Determination of phenolic and steroid endocrine disrupting compounds in environmental matrices
- 738 Downloads
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.
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.
KeywordsAlkylphenols analytical method development endocrine disrupting compounds estrogens nonylphenol solid phase extraction sediment total suspended solids ultrasonication water
Unable to display preview. Download preview PDF.
- 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) 124–129CrossRefGoogle 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.4b2Google Scholar
- 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, 1997Google Scholar
- 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/ECGoogle Scholar
- European Commission (2002): Commission Decision 2002/657/EC implementing Council Directive 96/23/EC concerning the performance of analytical methods and the interpretation of resultsGoogle Scholar
- 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)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.2007.04.061Google 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, 111–120CrossRefGoogle 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, 19–26CrossRefGoogle 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 17–18Google 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 63–80Google 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, 516–527CrossRefGoogle 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, 121–128CrossRefGoogle 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, 511–524CrossRefGoogle 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, DCGoogle Scholar
- 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 1.11Google Scholar