While biochar (BC) is used for contaminant remediation (i.e. antibiotics) in the field, geochemical aging can alter its chemical structure, releasing nano-sized BC (NBC, sizes ranging from approximately 200 nm to 500 nm), and further influence the environmental behaviour of antibiotics affiliated with BC. In this study, we comprehensively examined the sorption behaviour of NBCs with and without aging toward ciprofloxacin (CIP), their aggregation performance, and transport behaviour in porous media. The results showed that aging improved the oxygen-containing groups within the NBCs and made their surfaces more negatively charged. The thermodynamic enhancements of specific interactions (i.e. π-π interaction or Coulombic force) with CIP resulted in the enhancement of slow sorption (from 60-64% to 40-58%) and a higher normalised sorption capacity (Q). The aggregation of NBCs was affected by changes in individual specific interactions and interfacial forces between the NBCs before and after CIP sorption. Further, aging could enhance the transport of NBCs both in the absence and presence of CIP. In addition to the interaction with the quartz sand surface, the contributions of aggregation and chemical heterogeneity caused by rebalanced specific interactions with CIP, may explain the observed transport behaviours of the aged NBCs in porous media. Additionally, the presence of NBCs, regardless of aging, suppressed the transport of CIP. Thus, mechanisms such as increased sorption sites due to aggregation and competitive sorption between NBCs and CIP, rather than the contribution of co-transport from NBCs, might play an important role in determining the fate of CIP in the natural environment.
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