Application of Nucleotide-Based Kinetic Modeling Approaches to Predict Antibiotic Resistance Gene Degradation during UV- and Chlorine-Based Wastewater Disinfection Processes: From Bench- to Full-Scale.

This study investigated antibiotic resistance gene (ARG) degradation kinetics in wastewaters during bench- and full-scale treatment with UV light and chlorine─with the latter maintained as free available chlorine (FAC) in low-ammonia wastewater and converted into monochloramine (NH2Cl) in high-ammonia wastewater. Twenty-three 142-1509 bp segments (i.e., amplicons) of seven ARGs (blt, mecA, vanA, tet(A), ampC, blaNDM, blaKPC) and the 16S rRNA gene from antibiotic resistant bacteria (ARB) strains Bacillus subtilis, Staphylococcus aureus, Enterococcus faecium, Escherichia coli, Pseudomonas aeruginosa, and Klebsiella pneumoniae were monitored as disinfection targets by qPCR. Rate constants for ARG and 16S rRNA gene amplicon degradation by UV, FAC, and NH2Cl were measured in phosphate buffer and used to expand and validate several recently developed approaches to predict DNA segment degradation rate constants based solely on their nucleotide contents, which were then applied to model ARG degradation during bench-scale treatment in buffer and wastewater matrixes. Kinetics of extracellular and intracellular ARG degradation by UV and FAC were well predicted up to ∼1-2-log10 elimination, although with decreasing accuracy at higher levels for intracellular genes, while NH2Cl yielded minimal degradation under all conditions (agreeing with predictions). ARB inactivation kinetics varied substantially across strains, with intracellular gene degradation lagging cell inactivation in each case. ARG degradation levels observed during full-scale disinfection at two wastewater treatment facilities were consistent with bench-scale measurements and predictions, where UV provided ∼1-log10 ARG degradation, and chlorination of high-ammonia wastewater (dominated by NH2Cl) yielded minimal ARG degradation.

Evaluation of hydroxyl radical and reactive chlorine species generation from the superoxide/hypochlorous acid reaction as the basis for a novel advanced oxidation process.

The reaction of hypochlorous acid (HOCl) with superoxide radical (O2•-) - a source of hydroxyl radical (HO•) and various reactive chlorine species (RCS) - was investigated as the basis for a novel non-photochemical advanced oxidation process (AOP). Moderately stable (t1/2 ~ minutes) aqueous O2•- stocks were prepared by several approaches at pH>12 and either (a) added directly to aqueous free available chlorine (FAC; i.e., HOCl/OCl-) at circumneutral pH, or (b) premixed with alkaline FAC and then acidified to pH 7, to degrade various organic probe compounds via in situ generated HO• and RCS. Radical production was optimal at [HO2•/O2•-]0/[FAC]0 ~ 2, with ~0.8 mol HO• formed/mol FAC consumed, and HO• and RCS exposures reaching ~5×10-10 and ~10-9 M×s, respectively. Similar trends were observed in natural waters and organic matter-amended phosphate buffer containing up to 5 mgC/L of dissolved organic carbon. Direct formation of oxyhalides, trihalomethanes (THMs), and haloacetic acids (HAAs), was minimal, though THM and HAA formation was moderately enhanced during post-chlorination of O2•-/FAC-treated solutions. This process could provide a beneficial addition to the range of available AOPs due to its high radical exposures, simplicity, rapid time-scales, potential for on-site O2•- generation, and widespread accessibility of FAC and other reagents.

Oxidative transformation kinetics and pathways of albendazole from reactions with manganese dioxide.

Albendazole (ABZ) is a benzimidazole-based veterinary anthelmintic used extensively in the treatment of intestinal parasites. Due to its high hydrophobicity, ABZ tends to accumulate in soils and sediments in the environment. This study aims to investigate ABZ's possible degradation by manganese oxides. Minor effects from ionic strength and metal cations on ABZ degradation were observed. By contrast, decrease of pH greatly enhanced the reaction rate. Surface complexation between ABZ and MnO2 was indicated to be the dominant control in the reaction kinetics. Suppression by the presence of co-solvents was negatively proportional to the solvent polarities (suppression from high to low: diethyl ether ～ n-butanol > ethanol > methanol > acetonitrile). Humic acid was found to cause significant inhibition due to the reductive dissolution of MnO2. Four hydrolysis and six oxidative products were identified. ABZ and its hydrolysis products containing the propylthio side chain underwent the same oxidative transformation to form their corresponding sulfoxide compounds. Dehydrogenative coupling reaction between sulfoxide products and hydrolysis products could occur to generate dimers. All hydrolysis and oxidative products were eluted faster than ABZ in liquid chromatogram, suggesting that the spreading out of ABZ will be significantly enhanced if reacting with MnO2.