Forensic science; Forensic Chemistry; Odor analysis; Cadaver decomposition; Volatile Organic Compounds; VOCs; comprehensive two-dimensional gas chromatography (GCxGC); Time-of-flight mass spectrometry (TOFMS); mass spectral deconvolution
Abstract :
[en] Soon after death, the decay process of mammalian soft tissues begins and leads to the release of cadaveric volatile compounds in the surrounding environment. The study of postmortem decomposition products is an emerging field of study in forensic science. However, a better knowledge of the smell of death and its volatile constituents may have many applications in forensic sciences. Domestic pigs are the most widely used human body analogues in forensic experiments, mainly due to ethical restrictions. Indeed, decomposition trials on human corpses are restricted in many countries worldwide. This article reports on the use of comprehensive two-dimensional gas chromatography coupled with time-offlight mass spectrometry (GCxGC-TOFMS) for thanatochemistry applications. A total of 832 VOCs released by a decaying pig carcass in terrestrial ecosystem, i.e. a forest biotope, were identified by GCxGC-TOFMS. These postmortem compounds belong to many kinds of chemical class, mainly oxygen compounds (alcohols, acids, ketones, aldehydes, esters), sulfur and nitrogen compounds, aromatic compounds such as phenolic molecules and hydrocarbons. The use of GCxGC-TOFMS in study of postmortem volatile compounds instead of conventional GC-MS was successful.
Disciplines :
Chemistry
Author, co-author :
Dekeirsschieter, Jessica ; Université de Liège - ULiège > Sciences agronomiques > Entomologie fonctionnelle et évolutive
Stefanuto, Pierre-Hugues ; Université de Liège - ULiège > Département de chimie (sciences) > Chimie analytique, organique et biologique
Brasseur, Catherine ; Université de Liège - ULiège > Département de chimie (sciences) > GIGA-R : Laboratoire de spectrométrie de masse (L.S.M.)
Haubruge, Eric ; Université de Liège - ULiège > Services administratifs généraux > Vice-Recteur de Gembloux Agro Bio Tech
Focant, Jean-François ; Université de Liège - ULiège > Département de chimie (sciences) > Chimie analytique, organique et biologique
Language :
English
Title :
Enhanced Characterization of the Smell of Death by Comprehensive Two-Dimensional Gas Chromatography-Time-of-Flight Mass Spectrometry (GCxGC-TOFMS)
Publication date :
18 June 2012
Journal title :
PLoS ONE
eISSN :
1932-6203
Publisher :
Public Library of Science, San Franscisco, United States - California
Vass AA, (2001) Beyond the grave-understanding human decomposition. Microbiol Today 28: 190-192.
Vass AA, Barshick SA, Sega G, Caton J, Skeen JT, et al. (2002) Decomposition chemistry of human remains: a new methodology for determining the postmortem interval. J Forensic Sci 47: 542-553.
Statheropoulos M, Spiliopoulou C, Agapiou A, (2005) A study of volatile organic compounds evolved from decaying human body. Forensic Sci Int 153: 147-155.
Dent B, Forbes SL, Stuart BH, (2004) Review of human decomposition processes in soil. Environ Geol 45: 576-585.
Boumba VA, Ziavrou KS, Vougiouklakis T, (2008) Biochemical pathways generating post-mortem volatile compounds co -detected during forensic ethanol analyses. Forensic Sci Int 174: 133-151.
Statheropoulos M, Agapiou A, Zorba E, Mikedi K, Karma S, et al. (2011) Combined chemical and optical methods for monitoring the early decay stages of surrogate human models Forensic Sci Int 210: 154-163.
Vass AA, Smith RR, Thompson CV, Burnett MN, Wolf DA, et al. (2004) Decompositional Odor Analysis Database. J Forensic Sci 49: 760-769.
Vass AA, Smith RR, Thompson CV, Burnett MN, Dulgerian N, et al. (2008) Odor analysis of decomposing buried human remains. J Forensic Sci 3: 384-391.
Statheropoulos M, Mikedi K, Agapiou A, Georgiadou A, Karma S, (2006) Discrimant analysis of volatile organic compounds data related to a new location method of entrapped people in collapsed buildings of an earthquake. Analytica Chimica Acta 566: 207-216.
Statheropoulos M, Spiliopoulou C, Agapiou A, Pallis GC, SianoS E, (2007) Environmental aspects of VOCs evolved in the early stages of human decomposition. Sci Tot Envir 385: 221-227.
Hoffman EM, Curran AM, Dulgerian N, Stockam R, Eckenrode BA, (2009) Characterization of the volatile organic compounds present in the headspace of decomposing human remains. Forensic Sci Int 186: 6-13.
DeGreef LE, Furton KG, (2011) Collection and identification of human remains volatiles by non-contact, dynamic airflow sampling and SPME-GC-MS using various sorbent materials. Anal Bioanal Chem 401: 1295-1307.
Dekeirsschieter J, Verheggen FJ, Gohy M, Hubrecht F, Bourguignon L, et al. (2009) Cadaveric volatile organic compounds released by decaying pig carcasses (Sus domesticus L.) in different biotopes. Forensic Sci Int 189: 46-53.
Akdeniz N, Koziel JA, Ahn HK, Glanville TD, Crawford BP, et al. (2010) Laboratory scale evaluation of volatile organic compounds emissions as indication of swine carcass degradation inside biosecure composting units. Bioresour Technol 101: 71-78.
Kalinova B, Podskalska H, Ruzicka J, Hoskovec M, (2009) Irresistible bouquet of death- how are burying beetles (Coleoptera: Silphidae: Nicrophorus) attracted by carcasses. Naturwissenschaften 96: 889-899.
Hädrich C, Ortmann C, Reisch R, Liebing G, Ahlers H, et al. (2010) An electronic bidy-tracking dog? Int J Legal Med 124: 43-47.
Oesterhelweg L, Krober S, Rottmann K, Willhoft J, Braun C, et al. (2008) Cadaver dogs-a study on detection of contaminated carpet squares. Forensic Sci Int 174: 35-39.
Killam EW, (1990) The Detection of Human Remains. Springfield: Thomas. 263 p.
Komar D, (1999) The use of cadaver dogs in locating scattered, scavenged human remains: preliminary fields test results. J Forensic Sci 44: 405-408.
Qu G, Omotoso MM, GamalG, Feddes JJ, (2008) Development of an integrated sensor to measure odors. Environ Monit Assess 144: 277-283.
LeBlanc HN, Logan JG, (2010) Exploiting insect olfaction in forensic entomology. In: Amendt J, Campobasso CP, Goff ML, Grassberger M, editors. pp. 205-222 editors. Current concepts in forensic entomology. New York: Springer.
Frederickx C, Verheggen FJ, Haubruge E, (2011) Biosensors in forensic sciences. Biotechnol Agron Soc Environ 15: 449-458.
Notter SJ, Stuart BH, Dent BB, Keegan J, (2008) Solid-phase extraction in combination with GC/MS for the quantification of free fatty acids in adipocere. Eur J Lipid Sci Technol 110: 73-80.
Swann LM, Forbes SL, Lewis SW, (2010) Analytical separations of mammalian decomposition products for forensic science: a review. Analytica Chimica Acta 682: 9-22.
Robards K, Haddad PR, Jackson PE, (1995) Principles and practice of modern chromatographic methods. London: Academic Press Ltd. 495 p.
Ledford EB, Billesbach CA, (2000) Jet-Cooled Thermal Modulator for Comprehensive Multidimensional Gas Chromatography. J High Resolut Chromatogr 23: 202-203.
Focant JF, Reiner EJ, Macpherson K, Kolic T, Sjodin A, et al. (2004) Measurement of PCDDs, PCDFs, and non-ortho-PCBs by comprehensive two-dimensional gas chromatography-isotope dilution time-of-flight mass spectrometry (GC×GC-IDTOFMS). Talanta 63: 1231-1240.
Phillips JB, Beens J, (1999) Comprehensive two-dimensional gas chromatography: a hyphenated method with strong coupling between the two dimensions. J Chromatogr A 856: 331-347.
Patterson DG, Welch SM, Turner WE, Sjödin A, Focant JF, (2011) Cryogenic zone compression for the measurement of dioxins in human serum by isotope dilution at the attogram level using modulated gas chromatography coupled to high resolution magnetic sector mass spectrometry? J Chromatogr A 1218: 3274-3281.
van Deursen M, Beens J, Reijenga J, Lipman P, Cramers C, et al. (2000) Group-Type identification of oil samples using a comprehensive two-dimensional gas chromatography coupled to a time-of-flight mass spectrometer (GCxGC-TOF). J High Resolut Chromatogr 23: 507-510.
Focant JF, Pirard C, Eppe G, De Pauw E, (2005) Recent advances in mass spectrometric measurement of dioxins. J Chromatogr A 1067: 265-275.
Focant JF, Eppe G, Scippo ML, Massart AC, Pirard C, et al. (2005) Comprehensive two-dimensional gas chromatography with isotope dilution time-of-flight mass spectrometry for the measurement of dioxins and polychlorinated biphenyls in foodstuffs. J Chromatogr A 1086: 45-60.
Focant JF, Sjödin A, Patterson DG, (2003) Qualitative evaluation of thermal desorption-programmable temperature vaporization-comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry for the analysis of selected halogenated contaminants. J Chromatogr A 1019: 143-156.
Semard G, Adahchour M, Focant JF, (2009) Basic Instrumentation for GCxGC. In: Ramos L, editors. pp. 15-48 editor. Comprehensive two-dimensional gas chromatography. Amsterdam: Elsevier.
Cardeal ZL, de Souza PP, Gomes da Silva MDR, Marriott PJ, (2008) Comprehensive two-dimensional gas chromatography for fingerprint pattern recognition in cachaça production. Talanta 74: 793-799.
Silva I, Rocha SM, Coimbra MA, Marriott PJ, (2010) Headspace solid-phase microextraction combined with comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry for the determination of volatile compounds from marine salt. J Chromatogr A 1217: 5511-5521.
Cordero C, Liberto E, Bicchi C, Rubiolo P, Schieberle P, et al. (2010) Profiling food volatiles by comprehensive two-dimensional gas chromatography coupled with mass spectrometry: advanced fingerprinting approaches for comparative analysis of the volatile fraction of roasted hazelnuts (Corylus avellana L.) from different origins. J Chromatogr A 1217: 5848-5858.
Grassberger M, Frank C, (2004) Initial study of arthropod succession on pig carrion a central European urban habitat. J Med Entomol 41: 511-523.
Rodriguez WC, Bass WM, (1983) Insect activity and its relationship to decay rates of human cadavers in East Tennessee. J Forensic Sci 28: 423-432.
Catts EP, Goff ML, (1992) Forensic entomology in criminal investigations. Annu Rev Entomol 37: 253-272.
Anderson GS, VanLaerhoven SL, (1996) Initial studies on insect succession on carrion in Southwestern British Columbia. J Forensic Sci 41: 617-625.
Schoenly KG, Haskell NH, Hall RD, Gbur JR, (2007) Comparative performance and complementary of four sampling methods and Arthropod preference tests from human and porcine remains at the forensic anthropology center in Knoxville, Tennessee. J Med Entomol 44(5): 881-894.
Schotsmans EM, Denton J, Dekeirsschieter J, Ivaneanu T, Leentjes S, et al. (2012) Effects of hydrated lime and quicklime on the decay of buried human remains using pig cadavers as human body analogues. Forensic Sci Int 217: 50-59.
Harsanyi L, (1993) Differential diagnosis of human and animal bone. In: Grupe G, Garland AN, editors. editors. Histology of Ancient Human Bone: Methods and Diagnosis. Berlin: Springer-Verlag, 79-94.
Anderson GS, (2001) Insect succession on carrion and its relationship to determining time of death. In: Castner JH, Byrd JL, editors. pp. 143-175 editors. Forensic entomology: the utility of arthropods in legal investigations. Boston: CRC Press.
Gill-King H, (1997) Chemical and ultrastructural aspects of decomposition. In: Haglund WD, Sorg MH, editors. pp. 93-108 editors. Forensic taphonomy: the postmortem fate of human remains. Boston: CRC Press.
Campobasso CP, Di Vella G, Introna F, (2001) Factors affecting decomposition and Diptera colonization. Forensic Sci Int 120: 18-27.
Leco (2008) The Compare Feature of ChromaTOF™-Its Use in Forensic Chemistry to Assist with the Determination of the Cause of Death.
Gennard DE, (2007) Forensic Entomology: An Introduction. Chichester: Wiley. 224 p.
Bornemissza GF, (1957) An analysis of Arthropods succession in Carrion and the effect of its decomposition on the soil fauna. Aust J Zool 5: 1-12.
Reed HB, (1958) A study of dog carcass communities in Tennessee, with special reference to the insects. Am Midland Naturalist 59: 213-245.
Clark MA, Worrel MB, Pless JE, (1997) Postmortem changes in soft tissues. In: Haglund WD, Sorg MH, editors. pp. 151-160 editors. Forensic taphonomy: the postmortem fate of human remains. Boston: CRC Press.
Galloway A, (1997) The process of decomposition: a model from the Arizona-Sonoran Desert. In: Haglund WD, Sorg MH, editors. pp. 139-149 editors. Forensic taphonomy: the postmortem fate of human remains. Boston: CRC Press.
Adlam RE, Simmons T, (2007) The effect of repeated physical disturbance on soft tissue decomposition-are taphonomic studies an accurate reflection of decomposition? J Forensic Sci 52: 1007-1013.
Goff ML, (2010) Early postmortem changes and stages of decomposition. In: Amendt J, Campobasso CP, Goff ML, Grassberger M, editors. pp. 1-24 editors. Current concepts in forensic entomology. New York: Springer.
Prada PA, Curran AM, Furton KG, (2010) Comparison of extraction methods for the removal of volatile organic compounds (VOCs) present in sorbents used for human scent evidence. Anal Methods 2: 470-478.
Evans W, (1963) The Chemistry of Death. Springfield: Thomas. 101 p.
Vass AA, Bass WB, Wolt JD, Foss JE, Ammons JT, (1992) Time since death determinations of human cadavers using soil solution. J Forensic Sci 37: 1236-1253.
Callery PS, Geelhaar LA, (1984) Biosynthesis of 5-aminopentanoic acid and 2-piper-idone from cadaverine and 1-piperideine in mouse. J Neurochem 46: 1631-1634.
Chen X, Chen BM, Liu SG, Denga SG, Zhou P, (2008) Determination of Dothiepin in human plasma by LC-ESI-MS and its application to bioequivalence studies. Chromatographia 68: 941-947.
Lambourn J, Rees AA, (1974) A general practitioner study of dothiepin and amitriptyline. J Int Med Res 2: 210-213.
Keller T, Schneider A, Tutsch-Bauer E, (2000) Fatal intoxication due to dothiepin. Forensic Sci Int 109: 159-166.
Sorensen (2007) Animal welfare - an introduction. Kaliste E, eds. pp. 3-14 editor. The welfare of laboratory animals. Dordrecht: Springer.
Paterson S, Cordero R, Burlinson S, (2004) Screening and semi-quantitative analysis of post mortem blood for basic drugs using gas chromatography/ion trap mass spectrometry. J Chromatogr B 813: 323-330.
Kusano M, Medez E, Furton KG, (2011) Development of headspace SPME method for analysis of volatile organic compounds present in human biological specimens. Anal Bioanal Chem 400: 1817-1826.
Kovatsi L, Giannakis D, Arzoglou V, Samanidou V, (2011) Development and validation of a direct headspace GC-FID method for the determination of sevoflurane, desflurane and other volatile compounds of forensic interest in biological fluids: application on clinical and post-mortem samples. J Sep Sci 34: 1004-1010.