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The hydroxyl radical ( • OH) scavenging capacity is a useful parameter for the design and operation of an advanced oxidation process (AOP) in water treatment. The scavenging capacity may change with time, and it would be useful to continuously measure this change to be able to optimize AOP doses. In this study, we first reviewed current methods for scavenging capacity measurement to identify strengths and weaknesses of each method. This information helped guide the design of an external calibration method to allow straightforward laboratory and field measurement of • OH scavenging capacity. The method used low-pressure UV/H 2 O 2 as the • OH generation system, methylene blue (MB) as the probe compound, and isopropyl alcohol (IPA) as the standard. By monitoring, offline, the color decay of MB in a series of IPA solutions with different scavenging capacity, a calibration curve was established between the color decay rate and the scavenging capacity. The measured color decay in real water samples can then be used with this external calibration to estimate their scavenging capacity. Work was undertaken to ensure that the process would be robust under a wide range of water quality conditions. Parallel tests using this method compared with the benchmark methods confirmed its robustness and accuracy.

Drinking water treatment using UV/H 2 O 2 advanced oxidation typically results in residual H 2 O 2 that requires quenching to minimize its interference with downstream processes. Chemical quenching using chlorine or bisulfite are options, but there is some uncertainty in the literature about the kinetics of the bisulfite reaction, with some reports quoting the reaction as fast, and others as slow. Part of the contradictory information may be due to interference in H 2 O 2 analysis by bisulfite. An analytical method was developed to avoid this interference, in which monochloramine first selectively quenched bisulfite, and then H 2 O 2 was measured spectrometrically using titanium(IV) oxysulfate for color development. The confirmatory experiments suggested that the bisulfite reaction with H 2 O 2 is actually relatively slow, with a half-life in the order of hours to days depending on the pH and the reagent concentrations. As a result, within the typical pH range of drinking water treatment (e.g., 6-9), chlorine is preferred over bisulfite as the H 2 O 2 quenching agent on the basis of reaction kinetics. However, a decrease in pH will lead to an increase in the bisulfite-H 2 O 2 reaction rate along with a decrease in the Cl 2 -H 2 O 2 reaction rate, such that at pH < 5.7 bisulfite is the faster reagent. Both bisulfite and chlorine were observed to react with H 2 O 2 following a stoichiometric ratio of 1:1 in the natural water matrix tested., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The photolysis of chlorine by UV light leads to the formation of the hydroxyl radicals (OH) as well as reactive chlorine species (RCS) that can be effective as advanced oxidation processes (AOPs) for water treatment. Much of the research to date has been done at laboratory- or bench-scale. This study reports results from a model that demonstrates that the relative effectiveness of the UV/Cl 2 AOP compared to the more traditional UV/H 2 O 2 AOP is a function of optical path length. As such, the relative effectiveness of the two treatment options evaluated at small scale may not reflect the relative performance at full-scale, making results previously obtained at small-scale potentially less scalable. This study therefore compares the performance of UV/Cl 2 to UV/H 2 O 2 at a full-scale water treatment plant, using sucralose and caffeine as spiked surrogates for contaminants that are reactive solely to OH radicals, and to both OH and RCS, respectively. pH was varied between 6.5 and 8.0. The results demonstrated that when using a medium pressure UV lamp, UV/Cl 2 might lead to approximately twice the production of OH radicals as UV/H 2 O 2 at pH 6.5 when using the same molar oxidant concentration, but adding chlorine to the UV reactor at pH 8.0 had a negligible impact on OH radical concentration in comparison to UV alone. The study also confirmed previous small-scale results that RCS can be a major contributor to UV/Cl 2 treatment for compounds such as caffeine that are susceptible to RCS, with UV/Cl 2 effective at both pH 6.5 and 8.0 for such compounds. Disinfection byproducts were monitored, with adsorbable organohalide (AOX) formation increasing by approximately 10 μg-Cl/L due to chlorine photolysis, but only at pH 6.5 and not at pH 8.0. This implies that UV/Cl 2 might increase AOX mostly due to reaction between OH and organic precursors to make them more reactive with chlorine, and not due to RCS. The formation of specific DBPs of current or emerging regulatory interest was minimal under all conditions, except for chlorate. Chlorate yields were in the order of 6-18% of the photolysed chlorine., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

This study investigated the application of polyaluminum chloride (PACl) for the treatment of the oil sands process-affected water (OSPW). These coagulants are commonly used in water treatment with the most effective species reported to be Al13. PACl with 83.6% Al13 was synthesized using the slow base titration method and compared with a commercially available PACl in terms of aluminum species distribution, coagulation/flocculation (CF) performance, floc morphology, and contaminant removal. Both coagulants were effective in removing suspended solids, achieving over 96% turbidity removal at all applied coagulant doses (0.5-3.0 mM Al). The removal efficiencies of metals varied among different metals depending on their pKa values with metal cations having pKa values (Fe, Al, Ga, and Ti) below OSPW pH of 6.9-8.1 (dose dependent) being removed by more than 90%, while cations with higher pKa values (K, Na, Ca, Mg and Ni) had removals of less than 40%. Naphthenic acids were not removed due to their low molecular weights, negative charges, and hydrophilic characteristics at the OSPW pH. At the highest applied coagulant dose of 3.0 mM Al, the synthetic PACl reduced Vibrio fischeri inhibition effect to 43.3 ± 3.0% from 49.5 ± 0.4% in raw OSPW. In contrast, no reduction of toxicity was found for OSPW treated with the commercial PACl. Based on water quality and floc analyses, the dominant CF mechanism for particle removal during OSPW treatment was considered to be enmeshment in the precipitates (i.e., sweep flocculation). Overall, the CF using synthesized PACl can be a valuable pretreatment process for OSPW to create wastewater that is more easily treated by downstream processes., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

• The dominant radical scavengers during UV/H 2 O 2 and UV/Cl were identified. • The effect of TOC on UV/H 2 O 2 vs. UV/Cl varied with micropollutant type and pH. • pH-TOC regions where either UV/H 2 O 2 or UV/Cl was more efficient were identified. UV/Cl and UV/H 2 O 2 are advanced oxidation processes (AOPs) used for drinking water treatment and water reuse. This work explored the hypothesis that UV/Cl becomes more competitive to UV/H 2 O 2 at neutral-to-high pH as the concentration of total organic carbon (TOC) increases. Lab experiments and kinetic modelling were used to compare initial pseudo first-order contaminant decay rate coefficients between the AOPs at various pH and TOC conditions. The relative effect of increasing TOC concentrations on UV/Cl vs. UV/H 2 O 2 depended on the pH, contaminant, and organic matter reactivity towards radicals. For example, while the reaction rate coefficients during both AOPs generally decreased with increasing TOC, the UV/Cl reaction rate coefficients for the solely •OH-reactive sucralose decreased 41–138% less than the UV/H 2 O 2 coefficients as the TOC concentration was increased from 0 to 5 mg-C L−1. However, UV/Cl was more affected than UV/H 2 O 2 when targeting caffeine (a contaminant reactive to chlorine radicals). The data were used to define TOC-pH conditions for which either AOP would be more energy-efficient, under a set of standard conditions. The results suggest that UV/Cl may be competitive to UV/H 2 O 2 under a wider range of treatment scenarios than has been conventionally thought based on tests in pure water. [Display omitted] [ABSTRACT FROM AUTHOR]

• Peracetic acid (PAA) may exert chlorine demand in drinking water. • PAA's chlorine demand is mostly by H 2 O 2 from PAA hydrolysis, especially at pH ≥ 8. • Direct PAA reaction with chlorine is slow and the reaction rate is pH dependent. • In most cases, chlorine demand by PAA is < 20% of initial chlorine over 7 days. Peracetic acid (PAA) may be used in drinking water treatment for pre-oxidation and mussel control at the intake. PAA may exert a downstream chlorine demand, but full details of this reaction have not been reported. There are three possible mechanisms of this demand: (1) PAA may react directly with chlorine; (2) PAA exists in equilibrium with hydrogen peroxide, which is known to react with chlorine; and (3) as H 2 O 2 reacts with chlorine, PAA will hydrolyze to form more H 2 O 2 to re-establish PAA/H 2 O 2 equilibrium, thereby serving as an indirect reservoir of chlorine demand. While the H 2 O 2 reaction with chlorine is well known, the other mechanisms of possible PAA-induced chlorine demand have not previously been investigated. The observed molar stoichiometric ratio of PAA to free chlorine (n) for the presumed direct PAA + free chlorine reaction was determined to be approximately 2, and the corresponding observed reaction rate coefficients at pH 6, 7, 8, and 9 were 2.76, 3.14, 1.61, 10.1 M−n·s−1, respectively (at 25 °C). With these estimated values, a kinetic model was built to predict the chlorine demand by PAA. The results suggest that chlorine demand from PAA is likely to be negligible over the course of several days (e.g., < 20% chlorine loss) for most conditions except for high pH (e.g., >8) and high PAA:Cl 2 molar ratios (e.g., >2:1). [ABSTRACT FROM AUTHOR]