The EU-project ´SPICE-profiling´ (2015-2017) and other forensic initiatives targeted at NPS
Michael Pütz Federal Criminal Police Office (BKA), Germany Forensic Science Institute
Sarajevo, 03.07.2015 OSCE / UNODC Regional Workshop on „New Trends and Identification Techniques in Detection of NPS and Co-operation among LEA in South East Europe“
2
EU-projects Spice/Spice II plus
DPIP: Drug Prevention and Information Progr.
The EU-project (2010-2012) ‘SPICE and synthetic cannabinoids’: Spice and synthetic cannabinoids: Fast responses by means of forensic, toxicological and socio-scientific analyses with direct impact on prevention measures. Legal medicine, Universities (Toxicological and Drug Research), Police/Forensics, Drug Prevention and Monitoring Institutions Freiburg, Wien, Helsinki, Frankfurt, Wiesbaden, Warschau, Bern
Continuation (2013-2015) in the EU-project ´SPICE II plus´: Extension to substance classes of stimulant NPS (a. o. cathinone and piperazine derivatives), even stronger focus on prevention aspects and intensified co-operation with drug monitoring centres (DBDD, EMCDDA). Legal medicine, Universities (Toxicological and Drug Research), Police/Forensics, Drug Prevention and Monitoring Institutions Freiburg, Wien, Helsinki, Frankfurt, Wiesbaden, Bern, München, Lissabon
Prevention measures (drug supply/demand/harm reduction)
3
EU-projects Spice/Spice II plus
DPIP: Drug Prevention and Information Progr.
Product monitoring of ‘Spice’, ´bath salt´ and other NPS products
Identification of new compounds
Build-up of mass spectrometric libraries (EI-MS and ESI-MS/MS)
Assessment of toxicological properties and risk profiles
Development of bioanalytical methods (metabolism!)
Rapid detection, ‘profiling’ concepts, quantitation in drug material
Social research (prevalence, patterns of use)
International conference on ‘Spice’ prevention issues
‘Spice’ information and prevention website, brochure and flyers:
http://legal-high-inhaltsstoffe.de/
Results in positive serum samples (n=734) 05/2010 – 03/2012 (selection of compounds)
0%
20%
40%
60%
80%
100%
JWH-250 JWH-081, JWH-122 JWH-203, JWH-210, RCS-4 Scheduled to be controlled
Rel
ativ
e fr
eque
ncy
of o
ccur
renc
e
JWH-081 JWH-122 JWH-250 JWH-210 RCS-4 JWH-203 AM-2201 JWH-019 JWH-307 AM-1220
Method: Journal of Mass Spectrometry, Dresen et al. 2010, Kneisel et al. 2012
Prevalence of synthetic cannabinoids
67
9
7
3
12
1
Lebenszeit-Prävalenz 30-Tages-Prävalenz
Spice/ "Räuchermischungen"
2008 2009 2010 2011
Life time prevalence 30-day prevalence
‘Spice products’
2012: 7-8% of 15-18-year-old pupils in Frankfurt, Germany consumed SPICE-products
Prevalence of synthetic cannabinoids
- 2012: 7-8% of 15-18-year-old pupils in Frankfurt, Germany consumed SPICE-products
- 8 % of urine samples from ‘fitness to drive’ testing (negatively tested for THC-COOH) were positive for SC’s
- Positivity rates in forensic-psychiatric hospitals: up to > 80 % (trying to escape drug testing)
- Finland: 3 % of DRUID drivers had synthetic cannabinoids in their blood in addition to other drugs
- In some countries less problems with SC’s (why?)
77
62
61
57
3734
33
13
115
'High'
Curiosity
Legal availability
Relaxation
Variety
Non-detectability
Other drugs (temporarily) not available
(low) Price
Because friends comsume, too
Because I had problems
"wichtig/ sehr wichtig"
Goethe-Universität Frankfurt am Main Institut für Sozialpädagogik und Erwachsenenbildung
Online-survey: Motives for consumption (%)
(‚Legal highs‘)
‘Important / very important’
Brochures and Flyers directed to consumers and professional
http://legal-high-inhaltsstoffe.de/
Procedures for rapid detection, identifi-cation and quantification of seized NPS
- Ion Mobility Spectrometry (IMS)
- FT-IR and Raman spectroscopy
- Ambient MS (DESI–MS)
- Quantification (GC-FID, UHPLC-DAD, LC-MS)
► UNODC manual STNAR48 (released 06/2013, Auwärter/Pütz)
GTFCH Symposium Mosbach 10 Comparison of rapid detecting optical techniques for the identification of New Psychoactive Substances (NPS) in ‘Legal Highs’ and ‘Research Chemicals’
Rapid Detection Techniques Application fields & Challenges
Police Street- and traffic controls
Seizures and big events
Customs Suspicious material/samples
Forensics Clandestine drug labs
Explosives/Disarming
Short analysis time
Simple & safe handling
Portability
Reliable detection/analysis of substances/mixtures
GTFCH Symposium Mosbach 11 Comparison of rapid detecting optical techniques for the identification of New Psychoactive Substances (NPS) in ‘Legal Highs’ and ‘Research Chemicals’
Presumptive Drug Tests (Color reaction)
IMS (Ionmobility-spectrometry)
Ambient MS-Techniques (DESI-MS, DART)
Spectroscopic Techniques (FT-Infrared[IR] & Raman) Specific/Structural substance
information (fingerprint region)
Non-invasive
Quantification possible
Less sample preparation
Detection Limit ~ 5 – 10 %
Library dependent
Rapid Detection Techniques
GTFCH Symposium Mosbach 12 Comparison of rapid detecting optical techniques for the identification of New Psychoactive Substances (NPS) in ‘Legal Highs’ and ‘Research Chemicals’
Infrared vs. Raman Spectroscopy Pros & Cons
Source: HazMat ID Product Sheet, Smiths Detection (left) Progeny Product Sheet, Rigaku (right)
GTFCH Symposium Mosbach 13 Comparison of rapid detecting optical techniques for the identification of New Psychoactive Substances (NPS) in ‘Legal Highs’ and ‘Research Chemicals’
Infrared vs. Raman Spectroscopy Pros & Cons
FT IR Raman Basis Absorption of light by
functional groups/bonds Inelastic scattering of light by
molecules
Signal intensity High Low
Preheating necessary
Yes No
Spectrum Substraction
Yes No
Analysis through packaging
No Yes
Disturbed by Water Fluorescence (@785 nm)
Raman 785 nm vs. 1064 nm Synthetic Cannabinoids
GTFCH Symposium Mosbach 14 Comparison of rapid detecting optical techniques for the identification of New Psychoactive Substances (NPS) in ‘Legal Highs’ and ‘Research Chemicals’
0
500
1000
1500
2000
2500
3000
400 600 800 1000 1200 1400 1600
Inte
nsit
y
Ramanshift [cm-1]
XLR-11
1064 nm 785 nm
Raman Handheld-Systems (785 nm/1064 nm): Metrohm
N
O
F
CH3 CH3
CH3CH3
0
1000
2000
3000
4000
5000
6000
7000
8000
9000
400 600 800 1000 1200 1400 1600
Inte
nsit
y
Ramanshift [cm-1]
STS-135
1064 nm 785 nm
NH
N
O
F
GTFCH Symposium Mosbach 15 Comparison of rapid detecting optical techniques for the identification of New Psychoactive Substances (NPS) in ‘Legal Highs’ and ‘Research Chemicals’
0
500
1000
1500
2000
2500
400 600 800 1000 1200 1400 1600
Inte
nsit
y
Ramanshift [cm-1]
1064 nm
STS-135
0
200
400
600
800
1000
1200
400 600 800 1000 1200 1400 1600
Inte
nsit
y
Ramanshift [cm-1]
785 nm
XLR-11
Raman 785 nm vs. 1064 nm Synthetic Cannabinoids
Raman Handheld-Systems (785 nm/1064 nm): Metrohm
Enough Information for Identification
Not enough Information for Identification
GTFCH Symposium Mosbach 16 Comparison of rapid detecting optical techniques for the identification of New Psychoactive Substances (NPS) in ‘Legal Highs’ and ‘Research Chemicals’
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
1150 1250 1350 1450 1550 1650 1750Wavenumber [cm-1]
Herbal Blend 'R&B'
R&B Acetone Extract R&B untreated
Library Hits: R&B Untreated THC R&B Acetone extract JWH-210
Picture:http://i1.cpcache.com/product_zoom/1534831882/samsung_galaxy_s5_case.jpg?height=250&width=250&padToSquare=true
Herbal Blend + 50 µL acetone
Extraction
Transfer on ATR spot Result
Measure after drying
FT-IR Synthetic Cannabinoids – Herbal Blends
Pre-treatment: Acetone Extraction
FT-IR Mobile-System ‚HazMat ID®‘: Smiths Detection
GTFCH Symposium Mosbach 17 Comparison of rapid detecting optical techniques for the identification of New Psychoactive Substances (NPS) in ‘Legal Highs’ and ‘Research Chemicals’
-0.05
0
0.05
0.1
0.15
0.2
0.25
650 1150 1650 2150 2650 3150 3650Wavenumber cm-1
Bath Salt 'Mojo'
Mojo Mojo Residual
-0.04-0.02
00.020.040.060.080.1
0.120.140.160.18
650 850 1050 1250 1450 1650Wavenumber cm-1
Bath Salt 'Mojo' – Residual
MDPV Mojo Residual
FT-IR Synthetic Cathinones – Bath Salts
1. Library Hit: Lidocaine 2. Library Hit: MDPV
Spectrum Substraction
FT-IR Mobile-System ‚HazMat ID®‘: Smiths Detection
Conclusion
FT-IR Research Chemicals
Herbal Blends (pretreatment)
Bath Salts (concentration dep.)
× Liquids
× Packed Samples
GTFCH Symposium Mosbach 18 Comparison of rapid detecting optical techniques for the identification of New Psychoactive Substances (NPS) in ‘Legal Highs’ and ‘Research Chemicals’
Raman @1064 nm Research Chemicals
Bath Salts (concentration dep.)
Liquids (concentration dep.)
Packed Samples
× Herbal Blends
Combination of FT-IR and Raman (@1064 nm) spectroscopy can deliver reliable results with structural information in short time without lab environment
User must be trained Limits of both techniques must be known
15.04.2011 19 Identification of synthetic cannabimimetic substances in herbal mixtures
Rapid analysis of NPS by IMS
Ion Mobility Spectrometer DE-tector, Bruker Daltonik
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
10
20
30
40
50
Inte
nsitä
t
Driftzeit in ms
Coca
ine
Drift time window synthetic cannabinoids
Calib
rant
Drift time window classic drugs
20 SPICE II
Rapid detection of cathinone derivatives in bath salts by IMS
3D-plasmagram of bath salt sample ‚Mojo‘ identifes MDPV and lidocaine
“SPICE-Profiling: Assessment of the origin, supply chain and market development of NPS by forensic analysis of the compo-sition and of the chemical, metabolic and isotopic signatures”
ISEC 2013, priority EPSD, JUST/2013/ISEC/DRUGS/AG/ISEC/4000006421 Co-ordinator: BKA, Forensic Science Institute, Wiesbaden Funded Institute of Legal Medicine, Freiburg, Germany partners: INPS, French Police Forensic Science Institute, Lyon Associated Finnish National Customs Laboratory, Helsinki partners: LKA RP LKA SH LKA BY LKA HE Duration: 01.04.2015 – 31.03.2017 Budget: ~700 TEUR (90 % funded)
21
EU-project „SPICE-profiling“
ISEC: Fight Against and Prevention of Crime
22
„SPICE-profiling“: core activities
Workstream 1: Product monitoring of products containing NPS by qualitative and quantitative analysis of products composition (internet test purchases of products and pure substances, police and customs seizures).
Workstream 2: Method development for clinical and forensic analysis of human biosamples and application to forensic case work and clinical emergency cases.
Workstream 3: - Assessment of suitable synthesis impurities in unadulterated NPS samples by chemical analysis via GC-MS and UHPLC-MS and conducting controlled syntheses of synthetic cannabinoids. - Development of flexible impurity profiling procedures for synthetic cannabinoids and synthetic cathinones via GC-MS, creation of a representative database and multivariate analysis of impurity profiling and isotopic profiling data.
Workstream 4: Development, validation and harmonization of extraction techniques and of methods to determine isotope ratios using EA-IRMS and GC-IRMS-MS of synthetic cannabimimetic substances and application to establish links between different seizures and to link seizures to clandestine producers.
Clandestine production of NPS in China
24
Pictures taken from a YouTube video, showing the production of JWHs in a clandestine lab
titaniumwf.com Manufacture JWH. Sale of technology of synthesis JWH, MDPV 2011 [cited 2014 08 June]; Available from: www.youtube.com/watch?v=eho28ALAD-c
Scheme for profiling analysis
GC/MS
Combined impurities
Isolation
Flash column chromatography
Pure substance
Reference material
HS-GC, ICP-MS
Controlled synthesis
Identification, chrom. Profiling
EA-IRMS, GC-IRMS
Multivariate data analysis
Sample links, information on origin
Flash chromatography for isolation of main active NPS substances and combined fractions of impurities
Sepracore flash chromatography Full automated fraction control via UV/vis detector Two pumps for up to 50 bar Ready-made column cartridges and self-packed glass columns
Example: XLR-11 synthesis impurities
NH
O
NH
O
NUR-144
1. EtMgBrTHF2. ZnCl2Et2O
O
3. CH2Cl2
Cl
1. NaHDMF
2. DMFBr
O
NH
m/z 242C16H20NO+
O
N
F
O
+ H+
m/z 454C29H41FNO2
+
+ H+
N
F
F
+ H+
m/z 294C18H26F2N+
O
N
O
+ H+
m/z 366C24H32NO2
+
Published synthesis of UR-144 Frost, J.M., et al., Indol-3-ylcycloalkyl Ketones: Effects of N1 Substituted Indole Side Chain Variations on CB2 Cannabinoid Receptor Activity. Journal of Medicinal Chemistry, 2009. 53(1): p. 295-315.
XLR-11 impurities tentatively identified in extract of Manga XXL via UHPLC-MS n
Impurities hint to comparable synthesis route for XLR-11 starting from indole (high amounts of impurities)
Practical application of chromatographic impurity profiling in clandestine labs
distillation residue from white cannister (6,6 kg, 10 % amph.)
sample from distillation flask (res.,10 % amph.)
strong link (both samples ori- ginating from one production batch)
22.03.2011
29 Das Bundeskriminalamt - Zentralstelle der deutschen Kriminalpolizei
Basics of stable isotope ratio analysis
Isotope effects
1H1HO evaporates easier than 2H1HO
⇒ water steam is depleted in heavy hydrogen isotopes compared to lake water
precipitation is enriched in heavy hydrogen isotopes compared to water
steam
Example: water cycle
H2O (l) H2O (g)
33
EA-IRMS batch-to-batch comparison of 5F-PB-22 extracted from Spice-products
7.00
7.20
7.40
7.60
7.80
8.00
8.20
8.40
8.60
8.80
9.00
-26.10 -25.90 -25.70 -25.50 -25.30 -25.10 -24.90 -24.70 -24.50
δ15 N
AIR[
‰]
δ13CV-PDB[‰]
Made bin Belgium
Jamaican Gold Extreme
Bonsai Winter Boost
Love
R&B
Bubblegum
Yama
Blaze
Manga Extreme
Bonsai Citrus
Bonsai Summer Boost
Saarbrücken
Bonzai Summer Boost (2)
Jamaican Gold Supreme
VIP
Recent activity: MDMB-CHMICA
Large seizure of 40 Kg pure MDMB-CHMICA by LUX customs (December 2014)
Ca. 50 Mio. single doses
From Shanghai, Destination: Madrid
40 bags à 1 Kg
Samples of all 40 bags kindly provided to BKA (one bigger sample to distribute to LKÄ/BWZ)
First information: Batch production size!
Other ongoing EU initiatives related to NPS
EU-project RESPONSE (ISEC, 2015-2017) CLEN network (EU forensic customs labs, JRC, EMCDDA, DG TAXUD)
COLLECT, ANALYSE, ORGANIZE, EVALUATE, SHARE – A RESPONSE TO CHALLENGES IN FORENSIC DRUGS ANALYSES
project objectives and activities
Sonja Klemenc (RESPONSE project manager) ([email protected] and [email protected] )
MNZ GPU, National Forensic Laboratory, Vodovodna 95, 1000 Ljubljana, Slovenia
ENFSI- DWG meeting, 5th-8th May, Dublin 2015
38
PARTNERS
ENFSI- DWG meeting, 5th-8th May, Dublin 2015 39
Project was developed and will be implemented in close cooperation with ENFSI WORKING GROUP DRUGS Grant agreement number: JUST/2013/ISEC/DRUGS/AG/6413
Duration: from 5th January 2015 until 4th January 2017 Total project budget : 748.212,91 € (EU contribution: 90%, R Slovenia 10%)
Coordinator: Ministry of the Interior of the Republic Of Slovenia, Police – NATIONAL FORENSIC LABORATORY, Slovenia
Partners (co-beneficiaries): Ministry of the Interior, National Forensic Institute (INPS), France Hungarian Institute for Forensic Sciences (HIFS), Hungary National Institute of Criminalistics and Criminology (INCC), Belgium Institute for Forensic Medicine, Aarhus (UNI Aarhus), Denmark University of Copenhagen, Faculty of Health (UNI CPHG), Department of Forensic Medicine, Denmark Ministry of the Interior of the Republic of Croatia, Forensic Science Centre (MUP RH), Croatia University of Ljubljana, Faculty of Chemistry and Chemical Technology (FKKT), Slovenia
Associate partners: European Monitoring Centre for Drugs and Drug Addiction (EMCDDA), Portugal Forensic Science Lab, Dublin (FSL), R Ireland Forensic Science and Toxicology Lab, State General Laboratory, Ministry of Health (FSTL), Cyprus Judiciary Police, Scientific Police Laboratory (SPL), Portugal National Investigation Service Norway (KRIPOS), Norway National Institute for Public Health (NIJZ), Slovenia University of Ljubljana, Faculty of Medicine, Department of Toxicology (UNI LJ FM DT), Slovenia Association DrogArt (DrogArt) NGO, Slovenia
Project impact
ENFSI- DWG meeting, 5th-8th May, Dublin 2015 40
Forensic information is the key factor for the: Strategic Operational Evidential Judicial purposes
And influences the: Drug supply reduction Planning Risk assessment activities Coordination of activities at all EU levels and wider
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