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.     

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.     

ASTM standards for fire debris analysis: a review

The American Society for Testing and Materials (ASTM) recently updated its standards E 1387 and E 1618 for the analysis of fire debris. The changes in the classification of ignitable liquids are presented in this review. Furthermore, a new standard on extraction of fire debris with solid phase microextraction (SPME) was released. Advantages and drawbacks of this technique are presented and discussed. Also, the standard on cleanup by acid stripping has not been reapproved.Fire debris analysts that use the standards should be aware of these changes.     

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.     

Association of Ignitable Liquid Residues to Neat Ignitable Liquids in the Presence of Matrix Interferences Using Chemometric Procedures*,†

Abstract: In fire debris analysis, weathering of ignitable liquids and matrix interferences can make the identification of ignitable liquid residues (ILRs) difficult. An objective method was developed to associate ILRs with the corresponding neat liquid with discrimination from matrix interferences using principal components analysis (PCA) and Pearson product moment correlation (PPMC) coefficients. Six ignitable liquids (gasoline, diesel, ultra pure paraffin lamp oil, adhesive remover, torch fuel, paint thinner) were spiked onto carpet, which was burned, then extracted using passive headspace extraction, and analyzed by gas chromatography‐mass spectrometry. Both light and heavy burn conditions were investigated. In the PCA scores plot, ignitable liquids were discriminated based on alkane and aromatic content. All ILRs were successfully associated with the corresponding neat liquid using both PCA and PPMC coefficients, regardless of the extent of burning. The method developed in this research may make the association of ILRs with corresponding neat liquids more objective.     

Progress Toward the Determination of Correct Classification Rates in Fire Debris Analysis,,

Principal components analysis (PCA), linear discriminant analysis (LDA), and quadratic discriminant analysis (QDA) were used to develop a multistep classification procedure for determining the presence of ignitable liquid residue in fire debris and assigning any ignitable liquid residue present into the classes defined under the American Society for Testing and Materials (ASTM) E 1618‐10 standard method. A multistep classification procedure was tested by cross‐validation based on model data sets comprised of the time‐averaged mass spectra (also referred to as total ion spectra) of commercial ignitable liquids and pyrolysis products from common building materials and household furnishings (referred to simply as substrates). Fire debris samples from laboratory‐scale and field test burns were also used to test the model. The optimal model's true‐positive rate was 81.3% for cross‐validation samples and 70.9% for fire debris samples. The false‐positive rate was 9.9% for cross‐validation samples and 8.9% for fire debris samples.     

Effect of evaporation and matrix interferences on the association of simulated ignitable liquid residues to the corresponding liquid standard

Identification of an ignitable liquid in fire debris evidence can be complicated due to evaporation of the liquid, matrix interferences, and thermal degradation of both the liquid and the matrix. In this research, liquids extracted from simulated fire debris were compared to the original liquid using multivariate statistical procedures. Neat and evaporated gasoline and kerosene standards were spiked onto nylon carpet, which was subsequently burned. The ignitable liquid residues were extracted using a passive headspace procedure and analyzed by gas chromatography-mass spectrometry. Pearson product moment correlation coefficients, hierarchical cluster analysis, and principal components analysis were used to compare the liquids extracted from the carpet to the corresponding neat liquid. For each procedure, association of the extracts according to liquid type was possible, albeit not necessarily to the specific evaporation level. Of the three procedures investigated, principal components analysis offered the most promise since contributions from matrix interferences were essentially eliminated.     

Hierarchical Cluster Analysis of Ignitable Liquids Based on the Total Ion Spectrum

Gas chromatography–mass spectrometry (GC–MS) data of ignitable liquids in the Ignitable Liquids Reference Collection (ILRC) database were processed to obtain 445 total ion spectra (TIS), that is, average mass spectra across the chromatographic profile. Hierarchical cluster analysis, an unsupervised learning technique, was applied to find features useful for classification of ignitable liquids. A combination of the correlation distance and average linkage was utilized for grouping ignitable liquids with similar chemical composition. This study evaluated whether hierarchical cluster analysis of the TIS would cluster together ignitable liquids of the same ASTM class assignment, as designated in the ILRC database. The ignitable liquids clustered based on their chemical composition, and the ignitable liquids within each cluster were predominantly from one ASTM E1618‐11 class. These results reinforce use of the TIS as a tool to aid in forensic fire debris analysis.     

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.     

Prediction and preliminary standardization of fire debris constituents with the advanced distillation curve method

The recent National Academy of Sciences report on forensic sciences states that the study of fire patterns and debris in arson fires is in need of additional work and eventual standardization. We discuss a recently introduced method that can provide predicted evaporation patterns for ignitable liquids as a function of temperature. The method is a complex fluid analysis protocol, the advanced distillation curve approach, featuring a composition explicit data channel for each distillate fraction (for qualitative, quantitative, and trace analysis), low uncertainty temperature measurements that are thermodynamic state points that can be modeled with an equation of state, consistency with a century of historical data, and an assessment of the energy content of each distillate fraction. We discuss the application of the method to kerosenes and gasolines and outline how expansion of the scope of fluids to other ignitable liquids can benefit the criminalist in the analysis of fire debris for arson.     

Combined target factor analysis and Bayesian soft-classification of interference-contaminated samples: Forensic Fire Debris Analysis

A Bayesian soft classification method combined with target factor analysis (TFA) is described and tested for the analysis of fire debris data. The method relies on analysis of the average mass spectrum across the chromatographic profile (i.e., the total ion spectrum, TIS) from multiple samples taken from a single fire scene. A library of TIS from reference ignitable liquids with assigned ASTM classification is used as the target factors in TFA. The class-conditional distributions of correlations between the target and predicted factors for each ASTM class are represented by kernel functions and analyzed by Bayesian decision theory. The soft classification approach assists in assessing the probability that ignitable liquid residue from a specific ASTM E1618 class, is present in a set of samples from a single fire scene, even in the presence of unspecified background contributions from pyrolysis products. The method is demonstrated with sample data sets and then tested on laboratory-scale burn data and large-scale field test burns. The overall performance achieved in laboratory and field test of the method is approximately 80% correct classification of fire debris samples.     

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.     

Preferential extraction of hydrocarbons from fire debris samples by solid phase microextraction

Headspace analysis by extraction/GC-MS is a common method of detecting volatile hydrocarbon accelerants in fire debris samples. Solid-phase microextraction was tested to determine if there is selective extraction of chemically distinct compounds. It was found that both the polydimethylsiloxane (PDMS) and Carboxen/PDMS solid phase microextraction fibers show preferential extraction of aliphatic or aromatic compounds from the headspace depending on fiber type and temperature. The Carboxen/PDMS fiber type showed particular (although not exclusive) selectivity for extraction of aromatic hydrocarbons. Other experimental considerations of SPME are noted.     

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.     

Detection and Classification of Ignitable Liquid Residues in the Presence of Matrix Interferences by Using Direct Analysis in Real Time Mass Spectrometry,

Conventional Gas Chromatography‐Mass Spectrometry (GC‐MS) methods for the analysis of ignitable liquids (ILs) are usually time‐consuming, and the data produced are difficult to interpret. A fast IL screening method using direct analysis in real time mass spectrometry (DART‐MS) is proposed in this study. GC‐MS, QuickStrip DART‐MS, and thermal desorption DART‐MS methods were used to analyze neat ILs and thermal desorption DART‐MS without extraction was used to analyze ILs on five substrates (e.g., carpet, wood, cloth, sand, and paper). Compared to GC‐MS, DART‐MS methods generated different spectral profiles for neat ILs with more peaks in the higher mass range and also provided better detection of less volatile compounds. ILs on substrates were successfully classified (98 ± 1%) using partial least squares discriminant analysis (PLS‐DA) models based on thermal desorption DART‐MS data. This study shows that DART‐MS has great potential for the high‐throughput screening of ILs on substrates.     

Preparation and characterization of micro-bore wall-coated open-tubular capillaries with low phase ratios for fast-gas chromatography–mass spectrometry: Application to ignitable liquids and fire debris

Fast Gas Chromatography (GC) allows for analysis times that are a fraction of those seen in traditional capillary GC. Key modifications in fast GC include using narrow, highly efficient columns that can resolve mixtures using a shorter column length. Hence, a typical fast GC column has an inner diameter of 100–180 μm. However, to maintain phase ratios that are consistent with typical GC columns, the film thickness of fast GC stationary phases are also low (e.g., 0.1–0.18 μm). Unfortunately, decreased film thickness leads to columns with very low sample capacity and asymmetric peaks for analytes that are not sufficiently dilute. This paper describes micro-bore (50 μm i.d.) capillary columns with thick films (1.25 μm), and low phase ratios (10). These columns have greater sample capacity yet also achieve minimum plate heights as low as 110 μm. Hence, separation efficiency is much higher than would be obtained using standard GC columns. The capillary columns were prepared in-house using a simple static-coating procedure and their plate counts were determined under isothermal conditions. The columns were then evaluated using temperature programming for fast GC–MS analysis of ignitable liquids and their residues on fire debris exemplars. Temperature ramps of up to 75 °C min^?1 could be used and separations of ignitable liquids such as gasoline, E85 fuel, and lighter fluid (a medium petroleum distillate) were complete within 3 min. Lastly, simulated fire debris consisting of ignitable liquids burned on carpeting were extracted using passive headspace absorption-elution and the residues successfully classified.     

Progress Toward the Determination of Correct Classification Rates in Fire Debris Analysis II: Utilizing Soft Independent Modeling of Class Analogy (SIMCA)

A multistep classification scheme was used to detect and classify ignitable liquid residues in fire debris into the classes defined by the ASTM E1618‐10 standard method. The total ion spectra (TIS) of the samples were classified by soft independent modeling of class analogy (SIMCA) with cross‐validation and tested on fire debris. For detection of ignitable liquid residue, the true‐positive rate was 94.2% for cross‐validation and 79.1% for fire debris, with false‐positive rates of 5.1% and 8.9%, respectively. Evaluation of SIMCA classifications for fire debris relative to a reviewer's examination led to an increase in the true‐positive rate to 95.1%; however, the false‐positive rate also increased to 15.0%. The correct classification rates for assigning ignitable liquid residues into ASTM E1618‐10 classes were generally in the range of 80–90%, with the exception of gasoline samples, which were incorrectly classified as aromatic solvents following evaporative weathering in fire debris.     

Evaluation of Internal Standards for the Analysis of Ignitable Liquids in Fire Debris

Abstract:  An evaluation of eight compounds for use as an internal standard in fire debris analysis was conducted. Tests were conducted on tetrachloroethylene, chlorobenzene, n-octylbenzene, 3-phenyltolune, and deuterated compounds toluene-d8, styrene-d8, naphthalene-d8, and diphenyl-d10 to measure the extraction efficiency of each compound in the presence of an interfering volatile compound (carbon disulfide). Other tests were conducted to evaluate whether or not the presence of an ignitable liquid or pyrolysis/combustion products from fire debris would interfere with the identification of these compounds when used as an internal standard. The results showed that while any of the eight compounds could be used as an internal standard in fire debris analysis, the more volatile compounds (toluene-d8, tetrachloroethylene, chlorobenzene, and styrene-d8) showed better extraction efficiencies at room temperature than when heated to 60°C. Each of the less volatile compounds (naphthalene-d8, diphenyl-d10, n-octylbenzene, and 3-phenyltolune) performed well during extraction at 60°C, while naphthalene-d8 showed better extraction efficiency in the presence of competing volatiles when extracted at room temperature.     

A simple microthermal desorption device

A new method for thermal desorption of small samples is presented. The method uses a solid phase microextraction (SPME) holder with the fiber removed. The sample-for example, an ink sample on paper-is simply placed inside the needle of the holder, where normally an SPME fiber is positioned. The thermal desorption is then performed on any kind of gas chromatograph in a manner similar to that for SPME analysis. The needle of the SPME holder penetrates the injector septum; the temperature of the thermal desorption is simply the temperature of the injector. No solvents or liquid nitrogen cooling are used. The paper sample is kept inside the holder needle during the analysis. After the analysis is completed, the sample is removed from the needle by pushing forward the steel wire inside the needle in the way normally used to perform sampling with the SPME fiber. The desorbed compounds were analyzed by gas chromatography with a flame ionization detector or by gas chromatography-mass spectrometry. The optimum temperature for desorption of ink samples on paper was 200 degrees C. The influence of the paper matrix is negligible at that temperature. Laboratories lacking the commercial device for thermal desorption can use this cheap device for the analysis of, for example, writing ink, printing ink, and inkjet ink samples on paper. Other types of samples can be investigated but the size of samples suitable for analysis is limited.     

Alternative fuels in fire debris analysis: biodiesel basics

Alternative fuels are becoming more prominent on the market today and, soon, fire debris analysts will start seeing them in liquid samples or in fire debris samples. Biodiesel fuel is one of the most common alternative fuels and is now readily available in many parts of the United States and around the world. This article introduces biodiesel to fire debris analysts. Biodiesel fuel is manufactured from vegetable oils and/or animal oils/fats. It is composed of fatty acid methyl esters (FAMEs) and is sold pure or as a blend with diesel fuel. When present in fire debris samples, it is recommended to extract the debris using passive headspace concentration on activated charcoal, possibly followed by a solvent extraction. The gas chromatographic analysis of the extract is first carried out with the same program as for regular ignitable liquid residues, and second with a program adapted to the analysis of FAMEs.