A Simple and Effective Physical Characteristic Profiling Method for Methamphetamine Tablet Seized in China

Methamphetamine (MA) tablet production confers chemical and physical properties. This study developed a simple and effective physical characteristic profiling method for MA tablets with capital letter “WY” logos, which realized the discrimination between linked and unlinked seizures. Seventeen signature distances extracted from the “WY” logo were explored as factors for multivariate analysis and demonstrated to be effective to represent the features of tablets in the drug intelligence perspective. Receiver operating characteristic (ROC) curve was used to evaluate efficiency of different pretreatments and distance/correlation metrics, while “Standardization + Euclidean” and “Logarithm + Euclidean” algorithms outperformed the rest. Finally, hierarchical cluster analysis (HCA) was applied to the data set of 200 MA tablet seizures randomly selected from cases all around China in 2015, and 76% of them were classified into a group named after “WY‐001.” Moreover, the “WY‐001” tablets occupied 51–80% tablet seizures from 2011 to 2015 in China, indicating the existence of a huge clandestine factory incessantly manufacturing MA tablets.     

The identification of 2-chloro-4,5-methylenedioxymethylamphetamine in an illicit drug seizure

This work outlines the unequivocal identification of the "ecstasy" analog, 2-chloro-4,5-methylenedioxymethylamphetamine, using combined gas chromatography/mass spectroscopy (GC/MS) and proton magnetic resonance spectroscopy (1H-NMR). This compound was identified along with 3,4-methylenedioxymethylamphetamine (MDMA) in an illicit tablet seizure, which included 26 off-white tablets.     

Seizures of Clandestinely Produced Tablets in Santa Catarina,Brazil: The Increase in NPS from 2011 to 2017

Ecstasy is the name given to a large group of substances known as “club drugs” traded in the form of tablets, powder and liquid that present a varied composition, including mainly 3,4-methylenedioxymethamphetamine (MDMA) and analogous substances, in addition to the growing presence of new psychoactive substances. Based on this, clandestinely produced tablets (“ecstasy tablets”) seized by police in Santa Catarina in the period from 2011 to 2017 were analyzed. During the study period, 3472 seizures occurred, which resulted in total 498,443 tablets seized. Seventy nine substances were identified. In the year 2011, about 90% of the tablets contained MDMA. This number decreased to 66.6% in 2017. On the other hand, there was an increase in the number of tablets that mainly contained synthetic cathinones, as well as tryptamine and piperazine derivatives. Police seizures in the metropolitan region of Florianópolis and on the coast prevailed over the rest of the state.     

The Variability of Ecstasy Tablets Composition in Brazil

The content of ecstasy tablets has been changing over the years, and nowadays 3,4‐methylenedioxymethamphetamine (MDMA) is not always present in the tablets. The aim of this study was to investigate the chemical composition in the seized tablets labeled as ecstasy. We analyzed samples from 150 different seizures made by Sao Paulo's State Police by gas chromatography–mass spectrometry. MDMA was present in 44.7% of the analyzed samples, and another twenty different active substances were identified in these tablets, such as caffeine, 2C‐B, piperazines, amphetamines, phencyclidine, and others. Methamphetamine was present in 22% of these samples. The results demonstrate a huge shift in the pattern of trafficking of synthetic drugs, where MDMA has been replaced in tablets mostly by illicit psychoactive substances, in a clear attempt to bypass the law. The great variability in the tablets composition may lead to an increased risk of drug poisoning.     

A Fatality Following Ingestion of the Designer Drug Meta‐Chlorophenylpiperazine (mCPP) in an Asthmatic—HPLC‐MS/MS Detection in Biofluids and Hair

A 20‐year‐old man, a cocaine addict and regular ecstasy user, with a medical history of allergic asthma died after ingesting half a tablet earlier the same day. The white tablet, stamped with a “smiling sun” logo looked very much like an ecstasy tablet and was sold as such. He experienced a severe asthma attack just after ingesting the half tablet and it evolved over the next few hours into fatal cardiorespiratory arrest. Biological samples, taken after embalming, were analyzed by high‐performance liquid chromatography tandem mass spectrometry (HPLC‐MS/MS). Analysis revealed meta‐chlorophenylpiperazine (mCPP) in concentrations of 45.8 mg in a similar tablet obtained later from the drug dealer, 5.1 ng/mL in the bile, 0.3 ng/g in the liver, 15.0 ng/mL in the urine, and its absence in a hair sample (<0.02 ng/mg), which indicated he was not a regular user (whereas strong concentrations of MDMA and cocaine were found in the hair). Interrogated by the police after his arrest, the dealer said that he had sold the victim and for the very first time two tablets with the same “smiling sun” logo. The tablet used for analysis was from the same brand as the one ingested by the victim. The autopsy excluded other causes of death, while the histological analyses showed a large number of polynuclear eosinophils in the bronchial walls, confirming the asthmatic pathology. None of the other organs examined (larynx, liver, heart, adrenal glands, and kidneys) showed any distinctive signs, and in particular no inflammatory infiltrate. The death was the result of an asthma attack in an asthmatic person, violently decompensated following ingestion of approximately 20 mg of mCPP.     

Characteristics and trends of 3,4-methylenedioxymethamphetamine (MDMA) tablets found in Taiwan from 2002 to February 2005

One hundred and eighty-one 3,4-methylenedioxymethamphetamine (MDMA) containing tablets were sampled from confiscated drugs received by the Taiwan National Bureau of Controlled Drugs for testing from 2002 to February 2005. Sample tablets demonstrated various colors and logos. The appearances, contents of MDMA and other components in these tablets were analyzed in order to understand the characteristics and trends of MDMA use. Samples were analyzed using GC-MS methodology. Deuterated internal standards were used for drug quantification. The MDMA contents varied from 16 to 193 mg/tablet. 66-71% of the tablets seized each year contained only MDMA, and the content of MDMA in MDMA only tablets varied from 89 to 133 mg/tablet. There was a decreasing trend in MDMA content in these tablets over time. Other components commonly found besides MDMA included caffeine (18%), methamphetamine (7%), 3,4-methylenedioxyethylamphetamine (MDEA) (7%) and amphetamine (4%). 3,4-Methylenedioxyamphetamine (MDA), ketamine, ephedrine, diazepam, chlorzoxazone and nicotinamide were also detected. During the study period, the number of other drugs found as well as the combinations of different drugs detected in these tablets increased.     

14C analyses quantify time lag between coca leaf harvest and street-level seizure of cocaine

Measurements were made on the natural abundance (14)C content (Δ(14)C) of cocaine specimens seized between 2003 and 2009. The objective of this study was to determine the extent to which Δ(14)C analyses could quantify the "age" of recent cocaine seizures. Here "age" of a seized cocaine specimen is defined as the time period between when a coca leaf was harvested in South America and its seizure as cocaine at either the international or domestic street levels. Based on Δ(14)C analyses of seizure specimens, there were no statistically significant differences in the ages of domestic cocaine HCl and cocaine base specimens seized on the streets in different locations across the United States. Between 2007 and 2009, the average age of a street-level cocaine seizure in the United States was 24.6±1.1 months. Cocaine shipment seizures that were in excess of 150 kg during this time period had an average age of 18.2±1.4 months, whereas smaller shipment seizures were significantly older with an average age of 22.3±0.6 months. Analyses of the largest cocaine shipment seizures suggested that these seizures were composed of specimens with different ages, possibly representing accumulations over as much as a 31-month period.     

Chemical profiling of 3,4-methylenedioxymethamphetamine (MDMA) tablets seized in Hong Kong

During 2000-2001, the Government Laboratory of Hong Kong received over 600,000 ecstasy tablets in more than 2,600 cases. Using GC-MS or FTIR, the major amphetamine-type stimulants were identified, and the samples were categorized into four groups containing: (1) 3,4-methylenedioxymethamphetamine (MDMA), (2) methamphetamine (MA), (3) 3,4-methylenedioxyamphetamine (MDA), or (4) amphetamine. Our study revealed that in Hong Kong MDMA tablets have made up 98 and 71% of the total ecstasy tablets examined in 2000 and 2001, respectively. Among the MDMA cases, 613 cases involving a total of 123,776 tablets in 2001 were randomly selected, and their active ingredients, minor ingredients, and/or impurities were studied using GC-MS and HPLC. Based on the chemical profiles, and irrespective of their different physical characteristics, tablets obtained in different seizures could be determined as to whether or not they could have come from a common origin. The impurities detected in the MDMA tablets also served as excellent chemical markers from which plausible synthetic route(s) of the MDMA were inferred. Our study revealed that 3,4-methylenedioxyphenyl-2-propanone (MDP2P), 3,4-methylenedioxyphenyl-2-propanol (MDP), 3,4-methylenedioxy-N-methylbenzylamine (MDB), piperonal and N-formyl-3,4-methylenedioxymethamphetamine (N-formyl-MDMA) were the most common impurities detected in MDMA tablets seized in Hong Kong. The finding of the phosphate salt of MDMA is intriguing. Based on a presumptive color test, spectroscopic data (FTIR/ESI-MS) and the percentage of MDMA content in a purified phosphate salt of MDMA, the ratio of the phosphate to MDMA was determined to be 1:1, suggesting that the compound is a dihydrogen phosphate salt [i.e. (HMDMA)H2PO4].     

Analysis of ecstasy tablets: comparison of reflectance and transmittance near infrared spectroscopy

Calibration models for the quantitation of commonly used ecstasy substances have been developed using near infrared spectroscopy (NIR) in diffuse reflectance and in transmission mode by applying seized ecstasy tablets for model building and validation. The samples contained amphetamine, N-methyl-3,4-methylenedioxy-amphetamine (MDMA) and N-ethyl-3,4-methylenedioxy-amphetamine (MDE) in different concentrations. All tablets were analyzed using high performance liquid chromatography (HPLC) with diode array detection as reference method. We evaluated the performance of each NIR measurement method with regard to its ability to predict the content of each tablet with a low root mean square error of prediction (RMSEP). Best calibration models could be generated by using NIR measurement in transmittance mode with wavelength selection and 1/x-transformation of the raw data. The models build in reflectance mode showed higher RMSEPs using as data pretreatment, wavelength selection, 1/x-transformation and a second order Savitzky-Golay derivative with five point smoothing was applied to obtain the best models. To estimate the influence of inhomogeneities in the illegal tablets, a calibration of the destroyed, i.e. triturated samples was build and compared to the corresponding data of the whole tablets. The calibrations using these homogenized tablets showed lower RMSEPs. We can conclude that NIR analysis of ecstasy tablets in transmission mode is more suitable than measurement in diffuse reflectance to obtain quantification models for their active ingredients with regard to low errors of prediction. Inhomogeneities in the samples are equalized when measuring the tablets as powdered samples.     

Solid-phase extraction for profiling of ecstasy tablets

A solid-phase extraction (SPE) procedure has been developed for impurity profiling of illicit tablets containing 3,4-methylenedioxy-N-methyl-amphetamine (MDMA, ecstasy). Following initial comparison of liquid-liquid extraction and solid-phase extraction, SPE was found to be preferable because it afforded higher extraction efficiencies and shorter extraction times. Procedure blank samples were also analyzed to identify constituents of the extracts which did not originate in the ecstasy tablets. The developed procedure was subsequently applied to 12 samples of seized ecstasy tablets and a comparison was made of these samples to determine similarities and obtain inferences with respect to commonality of origin.     

Screening tablets for DOB using surface-enhanced Raman spectroscopy

2,5,-Dimethoxy-4-bromoamphetamine (DOB) is of particular interest among the various "ecstasy" variants because there is an unusually long delay between consumption and effect, which dramatically increases the danger of accidental overdose in users. Screening for DOB in tablets is problematic because it is pharmacologically active at 0.2-3 mg, which is c. 50 times less than 3,4-methylenedioxy-N-methylamphetamine (MDMA) and makes it more difficult to detect in seized tablets using conventional spot tests. The normal Raman spectra of seized DOB tablets are dominated by the bands of the excipient with no evidence of the drug component. Here we report the first use of on-tablet surface-enhanced Raman spectroscopy (SERS) to enhance the signal from a low concentration drug. Raman studies (785-nm excitation) were carried on series of model DOB/lactose tablets (total mass c. 400 mg) containing between 1 mg and 15 microg of DOB and on seized DOB tablets. To generate surface-enhanced spectra, 5 microL of centrifuged silver colloid was dispensed onto the upper surface of the tablets, followed by 5 microL of 1.0 mol/dm(3) NaCl. The probe laser was directed onto the treated area and spectra accumulated for c. 20 sec (10 sec x 2). It was found that the enhancement of the DOB component in the model tablets containing 1 mg DOB/tablet and in the seized tablets tested was so large that their spectra were completely dominated by the vibrational bands of DOB with little or no contribution from the unenhanced lactose excipient. Indeed, the most intense DOB band was visible even in tablets containing just 15 microg of the drug. On-tablet surface-enhanced Raman spectroscopy is a simple method to distinguish between low dose DOB tablets and those with no active constituent. The fact that unique spectra are obtained allows identification of the drug while the lack of sample preparation and short signal accumulation times mean that the entire test can be carried out in <1 min.     

NIR analysis of cellulose and lactose--application to ecstasy tablet analysis

Cellulose and lactose are the most frequently used excipients in illicit ecstasy production. The aim of this project was to use near infrared reflectance spectroscopy (NIRS) for the determination of the different chemical forms of these two substances, as well as for the differentiation of their origin (producer). It was possible to distinguish between the different chemical forms of both compounds, as well as between their origins (producers), although within limits. Furthermore, the possibilities to apply NIR for the analysis of substances such as found in illicit tablets were studied. First, a few cellulose and lactose samples were chosen to make mixtures with amphetamine at three degrees of purity (5, 10 and 15%), in order to study the resulting changes in the spectra as well as to simultaneously quantify amphetamine and identify the excipient. A PLS2 model could be build to predict concentrations and excipient. Secondarily, the technique was to be applied to real ecstasy tablets. About 40 ecstasy seizures were analysed with the aim to determine the excipient and to check them against each other. Identification of the excipients was not always obvious, especially when more than one excipient were present. However, a comparison between tablets appeared to give groups of similar samples. NIR analysis results in spectra representing the tablet blend as a whole taking into account all absorbing compounds. Although NIRS seems to be an appropriate method for ecstasy profiling, little is known about intra- and intervariability of compression batches.     

A review of recent advances in impurity profiling of illicit MDMA samples

Profiling illicit ecstasy tablets has the potential to become an invaluable tool in the crackdown on drug trafficking, but that potential has yet to be fully realized. The impurity profile of an ecstasy tablet can be used to determine the method employed to synthesize the actual controlled substance, which in most cases, is 3,4-methylenedioxymethamphetamine (MDMA). Tablets can then be linked to a common synthetic route, potentially to a common manufacturer, and possibly even to a common manufacturing batch, based on the impurities present. Current methods for profiling MDMA tablets typically involve extracting the organic impurities for analysis by gas chromatography-mass spectrometry. The potential of profiling the trace metals present in tablets has begun to be investigated while more robust statistical and chemometric procedures are being applied to compare and link tablets. This article reviews the recent advances in MDMA impurity profiling from 2002 up to the end of 2006.     

Impurity profiling of ecstasy tablets seized in Hong Kong by gas chromatography-mass spectrometry

In Hong Kong, ecstasy tablets are more commonly known as "Fing Tau Yuen", literally meaning "Shake Head Pills". The tablets contain mainly amphetamine-type stimulants (ATS) including 3,4-methylenedioxymethamphetamine (MDMA), 3,4-methylenedioxyamphetamine (MDA), methamphetamine (MA) and/or ketamine. Adulterant such as caffeine was also detected in the tablets. This paper reports a study on the impurity profiles of ecstasy tablets from 89 seizures in Hong Kong from 2002 to early 2004. Tablet samples were extracted by diethyl ether under alkaline condition and then analyzed by gas GC-MS. The chromatograms obtained were compared. A total of 19 identified impurities were selected as markers for impurity profiling. They are different precursors, intermediates and by-products. The data matrices were examined by hierarchical cluster analysis (HCA), and then the ecstasy tablets were classified into different groups. Cluster analysis of ecstasy tablets is shown to be capable of providing intelligence on clandestine laboratory networks.     

Isotope ratio mass spectrometry as a tool for forensic investigation (examples from recent studies).

The versatility of isotope ratio mass spectrometry is demonstrated by reference to diverse case studies. Variations in the natural isotopic composition of non-biological, organic materials are compared as a means by which samples may be associated or discriminated. These techniques may be used to augment or compliment conventional forensic methodologies. delta13C analysis was used to demonstrate that different masking tape had been recovered in two, apparently similar cases, involving the smuggling of money. Visually similar ecstasy tablets were compared by consideration of the delta13C and delta15N composition of MDMA extracted from the tablets. Although only a limited number of tablets were analysed, the isotopic similarity between two different seizures was sufficient to induce a guilty plea from a person suspected of possessing both. A combination of delta2H, delta13C, delta15N and delta18O together with GC-MS analyses were applied to small samples of seized heroin. Although GC-MS analysis indicated differences between the chemical composition of two of the heroin samples, isotopic analysis suggested similarities, which were confirmed by further delta2H, delta13C and delta18O isotopic analysis of the clingfilm in which the samples were wrapped.     

Automated shape annotation for illicit tablet preparations: A contour angle based classification from digital images

In order to facilitate forensic intelligence efforts in managing large collections of physical feature data pertaining to illicit tablets, we have developed an automated shape classification method. This approach performs categorical shape annotation for the domain of illicit tablets. It is invariant to scale, rotation and translation and operates on digital images of seized tablets. The approach employs two processing levels. The first (coarse) level is being based on comparing the contour curvature space of tablet pairs. The second (fine) level is a rule based approach, implemented as a classification tree, that exploits characteristic similarities of shape categories. Annotation is demonstrated over a collection of 169 tablets selected for their diverse shapes with an accuracy of 97.6% when 19 shape categories are defined.     

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.     

Using Cluster Analysis and ICP‐MS to Identify Groups of Ecstasy Tablets in Sao Paulo State,Brazil

The variations found in the elemental composition in ecstasy samples result in spectral profiles with useful information for data analysis, and cluster analysis of these profiles can help uncover different categories of the drug. We provide a cluster analysis of ecstasy tablets based on their elemental composition. Twenty‐five elements were determined by ICP‐MS in tablets apprehended by Sao Paulo's State Police, Brazil. We employ the K‐means clustering algorithm along with C4.5 decision tree to help us interpret the clustering results. We found a better number of two clusters within the data, which can refer to the approximated number of sources of the drug which supply the cities of seizures. The C4.5 model was capable of differentiating the ecstasy samples from the two clusters with high prediction accuracy using the leave‐one‐out cross‐validation. The model used only Nd, Ni, and Pb concentration values in the classification of the samples.     

An overview of seized illegal wildlife entering the United States

The current study analyses seizures made at US ports of entry between 2003 and 2013, with the aim to identify concentrations of illegal wildlife imports into the United States. Findings show that 94% of species seized belong to six groups – mammals, molluscs, birds, reptiles, fish and coral – with mammals and reptiles making up more than half of all seizure incidents. Additionally, most seized wildlife is imported as leather products, medicinal products and as meat. The majority of seizures emanate from six countries, and illegal wildlife is primarily brought to the US via airline baggage. Temporal trends of wildlife seizures point to increases in the seizures of all groups of species, with the exception of birds. Based on these findings, we recommend using situational crime prevention techniques at US ports of entry to reduce opportunities that enable this trade.