A robust multi-residue method for the monitoring of 25 endocrine disruptors at ultra-trace levels in surface waters by SPE-LC-MS/MS

Grobin, Andrej (author), Roškar, Robert (author), Trontelj, Jurij (author)

Estrogenic endocrine disruptors are one of the biggest ecotoxicological threats in water that pose a significant ecological burden and health-risk for humans due to their high biological activity and proven additive effects. Therefore, we have developed and validated the most comprehensive and ultra-sensitive analytical method published to date, for reliable quantification of 25 high-risk endocrine disruptors at their ecologically relevant concentrations: naturally excreted hormones (estradiol, estrone, estriol, testosterone, corticosterone, and progesterone), synthetic hormones used for contraception and menopausal symptoms (ethinylestradiol, drospirenone, chlormadinone acetate, norgestrel, gestodene, tibolone, norethindrone, dienogest, and cyproterone) and bisphenols (BPS, BPA, BPF, BPE, BPAF, BPB, BPC, and BPZ). It is based on a solid-phase extraction of water samples, followed by a robust dansyl chloride derivatization with detection by liquid chromatography-tandem mass spectrometry with a single sample preparation and two analytical methods using the same analytical column and mobile phases. The achieved limits of quantitation are in the sub-ng L$^{–1}$ range, and detection limits as low as 0.02 ng L$^{–1}$, meeting the newest proposal for environmental quality standards (EQS) by the EU water framework directive for estradiol and ethinylestradiol. The method was extensively validated and applied to seven representative Slovenian water samples, where we detected 21 out of 25 analytes; 13 were quantified in at least one sample. Estrone and progesterone were quantified in all samples, reaching levels up to 50 ng L$^{–1}$; ethinylestradiol was higher than the current EQS (0.035 ng L$^{–1}$) in three samples, and estradiol was above its EQS (0.4 ng L$^{–1}$) in one sample, proving the method's applicability and the necessity for monitoring these pollutants.

• Language: English
• Keywords: estrogenic endocrine disruptors, analytical methods, estrone, progesterone, LC-MS/MS analysis, validation criteria, bisphenols, hormone disruptors
• Work type: Article
• Typology: 1.01 - Original Scientific Article
• Organization: FFA - Faculty of Pharmacy
• Publication status: Published
• Publication version: Version of Record
• Year: 2023
• Number of pages: Str. 2606–2621
• Numbering: Vol. 15, iss. 21
• PID: 20.500.12556/RUL-146685
• UDC: 612.43:620.266.1
• ISSN on article: 1759-9679
• DOI: 10.1039/d3ay00602f
• COBISS.SI-ID: 154533891
• Publication date in RUL: 09.06.2023

Record is a part of a journal

• Title: Analytical methods
• Shortened title: Anal. methods
• Publisher: Royal Society of Chemistry
• ISSN: 1759-9679
• COBISS.SI-ID: 519831065

Licences

• License: CC BY-NC 3.0, Creative Commons Attribution-NonCommercial 3.0 Unported
• Link: http://creativecommons.org/licenses/by-nc/3.0/
• Description: You are free to reproduce and redistribute the material in any medium or format. You are free to remix, transform, and build upon the material. You must give appropriate credit, provide a link to the license, and indicate if changes were made. You may do so in any reasonable manner, but not in any way that suggests the licensor endorses you or your use. You may not use the material for commercial purposes. You may not apply legal terms or technological measures that legally restrict others from doing anything the license permits.

Secondary language

• Language: Slovenian
• Keywords: estrogenski endokrini motilci, analizne metode, estron, progesteron, LC-MS/MS analiza, validacijski kriteriji, bisfenoli, hormonski motilci

Projects

• Funder: ARRS - Slovenian Research Agency
• Project number: P1-0189
• Name: Farmacevtska tehnologija: od dostavnih sistemov učinkovin do terapijskih izidov zdravil pri otrocih in starostnikih