TiO2/β-SiC foam-structured photoreactor for continuous wastewater treatment

Introduction

This study of photocatalytic degradation of wastewater was carried out in alveolar cell ??-SiC foam-structured photocatalytic reactors working in a recirculation mode. The immobilization of TiO2 on ??-SiC foams was efficiently obtained through a sol?Cgel technique in acidic conditions.

Discussion

In order to optimize degradation yields obtained by the foam-structured prototype reactor for the photocatalytic water treatment, the operating conditions of the photoreactor have been investigated and the efficiency of the process was evaluated by measuring the photocatalytic degradation of Diuron (3-(3,4-dichlorophenyl)-1,1-dimethyl-urea)) under UV irradiation. Kinetic studies were carried out by investigating the influence of different parameters controlling the reaction (TiO2 loading and ??-SiC foam cell size). The ageing of TiO2/??-SiC foam photocatalytic materials and the mineralization (TOC, Cl?, NO3? and NH4+) of Diuron were investigated.     

Enhanced degradation of azo dye alizarin yellow R in a combined process of iron–carbon microelectrolysis and aerobic bio-contact oxidation

Purpose

With the aim of enhanced degradation of azo dye alizarin yellow R (AY) and further removal of the low-strength recalcitrant matter (LsRM) of the secondary effluent as much as possible, our research focused on the combination of aerobic bio-contact oxidation (ABO) with iron/carbon microelectrolysis (ICME) process.

Materials and methods

The combined ABO (with effective volume of 2.4?l) and ICME (with effectively volume of 0.4?l) process were studied with relatively short hydraulic retention time (HRT) of 4 or 6?h.

Results

At the HRT of 6?h with the reflux ratio of 1 and 2, the AY degradation efficiency in the final effluent was >96.5%, and the total organic carbon (TOC) removal efficiency were 69.86% and 79.44%, respectively. At the HRT of 4?h and the reflux ratio of 2, TOC removal efficiency and AY degradation efficiency were 73.94% and 94.89%, respectively. The ICME process obviously enhanced the total AY removal and the generated micromolecule acids and aldehydes then that wastewater backflow to the ABO where they were further biodegraded.

Conclusion

The present research might provide the potential options for the advanced treatment azo dyes wastewater with short HRT and acceptable running costs.     

Heterocatalytic Fenton oxidation process for the treatment of tannery effluent: kinetic and thermodynamic studies

Background, aim, scope

Treatment of wastewater has become significant with the declining water resources. The presence of recalcitrant organics is the major issue in meeting the pollution control board norms in India. The theme of the present investigation was on partial or complete removal of pollutants or their transformation into less toxic and more biodegradable products by heterogeneous Fenton oxidation process using mesoporous activated carbon (MAC) as the catalyst.

Materials and methods

Ferrous sulfate (FeSO₄·7H₂O), sulfuric acid (36?N, specific gravity 1.81, 98% purity), hydrogen peroxide (50% v/v) and all other chemicals used in this study were of analytical grade (Merck). Two reactors, each of height 50?cm and diameter 6?cm, were fabricated with PVC while one reactor was packed with MAC of mass 150?g and other without MAC served as control.

Results and discussion

The oxidation process was presented with kinetic and thermodynamic constants for the removal of COD, BOD, and TOC from the wastewater. The activation energy (Ea) for homogeneous and heterogeneous Fenton oxidation processes were 44.79 and 25.89?kJ/mol, respectively. The thermodynamic parameters ??G, ??H, and ??S were calculated for the oxidation processes using Van??t Hoff equation. Furthermore, the degradation of organics was confirmed through FTIR and UV?Cvisible spectroscopy, and cyclic voltammetry.

Conclusions

The heterocatalytic Fenton oxidation process efficiently increased the biodegradability index (BOD/COD) of the tannery effluent. The optimized conditions for the heterocatalytic Fenton oxidation of organics in tannery effluent were pH 3.5, reaction time?C4?h, and H₂O₂/FeSO₄·7H₂O in the molar ratio of 2:1.     

Occurrence and distribution of selected pharmaceuticals and personal care products in aquatic environments: a comparative study of regions in China with different urbanization levels

Purpose

We analyzed and compared the distributions of 13 target pharmaceuticals in different water samples from the Hangzhou metropolitan area and Linan County, Southeast China.

Methods

Sampling was conducted in five hospitals, two wastewater treatment plants (WWTPs), and Qiantang River. Samples were concentrated by solid-phase extraction and PPCP concentrations were determined by UPLC-MS/MS.

Results and discussion

Trimethoprim, erythromycin A dihydrate, norfloxacin, ofloxacin, diclofenac sodium, and atenolol were the most frequently detected pharmaceuticals in hospital effluents. Most of the pharmaceutical concentrations in hospital effluents were higher than those in the WWTP influents. Although both WWTPs adopt the anaerobic?Caerobic?Canoxic treatment process, the removal rates for pharmaceuticals, such as trimethoprim and diclofenac sodium, were completely different. Meanwhile, erythromycin A dihydrate, ofloxacin, penicillin-G, cephalexin, cefazolin, ibuprofen, and diclofenac sodium were detected in Qiantang River.

Conclusions

These results indicate that hospitals are more concentrated sources of pharmaceuticals than WWTPs, and the WWTPs are not the only route of entry of pharmaceuticals into aquatic environments in these two regions.     

In situ photoelectrochemical/photocatalytic study of a dye discoloration in a microreactor system using TiO2 thin films

Introduction

In this work, we report in situ studies of UV photoelectrocatalytic discoloration of a dye (indigo carmine) by a TiO₂ thin film in a microreactor to demonstrate the driving force of the applied electrode potential and the dye flow rate toward dye discoloration kinetics.

Methods

TiO₂ 65-nm-thick thin films were deposited by PVD magnetron sputtering technique on a conducting glass substrate of fluorinated tin oxide. A microreactor to measure the discoloration rate, the electrode potential, and the photocurrent in situ, was developed. The dye solutions, before and after measurements in the microreactor, were analyzed by Raman spectroscopy.

Results

The annealed TiO₂ thin films had anatase structure with preferential orientation (101). The discoloration rate of the dye increased with the applied potential to TiO₂ electrode. Further, acceleration of the photocatalytic reaction was achieved by utilizing dye flow recirculation to the microreactor. In both cases the photoelectrochemical/photocatalytic discoloration kinetics of the dye follows the Langmuir?CHinshelwood model, with first-order kinetics.

Conclusions

The feasibility of dye discoloration on TiO₂ thin film electrodes, prepared by magnetron sputtering using a flow microreactor system, has been clearly demonstrated. The discoloration rate is enhanced by applying a positive potential (E _AP) and/or increasing the flow rate. The fastest discoloration and shortest irradiation time (50?min) produced 80% discoloration with an external anodic potential of 0.931?V and a flow rate of 12.2?mL?min^?1.     

Application of central composite face-centered design and response surface methodology for the optimization of electro-Fenton decolorization of Azure B dye

Purpose

The aim of this work was to improve the ability of electro-Fenton technique for the remediation of wastewater contaminated with synthetic dyes using a model azo dye such as Azure B.

Methods

Batch experiments were conducted to study the effects of main parameters, such as dye concentration, electrode surface area, treatment time, and voltage. In this study, central composite face-centered experimental design matrix and response surface methodology were applied to design the experiments and evaluate the interactive effects of the four studied parameters. A total of 30 experimental runs were set, and the kinetic data were analyzed using first- and second-order models.

Results

The experimental data fitted to the empirical second-order model of a suitable degree for the maximum decolorization of Azure B by electro-Fenton treatment. ANOVA analysis showed high coefficient of determination value (R ²?=?0.9835) and reasonable second-order regression prediction. Pareto analysis suggests that the variables, time, and voltage produce the largest effect on the decolorization rate.

Conclusion

Optimum conditions suggested by the second-order polynomial regression model for attaining maximum decolorization were dye concentration 4.83?mg/L, electrode surface area 15?cm², voltage 14.19?V, and treatment time of 34.58?min.     

Reduction of dinitrotoluene sulfonates in TNT red water using nanoscale zerovalent iron particles

Purpose

This research was designed to investigate the feasibility of converting the dinitrotoluene sulfonates (DNTS) in TNT red water into the corresponding aromatic amino compounds using nanoscale zerovalent iron (NZVI).

Methods

NZVI particles were simultaneously synthesized and stabilized by sodium borohydride reduction in a nondeoxygenated system. The morphology, elemental content, specific surface area, and crystal properties of the NZVI were characterized before and after the reaction by environmental scanning electron microscope; energy dispersive X-ray; Brunauer, Emmett, and Teller; and X-ray diffraction, respectively. The reduction process was conducted at pH?=?6.3 at ambient temperature. The efficiency of the NZVI-mediated DNTS reduction process was monitored by HPLC, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy analyses.

Results

The properties of the NZVI particles prepared were found to be similar to those obtained through oxygen-free preparation and inert stabilization processes. Both 2,4-DNT-3-sulfonate (2,220?mg?L^?1) and 2,4-DNT-5-sulfonate (3,270?mg?L^?1) in TNT red water underwent a pseudo-first-order transformation when mixed with NZVI at room temperature and near-neutral pH. Their observed rate constants were 0.11 and 0.30?min^?1, respectively. Within 1?h of processing, more than 99% of DNTS was converted by NZVI-mediated reduction into the corresponding diaminotoluene sulfonates.

Conclusions

NZVI can be simultaneously prepared and stabilized in a nondeoxygenated system. NZVI reduction is a highly efficient method for the conversion of DNTS into the corresponding diaminotoluene sulfonates under near-neutral pH conditions. Therefore, NZVI reduction may be useful in the treatment of TNT red water and subsequent recovery of diaminotoluene from explosive wastewater.     

Characterization of PM10 atmospheric aerosol at urban and urban background sites in Fuzhou city, China

Background

PM₁₀ aerosol samples were simultaneously collected at two urban and one urban background sites in Fuzhou city during two sampling campaigns in summer and winter. PM₁₀ mass concentrations and chemical compositions were determined.

Methods

Water-soluble inorganic ions (Cl^?, NO ₃ ^? , SO ₄ ^2? , NH ₄ ⁺ , K⁺, Na⁺, Ca²⁺, and Mg²⁺), carbonaceous species (elemental carbon and organic carbon), and elements (Al, Si, Mg, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Br, and Pb) were detected using ion chromatography, thermal/optical reflectance, and proton-induced X-ray emission methods, respectively.

Results

PM₁₀ mass concentrations, as well as most of the chemical components, were significantly increased from urban background to urban sites, which were due to enhanced anthropogenic activities in urban areas. Elements, carbonaceous species, and most of the ions were more uniformly distributed at different types of sites in winter, whereas secondary ion SO ₄ ^2? , NO ₃ ^? , and NH ₄ ⁺ showed more evident urban-background contrast in this season. The chemical mass closure indicated that mineral dust, organic matters, and sulfate were the most abundant components in PM₁₀. The sum of individually measured components accounted for 86.9?C97.7% of the total measured PM₁₀ concentration, and the discrepancy was larger in urban area than in urban background area.

Conclusion

According to the principal component analysis?Cmultivariate linear regression model, mineral dust, secondary inorganic ions, sea salt, and motor vehicle were mainly responsible for the PM₁₀ particles in Fuzhou atmosphere, and contributed 19.9%, 53.3%, 21.3%, and 5.5% of PM₁₀, respectively.     

Superior photodecomposition of pyrene by metal ion-loaded TiO2 catalyst under UV light irradiation

Background

The photocatalytic degradation of pyrene under UV (125?W Hg-Arc, 10.4?mW/cm²) irradiation of TiO₂ aqueous suspension has been found to be highly improved with the dissolved transition metal ions like Cu²⁺, Fe³⁺, Ag⁺, and Au³⁺, etc. As the reduction potential of these metals lies below the conduction band (CB) position (?0.1?eV) of TiO₂, the photoexcited electron transfer occurs more readily and reduces electron?Chole recombination rate. Therefore, it has a beneficial influence on the photocatalytic ability of TiO₂ because of rapid Fermi energy equilibrium between the CB of TiO₂ and its surface adsorbed metal ions.

Results and discussion

The Fermi level is referred to as the electrochemical potential and plays an important role in the band theory of solids. When metal and semiconductor are in contact, electron migration from photoirradiated semiconductor to the deposited metal occurs at the interface until two Fermi levels equilibrate and enhanced the photocatalytic activity of semiconductor photocatalyst. Ni²⁺ having more negative reduction potential (?0.25?eV) than the CB of TiO₂ imparts negligible co-catalytic activity to TiO₂ photoreaction. It also revealed that loading of Au³⁺ ions displayed higher degradation rate of pyrene than Au photodeposition. Furthermore, when the amount of dissolved Fe⁺³ and Au³⁺ ions gradually increases from 0.1 to 2?wt.%, the pyrene photodecomposition rate also become faster.     

Remediation of 4-nonylphenol in aqueous solution by using free radicals generated by the oxidative reactions

Introduction

This study relates to use of zerovalent iron to generate hydroxyl free radicals and undergo subsequent oxidation to destroy 4-nonylphenol (NP) by mild process in aqueous solution and activation of oxygen gas (O₂) at room temperature. This technology is based on a novel oxidative mechanism mediated by zerovalent iron rather than commonly used reduction mechanism.

Materials and methods

A laboratory scale device consisting of a 250?ml pyrex serum vials fixed to a Vortex agitator was used. Different amounts of zerovalent iron powder (ZVI; 1, 10, and 30?g/l) at pH?4 and room temperature with bubbling of oxygen gas were investigated.

Results and conclusion

Experiments showed an observed degradation rate k _(obs) directly proportional to the amount of iron. 4-Nonylphenol degradation reactions demonstrated first-order kinetics with a half-life of about 10.5?±?0.5 and 3.5?±?0.2?min when experiments were conducted at [ZVI]?=?1 and 30?g/l respectively. Three analytical techniques were employed to monitor 4-nonylphenol degradation and mineralization: (1) spectrofluorimetry; (2) high-performance liquid chromatography; (3) total organic carbon meter (TOC meter). Results showed a complete disappearance of 4-nonylphenol after 20?min of contact with ZVI. The intermediate by-products of the reaction were not identified but the disappearance of NP was monitored by the three above-mentioned techniques.     

Removal of faecal indicator pathogens from waters and wastewaters by photoelectrocatalytic oxidation on TiO2/Ti films under simulated solar radiation

Purpose

The disinfection efficiency of water and secondary treated wastewater by means of photoelectrocatalytic oxidation (PEC) using reference strains of Enterococcus faecalis and Escherichia coli as faecal indicators was evaluated. Operating parameters such as applied potential (2?C10?V), initial bacterial concentration (10³?C10⁷?CFU/mL), treatment time (up to 90?min) and aqueous matrix (pure water and treated effluent) were assessed concerning their impact on disinfection.

Methods

PEC experiments were carried out using a TiO₂/Ti film anode and a zirconium cathode in the presence of simulated solar radiation. Bacterial inactivation was monitored by the culture method and real-time SYBR green PCR.

Results

A 6.2 log reduction in E. faecalis population was achieved after 15?min of PEC treatment in water at 10?V of applied potential and an initial concentration of 10⁷?CFU/mL; pure photocatalysis (PC) led to only about 4.3 log reduction, whilst negligible inactivation was recorded when the respective electrochemical oxidation process was applied (i.e. without radiation). PEC efficiency was generally improved increasing the applied potential and decreasing initial bacterial concentration. Regarding real wastewater, E. coli was more susceptible than E. faecalis during treatment at a potential of 5?V. Wastewater disinfection was affected by its complex composition and the contained mixed bacterial populations, yielding lower inactivation rates compared to water treatment. Screening the results obtained from both applied techniques (culture method and real-time PCR), there was a discrepancy regarding the recorded time periods of total bacterial inactivation, with qPCR revealing longer periods for complete bacterial reduction.

Conclusions

PEC is superior to PC in terms of E. faecalis inactivation presumably due to a more efficient separation and utilization of the photogenerated charge carriers, and it is mainly affected by the applied potential, initial bacterial concentration and the aqueous matrix.     

Enhancement of natural radioactivity in fertilized soil of Faisalabad, Pakistan

Background, goal, and scope

Natural radioactivity in phosphate rock (PR) is transferred to phosphate fertilizer (PF) during the manufacturing process of the PF. The continuous addition of the PF to the cultivated soil accumulates the radionuclides in the land and increases the level of radioactivity in the soil. The purpose of the present study was to investigate the enhanced level of accumulated radioactivity due to the continuous addition of the PF in the farmlands of Nuclear Institute of Agriculture and Biology (NIAB) at Faisalabad in Pakistan. The selected study area consisted of the highly fertilized farmlands and an unfertilized barren land of the NIAB.

Introduction

The understudy area is very fertile for the growth of various types of crops; therefore, four agricultural research institutes have been established at Faisalabad and NIAB is one of those. The NIAB has developed various research farmlands at different places in Pakistan. The crop yield has been increased by adding various fertilizers in the farmlands. The addition of the PF accompanied with the radionuclides enhances radioactivity in the fields. Human being is exposed directly or indirectly to this radiological hazard. A prolong exposure may become a cause of health risk.

Materials and methods

The area of study consisted of three types of lands: the land under cultivation for the last 40 and 30?years called Site 1 and Site 2, respectively, and the barren land was called Site 3. A total of 75 soil samples were collected within the crop rooting zone (up to 25?cm deep) of the soil of the NIAB farms. The samples were dried, pulverized to powder, sealed in plastic containers, and stored to achieve equilibrium between ²²⁶Ra and ²²²Rn. Activity concentrations of the radionuclides ²³⁸U (²²⁶Ra), ²³²Th, and ⁴⁰K in soil samples were determined by using a high resolution gamma ray spectrometry system, consisting of an high purity germanium detector coupled through a spectroscopy amplifier with a PC based MCA installed with Geni-2000 software.

Results

The measured activity concentration levels of ⁴⁰K were 662?±?15, 615?±?17, and 458?±?20?Bq?kg^?1, ²²⁶Ra were 48?±?6, 43?±?5, and 26?±?4?Bq?kg^?1, and that of ²³²Th were 39?±?5, 37?±?5, 35?±?5?Bq?kg^?1, respectively, in the soil of the Sites 1, 2, and 3. Gamma dose rate 1?m above the soil surface was 55, 51, and 40?nGy?h^?1 from Sites 1, 2, and 3, respectively. External dose rates in the rooms constructed of the bricks made of the soil from Sites 1, 2, and 3 were 161, 149, and 114?nGyh^?1, respectively.

Discussions

Activity concentration values of ⁴⁰K and ²²⁶Ra in the soil of Sites 1 and 2 were higher than that in the soil of Site 3. The relative rise of ⁴⁰K was 43?% and 34?% and that of ²²⁶Ra was 85?% and 65?% respectively in these sites. Activity concentrations of ²³²Th in all these sites were in the background range. Gamma dose rate 1?m above soil surface of Sites 1 and 2 was 40?% and 30?% respectively higher than that from the soil of Site 3. The rise in activity of ⁴⁰K and ²²⁶Ra and gamma dose from the Site 1 was greater than that from the Site 2. The least activity and dose were observed from the Site 3. Gamma dose in the dwellings made of fertilized soil bricks of Site 1 and Site 2 were respectively calculated to be 41?% and 32?% higher than that in the abodes made of unfertilized soil bricks of Site 3.

Conclusions

Activity concentrations of ²²⁶Ra and ⁴⁰K were observed to be enhanced in the fertilized farmlands of the NIAB. Outdoor and indoor gamma dose as radiological hazard were found to be increasing with the continuous addition of PF in the understudy farmlands.

Recommendations

It is recommended that naturally occurring radioactive metal should be removed during the process of manufacturing of the PF from the PR.

Prospective

The rise in radioactivity in the farmlands due to the addition of the PF can be a source of direct or indirect exposure to radiation that may enhance cancer risk of the exposed individuals.     

Evaluation of adsorption characteristics of an anionic azo dye Brilliant Yellow onto hen feathers in aqueous solutions

Purpose and aim

Removal of an anionic azo dye Brilliant Yellow has been carried out from its aqueous solutions by using hen feathers as potential adsorbent.

Materials and methods

Hen feathers procured from local poultry were cut, washed, and activated. Detailed chemical and physical analysis of hen feathers and its characterization through scanning electron microscopy, X-ray diffraction, and infrared measurements have been made. Procured dye has been adsorbed over under batch measurements and adsorption process is monitored using UV spectrophotometer.

Results

Optimum parameters for the adsorption of Brilliant Yellow over hen feathers have been determined by studying the effect of pH, temperature, concentration of dye, and amount of adsorbent. On the basis of Langmuir adsorption, isotherms feasibility of the ongoing adsorption has been ascertained and thermodynamic parameters have been calculated. Attempts have also been made to verify Freundlich, Tempkin, and Dubinin?CRadushkevich adsorption isotherm models. It is found that during adsorption, uniform distribution of binding energy takes place due to interaction of the dye molecules and the ongoing adsorption process is chemisorptions. The kinetic measurements indicate dominance of pseudo-second-order process during the adsorption. The mathematical treatment on the kinetic data reveals the rate-determining step to be governed through particle diffusion at 8?×?10^?5?M and involvement of film diffusion mechanism at higher concentration at temperatures at all the temperatures.

Conclusions

The developed process is highly efficient and it can be firmly concluded that hen feather exhibits excellent adsorption capacity towards hazardous azo dye Brilliant Yellow.     

Adsorptive removal of Pb2+ form aqueous solution by macrocyclic calix[4]naphthalene: kinetic, thermodynamic, and isotherm analysis

Background

The adsorption characteristics of Pb²⁺ ions from aqueous solutions onto calix[4]naphthalene have been investigated.

Method

Calix[4]naphthalene was prepared by the condensation of 1-naphthol and formaldehyde (1:2) in presence of hydrochloric acid at 80°C. The effect of various operation parameters, such as solution pH, initial metal ion concentration, contact time, and temperature, on the adsorption capacity of calix[4]naphthalene for Pb²⁺ have been investigated.

Result

Experimental results showed that the adsorption of Pb²⁺ ions increased with the increase in solution pH and temperature. Langmuir and Freundlich isotherms models were used to describe the adsorption behavior of Pb²⁺ by calix[4]naphthalene. Equilibrium data fitted well with the Langmuir isotherm model and the maximum adsorption capacity of calix[4]naphthalene for Pb²⁺ at 30°C was found to be 29.15 mg g^?1. Kinetic studies indicated that the adsorption followed pseudo-second order model and the thermodynamic studies revealed that the adsorption process was spontaneous and endothermic in nature. The obtained results demonstrated that calix[4]naphthalene can be used as an effective adsorbent for Pb²⁺ ions removal from water.     

Oxidation of ofloxacin by Oxone/Co2+: identification of reaction products and pathways

Oxidative degradation of ofloxacin (OFX) by sulfate free radicals (SO₄ ^??) in the UV/Oxone/Co²⁺oxidation process was investigated for the first time, with a special focus upon identifying the transformation products as well as understanding the reaction pathways. Thirteen main compounds were identified after the initial transformation of OFX; the detailed structural information of which were characterized by high-performance liquid chromatography–high resolution mass spectrometry and MS fragmentation analysis. The degradation pathways mainly encompassed ring openings at both the piperazinyl substituent and the quinolone moiety, indicating that the usage of SO₄ ^?? aided the oxidative degradation of OFX to undergo more facile routes compared to those in previous reports by using OH^?/h⁺ as the oxidant, where the initial transformation attacks were mainly confined to the piperazine moiety. Moreover, in this study, smart control over the pH conditions of the oxidation system via different modes of Oxone dosage resulted in the selective degradation of the functional sites of OFX molecule, where it was shown that the SO₄ ^??-driven destruction of the quinolone moiety of OFX molecule favored the neutral pH conditions. This would be beneficial for the reduction of bacterial resistance against quinolones in the aqueous environment.     

Degradation and mineralization of sulcotrione and mesotrione in aqueous medium by the electro-Fenton process: a kinetic study

Introduction

The degradation and mineralization of two triketone (TRK) herbicides, including sulcotrione and mesotrione, by the electro-Fenton process (electro-Fenton using Pt anode (EF-Pt), electro-Fenton with BDD anode (EF-BDD) and anodic oxidation with BDD anode) were investigated in acidic aqueous medium.

Methods

The reactivity of both herbicides toward hydroxyl radicals was found to depend on the electron-withdrawing effect of the aromatic chlorine or nitro substituents. The degradation of sulcotrione and mesotrione obeyed apparent first-order reaction kinetics, and their absolute rate constants with hydroxyl radicals at pH?3.0 were determined by the competitive kinetics method.

Results and discussion

The hydroxylation absolute rate constant (k _abs) values of both TRK herbicides ranged from 8.20?×?10⁸ (sulcotrione) to 1.01?×?10⁹ (mesotrione) L?mol^?1?s^?1, whereas those of the TRK main cyclic or aromatic by-products, namely cyclohexane 1,3-dione , (2-chloro-4-methylsulphonyl) benzoic acid and 4-(methylsulphonyl)-2-nitrobenzoic acid, comprised between 5.90?×?10⁸ and 3.29?×?10⁹?L?mol^?1?s^?1. The efficiency of mineralization of aqueous solutions of both TRK herbicides was evaluated in terms of total organic carbon removal. Mineralization yields of about 97?C98% were reached in optimal conditions for a 6-h electro-Fenton treatment time.

Conclusions

The mineralization process steps involved the oxidative opening of the aromatic or cyclic TRK by-products, leading to the formation of short-chain carboxylic acids, and, then, of carbon dioxide and inorganic ions.     

Improvement of biodegradability of PVA-containing wastewater by ionizing radiation pretreatment

Background

Polyvinyl alcohol (PVA) has been widely used as sizing agents in textile and manufacturing industry, and it is a refractory compound with low biodegradability.

Objective

The objective of this paper was to treat the PVA-containing wastewater using gamma irradiation as a pretreatment strategy to improve its biodegradability and to determine the roles of different kinds of radical species played during pretreatment.

Methods

Gamma radiation was carried out in a ⁶⁰Cobalt source station, PVA concentration was analyzed by using a visible spectrophotometer and specific oxygen uptake rate (SOUR, milligram of O₂ per gram of mixed liquor volatile suspended solids (MLVSS) per hour) was measured by a microrespirometer.

Results

The results showed that the biodegradability of PVA-containing wastewater with low initial concentration (e.g., 327.8?mg/l) could be improved greatly with increasing irradiation dose. However, PVA gel formation was observed at higher initial PVA concentration (e.g., 3,341.6?mg/l) and higher irradiation dose, which inhibited PVA degradation by aerobic microorganisms. However, the formed gel could be separated by microfiltration, which led to more than 90% total organic carbon (TOC) removal.

Conclusion

Ionizing radiation could be used as a pretreatment technology for PVA-containing wastewater, and its combination with biological process is feasible.     

Evaluation of substrate removal kinetics for UASB reactors treating chlorinated ethanes

Purpose

Lack of focus on the treatment of wastewaters bearing potentially hazardous pollutants like 1,1,2 trichloroethane and 1,1,2,2 tetrachloroethane in anaerobic reactors has provided an impetus to undertake this study. The objective of this exercise was to quantify the behavior of upflow anaerobic sludge blanket reactors and predict their performance based on the overall organic substrate removal.

Methods

The reactors (wastewater-bearing TCA (R2), and wastewater-bearing TeCA (R3)) were operated at different hydraulic retention times (HRTs), i.e., 36, 30, 24, 18, and 12?h corresponding to food-to-mass ratios varying in the range of 0.2?C0.7?mg chemical oxygen demand (COD) mg^?1 volatile suspended solids day^?1. The process kinetics of substrate utilization was evaluated on the basis of experimental results, by applying three mathematical models namely first order, Grau second order, and Michaelis-Menten type kinetics.

Results

The results showed that the lowering of HRT below 24?h resulted in reduced COD removal efficiencies and higher effluent pollutant concentrations in the reactors. The Grau second-order model was successfully applied to obtain the substrate utilization kinetics with high value of R ² (>0.95). The Grau second-order substrate removal constant (K ₂) was calculated as 1.12 and 7.53?day^?1 for reactors R2 and R3, respectively.

Conclusion

This study demonstrated the suitability of Grau second-order kinetic model over other models, for predicting the performance of reactors R2 and R3, in treating wastewaters containing chlorinated ethanes under different organic and hydraulic loading conditions.     

Formation of shaped barium sulfate-dye hybrids: waste dye utilization for eco-friendly treatment of wastewater

Purpose

Owing to the present complexity and difficulty of concentrated dye wastewater treatment, this work aimed to synthesize a reproducible waste-sorbing material for the treatment of wastewater by forming the dye-conjugating complex hybrid.

Methods

The inorganic/organic hybridization was applied to prepare the objective material by immobilizing waster dye-Mordant blue 9 (MB) with barium sulfate (BaSO₄). The composition and pattern of the formed material were determined by spectrometry and characterized by SEM and XRD, and their formation process was clarified. The adsorption of cationic dye-basic blue BO (BB) and copper ion was investigated..

Results

The hybrid of MB alone into growing BaSO₄ formed the pineapple-like particles while that of the MB/BB-conjugating complex was the rhombus material. The adsorption of BB on the MB–BaSO₄ hybrid was probably attributed to ion-pair equilibrium and that of Cu²⁺ may result from the complexation. The treatment of dye and heavy metal wastewaters indicated that the MB hybrid material removed 99.8% BB and 97% Cu²⁺ and the dye-conjugating hybrid with growing BaSO₄ 100% MB, 99.5% BB, and 44% Cu²⁺.

Conclusion

The waste MB–BaSO₄ hybrid material is efficient to treat cationic dye and Cu²⁺ wastewater. The dye-conjugating hybridization method is the first to be advanced for in situ wastewater treatment, and it showed a combined effect for the removal of both organic dyes and heavy metals.     

The effects of cerium on the growth and some antioxidant metabolisms in rice seedlings

Introduction

The aims of the present study are to investigate the effects of Ce³⁺ on the growth and some antioxidant metabolisms in rice seedlings (Oryza sativa L. cv Shengdao 16).

Materials and methods

The rice was treated with 0, 0.05, 0.1, 0.5, 1.0, and 1.5?mM Ce³⁺, respectively. The growth index of rice was measured. The chlorophyll content; catalase, superoxide dismutase, and peroxidase activities; and the level of hydrogen peroxide (H₂O₂), superoxide anion (O ₂ ^·? ), and malondialdehyde were assayed. The accumulation of Ce³⁺ and the uptake of mineral nutrition elements were analyzed with ICP-SF-MS.

Results and discussion

Hormetic effects of Ce³⁺ on the growth and some antioxidant metabolisms were found in the roots and shoots of rice. The roots can accumulate a much higher content of Ce³⁺ than shoots and Ce³⁺ mainly located in the cell wall of roots. Moreover, the uptake of K, Mg, Ca, Na, Fe, Mn, Zn, Cu, and Mo in the roots and shoots was affected with the exposure of different Ce³⁺ treatments, which indicated that Ce³⁺ affected the nutritional status of roots and shoots and further affected the growth of rice.

Conclusion

The appropriate amount of Ce³⁺ improved the defense system and growth of rice. The roots can accumulate a much higher content of Ce³⁺ than shoots. Moreover, the uptake of K, Mg, Ca, Na, Fe, Mn, Zn, Cu, and Mo in the roots and shoots was affected with the exposure of different Ce³⁺ treatments.