Skip to main content
SpringerLink
Log in

Determination of testosterone and its photodegradation products in surface waters using solid-phase extraction followed by LC–MS/MS analysis

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

Abstract

The formation of several by-products from the photodegradation of testosterone was previously observed under laboratory conditions. The objectives of the manuscript were to complete the identification of testosterone’s photoproducts and to develop an analytical method for the detection of testosterone as well as its three main photoproducts in natural sunlit surface waters. To accomplish these tasks, an efficient extraction method was developed based on solid-phase extraction, followed by the use of liquid chromatography coupled to tandem mass spectrometry, a selective and sensitive detection method. This analytical procedure has the capability of detecting target analytes in the ng/L range, with recoveries above 80 %. The methodology was successfully applied to the analysis of testosterone and its photoproducts in several surface waters.

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

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4

Similar content being viewed by others

References

  • Backe WJ, Ort C, Brewer AJ, Field JA (2011) Analysis of androgenic steroids in environmental waters by large-volume injection liquid chromatography–tandem mass spectrometry. Anal Chem 83:2622–2630

    Article  CAS  Google Scholar 

  • Bandelj E, van den Heuvel MR, Leush FDL, Shannon N, Taylor S, McCarthy LH (2006) Determination of the androgenic potency of whole effluents using mosquitofish and trout bioassays. Aquat Toxicol 80:237–248

    Article  CAS  Google Scholar 

  • Barbosa IR, Nogueira AJA, Soares AMVM (2008) Acute and chronic effects of testosterone and 4-hydroxyandrostenedione to the crustacean Daphnia magna. Ecotox Environ Safe 71:757–764

    Article  CAS  Google Scholar 

  • Barel-Cohen K, Shore S, Shemesh M, Wenzel A, Mueller J, Kronfeld-Schor N (2006) Monitoring of natural and synthetic hormones in a polluted river. J Environ Manag 78:16–23

    Article  CAS  Google Scholar 

  • Boxall ABA, SinClair CJ, Fenner K, Kolpin D, Maund S (2004) When synthetic chemicals degrade in the environment. Environ Sci Technol 38:368A–375A

    Article  CAS  Google Scholar 

  • Busetti F, Linge KL, Heitz A (2009) Analysis of pharmaceuticals in indirect potable reuse systems using solid-phase extraction and liquid chromatography–tandem mass spectrometry. J Chromatogr A 1216:5807–5818

    Article  CAS  Google Scholar 

  • Casey FXM, Hakk H, Simunek J, Larsen GL (2004) Fate and transport of testosterone in agricultural soils. Environ Sci Technol 38:790–798

    Article  CAS  Google Scholar 

  • Chapman OL, Rettig TA, Griswold AA, Dutton AI, Fitton P (1963) Photochemical rearrangements of 2-cyclohexenones. Tetrahedron Lett 29:2049–2055

    Article  Google Scholar 

  • Chapman OL, Sieja JB, Welstead WJ Jr (1966) Stereospecific rearrangement of an excited triplet ketone. JACS 88:161–162

    Article  CAS  Google Scholar 

  • Ekern S, Fenner K, Singer HP, Schwarzenbach RP, Hollender J (2009) Identification of transformation products of organic contaminants in natural waters by computer-aided prediction and high-resolution mass spectrometry. Environ Sci Technol 43:7039–7046

    Article  Google Scholar 

  • Escher B, Fenner K (2011) Recent advances in environmental risk assessment of transformation products. Environ Sci Technol 45:3835–3847

    Article  CAS  Google Scholar 

  • Finlay-Moore O, Hartel PG, Cabrera ML (2000) 17ß-Estradiol and testosterone in soil and runoff from grasslands amended with broiler litter. J Environ Qual 29:1604–1611

    Article  CAS  Google Scholar 

  • Gonçalves C, Perez S, Osorio V, Petrovic M, Alpendurada MF, Barcelo D (2011) Photofate of oseltamivir (Tamiflu) and oseltamivir carboxylate under natural and simulated solar irradiation: kinetics, identification of the transformation products, and environmental occurrence. Environ Sci Technol 45:4307–4314

    Article  Google Scholar 

  • Jacobsen AM, Lorenzen A, Chapman R, Topp E (2005) Persistence of testosterone and 17β-estradiol in soils receiving swine manure or municipal biosolids. J Environ Qual 34:861–871

    Article  CAS  Google Scholar 

  • Kolodziej EP, Harter T, Sedlak DL (2004) Dairy wastewater, aquaculture, and spawning fish as sources of steroid hormones in the aquatic environment. Environ Sci Technol 38:6377–6384

    Article  CAS  Google Scholar 

  • Kolpin DW, Furlong ET, Meyer MT, Thurman EM, Zaugg SD, Barber LB, Buxton HT (2002) Pharmaceutical, hormones, and other organic wastewater contaminants in U.S. streams, 1999–2000: a national reconnaissance. Environ Sci Technol 36:1202–1211

    Article  CAS  Google Scholar 

  • la Farre M, Perez S, Kantiani L, Barcelo D (2008) Fate and toxicity of emerging pollutants, their metabolites and transformation products in the aquatic environment. Trends Anal Chem 27:991–1007

    Article  CAS  Google Scholar 

  • Labadie P, Budzinski H (2005) Development of an analytical procedure for determination of selected estrogens and progestagens in water samples. Anal Bioanal Chem 381:1199–1205

    Article  CAS  Google Scholar 

  • Liu S, Ying GG, Zhao JL, Chen F, Yang B, Zhou LJ, Lai HJ (2011) 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 

  • Lopez de Alda MJ, Barcelo D (2001) Review of analytical methods for the determination of estrogens and progestogens in waste waters. Fresenius J Anal Chem 371:437–447

    Article  CAS  Google Scholar 

  • Lorenzen A, Chapman R, Hendel JG, Topp E (2005) Persistence and pathways of testosterone dissipation in agricultural soil. J Environ Qual 34:854–860

    Article  CAS  Google Scholar 

  • Nagabhushanam R, Kulkarni GK (1981) Effect of exogenous testosterone on the androgenic gland and testis of a marine penaied prawn, Parapenaeopsis hardwickii (Miers) (Crustacea, Decopoda, Penaeidae). Aquaculture 23:19–27

    Article  CAS  Google Scholar 

  • Petrovic M, Barcelo D (2007) LC–MS for identifying photodegradation products of pharmaceuticals in the environment. Trends Anal Chem 26:486–493

    Article  CAS  Google Scholar 

  • Petrovic M, Gros M, Barcelo D (2006) Multi-residue analysis of pharmaceuticals in wastewater by ultra-performance liquid chromatography–quadrupole-time-of-flight mass spectrometry. J Chromatogr A 1124:68–81

    Article  CAS  Google Scholar 

  • Rodil R, Quintana J, López-Mahía P, Muniategui-Lorenzo S, Prada-Rodríguez D (2009) Multi-residue analytical method for the determination of emerging pollutants in water by solid-phase extraction and liquid chromatography–tandem mass spectrometry. J Chromatogr A 1216:2958–2969

    Article  CAS  Google Scholar 

  • Schanzer W (1996) Metabolism of anabolic androgenic steroids. Clin Chem 42:1001–1020

    Google Scholar 

  • Shao B, Chen D, Zhang J, Wu Y, Sun C (2009) Determination of 76 pharmaceutical drugs by liquid chromatography–tandem mass spectrometry in slaughterhouse wastewater. J Chromatogr A 1216:8312–8318

    Article  CAS  Google Scholar 

  • Su MD (1996) The role of spin–orbit coupling and symmetry in photochemical rearrangements of α, β-unsaturated cyclic ketones. Chem Phys 205:277–308

    Article  CAS  Google Scholar 

  • Vulliet E, Cren-Olivé C (2011) Screening of pharmaceuticals and hormones at the regional, in surface and ground-waters intended to human consumption. Environ Pollut 159:2929–2934

    Article  CAS  Google Scholar 

  • Vulliet E, Baugros JB, Flament-Waton MM, Grenier-Loustalot MF (2007) Analytical methods for the determination of selected steroid sex hormones and corticosteroids in wastewater. Anal Bioanal Chem 387:2143–2151

    Article  CAS  Google Scholar 

  • Vulliet E, Wiest L, Baudot R, Grenier-Loustalot MF (2008) Multi-residue analysis of steroids at sub ng/L levels in surface and ground-waters using liquid chromatography coupled to tandem mass spectrometry. J Chromatogr A 1210:84–91

    Article  CAS  Google Scholar 

  • Vulliet E, Falletta M, Marote M, Lomberget T, Païssé JO, Grenier-Loustalot MF (2010) Light induced degradation of testosterone in waters. Sci Total Environ 408:3554–3559

    Article  CAS  Google Scholar 

  • Waters JA, Kondo Y, Witkop B (1972) Photochemistry of steroids. J Pharm Sci 61:321–334

    Article  CAS  Google Scholar 

  • Williams JR, Moore RH, Li R, Weeks CM (1980) Photochemistry of 11α- and 11β-hydroxy steroidal 1,4-dien-3-ones and 11α- and 11β-hydroxy steroidal bicycle[3.1.0]hex-3-en-2-ones in neutral and acidic media. J Org Chem 45:2324–2331

    Article  CAS  Google Scholar 

  • Wu C, Spongberg AL, Witter JD (2008) Use of solid phase extraction and liquid chromatography–tandem mass spectrometry for simultaneous determination of various pharmaceuticals in surface water. Int J Environ Anal Chem 88:1033–1048

    Article  CAS  Google Scholar 

  • Yamamoto A, Kakutani N, Yamamoto K, Kamiura T, Miyakoda H (2006) Steroid hormone profiles of urban and tidal rivers using LC/MS/MS equipped with electrospray ionization and atmospheric pressure photoionization sources. Environ Sci Technol 40:4132–4137

    Article  CAS  Google Scholar 

  • Zhang HC, Yu XJ, Yang WC, Peng JF, Xu T, Yin DQ, Hu XL (2011) MCX based solid phase extraction combined with liquid chromatography tandem mass spectrometry for the simultaneous determination of 31 endocrine-disrupting compounds in surface water of Shanghai. J Chromatogr B Analyt Technol Biomed Life Sci 879:2998–3004

    Article  CAS  Google Scholar 

  • Zimmerman HE, Lewis RG, McCullough JJ, Padwa A, Staley S, Semmelhack M (1966) The relation of cyclohexenone to cyclohaxadienone rearrangements. Mechanistic organic photochemistry. JACS 88:159–161

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Département Service Central d’Analyse, Institut des Sciences Analytiques, UMR5280 CNRS, Equipe TRACES, Université de Lyon, ENS-Lyon, 5 rue de la Doua, 69100, Villeurbanne, France

    Emmanuelle Vulliet & Barbara Giroud

  2. Département Laboratoire des Sciences Analytiques, Institut des Sciences Analytiques, UMR5280 CNRS, Université de Lyon, ENS-Lyon, 5 rue de la Doua, 69100, Villeurbanne, France

    Pedro Marote

Authors
  1. Emmanuelle Vulliet
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Barbara Giroud
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Pedro Marote
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Emmanuelle Vulliet.

Additional information

Responsible editor: Philippe Garrigues

Rights and permissions

Reprints and permissions

About this article

Cite this article

Vulliet, E., Giroud, B. & Marote, P. Determination of testosterone and its photodegradation products in surface waters using solid-phase extraction followed by LC–MS/MS analysis. Environ Sci Pollut Res 20, 1021–1030 (2013). https://doi.org/10.1007/s11356-012-1041-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11356-012-1041-7

Keywords

Search

Navigation