DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Surface interactions and degradation of a fluoroquinolone antibiotic in the dark in aqueous TiO2 suspensions

Abstract

Fluoroquinolone antibiotics (FQs) are important drugs used in human and veterinary medicine. Their detection in natural waters and waste water treatment plants, along with increased resistance to FQs among some bacteria, have generated an increased interest in the fate of these drugs in the environment. Partitioning of FQs between an aqueous solution and attendant substrates depends, in part, on the surface reactivity of the adsorbent, commonly a function of particle size, surface charge, and functional groups. In this paper, this study investigated the surface interactions between the FQ drug ofloxacin (OFL) and titanium oxide (TiO2), a common catalyst and widely-observed constituent in many consumer products. Raman and fluorescence spectroscopic techniques, as well as LC/MS, were used to determine the OFL moieties present on TiO2 surfaces and in attendant solutions. Raman spectra indicate that the C==O (ketone) group of the quinolone core, the NH+ of the piperazinyl ring, and CH3 of benzoxazine core are the most active in sorption onto the TiO2 surface. Raman spectra also show that the sorbed benzoxazine–quinolone core and piperazinyl moieties are readily desorbed from the surface by re-suspending samples in water. Importantly, we found that OFL could be degraded by reacting with TiO2 even in themore » dark. Complementary LC/MS analysis of the attendant supernatants indicates the presence of de-piperazinylated and de-carboxylated OFL breakdown products in supernatant solutions. Together, both Raman and LC/MS analyses indicate that TiO2 breaks the compound into piperazinyl and carboxylate groups which attach to the surface, whereas de-carboxylated and hydroxylated quinolone moieties remain in solution. Finally, the present study thus identifies the sorption mechanisms and breakdown products of OFL during dark reactions with TiO2, which is critically important for understanding the fate and transport of OFL as it enters the soil and aquatic environment.« less

Authors:
 [1];  [2];  [3]
  1. Hope College, Holland, MI (United States). Dept. of Geological and Environmental Sciences
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Environmental Sciences Division
  3. Hope College, Holland, MI (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1265525
Alternate Identifier(s):
OSTI ID: 1246487
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Science of the Total Environment
Additional Journal Information:
Journal Volume: 532; Journal ID: ISSN 0048-9697
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
60 APPLIED LIFE SCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Fluoroquinolone degradation; Titanium oxide nanoparticles; Ofloxacin; Antibiotics in wastewater; PPCP contamination

Citation Formats

Peterson, Jonathan W., Gu, Baohua, and Seymour, Michael D. Surface interactions and degradation of a fluoroquinolone antibiotic in the dark in aqueous TiO2 suspensions. United States: N. p., 2015. Web. doi:10.1016/j.scitotenv.2015.06.024.
Peterson, Jonathan W., Gu, Baohua, & Seymour, Michael D. Surface interactions and degradation of a fluoroquinolone antibiotic in the dark in aqueous TiO2 suspensions. United States. https://doi.org/10.1016/j.scitotenv.2015.06.024
Peterson, Jonathan W., Gu, Baohua, and Seymour, Michael D. Mon . "Surface interactions and degradation of a fluoroquinolone antibiotic in the dark in aqueous TiO2 suspensions". United States. https://doi.org/10.1016/j.scitotenv.2015.06.024. https://www.osti.gov/servlets/purl/1265525.
@article{osti_1265525,
title = {Surface interactions and degradation of a fluoroquinolone antibiotic in the dark in aqueous TiO2 suspensions},
author = {Peterson, Jonathan W. and Gu, Baohua and Seymour, Michael D.},
abstractNote = {Fluoroquinolone antibiotics (FQs) are important drugs used in human and veterinary medicine. Their detection in natural waters and waste water treatment plants, along with increased resistance to FQs among some bacteria, have generated an increased interest in the fate of these drugs in the environment. Partitioning of FQs between an aqueous solution and attendant substrates depends, in part, on the surface reactivity of the adsorbent, commonly a function of particle size, surface charge, and functional groups. In this paper, this study investigated the surface interactions between the FQ drug ofloxacin (OFL) and titanium oxide (TiO2), a common catalyst and widely-observed constituent in many consumer products. Raman and fluorescence spectroscopic techniques, as well as LC/MS, were used to determine the OFL moieties present on TiO2 surfaces and in attendant solutions. Raman spectra indicate that the C==O (ketone) group of the quinolone core, the NH+ of the piperazinyl ring, and CH3 of benzoxazine core are the most active in sorption onto the TiO2 surface. Raman spectra also show that the sorbed benzoxazine–quinolone core and piperazinyl moieties are readily desorbed from the surface by re-suspending samples in water. Importantly, we found that OFL could be degraded by reacting with TiO2 even in the dark. Complementary LC/MS analysis of the attendant supernatants indicates the presence of de-piperazinylated and de-carboxylated OFL breakdown products in supernatant solutions. Together, both Raman and LC/MS analyses indicate that TiO2 breaks the compound into piperazinyl and carboxylate groups which attach to the surface, whereas de-carboxylated and hydroxylated quinolone moieties remain in solution. Finally, the present study thus identifies the sorption mechanisms and breakdown products of OFL during dark reactions with TiO2, which is critically important for understanding the fate and transport of OFL as it enters the soil and aquatic environment.},
doi = {10.1016/j.scitotenv.2015.06.024},
journal = {Science of the Total Environment},
number = ,
volume = 532,
place = {United States},
year = {Mon Jun 15 00:00:00 EDT 2015},
month = {Mon Jun 15 00:00:00 EDT 2015}
}

Journal Article:

Citation Metrics:
Cited by: 21 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Mechanistic Considerations for the Advanced Oxidation Treatment of Fluoroquinolone Pharmaceutical Compounds using TiO 2 Heterogeneous Catalysis
journal, January 2010

  • An, Taicheng; Yang, Hai; Song, Weihua
  • The Journal of Physical Chemistry A, Vol. 114, Issue 7
  • DOI: 10.1021/jp911349y

A national reconnaissance of pharmaceuticals and other organic wastewater contaminants in the United States — I) Groundwater
journal, September 2008


Photocatalytic transformations of sulphonamides on titanium dioxide
journal, October 2004


Antibacterial Activity of Soil-Bound Antibiotics
journal, November 2005

  • Chander, Yogesh; Kumar, Kuldip; Goyal, Sagar M.
  • Journal of Environmental Quality, Vol. 34, Issue 6
  • DOI: 10.2134/jeq2005.0017

Reaction of forest floor organic matter at goethite, birnessite and smectite surfaces
journal, January 2001


Competitive sorption and desorption behavior for three fluoroquinolone antibiotics in a wastewater treatment wetland soil
journal, September 2010


Origins and Evolution of Antibiotic Resistance
journal, August 2010

  • Davies, J.; Davies, D.
  • Microbiology and Molecular Biology Reviews, Vol. 74, Issue 3
  • DOI: 10.1128/MMBR.00016-10

Stability of titania nanoparticles in soil suspensions and transport in saturated homogeneous soil columns
journal, April 2009


Contamination of Surface, Ground, and Drinking Water from Pharmaceutical Production
journal, January 2009

  • Fick, Jerker; Söderström, Hanna; Lindberg, Richard H.
  • Environmental Toxicology and Chemistry, Vol. 28, Issue 12
  • DOI: 10.1897/09-073.1

Trends in soil sorption coefficients within common antimicrobial families
journal, May 2010


Influence of Ionic Strength, pH, and Cation Valence on Aggregation Kinetics of Titanium Dioxide Nanoparticles
journal, March 2009

  • French, Rebecca A.; Jacobson, Astrid R.; Kim, Bojeong
  • Environmental Science & Technology, Vol. 43, Issue 5
  • DOI: 10.1021/es802628n

Occurrence and Fate of Antibiotics as Trace Contaminants in Wastewaters, Sewage Sludges, and Surface Waters
journal, September 2003

  • Giger, Walter; Alder, Alfredo C.; Golet, Eva M.
  • CHIMIA International Journal for Chemistry, Vol. 57, Issue 9
  • DOI: 10.2533/000942903777679064

Sorption of the antibiotic ofloxacin to mesoporous and nonporous alumina and silica
journal, March 2005

  • Goyne, Keith W.; Chorover, Jon; Kubicki, James D.
  • Journal of Colloid and Interface Science, Vol. 283, Issue 1
  • DOI: 10.1016/j.jcis.2004.08.150

Sorption of the Antimicrobial Ciprofloxacin To Aluminum and Iron Hydrous Oxides
journal, December 2005

  • Gu, Cheng; Karthikeyan, K. G.
  • Environmental Science & Technology, Vol. 39, Issue 23
  • DOI: 10.1021/es051109f

Synthetic TiO2 nanoparticle emission from exterior facades into the aquatic environment
journal, November 2008


Tetracycline as a selector for resistant bacteria in activated sludge
journal, January 2007


Pharmaceuticals, Hormones, and Other Organic Wastewater Contaminants in U.S. Streams, 1999−2000:  A National Reconnaissance
journal, March 2002

  • Kolpin, Dana W.; Furlong, Edward T.; Meyer, Michael T.
  • Environmental Science & Technology, Vol. 36, Issue 6
  • DOI: 10.1021/es011055j

Antibiotics in the aquatic environment – A review – Part I
journal, April 2009


Antibiotics in the aquatic environment – A review – Part II
journal, April 2009


Degradation of fluoroquinolone antibiotics and identification of metabolites/transformation products by liquid chromatography–tandem mass spectrometry
journal, March 2014


Determination of fluoroquinolone antibiotics in wastewater effluents by liquid chromatography–mass spectrometry and fluorescence detection
journal, February 2005


Evolution and spread of antibiotic resistance
journal, August 2002


Occurrence, behavior and effects of nanoparticles in the environment
journal, November 2007


17β-Estradiol Degradation by TiO 2 Photocatalysis as a Means of Reducing Estrogenic Activity
journal, October 2002

  • Ohko, Yoshihisa; Iuchi, Ken-ichiro; Niwa, Chisa
  • Environmental Science & Technology, Vol. 36, Issue 19
  • DOI: 10.1021/es011500a

Physicochemical properties of quinolone antibiotics in various environments
journal, June 2002


Visible-Light-Mediated TiO 2 Photocatalysis of Fluoroquinolone Antibacterial Agents
journal, July 2007

  • Paul, Tias; Miller, Penney L.; Strathmann, Timothy J.
  • Environmental Science & Technology, Vol. 41, Issue 13
  • DOI: 10.1021/es070097q

Fluoroquinolones in soil—risks and challenges
journal, November 2006


Stability of metal oxide nanoparticles in aqueous solutions
journal, January 2010

  • Tso, Chih-ping; Zhung, Cheng-min; Shih, Yang-hsin
  • Water Science and Technology, Vol. 61, Issue 1
  • DOI: 10.2166/wst.2010.787

Interaction of the fluoroquinolone antibiotic, ofloxacin, with titanium oxide nanoparticles in water: Adsorption and breakdown
journal, December 2012


Elimination of pharmaceuticals in sewage treatment plants in Finland
journal, March 2007


Titanium Dioxide Nanoparticles in Food and Personal Care Products
journal, February 2012

  • Weir, Alex; Westerhoff, Paul; Fabricius, Lars
  • Environmental Science & Technology, Vol. 46, Issue 4
  • DOI: 10.1021/es204168d

Oxidative Transformation of Fluoroquinolone Antibacterial Agents and Structurally Related Amines by Manganese Oxide
journal, June 2005

  • Zhang, Huichun; Huang, Ching-Hua
  • Environmental Science & Technology, Vol. 39, Issue 12
  • DOI: 10.1021/es048166d

Presence of therapeutic drugs in the environment
journal, May 2000


Works referencing / citing this record:

Removal of antibiotics from aqueous solutions by nanoparticles: a systematic review and meta-analysis
journal, January 2019

  • Malakootian, Mohammad; Yaseri, Mehdi; Faraji, Maryam
  • Environmental Science and Pollution Research, Vol. 26, Issue 9
  • DOI: 10.1007/s11356-019-04227-w