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, G. Záray, A. Vasanits, I. Molnár-Perl

Research output: Contribution to journalArticle

24 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

Fingerprint

Stigmasterol
Oximes
Waste Water
Cholestanol
Ketosteroids
Gas chromatography
Ether
Androsterone
Gas Chromatography-Mass Spectrometry
Mass spectrometry
Norethindrone
Estriol
Wastewater
Steroids
Derivatives
Progesterone
Estradiol
Cholesterol
Mestranol
Hydroxysteroids

Keywords

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

ASJC Scopus subject areas

  • Analytical Chemistry
  • Organic Chemistry
  • Biochemistry

Cite this

@article{b6b1d9eee8f440efb9ab2236dc15e68f,
title = "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",
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{\%}.",
keywords = "Aquatic environmental pollutant, Fragmentation patterns, Gas chromatography-mass spectrometry, Oximation, Steroids, Trimethylsilylation",
author = "N. Andr{\'a}si and A. Helenk{\'a}r and G. Z{\'a}ray and A. Vasanits and I. Moln{\'a}r-Perl",
year = "2011",
month = "4",
day = "8",
doi = "10.1016/j.chroma.2011.01.051",
language = "English",
volume = "1218",
pages = "1878--1890",
journal = "Journal of Chromatography",
issn = "0021-9673",
publisher = "Elsevier",
number = "14",

}

TY - JOUR

T1 - Derivatization and fragmentation pattern analysis of natural and synthetic steroids, as their trimethylsilyl (oxime) ether derivatives by gas chromatography mass spectrometry

T2 - Analysis of dissolved steroids in wastewater samples

AU - Andrási, N.

AU - Helenkár, A.

AU - Záray, G.

AU - Vasanits, A.

AU - Molnár-Perl, I.

PY - 2011/4/8

Y1 - 2011/4/8

N2 - 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%.

AB - 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%.

KW - Aquatic environmental pollutant

KW - Fragmentation patterns

KW - Gas chromatography-mass spectrometry

KW - Oximation

KW - Steroids

KW - Trimethylsilylation

UR - http://www.scopus.com/inward/record.url?scp=79952627790&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=79952627790&partnerID=8YFLogxK

U2 - 10.1016/j.chroma.2011.01.051

DO - 10.1016/j.chroma.2011.01.051

M3 - Article

VL - 1218

SP - 1878

EP - 1890

JO - Journal of Chromatography

JF - Journal of Chromatography

SN - 0021-9673

IS - 14

ER -