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https://doi.org/10.1007/s10337-021-04022-1
ORIGINAL
Received: 21 December 2020 / Revised: 19 February 2021 / Accepted: 23 February 2021 / Published online: 7 March 2021
© The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature 2021
Abstract
Investigation of an arson case presents several challenges to the forensic investigator. Identification of the ignitable liquid
residues in the fire debris is one of the crucial tasks that may help to determine the nature and cause of fire. Detection of the
ignitable liquids using different analytical methods has been practiced for a long period across the globe. Diesel is a petro-
leum product that shows stable burning than gasoline and it is frequently used as accelerant also. This study was conducted
to diagnose the efficiency of solvent as well as of the matrices for the detection of diesel residue. In this study, four different
matrices (cotton cloth, wood, glaze tile, and PVC) were selected to create simulated miniature version of arson with diesel as
an accelerant. After extinguishing the fire, diesel residues were extracted from the fire debris using hexane and diethylether
as extraction solvents under ultrasonication. Gas Chromatography coupled with mass spectrometry was used to identify
the major compounds from standard and burnt diesel. Diethylether extracted higher amount of diesel residues from the
burnt matrices than hexane. Tile and cotton proved to be the better matrices for the extraction in hexane solvent. However,
diethylether present advantageous results and significantly detected the diesel residues in tile, wood and cotton. Findings of
this study may help an investigator to select the suitable matrices and solvent for the extraction of diesel residues and may
efficaciously contribute in the forensic arson investigation.
Introduction affects the fire debris samples [2, 3]. Petroleum products
such as gasoline, diesel, and kerosene are commonly used
Arson is one of the most heinous offences against the man- by arsonist as an accelerant. Diesel is most common petro-
kind that causes serious harms to the property and the lives. leum product that is easily available in open market as well
Detection and analysis of the ignitable liquid (IL) traces as frequently used as an accelerant by an arsonist. Different
in fire debris is crucial task that provides the information hydrocarbons ranging from C8 to C23 are present in the die-
of evidential significance [1]. Investigation of an arson sel. Aromatic compounds such as alkyl-benzene have found
case presents several challenges to the forensic investiga- to most abundant in diesel while, naphthalene-based com-
tor. Extreme destructive nature of the fire destroys many pounds have reported to be less than that of previous ones
significant clues at scene of occurrence. In addition, deg- [4–6]. In the forensic context, while detecting the IL residue
radation due to weathering, as well as, extinguishers (e.g., (hereinafter called ILR), the role of extraction method, and
water, sand, and commercial fire extinguisher) also adversely the analytical technique becomes very critical and utmost
important. Extraction process enables the preconcentration
of the fire debris sample prior to the instrumental analysis.
* Ankit Srivastava Wide range of extraction methods namely solvent extraction,
ankit_forensic81@rediffmail.com headspace (HS) with solid-phase micro-extraction (SPME),
1 and activated carbon strips (ACS) has been reported as well
Dr. A.P.J. Abdul Kalam Institute of Forensic Science &
Criminology, Bundelkhand University, Jhansi, UP 284128, as research and analytical progress has also been reviewed
India [7]. Extraction process is followed by the instrumental
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414 V. K. Yadav et al.
analysis to detect the ILRs. Different analytical tools such as potentially recovered from the partially burnt remind, as the
gas chromatography (GC), isotope ratio mass spectroscopy absorbed petroleum in completely burnt material exhaust
(IRMS), capillary electrophoresis (CE), laser-induced break- during the whole burning process [17]. Hence, in the present
down spectroscopy (LIBS) [8], derivative ultra-violet (UV) study, the burning time has been kept low (approximately
spectroscopy [9], vibrational spectroscopy (infrared (IR) 30 s.) to simulate the partial burning phenomenon. A similar
spectroscopy and Raman spectroscopy) [10], and electronic timeframe had been used by Prather et al. in their study on
nose [11] have been reported for the detection of ILRs [12]. the effectiveness of evaporation of ignitable liquids from
GC has being applied for the detection of ILRs for a very different matrices [18]. Different household matrices such
long time [13]. Over the period, different variants of GC as Wood, Cotton Cloth, Tile, and Polyvinyl Chloride (PVC)
namely GC-flame ionization detector (GC-FID), GC-photo were simulated for arson using diesel as an accelerant. Influ-
ionization detection (GC-PID), GC–mass spectroscopy ence of different solvents on the extraction of the ILRs from
(GC–MS), and multi-dimensional GC have been reported the samples was also accessed. GC–MS characterization of
for the ILR analysis [14]. GC-FID has been a technique of the samples provides some significant findings that may be
choice for the arson analyst. Chromatogram recorded from helpful for the forensic purpose.
the fire debris sample may be compared with the chroma-
togram of known IL samples. Substrate may produce the
chromatogram that may completely or partially overlap with
the peaks of the accelerant and thus either IL may remain Experimental Section
unidentified or may be misinterpreted. Therefore, the inter-
pretation of the results requires an utmost care to obviate Materials
the misclassification. GC–MS analysis improves the speci-
ficity of the analysis then that of GC-FID. Total Ion Chro- Diesel, purchased from the local fuel station, was used as
matogram (TIC) offers the identification of the compound accelerant in this study. Wood (12 × 12 × 0.8 cm), Cotton
by interpreting the peak through its retention time (RT) and Cloth (12 × 12 × 0.1 cm), Tile (12 × 12 × 0.8 cm), and PVC
mass spectrum (m/z). The standard of American Society (12 × 12 × 0.3 cm) purchased from local market were used
for Testing and Materials (ASTM E1618-19) recommends as matrices. Hexane and diethylether of analytical grade
the use of GC–MS for the analysis of ILRs in fire debris purchased from Merck life science Pvt. Ltd. were used as
samples. In addition, ASTM presents a classification scheme solvents for the extraction.
that classifies the ILs into 8 categories. The interpretation of
the result is the challenge for the analyst and dependent of
the experience of the analyst [15]. Previously, Zhang et al.
[5] reported the detection of diesel residues in a bus arson Table 1 Experimental conditions
samples and presented the interference of internal decora- GC operational protocol
tive materials in the diesel samples. The authors emphasized
Injection temperature 280 °C
on the proper sampling and adoption of the proper GC–MS
Split ratio 25:1
method for the effective detection of the diesel. Aqel et al.
Carrier gas Helium
(2016) [16] reported the detection of gasoline and diesel in
Flow rate 0.7 ml min−1
different cloth samples using GC–MS. Persistence of the
Column DB-5 (30 m × 0.25 mm,
accelerants on cotton and polyesters were recorded less than 0.25 μm film thick-
that of wood and silk. In addition, Ji and co-authors [6] pro- ness)
nounced that the polyurethane wood causes significant inter- Initial oven temperature 75 °C (hold for 1 min)
ference in diesel identification, and therefore, advocate the Ramp rate 20 °C min−1
need of negative control diesel samples and proper database Final oven temperature 280 °C
of compounds that may be used for the effective interpreta- MS operational protocol
tion of the diesel presence.
In this paper, we present the detection of diesel form the Transfer line temperature 285 °C
simulated arson debris samples. In a typical arson scenario, MS ionization source temperature 230 °C
majorly two kinds of remainings are found, i.e., partially Mass quadrupole analyser temperature 150 °C
burnt and completely burnt. While, the accelerant can be m/z scan mode 50–550
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A Forensic Approach to Evaluate the Effect of Different Matrices and Extraction Solvents for… 415
Preparation and Extraction of Samples negative samples of all the matrices (matrices were burnt
without any accelerants) were prepared in both solvents,
5 ml of diesel was added to each piece of substrate and were i.e., hexane and diethylether. Thus, total 50 samples were
left undisturbed for 4 min and followed by the burring for analyzed by GC–MS in this approach.
30 s in a fume-hood. The identification of petroleum product
from an arson scene is only possible from the partially burnt
or semi-burnt materials. While, most of the time, no traces
GC–MS Analysis
of any petroleum products recovered from completely burnt
All the samples were analyzed by Agilent 7890B-5977A
remainings.
GC–MS. Experimental conditions are as summarized in
A beaker was placed inverted on the burning sample to
Table 1.
cease the oxygen supply thereby causing the extinguish-
ing of the fire. Burnt matrices were immediately placed in
a glass baker and 15 ml of extraction solvent was added.
Separate samples of each substrate were prepared for both
Results and Discussion
extraction solvents. This arrangement was ultra-sonicated
The present study has been carried out to identify the
for 10 min. Solvent was filtered and processed for GC–MS
extracted diesel residues from different burnt matrices. Real-
analysis. 5 samples of each substrate in both solvents were
life arson situation was simulated in miniature form to carry
prepared. In addition, as per the ASTM manual (ASTM E
out the experiment.
1386- 15) [19], standard samples of diesel (1% V/V) and
Fig. 2 Comparative efficiency
of extracted diesel residues
through hexane from different
matrices (Post-Burnt). HSD
standard diesel in hexane,
HDC diesel burnt with cot-
ton, extracted with Hexane,
HDW diesel burnt with wood,
extracted with hexane, HDT
diesel burnt with tile, extracted
with hexane, HDPVC diesel
burnt with PVC, extracted with
hexane
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416 V. K. Yadav et al.
Fig. 3 Total ion chromatogram of the post-burnt diesel residues extracted through hexane from different matrices: (a) tile, (b) wood, (c) cotton
and (d) PVC
Intra‑comparison of Samples Extracted by Hexane Figure 4 shows the TIC of the standard diesel sample in
diethylether. The samples extracted from tile and PVC,
In the TIC of standard diesel samples in hexane (Fig. 1), burnt with diesel showed the highest (33) and lowest
overall, 40 major organic compounds of 6 different classes (1) number of similar compounds, respectively, with the
were detected. Among these compounds, simple alkanes, standard among the four different matrices (Fig. 5). While,
branched alkanes and fatty acid methyl esters (FAME) are 22 compounds from wood and 12 compounds identified
the major contributors for diesel. The samples extracted from cotton samples. Figure 6 represents the TIC of the
from cotton and PVC, burnt with diesel showed the high- extracted samples from tile, wood, cotton and PVC by
est (32) and lowest (1) number of similar compounds, diethylether. The mass spectrometric data support the TIC
respectively, with the standard among the all four differ- obtained from all the samples (Table 4). Figure 7 shows
ent burnt matrices (Fig. 2). Figure 3 represents the TIC the negative samples extracted from burnt tile, wood, cot-
of the extracted samples from tile, wood, cotton and PVC ton and PVC burnt without diesel. The negative samples
by hexane. Table 2 shows the compounds common with lacking the significant compound peaks present in diesel.
standard diesel, found in the burnt extracts of matrices.
While, 5 compounds from wood and 3 compounds identi- Efficiency of Extraction
fied from tile samples. The number of m/z ratios of diesel
found in the standard and burnt samples also supports the As the obtained results of the residues extracted from four
results obtained from the TIC (Table 4). different matrices, diethylether proved to be the more effi-
cient solvent than hexane. Figure 8 clearly elaborates the
Intra‑comparison of Samples Extracted aforesaid statement as relatively significant number of com-
by Diethylether pounds were identified from the diesel residues extracted
from wood and tile by diethylether than extracted by hexane.
The GC–MS analysis of the standard diesel samples in While, diesel residues extracted by hexane from burnt cotton
diethylether showed similar results as obtained in hexane. gave highly significant similarity with the standard results
Similar to the samples in hexane, simple alkanes, branched and residues extracted by diethylether gave relatively lesser
alkanes and FAME are the major contributors (Table 3). number of similar compounds (12) but all the compounds
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A Forensic Approach to Evaluate the Effect of Different Matrices and Extraction Solvents for… 417
Table 2 List of the common compounds of diesel found in different substrates from post-burnt extracted samples by hexane
Compound class HSD HDT HDW HDC HDPVC
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418 V. K. Yadav et al.
Table 2 (continued)
Compound class HSD HDT HDW HDC HDPVC
identified in the results are target compounds for diesel potentially caused due to the physical structure of the matrix
which can be relevant for the identification. The variabil- and the affinity of the residual diesel (unburnt or partially
ity of the extracted compounds from different matrices is burnt) with the extraction solvents.
Table 3 List of the common compounds of diesel found in different substrates from post-burnt extracted samples by diethylether
Compound class DESD DEDT DEDW DEDC DEDPVC
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A Forensic Approach to Evaluate the Effect of Different Matrices and Extraction Solvents for… 419
Table 3 (continued)
Compound class DESD DEDT DEDW DEDC DEDPVC
Fatty acid methyl ester Pentadecanoic acid, Pentadecanoic acid, Pentadecanoic acid, Pentadecanoic acid, Pentadecanoic
14-methyl-, methyl 14-methyl-, methyl 14-methyl-, methyl 14-methyl-, methyl acid, 14-methyl-,
ester ester ester ester methyl ester
Hexadecanoic acid, Hexadecanoic acid, 8-Octadecenoic acid,
methyl ester 2-methyl-, methyl methyl ester
Hexadecanoic acid, ester 11-Octadecenoic acid,
2-methyl- Heptadecanoic acid, methyl ester, (Z)-
Heptadecanoic acid, 15-methyl-, methyl
15-methyl-, methyl ester
ester Heptadecanoic acid,
Heptadecanoic acid, 16-methyl-, methyl
16-methyl-, methyl ester
ester 8-Octadecenoic acid,
8-Octadecenoic acid, methyl ester
methyl ester cis-13-Octadecenoic
11-Octadecenoic acid, acid, methyl ester
methyl ester, (Z)- Nonadecanoic acid,
12-Octadecenoic acid, methyl ester
methyl ester
cis-13-Octadecenoic
acid, methyl ester
Nonadecanoic acid,
methyl ester
Aromatics 1,2,3,5-tetramethyl 1,2,3,5-tetramethyl 1,2,3,5-tetramethyl
Benzene Benzene Benzene
Alcohol Ethanol, 2-(octadecy- Ethanol, 2-(octadecy- Ethanol, 2-(octadecy-
loxy)- loxy)- loxy)-
Statistical analysis of all the samples showed good effi- residue from a simulated vehicle (Public Bus) arson scene.
ciency of data reproducibility. The number of compounds For this experiment, the group created a real-life scenario of
and the number of m/z ratio identified in the residues a public bus with all the interior and exterior features and put
extracted from different matrices showed very low the stand- diesel fuel inside it and burnt it. Post burnt diesel samples
ard deviation values ranges from 0.447214 to 1.81659, which were extracted using Hexane and anhydrous sodium sulfate
are significant for a good repetitive analysis. Table 5 depicts was spread to absorb the moisture. After 10 min, all the
the detailed standard deviation data for all the repeated sam- solutions were filtered and filtrates were volatilized to about
ple study. Few previous studies on the identification of burnt 1 mL. GC–MS and GC–HS–MS were used to identify the
diesel residues reported significant results for different sub- diesel residues and found satisfactory results but the com-
strates. Zhang et al. [5] performed the identification of diesel ponents of diesel substantially alter in different location due
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420 V. K. Yadav et al.
Fig. 5 Comparative efficiency
of extracted diesel residues
through diethylether from dif-
ferent matrices (Post-Burnt).
DESD standard diesel in diethy-
lether, DEDC diesel burnt with
cotton, extracted with diethyl-
ether, DEDW diesel burnt with
wood, extracted with diethyl-
ether, DEDT diesel burnt with
tile, extracted with diethylether,
HDPVC diesel burnt with PVC,
extracted with diethylether
Fig. 6 Total ion chromatogram of the post-burnt diesel residues extracted through diethylether from different matrices: (a) tile, (b) wood, (c) cot-
ton, and (d) PVC
to their discrete burning patterns. Alkylbenzene and alkanes by using gasoline and diesel. SPME method was used to
were the major contributors for the unburnt and semi-burnt extract the residual samples from the burnt matrices. The
diesel residues in the extracts. Polycyclic aromatic hydro- target compounds selected for the identification of diesel
carbons were the products of diesel combustion. This article ranges from tridecane to heptadecane of simple alkane class.
also reported the analysis of soot deposited on the window In addition, they kept the burnt sample up to 15 h after extin-
glass, which contains significant amount of PAH. Porous guishing. Majority of the target compounds for diesel were
seats absorb the diesel, while the identification of diesel was identified on wool and silk substrates up to 12 h post-extin-
interfered by the decomposition of the material composi- guish, in comparison to cotton and polyester surfaces. The
tion of the seat. Aqel et al. [16] selected wool, cotton, silk whole experiment concludes that diesel residues are more
and polyester as substrates to create simulated arson scene persistent on different substrates than gasoline.
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Table 4 Representation of mass values of standard diesel samples and burnt samples extracted by hexane
Mass values of standard diesel samples and burnt samples extracted by hexane
HSD HDT HDW HDC HDPVC
41, 43, 55, 57, 71, 74, 82,83, 85, 91, 41, 43, 55, 57, 71, 85, 97, 113, 155, 43,57,71,85, 113, 155, 159, 170, 198, 41, 43, 55, 57, 74, 97, 113, 127, 129, 41, 55, 97, 180, 207, 222, 264, 296
92, 97, 105, 106, 113, 119, 120, 170, 180, 207, 222, 264, 296 253 141, 143, 145, 155, 159, 160, 169,
127, 129, 141, 143, 145, 155, 159, 180, 183, 185, 193, 198, 199, 202,
160, 169, 170, 180, 183, 185, 193, 207, 211, 212, 221, 222, 225, 226,
198, 202, 207, 211, 212, 222, 225, 227, 240, 252, 253, 254, 255, 264,
226, 227, 240, 252, 253, 254, 264, 268, 270, 272, 280, 281, 296, 298,
268, 270, 272, 280, 281, 296, 305, 305, 306, 326, 327, 333, 355, 377,
306, 326, 327, 333, 355, 377, 385, 385, 387
387
Mass values of standard diesel samples and burnt samples extracted by diethylether
DESD DEDT DEDW DEDC DEDPVC
41, 43, 55, 57, 71, 74, 82,83, 85, 91, 41, 43, 55, 57, 71, 74, 85, 97, 113, 41, 43, 55, 71, 85, 97, 113, 127, 141, 43, 57, 71, 74, 85, 113, 127, 129, 43,74,129,143,185,227,207
A Forensic Approach to Evaluate the Effect of Different Matrices and Extraction Solvents for…
92, 97, 105, 106, 113, 119, 120, 127, 129, 141, 143, 145, 155, 159, 143, 145, 155, 159, 160, 169, 170, 141, 143, 145, 155, 159, 160, 169,
127, 129, 141, 143, 145, 155, 159, 160, 169, 170, 180, 183, 185, 193, 180, 183, 193, 198, 202, 207, 211, 170, 183, 185, 193, 198, 202, 207,
160, 169, 170, 180, 183, 185, 193, 198, 199, 207, 221, 211, 222, 225, 212, 222, 225, 227, 252, 253, 264, 211, 227, 253, 280, 296, 333
198, 202, 207, 211, 212, 222, 225, 227, 226, 240, 252, 253, 254, 255, 280, 296, 305, 326, 327, 333, 355,
226, 227, 240, 252, 253, 254, 264, 264, 268, 270, 272, 280, 281, 296, 377, 385
268, 270, 272, 280, 281, 296, 305, 298, 305, 306, 326, 327, 333, 377,
306, 326, 327, 333, 355, 377, 385, 355, 385, 387
387
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421
422 V. K. Yadav et al.
Fig. 7 Total ion chromatogram of the negative samples for different burnt matrices: (a) tile, (b) wood, (c) cotton, and (d) PVC
Fig. 8 Comparative efficiency of hexane and diethylether for the burnt with PVC, extracted with hexane, DESD standard diesel in
extraction of post-burnt diesel residue from different matrices. HSD diethylether, DEDC diesel burnt with cotton, extracted with diethy-
standard diesel in hexane, HDC diesel burnt with cotton, extracted lether, DEDW diesel burnt with wood, extracted with diethylether,
with hexane, HDW diesel burnt with wood, extracted with hexane, DEDT diesel burnt with tile, extracted with diethylether, HDPVC die-
HDT diesel burnt with tile, extracted with hexane, HDPVC diesel sel burnt with PVC, extracted with diethylether
Table 5 Standard deviation of HDC HDW HDT HDPVC DEDC DEDW DEDT DEDPVC
the quantitative data obtained
from repeated analysis of burnt Compound-based standard deviation of the repeated analysis
extracts
0.83666 0.447214 0.547723 0 0.894427 0.894427 0.83666 1.81659
m/z value-based standard deviation of the repeated analysis
0.547723 0.83666 0.894427 0.447214 0.83666 0.83666 1.095445 0.894427
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A Forensic Approach to Evaluate the Effect of Different Matrices and Extraction Solvents for… 423
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