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.

Qualitative drug analysis of hair extracts by comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry.

A technique using comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (GCxGC/TOFMS) is applied to a qualitative analysis of three sample extracts from hair suspected of containing various drug compounds. The samples were also subjected to a quantitative target analysis for codeine, morphine, 6-monoacetylmorphine (6-MAM), amphetamine, methamphetamine, methylenedioxyamphetamine (MDA), methylenedioxymethylamphetamine (MDMA), methadone, and benzylpiperazine (BZP) by liquid chromatography-tandem mass spectrometry (LC-MS/MS). GCxGC/TOFMS provided a non-specific procedure that identified various drugs, metabolites, and impurities not included in the target analysis.

The detection of various opiates and benzodiazepines by comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry.

A technique using comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (GC x GC/TOFMS) is applied to qualitative and quantitative drug testing. Human serum was 'spiked' with known quantities of benzodiazepines and a 'street heroin' mixture including some of the major metabolites and impurities. The sample components were extracted from the matrix by solid-phase extraction (SPE).

Ion trap mass spectrometry on a comet nucleus: the Ptolemy instrument and the Rosetta space mission.

In May 2014, the Rosetta spacecraft is scheduled to rendezvous with the comet Churyumov-Gerasimenko ('67P'). One of the instruments on board the 'Lander' which will descend on to the surface of the comet is a miniaturised GC/MS system that incorporates an ion trap mass spectrometer, specially developed for isotope ratio analysis. This article describes the development and optimisation of the ion trap for this unique application, and presents a summary of the range of pre-programmed experiments that will contribute to the characterisation of the solid and volatile cometary materials.

The microbiology of spacecraft hardware: lessons learned from the planetary protection activities on the Beagle 2 spacecraft.

We consider the aseptic assembly of the Beagle 2 Mars probe and how the requirements of COSPAR planetary protection category IVa were achieved. Several areas for future investigation became apparent. An ESA mission is outlined in which a microbial bioburden is recovered after Earth orbit to assess viability following re-entry through the atmosphere.

Mass-independent fractionation of oxygen isotopes during thermal decomposition of carbonates.

Nearly all chemical processes fractionate 17O and 18O in a mass-dependent way relative to 16O, a major exception being the formation of ozone from diatomic oxygen in the presence of UV radiation or electrical discharge. Investigation of oxygen three-isotope behavior during thermal decomposition of naturally occurring carbonates of calcium and magnesium in vacuo has revealed that, surprisingly, anomalous isotopic compositions are also generated during this process. High-precision measurements of the attendant three-isotope fractionation line, and consequently the magnitude of the isotopic anomaly (delta17O), demonstrate that the slope of the line is independent of the nature of the carbonate but is controlled by empirical factors relating to the decomposition procedure.

A technique for the determination of 18O/16O and 17O/16O isotopic ratios in water from small liquid and solid samples.

We have developed a new technique in which a solid reagent, cobalt(III) fluoride, is used to prepare oxygen gas for isotope ratio measurement from water derived either from direct injection or from the pyrolysis of solid samples. The technique uses continuous flow, isotope ratio monitoring, gas chromatography/mass spectrometry (irmGC/MS) to measure the delta18O and delta17O of the oxygen gas. Water from appropriate samples is evolved by a procedure of stepped pyrolysis (0-1000 degrees C, typically in 50 degrees C increments) under a flowing stream of helium carrier gas.

Beagle 2: a proposed exobiology lander for ESA's 2003 Mars Express mission.

The aim of the proposed Beagle 2 small lander for ESA's 2003 Mars Express mission is to search for organic material on and below the surface of Mars and to study the inorganic chemistry and mineralogy of the landing site. The lander will have a total mass of 60kg including entry, descent, and landing system. Experiments will be deployed on the surface using a robotic arm.

A nitrogen and argon stable isotope study of Allan Hills 84001: implications for the evolution of the Martian atmosphere.

The abundances and isotopic compositions of N and Ar have been measured by stepped combustion of the Allan Hills 84001 (ALH 84001) Martian orthopyroxenite. Material described as shocked is N-poor ([N] approximately 0.34 ppm; delta 15N approximately +23%); although during stepped combustion, 15N-enriched N (delta 15N approximately +143%) is released in a narrow temperature interval between 700 degrees C and 800 degrees C (along with 13C-enriched C (delta 13C approximately +19%) and 40Ar).

The origin of chondritic macromolecular organic matter: a carbon and nitrogen isotope study.

The N and C abundances and isotopic compositions of acid-insoluble carbonaceous material in thirteen primitive chondrites (five unequilibrated ordinary chondrites, three CM chondrites, three enstatite chondrites, a CI chondrite and a CR chondrite) have been measured by stepped combustion. While the range of C isotopic compositions observed is only delta 13C = 30%, the N isotopes range from delta 15N approximately -40 to 260%. After correction for metamorphism, presolar nanodiamonds appear to have made up a fairly constant 3-4 wt% of the insoluble C in all the chondrites studied.

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.

High precision delta(17)O isotope measurements of oxygen from silicates and other oxides: method and applications.

The use of infrared laser-assisted fluorination to release oxygen from milligram quantities of silicates or other oxide mineral grains is a well-established technique. However, relatively few studies have reported the optimisation of this procedure for oxygen-17 isotope measurements. We describe here details of an analytical system using infrared (10 µm) laser-assisted fluorination, in conjunction with a dual inlet mass spectrometer of high resolving power ( approximately 250) to provide (17)O and (18)O oxygen isotope measurements from 0.

Life on Mars: chemical arguments and clues from Martian meteorites.

Primitive terrestrial life-defined as a chemical system able to transfer its molecular information via self-replication and to evolve-probably originated from the evolution of reduced organic molecules in liquid water. Several sources have been proposed for the prebiotic organic molecules: terrestrial primitive atmosphere (methane or carbon dioxide), deep-sea hydrothermal systems, and extraterrestrial meteoritic and cometary dust grains. The study of carbonaceous chondrites, which contain up to 5% by weight of organic matter, has allowed close examination of the delivery of extraterrestrial organic material.

C, N, and noble gas isotopes in grain size separates of presolar diamonds from Efremovka.

Nanometer-size presolar diamonds from the Efremovka CV3 chondrite were physically separated into several grain size fractions by ultracentrifugation. The coarsest size fraction is the most enriched in carbon-12; the others have broadly similar carbon isotopic compositions. Measurement of noble gases shows that their concentration decreases with decreasing grain size.

C, N, and noble gas isotopes in grain size separates of presolar diamonds from efremovka.

Nanometer-size presolar diamonds from the Efremovka CV3 chondrite were physically separated into several grain size fractions by ultracentrifugation. The coarsest size fraction is the most enriched in carbon-12; the others have broadly similar carbon isotopic compositions. Measurement of noble gases shows that their concentration decreases with decreasing grain size.

Record of fluid-rock interactions on Mars from the meteorite ALH84001.

Allan Hills (ALH) 84001 is the most recently recognized member of a suite of meteorites--the SNCs--that almost certainly originated on Mars. Several factors distinguish ALH84001 from the other SNC meteorites. Preliminary studies suggest that it may be older than other martian meteorites.

Terrestrial carbon and nitrogen isotopic ratios from cretaceous-tertiary boundary nanodiamonds.

One hypothesis for the origin of the nanometer-size diamonds found at the Cretaceous-Tertiary (K-T) boundary is that they are relict interstellar diamond grains carried by a postulated asteroid. The (13)C/(12)C and (15)N/(14)N ratios of the diamonds from two sites in North America, however, show that the diamonds are two component mixtures differing in carbon and nitrogen isotopic composition and nitrogen abundance. Samples from a site from Italy show no evidence for either diamond component.

A new type of meteoritic diamond in the enstatite chondrite abee.

Diamonds with delta(13)C values of -2 per mil and less than 50 parts per million (by mass) nitrogen have been isolated from the Abee enstatite chondrite by the same procedure used for concentrating Cdelta, the putative interstellar diamond found ubiquitously in primitive meteorites and characterized by delta(13)C values of -32 to -38 per mil, nitrogen concentrations of 2,000 to 12,500 parts per million, and delta(15)N values of -340 per mil. Because the Abee diamonds have typical solar system isotopic compositions for carbon, nitrogen, and xenon, they are presumably nebular in origin rather than presolar. Their discovery in an unshocked meteorite eliminates the possibility of origins normally invoked to account for diamonds in ureilites and iron meteorites and suggests a low-pressure synthesis.

Evidence for multiple sources of diamond from primitive chondrites.

Fine-grained diamonds, the most abundant form of circumstellar dust isolated from primitive meteorites, have elemental and isotopic characteristics that are dependent on the host meteorite type. Carbon isotopic compositions vary from -32 to -38 per mil, and nitrogen associated with the diamond changes in overall abundance by over a factor of four from 0.2 to 0.

The formation of weathering products on the LEW 85320 ordinary chondrite: evidence from carbon and oxygen stable isotope compositions and implications for carbonates in SNC meteorites.

Isotopic analysis of nesquehonite recovered from the surface of the LEW 85320 H5 ordinary chondrite shows that the delta 13C and delta 18O values of the two generations of bicarbonate (Antarctic and Texas) are different: delta 13C = +7.9% and +4.2%; delta 18O = +17.

Interstellar carbon in meteorites.

The Murchison and Allende chondrites contain up to 5 parts per million carbon that is enriched in carbon-13 by up to + 1100 per mil (the ratio of carbon-12 to carbon-13 is approximately 42, compared to 88 to 93 for terrestrial carbon). This "heavy" carbon is associated with neon-22 and with anomalous krypton and xenon showing the signature of the s-process (neutron capture on a slow time scale). It apparently represents interstellar grains ejected from late-type stars.