Optimization and Application of a GC-MS Method for the Determination of Endocrine Disruptor Compounds in Natural Water

Abstract

Bisphenol A (BPA), 4-nonylphenol (4NP), estradiol (E 2 ), and ethinylestradiol (EE 2 ) are considered as endocrine disruptors or mutagens. These compounds are commonly called endocrine disrupter chemicals (EDCs). BPA and 4NP are widely used as plastic additives, lacquers, resins, or surfactants, while E 2 is one of the predominant female sex hormones during the reproductive years, and EE 2 is an estrogen derived from estradiol, used in the production of contraceptive pills. All of these can be usually found in wastewater. In Mexico, it is common for water from rivers, lakes, and canyons to be reused for different purposes. Unfortunately, there is little information on the concentration of many of the pollutants present in such bodies of water. To determine the presence of these compounds in samples of wastewater in the Apatlaco River, an accurate and reproducible method was developed by coupling gas chromatography to mass spectrometry (GC-MS). A solid-phase extraction with Chromabond RP-18 cartridges was carried out, and the elution was performed with an acetone/methanol mixture. After isolation, the solvent was removed and a silylation step was carried out using N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA). Recoveries for spiked samples were between 71.8% and 111.0%. The instrumental limits of detection (IDL) ranged between 24.7 and 37.0 ng mL −1 . In total, 16 samples were taken in 2015 at the microbasin of the Apatlaco River, located in the state of Morelos. The maximum concentrations found were 4NP (85.5 ng mL −1 ), BPA (174.6 ng mL −1 ), E 2 103.6 (ng mL −1 ), and EE 2 (624.3 ng mL −1 ).

Bisphenol A and Metabolites in Meat and Meat Products: Occurrence, Toxicity, and Recent Development in Analytical Methods

“…Before analysing samples by GC-MS, a derivatization step is needed to modify the slightly polar properties of BPA molecules thus producing a compound that is suitable for GC analysis (lower polarity, higher volatility, higher stability, and higher peak efficiency and detectability) [ 113 ]. Frequently used derivatization approaches include silylation [ 114 ], and acetylation [ 12 ]. Extracts obtained after clean-up steps were derivatized with commercially available derivatization reagents, such as acetic anhydride [ 9 , 12 , 14 ], N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) [ 115 ], N-methyl-N(trimethylsilyl)-trifluoroacetamide [ 6 ], and pentafluorobenzoylchloride (PFBCl, 5% v / v in hexane) [ 13 ].…”

“…While m/z 213 ion was used for the quantification, m/z 228, 255, 270, and 312 have been used for the qualification of BPA in extracts from meat and fish samples in GC-MS [ 81 , 88 ]. On the other hand, mass spectrum of BPA derivatized with BSTFA containing 1% trimethylchlorosilane (TMCS) showed m/z 357 as the most abundant ion, used for the quantification, with m/z 372, 207, and 73 being used for the confirmation [ 114 , 116 ]. Geens et al used selected ion monitoring mode for the analysis of BPA derivatized with PFBCl where the quantification ion was m/z 616, with m/z 408 being used for confirmation [ 13 ].…”

Occurrence and Risk Assessment of Steroidal Hormones and Phenolic Endocrine Disrupting Compounds in Surface Water in Cuautla River, Mexico

“…The procedure was adapted and modified from the studies carried out by Sánchez-Torres [34], Vallejo-Rodriguez [35] and Ronderos-Lara [33]. Briefly, the samples were quantitatively transferred to graduated cylinders at room temperature, the sampling volume was accurately measured, and immediately, 100 ng of DDE was added.…”

“…The differences of individual concentrations and strong variation between sampling sites in Cuautla River could be a Water 2019, 11, 2628 6 of 14 consequence of several factors, such as point discharges [25]; non-point sources, such as surface runoff from agricultural activity and sewage from a scattered residential area without a treatment plant [41]; and inconsistent and deficient efficiencies of treatment in WWTPs [42]. In addition to E 2 , EE 2 , BPA and 4-NP previously analyzed by Ronderos-Lara [33], in this study, we determined 4-t-OP. The individual concentrations of E 2 and EE 2 found in Cuautla River were lower than those reported in Apatlaco river basin locate also in Morelos, México, while those of BPA and 4-NP had similar orders of magnitude (Table 2).…”

“…In Mexico, few studies, to our knowledge, have simultaneously investigated the occurrence, estrogenic activity and toxicological risk of surface water; because of the presence of those five EDCs, most of the studies have mainly focused on the determination of those compounds in wastewater, spring water [30], wetlands [31] and groundwater [32]. Recently, the occurrence of two hormones and two phenolic EDCs, and the evaluation of health risk exposure based on synthetic hormone EE 2 were reported in surface water samples collected from Apatlaco River in Morelos State, Mexico [33].…”