Enhanced forward osmosis from chemically modified polybenzimidazole (PBI) nanofiltration hollow fiber membranes with a thin wall

To develop high-flux and high-rejection forward osmosis (FO) membranes for water reuses and seawater desalination, we have fabricated polybenzimidazole (PBI) nanofiltration (NF) hollow fiber membranes with a thin wall and a desired pore size via non-solvent induced phase inversion and chemically cross-linking modification. The cross-linking by p-xylylene dichloride can finely tune the mean pore size and enhance the salt selectivity. High water permeation flux and improved salt selectivity for water reuses were achieved by using the 2-h modified PBI NF membrane which has a narrow pore size distribution. Cross-linking at a longer time produces even a lower salt permeation flux potentially suitable for desalination but at the expense of permeation flux due to tightened pore sizes. It is found that draw solution concentration and membrane orientations are main factors determining the water permeation flux. In addition, effects of membrane morphology and operation conditions on water and salt transport through membrane have been investigated.     

Effect of composition on the properties of PEM based on polybenzimidazole and poly(vinylidene fluoride) blends

Inadequate performance, short term durability and high cost of polymer electrolyte membrane (PEM) are the major roadblocks that need to be resolved for successful commercialization of high temperature PEM fuel cell. In this report, we investigated the viability of previously developed miscible blend membranes of polybenzimidazole and poly (vinylidene fluoride) (PBI/PVDF), as potential PEMs. In addition, we have carried out several advanced analytical techniques such as dynamic mechanical analysis (DMA), ¹³C CP-MAS solid state NMR (SS-NMR) and wide-angle X-Ray diffraction (WAXD) to prove the miscible behavior of the polymer pair. Sub-ambient temperature DMA studies confirmed the miscible behavior of PBI/PVDF blends at different compositions based on single T_g criterion. SS-NMR and WAXD showed the presence of interactions between the functional groups of the polymers and their dependence on blend composition. Thermogravimetric analysis of phosphoric acid (PA) doped and undoped blend membranes confirmed the improved thermal stability of the membranes compared to neat PBI. The membranes exhibited excellent oxidative stability than pristine PBI membrane. The swelling ratio and volume after dipping in PA was found to be significantly low in the blend membranes owing to the hydrophobic nature of PVDF. Among the blends prepared, 90/10 and 75/25 membranes showed higher proton conductivity than PBI, attributed in part, to electronegativity of fluorine and crystallinity of PBI in PA that activate proton transport. The results demonstrated the potential usefulness of the blend membranes as PEM in fuel cell.     

Degradation of the antimicrobial triclocarban (TCC) with ozone

Triclocarban (TCC) has been used as an antimicrobial compound for many decades due to its sanitising properties. Recent studies showed that TCC is toxic and causes disruption to the endocrine system. In this work, ozone oxidation of TCC was studied in 70% acetonitrile:30% water solutions. Ozone degraded TCC effectively and the reaction rates increased substantially with ozone gas concentration, pH and temperature. Second-order-reaction kinetics was suitable to describe the chemical reaction. The effect of temperature was described by the Arrhenius equation and the activation energy was found equal to 31.0 kJ/mol. The stoichiometry of the reaction was one and the value of the rate constant at pH 7 was 5 × 10³ M⁻¹ s⁻¹.     

Oxidation of Aqueous Dimethyl Sulfoxide (DMSO) Using UV,O3, and UV/O3

Dimethyl sulfoxide (DMSO) is extensively used in industry and a large amount of wastewater that contains DMSO is discharged. This investigation evaluates the feasibility and effectiveness of the use of UV, O₃ and UV/O₃ to degrade aqueous DMSO. DMSO oxidation tests were performed with initial DMSO concentrations of 400–890 mg/L, at various ozone dosages (5.44, 8.25, 12.80 mg/L.min), solution pH values (acidic, alkaline, uncontrolled), and UV irradiation power intensities (0 and 2.25 W/L). Experimental results demonstrated that acidic conditions favored the degradation of DMSO and increased the mass of DMSO decomposition per unit mass of ozone consumption, in both the presence and the absence of UV. DMSO exhibited zero-order degradation kinetics when sufficient ozone was supplied. The cost of the ozone or UV/ozone process per unit volume of wastewater with a DMSO concentration of 2500 mg/L is comparable to that of the UV/H₂O₂-biological and electrolysis-biological processes described in the literature.     

Oil-Refinery Wastewater Treatment Aiming Reuse by Advanced Oxidation Processes (AOPs) Combined with Biological Activated Carbon (BAC)

The treatment of a refinery wastewater by Advanced Oxidation Processes (AOP) coupled with Biological Activated Carbon (BAC) was investigated aiming to generate water for reuse. O₃/UV and H₂O₂/UV processes were employed to oxidize the organic matter and the BAC process to remove residual organic matter from the AOP effluent. AOP promoted oxidation of recalcitrant organic matter as observed by moderate drops on the treated wastewater absorbance (31–79%) and TOC values (10–18%). BAC filters showed to be effective, reaching average efficiencies of 65% in a sufficiently long period of operation (84 days), while GAC filters were saturated after 28 days. Effluent TOC values in the range of 4 to 8.5 mg/L were achieved by the combined treatment (H₂O₂/UV + BAC), allowing water reuse.     

Removal of Natural Organic Matter from Groundwater Using Advanced Oxidation Processes at a Pilot Scale Drinking Water Treatment Plant in the Central Banat Region (Serbia)

To improve water quality, a pilot-scale evaluation into upgrading the conventional treatment process was conducted. By following DOC content, UV₂₅₄ absorbance, SUVA and by-products formation, three oxidative pre-treatments were evaluated: pre-ozonation (2.2 g O₃/m³); O₃/H₂O₂ process (2.2 g O₃/m³; H₂O₂:O₃ = 1:2) and O₃/H₂O₂ process (2.2 g O₃/m³; H₂O₂:O₃ = 2:1). The second pre-treatment gave the best results, with a final average DOC content of 0.9 mg C/L, UV₂₅₄ absorbance of 0.06 cm^?1 and the lowest THMFP of 130 μg/L. UV₂₅₄ absorbance can serve as a proper indicator for predicting THM and HAA formation, yielding a correlation coefficient ≥ 0.90.     

Combination of Ozone with Activated Carbon as an Alternative to Conventional Advanced Oxidation Processes

The objective of this study was to compare the efficiency of O₃/granular activated carbon (GAC) to enhance ozone transformation into ·OH radicals, with the common advanced oxidation processes (O₃/OH^?, O₃/H₂O₂). The results obtained with model systems under the given experimental conditions showed that the system O₃/OH^? (pH 9) and O₃/H₂O₂ (pH 7, [H₂O₂] = 1·10^?5 M) are more efficient than O₃/GAC (pH 7, [GAC] = 0.5 g/L) to enhance ozone transformation into ·OH radicals. However, in Lake Zurich water the O₃/GAC process has a similar efficiency as O₃/H₂O₂ for ozone transformation into ·OH radicals. The results also show that the presence of GAC during Lake Zurich water ozonation leads to (i) removal of hydrophilic and hydrophobic micropollutants, (ii) reduction of the concentration of CO₃ ^2?/HCO₃ ^?, and (iii) decrease of the concentration of dissolved organic carbon (DOC) present in the system.     

Efficiency of Ozonation and AOP for Methyl-tert-Butylether (MTBE) Removal in Waterworks

Methyl-tert-butylether (MTBE) is attracting more and more attention since it was discovered in groundwater and other raw water sources for waterworks and proved to difficult to remove during conventional treatment steps in drinking water production. Therefore advanced treatment processes have to be evaluated in addition to established treatment technologies. Laboratory based experiments were carried out studying ozonation with varying ozone concentrations at different pH values. For the elimination of MTBE the degradation through hydroxyl radicals was identified as the main degradation pathway. No decline of MTBE concentration occurred in experiments with molecular ozone, but AOP (Advanced Oxidation Processes) experiments where hydrogen peroxide (H₂O₂) was added showed a more efficient elimination. However, no complete mineralization was achieved — tert-butyl alcohol (tBA) and tert-butyl formate (tBF) were identified as metabolites. In natural waters (i.e., groundwater, bank filtrated water, and drinking water) the efficiency of MTBE removal was strongly dependent on the content of natural organic matter and alkalinity because of their scavenging characteristics. However, bromate formation was observed as well and could cause problems for drinking water production. Comparison with data gained from waterworks showed that conventional ozonation techniques as applied in waterworks are not able to remove MTBE efficiently.     

The physicochemical characteristics of modified carbon fibers by Fluorination

The surface of PAN-based carbon fiber was directly modified with fluorine-oxygen mixtures at room temperature. The surface characteristics of the modified fiber were determined by using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and dynamic contact angle analyzer. The surface free energy was also calculated with the Owens-Wendt geometric mean method using water and methylene iodide contact angle. The surface of carbon fiber was changed into hydrophilicity by the formation of semicovalent C-F bond and C-O bond depending on reaction conditions and the surface free energy of oxyfluorinated fiber was significantly increased.     

Aqueous Pesticide Degradation by Ozonation and Ozone-Based Advanced Oxidation Processes: A Review (Part I)

Pesticide pollution of surface water and groundwater has been recognized as a major problem in many countries because of their persistence in aquatic environment and potential adverse health effects. Among various water and wastewater treatment options, ozonation and ozone-based advanced oxidation processes, such as ozone/hydrogen peroxide, ozone/ultraviolet irradiation, and ozone/hydrogen peroxide/ultraviolet irradiation, are likely key technologies for degrading and detoxifying these pollutants in water and wastewater. In this paper, ozone-based treatment of four major groups of pesticides, namely carbamates, chlorophenoxy compounds, organochlorines, and organophosphates, are reviewed. Degree of pesticide degradation, reaction kinetics, identity and characteristics of degradation by-products and intermediates, and possible degradation pathways are covered and discussed.     

Aqueous Pesticide Degradation by Ozonation and Ozone-Based Advanced Oxidation Processes: A Review (Part II)

Pesticides are known to be persistent in surface water and groundwater supplies and as a result, their existence in these water sources has been recognized as a major problem in many countries. The occurrence of these persistent pesticides in water bodies can also cause potential adverse public and environmental health effects. Among many water and wastewater treatment options, ozonation and ozone-based advanced oxidation processes, such as ozone/hydrogen peroxide, ozone/ultraviolet irradiation, and ozone/hydrogen peroxide/ultraviolet irradiation, possess a high potential for degrading and detoxifying these pollutants in water and wastewater. In this paper, ozone based treatment of four major groups of pesticides, namely aniline-based compounds, pyridines and pyrimidines, triazines, and substituted ureas, as well as that of several miscellaneous pesticides are reviewed. Degree of pesticide degradation, reaction kinetics, identity and characteristics of degradation by-products, and possible degradation pathways are covered and discussed.     

The interaction of ozone with bio-fuel, revealed by electrical conduction and infrared spectroscopy

The interaction of ozone with bio-fuel has been investigated. The highly reactive gas promotes accelerated oxidation, along with changes of the electrical conductivity. The materials specific parameter is monitored by a specially designed thin-film resistor sensor, integrated within a micro-fluidic flow cell. Recordings of the ozone induced conductivity (OiC) are presented for bio-diesel samples, processed from cotton seed oil, blended with and without antioxidants, as well as for fuel grade ethanol, and for commercial Petrol-Diesel, serving as a reference. The time delay between onset of ozone induced oxidation and associated increase in the electrical conductivity defines the oxidative stability, usually revealing a time span, ranging from minutes to hours. For comparison, Rancimat tests have been performed for the same samples. Comparable induction times were obtained for the OiC method under low ozone flux conditions. The set-up is an easy to implement proposed test method, and allows for electronic on-line fuel quality monitoring.     

Influence of Carbonate on the Ozone/Hydrogen Peroxide Based Advanced Oxidation Process for Drinking Water Treatment

The influence of carbonate on the ozone/hydrogen peroxide process has been investigated. Carbonate radicals, which are formed from the reaction of bicarbonate/carbonate with OH radicals, act as a chain carrier for ozone decomposition due to their reaction with hydrogen peroxide. The efficiency of bicarbonate/carbonate as a promoter for the radical-based chain reaction in presence of hydrogen peroxide has been calibrated and compared to a well-known chain promoter (methanol) and an inhibitor (tert-butanol). Relative to tert-butanol, the hydrogen peroxide induced ozone decomposition is accelerated by bicarbonate/carbonate. Relative to methanol, bicarbonate/carbonate in presence of hydrogen peroxide is less effective as a promoter under comparable experimental conditions.     

Predicting Hydroxyl Radical Activity and Trace Contaminants Removal in Ozonated Water

There is a renewed interest in predicting R_CT following growing evidence that AOP is effective against many emerging contaminants. Five surface waters were investigated to evaluate the OH-radical activity using the R_CT concept, predict R_CT using traditional water quality characteristics and predict contaminants removal by ozonation and peroxone. It was shown that R_CT was dependent on water quality characteristics and could be modeled (R² = 0.92), using water characteristics and treatment conditions. Predictions of MIB oxidation closely matched the published data of Kawamura (2000 Kawamura, S. 2000. Integrated Design and Operation of Water Treatment Facilities, 2nd, New York: John Wiley & Sons, Inc.  [Google Scholar]) and bench-scale assays performed on one of the water under investigation.     

Effects Of Ozone On The Production Of Biodegradable Dissolved Organic Carbon (BDOC) During Water Treatment

This article deals with the oxidation effect of ozone on the increasing fraction of biodegradable organic matter with the “ozotest” method, a laboratory technique which simulates the effect of ozonation and allows a complete oxidation assessment. Ozone treatment was performed on river water samples and sand filter effluent samples. Ozone consumption, reduction of UV absorbance and BDOC formation were monitored with applied ozone doses from 0 to 10 mg/L and with contact times from 0 to 60 min. The BDOC formation was optimum at an applied ozone dose of 0.25-0.5 mg O₃ per mg DOC (contact time = 5 min) corresponding to apparition of traces of residual ozone and maximum UV reduction. Maximum ozone consumption, UV reduction and BDOC formation occurred simultaneously during the first two minutes of treatment. Concerning BDOC formation, applied ozone dose showed a greater effectiveness than contact time. For the same quantity of consumed ozone, a short contact time associated with a high ozone dose was preferable to a long contact time and a low ozone dose.     

Advanced Oxidation Treatment of Drinking Water: Part I. Occurrence and Removal of Pharmaceuticals and Endocrine-Disrupting Compounds from Lake Huron Water

The current study focuses on the occurrence of selected endocrine disrupting compounds, pharmaceuticals and personal care products in Lake Huron Water and their removal using ozone/hydrogen peroxide based pre-coagulation, advanced oxidation process (AOP). Raw Lake Huron water spiked with nine target compounds was treated in a dual train pilot scale treatment plant. None of the target chemicals showed any significant removals following conventional treatment processes (coagulation, sedimentation and filtration). Five of the nine target pollutants plummeted to concentrations below the method detection limits following AOP. For all the target compounds AOP treatment provided higher removal compared to conventional treatment.     

Reaction of SDS with Ozone and OH Radicals in Aqueous Solution

Ozone can be used as an antiseptic in cleaning systems. SDS (Sodium Dodecyl Sulfate) has proved to be a suitable surfactant in such systems. However, kinetic studies have showed that SDS reacts with ozone at high concentrations. In contrast, the natural decomposition of ozone to oxygen is retarded at low SDS concentrations. NMR spectroscopic analyses of SDS solutions being continuously treated with ozone and OH radicals, respectively, have been performed. ¹H-, ¹³C-, COSY-, HMBC- and HSQC-NMR spectra were recorded showing that small carboxyl acids were formed at exposure to ozone. Randomly positioned carbonyl groups were also found along the hydrocarbon chain. However, the largest product was caused by direct reaction of SDS with ozone. The predominant product most likely is a SDS-peroxide. ¹H –NMR spectra of the samples treated with OH radicals also show the formation of small carboxylic and carbonyl groups. However, there is no indication of oxidation of the sulphate group.