Clay minerals-mediated removal of Norfloxacin and Norfloxin-resistant bacteria from water environments and associated mechanisms

Abstract

Norfloxacin (NOR) is frequently detected in various water bodies and has the potential to promote the proliferation of NOR-resistant bacteria/genes in the environment. Efficiently removing residual NOR and NOR-resistant bacteria from contaminated water is critical to mitigating their environmental risks. This study investigated the ability of two common clay minerals, kaolinite and montmorillonite, to remove NOR and NOR-resistant bacteria from five different water environments (ultrapure water, simulated and real freshwater, and simulated and real seawater) and explored the underlying removal mechanisms. The results showed that both clays adsorbed NOR according to a pseudo-first-order kinetic model. In simulated and actual freshwater and seawater, the adsorption of NOR by kaolinite was 0.199, 0.120, 0.094, and 0.010 mg g⁻¹, while montmorillonite adsorbed NOR at significantly higher levels, with values of 2.880, 2.208, 0.433, and 0.067 mg g⁻¹, respectively. The primary mechanisms of adsorption included electrostatic interactions, cation exchange, and cation bonding and bridging. In addition to NOR sorption, culture tests revealed that montmorillonite exhibited significant antibacterial activity against NOR-resistant bacteria, achieving an inhibition ratio of 83.84 ± 4.01% when the initial concentrations of bacteria and montmorillonite were 1.68 ± 1.00 × 10⁵ CFU·mL⁻¹ and 40 mg mL⁻¹, respectively. Remarkably, montmorillonite maintained its high sorption capacity and antibacterial activity even after multiple reuse cycles. These findings highlight the promising application potential of montmorillonite, particularly in terms of its storage and long-distance distribution capabilities, making it an effective material for removing both NOR and NOR-resistant bacteria from the environment. However, it is important to note that under estuarine conditions, clay-bound NOR could be released if water quality changes. Therefore, we conclude that strategies to degrade and remove antibiotics adsorbed onto clay minerals should be developed to prevent the release of antibiotics when clay particles enter the ocean, thus avoiding further environmental contamination.