Iron minerals are important soil components; however, little information is available for the transformation of antibiotics on iron mineral surfaces, especially under limited moisture conditions. In this study, we investigated the catalytic performance of four iron minerals (maghemite, hematite, goethite, and siderite) for the hydrolysis of chloramphenicol (CAP) antibiotic at different moisture conditions. All the iron oxides could efficiently catalyze CAP hydrolysis with the half-lives <6 days when the surface water content was limited, which was controlled by the atmospheric relative humidity of 33–76%. Different minerals exhibited distinctive catalytic processes, depending on the surface properties. H-bonding or Lewis acid catalysis was proposed for surface hydrolytic reaction on iron oxides, which however was almost completely inhibited when the surface water content was >10 wt % due to the competition of water molecules for surface reactive sites. For siderite, the CAP hydrolysis was resistant to excessive surface water. A bidentate H-bonding interaction mechanism would account for CAP hydrolysis on siderite. The results of this study highlight the importance of surface moisture on the catalytic performance of iron minerals. The current study also reveals a potential degradation pathway for antibiotics in natural soil, which has been neglected before.

Phthalate esters (PAEs) have been extensively used as additives in plastics and wallcovering, causing severe environmental contamination and increasing public health concerns. Here, we find that hematite nanoparticles with specific facet-control can efficiently catalyze PAEs hydrolysis under ambient humidity conditions, with the hydrolysis rates 2 orders of magnitude higher than that in water saturated condition. The catalytic performance of hematite shows a significant facet-dependence with the reactivity in the order {012} > {104} ≫ {001}, related to the atomic array of surface undercoordinated Fe. The {012} and {104} facets with the proper neighboring Fe-Fe distance of 0.34-0.39 nm can bidentately coordinate with PAEs, and thus induce much stronger Lewis-acid catalysis. Our study may inspire the development of nanomaterials with appropriate surface atomic arrays, improves our understanding for the natural transformation of PAEs under low humidity environment, and provides a promising approach to remediate/purify the ambient air contaminated by PAEs.

Mobile antibiotic resistance genes (ARGs) in environmental systems may pose a threat to public health. The coexisting substituted aromatic pollutants may help the ARGs cross the extracellular polymeric substance (EPS) permeable barrier into the interior of cells, facilitating ARG dissemination, but the mechanism is still unknown. Here, we demonstrated that a specific antihydrolysis mechanism of mobile plasmid in the extracellular matrix makes a greater contribution to this facilitated dissemination. Specifically, fluorescence microtitration with a Tb 3+ -labeled pUC19 plasmid was used to study the formation of substituted aromatic− plasmid complexes associated with ARG dissemination. Manipulations of the endA gene and an EPS confirmed that these forming complexes antagonize the EPS-mediated hydrolysis of the plasmid. Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and computational chemistry demonstrated that substituents alter the polarity of aromatic molecules, making the carbon at the 6-position of 1,3-dichlorobenzene as well as the labile protons (−NH 2 /−OH) of mphenylenediamine, aniline, and 2-naphthol interact with the deprotonated hydroxy group of the phosphate (P−O•••H−C/N/ O), mainly via hydrogen bonds. Linear correlations among ARG disseminations, association constants, and bonding energies highlight the quantitative dependency of ARG proliferation on a combination of functionalities templated by D-ribose− phosphate.