Narcotics at street level in Denmark. A prospective investigation from 1995 to 2000

This article describes an investigation of illicit drugs at street level in six selected police districts in different regions of Denmark. The investigation was carried out during a 6-year period from 1995 to 2000. During the period, a total of 1244 samples were examined, as about 200 samples were seized each year. A total of 94% of the seized samples were familiar drugs: heroin base, heroin hydrochloride, cocaine hydrochloride and amphetamine sulphate. Only 2% of the samples contained designer drugs. From having constituted 53% of the samples in 1995, the frequency of heroin base fell during the period to 27% of the samples in 2000. The frequency of heroin hydrochloride was unchanged. In the same period, the frequency of cocaine hydrochloride increased from 10% of the samples in 1995 to about 25% of the samples in 2000. Apart from a few exceptions, cocaine had the same extension in all regions of Denmark after 1996. Amphetamine was more frequent in the west of Denmark, while heroin hydrochloride was more frequent in central Denmark. The purity of heroin base was lower in the period 1997-1999 than in the other years. During the entire period, the purity of cocaine hydrochloride and amphetamine sulphate fell, while the purity of heroin hydrochloride was unchanged. No significant differences between the various regions of Denmark were detected during the period in the purity of heroin hydrochloride, heroin base, cocaine hydrochloride or amphetamine sulphate. MDMA was the most frequent designer drug, but other types of designer drugs such as MDA and MDE and the less common PMA, PMMA and MBDB were also found.     

Investigation of trace inorganic elements in street doses of heroin

Sixteen trace elements found in 309 street heroin samples, piped water and contaminated water were determined using inductively coupled plasma-mass spectrometry. All the street heroin samples were found to contain high levels of sodium, a reflection of the use of sodium bicarbonate during heroin synthesis. Additionally, this element was also found to be one of the potential contaminants acquired from the piped water. Calcium could be derived from lime while iron, aluminum and zinc could have come from the metallic container used in the processing/cutting stage. The levels of these elements remained low in the heroin and it could be due to the dilution effects from the addition of adulterants. Statistical validation was performed with six links of related heroin samples using principal component analysis to find the best pretreatment for sample classification. It was obtained that normalization followed by fourth root showed promising results with 8% errors in the sample clustering. The technique was then applied to the case samples. Finally, the result suggested that the case samples could have originated from at least two major groups respectively showing unique elemental profiles at the street level.     

Chemical profiling of heroin recovered from the North Korean merchant vessel Pong Su

Heroin samples, seized from the North Korean merchant vessel Pong Su in Australian waters, were analyzed to determine geographic origin. Duplicate samples were analyzed by the National Measurement Institute's Australian Forensic Drug Laboratory and the United States Drug Enforcement Administration's Special Testing and Research Laboratory. Alkaloid ratios were determined by both liquid chromatography-diode array detection (LC-DAD) and capillary electrophoresis-diode array detection (CE-DAD) techniques. Acid/neutral manufacturing by-products were determined by solvent extraction followed by gas chromatography-mass spectrometry (GC-MS). Solvents, trapped in the heroin particles during manufacture, were detected by both static headspace GC-MS and purge and trap GC-MS. The alkaloid ratios obtained were consistent with heroin of a Southeast Asian (SEA) origin and principal component analysis of the alkaloid results demonstrated the presence of at least four subgroupings within the seizure. The solvent analysis detected diethyl ether and ethyl acetate, solvents typically seen in SEA heroin. However, the acid/neutral analysis revealed compounds not normally seen in heroin of a SEA origin. Furthermore, sterol-like molecules, always detected in the acid/neutral analysis of SEA heroin, were absent from the Pong Su samples. The Pong Su heroin, although similar to SEA heroin, has sufficient differences to classify it as having an unknown origin at the time of this writing.     

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.     

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.     

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.     

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.     

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.     

Isolation and purification of heroin from heroin street samples by preparative high performance liquid chromatography

The present study established a novel method using preparative high performance liquid chromatography to isolate and purify heroin·HCl from heroin street samples to be used as a reference standard. Different kinds of mobile phases and columns were used, ultimately the mobile phase consisting of hexane-isopropanol-methanol (65:28:7, v/v) and the SIL preparative column prepared in laboratory were selected as the final condition. Heroin was further purified by the drowning-out crystallization method using isopropanol-methanol (50:1, v/v) and hexane as drowning-out anti-solvents and salting-out agents, respectively. The purity was assessed by analytical high performance liquid chromatography and the confirmation of the chemical structure was performed by IR and NMR. About 110.7mg of heroin·HCl at a purity of over 99.52% was obtained from 180mg of heroin street samples which contained 156.15mg of heroin·HCl component by preparative high performance liquid chromatography. This method is suitable for preparing heroin standards in forensic science area.     

High pressure liquid chromatography analysis of heroin

A liquid-solid chromatographic system is described that will separate heroin from 26 substances encountered in heroin seizures. The effects of ammonia and water concentration on the retention of the drug substances were investigated. Three ‘brown’ heroin samples were analyzed by high pressure liquid chromatography (HPLC) and by gas-liquid chromatography (GLC) and the results evaluated and compared.     

The routine profiling of forensic heroin samples

A method for the routine profiling of illicit heroin samples received in casework has been developed which depends on simple and straightforward sample pretreatment, followed by gas chromatography on a capillary column using flame-ionization detection. The factors affecting the choice of each aspect of the procedure are discussed, as are the statistical data for sampling and the chromatography. Components of illicit heroin derived from opium and other adulterants have been identified. The significance of data from samples examined in 1986 is discussed.     

Is There a Relationship Between Street Heroin Purity and Drug‐Related Emergencies and/or Drug‐Related Deaths? An Analysis from Vienna,Austria*

This study examines the quality of street heroin seized in Vienna in 1999 and whether there was a relationship between the purity of street heroin and the number of heroin-related emergencies as well as the number of heroin-related deaths. Street heroin confiscated by the Viennese police, run-sheets of drug-related emergencies, and postmortem reports of drug-related deaths in Vienna in 1999 were analyzed. A total of 415 retail samples with a total weight of 128.02 g contained a median percentage of 6.5% diacetylmorphine (range: 0.0-47.0%). All the samples contained a diluent, mainly lactose, as well as adulterants, such as caffeine and/or paracetamol. During the study period, 75 heroin-related deaths and 387 heroin-related emergencies were registered in Vienna. Time-series analysis revealed no statistically significant relationship between the rate of heroin-related incidents and the diacetylmorphine concentration of street heroin samples confiscated in Vienna in 1999. The widely held belief that the number of heroin-related deaths could be explained simply through fluctuations in the purity of street heroin could not be substantiated, even though the results of this study do not rule out an association between the purity of heroin and heroin-related deaths/emergencies.     

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.     

FTIR法检验海洛因中的淀粉、葡萄糖、蔗糖

目的建立检验掺有淀粉、葡萄糖、蔗糖的海洛因的新方法。方法红外光谱。结果给出了用FTIR检验掺有淀粉、葡萄糖、蔗糖的海洛因的判据。结论用红外光谱法可以准确、无损鉴定掺杂淀粉、葡萄糖、蔗糖的海洛因。     

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.     

Geo-location of heroin and cocaine by stable isotope ratios

Analyses of the carbon and nitrogen stable isotope ratios in heroin and cocaine samples obtained from different geographic regions indicated stable isotope ratio combinations that were strongly correlated with geographic location. Further analyses of the isotope ratios of morphine derived from the deacetylation of heroin exhibited more pronounced isotopic differences among regions, increasing its potential as a tool for geo-location and for sample-to-sample comparison.     

血液和尿液样品中海洛因代谢物稳定性研究

目的对尿液和血液中海洛因代谢物3-β-D-葡萄糖醛酸吗啡（M3G）,吗啡,O6-单乙酰吗啡（O6）在180d内的稳定性进行研究。方法准备空白添加血液、尿液、染毒动物（大白兔）血液、尿液和吸食海洛因者血液、尿液样本,分别置于20℃、4℃、-20℃下,分别于0、1、2、4、7、14、28、56、112、156、180d时间点测定样品中M3G、吗啡,O6相对含量。结果在3种不同温度下,随保存时间的延长,血液、尿液中的O6含量均逐渐下降至零;血液中吗啡含量升高（空白血液添加组）或下降（染毒动物组）,在尿液则均升高;血液样中M3G含量均升高,尿样中则略有下降。下降和升高的幅度均随保存温度的下降而缩小。结论海洛因代谢物在-20℃时保存稳定性最佳。     

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.     

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%.     

Geographic origin determination of heroin and cocaine using site-specific isotopic ratio deuterium NMR

SNIF-NMR (Site-specific natural isotopic fractionation measured by deuterium NMR) was employed on 36 heroin samples from seven different known origins, and two cocaine samples from two different known origins. Heroin has two "synthetic" deuterium labeled sites (the two acetyls from acetic anhydride, each representing three equivalent nuclei) and 15 "natural" deuterium labeled sites (originating from the morphine produced in the opium plant). The "natural" sites have the potential for determining geographic location of the original opium plant, while the "synthetic" sites could assist in giving information about the commercial source of acetic anhydride used to convert morphine to heroin. Cocaine has 15 "natural" deuterium labeled sites. This study shows that SNIF-NMR has some use in determining the geographic origin of heroin and also has good potential for determining the geographical origin of cocaine.