Distinct effects of copper on the degradation of β-lactam antibiotics in fulvic acid solutions during light and dark cycle

This study revealed the dual roles of Cu(II) on the β-lactam antibiotics degradation in Suwannee River fulvic acid (SRFA) solution during day and night cycle. Amoxicillin (AMX) and ampicillin (AMP) were selected as the representative β-lactam antibiotics. Cu(II) played a key role in the dark degradation of AMX and AMP via catalytic hydrolysis and oxidation. However, Cu(II) mainly exhibited an inhibitory effect on SRFA-involved photochemical degradation of AMX and AMP. In the presence of 500 nM of Cu(II), the degradation rate of AMX and AMP in the light condition were around 5 times higher than that in the dark condition, suggesting the photodegradation of β-lactam antibiotics was much more pronounced than catalyzed hydrolysis and oxidation. The triplet excited state of SRFA ((3)SRFA∗) primarily contributed to AMX and AMP photodegradation. Hydroxyl radicals ((•)OH) and singlet oxygen ((1)O(2)) exhibited limit impacts. The redox cycle of Cu(II)/Cu(I) restricted the electron transfer pathway of (3)SRFA∗ with AMX and AMP. During the day and night cycles for 48 h, Cu(II) served as a stronger inhibitor rather than a promotor. These findings highlight the interactions between Cu(II) and SRFA are distinct under day and night conditions, which could further affect the fate of β-lactam antibiotics in natural environments.