The Impact of Natural Variation of OH Radical Demand of Drinking Water Sources on the Optimum Operation of the UV/H2O2 Process.

Hydroxyl radical (•OH) water demand is a key parameter which impacts the design and operation of UV/H2O2 process for water treatment. Long-term monitoring of the •OH water demand in water sources used for drinking water production indicated significant seasonal variations of this parameter (1.59 × 104 to 4.98 × 104 s-1), which coincided with the occurrence of algal blooming events. Pilot-scale tests at a drinking water treatment plant confirmed that the UV/H2O2 process performance for contaminant removal is predictable when the •OH water demand is accurately determined through a validated experimental method. A predictive tool was developed to identify the optimum operating conditions of the UV system with the UV/H2O2 process and it was used to demonstrate the significant impact of seasonal variations of •OH water demand on the operating costs.

Evaluation of Moringa oleifera seed extract by extraction time: effect on coagulation efficiency and extract characteristic.

The seed of Moringa oleifera (MO) is a well-known coagulant used in water and wastewater treatment, especially in developing countries. The main mechanism of MO seed extract in coagulation is the positive protein component for charge neutralization. The method for efficient extraction of MO seed is very important for high coagulation activity. In this study, the effects of extraction mixing speed and extraction time of MO on coagulation activity were evaluated using a distilled water extraction method. Although the rotation per minute for extraction did not affect the coagulation efficiency, the extraction time strongly affected the coagulation efficiency of the extract. To evaluate the characteristic change of MO extract by extraction time, the charge of MO extract and protein characteristic in MO extract were analysed. As the extraction time was short, more positive charge and higher protein content were observed. For detailed protein analysis, the fluorescence spectroscopic study (EEM analysis) was performed. The tryptophan-like peak increased at longer extraction times. For efficient extraction of MO seed, a short extraction time is strongly recommended.

Efficient removal of arsenic by strategically designed and layer-by-layer assembled PS@+rGO@GO@Fe3O4 composites.

The PS@+rGO@GO@Fe3O4 (PG-Fe3O4) hybrid composites for Arsenic removal were successfully fabricated and well dispersed using layer-by-layer assembly and a hydrothermal method. The PG-Fe3O4 hybrid composites were composed of uniformly coated Fe3O4 nanoparticles on graphene oxide layers with water flow space between 3D structures providing many contact area and adsorption sites for Arsenic adsorption. The PG-Fe3O4 hybrid composite has large surface adsorption sites and exhibits high adsorption capacities of 104 mg/g for As (III) and 68 mg/g for As (V) at 25 °C and pH 7 comparison with pure Fe3O4 and P-Fe3O4 samples.

Evaluation of the formation of oxidants and by-products using Pt/Ti, RuO2/Ti, and IrO2/Ti electrodes in the electrochemical process.

The aim of this study was to evaluate the formation of oxidants and by-products by using different electrode materials, such as Pt/Ti, RuO2/Ti, and IrO2/Ti, in the electrochemical process. The harmful by-products ClO3- and ClO4- were formed during the electrolysis of a Cl- electrolyte solution, as well as active chlorine, which is the most common water disinfectant. With regard to drinking water treatment, the most efficient electrode was defined as that leading to a higher formation of active chlorine and a lower formation of hazardous by-products. Overall, it was found that the Pt/Ti electrode should not be used for drinking water treatment applications, while the IrO2/Ti and RuO2/Ti electrodes are ideal for use.

Alternative Electrode Materials and Ceramic Filter Minimize Disinfection Byproducts in Point-of-Use Electrochemical Water Treatment.

Effects of various electrodes and prefiltration to minimize disinfection byproducts (DBPs) in electrochemical water disinfection was evaluated. The target microorganism, Escherichia coli O157:H7, was effectively inactivated even applying a solar-charged storage battery for the electrolysis process. Extent of microbial inactivation decreased with lower water temperature and higher pH in the free chlorine disinfection system. The RuO2/Ti electrode was most efficient because it produced the lowest concentration of chlorate and the highest generation of free chlorine. Prefiltration using a ceramic filter inhibited formation of halogenated DBPs because it removed precursors of DBPs. For safe point-of-use water treatment, the use of a hybrid prefiltration stage with the electrolysis system is strongly recommended to reduce risks from DBPs. The system is particularly suited to use in developing regions.

Evaluation of disinfection efficacy and chemical formation using MPUV ballast water treatment system (GloEn-Patrol).

This study was undertaken to evaluate the efficacy of inactivation of several indigenous marine species and the formation of oxidants and other by-products using medium-pressure ultraviolet (MPUV) ballast water treatment. The ballast water treatment system (BWTS) used in this study was composed of filtration modules as a pretreatment process, followed by a UV irradiation process equipped with a polychromatic MPUV lamp. The experiments were performed on seawater (Busan, >32 PSU) and brackish water (Nakdong River, 20-22 PSU) with flow rates of 50 and 250 m(3)/h. The disinfection efficacy of the system was evaluated using indigenous species (>50 microm and 10-50 microm) and surrogate microorganisms (E. coli and Enterococci group). The test results successfully met the D-2 regulation of the IMO (International Marine Organization). In addition, oxidants, such as H202, total residual oxidants (TRO) and OH radicals, and potential halogenated by-products, such as haloacetic acids, trihalomethanes and total organic halides, that had potentially formed after MPUV treatment, were measured. In conclusion, the ballast water treatment system employing the MPUV physical process not only effectively eliminated indigenous species in ballast water but also generated no harmful by-products.

Characterization of marine dissolved organic matter and its effect on ozonation.

As the marine industry develops, the importance of seawater treatment process is increasing. To treat seawater, oxidation processes have primarily been used, such as ballast water treatment systems, aquaculture farm operations, aquarium management, and seawater desalination. However, dissolved organic matter in seawater, whose characteristics vary spatially and seasonally, affects the efficiency of oxidation processes. Therefore, in this study, seawater samples were acquired from various locations in the Republic of Korea to understand the spatio-temporal patterns of marine dissolved organic matter. It was reported that the characterization of marine dissolved organic matter using liquid chromatography-organic carbon detector and excitation-emission matrix-parallel factor modeling. Furthermore, the effects of marine dissolved organic matter were evaluated on ozonation, an oxidation process. The results demonstrate that marine dissolved organic matter varies in its aquagenic, pedogenic, and intermediate characteristics based on region and season. These variations affect ozonation by influencing the consumption of oxidants (e.g., bromine). As a result, it was concluded that characterizing marine dissolved organic matter can help improve the effectiveness of oxidation processes, particularly ozonation.

The degradation of diethyl phthalate (DEP) during ozonation: oxidation by-products study.

The degradation of diethyl phthalate (DEP) in an aqueous solution during ozonation was investigated by identifying the oxidation intermediates using GC-MS. The experiments were carried out in semi-batch mode with a 1.5 mg l(-1)-min ozone dose. The proposed degradation pathways were divided into hydrolysis of the aliphatic chain (pathway (A)) and hydroxylation resulting from OH attack in the aromatic ring (pathway (B)). With increasing ozone dose, the aromatic ring of DEP was opened and acidic compounds, such as malonic acid, succinic acid and glutaric acid were formed. In addition, the ozonation of DEP for 18 min induced hydrogen peroxide (H(2)O(2)) generation at levels six times higher than pure water. Of the intermediates indentified, phthalic acid (PA) and phthalic anhydride (PAH) enhanced the degradation of DEP by promoting ozone decomposition.

Synergistic effect of sequential or combined use of ozone and UV radiation for the disinfection of Bacillus subtilis spores.

This study was performed to evaluate the inactivation efficiency or synergy of combined ozone and UV processes (combined ozone/UV process) or sequential processes (ozone-UV, UV-ozone) compared with individual unit processes and to investigate the specific roles of ozone, UV and the hydroxyl radical, which is formed as an intermediate in the combined ozone/UV process. The Bacillus subtilis spore, which has often been used as a surrogate microorganism for Cryptosporidium parvum oocysts, was used as a target microorganism. Compared to individual unit processes with ozone or UV, the inactivation of B. subtilis spores by the combined ozone/UV process was enhanced under identical conditions. To investigate the specific roles of ozone and UV in the combined ozone/UV process, sequential ozone-UV and UV-ozone processes were tested for degrees of inactivation. Additionally, the experiment was performed in the presence and absence of tert-butyl alcohol, which acted as a hydroxyl radical scavenger to assess the role of inactivation by the hydroxyl radical in the combined ozone/UV process. Among the five candidate processes, the greatest synergistic effect was observed in the combined ozone/UV process. From the comparison of five candidate processes, the hydroxyl radical and ozone were each determined to significantly enhance the overall inactivation efficiency in the combined ozone/UV process.

Removal of sulfamethoxazole, ibuprofen and nitrobenzene by UV and UV/chlorine processes: A comparative evaluation of 275 nm LED-UV and 254 nm LP-UV.

The aim of this study is to evaluate the micropollutant removal capacity of a 275 nm light-emitting diode (LED)-UV/chlorine system. The sulfamethoxazole, ibuprofen, and nitrobenzene removal efficiencies of this system were compared with those of a conventional 254 nm low-pressure (LP)-UV system as a function of the UV dose. In a direct photolysis system, the photon reactivity of sulfamethoxazole is higher than that of nitrobenzene and ibuprofen at both wavelengths. The molar absorption coefficients and quantum yields of each micropollutant were as follows: sulfamethoxazole (εSMX, 275 nmprotonated = 17,527 M-1 cm-1, ΦSMX, 275 nmprotonated = 0.239, εSMX, 275 nmdeprotonated = 8430 M-1 cm-1, and ΦSMX, 275 nmdeprotonated = 0.026), nitrobenzene (εNB, 275 nm = 7176 M-1 cm-1 and ΦNB, 275 nm = 0.057), and ibuprofen (εNB, 275 nm = 200 M-1 cm-1 and ΦIBF, 275 nm = 0.067). The photon reactivity of chlorine species, i.e., HOCl and OCl-, were determined at 275 nm (εHOCl, 275 nm = 28 M-1 cm-1, ΦHOCl, 275 nm = 1.97, εOCl-, 275 nm = 245 M-1 cm-1, and ΦOCl-, 275 nm = 0.8), which indicate that the decomposition rate of OCl- is higher and that of HOCl is lower by 275 nm photolysis than that by 254 nm photolysis (εHOCl, 254 nm = 60 M-1 cm-1, ΦHOCl, 254 nm = 1.46, εOCl-, 254 nm = 58 M-1 cm-1, and ΦOCl-, 254 nm = 1.11). In the UV/chlorine system, the removal rates of ibuprofen and nitrobenzene were increased by the formation of OH and reactive chlorine species. The 275-nm LED-UV/chlorine system has higher radical yields at pH 7 and 8 than the 254 nm LP-UV/chlorine system.

Characteristics of intracellular algogenic organic matter and its reactivity with hydroxyl radicals.

The aim of this study was to investigate the reactivity of intracellular algogenic organic matter (IOM) with hydroxyl radicals (·OH), a key reaction species in advanced oxidation processes. IOM was extracted from two green algae, Chlamydomonas reinhardtii and Scenedesmus sp., and two blue-green algae, Anabaena sp. and Microcystis aeruginosa using a freeze-thaw method. The second-order rate constants of the extracted IOM with ·OH were determined as 7.95 × 108 MC-1 s-1 (Chlamydomonas reinhardtii), 6.71 × 108 MC-1 s-1 (Scenedesmus sp.), 4.02 × 108 MC-1 s-1 (Anabaena sp.), and 4.45 × 108 MC-1 s-1 (Microcystis aeruginosa). These rate constants were significantly higher than values reported for dissolved organic matter in various water sources. This implies that IOM formation during algal bloom season could change the ·OH water matrix demand and adversely affect the performance of advanced oxidation processes. To investigate the physical and chemical composition characteristics of IOM and their relationship to the rate constants determined for the reaction between IOM and ·OH, liquid chromatography-organic carbon detection (LC-OCD) and fluorescence excitation-emission matrix & parallel factor analysis (FEEM-PARAFAC) were used. The IOM mainly consisted of low molecular weight (LMW) matter and protein-related compounds, as evidenced LMW neutrals (38-65%), biopolymers (7-19%), and tryptophan-like compounds (74-94%). Based on the composition characteristics of IOM, it was concluded that the molecular weight and the presence of nitrogen-containing compounds are influential parameters for determining the reactivity of IOM with ·OH.

Investigation of the estrogenic activities of pesticides from Pal-dang reservoir by in vitro assay.

Endocrine disruptors, when absorbed into the body, interfere with the normal function by mimicking or blocking the hormone system. To investigate compounds mimicking estrogen in the drinking water source of the residence of Seoul, the Pal-dang reservoir was monitored over a period of 5 years, between 2000 and 2004. Nine kinds of pesticide (carbaryl, DBCP, diazinon, fenitrothion, fenobucarb, flutolanil, iprobenphos, isoprothiolane and parathion) were found to exist in the river water sample. These compounds were detected at low concentrations in the water samples. The total concentration and those of each of these pesticides were below the permissible limits of the National Institute of Environmental Research (NIER), Korea. The estrogenic potencies of the nine pesticides were examined using an E-screen assay with MCF-7 BUS estrogen receptor (ER)-positive human breast cancer cells, with ER-negative MDA MB 231 cell lines also used to compare the results. From this, flutolanil and isoprothiolane were confirmed to have estrogenic activities as shown by the increasing MCF-7 BUS cell growth on their addition. In addition, the estrogen receptor alpha (ERalpha) protein, estrogen receptor-regulated progesterone receptor (PR) and pS2 mRNA levels on the addition of flutolanil and isoprothiolane were measured with MCF-7 BUS cells. It was observed that the levels of ERalpha protein decreased and those of the PR and pS2 genes increased on the addition of either flutolanil or isoprothiolane at concentrations of 10(-4) M, in the same manner as with the addition of 17beta-estradiol, which was used as the positive control. From these results, it was confirmed that flutolanil and isoprothiolane exhibit estrogenic activities, suggesting they might act through estrogen receptors.

Performance characterization and kinetic modeling of ozonation using a new method: ROH,O3 concept.

Ozonation is an effective treatment for removing various organic pollutants from aquatic systems. The Rct concept, which is defined as the ratio of OH exposure to O3 exposure, has been widely used to predict the removal efficiency of target compounds, but it has significant variations by water temperature and initial O3 dose which are crucial parameters in drinking water plant. The ROH,O3 concept, which is defined as the OH exposure by O3 consumption, was proposed as a kinetic parameter for characterization and kinetic modeling for ozonation. The ROH,O3 concept is independent of temperature and initial O3 dose. A higher ROH,O3 value indicates a higher OH formation when the same amount of O3 is consumed in different water samples; therefore, the OH yield from O3 decomposition of the water samples can be compared using the ROH,O3 values. The ROH,O3 concept can also be used to characterize and model the initial ozone demand phase, and it is more convenient method compared to Rct concept. Using the ROH,O3 concept, the dynamic O3 and OH kinetics and the removal efficiencies of iopromide and ibuprofen were well predicted (R2 = 0.98) over a wide range of experimental conditions (n = 124).

Characteristics and fate of natural organic matter during UV oxidation processes.

Advanced oxidation processes (AOPs) are widely used in water treatments. During oxidation processes, natural organic matter (NOM) is modified and broken down into smaller compounds that affect the characteristics of the oxidized NOM by AOPs. In this study, NOM was characterized and monitored in the UV/hydrogen peroxide (H2O2) and UV/persulfate (PS) processes using a liquid chromatography-organic carbon detector (LC-OCD) technique, and a combination of excitation-emission matrices (EEM) and parallel factor analysis (PARAFAC). The percentages of mineralization of NOM in the UV/H2O2 and UV/PS processes were 20.5 and 83.3%, respectively, with a 10 mM oxidant dose and a contact time of 174 s (UV dose: approximately 30,000 mJ). Low-pressure, Hg UV lamp (254 nm) was applied in this experiment. The steady-state concentration of SO4- was 38-fold higher than that of OH at an oxidant dose of 10 mM. With para-chlorobenzoic acid (pCBA) as a radical probe compound, we experimentally determined the rate constants of Suwannee River NOM (SRNOM) with OH (kOH/NOM = 3.3 × 108 M-1s-1) and SO4- (kSO4-/NOM = 4.55 × 106 M-1s-1). The hydroxyl radical and sulfate radical showed different mineralization pathways of NOM, which have been verified by the use of LC-OCD and EEM/PARAFAC. Consequently, higher steady-state concentrations of SO4-, and different reaction preferences of OH and SO4- with the NOM constituent had an effect on the mineralization efficiency.

Application of ozone, UV and ozone/UV processes to reduce diethyl phthalate and its estrogenic activity.

A research study to monitor the micropollutant levels present in the Han River, a major drinking water source for the Seoul Metropolitan district in Korea, was performed over a five-year period from 2000 to 2004, inclusive. Of the detected micropollutants, phthalates were found to be the major contaminants. In this study, the estrogenic activities of the detected phthalates and raw water samples contaminated with the pollutants were assessed by the E-screen assay using the MCF-7 breast cancer cell line. Of the phthalates, diethyl phthalate (DEP) and di(2-ethylhexyl) phthalate (DEHP) showed relatively high cell proliferation. Using DEP as a phthalate probe, three candidate processes, ozone alone, UV alone, and the ozone/UV combined, were evaluated for their efficiency in removing DEP and reducing its estrogenic activity. The ozone/UV process was shown to have the highest efficiency for the elimination of DEP and its by-products, leading to the complete mineralization of DEP. This study also found that the ozone/UV process is the best candidate to reduce the estrogenicity induced by DEP and its by-products.

Comparative evaluation of magnetite-graphene oxide and magnetite-reduced graphene oxide composite for As(III) and As(V) removal.

Arsenic removal using Fe3O4-graphene oxide composite (M-GO) and Fe3O4-reduced graphene oxide composite (M-rGO) was investigated. The M-GO was more effective to adsorb both As(III) and As(V) than M-rGO, because the more functional groups existing on the M-GO could lead to synthesize more Fe3O4 with M-GO. As(III) was more favorable to be adsorbed than As(V) onto both M-GO and M-rGO. According to the effect of pH on arsenic removal, the electrostatic interaction between the positively charged surface of Fe3O4-graphene based adsorbents and anionic As(V) species was a major factor to adsorb As(V). The adsorption mechanism of As(III), on the other hand, was strongly affected by a surface complexation, rather than electrostatic interactions. Consequently, in terms of the process energy consumption, energy saving could be achieved via omitting the reduction process to fabricate M-rGO from M-GO and the pre-oxidation process to convert As(III) to As(V).

Characterization of ozone decomposition in a soil slurry: kinetics and mechanism.

A series of soil slurry experiments were performed in a carefully conceived reactor set-up to investigate the characteristics of the catalytic decomposition of ozone on a sand and iron surface. Real time on-line monitoring of ozone in the reaction module was possible using flow injection analysis coupled with a computer-controlled UV detector and data acquisition system. The effects of the soil media and size, ozone dosage, pH and p-CBA as a probe compound were examined at the given experimental conditions. Two apparent phases existed, and ozone instantaneously decomposed within one second in the first phase. These were defined as the instantaneous ozone demand (ID) phase, and the relatively slow decay stage. The interactions of ozone with the soil organic matter (SOM) and metal oxides were attributed mostly to the instantaneous decomposition of ozone. From the probe (p-CBA) experiments, 60-68% of total p-CBA removal occurred during the ID phase. The generation of hydroxyl radicals (OH.) was demonstrated and was closely related with metal oxides as well as SOM. Metal oxides in soil surface were considered to have relatively faster reaction rate with ozone and provide more favorable reactive sites to generate higher amount of OH. than SOM. Even at one-tenth concentration of the sands, a goethite-induced catalytic reaction outfitted the removal rate ofp-CBA among all the soils tested. More than 40% of total p-CBA removal occurred on the soil surface. It was inferred that the radical reaction with the probe compound seemed to take place not only on the soil surface but also in the solid-liquid interface. Ozone decomposition and the reaction between OH. and p-CBA appeared to be independent of any change in pH.

Sonolytic degradation of methyl tert-butyl ether: the role of coupled Fenton process and persulphate ion.

The sonolytic degradation of methyl tert-butyl ether (MTBE) has been investigated at ultrasonic frequency of 20 kHz. The observed pseudo-first-order rate constant decreased from 1.25 x 10(-4) to 5.32 x 10(-5) s(-1) as the concentration of MTBE increased from 2.84 x 10(-2) to 2.84 x 10(-1) mM. The rate of degradation of MTBE increased with the increase of the power density of ultrasonicator and also with the rise in reactor system temperature. In the presence of oxidising agent, potassium persulphate, the sonolytic rate of degradation of MTBE was accelerated substantially. Tert-butyl formate (TBF) and acetone were found to be the major intermediates of the degradation of MTBE. It is found that the ultrasound/Fe2+/H2O2 method is promising process for the degradation of MTBE. More than 95% degradation of MTBE (2.84 x 10(-2) mM) along with its intermediate products has been achieved during the coupled ultrasound/Fe2+/ H2O2 method. Hence, the coupled ultrasound/Fe2+/H2O2 may be a viable method for the degradation MTBE within a short period of time than the ultrasound irradiation process only. A kinetic model, based on the initial rates of degradation of MTBE and TBF, provides a good agreement with the experimental results.

Kinetics and mechanisms of the sonolytic destruction of non-volatile organic compounds: investigation of the sonochemical reaction zone using several OH* monitoring techniques.

This study investigates the sonolytic degradation mechanism of non-volatile organic compounds and reaction sites for its degradation using various tools that allow OH* to be monitored, such as: the spin-trapping method of OH* detection using non-volatile nitrone trap 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), the hydrogen peroxide analytical methods and the p-chlorobenzoic acid (pCBA)-probe method. These methods can successfully monitor OH* produced during sonochemical processes, and identify the major reaction sites involving OH* of the three proposed reaction zones--within the cavity, in the bulk solution, and at the gas-liquid interfacial (shell) region. The patterns of hydrogen peroxide accumulation under the various conditions suggest that peroxides pre-form at the interfacial region, but the self-scavenging reaction by hydrogen peroxide simultaneously takes place in the same region. The simultaneously measured peroxide concentration, in the absence and presence of DMPO, and that of the DMPO-OH adduct indicated the peroxide production and DMPO-OH adduct formation reaction occur at the shell region. The sonolytic destruction efficiency of ultrasound coupled with Fe(II) has been also investigated. The coupled Fe(II)/ultrasound process was found to enhance the OH* production rate by 70% compared to the ultrasound process alone due to the reaction of Fe(II) with sonochemically produced hydrogen peroxide (Fenton's reaction). This accelerated reaction was also found to occur at the shell region rather than in the bulk solution. The enhancement effect of Fe(II)/ultrasound was also examined using pCBA as a probe. 2.8-fold and 3.6-fold increases of the pCBA degradation rate were observed at Fe(II) concentrations of 10 and 20 microM, respectively.

Transport characteristics of gas phase ozone in unsaturated porous media for in-situ chemical oxidation.

Laboratory column experiments were conducted by employing various porous media to delineate the characteristics of gaseous ozone transport in the unsaturated zone under various conditions. Water content, soil organic matter (SOM), and metal oxides (MOs) were found to be the factors most influential in the fate and transport of gaseous ozone in unsaturated porous media. The migration velocity of the gaseous ozone front was inversely proportional to the MO content of the porous media. Increased water content at fixed gas flux decreased the ozone breakthrough time proportionally as a result of reduced gas pore volume (PV) in the column, and increased pore water interfered with reactions of gaseous ozone with SOM and MOs on the surface of porous media. The feasibility of in-situ ozone injection for the remediation of unsaturated soils contaminated with either phenanthrene or diesel-range organics (DROs) was investigated under various conditions. The maximum removal after 1 h of ozone injection was achieved in columns packed with baked sand, followed, in descending order, by glass beads and by sand, indicating that catalytic ozone dccomposition with MOs in columns packed with baked sand enhanced hydroxyl radical formation and resulted in increased contaminant removal. Overall removal efficiency of multicomponent C10-C24 DROs after 14 h of ozonation was 78.7%. Ozone transport was retarded considerably because of the high ozone demand of DROs, requiring more than 6 h for the gaseous ozone to initially break through the soil column under the experimental conditions tested in this study. Overall, gaseous ozone was readily delivered and transported to remediate unsaturated soils contaminated with phenanthrene and DROs.