Geraint Morgan

CHO-bearing organic compounds at the surface of 67P/Churyumov-Gerasimenko revealed by Ptolemy

The surface and subsurface of comets preserve material from the formation of the solar system. The properties of cometary material thus provide insight into the physical and chemical conditions during their formation. We present mass spectra taken by the Ptolemy instrument 20 minutes after the initial touchdown of the Philae lander on the surface of comet 67P/Churyumov-Gerasimenko. Regular mass distributions indicate the presence of a sequence of compounds with additional -CH2- and -O- groups (mass/charge ratios 14 and 16, respectively). Similarities with the detected coma species of comet Halley suggest the presence of a radiation-induced polymer at the surface. Ptolemy measurements also indicate an apparent absence of aromatic compounds such as benzene, a lack of sulfur-bearing species, and very low concentrations of nitrogenous material.

Detection of Mycobacterium tuberculosis in Sputum by Gas Chromatography-Mass Spectrometry of Methyl Mycocerosates Released by Thermochemolysis

Tuberculosis requires rapid diagnosis to prevent further transmission and allow prompt administration of treatment. Current methods for diagnosing pulmonary tuberculosis lack sensitivity are expensive or are extremely slow. The identification of lipids using gas chromatography- electron impact mass spectrometry (GC-EI/MS) could provide an alternative solution. We have studied mycocerosic acid components of the phthiocerol dimycocerosate (PDIM) family of lipids using thermochemolysis GC-EI/MS. To facilitate use of the technology in a routine diagnostic laboratory a simple extraction procedure was employed where PDIMs were extracted from sputum using petroleum ether, a solvent of low polarity. We also investigated a method using methanolic tetramethylammonium hydroxide, which facilitates direct transesterification of acidic components to methyl esters in the inlet of the GC-MS system. This eliminates conventional chemical manipulations allowing rapid and convenient analysis of samples. When applied to an initial set of 40 sputum samples, interpretable results were obtained for 35 samples with a sensitivity relative to culture of 94% (95%CI: 69.2,100) and a specificity of 100% (95%CI: 78.1,100). However, blinded testing of a larger set of 395 sputum samples found the assay to have a sensitivity of 61.3% (95%CI: 54.9,67.3) and a specificity of 70.6% (95%CI: 62.3,77.8) when compared to culture. Using the results obtained we developed an improved set of classification criteria, which when applied in a blinded re-analysis increased the sensitivity and specificity of the assay to 64.9% (95%CI: 58.6,70.8) and 76.2% (95%CI: 68.2,82.8) respectively. Highly variable levels of background signal were observed from individual sputum samples that inhibited interpretation of the data. The diagnostic potential of using thermochemolytic GC-EI/MS of PDIM biomarkers for diagnosis of tuberculosis in sputum has been established; however, further refinements in sample processing are required to enhance the sensitivity and robustness of the test.

Low CO/CO 2 ratios of comet 67P measured at the Abydos landing site by the Ptolemy mass spectrometer

Comets are generally considered to contain the best-preserved material from the beginning of our planetary system, although the mechanism of their formation and subsequent evolution are still poorly understood. Here we report the direct in situ measurement of H2O, CO, and CO2 by the Ptolemy mass spectrometer onboard the Philae lander, part of the European Space Agency’s Rosetta mission, at the Abydos site of the Jupiter-family comet 67P/Churyumov-Gerasimenko. A CO/CO2 ratio of around 0.07 ± 0.04 is found at the surface of the comet, a value substantially lower than the one measured by ROSINA in the coma. Such a major difference is a potential indication of heterogeneity of the nucleus and not of changes in the CO/CO2 ratio of the coma with radial distance.

Instrumentation on Beagle 2: the astrobiology lander on ESA's 2003 Mars Express mission

The instrumentation on the 60 kg Beagle 2 lander for ESAs 2003 Mars Express mission will be described. Beagle 2 will be search for organic material on and below the surface of Mars in addition to a study of the inorganic chemistry and mineralogy of the landing site. The lander will utilize acquisitions and preparation tools to obtain samples from below the surface, and both under and inside rocks. In situ analysis will include examination of samples with an optical microscope, Mossbauer and fluorescent X-ray spectrometers. Extracted samples will be returned to the lander for analysis, in particular a search for organics and a measurement of their isotopic composition. The experiment configuration and design will be described along with the status of the project.

Methods in plant foliar volatile organic compounds research

Plants are a major atmospheric source of volatile organic compounds (VOCs). These secondary metabolic products protect plants from high-temperature stress, mediate in plant–plant and plant–insect communication, and affect our climate globally. The main challenges in plant foliar VOC research are accurate sampling, the inherent reactivity of some VOC compounds that makes them hard to detect directly, and their low concentrations. Plant VOC research relies on analytical techniques for trace gas analysis, usually based on gas chromatography and soft chemical ionization mass spectrometry. Until now, these techniques (especially the latter one) have been developed and used primarily by physicists and analytical scientists, who have used them in a wide range of scientific research areas (e.g., aroma, disease biomarkers, hazardous compound detection, atmospheric chemistry). The interdisciplinary nature of plant foliar VOC research has recently attracted the attention of biologists, bringing them into the field of applied environmental analytical sciences. In this paper, we review the sampling methods and available analytical techniques used in plant foliar VOC research to provide a comprehensive resource that will allow biologists moving into the field to choose the most appropriate approach for their studies.

Development and optimization of a gas chromatography/mass spectrometry method for the analysis of thermochemolytic degradation products of phthiocerol dimycocerosate waxes found in Mycobacterium tuberculosis

RATIONALE: The phthiocerol dimycocerosates (PDIMs) are certain stable and hydrophobic waxes found in the cell membrane of Mycobacterium tuberculosis, bacteria that cause an infectious disease of growing concern worldwide. Previous studies report the analysis of derivatives of the hydrolysed PDIMs from biological samples, following complex extraction and offline derivatization of PDIMs biomarkers, prior to their analysis by gas chromatography/mass spectrometry (GC/MS). METHODS: We developed and optimized a GC/MS method based on selected ion monitoring (SIM) to detect the derivatives produced via the thermally assisted hydrolysis and methylation (THM) of the PDIMs from the cell membrane of M. tuberculosis. The extraction of PDIMs from culture is simple, and their thermochemolysis is carried out automatically online, thus avoiding the time-consuming derivatization steps of hydrolysis and esterification, usually performed offline. RESULTS: For standard PDIMs in petroleum ether, our optimized method gave an excellent linearity (R2 = 0.99) at concentrations between 0.172 and 27.5 ng/mL, a good precision (RSD = 11.42 %), and a limit of detection (LOD) of 100 pg/mL. For the PDIMs extracted from dilutions of M. tuberculosis culture, the method gave good linearity (R2 = 0.9685) and an estimated LOD of 400 CFU/mL (CFU = colony forming units) in sterile distilled water. CONCLUSIONS: A GC/MS(SIM) method is presented for the rapid and quantitative detection of M. tuberculosis, based on the online thermochemolysis of lipidic biomarkers extracted from the bacterial culture. The method has the potential to be applied in human and veterinary clinical laboratories for the rapid diagnosis of tuberculosis in infected biological samples.

The use of static mass spectrometry to determine the combined stable isotopic composition of small samples of atmospheric methane.

Global budgets of atmospheric trace gases are increasingly being constrained by means of stable isotope measurements. Published analytical techniques for studying the parallel stable isotopic composition of methane (delta(13)C and deltaD) require prohibitively large quantities of methane for analysis, making them unsuitable for studies where sample size is small, e.g. soil methane fluxes. A highly sensitive static mass spectrometer has been developed which uniquely uses CH(4) as the analyte. The method requires only 8 ng of CH(4) for analysis (<10 mL ambient air), making replicated measurements of the isotopic composition of CH(4) in small samples feasible for the first time. This paper provides the first detailed description of the instrumentation and the analytical technique. The technique has been used to analyse small samples of air collected in Snowdonia over 21 months. The combined stable isotopic composition (delta(17)M) ranged from 29.5 to 35.5 per thousand, with an average value of 32.2 per thousand, and was strongly correlated with wind direction (p <0.01, r(2) = 0.71). Copyright 1999 John Wiley & Sons, Ltd.

SUBSURFACE CHARACTERIZATION OF 67P/CHURYUMOV–GERASIMENKO’S ABYDOS SITE

On November 12, 2014, the ESA/Rosetta descent module Philae landed on the Abydos site of comet 67P/Churyumov-Gerasimenko. Aboard this module, the Ptolemy mass spectrometer measured a CO/CO2 ratio of 0.07 +/- 0.04 which differs substantially from the value obtained in the coma by the Rosetta/ROSINA instrument, suggesting a heterogeneity in the comet nucleus. To understand this difference, we investigated the physico-chemical properties of the Abydos subsurface leading to CO/CO2 ratios close to that observed by Ptolemy at the surface of this region. We used a comet nucleus model that takes into account different water ice phase changes (amorphous ice, crystalline ice and clathrates), as well as diffusion of molecules throughout the pores of the matrix. The input parameters of the model were optimized for the Abydos site and the ROSINA CO/CO2 measured ratio is assumed to correspond to the bulk value in the nucleus. We find that all considered structures of water ice are able to reproduce the Ptolemy observation with a time difference not exceeding ~50 days, i.e. lower than ~2% on 67P/Churyumov-Gerasimenkos orbital period. The suspected heterogeneity of 67P/Churyumov-Gerasimenkos nucleus is also found possible only if it is constituted of crystalline ices. If the icy phase is made of amorphous ice or clathrates, the difference between Ptolemy and ROSINAs measurements would rather originate from the spatial variations in illumination on the nucleus surface. An eventual new measurement of the CO/CO2 ratio at Abydos by Ptolemy could be decisive to distinguish between the three water ice structures.

Development of sample clean up methods for the analysis of Mycobacterium tuberculosis methyl mycocerosate biomarkers in sputum extracts by gas chromatography–mass spectrometry

Highlights • We developed a sample clean-up method to detect tuberculosis from sputum by GC–MS.• Biomarkers recovered: 64–70% (standards solution), and 36–68% (sputum extracts).• Cholesterol removed: 93–98% (standards solution) and 62–92% (sputum extracts).• Less cholesterol in the filtered extracts avoids overloading of the analytical system.• Analyzing large sample batches will need fewer interruptions for system cleaning.

Determining the levels of volatile organic pollutants in urban air using a gas chromatography-mass spectrometry method.

The paper presents the application of a method based on coupled gas chromatography-mass spectrometry, using an isotopically labelled internal standard for the quantitative analysis of benzene (B), toluene (T), ethyl benzene (E), and o-, m-, p-xylenes (X). Their atmospheric concentrations were determined based on short-term sampling, in different sites of Cluj-Napoca, a highly populated urban centre in N-W Romania, with numerous and diversified road vehicles with internal combustion engines. The method is relatively inexpensive and simple and shows good precision and linearity in the ranges of 7–60 μg/m3 (B), 13–90 μg/m3 (T), 7–50 μg/m3 (E), 10–70 μg/m3 (X-m,p), and 20–130 μg/m3 (X-o). The limits of quantitation/detection of the method LOQ/LOD are of 10/5 μg/m3 (Xo), 5/3 μg/m3 (B, E, X-m,p), and of 3/1 μg/m3 (T), respectively.