Environmental Chemistry Environmental Chemistry Society
Environmental problems - Chemical approaches
RESEARCH ARTICLE

Investigation of an amoxicillin oxidative degradation product formed under controlled environmental conditions

Igal Gozlan A B , Adi Rotstein A B and Dror Avisar A C

A The Hydro-chemistry Laboratory, Department of Geography and Environmental Studies, Tel Aviv University, Tel Aviv, 69978, Israel.

B The Porter School of Environmental Studies, Tel Aviv University, Tel Aviv, 69978, Israel.

C Corresponding author. Email: droravi@post.tau.ac.il

Environmental Chemistry 7(5) 435-442 http://dx.doi.org/10.1071/EN10037
Submitted: 8 April 2010  Accepted: 2 August 2010   Published: 13 October 2010

Environmental context. Although amoxicillin is a widely used antibiotic, it is yet to be detected in the aquatic environment. This study traces the production of the amoxicillin-S-oxide degradation product, and shows that it is consistently obtained only under sunlight irradiation. This is the first study to demonstrate the formation, under controlled environmental conditions, of this chemically stable product of amoxicillin.

Abstract. Amoxicillin (AMX) is a widely used penicillin-type antibiotic, and its presence in the environment has been widely investigated. The formation and structure of an oxidised degradation product (DP) of AMX are described in the present work. The experiments were carried out in buffer solution (pH 7.5) containing AMX at a concentration of 100 μg mL–1, with and without acid and in field secondary effluent. The DP, AMX-S-oxide (sulfoxide), was consistently obtained only under sunlight irradiation and was significantly augmented by the addition of humic acid (5 mg L–1) and mainly in field secondary effluent, which acts as a natural photo-sensitiser. The structure of the AMX-S-oxide DP was determined by an LC-MS technique using a mobile phase of deuterated and non-deuterated solvents. A 1H NMR spectrum was obtained for the pure compound isolated by preparative HPLC. Further confirmation of the AMX-S-oxide structure was achieved by comparison of its UV spectrum with those of the two oxidation products, AMX-S-oxide and hydroxylated AMX, obtained by the ozonolysis of AMX.

Additional keywords: AMX-S-oxide, antibiotic residues, LC-MS, NMR, secondary effluent.


References

[1]  Richardson S. D.2004Environmental mass spectroscopy: emerging contaminates and current Issues.Anal. Chem.763337doi:10.1021/AC040060D

[2]  Kümmerer K.2001Drugs in the environment: emission of drugs, diagnostic aids and disinfectants into wastewater by hospitals in relation to other sources – a review.Chemosphere45957doi:10.1016/S0045-6535(01)00144-8

[3]  Kümmerer K.2009Antibiotics in the aquatic environment. Part I – a review.Chemosphere75417doi:10.1016/J.CHEMOSPHERE.2008.11.086

[4]  Kulshrestha P.Gies R. F.Aga D. S.2004Investigating the molecular interactions of oxytetracycline in clay and organic matter: insights on factors affecting its mobility in soil.Environ. Sci. Technol.384097doi:10.1021/ES034856Q

[5]  Derksen J. G. M.Rijs G. B. J.Jongbloed R. H.2004Diffuse pollution of surface water by pharmaceutical products.Water Sci. Technol.49213

[6]  Kümmerer K.2004Resistance in the environment.J. Antimicrob. Chemother.54311
doi:10.1093/JAC/DKH325

[7]  Minneman K. P., Wecker L., Larner J., Brody T. M. (Eds), Brody’s Human Pharmacology. Molecular to Clinical – 4th edn 2005 (Elsevier: Philadelphia, PA).

[8]  Tutt D. E.Schwartz M. A.1971Spectrophotometric assay of ampicillin (α aminobenzylpenicillin) involving initial benzoylation of the side chain a-amino group.Anal. Chem.43338doi:10.1021/AC60298A004

[9]  Gutiérez Navarro P.Hernández Blázquez I.Quintero Osso B.Martínez de las Parras P. J.Martínez Puentedura M. I.Márquez García A. A.2003Penicillin degradation catalyzed by Zn(II) ions in methanol.Int. J. Biol. Macromol.33159doi:10.1016/S0141-8130(03)00081-3

[10]  Ayim J. S. K.Rapson H. D. C.1972Zinc and copper(II) ion catalyzes of penicillins in alcohols.J. Pharm. Pharmacol.24172

[11]  Hernández Martínez J.Gutiérez Navarro P.Márquez Garcia A. A.Martínez de las Parras P. J.1999β-lactam degradation catalyzed by Cd2+ ion in methanol.Int. J. Biol. Macromol.25337
doi:10.1016/S0141-8130(99)00052-5

[12]  Gutiérez Navarro P.El Bekkouri A.Rodríguez Reinoso E.1998Spectrofluorimetric study of the degradation of α-amino β-lactam antibiotics catalysed by metal ions in methanol.Analyst1232263doi:10.1039/A804577A

[13]  Chatterjee N. R.Degani M. S.Singh C. B.1988Degradation of some aqueous semi-synthetic penicillin solutions in presence of copper(II) ions.Ind. J. Pharm. Sci.50128

[14]  Deshpande A. D.Baheti K. G.Chatterjee N. R.2004Degradation of β-lactam antibiotics.Curr. Sci.871684


[15]  Längin A.Radka A.König A.Kümmerer K.2009Deactivation and transformation products in biodegradability testing of β–lactams amoxicillin and piperacillin.Chemosphere75347
doi:10.1016/J.CHEMOSPHERE.2008.12.032

[16]  Zepp R. G.Cline D. M.1977Rates of direct photolysis in aquatic environments.Environ. Sci. Technol.11359doi:10.1021/ES60127A013

[17]  Arslan-Alaton I.Dogruel S.2004Pre-treatment of penicillin formulation effluent by advanced oxidation processes.J. Hazard. Mater.112105doi:10.1016/J.JHAZMAT.2004.04.009

[18]  Zepp R. G.Baughman G. L.Schlotzhauer P. F.1981Comparison of photochemical behavior of various humic substances in water. I. Sunlight induced reactions of aquatic pollutants photosensitized by humic substances.Chemosphere10109doi:10.1016/0045-6535(81)90174-0

[19]  Andreozzi R.Caprio V.Ciniglia C.De Champdore M.Giudice R. L.Marrotta R.Zuccato E.2004Antibiotics in the environment: occurrence in Italian STPs, fate, and preliminary assessment on algal toxicity of amoxicillin.Environ. Sci. Technol.386832doi:10.1021/ES049509A

[20]  Andreozzi R.Raffaele M.Nicklas P.2003Pharmaceuticals in STP effluents and their solar photo degradation in aquatic environment.Chemosphere501319doi:10.1016/S0045-6535(02)00769-5

[21]  Mangal N.Punjabi P. B.Bhardwaj R.Ameta S. C.1994Dye-sensitized photo-oxidation of amoxicillin by singlet oxygen.Philipp. J. Sci.123305

[22]  Valvo L.Alimonti S.Alimenti R.De Sena C.Signoretti E. C.Draisci R.Giannetti L.1997Investigation of a new amoxicillin sodium impurity unstable in solution.J. Pharmaceut. Biomed.15487
doi:10.1016/S0731-7085(96)01887-0

[23]  Nägele E.Moritz R.2005Structure elucidation of degradation products of the antibiotic amoxicillin with ion trap MSn and accurate mass determination by ESI TOF.J. Am. Soc. Mass Spectrom.161670doi:10.1016/J.JASMS.2005.06.002

[24]  Shan-Ying C.Chang-Qin H.Ming-Zhe X.2003Chromatographic determination of high-molecular weight impurities in amoxicillin.J. Pharmaceut. Biomed.31589doi:10.1016/S0731-7085(02)00711-2

[25]  Lamm A.Rotsein A.Gozlan I.Avisar D.2009Detection of amoxicillin- diketopiperazine-2′,5′ in wastewater samples.J. Environ. Sci. Health Part A441512doi:10.1080/10934520903263306

[26]  Andreozzi R.Canterino M.Marotta R.Paxeus N.2005Antibiotic removal from wastewaters: the ozonation of amoxicillin.J. Hazard. Mater.122243doi:10.1016/J.JHAZMAT.2005.03.004



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