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The photolysis of S(2)O(8)(2-) was studied for the removal of acetic acid in aqueous solution and compared with the H(2)O(2)/UV system. The SO(4)(-) radicals generated from the UV irradiation of S(2)O(8)(2-) ions yield a greater mineralization of acetic acid than the ()OH radicals. Acetic acid is oxidized by SO(4)(-) radicals without significant formation of intermediate by-products. Increasing system pH results in the formation of ()OH radicals from SO(4)(-) radicals. Maximum acetic acid degradation occurred at pH 5. The results suggest that above this pH, competitive reactions with the carbon mineralized inhibit the reaction of the solute with SO(4)(-) and also ()OH radicals. Scavenging effects of two naturally occurring ions were tested; in contrast to HCO(3)(-) ions, the presence of Cl(-) ions enhances the efficiency of the S(2)O(8)(2-)/UV process towards the acetate removal. It is attributed to the formation of the Cl() radical and its great reactivity towards acetate.

The kinetics of iodate formation is a critical factor in mitigation of the formation of potentially toxic and off flavor causing iodoorganic compounds during chlorination. This study demonstrates that the formation of bromine through the oxidation of bromide by chlorine significantly enhances the oxidation of iodide to iodate in a bromide-catalyzed process. The pH-dependent kinetics revealed species specific rate constants of k(HOBr + IO(-)) = 1.9 × 10(6) M(-1) s(-1), k(BrO(-) + IO(-)) = 1.8 × 10(3) M(-1) s(-1), and k(HOBr + HOI) < 1 M(-1) s(-1). The kinetics and the yield of iodate formation in natural waters depend mainly on the naturally occurring bromide and the type and concentration of dissolved organic matter (DOM). The process of free chlorine exposure followed by ammonia addition revealed that the formation of iodo-trihalomethanes (I-THMs), especially iodoform, was greatly reduced by an increase of free chlorine exposure and an increase of the Br(-)/I(-) ratio. In water from the Great Southern River (with a bromide concentration of 200 μg/L), the relative I-incorporation in I-THMs decreased from 18 to 2% when the free chlorine contact time was increased from 2 to 20 min (chlorine dose of 1 mg Cl(2)/L). This observation is inversely correlated with the conversion of iodide to iodate, which increased from 10 to nearly 90%. Increasing bromide concentration also increased the conversion of iodide to iodate: from 45 to nearly 90% with a bromide concentration of 40 and 200 μg/L, respectively, and a prechlorination time of 20 min, while the I-incorporation in I-THMs decreased from 10 to 2%.

a b s t r a c tThe quality and quantity of natural organic matter (NOM) has been observed to evolve which poses challenges to water treatment facilities. Even though NOM may not be toxic itself, its presence in water has aesthetic effects, enhances biological growth in distribution networks, binds with pollutants and controls the bioavailability of trace metals. Even though NOM has heterogeneous functional groups, the predominant ones are the carboxyl and the phenolic groups, which have high affinities for metals depending on the pH. The properties of both the NOM and the trace elements influence the binding kinetics and preferences. Ca 2þ prefers to bind with the carboxylic groups especially at a low pH while Zn 2þ prefers the amine groups though practically, most cations bind to several functions groups. The nature of the chemical environment (neighboring ligands) the ligand finds itself equally influences its preference for a cation. The presence of NOM, cations or a complex of NOM-cations may have significant impact on the efficiency of water processes such as coagulation, adsorption, ion exchange resin and membrane filtration. In coagulation, the complexation between the coagulant salts and NOM helps to remove NOM from solution. This positive influence can further be enhanced by the addition of Ca 2þ . A negative influence is however, observed in lime-softening method as NOM complexes with Ca 2þ . A negative influence is also seen in membrane filtration where divalent cations partially neutralize the carboxyl functional groups of NOM thereby reducing the repulsion effect on NOM and increasing membrane fouling. The formation of disinfection by-products could either be increased or reduced during chlorination, the speciation of products formed is modified with generally the enhancement of haloacetic acid formation observed in presence of metal cations. This current work, presents in details the interactions of cations and NOM in the environment, the preference of cations for each functional group and the possible competition between cations for binding sites, as well as the possible impacts of the presence of cations, NOM, or their complex on water treatment processes.

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In this case study, high sensitivity simple methods for the analysis of trihalomethanes (THM4), iodinated-trihalomethanes (I-THMs), haloacetic acids (HAAs), bromide, iodide and iodate have been developed. A one-step procedure for the analysis of haloacetic acids by head-space GC-MS provides good reproducibility and low limits of quantification (≤ 50 ng L-1). These methods were applied to characterize the formation of DBPs in a full scale drinking water treatment plant. In this treatment plant, the incorporation of bromine into THMs increases throughout the water treatment line, due to the formation of bromine reactive species favored by the decrease of competition between DOC and bromide towards chlorine. A linear correlation has been observed between the bromine incorporation factor and the Br-/DOC mass ratio. The conversion of iodine to iodate by chlorination occurs in this water due to the relatively high bromide concentration. Moreover, a higher formation of iodate compared to iodide levels in the raw water is observed indicating a degradation of organic iodinated compounds. The formation of I-THMs was constant in terms of quantity and speciation between campaigns despite fluctuating concentrations of DOC and total iodine in the raw water. A preferential 2 removal of DBPs formed by the intermediate chlorination in the order I-DBPs>Br-DBPs>Cl-DBPs occurs during the subsequent activated carbon filtration. The removal rates range from 25 to 36% for the regulated THM4, from 82 to 93% for the ∑I-THMs and 95% for haloacetic acids. The assessment of the relative toxicity shows that despite a much lower concentration of HAAs (less than 10% of the total mass of measured DBPs) compared to THMs, these compounds are responsible for 75% of the relative cytotoxicity of the treated water. Bromoacetic acid on its own accounts for more than 60% of the overall toxicity of the 17 compounds included in this study.

In this study, the degradation of four emerging contaminants (losartan potassium (LP), furosemide (FRSM), caffeine (CAF), and carbendazim (CBZ) under UV-C, UV-C/H2O2, and UV-C/S2O8 2was investigated. A comparative evaluation of the efficiency of UV-C/H2O2 and UV-C/S2O8 2in the degradation of these target CECs has not yet been reported. Moreover, target compounds were submitted to UV-C/AOPs individually in pure water and their simultaneous degradation was investigated in real surface water. Evolution of the acute toxicity of each compound during treatment was evaluated using Alivibrio fischeri. Quantum yields were determined for LP (0.011 to 0.016), FRSM (0.024 to 0.092), CAF (0.0007 to 0.0009), and CBZ (0.0016 to 0.0036) at different pH values. UV-C/H2O2 and UV-C/S2O8 2 achieved more than 98% removal of all compounds within 600 mJ cm-2 , and pseudo-fist-order kinetic constants (k'app) for the 2 degradation reactions were up to seven times higher in the presence of these oxidants when compared to k'app values obtained for UV-C photolysis. k'app measured for UV-C/H2O2 were higher than those calculated for UV-C/S2O8 2except in the case of LP. Acute toxicity analysis suggested the formation of toxic intermediates during the UV-C photolysis of LP and FRSM, and the degradation of LP via UV-C/S2O8 2also enhaced acute toxicity although electric energy efficiency per order identified UV-C/S2O8 2 as the most efficient process for the removal of this compound. Finally, different transformation products obtained during the degradation of caffeine under the different UV-C AOPs suggested that distinct degradation routes were involved in each treatment tested.