COURSE MODULE Midterm Module

Philippine Countryville
College, Inc. (Formerly: Philippine Computer
College, Inc.)
P-2B, Sayre Highway Panadtalan, Maramag

Criminology Department
Forensic 3: Forensic Chemistry and Toxicology
Semester of A.Y. 2020-2021
Instructor: Mr. Edbert O. Asong R.Crim
Facebook Account: Edbert Criminology Instructor Asong

Introduction

Criminologists, law enforcement agents, investigators and law practitioners should have at least
basic knowledge in Forensic Chemistry and Toxicology, to know what evidence to collect and submit for
laboratory examination and to know how to handle forensic evidence to prove their case of their defense.
Either way, the growing relevance of Forensic chemistry and Toxicology in law is undeniable.
Rationale

1. In the investigation and solution of crime, the need for scientific data gathering and forensic
investigation has become increasingly indispensible.
Intended Learning Outcomes

A. Students will able to discuss the importance of gunshot residue

B. Students will able to perform paraffin casting
C. Students will able to explain the principles behind the paraffin test
Activity No.1
Instruction: print this module and have a separate sheet with the question and answers encoded of your
activity two (2) and prepare for yourself for the assessment as soon as limited face to face will be allowed.
Discussion
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 of combustion are
formed which includes partially burned and unburned particles. These particles are deposited on the target as
definite pattern depending upon the distance between the muzzle of the gun and the target at the time of
discharge.

Upon the 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 persons’s hands or body parts does
not mean that he/she did not discharged 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 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

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COURSE MODULE Composition of Primer
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Primer elements may be easier to detect in residues because they do not get as hot as that of powder.
(Tassa et al, 1982b).
1. Major primer elemental composition: lead (Pb), barium (Ba), or Antimony (Sb).
2. Trace element: aluminium (Al), sulphur (S), tin (Sn), calcium (Ca), potassium (K), chlorine (Cl), or
silicon (Si)
3. Inorganic compound: mercury fulminates (present in most ammunition manufactured in Eastern
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 wound 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 ingredient 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 COPPER-ZINC)
2. Bullet cores: lead, lead antimony and few iron alloy
3. Bullet jackets: brass (9:1 copper-zinc), some are iron or aluminium alloy. Some contain nickel.

GUNSHOT RESIDUE EXAMINATION

Purpose:

Gunshot residue examinations are performed to help the investigators in determining whether a person
has discharged a firearm or not; 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 small firearms

There are two types of powder used in the ammunition of small firearms. These are

1. Black powder – this consists of a mixture of carbon (Charcoal), sulphur and potassium nitrate. This
mixture is used as an igniter in smokeless gun propellant. It consists of a mixture of 15% Charcoal,
10% Sulfur and 75% Potassium nitrates. Aluminium is added to enhance the burning property. When
the powder is burned, combustion reaction takes place:

2KNO3 + 2o2 + S + C CO2 + SO2 + k2O2 + 2NO2

2. Smokeless Powder – this mixture consists of Cellulose or glycerol nitrate combined with some
stabilizers (nitrobenzene or graphite nitrates, dichromate and oxalates). When this powder explodes,
the chemical reaction takes place

Cellulose nitrate: C12H14O4(NO3)6 + 6H2O+3N2+4CO2+8CO2+H2

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COURSE MODULE Glycerol nitrate: C3H5(NO3)3 + CO2 + H2O + N2 + O2
Midterm Module

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 of acase containing an initiating explosive
such as mercury fulminate, an oxidizing agent such as potassium chlorate or barium nitrate, and a fuel such as
antimony sulphide. This component is the basis for examination 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 Nuetron
Activation Analysis (NAA), atomic absorption spectrophotometry (AAS), Scanning Electron
microscopy with energy dispersive analysis (SEM-EDA) and inductively coupled plasma with the
mass spectrophotometry (ICP-MS) are used.

History of paraffin test/dermal nitrate or Diphenylamine test

Paraffin test was originated from Cuba when Dr. Gonzalo Iturrios first used paraffin for collecting
gunpowder residues from discharged firearm. In 1933, Teodoro Gonzales of Criminal Identification
Laboratory, Mexico City introduced the test in the United States. In this test, the hands were coated with the
layer of melted paraffin. After cooling, the cast were removed and treated with Diphenylamine (5% DPA in
60% sulfuric).

Methods of Examination

Paraffin test
To determine whether a person has discharge a firearm, the paraffin-Diphenylamine test is used. The
basis of this test is the presence of nitrates in the gunpowder residue. When a warm melted wax is applied on
the hands of the alleged shooter, it will cause the pores of the skin to open and exude the particles of
gunpowder residue. These particles of gunpowder residue are being extracted by the paraffin cast (with the
use of melted paraffin wax) and will appear as blue specks, when diphenylamine reagent (DPA for brevity) is
added on the cast. It must be noted that the specks are generally located on the area of the thumb and
forefingers.

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. Others 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 characteristics of “tailing” when positive
for the presence of gunpowder nitrates.

Principle behind the Paraffin Test.

While the burned and partially burned particles (gunpowder residue) is deposited on the target and in
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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 the 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 cast 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.

Materials and Apparatus in taking Paraffin Cast

- Paraffin wax (M.P. 38-40 C)
- Absorbent cotton
- Bond paper
- Burner
- Beaker or casserole
- Tong

Procedure
a. Heat the paraffin wax in a container until it melts. Allow cooling for few minutes so that it will not
burn the skin.
b. Let the subject wash his hands with water without using any soap or detergent. Wipe the hands of the
subject with clean absorbent cotton.
c. Let the subject place his hands on clean sheet of bond paper with the palms facing downward and the
fingers closed together. Using a spoon or tong with cotton, pour the melted paraffin wax on the hands
of the subject from the thumb and index fingers and the dorsal portion to the little finger side of the
hands.
d. Cover the hands and finger thoroughly with paraffin wax and place a thin layer of absorbent cotton to
reinforce the wax.
e. Pour another layer of the wax until the absorbent cotton has totally absorbed the wax.
f. Allow the wax to cool and solidify before peeling them off.
g. When cool, direct the subject to move his fingers first and slowly moving his hands out from the
casts.
h. Place on the bond paper the case number, name of the subject, time and date, technician who took the
cast, witnesses and label the right and the left hand.
i. Place another bond paper on the top of the paraffin casts and staple together.
j. Place the paraffin casts inside an envelope or a box for proper preservation

Note:
It must be noted that upon casting, the melted paraffin wax penetrates the minute crevices of the skin
thus; the burned and partially burned gunpowder nitrates which are embedded on the hands of the shooter are
extracted. Upon application of Diphenylamine (DPA) reagent on the paraffin casts, the appearance of “tailing
deep blue specks” indicates the presence of gunpowder nitrates.

Paraffin Wax
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Is a white, translucent, tasteless, odourless solid consisting of a mixture of solid hydrocarbons of
high molecular weight. It is insoluble in water and acids and soluble in benzene, ligroin, warm
alcohol, chloroform, turpentine, carbon disulphide and olive oil. Combustible, auto ignition
temperature 473 F (245 degree C)
- The melted paraffin wax penetrates the minute crevices of the skin upon application, thus,
adhering if there are particles present. When the casts are peeled, the burned and partially burned
particles are extracted. A person firing a gun will likely have the particles located above the thumb
and forefingers since these are the surfaces exposed to the gun.

What should be noted in the interpretation of results:

Time or reaction
- Number and characteristics of blue and minute specks
- The location and character of the blue specks
- Distribution and location
Different names of this test:
- Lunge’s test
- Diphenylamine test
- Dermal nitrate test
- Gonzales test- named after the one who improved the test

Substance gives false positive result:

1. Fertilizers
2. Explosives
3. Tobacco
4. Urine
5. Certain cosmetics
6. Food samples
7. Cigarettes

Factors that contributes negative result in paraffin test

1. Types of calibre of ammunition
2. Use of gloves
3. Length of the barrel
4. Age of the gun/efficiency of mechanism
5. Direction of firing
6. Wind direction and velocity
7. Humidity/percentage moisture in air
8. When 72 ours had already lapsed (3days)

Exercise No.2
Instruction: answers must be encoded with name and section
1. Discuss briefly the principles behind the Paraffin test.10pts
2. Is there any means of removing these nitrates from the hands? How long will they stay in the pores?
10pts
3. Is paraffin test result conclusive evidence? Why? 15pts
4. Discuss the following factors which contributes negative result in paraffin test
a. Types of calibre of ammunition

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COURSE MODULE b. Use of gloves
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c. Length of the barrel

d. Age of the gun/efficiency of mechanism
e. Direction of firing
f. Wind direction and velocity
g. Humidity/percentage moisture in air
h. When 72 ours had already lapsed (3days)

False Positive reaction - smear of blue color or a conglomeration of blue speaks on both dorsal and palm
aspects of the hand.

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 test has some value due to psychological effect on the persons whose hands
were found positive. Also, the finding of actual traces of gunpowder nitrates on the hand/s of the person does
not conclusively determine or establish that he has discharged a gun. It is possible that the GPR particle may
have been blown on the hand directly from the barrel of the gun being discharged by another person.

Assessment
Interview/oral recitation with the questioners
Demonstrations.
Online quiz/ Google form
Examination

Resources and Additional Resources

 Essentials of Forensic Chemistry and Toxicology (In Criminal Justice System) Revised edition
By: Arlyn M. Dascil-Cañete
 Forensic Chemistry and Toxicology
By: Alexander De Asis Urbano
 Forensic Chemistry Laboratory Manual
By: Leob Carlo B. Rondina, Ph.D
Irish A. Pioneta, MCJ (CAR)
Althea Lou F. Espero, MSCrim (CAR)

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