Oxolinic Acid Binding at Goethite and Akaganéite Surfaces: Experimental Study and Modeling

Environ Sci Technol. 2016 Jan 19;50(2):660-8. doi: 10.1021/acs.est.5b04940. Epub 2015 Dec 31.

Abstract

Oxolinic acid (OA) is a widely used quinolone antibiotic in aquaculture. In this study, its interactions with synthetic goethite (α-FeOOH) and akaganéite (β-FeOOH) particle surfaces were monitored to understand the potential fate of OA in marine sediments where these phases occur. Batch sorption experiments, liquid chromatography (LC) analyses of supernatants, attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy and multisite complexation (MUSIC) modeling were used to monitor OA binding at these particle surfaces. Both LC and ATR-FTIR showed that adsorption did not degrade OA, and that OA adsorption was largely unaffected by NaCl concentrations (10-1000 mM). This was explained further by ATR-FTIR suggesting the formation of metal-bonded complexes at circumneutral to low pHc = -log [H(+)] and with a strongly hydrogen-bonded complex at high pHc. The stronger OA binding to akaganéite can be explained both by the higher isoelectric point/point-of-zero charge (9.6-10) of this mineral than of goethite (9.1-9.4), and an additional OA surface complexation mechanism at the (010) plane. Geminal sites (≡Fe(OH2)2(+)) at this plane could be especially reactive for metal-bonded complexes, as they facilitate a mononuclear six-membered chelate complex via the displacement of two hydroxo/aquo groups at the equatorial plane of a single Fe octahedron. Collectively, these findings revealed that Fe-oxyhydroxides may strongly contribute to the fate and transport of OA-type antibacterial agents in marine sediments and waters.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Adsorption
  • Anti-Bacterial Agents / chemistry*
  • Ferric Compounds / chemistry*
  • Geologic Sediments / analysis*
  • Iron Compounds / chemistry*
  • Minerals / chemistry*
  • Models, Chemical
  • Oxolinic Acid / chemistry*
  • Water Pollutants, Chemical / chemistry*

Substances

  • Anti-Bacterial Agents
  • Ferric Compounds
  • Iron Compounds
  • Minerals
  • Water Pollutants, Chemical
  • akaganeite
  • goethite
  • Oxolinic Acid