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FORENSIC CHEMISTRY AND TOXICOLOGY

Forensic Chemistry- branch of Chemistry which deals with the application of chemical principles in the
solution of problems that arise in connection with the administration of justice.

Forensic Science - is the use of science and technology to enforce civil and criminal laws.

Scopes:
 It includes chemical side of criminal investigation.
 It includes the analysis of any material the quality of which may give rise to legal proceeding.
 It has invaded other branches of forensic sciences notably legal medicine, ballistics, questioned
documents, dactyloscopy and photography.

Physical Evidence- are articles and materials which are found in connection with an investigation and which
aid in establishing the identity of the perpetrator or the circumstances under which the crime was committed
or which in general assist in the prosecution of the criminal.

Types of Physical Evidence


4. Corpus Delicti– is the body of the crime or fact of specific loss or injury sustained. It constitutes the
essential parts or elements in the commission of the crime.
5. Associative Evidence – these are the pieces of evidence that will link the suspect to the crime scene. The
suspect may leave some clues at the scene such as weapons, tools, garments or prints.
6. Tracing Evidence – articles which assist the investigator in locating the criminal. Stolen goods in the
possession of the suspect in an example of tracing evidence.

BLOOD
-Has been called the circulating tissue of the body. It is referred to as highly complex mixture of cells,
enzymes, proteins and inorganic substances. Blood is opaque. On treatment with water or other reagents it
becomes transparent and assumes lake color. It is faintly alkaline.

Importance of the study of blood:

As circumstantial or corroborative evidence against or in favor of the perpetrator of the crime.


As evidence in case of disputed parentage.
As evidence in the determination of the cause of death and the length of time the victim survive the attack.
Determination of the direction of escape of the victim or the assailant.
Determination of the origin of the flow of blood.
As evidence in the determination of the approximate time the crime was committed.

Composition of blood:
Water – 90%
Solid – 10%
45% formed elements or the solid materials consisting of:
Red blood cells (RBC) or Erythrocytes
White blood cells (WBC) or Leucocytes
Blood platelets or Thrombocytes

55% Plasma – the fluid or liquid portion of blood where the cells are suspended.

Serum - A straw-yellow colored liquid formed when clotted blood is allowed to stand for sometime and the
clot contracts.

Place of Collection:
1. fluid blood may be collected from:
Victims of crimes of violence
Parents and child in case of disputed parentage.

2. dried blood or bloodstains may be collected from:


Smooth surface like walls, finished floors and table tops;

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Hard surface like axe, hammer, knives, stones and crowbars;
Glazed surface like glass, tiles, automobiles;
Bulky objects like blackboard, linoleum sheets, doors, window frames;
Clothing;
Blood absorbed by the soil.

EXAMINATION OF BLOOD

4 chronological tests for blood:


1. Preliminary Test
2. Confirmatory Test
3. Precipitin Test
4. Blood Grouping / Typing

I. PRELIMINARY TEST - used to demonstrate presence of blood (maybe blood).

Test Positive Result


1. Benzidine test- Intense blue color
2. Phenolphthalein test (Kastle-Meyer test) - Rose color or deep pink or permanganate color.
3. Guaiacum test (Van Deen or Day’s or Schoinbein Test) - Beautiful blue color
4. Leucomalahite Test- Bluish green
5. Luminol Test- Luminescence

Note: Oxidation is the principle involved in the color formation of the preliminary test for blood except in
luminol test.

Peroxidase– enzyme that accelerates the oxidation of several classes of organic compounds by peroxide.

II. CONFIRMATORY TEST- the actual proof that a stain is blood (surely blood)

A. Microscopic test
a.1. Useful for the demonstration and mensuration of blood corpuscles.
a.2. Distinction between mammalian, avian, piscine and reptilian blood.
a.3. Investigation of menstrual, lochial and nasal charges.

B. Microchemical or microcrystalline test

Test Positive Result


1. Teichmann Test or Heamin Crystal Test- Dark brown rhombic crystal of heamatin chloride
2. Haemochromogen crystal test or Takayama test- Large rhombic crystals of salmon pink color arranged in
clusters or sheaves.
3. Acetone-Haemin Test- Small dark diachronic acicular crystals of acetone haemin.

C. Spectroscopic examination- the most delicate and reliable test for the determination of the presence of
blood in both old and recent stains.

III. PRECIPITIN TEST


 Is the standard test used to determine whether the stain/blood is of human or animal origin.
 If human blood, the positive result is a white cloudy line or milky precipitate at the contact point of
the fluids.

IV. BLOOD GROUPING/TYPING

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SEMEN
Semen - a viscid whitish fluid of the male reproductive tract consisting of spermatozoa suspended in
secretion of accessory glands.

Parts of semen:
a. Seminal fluid
b. Formed cellular elements
b.1. Spermatozoa or sperm cells (400-500 Million / ejaculation)
b.2. Epithelial cells
b.3. Crystals of choline and lecithin

Cases Wherein Semen Has No Spermatozoa


Aspermia – a condition wherein males have no spermatozoa at all in their seminal fluid.
Oligospermia – a condition whereby males have abnormally low sperm counts or few spermatozoa.

Semen can be found fresh in:


Vaginal contents of the victim
Rectal contents of the victim

Semen can be found as wet or dried condition/secretion on:


Pubic hair
Skin around the genitals

Semen can be found as dry/stains on:


Underclothing
Bed sheets or bed clothing

EXAMINATION FOR SEMEN AND SEMINAL STAINS:


I. Physical examination – determines the physical appearance as to the feel, color, odor, ultraviolet light etc.

II. Chemical examination


A. Florence test– crystals of choline periodide which are dark brown, rhombic or needle shaped that appear
singly or in clusters.
B. Barberio test– crystals which are slender yellow-tinted, rhomboid needles with obtuse angle or appear as
ovoid crystals of spermine picrate.
C. Acid-Phosphatase test (Walker Test)– purple color

III. Microscopic examination

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- A small object with a pear-shaped head, behind which is a short neck and then a tail of about ten times as
long as its head.

IV. Biological examination


- The test was proposed by Farnum in 1901. This test is also known as spermato-precipitin which is of great
value in the identification in certain cases like for example bestiality. Only a secretor can be determined by
this test.
GUN POWDER AND OTHER EXPLOSIVES
In the investigation of crimes involving the use of firearms, three most important problems may arise:
- Determination of whether or not a person has fired a gun
- Determination of the probable gunshot range
- Determination of the approximate time of firing of the gun

Possible Locations Of Gunpowder Residue


- Residue of the barrel of the gun
- In or around the wound
- On the clothing of the person fired upon at close range
- On the exposed surface of the hand of the person firing the gun.

Paraffin Test (Dermal Nitrate test or Diphenylamine test or Lunge’s test) – a test to determine whether a
person fired a gun or not with his bare hands.
Positive Result – Deep blue specks develop when nitrates comes in contact with DPA reagent.

Other sources of nitrates:


1. Fertilizers 5. Urine
2. Explosives 6. Cosmetics
3. Tobacco 7. Detergents
4. Firecrackers

Possibilities that a person maybe found negative even if he actually fired a gun:
- Use of automatic pistol
- Direction of wind
- Wind velocity
- Excessive perspiration
- Use of gloves
- Knowledge of chemicals that will remove the nitrates

Determination of the probable gunshot range:


- The clothing of the victim with bullet perforations should be submitted for possible gunshot range.
- It is only possible to determine the probable gunshot range if the gun was fired from a distance of zero
(contact firing) to 36 inches (3 feet).

Distance of Firing Characteristics of Pattern


0-2 inches Gaping hole, smudging, tattooing and burning
2- 8 inches Smudging
8-36 inches Tattooing
Beyond 36 inches Evidence of powder tattooing is seldom present

Determination of the probable time the gun has been fired

Rust
» formation of rust inside the barrel after a gun has been fired is a good indication for the determination of
the approximate time the gun has been fired.
» if a gun has not been fired at all, no rust can be detected inside the barrel of the gun.
» if a gun has been fired, iron salts are formed and are found inside the barrel. This iron salts are soon
oxidized resulting in the formation of rust.

Presence of nitrite (NO2) – firearms could have been fired recently - BLUE
Presence of nitrate (NO3) – firearms could have been fired but not recently - YELLOW GREEN

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HAIR
Hair - Is a specialized outgrowth of the skin which occur everywhere on the human body except on the palm
of the hands and the sole of the feet. It is not completely round but maybe oval or flattened. Its width is not
always the same along its length. It starts out pointed and narrow and then strays more or less the same.

Two kinds of hair:


Real hair– generally long and stiff
Fuzz hair – generally short, fine at times curly and wooly

Parts of hair:
Root – portion embedded in the skin.
Shaft – portion above the surface of the skin. Most distinctive part of the skin.
Tip – sometimes termed as point. The distal end of an uncut hair shaft.

Parts of the shaft:


Cuticle – tells whether human or animal hair.
Cortex – tells the race of the hair whether Negroid, Caucasian or Mongoloid.
Medulla or core – tells whether the hair belongs to male or female.

Microscopic Examination Of Hair


 Color – melanin
 Length
 Character
 Width or breadth
 Character of the hair tip if present
 Manner by which hair had been cut
 Condition of root or base or bulb of hair
 Character of cuticle
 Character of cortex
 Presence of hair dye in hair
 Determination of whether naturally or artificially curled.
 Character of medulla

TEXTILE FIBERS
Textile Fibers - derived from Latin word “textilis” and the French “texere”, to weave, hence textile fiber
means that can be converted into yarn.

Classification Of Textile Fibers


Natural Fibers
a.1. Vegetable fibers ex. cotton
a.2. Animal fibers ex. wool
a.3. Mineral fibers ex. Asbestos

Synthetic Fibers or Artificial (Man-made)


b.1. Organic
b.1.1. Cellulosic
b.1.2. Non-cellulosic

b.2. Inorganic
b.2.1. Mineral
b.2.2. Metallic

Test For Textile Fibers


I. Burning or ignition test– a test that determines whether fiber is mineral, animal or vegetable fiber (easily
burned).
II. Flourescence test– Vegetable fibers exhibit a yellow fluorescence in ultraviolet light whereas animal
fibers show bluish fluorescence.
III. Microscopic examination– the most reliable and best means of identifying fiber.
IV. Chemical analysis of fibers

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A. Staining test– only animal fibers react with picric acid and Millon’s reagent while vegetable fiber reacts
with stannic chloride.
B. Dissolution test– wool and silk were dissolved in NaOH while cotton, linen, wild silk and cellulosic silk does
not.

GLASS
Glass - is a supercooled liquid which possesses high viscosity and rigidity. It is a non-crystalline inorganic
substance.

Composition Of Glass
Glass is usually composed of oxides like silica (SiO2), boric oxide (B2O3) and phosphorus pentoxide (P2O5).
For commercial use silica is the most important. It is the base of commercial glasses. It is made of silica sand
and other metallic oxides. Oxide is used for fluxing, durability and reduction of viscosity.

Analysis Of Glass
1. spectrographic test - an instrumental method of analysis which determines the presence of trace
elements.

2. x-ray diffraction test - not as effective as the spectrographic analysis. It determines the type of pattern of
glass. The type of pattern depends upon the composition of glass.

3. physical properties examination - the most sensitive method of determining differences of composition
of glass samples and depends upon the study of the physical properties of glass.

density– done by flotation method, a rapid and convenient method of determining the density of small glass
fragments.
refractive index– done by immersion method.

4. ultraviolet light examination- determines the differences in the appearance of the fluorescence thus
indication of physical and chemical properties.

5. polish marks- optical glass and other glassware are usually polished.

Analysis Of Broken Glass


The Principle of 3R’s Rule for Radial Crack– states that “stress lines on a radial crack will be at right angle to
the rear side of the glass.”
The Principle of RFC Rule for Concentric Crack– states that “stress lines on a concentric crack will be at right
angle to the front side”, that is the side from which the blow came rather than the rear side.

FOOT IMPRESSION AND TOOL IMPRESSION

Impression - a strong mark produced by pressure that goes below the surface. A stamp, form or figure
resulting from physical contact. It causes damage to object.
Imprint - weak mark made by pressure that stays on the surface.
Moulage - a faithful reproduction of an impression with the use of casting materials. It is admitted that
moulage cannot reproduce all characteristics of an object under all circumstances but whatever is missing in
a moulage it can be supplied by the photograph.
Casting Material - any material which can be changed from a plastic or liquid state to the solid condition.

METALLURGY (AS APPLIED TO CRIME DETECTION)

Metallurgy- the art of extracting and working on metals made by the application of chemical and physical
knowledge.
Metallography - branch of metallurgy that involves the study of the microstructures of metals and alloys.

Application Of Metallurgy In Criminal Investigation


1. Robbery
2. Theft
3. Hit and run
4. Bomb and explosion
5. Restoration of tampered serial numbers
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6. Nail examination
7. Counterfeit coins

Counterfeit Coins are coins made to imitate the real thing and used for gain.
1. Cast coins – coins made in molds
2. Struck coins – coins made by stamping or striking method. Are coins made to imitate the real thing and used
for gain.

Tampered serial numbers- are restored by the application of etching fluid.


Etching fluid is a fluid used to restore tampered serial numbers. Choice of etching fluid depends on the
structures of the metal bearing the original numbers.

SOIL (Petrography as applied to Crime Detection)

Petrography is the branch of geology that deals with the systematic classification and identification of rocks,
rock forming minerals and soils.

Types Of Soil
1. Alluvial soil – formed from soil particles that were washed, blown or moved by gravity to the lowlands.
2. Colluvial soil – formed from the decomposition of igneous, metamorphic and sedimentary rock, the
decomposed particles moved by gravity.
3. Sedentary soil – inactive, not migratory soil.

Constituents Of Soil
Igneous rock – produced by volcanic or intense heat.
Metamorphic rock - had undergone changed in structure, texture through pressure, heat and chemical
reaction. Like limestone into marble.
Sedimentary rock– or sandstone. Rocks formed by sediments

Density Gradient Apparatus- is being used in crime laboratory which quantitatively distinguishes particles
of characteristic appearance of properties in proving the identity or non-identity, depending on whether the
distributions found in two soils are the same or different.

Dust And Dirt– matters in the wrong place.


Dust– matter which is dry and in finely divided form.
Mud– dust mixed with water.
Grime(Heavy Dirt) – when dust is mixed with the sweat and greases of the human body this is formed.

Classification Of Dust
1. Dust deposited from the air– extremely fine dust particles present in the air everywhere. Its value in
crime detection is insignificant.
2. Road and footpath dust –produced by the wear and tear of the road surface by vehicular and pedestrian
traffic together with particles of soil carried by the wind or rain from adjoining regions.
3. Industrial dust– industries like cement, button, powdered gypsum and plaster of Paris factories, flour
milling, paint pigments, involves industrial processes impart a pronounce local character to the dust on the
neighboring roads and buildings.
4. Occupational dust– some of the finely powdered material maybe found on the clothing and footwear of
employees engaged in such industries.

DNA (DEOXYRIBONUCLEIC ACID)


DNA - functionally the hereditary material that contains the genetic information necessary for the duplication
of cells and for the production of proteins.

Biological evidences that can be submitted for dna analysis:


Blood and Bloodstain
Semen and Seminal stain
Hairs with follicles or root
Saliva or buccal swab
Bones and organs
Tissues and cells

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Cases where DNA analysis can be of help:
Sexual assault case like rape
Murder
Homicide
Robbery
Hit and run
Extortion
Paternity case
Identification of remains from mass disaster cases and missing person

Advantages of DNA:
1. DNA is stable.
2. DNA can be destroyed from wide variety of biological resources like blood, semen, hair, saliva and bone.
3. DNA can be replicated in the laboratory – from a very small amount of initial material through the process
of PCR (Polymerase Chain Reaction).
4. DNA shows greater variability from one individual to the next

How DNA analysis is done?


DNA TYPING is done by first carefully extracting DNA from the evidentiary samples. The DNA is then
analyzed to give a particular pattern. The patterns are compared with that of a known individual to determine
a match. In individual identification, the pattern obtained from the evidentiary sample is compared with that
of a suspect. If the patterns are different the evidentiary sample definitely has not originated from the
suspect. The DNA pattern of the evidentiary sample is similar to that obtained from the suspect, the
probability that the evidentiary sample is similar to that sample arose from the suspect, and not from a
random individual wherein population is calculated from a formula based on well-accepted concepts of
statistical probabilities and population genetics using an established population genetic database. Probability
calculations must show that no other person in the country or in the world could possess such DNA pattern
except the suspect. For example, the probability of a matched DNA pattern being present in the Philippines
indicates how many people are expected to possess such pattern. If probability of pattern is 1 per 20,000,
this means that there could be as many 3,600 (72 million/20,000) people having a pattern. Therefore, the
DNA test is inconclusive. However, if DNA pattern has a probability of 1 to 100 million, since there are only
almost 80 million people in the Philippines, and then the forensic sample must have come from the suspect.

FORENSIC TOXICOLOGY
Toxicology - is that branch of science that treats of poison, their origin, physical and chemical properties,
physiological action, and treatment of their noxious effect and methods of detection. The etymology of
toxicology came from “ toxico” that means poison and “ology” that means study or science.

Poison - from the medical point of view is a substance that when introduced into the body and is absorbed
through the blood stream and acting chemically is capable of producing noxious effect.

CLASSIFICATION OF POISON
1. According to kingdom
Animal e.g. cantharides
Vegetable e.g. strychnine
Mineral e.g. hydrochloric acid

2. According to Chemical Properties


A. Inorganic Poison – without carbon
a. Volatile e.g. bromine
b. Non-Volatile e.g. sulfuric acid
c. Mineral acid e.g. HCl
d. Mineral alkali’s e.g. NaOH

B. Organic Poison – with carbon


a. Volatile e.g. alcohol
b. Alkaloids e.g. strychnine
c. Animal Poison e.g. venom
d. Bacterial e.g. ptomaine
e. Organic Poison e.g. salicylic acid
f. Glucosides e.g. digitalis
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3. According to Physiological Action


A. Corrosives – highly irritant poisons that cause local destruction of tissue and characterized by nausea,
vomiting, great local distress. e.g. strong acids and alkalis
B. Irritants– one that produce irritation or inflammation of the mucus membrane and characterized by
vomiting, pain in the abdomen and purging. e.g. arsenic
C. Narcotics – one that produce stupor, complete insensibility or loss of feeling. e.g. Demerol and cocaine
D. Neurotics– one that act chiefly on the nervous system producing delirium, convulsion and respiration as
the outstanding symptoms. e.g. CO, alcohol, opium and strychnine
E. Tetanics– substances that act chiefly upon the spinal column producing such spasmodic and continuous
contraction of muscles as a result of stiffness or immobility of the parts to which they are attached.
F. Depressants or Sedatives– agent that retards or depresses the physiological action of an organ. e.g. nicotine
and cocaine
G. Asthenics or Exhaustives– agents that produce exhaustion, marked loss of vital or molecular power. e.g.
hydrocyanic acid

4. According to Pharmacological Action


A. Substance characterized by local action
B. Substance characterized by their action after absorption
C. Heavy metals and metalloids

5. According to Methods of Isolation


Volatile poisons are those isolated by distillation with or without current or steam.
Non- volatile poisons are those isolated by extraction with organic solvents.
Metallic poisons that are isolated by refluxion.
Substance for which special method of isolation are required.

Two Types of Poisoning:


I. From medical point of view
1. Acute poisoning – prompt action
2. Sub-acute poisoning – cases of short duration and extreme violence
3. Chronic poisoning – gradual deterioration of function of tissues

II. From legal point of view


1. Accidental poisoning
2. Suicidal poisoning
3. Homicidal poisoning
4. Undetermined

Actions Of Poisons
1. Local– changes produced on the part with which the poison comes in contact.
2. Remote– changes produced in distant parts away from the site of application.
3. Combined – the effect of poison is not only localized at the site but also affects remote organs.

Posology- a branch of science that treats of the form and quantity of medicine to be administered within a
certain period.

Kind Of Dose
1. Safe dose
2. Toxic or poisonous dose
3. Lethal dose
4. Minimum dose
5. Maximum dose

Distinguishing Poisoning From Disease


1. Symptoms of poisoning come suddenly upon a person who previously has been in good health, while
disease is usually preceded by a number of hours, days or even weeks of local or general disposition.
2. In case of poisoning, the symptoms commonly make their appearances after taking food or medicine.
3. If several persons take the same food and drinks, they should all show similar symptoms.
4. Diseases are generally much slower in their progress and are preceded by circumstances as exposure,
recognized symptoms and general or local indisposition of longer duration.
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General Treatment Of Poisoning


1. Removal of poison from stomach.
2. Administration of antidotes.
3. Elimination of poisons by excretion
4. Stimulation and other symptomatic treatment.
5. Special treatment.

Investigation Of Fatal Cases


In the investigation of fatal cases, it is not necessary that an investigator should be an expert on the poisons,
since a medico-legal officer and a toxicologist will assist him in his investigation, but it is important and will
be a great help to him if he knows the following:
1. Symptoms of various kind of poisoning;
2. The lethal dose of poisoning;
3. The length of the time that may elapse after the poison has been taken before death occurs;
4. Where the poison was obtained;
5. The chemical formula of the poison;
6. Other names it is known in the market;
7. Uses of poison.

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