ERM (effects range median). Furthermore, ΣHPAHs (heavy PAHs) and some individual PAHs in some industrial stations exceeded ERM, indicating adverse ecological risk effects frequently occur. Findings demonstrate that the surface sediment from Asaluyeh shore is highly to very highly contaminated with PAHs.

Surfactant-modified montmorillonite as a nanosized adsorbent for removal of an insecticide: kinetic and isotherm studies.

Surfactant-modified montmorillonites (MMT) were prepared using trimethyloctylammonium bromide (TMOAB) and employed as a nanosized adsorbent to remove diazinon from aqueous solutions. The prepared adsorbent was characterized using Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive X-ray (EDX). The dependence of removal efficiency on initial diazinon concentration, amount of adsorbent, pH of the solution and ionic strength was investigated. The affinity sequence for ion adsorption on TMOAB/MMT was in the order: without anion> sodium carbonate> sodium bicarbonate> sodium sulphate> sodium chloride. The adsorption kinetic and isotherm were best fit by a pseudo-second-order kinetic and Langmuir isotherm models, respectively.

Photocatalytic degradation of Metronidazole with illuminated TiO2 nanoparticles.

Metronidazole (MNZ) is a brand of nitroimidazole antibiotic, which is generally used in clinical applications and extensively used for the treatment of infectious diseases caused by anaerobic bacteria and protozoans. The aim of this investigation was to degrade MNZ with illuminated TiO2 nanoparticles at different catalyst dosage, contact time, pH, initial MNZ concentration and lamp intensity. Maximum removal of MNZ was observed at near neutral pH. Removal efficiency was decreased by increasing dosage and initial MNZ concentration. The reaction rate constant (k obs ) was decreased from 0.0513 to 0.0072 min(-1) and the value of electrical energy per order (EEo) was increased from 93.57 to 666.67 (kWh/m(3)) with increasing initial MNZ concentration from 40 to 120 mg/L, respectively. The biodegradability estimated from the BOD5/COD ratio was increased from 0 to 0.098. The photocatalyst demonstrated proper photocatalytic activity even after five successive cycles. Finally, UV/TiO2 is identified as a promising technique for the removal of antibiotic with high efficiency in a relatively short reaction time.

Photocatalytic reduction of hexavalent chromium with illuminated amorphous FeOOH.

In this study, photocatalytic reduction of hexavalent chromium [Cr(VI)] by amorphous FeOOH was investigated with variations in FeOOH dosage, pH, initial Cr(VI) concentration, purging gas, organic compounds and initial hydrogen peroxide concentration. Reduction and adsorption were identified as important processes for the removal of Cr(VI). FeOOH dosage was also an important parameter for the removal of Cr(VI). As the FeOOH dosage increased up to 0.5 g/L, the removal of Cr(VI) was continuously enhanced and then decreased above 0.5 g/L due to increased blockage of the incident UV light. The removal efficiency of Cr(VI) decreased with increasing pH, initial Cr(VI) concentration and initial hydrogen peroxide concentration. While the removal efficiency of Cr(VI) increased with purging of nitrogen gas compared to that of oxygen gas because of less competition between dissolved oxygen and Cr(VI) with the electron in the conduction band of FeOOH. The photocatalytic reduction of Cr(VI) was increased in the presence of citric acid and phenol, while it was decreased in the presence of EDTA and oxalic acid. The reaction rate constant (kobs) was decreased from 0.2141 to 0.0026 1/min and the value of electrical energy per order (EEo) was increased from 22.41 to 1846.15 (kWh/m3) with increasing initial Cr(VI) concentration from 10 to 50 mg/L, respectively. Finally, proper photocatalytic activity was maintained even after five successive cycles.

Effect of organic matter on cyanide removal by illuminated titanium dioxide or zinc oxide nanoparticles.

Effect of different type of organic compounds (humic acid, oxalate, ethylenediaminetetraacetic acid, nitrilotriacetic acid, phenol) on the photocatalytic removal of cyanide with TiO2 or ZnO was studied in this work with variation of the solution pH, contact time, initial cyanide concentration and type of organic compounds. Photocatalytic oxidation efficiency of cyanide with TiO2 was greatly affected by the solution pH. It increased as the solution pH decreased. Also maximum removal of cyanide by ZnO was observed near at neutral pH because of the reduced photocatalytic activity of ZnO at exceedingly low and high pH values originated from either acidic/photochemical corrosion of the catalyst and/or surface passivation with Zn(OH)2. Removal efficiency of cyanide greatly decreased in the presence of humic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid compared to that without presence of organic compound because of the competitive oxidation as well as surface blocking by relatively large organic compounds. The oxidation pattern of cyanide was better described by first-order kinetic model. Finally photocatalytic reaction with TiO2 or ZnO can be effectively applied to treat synthetic wastewater contaminated with cyanide.

Photocatalytic removal of Escherichia coli from aquatic solutions using synthesized ZnO nanoparticles: a kinetic study.

Development of effective and low-cost disinfection technology is needed to address the problems caused by an outbreak of harmful microorganisms. In this work, an effective photocatalytic removal of Gram-negative bacteria Escherichia coli from aqueous solution was reported by using ZnO nanoparticles under UV light irradiation. The effect of various parameters such as solution pH, ZnO dosage, contact time and initial E. coli concentration were investigated. Maximum photocatalytic disinfection was observed at neutral pH because of the reduced photocatalytic activity of ZnO at low and high pH values originated from either acidic/photochemical corrosion of the catalyst and/or surface passivation with Zn(OH)(2). As the ZnO dosage increased, the photocatalytic disappearance of E. coli was continuously enhanced, but was gradually decreased above 2 g/L of ZnO due to the increased blockage of the incident UV light used. The optimum ZnO dosage was determined as 1 g/L. Photocatalytic removal of E. coli decreased as initial E. coli concentration increased. Three kinetic models (zero-, first- and second-order equations) were used to correlate the experimental data and to determine the kinetic parameters.