Why is methenamine detected in Goma-2 dynamites originally methenamine free? An interpretation of relevant forensic results

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.     

Characterization of an odor permeable membrane device for the storage of explosives and use as canine training aids

The storage and use of explosives is regulated at the state and federal level, with a particular focus on physical security and rigorous accounting of the explosive inventory. For those working with explosives for the training and testing of explosive-detecting canines, cross-contamination is an important concern. Hence, explosives intended for use with canine teams must be placed into secondary storage containers that are new, clean, and airtight. A variety of containers meet these requirements and include screw-top glass jars (e.g., mason jars). However, an additional need from the explosive-detecting canine community is secondary containers that can also be used as training aids whereby the volatiles emitted by explosives are emitted in a predictable and stable manner. Currently, a generally accepted method for the storage of explosives and controlled emission of explosive vapor for canine detection does not exist. Ideally, such containers should allow odor to escape from the training aid but block external contaminates such as particulates or other volatiles. One method in use places the explosive inside a permeable cotton bag when in use for training and then stores the cotton bag inside an impermeable nylon bag for long-term storage. This paper describes the testing of an odor permeable membrane device (OPMD) as a new way to store and deploy training aids. We measured the evaporation rate and flux of various liquid explosives and volatile compounds that have been identified in the headspace of actual explosives. OPMDs were used in addition to traditional storage containers to monitor the contamination and degradation of 14 explosives used as canine training aids. Explosives were stored individually using traditional storage bags or inside an OPMD at two locations, one of which actively used the training aids. Samples from each storage type at both locations were collected at 0, 3, 6, and 9 months and analyzed using Fourier Transform Infrared (FTIR) Spectroscopy and Gas Chromatography–Mass Spectrometry (GC–MS) with Solid-Phase Microextraction (SPME). FTIR analyses showed no signs of degradation. GC–MS identified cross-contamination from ethylene glycol dinitrate (EGDN) and/or 2,3-dimethyl-2,3-dinitrobutane (DMNB) across almost all samples regardless of storage condition. The contamination was found to be higher among training aids that were stored in traditional ways and that were in active use by canine teams.     

Analysis of Explosives by GC‐UV

A mixture of explosives was analyzed by gas chromatography (GC) linked to ultraviolet (UV) spectrophotometry that enabled detection in the range of 178–330 nm. The gas‐phase UV spectra of 2,4,6‐trinitrotoluene (TNT), 2,4‐dinitrotoluene (DNT), ethylene glycol dinitrate (EGDN), glycerine trinitrate (NG, nitroglycerine), triacetone triperoxide (TATP), and pentaerythritol tetranitrate (PETN) were successfully recorded. The most interesting aspect of the current application is that it enabled simultaneous detection of both the target analyte and its decomposition products. At suitable elevated temperatures of the transfer line between the GC instrument and the UV detector, a partial decomposition was accomplished. Detection was made in real time and resulted in overlaid spectra of the mother compound and its decomposition product. Hence, the presented approach added another level to the qualitative identification of the explosives in comparison with traditional methods that relies only on the detection of the target analyte. As expected, the decomposition product of EGDN, NG, and PETN was NO, while TATP degraded to acetone. DNT and TNT did not exhibit any decomposition at the temperatures used.     

Performance testing of commercial containers for collection and storage of fire debris evidence

Fire debris evidence may contain ignitable liquid residues valuable in the investigation of a potential arson scene. The ability to obtain evidence containers that are contaminant-free and vapor-tight is essential to the analysis and storage of fire debris evidence. Commercial containers such as metal "paint" cans, glass mason jars, and polymer bags are often employed as fire debris evidence containers. The purpose of this research was to determine which of these three types of containers provided the most vapor-tight seal for the prevention of ignitable liquid vapor loss and to assess the potential for cross-contamination. Leak rates for each type of container were measured under controlled conditions. Simple mixtures of hydrocarbons were utilized in these experiments. Leak rates were determined based on the amounts of hydrocarbon recovered from activated charcoal located outside the test container and within a secondary container. Quantitation of the hydrocarbons recovered from activated charcoal was calculated using external standard calibration curves following analysis by gas chromatography-mass spectrometry. The results demonstrated that glass jars had the fastest leak rate followed by metal paint cans and properly heat-sealed polymer bags with the slowest leak rate. Each container exhibited a different leak mechanism, which resulted in an observable effect on the composition of hydrocarbons lost from the container. Hydrocarbon transfer from one container to another is also demonstrated. This study presents results that reveal the most vapor-tight container to be a properly heat-sealed copolymer bag.     

Testing for alpha-chloralose by headspace-GC/MS. A case report.

A case is presented involving an acute fatality resulting from self-administered alpha-chloralose, a rodenticide. A 18-year-old man was found dead at home, with several stains of vomit on the carpet. An empty box of three bags of 5 g 100% alpha-chloralose (Corbeaux nuisibles, Rh?ne Poulenc) was found near the body. The compound was identified and quantified by headspace gas chromatography coupled to mass spectrometry. Alpha-chloralose was converted by concentrated sulphuric acid into chloral, a volatile compound, that was, after chromatography on a HP5-MS capillary column, identified by the following ions, m/z 82, 111 and 148. Peripheral blood concentration was 175.7 mg/l. Alpha-chloralose was quantified in several tissues, indicating kidney sequestration. No other drugs, including ethanol, were detected.     

Comparison of the Volatile Organic Compounds from Different Biological Specimens for Profiling Potential*

Previous work has demonstrated the ability to differentiate individuals based on the analysis of human scent hand odor chemicals. In this paper, a range of forensic biological specimens are shown to also have the ability to differentiate individuals based upon the volatile organic compounds (VOCs) present. Human VOC profiles from hand odor, oral fluid, breath, blood, and urine of 31 individuals were analyzed by solid‐phase microextraction–gas chromatography–mass spectrometry (SPME‐GC‐MS) and combined methods of chromatogram comparison, Spearman rank correlation comparison, and principal component analysis. Intra‐specimen comparisons demonstrated the distinguishability of individuals above 99%. Inter‐specimen VOC profiles from the same individual were found to be too different to be used for scent‐matching purposes, with Spearman rank coefficients below 0.15. A 6‐month VOC profile monitoring of two individuals demonstrated the consistency of VOC profiles over time across specimens.     

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.     

Feasibility of Canine Detection of Mass Storage Devices: A Study of Volatile Organic Compounds Emanating from Electronic Devices Using Solid Phase Microextraction

Detection of canines are well‐known to be valuable in the location of contraband, such as explosives or narcotics. More recently, canines have been trained and utilized in the detection of concealed mass storage devices that might contain evidence of illegal activity such as child pornography. To lay the analytical foundation for this detection work, research was carried out to determine the volatile organic compounds associated with mass storage devices (MSD) that could be used by trained canines for detection. Headspace analysis of a variety of electronic devices was performed using solid phase microextraction (SPME) with gas chromatography/mass spectrometry (GC/MS). Analyses found several volatile compounds common to SIM and SD cards, as well as USB drives, including 2‐propenenitrile, styrene, isophorone, hydroxycyclohexyl phenyl ketone, and 2‐furanmethanol, tetrahydro. Results indicated that mass storage devices do have a characteristic odor profile making detection with minimal false alerts feasible for trained canines.     

Acute Poisoning Types and Prevalence in Shanghai,China, from January 2010 to August 2011

In recent years, the number of cases of acute poisoning has increased in China, yet; currently, there is no detailed report published that addresses acute poisoning in the mainland of China. We collected biological samples from 466 cases of suspected acute poisoning at the hospitals in Shanghai, China, and examined them using spectroscopy, chromatography and chromatography/mass spectrometry. Of the 466 cases, 230 cases (100 men and 130 women) were positively confirmed as acute poisonings. There were 80 types of compounds identified in this study. Medications were the most frequent substances identified, and the other substances included pesticides, multiple compounds, volatile compounds, natural toxins, and others. The results of this study indicate a need for strengthening the education about and management of the rational and safe use of drugs in Shanghai.     

Automated headspace solid-phase microextraction and capillary gas chromatography analysis of ethanol in postmortem specimens

Solid-phase microextraction (SPME) is a relatively new solventless sample preparation technique that allows simultaneous sampling, extraction, pre-concentration, and introduction of analytes from a sample matrix in a single procedure. This methodology has been used for the analysis of several drugs of forensic toxicology interest including volatile compounds. This paper describes a methodology for analysis of ethanol and other volatile compounds using automatic headspace solid-phase microextraction (HS-SPME) and capillary gas chromatography in postmortem specimens. The methodology was initially developed using standard solutions of acetaldehyde, acetone, methanol, and ethanol. Isobutanol was used as internal standard. Postmortem samples of blood, urine, and vitreous humor were obtained during medico-legal autopsies. To date, there are no published paper regarding alcohol analysis in vitreous humor specimens using HS-SPME and limited literature analyzing blood and urine samples. HS-SPME analysis showed that, under optimized conditions, ethanol and isobutanol (internal standard) were well-separated from other volatile compounds such as acetaldehyde, acetone, and methanol considered to be potential interferents in ethanol analysis. The calibration curves for each volatile compound demonstrated good linearity throughout the concentration range from 0.001 to 1.0 g/dl and the detection limit of ethanol in the studied specimens was approximately 0.0001 g/dl.     

Analysis of biofluids for flunitrazepam and metabolites by electrospray liquid chromatography/mass spectrometry

A rapid and sensitive liquid chromatography/electrospray ionization mass spectrometry (LC/MS) procedure has been developed for the analysis of biofluids containing flunitrazepam and its metabolites. Specimens were spiked with deuterated analogs of the analytes. Urine specimens were enzymatically hydrolyzed and blood specimens were untreated. Extractions were carried out using CleanScreen DAU SPE cartridges. The drugs were separated on a C18 column using a methanol-water-ammonium hydroxide (60:40: 0.03 v/v) mobile phase. After determination of base peaks using full scan mass spectrometry, the mass spectrometry method was optimized to operate in selected-ion monitoring (SIM) mode for the base peak of each analyte. Positive findings were confirmed by LC/MS/MS using the same mobile phase and column. This analytical procedure allows for the detection of low levels of flunitrazepam and metabolites in biofluids. It is useful for ascertaining the role of flunitrazepam in cases of drug-facilitated sexual assault.     

Situations of poisoning and analytical toxicology in Japan

Unprecedented poisoning terrorism by use of sarin took place in Japan in 1994 and 1995. On July 25, 1998, a curry poisoning incident in Wakayama occurred resulting in the death of four people and injury of 63 people. Since then, more than 30 imitative poisoning cases have been reported by mass communication within 1 year. In this brief review, we present some details of a series of poisoning cases and measures taken by the Japanese Government and non-government groups. In addition some research projects on analytical toxicology being conducted in our laboratories are also introduced; gas chromatography (GC) with cryogenic oven trapping for volatile organic compounds, and GC/surface ionization organic mass spectrometry for tertiary amino compounds are described especially as new techniques for biological samples.     

Performance Testing of the New AMPAC Fire Debris Bag Against Three Other Commercial Fire Debris Bags(*)

Abstract: Fire debris evidence is collected and stored in a wide range of containers, including various polymer bags. Four different polymer bags have been investigated, including the NYLON, DUO, ALU, and AMPAC bags. The latter is the successor of the Kapak Fire DebrisPAK^?. Microscopy and infrared spectroscopy were used to elucidate the composition of the bags. Gas chromatography/mass spectrometry was used to investigate performance parameters such as background volatiles, leak rate, cross‐contamination, recovery, and sorption. The NYLON bag was susceptible for leakage and cross‐contamination and showed decreased recoveries. The DUO and ALU bags showed some background volatiles, sorption, and poor recoveries. The AMPAC bag performed excellent: low background, no leakage or cross‐contamination, good recoveries, and only traces of sorption. Heat sealing proved to be the best method of closure. Preliminary studies on AMPAC bags showed that polyethylene clamps are easy to use on‐site and preserve ignitable liquids adequately for a limited period of time.     

Dynamic of the ageing of ballpoint pen inks: quantification of phenoxyethanol by GC-MS.

The ageing process of some inks were studied to evaluate whether it is possible to date them. We used gas chromatography coupled with mass spectrometry to measure the evaporation of volatile components. The selected approach thus follows the disappearance of one ink volatile component (phenoxyethanol) as a function of time. The ink ageing curve represents the ratio of an evaporating compound to a stable compound of ink according to time. The results obtained are thus independent of the quantity of ink sampled for analysis. We obtained for two pens, containing two different inks, a curve highlighting an exponential decrease of the evaporating compound. By fitting these curves we determined the limitations of dating a ballpoint pen ink. Two distinct behaviours were observed in two distinct modes, the first called 'fast mode' and the second called 'slow mode'. In order to try to explain the phenomenon, the studies were based on solvent diffusion theory in complex matrix (such as polymer on varnish). Calculations from certain parameters showed an extremely fast evaporation of ink solvents, as well as varying behaviour depending on the paper used. The results showed that it is not possible to date ballpoint pen inks with this method in document examination casework.     

Differentiation of black gel inks using optical and chemical techniques

Gel ink pens have become a common writing instrument in the United States. Questioned document examiners often attempt to optically differentiate gel inks from each other and from other non-ballpoint ink writings (e.g., those from roller-ball pens). Since early formulations were primarily pigment-based, they do not elute when analyzed by thin-layer chromatography. However, recent gel ink formulations (i.e., within the past five years) include dye-based inks that can be easily separated. This study differentiates black gel inks using optical and chemical techniques. The techniques include: microscopy, visible and near infrared reflectance, near infrared luminescence, thin-layer chromatography (TLC), spot tests, and gas chromatography/mass spectrometry (GC/MS). As a result of this study a flow chart has been developed allowing for a systematic determination of a questioned ink. In addition, an analysis of volatile compounds found in gel inks revealed that there are some unique ingredients that may be found in gel inks that are not typically found in other non-ballpoint inks.     

Evaluation of vapor profiles of explosives over time using ATASS (Automated Training Aid Simulation using SPME)

Despite numerous instrumental achievements, canines are still considered the most effective field method for explosive detection. However, due to strict explosive regulations and safety requirements, it can be a challenge for agencies with "bomb dogs" to train using neat explosive materials. This establishes a need for non-explosive canine training aids with the same volatile component profiles as the explosives that they represent. In order to compare mimic materials to their explosive counterparts, a technique must be established that not only allows for identification of volatile compounds but also can monitor changes in the headspace profile over time with respect to time and temperature. The Automated Training Aid Simulation using SPME (or ATASS) was developed for that purpose. As described, ATASS was used to observe changes in the volatile profile of three explosives (Composition C-4, 2,4-dinitrotoluene (DNT), and triacetone triperoxide (TATP)) and respective prototype training materials (0.1% by mass C-4, 1% by mass 2,4-DNT, and 1% by mass TATP). Samples were prepared in vials and metal tins within a gallon (≈ 3785 mL) paint can to simulate common field techniques for canine training. Monitoring these materials in real time provides a better understanding of the major volatile components present and how the relative abundances of these components can change over time. The results presented indicate that ATASS successfully allows for a sufficient comparison between explosive and non-explosive training materials.     

The evaluation of human hand odor volatiles on various textiles: a comparison between contact and noncontact sampling methods

The focus of this study is to compare contact and noncontact human scent collection procedures across an array of textiles (cotton, rayon, polyester, and wool) to determine an optimized collection method for human scent evidence. Six subjects were sampled in triplicate for each textile and collection mode, and the samples were then analyzed through headspace solid-phase micro-extraction in combination with gas chromatography/mass spectrometry (SPME-GC/MS). Contact sampling with cotton material has been shown to be the collection method that yielded the greatest number of volatile compounds and the highest scent mass amounts. Through Spearman rank correlations, it was shown that an individual's scent profile is more reproducible within samples collected on the same textile type than between different materials. Furthermore, contact sampling with cotton fabric demonstrated the greatest reproducibility producing the lowest amount of type I and type II errors with 90.85% of the samples distinguished at the 0.9 match/no match threshold.     

Alpha-phenylethylamine in illegally produced amphetamine.

The possibility of simultaneous synthesis of alpha-phenylethylamine and amphetamine from mixture of acetophenone and benzylmethylketone was studied. The structures of specific impurities were predicted and these compounds were synthesized and finally found in reaction mixtures, as well as in the final product. The data collected by gas chromatography, proton and carbon magnetic resonance, Fourier transform infrared spectrometry and mass spectrometry are presented.     

Chlorinated Opium Alkaloid Derivatives Produced by the Use of Aqueous Sodium Hypochlorite During the Clandestine Manufacture of Heroin

Abstract:  A clandestine chemist was observed producing heroin from crude morphine utilizing a solution of sodium hypochlorite during the process. Numerous chlorinated opium alkaloid derivatives were created when the morphine acetylation reaction was quenched and neutralized with a solution of sodium hypochlorite and ammonium hydroxide. Four of these compounds, 1-chloroheroin, 1-chloroacetylcodeine, 1-chloro-O⁶-monoacetylmorphine, and 2'-chloropapaverine, were characterized via preparative isolation, gas chromatography/mass spectrometry, nuclear magnetic resonance spectroscopy, and independent synthesis. These chlorinated derivatives were formed via electrophilic aromatic substitution with free chlorine during the illicit process. Although no illicit heroin exhibits containing these compounds have been observed in seizures to date, mass spectral data are provided for several of these compounds for their identification should they be seen within future seizures of illicit heroin.     

Decaying Mouse Volatiles Perceived by Calliphora vicina Rob.‐Desv.

Volatiles emitted by decaying human remains are in the focus of recent research. The identification of core volatiles in this field is of high importance, because cadaveric volatiles generally show high variation. In this study, the volatile profiles of five mice (Myodes glareolus) were sampled with charcoal filter tubes from their time of death until advanced decay. Eleven compounds were quantitated by means of gas chromatography–mass spectrometry. Electroantennographic experiments with female Calliphora vicina antennae led to the identification of dimethyl trisulfide, dimethyl disulfide, nonanal, hexan‐1‐ol, 1‐octen‐3‐ol, 3‐methylbutan‐1‐ol, and heptanal as electrophysiologically active compounds. When these were compared, dimethyl trisulfide (17 ng/μL) and dimethyl disulfide (11 ng/μL) were found to be emitted in higher concentrations. The roles of these compounds and nonanal as core volatiles for cadaver detection or postmortem time determination and their correlation to the stages of decay and the accumulated degree days are discussed.