Determination of Tetracyclines Residues in the Gulf of Gdańsk (Southern Baltic Sea) Sediments Using a Tandem Solid-Phase Extraction with Liquid Chromatography Coupled with Tandem Mass Spectrometry
Pharmaceuticals are biologically active and relatively persistent substances which have been recently recognized as a continuing threat to the aquatic environment. Numerous adverse effects may arise for aquatic non-target organisms from the presence of pharmaceutical residues. One of the main pharmaceutical contaminants are antibiotics which are in the environment in considerable concentrations and can have negative biological effects to marine microorganisms. Despite of this, the knowledge on antibiotics occurrence, behaviour and fate in the Baltic Sea is very limited. This study presents the preliminary results on tetracycline and oxytetracycline residues occurrence in the sediments collected from the Gulf of Gdańsk (southern Baltic Sea). Among the antibiotics, tetracyclines are one of the most popular class used for human and animal therapy and for animal breeding. The method for tetracyclines residues determination was optimized, using two types of Baltic sediments (sandy and muddy) spiked at nine concentration levels (from 1 to 1,000 ng g−1 d.w.) to achieve the best validation parameters. Acetonitrile and EDTA-McIlvaine extraction buffer solution (pH 4) (1:1) for extraction and tandem SPE technique with Discovery SAX and Oasis HLB cartridges for extracts clean-up were applied. Quantitative and qualitative determination of analysed antibiotics was performed with the use of liquid chromatography tandem mass spectrometry (LC-MS/MS) with electrospray ionization source in the positive mode. The recoveries for target antibiotics ranged from 78.8 to 131.1 % for tetracycline and 75.5–114.8 % for oxytetracycline. The LOD values ranged from 1.5 to 3.5 ng g−1 d.w. for tetracycline and from 1.2 to 2.2 ng g−1 d.w. for oxytetracycline. The developed method was applied in the determination of tetracyclines in six sediments collected in 2012 during r/v “Oceania” cruises. Oxytetracycline was identified in four of analyzed samples at concentrations from 21 to 625 ng g−1 d.w. Tetracycline was determined only in one sediment sample collected close to WWTP “Gdańsk Wschód” outlet (13.8 ng g−1 d.w.). None of the target compounds was identified in the accumulation area—the Gdańsk Deep.
KeywordsTetracyclines residues Sediments SPE-LC-MS/MS Baltic Sea
This work was supported by the Polish Ministry of Science and Higher Education (project no. N N306 300536), National Science Centre (project no. DEC-2011/01/N/ST10/06977) and by the Institute of Oceanology of the Polish Academy of Sciences (statutory task no.II.2).
- Beck I-C, Brunh R, Gandrass J, Ruck W (2009) Estrogenic and pharmaceutical compounds—investigations in the German Baltic Sea. Publications of GKSS Research Centre. www.coast.gkss.de/internet/Poster-Iris-2.pdf. Accessed 05 July 2010 (2009)
- Borecka M, Białk-Bielińska A, Siedlewicz G, Kornowska K, Kumirska J, Stepnowski P, Pazdro K (2013) A new approach for the estimation of expanded uncertainty of results of an analytical method developed for determining antibiotics in seawater solid-phase extraction disks and liquid chromatography coupled with tandem mass spectrometry technique. J of Chromatogr A. doi: 10.1016/j.chroma.2013.07.018
- HELCOM (2010) Baltic Sea Environment Proceedings No. 120B Hazardous substances in the Baltic Sea—an integrated thematic assessment of hazardous substances in the Baltic Sea. http://www.helcom.fi/stc/files/Publications/Proceedings/bsep120B.pdf. Accessed 23 April 2013
- Kołodziejska M (2009) Elaboration of a method for extraction, enrichment and quantitative determination of selected antibiotics applied in fish farms. M.Sc. thesis, University of Gdańsk, Chemistry Department, pp 92 (in polish)Google Scholar
- Kowalkiewicz Z, Pazdro K, Skauradszun M, Jankowska D, Niemirycz E (2013) The influence of persistent organic pollutants (POPs) on the toxicity of sediments from the southern part of the Baltic Sea. In: Rosińska J, Neumann M (eds) The functioning and protection of water ecosystems. Adam Mickiewicz University. Poznań, pp 138–152Google Scholar
- Kümmerer K (2008) Antibiotics in the environment. In: Kümmerer K (ed) Pharmaceuticals in the Environment, 3rd edn. Springer, Berlin, pp 75–88Google Scholar
- Na G, Gu J, Ge L, Zhang P, Wang Z, Liu C, Zhang L (2011) Detection of 36 antibiotics in coastal waters using high performance liquid chromatography-tandem mass spectrometry. Chin J Oceanol Limnol 29:1093–1102 Google Scholar
- Siedlewicz G, Kotlarska E, Pazdro K (2013) Impact of antibiotic residues present in Baltic Sea sediments on the growth of sedimentary bacteria. Monographs book series Wroclaw University of Technology Institute of Environmental Engineering, VII National Conference HYDROMICRO2013 Microorganisms–Human–Environment, accepted-in pressGoogle Scholar
- Staniszewska M, Burska D, Sapota G, Bogdaniuk M, Borowiec K, Nosarzewska I, Bolałek J (2011) The relationship between the concentrations and distribution of organic pollutants and black carbon content in benthic sediments in the Gulf of Gdańsk, Baltic Sea. Mar. Poll. Bull. 62:1464–1475CrossRefGoogle Scholar
- Yang JF, Ying GG, Zhao JL, Tao R, Su HC, Chen F (2010) Simultaneous determination of four classes of antibiotics in sediments of the Pearl Rivers using RRLC–MS/MS. Sci Total Environ 408:424–432Google Scholar
- Zhou L, Ying G, Zhao J, Yang J, Wang L, Yang B, Liu S (2011) Trends in the occurrence of human and veterinary antibiotics in the sediments of the Yellow River, Hai River and Liao River in northern China. Environ Pollut 159:188–1877Google Scholar