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.     

Comparative analysis of illicit heroin samples

The comparative analysis of street heroin samples is still an object of scientific discussion. A combination of a wide range of analytical techniques is necessary to obtain a valid amount of information about the sample composition, and it is impossible to define an unique analytical approach. We suggest a complete analytical sequence based on analysis of volatile compounds, opiates, diluents, adulterants and metals, by head space gas chromatography (HS/GC), gas chromatography mass spectrometry (GC/MS), thin layer chromatography (TLC), high pressure liquid chromatography (HPLC) and atomic absorption (AA) using a sample amount as low as 50-100 mg. The outlined procedure can be successfully applied to routine work, thus obtaining suitable information about a sample's chemical composition. This helps to attribute or exclude common sources of separate specimens. Results obtained on 33 street heroin samples confiscated in the metropolitan area of Rome are listed.     

海洛因技术分析在禁毒情报方面的应用

本文通过统计缴获样本的化学检测信息及案卷资料,得到有关毒品的来源、含量、地区分布及掺假情况等情报信息。这些情报信息可以作为我国禁毒部门从战术角度(样本间的比较)和战略角度(毒品来源确定)研判我国毒品形势的手段之一。     

Determination of impurities in illicit methamphetamine samples seized in Iran

In this study fifty samples of crystalline methamphetamine obtained from antinarcotics police of Iran seized during the year 2010 were analyzed. In order to determine the chemical characteristics of these samples, anion test, Gas Chromatography-Mass Spectrometry (GC-MS) and Liquid Chromatography-Mass Spectrometry (LC-MS) were carried out on the samples. All of the samples containing methamphetamine tested positive for chloride anion. The range of methamphetamine hydrochloride content in these samples was 33-95%. One sample out of 50 contained no methamphetamine. The fact that 1,2-dimethyl-3-phenylaziridine was the most frequently found impurity in the analyzed samples, indicates that most of the methamphetamine samples seized in Iran have been synthesized from pseudoephedrine as starting material.     

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.     

Analysis of carbohydrates in seized heroin using capillary electrophoresis

Illicitly produced heroin is commonly cut with carbohydrates to increase bulk. The analysis of these solutes is important for legal and intelligence purposes. A capillary electrophoresis (CE) method was developed for the qualitative analysis of dextrose, lactose, sucrose, inositol, and mannitol in heroin exhibits. For this method, a 64 cm (55.5 cm to detector window) by 50 mum capillary was used with the Agilent Basic Anion Buffer modified to pH 12.1. This separation was performed at 25 degrees C with a voltage of 20 kV and indirect detection with 2,6-pyridinedicarboxylic acid as the visualization reagent. The methodology is also applicable for the screening of inorganic and organic anions using indirect detection, and acidic adulterants using direct detection. For a run time of 13 min, the relative standard deviation (n = 6) of the methodology was better than 0.36% for migration times and less than 2.6% for corrected peak areas. For the analysis of carbohydrates and acidic adulterants in seized heroin, excellent agreement was obtained between CE and nuclear magnetic resonance spectroscopy.     

Drugs WorkBook (DWB): A tool for the analysis of illicit drugs in seized materials

Accurate and reliable analytical measurements are essential when data are to be used to assist the Court in deciding whether or not a drug offence has been committed and therefore about either the innocence or guilt of the accused. The Italian law on drugs demands that compliance with specification limits be assessed on the basis of the actual content of controlled substance contained in seized materials. As a consequence, the role of measurement uncertainty, significant figures and rounding errors becomes critical. In order to assist analysts of forensic toxicology laboratories with illicit drug-related cases, a software tool named Drugs WorkBook (DWB) has been developed. The tool is useful for the quantification of illicit drugs in seized materials along with their measurement uncertainties, the assessment of compliance to specification limits, the printing of comprehensive laboratory reports and the organization of case archives. Other quality control topics, such as control charts, are included. The tool's databases can be edited by the user and maintained up to date. The tool is made freely available to the scientific community.     

Heroin profiling: Predicting the country of origin of seized heroin

This short report presents an attempt to assess the feasibility of predicting the country of origin of heroin based on the concentration of selected alkaloids and adulterants in seized material. The method used to classify the data was a multivariate statistical analysis, based on a linear discriminant function, which assigns the illicit samples to the country of origin using objective and repeatable criteria. Previously, this has been done using subjective criteria which are open to interpretation. When confined to samples claimed to have originated from Turkey, Pakistan, India and South East Asia in the period 1990 to 1993, the method achieved a successful classification in 83% of cases.     

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.     

Determination of illicit drugs in seized materials: role of sampling and analysis in estimation of measurement uncertainty

The determination of illicit active ingredients in seized materials, in order to assess penal or administrative offences, is routinely carried out in many forensic toxicology laboratories. This paper presents main features of the protocol adopted in the Authors' laboratory for the above investigations. In particular, sampling and analysis are considered as the same measurement process quantifying their combined contribution to overall measurement uncertainty. Aspects concerning representative sampling in the case of single and multiple items are discussed. The effects of material heterogeneity are considered by analyzing separately distinct primary samples taken from different parts of the sampling target. Possible errors due to particles dimension that could arise when sub-sampling are also considered. Analytical precision, bias and other matrix effects are studied in order to quantify the component of the overall measurement uncertainty associated to the analysis of prepared test samples. Typical scenarios arising when measurement results are used to assess compliance with specification limits are also discussed revealing the crucial role of measurement uncertainty.     

Stable isotope analyses of heroin seized from the merchant vessel Pong Su

A new type of heroin HCl seized in Australia was examined by stable isotope analysis. The final origin/process classification of these samples by chromatographic signature profiles of the impurity/manufacturing by-products was previously determined to be "unknown" by two independent national laboratories. Various drug enforcement authorities speculated that the heroin might be from a new region or new illicit process due to the unusual chromatographic impurity profiles that were present. Samples from 20 different kilogram packages were examined for isotopic content to determine if the samples fit isotopic patterns of known origins or if they were unique to any known origins. Authentic specimens from Southeast Asian (N=59), Southwest Asia (N=37), South America (N=104), and Mexico (N=21) we concomitantly examined for comparison purposes. Both continuous flow elemental analysis-isotope ratio mass spectrometry and gas chromatography-isotope ratio mass spectrometry techniques were utilized. Heroin samples were also converted to morphine, without apparent isotopic fractionation, utilizing methanolic HCl for gas chromatography-isotope ratio mass spectrometry. The Pong Su samples were found to be isotopically and isotopically/alkaloidally distinct from the known origin/process classifications of Southwest Asian, Southeast Asian, South American, and Mexican.     

Levels of trace and major elements in illicit heroin

Ten elements, aluminum (Al), barium (Ba), calcium (Ca), cadmium (Cd), copper (Cu), iron (Fe), magnesium (Mg), manganese (Mn), lead (Pb), and zinc (Zn) were analyzed in 44 illicit heroin samples from Southeast Anatolia, Turkey. Illicit heroin samples were dissolved in nitric acid using microwave oven and were quantified by electrothermal atomic absorption spectrometry (Cd and Pb) and inductively coupled plasma-atomic emission spectrometry (Al, Ba, Ca, Cu, Fe, Mg, Mn, and Zn). The most abundant element was calcium, 4050 to 14,200 microg/g, which could be ascribed to the use of lime in the manufacturing process and/or as diluting agent. Iron (180 to 1470 microg/g), aluminum (42 to 2280 microg/g), and zinc (160 to 210 microg/g) were found at moderately high levels, possibly because of the use of metal pots in the acetic anhydride cooking process and also for storage. Cadmium and lead concentrations were at the lowest measured levels. The amounts of magnesium, manganese, barium, and copper were in the range of 100 to 800 micro/g, 3 to 17 microg/g, 4 to 30 microg/g, and 2 to 46 microg/g, respectively.     

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.     

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.     

Heroin abuse and a gas chromatographic method for determining illicit heroin samples in Singapore.

The abuse of heroin (diacetylmorphine) in Singapore escalated sharply in 1975 and 1976, as indicated by the 35-fold increase in the number of heroin seizures and the 20-fold increase in the urine samples containing morphine since 1974. A rapid and simple GC method has been described to estimate diacetylmorphine (and caffeine). Monoacetylmorphine and acetylcodeine may be ascertained by an additional step involving acetylation. All gas chromatograms of a large number of samples analyzed consistently had the same pattern, indicating that they possibly had a common origin. This GC "fingerprint," together with the quantitative data, appears to be characteristic of the illicit Asian or Chinese type of heroin found in Singapore. The proportions of the four major ingredients in some twelve typical samples have been tabulated. Statistical data confirming the accuracy and reproducibility of the analytical method have also been presented.     

The analysis of illicit methaqualone containing preparations by gas chromatography-mass spectrometry for forensic purposes

A validated gas chromatographic-mass spectrometric method for quantitative analysis of methaqualone (MTQ) in illicit preparations is reported. The method proved to have a coefficient of variation of below 5%. Four batches of seized tablets, two pairs with similar imprints, were analyzed. It was found that the average MTQ concentration in all four batches of tablets differed significantly (p = 0.01) rendering it impossible to conclude that, on the basis of MTQ concentration alone, the batches with a similar logo originated from the same manufacturer or manufacturing batch. Conversely, it can be said that in this case, the four batches originated from either different clandestine laboratories or manufacturing batches.