FORENSIC CHEMISTRY AND TOXICOLOGY
CHAPTER 4 - LESSON I – GUNSHOT AND GUNPOWDER RESIDUE
Lesson Outcome:
At the end of this lesson, students must have:
1. Identified the components of gunshot residue.
2. Explained the different aspects and methods of examination of gunshot residue.
Topic Outline
1. Components of Gunshot Residue
2. Components of Primer
3. Composition of Gunpowder
4. Gunshot Residue Examination
5. Detection of Gunshot Residue
6. Paraffin test
7. Firearm examination
8. Collection, Preservation, and Transit of Specimen
Gunshot Residue
● Defined as the total residues resulting from the discharge of a firearm.
Components of Gunshot Residue
1. Primer or lead residue
2. Gunpowder residue
3. Elemental component from cartridge residue
Figure 1. Component of a bullet
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Composition of Primer
Three major components in the primer compound play major roles in identification of Gunshot Residue
(GSR):
1. The initiator: Lead styphnate, which is set off with a sharp blow, as when the firing strikes the
primer cap.
2. The oxidizer: Barium nitrate, which gives up its oxygen readily. The oxygen is needed to burn the
fuel.
3. The fuel: Antimony sulfide, which burns at a very high rate. This initial burn ignites the gunpowder,
which propels the bullet.
Gunpowder – classified as low explosive because of its slow decomposition rate and low brisance.
Composition of Gunpowder
1. Contains up to 23 organic compounds (according to FBI study)
2. Nitrocellulose is virtually always present along with nitrate and nitrogen containing compound such as
Diphenylamine or DPA (stabilizer in powder).
GUNSHOT RESIDUE EXAMINATIONS
Primary Objectives of gunshot residue detection:
a. Determine if an individual fired or handled a recently discharged firearm
b. Determine whether the surface was in close proximity to a weapon during discharge
c. Determine the muzzle-to-target distance
Types of Powder used in the ammunition of small firearms
1. Black Powder
2. Smokeless Powder
Black Powder
● Is an explosive mixture of sulfur (10%), charcoal (15%) and potassium nitrate (KNO3) (75%) that
burns rapidly, producing volumes of hot solids and gases which can be used as a propellant in firearms
and as a pyrotechnic composition in fireworks.
Smokeless Powder
● Modern smokeless powder contain nitrocellulose as oxidizing agents. Other ingredients may be added
to increase performance, or chemical stability, to facilitate processing and handling, or to minimize
muzzle flash.
FORMATION OF GUNSHOT RESIDUE
The gases, vapors and particulate matter formed by the discharge of a cartridge in a firearm are
collectively known as gunshot residue (GSR). Anything present in the cartridge, and even the firearm itself,
may contribute to the residues, which therefore contain both organic and inorganic components. The main
sources of the inorganic components are the bullet and the primer composition, and the main source of the
organic components is the propellant. GSR are therefore a complex heterogeneous mixture. The detection,
identification and quantification of GSR can provide significant evidence in several areas associated with
incidents involving the use of firearms.
Gunshot residue (GSR) will attach to the shooter’s hands and clothing via impact because they are in
such close proximity to the weapon when it is fired. However, absence of gunpowder residues on the person’s
hands or body parts does not mean that he/she did not discharge a firearm.
COLLECTION OF GUNSHOT RESIDUE
Hand Sampling Methods include:
1. Swabbing – using cloth, cotton wool or filter paper, moistened with dilute acid.
2. Washing – using very dilute acid.
3. Film lifts – using a paraffin ‘glove’, or film-forming polymers.
4. Adhesive lifts – using adhesive tape or adhesive stubs.
DETECTION OF GUNSHOT RESIDUE
The following are common methods used by most crime laboratories to detect gunshot residue:
1. Paraffin test
2. Lead residue examination
3. Gunpowder examinations
Figure 2. Spread of shot pattern after firing a shotgun at different distances from a cloth target. Muzzle
(a) in contact with cloth, (b) 2 feet, (c) 6 feet, (d) 10 feet
and (e) 15 feet from the cloth.
QUALITATIVE AND QUANTITATIVE TECHNIQUES TO DETECT GUNSHOT RESIDUE
1. Paraffin test
2. Modified Greiss test
3. Neutron Activation Analysis
4. Flameless Atomic Absorption Spectroscopy
5. Scanning Electron Microscopy coupled with Energy Dispersive X-ray
6. Inductively-Coupled Plasma Mass Spectrometry
1) PARAFFIN TEST (Dermal nitrate or Diphenylamine test)
The first method for determining whether or not someone had fired a gun by GSR was the paraffin test,
also known as the dermal nitrate or diphenylamine test. Teodoro Gonzalez of the Criminal Identification
laboratory in Mexico City first applied this test in the United States in 1933. The test was performed by
covering a suspect's hand with a layer of paraffin, which, after cooling, could be broken off and the paraffin
treated with an acid solution of diphenylamine, a reagent used to detect the presence of nitrates or nitrites.
A positive result would then be read as blue flecks on the wax. Although this did provide positive results for
those who fired a gun, it also gave positive results for others who may have come in contact with nitrates
or nitrites from other sources, substances common in acid rain, fertilizers, waste water, and sewer lines.
a) Method of Examination of Paraffin Test
To determine whether a person has discharged 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 paraffin 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 is added on
the cast. It must be noted that the specks are generally located on the area of the thumb and forefingers.
b) Principle of 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 those 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 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.
2) MODIFIED GREISS TEST
This test detects nitrite compounds, which are a by-product of the combustion of cellulose nitrate, the
primary component of gunpowder. Nitrite compounds are transferred from the surface of interest onto a piece
of chemically treated paper with a white background, resulting in a series of pinpoint orange color reactions
representing a mirror image of the locations of the nitrite compounds on the surface.
Figure 2. Nitrite residues have been transferred from a surface
onto a piece of chemically treated paper, where they react to
form the orange dots that are visible in this image. This transfer
is particularly helpful when the surface in question is dark-
colored.
3) NEUTRON ACTIVATION ANALYSIS (NAA)
Neutron activation analysis is the most effective technique for the detection of antimony
(Sb) and barium (Ba) of gunshot residues on the hands of a suspect. However, this method is not currently
used due to complex nature of the statistical treatment of the data required for these calculations.
4) SCANNING ELECTRON MICROSCOPY (SEM)
Scanning electron microscopy coupled with wavelength or energy-dispersive x-ray detection (WDX or
EDX) has since been extensively applied to GSR analysis and has become the internationally accepted analysis
method.
The reliability of SEM techniques is based on the detection of lead (Pb), antimony (Sb), and barium (Ba)
in discrete particles originating from the primer.
5) FLAMELESS ATOMIC ABSORPTION SPECTROMETRY (FAAS)
Flameless atomic absorption spectrometry is the most popular for the quantitative determination of
elements associated with gunshot residue such as lead, antimony, barium, copper, and mercury.
Gunpowder Residue Test on Firearms
The diphenylamine reagent is also applied to cotton swabbing of the barrel and chambers of the gun to
determine if the firearm was discharged. A deep blue color resulting from the reaction of nitrates with the
reagent indicates presence of gunpowder residue.
Established Forensic Rules in GPR Determination
a. The Forensic Chemist on case shall conduct the gunpowder residue examination (GPR) without delay.
b. After the examination is done, the firearm shall be returned to the representative of the requesting unit
if the request is solely for
Gunshot Range Determination
When a firearm is discharged, gunpowder residue may also be deposited on the clothing of the victim.
The size and density of the pattern of gunpowder residue found on the clothing are the main factors
considered in determining the approximate distance of the shooter to the victim. As the distance to the victim
increases, the size of pattern expands while density decreases and vice-versa.
The clothing must be carefully packaged so as not to dislodge any GSR particles. The packaging technique
that best accomplishes this is to place clean wrapping paper on each layer of the clothing. Clothing should be
placed in a box, and folding avoided as much as possible. For GSR pattern determination of the range of fire,
the firearm and matching ammunition must be submitted to the laboratory.
Distance determination – the method of determining the distance between the firearm and the target. This
is usually based on the distance of the powder patterns or the spread of the shot pattern.
Importance of Distance Determination
1. In connection to self-defense pleas
2. In the distinction between murder and suicide. It is possible to state with certainty the distance of the
gun from the target by means of the patterns and residues left on the target. Not only the type of gun,
but also the condition and type of ammunition that will affect the pattern.
In ascertaining the gunshot range (GSR) the examiner should note and observe the following:
1. Entrance and exit holes
2. Powder residue pattern (Burning, singeing, smudging, tattooing – a black 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 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):
1. Direct contact
2. 2 inches to 36 inches away
3. 36 inches away or more
Characteristics of Gunshot Wounds
a. Direct/Contact wounds
The principal damage is more visible due to the flame and the muzzle blast than to the penetration of
bullet. The following observations may be noted:
1. Gaping hole where fabric is badly torn
2. Blackened area surrounding the bullet hole
3. The presence of partially burned powder residues around the entrance hole
b. Wounds inflicted at a distance from 2-36 inches
If the gun is discharged closely to the body of the victim, two types of discoloration will be observed
around the hole of the entrance namely:
1. Smudging
2. Powder tattooing (black coarsely peppered pattern)
Smudging – produced when the gun is held from about 2 inches to the maximum of 8 inches. The
smoke and soot from the burned pores are deposited around the hole of the entrance producing a dirty
appearance.
Factors that affect the size of the smudge:
A. Length of the barrel
A 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 from the muzzle end of the gun. It takes a bullet
to travel in more time, thus, using up/burning up more, if not all, of the nitrates. In a
short barrel, the bullet travels through the barrel in less time leaving behind a greater
amount 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 in a new weapon compared to an old one. Besides, leakage of gunpowder more
likely to happen in the old weapon where the breech mechanism is no longer tightly fitted.
C. Direction of 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 Direction and Velocity
In high velocity (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.
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.
Scorching or Singeing
If a firearm was discharged very close to the target as in a case of alleged suicide and travelstraveled
only a short distance from it. This distance will vary with the length of the barrel, the size of the powder charge
and the degree to which the bullet fill the barrel.
The presence of scorch is a proof that the firearm was discharged a few inches away from the target. Scorching
is very rare if the victim was shot 3 inches or more away from the muzzle.
COLLECTION, PRESERVATION, AND TRANSIT OF SPECIMEN
Important points to remember in the collection, preservation and transit of specimen:
A. Clothing removed from the victim should be cautiously and carefully handled to prevent powder
residues from becoming dislodged.
B. Do not wad the specimen or pack it loosely for shipment.
C. Secure the area to be tested between two layers of heavy cardboard fastened together tightly to
prevent the specimen from becoming postlude about in the transit.
D. Each specimen should be wrapped tightly and marked.
E. Clothing heavily smeared with blood should be dried thoroughly before packing.
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.
References:
Arlyn M. Dascil-Canete. (2014). Forensic Chemistry and Toxicology. An essential tool in effective Criminal
Justice System. Revised and Expanded Edition.
Marilyn T. Miller (2018). Crime Scene Investigation. Laboratory Manual. 2nd Edition.
P.C. White (2004). Crime Scene to Court. The Essentials of Forensic Science – Royal Society of Chemistry. 2nd
Edition.
