Module in Forensic Chemistry Lesson 7
Module in Forensic Chemistry Lesson 7
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Course Outcomes:
1. Familiarize with the principles involved in the chemical examination of the physical
evidence for law enforcement purpose
2. Identify various methods used in the chemical examination of physical evidence for the
the solution to crime.
3. Appreciate the study of forensic chemistry and toxicology as a scientific
medium in crime detection and solution;
4. Develop necessary skills in the manipulation of different apparatus used in the
examination of physical evidence to the solution of the crime.
Learning Outcomes:
Overview
Lesson 7 covers of the examination of the chemical aspects of documents on paper
and inks.
At first, it seems that the examination of questioned documents is hardly within the
province chemist, but if we consider the fact that the essential materials in a document
examination of any kind are the paper and ink or pencil, and the chemical examination of
inks, papers, erasures, alterations, and sequence of writing is often associated with such
examination, it will be very evident that there is a large amount of purely chemical work in
documentation examination.
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Discussion
1. Key Concept
Document
An official paper
that gives
information about
something or that
is used as proof of
something .
Paper
The material that is
used in the form of
thin sheets for
writing or printing
on, wrapping things,
etc.
Ink
Colored liquid that is
used for writing or
printing
Main Tasks:
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Scrutiny is first made of the document as a hole in the usual way be reflected light.
By transmitting by ultra-violet light, both sides of the paper being inspected.
The document is then examined in detail with a lens and any doubtful portions
examined further with a stereoscope, special search being made for evidence of
alterations erasures or when the sequence of writing is in question an enlarged
photograph will be found very helpful
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One of the earliest substances used for writing was Egyptian papyrus, the
pith of which was sliced into layers that were beaten and pressed together
into sheets and it is from the name “papyrus” that the word paper was
derived.
After papyrus came parchment and vellum which are still used for many
legal documents, the former being made from the skin of sheep and goats
and the latter from the more delicate skin of calves and kids.
Parchment and vellum were succeeded by rags, at first linen rags, and
afterward a mixture of linen and cotton, or cotton only.
The introduction of paper made from a variety of fibrous materials started
about the middle of the 19th century.
Straw was first used in 1800; from soda wood pulp between 1845 and
1880; from mechanical wood pulp between 1880 1890.
The present ordinary bond paper, is a thin sheet of matted or felted
vegetable fiber, usually wood pulp with a specified amount of filler such as
clay, and sizing such as rosin or starch. These constituents, along with the
physical structure of the sheet itself form the basis for the examination
and comparison of paper.
The history of paper started just after the start of the Gregorian calendar.
Papyrus paper is derived from the Greek word pápyros, the name for the papyrus
plant. This plant grows only on the shorelines of streams in the Middle East, like
the river Nile (a river in Africa which flows into the Mediterranean Sea in Egypt).
The "paper" from the papyrus plant was first used by the Babylonians and
thereafter by the Egyptians (around 3000 B.C.). Also, the Greeks and Romans
used papyrus, amongst others for contractual obligations.
The "paper" from the papyrus plant was made from the stem of the plant. The
outer rind is first stripped off, and the sticky fibrous inner pith is cut lengthwise
into thin strips. The strips are then placed side by side on a hard surface with
their edges slightly overlapping, and then another layer of strips is laid on top at
a right angle. While still moist, the two layers are hammered together, mashing
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Papyrus Plant
2. The probable age of the paper, and in cases connected with counterfeit bills and
stamps, the composition of the paper.
Erasures
Removal of writings from the paper; may be made by mechanical or
chemical means:
Mechanical: rubber pencil erasures, ink erasures, and knives
Chemical:
an oxidizing agent which bleaches the provisional blue dye of
the ink
a reducing agent remove the ferric tannic by the change of pH
or complex formation
3. Polarized Light
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The tests of paper are accomplished by cutting out very small pieces of the
document and treated with chemicals.
A. The fiber composition of the paper may be determined by boiling a small piece of the
document in a 5% NaOH solution. The liquid is then poured off and the fragment of paper
is washed and treated out on a glass slide and then suitably stained according to the
following table:
(a) Potassium iodide 2 gms., Iodine 1.5 gms., glycerine 2cc., water 20 cc.
(b) (1) Zinc chloride 20 gms., water 10cc.
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1. Gelatine: This is extracted by boiling water the paper in water and the
solution obtained is tested with a dilute tannic acid solution. Yellow
precipitate indicates gelatin.
2. Rosin: This is extracted by heating the paper on the bath 95% alcohol.
The solution obtained is evaporated to dryness and the residue dissolved
in acetic anhydride, cooled transferred to a small porcelain dish and a
strong sulfuric acid is added. Reddish-violet color quickly changing to red-
brown shows rosin. A simpler test is to place a few drops of ether on the
paper and if rosin is present a brown ring will be formed when ether
evaporates.
3. Starch: This may be identified on the paper by the blue color which is
produced by the addition of a dilute iodine solution.
4. Casein: This may be detected by the addition of Killons reagent on the
paper. The pink color will be formed if casein is present.
C. Watermark – the watermark, if present, is one of the most important features in the
comparison of the paper. It is a distinctive mark covered with wire cloth and known as
dandy rolls and serves as a means whereby the paper can be identified as the product of a
particular manufacturer. This dandy roll is made up of several designs all of which are after
may be examined on the paper with the aid of transmitted light. Sometimes a list may be
placed on the age of the document using a watermark, should not be taken as infallible
proof of age since paper earlier date may be used later. Sometimes watermark is forged on
the finished paper using a stamp used with was or an oily medium, which imparts
transparency to that part of the paper where the design appears. Such watermarks can be
removed generally by gentle sponging with other or by exposure to ultra-violet light.
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(a) The stub of paper remaining in the tablet if the sheet of paper is carelessly torn
out may be carefully matched with the torn sheet of paper in question.
(b) The edges of the paper, brought about by writing with a considerable amount of
pressure on the sheet immediately above, may be matched with the writing on the
questioned sheet.
(c) The edges of the paper, when examined under low magnification may disallow
certain irregularities which are due to defects in the edges of the knife or cutting instrument
similar to the marking on a piece of wood made with a damaged ax blade.
(d) Fragment of the glue or other adhesive found clinging to the top edge of the
sheet in question may be given to the color, size, and exact location of the fragment in
question.
(e) The transfer of ink writing to a sheet of paper immediately above should be
considered, particularly if the writing was done in a notebook that was closed before the ink
was dry or if blotted attached to a table next to the front cover. A small mirror may be used
to read the message if legible.
This description does not apply to dry toner – printing material commonly used in
photocopiers, laser printers, and some facsimile machines. Dry toner has a different
composition to facilitate a markedly different process for printing a document and is
discussed later.
Thermal transfer printing applies to printing processes that utilize heat to produce
an image by either physical or chemical means or by a combination of both.
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1. Gallotanic ink
The most frequently used for marking entries in record books and
business purposes in general
The ink was originally an Arabic invention- a solution of iron salt and nut-gall
Ink can penetrate in the interstices of the fibers thereby inscribing the writing in the
body of the paper and not merely on the surface, thus marking its removal more
difficult to accomplish
The color changes undergone by gallotannic ink in the process of oxidation provides
a valuable means of estimating the approximate age of writing:
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2. Logwood Ink
Runge used logwood extract with potassium chromate as the principal
constituent of a new type of ink.
In 1857, alum. copper sulfate and logwood extract were used.
In 1875, copper sulfate and logwood were mixed to form a variation
of logwood ink
Iron compounds were never used.
1882 potassium dichromate was used as the principal ingredient to be
added to logwood extract; hydrochloric acid was used to prevent the
formation of a precipitate and phenol to act as a preservative.
Contains two well-defined compounds: hematoxylin and haematin
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There are also toy invisible ink pens which have two tips—one tip for invisible ink
writing, and another tip for developing the ink. Invisible ink is sometimes used to
print parts of pictures or text in books for children to play with, always including a
"decoder pen" which is used to show the invisible parts of texts or pictures, thus
revealing answers to questions printed in regular ink or completing missing parts of
pictures.
Properties of an “ideal” invisible ink
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Cola drink
The honey solution, sugar (sugar turns into caramel by dehydration)
Lemon, apple, orange, or onion juice (organic acids and the paper forms ester under
heat)
Milk (lactose dehydrates)
Bodily fluids such as blood serum.
Soap water (carboxylic partially oxidizes)
Wine, or vinegar
Cobalt chloride, which turns blue when heated and becomes invisible again after a
while (if not overly heated)
The writing is rendered visible by heating the paper, either on a radiator, by ironing it, using
a hairdryer, or by placing it in an oven. A 100-watt light bulb is less likely to damage the
paper.
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Some inks glow faintly (fluoresce) when under an ultraviolet lamp. This is a property
of many substances, particularly organic substances and body fluids.
Other inks work in a near opposite way by absorbing ultraviolet light but without fluorescing.
When these are used on fluorescent paper, the inked areas fluoresce less than the
surrounding paper area when under an ultraviolet lamp. This is especially a property of inks
with a yellow tint.
Some UV-visible inks may be detected on a photocopy, due to the relatively strong
ultraviolet component in light from the photocopier scanning head.
Examples of inks revealed by ultraviolet light are:
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a.
The
b. The whole document and then parts in questions should be examined with
the naked eye, using reflected light and then transmitted light. Ultra-violet light
may be used to detect marks and other stains present in the document not visible
with the naked eye.
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1. Age of Inks
The color is black, are based on the observation that within a few hours the color of
the ink writing becomes perceptibly, darker because the dye
contained therein is influenced by the light of the room, the oxygen of the air, and the
acidity or alkalinity of the paper.
If the writing is made with gallotannic ink, the color undergoes an orderly series of
change: first reaching a maximum degree of blackening the first year or two, then
gradually fading out over many years until only a rust-colored deposit remains
The approximate age of the ink and the distinction between two documents written
one year or less may be established by the use of filters and paper
chromatography.
“This method of examination used in the Palomo case where the opinion of the writer, which was
supported by photographs, was sustained by the late Judge Ibanez. In that case, the documents
were established to have written with the same pen by measuring the width of the writings, with
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The age of the document may be estimated from the paper; sometimes a
limit may be placed to the age of the document using the watermarks, the
earliest known dating from 1282.
A document is a fraud if it contains a watermark that was not in existence at
the time the document purports to have been executed.
The individual parts of the dandy roll are subject to wear and tear which
become progressively more as time goes by
Illegible Writing
Erasures
It means the removal of writings from the paper; may be made by mechanical or
chemical means: Rubber pencil erasures, ink erasures, and knives are examples of
abrasive materials that are used for mechanical erasures; chemical indicators:
made of an oxidizing agent which bleaches the provisional blue dye of the ink, if of
the gallotannic type, and another agent which remove the ferric tannate by the
change of pH, reduction, or complexion formation
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2. Ultra-Violet Light
Some colored ink is fluorescent so that if the erasures have not removed all
the inks from the fibers of the paper, traces may be seen in the interstices of the
paper when viewed under the ultra-violet light.
3. Polarized Light
This is useful for developing pencil writing which was erased; based on the
fact that traces of graphite which cannot be seen in the ordinary light can be
detected in polarized light; the light transmitted through a polarizing screen is used
in photography may be used on the document may be viewed through the power of
the polarizing microscope.
4. Photography
A photograph of the erased surface may be made using the process film,
panchromatic film, or infra-red film; proper filter must be used.
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References
Dascil-Canete, Arlyn M. (2014). Forensic Chemistry and Toxicology, An essential tool
in an effective Criminal Justice System. Wiseman’s Book Trading
Garcia Orodio, Gladys Mae (2014). Forensic Chemistry and Toxicology (with
Laboratory Manual)Purely Books Trading and Publishing Corp.
https://www.google.com/search?
q=Enzyme+Multiple+Immuno+Assay+Technique&oq=Enzyme+Multiple+Immuno+Assay+Tec
hnique&aqs=chrome..69i57j0l5.2293j0j9&sourceid=chrome&ie=UTF-8
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Checkpoint
Activity 1:
Instruction:
Describe the general features of the following miscellaneous problems in
document examination:
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Do this
Activity 2:
MULTIPLE CHOICE: Choose the correct answer from the choices in each item and
write the letter on a piece of paper.
_____ 1. They are essential materials in a document;
a) writing instrument used
b) paper
c) ink
d) b and c
e) none of the above
_____ 2. The proper manner of folding the document before it will be sent to the laboratory
for examination;
a) folded new lines
b) any desired fold
c) folded old lines
d) folded according to size of the document
e) none of the above
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_____4. During the examination of the document: the table to be used should be;
a) filled up with examination tools
b) clean on which there should not be any bottles containing inks, liquid or
chemicals that covered soil or damage the document
c) tilted at a certain angle to facilitate examination
d) a and c
e) None of the above
_____5. A careful scrutiny is first made of the document as a whole in the usual way by
applying;
a) refracted light
b) reflected light
_____6. They are the type of paper which are used for many legal documents;
a) papyrus
b) rags
c) parchment and vellum
d) bond paper
e) all of the above
_____ 8. Which is NOT included in the physical tests causing no perceptible change;
a) measurement of the length and width of the paper
b) accelerated tests
c) determination of the thickness of the paper
d) texture gloss and finish
e) color of paper
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____ 10. It is the most significant and primary consideration in the analysis of document;
a) brand of ink
b) type of ink
c) composition of ink
d) age of ink
e) color of ink
____ 11. It is the most frequently used type of ink today for marking entries in record
books and business purposes;
a) Logwood ink
b) Aniline ink
c) India ink
d) Gallotonic ink
e) Ball-Poin Pen Inks
____ 12. The indicator to determine the approximate age of the document;
a) color test for the ink turning black or darker
b) matching the color of the ink with standard colors
c) chemical reaction which may reveal some information concerning in the
length of time the ink has been in the paper
d) a, b, and c only
e) None of the above
____13. They are substances used as invisible (secret ink) and often referred to as;
a) Chinese ink
b) sympathetic ink
c) Ball-Point Pen Ink
d) Colored Writing Ink
e) Gallotonic Ink
____14. The cancellation marks used in documentary and postage stamps may be erased
to appear genuine by the;
a) oxidizing agent for bleaching
b) reduction agent
c) polarizing agent
d) and b only
e) none of the above
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Assessment
CASE STUDY
Instruction:
Read the given sample cases and answer the questions below.
Case study 1
This case scenario involves associating counterfeit documents. Two different driver’s licenses
suspected to be counterfeit were submitted for analysis at different times. Although they
contained different biographical information, photographs, and identification numbers, a
physical examination revealed the barcodes printed on the back of the driver licenses to be the
same. Barcodes on authentic licenses are always unique. A chemical examination of the inks
could help establish whether the barcodes were printed from the same source, or if multiple
suspects used electronic images of the barcodes. A chemical analysis revealed that the
barcodes were created with an inkjet printer, which did not conform to the authentic
specimens. Assume specimen document was presented.
Case study 2
A female reported to authorities that she was receiving numerous letters of a threatening nature
that were becoming progressively more violent. Crayons, markers, and an array of pens used on
different types of paper were used to write the questioned letters. A suspect was developed,
but no fingerprints were identified on the documents and the questioned handwriting was
disguised. Therefore, it was concluded that identification was not feasible based on
comparisons with known handwriting. Investigators obtained a search warrant and during the
search numerous materials were seized, including crayons, markers, pens, a notepad, and ruled
paper. One of the threatening letters was torn and, therefore, was compared with a torn page
from a notepad that belonged to the suspect. A comparison was conducted and it was found that
the torn edges from the letter and the notepad were exactly aligned. The results from this
examination are sometimes referred to as a torn match. Assume specimen document was presented.
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1. What evidence can be used to associate a questioned document in the crime scene and/
or victim?
2. Are there other forensic examinations that can be performed?
3. How was the questioned document produced?
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