PMID- 21981935
OWN - NLM
STAT- MEDLINE
DCOM- 20120110
LR  - 20111018
IS  - 1873-3778 (Electronic)
IS  - 0021-9673 (Linking)
VI  - 1218
IP  - 45
DP  - 2011 Nov 11
TI  - The role of the acquisition methods in the analysis of natural and synthetic 
      steroids and cholic acids by gas chromatography-mass spectrometry.
PG  - 8264-72
LID - 10.1016/j.chroma.2011.09.006 [doi]
AB  - An exhaustive GC-MS acquisition study was performed, for the simultaneous 
      analysis of natural and synthetic steroids and cholic acids (in order to insert 
      them into the last tierce of our multiresidue analysis system), such as 
      androsterone, beta-estradiol, transdehydroandro-sterone, transdehyroandrosterone, 
      mestranol, dihydrotestosterone, ethinylestradiol, testosterone, norethisterone, 
      estriol, 4-androstene-3,17-dione, gestodene, levonorgestrel, etonogestrel, 
      coprostanol, progesterone, cholesterol, medroxyprogesterone-acetate, lithocholic 
      acid, stigmasterol, cholic acid, chenodeoxycholic acid, beta-sitosterol, 
      ursodeoxycholic acid, 3-hydroxy-7-ketocholic acid and dehydrocholic acid, in 
      total 26 compounds. As novelties to the field, for the trimethylsilyl (TMS) oxime 
      ether/ester derivatives of steroids and cholic acids, at first, a tandem mass 
      spectrometric (MS/MS), multiple reaction monitoring (MRM) type acquisition method 
      has been developed in a single run; also for the first time, the three 
      acquisition techniques, the full scan (FS), the selective ion monitoring (SIM), 
      in our case the multiple ion monitoring (MIM) and the currently optimized MRM 
      methods, have been compared; all three, in parallel, under strictly the same 
      derivatization/instrumental conditions, both in matrix free solutions and 
      municipal wastewater from two Hungarian wastewater treatment plants (WWTPs). 
      Critical evaluation of the three acquisition protocols was collated on their 
      analytical performances and validated under the same conditions. The data of six 
      point calibration curves for FS, MIM and MRM methods, showed that both R(2) 
      (0.9995, 0.9858, 0.9975) and RSD (5.3, 5.8, 5.0), for two parallel 
      derivatizations, each injected three times, proved to be independent of the 
      acquisition processes. Whereas, for the method limit of quantification (LOQ) and 
      the instrument limit of quantification (ILQ) values showed considerable 
      differences. LOQ data, were decreasing in the FS, MIM, MRM line (expressed in 
      ng/L), for all steroids and cholic acids. The same trend was determined in terms 
      of the ILQ values. The practical utility of the optimized acquisition techniques 
      was confirmed by the quantitation of the steroids and cholic acids contents of 
      wastewater samples. Results confirmed the importance of the MRM acquisition 
      method, even in comparison to the MIM one: with particular interest in selected 
      cases: avoiding the extreme overestimation of the beta-estradiol (156-1325%) and 
      that of the ethinylestradiol (582-831%) concentrations in the wastewater samples.
CI  - Copyright (c) 2011 Elsevier B.V. All rights reserved.
FAU - Andrasi, N
AU  - Andrasi N
AD  - Institute of Chemistry, Department of Analytical Chemistry, L. Eotvos University, 
      H-1518, Budapest 112, P.O. Box 32, Hungary.
FAU - Helenkar, A
AU  - Helenkar A
FAU - Vasanits-Zsigrai, A
AU  - Vasanits-Zsigrai A
FAU - Zaray, Gy
AU  - Zaray G
FAU - Molnar-Perl, I
AU  - Molnar-Perl I
LA  - eng
PT  - Journal Article
PT  - Research Support, Non-U.S. Gov't
DEP - 20110914
PL  - Netherlands
TA  - J Chromatogr A
JT  - Journal of chromatography. A
JID - 9318488
RN  - 0 (Cholic Acids)
RN  - 0 (Sewage)
RN  - 0 (Steroids)
RN  - 0 (Water Pollutants, Chemical)
SB  - IM
MH  - Calibration
MH  - Cholic Acids/*analysis/chemistry
MH  - Gas Chromatography-Mass Spectrometry/*methods
MH  - Reproducibility of Results
MH  - Sensitivity and Specificity
MH  - Sewage/chemistry
MH  - Solid Phase Extraction
MH  - Steroids/*analysis/chemistry
MH  - Tandem Mass Spectrometry/*methods
MH  - Water Pollutants, Chemical/*analysis/chemistry
EDAT- 2011/10/11 06:00
MHDA- 2012/01/11 06:00
CRDT- 2011/10/11 06:00
PHST- 2011/06/20 00:00 [received]
PHST- 2011/09/02 00:00 [revised]
PHST- 2011/09/05 00:00 [accepted]
PHST- 2011/10/11 06:00 [entrez]
PHST- 2011/10/11 06:00 [pubmed]
PHST- 2012/01/11 06:00 [medline]
AID - S0021-9673(11)01351-3 [pii]
AID - 10.1016/j.chroma.2011.09.006 [doi]
PST - ppublish
SO  - J Chromatogr A. 2011 Nov 11;1218(45):8264-72. doi: 10.1016/j.chroma.2011.09.006. 
      Epub 2011 Sep 14.