CHE 801

(CLASSICAL METHODS OF ANALYSIS)

Importance of analytical chemistry in forensic investigations

By

RUFAI HABEEB ADEMOLA

MTECH00011107

MTECH CHEMISTRY (ANALYTICAL)

 Introduction

Analytical chemistry is the science that addresses methods used to determine the quantitative or
qualitative composition of unknown samples. Although frequently neglected, the nature of the
sample and the use of the analytical chemical information play important roles in selecting and
executing the appropriate chemical analysis technique. (Encyclopedia Briticannia). The word
forensic comes from the Latin word forensis: public, to the forum or public discussion. A
relevant, modern definition of forensic is: relating to, used in, or suitable to a court of law
(Merriam Webster Dictionary). Any science used for the purposes of the law is a forensic
science. (Hassouna., 2017)

Brief History of forensic science

Using scientific evidence to solve crimes is nearly as old as courtrooms themselves. When the
ancient Greek scientist Archimedes was asked to find out whether a goldsmith had swapped
silver for gold when crafting a crown, he turned to water for a solution. Using specific weights of
the two metals, he calculated how much water each would displace, to provide the king with
evidence of the craftsman’s dishonesty. Advances in scientific methods – ranging from
microscopy to study hairs and fibers, to chemical analyses of poison or paint, and better ways to
dissect DNA – have since informed the practice of law. Even prior to Archimedes’ tests,
historical records suggest that individuals attempted to use fingerprints or tested inks and dyes to
study documents. The first U.S. crime laboratory was established in Los Angeles in 1924,
followed by the Federal Bureau of Investigation (FBI) crime lab in 1932. Since then, forensic
applications of science have kept pace with new discoveries across disciplines. Investigators
often draw on fields such as toxicology or analytical chemistry to sift through data. Techniques
such as mass spectrometry and Raman spectroscopy can help analyze trace evidence such as
hairs, gunshot residue, ink, or drugs and poisons. As science has progressed, these methods have
been extended beyond human crimes. Wildlife forensic scientists use similar means to solve
mysterious animal deaths or track illegal materials such as poached animal parts or wood from
endangered forests. Similarly, environmental forensic cases track down the source of pollutants,
or fingerprint nuclear fuels for better security. Over the last decades, forensic approaches have
expanded from human crimes to also encompass environmental law, oversee international
weapons treaties, and inform global health measures for epidemic infections. (Wikipedia)

Development of forensic science

In 16th-century Europe, medical practitioners in army and university settings began to gather
information on the cause and manner of death. Ambroise Paré, a French army surgeon,
systematically studied the effects of violent death on internal organs. Two Italian surgeons,
Fortunato Fidelis and Paolo Zacchia, laid the foundation of modern pathology by studying
changes that occurred in the structure of the body as the result of disease. In the late 18th
century, writings on these topics began to appear. These included ‘A Treatise on Forensic
Medicine and Public Health’ by the French physician Francois Immanuele Fodéré and ‘The
Complete System of Police Medicine’ by the German medical expert Johann Peter Frank.

As the rational values of the Enlightenment era increasingly permeated society in the 18th
century, criminal investigation became a more evidence-based, rational procedure − the use of
torture to force confessions was curtailed, and belief in witchcraft and other powers of
the occult largely ceased to influence the court's decisions. Two examples of English forensic
science in individual legal proceedings demonstrate the increasing use of logic and procedure in
criminal investigations at the time. In 1784, in Lancaster, John Toms was tried and convicted for
murdering Edward Culshaw with a pistol. When the dead body of Culshaw was examined, a
pistol wad (crushed paper used to secure powder and balls in the muzzle) found in his head
wound matched perfectly with a torn newspaper found in Toms's pocket, leading to the
conviction.

In Warwick 1816, a farm laborer was tried and convicted of the murder of a young maidservant.
She had been drowned in a shallow pool and bore the marks of violent assault. The police found
footprints and an impression from corduroy cloth with a sewn patch in the damp earth near the
pool. There were also scattered grains of wheat and chaff. The breeches of a farm labourer who
had been threshing wheat nearby were examined and corresponded exactly to the impression in
the earth near the pool.
 Analytical science in forensic investigations

The forensic sciences are used around the world to resolve civil disputes, to justly enforce
criminal laws and government regulations. Forensic scientists may be involved anytime an
objective, scientific analysis is needed to find the truth and to seek justice in a legal proceeding.
Early on, forensic science became identified with law enforcement and the prosecution of
criminal cases - an image enhanced by books, television, and movies. This is misleading because
forensic science is objective, unbiased, and applies equally to either side of any criminal, civil, or
other legal matter. Forensic investigations involve the discovery and characterization of evidence
that can be used to reconstruct a chronology of events associated with the commission of a crime
or other matters being adjudicated. As they become available, increasingly sophisticated
analytical tools and methods are being employed to detect and discriminate evidence. Multiply
hyphenated techniques, such as gas chromatography/ mass spectrometry with retention time
locking (GC/MS/RTL), liquid chromatography/time-of-flight mass spectrometry (LC/ MS/TOF),
micro fluidic-based capillary electrophoretic analysis of mitochondrial DNA (mtDNA), and laser
ablation inductively coupled plasma mass spectrometry (LA/ICP/MS), are able to uncover
forensically germane information by providing unprecedented levels of analytical selectivity and
sensitivity, extracting genetic signatures from previously overlooked biological sources, and
sequentially micro deconstructing samples so as to map the spatial variation and concentration of
elemental constituents. These new ranges of information and rich data sets can contribute facts
crucial to the reconstruction of events and thereby increase the probability of an accurate finding
in the matters under investigation. The term forensic science is associated with the application of
analytical tools and techniques in the discovery of evidence deemed relevant in the investigation
of a crime or in some other legal proceeding. Sources of evidence may be biological samples
from persons living or dead, physical objects and their disposition, deposited trace materials,
alteration or disruption of a setting, as well as circumstantial references connecting these data.
The evolving power and sophistication of analytical instrumentation has made it possible to
perform forensic investigations at ever smaller size scales with greater sensitivity and finer
ranges of differentiation. As a result, it is now possible to routinely uncover evidence formerly
indiscernible or inaccessible. As earlier stated; Analytical chemistry is the science that addresses
methods used to determine the quantitative or qualitative composition of unknown samples.
Although frequently neglected, the nature of the sample and the use of the analytical chemical
information play important roles in selecting and executing the appropriate chemical analysis
technique. Forensic chemistry is a timely subject that serves as a palette from which we can
stimulate the interests and abilities of our students. One of the most important aspects of criminal
justice is forensic science, or the practice of scientifically examining physical evidence collected
from the scene of a crime or a person of interest in a crime. Many people consider forensic
science the application of science to law enforcement. Two of the most common crimes that are
determined in the forensic science lab are drug-related crimes and sex crimes. It is in the crime
lab that the chemical makeup of an unidentified substance recovered from a suspect is
determined to be cocaine, marijuana or a controlled substance. This is used as evidence in court
to prove that a person was in possession of illegal drugs. Forensic toxicology can determine if a
person was drunk behind the wheel of a car after a fatal accident, or if someone was poisoned to
death. DNA evidence recovered from a victim’s body can help determine who was responsible
for a physical or sexual assault. This evidence is commonly used in court to put sex offenders
and child molesters behind bars, and to set innocent people free.

Analytical methods in forensic chemistry

The major analytical techniques that are widely implemented are as follows:

 Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICPMS)

The broken glass involved in a crime could provide important clues like the direction of bullets,
the force of impact or the type of weapon used in a crime. Through its highly sensitive isotopic
recognition ability, the LA-ICP-MS machine breaks glass samples of almost any size down to
their atomic structure. Then, forensic scientists are able to match even the smallest shard of glass
found on clothing to a glass sample from a crime scene. (Atiya syed., 2017)

 Alternative Light Photography

Using ultraviolet light through to infrared light we can uncover a lot of information that may not
be seen in visible light. We look at using ultraviolet light to enhance bruises and bite marks, and
search for trace evidence. Infrared photography is used to enhance difficult to see blood on dark
and patterned clothing, and tattoos post-mortem difficult to see due to decomposition, lividity
and burning . (Atiya syed., 2017)

 DNA Sequencer

Most people are familiar with the importance of DNA testing in the forensic science lab.
Most forensic scientists and crime lab technicians use DNA profiling to identify criminals
and victims using trace evidence like hair or skin samples. In cases where those samples are
highly degraded, however, they often turn to the more powerful DNA sequencer, which
allows them to analyze old bones or teeth to determine the specific ordering of a person’s
DNA nucleobases, and generate a “read” or a unique DNA pattern that can help identify that
person as a possible suspect or criminal. (Atiya syed., 2017)

 Forensic Carbon-14 Dating :

Carbon dating has long been used to identify the age of unknown remains for anthropological
and archaeological findings. Since the amount of radiocarbon has increased and decreased to
distinct levels over the past 50 years, it is now possible to use this technique to identify forensic
remains using this same tool. The only people in the forensic science field that have ready access
to Carbon-14. (Atiya syed., 2017)

 Automated Fingerprint Identification (AFIS)

Using this technique, crime scene investigators, forensic scientists and police officers can
quickly and easily compare a fingerprint at a crime scene with an extensive virtual database. In
addition, the incorporation of magnetic fingerprinting dust allows investigators to get a perfect
impression of fingerprints at a crime scene without contamination. (Atiya syed., 2017)

 High-Performance Liquid Chromatography (HPLC)

Also know as high-pressure liquid chromatography is an instrumental system based on

chromatography that is widely used in forensic science. HPLC is used in drug analysis,
toxicology, explosives analysis, ink analysis, fibers and plastics to name a few forensic
applications. Like all chromatography, HPLC is based on selective partitioning of the molecules
of interest between two different phases. Here, the mobile phase is a solvent or solvent mix that
flows under high pressure over beads coated with the solid stationary phase. While traveling
through the column, molecules in the sample partition selectively between the mobile phase and
the stationary phase. Those that interact more with the stationary phase will lag behind those
molecules that partition preferentially with the mobile phase. As a result, the sample introduced
at the front of the column will emerge in separate bands, with the bands emerging first being the
components that interacted least with the stationary phase and as a result moved quicker through
the column. The components that emerge last will be the ones that interacted most with the
stationary phase and thus moved the slowest through the column. A detector is placed at the end
of the column to identify the components that elute. Occasionally, the eluting solvent is collected
at specific times correlating to specific components. This provides a pure or nearly pure sample
of the component of interest. This technique is sometimes referred to as preparative
chromatography. (Atiya syed., 2017)

 Gas Chromatography (GC)

This is an instrumental technique used forensically in drug analysis, arson, toxicology, and the
analyses of other organic compounds. GC exploits the fundamental properties common to all
types of chromatography, separation based on selective partitioning of compounds between
different phases of materials. Here, one phase is an inert gas helium, hydrogen or nitrogen that is
referred to as the mobile phase (or carrier gas), and the other is a waxy material (called the
stationary phase) that is coated on a solid support material found within the chromatographic
column. (Atiya syed., 2017)

 Ion chromatography (IC)

This is an instrumental technique that can be used to detect anions (negatively charged atoms or
molecules such as Cl¯) and cations (positively charged species such as Na+ ). IC has been
applied in forensic science for the analysis of gunshot residue (GSR) and explosives. The ions of
interest include ammonium (NH4+), nitrate (NO3¯), and chlorate (ClO4¯), species that are often
detected using color change or presumptive tests. (Atiya syed., 2017)
 Summary

The role of analytical science in forensic investigations is becoming increasingly important due
to the major developments in analytical chemistry and advances in molecular biology. Forensic
Science involves the analysis of biological, chemical or physical samples collected as evidence
during a criminal investigation. The key problem solving and analytical skills developed in
forensic & analytical science are widely sought after in many other industrial sectors including
the oil, gas, pharmaceutical and food industries. The skills of the forensic scientist provide
crucial scientific evidence which may link a suspect with the scene of the crime, the victim or the
weapon.

Forensic analytical chemistry has two main purposes, namely identification and comparison.
By-products of the identification process are databases comprising analytical results, qualitative
and, where possible, quantitative. The importance of analytical databases in forensic science
cannot be emphasized enough, because they will influence the significance placed upon a match
between control and suspect samples. In a world where mass production has largely taken over
from small, independent manufacturers of, for example, materials such as paint and glass,
stringent quality control means little variation in chemical composition from batch to batch. As a
consequence, the search for, and identification of, new, more sensitive chemical discriminators,
has become important. Any new analytical method offering greater sensitivity, however, brings
with it a concomitant increase in the dangers posed by contamination, and method validation
must take this into account.
 References

1. Atiya Syed. Analytical Chemistry: Core of forensic science. Imperial journal of

interdisciplinary research. 2017; 3(11): 2454-1362
2. David F. Rendle. Advances in chemistry applied to forensic science. Chemical Society
Reviews.2005; 34: 1021–1030
3. Hassouna MEM (2017). The Role of Analytical Chemistry in Forensic Sciences.
Forensic Research and Criminology International Journal 4(5): 00130. DOI:
10.15406/frcij.2017.04.00130
4. https://en.wikipedia.org/wiki/Forensic_science