Forensic Science International

101 (1999) 167–176

A study to investigate the evidential value of blue

and black ballpoint pen inks in Australia
a, b c d
Claude Roux *, Michelle Novotny , Ian Evans , Chris Lennard
a
Department of Chemistry, Materials and Forensic Science, University of Technology Sydney,
P.O. Box 123, Broadway, NSW 2007, Australia
b
Forensic Document Services Pty Ltd., P.O. Box 543, Queanbeyan, NSW 2620, Australia
c
Forensic Services, Australian Federal Police, Locked Bag A3000, Sydney South, NSW 2000, Australia
d
Forensic Services, Australian Federal Police, G.P.O. Box 401, Canberra, ACT 2601, Australia

Received 11 May 1998; received in revised form 4 January 1999; accepted 3 February 1999

Abstract

The aim of this project was to investigate the evidential value of blue and black ballpoint pen
inks in Australia. For this purpose, 49 blue and 42 black ballpoint pen inks, of different brands,
models and batches, representative of those ballpoint pens available on the Australian market at
the time of the study, were analysed by three techniques: filtered light examination (FLE);
reflectance visible microspectrophotometry (MSP); and thin-layer chromatography (TLC). The
results showed that the power of the individual techniques to discriminate inks between and within
brands, models and batches varied, the most informative techniques being TLC.FLE.MSP. The
greatest degree of differentiation was achieved when using a combined sequence of techniques, the
discriminating power being 0.99 and close to 1 for blue and black inks, respectively (different
brands and models). In respect to the discrimination between different batches of a same brand and
model, it was shown that 14 out of the 33 pairs compared could be discriminated. Overall, this
study confirmed the high value of the examination of inks when applied to ballpoint pens available
in Australia, especially when a combined sequence of techniques is applied.  1999 Elsevier
Science Ireland Ltd. All rights reserved.

Keywords: Forensic science; Document examination; Inks; Ballpoint pens; Evidential value

*Corresponding author.
0379-0738 / 99 / $ – see front matter  1999 Elsevier Science Ireland Ltd. All rights reserved.
PII: S0379-0738( 99 )00021-3
168 C. Roux et al. / Forensic Science International 101 (1999) 167 – 176

1. Introduction

The primary materials which make up a document are the support, usually paper,
cardboard or polymer, and the text, which may be deposits of ink (writing, printing,
typewriter ribbon or stamp pad inks, and paper ruling), carbon copies, photocopier toner
or pencil (lead or coloured). Secondary materials which can become part of a document
include correcting materials, erasure residues, adhesives, stains and even fingerprints.
The scientific examination of these materials can be of paramount importance to a civil
and / or criminal investigation. This research focussed on pen ink writings on a paper
support since ink undoubtedly constitutes the most commonly analysed material.
Numerous authors have discussed the value of individual techniques and have
proposed standard protocols for forensic ink examination [1–20]. However, there is little
or no information regarding the application of a sequence of selected standard
techniques (both non-destructive and destructive) to the Australian population of blue
and black ballpoint pen inks, on the calculation of their respective discriminating
powers, and on the collective discriminating power at the finish. This research was to
address the lack of data in these areas, and further, to prepare the groundwork for a
database of information on the ballpoint pen writing inks available in Australia.
The aim of this research was to analyse a range of blue and black commercial
ballpoint pens available on the Australian market, by: (1) filtered light examination (FLE
– visible luminescence, infra-red luminescence and infra-red reflectance), (2) reflectance
microspectrophotometry (MSP), (3) and thin-layer chromatography (TLC), in order to
compare and investigate the discriminating abilities of the different techniques when
applied to: (a) different brands, (b) different models of the same brand, and (c) different
batches of the same brand and model.

2. Material and methods

2.1. Sampling

The study targeted the predominant blue and black ballpoint pen inks. Sample pens
were collected from supermarkets, variety stores, newsagents, stationers and pen
company warehouses in and around Sydney, to form as comprehensive a collection as
possible of pens representative of those available (at the time of the study) throughout
Australia. The samples collected are listed in Tables 1 and 2.
Enquiries were made of the majority of ballpoint pen companies as to the origins of
each of the ballpoint inks – whether the ink was imported, manufactured by another
company, or manufactured by their own company. None of the companies with which
contact was made, had a common ink supplier. UNI-Ball (Mitsubishi), Pentel, BIC,
Sheaffer, Penline-Mon Ami and Pilot manufacture their own inks (or have a company
which produces ink specific to their own company) either in Australia or elsewhere in
the world. Papermate and Staedtler import from other companies overseas. The
remainder of companies did not supply the requested information.
 C. Roux et al. / Forensic Science International 101 (1999) 167 – 176 169

Table 1
Samples of blue and black ballpoint pen inks used in the study
Brands and models Blue inks Black inks
Luxor Ranger Y Y
Wilson Sly 400 Y Y
DATS Skeleton Pen Y Y
KMART Price Brand Y –
Stationery Cupboard Y –
Melody Y –
Horizon 10 in 1 Y Y
Inoxcrom TODAY B320 Y –
Inoxcrom TWT Y –
Inoxcrom Tungsten Y –
Penline Classic Y –
Artic Y Y
Schwan STABILiner Y –
Artline Y Y
Pentel BK70 Y Y
Pentel Superb BK77 Y Y
UNI Mitsubishi SA-S Y Y
UNI Lacknock Y Y
Staedtler STICK Y Y
Staedtler 424M Y Y
Pilot Better Retractable Y Y
Pilot BP-S Y Y
Pilot BP-SGP Y Y
Papermate Flexgrip Y Y
Papermate Replay Y Y
Papermate Kilometric Y Y
Papermate Dynagrip Y –
Papermate Malibu – Y
BIC Soft Feel Y Y
BIC Medium (‘Crystal’) Y Y
BIC Clear Clic Y Y
BIC Clic 2000 Y Y
BIC Refill Y Y
BIC Citation Y –
BIC 4 Colour Y Y
BIC Biro Y Y
Parker Y Y
Schmidt Refill (for Parker) Y Y
Sheaffer – Y
Y, indicates the colours of those brands and models sampled.
(–), indicates the colours of those brands and models not sampled.

Unlined sheets of A4 ‘Champion’ office paper were used to support the ink samples.
All sheets were stored in plastic sleeves, within an A4 paper envelope which was in turn
kept inside a desk drawer. One line of writing in three sections was constructed for each
of 49 blue and 42 black ballpoint pen inks.
170 C. Roux et al. / Forensic Science International 101 (1999) 167 – 176

Table 2
Batch samples of blue and black ballpoint pen inks used in the study
Batches and dates of manufacture Blue inks Black inks
BIC 4 Colour
6 / 12 / 95 Y –
7 / 12 / 95 – Y
7 / 3 / 96 – Y
6 / 4 / 96 Y –
2 / 7 / 96 – Y
3 / 7 / 96 Y –
BIC Medium (‘ Crystal’)
Pre 1994 Y –
7 / 95 – Y
8 / 95 Y –
5 / 96 Y –
6 / 96 – Y
4 / 97 Y Y
5 / 97 – Y
BIC Soft Feel
8 / 94 Y Y
6 / 95 Y –
7 / 95 – Y
11 / 95 Y Y
BIC Clic 2000
9 / 93 – Y
2 / 94 – Y
7 / 94 – Y
5 / 96 Y –
12 / 96 Y –
2 / 97 – Y
3 / 97 Y –
Y, indicates the colours of those brands and models sampled.
(–), indicates the colours of those brands and models not sampled.

2.2. Filtered light examination

Filtered light examination (FLE) was undertaken using a forensic image capture and
enhancement system (Poliview, Rofin Australia) in conjunction with a tunable xenon arc
lamp (Polilight, Rofin Australia) to analyse the following optical properties of the inks:
visible luminescence, with excitation between 350 and 650 nm, infra-red luminescence,
with excitation at 450 nm, infra-red reflectance, with illumination in the near infra-red
region (700–1000 nm).
Various barrier filters between 350 and 1000 nm were used for observation of the
luminescence, reflectance and absorbance of the inks. The inks were initially viewed
collectively for grading as strong, weak, of similar luminescence / reflectance to the paper
or of no luminescence / reflectance. Following this, the ink samples that remained
non-differentiable were viewed side-by-side, each combination in turn, for individual
 C. Roux et al. / Forensic Science International 101 (1999) 167 – 176 171

comparison using the observation filters to determine which of the ink combinations
were distinguishable.

2.3. Microspectrophotometry

Microspectrophotometry measurements (MSP) were achieved using a Rofin

Microcolourite / BH-2 Olympus microspectrophotometer in reflection mode. The intensi-
ty (in % reflectance) vs. wavelength ( l, in nm) was measured between 380 and 880 nm,
at 50 scans per measurement. Five measurements were made to account for variation,
and one plot of the five spectra for each ink was obtained. Further treatment of the data
with a spectral software allowed the results to be presented in the form of average
spectra. A computerized comparison could then be carried out by using threshold
percentage match values based on the variability observed between five replicate
measurements of the same sample.
By threshold percentage match value it is meant that any percentage match (of any ink
with the target ink, between 0 and 100%) which falls below the threshold value, can be
said to be discernible from the target ink; alternatively, any percentage match (of any ink
with the target ink, between 0 and 100%) which falls above the threshold value, can be
said to be undifferentiable from the target ink. The lowest of these values, i.e. that which
showed the largest variation among the five measurements of the same ink has been
taken as the general threshold value (or error) applied to each ink of the same colour
(blue or black). This ultimately determined which inks were differentiable. The MSP
spectra of those ink combinations which were classed as undifferentiable proceeding the
statistical analysis, were then compared visually side by side considering the overall
shape of the spectra, the location of maxima and minima and the presence of shoulders
or plateaus.
The MSP spectra obtained from the analysis of the different batches (as opposed to
brands and models) of ballpoint pen inks were immediately compared visually side by
side. This alternative was used because there were only a few spectra to be compared,
and results from the statistical analysis of the brand and model ballpoint pens proved to
be too conservative to provide any result other than ‘not discernable’ when applied to
inks of different batches of the same brand and model (despite obvious signs of disparity
between spectra).

2.4. Thin-layer chromatography

Thin-layer chromatography (TLC) analyses were performed using Whatman Linear-K

Preadsorbent 19 and 6 channel plates, a micro-hole punch (with a diameter of 0.85 mm,
for extraction of paper / ink samples), Alltech glass vials, inserts and springs, and two
solvent systems, as detailed in Refs. [21,22]:

Solvent system I – ethyl acetate / absolute ethanol / water (70:35:30, v / v)

Solvent system II – n-butanol / absolute ethanol / water (50:10:15, v / v)
172 C. Roux et al. / Forensic Science International 101 (1999) 167 – 176

The inks were extracted from the paper support with pyridine. Rhodamine 6G was used
as a reference and a paper blank was included in each run. Two runs of each solvent
system for each set of blue and black inks were conducted. Fluorescence between 350
and 650 nm using the Polilight was noted. The retention factors (R f ) and colours of the
bands were charted on graph paper, and the TLC plates were image recorded using the
Poliview. A combination of R f values (normalised against the rhodamine 6G reference),
band colouring and relative band intensity, was used to determine which inks were
discernible.

2.5. Discriminating power

The discriminating powers (DP) of the different brands and different models of the
same brand were calculated according to Smalldon and Moffat [23], where:
Number of discriminated pairs
DP 5 ]]]]]]]]]
Number of possible pairs
It should be noted that: the discriminating powers for the different batches of the same
models were not calculated due to insufficient sample sizes for each model of ink.

3. Results and discussion

The results are shown in Table 3.

FLE is the most commonly used analytical technique in forensic ink analysis, largely
for its non-destructive nature. The results of all three of visible luminescence, infra-red
luminescence and infra-red reflectance, were, for the purposes of this research,
considered collectively. Each of the possible combinations differentiable by any or all of
the three, were considered differentiable by FLE. It should be noted, however, that
although the three methods separately favoured differentiation of blue ballpoint inks, the
combined discriminating power of FLE for the black ballpoint inks was considerably
higher. This was because visible luminescence, infra-red luminescence and infra-red
reflectance tended to discriminate different combinations within the range of black inks,
but much the same combinations of blue.
Reflectance MSP results showed considerable variation within one ink. For each ink
analysed, there were five spectra obtained, in order to account for variability, and the
best efforts were made to avoid placing the ‘bronzed’ areas of the ink line [9] in the field

Table 3
Discriminating powers of the individual and combined techniques
Technique Blue inks Black inks
Filtered light examination 0.83 0.96
Microspectrophotometry 0.83 0.83
Thin-layer chromatography 0.98 0.99
Combined sequence 0.99 close to 1
 C. Roux et al. / Forensic Science International 101 (1999) 167 – 176 173

of vision of the microscope. Shifts in wavelength did not occur in the reflectance profiles
of any one ink, although changes in the % Reflectance between the five spectra for any
of the individual inks were apparent. The threshold percentage match values calculated
from the results of the various percentage matches were 82.0 and 49.3% for the blue and
black ballpoint inks, respectively. It should be pointed out here that these values do not
suggest that 82.0 and 49.3% of blue and black inks, respectively, were differentiable.
Further consideration of the various percentage match lists for each ink as a target,
yielded results at this stage of 30.9% of blue inks and 22.7% of black inks being
distinguishable.
In carrying out the statistical calculations on the MSP data, a very conservative
approach to so called error and range of variation was adopted, so as to include with
uncertainty, the inks in the ‘possible match’ category, i.e. more inks classified as not
differentiable, rather than exclude an ink which could possibly be a match. This may
underestimate the actual value of this examination.
Any MSP ink spectra combinations not discriminated by the computer search were
then compared visually side by side for any obvious differences. If there was any doubt
at all as to the ‘differences’ between two spectra, especially when considering the
possible effects of bronzing on the intensity of the vertical scale, the combinations were
designated undifferentiable. Following this culling procedure, only 17.4% of blue inks
and 17.5% of black inks (with respect to brands and models only) remained undifferenti-
able. The technique therefore showed no apparent favour for the distinguishing of one
colour over the other.
TLC is known to differentiate on the basis that it separates different components of a
substance. By separating a substance into its numerous components, comparisons can be
made with other substances on potentially more than just one or two different aspects.
The defining of more possibilities for measurement decreases the probability of chance
matches and allows for a greater discriminating power.
All inks were analysed by both solvent systems, even though Solvent System II is
traditionally only employed for inks not differentiated by Solvent System I. Two sets of
TLC plates in each solvent system were run to check the overall reproducibility, and
allow for calculation of errors. On any one day, the chromatography analysis concen-
trated on one colour ink, one solvent system and two runs undertaken consecutively to
maintain uniform environmental conditions. Only one tank was used, and all solutions
were made fresh daily with analytical grade chemicals from previously unopened bottles,
and of volumes sufficient to supply the tank for both runs. A rhodamine 6G reference
was used in the centre channel of each TLC plate. Three plates required to cover the
range of blue brand and model inks, and two plates for the black brand and model inks.
It was found that the paper support did not introduce any banding effects with either of
the two solvent systems.
The discriminating abilities of each of the solvent systems for both the blue and black
ballpoint inks are very high and similar in the 0.96–0.98 mark.
The respective discriminating powers of each technique increased in the same order
for both blue and black inks (see Table 3): MSP,FLE,TLC.
Only the FLE showed a particularly significant favouring of one ink colour (black,
where DP50.96) over the other (blue, where DP50.83). As a result of the significant
174 C. Roux et al. / Forensic Science International 101 (1999) 167 – 176

Table 4
Individual and collective discrimination of the blue inks from batches of the same models and brand
Technique 4 Colour Medium Clic 2000 Soft Feel
Filtered light examination 0/3 0/6 0/3 0/3
Microspectrophotometry 0/3 0/6 0/3 2/3
Thin-layer chromatography 0/3 5/6 2/3 0/3
Combined sequence 0/3 5/6 2/3 2/3

difference, the overall DP for the combined sequence of all three techniques did slightly
favour the black inks. This final difference between the overall discriminating powers of
the blue and black inks was not as large as perhaps indicated by DPs of the individual
techniques, an incongruity possibly explained by the different techniques targeting
different combinations of blue inks, thereby covering a greater range of combinations
overall (i.e. boosting the DP). The very high values of the discriminating powers for
blue and black of the combined techniques suggests that this particular sequence is
indeed effective – it employs methods which individually target a variety of aspects and
characteristics of the pen inks so that when combined, can successfully distinguish
between a wide range of brands and models of inks.
Manufacturing details were provided by BIC Australia with regard to which models of
BIC pens used inks produced (by BIC) in Australia, New Zealand or the United States.
It was interesting to note that the country of ink manufacture had no influence on which
combinations of BIC models were found to be differentiable. For example, with respect
to blue ballpoint inks, the BIC 4 Colour and BIC Medium (‘Crystal’) inks were
differentiable by both solvent systems of TLC, yet BIC Medium (‘Crystal’) and BIC
Soft Feel were not differentiated by any of the techniques. BIC 4 Colour and BIC
Medium (‘Crystal’) both use BIC Australia manufactured inks, whilst BIC Soft Feel
inks are imported from BIC in the United States. This suggests that the ink formulation
is created to suit particular models and styles of ballpoint pens, rather than common
formulations for inks from the same country.
In respect to comparisons of several batches of the same brand and model, the number
of differentiable pairs of inks out of a total number of pairs of inks from different
batches are shown in Tables 4 and 5.
In this case, blue batch inks tended to have a higher degree of discrimination than
black inks. The more successful techniques were MSP and TLC. Given that there was
only a very small sample population, the results of the three techniques together showed

Table 5
Individual and collective discrimination of the black inks from batches of the same models and brand
Technique 4 Colour Medium Clic 2000 Soft Feel
Filtered light examination 0/3 0/6 3/6 0/3
Microspectrophotometry 2/3 0/6 3/6 0/3
Thin-layer chromatography 2/3 0/6 3/6 0/3
Combined sequence 2/3 0/6 3/6 0/3
 C. Roux et al. / Forensic Science International 101 (1999) 167 – 176 175

that for those instances where the ink combinations were successfully distinguished, only
one technique was successful, or the same pairs were targeted by both / all three. In other
words, an apparent diverse range of combinations of different batches within any one
model of the same brand, was covered by only one or two of the techniques, not by the
sequence as a whole. For example, with respect to the black BIC 4 Colour pen inks, two
combinations of inks from a total of three, were differentiated, but both were
differentiated by MSP and TLC. In the case of blue BIC Medium (‘Crystal’) pen inks,
five combinations of inks from a total of six were successfully discriminated, but all
were by TLC. And to an extreme, three black BIC Clic 2000 ink combinations out of a
possible six were distinguished, all three being classified so by all three techniques. A
more extensive range of ballpoint pen inks from different batches of the same model and
brand, is required to validate the success or failure of this particular sequence of
techniques as applied to such subjects. However, it has been shown that the potential of
discriminating different batches of the same brand and model exists.

4. Conclusions

Forty nine blue and 42 black commercial ballpoint pen inks, of different brands,
models and batches available on the Australian market, were analysed using a standard
protocol for forensic examination of inks.
The discriminating powers calculated for the sequence of techniques when applied to
this population of blue and black ballpoint pen inks were 0.99 and close to 1,
respectively. Thin-layer chromatography had the highest discriminating power for the
individual techniques at 0.98 for blue and 0.99 for black.
From the results obtained in the analysis of inks from batches of the same models and
brand, it has been shown that it is possible to detect differences between batches of the
same brands and models of ballpoint pen inks. To obtain useful and detailed information
from batch ink analysis, it would be worthwhile to target a more extensive range, even a
few ranges, of batch inks, along with collaboration with the pen manufacturing industry,
for possible application in document examination areas such as dating. Thin-layer
chromatography was the most successful individual technique in discriminating between
two inks from different batches of the same models and brand of ballpoint pen.
Our results suggest that the common protocol including FLE, MSP and TLC is
extremely selective and lead to a highly reliable class identification.

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