Pyrolysis Products of Linear Alkylbenzenes— Implications in Fire Debris Analysis*

Abstract: In this case report, potential interferences from an improvised fire‐extinguishing agent, a dishwashing liquid, containing linear alkylbenzene sulfonates (LAS), was studied. The presence of linear alkylbenzenes (LABs) in the fire debris sample was identified from the summed ion profile (SIP) analysis. It was found that the LAS from dishwashing liquids produce LABs by thermal degradation. Direct pyrolysis of a LAS‐containing dishwashing liquid at 300°C yielded a distribution of LABs in the SIP. LABs began to break down at pyrolysis temperatures between 450 and 500°C and completely break down by 800°C. Observed pyrolysis breakdown products of LABs included toluene, ethylbenzene, meta‐, para‐, and ortho‐xylenes, propylbenzene, indane, naphthalene, and 1‐ and 2‐methylnaphthalenes. These data suggested the presence of LABs in fire debris evidence might complicate subsequent analysis because their breakdown products contained some of the target compounds common to ignitable liquid identification. Therefore, a positive determination of the presence of foreign ignitable liquids should be carefully evaluated when there is a presence of LABs in the SIP.     

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.     

The Identification of Spiromesifen,a Recently Introduced Pesticide,Using Approaches to Chemical Unknown Analysis

An unknown, viscous, opaque, white liquid with a strong, unpleasant odor was submitted with a request for identification. It was analyzed using infrared (IR) spectroscopy, gas chromatography–mass spectrometry, and X‐ray fluorescence spectroscopy. It was found to contain glycerin as well as another compound. IR and mass spectral data were readily obtained for this second component, but it was not easily identified as common instrument libraries had no matching spectra. After an extensive literature search, the unknown compound was identified as spiromesifen, a recently introduced pesticide. The IR spectrum and electron impact mass spectrum of spiromesifen are presented here as these are not available in the published literature. This case report also provides useful approaches for searching for and identifying an unknown compound when it is not found in a laboratory's spectral libraries.     

A Rare Case of Poisoning with a Volatile Substance: Quantitative Determination of n‐Butane in Postmortem Tissue

Poisoning with volatile substances remains exceptional. Authors report the case of a married couple who were found in a car with a butane gas bottle: the woman was dead and her husband alleged it was an unsuccessful suicide pact. A specific research of volatile substances on postmortem samples with headspace gas chromatography–mass spectrometry following a quantitative determination was performed. The n‐butane concentrations detected were composed of 610 μg/L (cardiac blood), 50 μg/kg (brain), 134 μg/kg (lungs), 285 μg/kg (liver), and 4090 μg/kg (heart) and were compatible with the rare lethal concentrations evoked in the literature. The cause of death was determined to be asphyxiation through n‐butane criminal poisoning. Authors recommendation therefore is to take samples immediately and place them in properly sealed containers and hence analyzing the samples as soon as possible after collecting them or storing them under ?30°C (?22°F) if analyses cannot be performed immediately.     

Relationship between the Change Rules of Volatile Organic Compounds in Rat Muscle and Postmortem IntervalCSCD

Objective: To explore the relationship between the change rules of volatile organic compounds (VOCs) in rat muscle and postmortem interval (PMI). Methods: A total of 120 healthy rats were divided randomly into 12 groups (10 for each group). After the rats were sacrificed by cervical dislocation, the bodies were kept at (25±1) ℃ Rat muscle samples were separately obtained at 12 PMI points, including 0, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 d. The VOCs in rat muscles were collected, detected and ana-lyzed by headspace solid-phase micro extraction (HS-SPME) coupled to gas chromatography-mass spec-trometer (GC-MS). Results: In total, 15 species of VOCs were identified, including 9 aromatic compounds, 3 sulfur compounds, 2 aliphatic acids and 1 heterocyclic compound. The species of VOCs increased with PMI: no species were detected within 1 day, 3 species were detected on day 2, 9 on day 3, 11 on day 4, 14 from day 5 to 7, and 15 from day 8 to 10. Total peak area of 15 species of VOCs was significantly correlated to PMI (adjusted R2=0.15-0.96): the regression function was y=-17.05 x2+164.36x-246.36 (adjusted R2=0.96) from day 2 to 5, and y=2.24x+101.13 (adjusted R2=0.97) from day 6 to 10. Conclusion: The change rules of VOCs in rat muscle are helpful for PMI estimation. © 2017 by the Editorial Department of Journal of Forensic Medicine.     

Analysis of condom lubricants for forensic casework

The detection of DNA is inhibited in cases of sexual assault involving condom use. Trace evidence, including condom lubricant residues, provides crucial associative evidence in such cases. The existing Fourier transform infrared spectroscopy (FTIR) methods for lubricant analysis and detection are limited with regard to sensitivity and discrimination. The aim of this research was to establish a new method as an alternative to FTIR for the analysis of condom lubricant residues. Pyrolysis gas chromatography-mass spectrometry (PyGC-MS) and GC-MS are highly sensitive methods of analysis for a wide range of chemical substances. PyGC-MS and GC-MS were used to analyze condom lubricants in standard solution, from clean swabs and from postcoital swabs. Pyrolysis of polydimethylsiloxane (PDMS) lubricant forms cyclic products known as cyclic dimethyl siloxanes (DMS), which are separated and detected by the GC-MS. The polyethylene glycol (PEG) lubricant can be analyzed by GC-MS directly from solution. The methods of extraction and analysis presented in this paper were shown to be significantly more sensitive than FTIR for the analysis of PDMS and PEG condom lubricants. PDMS was detected as low as 1 mug in standard solution and from clean swabs using the PyGC-MS method. PEG was detected as low as 0.5 microg from standard solution and 50 mug from clean swabs using the GC-MS method. Unfortunately, we were unable to provide further discrimination between condom brands and subbrands. The methods established throughout the research were used successfully to detect condom lubricants from donated postcoital swabs. Lubricants were detected in abundance on swabs 12 h postcoitus. Recommendations are made regarding implementation of new methods for routine analysis of casework samples along with strict pyrolysis interpretation criteria to minimize the possibility of misinterpretation of false positives.     

Recovery and detection of urea nitrate in traces

Urea nitrate (uronium nitrate, UN) is a powerful improvised explosive, frequently used by terrorists in the Israeli arena. It was also used in the first World Trade Center bombing in New York in February 1993. It is difficult to identify UN in postexplosion debris, because in the presence of water it readily decomposes to its original components, urea and nitric acid. A method for the recovery and detection of urea nitrate in traces is described. The residues are extracted with hot acetone, and the extract chromatographed on chromosorb G-HP. The eluent is analyzed by liquid chromatography mass spectrometry using atmospheric pressure chemical ionization (APCI). By applying this technique, we were able to identify urea nitrate in actual exhibits. It was found that UN can be also formed during the analytical procedure, by certain combinations of urea, nitrate ions, and a source of protons and, hence, the presence of the characteristic adduct ion does not necessarily indicate an "authentic" urea nitrate. Several solutions are suggested to overcome this ambiguity.     

Ballpoint pen inks: the quantitative analysis of ink solvents on paper by solid-phase microextraction

We wish to describe further developments to a method previously reported on the detection of 2-phenoxyethanol in ink. The solid-phase microextraction (SPME) sampling technique, together with gas chromatography-mass spectrometry (GC-MS), has been used to quantify solvents in writing ink. In conventional approaches, the analysis of ink on documents requires some degree of destructive sampling. The methods commonly used remove ink samples from paper using a scalpel or a paper punch. To avoid document destruction, a sampling cell was constructed that allows solvents to be adsorbed directly onto the SPME fiber from the headspace above the document surface. Analytes (ink volatiles) are then desorbed from the SPME fiber on a gas chromatograph equipped with a mass selective detector (GC-MSD). With this method, it was possible to detect the presence of ink solvents on documents for a period lasting up to c. 2 years.     

Four new illicit cocaine impurities from the oxidation of crude cocaine base: formation and characterization of the diastereomeric 2,3-dihydroxy-3-phenylpropionylecgonine methyl esters from cis- and trans-cinnamoylcocaine

Four new impurities have recently been detected in the gas chromatographic signature profiles of many illicit cocaine hydrochloride exhibits. These impurities are only seen in exhibits that have been oxidized and are most prominent in samples that have been highly oxidized. Exhibits containing these compounds were subjected to gas and liquid chromatographic-mass spectrometric analyses to determine the identity of the impurities. These impurities were subsequently synthesized to verify their structures. Four diastereomeric diols formed from the oxidation of cis- and trans-cinnamoylcocaine were characterized by nuclear magnetic resonance spectrometry, mass spectrometry, and synthesis. Oxidation of cis-cinnamoylcocaine in neutral conditions yielded (2R,3R)-dihydroxy-3-phenylpropionylecgonine methyl ester and (2S,3S)-dihydroxy-3-phenylpropionylecgonine methyl ester, while trans-cinnamoylcocaine produced (2R,3S)-dihydroxy-3-phenylpropionylecgonine methyl ester and (2S,3R)-dihydroxy-3-phenylpropionylecgonine methyl ester. The recent appearance of these new impurities suggests that some illicit cocaine processors have modified their oxidation procedures of crude cocaine base for transformation into illicit refined cocaine hydrochloride.     

Apparent effects of glyphosate on alkaloid production in coca plants grown in Colombia

During the routine analysis of coca leaf material from South America, alkaloids in Erythroxylum coca var. ipadu (ECVI) leaf samples from fields suspected of being treated with glyphosate were compared with those from non-treated E. coca var. ipadu and Erythroxylum novogranatense var. novogranatense (ENVN) plants. Cocaine levels in leaf tissue from non-treated ECVI and ENVN were 0.53+/-0.08% and 0.64+/-0.08% (w/w), respectively, whereas leaves from treated plants were nearly devoid of cocaine. Further analysis demonstrated the presence of several previously undescribed N-nortropane alkaloids, several of which were tentatively identified. The results suggest that applications of glyphosate to coca plants can have dramatic effects on the quantity and quality of alkaloids produced by surviving or subsequent leaves. The analytical data presented will be of value to forensic chemists who encounter illicit cocaine preparations containing alkaloids produced from coca plants treated with glyphosate.