ArsonAnalysis of Fire

Arson Investigation

Module-5
Arson: Introduction,
Chemistry of fire,
Scientific investigation and evaluation of clue materials
Collection and preservation,
Analysis of flammable residues.
Terminology of Fire
 Fire
 Fire triangle
 Heat-
 Temperature-
 Thermal Equilibrium-
 Heat of vaporization
 Heat of fusion
 Flammable liquids
 Combustible liquids
 Flashover
 Flashpoint
 Auto Ignition point
 Exothermic
 Endothermic
 First law of thermodynamics
 ARSON

Fire is a self sustained chemical reaction that

releases energy in form of heat and light. A fire is
classified as ARSON if it is deliberately set for the
purpose of destroying property.

Or
 Arson is defined as purposely setting fire to a
house, building or other property.
The specific legal definition of arson varies from state to
state. However, a working definition of arson is: the
malicious burning of homes, residences, buildings, or
other types of real property. Malicious burning in this
context is intended to also include incendiary
explosions as well as fire.

What is any person burns his own property willfully?

Categories of Arsons
In some states, the crime of arson is divided into three
degrees:
 First-degree arson is usually the burning of an inhabited
house or building at night.

 Second-degree arson is the burning at night of an

uninhabited building. “Uninhabited” means no humans
inside the building.

 Third-degree arson is the burning of any building or

property with intent to defraud or injure a third party.
Cause of Fire:
 Natural  Undetermined
 Accidental  Intentional
 Reasons for Arson
1. Revenge: Harming
2. Personal gain: Insurance
3. Vandalism: (Damaging)
4. To conceal another crime: (Burglaries and murders)
5. Rioting: Pillaging, looting in civil riots.
6. Abnormal psychology: (firebugs, persons who want to be
heroes at fires, people wishing to purify the world, self-
appointed angels of justice.
 Elements of FIRE Triangle
 Basically three elements are essential fire to take place:
1. Source of Fuel
2. Source of Heat
3. Oxygen gas

FIRE Triangle Oxygen Heat

Fuel

If any of these three Elements is removed, the FIRE will extinguish

 HEAT SOURCES
OXYGEN SOURCE
• Approx. 16% Required • To Reach Ignition Temp.
• Normal air contains 21% of oxygen • Open Flame, the Sun, Hot
• Some Fuels contains its own Surface, Sparks & Arcs, Friction,
oxygen supply Chemical Action, Elec. Energy &
Gas Compression

Oxygen Heat
Fuel

GASES LIQUIDS SOLIDS

• Gasoline, • Coal, Wood,
• Natural Gas,
• Kerosene, • Paper, Cloth,
• Propane,
• Turpentine, • Wax, Grease,
• Butane,
• Alcohol, • Leather, Plastic,
• Hydrogen,
• Paint, Varnish, Olive • Grain, Hay,
Acetylene,
oil, Lacquer
 Fire Tetrahedron
 The combustion reaction can be
characterized by four
components:
1. Fuel,
2. Oxidizing agent,
3. Heat, and
4. An uninhibited chemical chain reaction.
 These four components have
been classically symbolized by a
four-sided solid geometric form
called a tetrahedron. Fires can
be prevented or suppressed by
controlling or removing one or
more of the sides of the
tetrahedron.
Chemistry of Fire
 Chemically, fire is a type of oxidation, which is the
combination of oxygen with other substances to produce
new substances.

 To start fire, the minimum temperature needed to

spontaneously ignite fuel, known as ignition temperature,
must be reached.

 The heat evolved when a substance burns is known as heat

of combustion.

 A liquid burns when the temperature is high enough to

vaporize it (flash point), while a solid must be hot enough
to decompose into gaseous products (pyrolysis).
 Accelerants
 Can easily be defined as any substance that will combust.
 In arson cases, an accelerant is any material that is used to
start the fire.

1. Gasoline Can exist in one of three phases:

2. Kerosene  Solid
3. Diesel  Liquid
4. Charcoal starters  Gas
5. Automobile additives
6. Butane
Accelerant in Arson
 Solid accelerants include paper, fireworks, highway flares, and
black powder.

 Liquid accelerants fall into two broad categories: petroleum

distillates, which include gasoline and other petroleum products; and
non-petroleum products such as methanol, acetone (used in nail
polish remover), and turpentine.

 Gas: Butane (cigarette lighter fuel), propane, and natural gas are
examples of gaseous accelerants, which do not leave any residue at a
fire scene.
 Petroleum distillates are derived from crude oil and are also called
hydrocarbons or petroleum hydrocarbons. In crude oil, volatility of
the individual components range from extremely volatile
substances such as propane (a gas at room temperature) to asphalt,
which remains solid even at high temperatures.

 Petroleum distillates such as gasoline and kerosene

are not single
hydrocarbons but mixtures of different components with similar
volatilities. The volatility of an accelerant is an important
consideration in the combustion process, determining how much
residue will be left and how quickly it will evaporate after
the fire is out.

 Related to volatility is the flash point, defined as the temperature at

which a liquid will give off enough vapor to form an ignitable
mixture.
Classification of Accelerants
 Classification based on ignition
 Flammable Liquids: Any liquid that produces sufficient
vapors to support combustion at a temperature lower than
37.8◦C . Examples –Petrol (Gasoline)

 Combustible Liquids: Any liquid that produces sufficient

vapors to support combustion at a temperature higher than
37.8◦C . Examples –Kerosene (Ghaslat)

Why 37.8 degree centigrade?????????

1. Flash point - The lowest temperature at which a particular
flammable liquid gives off vapors (vaporizes) and therefore
can ignite.

2. Ignition temperature -is the temperature required for a

liquid to continue to emit vapors that can sustain
combustion.

A flammable liquid in its liquid state will not burn. It only will
ignite when it vaporizes into a gaseous state. All flammable
liquids give off vapors that can ignite and burn when an ignition
source such as a lighted cigarette or spark is present.
Methods
Arsonists use several different methods to set fires, although some are more
common than others.
 The most common method involves the pouring of an accelerant—an ignitable liquid
such as gasoline, kerosene, or lighter fluid— throughout the structure. The accelerant
allows for easy ignition and also increases the rate and spread of the fire, which will
follow the pour pattern of the accelerant. Many kinds of accelerants are readily
available to arsonists; some are particularly dangerous because of their tendency to
explode rather than just burn.
 Some arsonists start fires by using incendiary devices, which can range from simple
to very complex in their construction.
 Simple incendiary devices include lighted candles and flares, which can ignite their
surroundings.
 Another frequently seen incendiary device is the Molotov cocktail: an ignitable liquid
contained in a glass bottle along with a cloth soaked in the liquid fuel.
 Other chemical incendiary devices, such as those that utilize white phosphorus.
 More complicated incendiary devices that operate on timers or other signals are seen
occasionally in civilian arson cases.
 Fire investigators are careful to collect any evidence of incendiary devices found at
fire scenes; such evidence may include shattered glass, burned cloth, wires,
batteries, and other items that may have been used in timing mechanisms.
Arson Investigation Scheme
1. Observe the Fire and Scene Conditions
 Procedure: While approaching a fire scene, first
responders should observe and mentally note the
following conditions and activities and, as soon as
conditions permit, initiate permanent documentation
of the information (e.g., written notes, voice
recordings, videotapes):
A. The presence, location, and condition of victims and witnesses.
B. Vehicles leaving the scene, bystanders, or unusual activities near the scene.
C. Flame and smoke conditions (e.g., the volume of flames and smoke; the
color, height, and location of the flames; the direction in which the flames
and smoke are moving).
D. The type of occupancy and use of the structure (e.g., a residential occupancy
being used as a business).
E. Conditions of the structure (e.g., lights turned on; fire through the roof;
walls standing; open, closed, or broken windows and doors).
F. Conditions surrounding the scene (e.g., blocked driveways, debris, damage
to other structures).
G. Weather conditions.
H. Unusual characteristics of the scene (e.g., the presence of containers,
exterior burning or charring on the building, the absence of normal
contents, unusual odors, fire trailers
I. The fire suppression techniques used, including ventilation,
J. forcible entry, and utility shutoff measures.
K. The status of fire alarms, security alarms, and sprinklers.
Exercise safely
 Procedure: Upon arrival at the scene, first
responders should:
A. Evaluate the scene for safety hazards (e.g., structural
collapse of the building; smoke; electrical, chemical,
or biological hazards; other health risks).
B. Establish safety/hazard zones.
C. Communicate hazards to other personnel arriving at
the scene.
D. Use tools and personal protective equipment
appropriate to the task during all operations.
 3. Preserve the Fire Scene
 Principle: Evidence at a fire scene takes many different
forms, some of which are transient (i.e., they are not
permanent and may disappear quickly, such as
impressions in snow or evaporating liquids).
 First responders must understand how rescue, medical,
fire suppression, overhaul, and salvage efforts can
adversely affect different forms of evidence and take steps
to preserve evidence accordingly.
 First responders should assess the fire scene to identify
potential evidence, take preliminary steps to preserve it,
and notify appropriate authorities about its existence.
 Procedure to preserve evidence
A. Observe and mentally note evidence that may be present at the scene, such as:
 Fire patterns (including multiple fire locations).
 Burn injuries to victims and fire patterns on clothing.
 Trailers, ignitable liquids, or other unusual fuel distribution (e.g., piles of
newspapers, furniture pushed together).
 Incendiary/ignition/explosive devices (e.g., lighters, matches, timing devices).
 Shoe prints and tire impressions.
 Broken windows and doors.
 Distribution of broken glass and debris.
 Indications of forced entry (tools and tool marks).
 Containers.
 Discarded clothing.
 Trace evidence (e.g., hairs, fibers, fingerprints, blood, other body fluids).
 Evidence of crimes in addition to the possible arson (e.g., weapons, bodies, drugs,
clandestine drug laboratory equipment).
 Witnesses, bystanders, and victims.
 Any other unusual items or the absence of normal contents or structural
components.
B. Recognize threats to evidence (i.e., its movement, removal, contamination,
or destruction) from any of the following sources:
 Fire suppression activities, such as a straight stream applied at the point of
origin or deluge applications that may wash away or dilute potential evidence.
 Overhaul activities that destroy fire patterns.
 Salvage activities that involve moving or removing potential physical evidence.
 Use of a tool in any manner that causes destruction of evidence.
 Movement of knobs, switches, and controls on appliances and utilities.
 Weather conditions that affect transient evidence (i.e., wind, precipitation, or
temperature changes).
 Personnel walking through the scene.
 Witnesses and victims leaving the scene.
 Medical intervention and treatment of victims (e.g., by damaging evidence at
the scene or destroying victims’ clothing).
 Premature removal or movement of bodies.
 Vehicles at the scene (e.g., that introduce fluid to the scene through vehicle
leaks or destroy other evidence, including shoe prints and tire impressions).
 Contamination from external sources, such as fuel-powered tools or
equipment.
C. Protect evidence by:
 Limiting excessive fire suppression, overhaul, and salvage.
 Avoiding needless destruction of property.
 Leaving bodies undisturbed.
 Flagging items of evidence with cones or markers.
 Recording observations through written notes or voice recordings.
 Covering items or areas containing evidence with objects that will not
contaminate the evidence (e.g., clean boxes or tarpaulins).
 Isolating items or areas containing evidence with rope, barrier tape, barricades,
or sentries.
 Retaining and securing clothing items removed from victims and suspects.
 Obtaining information about victims and witnesses (i.e., their names,
addresses, and telephone numbers).
 Preserving transient evidence (e.g., trace evidence, shoe prints, tire
impressions).
 Removing evidence at risk of imminent destruction by the fire or the structural
collapse of the damaged building.
 Ensuring that later arriving investigators are fully apprised of the evidence
discovered.
Section C. Documenting the Scene
 Principle: Photographic documentation creates a
permanent record of the scene and supplements the
written incident report(s), witness statements, or
reports on the position of evidence. The investigator
should create and preserve an accurate visual record of
the scene and the evidence prior to disturbing the
scene. Additional photography or videography should
occur as the investigation progresses.
 Procedure: The scene should be photographed prior
to the disturbance or removal of any evidence and
throughout the scene investigation. The investigator
(or other individual responsible for evidence) should:
A. Photograph and/or videotape the assembled crowd and the
fire in progress.
B. Remove all nonessential personnel from the background
when photographing the scene and evidence.
C. Photograph the exterior and interior of the fire scene
(consider walls, doors, windows, ceilings, floors) in a
systematic and consistent manner. (Videotaping may serve
as an additional record but not as a replacement for still
photography.)
D. Photograph any points or areas of origin, ignition sources,
and first material ignited.
E. Photograph any physical reconstruction of the scene.
F. Maintain photo and video logs.
Record the date, the name of the photographer, and the
subject.
How to Identify, Collect and Preserve
Evidence

 Principle: Collecting evidence at a fire scene requires

attention to documenting and maintaining the
integrity of the evidence. The investigator should
ensure that evidence collectors identify and properly
document, collect, and preserve evidence for
laboratory analyses, further investigations, and court
proceedings. This will ensure that critical evidence is
not contaminated or lost prior to analysis and that the
chain of custody is maintained.
Procedure: To optimize the recovery and evaluation of physical
evidence, evidence collectors should:
A. Take precautions to prevent contamination. (See “Prevent
Contamination.”)
B. Document the location of evidence using written notes,
sketches, photographs, photo and video logs, the evidence
recovery log, evidence tags, and container labels. When evidence
is excavated, additional photographs may be of value.
C. Take special care to collect evidence in any areas of origin (such
as the first fuel ignited and ignition source) in cases where the
fire is not accidental.
D. Place evidence in labeled containers for transportation and
preservation. Evidence collected for laboratory identification of
ignitable liquids must be immediately placed in clean, unused,
vaportight containers (e.g., clean, unused paint cans; glass jars;
laboratory-approved nylon or polyester bags) and then sealed.
E. Label each container so that it is uniquely identified.
Labeling may include the name of the investigator, date and
time of collection, case number, sample number,
description, and location of recovery.
F. Collect and preserve suitable comparison samples but
recognize that such samples may be unavailable.
G. Package evidence in accordance with their laboratories’
policies and procedures.
H. Recognize the presence of other physical evidence, such as
blood stains, shoe prints, latent prints, and trace evidence,
and use proper preservation and collection methods or
seek qualified assistance.
 Summary: Proper collection and packaging preserve the
value of physical evidence.
Prevent Contamination

 Principle: Preventing contamination during evidence

collection protects the integrity of the fire scene and
evidence. The investigator should ensure that access to
the fire scene after fire suppression is controlled and
that evidence is collected, stored, and transported in
such a manner that it will not be contaminated.
Procedure
 Establish and maintain strict control of access to the scene.
 Recognize that fuel-powered tools and equipment present potential contamination
sources and should be avoided. When it is necessary to use these tools and equipment, the
investigator should document their use.
 Wear clean, protective outer garments, including footwear.
 Use clean disposable gloves for collecting items of evidence. (To avoid cross-contamination,
gloves should be changed between collection of unrelated items of evidence or when visibly
soiled.)
 Use clean tools for collecting items of evidence from different locations within a scene.
(Disposable tools also can be used.)
 Place evidence in clean, unused containers and seal immediately.
 Store and ship fire debris evidence containers of evidence collected from different scenes in
separate packages.
 Package liquid samples to prevent leakage and ship them separately from other evidence.
 Store and ship fire debris evidence separately from other evidence.
 Follow any specific laboratory requests, such as submitting an unused sample container or
absorbent medium for detection of any contaminants.
 Summary: Attention to scene control and evidence collection and packaging helps to
prevent contamination and ensures the integrity of the evidence.
Package and Transport Evidence
 Principle: Preventing changes in the condition of a
sample after it has been collected ensures the integrity
of the evidence and requires controlled packaging and
transportation. The investigator should ensure that
packaging, transportation, and storage procedures are
followed to prevent any destructive changes in the
condition of samples.
Procedure:
To minimize changes in the condition of samples, the personnel
responsible for packaging and transport should:
A. Take precautions to prevent contamination. (See “Prevent
Contamination.”)
B. Package fragile items carefully.
C. Freeze or immediately transport items containing soil to the
laboratory.
D. Transport all volatile samples to the laboratory in a timely
manner.

 Summary: Adherence to approved packaging and

transportation procedures safeguards the condition of the
evidence and ensures its continued integrity.
Establish and Maintain the Chain of Custody
 Principle: Establishing and maintaining a chain of custody verifies
the integrity of the evidence. The investigator should ensure that
the chain of custody is maintained.
Procedure: Personnel responsible for the chain of custody should:
A. Maintain written records documenting the sample number,
description of the evidence, date and location where it was found,
collector’s name, and miscellaneous comments.
B. Document all transfers of custody, including the name of the
recipient and the date and manner of transfer.
C. Document the final disposition of the evidence.

Summary: Maintaining the chain of custody for evidence, from

collection through final disposition, ensures its integrity.
 Typical Characteristics of an Arson or Incendiary Fire
 Multiple origins of fire, especially several points of fire origin that are
unconnected to each other.
 The point of origin is in an area where there is no rational ignition potential. For
example, a breakout of fire in the middle of a fireproof carpet with no obvious
ignition source available.
 Use of accelerants such as gasoline, kerosene, turpentine, etc. Often these agents
are detectable by their lingering odor, the “pour” patterns they produce on floors
when ignited, and by chemical analysis.
 The presence of trailers. These are fire or burn pathways that exhibit flammable
liquid pour patterns. Trailers are used by the arsonist to accelerate the spread of
fire to more areas of the building. This reduces the burn time of the building so that
more of the building will have burned up by the time the fire department arrives.
 The finding of deliberately arranged fire load. This is where everyday items
typically found in the building are rearranged to enhance the fire. Examples
include closets stuffed with crumpled newspapers, flammable clothing piled in
heaps on floor around stoves and heaters, mattresses laid over space heaters,
blankets laid over torpedo type heaters, kerosene heaters placed under clothes
hung on a clothesline, open gas cans placed near high wattage light bulbs, etc. In
essence, solid flammable materials are substituted for liquid type accelerants.
 An unusually fast consuming fire for the time involved, and a very high burning
temperature in areas where the fire load is, in all respects, very ordinary.
 Tampering with fire protection and alarm systems. This is done to give the fire
a longer time to burn.
 Unnatural fire pattern. A fire pattern that does not follow the rules and has
burned in an unusual or unnatural sequence. Natural fires always follow the
physical laws of heat transfer and chemical combustion in a logical progression
through the fire load. Human intervention usually subverts the normal logical
progression of the fire, making the fire progression appear out of order.
 The finding of timers and incendiary devices. Timers are devices used to delay
the start of the fire so that the arsonist can get away safely,
 Tampering with heating and air conditioning equipment to enhance fire spread.
Moving air will help spread a fire through a building faster. Thus, many arsonists
make sure that the blowers are on during a fire used on the timer for the
blower’s operation.
 Tampering with utility systems. Sometimes the electrical wall outlets are rigged
to short and catch fire. The arsonist hopes to create a “V” pattern emanating
from the wall outlet, which the fire investigator will blame on electrical
shorting in the building wiring.
Fire Clues
Point of Origin (POO): Defined as where the fire originated. Burn patterns and
other damage can help determine the point of origin, or the location where
the fire started.
 Cause of fire may be near the POO.
 Fire usually burns longer at POO.
 If accelerants or ignition devices used, they may be present at the POO.
 Multiple POO’s MAY indicate arson.
 “V” patterns usually point to the POO.
 Extensive ceiling damages may be present above the POO.
Methods to detect point of ignition
1. Depth of charring
2. Spalling of plaster
3. Distortion and meting of glass, plastic and metals
4. Damage to concrete
5. Funnel or V pattern
6. Ceiling damage
7. Holes in floor or Chimney effect
8. Curing of soots
 Fire Patterns
1. Char Patterns – Created by very hot fires that burn very quickly
and move fast along its path, so that there can be sharp lines
between what is burned and what isn't.
 A char pattern on a door would help an investigator determine
which side of the door the fire was on.
 A char pattern on the floor would help investigators determine
the use of an accelerant and its path.
2. V-Patterns - Fire burns up, in a V-shaped pattern, so a fire that
starts at an outlet against a wall leaves a char pattern that points
to the origin.
 A very narrow V-shape might indicate a fire that was hotter
than normal, such as one helped along by an accelerant.
 A wide V-shape might indicate a fire that was slow burning.
 A U-shape could indicate that there was a "pool of origin" rather
than a point of origin, such as might be caused by, say, a puddle
of gasoline.
3. Chimney Effect - Since fire burns upwards, there can be a "chimney
effect" where the fire ignites at a point, the superheated gases rise
upward and form a fireball, which continues straight up to burn a hole
in the ceiling. If the roof is not entirely burnt, and the fire investigator
finds such a hole, the origin of the fire could be directly underneath.

 Color of smoke – Determine what type material was burning

 Color of flames – Indicates at what temperature the fire was burning.
 Heat Shadows - Occur when heavy furniture shields part of a wall; can
help determine the origin point.
 Glass - Glass fragments, windows, and light bulbs can provide clues to a
fire.
 Light bulbs tend to melt toward the heat source, so the "direction of
melt" can indicate the direction of the fire.
 The shattered or cracked glass of the windows can provide
indications as to how a fire burned.
 A dark soot layer on the glass could indicate a slow, smoldering fire.
 Clear glass with an abnormal pattern of cracking could imply a very
hot fire, possibly due to an accelerant.
Accident or Arson?
 Accidental Nature
 Heating System
 Electrical appliances
 Lightning
 Children playing with matches
 Smoking
 Non-Accident
 Odors – Gas, kerosene, or other accelerants
 Furnishing – Removal of personal objects and valuables
 Locked windows, blocked doors
 Two or more points of origin
 Look for v-patterns (can be a sign that an accelerant was used)
 Floors charred –Can indicate use of an accelerant
 Trailers that lead the fire from one place to another
Live or dead at time of arson
If person is alive during a fire, there is usually a-
1. Deposit of soot in the nose, mouth, or throat, indicating that he person was
still breathing during the fire.
2. Elevated levels of carbon monoxide in the blood also indicate he person
was breathing after the fire was burning.
3. Additionally, most victims of the fire itself are found face down, except on
bed or on other pieces of furniture.
4. In fire deaths, the body is often found in a “pugilistic attitude” in which the
arms are drawn in and the hands curled up on what looks like a defensive
posture of a boxer. This is a result of the heat of the fire, which can cause
the large muscles to contract.
5. The post-mortem, “boxer-like” body posture of flexed elbows and knees
and clenched fists, caused by the shrinkage of body tissues and muscle due
to dehydration caused by heating. The pugilistic attitude can be mistaken
for a pre-death attempt to shield oneself from an attacker.
6. If the death is a homicide, then evidences such as weapons and bloodstain
patterns may be left at the scene.
Collection of Evidence
1. Even in a large fire, accelerant residues of
flammable liquids may be left behind.
2. Unusual burn pattern may suggest use of liquid
accelerant.
3. Accelerant remains can be detected by tracing
the point of origin or canine use.
What evidence can be collected?
 Paper/Trash – not much evidence
 Accelerant – rapid start
 Chemical device (propellant)
 Electronic device for delayed ignition
 Unburned portions of chemical and electronic devices may be
left behind.

 Along with sample from point of origin, a control sample

should be collected. (material from a different room/location)

 Take care because most of the evidence are transient in nature

 Evidence Containers
The evidence container should have
the following qualities:
Air tight
Highly resistant to breakage
Prevents cross contamination
Good integrity seal

 Metal cans: airtight, but old cans might rust.

 Special airtight plastic evidence bags: must be properly sealed
 Glass Jars:
 At a fire scene, the presence of accelerants can be determined using
several procedures including-
 Trained dogs,
 Chemical color tests, and
 Portable instruments and sensors.
Materials such as wood and carpet absorb liquid accelerants, so
samples of these materials can harbor valuable evidence. It is
important for the investigator to collect control samples since
carpets and other synthetic materials can interfere with or lead to
false positives during laboratory analysis.
Evidence from the scene is usually collected in glass jars or
metallic paint cans that are tightly sealed to prevent vapors from
escaping. As shown in the figure on the previous page, once the
can is sealed, any volatile accelerants present will continue to
evaporate into the headspace above the debris.
Steps to Recover and Identify Accelerants

 Collect samples.
 Extract the fire debris and obtain a sample for instrumental
analysis.
 Carry out instrumental analysis.
 Interpret the results.
Scheme of Analysis
Step-1. Extraction of samples from debris
1. Direct extraction (Syringing)
2. Solvent extraction (Carbon disulphide)
3. Head space method (Passive)
4. Adsorption/elution
5. SPME
6. Distillation (Steam)

Step-2. Clean-up (if required)

1. Filtration
2. Acid stripping
Step-3. Analysis
1. GC, GC-MS
2. FTIR
3. SEM (explosive residues)
 Solvent extraction
 In a solvent extraction, the fire debris is washed with a
solvent that will dissolve the accelerant residue but not the
debris.
 The extract can then be injected directly into the GC-MS.

 A drawback of solvent extraction is that large amounts of potentially

hazardous solvents are required to perform an efficient extraction;

Although solvent extraction was at one time a popular method, it has generally
been replaced by quicker, more efficient techniques.
 Passive headspace extraction
In passive headspace extraction, the metal can used to collect
the debris is heated so that any accelerant present is
vaporized and becomes saturated within the area above the
debris in the can, which is known as the headspace. A small
hole is made in the top of the can and a gastight syringe is
used to draw up a sample of the vapor in the headspace,
which can then be injected into the GC-MS.
Passive headspace extraction is biased toward the more
volatile components, but it minimizes the capacity for cross-
contamination of the evidence because the accelerant
residue is extracted from the same container in which the
debris was collected.
Adsorption/elution
A variation of the passive headspace extraction
technique is adsorption/elution, in which the debris is
heated in the can with a strip of activated charcoal
suspended in the headspace.
The accelerant vapor is trapped on the strip, from
which it is dissolved by a solvent for injection into the
GC-MS.
Adsorption/elution is affected by the same volatility
bias as the passive headspace method, but because the
vapor is concentrated onto the charcoal strip,
adsorption/ elution greatly decreases the potential loss
of low-volatility compounds.
 Solid-phase microextraction (SPME)
 The solid-phase microextraction (SPME) technique employs a
coated fiber that is housed in a retractable apparatus.
 The can containing the debris is heated, and this fiber is subjected to
the headspace of the can, where the accelerant vapor adsorbs onto
the fiber.
 One advantage of SPME is that the fiber apparatus can be placed
directly into the injection port of the GC-MS. The heat of the
injection port causes the accelerant trapped on the fiber to desorb
from the fiber so that it can be carried into the instrument for
analysis.
 Another advantage of SPME is its potential use for on-site accelerant
collection. An investigator can use the SPME fiber apaparatus to
adsorb accelerant vapor at the fire scene; with the fiber retracted into
the apparatus, it is protected from the environment and can be
transported directly to the laboratory for analysis.
 Samples extraction methods for GC analysis
Extraction: The accelerant is extracted from the sample using some methods.
Accelerant can also be sampled directly.
1. Direct sampling: Syringe method (2ml to 2 µl)

2. Head Space method: Container with adsorbent material (Charcoal

or Tenax)
1. Cold headspace: (Pumping) The can is punctured and a syringe is used to
withdraw a headspace sample that is injected into the GC.
2. Heated headspace: (Heating) Prior to syringe introduction, the can is heated.
3. Purge-and-trap: Inlet and outlet holes are put in the can lid. A stream of
filtered air is pumped in through the inlet and a charcoal trap is placed on the
outlet. The can may be heated, and vapors are trapped on the charcoal. The
trapped compounds can be removed using heat (thermal desorption) or solvent
extraction.
 Headspace -GC
1. A technique used in the analysis of arson evidence.
2. The headspace is the air or other gas that sits over a sample (solid or liquid) that is
enclosed in a sealed container.
3. Fire debris, for example, is usually collected in paint cans, filling a portion but not
all of the can’s volume.
4. The lid is sealed, creating an enclosed air space above the fire debris.
5. Any materials that are volatile enough (evaporate at a low enough temperature)
will collect in this headspace. In an arson case, the components of interest are
any accelerants such as gasoline used to start and sustain a fire.
6. Headspaces can be cold, or the container may be heated to increase volatilization.
7. The headspace can also be dynamic, meaning that it is periodically swept out of
the container and directed over a material that can trap the components contained
in it.
8. This technique is also known as purge-and-trap.
9. In the analysis of fire debris, several variations of headspace sampling have been or
are used including cold headspace, heated headspace with collection on a charcoal
trap, collection of headspace vapors on a charcoal strip, and dynamic headspace
with a charcoal trap.
Solid Phase Microextraction (SPME)
 Charcoal strip/ Solid Phase Microextraction (SPME): A
charcoal strip or other adsorptive material is lowered into
the can or placed on an inlet drilled into the can. A vacuum
can be used to draw sample through the trap or a stream
of filtered air can be pumped into the can to force
headspace to flow out through the trap. The can may be
heated, with a thermometer inserted in the can to monitor
temperature.
 Solid phase extraction (SPE) and solid phase microextraction
(SPME) A group of related techniques used to extract
compounds from water, other liquids, or gases. It has
developed as an alternative to solvent extraction for
sample preparation.
 A simple illustration of solid phase extraction is the use of
charcoal filters to purify drinking water. The charcoal
removes contaminants from the water by adsorbing them.
This adsorption of compounds on a sorbent is similarly
exploited in solid phase extraction, in which the sample,
usually water, is passed over the sorbent to remove the
compounds of interest. The sorbent is then rinsed to
remove unwanted materials to the extent possible. The
compounds of interest are then desorbed (eluted) off the
sorbent using heat or a solvent. This solvent extract is then
concentrated down to a small volume that is ready for
analysis, most often using gas chromatography (gc) or high
performance liquid chromatography (HPLC). The process
cleans the sample and pre concentrates it since a very large
volume of sample can be passed over the sorbent. Even if this
sample is very dilute, a large volume will still deposit a
significant amount of the compound(s) of interest on the
sorbent.
 Accelerant Identification : Extraction Methods

Steam distillation
Vacuum distillation
Solvent extraction
Charcoal sampling
Swept headspace
Analysis

The vial is automatically

injected on the gas
chromatograph / mass
selective detector (GC/MSD).
The GC will separate all of the
sample’s components.
The MSD will identify the
sample’s components.

GC-MS
 An Ignitable Liquid No Ignitable Liquids
Is Detected Were Detected
1. “Sample contains a medium  We can look at this in four different
petroleum distillate (MPD), some ways...
examples are paint thinners and 1. No ignitable liquids were ever used
mineral spirits”. 2. Ignitable liquids were used to start the
fire, but have been totally consumed.
2. “Sample contains a mixture of 3. Ignitable liquids are still present;
gasoline and a heavy petroleum however, not in the collected sample.
distillate (HPD). Some examples of 4. Ignitable liquids are still present in the
a HPD are diesel fuels and heating collected sample; however, they are too
oils.” dilute to be detected.
Fire Investigation Terms
 Fire - Produced when a substance undergoes rapid oxidation involving
heat and light.
 Fire Triangle – Shows the three elements needed to produce and sustain a
fire.
 Flash Point – The lowest temperature to which a substance must be
heated in order for the substance to give off vapors which will burn when
exposed to a flame or ignition source.
 Point of Origin – The location where the fire started.
 Burn patterns –Noticeable patterns created by the fire as it burns.
 Accelerants – Substances, such as gasoline, paint thinner, and alcohol, that
accelerate the burning process.
 Convection. Convection is the transfer of heat energy by the movement of
heated liquids or gases from the source of heat to a cooler part of the
environment.
 Conduction. Conduction is the form of heat transfer that takes place
within solids when one portion of an object is heated. Energy is transferred
from the heated area to the unheated area at a rate dependent on the
difference in temperature and the physical properties of the material.
 Arson – A fire started deliberately.