Nontargeted identification and predicted toxicity of new byproducts generated from UV treatment of water containing micropollutant 2-mercaptobenzothiazole.

Comprehensive identification of byproducts including intermediate transformation products (TPs) of micropollutants in source water is challenging and paramount for assessment of drinking water quality and treatment technologies. Here, we have developed a nontargeted analysis strategy coupled with computational toxicity assessment to identify indistinguishable TPs including isomers with large differences in toxicity. The new strategy was applied to study the UV treatment of water containing micropollutant 2-mercaptobenzothiazole (2-MBT), and it enabled successful identification of a total of 22 organic TPs. Particularly, the structures of nine new TPs were identified for the first time; in addition, three isomers (P2, P3, and P4) were distinguished from the toxic contaminant 2-hydroxybenzothiazole (2-OH-BT). Computational assessments indicate that estrogenic activity of the three isomers (P2-P4) is higher than that of 2-OH-BT. Mass balance study shows that the 22 organic products accounted for 70% of the 2-MBT degraded, while 30% may degrade to inorganic products. Most TPs are resistant to UV photolysis. Computational toxicity assessment predicted the TPs to increase inhibition of human thyroperoxidase activity although they have lower aquatic toxicity compared to original 2-MBT. This study emphasizes the importance of monitoring the 2-MBT photodegradation products and the overall toxicity of finished water whose production included a UV light-based treatment process.

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.

Direct UV photolysis of selected pharmaceuticals, personal care products and endocrine disruptors in aqueous solution.

Pharmaceuticals and personal care products (PPCPs), and endocrine disrupting compounds (EDCs) are micropollutants of emerging concern that have been detected in the aquatic environment and in some cases, in drinking water at nanogram per liter levels. The goal of this study was to evaluate the removal of 15 model PPCPs and EDCs from water by direct UV photolysis, using either low (LP)-or medium (MP) -pressure mercury vapor arc lamps. Some of the model compounds are either weak bases or weak acids, and therefore, the pKa values were determined or confirmed for those compounds using spectrophotometric titrations. The molar absorption coefficients of ionized and non-ionized forms were also determined. The quantum yields at 253.7 nm in phosphate buffer solutions of pH 7.2 were determined to be 0.033 ± 0.004 for sulfamethoxazole, 0.0035 ± 0.0008 for sulfachloropyridazine, 0.006 ± 0.002 for acetaminophen, 0.34 ± 0.07 for triclosan, 0.35 ± 0.14 for estrone, 0.08 ± 0.05 for 17α-ethinylestradiol, 0.086 ± 0.012 for ibuprofen. The quantum yield for 4-n-nonylphenol photolysis at 253.7 nm varied with the initial concentration from 0.32 ± 0.08 at 23 µg/L to 0.092 ± 0.006 at 230 µg/L. The pseudo-first order rate constants determined for direct photolysis at 253.7 nm of the studied micropollutants followed the order: triclosan ≈ sulfamethoxazole >> 4-n-nonylphenol ≈ sulfachloropyridazine ≈ estrone > acetaminophen ≈ 17α-ethinylestradiol ≈ ibuprofen. In contrast to the results observed for the monochromatic radiation (LP lamp), all 15 model compounds photolyzed under exposure to the broadband radiation emitted by the MP lamp.

Efficient removal of microcystin-LR by UV-C/H2O2 in synthetic and natural water samples.

The destruction of the commonly found cyanobacterial toxin, microcystin-LR (MC-LR), in surface waters by UV-C/H(2)O(2) advanced oxidation process (AOP) was studied. Experiments were carried out in a bench scale photochemical apparatus with low pressure mercury vapor germicidal lamps emitting at 253.7 nm. The degradation of MC-LR was a function of UV fluence. A 93.9% removal with an initial MC-LR concentration of 1 µM was achieved with a UV fluence of 80 mJ/cm(2) and an initial H(2)O(2) concentration of 882 µM. When increasing the concentration of MC-LR only, the UV fluence-based pseudo-first order reaction rate constant generally decreased, which was probably due to the competition between by-products and MC-LR for hydroxyl radicals. An increase in H(2)O(2) concentration led to higher removal efficiency; however, the effect of HO scavenging by H(2)O(2) became significant for high H(2)O(2) concentrations. The impact of water quality parameters, such as pH, alkalinity and the presence of natural organic matter (NOM), was also studied. Field water samples from Lake Erie, Michigan and St. Johns River, Florida were employed to evaluate the potential application of this process for the degradation of MC-LR. Results showed that the presence of both alkalinity (as 89.6-117.8 mg CaCO(3)/L) and NOM (as ∼2 to ∼9.5 mg/L TOC) contributed to a significant decrease in the destruction rate of MC-LR. However, a final concentration of MC-LR bellow the guideline value of 1 µg/L was still achievable under current experimental conditions when an initial MC-LR concentration of 2.5 µg/L was spiked into those real water samples.

Pilot-scale UV/H2O2 advanced oxidation process for surface water treatment and downstream biological treatment: effects on natural organic matter characteristics and DBP formation potential.

The effects of the advanced oxidation process (AOP) of ultraviolet radiation in combination with hydrogen peroxide (UV/H2O2) on the structure and biodegradability of dissolved natural organic matter (NOM) and on the formation of disinfection by-products (DBPs) through the post-UV/H2O2 chlorination were investigated using UV reactors equipped with either low-pressure amalgam lamps or medium-pressure mercury vapour lamps. With electrical energy doses and H2O2 concentrations typically applied in full-scale UV systems for water remediation, the UV/H2O2 AOP partially oxidized NOM, reducing its degree of aromaticity and leading to an increase in the level of biodegradable species. Also, when combined with a downstream biological activated carbon (BAC) filter, UV/H2O2 AOP reduced the formation of DBPs by up to 60% for trihalomethanes and 75% for haloacetic acids. Biological activated carbon was also shown to effectively remove biodegradable by-products and residual H2O2.

Photocatalytic degradation of dichlorvos in aqueous TiO2 suspensions.

INTRODUCTION: In the present work, we explored the kinetics of dichlorvos (2,2-dichlorvinyl dimethyl phosphate, DDVP) decay through UV-A light-induced TiO(2) photocatalysis at pH 4 and 9, and the formation of degradation intermediates and final products under specific experimental conditions. Experimental observations and theoretical considerations allowed us to suggest the degradation mechanism of DDVP by the UV/TiO(2) process in aqueous solution. METHODS: The irradiation experiments were carried out in a photoreactor using a 228-W medium-pressure Hg vapor lamp. The concentration of DDVP, phosphate ion and formaldehyde as reaction intermediate, are determined spectrophotometrically. Chloride ion concentration was measured potentiometrically. RESULTS: The photocatalytic degradation rate of dichlorvos (DDVP) under UV irradiation (360-380 nm) was optimized with respect to the flow rate of O(2) gas sparged into the solution and photocatalyst concentration for a constant dichlorvos concentration (1.66 x 10(-4) M) at pH 4. Kinetic data were obtained at pH 4 and pH 9 for dichlorvos and the inorganic species released through its photo-induced degradation. The proposed mechanism which assumes the formation of some toxic intermediates resistant to mineralization is supported by theoretical calculations and the observed inorganic mass balances. CONCLUSIONS: The calculated pseudo-first-order rate constants were dependent on the dissolved oxygen level at low O(2) flow rate, but somewhat independent on the initial pH. The decrease of pH during the irradiation suggests the formation of organic acids. The presence of organic intermediates was confirmed also by TOC measurements. A plausible reaction mechanism of DDVP degradation through the UV-A/TiO(2) process was proposed.

Trichloroethene degradation by UV/H2O2 advanced oxidation process: product study and kinetic modeling.

The broadband UV irradiation of 1.1 mM trichloroethene (TCE) aqueous solution in the presence of 10.4 mM H2O2 resulted in formic, oxalic, dichloroacetic (DCA), and monochloroacetic (MCA) acids, as organic byproducts. The organic chlorine was converted completely to chloride ion as a final product. TCE and its degradation products were completely mineralized in 30 min, under a volume-averaged UV-C irradiant power of 35.7 W/L from a 1 kW medium-pressure mercury vapor arc lamp. TCE degraded primarily through hydroxyl radical-induced reactions and onlyto a low extentthrough direct UV photolysis and chlorine atom-induced chain reactions. The experimental patterns of TCE, H2O2, and detected reaction products combined with the literature information on radical reactions in the aqueous phase were used to postulate a degradation mechanism and to develop a kinetic model to predict the TCE decay, formation and degradation of byproducts, and pH and oxygen profiles. The agreement between the model calculations and the experimental data is satisfactory.

The iodide/iodate actinometer in UV disinfection: determination of the fluence rate distribution in UV reactors.

Thirty-seven Suprasil quartz spheres, each approximately 1 cm in diameter and containing an iodide-iodate actinometric solution, were attached to a metal rack and inserted into a bench-scale UV reactor filled with water. The spheres were located at various distances and heights around a 12.4 W low-pressure Hg lamp housed inside a 3.2 cm-radius quartz sleeve in the middle of an annular batch reactor. UV light exposure at 254 nm was performed with the percent transmittance of the water present in the reactor at either 73% or 100% defined over a 1 cm path length. The spheres were simultaneously exposed to the UV light for a given period of time, after which the solutions were removed from the spheres and the yield of triiodide determined from the increase in absorbance at 352 nm. The resulting fluence rate at each site was then calculated on basis of the yield of triiodide. These results were compared with the predictions of a mathematical model based on the multiple point source summation approximation, including reflection and refraction at the air-quartz-water interface. Initially, the agreement was not satisfactory, especially in regions at an oblique angle to the lamp. The model was modified from a multiple point source model to a multiple cylindrical segment model by incorporating a cosine factor. The agreement between the new model and the experimental data was excellent and these experiments provide a strong validation of the model, even under conditions in which the fluence rate varied by >1000-fold between extreme sites in the reactor.

UV photolysis of trichloroethylene: product study and kinetic modeling.

Direct UV photolysis of trichloroethylene (TCE) in dilute aqueous solution generated chloride ions as a major end product and several reaction intermediates, such as formic acid, di- and monochloroacetic acids, glyoxylic acid, and, to a lesser extent, mono- and dichloroacetylene, formaldehyde, dichloroacetaldehyde, and oxalic acid. Under prolonged irradiation, these byproducts underwent photolysis, and a high degree of mineralization (approximately 95%) was achieved. TCE decays through the following major pathways: (1) TCE + h nu --> ClCH=C*Cl + Cl*; (2) TCE (H2O) + h nu --> ClCH(OH)-CHCl2; (3) TCE + h nu --> HC[triple bond]CCl + Cl2; (4) TCE + h nu --> ClC[triple bond]CCl + HCl; (5) TCE + Cl* --> Cl2HC-C*Cl2. A kinetic model was developed to simulate the destruction of TCE and the formation and fate of byproducts in aqueous solution under irradiation with polychromatic light. By fitting the experimental data, the quantum yields for the four photolysis steps were predicted as phi(1) = 0.13, phi(2) = 0.1, phi(3) = 0.032, and phi(4) = 0.092, respectively. The reaction mechanism proposed for the photodegradation of TCE accounts for all intermediates that were detected. The agreement between the computed and experimental patterns of TCE and reaction products is satisfactory given the complexity of the reaction mechanism and the lack of photolytic kinetic parameters that are provided in the literature.

Quantum yield of the iodide-iodate chemical actinometer: dependence on wavelength and concentrations.

The quantum yield (QY) of the iodide-iodate chemical actinometer (0.6 M KI-0.1 M KIO3) was determined for irradiation between 214 and 330 nm. The photoproduct, triiodide, was determined from the increase in absorbance at 352 nm, which together with a concomitant measurement of the UV fluence enabled the QY to be calculated. The QY at 254 nm was determined to be 0.73 +/- 0.02 when calibration was carried out against a National Institute of Standards and Technology traceable radiometer or photometric device. At wavelengths below 254 nm the QY increased slightly, leveling off at -0.80 +/- 0.05, whereas above 254 nm the QY decreases linearly with wavelength, reaching a value of 0.30 at 284 nm. In addition, the QY was measured at different iodide concentrations. There is a slight decrease in QY going from 0.6 to 0.15 M KI, whereas below 0.15 M KI the QY drops off sharply, decreasing to 0.23 by 0.006 M KI. Calibration of the QY was also done using potassium ferrioxalate actinometry to measure the irradiance. These results showed a 20% reduction in QY between 240 and 280 nm as compared with radiometry. This discrepancy suggests that the QY of the ferrioxalate actinometer in this region of the spectrum needs reexamination.

Optimal methods for quenching H2O2 residuals prior to UFC testing.

In this paper, the quenching of hydrogen peroxide by catalase, sodium hypochlorite, sodium thiosulfate and sodium sulfite, prior to UFC testing, was investigated. Sodium hypochlorite, sodium thiosulfate and sodium sulfite were found to be unsuitable for quenching H2O2 residuals because the procedures are time-consuming and complicated in that they require potentially multiple measurements of the peroxide and chlorine residuals. In contrast, quenching of peroxide with catalase is a simple procedure. Catalase doses of less than 0.2 mg/L were found to have no impact on DBP (TTHM, HAA and aldehyde) formation in the UFC test, and the time that was needed to quench 100 mg/L peroxide (room temperature, pH 8.3) was less than 10 min. In addition, peroxide was found to react with DPD reagents that are used to measure chlorine residuals, a phenomenon that may lead to falsely high chlorine residuals in the UFC test.