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Knowledge of opioid tolerance in a deceased person is important for distinguishing between therapeutic and toxic opioid concentrations for that particular individual when interpreting postmortem toxicological results. However, no biomarkers for opioid tolerance are currently available. This review aimed to study the existing literature on mechanisms or changes in signaling pathways related to chronic opioid use, which could be relevant for further studies to identify biomarkers for opioid tolerance. We performed a systematic literature search using the PRISMA 2020 guidelines using the MeSH terms "opioid tolerance AND biomarkers" in PubMed, Embase, WebofScience, and the Cochrane library. A review of the search results yielded seven studies on animal models or humans, identifying and evaluating thirteen possible biomarkers in terms of specificity for changes induced by opioids and other aspects to be considered as potential biomarkers. We evaluated nine potential biomarkers as unlikely to be specific for opioid tolerance, and one had contradictory results in terms of upregulation or downregulation. However, methylation of the promoter region of the μ-opioid receptor gene, increased activity of soluble puromycin-sensitive aminopeptidase, altered miRNA profile, or other multiple component profiling may be interesting to study further as biomarkers for opioid tolerance in forensic postmortem cases. • Biomarkers for opioid tolerance could assist interpretation of postmortem opioid concentrations. • Through a thorough literature review we identified several possible biomarkers. • The majority of identified biomarkers were most likely not specific for opioid tolerance. • Methylation of the μ-opioid receptor gene and activity of soluble puromycin-sensitive aminopeptidase may be interesting. • Altered miRNA profile, or other multiple component profiling may be interesting to study further as well. [ABSTRACT FROM AUTHOR]

Since its first employment in World War I, chlorine gas has often been used as chemical warfare agent. Unfortunately, after suspected release, it is difficult to prove the use of chlorine as a chemical weapon and unambiguous verification is still challenging. Furthermore, similar evidence can be found for exposure to chlorine gas and other, less harmful chlorinating agents. Therefore, the current study aims to use untargeted high resolution mass spectrometric analysis of chlorinated biomarkers together with machine learning techniques to be able to differentiate between exposure of plants to various chlorinating agents. Green spire (Euonymus japonicus), stinging nettle (Urtica dioica), and feathergrass (Stipa tenuifolia) were exposed to 1000 and 7500 ppm chlorine gas and household bleach, pool bleach, and concentrated sodium hypochlorite. After sample preparation and digestion, the samples were analyzed by liquid chromatography high resolution tandem mass spectrometry (LC-HRMS/MS) and liquid chromatography tandem mass spectrometry (LC-MS/MS). More than 150 chlorinated compounds including plant fatty acids, proteins, and DNA adducts were tentatively identified. Principal component analysis (PCA) and linear discriminant analysis (LDA) showed clear discrimination between chlorine gas and bleach exposure and grouping of the samples according to chlorine concentration and type of bleach. The identity of a set of novel biomarkers was confirmed using commercially available or synthetic reference standards. Chlorodopamine, dichlorodopamine, and trichlorodopamine were identified as specific markers for chlorine gas exposure. Fenclonine (Cl-Phe), 3-chlorotyrosine (Cl-Tyr), 3,5-dichlorotyrosine (di-Cl-Tyr), and 5-chlorocytosine (Cl-Cyt) were more abundantly present in plants after chlorine contact. In contrast, the DNA adduct 2-amino-6-chloropurine (Cl-Ade) was identified in both types of samples at a similar level. None of these chlorinated biomarkers were observed in untreated samples. The DNA adducts Cl-Cyt and Cl-Ade could clearly be identified even three months after the actual exposure. This study demonstrates the feasibility of forensic biomarker profiling in plants to distinguish between exposure to chlorine gas and bleach. [Display omitted] • Novel chlorinated biomarkers in vegetation were analyzed by LC-HRMS/MS. • LDA facilitated classification of plants exposed to either chlorine gas or bleach. • Chlorinated DNA and protein adducts were identified using reference standards. • DNA adducts in plants could be detected more than three months after exposure. [ABSTRACT FROM AUTHOR]

Cartridges, bullets, and casings (CBCs) are commonly recovered after shooting incidents and could provide valuable DNA information from touch DNA that has been left behind during handling of bullets and loading of guns. Direct PCR, in which the DNA extraction and quantification steps are bypassed, has been shown to provide comparable and sometimes better results from touch DNA and trace DNA samples. Here, direct PCR was applied to touch DNA retrieved from bullet casings from three ammunition types and guns. The results were evaluated to determine whether the technique should be recommended as a standard operating protocol for forensic DNA analysts. Three experiments were carried out to investigate the following: the effect of firing bullets on DNA deposited on bullet casings; the effect of gun and ammunition types on short tandem repeat (STR) profile quality; and the feasibility of using direct PCR in real-world cases via typing of mock casework samples. DNA extraction resulted in a loss of about 40% of DNA originally deposited, and firing a bullet reduced the amount of DNA recovered by 27%. Using the direct PCR protocol, conventional extraction protocol, and dilution protocol on touch DNA from fired bullet casings, we recovered means (and 95% credible intervals), respectively, of 11.1 (7.9-13.9), 5.6 (3.0-7.7), and 2.3 (0.2-4.0) alleles. No statistical difference in alleles recovered was observed between different calibers of ammunition fired from three guns (9mm, 7.62mm, and 5.56mm from Glock Model 19, AK47, and Tavor T-21, respectively). As expected, mixed DNA profiles were observed in 40% of the mock casework samples, in which guns were shared between volunteers. This study showed that direct amplification of touch DNA from bullet casings improved STR profiles. As direct PCR is quicker, cheaper, and resulted in more alleles recovered, forensic DNA analysts may benefit from using direct PCR. [ABSTRACT FROM AUTHOR]

Blotter papers laced with lysergic acid diethylamide (LSD) have been abused traditionally for their hallucinogenic properties. In recent years, new psychedelic phenethylamines such as 2,5-dimethoxyphenethylamines (2C) and their N-benzylhydroxy (25-NBOH) and N-2-methoxybenzyl derivatives (25-NBOMe) have emerged in the illicit drugs market. Traditionally, gas chromatography-mass spectrometry (GC-MS) is regarded as the gold standard for illicit drugs analysis. However, with the emergence of new psychoactive substances (NPS) which are thermally labile (such as the 25-NBOH drugs which undergo thermal degradation to their respective 2C drugs), alternative non-thermal techniques have to be developed in order to prevent misidentification. In this study, a single, targeted, non-thermal analytical method using the liquid chromatography-tandem mass spectrometry (LC-MS/MS) to simultaneously identify these new phenethylamines and their derivatives was developed and validated. Twelve phenethylamines and their derivatives, as well as LSD were simultaneously analysed using the LC-MS/MS in a multiple reaction monitoring (MRM) detection mode. The method developed was validated and applied for the analysis of phenethylamines and their derivatives commonly found in seized exhibits such as blotter papers and Ecstasy tablets. [ABSTRACT FROM AUTHOR]

The structural identification and the monitoring of the relative concentrations of a wide range of major (3) and minor secondary (16) metabolites used as marker substances for profiling of cannabis resin using GC-FID at the Swedish National Forensic Centre (NFC) has facilitated the mapping of their chemical and physical behaviors over a period of 48months whilst stored under different conditions (exposure to light, exposure to air, temperature). In all cases the behavior of this group of sesquiterpenes, sesquiterpenoids, cannabinoids and waxes could be directly related to their chemical lability/functionality. In particular, the identification of homologue triads for both Δ9-tetrahydrocannabinol (THC) and cannabidiol (CBD) together with a group of seemingly chemically inert substances (for example, cannabicyclol(CBL) and the waxes (n-alkanes)) has created new tools for the establishment of common origins between samples of cannabis resins aged under different conditions. Since sampling of the resin blocks in NFC's method for profiling of cannabis resin is made below the surface, the effects of light incursion were found to be negligible. The effects of exposure to air (and indirectly temperature) were found to be more significant, not unexpectedly as many of the observed transformations were based on oxidation or rearrangement processes. [ABSTRACT FROM AUTHOR]

The source inference of ignitable liquids in forensic science is still a challenging and ongoing research area. In real case applications, specimens of different natures, which may have been exposed to fire or not, may have to be compared. These comparisons are difficult since specimens may have been altered by evaporation, combustion or both. Plus, the extent of the alteration is often difficult to evaluate. Most studies concerning source inference of ignitable liquids worked on neat samples or samples altered by evaporation. However, there is a lack of studies comparing the influence of evaporation and combustion within a source inference framework. In this study, the same collection of gasoline samples was altered by both evaporation under a nitrogen stream and combustion of the gasoline adsorbed on a matrix. The possibility to link gasoline samples sharing a common source was then explored using an adaptive untargeted chemometrics workflow from feature detection to feature selection. This data treatment approach was successfully applied to the data and it was shown that the possibility to link samples with a common source was not compromised despite evaporation or combustion for degrees of alteration from 0% to 99%. [ABSTRACT FROM AUTHOR]

The forensic literature shows a clear trend towards increasing use of chemometrics (i.e. multivariate analysis and other statistical methods). This can be seen in different disciplines such as drug profiling, arson debris analysis, spectral imaging, glass analysis, age determination, and more. In particular, current chemometric applications cover low-dimensional (e.g. drug impurity profiles) and high-dimensional data (e.g. Infrared and Raman spectra) and are therefore useful in many forensic disciplines. There is a dominant and increasing need in forensic chemistry for reliable and structured processing and interpretation of analytical data. This is especially true when classification (grouping) or profiling (batch comparison) is of interest. Chemometrics can provide additional information in complex crime cases and enhance productivity by improving the processes of data handling and interpretation in various applications. However, the use of chemometrics in everyday work tasks is often considered demanding by forensic scientists and, consequently, they are only reluctantly used. This article and following planned contributions are dedicated to those forensic chemists, interested in applying chemometrics but for any reasons are limited in the proper application of statistical tools - usually made for professionals - or the direct support of statisticians. Without claiming to be comprehensive, the literature reviewed revealed a sufficient overview towards the preferably used data handling and chemometric methods used to answer the forensic question. With this basis, a software tool will be designed (part of the EU project STEFA-G02) and handed out to forensic chemist with all necessary elements of data handling and evaluation. Because practical casework is less and less accompanied from the beginning to the end out of the same hand, more and more interfaces are built in through specialization of individuals. This article presents key influencing elements in the forensic workflow related to the most meaningful chemometric application and evaluation. [ABSTRACT FROM AUTHOR]

The detection and interpretation of gunshot residue (GSR) can play an important role in the investigation of firearm related incidents. Recently, the potential of organic compounds to provide an additional means to discriminate between GSR and environmental particles, in particular in cases where lead-free ammunition is used, has been highlighted. This work describes a method for the extraction and detection of complementary organic and inorganic compounds from a single GSR sample, using a methodology that makes implementation in the current standard procedure feasible. GSR samples were collected from the shooter's hands following double and single discharges, using the traditional adhesive carbon aluminium stubs. Analysis of organic compounds was performed using solid-phase microextraction gas chromatography mass spectrometry (SPME-GC-MS), followed by analysis of the traditional inorganic particles using scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDX). Detection of both categorised organic GSR compounds (e.g. ethyl centralite, diphenylamine and 2-nitrodiphenylamine) and characteristic inorganic GSR has been achieved. Given the fact that the detected organic GSR compounds are relevant with respect to the confirmation of GSR materials, this method has successfully demonstrated the ability to obtain a total chemical profile from a single GSR sample, which has the potential to increase the probative value of GSR evidence. [ABSTRACT FROM AUTHOR]

The GIFT CBRN project (Generic Integrated Forensic Toolbox for chemical, biological, radiological and nuclear incidents), funded under the Seventh Framework Programme of the European Commission, has been set up to find solutions for investigating incidents involving CBRN agents. Regarding the forensic point of view, specific tools and procedures to assist forensic investigators to perform a crime scene investigation (CSI) and methodologies to enable the subsequent analysis of the evidences (contaminated with CBRN agents) seized at the crime scene have been developed. To validate the procedures and methods developed within this project and to test them, three field-exercises engaged with one type of agent at the time (i.e. a RN-agent, a B-agent or a C-agent) has been held. The Belgian Defence Laboratories (DLD) in collaboration with Royal Military Academy (RMA) and the National Institute of Criminalistics and Criminology (NICC) has organized the chemical field exercise in Belgium. CSI teams of the Belgian Federal Police (experienced in crime scene investigation, fingerprints and digital forensics but at the time of the exercise not trained to perform their activities in CBRN conditions), SIBCRA teams (experienced in the sampling and identification of CBRN agents in hazardous environments) and the Civil Protection (experienced in entering zones with potential chemical hazards in full individual protective equipment) were involved. Since those teams never worked together in CBRN conditions, the exercise was used to establish the first operating procedure for CSI and laboratory analysis for CBRN and forensic materials in Belgium. The main steps of the procedure applied during this filed-exercise are described is this manuscript. The first step was the reconnaissance performed to (i) identify/quantify the threat agent involved, (ii) to document the scene and (iii) to collect priority forensic evidences. The second step focused on the collection of other forensic evidences, the sampling of DNA traces and the revelation of fingerprints at the scene. The collection of CBRN agents was performed during step 3. Step 4 concentrated on the decontamination and transport of evidences and traces sampled in the contaminated zone. The revelation of fingerprints in a glovebox (step 5) was finally demonstrated. In conclusion, this field-exercise was an opportunity for the different Belgium services to work together, to learn from each other, and to work towards the establishment of a national operating procedure to manage investigations in CBRN conditions. [ABSTRACT FROM AUTHOR]

Lanthanide-based (Eu and Tb) metal organic frameworks (MOFs) synthesized in this work are highly fluorescent crystalline structures that form through a self-assembly process in an aqueous environment. Various bio-organic molecules, including proteins and amino acids, can act as inducing agents for this process. The fact that these components are present in fingermark secretions, in combination with the excellent luminescent properties of the MOFs, create a visualisation method for (latent) fingermarks. The aqueous MOF precursor solutions are not ideal for the visualisation of latent fingermarks on non-porous surfaces, such as aluminium foil and glass. However, they offer a simple, non-toxic, long-lasting and effective approach for the visibility enhancement of fingermarks treated with cyanoacrylate fuming on aluminium foil and glass and latent fingermarks on the adhesive side of a transparent tape. The luminescent properties of MOF-treated fingermarks persevered for at least 12 months, providing great alternative for commonly used organic dyes such as Basic Yellow 40 and Gentian Violet. In this communication we evaluate the applicability of the proposed method for the forensic fingermark workflow. [ABSTRACT FROM AUTHOR]

A shooting event involved several types of ammunition that were all shot from a single firearm. GSR analysis of samples taken from the suspect's hands, hair and from his clothes was carried out. Mixed compositions particles were found among other GSR particles, attributed to the weapon memory effect. SEM/EDX analysis of these particles highlighted a particle with defined domains containing distinct groups of elements. Some of these elements were absent in the primers mixtures of the ammunition used in the shooting event. X-ray mapping indicated that these domains might have been incorporated into the particle within several shooting cycles. This combination of compositions created an opportunity to shed light on the formation mechanism of "memory effect" particles. The aim of the study is to highlight such particles way of formation. [ABSTRACT FROM AUTHOR]

The number of samples sent to forensic laboratories as well as the complexity of the drug situation has increased tremendously during recent years. At the same time the amount of data gathered from chemical measurements has been mounting. This creates challenges for forensic chemists: how to handle the data, how to reliably answer the questions asked, and how to examine the data to find new properties or how to disclose connections with respect to source attribution of samples within a case or retrospective to past cases, stored in a database. Previously published articles Chemometrics in Forensic Chemistry – Part I and II discussed where in the forensic workflow of routine casework chemometrics is applied, and presented examples of chemometric methods used in cases of illicit drugs. This article explains through examples that the chemometric results must never stand-alone. Before such results are reported, quality assessment steps, which may consist of operational, chemical, and forensic assessments are required. In each case a forensic chemist needs to consider the suitability of chemometric methods, based on their strengths, weaknesses, opportunities and threats (SWOT). This is because while chemometric methods are powerful tools managing complex data, they are to some extent chemically blind. • Importance of quality assessment of chemometric output. • Demonstrating the assessment process of chemometric results in forensic chemistry. • SWOT analysis of chemometrics applied in forensic chemistry. [ABSTRACT FROM AUTHOR]

Quinolin-8-yl 1-(5-fluoropentyl)-1H-indole-3-carboxylate (5-Fluoro-PB-22 or 5F-PB-22; QUPIC N-(5-fluoropentyl) analog), is a synthetic cannabinoid which mimics the effects of cannabis. Several countries have reported numerous detections of this compound and its abuse has led to adverse effects including death. The aim of this study was to separate and identify the fluoropentyl positional isomers of fluoro-PB-22 using gas chromatography-mass spectrometry, solid deposition gas chromatography-infrared detection spectroscopy and 1H and 13C nuclear magnetic resonance spectroscopy. Data acquired from these multiple techniques can assist forensic laboratories lacking the reference drug standard(s) to identify the specific isomer of fluoro-PB-22 in seized material. [ABSTRACT FROM AUTHOR]

In the course of providing assistance to legal counsel in a matter that involved the analysis of firearms propellant by gas chromatography/mass spectrometry it was noticed that phenoxazine was reported as a component of 0.22 calibre propellant that contained diphenylamine as the stabiliser. The research was conducted to find how phenoxazine was formed. The results showed that the compound was not phenoxazine but a diphenylamine derivative 4-(phenylimino) cyclohexa-2,5-dien-1-one that formed in the injection port of the gas chromatograph. In addition a second artefact was found to form in the ion source of the mass spectrometer. While the presence of the artefacts does not affect the ability to identify particles as propellant they may impact on comparison with source ammunition. [ABSTRACT FROM AUTHOR]

In this study, electrolyte (sodium (Na), chlorine (Cl), and magnesium (Mg)) and total protein (TP) concentrations and volume of liquid in the sphenoid sinus were examined to determine their usefulness to elucidate whether drowning occurred in freshwater or seawater. We examined 68 cases (seawater drowning group: 27 cases, freshwater drowning group: 21 cases, non-drowning group: 20 cases). There was a significant difference in Na, Cl, Mg, and TP concentrations of liquid in the sphenoid sinus among the three groups (seawater drowning, freshwater drowning, and non-drowning groups). To distinguish freshwater drowning from seawater drowning, Na, Cl, and Mg concentrations of liquid in the sphenoid sinus might serve as useful indicators. [ABSTRACT FROM AUTHOR]

Human scent has been demonstrated to allow for the differentiation of individuals. The extent of this differentiation may allow scent to be used as a characteristic, capable of revealing information on an individual's traits. The ability to use scent as a biometric human feature has enabled the use of scent as forensic evidence. However, its reliability, value, and admissibility in courts of law have sometimes been challenged as a result of limited scientific validation. Full acceptance of human scent evidence has been hindered by the limited availability of peer reviewed information that provides greater understanding of how human scent originates and how it may be used. The objective of this study is to report new data that further enhances our understanding of the value of human scent evidence and its acceptance in courts of law. In order to fulfill this objective, volatile organic compound combinations were identified as markers for race/ethnicity and gender from hand odor samples from 105 individuals. The accuracy of human classification by race/ethnicity and gender, on the basis of these markers, was determined and validated. Overall accuracies of 80% and 72% were obtained for the classification of subjects by gender and race/ethnicity, respectively. The results obtained demonstrate that the identified VOC marker combinations represent a viable resource for the classification and/or differentiation of persons of interest and, as such, may be considered a valuable forensic tool for subject identification. [ABSTRACT FROM AUTHOR]

The synthetic cannabinoids (SCs) represent the most recent advent of the new psychotropic substances (NPS) and has become popularly known to mitigate the effects of the Δ(9)-THC. The SCs are dissolved in organic solvents and sprayed in a dry herbal blend. However, little information is reported on active ingredients of SCs as well as the excipients or diluents added to the herbal blend. In this work, the direct infusion electrospray ionization Fourier transform ion cyclotron mass spectrometry technique (ESI-FT-ICR MS) was applied to explore the chemical composition of nine samples of herbal extract blends, where a total of 11 SCs (UR-144, JWH-073, XLR-11, JWH-250, JWH-122, AM-2201, AKB48, JWH-210, JWH-081, MAM-2201 and 5F-AKB48) were identified in the positive ionization mode, ESI(+), and other 44 chemical species (saturated and unsaturated fatty acids, sugars, flavonoids, etc.) were detected in the negative ionization mode, ESI(-). Additionally, CID experiments were performed, and fragmentation pathways were proposed to identify the connectivity of SCs. Thus, the direct infusion ESI-FT-ICR MS technique is a powerful tool in forensic chemistry that enables the rapid and unequivocal way for the determination of molecular formula, the degree of unsaturation (DBE-double bond equivalent) and exact mass (<1ppm) of a total of 55 chemical species without the prior separation step. [ABSTRACT FROM AUTHOR]

During the lifetime of a cocaine batch from production end to consumption, several alterations may occur, leading to possible changes in the original impurity profile. Such profile changes may eventually result in erroneous forensic evaluations. In the present study, the stability of both the alkaloid and the residual solvent impurity profiles of cocaine were evaluated over a period of 12 months under different storage conditions (temperature, purity and weight) using GC-MS and HS-GC-MS, respectively. The sample purity (p<0.001), time of storage (p<0.001) and storage temperature at 37°C (p<0.01) significantly influenced the alkaloid impurity profile. The most significant change was observed in low purity samples stored at 37°C. In contrast, no changes were observed in the residual solvent profile at all storage conditions for the entire 12-month study period. This finding indicates that the residual solvent profile may be more applicable than the corresponding alkaloid profile when cocaine seizures subjected to different storage conditions are compared. Our results clearly demonstrate that cocaine alkaloid profiles change over time and are most susceptible to sample purity and storage temperature. As a consequence, storage conditions and purity should be taken into account when cocaine comparison is conducted in criminal cases. [ABSTRACT FROM AUTHOR]

A tragic car accident took place in one of the villages of southern Poland. Three teenagers were traveling by car - a woman and two men (identical twins). None of the participants had their seat belts fastened, and the men were under the influence of alcohol and drugs. As a result of losing control of the vehicle, the woman died instantly, but she was not the driver. The driver was one of the men, but neither pleaded guilty. The police and the prosecutor's office had to clearly identify the perpetrator and prove his guilt, which was possible based on the analysis of the collected microtraces. The article describes the collected evidence and presents the results of microtraces analysis, on the basis of which the perpetrator of the accident was determined and convicted. In this particular case it was difficult because the suspects were identical twins and commonly used forensic examinations (such as forensic genetics, anthropology, dactyloscopy, traceology, osmology) did not bring a satisfactory result. Only the analysis of microtraces turned out to be groundbreaking. [ABSTRACT FROM AUTHOR]

Forensic chemical analysis of fire debris addresses the question of whether ignitable liquid residue is present in a sample and, if so, what type. Evidence evaluation regarding this question is complicated by interference from pyrolysis products of the substrate materials present in a fire. A method is developed to derive a set of class-conditional features for the evaluation of such complex samples. The use of a forensic reference collection allows characterization of the variation in complex mixtures of substrate materials and ignitable liquids even when the dominant feature is not specific to an ignitable liquid. Making use of a novel method for data imputation under complex mixing conditions, a distribution is modeled for the variation between pairs of samples containing similar ignitable liquid residues. Examining the covariance of variables within the different classes allows different weights to be placed on features more important in discerning the presence of a particular ignitable liquid residue. Performance of the method is evaluated using a database of total ion spectrum (TIS) measurements of ignitable liquid and fire debris samples. These measurements include 119 nominal masses measured by GC-MS and averaged across a chromatographic profile. Ignitable liquids are labeled using the American Society for Testing and Materials (ASTM) E1618 standard class definitions. Statistical analysis is performed in the class-conditional feature space wherein new forensic traces are represented based on their likeness to known samples contained in a forensic reference collection. The demonstrated method uses forensic reference data as the basis of probabilistic statements concerning the likelihood of the obtained analytical results given the presence of ignitable liquid residue of each of the ASTM classes (including a substrate only class). When prior probabilities of these classes can be assumed, these likelihoods can be connected to class probabilities. In order to compare the performance of this method to previous work, a uniform prior was assumed, resulting in an 81% accuracy for an independent test of 129 real burn samples. [ABSTRACT FROM AUTHOR]

The GC-MS properties of the synthetic cannabinoid drug of abuse 3-(1-naphthoyl)-1-pentylindole (JWH-018) and all 5 of its' regioisomeric 1-naphthoyl substituted 1-n-pentylindoles are compared in this report. These compounds have the 1-naphthoyl-group attached at each of the possible substituent positions of the indole ring. The six compounds have the same elemental composition C24H23NO and the same substituents attached to the indole ring. The electron ionization mass spectra showed equivalent regioisomeric major fragment ions resulting from cleavage of the groups attached to the central indole nucleus. The characteristic (M-17)+ fragment ion at m/z 324 resulting from the loss of an OH group was significant in the EI-MS of 3-, 4-, 5- and 6-(1-naphthoyl)-1-pentylindole. Fragment ions occurred at m/z 127 and 155 for the naphthyl and naphthoyl cations common to all six regioisomeric substances. Indole containing fragments produced the cations at m/z 284, 270, 214 and 186. The unique fragment at m/z 141 observed in the 1,2- and 1,7-isomers resulted from a rearrangement involving the two indole substituents to yield the C10H7CH2+ cation. The major points of EI-MS differentiation of the synthetic cannabinoid JWH-018 from the other five isomers are the high relative abundance of both the m/z 144 ion and the m/z 324 ion in the JWH-018 spectrum. GC separations on a capillary column containing a trifluoropropyl methyl polysiloxane (Rtx-200) stationary phase provided excellent resolution of these six compounds. The elution order appears related to the relative distance between the two indole substituents with the lowest retention associated with minimum distance between the groups attached to the indole nucleus. [ABSTRACT FROM AUTHOR]

This work examines the organic impurity profile of 3,4-methylenedioxymethamphetamine (MDMA) that has been synthesised from catechol (1,2-dihydroxybenzene), a common chemical reagent available in industrial quantities. The synthesis of MDMA from catechol proceeded via the common MDMA precursor safrole. Methylenation of catechol yielded 1,3-benzodioxole, which was brominated and then reacted with magnesium allyl bromide to form safrole. Eight organic impurities were identified in the synthetic safrole. Safrole was then converted to 3,4-methylenedioxyphenyl-2-propanone (MDP2P) using two synthetic methods: Wacker oxidation (Route 1) and an isomerisation/peracid oxidation/acid dehydration method (Route 2). MDMA was then synthesised by reductive amination of MDP2P. Thirteen organic impurities were identified in MDMA synthesised via Route 1 and eleven organic impurities were identified in MDMA synthesised via Route 2. Overall, organic impurities in MDMA prepared from catechol indicated that synthetic safrole was used in the synthesis. The impurities also indicated which of the two synthetic routes was utilised. [ABSTRACT FROM AUTHOR]

Ethyl glucuronide (EtG) is widely used as a marker for assessment of alcohol consumption behavior. In this study the influence of special cleansing shampoos on ethyl glucuronide concentrations in hair was investigated. For that purpose an optimized LC-MS/MS method was developed using a Hypercarb™ porous graphitic carbon (PGC) column and validated according to the guidelines of the German Society of Toxicological and Forensic Chemistry (GTFCh). Twenty-five hair samples of persons with known alcohol consumption behavior were investigated (21 positive samples and 4 blank samples). The hair samples were divided into two strands of hair and were analyzed after treatment with one out of four cleansing shampoos and without shampoo treatment. EtG concentrations in hair did not show any significant differences after a single application of the different cleansing shampoos. EtG was still detectable in all the positive hair samples without significant concentration change. These results clearly demonstrated that a single application of the tested cleansing shampoos did not remove EtG from hair and therefore had no influence on EtG concentration in analytical hair analysis. [ABSTRACT FROM AUTHOR]

The recovery of low molecular weight oxygenates in fire debris samples is severely compromised by the use of heated passive headspace concentration with an activated charcoal strip, as outlined in ASTM E- 1412. The term "oxygenate" is defined herein as a small, polar, organic molecule, such as acetone, methanol, ethanol, or isopropanol, which can be employed as an ignitable liquid and referred to in the ASTM classification scheme as the "oxygenated solvents" class. Although a well accepted technique, the higher affinity of activated carbon strips for heavy molecular weight products over low molecular weight products and hydrocarbons over oxygenated products, it does not allow for efficient recovery of oxygenates such as low molecular weight alcohols and acetone. The objective of this study was to develop and evaluate a novel method for the enhanced recovery of oxygenates from fire debris samples. By optimizing conditions of the heated passive headspace technique, the utilization of zeolites allowed for the successful collection and concentration of oxygenates. The results demonstrated that zeolites increased the recovery of oxygenates by at least 1.5-fold compared to the activated carbon strip andmay complement the currently used extraction technique. [ABSTRACT FROM AUTHOR]

The study was designed to obtain a comprehensive view on the prevalence of gunshot residue and the factors influencing their dispersion. 273 specimens collected from people of various professions, representing both users and non-users of firearms, as well as from the interior of a forensic laboratory were examined for the presence of gunshot residue. In specimens taken from hands of 100 people declaring no contact with firearms only one spherical particle containing lead, antimony and barium was found. Numbers of particles found in specimens collected from hands of 50 shooters varied from zero to numbers greater than 100 and were strongly correlated with the time interval between last shooting and collecting specimens. Within the first 4 h after shooting particles are being lost from the shooter's hands, and so transferred from shooters to their environment. Thus, the relatives of five hunters were examined during both the close and open hunting seasons to trace the potential secondary transfer in practice. Using the criterion of low risk of contamination with gunshot residue, i.e. 5 h after last handling a gun, only few specimens were encountered among these collected from hands of firearm users that contained characteristic particles and these occurred in small numbers. Frequent shooters, e.g. shooting instructors or firearm examiners, formed a class for themselves of high risk of contamination with gunshot residue. As a result of continuous monitoring of the laboratory (55 specimens examined so far), where the examinations of gunshot residue are being carried out, it has been proved that the laboratory is free from contamination and so confirmed the usefulness of protocols worked out. The obtained information provided empirical bases to the minimisation of the risk of contamination of the evidence as well as for the evaluation of the analytical findings in the expertise on gunshot incidents. [ABSTRACT FROM AUTHOR]

Colombian coca farmers have historically cultivated three varieties of coca for cocaine production (Erythroxylum novogranatense var. novogranatense, Erythroxylum novogranatense var. truxillense, and Erythroxylum coca var. ipadu). Within the past 13 years, 15 new cultigens of cocaine-bearing Erythroxylum have been propagated by Colombian coca farmers; each with differing physical characteristics, yet producing cocaine alkaloids at similar levels found in the historical and native varieties. Fifteen new cultigens were collected from throughout Colombia and propagated along with the three historical varieties within an experimental field in Colombia. Five plants/cultigen were randomly selected and examined for alkaloid content to determine their varietal characteristics when compared to the three known varieties. Ten cultigens gave classic Erythroxylum coca var. ipadu alkaloid profiles, four cultigens produced alkaloid profiles consistent with a hybridization of Erythroxylum novogranatense and Erythroxylum coca var. ipadu, while one cultigen gave heterogeneous alkaloid profiles that could not be characterized. [ABSTRACT FROM AUTHOR]

Cannabis products rich in cannabidiol (CBD) and low in Δ9-tetrahydrocannabinol (THC) (e.g., light cannabis in Italy) are becoming widely popular and available on the market as replacements for THC preparations and tobacco for their recreational and/or therapeutic benefits. In this paper, which aims to establish alternative discrimination parameters between hair samples from CBD-rich and THC-prevalent cannabis users, cannabinoid concentrations, such as THC, CBD, 11-nor-9-carboxy-Δ9-tetrahydrocannabinol (THC-COOH) and 11-hydroxy-Δ9-tetrahydrocannabinol (11-OH-THC) were quantified in 127 hair samples by a GC-MS/MS technique. Initially, this analysis was able to discriminate two cohorts: cohort 1 (individuals with THC values ≥ 0.05 ng/mg and THC-COOH ≥ 0.2 pg/mg or THC-positive users, n = 60) and cohort 2 (individuals with THC values ranging between 0.01 and 0.05 ng/mg and THC-COOH or 11-OH-THC ≥ LOQs, n = 67). The evaluation of CBD/THC ratio in cohort 2 identified two further sub-cohorts 2a (CBD/THC<<1 or ~ 1, THC-prevalent cannabis users) and 2b (CBD/THC>>1, suspected CBD-rich and THC-low cannabis users). The latter showed unusual profiles for THC metabolites, in particular for 11-OH-THC. Statistical evaluation of the data of cohort 1, cohort 2a and cohort 2b yielded significant differences in CBD/THC and THC/11-OH-THC. Based on the analysis of 337 seized cannabis samples and 630 CBD-rich/light cannabis samples by GC-FID and GC-MS, respectively, we also evaluated statistical differences in the CBD/THC ratio between biological (hair) and plant-derived samples. Considering the legal implications of a positive result, the obtained findings could be relevant for the interpretation of cannabinoid concentrations in hair. Further studies are necessary to elucidate the reason behind the unusual metabolic ratios. [ABSTRACT FROM AUTHOR]

Hand-held, portable X-Ray fluorescence instruments (pXRF) provide a means of rapid, in-situ chemical characterisation that has considerable application as a rapid trace evidence characterisation tool in forensic geoscience. This study presents both a control test study which demonstrates optimisation of the data collection process, alongside a range of individual forensic case studies, including heavy metal contamination, conflict archaeology, forensic soil characterisation, and verification of human remains, which together validate the technique and provide some comparison between field-based and laboratory-based pXRF applications. Results highlight the time-efficiency and cost-effectiveness of in-situ, field-based pXRF analyses for material characterisation when compared with other trace evidence methods. Analytical precision of various analytes during in-situ analysis was sufficient to demonstrate considerable application of field-based pXRF as a tool for rapid identification of specific areas of interest to be further investigated. Laboratory-based pXRF analyses yielded greater accuracy which could provide an efficient compromise between field-based pXRF and traditional laboratory-based analytical techniques (e.g. WD-XRF, ICP-MS). Further studies should collect more advanced datasets in more diverse locations to further validate the techniques capability to rapidly conduct geochemical surveys in a range of environments. [ABSTRACT FROM AUTHOR]

Questioned document examination in a wide variety of criminal and civil cases often focuses on the identification and comparison of stamp inks. Increasingly frequent counterfeiting of documents, especially those that have been stamped, has led to a growing need for instrumental methods that will allow an in-depth examination of stamp inks on a document. Therefore, the usefulness of two capillary electrophoresis techniques: micellar electrophoretic capillary chromatography with UV/Vis diode array detection (MECC-DAD) and capillary zone electrophoresis with electrospray mass spectrometric detection (CZE-ESI/MS) was verified for this purpose. Violet, red, blue and green stamp inks on paper surfaces were investigated. Electropherograms and mass spectra of inks purchased from 10 different producers were obtained in accordance with optimized and validated analytical procedures. It was shown that effective differentiation of individual inks was possible in terms of migration time and UV/ Vis spectra provided that there was more than one characteristic peak. However, the most problematic inks with only one very similar (or identical) dye component - violet and blue ones - were additionally differentiated by CZE-MS. The obtained results showed that the proposed procedures can be useful for the objective analysis of questioned documents involving stamp inks. Consequently, the developed methods can be applied in the forensic field, including in the investigation of the authenticity of documents. [ABSTRACT FROM AUTHOR]

Trace biological materials contain volatile profiles that have yet to be evaluated to determine their value in forensic investigations. The volatiles released by different biological specimens (hand odor, hair, fingernails and saliva) collected from twenty individuals were identified using a solid phase microextraction-gas chromatography-mass spectrometry method. The human scent compounds from each specimen, per subject, were evaluated using Spearman rank correlation to assess the applicability of these compounds for the differentiation of individuals. The volatile organic compounds from each specimen type were readily identified and discriminated. When conducting inter-subject discrimination within a single specimen type, greater than 98.9% of the samples, or individuals, were differentiated for all specimen types. When conducting inter-subject discrimination among the four specimen types 99.6% of the samples were differentiated, at the 0.9 correlation coefficient threshold. Additionally, the only occurrence of cross-correlation between specimen types was observed between hair and fingernails while there were no cross-correlations with hand odor or saliva thereby demonstrating the distinctiveness of these specimens. [ABSTRACT FROM AUTHOR]

The method of sample recovery for trace detection and identification of explosives plays a critical role in several criminal investigations. After bombing, there can be difficulties in sending big objects to a laboratory for analysis. Traces can also be searched for on large surfaces, on hands of suspects or on surfaces where the explosive was placed during preparatory phases (e.g. places where an IED was assembled, vehicles used for transportation, etc.). In this work, triacetone triperoxide (TATP) was synthesized from commercial precursors following reported methods. Several portions of about 6 mg of TATP were then spread on different surfaces (e.g. floors, tables, etc.) or used in handling tests. Three different swabbing systems were used: a commercial swab, pre-wetted with propan-2-ol (isopropanol) and water (7:3), dry paper swabs, and cotton swabs wetted with propan-2-ol. Paper and commercial swabs were also used to sample a metal plate, where a small charge of about 4 g of TATP was detonated. Swabs were sealed in small glass jars with screw caps and Parafilm® M and sent to the laboratory for analysis. Swabs were extracted and analysed several weeks later by gas chromatography/mass spectrometry. All the three systems gave positive results, but wetted swabs collected higher amounts of TATP. The developed procedure showed its suitability for use in real cases, allowing TATP detection in several simulations, including a situation in which people wash their hands after handling the explosive. [ABSTRACT FROM AUTHOR]

Abstract: After the train bombing in Madrid (Spain) on 11 March 2004, methenamine was detected in some of the specimens of Goma-2 ECO dynamite submitted to the forensic laboratories when analyzed by gas chromatography coupled with mass spectrometry detection (GC–MS). Methenamine is synthesized from formaldehyde and ammonia through a condensation reaction. However, neither methenamine nor any of these compounds were used to manufacture Goma-2 ECO dynamite. Four different experiments were designed in order to explain the presence of methenamine detected in the dynamite samples analyzed. In the first one, GC–MS was used to analyze the individual components of Goma-2 ECO provided by the manufacturer and the components mixed in a raw paste. Methenamine was detected in the manufacturer''s ammonium nitrate and in the raw paste. The other experiments were designed to find the precursors sources for methenamine generation in Goma-2 ECO. Results revealed that these sources could be ammonium nitrate for ammonia and sawdust for formaldehyde. Under heating conditions, dynamite could produce these precursors, which could condense in the injection port of the GC–MS system and generate methenamine. However, methenamine was not always detected in these dynamites. This was explained by the existence of two opposite effects: (a) dynamite stability makes difficult that ammonium nitrate releases ammonia and (b) there is a gradual loss of formaldehyde in sawdust along the time. Both effects can prevent the formation of an amount of methenamine large enough to be detected. [Copyright &y& Elsevier]

Abstract: The highly toxic anticoagulant rodenticide brodifacoum is an organic compound that has two diastereomeric forms. In this paper, we consider the hypothesis that the relative population of the diastereomers is a characteristic of forensic value for the association or source attribution of specimens of brodifacoum. In general, the stereoisomer distribution in an organic compound depends on the reagents, conditions, and methods used for synthesis and purification, and may vary over time due to differential stabilities of the stereoisomers. The stereoisomer distribution may thus serve as an identifier of the production methods and history of samples and provide a basis for comparing recovered specimens. We refer to this novel approach for signature detection as stereoisomer distribution analysis or SDA. If the stereoisomers are diastereomers, quantitative determination of the diastereomer ratio in a specimen can be performed by a number of techniques, notably gas or liquid chromatography or nuclear magnetic resonance (NMR) spectroscopy. This paper describes an NMR spectroscopic analysis of ten commercial technical grade brodifacoum samples from distinct batches originating from three different sources. The results reveal detectable source-to-source and batch-to-batch variations in diastereomer ratios. [Copyright &y& Elsevier]

Abstract: The ring substituted methyl isomers of methcathinone, 2-, 3- and 4-methylmethcathinone were analysed. The 2- and 3-isomers were synthesized. The 4-methylmethcathinone isomer is also known as mephedrone and has been widely studied. We present GCMS, NMR and IR data for the three isomers. We show that the three isomers can be separated by GCMS and that the IR spectra for the three compounds can be used to distinguish between them. A seized sample was analysed and it was found to contain 4-methylmethcathinone and benzocaine. [Copyright &y& Elsevier]

Abstract: In the process of questioned document examination, the discrimination of inkjet printing inks is becoming more necessary due to increasingly frequent counterfeiting of documents printed by inkjet printers. Therefore, a method based on micellar electrophoretic capillary chromatography (MECC) has been developed and applied to analysis of such inks extracted from paper. With the use of an optimized and validated analytical procedure, multielectropherograms of inks taken from various models of printers made by various producers (Hewlett-Packard, Epson, Brother, Lexmark and Canon) were created. It was shown that effective differentiation of individual inks was possible in terms of migration time, order and specific shapes of characteristic peaks. By comparison of recorded UV–Vis spectra, the identification of main dyes was also achievable. The usefulness of the method was confirmed by an intralaboratory test of utility, in which several forged printouts were successfully examined. The obtained results proved that the proposed procedure is a useful tool that could be applied to ink discrimination and group identification of dyes originating from inkjet printing inks. Consequently, the developed method can be applied in the forensic field, including investigation of the authenticity of documents. [Copyright &y& Elsevier]

Abstract: The purpose of this work was to study the appropriateness of polyethylene bags for the preservation of explosive specimens. To this end, specimens of two types of dynamites, Goma-2 EC, containing nitroglycol (EGDN) and dinitrotoluene (DNT), and Goma-2 ECO, containing only EGDN, were placed individually inside bags and introduced into hermetically sealed glass jars, which were stored for a period of time. Losses of volatile compounds were studied by headspace analysis using gas chromatography coupled to mass spectrometry (GC–MS). The cross-contamination between dynamites was studied by using high performance liquid chromatography with mass spectrometry (HPLC–MS) to analyse the extracts obtained after a sequential solvent extraction of these specimens. Polyethylene bags permit the loss of volatile compounds since EGDN and DNT were detected in the headspaces of the jars. Moreover, cross-contamination between dynamites was also demonstrated since DNT content decreased in the dynamite containing this compound and increased in the dynamite that had not contained it. [Copyright &y& Elsevier]

Abstract: Segmental analysis of hair for drugs, metabolites, and poisons has been widely reported in the scientific literature over the past two decades. Two fundamental assumptions in interpreting results of such analyses are (1) an average linear growth rate of head hair of 1cm/month and (2) that sample collections occur with the hair being cut directly next to the scalp. The purpose of this study was to evaluate the variability associated with growth rate of human head hair, as well as the ability to uniformly collect hair next to the scalp. The results were used to determine how these factors affect the interpretation of results generated in segmental analysis of hair. A thorough literature review was conducted to assess the range of linear growth of human head hair from the vertex posterior and occipital regions. The results were compiled to establish the average (1.06cm/month), as well as the range of possible growth rates of head hair. The range was remarkable and suggests that conclusions based on the 1-cm/month growth rate could be significantly skewed. A separate study was undertaken to evaluate collection of hair next to the scalp. Fourteen individuals were provided oral instructions, as well as a written standard collection procedure for head hair. The experience levels among the collectors varied from novice to expert. Each individual collected hair from dolls with short- and long-hair. Immediately following each collection, the sampling area was evaluated to determine how close to the scalp the cuts were made, as well as the variability in the lengths of hair remaining at the sampled area. From our collection study, we determined that 0.8±0.1cm of hair was left on the scalp after cutting. When taking into account the amount of hair left on the scalp after collecting, the use of a growth rate of 1.06cm/month, and the assumption that it takes two weeks for newly formed hair in the follicle to reach the scalp, we find that the first 1-cm segment of hair typically corresponds to hair formed 1.3±0.2 to 2.2±0.4 months (95% confidence) earlier. The impact of these findings as it relates to the corresponding time for each additional segment is demonstrated. As a result, we recommend that hair collection be delayed 8 weeks after a suspected ingestion to ensure that the sample fully represents the exposure period. The results of this study suggest that the variability in the growth rate of human head hair, as well as the inconsistent collection of hair, significantly affect the interpretation of results from segmental analysis of hair. [Copyright &y& Elsevier]

Abstract: A fast and simple LC–MS/MS method was developed for screening mephedrone, butylone, methylenedioxypyrovalerone (MDPV), flephedrone, methylone and methedrone in bulk powder samples. Samples were separated on a reverse phase column using gradient elution with mixtures of water, acetonitrile and formic acid. After optimization a limit of detection of about 2ngmL−1 was achieved using multiple reaction monitoring (MRM) mode. Total run time was less than 8min. Typical fragmentation characteristics of the studied compounds are discussed. The method was successfully applied to several unknown bulk powder samples seized by the Hungarian Customs and Finance Guard. One of the samples contained the new designer drug 4′-methylethcathinone (4-MEC), which was identified and characterized by LC–MS/MS, NMR, FT-IR and LC–TOF-MS techniques. The method is also deemed to be applicable for the screening of simple dosage forms such as tablets and capsules. [Copyright &y& Elsevier]

Abstract: Multilayered glitter particles were cut with a microtome into thin cross-sections and examined using an FT-IR microscope with a synchrotron infrared source. The high brightness of the synchrotron source enabled high-quality infrared spectra to be quickly obtained from individual layers in the glitter particle cross-section, providing additional chemical information that could increase the glitter particle''s value as associative evidence in criminal cases. [Copyright &y& Elsevier]

Abstract: Aim: To estimate the prevalence of driving with blood drug concentrations above the recently proposed Norwegian legal limits for drugged driving in random traffic. The results from a roadside survey of 10,816 drivers was used as basis for the estimation, and the most prevalent drugs were included. Methods: Three approaches were used to estimate the prevalence of drug concentrations above the proposed legal limits in blood based on drug concentrations in oral fluid: comparison with drug concentrations observed in oral fluid and blood in pharmacokinetic studies, estimating the prevalence of drug concentrations in blood by calculating the prevalence of drug concentrations in oral fluid that were larger than the limit in blood multiplied with mean oral fluid/blood ratios, and a mathematical simulation mimicking the relationship between drug concentration distributions in blood and oral fluid for populations of drug users. Results: In total, alcohol or drugs were detected in 5.7% of the samples of oral fluid from drivers in normal traffic; 3.8% (n =410) were positive for the drugs that we included in the assessment. The estimation of drug concentrations in blood suggested that about 1.5% had concentrations above the proposed legal limits in blood for the studied drugs, which is about 40% of those who were positive for the drugs in oral fluid. Conclusion: The estimated prevalence of driving with concentrations of psychoactive drugs in blood above the proposed legal limits was for illegal drugs 0.4% and for medicinal drugs 1.1%. These may be regarded as minimum estimates as some drugs were not included in the assessment. These prevalences are higher than the prevalence of driving with blood alcohol concentrations above the legal limit of 0.2g/kg in Norway. [Copyright &y& Elsevier]

Abstract: The study was carried out to investigate external contamination of hair by blood in heroin-related post-mortem cases. Solutions were prepared containing 0.05, 0.1, 0.2, 0.5 and 3.0μg/mL of 6-monoacetylmorphine (6-AM) only or morphine only in human blood. Samples of approximately 3.2g of drug-free hair were contaminated by soaking in the blood solutions for 5min. They were then removed and left at room temperature. Approximately 0.5g of hair was collected from each of the blood soaked hair samples at 6h, 1, 2, 4 and 7 days after contamination. As each hair sample was collected it was shampoo-washed to prevent further drug absorption. Hair samples were analysed in triplicate using a fully validated method described previously. 6-AM broke down to morphine in all samples. In hair contaminated with blood containing 0.05, 0.1 and 0.2μg/mL 6-AM or morphine drug was either not detected or was detected below the limit of quantitation (0.2ng/mg hair) at all contamination times. In hair contaminated with blood spiked with 0.5μg/mL morphine, the concentration in hair ranged from 0.54 to 0.91ng/mg and in hair contaminated with blood spiked with 3.0μg/mL, from 3.25 to 5.77ng/mg. The concentrations of 6-AM ranged from 0.65 to 1.11ng/mg and morphine from 0.34 to 0.80ng/mg in hair contaminated with 0.5μg/mL 6-AM in blood. 6-AM ranged from 2.12 to 3.67ng/mg and morphine from 0.84 to 2.05ng/mg in hair contaminated with 3μg/mL 6-AM in blood. For 6-AM and morphine ANOVA statistical evaluation showed no significant difference among the concentrations over time. [Copyright &y& Elsevier]

Abstract: Fingermarks formed in or by blood often require specific development techniques. This review examines techniques and materials that may be used to enhance and record fingermarks deposited in blood or fingermarks generated by blood-contaminated papillary ridges. A large number of techniques are presented here and are discussed from a chemical as well as practical perspective. It is concluded that an optimized sequence of techniques targeting both latent (non-bloody) and bloody fingermarks must be applied to detect and enhance the maximum number of marks, and therefore optimize the information content from exhibits that may bear marks in blood. [Copyright &y& Elsevier]

Abstract: In 2008, the New Zealand Government passed an amendment to reschedule what were, at the time, the active ingredients of ‘party pills’ in New Zealand. Since then, submissions of tablets and powders to the Institute of Environmental Science and Research (ESR) Limited have included ingredients not previously seen among drug seizures in New Zealand. These new components, confirmed by the synthesis of standards, included some beta-ketone (βk) analogues of 3,4-methylenedioxyamphetamine (MDA). Though not yet seen in tablet or powder seizures, the synthesis and the analytical data for βk-DMBDB ((beta-ketone)-N,N-dimethyl-1-(1,3-benzodioxol-5-yl)-2-butanamine) are reported here for the first time. [Copyright &y& Elsevier]

Abstract: Vitreous humor (VH) is used for postmortem diagnosis of metabolic diseases and to clarify the postmortem interval. Because of its viscous nature, this fluid has to be liquefied prior to analysis; however variations in measured concentrations of the analytes are ascribed to different pre-analytical treatment methods with regard to. The aim of this study was to compare different pre-analytical methods. Centrifugation, heat treatment, enzymatic digestion and liquefying by ultrasound were compared using a collection of 120 samples obtained from 2003 to 2007. The determined parameters were: sodium, potassium, chloride, calcium, glucose, creatinine, urea and lactate. Analyses were performed either photometrically or by using ion-selective electrodes. Heat and hyaluronidase treatment generate slightly higher and lower values in the measurement of electrolytes and glucose. However, in the determination of calcium concentration, both methods (heat especially) are associated with extreme low or high values. Only differences between ultrasound and centrifugation treatment show comparatively small variations and are close to instrument accuracy. Therefore, we recommend centrifugation, combined with mixing, as the best and easiest method in which to prepare frozen samples for analysis. Additionally, the measurement of lactate shows that analytical methods, calibrated for serum and urine, cannot be easily applied for VH. [Copyright &y& Elsevier]

Abstract: An agrochemical spreading agent was found near the slightly decomposed corpse of a deceased female. The appearance of the stomach contents suggested that ingestion of a surfactant had occurred before death. The spreading agent was found to contain nonionic nonylphenol ethoxylates (NPEO n ) and anionic sulfonated naphthalene-formaldehyde condensates (SNFC n ). A solid phase extraction cartridge containing a mixed reversed phase-weak anion exchange sorbent (Oasis WAX, Waters) was used to successfully extract both NPEO n and SNFC n from the blood. The cartridge was preconditioned with methanol and acetic acid (AcOH). After the dilute blood sample was applied to the cartridge, it was washed with AcOH, and then NPEO n and SNFC n were eluted with methanol/dichloromethane (7:3, v/v) and 5% NH3/80% methanol, respectively. The concentrations of NPEO n=2–9 and SNFC n=0 in the blood sample were 7.7μg/mL and 1.8mg/mL, respectively. It is possible that postmortem changes increased the concentration of SNFC n =0 monomer by breaking down the polymer. However, the behavior of these compounds in the human body is unclear and further case studies are needed to investigate this result. [Copyright &y& Elsevier]

Abstract: A comprehensive study was made, where desorption atmospheric pressure photoionization (DAPPI) was applied to the direct analysis of confiscated drugs and pharmaceuticals of various forms and matrices. The analyzed samples included herbal products [Catha edulis (khat), Psilocybe mushrooms, opium and Spice], designer drugs in tablet and powder form [e.g. meta-chlorophenylpiperazine (mCPP), 3-fluoromethamphetamine (3-FMA), methylenedioxypyrovalerone (MDPV) and methylone], and anabolic steroids in oil and tablets. The analyses were performed with ion trap mass spectrometer in MS and MS2 modes and the obtained spectra were compared with GC–MS results. Contamination of the mass spectrometer was avoided by careful adjustment of the distance of the sample from the mass spectrometer inlet. DAPPI proved to be a fast and specific analysis technique, which does not require any sample preparation, and which therefore suits well to this type of forensic analysis. [Copyright &y& Elsevier]

Abstract: This study investigated the feasibility of using volatile impurities from the rodenticide tetramethylenedisulfotetramine (TETS) for the discrimination of TETS produced by three synthetic routes. Each route was used to make one batch of TETS by reacting sulfamide with one of three formaldehyde analogs in the presence of either trifluroacetic acid (TFA) or hydrochloric acid. Ten impurities useful for differentiating the three TETS batches were discovered and tentatively identified by headspace solid-phase microextraction comprehensive two-dimensional gas chromatography–mass spectrometry (HS-SPME/GC×CG–MS). Of the ten identified impurities, the alkyl trifluoroacetate and alkyl chloride impurities distinguished TETS routes based on their use of either TFA or HCl as catalyst. On the other hand, four 6-carbon ketone impurities appeared to be batch specific rather than route specific and hence potentially useful for sample matching. Interestingly, 1,3,5-trioxane was not found in the TETS batch where it was used as a reactant, but instead was found in the two batches that did not have 1,3,5-trioxane as the reactant. In brief, the limited work discussed in this paper supports: (1) the feasibility of sampling and detecting volatile organic impurities from a solid chemical-threat agent, (2) the probable forensic benefit of catalysts acting as reactants in side reactions, (3) the uniqueness of a synthetic batch''s impurity profile for potential sample matching, and (4) the possibility that some impurities, such as formaldehyde analogs, are not forensically helpful and may lead to an incorrect estimate about the synthetic route if not supported by sound chemical knowledge. [Copyright &y& Elsevier]