Competitive study of homogeneous and heterogeneous Fenton-like flow-through propoxur oxidation in ROC solution.

Reverse osmosis is used as a tertiary treatment for wastewater reclamation. However, sustainable management of the concentrate (ROC) is challenging, due to the need for treatment and/or disposal. The objective of this research was to investigate the efficiency of homogeneous and heterogeneous Fenton-like oxidation processes in removing propoxur (PR), a micro-pollutant compound, from synthetic ROC solution in a submerged ceramic membrane reactor operated in a continuous mode. A freshly prepared amorphous heterogeneous catalyst was synthesized and characterized, revealing a layered porous structure of 5-16 nm nanoparticles that formed aggregates (33-49 µm) known as ferrihydrite (Fh). The membrane exhibited a rejection of >99.6% for Fh. The homogeneous catalysis (Fe3+) exhibited better catalytic activity than the Fh in terms of PR removal efficiencies. However, by increasing the H2O2 and Fh concentrations at a constant molar ratio, the PR oxidation efficiencies were equal to those catalyzed by the Fe3+. The ionic composition of the ROC solution had an inhibitory effect on the PR oxidation, whereas increased residence time improved it up to 87% at a residence time of 88 min. Overall, the study highlights the potential of heterogeneous Fenton-like processes catalyzed by Fh in a continuous mode of operation.

Comparing the effects of Cu-Ti/RuO2-IrO2 electrode configuration on the electro-reduction of nitrate.

Nitrate pollution is a global problem as it affects both the environment and human health. The objective of this research was to study the effect of electrode configuration on the electro-reduction of nitrate. Coaxial cylindrical (inner rod and outer tube copper cathodes) and vertical plate parallel copper cathodes paired with Ti/RuO2-IrO2 (rod, tube, and plate) configurations were studied under various current densities and initial nitrate concentrations. The efficiency of each configuration was determined based on the removal efficiency of nitrate, specific energy consumption, mass transfer coefficients, and first order rate constants. Additionally, the overall systems' resistance and geometric factors are discussed. It was found that the performances of the inner rod and outer tube copper cathodes were similar. The vertical plate parallel configuration was superior to the coaxial cylindrical electrode setup, as evident from a higher maximum nitrate removal of 74 and 56% at a current density of 7 mA/cm2 and lower energy consumption of 46.7 × 10-3 and 54.3 × 10-3 kWh/mmol NO3- at 36.4 mA/cm2, respectively. In addition, the mass transfer coefficients and first order rate constants were higher in all conditions tested for the vertical plate parallel configuration.

Electrochemical removal of nitrate from a Donnan dialysis waste stream.

The objective of this work was to investigate electrochemical removal of nitrate from a high salinity waste stream generated by Donnan dialysis. Donnan dialysis for nitrate removal is a promising technique. It produces a distinctive composition of a high salinity waste stream of NaCl or Na2SO4 that requires a viable disposal method. The waste stream has the full anionic composition of contaminated groundwater, but the only cation is sodium. Experiments were conducted in a batch system setup. A copper cathode was chosen over brass, aluminum and graphite cathodes. A dimensionally stable anode (DSA), Ti/PbO2, was selected over a Ti/Pt anode. Electrochemical denitrification of high salinity Donnan dialysis nitrate wastes was successfully achieved, with different behavior exhibited in high salinity NaCl solution than in high salinity Na2SO4 solution. NaCl inhibited nitrate removal at high salinities while Na2SO4 did not. The maximum removals after 4 h operation in the high salinity wastes were 69 and 87% for the NaCl and Na2SO4 solutions respectively.

Modeling Remineralization of Desalinated Water by Micronized Calcite Dissolution.

A widely used process for remineralization of desalinated water consists of dissolution of calcite particles by flow of acidified desalinated water through a bed packed with millimeter-size calcite particles. An alternative process consists of calcite dissolution by slurry flow of micron-size calcite particles with acidified desalinated water. The objective of this investigation is to provide theoretical models enabling design of remineralization by calcite slurry dissolution with carbonic and sulfuric acids. Extensive experimental results are presented displaying the effects of acid concentration, slurry feed concentration, and dissolution contact time. The experimental data are shown to be in agreement within less than 10% with theoretical predictions based on the simplifying assumption that the slurry consists of uniform particles represented by the surface mean diameter of the powder. Agreement between theory and experiment is improved by 1-8% by taking into account the powder size distribution. Apart from the practical value of this work in providing a hitherto lacking design tool for a novel technology. The paper has the merit of being among the very few publications providing experimental confirmation to the theory describing reaction kinetics in a segregated flow system.

Challenges and Solutions for Global Water Scarcity.

Climate change, global population growth, and rising standards of living have put immense strain on natural resources, resulting in the unsecured availability of water as an existential resource. Access to high-quality drinking water is crucial for daily life, food production, industry, and nature. However, the demand for freshwater resources exceeds the available supply, making it essential to utilize all alternative water resources such as the desalination of brackish water, seawater, and wastewater. Reverse osmosis desalination is a highly efficient method to increase water supplies and make clean, affordable water accessible to millions of people. However, to ensure universal access to water, various measures need to be implemented, including centralized governance, educational campaigns, improvements in water catchment and harvesting technologies, infrastructure development, irrigation and agricultural practices, pollution control, investments in novel water technologies, and transboundary water cooperation. This paper provides a comprehensive overview of measures for utilizing alternative water sources, with particular emphasis on seawater desalination and wastewater reclamation techniques. In particular, membrane-based technologies are critically reviewed, with a focus on their energy consumption, costs, and environmental impacts.

A hybrid iron oxyhydroxide agglomerates-ultrafiltration process for efficient removal of chromate.

Hexavalent chromium (Cr(VI)) is often detected in groundwater, surface water and soils. The objective of the research was to study a hybrid process of adsorption onto iron oxyhydroxide agglomerates (IOAs) and ultrafiltration (UF) for removal of Cr(VI) from aqueous solution. Initially, the adsorption of the chromium onto IOAs was characterized by SEM and Raman analyses. Next, the IOAs dosages, required to obtain the regulatory limit of Cr(VI) ≤ 0.05-0.10 mg/L, at varying initial Cr(VI) concentrations, were determined in batch beaker tests and stirred tank reactor. The UF membrane held back efficiently the IOAs, at varying IOAs dosages, transmembrane pressures, and filtration velocities. Cake filtration was determined as the predominant fouling mechanism of the UF membrane. The fouling was reversible by backwash yet, faster fouling rates were obtained in consecutive filtration/backwash cycles. The results point to the applicability of the hybrid adsorption/UF process as a potent method for chromium removal from contaminated water.

Removal of silica from brackish water by integrated adsorption/ultrafiltration process.

A lab-scale unit of the hybrid continuous stirred tank reactor (CSTR) adsorption/ultrafiltration (UF) system was used to evaluate the removal efficiency of silica from brackish water. The semi-batch adsorption process was carried out using iron oxy/hydroxide agglomerates (IOAs) as adsorbent and hollow fiber ultrafiltration membrane as a barrier to the adsorbent passage to the product water. The effect of residence time, concentration of silica, and adsorbent dosage on the silica removal and UF membrane blockage was examined. It was found that a short residence time of 15 min was sufficient to achieve the maximum adsorption capacity similar to that obtained in batch isotherm experiments. The adsorption capacity increased with the augmentation of the silica concentration and decreased with the increase in the adsorbent dosage. The UF was effectively employed to separate the loaded adsorbent without fouling the membrane until breakthrough. A simple model was applied to accurately predict the adsorption breakthrough curves.

Comparative disinfection efficiency of pulsed and continuous-wave UV irradiation technologies.

Pulsed UV (PUV) is a novel UV irradiation system that is a non-mercury lamp-based alternative to currently used continuous-wave systems for water disinfection. PUV polychromatic irradiation disinfection efficiency was compared to that from continuous-wave monochromatic low-pressure (LP) and polychromatic medium-pressure (MP) UV systems, using two types of actinometry (ferrioxalate and iodide-iodate) and an absolute spectral emission method for fluence measurement. All three methods were in good agreement. Once accurate and reliable methods for fluence measurement were established, the inactivation of Escherichia coli and pathogen surrogates phage T4 and T7 were investigated under each technology. Inactivation was significantly faster using PUV irradiation compared to LP or MP UV lamps at equivalent fluence levels. A significant fraction of the enhanced PUV inactivation efficiency was due to wavelengths greater than 295 nm.

Photodegradation of metolachlor applying UV and UV/H2O2.

Metolachlor is one of the most widely used herbicides in the world for controlling weeds. It has been detected in both ground and surface waters in the United States, and there are rising concerns in regard to its health risks and in developing effective treatment processes for its removal from water. Degradation of metolachlor via ultraviolet (UV) photolysis and an UV/hydrogen peroxide advanced oxidation process (AOP) was studied. The quantum yield of metolachlor at 254 nm was found to be 0.302 +/- 0.001 mol E-1 through direct UV photolysis in the range of pH 6-8. The second-order rate constant of the reaction between metolachlor and hydroxyl radical was determined to be 9.07 (+/-0.21) x 10(9) M-1 s-1 by using a competition kinetics model that utilized nitrobenzene as a reference compound. In addition, these parameters were successfully applied in modeling the kinetics of elimination of metolachlor using an UV/H2O2 process in both laboratory and natural waters. The formation of several photolysis byproducts was identified using gas chromatography/mass spectrometry, and a scheme for the metolachlor photodegradation pathway is proposed.

Aqueous photodegradation and toxicity of the polycyclic aromatic hydrocarbons fluorene, dibenzofuran, and dibenzothiophene.

Decay kinetics resulting from the application of UV and UV/H(2)O(2) to the polycyclic aromatic hydrocarbons (PAHs) fluorene, dibenzofuran and dibenzothiophene was studied. Batch experiments were conducted with both low-pressure monochromatic (253.7nm) and medium pressure polychromatic (200-300nm) UV sources alone or in the presence of up to 25mg/L hydrogen peroxide, in a quasi-collimated beam apparatus. Degradation of all three PAHs, by both UV and UV/H(2)O(2), exhibited pseudo-first-order reaction kinetics and low quantum yields ranging from 1.4x10(-3) to 1.8x10(-2)mol/E using both UV lamps. Toxicity testing using a bioluminesence inhibition bioassay was correlated to the decay in concentration of the PAHs as analyzed analytically using HPLC. Results demonstrated that treatment efficacy of oxidative PAH degradation measured by following the decay of the target compound is best complemented by also evaluating the toxicity of the treated water due to byproduct formation concerns.

Photolysis, oxidation and subsequent toxicity of a mixture of polycyclic aromatic hydrocarbons in natural waters.

Photodegradation of a mixture of three polycyclic aromatic hydrocarbons fluorene (FLU), dibenzofuran (DBF), and dibenzothiophene (DBT) using UV and UV/H2O2 processes was studied. Treating a mixture of the PAHs stimulated a more realistic contamination composition present in polluted water. Effects of pH, PAH concentration, and water matrix composition on removal rates and efficiencies of these compounds are discussed. Batch experiments were conducted using both monochromatic low pressure (LP, 253.7 nm) and polychromatic medium pressure (MP, 200-400 nm) UV sources, in a quasi-collimated beam setup. A synergistic effect was observed during direct photolysis and LP-UV/H2O2 of the mixture as compared to photodegradation as a single component in an aqueous solution. Similar results were obtained for FLU using MP-UV/H2O2 whereas, degradation of DBF and DBT was inhibited in a mixture. Natural water enhanced the direct photolysis compared to laboratory buffered water, whereas, degradation of the PAHs in the natural water was inhibited using UV/H2O2 process. Toxicity testing using a luminescent inhibition bioassay was correlated to intermediates generated during UV-based oxidation reactions.

Inactivation of E. coli, B. subtilis spores, and MS2, T4, and T7 phage using UV/H2O2 advanced oxidation.

The goal of this study was to evaluate the potential of an advanced oxidation process (AOP) for microbiocidal and virucidal inactivation. The viruses chosen for this study were bacteriophage MS2, T4, and T7. In addition, Bacillus subtilis spores and Escherichia coli were studied. By using H(2)O(2) in the presence of filtered ultraviolet (UV) irradiation (UV/H(2)O(2)) to generate wavelengths above 295nm, the direct UV photolysis disinfection mechanism was minimized, while disinfection by H(2)O(2) was also negligible. Virus T4 and E. coli in phosphate buffered saline (PBS) were sensitive to >295nm filtered UV irradiation (without H(2)O(2)), while MS2 was very resistant. Addition of H(2)O(2) at 25mg/l in the presence of filtered UV irradiation over a 15min reaction time did not result in any additional disinfection of virus T4, while an additional one log inactivation for T7 and 2.5 logs for MS2 were obtained. With E. coli, only a slight additional effect was observed when H(2)O(2) was added. B. subtilis spores did not show any inactivation at any of the conditions used in this study. The OH radical exposure (CT value) was calculated to present the relationship between the hydroxyl radical dose and microbial inactivation.

Degradation of the pharmaceutical metronidazole via UV, Fenton and photo-Fenton processes.

Degradation rates and removal efficiencies of Metronidazole using UV, UV/H2O2, H2O2/Fe2+, and UV/H2O2/Fe2+ were studied in de-ionized water. The four different oxidation processes were compared for the removal kinetics of the antimicrobial pharmaceutical Metronidazole. It was found that the degradation of Metronidazole by UV and UV/H2O2 exhibited pseudo-first order reaction kinetics. By applying H2O2/Fe2+, and UV/H2O2/Fe2+ the degradation kinetics followed a second order behavior. The quantum yields for direct photolysis, measured at 254 nm and 200-400 nm, were 0.0033 and 0.0080 mol E(-1), respectively. Increasing the concentrations of hydrogen peroxide promoted the oxidation rate by UV/ H2O2. Adding more ferrous ions enhanced the oxidation rate for the H2O2/Fe2+ and UV/H2O2/Fe2+ processes. The major advantages and disadvantages of each process and the complexity of comparing the various advanced oxidation processes on an equal basis are discussed.

Degradation and by-product formation of diazinon in water during UV and UV/H(2)O(2) treatment.

Kinetics and degradation products resulting from the application of UV and UV/H(2)O(2) to the US EPA Contaminant Candidate List pesticide diazinon were studied. Batch experiments were conducted with both monochromatic (low pressure [LP] UV 253.7 nm) and polychromatic (medium pressure [MP] UV 200-300 nm) UV sources alone or in the presence of up to 50 mg l(-1) H(2)O(2), in a quasi-collimated beam apparatus. Degradation of diazinon by both UV and UV/H(2)O(2) exhibited pseudo first order reaction kinetics, and quantum yield of 8.6 x 10(-2) and 5.8 x 10(-2) mol E(-1) for LP and MP lamps respectively. Photolysis studies under MP UV lamp showed 2-isopropyl-6-methyl-pyrimidin-4-ol (IMP) to be the main degradation product of diazinon at aqueous solution pH values of 4, 7 and 10. Trace levels up to 1.8 x 10(-3) microM of diazinon oxygen analogue diethyl 2-isopropyl-6-methylpyrimidin-4-yl phosphate (diazoxon) were detected only during the UV/H(2)O(2) reaction. Decay of both products was observed, as the UV/H(2)O(2) reaction prolonged, yet no mineralization was achieved over the UV fluence levels examined. Photolysis kinetics, quantum yield and UV/H(2)O(2) degradation of the reaction product IMP was determined using MP UV lamp at pH values of 4, 7 and 10.

Trihalomethanes aqueous solutions sono-oxidation.

Ultrasonic (US) irradiation, hydrogen peroxide (H(2)O(2)), Fenton's oxidation and the combination of the processes were investigated for destruction and removal of the following trihalomethanes (THMs) compounds from aqueous solutions: CHCl(3), CHBrCl(2), CHBr(2)Cl, CHBr(3), and CHI(3). H(2)O(2) had no significant effect on the THMs sonodegradation. The coupled US and Fenton processes did not affect the CHCl(3), CHBrCl(2), and CHBr(2)Cl sonolysis efficiency. Nevertheless, the sonodegradation of CHBr(3) was enhanced. CHI(3) was degraded by Fenton's oxidation rather than by the US irradiation during the sonication/Fenton treatment. The combination of sonication with H(2)O(2) or Fenton's reagent did not affect the mineralization of the THMs aqueous mixture.

Sonochemical removal of trihalomethanes from aqueous solutions.

In this research, ultrasound irradiation was employed to degrade the trihalomethanes, THMs: CHCl3, CHBrCl2, CHBr2Cl, CHBr3, and CHI3. The kinetics reaction rates and removal efficiencies of the THMs compounds, as a sole component in the aqueous solutions, were studied. Batch experiments were conducted at an ultrasonic frequency of 20 kHz and acoustic intensity of 3.75 W/cm2. The first-order degradation rate constants and the sonolysis efficiencies followed the decreasing order of CHCl3 > CHBrCl2 > CHBr2Cl > CHBr3 > CHI3. Up to 100% of the CHCl3 was removed, while only 60% of the CHI3 was sonodegraded, after 180 min sonication. The THMs vapor pressure was found to be the most important parameter affecting the sonodegradation kinetics and efficiency, while the bond dissociation energy and hydrophilic/hydrophobic characteristics of the THMs compounds were found to be of secondary importance.

Effect of various reaction parameters on THMs aqueous sonolysis.

Ultrasonic irradiation was investigated for destruction of the following THMs: CHCl(3), CHBrCl(2), CHBr(2)Cl, CHBr(3), and CHI(3). The effect of pH, temperature, and the organics initial concentration on the THMs sonodegradation at acoustic frequency of 20 kHz was studied. An increase of the solution temperature resulted in a faster sonodegradation rates. Initial aqueous solution pH, in the range from 3 to 10, was found to have little effect on the degradation of the THMs. The THMs sonolysis efficiency was reduced when the initial organic compounds concentration was increased from 10 mg l(-1) to 300 mg l(-1).

Rotating cylinder technique for assessing the effectiveness of anti-scalants.

A novel technique for evaluating the relative inhibition effectiveness of different anti-scalants is presented. The technique is based on the ability of anti-scalants to modify the scale deposition mechanism from mass transfer control to surface control. A rotating cylinder system which is known to provide well controlled mass transfer conditions is used to determine the scaling rate of a supersaturated solution dosed with various feed concentrations of an anti-scalant. Mass transfer conditions were characterized by turbulent flow at hydrodynamically smooth surface. In the absence of an anti-scalant, scale deposition is mass transfer controlled and scaling rate increases with rotation speed. With sufficient anti-scalant dosage, precipitation is modified to surface control and rotation speed has no effect on the scale deposition rate. Determination of the critical anti-scalant dosage enabling surface controlled precipitation provides a sensitive technique for comparing the relative effectiveness of different anti-scalants.

Synthesis, performance, and modeling of immobilized nano-sized magnetite layer for phosphate removal.

A homogeneous layer of nano-sized magnetite particles (<4 nm) was synthesized by impregnation of modified granular activated carbon (GAC) with ferric chloride, for effective removal of phosphate. A proposed mechanism for the modification and formation of magnetite onto the GAC is specified. BET results showed a significant increase in the surface area of the matrix following iron loading, implying that a porous nanomagnetite layer was formed. Batch adsorption experiments revealed high efficiency of phosphate removal, by the newly developed adsorbent, attaining maximum adsorption capacity of 435 mg PO(4)/g Fe (corresponding to 1.1 mol PO(4)/mol Fe(3)O(4)). It was concluded that initially phosphate was adsorbed by the active sites on the magnetite surface, and then it diffused into the interior pores of the nanomagnetite layer. It was demonstrated that the latter is the rate-determining step for the process. Innovative correlation of the diffusion mechanism with the unique adsorption properties of the synthesized adsorbent is presented.

Adsorption-desorption mechanism of phosphate by immobilized nano-sized magnetite layer: interface and bulk interactions.

Phosphate adsorption mechanism by a homogenous porous layer of nano-sized magnetite particles immobilized onto granular activated carbon (nFe-GAC) was studied for both interface and bulk structures. X-ray Photoelectron Spectroscopy (XPS) analysis revealed phosphate bonding to the nFe-GAC predominantly through bidentate surface complexes. It was established that phosphate was adsorbed to the magnetite surface mainly via ligand exchange mechanism. Initially, phosphate was adsorbed by the active sites on the magnetite surface, after which it diffused into the interior of the nano-magnetite layer, as indicated by intraparticle diffusion model. This diffusion process continues regardless of interface interactions, revealing some of the outer magnetite binding sites for further phosphate uptake. Desorption, using NaOH solution, was found to be predominantly a surface reaction, at which hydroxyl ions replace the adsorbed phosphate ions only at the surface outer biding sites. Five successive fix-bed adsorption/regeneration cycles were successfully applied, without significant reduction in the nFe-GAC adsorption capacity and at high regeneration efficiency.