Drug testing data from the 2007 Pan American Games: δ 13C values of urinary androsterone, etiocholanolone and androstanediols determined by GC/C/IRMS

Abstract

The main purpose of this article is to show the application of the CG/C/IRMS in real time during competition in the steroid confirmation analysis. For this reason, this paper summarizes the results obtained from the doping control analysis during the period of the 2007 Pan American Games held in Rio de Janeiro, Brazil. Approximately 5600 athletes from 42 different countries competed in the games. Testing was performed in accordance to World Anti-Doping Agency (WADA) technical note for prohibited substances. This paper reports data where abnormal urinary steroid profiles, have been found with the screening procedures. One 8 mL urine sample was used for the analysis of five steroid metabolites with two separate analyses by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Urine samples were submitted to GC/C/IRMS for confirmation analysis to determine the (13)C/(12)C ratio of selected steroids. Fifty-seven urine samples were analyzed by GC/C/IRMS and the delta(13)C values ( per thousand) of androsterone, etiocholanolone, 5beta-androstane-3alpha, 17beta-diol (5beta-diol), 5alpha-androstane-3alpha, 17beta-diol (5alpha-diol) and 5beta-pregnane-3alpha, 20alpha-diol (5beta-pdiol), the endogenous reference compound are presented. One urine sample with a testosterone/epitestosterone (T/E) ratio of 4.7 was confirmed to be positive of doping by GC/C/IRMS analysis. The delta values of 5beta-diol and 5alpha-diol were 3.8 and 10.8, respectively, compared to the endogenous reference compound 5beta-pdiol, which exceeded the WADA limit of 3 per thousand. The results obtained by CG/C/IRMS confirmation analyses, in suspicious samples, were conclusive in deciding whether or not a doping steroid violation had occurred.

Human pheromones and food odors: epigenetic influences on the socioaffective nature of evolved behaviors

“…This could have a significant impact on the metabolism of DHEAS, which appears to be the precursor to primate-specific ratios of specific metabolites of steroid hormones such as androsterone (A) and etiocholanolone (E). The A/E ratio is a measure of individual physical fitness in men (Aguilera et al, 2009) and has been linked to sexual preferences (Margolese & Janiger, 1973). Less speculation is required with regard to the effects of endocrine disruptors on GnRH, the effects of plant odors on the hormone estradiol in women (Fukui, Toyoshima, & Komaki, 2011), and the effect of pheromones on hormones associated with mate choice.…”

Systematic comparison of δ13C measurements of testosterone and derivative steroids in a freeze‐dried urine candidate reference material for sports drug testing by gas chromatography/combustion/isotope ratio mass spectrometry and uncertainty evaluation using four different metrological approaches

“…Precision values of the measurement of carbon isotope ratios of urinary steroids have been reported, with standard deviations of measurement results varying between 0.11‰ and 0.77‰. [19][20][21][22][23][24] However, as these are precision values, they do not take into account all bias effects. A clear description of published estimates of measurement uncertainties for GC/C/IRMS measurements has not been published.…”

Annual banned‐substance review: analytical approaches in human sports drug testing

“…The applicability of such methods in great sporting events was recently described for the 2007 Pan American Games yielding one adverse analytical finding. [17] As an alternative to carbon isotope ratio analysis, the use of deuterium/hydrogen ratio determination was suggested as a means to differentiate endogenously produced steroids from synthetically derived analogs. [18] In this pilot study, the possibility of isolating and measuring ten different steroids (androsterone, etiocholanolone, testosterone, epitestosterone, 5α-androstane-3α,17β-diol, 5β-androstane-3α,17β-diol, 5α-androst-16-en-3α-ol, 11β-hydroxyandrosterone, pregnanediol, and dehydroepiandrosterone) at detection limits of 10-15 ng/mL from a single urine sample (20 mL) was shown using a GC/thermal conversion (TC)/IRMS set-up.…”