Photo-transformation of ofloxacin in natural aquatic conditions: Impact of indirect photolysis on the product profile and transformation mechanism.

The natural phototransformation of organic pollutants in the environment depends on several water constituents, including inorganic ions, humic substances, and pH. However, the literature information concerning the influence of various water components on the amount of phototransformation and their impact on the development of various transformation products (TPs) is minimal. This study investigated the phototransformation of ofloxacin (OFL), a fluoroquinolone antibiotic, in the presence of various water components such as cations (K+, Na+, Ca2+, NH4+, Mg2+), anions (NO3-, SO42-, HCO3-, CO32-, PO43-), pH, and humic substances when exposed to natural sunlight. The study reveals that neutral pH levels (0.39374 min⁻1) enhance the phototransformation of OFL in aquatic environments. Carbonate, among anions, shows the highest rate constant (2.89966 min⁻1), significantly influencing OFL phototransformation, while all anions exhibit a notable impact. In aquatic environments, indirect phototransformation of OFL, driven by increased reactive oxygen species, expedites light-induced reactions, potentially enhancing OFL phototransformation. A clear difference was visible in the type of transformation products (TPs) formed during direct and indirect photolysis. The impact of indirect photolysis in the product profile was evaluated by examining the unique properties of TPs in direct and indirect photolysis. The primary transformation products were generated by oxidation and cleavage processes directed towards the ofloxacin piperazinyl, oxazine, and carboxyl groups. The toxicity assessment of TPs derived from OFL revealed that among the 26 identified TPs, TP3 (demethylated product), TP7 and TP8 (decarboxylated products), and TP15 (piperazine ring cleaved product) could potentially have some toxicological effects. These findings suggest that the phototransformation of OFL in the presence of various water components is necessary when assessing this antibiotic's environmental fate.

Identifying the Transients and Transformation Products in Hydroxyl Radical-Methimazole Reactions Using DFT and UPLC-Q-TOF MS/MS Approaches.

Oxidative reactions of the hydroxyl radical (·OH) with methimazole (MMI), an antithyroid drug, are crucial for understanding its fate in oxidizing environments. By synergistically integrating density functional theory and ultraperformance liquid chromatography-quadrupole time-of-flight tandem mass spectrometry (UPLC-Q-TOF MS/MS) techniques, we elucidated the transients and transformation products (TPs) arising from the ·OH-MMI reactions. We probed two hydrogen-atom abstraction (HA) reactions, three radical adduct formation reactions, and single electron transfer (SET) at the M06-2X/6-311++G(d,p)/SMD(water) level. All proposed reaction channels, except for HA from the methyl group and SET, were found to be barrier-free. SET is the dominant oxidation pathway, accounting for 44% of oxidations, as determined by branching ratio analysis. The selenium analogue, MSeI, exhibited minor reactivity differences compared to MMI, yet its overall patterns resembled those of ·OH-MMI reactions. TPs were generated experimentally by reacting MMI with ·OH produced by UV-photolysis of H2O2. Eight TPs were identified from an approximately 24% degradation of MMI using UPLC-Q-TOF MS/MS analysis, and an additional two TPs were identified from the approximately 52% degraded MMI sample. The exact identities of all of the TPs were established through their corresponding fragmentation patterns. This study elucidates the drug's susceptibility to free radical species under physiologically relevant conditions.

Organic micropollutant removal and phosphate recovery by polyelectrolyte multilayer membranes: Impact of buildup interactions.

Polyelectrolyte multilayer (PEM) deposition conditions can favorably or adversely affect the membrane filtration performance of various pollutants. Although pH and ionic strength have been proven to alter the characteristics of PEM, their role in determining the buildup interactions that control filtration efficacy has not yet been conclusively proved. A PEM constructed using electrostatic or non-electrostatic interactions from controlled deposition of a weak polyelectrolyte could retain both charged and uncharged pollutants from water. The fundamental relationship between polyelectrolyte charge density, PEM buildup interaction, and filtration performance was explored using a weak-strong electrolyte pair consisting of branching poly (ethyleneimine) and poly (styrene sulfonate) (PSS) across pH ranges of 4-10 and NaCl concentrations of 0 M-0.5 M. PEI/PSS multilayers at acidic pH were dominated by electrostatic interactions, which favored the selective removal of a charged solute, phosphate over chloride, while at alkaline pH, non-electrostatic interactions dominated, which favored the removal of oxybenzone (OXY), a neutral hydrophobic solute. The key factor determining these interactions was the charge density of PEI, which is controlled by pH and ionic strength of the deposition solutions. These findings indicate that the control of buildup interactions can largely influence the physico-chemical and transport characteristics of PEM membranes.

Occurrence and distribution of steroid hormones (estrogen) and other contaminants of emerging concern in a south indian water body.

Steroid hormones (SHs) are among the important classes of Contaminants of Emerging Concern (CECs) whose detection in aquatic environments is vital due to their potential adverse health impacts. Their detection is challenging because of their lower stability in natural conditions and low concentrations. This study reports the presence of steroid hormones in a major river system, the Periyar River, in Kerala (India). Water samples were collected from thirty different river locations in the case of SHs and five locations within these in the case of other CECs. These were subjected to LC-MS/MS and LC-Q-ToF/MS analyses. Five SHs, estriol, estrone, 17 ß estradiol, progesterone, and hydroxy progesterone, were separated and targeted using MS techniques. The studies of the water samples confirmed the presence of the first three estrogens in different sampling sites, with estrone present in all the sampling sites. The concentration of estrone was detected in the range from 2 to 15 ng/L. Estriol and estradiol concentrations ranged from 1.0 to 5 ng/L and 1-6 ng/L, respectively. The hormones at some selected sites were continuously monitored for seven months. The chosen areas include the feed water sites for the drinking water treatment plants across the river. The monthly data revealed that estrone is the only SHs detected in all the samples in the selected months. The highest concentration of SH was found in August. Twelve CECs belonging to pharmaceuticals and personal care products were identified and quantified. In addition, 31 other CECs were also identified using non-target analysis. A detailed study of the hormone mapping reported here is the first from any South Indian River.