Determination of phenolic and steroid endocrine disrupting compounds in environmental matrices

Abstract

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 (mono- and di-ethoxylates of nonylphenol and octylphenol), bisphenol A, the estrogens (estriol, estrone, 17beta-estradiol, 17alpha-estradiol) and the synthetic steroids (mestranol and 17alpha-ethynylestradiol). 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. 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, 17beta-estradiol, 17alpha-estradiol, mestranol and 17alpha-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. 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.