Heroin profiling: mannitol hexaacetate as an unusual ingredient of some illicit drug seizures

Mannitol hexaacetate (MHA) has been detected by GC-MS in some brown illicit drug seizures in which diacetylmorphine (DAM) was completely lacking. The presence of MHA as a genuine ingredient of the drug seizures rather than a storage- or an analytical artifact, formed by transacetylation of mannitol with the DAM in the heroin, has been verified. It is argued that MHA was formed as a result of the addition of mannitol, as diluent, before the acetylating step in the process of the heroin preparation. This early dilution in the production and distribution chain of the illicit drug is deemed as peculiar, nonetheless it may be highly indicative of a specific production process of heroin in a trafficking organization.     

Automated Mapping of Explosives Particles in Composition C‐4 Fingerprints*†‡

Abstract: A method is described to perform automated mapping of hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX) particles in C‐4 fingerprints. The method employs polarized light microscopy and image analysis to map the entire fingerprint and the distribution of RDX particles. This method can be used to evaluate a large number of fingerprints to aid in the development of threat libraries that can be used to determine performance requirements of explosive trace detectors. A series of 50 C‐4 fingerprints were characterized, and results show that the number of particles varies significantly from print to print, and within a print. The particle size distributions can be used to estimate the mass of RDX in the fingerprint. These estimates were found to be within ±26% relative of the results obtained from dissolution gas chromatography/μ‐electron capture detection for four of six prints, which is quite encouraging for a particle counting approach. By evaluating the average mass and frequency of particles with respect to size for this series of fingerprints, we conclude that particles 10–20 μm in diameter could be targeted to improve detection of traces of C‐4 explosives.     

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.     

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.     

Capillary gas chromatographic analysis of illicit diamorphine preparations

An improved capillary gas chromatographic method for the analysis of illicit diamorphine preparation is reported. The method was able to resolve the impurities and more frequent adulterants and contaminants present in street heroin preparations with a diamorphine detection limit of 0.2 ng in split-less mode.     

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.     

DNA on drugs

The use of illicit drugs is a continuing blight on society. Detecting DNA from individuals involved in the manufacturing and distribution of drugs can provide valuable investigative information or strategic intelligence which, in turn, can be used to disrupt the supply and distribution of illicit drugs. Our study details the transfer, persistence, prevalence, and recovery of human DNA on the exterior of tablets and capsules, as well as within drug powders. Various experiments were conducted to mimic stages in the creation and packaging of tablets and capsules. We showed that the act of brief contact (1–3 s) is sufficient to generate informative DNA profiles that can be uploaded and compared to databases internationally. This work complements chemical drug profiling data by linking seizures to each other and individuals via DNA profiles, providing information to prosecution or intelligence agencies. The generation of DNA information from illicit drug preparations is another tool that can be used in the fight against illicit drug manufacture and distribution.     

An epidemic of intravenous narcoticism deaths associated with the resurgence of black tar heroin

In the latter part of 1985, a dramatic rise in the number of illicit narcotic (heroin) related deaths in the State of New Mexico became apparent, and this increase persisted through the majority of the following year. A careful inspection of samples of narcotics found at the scenes of death, coupled with changes in the illicit drug traffic detected by local and state law enforcement agencies, revealed that the rising death rate corresponded with the distinctively increased availability of a form of heroin that is produced in Mexico, commonly termed "black tar" heroin. An analysis of heroin deaths, comparing characteristics of cumulative deaths in the six years before the increase with those deaths associated with the apparent epidemic, revealed several significant observations. These factors, along with the distinctive physical features of black tar heroin, suggest that the rise in the narcotic abuse death rate may be related to both unfamiliarity with this type of heroin on the part of the user and the inherent difficulty of diluting nonpowdered forms of the drug to sublethal levels.     

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.     

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.     

Are arrest statistics a valid measure of illicit drug use? The relationship between criminal justice and public health indicators of cocaine,heroin, and marijuana use

Several alternative indicators are currently available to researchers, policy makers, and practitioners for gauging levels and patterns of illicit drug use within and across communities. Yet there exists little information that allows reliable comparisons across indicators to determine whether they tell essentially the same story about variation in the prevalence of drug use. In particular, it remains unclear how closely arrest statistics, the leading law enforcement indicator of illicit drug use, correspond to other law enforcement indicators, such as urine tests of jail inmates, or to public health measures, such as emergency departments' and medical examiners' reports. In this paper we assess the relationships between alternative law enforcement and public health indicators of cocaine, heroin, and marijuana use for a sample of large U.S. cities. We find pronounced convergence across measurement systems in cocaine and heroin use, but little convergence for marijuana use. In addition to other research and policy implications, these results increase confidence in the use of arrest data to assess variation across urban areas in cocaine and heroin use.     

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.     

idPAD: Paper Analytical Device for Presumptive Identification of Illicit Drugs

As drug overdose deaths across the United States continue to rise, there is increasing interest in field testing of illicit substances. This work discusses a paper-based analytical device (idPAD) that can run a library of 12 colorimetric tests at the same time, each detecting different chemical functional groups and materials found in illicit drugs, distractor substances, and cutting agents. The idPAD requires no electricity, costs less than $2 USD, and requires minimal training to operate. The results of the 12 tests form a color barcode which is “read” by comparison to standard images. The accuracy of the idPAD was assessed using samples of heroin, cocaine HCl, crack, and methamphetamine at concentrations of 25%–100% in a lactose matrix, as well as pure lactose. Based on 840 “reads” by three different users, the idPAD showed 95% sensitivity and 100% specificity for detecting these drugs; the most common error was mistaking cocaine HCl for crack or crack for cocaine HCl. In a second step, samples of heroin, cocaine, and methamphetamine (n = 30) and distractor substances (pharmaceuticals, cutting agents, and other illicit drugs, n = 64) were tested by two readers, yielding a sensitivity of 100% and specificity of 97%. Targeted substances were detected reliably at 55–180 μg/lane, and the idPAD was found to be stable for at least 3 months when stored at room temperature. The library approach used in the idPAD may provide the accuracy and robustness necessary for a presumptive field drug test.     

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.     

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%.     

Particle characteristics of trace high explosives: RDX and PETN

The sizes of explosives particles in fingerprint residues produced from C-4 and Semtex-1A were investigated with respect to a fragmentation model. Particles produced by crushing crystals of RDX and PETN were sized by using scanning electron microscopy, combined with image analysis, and polarized light microscopy was used for imaging and identifying explosive particles in fingerprint residues. Crystals of RDX and PETN fragment in a manner that concentrates mass in the largest particles of the population, which is common for a fragmentation process. Based on the fingerprints studied, the particle size to target for improving mass detection in fingerprint residues by ion mobility spectrometry (IMS) is > or = 10 microm in diameter. Although particles smaller than 10 microm in diameter have a higher frequency, they constitute < 20% of the total mass. Efforts to improve collection efficiency of explosives particles for detection by IMS, or other techniques, must take into consideration that the mass may be concentrated in a relatively few particles that may not be homogeneously distributed over the fingerprint area. These results are based on plastic-bonded explosives such as C-4 that contain relatively large crystals of explosive, where fragmentation is the main process leading to the presence of particles in the fingerprint residues.     

The Prevalence of Paraphernalia Found at the Scene of Drug‐Related Deaths

Many illicit drugs involve the use of paraphernalia, and the presence of paraphernalia found at the scene of death may suggest that the death is drug‐related. Few sources of objective data are available regarding the prevalence of drug paraphernalia found at the scene of drug‐related deaths or the likelihood of a death with drug paraphernalia found at the scene to be drug‐related. This study reviews the deaths which were investigated by the Bexar County Medical Examiner's Office in an attempt to provide objective data. Over 4000 deaths with scene investigations were reviewed, and the presence of paraphernalia was found to be strongly associated with the death being drug‐related, heroin‐related, or cocaine‐related with the relative risk for each being 5.0, 15.4, and 6.6, respectively. This confirms that the presence of drug paraphernalia at the scene of death strongly suggests the death to be drug‐related and in particular heroin‐related.     

Particle size distribution analysis of soils using laser diffraction

The use of laser diffraction for the particle size distribution analysis of the sub-63 μm fraction of soil samples is described. Each sub-63 μm fraction was obtained from the wet sieving of 1500 mg of whole soil. Using similarity probabilities, the data obtained, when combined with other information from wet sieving and/or organic matter content, will enable the correct identity of a given soil sample with that of an unknown to be made. Although the sub-63 μm fraction can account for 450 mg or more of the total soil content, analyses of this fraction can be conducted on sample sizes as small as 100 mg.     

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.