Sudha Rani Batchu

Oxidation of Trimethoprim by Ferrate(VI): Kinetics, Products, and Antibacterial Activity

Kinetics, stoichiometry, and products of the oxidation of trimethoprim (TMP), one of the most commonly detected antibacterial agents in surface waters and municipal wastewaters, by ferrate(VI) (Fe(VI)) were determined. The pH dependent second-order rate constants of the reactions of Fe(VI) with TMP were examined using acid-base properties of Fe(VI) and TMP. The kinetics of reactions of diaminopyrimidine (DAP) and trimethoxytoluene (TMT) with Fe(VI) were also determined to understand the reactivity of Fe(VI) with TMP. Oxidation products of the reactions of Fe(VI) with TMP and DAP were identified by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Reaction pathways of oxidation of TMP by Fe(VI) are proposed to demonstrate the cleavage of the TMP molecule to ultimately result in 3,4,5,-trimethoxybenzaldehyde and 2,4-dinitropyrimidine as among the final identified products. The oxidized products mixture exhibited no antibacterial activity against E. coli after complete consumption of TMP. Removal of TMP in the secondary effluent by Fe(VI) was achieved.

Photodegradation of antibiotics under simulated solar radiation: implications for their environmental fate.

Roxithromycin, erythromycin, ciprofloxacin and sulfamethoxazole are frequently detected antibiotics in environmental waters. Direct and indirect photolysis of these problematic antibiotics were investigated in pure and natural waters (fresh and salt water) under irradiation of different light sources. Fundamental photolysis parameters such as molar absorption coefficient, quantum yield and first order rate constants are reported and discussed. The antibiotics are degraded fastest under ultraviolet 254 nm, followed by 350 nm and simulated solar radiation. The composition of the matrix (pH, dissolved organic content, chloride ion concentration) played a significant role in the observed photodegradation. Under simulated solar radiation, ciprofloxacin and sulfamethoxazole degrade relatively quickly with half-lives of 0.5 and 1.5h, respectively. However, roxithromycin and erythromycin, macrolides are persistent (half-life: 2.4-10 days) under solar simulation. The transformation products (15) of the targeted antibiotics produced under irradiation experiments were identified using high resolution mass spectrometry and degradation pathways were proposed.

Oxidation of Microcystin-LR by Ferrate(VI): Kinetics, Degradation Pathways, and Toxicity Assessments

The presence of the potent cyanotoxin, microcystin-LR (MC-LR), in drinking water sources poses a serious risk to public health. The kinetics of the reactivity of ferrate(VI) (Fe(VI)O4(2-), Fe(VI)) with MC-LR and model compounds (sorbic acid, sorbic alcohol, and glycine anhydride) are reported over a range of solution pH. The degradation of MC-LR followed second-order kinetics with the bimolecular rate constant (kMCLR+Fe(VI)) decreasing from 1.3 ± 0.1 × 10(2) M(-1) s(-1) at pH 7.5 to 8.1 ± 0.08 M(-1) s(-1) at pH 10.0. The specific rate constants for the individual ferrate species were determined and compared with a number of common chemical oxidants employed for water treatment. Detailed product studies using liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS) indicated the oxidized products (OPs) were primarily the result of hydroxylation of the aromatic ring, double bond of the methyldehydroalanine (Mdha) amino acid residue, and diene functionality. Products studies also indicate fragmentation of the cyclic MC-LR structure occurs under the reaction conditions. The analysis of protein phosphatase (PP1) activity suggested that the degradation byproducts of MC-LR did not possess significant biological toxicity. Fe(VI) was effective for the degradation MC-LR in water containing carbonate ions and fulvic acid (FA) and in lake water samples, but higher Fe(VI) dosages would be needed to completely remove MC-LR in lake water compared to deionized water.

Understanding the magnitude of emergent contaminant releases through target screening and metabolite identification using high resolution mass spectrometry: Illicit drugs in raw sewage influents

A QExactive Orbitrap was used for the identification of phase I and II transformation products (TPs) of illicit drugs in raw sewage influents. Two operating modes (targeted MS(2) and Data-dependent screening) were used for data acquisition. Even though, data-dependent scan is a faster route towards the potential identification of metabolites, it suffered from its limitation to provide enough data points across the chromatographic peak during the MS(2) cycle in contrast to targeted MS(2). Therefore, the later technique was implemented as the method of choice in this study for the positive confirmation and quantitation of TPs (n=54). The vast majority of the identified TPs were products of phase I transformation reactions, with the latter being more prevalent in the nature. Estimated mole fractions showed that for a large number of the analytes, TPs must also be monitored in order to fully understand their environmental fate and calculate potential consumption.

Stability of dioctyl sulfosuccinate (DOSS) towards hydrolysis and photodegradation under simulated solar conditions

Dioctyl sulfosuccinate (DOSS) is one of the main components of Corexit® EC9500A, a chemical dispersant formulation used at the surface and at depth during the response to the Deepwater Horizon incident. Despite being a high volume use chemical, data on its environmental stability are scarce. Hydrolysis and photodegradation of DOSS in both pure water and seawater were reported in the present study. DOSS photodegraded much faster under ultraviolet light source (254 nm, with half-life in hours) compared to relevant environmental light sources i.e., 350 nm and solar simulator (with half-lives in days). LC/MS-MS analysis of hydrolysis and photo-irradiated samples showed the presence of a common degradation product. MS/MS fragmentation of that product indicated a substitution of an octyl group by a hydroxyl group with a corresponding formula of C12H21O7S, which was confirmed by HRMS detection (Q-TOF, m/z 309.1017, +1.29 ppm).

Photodegradation of sulfonamide antibiotics in simulated and natural sunlight: Implications for their environmental fate

The photochemical fate of seven sulfonamides was investigated in matrices representative of natural water bodies under various light sources. Fundamental photolysis parameters such as molar absorption coefficient, quantum yield (QY) and first-order rate constants were determined. The photolysis decay rate was dependent on the protonation state of the molecule, pH of the water sample and dissolved organic matter. Natural organic matter was the most significant factor in the indirect photolysis of sulfonamides. Half-lives were in the range of minutes at 254 nm to days under natural sunlight. Under natural sunlight, all sulfonamides showed higher removal rates in natural waters implying that indirect photolysis is the predominant mechanism.