Comprehensive two-dimensional gas chromatography (GC x GC) measurements of volatile organic compounds in the atmosphere

Abstract. During the MINOS campaign in August 2001 comprehensive two-dimensional gas chromatography (GC×GC) was applied to the in situ measurements of atmospheric volatile organic compounds (VOCs) at the Finokalia ground station, Crete. The measurement system employs a thermal desorption unit for on-line sampling and injection, and a GC×GC separation system equipped with a flame ionization detector (FID) for detection. The system was optimized to resolve C7 − C14 organic components. Two-dimensional chromatograms from measurements of Finokalia air samples show several hundred wellseparated peaks. To facilitate peak identification, cartridge samples collected at Finokalia were analyzed using the same GC×GC system coupled with a time-of-flight mass spectrometer (TOF-MS). The resulting mass spectra were deconvoluted and compared to spectra from a database for tentative peak identification. About 650 peaks have been identified in the two-dimensional plane, with significant signal/noise ratios (>100) and high spectra similarities (>800). By comparing observed retention indices with those found in the literature, 235 of the identifications have been confirmed. 150 of the confirmed compounds show up in the C7 − C14 range of the chromatogram from the in situ measurement. However, at least as many peaks remain unidentified. For quantification of the GC×GC measurements, peak volumes of measured compounds have been integrated and externally calibrated using a standard gas mixture.

A Bitter Pill: The Primordial Lithium Problem Worsens

The lithium problem arises from the significant discrepancy between the primordial 7Li abundance as predicted by BBN theory and the WMAP baryon density, and the pre-Galactic lithium abundance inferred from observations of metal-poor (Population II) stars. This problem has loomed for the past decade, with a persistent discrepancy of a factor of 2--3 in 7Li/H. Recent developments have sharpened all aspects of the Li problem. Namely: (1) BBN theory predictions have sharpened due to new nuclear data, particularly the uncertainty on 3He(alpha,gamma)7Be, has reduced to 7.4%, and with a central value shift of ~ +0.04 keV barn. (2) The WMAP 5-year data now yields a cosmic baryon density with an uncertainty reduced to 2.7%. (3) Observations of metal-poor stars have tested for systematic effects, and have reaped new lithium isotopic data. With these, we now find that the BBN+WMAP predicts 7Li/H = (5.24+0.71-0.67) 10^{-10}. The Li problem remains and indeed is exacerbated; the discrepancy is now a factor 2.4--4.3 or 4.2sigma (from globular cluster stars) to 5.3sigma (from halo field stars). Possible resolutions to the lithium problem are briefly reviewed, and key nuclear, particle, and astronomical measurements highlighted.Comment: 21 pages, 4 figures. Comments welcom

Coupled-channel effective field theory and proton-7^7Li scattering

We apply the renormalisation group (RG) to analyse scattering by short-range forces in systems with coupled channels. For two S-wave channels, we find three fixed points, corresponding to systems with zero, one or two bound or virtual states at threshold. We use the RG to determine the power countings for the resulting effective field theories. In the case of a single low-energy state, the resulting theory takes the form of an effective-range expansion in the strongly interacting channel. We also extend the analysis to include the effects of the Coulomb interaction between charged particles. The approach is then applied to the coupled $p+{^7}$Li and $n+{^7}$Be channels which couple to a $J^P=2^-$ state of $^8$Be very close to the $n+{^7}$Be threshold. At next-to-leading order, we are able to get a good description of the $p+{^7}$Li phase shift and the ${^7}$Be(n,p)${^7}$Li cross section using four parameters. Fits at one order higher are similarly good but the available data are not sufficient to determine all five parameters uniquely.Comment: 22 pages, 2 figures, RevTeX4, typos corrected, accepted for publication in European Physical Journal

Improved dd+4^4He potentials by inversion, the tensor force and validity of the double folding model

Improved potential solutions are presented for the inverse scattering problem for $d$+$^4$He data. The input for the inversions includes both the data of recent phase shift analyses and phase shifts from RGM coupled-channel calculations based on the NN Minnesota force. The combined calculations provide a more reliable estimate of the odd-even splitting of the potentials than previously found, suggesting a rather moderate role for this splitting in deuteron-nucleus scattering generally. The approximate parity-independence of the deuteron optical potentials is shown to arise from the nontrivial interference between antisymmetrization and channel coupling to the deuteron breakup channels. A further comparison of the empirical potentials established here and the double folding potential derived from the M3Y effective NN force (with the appropriate normalisation factor) reveals strong similarities. This result supports the application of the double folding model, combined with a small Majorana component, to the description even of such a loosely bound projectile as the deuteron. In turn, support is given for the application of iterative-perturbative inversion in combination with the double folding model to study fine details of the nucleus-nucleus potential. A $d$-$^4$He tensor potential is also derived to reproduce correctly the negative $^6$Li quadrupole moment and the D-state asymptotic constant.Comment: 22 pages, 12 figures, in Revte

Smith-Waterman peak alignment for comprehensive two-dimensional gas chromatography-mass spectrometry

<p>Abstract</p> <p>Background</p> <p>Comprehensive two-dimensional gas chromatography coupled with mass spectrometry (GC × GC-MS) is a powerful technique which has gained increasing attention over the last two decades. The GC × GC-MS provides much increased separation capacity, chemical selectivity and sensitivity for complex sample analysis and brings more accurate information about compound retention times and mass spectra. Despite these advantages, the retention times of the resolved peaks on the two-dimensional gas chromatographic columns are always shifted due to experimental variations, introducing difficulty in the data processing for metabolomics analysis. Therefore, the retention time variation must be adjusted in order to compare multiple metabolic profiles obtained from different conditions.</p> <p>Results</p> <p>We developed novel peak alignment algorithms for both homogeneous (acquired under the identical experimental conditions) and heterogeneous (acquired under the different experimental conditions) GC × GC-MS data using modified Smith-Waterman local alignment algorithms along with mass spectral similarity. Compared with literature reported algorithms, the proposed algorithms eliminated the detection of landmark peaks and the usage of retention time transformation. Furthermore, an automated peak alignment software package was established by implementing a likelihood function for optimal peak alignment.</p> <p>Conclusions</p> <p>The proposed Smith-Waterman local alignment-based algorithms are capable of aligning both the homogeneous and heterogeneous data of multiple GC × GC-MS experiments without the transformation of retention times and the selection of landmark peaks. An optimal version of the SW-based algorithms was also established based on the associated likelihood function for the automatic peak alignment. The proposed alignment algorithms outperform the literature reported alignment method by analyzing the experiment data of a mixture of compound standards and a metabolite extract of mouse plasma with spiked-in compound standards.</p

Can volatile organic metabolites be used to simultaneously assess microbial and mite contamination level in cereal grains and coffee beans?

A novel approach based on headspace solid-phase microextraction (HS-SPME) combined with comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GC×GC-ToFMS) was developed for the simultaneous screening of microbial and mite contamination level in cereals and coffee beans. The proposed approach emerges as a powerful tool for the rapid assessment of the microbial contamination level (ca. 70 min versus ca. 72 to 120 h for bacteria and fungi, respectively, using conventional plate counts), and mite contamination (ca. 70 min versus ca. 24 h). A full-factorial design was performed for optimization of the SPME experimental parameters. The methodology was applied to three types of rice (rough, brown, and white rice), oat, wheat, and green and roasted coffee beans. Simultaneously, microbiological analysis of the samples (total aerobic microorganisms, moulds, and yeasts) was performed by conventional plate counts. A set of 54 volatile markers was selected among all the compounds detected by GC×GC-ToFMS. Principal Component Analysis (PCA) was applied in order to establish a relationship between potential volatile markers and the level of microbial contamination. Methylbenzene, 3-octanone, 2-nonanone, 2-methyl-3-pentanol, 1-octen-3-ol, and 2-hexanone were associated to samples with higher microbial contamination level, especially in rough rice. Moreover, oat exhibited a high GC peak area of 2-hydroxy-6-methylbenzaldehyde, a sexual and alarm pheromone for adult mites, which in the other matrices appeared as a trace component. The number of mites detected in oat grains was correlated to the GC peak area of the pheromone. The HS-SPME/GC×GC-ToFMS methodology can be regarded as the basis for the development of a rapid and versatile method that can be applied in industry to the simultaneous assessment the level of microbiological contamination and for detection of mites in cereals grains and coffee beans

Advances in structure elucidation of small molecules using mass spectrometry

The structural elucidation of small molecules using mass spectrometry plays an important role in modern life sciences and bioanalytical approaches. This review covers different soft and hard ionization techniques and figures of merit for modern mass spectrometers, such as mass resolving power, mass accuracy, isotopic abundance accuracy, accurate mass multiple-stage MS(n) capability, as well as hybrid mass spectrometric and orthogonal chromatographic approaches. The latter part discusses mass spectral data handling strategies, which includes background and noise subtraction, adduct formation and detection, charge state determination, accurate mass measurements, elemental composition determinations, and complex data-dependent setups with ion maps and ion trees. The importance of mass spectral library search algorithms for tandem mass spectra and multiple-stage MS(n) mass spectra as well as mass spectral tree libraries that combine multiple-stage mass spectra are outlined. The successive chapter discusses mass spectral fragmentation pathways, biotransformation reactions and drug metabolism studies, the mass spectral simulation and generation of in silico mass spectra, expert systems for mass spectral interpretation, and the use of computational chemistry to explain gas-phase phenomena. A single chapter discusses data handling for hyphenated approaches including mass spectral deconvolution for clean mass spectra, cheminformatics approaches and structure retention relationships, and retention index predictions for gas and liquid chromatography. The last section reviews the current state of electronic data sharing of mass spectra and discusses the importance of software development for the advancement of structure elucidation of small molecules