Mont Blanc, the summit of Western Europe, is a popular but demanding high-altitude ascent. Drug use is thought to be widespread among climbers attempting this summit, not only to prevent altitude illnesses, but also to boost physical and/or psychological capacities. This practice may be unsafe in this remote alpine environment. However, robust data on medication during the ascent of Mont Blanc are lacking. Individual urine samples from male climbers using urinals in mountain refuges on access routes to Mont Blanc (Goûter and Cosmiques mountain huts) were blindly and anonymously collected using a hidden automatic sampler. Urine samples were screened for a wide range of drugs, including diuretics, glucocorticoids, stimulants, hypnotics and phosphodiesterase 5 (PDE-5) inhibitors. Out of 430 samples analyzed from both huts, 35.8% contained at least one drug. Diuretics (22.7%) and hypnotics (12.9%) were the most frequently detected drugs, while glucocorticoids (3.5%) and stimulants (3.1%) were less commonly detected. None of the samples contained PDE-5 inhibitors. Two substances were predominant: the diuretic acetazolamide (20.6%) and the hypnotic zolpidem (8.4%). Thirty three samples were found positive for at least two substances, the most frequent combination being acetazolamide and a hypnotic (2.1%). Based on a novel sampling technique, we demonstrate that about one third of the urine samples collected from a random sample of male climbers contained one or several drugs, suggesting frequent drug use amongst climbers ascending Mont Blanc. Our data suggest that medication primarily aims at mitigating the symptoms of altitude illnesses, rather than enhancing performance. In this hazardous environment, the relatively high prevalence of hypnotics must be highlighted, since these molecules may alter vigilance.

Nonpolar anabolic steroids are doping agents that typically do not provide strong signals by electrospray ionization-mass spectrometry (ESI-MS) owing especially to the low polarity of the functional groups present. We have investigated the addition of anions, in ammonium salt form, to anabolic steroid samples as ionization enhancers and have confirmed that lower instrumental limits of detection (as low as 10 ng/mL for fluoxymesterone-M) are obtained by fluoride anion attachment mass spectrometry, as compared to ESI(+)/(-) or atmospheric pressure photoionization (APPI)(+). Moreover, collision-induced decomposition (CID) spectra of precursor fluoride adducts of the bifunctional steroid "reduced pregnenolone" (containing two hydroxyl groups) and its d4-analogue provide evidence of regiospecific decompositions after attachment of fluoride anion to a specific hydroxyl group of the steroid. This type of charting of specific CID reaction pathways can offer value to selected reaction monitoring experiments (SRM) as it may result in a gain in selectivity in detection as well as in improvements in quantification.

The gas-phase behaviour of organophosphorus compounds such as diethylmethylphosphonate towards electron impact (EI) ionization occurring in a quadrupole ion-trap instrument is investigated. If all ions observed in conventional EI mass spectra are detected, ion/molecule reactions are seen to occur leading to formation of protonated molecules and adduct ions such as 2Mf' and [2M + HI+. The keto-to-enol-like isomerization of the molecular M" ion seems to favour proton transfer to neutral M species and a "self chemical ionization" ion is observed with corresponding fragment ions.Concomitant formation of MH' and odd-electron M+' ions has been observed under electron impact conditions for various classes of compounds, organophosphorus esters for example. In particular, under G U M S conditions using a conventional electron impact (EI) ion source, the relative abundance of [ M + H ] + ions increases as the sample pressure rises.' The presence of heteroatoms such as oxygen or nitrogen in aliphatic molecules can favour this process called 'self ionization'. By using mass spectrometers that allow ion storage, such as ion-trap instruments and ion cyclotron resonance mass spectrometers, 'self chemical ionization' is more easily observed since longer residence times result in ion/molecule collisions even at low sample pressures.2,"4,5Phosphonate compounds are characterized by an [M + l]+/(M+') ratio larger than that predicted for the natural isotopic ratio.6 For instance, diethylmethylphosphonate was characterized by a low abundance M+' ion (mlz 152) accompanied by a signal at m/z 153 (30% of M+*) (see Fig. 2). However, if all expected fragment ions observed in conventional EI mass spectra (and reported in library data) are detected, several experiments performed in ion-trap mass spectrometers show that the MH+ ion intensity depends on conditions of sample ion preparation and ion residence times in the instrument. This behaviour suggests that MH+ is produced by ion/molecule reactions between M+'(and/or fragment ions) and neutral molecules, M. Furthermore, adduct ions such as the dimeric [2M + HI+ species can be observed when concentrations or residence times are increased. In this preliminary study, the effect of the concentration and the storage time on the yield of MH+ ions is investigated and a mechanism of formation is discussed.