Drug detection; Drug detection dogs; Forensic chemistry; PLS-DA; Volatolomic; Animals; Discriminant Analysis; Dogs; Gas Chromatography-Mass Spectrometry; Humans; Illicit Drugs; Least-Squares Analysis; Substance Abuse Detection; Volatile Organic Compounds; Pathology and Forensic Medicine; Law
Abstract :
[en] Understanding the intricate chemical profiles of illicit drugs is crucial for combating their unregulated distribution. While gas sensors have been proposed for their detection, dogs remain the primary tool used for law enforcement agencies. However, concerns about their reliability persist due to limited information on the specific odor they detect. To improve both sensor development and dogs training, robust chemical characterisation is needed.This study aims to characterize the volatile chemical profiles released by illicit drugs seized by the Belgian Police—including amphetamine, cannabis, opium, cocaine, heroin, MDMA, and ketamine—using headspace volatile sampling coupled with gas chromatography and mass spectrometry. In addition to identifying the most abundant compounds for each drug, a partial least square discriminant analysis (PLS-DA) was employed to define their chemical signature. The model achieved a 92% success rate in detecting and differentiating the tested drugs.These findings highlight the potential for field-deployable gas sensors targeting key signature compounds, and may significantly enhance the detection dog’s performance.
Disciplines :
Zoology Chemistry
Author, co-author :
Martin, Clément ; Université de Liège - ULiège > Département GxABT > Entomologie, Phytopathologie et Productions Innovantes (EPPI) ; Drugs Expertise Center, National Institute of Criminalistic and Criminology (INCC), Brussel, Belgium
Soyeurt, Hélène ; Université de Liège - ULiège > Département GxABT > Modélisation et développement
Meert, Natalie; Drugs Expertise Center, National Institute of Criminalistic and Criminology (INCC), Brussel, Belgium
Ruhland, Fanny ; Université de Liège - ULiège > TERRA Research Centre > Entomologie, Phytopathologie et Productions Innovantes (EPPI)
Diederich, Claire; NARILIS and Dept. of Veterinary Medicine (IVRU), University of Namur, Namur, Belgium
Verheggen, François ; Université de Liège - ULiège > TERRA Research Centre > Entomologie, Phytopathologie et Productions Innovantes (EPPI)
Language :
English
Title :
Profiling the volatile organic compound signature of illicit drugs
Alternative titles :
[fr] Analyse de la signature des composés organiques volatils présents dans les drogues illicites
EUDA, Drug supply, production and precursors - the current situation in Europe (European Drug Report 2024), in: 2024. 〈https://www.euda.europa.eu/publications/european-drug-report/2025/drug-supply-production-and-precursors_en〉 (accessed June 19, 2025).
A. Żubrycka, A. Kwaśnica, M. Haczkiewicz, K. Sipa, K. Rudnicki, S. Skrzypek, L. Poltorak, Illicit drugs street samples and their cutting agents. The result of the GC-MS based profiling define the guidelines for sensors development, Talanta. 237 (2022). https://doi.org/10.1016/j.talanta.2021.122904.
L. Dujourdy, V. Dufey, F. Besacier, N. Miano, R. Marquis, E. Lock, L. Aalberg, S. Dieckmann, F. Zrcek, J.S. Bozenko, Drug intelligence based on organic impurities in illicit MA samples, Forensic Sci. Int. 177 (2008) 153–161. https://doi.org/10.1016/j.forsciint.2007.11.013.
M. Marchini, C. Charvoz, L. Dujourdy, N. Baldovini, J.J. Filippi, Multidimensional analysis of cannabis volatile constituents: Identification of 5,5-dimethyl-1-vinylbicyclo[2.1.1]hexane as a volatile marker of hashish, the resin of Cannabis sativa L., J. Chromatogr. A. 1370 (2014) 200–215. https://doi.org/10.1016/j.chroma.2014.10.045.
F. Franchina, L. Dubois, J.-F. Focant, High-Dimensional Analytical Strategies For Accurate Metabolite Profiling: Application To Cannabis, in: GCxGC Symp., 2021. https://orbi.uliege.be/handle/2268/261101 (accessed June 19, 2025).
D. Carby-Robinson, P.W. Dalsgaard, C.B. Mollerup, K. Linnet, B.S. Rasmussen, Cocaine profiling method retrospectively developed with nontargeted discovery of markers using liquid chromatography with time-of-flight mass spectrometry data, Drug Test. Anal. 14 (2022) 462–473. https://doi.org/10.1002/dta.3130.
S. Materazzi, A. Gregori, L. Ripani, A. Apriceno, R. Risoluti, Cocaine profiling: Implementation of a predictive model by ATR-FTIR coupled with chemometrics in forensic chemistry, Talanta. 166 (2017) 328–335. https://doi.org/10.1016/j.talanta.2017.01.045.
S. Choe, J. Lee, H. Choi, Y. Park, H. Lee, J. Jo, Y. Park, E. Kim, J. Pyo, H.J. Lee, S. Kim, Estimation of the synthetic routes of seized methamphetamines using GC-MS and multivariate analysis, Forensic Sci. Int. 259 (2016) 85–94. https://doi.org/10.1016/j.forsciint.2015.12.018.
S. Giannoukos, A. Agapiou, S. Taylor, Advances in chemical sensing technologies for VOCs in breath for security/threat assessment, illicit drug detection, and human trafficking activity, J. Breath Res. 12 (2018). https://doi.org/10.1088/1752-7163/aa95dd.
R.Z. Al Bakain, Y.S. Al-Degs, J.V. Cizdziel, M.A. Elsohly, Comprehensive classification of USA cannabis samples based on chemical profiles of major cannabinoids and terpenoids, J. Liq. Chromatogr. Relat. Technol. 43 (2020) 172–184. https://doi.org/10.1080/10826076.2019.1701015.
C. Martin, C. Diederich, F. Verheggen, Cadaver Dogs and the Deathly Hallows — A Survey and literature review on selection and training procedure, Animals. 10 (2020) 1–19. https://doi.org/doi:10.3390/ani10071219.
Z. Haddi, A. Amari, H. Alami, N. El Bari, E. Llobet, B. Bouchikhi, A portable electronic nose system for the identification of cannabis-based drugs, Sensors Actuators, B Chem. 155 (2011) 456–463. https://doi.org/10.1016/j.snb.2010.12.047.
T. Jezierski, E. Adamkiewicz, M. Walczak, M. Sobczyńska, A. Górecka-Bruzda, J. Ensminger, E. Papet, Efficacy of drug detection by fully-trained police dogs varies by breed, training level, type of drug and search environment, Forensic Sci. Int. 237 (2014) 112–118. https://doi.org/10.1016/j.forsciint.2014.01.013.
L.S. Leite, V. Visani, P.C.F. Marques, M.A.B.L. Seabra, N.C.L. Oliveira, P. Gubert, V.W.C. de Medeiros, J.O. de Albuquerque, J.L. de Lima Filho, Design and implementation of an electronic nose system for real-time detection of marijuana, Instrum. Sci. Technol. 49 (2021) 471–486. https://doi.org/10.1080/10739149.2021.1887213.
S. Rice, J.A. Koziel, Odor impact of volatiles emitted from marijuana, cocaine, heroin and their surrogate scents, Data Br. 5 (2015) 653–706. https://doi.org/10.1016/j.dib.2015.09.053.
N. Wiebelhaus, D. Hamblin, N.M. Kreitals, J.R. Almirall, Differentiation of marijuana headspace volatiles from other plants and hemp products using capillary microextraction of volatiles (CMV) coupled to gas-chromatography–mass spectrometry (GC–MS), Forensic Chem. 2 (2016) 1–8. https://doi.org/10.1016/j.forc.2016.08.004.
M. Chiarotti, R. Marsili, A. Moreda-Piñeiro, Gas chromatographic-mass spectrometric analysis of residual solvent trapped into illicit cocaine exhibits using head-space solid-phase microextraction, J. Chromatogr. B Anal. Technol. Biomed. Life Sci. 772 (2002) 249–256. https://doi.org/10.1016/S1570-0232(02)00109-5.
S. Gura, P. Guerra-Diaz, H. Lai, J.R. Almirall, Enhancement in sample collection for the detection of MDMA using a novel planar SPME (PSPME) device coupled to ionmobility spectrometry (IMS), Drug Test. Anal. 1 (2009) 355–362. https://doi.org/10.1002/dta.81.
M. Dei Cas, S. Arnoldi, L. Monguzzi, E. Casagni, C. Morano, E. Vieira de Manincor, C. Bolchi, M. Pallavicini, V. Gambaro, G. Roda, Characterization of chemotype-dependent terpenoids profile in cannabis by headspace gas-chromatography coupled to time-of-flight mass spectrometry, J. Pharm. Biomed. Anal. 203 (2021) 114180. https://doi.org/10.1016/j.jpba.2021.114180.
J. Vercammen, P. Sandra, E. Baltussen, T. Sandra, F. David, Considerations on static and dynamic sorptive and adsorptive sampling to monitor volatiles emitted by living plants, HRC J. High Resolut. Chromatogr. 23 (2000) 547–553. https://doi.org/10.1002/1521-4168(20000901)23:9<547::AID-JHRC547>3.0.CO;2-7.
V. Reinstadler, R. Gutmann, F. Pitterl, K. Winkler, H. Oberacher, Gas Chromatography—High-Temperature Proton-Transfer Reaction Mass Spectrometry as a Novel Tool for Forensic Drug Testing, Separations. 9 (2022). https://doi.org/10.3390/separations9110328.
B. Mitrevski, B. Veleska, E. Engel, P. Wynne, S.M. Song, P.J. Marriott, Chemical signature of ecstasy volatiles by comprehensive two-dimensional gas chromatography, Forensic Sci. Int. 209 (2011) 11–20. https://doi.org/10.1016/j.forsciint.2010.11.008.
S. Rice, J.A. Koziel, The relationship between chemical concentration and odor activity value explains the inconsistency in making a comprehensive surrogate scent training tool representative of illicit drugs, Forensic Sci. Int. 257 (2015) 257–270. https://doi.org/10.1016/j.forsciint.2015.08.027.
K.G. Furton, N.I. Caraballo, M.M. Cerreta, H.K. Holness, Advances in the use of odour as forensic evidence through optimizing and standardizing instruments and canines, Philos. Trans. R. Soc. B Biol. Sci. 370 (2015). https://doi.org/10.1098/RSTB.2014.0262.
T.R. Fiorentin, M. Fogarty, R.P. Limberger, B.K. Logan, Determination of cutting agents in seized cocaine samples using GC–MS, GC–TMS and LC–MS/MS, Forensic Sci. Int. 295 (2019) 199–206. https://doi.org/10.1016/j.forsciint.2018.12.016.
S. Dellicour, T. Lecocq, GCALIGNER 1. 0: An alignment program to compute a multiple sample comparison data matrix from large eco-chemical datasets obtained by GC, J. Sep. Sci. 36 (2013) 3206–3209. https://doi.org/10.1002/jssc.201300388.
M.J. Anderson, Distance-based tests for homogeneity of multivariate dispersions., Biometrics. 62 (2006) 245–253.
H. Lai, I. Corbin, J.R. Almirall, Headspace sampling and detection of cocaine, MDMA, and marijuana via volatile markers in the presence of potential interferences by solid phase microextraction-ion mobility spectrometry (SPME-IMS), Anal. Bioanal. Chem. 392 (2008) 105–113. https://doi.org/10.1007/s00216-008-2229-z.
S. Mascrez, J. Aspromonte, G. Purcano, Enhance the Performance of Solid-Phase Microextraction by Exploiting Vacuum-Assisted Headspace and Multicumulative Trapping for Olive Oil Characterization, LCGC North Am. (2023) 18–21. https://doi.org/10.56530/LCGC.NA.OC7576I2.
S. Elia, M. Stylianou, A. Agapiou, Advanced micro-extraction techniques ( SPME, HiSorb) for the determination of goat cheese whey wastewater VOCs, J. Environ. Manage. 351 (2024) 119934. https://doi.org/10.1016/j.jenvman.2023.119934.
V.L. Colley, J.F. Casale, Differentiation of South American crack and domestic (US) crack cocaine via headspace-gas chromatography/mass spectrometry, Drug Test. Anal. 7 (2015) 241–246. https://doi.org/10.1002/dta.1729.
N. Stojanovska, S. Fu, M. Tahtouh, T. Kelly, A. Beavis, K.P. Kirkbride, A review of impurity profiling and synthetic route of manufacture of methylamphetamine, 3,4-methylenedioxymethylamphetamine, amphetamine, dimethylamphetamine and p-methoxyamphetamine, Forensic Sci. Int. 224 (2013) 8–26. https://doi.org/10.1016/j.forsciint.2012.10.040.
S. El-Akaad, S. De Saeger, N. Beloglazova, Molecularly imprinted polymer based capacitive sensing of a specific Leuckart marker 4-methyl-5-phenylpyrimidine in wastewater, Sensors Actuators B Chem. 343 (2021) 130116. https://doi.org/10.1016/j.snb.2021.130116.
K. Norman, | Austin, L. Ciesielski, J.R. Wagner, Identification and associated hazards of clandestine drug laboratories Drug Compounds Toxicology > Drug Analysis Crime Scene Investigation > Crime Scene Examination, (2020). 〈https://doi.org/10.1002/wfs2.1393〉.
N.F. Montiel, M. Parrilla, N. Sleegers, F. Van Durme, A.L.N. Van Nuijs, K. De Wael, Electrochemical sensing of amphetamine-type stimulants (pre)-precursors to fight against the illicit production of synthetic drugs, Electrochim. Acta. 436 (2022). https://doi.org/10.1016/j.electacta.2022.141446.
B. Erdélyi, A. Szabó, L. Birincsik, Á. Hoschke, Process development of methylenedioxyphenyl-acetone chiral bioreduction, J. Mol. Catal. B Enzym. 29 (2004) 195–199. https://doi.org/10.1016/j.molcatb.2003.10.015.
J.Y.K. Cheng, M.F. Chan, T.W. Chan, M.Y. Hung, Impurity profiling of ecstasy tablets seized in Hong Kong by gas chromatography-mass spectrometry, Forensic Sci. Int. 162 (2006) 87–94. https://doi.org/10.1016/j.forsciint.2006.02.055.
F. Palhol, S. Boyer, N. Naulet, M. Chabrillat, Impurity profiling of seized MDMA tablets by capillary gas chromatography, Anal. Bioanal. Chem. 374 (2002) 274–281. https://doi.org/10.1007/s00216-002-1477-6.
J.M. Poupko, W.L. Hearn, F. Rossano, Drug Contamination of U.S. Paper Currency and Forensic Relevance of Canine Alert to Paper Currency: A Critical Review of the Scientific Literature, J. Forensic Sci. 63 (2018) 1340–1345. https://doi.org/10.1111/1556-4029.13755.
F.M. Hauser, J.W. Hulshof, T. Rößler, R. Zimmermann, M. Pütz, Characterisation of aqueous waste produced during the clandestine production of amphetamine following the Leuckart route utilising solid-phase extraction gas chromatography–mass spectrometry and capillary electrophoresis with contactless conductivity dete, Drug Test. Anal. 10 (2018) 1368–1382. https://doi.org/10.1002/dta.2394.
L. Cecchi, M. Migliorini, E. Giambanelli, A. Cane, B. Zanoni, V. Canuti, N. Mulinacci, F. Melani, Is the volatile compounds profile a suitable tool for authentication of virgin olive oils (Olea europaea L.) according to cultivars? A study by using HS-SPME-GC-MS and chemometrics, Food Control. 139 (2022) 109092. https://doi.org/10.1016/j.foodcont.2022.109092.
C. Martin, M. Malević, C. Diederich, F. Verheggen, Copycatting the smell of death: Deciphering the role of cadaveric scent components used by detection dogs to locate human remains, J. Forensic Sci. (2023). https://doi.org/10.1111/1556-4029.15277.
E. Göl, I. Çok, New psychoactive substances in Turkey: Narcotics cases assessed by the Council of Forensic Medicine between 2016 and 2017 in Ankara, Turkey, (2018). 〈https://doi.org/10.1016/j.forsciint.2018.11.003〉.