The Use of Montomorillonte as an absorbent for ignitable liquids from porcine skin Final
1. 0
The Use of Montmorillonite as an absorbent for
ignitable liquids from porcine skin
By Matthew Perryman
Submitted in partial fulfilment of the requirements for
the degree of Bachelor of Science of Anglia Ruskin
University.
June 2011
Faculty of Science and Technology
Anglia Ruskin University
Cambridge
2. I
Acknowledgements
I would humbly like to thank Dr. Sarah Hall and Garry White, Ph.D student and part-
time lecturer, for helping me get through my work and guiding me in the right
direction, for helping me overcome difficulties, whether the nature of them was
classed as scientific or other.
I would also like to thank the other lecturers, who teach at Anglia Ruskin
University, Cambridge Campus, for imparting their expert knowledge of their
respective subjects to myself, also a special mention of gratitude to Joanne Hooson
and Kevin Bright, the technicians of the Forensic Science department, without them I
would have been stuck long ago.
Finally I would like to impart my warmest thanks my house mates and class
mates; Gemma Louise Green, Samuel Charles Kennedy, and Dawn Marie Walker for
putting up with me during this period, by continuously proof-reading my work and
aiding me with constructive criticism, allowing me to complete this piece of work
before you.
3. II
Table of Contents
ABSTRACT .......................................................................................................................................III
LIST OF TABLES.................................................................................................................................1
LIST OF FIGURES AND IMAGES .........................................................................................................2
LIST OF EQUATIONS .........................................................................................................................3
LIST OF GRAPHS ...............................................................................................................................4
LIST OF ABBREVIATIONS ..................................................................................................................5
1 INTRODUCTION .......................................................................................................................6
1.1 THE CHEMISTRY OF FIRE..............................................................................................................6
1.2 FIRE SCENARIOS ......................................................................................................................13
1.3 WHAT ARE ACCELERANTS AND IGNITABLE LIQUIDS? .......................................................................15
1.4 THE CHEMISTRY OF ORGANICS ...................................................................................................17
1.5 THE INVESTIGATIVE PROCEDURE OF ARSON ..................................................................................25
1.6 ADSORPTION AND ADSORBENTS .................................................................................................29
1.7 MONTMORILLONITE.................................................................................................................30
1.8 METHODS AND CHROMATOGRAPHY............................................................................................31
1.9 DATA INTERPRETATION.............................................................................................................34
2. AIM........................................................................................................................................38
3. MATERIALS ............................................................................................................................39
4. RESULTS/DISCUSSION............................................................................................................42
5. CONCLUSION .........................................................................................................................62
6. REFERENCES...........................................................................................................................64
7. APPENDIX 1 ...........................................................................................................................73
7.1 ASTM METHODS ...........................................................................................................................73
E1386-10......................................................................................................................................73
E1618-06......................................................................................................................................74
8. APPENDIX 2................................................................................................................................85
8.1 GC-MS CHROMATOGRAMS AND SIMILARITY SEARCHES .........................................................................86
4. III
Abstract
Arson is a serious crime, that affects society through three main factors cost,
property damage and loss of life. Because of this this is why fire investigators and
forensic scientist strive to have the most up to date methods and the most sensitive
and reliable equipment.
Classification of ignitable liquids has been updated to include many new
categories due to developments in the petroleum industry. Techniques such as
steam or vacuum distillation and gas chromatography (GC) with flame ionization
detection that may have been considered acceptable— even a benchmark—40
years ago, are nowadays generally disfavoured. (Pert, Baron, Birkett 2006) even
with advances in these analytical technique, there is still not one standard method
used for recovering the liquid residues of ignitable liquids from fire scenes, and
more importantly any suspects.
5. 1
List of Tables
1.1 Alkane Prefixes
1.2 Steps of Pattern Recognition
3.1 Standards run for comparison
3.2 Newman Method for GC/FID and GC/MS
4.1 ASTM Classification of ignitable liquids
4.2 Previous ASTM Classification of ignitable liquids
4.3 GC/MS Results
4.4 Averaged GC/MS Results
4.5 Figures for Standard Deviation of 1 hour evaporation
4.6 Figures for Standard Deviation of 2 hour evaporation
4.7 Figures for Standard Deviation of 3 hour evaporation
6. 2
List of Figures and Images
1.1 A Fire Tetrahedron
1.2 Pyrolysis Diagram
1.3 Cyclohexatriene and Benzene
1.4 Naphthalene
1.5 Structural Formulae of C3 and C4 – Alkylbenzenes
1.6 Spiking n-Alkanes
1.7 The Three Musketeers Group
1.8 The Castle Group
1.9 The Gang of Four Group
1.10 The Twin Towers Group
4.1 BBQ lighter fluid 1:500µl in Pentane
4.2 BBQ lighter fluid 1 hour evaporation
4.3 BBQ lighter fluid 2 hour evaporation
4.4 BBQ lighter fluid 3 hour evaporation
4.5 Pentadecane library search
4.6 2nd Repeat of 1 hour evaporation, 5th Peak
4.7 Dodecane Chromatogram and Mass Spectrum
4.8 2nd Repeat of 1 hour evaporation, 2nd Peak
4.9 1st Repeat of 2 hour evaporation, 2nd Peak
4.10 2nd Repeat of 2 hour evaporation, 2nd Peak
7. 3
List of Equations
1. The Complete Oxidation of Methane
2. The Oxidation of Methane in Air
3. Standard Deviation of 1 hour evaporation
4. Standard Deviation of 2 hour evaporation
5. Standard Deviation of 3 hour evaporation
8. 4
List of Graphs
1 Averaged Results of all repeats
2 Averaged Results of 1 hour evaporation
3 Averaged Results of 2 hour evaporation
4 Averaged Results of 3 hour evaporation
9. 5
List of Abbreviations
amu = Atomic Mass Units
ASTM = American Society for Testing and Materials
ENFSI = European Network of Forensic Science Institutes
FID = Flame Ionisation Detector
GC = Gas Chromatograph/Gas Chromatography
IUPAC = International Union of Pure and Applied Chemistry
ILR = Ignitable liquid residue
M/Z = Mass to Charge Ratio
MS = Mass Spectroscopy
NFPA = National Fire Protection Association
PPE = Personal Protection Equipment
PSI = Pounds Per Square Inch
SOCO = Scene of Crime Officer
TIC =Total Ion Chromatogram
MPD = Medium Petroleum Distillate
10. 6
1 Introduction
1.1 The Chemistry of Fire
Dehaan (2007), has stated that fire, which is commonly known as combustion is an
exothermic reaction, the energy released from the reaction normally comes in the
form of heat and light energy. As well as being exothermic the reaction is self-
sustaining and self-propagating, i.e. the reaction renews itself and continues
without outside assistance, for it to be self-sustaining the reaction needs specific
reagents outlined in a model known as the ‘Fire Triangle’.
The fire triangle is a simple model for understanding what ingredients are
needed for a fire to propagate.
As stated in the triangle the main ingredients needed are Heat, Oxygen (or
other oxidiser) and Fuel if any of these are removed the fire will become
extinguished. A more advanced model is the fire tetrahedron, not only does it show
the main ingredients it also shows that fires have to have uninhibited chain
reactions to continue burning without human intervention, hence the fire will
continue to self-propagate if the reagents are present.
11. 7
Figure 1.1: a Fire Tetrahedron, a more advanced version of the fire triangle, accounting for self-
propagating chain reactions1
The NFPA (2004 p.11), describe a fuel as being:
“A material that will maintain combustion under specified environmental
conditions”
Similarly but in more of a layman’s term Drysdale (2004) states fuel as being:
“A free term to describe something that is burning.”
Fuel, like any other material on the planet can be classified into three states, solid,
liquid and gas. Solid will melt into a liquid, to which then liquid will vaporise into a
gas.
A state is classed, if the characteristics of the material in that class are under 18-
21oC (65-70oF) and have a pressure of 14.7 pounds per square inch (PSI) (Redsicker
and O’Connor, 1986).
Gases are classed as having a rapid and random movement of atoms with
no definite shape or volume. When a gaseous fuel diffuses in a container it will
1
Redsicker, O’Conner, 1986, p56
12. 8
eventually reach a flammable (explosive) range, this is a range of saturation where
ignition can happen with the right amount of thermal energy. This range varies
from gas to gas but with natural gas (methane) the range is 5-15%.
The combustibility of solids is dependent on the size and the configuration
of the mass of the solid. I.e. a finely divided powder will differ in combustibility to a
solid block of wood normally due to a larger surface area. The larger the mass, the
greater the loss of energy through conduction.
Liquids have a definite volume. When dealing with liquids the term boiling
point appears in a lot of literature. Colloquially Boiling point is used for when a
liquid boils and vaporises into a gas but a more scientific definition is; the
temperature at which a continuous stream of vapour bubbles are produced from
the liquid and the vapour pressure of these bubbles are normal in relation to
atmospheric pressure (14.7 PSI).
Two other terms that appear continuously in the literature related to Fire
investigation is Fire point and Flash point, sometimes these two terms are confused
with each other.
Flash Point is the temperature is when a liquid will give off enough vapour
to form an ignitable liquid (a liquid with an explosive range), for example the flash
point of petrol is 10oC (50oF) while kerosene is 38oC (100oF).
Fire point is the temperature that a liquid will produce vapours that will
sustain combustion, because the main element is the sustainability of combustion,
fire point temperatures are several degrees higher than the flash points of the same
fuel. Petrol has a fire point of 257oC (495oF) while kerosene has a fire point of 43oC
(110oF).
13. 9
When a fuel is heated, as the substance increases in temperature it may
begin to change state, so solid to liquid or gas, and liquid to gas, during this process
the fuel may undergo thermal degradation without reacting with an oxidant, this is
called Pyrolysis. Stauffer (2001) and Drysdale (2004) both state that it is necessary
for the combustion. Pyrolysis will produce low molecular weight molecules that can
volatise from the surface and enter the flame that occurs with combustion.
Moldoveanu (1964) states that:
‘Pyrolysis is not a phase change, but a chemical process, or more specifically; a
thermal degradation process as it occurs under heat and degrades larger molecules
into smaller ones.’
When vapour starts to form from the fuel as it heated, if there is a
sufficient amount of an oxidising reagent and a significant ignition source a flame
will occur.
According to Koussaifes (2004) oxidation is:
“A process where oxygen combines with other elements to generate CO, CO2, H2O,
and other stable molecules. Oxidation is usually an exothermic reaction.”
Oxidations most basic meaning is the loss of electrons from one reactant to
another. (Dehaan, 2007) as mention previously for ignition of a flame or fire, the
presence of heat, fuel and an oxidising agent is required.
When looking at oxidation reactions, the complete oxidation of methane is one of
the simplest.
CH4 + 2O2 CO2 +2H2O
Equation 1: The complete oxidation of Methane
14. 10
This reaction is one involving a ratio of fuel to oxidant that is theoretically correct
for the complete oxidation to occur, this ratio is also known as the Stoichiometric
mixture.
Most combustion processes though do not occur in oxygen rich
environments but rather is more common to occur is air, which is approximately
21% Oxygen and 79% Nitrogen, so if the oxidation of methane occurs in air the
equation can be rewritten as:
CH4 + 2(O2 + N2) CO2 + 2H2O +2.N2
Fuel + (Oxidant + Diluent) Combustion Products + Diluent
Equation 2: The oxidation of Methane in Air
Here the diluent plays no part in the chemical process but will participate in the
physical process which aids in the dissipation in some of the thermal energy
produced from combustion.
Incomplete oxidation can be very common in combustion reactions, this is where
the oxygen supply has been restricted or lowered and the availability of carbon has
increased, so rather than carbon dioxide being produced carbon monoxide (CO) is
produced, carbon monoxide is one of the most common causes of death in house
fires, carbon monoxide inhibits haemoglobins ability to transport oxygen around
the body. Also Carbon monoxide itself can be a fuel for the pre-existing flame or
fire, it has a fire point of 609oC (1128oF).
When looking at any oxidation reaction, it is clear to see that water vapour
occurs as a combustion product, this is primarily because hydrogen is found in
almost all fuels, even complex mixtures so the burning of any common fuel will
result in water vapour in large quantities being formed.
15. 11
Figure 1.2: Pyrolysis diagram, incorporating the changes of states and the reactions associated
with them2
In the majority of all fires, the oxidising agent is Oxygen, present in the air
and earth’s atmosphere at 21%, other oxidisers normally come in a chemical form;
Ammonium Nitrate (NH4NO3), Potassium Nitrate (KNO3) and Hydrogen Peroxide
(H2O2) as examples. In an oxygen rich environment, ignition and combustion can
occur with more ease.
The ability of a flame to self-propagate allows a flowing fuel air system to
support a stationary flame.
Stationary flames are of two general types:
1. Diffusion flames, where both neat fuel and all the air required for
combustion ‘mx’ across the boundary where combustion occurs. These
flames may be laminar or turbulent according to the rates of flow and
mixing. Practical examples include Bunsen Burners and candles. These
flames therefore can range in height from centimetres to meters.
2
Drysdale, 1999 cited in Dehaan, 2007
Gas
Solid
LiquidPyrolysis
1
.
2
.
3
.4
.
5
. 6
.
1. Deposition
2. Sublimination
3. Condensation
4. Boiling
5. Melting
6. Freezing
16. 12
2. Premixed flames, where the fuel and a proportion of the stoichiometric air
requirement are mixed (usually within their flammability limits) before
combustion takes place. This is known as primary aeration, secondary air is
induced into the flame to complete the combustion.
The Physical process of diffusion and turbulence are of predominate importance in
determining the stability of a flame, also its shape and luminosity.
According to Tedder and Nechvatal (1975) there is an established
knowledge that that under steady burning conditions the fuel and oxygen do not
actually come into contact with each other but are separated by a boundary where
the concentration of each is zero. Reaction occurs on both sides of this high-
temperature boundary and the general mechanism for hydrocarbon fuels appears
to be one of carbon formation (via a pyrolysis process, see fig. 1.2) on the fuel side
and the formation of reactive radicals on the oxidant side.
Premixed flames are characterized by their burning velocity or rate of propagation
of the flame front into the unburnt premixed fuel-air mixture. This velocity depends
primarily on the inlet composition, temperature and pressure of the mixture .
A detailed discussion of the structure of flames is given by Frinstrom and
Westenbeg (1965)
17. 13
1.2Fire Scenarios
When a fire has occurred, there are normally three standard scenarios
associated with its beginning. Firstly, the fire may have started due to natural
causes, the temperature of the ambient environment may have exceeded the
ignition point of certain materials located at the scene of the fire, these materials
vary from scene to scene, i.e. a household environment would have many materials
with varying ignition points, while say a bale of hay in a field would only have one
ignition point. This ignition then in turn causes a flame which can escalate into a
fully-fledged fire in a matter of minutes. Secondly there may have been an electrical
fault (this occurrence is more common in household environments) which causes a
spark, if this spark comes into contact with an ignitable liquid that is at its minimum
flammability limit, there may be enough residual heat in the spark to ignite the
liquid and cause a flame, although this scenario is commonly used if the
investigators cannot identify the real cause of a fire.
The final cause of fire occurs with human assistance, this means a fire is set
deliberately using flammable materials.
The term Arson is commonly used to describe a crime that involves the intentional
burning of property. It originates from the Anglo-French word meaning ‘the act of
burning’. The common law definition of arson was the wilful and malicious burning
of a dwelling, over the years, state statues and federal law have replaced the
common law definition Most of today’s arson laws involve the intentional burning
of property, not only dwellings (Hine 2004). According to the UK Criminal Damage
Act 1971,
18. 14
‘an offence committed under this section by destroying or damaging a property by
fire shall be charged as arson’.
According to the National Fire Protection Association (NFPA) in 2007 there was an
estimated 485,500 structure fires and 26,500 of these fires were set intentionally.
This being a respective decrease of 6.7% and 13.1% increase on 2000.
While according to the Department of Communities and Local Government (DCLG)
formerly the Office of the Deputy Prime Minister (ODPM), in 2007 804,000 fires and
false alarms were attended to in the UK, a 9% decrease from 2000. While in the
year ending 30th September the year of intentional fires (Arson) fell by 17% to
67,900 incidents.
19. 15
1.3 What are Accelerants and Ignitable Liquids?
When Arson is committed the fire is normally advanced with a substance that is
flammable, most of these substances are liquid and tend to be brought to the
scene.
These fluids can be defined as an ‘ignitable liquid’ or an ‘accelerant’ firstly the
definition between ignitable liquid and accelerant is very different; even though
chemically they may be identical their roles in a fire are extremely different.
(Stauffer, Dolan, Newman 2008)
Firstly an accelerant is a substance, normally a liquid hydrocarbon which is
used to increase the rate of combustion for materials that do not readily burn.
While an Ignitable liquid is a liquid that will readily ignite when exposed to an
ignition source. (Almirall & Furton, 2004)
A more technical definition of an ignitable liquid is a liquid with a
flashpoint less than 93.3oC. Ignitable liquids are common in many solvents and
products, a few examples being; polishes, insecticides, cleaning solvents, paint
thinners, engine fuels etc. (Newman 1967)
The most commonly used liquid accelerants include gasoline (petroleum),
lighter fluid, kerosene, and turpentine. (Farwell 1997)
Although it is possible to set large, very destructive structure fires without
the use of flammable liquids, by far the most commonly detected arson means is
the pouring or the spilling of a flammable liquid. (Desty, D.H., & Goldup, A., &
Geach, C. J., 1958) The Identification of an ignitable liquid in a scene is not typically
sufficient, in itself, for determining that a fire was incendiary. Conversely the lack of
identification of an ignitable liquid does not preclude that the fire was not
20. 16
incendiary or that an accelerant was not used in its perpetuation. To reiterate, if,
say for example Kerosene is used in a camping light or in a home heating system it
is classed as an ignitable liquid, but if it is intentionally spread through a structure,
vehicle or onto a person and ignited it becomes an accelerant.
21. 17
1.4 The Chemistry of Organics
Organic Chemistry historically has been used to describe the chemistry of
compounds derived from life forms, until German Professor Friedrich Wöhler
synthesised Urea in 1828, it was though that all organic compounds had to have
originated from a living organism, thus the term organic. (McMurry, 1988)
Most accelerants are alkane based, many alkanes occur naturally and
natural gases and petroleum deposits are the major sources.
In the case of Medium Petroleum Distillates, the main compounds include as well as
alkanes; cycloalkanes, some alkylbenzenes, and some naphthalene’s.
An aromatic compound, can normally be classified as a compound with an
unusually large resonance energy, this is defined as a compound with delocalised
electrons, and these compounds according to Bruice (2004) are:
‘more stable than if all the electrons were localised. The extra stability a compound
gains from having delocalised electrons is called delocalisation energy or resonance
energy.’
So in essence a compound that is stabilised by delocalised electrons has resonance.
One way to understand resonance is to look at benzene and a hypothetical
compound called cyclohexatriene, both have 3 pairs of delocalised π electrons.
Figure 1.3: Cyclohexatriene and Benzene
22. 18
It is known that the ΔHO for the hydrogenation of cyclohexane, a compound with
one localised double bond is -28.6 kcal/mol. So with the hydrogenation of
cyclohexatriene should have a ΔHO three times as much: -85.8kcal/mol.
When the ΔHO for the hydrogenation of benzene is determined it was found to be -
49.8 kcal/mol, obviously much less than what was calculated. This is because the
hydrogenation of benzene and cyclohexatriene both from cyclohexane, the
difference in the ΔHO can be accounted for only there difference in energies.
Because benzene and cyclohexatriene have different energies they must therefore
be different compounds. Benzene is 36kcal/mol more stable than cyclohexatriene.
So since the ability to delocalise electrons increases the stability of a molecule, it
has been concluded by Bruice (2004) that:
“A resonance hybrid is more stable than the predicted stability of any of its
resonance contributors”
So now that we have an understanding of resonance energy we can have a look at
the structural features that aromatic compounds have in common:
1. It must have an uninterrupted cyclic cloud of π electrons.
2. The π cloud must contain an odd number of pairs of π electrons.
So for a compound to be classed as aromatic it has to have resonance and follow
these two structural criteria.
When looking at aromaticity of a molecule it must obey what is known as the
Hückel Rule. This rule states that the ring system must have 4n + 2π electrons, to
obey this rule the molecule must be cyclic and planar (Patrick, 2000).
23. 19
Naphthalene’s are polycyclic compounds made up of two benzene like
rings fused together.
Figure 1.4: Naphthalene
All Polycyclic compounds are aromatic hydrocarbons that can be represented by a
number of different resonance forms.
Alkyl groups are formed is a hydrogen atom is removed from an alkane,
the groups are not stable compounds they are merely parts of larger compounds
Finally Cycloalkanes, chemists in the late 1800’s knew that cyclic molecules
existed, but the limitations of ring sizes were unclear. Numerous compounds
containing five and six membered rings were known, but smaller and larger ring
sixes had not been prepared.
A theoretical interpretation of this observation was proposed in 1885 by Adolf von
Baeyer. He suggested that since carbon prefers to have tetrahedral geometry with
bond angles of approximately 109o, ring sizes other than 5 or 6 may be too strained
to exist.
Baeyer based his hypothesis on the simple geometric notion that a three
membered ring should be an equilateral triangle with bond angles of 60o, a four
membered ring would be square with bond angles of 90o and a five membered ring
would be a pentagon with bond angles of 108o etc.
According to Baeyer’s analysis, cyclopropane would have a large amount of
angle strain due to the 49o difference between its bonds and the desired
24. 20
tetrahedral of 109o. So on this basis cyclopentane should be strain free while
everything above C7 would be too strained to exist.
To measure the amount of strain in a compounds, the measurement of the total
energy of the compounds is subtracted from the energy of a strain free reference
compounds. The difference between the two values should represent the amount
of energy in the molecule due to strain.
Baeyer’s theory was wrong for the simple reason that he assumed rings were flat
while in reality they adopt a puckered three dimensional shape.
Alkanes are simple hydrocarbons that can be used for fuels, cooking etc.
Alkanes are naturally occur in crude oil and are a major component of many fuels
and solvents derived from petroleum, petroleum has to be refined into different
fractions before it can be used as it a complex mixture of hydrocarbon’s.
Crude oil is an extremely complex mixture of hydrocarbons, the mixture of
hydrocarbons located in crude oil will vary from geographical location to location.
The three main series of hydrocarbons are present in all crude oil mixes, Arenes,
Cycloalkanes and Alkanes. Arenes are basically hydrocarbons which contain one or
more benzene rings. At a given boiling point, the densities of the hydrocarbons
present decrease in the order of arenes to cycloalkanes to alkanes. This provides a
method for comparing the composition of different oils. (Ratcliff, et al. 2000,
McMurray 2000)
Alkanes are one of the simplest organic compounds, their general formula
is displayed as CnH2n+2, so for example butane which has a formula of C4 H10 (C3
H2x4+2).
25. 21
Ratcliff et al (2000) describe alkanes as being non-polar, and saturated
hydrocarbons due to all the carbon to carbon bonds being single in nature. They are
mainly characterised by C-H and C-C bonds.
It should be noted that the nomenclature of Alkanes follow a set pattern, with the
exception of the first four (methane, ethane, propane and butane), this pattern is a
numerical prefix and the termination of –ane, the numerical prefixes originate from
Greek and Latin roots.
26. 22
Number Prefix Number Prefix
1 Mono- 21 Eicosa-
2 Di- 22 Docosa-
3 Tri- 23 Tricosa-
4 Tetra- 24 Tetracosa-
5 Penta- 25 Pentacosa-
6 Hexa- 26 Hexacosa-
7 Hepta- 27 Heptacosa-
8 Octa- 28 Octacosa-
9 Nona- 29 Nonacosa-
10 Deca- 30 Triaconta-
11 Undeca 31 Hentriconta-
12 Dodeca- 32 Dotriaconta-
13 Trideca- 33 Tritriaconta-
14 Tetradec- 40 Tetraconta-
15 Pentadeca- 50 Pentaconta-
16 Hexadeca- 60 Hexaconta-
17 Heptadeca- 70 Heptaconta-
18 Octadeca 80 Octaconta-
19 Nonadeca 90 Nonaconta-
20 Icosa- 100 Hecta-
Table 1.1: Numerical prefixes used to name the number of carbon atoms in the main Aliphatic
chain
27. 23
All Alkanes with four or more carbon atoms in them (Butane and higher) can also
exhibit structural isomerism. i.e. there are two or more structural formulae for the
same molecular formula. As well as being straight chain hydrocarbons, some
alkanes can be known as cyclic compounds of cycloalkanes. This means that like in
straight chained molecules there are only Carbon and Hydrogen atoms, joined with
single bonds between each atom but the atoms join into a ring structure.
Cycloalkanes no longer follow the general formula of CnH2n+2, to form the ring they
lose two Hydrogen atoms, therefore changing the formula to CnH2n.
The term paraffin, is deemed obsolete by the International Union for Pure and
Applied Chemistry (IUPAC), but it is still commonly used as the synonym for alkanes
in the petroleum industry.–
Petroleum classes of accelerants are divided into boiling point ranges: most
fall in the C5-C20 range: lighter product (C4-C9) , medium (C8-C13) and heavy products
(C9-C20+). The boiling points increase with molecular weight. The more branches the
lower boiling point e.g.: Octane (125.7oC) and isooctane 2,2,4-trimethylpentane
(99.3 oC). Due to Van Der Waal forces. Petroleum classes are being described here
because they will be the focus of the experimental methodology mentioned later in
the document. This applies for most straight chained alkanes as well.
Figure 1.5: Structural formulae of 1, 3, 5 Trimethylbenzene, 1, 2, 4 Trimethylbenzene, 1, 2, 3
Trimethylbenzene and 1, 2, 3, 5 Trimethylbenzene
28. 24
Alkanes are virtually insoluble in water, when a molecular substance
dissolves in water, the intermolecular forces need to be broken in the case of
alkanes, those forces are Van Der Waal, with this the intermolecular forces of the
water need to be broken so the molecular substance can fit between the
molecules, the forces within the water are hydrogen bonds.
Breaking these bonds requires energy, the amount of energy to break Van der
Waal’s in alkanes normally is pretty negligible but a lot more energy is required to
break hydrogen bonds. So therefore as the energy released from the destruction of
Van der Waal’s is not enough to displace the hydrogen bonds of water this makes
Alkanes insoluble in water.
But if the alkane is dissolved in an organic solvent the main attraction between the
solvent molecules are most likely to be Van der Waals, either dispersions – or
dipole-dipole attractions, therefore the Van der Waals are broken and replaced by
new Van Der Waals forces, thus making Alkanes soluble in Organic solvents.
29. 25
1.5 The Investigative Procedure of Arson
Over the years, the art of fire investigation has evolved further and further into
a science based undertaking. This is due to the increased research that has been
conducted in the areas of ignition, fire growth and material performance, as well as
many other fields. This research is being conducted worldwide by a variety of
forensic scientists and fire investigators.
Because of this evolution no longer can a fire investigator, of any sort, base
his or her opinion on unsupported beliefs and mere experience. (Hine 2004) If a fire
investigator chooses to ignore this belief, then not only will the cases that they
work on be thrown into disrepute, due to the evolution of evidence needed in
court, but also their reputation as well. Their opinion, backed with scientific
evidence must be sound and stand the challenge of reasonable examination from
the prosecution or defence if in court or the council of their peers for other
matters.
The NFPA defines the scientific method as:
‘…the systematic pursuit of the knowledge involving the recognition and formulation
of a problem, the collection of data through observation and experiment, and the
formulation of testing and hypothesis.’
The evolution of fire investigation has proliferated into the area of
Forensics, now Forensic analysis, used to aid and assist fire investigators is
becoming more and more common, just as the basis of science in fire investigation
is becoming as so. Normally this analysis will typically involve analytical methods of
fire debris, but sometimes can range to the disciplines of tool-mark identification,
fingerprint analysis, trace evidence recovery, DNA analysis, occasionally Pathology
30. 26
and more commonly engineering. A dialogue between the fire investigator and the
lab or the persons involved is paramount to the successful evaluation and analysis
of evidence (Hine 2004).
In any investigation to reduction and elimination of contamination is the
focal priority, in the case of fire investigation this priority becomes an inevitability.
The potential for this contamination can occur through the use of tools, other
pieces of evidence, equipment, evidence containers, clothing and footwear.
Therefore normally all items used for the collection of evidence at a fire scene are
thoroughly decontaminated before each use. In the case of clothing, fire
investigators and anyone who is there to collect evidence such as SOCO’s, may
wear disposable PPE such as full body Tyvek™ suits. Fire fighters, now know that if
they have been called to quench a fire that has been turned into a crime scene, that
they must relinquish their boots for trace evidence recovery and in some cases
other parts of their PPE.
Also present may be standard background contamination may be present from
items found at the scene, for example according to Hine (2004) Medium petroleum
distillates are often used as a carrier for insecticides, flooring adhesives contain
solvents and various commercial cleaning supplies are petroleum based.
Comparison samples are defined as materials that are not suspected to contain any
contamination and accurately represent the pre-fire condition of the material to be
tested. The comparison sample is typically collected as close to the original sample
as practical, but ideally in an unburned area and not exposed to water. If this is not
possible then a sample should be taken in an area where the presence of an
ignitable liquid is not suspected.
31. 27
In cases of Arson the suspected perpetrator will normally take an accelerant
with them to the scene of the crime (Bertsch, Holzer, Sellers, 1993, Stauffer, Dolan,
Newman, 2007). This is primarily done because of the risk that there may be less
effective accelerants present at the scene or no kinds of ignitable liquids present at
all.
It is also uncommon for the suspect to initiate a fire by igniting a container
of accelerant or ignitable liquid, or to open the said container and ignite the
internal contents. This minimises the chance of the spreading the fire due to the
lack of dispersion of the accelerant. More commonly the suspected perpetrator
would distribute the accelerant around the vicinity, so in a building they would
splash items such as furniture or make trails to ensure room to room transfer of the
fire, finally also by pooling the accelerant to make a larger concentration of fire.
In this act of spreading the suspect may unintentionally transfer the
accelerant to their hands, wrists and arms. To stop this transfer the suspected
perpetrator may have planned ahead and donned protective apparel such as
gloves. This transfer may occur when the suspect is removing the apparel or
through direct absorption through the material.
Redsicker and O’Connor (1986) also identify that Liquid Hydrocarbon fuels can be
absorbed into the skin after even brief exposure. The warmth of the living tissue
can cause rapid desorption of the volatiles in the fuel. They also state that over the
years many methods to extract these trace volatile from the skin have been
incorporated ranging from canine detection to swabbing with wet solvent gauzes,
but both were unsuccessful therefore if the suspect is later arrested by the
authorities and questioned in connection with the Arson, the authorities will need
32. 28
evidence proving or disproving his or her presence and culpability to the offence.
The suspect may or may not be the owner of the damaged property or items
involved, police and authorities normally arrest suspects soon after the incident on
the basis of the suspect’s odour, most accelerants being pungent are easy do detect
with the olfactory sense. It is then very difficult for them to actually prove that
there is accelerant on said suspects just from a in situ physical examination because
of this it can then be extremely difficult to charge someone without justifiable
evidence.
There is no standard method for the recovery of suspected accelerant
residue from accused suspects though there has been so research into the area,
which will be mentioned in the discussion later. The residue also may vary in
accumulative volume due to evaporation, suspects may not be brought in by police
officers for many days after the crime has been committed, meaning that the test
itself has to be quick, reproducible, cost effective, cause no discomfort for the
suspect and be able to retrieve potentially trace samples of residue due to
evaporation of the flammable substance.
The most common hydrocarbon adsorbent used in chemical spill or other ecological
disasters is a naturally occurring clay called Montmorillonite.
33. 29
1.6Adsorption and Adsorbents
Adsorption is the process through which a chemical substance accumulates at the
common boundary of two contiguous phases. If the reaction produces enrichment
of the substance in an interfacial layer, the process is termed positive adsorption. If
instead a depletion of the substance is produced, the process is termed negative
adsorption. If one of the contiguous phases involved is solid and the other fluid, the
solid phase is termed the adsorbent and the matter which accumulates at its
surface is an adsorbate. A chemical species in the fluid phase that potentially can be
adsorbed is termed an adsorptive. (Sposito, 2003)
On the matter of adsorption Chavez, Pablo & Garcia (2009) state:
‘Adsorption has been established as an effective and economical technology to
concentrate and remove contaminants from aqueous phases and soils. In the
process, contaminants are separated from the aqueous phase and immobilized in
the adsorbent from which they can safely be disposed or recovered. Among the
preferred absorbers are natural clays and zeolites which are usually considered by
their low cost, ample distribution and preference for specific contaminants’.
34. 30
1.7 Montmorillonite
Montmorillonite is a naturally occurring hydrated layered aluminium silicate. It is
formed primarily through the alteration of igneous products such as volcano ash
and through geological weathering and hydrothermal alteration.
Hoffman, Endell and Wilm (1933) published the structure of
montmorillonite, showing that the internal structure of Montmorillonite naturally
occurs as a sequence of layers stacked on top of each other with a thickness ranging
from 1 to 1.5nm. These layers are the major building blocks of the mineral itself.
These layers are strongly two dimensional and they have been commonly referred
to as ‘stacks of cards’ (MOD 2009). The paper also described the expanding quality
of these layers, Gruner (1935) and Marshall (1935) pointed out possible
replacements within the montmorillonite structure. Because of this unique
structure Montmorillonite can absorb substantial amounts of water and in fact any
other liquid. As the liquid is sorbed, it hydrates the layers at the interlayer cation
site, hence causing swelling, this resultant swelling allows the mineral to absorb up
to ten times its weight in liquid.
It must be noted that Montmorillonite, as well as being the name of a single
mineral, is also used for the nomenclature for a group of minerals all with
expanding lattices (Grim 1968), the names Montmorillonid (MacEwan 1951) and
Montmorin (Correns 1950) were suggested as group names, but neither found
favour, the more common names for the group are: Montmorillonite and Smectite
(Brown 1955). Because of this in depth research into this particular clay and its uses
in other fields, it is the perfect candidate for the methodology at hand, in relation
to recovering ignitable liquid residues.
35. 31
1.8 Methods and Chromatography
When looking at sample analysis, the analytical equipment used is dependent on
the extraction methods used in the steps beforehand.
According to Chasteen (2004) reports from two American national proficiency
testing organisations clearly indicate that passive headspace analysis method found
in ASTM E1412 ‘Standard practice for Separation of Ignitable Liquid Residues from
Fire Debris Samples by Passive Headspace Concentration with Activated Charcoal’ is
the most common method used for the preparation of Fire Debris for further
instrumental analysis, while the ASTM method E1618, ‘Standard Test Method for
Ignitable Liquid Residues in Extracts from Fire Debris Samples by GC/MS’ which was
used in the methodology of this research, is the most common analytical method
used.
When looking at all the standards used for fire debris the main
instrumental technique that is employed is Gas Chromatography, it is used for its
ability to have the maximum amount of resolution, detectability and simplicity.
Though with this helpful capabilities there are some major limitations; the actual
analytes and their chemical analogues that are produced by derivitisation need to
be volatile, they need to be thermally stable at the temperature required for
volitisation and also any of the column coatings/stationary phases need to be
thermally stable. Until 1986 GC was restricted to a upper temperature limit of
approximately 375oC, due to column degradation. This mean all analytes had to
have an atmospheric boiling point of 500oC and be under 1000 amu. Recent
developments (Lipsky and Duffy, 1986) extended the upper limit to the 440oC
range. These developments allowed for a widened range of boiling points and for
36. 32
more simple derivitisation reactions for introducing sufficient volatility (Drozd,
1981).
The basic requirement for an ‘idea’ chromatographic detector is that its
sensitive electrical response should be identical to the analyte concentration
profiles at the end of the column (i.e. the detector input). In theory, then, the
detector should not affect the number of theoretical plates, the analyte retention
times, or the gas flow rates and gas flow patterns. Unfortunately, these theoretical
requirements cannot be exactly satisfied with practical detectors. Therefore, non-
ideal, yet useable detectors must have response time constants and effective
volumes that are compatible with the particular GC conditions such as column type,
flow rate etc. This is confirmed by Farwell (1997).
The FID used to be regarded as the universal detector, it is still used in bulk
today, and the outstanding features are:
High sensitivity to virtually all organic compounds
Little or no response to water, carbon dioxide and carrier gas impurities and hence
gives a zero signal when no analyte is present;
A stable baseline; it is not significantly affected by fluctuations in temperature or
carrier gas flow-rate and pressure; and
Good linearity, LDR, over a wide sample concentration range.
The detector is a minute hydrogen air flame with an electrode located above, which
collects ions formed by the analyte molecules. The flame processes are complex
and according to (David, 1974 and Hill, McMinn 1992):
‘…only forms a small contribution to the overall ionisation process’
37. 33
The Ions travel to the collector electrode which is maintained at a negative
potential (approx. -150V) with respect to the flame jet. Thus, the electrical current
observed (about 10-14A) is due to the concentration of the charged species present
in the flame and the chemical structure of the molecules. The sensitivity is generally
in the region of 0.015 coulombs g-1 (carbon) with a linear dynamic range of 107, and
overall response varies slightly for a given type of compounds and carbon number.
The signal is amplified and conditioned by an electrometer amplifier with a high
input impedance to produce an output signal typically over 0-10mV or 0-1V range,
enabling a chart recorder, integrator or computer face to be easily used to produce
the chromatogram and data. Materials not detected by FID include: H2,O2, SiCl4,
H2S, SO2, COS, CS2, NH3, NO, NO2, N2O, CO, CO2, H2O, Ar, Kr, Ne, Xe; HCHO and
HCOOH have a very small response (Braithwaite, 1999).
GC/MS is now largely the more dominant of the two detectors used in fire
debris analysis. This is due to its sensitivity and specificity (Smith, 1990).
Mass Spectrometry is based upon the ionisation of solute molecules in the
ion source and the separation of the ions generated on the basis of their mass to
charge (M/Z) ratio by an analyser. These analysers can vary but most likely will be a
magnetic sector analyser or a quadrupole mass filter, or an ion trap.
The MS, in acquisition mode will scan the total mass range (30-600 amu), every few
seconds, it will then sum all the ions detected and produce a chromatograph, this is
known as a Total Ion Chromatogram or TIC (Fowlis, 1994).
38. 34
1.9 Data Interpretation
The Interpretation of data, is normally, pattern recognition. If fire samples
contained only ignitable liquids then this task would be much simpler and would
most likely be performed by software alone. Unfortunately pyrolysis products are
often apparent and can obscure the patterns. The two main factors that are
considered with pattern recognition is the retention times and the target
molecules.
Step Aim
1
Look for C4 benzenes:
Trimethylbenzenes and
Diethylbenzenes. If present gasoline and
aromatic products can be considered.
2
Look for alkane series, if present then
petroleum distillated or pseudo-
kerosene has to be considered
3
Look For Terpenes, consider the
presence of Wood.
4
Look for early Oxygenated compounds.
They usually elute early, normally before
the solvent. Often only have a single
peak and they may indicate alcohols or
acetone
5
Look for unusual peak patterns, consider
naphthenic-paraffinic
6 Look for common pyrolysis patterns.
Table 1.2: The Main Steps for pattern recognition, suggested by Koussaifes (2004) and Stauffer,
Dolan, Newman, (2008)
As well as these steps Stauffer et. al. (2008) also recommend looking for specific
patterns that are associated with certain types of ignitable liquids.
The first set of patterns are those of Spiking n-Alkanes, these are the most easily
recognisable, they are comprised of a Gaussian distribution of alkanes that are
associated with the standard petroleum distillates.
39. 35
Figure 1.6: Spiking n-Alkanes
The next set of patterns has been named; The Three Musketeers, this is due to
three peaks representing four compounds, (obviously two of which coelute), These
are C2-Alkylbenzenes, in the order of Ethyl Benzene, M and P Xylene, co-eluting
then O Xylene, these elution’s (according to Stauffer et. al.) occur between Octane
and Nonane.
Figure 1.7: The Three Musketeers
This group of C3-Alkylbenzenes is very important grouping for petroleum products
where aromatics have not been removed. Eluting between Nonane and Decane, the
castle group is very evident on the TIC’s of gasoline and aromatic solvents. This
grouping follows in the order of:
N-Propylbenzene
3-Ethyltoluene
40. 36
4-Ethyltoluene
1,3,5 Trimethylbenzene
2-Ethyltoluene
This group is called the Castle Group.
Figure 1.8: The Castle Group
C4-alkylbenzenes, elute between Decane and Undecane it is composed of C4-
alkylbenzenes that have not been clearly identified due to the number of isomers.
Its main components are 1,2,4,5 and 1,2,3,5 tetramethylbenzene. These are the
Gang of Four.
Figure 1.9: The Gang of Four
41. 37
Finally 2 and 1-Methyl naphthalene will elute either side of Tridecane. These are
the Twin Towers.
Figure 1.10: The Twin Towers
42. 38
2. Aim
I aim to see whether it is possible to recover accelerants, in varying degrees of
evaporation, from porcine skin acting as a human analogue.
This method will incorporate the use of Passive Headspace Analysis with activated
charcoal strips and then further instrumental analysis with the use of GC/FID and
GC/MS.
43. 39
3. Materials
1ml of barbeque lighter fluid was poured onto a 7.5 x 7.5 cm onto porcine skin. The
skin
was then left for variable periods (1 hour, 2 hours and 3 hours).
After the allotted time 5g of fine montmorillonite clay was lighter dusted
over the entire are of the skin and pressure/rubbing was applied.
After five minutes the montmorillonite, was sampled using a toothbrush,
was scraped into a preconditioned/decontaminated tin.
If analysis was not immediately carried out immediately, a nylon 66 (Rislan) bag was
used instead of the tin and sealed with a swan neck tie.
A charcoal strip was then suspended in the headspace of the tin which
was, decontaminated at 180oC for 2 hours. The tin was sealed and placed into the
oven at 70oC for 18 hours.
After 18 hours the charcoal strip was placed into a vial containing 10 ml of pentane
via tweezers and was agitated for 10 minutes. (Appendix 1: ASTM method E1386-
10)
The pentane was then analysed using GC-MS or stored at -20oC for later
analysis.
Standards were prepared for comparison.
44. 40
Type of Standard Name
n-Alkanes
Nonane
Decane
Undecane
Dodecane
Tetradecane
Hexadecane
Heptadecane
Cyclohexanes Propylcyclohexane
Trimethylbenzenes
1, 2, 3 Trimethylbenzene
1, 2, 4 Trimethylbenzene
1, 3, 5 Trimethylbenzene
Tetramethylbenzenes 1, 2, 3, 5 Tetramethyl Benzene
Dimethylnaphthalene 1, 3 Dimethylnaphthalene
Table 3.1: Table showing standards run for sample comparison
The vials will be placed into a GC/FID loading tray; this analysis will only be
done once as a ‘proof of concept’ experiment.
The method used is known as the ‘Newman’ Method and is listed below in more
detail.
45. 41
Experiment Time (Per Sample) 23.17 min
Delay Time (Per Sample) 2.50 min
Run Time (Per Sample) 22.17 min
Injection Volume 1µl
Oven Temperature
Program
Initial Temperature 50o
C
Hold Time 2.50 min
Ramp Temperature Intervals 15o
C until 300o
C
Hold Time 4 min
Autosampler Capacity 5µl
Autosampler Injection Volume 1µl
Washes
Pre-Injection Solvent 2
Pre-Injection Sample 3
Post-Injection Solvent 3
Carrier Flow Rate 25
Detector Offset 5.0 Mv
Split Helium 20:1
Column Type ZB1
Column Length 30 m
Injection Port Temperature 260o
C
Table 3.2: A table showing the core elements of the Newman Method for GC-FID and GC-MS
A Total Ion Chromatogram will be taken using ASTM Standard E1618-06, this
document can be found in the appendix.
46. 42
4. Results/Discussion
Figure 4.1: BBQ Lighter fluid 1:500µl in pentane
Figure 4.2: BBQ lighter fluid run after 1 hour’s evaporation
Figure 4.3: BBQ lighter fluid after 2 hour’s evaporation
47. 43
Figure 4.4: BBQ lighter fluid after 3 hour’s evaporation
As mentioned in the introduction when trying to identify Ignitable liquid residues
certain patterns are examined to see whether they are present, the guidelines that
are recommended and the patterns needed are displayed in table: 1.2 and figures:
1.6-1.10. The sample is known, it is BBQ lighter fluid which is a medium petroleum
distillate. Which should range in the C8-C13 range of alkanes. Table 1.2 states that
spiking n-alkanes (figure: 1.6) should be present so when examining figures …-….
there is evidence to support that spiking n-alkanes are present, the figures do not
chow a perfect distribution. It has to be noted that these samples as well as
displaying varying stages of evaporation they have been placed onto a substrate
which absorbs liquids naturally so some loss of intensity and certain peaks may
have occurred causing this non ideal distribution.
48. 44
Class Light (C4-C9) Medium (C8-C13) Heavy (C8-C20+)
Gasoline Fresh is typically in the range of C4-C12
Petroleum
Distillates (Including
dearomatised)
Petroleum Ether
Some Lighter Fluids
Some Camping Fuels
Some Charcoal
Starters
Some Paint Thinners
Some Dry-Cleaning
Solvents
Kerosene
Diesel Fuels
Some Jet Fuels
Some Charcoal
Starters
Isoparaffinic
Products
Av-Gas
Some Specialty
Solvents
Some Charcoal
Starters
Some Paint Thinners
Some Copier Toners
Some Commercial
specialty solvents
Napthenic Parrafinic
products
Cyclohexane-based
solvents/products
Some Charcoal
Starters
Some Insecticides
Some Lamp Oils
Some Insecticides
Some Lamp Oils
Industrial Solvents
Aromatic Products Some Paint and
Varnish Removers
Some engine cleaners
Xylene Based
Products
Toluene Based
Products
Some engine
cleaners
Specialty solvents
Some Insecticides
Fuel additives
Some Insecticides
Industrial Cleaning
Solvents
Normal-Alkenes
Products
Solvents:
Pent/Hex/Heptane
Some Candle Oils
Some Copier Toners
Some Candle Oils
Some Copier Toners
Oxygenated
Solvents
Alcohols
Ketones
Some Lacquer
Thinners
Fuel Additives
Surface prep solvents
Some Lacquer
Thinners
Industrial Solvents
Metal cleaners/gloss
removers
Others – Misc Single Component
Products
Some Blended
Products
Some Enamel
reducers
Turpentine products
Some Blended
Products
Speciality products
Some Blended
Products
Speciality products
Table 4.1: ASTM E1618-06 IL Liquid Classification Scheme3
3
ASTM cited in Stauffer, Dolan, Newman, 2008
49. 45
It must be noted that the standards that follow the prefix of 1618 has changed over
the years to include new classifications and updates to the old system, these can be
seen in the table below
Class Number Class Name
1 Light Petroleum Distillates (LPD)
2 Gasoline
3 Medium Petroleum Distillates (MPD)
4 Kerosene
5 Heavy petroleum distillates (HPD)
0 Miscellaneous
0.1 Oxygenated Solvents
0.2 Isoparrafins
0.3 Normal Alkanes
0.4 Aromatic Solvents
0.5 Naphthenic/paraffinic solvents
Table 4.2: Previous ASTM classing system for Ignitable Liquids
DeHaan (2002) wrote an excellent description of the changes that occurred in the
last several years. As an example, more and more products were classified in the ‘‘0
miscellaneous’’ category and the number of subcategories of this class exceeded
the total number of classes
More categories have been defined, and each category is divided in three
subcategories ‘‘light, medium and heavy’’, with the exception of the gasoline
category. ‘‘Light’’ means a carbon range from C4 to C9,‘‘medium’’ from C8 to C13,
and ‘‘heavy’’ from C8 to C20 and above. Criteria to interpret and identify ignitable
liquid residues are not as specific in E 1387 as they are in E 1618, since the latter
includes mass spectral.
According to the ASTM a medium petroleum distillate (Class 3 liquid) will
have present within them: Nonane, Decane, Undecane, Dodecane, C3-
Alkylbenzenes, C4-Alkylbenzenes and Cyclohexanes.
50. 46
Now the standards that were run as a comparison for the samples are shown in
table 3.1, out of all the standards that were run the ones that eluted in
correspondence with the samples were the alkanes except for heptadecane.
Looking at table 4.3, there were two unidentified peaks eluted at 10 minutes and 12
minutes (the third and fifth major peak respectively), when looking at the alkane
standards logical thinking would suggest these peaks represent tridecane and
pentadecane. Pentadecane was identified using the internal library search located
on the GCMS, this is represented in figure 4.5.
Figure 4.5: Pentadecane library search the library result is located on the bottom
51. 47
Figure 4.6: Chromatogram and Mass Spectrum of the 2nd
repeat of 1 hour evaporation
Above in figure 4.6 is the chromatogram and mass spectrum of peak 5, (which
should be pentadecane) from the 2nd set of 1 hour evaporations. When looking at
the mass spectrum below it is evident that the main ions present are 43, 57, 71 and
85 (which has not been labelled) . Now according to Newman, Gilbert, Lothridge
(1998) the main ions located in an alkane are 43, 57, 71, and 85, when coupling
these findings with the logical flow in retention time and the similarity search
conducted (see fig 4.5) there is enough evidence to identify this fifth peak as
pentadecane.
Unfortunately when looking into the unidentified 3rd peak, there was not
substantial evidence to identify this peak as tridecane, and identification cannot be
done on retention time alone.
53. 49
Continued from Overleaf
Name Retention
Time
(Minutes)
Peak Height
(A.U)
Believed Alkane
Average Elution Time: 7 -14 minutes
BBQ Lighter
Fluid 2 Hour
Evaporation
Run 2
8.225 46,988,051 Undecane
9.932 109,126,914 Dodecane
10.488 110,692,277 Tridecane
11.442 106,276,743 Tetradecane
12.350 104,734,474 Pentadecane
13.208 29,368,655 Hexadecane
Average Elution Time: 7 -14 minutes
BBQ Lighter
Fluid 3 Hour
Evaporation
Run 1
8.226 40,474,829 Undecane
9.383 73,291,914 Dodecane
10.458 115,559,781 Tridecane
11.440 76,155,955 Tetradecane
12.350 79,167,310 Pentadecane
13.210 16,943,003 Hexadecane
Average Elution Time: 7 -14 minutes
BBQ Lighter
Fluid 3 Hour
Evaporation
Run 2
8.234 30,629,382 Undecane
9.392 62,780,337 Dodecane
10.458 104,421,796 Tridecane
11.442 109,478,348 Tetradecane
12.358 63,084,869 Pentadecane
13.216 14,314,641 Hexadecane
Table 4.3: Results obtained from GC-MS Analysis, main elution period occurred in the space of 7-14
minutes.
Now looking at the table above, when looking at the retention times obtained from
the standards that were run and also the reference sample of BBQ lighter fluid, it is
evident to see that the variation between the retention times is almost
insignificant, although there appears to be one anomaly within the results. The
retention time for dodecane is 9.383 minutes, while the retention times found in
the samples vary from 9.932minutes to the standard, 9.383 minutes. This does
indicate that the peaks resolved in some of the samples (1 hour evaporation and 2
hour evaporation) may actually not be dodecane.
54. 50
BBQ Lighter Fluid 1 Hour
Evaporation
BBQ Lighter Fluid 2 Hour
Evaporation
BBQ Lighter Fluid 3
Hour Evaporation
Average
R.T.
Average P.H.
Average
R.T.
Average P.H.
Average
R.T.
Average P.H.
8.227 55,832,507 8.226 47,182,473 8.230 35,552,106
9.932 108,544,337 9.932 113,982,839 9.388 68,036,126
10.450 108,402,195 10.478 108,061,976 10.458 109,990,789
11.433 103,471,211 11.441 105,873,676 11.441 92,817,152,
12.350 82,752,768 12.354 91,071,889 12.354 71,126,090
13.209 20,837,156 13.208 35,835,729 13.213 15,628,822
Table 4.4: Averaged results of 2 sets of data for each hour of evaporation
Figure 4.7: Chromatogram and Similarity search of Dodecane Standard
Now in figure 4.7, this shows the chromatogram of the dodecane standard and the
search conducted within the internal library of the GC MS, it is clear that not only
are the target ions present but they are present in the same ratio.
55. 51
Figure 4.8: 2nd
repeat of BBQ 1 hour evaporation, focussing on the 2nd
major peak
Figure 4.9: 1st
repeat of BBQ 2 hour evaporation, focussing on the 2nd
major peak
56. 52
Figure 4.10: 2nd
repeat of BBQ 2 hour evaporation, focussing on the 2nd
major peak
In all of the above chromatograms, they show the 2nd peak, when looking at figure…
on comparing the mass spectrum it is clear that the main ions (43, 57, 71 and 85)
are present but there are extra ions that have not affected the ratios but could
cause the similarity searches to give a false identification. When also looking at the
general shape of the peak in figure 4.7, the peak is sharp in its resolution, in essence
an ideal peak but the peaks shown here have slight tailing and are not entirely
Gaussian, this lack of resolution, (as mentioned before) could be due to the alkane
itself being absorbed into the porcine skin.
Upon looking at the chromatograms obtained (figures 4.2-4.4) for all of the
runs none of the patterns in figures 1.7-1.10 were identified.
For example the Three Musketeers pattern (figure 1.7) was not identified and
according to Stauffer et al. (2008) this specific pattern should elute between octane
57. 53
and nonane, with the results obtained the earliest alkane eluted was decane, this is
also true for the Castle group which elutes between nonane and decane. One group
that could have been identified according to Stauffer et al. (2008) was the gang of
four. These elute between decane and undercane and are made up of C4-
alkylbenzenes, now 1, 2, 3, 5 – tetramethylbenzene was run as a standard but its
retention time did not fall into the retention times obtained from the samples.
The final pattern, (the Twin Towers, {figure 1.10}) elutes either side of tridecane,
now this made identification a little more difficult, because tridecane was not
positively identified and no standards were run that encompass the target
molecules in this pattern, it could not be identified and even if it could be there
would be no hard evidence to back up the identification.
Graph 1: Averaged results of all 3 sample types with Alkane standards. Please note that the alkane
standards are read from the y-axis located on the right
C11
C12
C14
C16
17.2
17.3
17.4
17.5
17.6
17.7
17.8
17.9
18
18.1
18.2
18.3
0
20
40
60
80
100
120
8 9 10 11 12 13 14
PeakHeight(AU)
x10000
PeakHeight(Au)
Millions
Retention Time (Minutes)
Peak Height against Retention Time
BBQ 1hr Evaporation BBQ 2hr Evaporation
BBQ 3hr Evaporation Alkane Standards (1:1000)
58. 54
Graph 2: Averaged results of the 1 hour evaporation with standard deviation error bars
Graph 3: Averaged results of the 2 hour evaporation with standard deviation error bars
0
20
40
60
80
100
120
8 9 10 11 12 13 14
PeakHeight(Au)
Millions
Retention Time (Minutes)
Peak Height against Retention Time
BBQ 1hr Evaporation
0
20
40
60
80
100
120
8 9 10 11 12 13 14
PeakHeight(Au)
Millions
Retention Time (Minutes)
Peak Height against Retention Time
BBQ 2hr Evaporation
59. 55
Graph 4: Averaged results of the 3 hour evaporation with standard deviation error bars
xi (xi – μ) (xi – μ)2
55832507 -24140855.25 582780892201452
108544337 28570974.75 816300598165137
108402195 28428832.75 808198531527472
103471211 23497848.75 552148895877877
82752768 2779405.25 7725093543727.56
20837156 -59136206.25 3497090889642540
Total 479840173.50 0 6264244900958210
n = 6
Table 4.5: Figures from the averaged results of 1 hour evaporation
μ = (Σxi / n) = 479840173.50/6 = 79973362.25
σ = √Σ(xi – μ)2
/ (n-1) = √6264244900958210/5 = 35395606.79
Equation 3: Standard Deviation calculation4
4
Lucy (2006)
0
20
40
60
80
100
120
8 9 10 11 12 13 14
PeakHeight(Au)
Millions
Retention Time (Minutes)
Peak Height against Retention Time
BBQ 3hr Evaporation
60. 56
xi (xi – μ) (xi – μ)2
47,182,473 -36485623.75 1331200740426560
113,982,839 30314742.25 918983597683935
108,061,976 24393878.75 595061320469701
105,873,676 22205578.75 493087727622452
91,071,889 7403791.75 54816132277368
35,835,729 -47832367.75 2287935404571240
Total 502008580.50 0 5681084923051260
n = 6
Table 4.6: Figures from the averaged results of 2 hour evaporation
μ = (Σxi / n) = 502008580.50/6 = 83668096.75
σ = √Σ(xi – μ)2
/ (n-1) = √5681084923051260/5 = 33707817.86
Equation 4: Standard Deviation calculation4
xi (xi – μ) (xi – μ)2
35,552,106 -29973074.92 898385220159933
68,036,126 2510945.08 6304845194776.20
109,990,789 44465608.08 1977190301924160
92,817,152 27291971.08 744851685431556
71,126,090 5600909.08 31370182522426.40
15,628,822 -49896358.42 2489646583577100
Total 393151082.50 0 6147748818809960
n = 6
Table 4.7: Figures from the averaged results of 2 hour evaporation
μ = (Σxi / n) = 393151082.50/6 = 65525180.42
σ = √Σ(xi – μ)2
/ (n-1) = √6147748818809960/5 = 35064936.39
Equation 5: Standard Deviation calculation4
To reiterate on the results obtained so far. All chromatograms show Gaussian
distribution, with spiking n-alkanes, and an overall retention time which falls into
the same bracket as a medium petroleum distillate. Out of all the alkanes identified,
only two match the alkanes suggested by the ASTM for MPDs, this may be because
that the results that the ASTM obtained were obtained from American products,
4
Lucy (2006)
4
Lucy (2006)
61. 57
and it is generally known that the chemical formulae of petroleum distillates vary
from manufacturer to manufacturer and therefore from country to country.
It must be noted that identification of the samples was made difficult due to the
column overload as the samples were neat BBQ lighter fluid, this is representative
of what would occur in an actual arson case, it would be very rare for an arsonist to
dilute any ignitable liquid down (Bertsch, Holzer, Sellers, 1993).
For further identification ideally, other patterns should be matched rather
than just one type (n-alkanes), but due to the retention times at which these
patterns appear and the retention times obtained from the sample these patterns,
as previously mentioned, were not identified.
Other items that should have been identified, again according to the ASTM,
were cyclohexanes, Trimethylbenzenes and Tetramethylbenzenes, again like
Nonane and Decane, it appears from looking at the chromatograms and similarity
(figures A2-12 – A2-14, located in Appendix 2) and table 4.1 that these have eluted
before the samples initial retention time.
Other research in the area of fire debris analysis has covered a
myriad of areas which also has caused some dispute within the forensic science
population. When considering passive headspace analysis, activated charcoal strips
are normally used but Jacowski (1997 cited in Langford et al 2005) suggests that
tenax™ would be a better absorbent. Some argue that the analysis of headspace
has a unique disadvantage in that it discriminates higher boiling compounds to
lower boiling compounds which can easily lead to the misclassification of the
sample (Hendrikse, 2007). (Dolan, 2003) also feels this way about steam distillation,
and he goes on to further state that although GC–MS is currently the dominant
62. 58
force in fire debris analysis, research into applications of other instrumental
methods continues.
The goal, in any kind of research into an instrumental technique, is to
increase sensitivity and minimize the challenges associated with complex
chromatograms due to co-extraction of products produced by the pyrolysis and
partial combustion of the matrix material. One area of research involves the
application of gas chromatography–mass spectrometry/mass spectrometry (GC–
MS/MS) to fire debris analysis. It has been shown that GC–MS/MS may be able to
identify ignitable liquids in cases in which identification by GC–MS was not possible.
The advantages offered by GC–MS/ MS include an increased ability to filter out
undesirable components, allowing the analyst to focus on the data relevant to
ignitable liquids. This ability to minimize the contributions of matrix-related
compounds can potentially result in a significant increase in the overall sensitivity.
Research in this area is still in its early stages, and because analysis by GC–MS/MS
requires fairly costly specialized instrumentation, it has not yet garnered a
widespread following. Another novel approach to the instrumental aspect of fire
debris analysis involved a study of the potential utility of two-dimensional gas
chromatography (GC×GC) (Frysinger and Gaines, 2000). The benefit of GC×GC is
that it allows for a much greater resolution due to the fact that the ignitable liquid
or extract is subjected to two individual separations, each relying upon different
characteristics of the components being separated.
Sutherland (1997) and DeVos, Froneman, Rohwer, Sutherland (2002).
Others argue that it is not the absorbent, but how it is packaged Dietz (1991) came
up with a prototype container which combined the simplicity of passive headspace
63. 59
analysis and the effectiveness of purge and trap. The device, which has now been
named the ‘C-bag’ uses granular activated charcoal encapsulated within an
envelope of porous paper. The other device, which has been referred to as the
"charcoal strip," was originally taken from a commercial organic vapour detection
badge. As a result of this research, the strips are now sold separately without a
plastic badge.
Others, on the other hand, argue the different uses of substrates in testing
kits, for example Twibell et al (1984) feel that the national hand test kit (exclusively
used in the UK) has been employed to recover accelerants and they also feel that
montmorillonite could be incorporated into a modified version of the kit. Tontarski
(1985) conducted a study using three absorbents to recover hydrocarbon
accelerants from concrete, in his research he found that calcium carbonate was
used by the arsons unit of the Houston ATF Bureau5. In his research he used a
sweeping compound, flour and the calcium carbonate as a control absorbent. Now
the method he suggested did not differ much from my own the only difference was
that he suggested the material be left for half an hour rather than five minutes, but
it must be reminded that Tontarski was working with concrete and not an analogue
of a suspect.
White, Hall (2010) went on to further expand on Tontarski’s original plans in one
study they a variety of absorbents, based on research into Fire services within the
UK, they found that the most common absorbents that were used for the recovery
of ignitable liquid residues, were; sand, Tampax®, Tenalady ®, Non-Clumping Cat
litter, gardeners’ line, squeequee/paper and talcum powder. The method
5
The Fire and Arson Investigator, Vol. 31, No. 3, Jan.-March 1981, p. 7.
64. 60
incorporated was similar to Tontarski’s work but they used ASTM E1618-10 when
analysing the samples at a later date. In this work and in their other study (also
conducted in 2010) showed that the cat litter was a very effective absorbent,
absorbing all target compounds up to C16, therefore substances such as diesel could
not be detected. The main ingredient of the cat litter used is Montmorillonite. This
substance appears in the literature in areas not concerning forensic fire
investigation but more so it is slowly beginning to appear.
This substance has been worked on in 3 separate studies with promising results so
far.
As well as these outstanding pieces of research it appears that the idea of
recovering IGNITABLE LIQUID RESIDUE’s off of suspected persons is becoming a
more popular research topic, Montani, Comment, Delémont (2010) but rather than
using an external absorbent substrate they examined whether specific types of
latex and nitrile gloves could act as an absorbent and not create too much
interference so it would hinder the identification process, research conducted by
Darrer, Jacquemet-Papilloud, Delémont (2000) (which was the primary basis for
Montani et al’s research) also considered this idea. At the same period, Coulson,
Morgan-Smith (2000) were conducting research into the recovery and they found
that if 2L of ignitable liquids are poured onto the floor (especially petrol), that up to
30ml of ignitable liquids could be recovered from the shoes and clothing. As well as
all these other studies providing alternate methods to the use of montmorillonite
and invaluable information, Mattaro, Kupper, Nylander-French (2003) were seeing
if they could estimate dermal exposure to jet fuel (Naphthalene) using adhesive
tape. There method involved a smaller amount of ignitable liquid (25μl) but shorter
65. 61
evaporation times, (5, 10, 15 and 20 minutes). There sampling method covered a
broad population and according to their results 68% of the ignitable liquid was
recovered after the time period but on the last time period only 0.8% was collected.
It has to be noted that they were working with a type of fuel that will not be
commonly come across in arson cases so with more common fuels their
methodology may hold onto the sample for longer allowing a better recovery rate.
An interesting piece of research that is not directly related but could aid in
the development of more technology related to ignitable liquid residue recovery
was conducted by Hieda et al. (2004). In their research they found that the skin had
an affinity for hydrocarbons and they felt that further sampling along with blood
level counts would create a greater picture. Nonetheless they sate that skin is a
valuable forensic sample in fire investigation.
Further research that could be conducted with either montmorillonite or
recovering ignitable liquid residues from skin, when looking at montmorillonite, the
most logical option appears to be, to create a container for the montmorillonite
that a person would place their hands into, similar to Montani, Comment,
Delémont (2010). This could also lead to Twibell’s idead of creating a field kit using
montmorillonite for the detection of explosives and ignitable liquid residues.
According to Hieda et al. (2004), when sampling skin for ignitable liquid
residue recovery, blood samples should be taken, this could be further research
seeing whether the human body could absorb target molecules of ignitable liquids
into the blood stream and whether they could then be recovered. Unfortunately for
that research, I feel that ethics could become a problem.
66. 62
5. Conclusion
In conclusion, when looking at the results obtained, there is evidence strengthening
the case that montmorillonite, can be a suitable, cost effective absorbent when
recovering ignitable liquid residues from skin and still allow for a positive
identification of the sample in question. It has the benefits of being easily
obtainable, it is cost effective and the actually recovery is very quick.
Other research (White, Hall, 2010) has identified that it has the ability to
absorb all target molecules in a light petroleum distillate and in petrol, coupled with
this research it can know be stated that montmorillonite can absorb all alkanes up
to C16 and the associated target molecules that are located within the different cuts
of the distillates. However as a precaution which should be taken generally and not
just when using montmorillonite, but when looking at ignitable liquid residues a full
range of standards should be employed to allow for identification, as mentioned in
table 3.1 these standards at a minimum should include; Alkanes ranging from
Nonane to Heptadecane, Cyclohexanes, C3, and C4 – Alkylbenzenes. As mentioned
early due to the chemical composition of many medium petroleum distillates
varying from manufacturer and manufacturer this full range allows for the greatest
chance of a correct, positive identification.
Also weathered standards of reference samples should be run as well to
allow for natural evaporation and absorption and for the washing of skin etc.
There are however limitations to the methodology, first of all because
montmorillonite is such an effective absorbent, when it is prepared it should be
prepared in either a dedicated lab or in the presence of desiccators to limit the
67. 63
amount of background absorption that may occur. Also a dedicated tool should be
used to transfer the montmorillonite into either the container or nylon bag, it
should be sometime non-absorbent, sterile, disposable and should not interfered
with the instruments used for analysis.
One critical point that has come to my attention is that the porcine skin was not
heated to a normal body temperature, when the experiment occurred the skin was
at room temperature (22oC), and this temperature may have been too cold to allow
for significant absorption into the skin, though the other extreme of this would also
be detrimental to the methodology if the skin was too hot then evaporation may
outweigh absorption and not enough sample may not be transferred form the skin
onto the substrate.
To reiterate montmorillonite, has appeared in literature related to fire
debris analysis throughout the years and it is effective at absorbing medium
petroleum distillates from porcine skin.
68. 64
6. References
1) Anon, 2009, Fullers Earth Special, Ministry of Defence, Defence Standard 68-
142, Issue 2
2) Bertsch. W, Holzer. G, Sellers. C, 1993, Chemical Analysis for the Arson
Investigator and Attorney, Huethig Buch Verlag, Munich, p.84
3) Braithwaite. A, Smith. F.J, 1999, Chromatographic Methods, 5th ed. UK, Kluwer
Academic Publishers, p.232
4) Brown, G., 1955, Report of the Clay Minerals Group Sub-Committee on
Nomenclature for Clay Minerals, Clay Minerals Bulletin¸ 2: 294-302
5) Bruice, P.Y. 2004, Organic Chemistry, 4th edition, USA, Pearson, p.275-278, 594-
595
6) Caputo, D., Pepe, F., 2007, Experiments and data processing of ion exchange
equilibria involving Italian natural zeolites: a review, Microporous and
Mesoporous Materials, 105:222–231.
7) Chasteen. C.E, n.d, Essential Tools for the Analytical Laboratory: Facilities,
Equipment, and Standard Operating Procedures in. Almirall, J., Furton, K., ed.
2004, Analysis and Interpretation of Fire Scene Evidence. Taylor & Group. USA.
p.108, 112
8) Chavez, M.L., De Pablo, L., Garcia, T.A., 2010, Adsorption of Ba2+ by Ca-
exchange clinoptilolite tuff and montmorillonite clay, Journal of Hazardous
Materials, 175:216–223
9) Clark, J., 2003, An introduction to Alkanes and Cycloalkanes [Online]. Available
at: http://www.chemguide.co.uk/organicprops/alkanes/background.html#top,
[accessed 5th October 2010]
69. 65
10) Cole, A., 2003, Fire Protection Handbook, 19th Edition, National Fire Protection
Association, USA
11) Correns, C.W., 1950, Objection to the Name Montmorillonoid, Clay Minerals
Bulletin, 1:6:194-195
12) Coulson. S. A, Morgan-Smith. R. K, 2000, The transfer of petrol onto clothing
and shoes while pouring petrol around a room, Forensic Science International,
112:2-3:135-141
13) Criminal Damage Act 1971. (c.48) London: HMSO
14) Daeid, N.N. ed. 2004, Fire Investigation, CRC, USA, p.2
15) Darrer. M, Jacquemet-Papilloud. J, Delémont. O, 2008, Gasoline on hands:
preliminary study on collection and persistence, Forensic Science international,
112:2-3:135-141
16) David, D.J, 1974, Gas Chromatography Detectors, John Wiley, New York
17) DeHaan. J. 2002, Our changing world 2. Ignitable liquids: petroleum distillates,
petroleum products, and other stuff, Fire Arson Investigator, 52:3:46-47
18) Dehaan. J.D., 2007, Kirk’s Fire Investigation, 6th Edition, Pearson, USA, p.12,
p.65, p.219, p.225, p.448
19) Department of Communities and Local Governments, 2006, Arson Control
Forum: Annual Report 2006. DCLG, UK.
20) Department of Communities and Local Governments, 2009, Fire Statistics,
2007, DCLG, UK.
21) Desty, D.H., & Goldup, A., & Geach, C. J., 1958, Gas Chromatography 1960,
Butterworths, London p.156.
70. 66
22) DeVos. B. J, Froneman. M, Rohwer. E, Sutherland. D. A, 2002, Journal of
Forensic Science, 47:736-756
23) Dietz, W. R, 1991, Improved Charcoal Packaging for Accelerant Recovery,
Journal of Forensics Sciences, 36:1:111-121
24) Drozd, J., 1981, Chemical Derivitisation in Gas Chromatography, Elsevier
Amsterdam, p178-222
25) Drysdale. D., 2004, An Introduction to Fire Dynamics, 2nd Edition, UK, Wiley p.2-
6
26) Farwell. S, 1997, Modern Gas Chromatographic Instrumentation. In Ewing.
G.W, Analytical Instrumentation Handbook, USA, Marcel Dekker, Ch.23
27) Fowlis, I.A., 1994, Gas Chromatography, 2nd Edition, John Wiley & Sons, U.K.
p.150
28) Frinstrom. R.M., Westenberg. A.A., 1965, Flame Structure, McGraw-Hill. New
York, p.56
29) Frysinger. G. S, Gaines. R. B, 2002, Journal of Forensic Sciences, 47:471-482
30) Gedik, K., Imamoglu, I., 2008, Removal of cadmium from aqueous solutions
using clinoptilolite: influence of pretreatment and regeneration, Journal of
Hazardous Materials, 155:385–392.
31) Grim, R.E, 1986, International series in the Earth and Planetary Sciences, USA,
McGraw-Hill, pg 41
32) Gruner, J.W, 1935, Structural Relations of Nontronites and Montmorillonites,
American Mineralogist, 20:475-483
33) Gupta, S.S, Bhattacharyya, K.G., 2008, Immobilization of Pb(II), Cd(II) and Ni(II)
ions on kaolinite and montmorillonite surfaces from aqueous medium, Journal
of Environmental Management, 87:46–58.
71. 67
34) Gupta, S.S, Bhattacharyya, K.G.,2008, Influence of acid activation on adsorption
of Ni(II) and Cu(II) on kaolinite and montmorillonite: kinetic and
thermodynamic study, Chemical Engineering Journal, 136:1–13
35) Hendrickse. J, 2007, ENFSI collaborative testing program for ignitable liquid
analysis: A review, Forensic Science International, 167:213-219
36) Hieda, Y., Tsujino, Y., Xue, Y., Takayama, K., Fujihara, J., Kimura, K., Deiko, S.,
2004, Skin analysis following dermal exposure to kerosene in rats: The effects of
post-mortem exposure and fire, International Journal of Legal Medicine,
118:1:41-46
37) Hill, H.H, McMinn. D.G, 1992, Detectors in Capillary Chromatography, John
Wiley, New York
38) Hine. G.A, n.d, Fire Scene Investigation: An introduction for Chemists in.
Almirall, J., Furton, K., ed. 2004, Analysis and Interpretation of Fire Scene
Evidence. Taylor & Group. USA. p. 35, 44
39) Hoffman, U., Endell, K., Wilm, D., 1933, Kristallstruktur und Qullung von
Montmorillonit, Zeitschrift fur Kristallographie, 86: 340-347
40) Inglezakis, V.J., Stylianou, M.A., Gkantzou, D., Loizidou, M.D., 2007, Removal of
Pb(II) from aqueous solutions by using clinoptilolite and bentonite as
adsorbents, Desalination 210 p.248–256.
41) Jacowski. J.P, 1997, The incidence of ignitable liquid residues in fire debris as
determined by a sensitive and comprehensive analytical scheme. Journal of
Forensic Sciences, 42:828-832
42) Karter, M, 2010, U.S Fire Loss for 2009, National Fire Prevention Association
Journal, NFPA, USA
72. 68
43) Koussaifes. P., M., 2004, The Interpretation of Data Generated from Fire Debris
Examination: Report Writing and Testimony. In Almirall. J., R., Furton. K., G.,
Analysis and Interpretation of Fire Scene Evidence, USA, CRC Press, Ch. 7, p.219
44) Langford. A, Dean. J, Reed. R, Holmes. D, Weyers. J, Jones. A, 2005, Practical
skills in Forensic Science, Pearson UK. p.374-382
45) Leigh, G.J, Favre, H.A, Metanomski, W.V, 1998, Principles of chemical
nomenclature: A guide to IUPAC recommendations, Blackwell Science, Oxford,
United Kingdom
46) Linville, J., 2001, Fire Protection Handbook, 16th ed., National Fire Protection
Association, USA
47) Linville, J., 2002, Fire Protection Handbook, 17th ed., National Fire Protection
Association, USA
48) Lipsky, S.R, Duffy, M. L, 1986, High temperature gas chromatography: the
development of new aluminium clad flexible fused silica glass capillary columns
coated with thermostable nonpolar phases: Part 1, Journal of High Resolution
Chromatography, 9:7:378
49) Lipsky, S.R, Duffy, M.L, 1986, Journal of liquid chromatography and Gas
Chromatography, 4:898
50) Lister, T., Renshaw, J., 2004, Essential AS Chemistry, Croatia, Nelson Thornes,
p.90
51) Lucy. D, 2006, Introduction to Statistics for Forensic Scientists, John Wiley &
Sons, UK, p.30
73. 69
52) MacEwan, D.M.C., 1951, The Montmorillonite Minerals ‘X-ray Identification and
Structures of Clay Minerals, ch.4 p.86-187, Mineralogical Society of Great
Britain Monograph
53) Mark, P., Sandercock, L., 2007, Fire Investigation and ignitable liquid residue
analysis – A review: 2001-2007, Forensic Science International, 176, p93-110
54) Marshall, C.E, 1935, Layer Lattices and Base-Exchange Clays, Zeitschrift fur
Kristallographie, 91:433-449
55) Mattorano, D.A., Kupper, L.L., Nylander-French, L.A, 2004, Estimating dermal
exposure to jet fuel (naphthalene) using adhesive tape strip samples, Annals of
Occupational Hygiene, 48:2:139-146
56) McMurry, J., 1988, Organic Chemistry, 2nd ed., Brookes/Cole Publishing, Pacific
Grove, CA. p.120
57) McMurry, J., 2000, Organic Chemistry, 5th ed., Brookes/Cole Publishing, Pacific
Grove, CA. p.84,100, 120-123
58) Moldoveanu, S.C., 1998, Analytical Pyrolysis of natural organic polymers,
Techniques and instrumentation in analytical chemistry, Vol. 20, Elsevier,
Amsterdam, Netherlands.
59) Montani. I, Comment. S, Delémont. O, 2009, The sampling of ignitable liquids
on suspects hands, Forensic Science International, 194:115-124
60) Newman, R, 1967, Modern laboratory techniques involved in the analysis of
fire debris samples. In Daéid. N.N, Fire Investigation, USA, CRC Press, Ch.10
61) Newman. R, Gilbert. M, Lothridge. K, 1998, GC-MS Guide to Ignitable Liquids,
CRC Press, USA, p.2
74. 70
62) Newman. R.T., Dietz W.R., Lothridge K., 1996, The use of activated charcoal
strips for fire debris extractions by passive diffusion. Part 1: The Effects of time,
temp, strip size and Concentration, Journal of Forensic Sciences., 41:361
63) NFPA 921, 2004, Fire and Explosion Investigations 2004 Edition, USA, NFPA p.11
64) Oxford Dictionaries, n.d., [online] Available at:
http://oxforddictionaries.com/view/entry/m_en_gb0019180#m_en_gb001918
0, [Accessed 31/10/2010]
65) Patrick. G.L, 2000, Organic Chemistry, USA, BIOS Scientific Publishers, p.160
66) Pert, A.D., Baron, M.G., Birkett, J.W., 2006, Review of Analytical Techniques for
Arson Residues, Journal of Forensic Science, 51:5
67) Quintiere, J. 1998, Principles of Fire Behaviour, Delmar, USA, p.2
68) Ratcliff, B. et al., 2000, Chemistry 1, Dubai, Cambridge University Press, p.100-
102
69) Redsicker. R.D, O’Connor. J.J, 1986, Practical Fire and Arson Investigation, 2nd
Edition, USA, CRC Press p.60-65, p.277
70) Scott, R, n.d, Gas Chromatography Detectors, [E-Book], Library4Science.
Available at http://www.chromatography-online.org/GC-Detectors/Flame-
Ionization/FID-Design/rs37.html [accessed 19th March 2010]
71) Shields. T., J., Silcock. G., W., H., 1987, Buildings and Fire, Singapore, Longman
Scientific & Technical, p.66-67
72) Smith, M.S, 1990, Gas chromatography-mass sprctrometry in arson analysis ,
In. Ho. M.H., 1990, Analytical methods in forensic science, Ellis Horwood, UK.
16-28
75. 71
73) Sorptive Minerals Institute, 2007, Minerals & Ores [Online]. (Updated 16th June
2007) Available at : http://www.sorptive.org/content/page04.shtml, [accessed
15th March 2010]
74) Spencer, A., Colonna, G., 2002, Fire Protection Guide to Hazardous Materials,
National Fire Protection Association, USA
75) Stauffer, E., 2001, Identification and characterisation of interfering products in
fire debris analysis, Master’s Thesis, International Forensic Research Institute,
Florida International University, Miami, FL
76) Stauffer, E., Dolan, J.A., Newman, R., 2008, Extraction of Ignitable Liquid
Residues from Fire Debris. Fire Debris Analysis, Academic Press, USA, p.296,
p.387-426
77) Sutherland. D. A, 1997, Canadian Society Forensic Science Journal, 30:185-199
78) Technical Working Group on Fire and Explosives, 1998, Final results for
Explosive/Fire debris analysts (Survey), [Online], National Centre for Forensic Science,
available at http://tqgfex.org. [Accessed 10th February 2011]
79) Tontarski. R. E, 1985, Using Absorbents to Collect Hydrocarbon Accelerants
from Concrete, Journal of Forensic Sciences 30:4:1230-1232
80) Twibell. J.D, Wright. T, Sanger. G.D, Bramley. R.K, Lloyd. J.B, Downs. N.S, 1984,
The Efficient Extraction of Some Common Organic Explosives from Hand Swabs
for Analysis by Gas, Liquid and Thin-Layer Chromatography, Journal of Forensic
Sciences, 7:36:36
81) Van Herwijnen, R., Hutchings, T.R., Al-Tabbaa, A., Moffat, A.J., Johns, M.L.,
Ouki, S.K., 2007, Remediation of metal contaminated soil with mineral-
amended composts, Environmental Pollution 150:347-354
76. 72
82) White, G., Hall, S., 2010, The effectiveness of adsorbents to sample ignitable
liquid residues using GC-MS, Forensic Analysis Conference (RSC). Huddersfield
University. UK
83) White, G., Hall, S., 2010, The use of adsorbents for detecting ignited petrol
residue on concrete using a passive headspace technique and GC-MS. 6th
National FORREST Conference 2010, Coventry University. UK
84) Willett, J.E, 1987, Gas Chromatography, UK, John Wiley, p.24, 34
94. 90
Figure A2-15: Nonane Standard
Figure A2-16: Decane Standard
Figure A2-17: Undecane Standard
Figure A2-18: Dodecane Standard
Figure A2-19: Tetradecane Standard
95. 91
Figure A2-20: Hexadecane Standard
Figure A2-21: Heptadecane Standard
Figure A2-22: Undecane similarity search
Figure A2-23: Dodecane similarity search
98. 94
The Use of Montmorillonite as an absorbent for ignitable liquids from porcine skin
By Matthew Perryman
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