Skip to main content
SpringerLink
Log in

β-Estradiol and ethinyl-estradiol contamination in the rivers of the Carpathian Basin

  • Research Article
  • Published:
Environmental Science and Pollution Research Aims and scope Submit manuscript

Abstract

17β-Estradiol (E2) and 17α-ethinyl estradiol (EE2), which are environmental estrogens, have been determined with LC-MS in freshwater. Their sensitive analysis needs derivatization and therefore is very hard to achieve in multiresidue screening. We analyzed samples from all the large and some small rivers (River Danube, Drava, Mur, Sava, Tisza, and Zala) of the Carpathian Basin and from Lake Balaton. Freshwater was extracted on solid phase and derivatized using dansyl chloride. Separation was performed on a Kinetex XB-C18 column. Detection was achieved with a benchtop orbitrap mass spectrometer using targeted MS analysis for quantification. Limits of quantification were 0.05 ng/L (MS1) and 0.1 ng/L (MS/MS) for E2, and 0.001 ng/L (MS1) and 0.2 ng/L (MS/MS) for EE2. River samples contained n.d.–5.2 ng/L E2 and n.d.–0.68 ng/L EE2. Average levels of E2 and EE2 were 0.61 and 0.084 ng/L, respectively, in rivers, water courses, and Lake Balaton together, but not counting city canal water. EE2 was less abundant, but it was still present in almost all of the samples. In beach water samples from Lake Balaton, we measured 0.076–0.233 E2 and n.d.–0.133 EE2. A relative high amount of EE2 was found in river Zala (0.68 ng/L) and in Hévíz-Páhoki canal (0.52 ng/L), which are both in the catchment area of Lake Balaton (Hungary).

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3

Similar content being viewed by others

References

  • Abhishek G, Swati G, Priti T (2015) High-sensitivity simultaneous liquid chromatography–tandem mass spectrometry assay of ethinyl estradiol and levonorgestrel in human plasma. J Pharm Anal 5:316–326

    Article  Google Scholar 

  • Anari MR, Bakhtiar R, Zhu B, Huskey S, Franklin RB, Evans DC (2002) Derivatization of ethinylestradiol with dansyl chloride to enhance electrospray ionization: application in trace analysis of ethinylestradiol in rhesus monkey plasma. Anal Chem 74:4136–44

    Article  CAS  Google Scholar 

  • Andrási N, Molnár B, Dobos B, Vasanits-Zsigrai A, Záray G, Molnár-Perl I (2013) Determination of steroids in the dissolved and in the suspended phases of wastewater and Danube River samples by gas chromatography, tandem mass spectrometry. Talanta 115:367–373

    Article  Google Scholar 

  • Aris AZ, Shamsuddin AS, Praveena SM (2014) Occurrence of 17 alpha-ethynylestradiol (EE2) in the environment and effect on exposed biota: a review. Environ Int 69:104–119

    Article  CAS  Google Scholar 

  • Avar P, Maász G, Takács P, Lovas S, Zrínyi Z, Svigruha R, Takátsy A, G.-Tóth L, Pirger Z (2015) HPLC-MS/MS analysis of steroid hormones in environmental water samples. Drug Test Anal. doi:10.1002/dta.1829

    Google Scholar 

  • Bado-Nilles A, Techer R, Porcher JM, Geffard A, Gagnaire B, Betoulle S, Sanchez W (2014) Detection of immunotoxic effects of estrogenic and androgenic endocrine disrupting compounds using splenic immune cells of the female three-spined stickleback, Gasterosteus aculeatus (L.). Environ Toxicol Pharm 38:672–683

    Article  CAS  Google Scholar 

  • Belfroid AC, Van der Horst A, Vethaak AD, Schafer AJ, Rijs GBJ, Wegener J, Cofino WP (1999) Analysis and occurrence of estrogenic hormones and their glucuronides in surface water and waste water in The Netherlands. Sci Total Environ 225:101–108

    Article  CAS  Google Scholar 

  • Bhandari RK, Deem SL, Holliday DK, Jandegian CM, Kassotis CD, Nagel SC, Tillitt DE, Saal FSV, Rosenfeld CS (2015) Effects of the environmental estrogenic contaminants bisphenol A and 17 alpha-ethinyl estradiol on sexual development and adult behaviors in aquatic wildlife species. Gen Comp Endocr 214:195–219

    Article  CAS  Google Scholar 

  • Cargouet M, Perdiz D, Mouatassim-Souali A, Tamisier-Karolak S, Levi Y (2004) Assessment of river contamination by estrogenic compounds in Paris area (France). Sci Total Environ 324:55–66

    Article  CAS  Google Scholar 

  • Chitescu CL, Kaklamanos G, Nicolau AI, Stolker AA (2015) High sensitive multiresidue analysis of pharmaceuticals and antifungals in surface water using U-HPLC-Q-Exactive Orbitrap HRMS. Application to the Danube river basin on the Romanian territory. Sci Total Environ 532:501–11

    Article  CAS  Google Scholar 

  • Costa DDM, Neto FF, Costa MDM, Morais RN, Garcia JRE, Esquivel BM, Ribeiro CAO (2010) Vitellogenesis and other physiological responses induced by 17-beta-estradiol in males of freshwater fish Rhamdia quelen. Comp Biochem Phys C 151:248–257

    Google Scholar 

  • Desbrow C, Routledge EJ, Brighty GC, Sumpter JP, Waldock M (1998) Identification of estrogenic chemicals in STW effluent. 1. Chemical fractionation and in vitro biological screening. Environ Sci Technol 32:1549–1558

    Article  CAS  Google Scholar 

  • European Parliament (2008): Directive, 2008/105/EC O.J. L 348/84 (16 December)

  • European Parliament (2013): Directive, 2013/39/EU O.J. L 229/1 (24 August)

  • European Parliament (2015): Commission Implementing Decision, 2015/495/EU O.J. L 78 (20 March)

  • Faludi T, Balogh C, Serfőző Z, Molnár-Perl I (2015) Analysis of phenolic compounds in the dissolved and suspended phases of Lake Balaton water by gas chromatography-tandem mass spectrometry. Environ Sci Pollut R 22:11966–11974

    Article  CAS  Google Scholar 

  • Franke AA, Custer LJ, Morimoto Y, Nordt FJ, Maskarinec G (2011) Analysis of urinary estrogens, their oxidized metabolites, and other endogenous steroids by benchtop orbitrap LCMS versus traditional quadrupole GCMS. Anal Bioanal Chem 401:1319–1330

    Article  CAS  Google Scholar 

  • Garriz A, Menendez-Helman RJ, Miranda LA (2015) Effects of estradiol and ethinylestradiol on sperm quality, fertilization, and embryo-larval survival of pejerrey fish (Odontesthes bonariensis). Aquat Toxicol 167:191–199

    Article  CAS  Google Scholar 

  • Gorga M, Petrovic M, Barcelo D (2013) Multi-residue analytical method for the determination of endocrine disruptors and related compounds in river and waste water using dual column liquid chromatography switching system coupled to mass spectrometry. J Chromatogr A 1295:57–66

    Article  CAS  Google Scholar 

  • Hallgren S, Volkova K, Reyhanian N, Olsen KH, Hallstrom IP (2011) Anxiogenic behaviour induced by 17alpha-ethynylestradiol in male guppies (Poecilia reticulata). Fish Physiol Biochem 37:911–8

    Article  CAS  Google Scholar 

  • Huang B, Sun W, Li X, Liu J, Li Q, Wang R, Pan X (2015) Effects and bioaccumulation of 17beta-estradiol and 17alpha-ethynylestradiol following long-term exposure in crucian carp. Ecotoxicol Environ Saf 112:169–76

    Article  CAS  Google Scholar 

  • Ismail Ahmad SZZ, Usuki Y, Kitajima S, Arizono K (2007) The level of 17β-estradiol in aquatic environments around Klang Valley. Malays Appl Biol 36:85–87

    Google Scholar 

  • James MO (2011) Steroid catabolism in marine and freshwater fish. J Steroid Biochem 127:167–175

    Article  CAS  Google Scholar 

  • Janer G, Lavado R, Thibaut R, Porte C (2005) Effects of 17beta-estradiol exposure in the mussel Mytilus galloprovincialis: a possible regulating role for steroid acyltransferases. Aquat Toxicol 75:32–42

    Article  CAS  Google Scholar 

  • Jarosova B, Blaha L, Giesy JP, Hilscherova K (2014) What level of estrogenic activity determined by in vitro assays in municipal waste waters can be considered as safe? Environ Int 64:98–109

    Article  CAS  Google Scholar 

  • Ke YY, Bertin J, Gonthier R, Simard JN, Labrie F (2014) A sensitive, simple and robust LC-MS/MS method for the simultaneous quantification of seven androgen- and estrogen-related steroids in postmenopausal serum. J Steroid Biochem 144:523–534

    Article  CAS  Google Scholar 

  • Ketha H, Girtman A, Singh RJ (2015) Estradiol assays—the path ahead. Steroids 99:39–44

    Article  CAS  Google Scholar 

  • Kim SH, Tian Q, Fang JS, Sung SW (2015) Removal of 17-beta estradiol in water by sonolysis. Int Biodeter Biodegrad 102:11–14

    Article  Google Scholar 

  • Koal T, Schmiederer D, Pham-Tuan H, Rohring C, Rauh M (2012) Standardized LC-MS/MS based steroid hormone profile-analysis. J Steroid Biochem 129:129–138

    Article  CAS  Google Scholar 

  • Kuch HM, Ballschmiter K (2001) Determination of endocrine-disrupting phenolic compounds and estrogens in surface and drinking water by HRGC-(NCI)-MS in the picogram per liter range. Environ Sci Technol 35:3201–3206

    Article  CAS  Google Scholar 

  • Kuster M, López de Alda MJ, Hernando MD, Petrovic M, Martín-Alonso J, Barceló D (2008) Analysis and occurrence of pharmaceuticals, estrogens, progestogens and polar pesticides in sewage treatment plant effluents, river water and drinking water in the Llobregat River Basin (Barcelona, Spain). J Hydrol 358:112–123

    Article  CAS  Google Scholar 

  • LaFleur AD, Schug KA (2011) A review of separation methods for the determination of estrogens and plastics-derived estrogen mimics from aqueous systems. Anal Chim Acta 696:6–26

    Article  CAS  Google Scholar 

  • Li XN, Franke AA (2015) Improved profiling of estrogen metabolites by orbitrap LC/MS. Steroids 99:84–90

    Article  CAS  Google Scholar 

  • Liu JL, Wang RM, Huang B, Lin C, Wang Y, Pan XJ (2011a) Distribution and bioaccumulation of steroidal and phenolic endocrine disrupting chemicals in wild fish species from Dianchi Lake, China. Environ Pollut 159:2815–2822

    Article  CAS  Google Scholar 

  • Liu S, Ying GG, Zhao JL, Chen F, Yang B, Zhou LJ, Lai HJ (2011b) Trace analysis of 28 steroids in surface water, wastewater and sludge samples by rapid resolution liquid chromatography-electrospray ionization tandem mass spectrometry. J Chromatogr A 1218:1367–1378

    Article  CAS  Google Scholar 

  • Liu Y, Guan YT, Mizuno T, Tsuno H, Zhu WP (2009) A pretreatment method for GC-MS determination of endocrine disrupting chemicals in mollusk tissues. Chromatographia 69:65–71

    Article  CAS  Google Scholar 

  • Loos R, Locoro G, Contini S (2010) Occurrence of polar organic contaminants in the dissolved water phase of the Danube River and its major tributaries using SPE-LC-MS2 analysis. Water Res 44:2325–2335

    Article  CAS  Google Scholar 

  • Martyniuk CJ, Gerrie ER, Popesku JT, Ekker M, Trudeau VL (2007) Microarray analysis in the zebrafish (Danio rerio) liver and telencephalon after exposure to low concentration of 17alpha-ethinylestradiol. Aquat Toxicol 84:38–49

    Article  CAS  Google Scholar 

  • Matozzo V, Gagne F, Marin MG, Ricciardi F, Blaise C (2008) Vitellogenin as a biomarker of exposure to estrogenic compounds in aquatic invertebrates: a review. Environ Int 34:531–545

    Article  CAS  Google Scholar 

  • Moraes FC, Rossi B, Donatoni MC, de Oliveira KT, Pereira EC (2015) Sensitive determination of 17 beta-estradiol in river water using a graphene based electrochemical sensor. Anal Chim Acta 881:37–43

    Article  CAS  Google Scholar 

  • Nie MH, Yan CX, Dong WB, Liu M, Zhou JL, Yang Y (2015) Occurrence, distribution and risk assessment of estrogens in surface water, suspended particulate matter, and sediments of the Yangtze Estuary. Chemosphere 127:109–116

    Article  CAS  Google Scholar 

  • Patrolecco L, Capri S, Ademollo N (2015) Occurrence of selected pharmaceuticals in the principal sewage treatment plants in Rome (Italy) and in the receiving surface waters. Environ Sci Pollut R 22:5864–5876

    Article  CAS  Google Scholar 

  • Pojana G, Gomiero A, Jonkers N, Marcomini A (2007) Natural and synthetic endocrine disrupting compounds (EDCs) in water, sediment and biota of a coastal lagoon. Environ Int 33:929–936

    Article  CAS  Google Scholar 

  • Popescu IL, Aboul-Enein H, Tanase IG, Ghica I, Bala C (2008) Validation of a quantitative method determination of estradiol in pharmaceutical products using UV–vis molecular absorption spectrometry. Anal Lett 41:3272–3296

    Article  CAS  Google Scholar 

  • Reyhanian N, Volkova K, Hallgren S, Bollner T, Olsson PE, Olsen H, Hallstrom IP (2011) 17alpha-Ethinyl estradiol affects anxiety and shoaling behavior in adult male zebra fish (Danio rerio). Aquat Toxicol 105:41–8

    Article  CAS  Google Scholar 

  • Ripolles C, Ibanez M, Sancho JV, Lopez FJ, Hernandez F (2014) Determination of 17 beta-estradiol and 17 alpha-ethinylestradiol in water at sub-ppt levels by liquid chromatography coupled to tandem mass spectrometry. Anal Methods-Uk 6:5028–5037

    Article  CAS  Google Scholar 

  • Robinson BJ, Hellou J (2009) Biodegradation of endocrine disrupting compounds in harbour seawater and sediments. Sci Total Environ 407:5713–5718

    Article  CAS  Google Scholar 

  • Robles TA (2010) Use of oral contraceptives, decision making in medicine (third edition), pp. 616–619

  • Sebők A, Vasanits-Zsigrai A, Helenkár A, Záray G, Molnár-Perl I (2009) Multiresidue analysis of pollutants as their trimethylsilyl derivatives, by gas chromatography–mass spectrometry. J Chromatogr A 1216:2288–2301

    Article  Google Scholar 

  • Shinichi Miyagawa TS, Taisen Iguchi (2016) Handbook of hormones

  • Skotnicka-Pitak J, Garcia EM, Pitak M, Aga DS (2008) Identification of the transformation products of 17 alpha-ethinylestradiol and 17 beta-estradiol by mass spectrometry and other instrumental techniques. Trac-Trend Anal Chem 27:1036–1052

    Article  CAS  Google Scholar 

  • Tan Y, Wei TX (2015) Detection of 17 beta-estradiol in water samples by a novel double-layer molecularly imprinted film-based biosensor. Talanta 141:279–287

    Article  CAS  Google Scholar 

  • Torres NH, Aguiar MM, Ferreira LFR, Americo JHP, Machado AM, Cavalcanti EB, Tornisielo VL (2015) Detection of hormones in surface and drinking water in Brazil by LC-ESI-MS/MS and ecotoxicological assessment with Daphnia magna. Environ Monit Assess 187

  • Williams RJ, Johnson AC, Smith JJL, Kanda R (2003) Steroid estrogens profiles along river stretches arising from sewage treatment works discharges. Environ Sci Technol 37:1744–1750

    Article  CAS  Google Scholar 

  • Wise A, O’Brien K, Woodruff T (2011) Are oral contraceptives a significant contributor to the estrogenicity of drinking water? Environ Sci Technol 45:51–60

    Article  CAS  Google Scholar 

  • Xu L, Spink DC (2008) Analysis of steroidal estrogens as pyridine-3-sulfonyl derivatives by liquid chromatography electrospray tandem mass spectrometry. Anal Biochem 375:105–114

    Article  CAS  Google Scholar 

  • Xu X, Akki S, Silverman S, Werth CJ (2013) Detection of 17b-estradiol in drinking water sources using DNA aptamer-based electrochemical detection. Abstr Pap Am Chem S 245

  • Yan ZH, Lu GH, Liu JC, Jin SG (2012) An integrated assessment of estrogenic contamination and feminization risk in fish in Taihu Lake, China. Ecotoxicol Environ Saf 84:334–340

    Article  CAS  Google Scholar 

  • Zou YM, Zhang Z, Shao XL, Chen Y, Wu XY, Yang LQ, Zhu JJ, Zhang DM (2014) Hollow-fiber-supported liquid-phase microextraction using an ionic liquid as the extractant for the pre-concentration of bisphenol A, 17-beta-estradiol, estrone and diethylstilbestrol from water samples with HPLC detection. Water Sci Technol 69:1028–1035

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was supported by the state of Hungary under grant OTKA PD-109099.

Author information

Authors and Affiliations

  1. Department of Analytical Biochemistry, Institute of Biochemistry and Medical Chemistry, University of Pécs, Pécs, 7624, Hungary

    Péter Avar, Gábor Maász & Anikó Takátsy

  2. Adaptive Neuroethology, Department of Experimental Zoology, Tihany, 8237, Hungary

    Zita Zrínyi, Gábor Maász, Sándor Lovas & Zsolt Pirger

  3. Department of Hydrozoology, Balaton Limnological Institute, MTA Centre for Ecological Research, Tihany, 8237, Hungary

    László G.-Tóth

Authors
  1. Péter Avar
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Zita Zrínyi
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Gábor Maász
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Anikó Takátsy
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Sándor Lovas
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. László G.-Tóth
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Zsolt Pirger
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Péter Avar.

Additional information

Responsible editor: Ester Heath

Highlights: Method is proposed for simultaneous determination of 17β-estradiol and 17α-ethinyl estradiol. Derivatization is necessary to reach low LOQ. Low nanograms per liter presence of estrogens in selected European Rivers has been detected.

Electronic supplementary material

Below is the link to the electronic supplementary material.

ESM 1

(PPTX 1288 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Avar, P., Zrínyi, Z., Maász, G. et al. β-Estradiol and ethinyl-estradiol contamination in the rivers of the Carpathian Basin. Environ Sci Pollut Res 23, 11630–11638 (2016). https://doi.org/10.1007/s11356-016-6276-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11356-016-6276-2

Keywords

Search

Navigation