The antibacterial agents triclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol) and chlorophene (4-chloro-2-(phenylmethyl)phenol) show similar susceptibility to rapid oxidation by manganese oxides (delta-MnO2 and MnOOH) yielding Mn(II) ions. Both the initial reaction rate and adsorption of triclosan to oxide surfaces increase as pH decreases. The reactions are first-order with respect to the antibacterial agent and MnO2. The apparent reaction orders to H+ were determined to be 0.46 +/- 0.03 and 0.50 +/- 0.03 for triclosan and chlorophene, respectively. Dissolved metal ions (Mn(II), Zn(II), and Ca(II)) and natural organic matter decrease the reaction rate by competitively adsorbing and reacting with MnO2. Product identification indicates that triclosan and chlorophene oxidation occurs at their phenol moieties and yields primarily coupling and p-(hydro)quinone products. A trace amount of 2,4-dichlorophenol is also produced in triclosan oxidation, suggesting bond-breaking of the ether linkage. The experimental results support the mechanism that after formation of a surface precursor complex of the antibacterial agent and the surface-bound Mn(IV), triclosan and chlorophene are oxidized to phenoxy radicals followed by radical coupling and further oxidation to form the end products. Compared to several structurally related substituted phenols (i.e., 2-methyl-4-chlorophenol, 2,4-dichlorophenol, 3-chlorophenol, and phenol), triclosan and chlorophene exhibit comparable or higher reactivities toward oxidation by manganese oxides. The higher reactivities are likely affected by factors including electronic and steric effects of substituents and compound hydrophobicity. Once released into the environment, partitioning of triclosan and chlorophene to soils and sediments is expected because of their relatively hydrophobic nature. Results of this study indicate that manganese oxides in soils will facilitate transformation of these antibacterial agents.
Peracetic acid (PAA) is a widely used disinfectant, and combined UV light with PAA (i.e., UV/PAA) can be a novel advanced oxidation process for elimination of water contaminants. This study is among the first to evaluate the photolysis of PAA under UV irradiation (254 nm) and degradation of pharmaceuticals by UV/PAA. PAA exhibited high quantum yields (Φ = 1.20 and 2.09 mol·Einstein for the neutral (PAA) and anionic (PAA) species, respectively) and also showed scavenging effects on hydroxyl radicals (k = (9.33 ± 0.3) × 10 M·s and k = (9.97 ± 2.3) × 10 M·s). The pharmaceuticals were persistent with PAA alone but degraded rapidly by UV/PAA. The contributions of direct photolysis, hydroxyl radicals, and other radicals to pharmaceutical degradation under UV/PAA were systematically evaluated. Results revealed that OH was the primary radical responsible for the degradation of carbamazepine and ibuprofen by UV/PAA, whereas CHC(═O)O and/or CHC(═O)O contributed significantly to the degradation of naproxen and 2-naphthoxyacetic acid by UV/PAA in addition to OH. The carbon-centered radicals generated from UV/PAA showed strong reactivity to oxidize certain naphthyl compounds. The new knowledge obtained in this study will facilitate further research and development of UV/PAA as a new degradation strategy for water contaminants.
Fe(II) is an excellent promoter for advanced oxidation processes (AOPs) because of its environmental ubiquity and low toxicity. This study is among the first to characterize the reaction of peracetic acid (PAA) with Fe(II) ion and apply the Fe(II)/PAA AOP for degradation of micropollutants. PAA reacts with Fe(II) (k = 1.10 × 105–1.56 × 104 M–1 s–1 at pH 3.0–8.1) much more rapidly than H2O2 and outperforms the coexistent H2O2 for reaction with Fe(II). While PAA alone showed minimal reactivity with methylene blue, naproxen, and bisphenol-A, significant abatement (48–98%) of compounds was observed by Fe(II)/PAA at initial pH of 3.0–8.2. The micropollutant degradation by Fe(II)/PAA exhibited two kinetic phases (very rapid then slow) related to PAA and H2O2, respectively. Based on experimental evidence, formation of carbon-centered radicals (CH3C(O)O•, CH3C(O)•, and •CH3), •OH, and Fe(IV) reactive intermediate species from the PAA and Fe(II) reactions in the presence of H2O2 is hypothesized. The carbon-centered radicals and/or Fe(IV) likely played an important role in micropollutant degradation in the initial kinetic phase, while •OH was important in the second reaction phase. The transformation products of micropollutants showed lower model-predicted toxicity than their parent compounds. This study significantly advances the understanding of PAA and Fe(II) reaction and demonstrates Fe(II)/PAA to be a feasible advanced oxidation technology.
Photoactivation of aqueous chlorine could promote degradation of chlorine-resistant and photochemically stable chemicals accumulated in swimming pools. This study investigated the degradation of two such chemicals, N,N-diethyl-3-methylbenzamide (DEET) and caffeine, by low pressure ultraviolet (UV) light and simulated sunlight (SS) activated free chlorine (FC) in different water matrices. Both DEET and caffeine were rapidly degraded by UV/FC and SS/FC but exhibited different kinetic behaviors. The degradation of DEET followed pseudo-first-order kinetics, whereas the degradation of caffeine accelerated with reaction. Mechanistic study revealed that, under UV/FC, ·OH and Cl· were responsible for degradation of DEET, whereas ClO· related reactive species (ClOrrs), generated by the reaction between FC and ·OH/Cl·, played a major role in addition to ·OH and Cl· in degrading caffeine. Reaction rate constants of DEET and caffeine with the respective radical species were estimated. The imidazole moiety of caffeine was critical for the special reactivity with ClOrrs. Water matrix such as pH had a stronger impact on the UV/FC process than the SS/FC process. In saltwater matrix under UV/FC and SS/FC, the degradation of DEET was significantly inhibited, but the degradation of caffeine was much faster than that in nonsalty solutions. The interaction between Br and Cl may play an important role in the degradation of caffeine by UV/FC in saltwater. Reaction product analysis showed similar product patterns by UV/FC and SS/FC and minimal formation of chlorinated intermediates and disinfection byproducts.
To minimize environmental pharmaceutical micropollutants, treatment of human urine could be an efficient approach due to the high pharmaceutical concentration and toxic potential excreted in urine. This study investigated the degradation kinetics and mechanisms of sulfamethoxazole (SMX), trimethoprim (TMP) and N4-acetyl-sulfamethoxazole (acetyl-SMX) in synthetic fresh and hydrolyzed human urines by low-pressure UV, and UV combined with H2O2 and peroxydisulfate (PDS). The objective was to compare the two advanced oxidation processes (AOPs) and assess the impact of urine matrices. All three compounds reacted quickly in the AOPs, exhibiting rate constants of (6.09-8.53) × 10(9) M(-1)·s(-1) with hydroxyl radical, and (2.35-16.1) × 10(9) M(-1)·s(-1) with sulfate radical. In fresh urine matrix, the pharmaceuticals' indirect photolysis was significantly suppressed by the scavenging effect of urine citrate and urea. In hydrolyzed urine matrix, the indirect photolysis was strongly affected by inorganic urine constituents. Chloride had no apparent impact on UV/H2O2, but significantly raised the hydroxyl radical concentration in UV/PDS. Carbonate species reacted with hydroxyl or sulfate radical to generate carbonate radical, which degraded SMX and TMP, primarily due to the presence of aromatic amino group(s) (k = 2.68 × 10(8) and 3.45 × 10(7) M(-1)·s(-1)) but reacted slowly with acetyl-SMX. Ammonia reacted with hydroxyl or sulfate radical to generate reactive nitrogen species that could react appreciably only with SMX. Kinetic simulation of radical concentrations, along with products analysis, helped elucidate the major reactive species in the pharmaceuticals' degradation. Overall, the AOPs' performance was higher in the hydrolyzed urine than fresh urine matrix with UV/PDS better than UV/H2O2, and varied significantly depending on pharmaceutical's structure.
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