Analyse von heroinproben mit der Kapillargaschromatographie. Vergleich von Glaskapillartrennsäule und gepackter Säule

In forensic examination of illicit heroin samples high-resolution capillary gas chromatography is compared with gas chromatography with packed columns. Separation efficiency, reproducibility of qualitative and quantitative determinations and stability of the columns are examined.A practical method with silylation of the samples is presented which allows safe identification and quantification of many various compounds contained in illicit heroin samples. The gas chromatographic data of 35 substances (opium alkaloids and synthetic derivatives, adulterants and diluents) are listed. The method also allows the quantification of morphine, opium, and cocaine samples.     

Analytical studies on illicit heroin. II. Comparison of samples

A rapid method for the comparative analysis of illicit heroin samples has been developed. It is based on high pressure liquid chromatography using an ultraviolet and a fluorimetric detector simultaneously. The two detectors give so much information that reliable conclusions can be made.     

Noscapine as an adulterant in illicit heroin samples

In this short report the evidence is given (based on the analyses of 22 case samples) that noscapine can be used as an adulterant in illicit heroin samples. In this context, the appearance of illicit heroin samples characterised by a high noscapine content (up to 61%) and a high noscapine/whole morphine ratio (up to 3.5) is highlighted. All samples discussed in the paper (132) were seized in Slovenia, in the period from 1997 to 1999 and were analysed by gas chromatography-mass spectrometry.     

Impurities, adulterants and diluents of illicit heroin in Denmark (Jutland and Funen)

The contents of impurities, adulterants and diluents in 77 samples of illicit heroin were determined by a combination of high-performance liquid chromatography and gas chromatography. The origin of each sample was characterized by calculating the content of the opium alkaloids in relation to the heroin content. The routes of distribution were compared by determination of the contents of caffeine, procaine and sugars. The results were used as a "chemical fingerprint" of each sample. The results indicate that it is difficult to prove, with certainty, that two samples are identical. However, in most cases, by determining the amounts of impurities, adulterants and diluents in heroin samples, it will be possible to ascertain whether two samples are different and, in many cases, to determine with reasonable certainty whether two samples are identical.     

Signature Profiling and Classification of Illicit Heroin by GC-MS Analysis of Acidic and Neutral Manufacturing Impurities

Abstract:  The illicit manufacture of heroin results in the formation of trace level acidic and neutral impurities. These impurities are detectable in illicit heroin and provide valuable information about the manufacturing process used. The isolation, derivatization, and semiquantitative analysis of neutral and acidic heroin manufacturing impurities by programmed temperature vaporizing injector-gas chromatography-mass spectrometry (PTV-GC-MS) is described. Trace acidic and neutral heroin impurities were isolated from basic fractions using liquid–liquid extraction. Extracted impurities were treated with N -Methyl- N -trimethylsilyltrifluoroacetamide followed by PTV-GC-MS analyses. Semiquantitative data were obtained using full scan mass spectrometry utilizing unique ions or ion combinations for 36 trace impurities found in crude and/or highly refined heroin samples. Minimum detection limits for acidic and neutral impurities were estimated to be at the 10⁻⁷ level relative to total morphine. Over 500 authentic heroin samples from South America, Mexico, Southwest Asia, and Southeast Asia were analyzed. Classification of illicit heroin based on the presence or absence and relative amounts of acidic and neutral impurities is presented.     

A quantitative densitometric determination of heroin and cocaine samples by high-performance thin-layer chromatography

The traditional thin-layer chromatography (TLC) is a sensitive technique frequently used in chemical analysis for semiquantitative determinations. In the last years a high-performance thin-layer chromatography system (HPTLC) has been developed. It assures quantitative determinations with direct densitometric measurements of chromatographic spots in situ on the plate. Here, we wish to report a method for the drug determination in street samples, that employs a CAMAG TLC/HPTLC Scanner Photodensitometer and a CAMAG LINOMAT III for sample application. Samples of illicit drug traffic (50 samples of street heroin and 30 samples of street cocaine) are tested and the gas-liquid chromatography (GLC) and HPTLC determinations are compared. The HPTLC method has proven to be sensitive, precise and accurate for quantitative determinations of drugs in street samples. Furthermore this method may be useful in forensic chemistry to show a "fingerprint" of each sample.     

Chlorinated Opium Alkaloid Derivatives Produced by the Use of Aqueous Sodium Hypochlorite During the Clandestine Manufacture of Heroin

Abstract:  A clandestine chemist was observed producing heroin from crude morphine utilizing a solution of sodium hypochlorite during the process. Numerous chlorinated opium alkaloid derivatives were created when the morphine acetylation reaction was quenched and neutralized with a solution of sodium hypochlorite and ammonium hydroxide. Four of these compounds, 1-chloroheroin, 1-chloroacetylcodeine, 1-chloro-O⁶-monoacetylmorphine, and 2'-chloropapaverine, were characterized via preparative isolation, gas chromatography/mass spectrometry, nuclear magnetic resonance spectroscopy, and independent synthesis. These chlorinated derivatives were formed via electrophilic aromatic substitution with free chlorine during the illicit process. Although no illicit heroin exhibits containing these compounds have been observed in seizures to date, mass spectral data are provided for several of these compounds for their identification should they be seen within future seizures of illicit heroin.     

Illicitly imported heroin products: some physical and chemical features indicative of their origin

Samples taken from over 200 seizures of imported illicit heroin preparations of known geographical origin have been examined by gas liquid chromatography (GLC). The chromatographic characteristics were considered in conjunction with the physical appearance of the materials and it was found possible in many instances to discriminate between samples of different origin. Thus by carrying out GLC and HPLC and a visual inspection on a sample of unknown provenance, it may be possible to give an opinion as to its geographical origin.     

The detection of acetylcodeine and 6-acetylmorphine in opiate positive urines

Acetylcodeine (AC), an impurity of illicit heroin synthesis, was investigated as a urinary biomarker for detection of illicit heroin use. One hundred criminal justice urine specimens that had been confirmed positive by GC/MS for morphine at concentrations >5000 ng/ml were analyzed for AC, 6-acetylmorphine (6AM), codeine, norcodeine and morphine. The GC/MS analysis was performed by solid phase extraction and derivatization with propionic anhydride. Total codeine and morphine concentrations were determined by acid hydrolysis and liquid/liquid extraction. AC was detected in 37 samples at concentrations ranging from 2 to 290 ng/ml (median, 11 ng/ml). 6AM was also present in these samples at concentrations ranging from 49 to 12 600 ng/ml (median, 740 ng/ml). Of the 63 specimens negative for AC, 36 were positive for 6AM at concentrations ranging from 12 to 4600 ng/ml (median, 124 ng/ml). When detected, the AC concentrations were an average of 2.2% (0.25 to 10.2%) of the 6AM concentrations. There was a positive relationship between AC concentrations and 6AM concentrations (r=0.878). Due to its very low concentration in urine, AC was found to be a much less reliable biomarker for illicit heroin use than 6AM in workplace or criminal justice urine screening programs. However, AC detection could play an important role in determining if addicts in heroin maintenance programs are supplementing their supervised diacetylmorphine doses with illicit heroin.     

Component analysis of illicit heroin samples with GC/MS and its application in source identification

A novel method based on GC/MS and GC for component analyses of seized illicit heroin was established by using SKF525A as an internal standard. The main components in illicit heroin products such as heroin, O3-acetylmorphine, monoacetylcodeine, and O6-acetylmorphine were determined quantitatively and the organic adulterants such as paracetamol, acetaminophen caffeine and theophylline were detected qualitatively using the developed method. With these obtained data, 500 seized illicit heroin samples were divided into nine groups. The decomposition pattern of heroin was studied. The dependencies of both the decomposition pattern and the content ratios of monoacetylcodeine to heroin and monoacetylcodeine to O6-acetylmorphine on the source of the seized illicit heroin were observed. This information was used to develop a novel method for its source identification. The examination results were in agreement with the practical cases, thus providing significant information for detection of criminal cases involving illicit heroin.     

Particle size analysis of six illicit heroin preparations seized in the U.K.

Illicit heroin is rarely pure and may contain a number of other substances. The total particle size distribution in six illicit heroin preparations was analysed using a Malvern 2600 Particle Analyser and by sieving. The pattern of heroin distribution amongst these particles was determined by HPLC. The results show that a representative illicit heroin particle is approximately 45 μm in diameter (137 pmol heroin) and that particles occur over a wide size range, from at least 5.8 to 564 μm in diameter. Aggregated data for the samples studied showed that the overall distribution of heroin particle size largely follows the total particle size distribution, but that this correlation is not necessarily true for individual drug preparations. These results have important implications for any system designed to detect concealed illicit heroin preparations by collection and analysis of drug particles.     

Qualitative and quantitative analysis of seized street drug samples and identification of source

In this paper we describe the identification of constituents of the illicit drugs seized from different regions of eastern India by GC-MS. The constituents were identified to be heroin, acetyl morphine, morphine and acetyl codeine. Quantitative estimation of the constituents were made by GC-MS and HPTLC. In view of non-availability of the authentic samples of drugs of different origin, nothing positive can be said about the origin of illicit drug samples. The possibility of isotopic substitution, an important method for identification of source, was examined from the comparison of the intensity of different (ion) peaks 369 (heroin, m/z=369), 370, 371 and 372 using selective ion monitoring mode. No isotopic substitution in the constituents was observed. Attempts were made to identify the source of the illicit samples from heroin/acetylcodeine ratios in the way described in the literature.     

GC法和GC/MS法在地区毒品情报分析中的应用

目的探讨气相色谱法(GC)和气相色谱/质谱联用法(GC/MS)在地区毒品情报分析中的应用,并用于实际样品分析。方法采用GC/MS法定性分析毒品样品中的主成分、痕量杂质、掺假剂和稀释剂,并选择GC/FID法和内标标准曲线法定量分析上述各组分,通过定性和定量数据的统计和分析,推断该地区的毒品状况。结果用GC/MS定性分析、GC/FID定量分析,和数据的统计比对,获得了某省某年27起海洛因毒品大案样品主成分、痕量杂质、掺假剂和稀释剂组成及含量的特征,发现该省缴获的大宗海洛因毒品主要以掺假和稀释后的产品出现,且咖啡因和扑热息痛为两种主要的掺假剂和稀释剂。结论GC/MS和GC/FID法在地区毒品情报分析和打击毒品犯罪中可以发挥重要作用。     

Isolation and identification of unique marker compounds from the Tasmanian poppy Papaver somniferum N. Implications for the identification of illicit heroin of Tasmanian origin

Tasmanian opium accounts for 25% of the world's legal supply of opium straw, and in 1998-99 sufficient numbers of flower pods (66,013) to manufacture ca 500 kg of heroin were stolen. Whilst the heroin signature program has been developed to determine the origin of heroin from other key producers, no such signature currently exists for Tasmanian derived heroin. Tasmanian poppies contain a unique alkaloid, oripavine, which is the source of 'marker' impurities in illicit heroin produced from Tasmanian poppy straw. Treatment of oripavine (500mg) under Thiboumery and Mohr heroin processing conditions, followed by simple evaporative workup afforded 613 mg of a dark orange residue, which upon extensive chromatographic purification yielded oripavine 3-acetate (2) 22 mg; 3-acetyl-N-acetyldesthebaine (3) 35 mg; 3-acetyl-6-methoxy-4,5-epoxyphenanthrene (4) 5.8 mg; 3,4-diacetyl-6-methoxyphenanthrene (5) 27 mg; and 3,4,6-methoxy-5-[2(N-methylacetamido)]ethylphenanthrene (6) 52 mg. Compounds (2-6) are derived from oripavine and are unique to heroin derived from the Tasmanian poppy Papaver somniferum N. Analysis of illicit heroin samples seized from Turkey, Pakistan, Columbia and Myanmar did not reveal any of the aforementioned marker compounds. We have, however, identified four of these marker compounds (3-6) in seized heroin samples from Australia suggesting that they are of Tasmanian origin. Complete details of the isolation and identification of these compounds are provided.     

Illicit drug abuse in the Marmara region of Turkey

Data on the analysis of 840 illicit drug samples of a total weight of 749.677 kg, confiscated in the Marmara Region, Turkey, from January 1986 to April 1987 is presented. The majority (82.3%) of all cases examined by the Division of Narcotic Drugs Research Laboratories of the Council of Forensic Medicine of Turkey, related to Cannabis products. Heroin represented 16.7% and all other controlled drugs made up the remaining 1%. From the 691 samples analyzed, 43.15% was Cannabis plant material. From the 140 illicit heroin samples analyzed by capillary gas chromatography, 61% had a diacetylmorphine content between 30 and 48%. O-6-monoacetylmorphine was detected in 43% of the samples ranging from 0.4 to 8.6%. Almost half (46.6%) of all heroin samples contained procaine ranging from 0.7 to 22%.     

A simplified clustering method for novice narcotic chemists

Statistical classification remains the most useful statistical tool for forensic chemists to assess the relationships between samples. Many clustering techniques such as principal component analysis and hierarchical cluster analysis have been employed to analyze chemical data for pattern recognition. Due to the feeble foundation of this statistics knowledge among novice drug chemists, a tetrahedron method was designed to simulate how advanced chemometrics operates. In this paper, the development of the graphical tetrahedron and computational matrices derived from the possible tetrahedrons are discussed. The tetrahedron method was applied to four selected parameters obtained from nine illicit heroin samples. Pattern analysis and mathematical computation of the differences in areas for assessing the dissimilarity between the nine tetrahedrons were found to be user-convenient and straightforward for novice cluster analysts.     

Neutral heroin impurities from tetrahydrobenzylisoquinoline alkaloids

Laudanosine, reticuline, codamine, and laudanine are members of the tetrahydrobenzylisoquinoline family of natural products. These alkaloids are present in the opium poppy, Papaver somniferum, and are subsequently found as impurities in clandestinely processed morphine. Morphine is then synthesized to heroin using hot acetic anhydride. During the course of this study, it was determined that these four tetrahydrobenzylisoquinolines undergo degradation to a series of 18 neutral impurities when subjected to hot acetic anhydride. Based on the degradation pathway, these new impurities were categorized into two sets of impurities called the C1-acetates compounds and the stilbene compounds. Synthesis, isolation, and structural elucidation information is provided for the tetrahydrobenzylisoquinoline alkaloids, and the new neutral impurities have been studied. Several hundred authentic heroin samples were analyzed using an established heroin signature program method. This methodology features the detection of trace neutral impurities present in heroin samples. It was determined that all 18 new impurities were detected in various quantities in four different types of heroin samples. Analytical results featuring these new impurities are reported for South American-, Southwest Asian-, Mexican-, and Southeast Asian-type heroin samples. These new impurities, coupled with other established forensic markers, enhance the ability to classify illicit heroin samples.     

Gas chromatographic method validation for the analysis of major components in illicit heroin seized in Malaysia

Apart from routine analysis of total morphine content required by the criminal justice system, quantification of other major components in illicit heroin has not been considered by the Malaysian enforcement laboratory. In order to quantify various other cutting agents in addition to alkaloids, a gas chromatographic (GC) method was developed to facilitate simultaneous quantification of eight target analytes commonly found in illicit heroin seized in Malaysia within a 12 min run time. The validation results demonstrated high selectivity with the use of an HP Ultra 2 capillary column. Different solvents were studied and methanol:chloroform (1:9) proved best for sample dissolution. The method was repeatable and reproducible. The study ranges covering 50-150% of the preferred concentrations of the eight analytes obtained r(2)>0.9997. Limits of detection up to 6μg/mL were also obtained and the method achieved 99-102% recovery. The capability of the method in heroin profiling was verified using samples from ten case samples.     

A methodology for illicit heroin seizures comparison in a drug intelligence perspective using large databases

To characterise links between different illicit drugs chemical profiles, various distance or correlation measurements are available.Different comparison methods have been tested and a method based on a correlation coefficient using a square cosine function was chosen to compare heroin chemical profiles. Its functioning and graphical representation are described. An assessment of the number of false positives is calculated and lead to a negligible number.Moreover, it emerges from the studies that possible variations in impurity peak areas subject to possible degradations do not influence the C correlation value nor question the already established links.This solid, reliable and simple method appears therefore suitable for heroin samples comparison, links profiling and routine use.     

Mycoflora of potential sanitary interest present in illicit heroin

The injection of heroin mixtures poses difficult problems in some cases to both pathologist and toxicologist in evaluating the cause of death. Direct heroin toxicity, allergic or idiosyncratic reactions, and bacterial and mycotic infections are different complications that can be found in these cases. The mycotic profile (mycoflora) present in illicit heroin from street samples (sachets) has been studied. The profile was obtained after incubating the samples at pH5 in 2% and 3% agar-maltose media. Only two samples (nos. 24 and 26) yielded negative results. Twenty-seven taxa were isolated. Penicillium and Aspergillus were the genera most frequently found in the samples. Other genera, such as Cladosporium, Absidia, Rhizopus and Micelia sterilia were also detected. Most of the fungi isolated presented a high allergenic potential and were liable to result in allergic reactions connected with "drug deaths". All the fungi found were commonly present in our environment.