Skip to main content
SpringerLink
Log in

Determination of phenolic and steroid endocrine disrupting compounds in environmental matrices

  • Research Article
  • Area 6.4 · Monitoring and Fate of Persistent Chemicals
  • Published:
Environmental Science and Pollution Research Aims and scope Submit manuscript

Abstract

Background. aim and scope

Many pollutants have received significant attention due to their potential estrogenic effect and are classified as endocrine disrupting compounds (EDCs). EDCs comprise many classes of organic compounds. The development or optimization of analytical protocols for the simultaneous determination of EDCs in environmental samples is an analytical challenge because these compounds exhibit different physicochemical characteristics, they occur in the aquatic environment in relatively low concentrations and, furthermore, environmental samples are considered as complex matrices.

The aim of this study is the development of analytical methods for the simultaneous determination of phenolic and steroid EDCs in aqueous and solid samples. The target compounds are 4-nonylphenol, 4-octylphenol, their ethoxylate oligomers (monoand di-ethoxylates of nonylphenol and octylphenol), bisphenol A, the estrogens (estriol, estrone, 17β-estradiol, 17α-estradiol) and the synthetic steroids (mestranol and 17α-ethynylestradiol).

Materials and Methods

Solid phase extraction employing Oasis HLB cartridges and different elution solvents was used for the recovery studies of the target compounds from various types of water samples (ultrapure water, artificial seawater, river water and seawater). Ultrasonic assisted extraction was applied for the recovery of the target EDCs from the solid samples. The recoveries were assessed using various solvents for the extraction and the elution of EDCs from different SPE cartridges used for clean up. Gas chromatography-mass spectrometry after derivatization with N,O-bis(trimethylsilyl)-trifluoroacetamide was employed for the determination of these compounds.

Results and Discussion

The recovery rates of three elution solvents (methanol, acetone and ethylacetate) for the extraction of target EDCs from artificial seawater were assessed after preconcentration on SPE cartridges. Acetone showed better recoveries and was further tested for its extraction efficiency in different water types (river water, seawater). Ultrasonic assisted extraction was used for the recovery of target EDCs from solid matrices. Acetone, methanol, mixture of acetone-methanol (1:1) and ethylacetate were used as extraction solvents. Ethylacetate and the mixture of acetone-methanol (1:1) exhibited better extraction efficiencies. An additional clean up step was necessary for sediment samples. Different SPE cartridges were employed for clean up of the extracts (Oasis HLB, C18, Florisil, silica, combination of silica and alumina). Florisil cartridges were finally used. The proposed methods were further validated on the determination of target EDCs in field collected samples (river water, seawater, wastewater, total suspended solids and sediments) from the major area of Thessaloniki, Greece.

Conclusions

Efficient and accurate integrated methods for the simultaneous determination of alkylphenols (nonylphenol, octylphenol), their ethoxylate oligomers (mono-and di-ethoxylate of nonylphenol and octylphenol), bisphenol A and steroids (estriol, estrone, 17β-estradiol, 17α-estradiol, mestranol and 17α-ethynylestradiol) in aqueous and solid samples were developed. The proposed methods were applied for the determination of the target compounds in representative environmental samples in the area of Thessaloniki, Northern Greece.

Recommendations and Perspectives

This study confirms the occurrence of selected EDCs in inland and marine waters in the area of Thessaloniki, Northern Greece. Since there is no previous data on the occurrence of the target EDCs in the major area, an extended survey is in progress to evaluate the occurrence and fate of these compounds.

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

Similar content being viewed by others

References

  • Ahel M, Giger W, Koch M (1994): Behaviour of alkylphenol polyethoxylate surfactants in the aquatic environment: I. Occurrence and transformation in sewage treatment. Water Res 28, 1131–1142

    Article  CAS  Google Scholar 

  • Ahel M, Schaffner C, Giger W (1996): Behaviour of alkylphenol polyethoxylate surfactants in the aquatic environment: III. Occurrence and elimination of their persistent metabolites during infiltration of river water to groundwater. Water Res 30, 37–46

    Article  CAS  Google Scholar 

  • Andreu V, Ferrer E, Rubio JL, Font G, Picó Y (2007): Quantitative determination of octylphenol, nonylphenol, alkylphenol ethoxylates and alcohol ethoxylates by pressurized liquid extraction and liquid chromatography-mass spectrometry in soils treated with sewage sludges. Sci Tot Environ 378(1–2) 124–129

    Article  CAS  Google Scholar 

  • Bartolomè L, Cortazar E, Raposo JC, Usobiaga A, Zuloaga O, Etxebarria N, Fernádez LA (2005): Simultaneous microwaveassisted extraction of polycyclic aromatic hydrocarbons, polychlorinated biphenyls, phthalate esters and nonylphenols in sediments. J Chromatogr A 1068, 229–236

    Article  Google Scholar 

  • Basheer C, Parthiban A, Jayaraman A, Kee Lee H, Valiyaveettil S (2005): Determination of alkylphenols and bisphenol-A. A comparative investigation of functional polymer-coated membrane microextraction and solid-phase microextraction techniques. J Chromatogr A 1087, 274–285

    Article  CAS  Google Scholar 

  • Céspedes R, Lacorte S, Raldua D, Ginebreda A, Barcelo D, Pina B (2005): Distribution of endocrine disruptors in the Llobregat River basin (Catalonia NE Spain). Chemosphere 61, 1710–1719

    Article  Google Scholar 

  • Eaton AD, Clesceri LS, Greenberg AE, Franson MAH (1995): Standard methods for the examination of water and wastewater, 19th edition. American Water Works Association, Water Environment Federation, Section 8010E.4b2

  • European Commission (1997): European Workshop on the Impact of Endocrine Disrupters in Human Health and the Environment. Environment and Climate Research Programme, DG XII, Report EUR 17549, 1997

  • European Commission (2001): Decision No 2455/2001/EC of the European Parliament and of the Council of 20 November 2001 establishing the list of priority substances in the field of water policy and amending Directive 2000/60/EC

  • European Commission (2002): Commission Decision 2002/657/EC implementing Council Directive 96/23/EC concerning the performance of analytical methods and the interpretation of results

  • European Commission (2003): Directive 2003/53/EC of the European Parliament and of the council of 18 June 2003 amending for the 26th time Council Directive 76/769/EEC relating to restrictions on the marketing and use of certain dangerous substances and preparations (nonylphenol, nonylphenol ethoxylate and cement)

  • Fiedler S, Foerster M, Glaser B, Zech W (2006): Alkylphenols in sediments of the Atlantic Rainforest south-west of São Paulo, Brazil. Chemosphere 66, 212–218

    Article  Google Scholar 

  • Fu M, Li Z, Gao H (2007): Distribution characteristics of nonylphenol in Jiaozhou Bay of Qingdao and its adjacent rivers. Chemosphere, doi:10.1016/j.chemosphere.2007.04.061

  • Fürhacker M, Scharf S, Weber H (2000): Bisphenol A: Emissions from point sources. Chemosphere 41, 751–756

    Article  Google Scholar 

  • Gibson R, Wang M-J, Padgett E, Beck AJ (2005): Analysis of 4-nonylphenols, phthalates, and polychlorinated biphenyls in soils and biosolids. Chemosphere 61, 1336–1344

    Article  CAS  Google Scholar 

  • González S, Petrovic M, Barcelo D (2004): Simultaneous extraction and fate of linear alkylbenzene sulfonates, coconut diethol amides, nonylphenol ethoxylates and their degradation products in wastewater treatment plants, receiving coastal waters and sediments in the Catalonian area (NE Spain). J Chromatogr A 1052, 111–120

    Article  Google Scholar 

  • Isobe T, Nishiyama H, Nakashima A, Tanaka H (2001): Distribution and behavior of nonylphenol, octylphenol and nonylphenol monoethoxylate in Tokyo Metropolitan area: Their association with aquatic particles and sedimentary distributions. Environ Sci Technol 35, 1041–1049

    Article  CAS  Google Scholar 

  • Jeannot R, Sabik H, Sauvard E, Dagnac T, Dohrendorf K (2002): Determination of endocrine-disrupting compounds in environmental samples using gas and liquid chromatography with mass spectrometry. J Chromatogr A 974, 143–159

    Article  CAS  Google Scholar 

  • Jonkers N, Laane RWPM, de Voogt P (2005): Sources and fate of nonylphenol ethoxylates and their metabolites in the Dutch coastal zone of the North Sea. Mar Chem 96, 115–135

    Article  CAS  Google Scholar 

  • Kawaguchi M, Inoue K, Yoshimura M, Sakui N, Okanouchi N, Ito R, Yoshimura Y, Nakazawa H (2004): Trace analysis of phenolic xenoestrogens in water samples by stir bar sorptive extraction with in situ derivatization and thermal desorptiongas chromatography-mass spectrometry. J Chromatogr A 1041, 19–26

    Article  CAS  Google Scholar 

  • Knepper TP, Berna JL (2003): Surfactants properties, production, and environmental aspects in analysis and fate of surfactants in the aquatic environment. In: Knepper TP, Barcelì D, De Voogt P (eds), Analysis and fate of surfactants in the aquatic environment. Elsevier Science BV Amsterdam, The Netherlands, pp 17–18

    Google Scholar 

  • Laganà A, Bacaloni A, De Leva I, Faberi A, Fago G, Marino A (2004): Analytical methodologies for determining the occurrence of endocrine disrupting chemicals in sewage treatment plants and natural waters. Anal Chim Acta 501, 79–88

    Article  Google Scholar 

  • Liu R, Zhou JL, Wilding A (2004a): Simultaneous determination of endocrine disrupting phenolic compounds and steroids in water by solid-phase extraction-gas chromatography-mass spectrometry. J Chromatogr A 1022, 179–189

    Article  CAS  Google Scholar 

  • Liu R, Zhou JL, Wilding A (2004b): Microwave-assisted extraction followed by gas chromatography-mass spectrometry for the determination of endocrine disrupting chemicals in river sediments. J Chromatogr A 1038, 19–26

    Article  CAS  Google Scholar 

  • Long JLA, House WA, Parker A, Rae JE (1998): Micro-organic compounds associated with sediments in the Humber rivers. Sci Total Env 210/211, 229–253

    Article  CAS  Google Scholar 

  • Lye CM, Frid CLJ, Gill ME, Cooper DW, Jones DM (1999): Estrogenic Alkylphenols in Fish Tissues, Sediments, and Waters from the U.K. Tyne and Tees Estuaries. Environ Sci Technol 33, 1009–1014

    Article  CAS  Google Scholar 

  • Metzler M, Pfeiffer E (2001): Chemistry of natural and anthropogenic endocrine active compounds. In: Metzler M (ed), Endocrine Disruptors, Part I. The Handbook of Environmental Chemistry. Springer-Verlag, Berlin, Heidelberg, pp 63–80

    Google Scholar 

  • Noppe H, Verslycke T, De Wulf E, Verheuden K, Monteyne E, Van Caeter P, Janssen CR, De Brabander HF (2007): Occurrence of estrogens in the Scheldt estuary: A 2-year survey. Ecotox Environ Saf 66, 1–8

    Article  CAS  Google Scholar 

  • Núñez L, Turiel E, Tadeo JL (2007): Determination of nonylphenol and nonylphenol ethoxylates in environmental solid samples by ultrasonic-assisted extraction and high performance liquid chromatography-fluorescence detection. J Chromatogr A 1146(2) 157–163

    Article  Google Scholar 

  • Peng X, Whang Z, Yang C, Chen F, Mai B (2006): Simultaneous determination of endocrine-disrupting phenols and steroid estrogens in sediment by gas chromatography-mass spectrometry. J Chromatogr A 1116, 51–56

    Article  CAS  Google Scholar 

  • Petrovic M, Eljarrat E, Lìpez de Alda MJ, Barcelì D (2002): Recent advances in mass spectrometric analysis related to endocrine disrupting compounds in aquatic environmental samples. J Chromatogr A 974, 23–51

    Article  CAS  Google Scholar 

  • Petrovic M, Barcelì D, Diaz A, Ventura F (2003): Low nanogram per liter determination of halogenated nonylphenols, nonylphenol carboxylates, and their non-halogenated precursors in water and sludge by liquid chromatography electrospray tandem mass spectrometry. J Am Soc Mass Spectrom 14, 516–527

    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 Intern 33(7) 929–936

    Article  CAS  Google Scholar 

  • Shareef A, Angove MJ, Welss JD (2006): Optimization of silylation using N-methyl-N-(trimethylsilyl)-trifluoroacetamide, N,O-bis(trimethylsilyl)-trifluoroacetamide and N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide for the determination of the estrogens estrone and 17a-ethynylestradiol by gas chromatography-mass spectrometry. J Chromatogr A 1108, 121–128

    Article  CAS  Google Scholar 

  • Snyder SA, Keith TL, Verbugge DA, Snyder EM, Gross TS, Kannan K, Giesy JP (1999): Analytical methods for the detection of selected estrogenic compounds in aqueous mixtures. Environ Sci Technol 33, 2814–2820

    Article  CAS  Google Scholar 

  • Soliman MA, Pedersen JA, Suffet IH (2004): Rapid gas chromatography — mass spectrometry screening method for human pharmaceuticals, hormones, antioxidants and plasticizers in water. J Chromatogr A 1029, 223–237

    Article  CAS  Google Scholar 

  • Sonnenschein C, Soto MA (1998): An updated review of environmental estrogen and androgen mimics and antagonists. J Steroid Biochem Molec Biol 65, 143–150

    Article  CAS  Google Scholar 

  • Stachel B, Ehrhorn U, Heemken OP, Lepom P, Reincke H, Sawal G, Theobald N (2003): Xenoestrogens in the River Elbe and its tributaries. Environ Pollut 124, 497–507

    Article  CAS  Google Scholar 

  • Staples AC, Dorn BP, Klecka MG, O’Block TS, Harris RL (1998): A review of the environmental fate, effects, and exposures of bisphenol A. Chemosphere 36, 2149–2173

    Article  CAS  Google Scholar 

  • Vethaak AD, Lahr J, Schrap SM, Belfroid AC, Rijs GBJ, Gerritsen A, de Boer J, Bulder AS, Grinwis GCM, Kuiper RV, Legler J, Murk TAJ, Peijenburg W, Verhaar HJM, de Voogt P (2005): An integrated assessment of estrogenic contamination and biological effects in the aquatic environment of The Netherlands. Chemosphere 59, 511–524

    Article  CAS  Google Scholar 

  • Voutsa D, Hartmann P, Schaffer C, Giger W (2006): Benzotriazols, alkylphenols and bisphenol A in municipal wastewaters and in the Glatt River, Switzerland. Env Sci Pollut Res 13, 333–341

    Article  CAS  Google Scholar 

  • Ying G-G, Williams B, Kookana R (2002a): Environmental fate of alkylphenols and alkylphenol ethoxylates — A review. Environ Intern 28, 215–226

    Article  CAS  Google Scholar 

  • Ying G-G, Kookana SR, Ru Y-J (2002b): Occurrence and fate of hormone steroids in the environment. Environ Intern 28, 545–551

    Article  CAS  Google Scholar 

  • US EPA (1997): Special report on Environmental Endocrine Disruption: An Effects Assessment and Analysis. Office of Research and Development, EPA/630/R-96/012, Washington, DC

  • US EPA, Title 40 Code of Federal Regulations Part 136 Guidelines establishing test procedures for the analysis of pollutants. Appendix B. Definition and procedure for the determination of the Method Detection Limit — Revision 1.11

  • Zhang K, Zuo Y (2005): Pitfalls and solution for simultaneous determination of estrone and 17+—ethinylestradiol by gas chromatography — mass spectrometry after derivatization with N, O-bis(trimethylsilyl)trifluoroacetamide. Anal Chim Acta 554, 190–196

    Article  CAS  Google Scholar 

  • Zuccato E, Castiglioni S, Fanelli R, Reitano G, Bagnati R, Chiabrando C, Pomati F, Rossetti C, Calamari D (2006): Pharmaceuticals in the Environment in Italy: Causes, Occurrence, Effects and Control. Env Sci Pollut Res 13, 15–21

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Chemistry Department, Environmental Pollution Control Laboratory, Aristotle University of Thessaloniki, 54124, Thessaloniki, Greece

    Anastasia Arditsoglou & Dimitra Voutsa

Authors
  1. Anastasia Arditsoglou
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Dimitra Voutsa
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Dimitra Voutsa.

Additional information

ESS-Submission Editor: Prof. Dr. Thomas Braunbeck (Braunbeck@zoo.uni-heidelberg.de

Rights and permissions

Reprints and permissions

About this article

Cite this article

Arditsoglou, A., Voutsa, D. Determination of phenolic and steroid endocrine disrupting compounds in environmental matrices. Environ Sci Pollut Res 15, 228–236 (2008). https://doi.org/10.1065/espr2007.12.459

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1065/espr2007.12.459

Keywords

Search

Navigation