A comparison of extraction and adsorption methods for the recovery of accelerants from arson debris

Two different methods of recovering arson accelerants from fire debris are compared: distillation with addition of n-hexane and adsorption onto activated charcoal. Both procedures involve the use of the gas chromatography/mass spectrometry (GC/MS) utilizing specific mass ion programs. Some casework examples have been analyzed and the results show that, in spite of the advantages of short application times in the adsorption method, the distillation technique presented a higher degree of efficiency.     

Compositional analysis for identification of arson accelerants by electron ionization Fourier transform ion cyclotron resonance high-resolution mass spectrometry

Elemental compositions of each of 100 to 500 different constituents (i.e., every peak in a mass-to-charge ratio range, 50 < m/z < 300) of lighter fluid, kerosene, turpatine, gasoline, diesel fuel, and two brands of mineral spirits (and their weathered analogs) make possible direct identification of each accelerant in a experimental fire, based on electron ionization 6.0 Tesla Fourier transform ion cyclotron resonance (EI FT-ICR) ultrahigh resolution mass spectrometry. Septum injection of as little as 500 nL of accelerant into an all-glass heated inlet system yields definitive elemental compositions (molecular formulas) based on accurate (< +/-1 ppm average error) mass measurement alone. Extraction and EI FT-ICR mass analysis of fire debris from a controlled burn of a couch with simple (lighter fluid) and complex (turpatine) ignitable liquid yielded dozens of elemental compositions serving as a unique "fingerprint" for each petroleum product, despite the presence of up to 249 additional extracted matrix and pyrolysis components. Forty-five of 56 lighter fluid constituents and 126 of 133 turpatine constituents (not counting 13C-containing species) were identified in the debris from a fire staged for each respective accelerant.     

固相微萃取与气相色谱仪联用技术在火场助燃剂检验中的应用

目的建立检验纵火案件现场燃烧残留物中助燃剂的一种方法。方法利用固相微萃取器吸附浓缩燃烧残留物中的挥发性气体,使用气相色谱仪对挥发性气体进行定性分析。结果固相微萃取与气相色谱仪联用能较好地对火场不同介质燃烧残留物中汽油、煤油、柴油等助燃剂进行种类认定。结论该方法简便易行。     

152例火场尸体的法医学检验分析

目的 探讨火场尸体的法医学检验特点及其鉴定。方法 对86起火场中152例尸体的相关检验资料进行回顾性研究。结果 152例火场尸体,生前烧死109例,纵火焚尸38例,无明显高温作用的尸体5例。主要死因有“烧死综合征”100例,火场有毒气体中毒8例,机械性损伤32例(含高坠死4例),机械性窒息5例,电击、服毒各1例;不能确定死因5例。自杀5例,他杀40例,意外107例。在生前烧死尸体,87例呼吸道内有炭末沉着,71例皮肤局部烧伤边缘组织有红肿,46例检见水泡,17例有“闭眼反应”征象,大部分尸体血中HbCO浓度超过20％;纵火焚尸少见或不见上述改变。结论 检验火场尸体,根据烧死尸体征象和血中HbCO浓度检测,并结合火场勘验资料综合分析,其死因鉴定和死亡方式推断结论方能准确。     

火场中尸体的法医学分析

火场中的尸体是法医病理工作者较常见的案件,在这种案件中,判断是生前烧死还是死后焚尸具有非常重要的意义。本文就相关文献关于火灾死亡案件的尸体内部、外部征象、现场特点、以及以COHb为主的实验室结果加以综述,目的在于阐明这些特征在实际案件中的作用和应用,为法医工作者解决此类案件提供参考。     

The recovery of finger marks from soot-covered glass fire debris.

This study aimed to expand the scope of previous research by assessing the effectiveness of soot-removal techniques on glass from petrol-bomb debris using methods of 1% and 2% sodium hydroxide (NaOH) solutions, ultrasonic bath and vacuum suction. Of particular interest were the 1% and 2% NaOH solutions applied to the soot-covered surfaces. Petrol bombs containing petrol or a 50:50 mix of petrol and motor oil were exploded and the debris was collected for analysis. Favourable results were found to varying degrees using each of the soot-removal methods with the 1% and 2% NaOH wash solutions, being the most useful. The 2% NaOH solution also proved successful as a soak to loosen and remove heavy contamination of soot and accelerants without damaging the finger mark beneath. This study also found that recovery of finger marks in blood from beneath soot using the 2% NaOH solution was possible. Finger marks were also applied to glass bottles with plastic adhesive labels, and providing the fire damage is not too great marks were also retrievable. Results from this study lead to the conclusion that the NaOH wash solution is ideally suited for soot removal to reveal latent and blood-contaminated marks both within the laboratory and at crime scenes.     

建立火场样品中汽油残留物ATD-GC-MS检验结果的评价方法

目的建立火场中汽油燃烧残留物ATD-GC-MS检验结果评价方法。方法将模拟燃烧样品用ATD-GC-MS法检验,检验结果通过对芳烃、烷烃、茚满、和萘系列的4个特征离子色谱图与已知汽油作比较,并利用向量夹角法计算样品与汽油色谱指纹图的相似度来对检验结果作评价。结果有汽油作助燃剂的模拟燃烧样品与汽油色谱指纹图的相似度一般大于90%,无汽油作助燃剂的样品则在60%以下。结论利用样品的4个特征离子色谱图与已知汽油作比较,并结合样品与汽油色谱指纹图相似度的计算,能对检验结果作出客观、可靠和准确的评价。     

Forensic analysis of ignitable liquids in fire debris by comprehensive two-dimensional gas chromatography

The application of comprehensive two-dimensional gas chromatography (GC x GC) for the forensic analysis of ignitable liquids in fire debris is reported. GC x GC is a high resolution, multidimensional gas chromatographic method in which each component of a complex mixture is subjected to two independent chromatographic separations. The high resolving power of GC x GC can separate hundreds of chemical components from a complex fire debris extract. The GC x GC chromatogram is a multicolor plot of two-dimensional retention time and detector signal intensity that is well suited for rapid identification and fingerprinting of ignitable liquids. GC x GC chromatograms were used to identify and classify ignitable liquids, detect minor differences between similar ignitable liquids, track the chemical changes associated with weathering, characterize the chemical composition of fire debris pyrolysates, and detect weathered ignitable liquids against a background of fire debris pyrolysates.     

A solid-phase microextraction method for the detection of ignitable liquids in fire debris

A solid-phase microextraction (SPME) procedure involving direct contact between the SPME fibers and the solid matrix and subsequent gas chromatography/mass spectrometric analysis for the detection of accelerants in fire debris is described. The extraction performances of six fibers (100 mum polydimethylsiloxane, 65 mum polydimethylsiloxane-divinylbenzene, 85 mum polyacrylate, 85 mum carboxen-polydimethylsiloxane, 70 mum Carbowax-divinylbenzene, and 50/30 mum divinylbenzene-Carboxen-polydimethylsiloxane) were investigated by directly immersing the fibers into gasoline, kerosene, and diesel fuel. For simulated fire debris, in the direct contact extraction method, the SPME fiber was kept in contact with the fire debris matrix during extraction by penetrating plastic bags wrapping the sample. This method gave comparable results to the headspace SPME method in the extraction of gasoline and kerosene, and gave an improved recovery of low-volatile components in the extraction of diesel fuel from fire debris. The results demonstrate that this procedure is suitable as a simple and rapid screening method for detecting ignitable liquids in fire debris packed in plastic bags.     

火场样品中汽油与稀释剂燃烧残留物的区分方法探讨

目的探讨火场样品中汽油与稀释剂燃烧残留物的区分方法。方法样品用ATD—GC—MS法检验,检验结果通过对芳烃、烷烃、茚满、和萘系列的4个特征离子色谱图与已知汽油和稀释剂作比较,并结合向量夹角法计算样品与汽油色谱指纹图的相似度来区分汽油与稀释剂残留物。结果个别品种的稀释剂燃烧残留物与汽油很相似,但彼此有某些差别。结论使用本方法,一般能将汽油与稀释剂燃烧残留物区分开。     

The use of 13C NMR spectroscopy in forensic drug analysis

¹³C NMR spectroscopy has been used for analysis of fourteen compounds which, according to Swedish laws are defined as narcotic drugs or are substances often found in combination with these drugs. The carbon-13 NMR method seems to be well suited for analysis of complex forensic drug mixtures because no preliminary separation of components is required.     

The effect of compressed air foam on the detection of hydrocarbon fuels in fire debris samples

In 1998/99 the New Zealand Fire Service implemented compressed air foam delivery systems for the suppression of fires in rural areas. This study investigated whether the introduction of the foam to the seat of the fire created any problems in subsequent analyses of fire debris samples. No significant interferences from the foam were found when the samples were analysed by direct headspace using activated carbon strips. The only foam component detected was limonene.     

Crime scene analysis and the escalation of violence in serial rape.

The current study examines the crime scene behavior manifest by 108 serial rapists responsible for the perpetration of 565 rapes across various cities within the US. The goal of the current study is to identify which aspects of crime scene behavior reported to law enforcement by the victim are most useful in predicting, early in a series of offenses, which rapists are most likely to escalate into higher and, at times, life threatening levels of violence. Using 58 scales that quantify the verbal, physical, and sexual behavior manifest by a rapist in his interaction with his victim during his first reported rape and 36 modal variables that summarized approach, timing, demographics, and weapon usage across the series of rapes, the study attempts to differentiate between those rapists who escalate in their use of blunt force (Increasers) from those who do not (Non-Increasers). A logistic regression indicates that rapists who are white rather than of minority status and who, at the time of their first reported rape, rape their victims for longer periods of time and use more profanity are more likely to escalate in their level of blunt force than those rapists who do not exhibit these behaviors. The relevance of this type of predictive framework for law enforcement in its attempts to prioritize particular investigations is discussed.     

A study of the effects of a Micelle Encapsulator Fire Suppression Agent on dynamic headspace analysis of fire debris samples

The effects of a Micelle Encapsulator Fire Suppression Agent (F-500, Hazard Control Technologies Inc., Fayetteville, Georgia) on the routine analysis of fire debris samples by Gas Chromatography (GC) were studied. When mixed with water the product can be used in the suppression of Class A and Class B fires. Laboratory tests were performed to determine whether or not the product has any effect on the analysis for ignitable liquids by GC, in particular for gasoline, medium petroleum distillates. and heavy petroleum distillates. Test burns were suppressed using either the micelle encapsulator or water and samples collected from these burns were analyzed. The results of analysis show that use of the micelle encapsulator at a fire scene may affect the chromatographic data obtained from samples collected by the investigator. However, the effect does not prevent the identification of common ignitable liquids in fire debris samples.     

The evaluation of evidence in the forensic investigation of fire incidents. Part II. Practical examples of the use of Bayesian networks

This paper extends a previous discussion of the use of Bayesian networks for evaluating evidence in the forensic investigation of fire incidents. Bayesian networks are proposed for two casework examples and the practical implications studied in detail. Such networks were found to provide precious support in addressing some of the wide range of issues that affect the coherent evaluation of evidence.     

Sampling and recovery of ignitable liquid residues (ILRs) from fire debris using capillary microextraction of volatiles (CMV) for on-site analysis

A new, fast, and ultra-sensitive headspace sampling method using the Capillary Microextraction of Volatiles (CMV) device is demonstrated for the analysis of ignitable liquid residues (ILRs) in fire debris. This headspace sampling method involves the use of a heated can (60°C) to aid in the recovery of volatile organic compounds (VOCs) from medium and heavy petroleum distillates. Our group has previously reported the utility of CMV to extract gasoline at ambient temperature in less than 5 min in the field. This work evaluates the recovery and analysis of low mass loadings (tens of ng) of VOCs from charcoal lighter fluid, kerosene, and diesel fuel. Nonane, decane, undecane, tridecane, tetradecane, and pentadecane were selected for evaluation of recovery to represent these ILR classes. The face-down heated can headspace sampling technique was compared to the previously reported, non-heated, paper cup headspace sampling technique. Mass recovery improvements of 50%–200% for five of the six target compounds in diesel fuel were achieved compared to the non-heated sampling method. The average relative standard deviation (reported as % RSD) between the replicate trials decreased from an average of 28% to 6% when using the heated can method. Ignitable liquids were spiked onto burned debris in a live burn exercise and sampled using the heated can and paper cup headspace sampling techniques. The heated sampling technique reported here, for the first time, demonstrates an effective extraction method that when coupled to a portable GC–MS instrument allows for a sampling and analysis protocol in the field in less than 30 min.     

A review of the analysis of vegetable oil residues from fire debris samples: spontaneous ignition, vegetable oils, and the forensic approach

This paper reviews the literature on the analysis of vegetable (and animal) oil residues from fire debris samples. The process of self-heating and spontaneous ignition is well-known by fire investigators and causes many fires. Vegetable oils are often the chemicals that originate such phenomenon. Vegetable oils are composed of lipids, which contain fatty acids. The autooxidation of the double bonds present in unsaturated fatty acids is the exothermic reaction at the origin of the self-heating process. The degree of unsaturation of fatty acids directly influences the propensity of an oil to undergo self-heating and, eventually, spontaneous ignition. When fire debris samples are collected, it is possible to examine them at the laboratory to extract and identify vegetable oil residues. This is typically performed by solvent extraction, followed by gas chromatographic(-mass spectrometric) analysis of the extract. Such analyses differ from ignitable liquid residue analyses, so a different forensic approach is necessary.