Carbon and nitrogen isotopic analysis of morphine from opium and heroin samples originating in the four major heroin producing regions

Abstract

The forensic analysis of stable isotopes is a valuable tool to geo-source natural or semisynthetic drugs such as cocaine and heroin. The present study describes a novel methodology to isolate morphine from opium for isotopic analysis. Furthermore, this isotopic data from regional sources is corroborated with morphine data obtained from seized heroin (deacetylated to morphine) from the same regions. All five primary alkaloids of opium, namely, morphine, codeine, thebaine, noscapine, and papaverine, were quantified using high performance liquid chromatography with photodiode array (PDA) detector before the preparative experiment to gather a complete major alkaloidal profile. Morphine fractions of authentic opium submissions from Mexico, South America, Southwest Asia, and Southeast Asia were isolated and collected using preparative high performance liquid chromatography, and the collected morphine samples were subsequently analyzed by isotope ratio mass spectrometry. Carbon and nitrogen isotope data are presented. The data demonstrate that nitrogen ratios are capable of differentiating samples from Mexico and South America while carbon ratios are able to distinguish Southwest Asian samples from other source regions. Analogous results have routinely been observed (as part of Heroin Signature Program analysis) for morphine obtained from deacetylated authentic heroin samples from the same source regions. The results suggest that the poppy growing region has a greater influence on the carbon and nitrogen isotope values than the heroin manufacturing processes employed. When utilized in conjunction with existing signature methodologies, carbon and nitrogen isotope ratio data can enhance the ability to geo-source heroin.

Addressing the challenges in forensic drug chemistry II

“…As shown by Lansdown and colleagues, the combination of IRMS and organic impurity profiling allowed for the correct assignment of methamphetamine samples synthesized from different pre‐precursors and reductive amination 14 . In another contribution from the DEA's Special Testing and Research Laboratory, Thompson and coworkers performed IRMS analyses on preparative HPLC collected morphine from opium and on heroin samples after hydrolysis to morphine, which allowed the investigators to corroborate regional differences for deacetylated heroin's carbon and nitrogen data with the data of morphine samples isolated from authentic opium collected from those growing regions 15 . In the world of doping control analysis, the misuse of testosterone and boldenone preparations and how they can be differentiated from steroids produced in vivo is of significant concern to scientists working in the field of sports drug testing.…”

“…14 In another contribution from the DEA's Special Testing and Research Laboratory, Thompson and coworkers performed IRMS analyses on preparative HPLC collected morphine from opium and on heroin samples after hydrolysis to morphine, which allowed the investigators to corroborate regional differences for deacetylated heroin's carbon and nitrogen data with the data of morphine samples isolated from authentic opium collected from those growing regions. 15 In the world of doping control analysis, the misuse of testosterone and boldenone preparations and how they can be differentiated from steroids produced in vivo is of significant concern to scientists working in the field of sports drug testing. Piper and Thevis analyzed seized samples of testosterone and boldenone products using carbon isotope ratios (CIR).…”

Interpol Review of Drug Analysis 2019-2022

“…2019 novel and sensitive sensor for morphine based on electrochemically synthesized poly(p-aminobenzenesulfonicacid)/reduced grapheneoxide (poly(p-ABSA)/RGO) composite modified glassy carbon electrode [ 212 ]; nine step method to synthesize morphine from o-vanillin [ 213 ]; immunochromatographic lateral flow strip with gold nanoparticles labeling was developed for monitoring of morphine [ 214 ]; electrochemical sensor for detection of morphine [ 215 ]; 2020 Review of electrochemical detection methods of differeent moodified electrodes for deteection of morphine [ 216 ]; synthesis and use of poly(cetyltrimethylammoniumbromide)/graphene oxide (poly(CTAB)/GO) composite as novel sensor for morphine detection [ 217 ]; sensor for determination of morphine and diclofenac via differential pulse voltammetric, cyclic voltammetric, and chronoamperometry [ 218 ]; fluorescence immunoassay method for detection of morphine [ 219 ]; 2021 surface ionization mass spectrometry method for the direct detection and analysis of morphine [ 220 ]; a quantitative lateral flow immunoassay instrument that uses magnetic resistance sensors for quantitative measurement of morphine [ 221 ]; comparison of two different sensing platforms (electrochemical impedance spectroscopy and a quartz crystal microbalance) for the detection of morphine [ 222 ]; evaluation of the use of plant extracts and herbal products as a SPME sorbet for use with RP-HPLC and LC-MS/MS for detection of Morphine and Codeine [ 223 ]; electrochemical sensor for DPV determination of morphine [ 224 ]; utilization of a gas-phase chloride attachment with IMS for selective detection of morphine in a morphine/codeine mixture [ 225 ]; N,Cl-doped deep eutectic solvents-based carbon dots as a selective fluorescent probe for determination of morphine in food [ 226 ]; electrochemical sensor for detection of morphine in drug samples [ 227 ]; 2022 electrochemical sensor for simultaneous detection of Diclofenac and Morphine [ 228 ]; sensor for detection of morphine [ 229 , 230 ]; methodology to isolate morphine from opium and heroin (deacetylated to morphine) for isotopic analysis and regional analysis of submissions from Mexico, South America, Southwest Asia, and Southeast Asia [ 231 ]; electrochemical sensors for detection of morphine in unprocessed coffee and milk [ 232 ].…”

Turning a 3D Printer into a HPLC Fraction Collector: A Tool for Compound-Specific Stable Isotope Measurements

“…The chromatographic column has stronger affinity for some compounds compared to others, and this makes compounds elute from the column at different times. There have been numerous studies in which samples separated by HPLC have been subsequently measured using isotope ration mass spectrometry (IRMS), for a range of chemical elements [15][16][17][18][19][20][21][22]. HPLC-IRMS can be achieved using online HPLC-IRMS, where a HPLC pump is directly connected to an IRMS machine [23], but this approach has some limitations: it is limited to carbon isotopes only (while IRMS can measure many different elements); it can only operate using low-flow water as the mobile phase (in contrast, HPLC can operate using many other solvents, including organic solvents, which cannot be used for online HPLC-IRMS); and it demands the use of corrosive chemicals and fragile membranes/filaments, which make the operation of the system highly labor (and capital)-intensive [24].…”