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.
Keywords Alkylphenols - analytical method development - endocrine disrupting compounds - estrogens - nonylphenol - solid phase extraction - sediment - total suspended solids - ultrasonication - water
ESS-Submission Editor: Prof. Dr. Thomas Braunbeck (Braunbeck@zoo.uni-heidelberg.de