Degradation of enoxacin with different dissociated species during the transformation of ferrihydrite-antibiotic coprecipitates.

Ferrihydrite acts as a natural reservoir for nutrient elements, organic matter, and coexisting pollutants through adsorption and coprecipitation. However, the degradation of emerging fluoroquinolone antibiotics during the transformation of ferrihydrite coprecipitates, especially those with various dissociated species, remains insufficiently explored. In this study, Enoxacin (ENO), employed as a model antibiotic, was introduced to prepare ferrihydrite-ENO coprecipitates. The influence of coprecipitated ENO on the transformation of the ferrihydrite-ENO coprecipitate was investigated across different pH conditions. The results revealed that ferrihydrite-ENO coprecipitates thermodynamically transformed into more stable goethite and/or hematite under all pH conditions. In neutral and alkaline conditions, ENO promoted the transformation of coprecipitates into goethite while hindering hematite formation. Conversely, under acidic conditions, ENO directly obstructed the transformation of coprecipitates into hematite. Different dissociated species of ENO displayed distinct degradation pathways. The cationic form of ENO exhibited a greater tendency for hydroxylation and defluorination, while the zwitterion form leaned toward piperazine ring oxidation, with limited preference for quinolone ring oxidation. The anionic form of ENO exhibited the fastest degradation rate. It is essential to emphasize that the toxicity of the degradation products was intricately connected to the specific reaction sites and the functional groups they acquired post-oxidation. These findings offer fresh insights into the role of antibiotics in coprecipitation, the transformation of ferrihydrite coprecipitates, and the fate of coexisting antibiotics.

The pH dependence and role of fluorinated substituent of enoxacin binding to ferrihydrite.

The sorption of antibiotics on iron (hydr)oxides is an important process that influences their environmental fate. Ferrihydrite (Fh) nanosized iron hydroxide is omnipresent in nature. However, the sorption mechanism of fluoroquinolone (FQ) antibiotics on Fh is unclear. Here, a combined experimental and computational study was conducted to investigate the sorption of enoxacin (ENO) as one model of FQs on Fh. Pipemidic acid (PPA), as a structural analog of ENO, was selected to compare the effect of fluorinated substituent on the sorption mechanism. Results indicated that the average Kd values of ENO at pH = 7.0 and 8.0 were 1.72 and 2.75 times higher than those at pH in the ranges of 4.0-6.0 and 9.0-10.0, respectively. The main sorption mechanisms included electrostatic, hydrophobic interaction, and inner-sphere complexation. The fluorinated substituent of ENO facilitated its sorption on Fh through enhancing its hydrophobicity as well as modifying its dissociation constants and charge distribution. The findings give new insights into the significant influence of active fluorinated substituents on the environmental behaviors of fluorinated pharmaceuticals.

Development of phytoremediator screening strategy and exploration of Pennisetum aided chromium phytoremediation mechanisms in soil.

Screening of chromium (Cr) phytoremediators (i.e., hyperaccumulator plants and accumulation plants) is essential for the phytoremediation of Cr-contaminated soils but less tackled previously. In this study, we proposed a stepwise strategy for screening Cr phytoremediators and explored tolerance mechanism of the screened species. To achieve effective screening of Cr phytoremediators, seed germination, hydroponic, and pot experiment were performed sequentially, and an improved indicator system was established accordingly. Pennisetum was selected from nine plants, with its high growth rate and Cr remediation efficiency successfully demonstrated in the field. Antioxidant enzymes (i.e., superoxide dismutase (SOD) and catalase (CAT)) and photosynthesis under Cr stress were monitored for tracking the tolerance mechanism. Results showed that the enhanced SOD and CAT contributed to the strong tolerance of Pennisetum to Cr. The SOD and CAT were positively correlated with net photosynthetic rate (Pn), resulting in a phenomenon that Cr had no significant effect on Pn of Pennisetum even at 400 mg kg-1. The research findings helped obtain powerful Cr phytoremediators, deepen our understanding of the tolerance mechanisms associated with phytoremediation, and eventually facilitate effective Cr removal in soil.