7

The materials of handwritten documents:

substances and techniques

In this chapter the substances from which documents are prepared and the techniques
which are used to test these materials are considered. It is possible only to describe in
outline the make-up of paper, inks and other materials; discussion of the principles of
the methods of their examination is also brief, but special processes and the apparatus
required for their application are dealt with in Chapter 10.
Photocopy toners and printing inks are covered in Chapter 8, and typewriter ribbons
are referred to in Chapter 6.

Paper

Most documents are based on paper, and those which are not are too rare to be
considered here. Electronically stored information is likely to play an increasingly
important part in administrative and financial activities, destined perhaps largely to
replace conventional paper-based documents. The examination of this type of stored
information, whether on tape or disc or in any other form, is not dealt with in this
book. These areas are not regarded as the province of the forensic document examiner.

Manufacture of paper

Paper is made from pulped fibres which originate from wood, linen or cotton rag,
esparto, hemp or straw. To enable wood fibres to be used—and wood is the most
common fibre constituent—it is first treated to break it down to a suitably fine pulp.
This is done by mechanical or chemical means, a variety of chemicals being used for
the process. The fibre pulp is mixed with a large quantity of water and other materials.
These include size, which is made from gelatin, resins or similarly effective materials
which assist in binding the fibres, minerals such as kaolin to add weight, and dyes and
‘whiteners’ to achieve the right colour. The mixture is then passed over a frame where
it loses much of its water and becomes a wet matted fibre mass spread evenly over the

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surface. The frame, which itself gives a characteristic wire pattern to the paper, may
incorporate a ‘dandy roll’, or other devices to reduce the fibre content in an area with
a recognisable shape. This produces a watermark, which will be more transparent
than the rest of the paper.
The fibre mat is finally pressed and heated until it is dried. Some papers are specially
coated to produce a surface suitable for the proposed use of the final product. After
collection on a large roll the paper is cut to the required dimensions.

Testing of paper

The methods of manufacture described above give rise to differences in the end product
which can be tested in the laboratory. Invaluable information can be obtained which
allows different samples of paper to be compared and dated. In addition, it may be
possible for the country of origin of a piece of paper to be discovered. Other techniques
can determine what has happened to the paper after its manufacture, and thus provide
useful guidance in the investigation of crime.
Some of the tests which are employed can be performed without damage to the
specimen being tested, but others require the removal and destruction of a small part
of the piece of paper.

Non-destructive tests

Most of the operations in the manufacture of paper provide features which can
distinguish one type from another either by direct observation or by more elaborate
techniques. Colour, shape, size and thickness of the sheets, the watermark and ‘laid’
marks from the dandy roll and patterns produced by the frame, the appearance of the
surface, which may be evenly coloured or mottled, can all be examined by simple
observation and measurement. The ‘feel’ of the paper, how smooth it is or how stiff,
can be ascertained by handling, and by the noise it makes when shaken. These
apparently crude tests nevertheless have value in comparing two pieces of paper. They
detect difference in make-up with a certainty as great as more sophisticated methods,
and have the advantage that nothing is damaged or destroyed.

Fluorescence

When light falls on certain compounds and is absorbed it excites radiation at a higher
wavelength. This is described as luminescence, which term embraces both fluorescence
and phosphorescence; the former term referring to an immediate effect and the latter
to one where the emitted light is delayed.
Fluorescence can also be tested without change to the paper. This phenomenon, of
interest in many areas of document examination and other branches of forensic science,
depends on the absorption of light and its simultaneous emission at a different
wavelength. The eye is sensitive to a range of wavelengths, from about 400 nanometres
(nm), which it sees as violet, to about 700 nm, which it sees as red. The wavelengths
in between are seen as the other colours of the spectrum, and a combination of all is
seen as white light. Ultraviolet radiation (UV), which as its name suggests is radiation

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beyond the violet end of the visible spectrum, has a wavelength between about 200
and 400 nm and will produce fluorescence in the visible part of the spectrum. Different
substances fluoresce with different wavelengths and intensities. Under the ultraviolet
lamp, some papers emit a strong luminescence, while in others it is weak or not
present at all. There is a wide variety in the colours of the fluorescences excited by
ultraviolet radiation by different papers, and subtle differences in shade can be easily
detected. Similarly, fluorescence also occurs in the infrared region when papers are
excited by radiation of shorter wavelength in the visible region. This can also be used
to differentiate papers. Infrared is radiation with a wavelength greater than about
700 nm and is, like ultraviolet, out of the range to which the eye is sensitive. This type
of fluorescence therefore cannot be seen by the eye, but can be detected by photographic
and electronic means described later (see p. 103).

Destructive tests

Further tests can be carried out if a small amount of the paper can be removed. This
may not be allowed if it is necessary for the document to remain undamaged, but the
possible advantage of gaining extra information has to be weighed against the value
of the document remaining intact. Usually, only small areas of paper need to be removed
to determine the fibre type, the method of pulping, the dyes present, and the inorganic
elements in the paper.
The first examination, known as ‘fibre furnish’, involves the breakdown of a portion
of paper, using water or on occasions dilute acid or alkali, into a pulp in which the
individual fibres can be examined microscopically. This enables the determination of
the original method of pulp preparation (whether mechanical or chemical) to be
determined, and different varieties of fibres to be identified. These can be materials
such as cotton, grasses and straw, and many varieties of fibres from different species
of wood. Tests can also be performed to determine the chemicals used during
manufacture to prepare the pulp from shredded wood.
Other tests determine the elemental composition of the paper, or identify the
materials used for the surface coating. The scanning electron microscope in its analytical
mode (see Chapter 10) can be used for the former, the X-ray diffraction for the latter.
X-ray diffraction uses X-rays to indicate the crystalline structure of the material,
which is characteristic of the compound.
Further techniques can be used on coloured paper. Thin layer chromatography and
absorption spectroscopy can be applied to the dyes in paper. Because these tests are
more commonly used on inks they are considered later (pp. 105 and 109).

Comparison of paper

In forensic science the tests previously outlined are usually carried out for one purpose,
the comparison of one piece of paper with another. The significance of this is to show
whether or not two pieces have a common origin, or to indicate the genuineness or
otherwise of a possibly counterfeit document by comparing its paper with that of the
genuine article. In the latter the examination may be assisted by the introduction of
small pieces of paper (planchettes) or coloured coarse fibres into special security papers
as a safeguard.

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When two papers are found to be different they can normally be assigned different
origins. However, there may be another reason for this. The source of a piece of paper
may be a writing pad or a similar block of different sheets. Although it might be
assumed that all the paper in one such pad might be the same, this is not always so.
Machines which make up blocks of sheets of paper may use multiple reels. Paper
from several reels is fed into the machine so that each reel provides parts of the block.
The resultant pad will contain paper from each reel in sequence.
When papers are found to be the same, consideration has to be given to all the
possible reasons for this. Clearly, they could be from the same source and the same
batch, but care must be taken not to overestimate the significance of the similarity. A
large batch or carefully controlled manufacture leading to a very consistent product
means that a considerable quantity of paper would also be similar, allowing for the
very real possibility of a chance match between two samples.

Mechanical fits

A more certain indication of a common source of two pieces of paper is the possibility
of a mechanical fit between two or more pieces which were once one piece and have
been torn apart. Often the fit is obvious, hardly requiring close examination, but
this is not always so. Confusion can arise when two identical sheets are placed
together and then torn in two in one action. One piece of one will nearly fit the
other because the general shape of both tears is the same. Erroneous conclusions
may also be drawn from a torn edge which appears to have overlapping areas, the
apparently extra paper suggesting that the two pieces could not have been one. This
occurs because the tear is not always perpendicular through the thickness of the
paper but can be at an acute angle, resulting in surfaces, which were exactly opposite
each other, ending on different parts of the divided sheet. In other cases, fibres can
be pulled out of the tears and can modify the shape of the resulting edges. Testing
the pages by the ESDA method normally used for detecting indented impressions
can be helpful in identifying those parts of the torn edges where the paper is thin.
(See Chapter 9, reference 3.)
In most cases when two torn edges are fitted together, it can be proved that the
pieces did or did not form one piece. The irregular tear pattern normally found could
not be deliberately or accidentally reproduced in another specimen. The problem is
often made easier when ink lines, folds or watermarks cross the torn edge. The chance
that these would be exactly in the same position in another piece of paper must be
very low, and the presence of such artefacts adds another parameter to the accumulation
of evidence against a coincidental match.
Sheets of paper designed to be torn apart have perforations which are usually
circular but can be elliptical. Other perforations are made with short cuts separated
by narrow strips of uncut paper. When the page is torn apart the breaks which
occur in the paper between the holes will not normally be even. Instead, the tongues
of paper which remain on either side of the torn perforation will be of varying
lengths, the longer tongues on one side corresponding to shorter ones on the other.
It is therefore often possible to show that two parts of a perforated document were
at one time joined.
Although book matches can hardly be regarded as documents, they too can provide
invaluable evidence by the same processes of mechanical fits of paper. Matches left

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at the scene of a crime have been shown to originate from a book in the possession
of a suspect [21].

Watermarks

Watermarks are produced in the manufacture of paper by a thinning out of the fibres
in the required shape and area. When the paper is finally completed there is little
reduction in the dimensional thickness, but there are fewer fibres present. This makes
the watermark more translucent than the surrounding area and so creates the familiar
effect of the appearance of an image when the paper is held up to the light.
When printing, typewriting, writing or other marks are made on the paper the
watermark is more difficult to examine. To overcome this problem it is necessary to
employ methods which are sensitive to the difference in mass of paper but which do
not detect the extraneous information on the paper. If the writing or printing is not
visible in infrared it can be ‘removed’ by photography or electronic means, using light
transmitted through the paper and a filter which allows only infrared to pass through
the lens. This method is more commonly employed for the comparison of inks or the
apparent removal of obliterating inks, and is dealt with elsewhere (p. 105).
A more elegant method of displaying watermarks so that their details are clear is
the use of soft X-rays or beta particles emitted by a radioactive source. This can be
achieved by using a sheet of polystyrene containing carbon-14, a radioactive isotope
which emits a steady stream of beta particles of low activity. The handling of the
material is therefore not hazardous. However, as the radiation is of low power, long
exposure to photographic film is needed. To reproduce an image of the watermark
the paper is placed between the sheet of radioactive polystyrene and a piece of light-
sensitive photographic paper. After several hours’ exposure—it is usually convenient
to leave it overnight—the latent image of the watermark will be present on the
photographic paper. The radiation has passed through the document attenuated to
varying degrees dependent on the mass of the fibres present in the paper. The thinner
paper of the watermark allows more radiation to pass than does the rest of the paper,
and so its shape is reproduced as a photograph. Any printing or writing will have
little mass compared with that of the paper in either its thicker or thinner areas, and
will therefore not be detected.
The watermark can give clear information as to the origin of the paper. From it the
manufacturer can be identified, and, if the design is periodically changed and records
of these changes kept, the period in which the paper was made can be discovered. The
value of a watermark as a means of security is very high. Although it is possible to
imitate one by printing or drawing, the results are rarely convincing. It is particularly
difficult to copy the complicated multi-tone watermarks produced in high quality
security papers.

Dating of paper

The methods of production of paper have changed over the centuries. New materials
have been introduced into the manufacturing process which can then be found in the
final product. Antique documents counterfeited with modern paper can be shown not

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to be authentic because certain materials are present which could not have been used
at the purported date of the document.
The Vinland map, for many years considered to be centuries old, was proved to be
a fake by the discovery of titanium dioxide in its paper. This was not used until
modern times. Two sets of diaries, claimed to be by Mussolini and Hitler, were shown
to be spurious by the discovery of straw fibres and optical brighteners respectively
[26, 45]. The inclusion of these components in the paper could not have occurred at
the professed date of the writings, as they were introduced considerably later. In the
case of fake paintings purporting to be by the nineteenth century painter Samuel
Palmer, part of the paper used in a picture was shown to be of modern origin.
In most criminal investigations smaller time scales are of significance. A document
may purport to have been produced a year before the actual date of manufacture. In
such cases, only if a change of practice in the manufacture has occurred between the
two possible dates of production can any evidence be adduced to show which is the
actual date. Changes in practices occur when different types of pulp are used,
incorporating different varieties of wood for instance, and records of these may be
kept by the paper mills. Some manufacturers regularly change the dandy roll which
produces the watermark because it is in their interest to know when the paper was
made if there are complaints about its quality. This is of evidential value if the date of
a document is in dispute.
To adduce such evidence the cooperation of the producer of the paper is required,
either by providing information from records or by supplying samples of each different
batch when changes are made.

Envelopes

Evidence of the manufacturer may be also provided by the design of envelopes. The
size and shape of the envelope, the shape of the flaps, the type of glue and the pattern
it forms, all vary between manufacturers, and, in some cases, batches. These can
therefore be usefully compared. Some self-seal envelopes bear printed codes which
may indicate the date of manufacture and provide another parameter for comparison.

Writing materials

The materials used to produce a line of writing on paper can provide considerable
information over and above that obtained from whatever can be read. Evidence of
considerable value may be supplied to the court from comparison of different inks,
detection of ink which has been erased, and occasionally, determination of the date
inks were placed on the document. Techniques for these investigations need to deal
with very small amounts of material; the quantity of pencil lead or ink deposited on
paper is far less than its appearance suggests. Although a complete analysis is not
possible, many tests, often non-destructive, can be used and are described below.
These tests cannot identify the particular instrument used, but the type of ink or other
material can be compared. Matching inks indicate that they could have come from
the same source, but also from different sources of similar ink. Differences in inks
found on one document are usually more significant.

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Pencils

Pencils are rarely the subject of forensic investigation, as most documents are completed
in ink. In any examination of the mark made by a dry instrument the amount of
substance left on the paper is very small, and the variation between different products
is not great. Ordinary ‘lead’ pencils are made with graphite mixed with varying amounts
of clay or other fillers, a greater proportion of which increases the hardness of the
product. Softer leads have a higher percentage of graphite. Coloured pencils or crayons
are made of wax and coloured pigments; different waxes provide a range of hardness
to the core of the pencil.
The use of pencils and crayons depends on the friction caused when they are
applied to the writing surface. Finely divided residue breaks from the solid core and
is embedded in the irregularities of the paper surface. The particles remain on the
surface and do not penetrate into the fibres, enabling them to be removed by pressure
from a rubber eraser.
Analysis of the small amounts of graphite or wax present on paper requires sensitive
techniques. Scanning electron microscopy in its analytical mode can give a quantitative
assessment of the elemental composition of the written line. There is a high proportion
of inorganic material in the composition of pencil and crayon leads, and, although
the quantity present is small, it is adequate to distinguish between different products.
Erased pencil lines may contain a few traces of graphite which can be detected by
increasing the contrast between their absorption of light and that of the paper or
whatever substrate on which they occur. Photography using appropriate filters allowing
infrared to pass, electronic means of detection, or computer-based image enhancement
methods, described elsewhere (pp. 145, 157 and 160), sometimes assist and allow
what was erased to be detected.

Inks

The application of a coloured liquid or paste to paper as a vehicle for printed or

written information is the basis of the vast majority of documents.
Inks used in printing differ considerably from those employed for writing. They
are conveniently considered in Chapter 8 where printing techniques are discussed.
Similarly, in that chapter photocopy toners, now of considerable and increasing
importance, are dealt with. The present chapter considers the manufacture and
examination of inks used in hand-held writing instruments.

Liquid inks

Inks were first developed thousands of year ago in China, and for centuries were
based on carbon particles suspended in an aqueous dilute solution of glue. Today’s
so-called Indian inks, made in much the same way, produce a jet black permanent
writing line.
Subsequently, iron-tannin inks, mixtures of salts of iron and tannin with some
glue, were developed, and they continued in use in a modified form until recent times.
The most important modification made in the nineteenth century was the addition of

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the dye indigo. This gave a blue colour to the line of writing which after a time turned
black as the iron-tannin components oxidised. The mixture was therefore known as
blue-black.
The use of dyes was extended firstly to replace part of the iron-tannin component
and then to replace all of it. The advent of the fountain pen which, unlike earlier quill
and iron nib pens, carried its own supply of ink, hastened this development. The use
of dyes increased the range of colours available and enabled washable inks, with
entirely water-soluble colouring materials which could easily be removed, to be
developed. Other changes, including the addition of alcohols, were made to make the
ink dry faster.

Ball-point inks

The invention of the rolling ball pen introduced a new concept to placing ink on
paper. A ball at the end of a tube picks up ink from the reservoir above it and transfers
it to the paper surface. Because the ball rotates so long as the pen is in motion across
the paper, the flow of the ink is continuous and applies the required amount to the
written line.
Ball-point inks are not based on an aqueous solvent but on a quick-drying paste.
Mixtures of dyes provide the colouring matter, and an important constituent is the
resinous material which remains after the solvent has evaporated and serves to bind
the ink to the paper. The convenience of the ball-point pen has given it pride of place
amongst all other forms of writing instrument. But far the majority of handwritten
documents are now completed with one, and it appears that it will remain the most
popular form of pen for years to come.

Fibre tipped and roller ball pens

After the development of the ball-point pen, felt-tipped and fibre-tipped markers were
produced. These depend on a compressed fibre stylus transferring ink from the reservoir
to the paper by capillary action through the gaps between the fibres. In felt-tipped
markers the fibres are less densely packed, and the writing tip is wider. In a fibre pen
a more compressed fibre bundle can be made sufficiently narrow to produce a line
similar to that of a fountain pen. The inks used in these instruments are water-based,
with alcohols and other solvents added to induce quick drying, and for colour use
dyes similar to those of other aqueous inks.
A further development in pen design produced roller ball pens, employing the same
principle of ink delivery as that of the ball-point pen but using an aqueous-based ink.
The inks used in these pens, like those in felt-tipped pens, depend on water-soluble
dyes for their colour.

The examination of inks

It is sometimes necessary to show whether or not a particular pen was used to write
certain material. More often it is necessary to show whether or not two inks on one
document are the same. By adding extra writing the meaning of the wording or the

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amount of money can be greatly changed. Additions range from long passages to a
single digit as simple as a figure ‘1’ which can increase the apparent value of a document
many times.
During the manufacture and development of pens and inks tests are performed
with the aim of improvement of quality, reduction of cost and other factors of
importance to the maker. Ample quantities are available and complications, such as
the presence of paper, can be removed or controlled. In contrast, the examination by
the forensic document examiner is made on a small amount of ink already dried on
the paper. There are extra problems in that the document is preferably not damaged.
The first techniques employed, therefore, are those designed to obtain as much
information as possible from the ink by visual or other non-destructive means. After
this, those requiring samples to be taken from the paper are used. The methods are
described in this order.

Visual examination

The eye is in itself a powerful scientific instrument, capable of discovering much

information from an examination of ink on paper. With the aid of a microscope,
using low power, giving a magnification of up to one hundred times, the appearance
of a line written on paper may give invaluable information. The appearance of ball-
point ink under a magnification of around 20 to 50 times provides clear evidence of
its origin. As ball-point inks are only partly absorbed into the paper, they have a
characteristic glossy appearance, and their pasty texture is unmistakable. In many
cases striations caused by imperfect or dirty ball housings are apparent, and there is a
tendency, just after the pen has turned a corner, for an extra amount of ink to be
deposited in the line. The extra pressure required when writing with a ball-point pen
will frequently produce indentations in the paper.
In contrast, a water-based or ‘wet’ ink, will colour the paper by being absorbed
into it, in effect by dyeing it in a narrow line. The ink itself will not be visible as a
layer of added material but rather as a coloured area of an evenly textured surface.
Whether the line is made with a modern fountain pen with a tipped nib giving an even
width, or with a fibre tipped or roller ball pen will not normally be apparent from the
appearance, even under magnification. The depth of indentation will be small or non-
existent, but a faulty instrument may leave some indication; the housing of a rolling
ball pen when it is held at an oblique angle to the paper may leave an indentation
parallel to the line. However, the use of a wide pen nib will be shown by the variable
width of the line.
Other non-ink writing instruments will leave characteristic traces. Pencils and
crayons smear solid deposits on the paper, and these can be seen as such under the
microscope. The shiny appearance of graphite and the waxy look of crayon on the
surface of the paper are unlikely to be confused with other materials. Carbon paper
impressions can sometimes cause problems, but their most distinctive feature is the
gradual shading of the edges of the line. This, produced by the lower pressure of the
depressed paper away from the centre of the writing instrument, contrasts with the
sharp cut-off of the edges of writing made directly on the paper.
Apart from the distinction between different types of ink, variations can be detected
between inks of the same type. The texture may vary considerably, especially within
ball-point inks, and the width of line will depend on the size of the ball or stylus used.

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The presence of striations in a ball-point line can also distinguish between different
pens. Erasable ball-point inks have a characteristic appearance under magnification
of about 100 ×. Because they use a rubber-based vehicle which shows fine strings of
ink, they can be distinguished from normal ball-point inks.
As well as differences in appearance, colour is very significant in the comparison of
inks. Shades and depth of colour vary considerably, and under the microscope
differences between inks can be detected visually. Care has to be taken because a line
made at one time by a single instrument can vary in intensity.

Examination of colour

Reasons for the colour of an ink are conveniently discussed at this point. Light is
essentially electromagnetic radiation of certain wavelengths or frequencies which can
be detected by the eye. Not only can the eye detect this radiation, but it can distinguish
between the wavelengths present. Thus, if light with a wavelength of 550 nm strikes
the eye it is recognised as yellow light, whereas if the radiation has a wavelength of
450 nm it appears blue. The eye is sensitive to radiation ranging in wavelength from
about 400 to 700 nm and sees this spectrum in colours ranging from violet to red, as
in a rainbow.
Sources of light are rarely monochromatic, that is, of one wavelength. Sunlight
and the radiation from an incandescent electric light bulb contain wavelengths in the
whole range, and their combined effect on the eye causes it to see white light. If a
mixture of two wavelengths impinge on the eye a third colour will be seen. A mixture
of red and green light will be seen as yellow, a colour also seen when monochromatic
light at a wavelength between those of red and green light is detected. A demonstration
of the range of colours available from only three sources, red, green and blue light, is
daily seen in the natural hues appearing on a television screen. Even white light can be
created from these three colours.
However, most colour detected by the eye is not from mixtures of different lights
but from light reflected by coloured materials. Certain compounds absorb light at
particular wavelengths. They do this because they have in their structure combinations
of atoms, called chromophors, which have this property, and these absorb no single
wavelengths but a range or ranges of wavelengths. If white light falls on compounds
which appear coloured, part of it is absorbed at the appropriate wavelengths and the
rest is reflected. It is the reflected light, that part of the spectrum which is not absorbed,
which is detected by the eye. Because it contains some of the wavelengths but not the
whole spectrum it will appear not white but coloured. Thus if the blue, green and
yellow components of white light are absorbed, the remaining red will be reflected,
giving the object a red colour. If all the wavelengths of the incident white light are
absorbed the object will appear black. Illumination by a single wavelength or a narrow
band automatically eliminates other colours; a red jumper is not seen as red under a
sodium street lamp.

Absorption spectra and the examination of inks

When wavelengths or colours of light are referred to above it must be understood

that this is a range rather than an individual value. Any substance which absorbs

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some colours and reflects others does so in a way which can be recorded on a graph.
If the absorption at a particular wavelength is, say, 50% and at another is 75% and
at a third is 100%, these can be plotted as points on a graph on which one axis
represents the wavelength and the other the percentage absorption. If the points are
connected with a line, which continues for all the wavelengths measured, the
absorption spectrum of that substance will be produced. Typically, for an ink this
will consist of a curved line with peaks and troughs. The peaks will indicate those
wavelength ranges which are strongly absorbed and the troughs those at which the
light is reflected, at least in part.
Inks are made up of mixtures of dyes which, in combination, absorb the appropriate
wavelengths to give the required colour. The dyes used are not common to all inks, so
there is considerable variation both in the colour and the absorption spectrum of the
combinations. Sources of reflected light with two different absorption spectra can
appear identical because the eye mixes the combination of wavelengths reflected. The
emitted colours of red and green, which are together seen as yellow, is an example of
the same phenomenon. Therefore because two very similar colours can be produced
with different dyes with different absorption spectra the fact that two inks look the
same is not an indication that they are. Methods have therefore been devised to detect
these differences.
The simplest method is to use light of a colour other than white and observe both
inks under it. This will detect differences if those parts of the coloured incident light
which are reflected from the inks appear different to the eye. This separation does not
occur very frequently.
Another method of detecting differences in the spectrum is to use a dichroic filter.
This is a combination of two coloured glass or gelatin filters bound together so that
light passing through one must pass through the other. A useful combination is that
using a red and green filter. Light passing through both filters will be partly absorbed,
dependent on the absorption spectrum of the combination of the two filters. The light
which is thus transmitted will consist of small ‘windows’ at certain wavelengths. If a
small quantity of a particular colour is reflected and is of the same wavelength as a
window, that colour will be visible. A difference in absorption at that wavelength in
two inks which appear similar will therefore be detected.
A more sophisticated method of determining the absorption curve is to measure it
with special equipment. The problem of only a small amount of material being available
in the width of a line has been to some extent overcome by a refinement in technique.
The apparatus used for this is the microspectrophotometer. Because of the complexity
and expense of this method it is not in common use.

Ultraviolet and infrared radiation

From about 200 nm to 400 nm where violet light begins the visible wavelengths, the
radiation is described as ultraviolet. Similarly, in the range from about 700 nm upwards
infrared radiation can be generated. Although not detected by the eye ultraviolet and
infrared radiation are absorbed like visible light.
Most blue and black inks absorb ultraviolet, so that little is gained by examining
its absorption and reflectance. In contrast, while visible light is absorbed by different
inks of a similar colour in ways which are only slightly different, there is a very big
contrast between certain inks in their infrared absorption (see Figure 7). Whether or

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Figure 7 Two black inks of different manufacture photographed in (a) normal light and (b) infrared
radiation, showing the difference of absorption in the infrared region

not an ink absorbs infrared also depends on the chromophors in the molecules of the
dyes present. Some will absorb a range of frequencies which extends well into the
infrared range, while in others the absorption will be confined to the visible or near
infrared. This variation will not affect the colour of the ink because the eye will not
detect the presence or absence of infrared radiation.
Therefore the absorption spectrum of an ink may show that it continues to absorb
radiation from the red through to the infrared, or the absorption may fall to nothing
near the end of the red end of the spectrum. In the first case the ink when radiated
with infrared will absorb it, but in the second case it will not. In the latter event the
radiation will pass through it or be reflected through it as if it were invisible or
transparent.
Infrared radiation is not of a single wavelength but a range of wavelengths. For
convenience of detection in document examination it can be regarded as having
wavelengths between 700 nm and 1000 nm, although it extends far beyond this into
the range where it is used as a means of identification of chemical compounds. As it is
not visible it must be detected by other means. These are by photography, using
emulsions which are suitably sensitive, and by electronic means whereby a photoelectric
cell picks up an image and makes it visible on a visual display unit.

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Detection of infrared radiation

Photography was the first method employed to detect infrared radiation. Suitable
filters which allow only the appropriate wavelengths of radiation to pass are placed
over the lens and a film sensitive to infrared is used. Good quality photographs can be
obtained by this method. Later, image converters and closed circuit television systems
using infrared sensitive tubes were introduced, again using suitable filters and light
sources. These were followed by purpose-built apparatus, the VSC/1. made by Foster
and Freeman Ltd. described in Chapter 10, which incorporated light sources, filters,
a visual display unit, lenses and sensitive tubes. This enables a wide range of
examinations to be carried out in ideal conditions. Further modifications to the VSC/
1 and similar apparatus developed by other manufacturers, such as the Docucenter
made by Projectina AG of CH-9435 Heerbrugg, Switzerland, incorporate improved
light sources, image enhancement techniques and video printers which enable an
immediate record to be made of what appears on the screen of the monitor.

Infrared absorption

The devices described above provide a sensitive method of detecting differences between
inks. Some inks contain components which absorb into the far infrared and so are
detectable throughout the range. Others contain dyes which absorb only in the visible
part of the spectrum and are therefore invisible when viewed in the near infrared,
around 730 nm. Others absorb further into the infrared region, becoming ‘invisible’
at around 800 nm. It is therefore possible to test the similarity of inks by determining
at what wavelength they cease to absorb infrared radiation and become ‘invisible’. In
some cases it is possible to discover a clear difference between two inks on a document,
one disappearing at a certain wavelength while the other remains visible. When
comparing two ink lines by this method care must be taken to allow for the fact that
a thicker, more intense line will show up more clearly than a weaker one of the same
ink in the same conditions. The difference can be mistaken for that between two inks,
one absorbing more strongly than the other.
A second effect of the varying absorbencies of different inks is in cases where an
entry has been heavily obliterated with another ink. If the added ink is invisible in
infrared and the original entry is in an ink which absorbs infrared, the original will be
detected as if the obliteration were not there (Figure 8).
Apart from comparison of two inks, the technique of examining documents in
infrared conditions has other uses. Firstly, pencil lead, which is made largely of graphite,
absorbs throughout the infrared range as well as in the visible spectrum. If a simulated
signature is made by writing over pencil lines in an ink which is transparent in any
part of infrared radiation, the graphite can easily be detected. Even when the pencil
line is removed by an eraser, traces may still remain, and, without the overwriting ink,
can be clearly identified.
Secondly, it aids in the interpretation of postmarks which are made less clear by
the pattern of the postage stamp beneath them. The ink of most cancellation marks is
based on carbon black which strongly absorbs infrared wavelengths while the pigments
of the printing ink may not. The contrast is therefore improved, and in many cases
the postmark can be read.

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Figure 8 (a) An obliteration of one black ink with another, photographed in normal light (b) The same
photographed using infrared radiation

A similar increase in contrast can enable a faint trace of largely erased pencil writing
to be identified. Such lines are often much clearer when examined in the infrared
range than when they are observed in normal light. The same method can be used to
detect traces of other infrared-absorbing material including some printing inks, which
remain after removal of most of the material. In rare cases erased writing inks may be
also revealed.

Ultraviolet fluorescence

Ultraviolet fluorescence produced by paper varies greatly, and, as has been discussed
earlier in this chapter, can be used as a means for testing whether two or more pieces
are similar or different. Other materials such as glues, adhesive tapes and sealing
waxes can also be distinguished by their fluorescences. The application of solvents or
chemical to paper can cause the fluorescence to change, so that when they have dried
and apparently have left no trace, an area of different fluorescence will be found
when the document is examined under ultraviolet radiation.
Red inks may fluoresce under radiation from an ultraviolet lamp, and this may
give a means of distinguishing one ink from another if they are both of similar

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appearance. Fluorescence in the higher wavelength range of the ultraviolet region can
be produced by ultraviolet radiation of lower wavelength, and some differences between
inks in this respect have been reported [64]. As the fluorescence is not in the visible
region and cannot be observed, special equipment is needed to detect it. This, in
addition to the likelihood that differences which can be detected by these means can
also be found by other techniques, has resulted in little use being made of this
phenomenon.
Inks affected by chemical action rendering them invisible may leave traces in the
paper. These inks, if they are not diffused by the solution, may be detected by their
fluorescence emitted when ultraviolet radiation falls on them; ultraviolet examination
may therefore reveal the writing which has been erased. This method was more useful
in the past, as the older formulations of ink were more likely to leave evidence enabling
their detection by this means. Infrared luminescence, described below, is more successful
for the dye-based inks of today.
Some modern inks, however, are intended to be visible only in ultraviolet radiation.
These are special preparations used to mark items to enable their identification if they
are recovered after a theft. There are also those inks used to write signatures on
various documents which for security reasons are visible only when viewed under
ultraviolet. It is rare for any of these ‘invisible’ inks to be involved in any laboratory
examination.

Infrared luminescence

A confusion of terms exists when fluorescence is referred to in document examination.

In discussing fluorescence excited by ultraviolet radiation the term ultraviolet
fluorescence is used. In contrast, by infrared luminescence, document examiners mean
that luminescence emitted in the infrared region, excited by visible light. The
inconsistency of these terms is now too widely accepted to change except for reasons
of pedantry. The term luminescence rather than fluorescence is usually applied to
those emissions in the infrared range, again without a completely logical reason.
Similarly those who argue that great precision in the use of terms should be applied
may feel that the term light should not be applied to infrared and ultraviolet radiation,
because they cannot be perceived by the eye. However, as with the other terms, provided
that no misunderstanding occurs, the terms most commonly employed and understood
can be used.
Infrared luminescence together with luminescence in the red region of the spectrum
is emitted by inks, papers and the remains of erased inks when radiation of
appropriate wavelength falls on the document (see Figure 9). In the same way that
fluorescence excited by ultraviolet radiation is of a higher wavelength and normally
occurs in the visible range, so visible light excites fluorescence only in the longer
wavelength regions in the visible spectrum or in the infrared region. The efficiency
of the excitation of luminescence is not great, so a high intensity is required to
produce a detectable result. With infrared luminescence there is also the problem
that, in contrast to that excited by ultraviolet radiation, little or nothing can be seen
by direct vision. It is therefore necessary to use either photographic or electronic
means. Suitable sources for the excitation of infrared luminescence are provided by
intense tungsten filament or quartz iodine or xenon arc lamps, with appropriate
glass or gelatin filters or with a saturated solution of copper sulphate. These allow

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Figure 9 Three blue inks of different manufacture photographed in (a) normal light and (b) conditions
suitable for the excitation and detection of infrared luminescence

the green-blue exciting radiation to pass, but prevent infrared or red light from the
source from falling on to the document thus illuminated. Further protection from
adventitious strong light must also be provided, as this too can swamp the weak
luminescence.
With this illumination the document will reflect green-blue light as well as emitting
infrared or red luminescence from those areas which will generate it. A further filter
is therefore needed to eliminate the exciting light from the means of detecting the
luminescence.
The luminescence can be detected by photography or a video camera with a suitably
sensitive tube but normally the specially designed apparatus such as the VSC/1 is
used. Different luminescence from different inks can be detected using a range of
filters and the results recorded on a video printer.
An extension of the use of green-blue light to excite luminescence is to use the light
from a laser. The advantage of this is that the light is intense and monochromatic, so
the need to filter out unwanted radiation does not arise. This means that visible
luminescence much closer in wavelength to the exciting light can be detected.
Observation of visible luminescence is made through filters which are specially made
to cut out the laser wavelengths. These are normally incorporated into goggles which

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are in any case necessary to protect the eyes. Alternatively, the luminescence can be
recorded either by photoelectric or photographic methods, which are the only ways
of detecting radiation emitted in the infrared range.

Comparison of inks using infrared luminescence

Infrared luminescence has proved to be of immense value in the examination of

documents, far exceeding in importance the effects of ultraviolet radiation.
Firstly, although many inks luminesce in the infrared region, some do not (see
Figure 9). Secondly, there is a further variation between different inks both in the
wavelength range at which the luminescence appears and in its intensity. Because
examination of inks normally takes place on paper which itself may produce
fluorescence, that of an ink will appear different on different papers. If the fluorescence
of the paper is stronger than that of the ink the latter will appear not to fluoresce. In
most cases, however, inks are examined for the purpose of comparison of two writings
on one document. The typical case is where an addition or alteration may have been
made at a later date.
If it is necessary to compare ink from a pen or a bottle with ink on a document, a
mark can be made with the ink on the same page. Comparison under infrared
luminescence conditions can then be made.
The distinction between different inks was discussed earlier when absorption or
reflection of infrared radiation was considered. Observation of the questioned entries
on a document in conditions which will detect infrared luminescence will often
distinguish between two inks, whether or not they can be separated by infrared
reflection. In some cases differences in luminescence can be detected only by a change
of wavelength of the exciting radiation. Again, care must be taken if there appears to
be a slight difference between two inks. This could be caused by different quantities
of ink on the surface.
The fact that luminescence will be quenched by materials which will absorb its
wavelength can also cause complications. An ink absorbing radiation at, say, 750 nm
may also contain a component which emits luminescence at this wavelength. This
will then not be detectable, because it is self-absorbed, but if the component spreads
away from the quenching constituent its fluorescence will be observable. This can
occur when the surface is moistened, the water or other solvent removing the fluorescing
component from the body of the ink. If this happens in only a part of the document
the luminescence of that part may erroneously be taken to indicate a different ink.
Generally, however, infrared luminescence can complement infrared reflectance in
distinguishing two different inks in one document.
The complications caused by relative fluorescences are increased because the
wavelengths at which they occur may be different. By changing the filters in front of
the detector, different effects are observed. An ink will appear brighter than its
background at one wavelength and less so at another. The effect of absorption of light
at a particular wavelength will also reduce the fluorescence of an ink, so that that
from the paper will be greater.
Comparison of inks on the same background, using the luminescence of ink,
depends, therefore, on a system which will enable its detection to be made at a
number of different wavelengths, from about 650 nm to 900 nm. The same system
or apparatus can be used for the detection of erasures and alterations. Photographic

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methods require a separate exposure to be made at each wavelength, but apparatus

such as the VSC/1 described in Chapter 10, are designed for this purpose. Their
flexibility enables examinations under a wide range of different wavelengths and
light conditions to be made.

Erasures

While the use of ultraviolet, referred to earlier (p. 102), has been of decreasing value
in the detection of erased writings, modern inks have proved to be more productive of
luminescence excited by visible light. Inks which have been made invisible by removing
the coloured components can be detected by the luminescence of whatever remains
on or just below the surface. Erasures are made by three methods, the mechanical
removal of the ink by scraping the surface until all the visible ink has been removed,
the treatment by bleaching solutions which convert the dye into colourless compounds,
and the removal of the soluble dyestuffs by suitable solvents. In all these processes it
is possible that traces will remain which will fluoresce or luminesce when illuminated
with visible light.
As previously noted, the fluorescence will be weak, so sensitive methods of detection
are required. Again, the observation will be affected by the luminescence of the paper
which can in some cases be greater than that of the traces of ink residues. It is therefore
necessary to observe the erased area in all possible variations of wavelength. Sometimes,
too, the exciting light can be varied. The laser is a particularly useful tool for erasures
on documents because it provides high intensity illumination and because luminescence
which is close in colour to the exciting light can be detected.
It is not always clear what is being observed. When an ink dries on the paper,
certain components may penetrate more deeply into the surface than others. If these
are not visible there will be no reason to remove them when mechanical erasure is
being made. If they are not soluble they will not be taken out when the coloured
components are dissolved away. If the dyes are converted to other compounds these
may luminesce, even if the original ink did not. The reasons for what has occurred are
not so important as the fact that the ink or its remnants can be detected and the
erased entry identified.
Infrared luminescence can be of value in detecting erasures of other materials such
as typewriter ribbon and stamp and pad inks.
In some cases it is not possible by this method to find out what has been erased: not
every erased ink will produce a luminescent trace. Usually, however, evidence will be
found to show that something has happened to the paper surface, that some action
has taken place. A ring of fluorescence, rather like a tide mark, different from that of
the rest of the surface is an indication that a liquid has been applied to the paper. This
in itself can be of importance to show that the present entry is not necessarily the
original one.
When written entries are altered by removing parts of an ink line it may be possible
by simple observation to determine what was originally present. Although the more
sophisticated methods described above are available, they do not always produce
satisfactory results. With or without the aid of a microscope, traces of ink or pencil
may be detected and visually pieced together to identify an erased entry. This is best
done with a number of lighting facilities available. Oblique lighting, exploiting any

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indentations of remaining writing which may be present, and different coloured filters,
to ensure the greatest contrast between the ink and the paper, will be of assistance. It
is not always the brightest of illumination which is most effective; sometimes the best
results are obtained in low light levels.
Traces of pencil from an erased entry can be enhanced by photography using high
contrast conditions or infrared film. Electronic means of detecting infrared can also
be employed to make the traces more visible.
Indirect methods can also be of assistance. Indented impressions on the piece of
paper below the erased writing or ‘reverse impressions’ on the back of the page detected
electrostatically (see Chapter 9) have been of value. In one case these, combined with
enhanced visibility of traces of a pencil line, were used to identify very significant
erased pencil writings.

Obliterations

Obliterations of an entry are sometimes made in a different ink. As has been mentioned
earlier it may be possible to decipher the original by examination under infrared
radiation if the overlying ink does not absorb infrared radiation and the covered
entry does. If both react in the same way in these conditions the technique will be of
no value. However, if one luminesces, the problem may be solved (see Figure 10). A
luminescent ink under a non-luminescent one will be visible, provided that the
obliterating ink does not absorb the luminescence. On the other hand, if the covering
ink is luminescent and the obliterated entry absorbs that fluorescence, a dark area
corresponding to the shape of the latter will be apparent. The luminescence of the
covering ink is quenched by the ink of the original writing below it. Sometimes careful
control of the lighting and filtration conditions is required.
When an ink has been heavily written over and the techniques using infrared
reflectance or absorption described above are not effective, microscopic examination
may prove able to solve the problem. If the obliterating ink is of a different colour the
choice of filters to render it as invisible as possible can help. A photograph taken in
conditions which give the greatest contrast for the original ink and its background
and the lowest for the obliterating ink, will sometimes ‘remove’ much of the
obliteration.
In some of these cases it is possible to identify an obliterated entry because there is
sufficient of it uncovered to provide the evidence. By making an enlarged photograph
under the most favourable conditions and then ‘whitening out’ on it those lines which
are clearly in the obliterating ink, the portions of the original entry which remain,
even though they are not complete, are more easily read without the distraction of the
overwriting.
Obliterations are also made with typewriting correction fluids; these are dealt with
in Chapter 6.

Other luminescence effects

Luminescence has been observed under laser radiation when a component of an ink
has been off-set from another page with which it has been in contact. It is not clear
what part of the ink has been ‘printed’ on to the adjacent page, but the effect is

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Figure 10 (a) An obliteration of one blue ink with another, photographed in normal light (b) The same
photographed in conditions suitable for the detection of infrared luminescence. Although the obliterating
ink luminesces strongly, the non-luminescing ink absorbs the luminescence.

detectable only under the laser. Many substances luminesce strongly in laser light and
may be transferred from one source to another. Transparent plastic tends to absorb
traces of ink or paint from credit cards, so wallets specially designed for these will
often show an impression of the details from the cards which they once contained.
A case has been reported where a vehicle index number was written on a hand and
later washed off. Traces of the number could be detected by their fluorescence under
laser light many hours later. Prints made with fingers contaminated with fluorescent
materials can also be detected [16].

Destructive techniques

So far the methods described to examine inks have not included those where there is
need for any damage to be made to the document. They have the advantage that the
ink, erased or not, the paper, and any other marks on it are not affected in any way.
Other tests may be performed which provide additional information but which require
portions of ink or other materials to be removed. Earlier, mention has been made of

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methods used to test paper which require the taking of a sample on which to operate.
Similarly, the components of writing inks, whether they are from ball-point pens,
fountain pens, or fibre tipped pens and markers, can be further examined by chemical
techniques which cannot be performed except away from the paper.
Needless to say, there is no point in causing damage to a document if any
information so obtained would not carry the case any further. If, for example, two
inks have been shown to be different by non-destructive methods, there is no need
to proceed with further work. If it is important to discover whether two inks are
similar or different and they cannot be distinguished by visual and other non-
destructive means, further work is necessary. Before any damage is made to the
document it is important to make a permanent record of the entries to be tested. A
high quality photograph is best for this, but a photocopy could provide a substitute
if photography is not possible.
The methods used for the further examination of inks, usually for comparison
purposes, can exploit the variation found either in the colouring materials or other
components of the ink. Dyestuffs provide the best opportunity of discrimination
between two different inks. The most sensitive method to detect the components that
are dried on the paper is to exploit their strong colour and to use methods which
depend on this.

Chromatography

The principle of chromatography is that individual components of a mixture are

separated and therefore identified or compared with others. Two methods are employed
in the examination of inks, thin layer chromatography and high-performance liquid
chromatography. The former is in more general use. The principle depends on a small
amount of the material being analysed being introduced on to a ‘stationary phase’,
which will absorb it. The ‘moving phase’, a fluid, is then passed through the stationary
phase and carries the material with it. The speed of travel of the material through the
stationary phase is dependent on its composition. Different compounds will travel at
different rates, so the method is ideal for separating mixtures and identifying their
components by the speed or distance of travel.

Thin-layer chromatography

A coating of silica gel spread evenly on a background of plastic or aluminium constitutes

the stationary phase in thin-layer chromatography. The materials being analysed are
introduced to the plate—the name given to the layer and its support—by adding
drops of a solution of it, one at a time, to a small area near the bottom edge. As the
solvent dries between each drop the material is concentrated in a small spot of about
2 mm in diameter. This is known as ‘spotting’ the material. The plate is then dipped
into a suitable solvent, the eluate, so that this rises by capillary action through the
thin layer. As it does so it takes with it the different components of the mixture which,
because they rise at different rates, are separated. When the eluate has nearly reached
the top of the plate, the plate is removed and the components of the material being
analysed remain in the positions they have reached.

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In the analysis of an ink it is necessary firstly to dissolve it in a solvent such as a

pyridine—water mixture. To do this a portion of the ink line is removed, either by
cutting out small circles with a ground-down hypodermic needle or by slicing a thin
sliver from the surface of the paper. A suitable amount of ink is provided by about a
centimetre of a normal line or the equivalent number of cut-out discs. This is dissolved,
and the solutions of inks which are to be compared are ‘spotted’ along a line near the
bottom edge of the plate. This is then placed in a shallow quantity of eluate which is
typically a mixture of solvents such as ethanol, butanol, or ethyl acetate. When the
eluate has travelled to near the top of the plate, the plate is removed and the run is
complete. The individual dyes present in the inks are each positioned at a fixed place
and will not move further. By running two or more inks side by side a comparison of
the components can be made by direct observation. A standard ink is run on the plate
to check if the system is working properly. Further examination of the plates under
different lighting conditions can be made so that fluorescence under ultraviolet and
luminescence under visible light provided by a laser or more conventional sources,
can be compared. The inks can also be run using other eluates.
Some indication of the relative proportions of each component is obtained by direct
observation, but futher examination with a densitometer can provide quantitative
information about the proportion of each dye in the formulation.
It is necessary to place extracts of the paper of the documents on the plate. Paper
may contain dyes which might be attributed to the ink.

High-performance liquid chromatography

Instead of the solution of the ink being evaporated as a spot on a chromatography

plate, it can be forced by high pressure through a column of absorbent material in a
glass tube which, like that of a thin-layer chromatography plate, will slow down the
passage of each component to a rate which is dependent on its physical properties. As
each component will be retarded to a different degree a separation is again achieved.
Instead of leaving the dyes on the column the pressure is continued until they have all
passed through the column. They are detected as they emerge by a device which
measures their absorption or colour at a particular wavelength or at a number of
wavelengths. As the absorption is proportional to the quantity of material present a
quantitative assessment of each component is achieved.
The results are obtained as a graph with peaks representing the presence and
proportion of each component. The advantage that high-performance liquid
chromatography has over thin-layer chromatography is in its ability to determine
more accurately the proportion of the major components of the mixture of dyes. A
disadvantage is that the cost of the apparatus is considerably more than that required
for thin-layer chromatography.

Further chemical tests

In certain cases it is possible to distinguish between two inks by their solubility. When
a drop of a solvent is applied to a line of writing the dyes may ‘bleed’ into the
surrounding paper. Generally speaking most ball-point inks are based on similar vehicles

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which bind them to the paper surface and react in the same ways to whatever solvent
is applied. Other inks may or may not be soluble in water, so could be quickly
distinguished from each other by the application of a simple test, making a saving in
time and avoiding further change to the document.
When an iron-based ink, now rarely found, has been made invisible by chemical
agents, the coloured compounds having been converted to colourless ones, it is possible
to perform a further chemical reaction to create another coloured iron salt and render
the ink visible again. This can be done in two ways. In the first the document is
exposed to fumes of thiocyanic acid prepared by mixing potassium thiocyanate and
dilute sulphuric acid. Any iron salts in the paper are converted to the red-brown ferric
thiocyanate. In the second method a dilute solution of potassium ferrocyanide can be
applied to the surface, and the iron-containing ink traces will turn dark blue as they
combine to form ferric ferrocyanide.

Other components of inks

Apart from the dyes present in the ink dried on to a piece of paper there are other
components. The most important of these is the vehicle which in the case of ball-
point inks is a mixture of resins with, in a recently applied ink line, traces of the
solvent. In water-based inks there is a much smaller amount of vehicle. The very small
amounts which are present on the surface of a written document are insufficient for
any practicable comparison to be made. Although the amounts of dyes present are
not appreciably greater, their strong absorption of light and other optical properties
make their examination easier. One exception is that erasable ball-point inks contain
a rubber-based compound which is sufficiently different from conventional vehicles
to be distinguished from them.

Relative ageing of ball-point inks

Distinction between vehicles can be made by exploiting the ease of detection of

colouring material. The solubility of dried ball-point inks in certain solvents is
dependent on the length of time that the ink has been on the paper. It is possible to test
how soluble an ink is by dissolving it and measuring the amount of colour which has
been extracted in a certain time. By taking samples of solution at intervals, say, one
and two minutes after the dried ink has been introduced into the solvent, the rate of
dissolution can be determined. If the rate is faster for one sample than for another
sample of the same ink on the same document, this indicates that the first sample has
dried to a lesser extent and has therefore been on the document for a shorter time. It
is important that like is compared with like. A different ink or a different surface
would give a result which could be misleading. It is possible for inks aged between a
few weeks and about nine months to be usefully tested.
The method is of value, therefore, only when the times of writing of two similar
inks on the same document are in dispute. This is likely to occur if an extra sentence
is suspected to have been added, so before attempting to test for the relative ageing of
inks it is necessary to test them by the methods previously described to determine
whether or not they are of the same formulation. If they are, the solubility tests will
be of value; if they are not, the problem may have been solved by the difference

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between the inks, which in itself could provide evidence that all was not quite
straightforward. The technique is not yet universally employed.

Dating of inks

The relative ageing of ink cannot put a precise time on the act of writing. This is not
possible by any other means of ink analysis, but if an ink can be shown to have been
made only after a certain date, any writing made with it cannot have been made
before then. The principle has been applied when the dates in question have spanned
the introduction of a new type of ink, from ball-point pens for example. With the
wide variety of different ink formulations and the many manufacturers at work today,
such dating methods require comprehensive records and cooperation with ink
producers so that well founded information is made available.
In the USA the Laboratory of the Alcohol, Tobacco and Firearms of the US Treasury
has built up such a collection of ink formulations, but this appears to be unique. In
addition, the same laboratory has arranged with producers of inks in the USA to ‘tag’
their products with special chemicals, compounds of rare earth metals, to indicate the
year of manufacture. These compounds, introduced in very small proportions, can be
detected only by sensitive analytical procedures such as cathodoluminescence, X-ray
fluorescence, and ion probe spectrometry. Their presence also provides another means
of distinguishing between two inks where such a comparison is significant.
The relative time of writing of two entries on a document can be determined on
occasions when one crosses a fold after the latter has been made but the other does
not. Sometimes writing on the back of a page will be affected by crossing heavy
indentations on the front which protrude from the surface of the back. Indented
impressions on an underlying page may show an absence of one entry indicating that
this was not made at the same time as the rest. Similarly, impressions detected on the
back of the page may differ because the surfaces on which the page was resting were
different for the two entries. As with much of forensic science particular individual
circumstances may enable a more unconventional approach to be employed.

Further reading

[1] ALLEN, M.J. AND RIMMER, P.A. (1988) The dating of a will, Journal of the Forensic
Science Society, 28, 199.
[2] BERTOCHI, M.P. (1977) Envelope association through manufacturing characteristics,
Journal of Forensic Sciences, 22, 815.
[3] BLACKLEDGE, R.D. AND IWAN, M. (1983) Differentiation between inks of the same
brand by infrared luminescence photography of their thin layer chromatograms, Forensic
Science International, 21, 165.
[4] BLACKLOCK, R.E. (1987) The laser. A tool for questioned document examination,
Journal of Police Science and Administration, 15, 125.
[5] BOYD, P.F.J. (1983) Laser technology. A new concept to challenge the forensic document
examiner, Canadian Society of Forensic Science Journal, 16, 7.
[6] BRUNELLE, R.L. AND REED, R.W. (1984) Forensic Examination of Ink and Paper,
Springfield, Illinois, Charles [Link].
[7] BRUNELLE, R.W., CANTU, A.A. AND PROUGH, R.S. (1987,1988) Various papers
on dating of ink, Journal of Forensic Sciences, 32, 1151, 1502, 1511, 1522; 33, 744.

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