Forensic analysis of wooden safety matches -- a case study.

In this case, an individual was suspected of attempting to burn materials potentially relating to a murder case. A number of spent and unspent matches were seized at the scene by police for forensic examination. Coincidentally, a police raid at the suspect's house revealed a number of matchboxes, all of the same brand, containing matches that had a visual similarity to those recovered at the scene. Stable Isotope Profiling (SIP) was used to assess whether matches could either be distinguished or shown to be indistinguishable by 13C and 2H isotopic composition. These results were then compared to those from the X-ray diffraction (XRD) analysis of match heads and microscopy of the wood. SIP showed the scene matches and seized matches to be different, which was confirmed by XRD and microscopy analyses.     

The Potential of Isotope Ratio Mass Spectrometry (IRMS) and Gas Chromatography‐IRMS Analysis of Triacetone Triperoxide in Forensic Explosives Investigations

Studying links between triacetone triperoxide (TATP) samples from crime scenes and suspects can assist in criminal investigations. Isotope ratio mass spectrometry (IRMS) and gas chromatography (GC)‐IRMS were used to measure the isotopic compositions of TATP and its precursors acetone and hydrogen peroxide. In total, 31 TATP samples were synthesized with different raw material combinations and reaction conditions. For carbon, a good differentiation and a linear relationship were observed for acetone–TATP combinations. The extent of negative (δ¹³C) fractionation depended on the reaction yield. Limited enrichment was observed for the hydrogen isotope (δ²H) values of the TATP samples probably due to a constant exchange of hydrogen atoms in aqueous solution. For oxygen (δ¹⁸O), the small isotopic range and excess of water in hydrogen peroxide resulted in poor differentiation. GC‐IRMS and IRMS data were comparable except for one TATP sample prepared with high acid concentration demonstrating the potential of compound‐specific isotope analysis. Carbon IRMS has practical use in forensic TATP investigations.     

Evaluation of a Headspace Solid‐Phase Microextraction Method for the Analysis of Ignitable Liquids in Fire Debris

The chemical analysis of fire debris represents a crucial part in fire investigations to determine the cause of a fire. A headspace solid‐phase microextraction (HS‐SPME) procedure for the detection of ignitable liquids in fire debris using a fiber coated with a mixture of three different sorbent materials (Divinylbenzene/Carboxen/Polydimethylsiloxane, DVB/CAR/PDMS) is described. Gasoline and diesel fuel were spiked upon a preburnt matrix (wood charcoal), extracted and concentrated with HS‐SPME and then analyzed with gas chromatography/mass spectrometry (GC/MS). The experimental conditions—extraction temperature, incubation and exposure time—were optimized. To assess the applicability of the method, fire debris samples were prepared in the smoke density chamber (SDC) and a controlled‐atmosphere cone calorimeter. The developed methods were successfully applied to burnt particleboard and carpet samples. The results demonstrate that the procedure that has been developed here is suitable for detecting these ignitable liquids in highly burnt debris.     

Forensic analysis of explosives using isotope ratio mass spectrometry (IRMS) — Preliminary study on TATP and PETN

The application of isotopic techniques to investigations requiring the provision of evidence to a Court is limited. The objective of this research was to investigate the application of light stable isotopes and isotope ratio mass spectrometry (IRMS) to solve complex forensic cases by providing a level of discrimination not achievable utilising traditional forensic techniques.Due to the current threat of organic peroxide explosives, such as triacetone triperoxide (TATP), research was undertaken to determine the potential of IRMS to differentiate samples of TATP that had been manufactured utilising different starting materials and/or manufacturing processes. In addition, due to the prevalence of pentaerythritoltetranitrate (PETN) in detonators, detonating cord, and boosters, the potential of the IRMS technique to differentiate PETN samples from different sources was also investigated.Carbon isotope values were measured in fourteen TATP samples, with three definite groups appearing in the initial sample set based on the carbon data alone. Four additional TATP samples (in a second set of samples) were distinguishable utilising the carbon and hydrogen isotopic compositions individually, and also in combination with the oxygen isotope values. The 3D plot of the carbon, oxygen and hydrogen data demonstrated the clear discrimination of the four samples of TATP. The carbon and nitrogen isotope values measured from fifteen PETN samples, allowed samples from different sources to be readily discriminated.This paper demonstrates the successful application of IRMS to the analysis of explosives of forensic interest to assist in discriminating samples from different sources. This research represents a preliminary evaluation of the IRMS technique for the measurement of stable isotope values in TATP and PETN samples, and supports the dedication of resources for a full evaluation of this application in order to achieve Court reportable IRMS results.     

Comparative analysis of 1-phenyl-2-propanone (P2P), an amphetamine-type stimulant precursor, using stable isotope ratio mass spectrometry: Presented in part as a poster at the 2nd meeting of the Joint European Stable Isotope User Meeting (JESIUM), Giens, France, September 2008

The isotope ratios of amphetamine type stimulants (ATS) depend as well on the precursor as the synthetic pathway. For clandestine production of amphetamine and methamphetamine, 1-phenyl-2-propanone (P2P, benzylmethylketone) is a commonly used precursor.Our aim was to determine the variation of the isotope ratios within precursor samples of one manufacturer and to compare seized samples of unknown sources to these values. δ¹³C_V-PDB, δ²H_V-SMOW and δ¹⁸O_V-SMOW isotope ratios were determined using elemental analysis (EA) and gas chromatography (GC) coupled to an isotope ratio mass spectrometer (IRMS). The comparison of all seized samples to the data of the samples of one manufacturer revealed considerable differences. The results show that IRMS provides a high potential in differentiating between precursors from different manufacturers for the clandestine production of ATS and identifying corresponding sources.     

Recovery of fingerprints from fire scenes and associated evidence.

A lack of information concerning the potential recovery of fingerprints from fire scenes and related evidence prompted several research projects. Latent prints from good secretors and visible prints (in blood) were placed on a variety of different surfaces and subsequently subjected to "real life" fires in fully furnished compartments used for fire investigation training purposes. The items were placed in various locations and at different heights within the compartments. After some initial success, further tests were undertaken using both latent and dirt/grease marks on different objects within the same types of fire compartments. Subsequent sets of tests involved the recovery of latent and visual fingerprints (in blood, dirt and grease) from different types of weapons, lighters, plastic bags, match boxes, tapers, plastic bottles and petrol bombs that had been subjected to the same fire conditions as previously. Throughout the entire series of projects one of the prime considerations was how the resultant findings could be put into practice by fire scene examiners in an attempt to assist the police in their investigations. This research demonstrates that almost one in five items recovered from fire scenes yielded fingerprint ridge detail following normal development treatments.     

Forensic analysis of explosives using isotope ratio mass spectrometry (IRMS) — Discrimination of ammonium nitrate sources

An evaluation was undertaken to determine if isotope ratio mass spectrometry (IRMS) could assist in the investigation of complex forensic cases by providing a level of discrimination not achievable utilising traditional forensic techniques. The focus of the research was on ammonium nitrate (AN), a common oxidiser used in improvised explosive mixtures.The potential value of IRMS to attribute Australian AN samples to the manufacturing source was demonstrated through the development of a preliminary AN classification scheme based on nitrogen isotopes. Although the discrimination utilising nitrogen isotopes alone was limited and only relevant to samples from the three Australian manufacturers during the evaluated time period, the classification scheme has potential as an investigative aid.Combining oxygen and hydrogen stable isotope values permitted the differentiation of AN prills from three different Australian manufacturers. Samples from five different overseas sources could be differentiated utilising a combination of the nitrogen, oxygen and hydrogen isotope values. Limited differentiation between Australian and overseas prills was achieved for the samples analysed.The comparison of nitrogen isotope values from intact AN prill samples with those from post-blast AN prill residues highlighted that the nitrogen isotopic composition of the prills was not maintained post-blast; hence, limiting the technique to analysis of un-reacted explosive material.     

Stable isotope analysis of white paints and likelihood ratios

Architectural paints are commonly found as trace evidence at scenes of crime. Currently the most widely used technique for the analysis of architectural paints is Fourier Transformed Infra-Red Spectroscopy (FTIR). There are, however, limitations to the forensic analysis of white paints, and the ability to discriminate between samples.Isotope ratio mass spectrometry (IRMS) has been investigated as a potential tool for the analysis of architectural white paints, where no preparation of samples prior to analysis is required. When stable isotope profiles (SIPs) are compared, there appears to be no relationship between paints from the same manufacturer, or between paints of the same type. Unlike existing techniques, IRMS does not differentiate resin samples solely on the basis of modifier or oil-type, but exploits additional factors linked to samples such as geo-location where oils added to alkyd formulations were grown. In combination with the use of likelihood ratios, IRMS shows potential, with a false positive rate of 2.6% from a total of 1275 comparisons.     

平板玻璃受热后折射率的变化规律初探

目的探索平板玻璃受热后折射率的变化规律。方法首先采用差示扫描量热仪测定玻璃样品的转变温度Tg,将样品加热至不同的温度(温度范围从室温到Tg以上),自然冷却至室温后再用GRIM3测量折射率。结果加热温度在Tg以下时,玻璃的折射率基本不变,加热温度在Tg以上时,折射率有明显变化。结论对于从火灾和爆炸现场提取的玻璃,在进行折射率比对时应当考虑现场高温对测量值的影响,并进行必要的修正。     

Background survey of polyethylene in the Australian Capital Territory – A demonstration of variability in isotopic abundance values and their application to forensic casework

Plastics including adhesive tapes, cable ties, and packaging are common evidence types encountered in forensic investigations and casework. Traditional examination techniques such as Fourier Transform Infrared (FTIR) spectroscopy lack specificity and are unable to discern differences within the same polymer structures leaving the analyst with a generic identification. High quality manufacturing methods further amplify the limitations in detecting variability between samples. Isotope Ratio Mass Spectrometry (IRMS) has been shown to be a valuable technique in further discriminating plastics. Discrimination is achieved by analysing the relative abundances of stable isotopes within a sample, with differences detected in isotope ratios possibly attributed to the source of raw materials and fractionation during the manufacturing process. A survey of cling wraps and re-sealable zipper storage bags collected in the Australian Capital Territory was undertaken to assess the variability in carbon and hydrogen isotope ratios of different brands and samples. The results of this research are discussed, particularly with respect to within and between brand trends, and a case study is presented as an example of the value of including IRMS in a casework context.     

Simultaneous identification and δ¹³C classification of drugs using GC with concurrent single quadrupole and isotope ratio mass spectrometers

In this study, δ13C values of six cocaine samples were identified and classified using a single quadrupole mass spectrometer and an isotope ratio mass spectrometry (IRMS) as simultaneous gas chromatography detectors. Our instrument modification is simple to use and is useful (i) when the sample is of limited size or can only be injected once, (ii) to help identify peaks in a complicated IRMS chromatogram, and (iii) to help differentiate very simple systems when impurity profiling is not possible. The EI-MS confirmed the identity of cocaine in each sample. The IRMS data distinguished 12 of the 15 possible pair-wise comparisons at the 95% CL. Three samples could not be differentiated by their δ13C ratios for cocaine. ANOVA demonstrated that the measurement variance was consistently larger than the sample variance. As the δ13C values clearly show, this technique enables the exclusion of a potential common source even when two samples have otherwise identical chemical and physical properties.     

The evaluation of the extent of transporting or "tracking" an identifiable ignitable liquid (gasoline) throughout fire scenes during the investigative process

Tests have determined that boots or shoes of individuals at a fire scene do not transport sufficient contaminants ("tracking") through the fire scene to produce a positive laboratory result for the presence of gasoline in a fire scene that was not present at the time of the fire. Questions about the validity of forensic laboratory results have been raised on the basis that low-level gasoline residues detected in the laboratory samples could have been the result of transporting the residue by footwear contaminated from the fire scene ("tracking"). The data collected in this study establish that "tracking" does not lead to false-positive laboratory results. Canines trained and experienced in the detection of trace ignitable liquid residues were also utilized in this study. The canine results confirmed that properly trained canines show a higher sensitivity than do standard ASTM laboratory techniques for fire debris analysis. In a few cases, canines responded to contamination, but laboratory testing (which is the definitive indicator) did not produce positive results.     

Background interference from car carpets—the evidential value of petrol residues in cases of suspected vehicle arson

This study was undertaken to test the theory that there is a natural occurrence of petrol on the carpet or carpet mats of motor vehicles that would interfere with the potential determination of arson residues. Part of this study was also to determine what levels of background interference due to the carpet matrix are likely to be encountered in the general population of motor vehicles. The study was conducted in three parts.

• 1.A persistence study was conducted to determine the evaporation and persistence of unleaded petrol on carpet. The results indicate that small volumes of petrol (less than 100 μl) are unlikely to be detected on carpet after a 24 h period. Larger volumes will be detected after this period, but will generally not be detectable after 1 week.
• 2.A known history study was conducted by the insertion of carpet mats, for varying lengths of time, into the driver area of separate vehicles, with subsequent analysis for the presence of petrol. A ‘history’ sheet was completed by the occupants of the vehicles during the insertion periods to record the frequency of contact with petrol, and general usage of the vehicles. The results indicate that petrol will not normally be found on previously uncontaminated carpet mats after a 6-week period of use in a vehicle, however, the occupation and behaviour of the occupants can affect the types of compounds deposited onto the carpet.
• 3.An unknown history study was conducted via the collection of carpet or carpet mat samples from vehicles with an unknown history, and subsequent analysis for the presence of petrol. Six of the 150 samples examined contained petrol. These results indicate that only a small proportion of motor vehicles will exhibit the presence of petrol on carpet or carpet mats, and then only as evaporated petrol.

All of the above findings increase the evidential value of finding significant volumes of fresh or slightly evaporated petrol on carpet products in motor vehicles.     

Cryptic chemical identification as a crime intelligence aid.

A dead body was found near the sea and a commercial port in north-east Italy. The man had been shot and then burnt, by using a large volume of fire accelerant. The chemical composition of the flammable mixture had to be determined in order to aid police investigations. GC-MS analysis of residual cloth and soil identified a common gasoline, together with some unrelated compounds deriving from the container used to carry the inflammable liquid. A reconstruction of the event, an examination of the surroundings where the crime took place and the cryptic chemicals found, enabled the investigators to restrict and intensify their enquiries within a specific area.     

Linking ammonium nitrate-aluminum (AN-AL) post-blast residues to pre-blast explosive materials using isotope ratio and trace elemental analysis for source attribution

Forensic science practitioners are often called upon to attribute crimes using trace evidence, such as explosive remnants, with the ultimate goal of associating a crime with a suspect or suspects in order to prevent further attacks. The explosive charge is an attractive component for attribution in crimes involving explosives as there are limited pathways for acquisition. However, there is currently no capability to link an explosive charge to its source via post-blast trace residues using isotope ratios or trace elements. Here, we sought to determine if pre-blast attribution signatures are preserved after detonation and can be subsequently recovered and detected. A field study was conducted to recover samples of post-blast explosives from controlled detonations of ammonium nitrate-aluminum (AN-Al), which were then analyzed via isotope ratio mass spectrometry (IRMS) and inductively coupled plasma-mass spectrometry (ICP-MS) for quantitation and profiling of isotopes ratio and trace element signatures, respectively. Oxygen and nitrogen isotope ratios from AN-Al yielded some of the most promising results with considerable overlap within one standard deviation of the reference between the spreads of pre- and post-blast data. Trace element results from AN-Al support the findings in the isotope ratio data, with 26 elements detected in both pre- and post-blast samples, and several elements including B, Cd, Cr, Ni, Sn, V, and Zn showing considerable overlap. These preliminary results provide a proof-of-concept for the development of forensic examinations that can attribute signatures from post-blast debris to signatures in pre-blast explosive materials for use in future investigations.     

Forensic Analysis of Explosives Using Isotope Ratio Mass Spectrometry (IRMS)—Part 2: Forensic Inter-Laboratory Trial: Bulk Carbon and Nitrogen Stable Isotopes in a Range of Chemical Compounds (Australia and New Zealand)

Abstract:  Comparability of data over time and between laboratories is a key issue for consideration in the development of global databases, and more broadly for quality assurance in general. One mechanism that can be utilized for evaluating traceability is an inter-laboratory trial. This paper addresses an inter-laboratory trial conducted across a number of Australian and New Zealand isotope ratio mass spectrometry (IRMS) laboratories. The main objective of this trial was to determine whether IRMS laboratories in these countries would record comparable values for the distributed samples. Four carbon containing and four nitrogen containing compounds were distributed to seven laboratories in Australia and one in New Zealand. The laboratories were requested to analyze the samples using their standard procedures. The data from each laboratory was evaluated collectively using International Standard ISO 13528 ( Statistical methods for use in proficiency testing by inter-laboratory comparisons ). "Warning signals" were raised against one participant in this trial. "Action signals" requiring corrective action were raised against four participants. These participants reviewed the data and possible sources for the discrepancies. This inter-laboratory trial was successful in providing an initial snapshot of the potential for traceability between the participating laboratories. The statistical methods described in this article could be used as a model for others needing to evaluate stable isotope results derived from multiple laboratories, e.g., inter-laboratory trials/proficiency testing. Ongoing trials will be conducted to improve traceability across the Australian and New Zealand IRMS community.     

Fire investigation and ignitable liquid residue analysis--a review: 2001-2007

Next to natural disasters fires cause some of the greatest losses to property and human life around the world. Arson, the deliberate setting of a fire to destroy property or to take a human life, is one of the most difficult crimes to investigate because much of the evidence at the scene is destroyed by the fire. Fortunately, the science of fire investigation is not static and more information to help investigators determine the origin and cause of a fire through careful examination of the scene and laboratory analysis of fire debris is published every year. This review article provides an overview of the scientific literature describing research and best practices in the fields of fire scene investigation as well as ignitable liquid residue analysis. This review is a compilation of articles published between late 2001 and early 2007. Conference proceedings for which full papers have not been published were intentionally excluded from this review. Some of the information contained in this review was presented at the 14th Interpol Forensic Science Symposium held in Lyon, France in October 2004.     

Palynological Investigation of Mummified Human Remains

Pollen analysis was applied to a mummified homicide victim in Nebraska, U.S.A., to determine the location of death. A control sample showed the normal ambient pollen in the garage crime scene. Ambient windborne types, common in the air of the region, dominated the control. Internal samples were analyzed from the sacrum, intestine, and diaphragm. Microfossils were recovered from the rehydrated intestine lumen. The intestinal sample was dominated by Brassica (broccoli). The sacrum sample was high in dietary types but with a showing of ambient types. The pollen from the diaphragm was dominated by ambient pollen similar to the control samples. The discovery of diverse pollen spectra from within a single mummy was unexpected. They show that ingested and inhaled pollen mixed in the corpse. The data linked the decedent to a specific crime scene in her Nebraska home in the southern tier of eastern counties on the border with Kansas.     

Using Alkylate Components for Classifying Gasoline in Fire Debris Samples

The characteristic that discriminates gasoline from other ignitable liquids is that it contains high‐octane blending components. This study elaborates on the idea that the presence of gasoline in fire debris samples should be based on the detection of known high‐octane blending components. The potential of the high‐octane blending component alkylate as a characteristic feature for gasoline detection and identification in fire debris samples is explored. We have devised characteristic features for the detection of alkylate and verified the presence of alkylate in a large collection of gasoline samples from petrol stations in the Netherlands. Alkylate was detected in the vast majority of the samples. It is demonstrated that alkylate can be detected in fire debris samples that contain traces of gasoline by means of routine GC‐MS methods. Detection of alkylate, alongside other gasoline blend components, results in a more solid foundation for gasoline detection and identification in fire debris samples.     

The Differentiation of Menstrual from Venous Blood and Other Body Fluids on Various Substrates Using ATR FT‐IR Spectroscopy

Crime scene investigators and laboratory analysts use chemical tests to detect and differentiate body fluids. Testing often requires a sample of the stain, and the chemicals may cause degradation of the fluid or interfere with subsequent tests. Colorimetric chemical tests do not differentiate between different types of the same fluid, such as venous and menstrual blood, and there is no presumptive test available to simultaneously differentiate several body fluids. In this study, we recorded ATR FT ‐IR spectra of venous and menstrual blood, semen, saliva, and breastmilk. Neat and simulated casework body fluid samples were analyzed on cotton, nylon, wood, paper, and glass substrates. Differences in fluid composition, including proteins and small molecules, resulted in spectral differences. Venous and menstrual blood is differentiated by the peak at 1039 cm^?1 attributed to phosphoric acid found in menstrual blood. Peak intensity is influenced by the porosity and weave of the substrate fabric.