Graphitized carbon black in quartz tubes for the sampling of indoor air nicotine and analysis by microwave thermal desorption-capillary gas chromatography

Nicotine in a smoky indoor air environment can be determined using graphitized carbon black as a solid sorbent in quartz tubes. The temperature stability, high purity, and heat absorption characteristics of the sorbent, as well as the permeability of the quartz tubes to microwaves, enable the thermal desorption by means of microwaves after active sampling. Permeation and dynamic dilution procedures for the generation of nicotine in the vapor phase at low and high concentrations are used to evaluate the performances of the sampler. Tube preparation is described and the microwave desorption temperature is measured. Breakthrough volume is determined to allow sampling at 0.1-1 L/min for definite periods of time. The procedure is tested for the determination of gas and paticulate phase nicotine in sidestream smoke produced in an experimental chamber.

Indirect hydrogen analysis by gas chromatography coupled to mass spectrometry (GC-MS).

Gas chromatography (GC) is an analytical tool very useful to investigate the composition of gaseous mixtures. The different gases are separated by specific columns but, if hydrogen (H2 ) is present in the sample, its detection can be performed by a thermal conductivity detector or a helium ionization detector. Indeed, coupled to GC, no other detector can perform this detection except the expensive atomic emission detector. Based on the detection and analysis of H2 isotopes by low-pressure chemical ionization mass spectrometry (MS), a new method for H2 detection by GC coupled to MS with an electron ionization ion source and a quadrupole analyser is presented. The presence of H2 in a gaseous mixture could easily be put in evidence by the monitoring of the molecular ion of the protonated carrier gas. Copyright © 2013 John Wiley & Sons, Ltd.

Comparative analysis of the roles of HtrA-like surface proteases in two virulent Staphylococcus aureus strains.

The HtrA surface protease is involved in the virulence of many pathogens, mainly by its role in stress resistance and bacterial survival. Staphylococcus aureus encodes two putative HtrA-like proteases, referred to as HtrA(1) and HtrA(2). To investigate the roles of HtrA proteins in S. aureus, we constructed htrA(1), htrA(2), and htrA(1) htrA(2) insertion mutants in two genetically different virulent strains, RN6390 and COL. In the RN6390 context, htrA(1) inactivation resulted in sensitivity to puromycin-induced stress. The RN6390 htrA(1) htrA(2) mutant was affected in the expression of several secreted virulence factors comprising the agr regulon. This observation was correlated with the disappearance of the agr RNA III transcript in the RN6390 htrA(1) htrA(2) mutant. The virulence of this mutant was diminished in a rat model of endocarditis. In the COL context, both HtrA(1) and HtrA(2) were essential for thermal stress survival. However, only HtrA(1) had a slight effect on exoprotein expression. The htrA mutations did not diminish the virulence of the COL strain in the rat model of endocarditis. Our results indicate that HtrA proteins have different roles in S. aureus according to the strain, probably depending on specific differences in the regulation of virulence factor and stress protein expression. We propose that HtrA(1) and HtrA(2) contribute to pathogenicity by controlling the production of certain extracellular factors that are crucial for bacterial dissemination, as revealed in the RN6390 background. We speculate that HtrA proteins act in the agr-dependent regulation pathway by assuring folding and/or maturation of some surface components of the agr system.

Ink dating using thermal desorption and gas chromatography / mass spectrometry: comparison of results obtained in two laboratories

Recent ink dating methods focused mainly on changes in solvent amounts occurring over time. A promising method was developed at the Landeskriminalamt of Munich using thermal desorption (TD) followed by gas chromatography / mass spectrometry (GC/MS) analysis. Sequential extractions of the phenoxyethanol present in ballpoint pen ink entries were carried out at two different temperatures. This method is applied in forensic practice and is currently implemented in several laboratories participating to the InCID group (International Collaboration on Ink Dating). However, harmonization of the method between the laboratories proved to be a particularly sensitive and time consuming task. The main aim of this work was therefore to implement the TD-GC/MS method at the Bundeskriminalamt (Wiesbaden, Germany) in order to evaluate if results were comparable to those obtained in Munich. At first validation criteria such as limits of reliable measurements, linearity and repeatability were determined. Samples were prepared in three different laboratories using the same inks and analyzed using two TDS-GC/MS instruments (one in Munich and one in Wiesbaden). The inter- and intra-laboratory variability of the ageing parameter was determined and ageing curves were compared. While inks stored in similar conditions yielded comparable ageing curves, it was observed that significantly different storage conditions had an influence on the resulting ageing curves. Finally, interpretation models, such as thresholds and trend tests, were evaluated and discussed in view of the obtained results. Trend tests were considered more suitable than threshold models. As both approaches showed limitations, an alternative model, based on the slopes of the ageing curves, was also proposed.

Structural analysis, clay mineralogy and K-Ar dating of fault gouges from Centovalli Line (Central Alps) for reconstruction of their recent activity

Between the cities of Domodossola and Locarno, the complex ``Centovalli Line'' tectonic zone of the Central Alps outlines deformation phases over a long period of time (probably starting similar to 30 Ma ago) and under variable P-T conditions. The last deformation phases developed gouge-bearing faults with a general E-W trend that crosscuts the roots of the Alpine Canavese zone and the Finero ultramafic body. Kinematic indicators show that the general motion was mainly dextral associated with back thrusting towards the S. The <2 mu m clay fractions of fault gouges from Centovalli Line consist mainly of illite, smectite and chlorite with varied illite-smectite, chlorite-smectite and chlorite-serpentine mixed-layers. Constrained with the illite crystallinity index, the thermal conditions induced by the tectonic activity show a gradual trend from anchizonal to diagenetic conditions. The <2 and <0.2 mu M clay fractions, and hydrothermal K-feldspar separates all provide K-Ar ages between 14.2 +/- 2.9 Ma and roughly 0 Ma, with major episodes at about 12,8, 6 and close to 0 Ma These ages set the recurrent tectonic activity and the associated fluid circulations between Upper Miocene and Recent. On the basis of the K-Ar ages and with a thermal gradient of 25-30 degrees C/km, the studied fault zones were located at a depth of 4-7 km. If they were active until now as observed in field, the exhumation was approximately 2.5-3.0 km for the last 12 Ma with a mean velocity of 0.4 mm/y. Comparison with available models on the recent Alpine evolution shows that the tectonic activity in the area relates to a continuum of the back-thrusting movements of the Canavese Line, and/or to several late-extensional phases of the Rhone-Simplon line. The Centovalli-Val Vigezzo zone therefore represents a major tectonic zone of the Central-Western Alps resulting from different interacting tectonic events. (C) 2011 Elsevier B.V. All rights reserved.

Oxygen-isotope thermometry of quartz-calcite veins - Unraveling the thermal-tectonic history of the subgreenschist facies Morcles nappe (Swiss Alps)

Combined structural analysis and oxygen isotope thermometry of syntectonic quartz-calcite fibrous veins can be used to correlate the thermal history of deformed rocks,vith specific structural and tectonic events. Results are presented for the Mercies nappe in the western Helvetic Alps, Switzerland, where mineral parageneses, illite `'crystallinity,'' and fluid inclusion chemistry record an apparent peak metamorphic temperature gradient that increased across the Morcles nappe from anchizonal conditions in the foreland to epizonal conditions in its hinterland root zone. Twenty-seven quartz-calcite veins were analyzed in this study in order to determine the temperatures of veining during formation and deformation of the nappe, Peak metamorphic temperatures ranged from approximate to 260 to 290 degrees C in the shallower, foreland localities and to approximate to 330 to 350 degrees C in the deeper, more hinterland localities at the end of S1-foliation formation, related to large-scale folding. Temperatures gradually decreased throughout the nappe during subsequent development of the S2 foliation and S3 crenulation cleavage, Uplift and erosion of the overlying nappe pile resulted in slow cooling of the Morcles nappe during the waning stages of the Alpine Orogeny. The dominant foliation-forming deformation of the Morcles nappe occurred at elevated temperatures over the course of 10 to 15 Ma. Combined structure-oxygen isotope analyses of quartz-calcite veins yield better temperature and temporal constraints on the thermal histories of subgreenschist vein-bearing tectonites than do other geothermometers.

When gas analysis assists with postmortem imaging to diagnose causes of death.

Postmortem imaging consists in the non-invasive examination of bodies using medical imaging techniques. However, gas volume quantification and the interpretation of the gas collection results from cadavers remain difficult. We used whole-body postmortem multi-detector computed tomography (MDCT) followed by a full autopsy or external examination to detect the gaseous volumes in bodies. Gases were sampled from cardiac cavities, and the sample compositions were analyzed by headspace gas chromatography-mass spectrometry/thermal conductivity detection (HS-GC-MS/TCD). Three categories were defined according to the presumed origin of the gas: alteration/putrefaction, high-magnitude vital gas embolism (e.g., from scuba diving accident) and gas embolism of lower magnitude (e.g., following a traumatic injury). Cadaveric alteration gas was diagnosed even if only one gas from among hydrogen, hydrogen sulfide or methane was detected. In alteration cases, the carbon dioxide/nitrogen ratio was often >0.2, except in the case of advanced alteration, when methane presence was the best indicator. In the gas embolism cases (vital or not), hydrogen, hydrogen sulfide and methane were absent. Moreover, with high-magnitude vital gas embolisms, carbon dioxide content was >20%, and the carbon dioxide/nitrogen ratio was >0.2. With gas embolisms of lower magnitude (gas presence consecutive to a traumatic injury), carbon dioxide content was <20% and the carbon dioxide/nitrogen ratio was often <0.2. We found that gas analysis provided useful assistance to the postmortem imaging diagnosis of causes of death. Based on the quantifications of gaseous cardiac samples, reliable indicators were determined to document causes of death. MDCT examination of the body must be performed as quickly as possible, as does gas sampling, to avoid generating any artifactual alteration gases. Because of cardiac gas composition analysis, it is possible to distinguish alteration gases and gas embolisms of different magnitudes.

Thermal Degradation of Small Molecules: A Global Metabolomic Investigation.

Thermal processes are widely used in small molecule chemical analysis and metabolomics for derivatization, vaporization, chromatography, and ionization, especially in gas chromatography mass spectrometry (GC/MS). In this study the effect of heating was examined on a set of 64 small molecule standards and, separately, on human plasma metabolite extracts. The samples, either derivatized or underivatized, were heated at three different temperatures (60, 100, and 250 °C) at different exposure times (30 s, 60 s, and 300 s). All the samples were analyzed by liquid chromatography coupled to electrospray ionization mass spectrometry (LC/MS) and the data processed by XCMS Online ( xcmsonline.scripps.edu ). The results showed that heating at an elevated temperature of 100 °C had an appreciable effect on both the underivatized and derivatized molecules, and heating at 250 °C created substantial changes in the profile. For example, over 40% of the molecular peaks were altered in the plasma metabolite analysis after heating (250 °C, 300s) with a significant formation of degradation and transformation products. The analysis of 64 small molecule standards validated the temperature-induced changes observed on the plasma metabolites, where most of the small molecules degraded at elevated temperatures even after minimal exposure times (30 s). For example, tri- and diorganophosphates (e.g., adenosine triphosphate and adenosine diphosphate) were readily degraded into a mono-organophosphate (e.g., adenosine monophosphate) during heating. Nucleosides and nucleotides (e.g., inosine and inosine monophosphate) were also found to be transformed into purine derivatives (e.g., hypoxanthine). A newly formed transformation product, oleoyl ethyl amide, was identified in both the underivatized and derivatized forms of the plasma extracts and small molecule standard mixture, and was likely generated from oleic acid. Overall these analyses show that small molecules and metabolites undergo significant time-sensitive alterations when exposed to elevated temperatures, especially those conditions that mimic sample preparation and analysis in GC/MS experiments.