Yatar,Lilia Rosa T.

March 4 ,2020 FORMED2

(5:00-6:00)

Term Paper

GUNSHOT RESIDUE ANALYSIS

INTRODUCTION:

Gunshot residue is an area of forensic science that is often understimated and underappreciated

by the forensic community. The residue exits the muzzle and all other firearm openings, such as the

ejector port or the barrel-drum gap ,a part of GSR travels with the bullet and is thus generally detected

on the target, the remainder loses its kinetic energy and then settles down on surfaces around the

firearm, including on the shooter. Gunshot residue is one of the most coon and heavily. GRS may directly

link an otherwise unknown subject to an environment of weapon discharge. For GRS evidence to be

significant in any factors must be considered that is typically found on the hands or clothing of persons

who have been in the environment of discharging fiream.Firing a weapon produces combustion of both

the primer and powder of the cartridge.Organic GSR primarily comes from materials derived from the

propellant powder and are compounds classified either as explosives or additives based on their

chemical composition. These organic residues derive from the so-called "smokeless powder" typically

utilized in small arms ammunition. The explosives can include a single-basse of nitrocellulose or a dual

base with both nitrocellulose and nitroglycerine. Additives include stabilisers, plasticisers, deterrents,

coolants, flash inhibitors and other components intended to improve the performance of the powder.

Stabilizers most often detected include diphenylamine (DPA), ethyl centralite (EC) and/or methyl

centralite (MC). Organic GSR can be detected on the hands up to several hours after discharge despite

losses due to evaporation and skin permeation. However, skin oils and lotions can interfere with organic

GSR detection. The complexities, time, and cost of methods for organic GSR detection generally

preclude routine usage (Taudte et al, 2016) (Vachon and Martinez, 2019).
 In other words the residue of the combustion products, called gunshot residue (GSR), can consist
of both burned and unburned primer or powder components, combined with additional residues from
the surface of the bullet, surface of the cartridge case, and lubricants used on the firearm. Residues can
be either inorganic or organic in nature.two kinds of residue are created: organic and inorganic.
Inorganic residues, like the elements barium and antimony, derive from the metallic components of the
firearm (the bullet and the casing), as well as from the primer, which is the mix of chemicals that
detonates the propellant. Organic residues, like the complex hydrocarbons nitroglycerin and
diphenylamine, are created by the propellant, which literally explodes to force the bullet out of the
firearm’s barrel. most firearms produce similar GSR profiles, organic GSR varies significantly across
different types of ammunition (which incorporate different kinds of propellants). If this technique is
determined to be effective, crime scene investigators will have a third forensic tool at their disposal, in
addition to ballistics (the analysis of firing characteristics, bullet trajectories, and points of impact) and
GSR analysis. (Vachon and Martinez, 2019).Residues most often derive from the primer cap, which
typically contains a mixture of components: the shock sensitive explosive lead styphnate, oxidizer
barium nitrate, and antimony sulfide fuel. Thus, the most commonly encountered residue metals are
lead (Pb), barium (Ba), and antimony (Sb) , (Vachon and Martinez, 2019). The cartridge case, bullet,
bullet coating, and metal jacket also contain specific elements that can be detected. Virtually all
cartridge cases are made of brass (70% copper and 30% zinc). A few have a nickel coating. Primer cases
are of similar composition (Cu-Zn). Bullet cores are most often lead and antimony, with a very few
having a ferrous alloy core. Bullet jackets are usually brass (90% copper with 10% zinc), but some are a
ferrous alloy and some are aluminum. Some bullet coatings may also contain nickel (Ravreby, 1982).

DETECTION OF PROPELLANT OR ORGANIC RESIDUE

PARAFIN TEST:

The first chemical test documented for GSR was the paraffin test, also called the dermal nitrate test,
introduced by T. Gonzalez at the Mexico City Police Laboratory .It consisted of applying molten paraffin
to the hand and, after removal, spraying it with diphenylamine in concentrated sulfuric acid to produce
a blue reaction product (Thulman 2001).The paraffin test targeted nitrates and nitrites. However, it was
abandoned due to its unreliability as it was found to react with both nitrates and chlorates leading to an
unacceptably high rate of false positive results .

MODIFIED GRIES TEST:

This ion, formed by the burning of propellant, is the target of the modified Griess test that results in an
orange colour.Both the paraffin and modified Griess tests detect residues from the propellant. However,
assays for metallic elements are also available and frequently used in casework. A list of the most
common methods is provided in the Best Practice Manual published by ENFSI.The Modified Griess Test
is a chemically specific chromophoric (color-producing) test for the presence of nitrite compounds, such
as those produced by the burning of smokeless powder. This test focuses on the analysis of the size and
density of patterns of nitrite residues on a victim’s clothing or other objects as well as their reproduction
at known distances using the suspect’s firearm in combination with the same type of ammunition.It is
important to keep in mind that the Modified Griess Test does not yield a positive result for nitrate
compounds, such as completely unburned smokeless powder particles. When smokeless powder burns
or partially burns, nitrite compounds are formed, which may be detected by the use of the Modified
Griess Test (Germani 1991).

MICROSCOPY:

The scanning electron microscope can be the most powerful tool for forensic scientists to determine the
proximity to a discharging firearm and/or the contact with a surface exposed to GSR. Particle analysis
can identify individual gunshot residue particles through both morphological and elemental
characteristics. When particles are detected on the collected sample, the analytical results can be
interpreted following rules of a formal general interpretative system, to determine whether they come
from the explosion of a primer or from other possible sources(Harrison 1951). The particles on the
sample are compared with an abstract idea of "unique" GSR particle produced by the sole source of the
explosion of a primer. "Uniqueness" is not the only problem related to GSR detection and identification
for a forensic scientist. With "not-unique" particles interpretation of results is extremely important.

SEM-EDX:

SEM/EDX analysis of Gunshot Residue (GSR) for the investigation of a crime case perpetrated with
firearms, one has to cope more and more frequently with limitations of this technique due to the use of
lead-free ammunition or ammunition lacking heavy metals.Several different methods can be employed
to test for gunshot residue (GSR) on a deceased person's hands, including scanning electron microscopy
with energy-dispersive x-ray spectroscopy (SEM-EDX) .techniques has been extensively studied,
especially on living individuals. The current studies (Part I and Part II) were designed to compare the use
and utility of the different GSR testing techniques in a medical examiner setting. In Part I, the hands of
deceased persons who died from undisputed suicidal handgun wounds were tested for GSR by SEM-EDX
over a 4-year period. A total of 116 cases were studied and analyzed for caliber of weapon, proximity of
wound, and results of GSR testing, including spatial deposition upon the hands. It was found that in only
50% of cases with a known self-inflicted gunshot wound was SEM-EDX positive for at least 1 specific
particle for GSR.Since only 50% of cases where the person is known to have fired a weapon immediately
prior to death were positive for GSR by SEM-EDX, this test should not be relied upon to determine
whether a deceased individual has discharged a firearm.The low sensitivity, along with the low
percentage of cases with a discernible pattern, limits the usefulness of GSR test results by SEM-EDX in
differentiating self-inflicted from non-self-inflicted wounds (Koons and Havekost 1989).

CHROMATOGRAPHY (Thin-Layer Chromatography):

Chromatography, in its many forms, has provided the residue chemist with one of the most significant

techniques for the separation and subsequent identification of pesticide residues. The growing need for

general but systematic analytical procedures for the detection of several pesticides has been largely

fulfilled by the introduction of chromatographic techniques.TLC is aaltern technique which can be used

for detecting known pesticides residue .Thin-layer chromatography (TLC) was widely used in the 1960s

and 1970s for pesticide residue analysis, but only to a limited extent since gas–liquid chromatography

(GLC) and high performance liquid chromatography (HPLC) have become readily available. In recent

years, there have been various developments in the quality of plate coating and in detection systems, as

well as in extraction and cleanup methods, that make it possible to apply TLC according to the current

international quality standards. The TLC methods described in this publication are intended for

laboratories where irregular supply of electricity, lack of service or limited budget do not allow

continuous use of GLC and HPLC techniques, and where application of mass spectrometric detection is

not feasible. TLC analytical techniques allow for screening, semi-quantitative determination and

confirmation of pesticide residues and other organic trace contaminants, and have only minor

requirements on equipment and laboratory infrastructure. TLC methods are therefore particularly
suitable for laboratories working on limited budgetary resources.The TLC methods described in this

publication are intended for laboratories where irregular supply of electricity, lack of service or limited

budget do not allow continuous use of GLC and HPLC techniques, and where application of mass

spectrometric detection is not feasible. TLC analytical techniques allow for screening, semi-quantitative

determination and confirmation of pesticide residues and other organic trace contaminants and have

only minor requirements on equipment and laboratory infrastructure. TLC methods are therefore

particularly suitable for laboratories working on limited budgetary resources (Joseph Sherma 2000).

GAS CHROMATOGRAPHY:

One such technique is unfired propellant analysis by gas chromatography – mass spectrometry (GC-MS).
This technique focuses on the organic constituent make up of the propellant paying particular attention
to diphenylamine, ethyl centralite and dibutyl phthalate. It was proposed that different batches of
ammunition could be discriminated or matched to each other by using this technique (Joseph Sherma
2000). However, since the main constituents of unfired propellant are highly reactive, it was not possible
to accomplish batch determination of ammunition. However, by improving extraction techniques and by
removing oxygen (a catalyst for the degradation of diphenylamine) a superior method was established
to help in the analysis of unfired propellant. Furthermore, it was shown that whilst differentiating
batches of the same ammunition was not possible, the improved methods have helped identify different
types of the same brand of ammunition. With the aid of future studies to fully explore this avenue, the
analysis of unfired propellant could one day become an integral part of forensic science.

HIGH PERFORMANCE LIQUID CHROMATOGRAPHY:

A procedure for the detection of gunshot residue via the organic constituent diphenylamine is
described. The method incorporates high-performance liquid chromatography with electrochemical
detection.high performance liquid chromatography (HPLC) and related techniques have become the
dominant analytical separation tools in such areas as pharmaceutical, chemical and food industries and
environmental monitoring. Contrary to gas chromatography (GC), HPLC allows to determine low-volatile
and thermolabile compounds. A variety of packings and bonded phases as well as eluents and their
combinations make this technique very useful in analysis of food contaminants, including pesticide
residues (Joseph Sherma and High performance liquid chromatography 2015 ).
MASS SPECTROMETRY:

It is highly and selective analytical technique used to detect, although organic compound found in
ammunition can contribute organice gunshot residue that mainly originates from propellant powder .
Mass spectrometry has been increasingly investigated in the field of GSR analysis for application to both
inorganic andorganic GSR.The most common collection technique applied to OGSRis swabbing during
which there is the potential for simultane-ous collection of interfering substances on skin or
garments.Terefore, a chromatograph is commonly placed in front ofthe MS instrument to separate the
compounds of interestfrom any interference still present afer extraction. The use of tandem mass
spectrometry others outstanding sensitivityand selectivity and chromatographic separation may only be
necessary.

MICELLAR ELECTROKINETIC CAPILLARY ELECTROPHORESIS (MECE):

Usually gunshot residue (GSR) analysis examines samples for the presence of inorganic primer
compounds, in particular lead (Pb), barium (Ba), and antimony (Sb). Alternative methods are needed
because of the advent of primers that do not contain these metals. Micellar electrokinetic capillary
electrophoresis (MECE) has been used to examine characteristic organic gunpowder components
(COGC), including nitroglycerin (NG), diphenylamine (DPA), ethylcentralite (EC), and others. The purpose
of this project was to develop MECE for implementation in GSR casework. In order to do this, it was
necessary to: (a) establish a sample collection and preparation method fur use with both MECE and
scanning electron microscopy (SEM): (b) determine that the minimum detection limits for COGC were in
the picogram range: (c) show that no residues were identified in samples from the general population
at or above these levels: and (d) quantitatively identify the common chemicals used in more than 100
commercially available ammunitions and reloading powders (Journal of biomedicine and biotechnology
2014).

CONCLUSION:

Gunshot residue examinations continue to improve through research, advancements, and more
integrated communication among analysts. Further, technology has made GSR analysis quicker and
easier. And, understanding of and confidence in GSR interpretation have increased. In light of the
importance of GSR analysis to many investigations, these improvements are encouraging to the law
enforcement community and the justice system.Therefore to facilitate the best use of resources, field
investigators should have a clear understanding of the utility and shortcomings of an examination, such
as GSR. Communication with the laboratory analyst prior to collection may serve as the best gauge as to
whether the analysis of GSR will clarify or muddy an investigative path.

REFERENCES

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