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See detailA new method for identifying experimental and Palaeolithic hafting adhesives using GC×GC-HRTOFMS
Cnuts, Dries ULg; Perrault, Katelynn ULg; Dubois, Lena ULg et al

Poster (2016, September)

Hafting adhesives can be seen as an indication of the cognitive and technical capabilities of the manufacturers and therefore play a key role in the debate on human evolution [1], [2]. These adhesives are ... [more ▼]

Hafting adhesives can be seen as an indication of the cognitive and technical capabilities of the manufacturers and therefore play a key role in the debate on human evolution [1], [2]. These adhesives are mainly from plant origin (resins, gums or tar) and are often mixed with beeswax and other additives in order to make them less brittle. Archaeological evidence indicates that these adhesives were already in use in the Paleolithic from at least 120.000 years ago [3]. Discoveries for this period are however very rare and only become abundant from the Neolithic onwards [4]. Their longer exposure to biochemical alteration processes limits the chance of survival in the archaeological record. If they are present on Paleolithic stone tools, they appear often in such small quantities that they are challenging to identify by traditional gas chromatography – mass spectrometry (GC-MS) or even to remove them effectively from the stone tool. The destructive nature of traditional GC-MS analysis can damage these rare samples for other analyses. Our study aims to overcome this problem by using headspace solid phase microextraction (HS-SPME) for sample extraction and analysis by comprehensive two-dimensional gas chromatography –high-resolution time-of-flight mass spectrometry (GC×GC-HRTOFMS), which has the benefit of analyzing the volatile organic compound (VOC)s from the substance and it does not destroy the complete matrix of the adhesive. We present the results of a pilot study intended to examine the potential of this technique for analyzing Palaeolithic adhesives. The study involved (1) an examination of experimental compound adhesives (containing pine and spruce resin, acacia gum and birch tar; beeswax and additives like charcoal, flax or ochre), (2) a blind test on experimental samples to test the reliability of the method and to determine the minimal quantity necessary for analysis, and (3) the analysis of different Palaeolithic adhesives and of experimental samples of at least 15 years old. The analysis was done on extracted and non-extracted adhesives. A unique chromatographic fingerprint was obtained for all experimental adhesive samples. The VOC profile of these adhesives proved to be extremely complex and therefore benefitted significantly from multidimensional separation techniques. GC×GC-HRTOFMS provided an optimal chromatographic separation of adhesive components. HRTOFMS data was used in order to obtain high-resolution mass spectral data to contribute to compound identification. Our study demonstrates that GC×GC-HRTOFMS is a well suited method for identifying small quantities of compound adhesives with significant potential for Palaeolithic contexts. The additional sensitivity afforded by this technique in comparison to traditional GC-MS is a substantial benefit for these quantities. Furthermore, by only analyzing the VOCs of the adhesives, these rare archeological samples are not destroyed and can still be used for other types of analysis. [1] L. Wadley, ‘Compound-Adhesive Manufacture as a Behavioral Proxy for Complex Cognition in the Middle Stone Age’, Curr. Anthropol., vol. 51, no. s1, pp. S111–S119, Jun. 2010. [2] L. Barham, From Hand to Handle: The First Industrial Revolution. Oxford: Oxford University Press, 2013. [3] P. P. A. Mazza, F. Martini, B. Sala, M. Magi, M. P. Colombini, G. Giachi, F. Landucci, C. Lemorini, F. Modugno, and E. Ribechini, ‘A new Palaeolithic discovery: tar-hafted stone tools in a European Mid-Pleistocene bone-bearing bed’, J. Archaeol. Sci., vol. 33, no. 9, pp. 1310–1318, Sep. 2006. [4] M. Regert, ‘Investigating the history of prehistoric glues by gas chromatography-mass spectrometry.’, J. Sep. Sci., vol. 27, no. 3, pp. 244–54, Feb. 2004. [less ▲]

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See detailPostmortem Internal Gas Reservoir Monitoring Using GCxGC-HRTOFMS
Stefanuto, Pierre-Hugues ULg; Perrault, Katelynn ULg; Grabher, Silke et al

in separations (2016), 3(24),

Forensic investigations often require postmortem examination of a body. However, the collection of evidence during autopsy is often destructive, meaning that the body can no longer be examined in its ... [more ▼]

Forensic investigations often require postmortem examination of a body. However, the collection of evidence during autopsy is often destructive, meaning that the body can no longer be examined in its original state. In order to obtain an internal image of the body, whole body postmortem computed tomography (PMCT) has proven to be a valuable non-destructive tool and is currently used in medicolegal centers. PMCT can also be used to visually locate gas reservoirs inside a cadaver, which upon analysis can provide useful information regarding very volatile compounds that are produced after death. However, the non-targeted profiling of all potential volatile organic compounds (VOCs) present in these reservoirs has never been attempted. The aim of this study was to investigate the VOC profile of these reservoirs and to evaluate potential uses of such information to document circumstances surrounding death, cause of death and body taphonomy. Comprehensive two-dimensional gas chromatography coupled to time-of-flight high-resolution mass spectrometry (GC GC-HRTOF-MS) was used for VOC measurements. This study demonstrated that the chemical composition of VOCs within the gas reservoirs differed between locations within a single body but also between individuals. In the future, this work could be expanded to investigate a novel, non-destructive cadaver screening approach prior to full autopsy procedures. [less ▲]

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See detailExploring variable electron ionization for forensic blood VOC profiling
Dubois, Lena ULg; Perrault, Katelynn ULg; Stefanuto, Pierre-Hugues ULg et al

Scientific conference (2016, July 07)

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See detailTime travelling into human prehistory using GC×GC-TOFMS
Perrault, Katelynn ULg; Dubois, Lena ULg; Stefanuto, Pierre-Hugues ULg et al

Scientific conference (2016, July 07)

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See detailStatistical comparisons of beer types using GC×GC-HRTOFMS
Stefanuto, Pierre-Hugues ULg; Dubois, Lena ULg; Perrault, Katelynn ULg et al

Scientific conference (2016, June 02)

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See detailVOC monitoring by GCxGC-HRTOFMS
Stefanuto, Pierre-Hugues ULg; Perrault, Katelynn ULg; Dubois, Lena ULg et al

Scientific conference (2016, June 02)

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See detail“The Sweet Smell of Chemistry” - Characterization of volatile mixtures from Life Sciences
Stefanuto, Pierre-Hugues ULg

Doctoral thesis (2016)

From a Separation Science standpoint, Life Sciences represent a broad source of complex compound mixtures that require powerful analytical strategies to be considered when characterization is aimed. The ... [more ▼]

From a Separation Science standpoint, Life Sciences represent a broad source of complex compound mixtures that require powerful analytical strategies to be considered when characterization is aimed. The depiction of the complex volatile organic compound (VOC) component of these mixtures is an important part of such characterization. The aim of this doctoral work was to develop a versatile analytical approach to resolve such VOC samples. For the characterization of complex VOC mixtures, comprehensive two-dimensional gas chromatography (GC×GC) is the method of choice. The combination of two GC separation columns offers higher peak capacity than single dimension GC (1D GC). Moreover, the hyphenation of GC×GC to a mass spectrometer provides an extra dimension of identification, especially when high-resolution (HR) time-of-flight mass spectrometers (TOFMS) is used. However, the optimization of the GC×GC conditions is not straightforward. Currently, there are no defined strategies to obtain the best capabilities these instruments, not only in terms of the optimization of the separation itself, but also mainly in terms of data processing efficiency. The first section of this work was devoted to the evaluation of theoretical aspects and the definition of a specific optimization strategy for GC×GC separation. The first part dealt with the heavily debated concept of ‘orthogonality’ was specifically investigated by means of a metric calculation, the Orthogonality Index (OI), linked to a new nomenclature describing the separation space usage. The second part was focused on the development of an optimization strategy for the sampling and the chromatographic separation of VOCs, as well as the processing of large sets of GC×GC data. This was conducted on complex beer aroma headspace replicates for sampling method selection, peak dispersion optimization, and robust multivariate statistical treatment. The third part of this theoretical investigation relied on the implementation of fast-GC conditions for GC×GC separation. The idea was to evaluate the effect of combining short columns, fast modulation, high temperature ramping, and high flow on GC×GC efficiency for explosive headspace analyses. In the second section, the focus was directed to challenging applications in the area of thanatochemistry, i.e. the chemistry of death, especially considering the volatile fraction of cadaveric decomposition, a complex chemical process releasing numerous VOCs. In this context, soil surrounding decomposing remains, headspace of cadavers, and more “specific” matrices (i.e. synthetic solutions and internal gas from decomposition) were analyzed by GC×GC TOFMS. Major attention was dedicated to the development of an analytical and data mining procedures for these complex VOC samples with emphasis on the study of the impact of different parameters on the cadaveric decomposition process. [less ▲]

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See detailPeak dispersion evaluation and optimization in GC×GC
Stefanuto, Pierre-Hugues ULg; Dimandja, Jean-Marie; Focant, Jean-François ULg

Poster (2016, May 30)

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See detailGC×GC-HRTOFMS to better understand cloak-and-dagger activities of Madagascar Mantella frogs
Stefanuto, Pierre-Hugues ULg; Brasseur, Catherine; Cecchini, Harisoa et al

Poster (2016, May 30)

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See detailGC×GC-TOFMS for forensic blood VOC profiling
Dubois, Lena ULg; Perrault, Katelynn ULg; Stefanuto, Pierre-Hugues ULg et al

Poster (2016, May 30)

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See detailA New Approach for the Characterization of Organic Residues from Stone Tools Using GC×GC-TOFMS
Perrault, Katelynn ULg; Stefanuto, Pierre-Hugues ULg; Dubois, Lena ULg et al

in Separations (2016), 3(2), 16

Headspace solid-phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC-MS) have traditionally been used, in combination with other analyses, for the chemical characterization of ... [more ▼]

Headspace solid-phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC-MS) have traditionally been used, in combination with other analyses, for the chemical characterization of organic residues recovered from archaeological specimens. Recently in many life science fields, comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GC×GC-TOFMS) has provided numerous benefits over GC-MS. This study represents the first use of HS-SPME-GC×GC-TOFMS to characterize specimens from an experimental modern reference collection. Solvent extractions and direct analyses were performed on materials such as ivory, bone, antlers, animal tissue, human tissue, sediment, and resin. Thicker film column sets were preferred due to reduced column overloading. The samples analyzed by HS-SPME directly on a specimen appeared to give unique signatures and generally produced a higher response than for the solvent-extracted residues. A non-destructive screening approach of specimens may, therefore, be possible. Resin and beeswax mixtures prepared by heating for different lengths of time appeared to provide distinctly different volatile signatures, suggesting that GC×GC-TOFMS may be capable of differentiating alterations to resin in future studies. Further development of GC×GC-TOFMS methods for archaeological applications will provide a valuable tool to uncover significant information on prehistoric technological changes and cultural behavior. [less ▲]

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See detailGCxGC-TOFMS for the Investigation of Archeological Mysteries
Perrault, Katelynn ULg; Dubois, Lena ULg; Stefanuto, Pierre-Hugues ULg et al

Scientific conference (2016, March)

Detailed reference viewed: 17 (6 ULg)