Derivatization and fragmentation pattern analysis of natural and synthetic steroids, as their trimethylsilyl (oxime) ether derivatives by gas chromatography mass spectrometry: Analysis of dissolved steroids in wastewater samples

N. Andrási, A. Helenkár, Gy Záray, A. Vasanits, I. Molnár-Perl

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

This paper reports the extension of our multiresidue analysis (MA) procedure with 18 natural and synthetic steroids; permitting the identification and quantification, in total of 81 pollutants from one solution, by a single injection, as their trimethylsilyl (TMS)-oxime ether/ester derivatives, by gas chromatography-mass spectrometry (GC-MS), within 31 min. As a novelty to the field, basic researches, such as fragmentation pattern analysis and derivatization optimization studies were performed for androsterone, transdehydroandrosterone, transandrosterone, mestranol, dihydrotestosterone, ethinylestradiol, testosterone, norethisterone, estriol, 4-androstene-3,17-dione, gestodene, levonorgestrel, etonogestrel, coprostanol, progesterone, cholesterol, medroxy-progesterone-acetate, stigmasterol and β-sitosterol. Results confirmed that (i) the TMS oxime-ether derivatives of the keto steroids provide from 1.40 times (gestodene) up to 4.25 times (norethisterone) higher responses compared to their TMS-ether ones, and (ii) the distribution of syn/anti oximes is characteristic to the ketosteroid species examined. Based on our optimized mass fragmentation, solid phase extraction (SPE) and derivatization studies separations have been performed in the total ion current (TIC) mode, identification and quantification of compounds have been carried out on the basis of their selective fragment ions. Responses, obtained with derivatized standards proved to be linear (hydroxysteroids), or have been calculated from calibration curves (ketosteroids) in the range of 1.88-750 ng/L levels. Limit of quantitation (LOQ) values varied between 1.88 ng/L and 37.5. ng/L concentrations. The most important practical messages of this work are the high androsterone (0.744-4.28. μg/L), transandrosterone (0.138-4.00. μg/L), coprostanol (2.11-302. μg/L), cholesterol (0.308-41. μg/L), stigmasterol (1.21-8.40. μg/L) and β-sitosterol (1.12-11.0. μg/L) contents of influent wastewaters. β-Estradiol (100 ng/L) and estriol (54 ng/L) were found in one influent sample, only. Reproducibilities, characterized with the relative standard deviation percentages (RSD%) of measurements, varied between 1.73 RSD% (β-estradiol) and 5.4 RSD% (stigmasterol), with an average of 4.82 RSD%.

Original languageEnglish
Pages (from-to)1878-1890
Number of pages13
JournalJournal of Chromatography A
Volume1218
Issue number14
DOIs
Publication statusPublished - Apr 8 2011

Keywords

  • Aquatic environmental pollutant
  • Fragmentation patterns
  • Gas chromatography-mass spectrometry
  • Oximation
  • Steroids
  • Trimethylsilylation

ASJC Scopus subject areas

  • Analytical Chemistry
  • Biochemistry
  • Organic Chemistry

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