LESSON 7.

GUN POWDER RESIDUE AND PARAFFIN TEST

• Basically, gunshot residue comes from the powder component of bullet, elements from cartridge cases and gun
barrel where the bullet passes.

• When these components are burned, certain products combustion are formed which includes partially burned
These particles are d deposited and unburned particles.

• These on the target as definite pattern depending upon td distance between the muzzle of the gun and the
target at the time of discharge.

• Upon discharge of firearm, gunpowder residues (nitrates) may be deposited on a person at close proximity, so
the interpretations as to who discharged the firearm should be made with caution. (Thorton, 1986).

• Hand or body part close to the fired weapon may have gunpowder residues consistent with having discharged
the weapon.

• However, absence of gunpowder residues on the person's hands or body parts does not mean that he/she did
not discharge a firearm.

• Gunpowder residue may be found on the skin or clothing of the person who discharged the gun, on the
entrance bullet hole of garment or wound of the victim, or on other target materials at the scene.
Components of
gunshot residue

1. Primer or lead
residue

2. Gunpowder
residue

3. Elemental
component from
cartridge cases
residues.
Composition of Primer
Primer. may be easier to detect in
residues elements may be because they do not
get as hot as that of powder. (Tassa et al, 1982b)

1. Major primer elemental composition: lead

(Pb), et al, 1982b). barium (Ba), or Antimony (Sb).
2. Trace element: aluminum (Al), sulfur (S), tin
(Sn), , calcium (Ca), potassium (K), chlorine (CI), or
silicon(Si)
3. Inorganic compound: mercury fulminates
(present in most ammunition manufactured in
Éastern Europe and used in Middle East).

In addition, these residues gradually

adhere to the discharged bullets. Thus, primer
residue can be found in targets or wounds at
considerable distance from the muzzle up to 200
meters.
Composition of gunpowder
1. Contains up to 23 organic
compounds (FBI study)
2. Nitrocellulose is virtually always
present along with nitrate and nitrogen
containing compound such as
Diphenylamine or DPA (stabilizer in the
powder).

Types of gunpowder
1. Single based- when the basic
ingredients is nitrocellulose
2. Double based - nitrocellulose + 1 to
40% nitroglycerine
3. Triple based - nitrocellulose +
nitroglycerine nitroguanidine.

These can be differentiated

using a mass spectrophotometer.
Composition of cartridge case,
bullet coating and metal jacket
1. Cartridge and primer cases; BRASS
(7:3 and ZINC) COPPER

2. Bullet cores: lead, lead, antimony and

few iron alloy

3. Bullet jackets: brass (9:1 copper-zinc),

come are iron or aluminum alloy. Some
contain nickel.
GUNSHOT RESIDUE EXAMINATIONS
Purpose
Gunshot residue examinations are performed to help the investigators in determining; whether a
firearm was discharged or not; and the possible gunshot range or the distance of the shooter to the victim.
Both hands of the suspect as well as those of the victim, the firearms and clothing of the victim must be
examined to determine the presence of gunpowder nitrates.
Types of Powder used in the ammunition of 2. Smokeless Powder - This mixture
small firearms consists of Cellulose or glycerol nitrate
combined with some stabilizers
There are two types of powder used in the ammunition (nitrobenzene or graphite nitrates,
of small firearms. dichromate and oxalates). When this
powder explodes, the chemical
These are:
reaction takes place
1. Black Powder - this consists of a mixture of carbon
(Charcoal), sulfur and potassium nitrate. This Cellulose nitrate: C12H1404(NO3}6
mixture is used as an igniter in smokeless gun +6H20+3N2+4CO24+8C0+H2
propellant. It consists of a mixture of 15% Čharcoal,
10% Sulfur and 75% Potassium nitrates. Aluminum is
added to enhance the burning property. When this
Glycerol nitrate:
powder is burned, combustion reaction takes place: C3H5(NO3)3+C02+H20+N2+02

2KNO3 + 2o2 + S + C CO2 + SO2 + k202 + 2NO2

Primers

To explode a low explosive, flame is required. In guns, the

flame is applied by means of a primer. Primer produces flame on
percussion. A typical primer consists such as mercury fulminate, an
oxidizing agent such as potassium chlorate or barium nitrate, and a
fuel such as antimony sulfide. This component is the basis for residues
for determination. of gunshot residue particularly primer residues for
distance determination .
DETECTION OF GUNSHOT RESIDUE

The following are common methods used by most crime laboratories to detect gunshot residue:

1. Paraffin test

2. Lead residue (detection limit: up to 30 feet and always present on the opposite sides of the penetrated
target). Reported from intermediate glass target present (Messler and Armstrong, 1978).

3. Gunpowder residue examination (detection limit: highly variable up to 20 cm, and up to 21 inches is
common)

4. Other examinations

The last two methods are classical. Color development or modern methods such as Neutron
Activation Analysis (NAA), atomic absorption spectrophotometry (AÀS), Scanning, Electron Croscopy with
energy dispersive analysis (SEM- BDA) and inductively coupled plasma with mass Spectrophotometry (ICP-
MS) are used.
History of Paraffin test/dermal Methods of Examination
nitrate or Diphenylamine test
Paraffin Test
• Paraffin test was originated from Cuba
Dr. Gonzalo Iturrios first used paraffin To determine whether a person has discharged a
for collecting gunpowder residues from firearm, the Paraffin-Diphenylamine test is used, The basis
discharged firearm. of this test is the presence of nitrates in the gunpowder
residue. When a warm melted paraffin wax is applied on
• In 1938 Identification Teodoro the hands of the alleged shooter, it will cause thể pores of
Gonzales of Criminal Identification the skin to open and exude the particles of gunpowder
Laboratory Mexico City introduced the residue. These particles of gunpowder residue are being
test in the United States, this test, the extracted by the paraffin cast (with the use of melted
hands were coated with a láyer of paraffin wax) and will appear as blue as specks, when
melted paraffin. diphenylamine reagent (DPA for brevity is added on the
cast. It must be noted that the specks are generally located
• After cooling, the casts were removed on the area of the thumb and forefingers
and treated with Diphenylamine, (5%
DPA 60% sulfuric)
Note:

-The blue color that appears

indicates the reaction of nitrates
with diphenylamine reagent.
Thus, nitrate from other sources
like fertilizers will give the same
reaction. Other substances
similar to nitrate known as
Oxidizers will also react with the
reagent in the same way.

However, it must also be noted

that the blue specks have the
characteristic of “tailing".
What is the Principle behind the Paraffin test?
While the burned and partially burned particles (gunpowder residue) is deposited on the target and in the barrel of the
gun some of these burned and partially burned particles may escape around the breech of the gun and some may be
embedded on the exposed surface of the hand/s of the person discharging the firearm

Thus the presence of these residues can be detected by way of paraffin examination.

As a rule, in paraffin examination, the Forensic Chemist/ Chemical officer should personally conduct the paraffin casting
on the alleged shooter. However a competent laboratory technician under the supervision of the examiner-on-case may
also perform the paraffin casting. But it is the Forensic Chemist/Chemical officer who should examine the paraffin casts
taken from both hands of the alleged shooter to determine the presence of gunpowder nitrates.

Paraffin casting of the alleged shooter shall only be done within seventy-two (72) hours from the time of the alleged
shooting incident. No person shall be subjected to paraffin casting after the lapse of the specified period.

Embalmed cadaver who allegedly discharged a firearm shall no longer be subjected to paraffin examination because of the
impossibility of extracting the gunpowder nitrates from the former's hands.
 Paraffin Wax
Note:
Paraffin wax -is a white, translucent, tasteless odorless solid consisting
It must be noted that upon casting, of a mixture of solid hydrocarbons of high molecular weight. It is
the melted paraffin wax penetrates insoluble in water and acids and soluble in benzene, ligroin, warm
the minute crevices of the skin alcohol, chloroform, turpentine, carbon disulfide, and olive oil.
thus, the burned and partially
burned gunpowder nitrates which Combustible, auto ignition temperature 473 F (245 degree C) The
are embedded on the hands of the melted paraffin wax penetrates the minute crevices of the skin upon
shooter are extracted. Upon application, thus, adhering if there are particles present.
application of Diphenylamine (DPA)
reagent on the paraffin casts, the When the casts are peeled, the burned and partially burned particles
appearance of "tailing deep blue are extracted. A person firing a gun will likely have the particles
specks" indicates the presence of located above the thumb and forefingers since these are the surfaces
gunpowder nitrates. exposed to the gun.
 Question:
What should be noted in the interpretation
Is there any means of removing nitrates from the hands?
of results:
How long will they stay in the pores?
Time of reaction
Answer:
None. Ordinary washing will not remove the nitrates from
• Number and characteristic of blue and
the pores of the skin. Usually, gunpowder nitrates that are
minute specks
embedded on the skin stay for 72 hours.
• The location and character of the blue
That is why paraffin casting should be conducted within the
specks
specified period.
• Distribution and location
Different names of this test:
Substances giving false positive result
Lunge's test
1. fertilizers
Diphenylamine test
2. explosives
Dermal nitrate test
3. tobacco
Gonzales test - named after the one who 4. Urine
improved the test 5. certain cosmetics
6. food samples
7. cigarette
 Question:
Question: Is paraffin test result a conclusive evidence? Why?

Will these substances not give positive Answer: No. It is just a corroborative evidence which intends to
result for paraffin test? support the testimony of eyewitness/ es, There are instances
wherein a person who actually discharged a firearm would still give
Answer: If the hands of the subject a negative result to the paraffin test because of several factors.
person are contaminated with nitrates
other than from gunpowder, one will Question:
expect to find smudges or just a smear
What are these factors?
of blue color or a conglomeration of
blue specks. Answer:
1. Types of caliber of ammunition
But nitrate from gunpowder appear 2. Use of gloves
as blue speck with tailing because 3. Length of the barrel
these particles were embedded into 4. Age of the gun/efficiency of mechanism
the hands with force. 5. Direction of firing
6. Wind direction and velocity
7. Humidity /percentage moisture in air
8. When 72 hours had already lapsed (3 days)
Types of caliber of ammunition. False Positive result

A hand discharging a revolver is 1. Contamination or transfer of

more likely to give a positive result for gunshot residue (GSR) to the body
gunpowder nitrates compared to that of a by mishandling, or when the body
hand discharging a pistol. is heavily contaminated by GSR
In an automatic pistol, the chamber from previous shooting.
is an integral part of the barrel, whereas in the 2. Washing of hands where samples
revolver, the chamber is located in the cylinder are collected
separated from the barrel with airspace. 3. Type of ammunition such as rifle
Thus, leakage of powder in a and shotgun
revolver is more likely to occur

Length of the barrel. Age of the gun/efficiency of mechanism.

A weapon of 2-inch barrel will deposit residue over a larger Complete combustion or the conversion of into its
area than a weapon of 5-inch barrel (even if they are end product (CO,CO,N,O,-OH) is more likely to
discharged from the same distance with the same type of occur in a new weapon compared to an old one.
ammunition). In a longer barrel, the hand is farther away Besides, leakage of gunpowder is more likely to
from the muzzle end of the gun. It takes a bullet to travel in happen in the old weapon where the breech
more time, thus using up/burning up more, if not all, of the mechanism is no longer tightly fitted.
nitrates. In short barrel, the bullet travels through the barrel
in less time leaving behind a greater amount of unburned
particles.
Direction of firing. Humidity/percentage moisture in air
More powder residues will be Humidity lessens the extent of combustion yielding more gunpowder
obtained when the gun is nitrates.
discharged pointing upward than
downward. Gunpowder residues False Positive reaction - smear of blue color or a conglomeration of blue
have weight and will naturally fall specks on both dorsal and palm aspects of the hand.
down because of gravity.
Failure to find traces of nitrate on the hand of the person does
not prove that he did not fire a gun. But it is submitted that the paraffin
Wind direction and velocity. test has some value to the psychological effect on the persons whose
hand were found positive. Also, the finding of actual traces of
In high velocity( strong wind), the gunpowder nitrates on the hand/s the person does not conclusively
powder residues will be blown in determine or establish that he has discharged a gun. It is possible that
the In high velocity direction of the the GPR particle may have been blown on the hand directly from the
wind. One is more likely to be barrel of the gun being discharged by another person.
positive for gunpowder nitrates
there is no wind, or the wind
direction is towards the shooter.
Gunpowder Residue Test
on Firearms Established Forensic Rules:

The diphenylamine a. The Forensic Chemist on case shall conduct

reagent is also applied to cotton
swabbing of the barrel and
the gunpowder residue examination (GPR)
chambers of the gun to determine without delay.
if the firearm was discharged. A
deep blue color resulting from the
reaction of nitrates with the
a. After the examination is done, the firearm
reagent indicates presence of shall be returned to the representative of the
gunpowder residue. requesting unit if the request is solely for
gunpowder residue (GPR) examination, or
submitted to the FAID if ballistic examination
is required.
 Importance of Distance Determination
Gunshot Range (GSR) 1. In connection to self-defense pleas
Determination Distance determination . –
2. In the distinction between murder and
suicide. It is possible to state with
(Also known as gunshot distance the method of
certainty the distance of the gun from
determination) determining the distance
the target by means of the patterns
between the firearm and the
and residues left on the target. Not
When a firearm is target.
only the type of gun, but also the
discharged, gunpowder residue This is usually based
condition and type of ammunition that
may also be deposited on the on the distance of the powder
will affect this pattern.
clothing of the victim. The size and patterns or the spread of the
density of the pattern of shot pattern.
In ascertaining the gunshot
gunpowder residue found on the range (GSR) the examiner should note and
clothing are the main factors observe the following:
considered in determining the
approximate distance of the 1. Entrance and Exit holes
shooter to the victim. As the
distance to the victim increases the 2. Powder residue pattern (Burning,
size of pattern expands while singeing, smudging, tattooing a black
density decreases aria vice-versa. coarsely peppered pattern)
Entrance and Exit holes:

• Entrance hole contains

gunpowder residue (bullet wipe
residue) and it is slightly burned.
The diameter of entrance hole
is smaller than the exit hole.

• The exit hole is frayed outward

while entrance hole is inward.

Other Entrance hole characteristics:

a. Angled bullet entrance hole has

elongated hole.

b. Contact fires have uneven margins but

all entrance holes typically have even
margins.

c. Grazing bullet hole (several small holes

created from a folded garment)
Classification of gunshot
distance
• Burning (direct)
• Singeing (1 to 2 inches)
• Smudging (2 to 8
inches)
• Tattooing (8 to 18
inches)
The distance of the muzzle of the gun to
the target is classified into three (3): Tests for Gunshot Residue (GSR)

1. Direct contact • Nitrite and

2. 2 inches to 36 inches away • Lead residue chemical
3. 36 inches away or more examination

Characteristics of Gunshot wounds

b. Wounds inflicted at a Distance from 2-36 inches:
a. Direct/Contact wounds
If the gun discharged closely to the body of the
The principal damage is more
victim two( 2) types of discoloration will be observed around
visible due to the flame and the muzzle
the hole of the entrance namely:
blast than to the penetration of bullet.
(1) smudging and
(2) powder tattooing (black coarsely pepper pattern)
The following observations may be noted:
1. Gaping hole where fabric is badly torn
Smudging is produced when the gun is held from
2. Blackened area surrounding the bullet
about 2 inches to the maximum of 8 inches. The smoke and
hole
soot from the burned pores are deposited around the hole of
3. The presence of partially burned
the entrance producing a dirty appearance.
powder residues around the entrance
hole
The size of the smudge depends upon the following’
A. Length of the barrel:
Weapon of 2-inch barrel will deposit residue over a larger area than a weapon of 5-inch barrel (even if they are fired from the
distance with the same type of ammunition in a longer barrel, the hand is farther away the muzzle end of the gun. It takes a
bullet to o travel in more time, thus, using up/burning more, if not all, of the nitrates. In á short barre the bullet travels
through the barrel in less time leaving greater mount of unburned particles.

B. Age of the gun/efficiency of mechanism.

Complete combustion or the conversion of all nitrates into its end product is more likely to occur weapon compared in a new
to an old one. Besides, leakage of gunpowder is more likely to happen in the old weapon where the breech mechanism is no
longer tightly fitted

c Direction Firing.
More powder residues will be obtained when the gun is fired upward than downward. Gunpowder residues have weight and
will naturally fall down because of gravity.

D. Wind and Velocity.

In high velocity Direction (strong wind), the powder residues will be blown in the direction of the wind. One is more likely to
be positive for gunpowder nitrates if there is no wind, or the direction is away from the body.

E. Humidity/percentage moisture in air.

Humidity lessens the extent of combustion yielding more gunpowder nitrates.
Powder tattooing produces black coarsely peppered pattern. Individual specks of tattooing around the
hole are visible by the naked eye.

The area of blackening around the perforation Will be found to diminish in size as the muzzle of
the gun is held further away from the target.

Take note that the size of the area of powder tattooing will also depend on the following:
Caliber
Powder charge
Distance of firing

Individual specks of tattooing around the hole are visible are visible to the naked eye. The area
of blackening around the perforation will be found to diminish in size as the muzzle of the gun is held
further and at the distance of 8 inches, blackening around the hole will completely disappear . A few
individual specks of tattooing will be visible to the naked eye.
C. Wounds inflicted at a Distance of more than 36 inches:

• Powder tattooing is seldom present

• Nitrates found will not be sufficient for GSR

Bullet Comparison - a type of examination using of an empty shell containing characteristic marks a microscope which
is commonly used in comparison of an empty shell containing characteristic marks from groves of the gun barrel and
firing pin of specific firearm used.

Other methods of examination - To determine whether the victim was holding a firearm, one method used is by
spraying the hands of the victim with ferrozine spray to determine the presence of iron traces. (Lee, 1986)
Hydroxyguinoline test with fluorescent can also be used. (Stevens and Messle 1974).

A suicide victim's hands are stained with orange- brown color upon contact with gun barrels following death,
presumably from perspiration with prolonged post-mortem interval of intact.

Latent fingerprints can be detected in cartridge and expended shell casing. It is latent because the substance from
perspiration, mixed with oils from sebaceous glands, are transferred via a substance on the skin ridges to an object.
increase of temperature and low humidity decreases persistence of fingerprints. Brass retains fingerprint than nickel-
plated materials. (Given, 1976)
FIREARM EXAMINATION

Methods used to determine the probable time the firearm has been discharged:

a. Lucas test
A characteristic smell that decreases in intensity with lapse of time is present immediately after firing but
even after several weeks some slight smell remains.

b. Odor (Hydrogen Sulfide)

This is another product resulting from combustion of gunpowder which is present in the gaseous state. This
compound can be detected by means of lead acetate paper test.

If the breech of the gun is kept closed, this persists between 2-3 hours

Sulfide - the greater part disappears in about 4-5 hours but frequently a trace remains for a longer time. the
longest period being 10 hours.
c. Odor of the Barrel (rusting)
As a rule, no rust can be detected inside the barrel of a firearm if such firearm has not been discharged. But if
the firearm has been discharged, iron salts are formed and can be detected inside the barrel. These iron salts are soon
oxidized resulting in the formation of rust. The formation of rust is affected by the humidity of the air so that in the
interpretation of the result, this factor must always be considered.

d. Presence of Nitrates (by cotton swabbing method)

Nitrates diminish after a lapse of time. Nitrates can be detected by swabbing a portion of residue in a barrel
and mixing the residue with Diphenylamine solution (DPA).

e. Dermal Nitrate test

The test is designed to determine the presence of gunpowder nitrates on the hands of the alleged shooter.
 COLLECTION, PRESERVATION AND TRANSIT OF SPECIMEN

Other Methods of Examination Important points to remember in the collection, preservation and
transit of specimen:
The following are the sophisticated
instruments used to determine the gunshot a Clothing removed from the victim should be cautiously and
range residue carefully handled to prevent powder residues from becoming
dislodged.
b. Do not wad the specimen or pack it loosely for shipment.
• (GSR): AAS -Atomic Absorption c. Secure the area to be tested between two layers of heavy
Spectrophotometer cardboard fastened together tightly to prevent the specimen from
• NAA- Neutron Activation Analysis becoming postlude about in the transit.
• SEM-EDX -Scanning Electron Microscope d. Each specimen should be wrapped tightly and marked.
with Energy Dispersive X-ray Analysis e. Clothing heavily smeared with blood should be dried thoroughly
• ICP-MS - Inductively couled plasma with before packing.
Mass Spectrophotometry f. Gun recovered from the scene of the crime and ammunition
available should be preserved.
g. Person suspected to have discharged a firearm should be
subjected to a paraffin test. (Cover his hands with paper bags to
avoid contamination). Examination must be performed immediately
and in no case should it be postponed 72 hours after the shooting.