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thesis entitled

Ink Identification by High Performance Liquid Chromatography
Library Matching

presented by

Marilyn L. Bagley

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INK IDENTIFICATION BY HIGH PERFORMANCE LIQUID CHROMATOGRAPHY
LIBRARY MATCHING

By

Marilyn L. Bagley

A THESIS

Submitted to
Michigan State Universtiy
in partial fulfillment of the requirements
for the degree of

MASTER OF SCIENCE
School of Criminal Justice

2003

ABSTRACT

INK IDENTIFICATION BY HIGH PERFORMANCE LIQUID CHROMATOGRAPHY
LIBRARY MATCHING

By
Marilyn L. Bagley

Ink identifications have typically been performed by utilizing normal phase thin
layer chromatography in both the initial screening step and the final identification step.
This research focused on substituting high performance liquid chromatography (HPLC)
as the final technique used in ink identifications. Forty-four ballpoint ink samples were
analyzed by reversed phase high performance liquid chromatography. Using Waters
Empower software, a processing method was developed with which to objectively
analyze the ink chromatograms. Within each sample set of thirteen to seventeen known
ink samples, a library was created of the resulting processed chromatograms. By
processing an unknown sample of ink and comparing it to the processed chromatograms
in the library for its respective sample set, a quantitative measure of the degree of
correspondence of a sample to the library was obtained. Utilizing this quantitative
measure, as well as visually inspecting the three-dimensional photo diode array printouts
generated for each ink sample, it was shown that this method of HPLC ballpoint ink

identification is quite effective.

ACKNOWLEDGEMENTS

I would first like to thank Speckin Forensic Laboratories for providing me with
the ink samples from their ink library that permitted this research to occur. Also, I would
like to thank Roger Bolhouse for his support and feedback throughout both the research
and writing portions of this thesis project.

Throughout the time I have worked on this research project, I have been fortunate
to receive immeasurable support from numerous sources. I would like to thank my
advisor, Dr. Siegel, for his patience and suggestions throughout this research. To my
friends and family, I want to thank you for listening to me when things weren’t going as
smoothly as I would have liked and for constantly telling me that it all would end
someday. I truly appreciate the patience that my sisters, Natalie and Darlene, and my
father exhibited when I would call from the chemistry lab full of frustration; they never

failed to make me laugh before we hung up.

iii

TABLE OF CONTENTS

LIST OF FIGURES .................................................................................. vi
CHAPTER 1
INTRODUCTION .................................................................................... l
1.1 The Ball Point Pen ...................................................................... 1
1.2 Ink ........................................................................................ 2
1.3 The Value of Ink as Forensic Evidence .............................................. 3
1.4 Established Methods for Ink Identification .......................................... 4
1.5 High Performance Liquid Chromatography in Ink Analysis ...................... 6
1.6 Why Use the HPLC for Ink Identifications? ......................................... 8
CHAPTER 2
METHODS AND MATERIALS .................................................................. 10
2.1 Chemicals ............................................................................... 10
2.2 Ink Samples ............................................................................ 10
2.3 High Performance Liquid Chromatography ....................................... 10
2.4 Processing Data with Waters Empower Software ................................ 11
2.5 Thin Layer Chromatography ......................................................... 12
CHAPTER 3
RESULTS AND DISCUSSION ................................................................... 13
3.1 High Performance Liquid Chromatography ................ i ....................... 13
3.2 Thin Layer Chromatography ......................................................... 43
CHAPTER 4
CONCLUSIONS AND FUTURE DIRECTION ................................................ 47
APPENDICES ....................................................................................... 50
A. Instrument Method for inkrev 2 ...................................................... 51
B. Processing Data with Waters Empower Software ................................. 56
B.1 Deriving a Max Plot Chromatogram ...................................... 58
B.2 Building a PDA Processing Method ...................................... 61
B.3 Creating a Library; Adding and Matching Spectra to an Existing
Library ........................................................................ 64
8.4 Creating and Printing Reports ............................................. 68
C. HPLC Reports for Blue Ball Point Inks That Were Identified to a Reasonable
Degree of Certainty by Library Matching .......................................... 70
Cl Sample Run 1 ................................................................. 72
C2 Sample Run 2 ................................................................. 93
C3 Sample Run 3 ............................................................... 104
CA Sample Run 4 ............................................................... 119

D. HPLC Reports for Black Ball Point Inks That Were Identified to a Reasonable

Degree of Certainty by Library Matching ....................................... 132
D.1 Sample Run 1 ............................................................... 134
D.2 Sample Run 2 ............................................................... 141
D3 Sample Run 3 ............................................................... 148
DA Sample Run 4 ............................................................... 153

E. HPLC Reports for Blue Ball Point Inks That Were Not Identified to a
Reasonable Degree of Certainty, but Were Listed as Possible Matches by

Library Matching ..................................................................... 168
El Sample Run 1 ............................................................... 170
E2 Sample Run 2 ............................................................... 177
B.3 Sample Run 3 ............................................................... 186

F. HPLC Reports for Black Ball Point Inks That Were Not Identified to a
Reasonable Degree of Certainty, but Were Listed as Possible Matches by

Library Matching ..................................................................... 193
F .1 Sample Run 2 ............................................................... 195
G. HPLC Reports for Blue Ball Point Inks That Were Not Identified ........... 202
0.1 Sample Run 3 ............................................................... 204
H. HPLC Reports for Blue Ball Point Inks That Were Run Against Only Their
Counterparts in a Library ............................................................ 207
H.1 Sample Run 1 ............................................................... 209
H.2 Sample Run 2 ............................................................... 216
H.3 Sample Run 3 ............................................................... 229
1. HPLC Reports for Black Ball Point Inks That Were Run Against Only Their
Counterparts in a Library ..................................... . ...................... 238
1.1 Sample Run 2 ................................................................. 240
LIST OF REFERENCES ......................................................................... 249

LIST OF FIGURES

Figure 1: HPLC report for ink sample Bic B162D ............................................. 17
Figure 2: HPLC report for ink sample Zebra B7D. . . . . . ..................................... 19
Figure 3: HPLC report for ink sample Bic B388D ............................................. 21
Figure 4: HPLC report for ink sample Pilot B 103D (2"d time run) ........................... 23
Figure 5: HPLC report for ink sample Papermate B68D ....................................... 25
Figure 6: HPLC report for ink sample Papermate B376G ..................................... 27
Figure 7: PDA printout for ink sample Senator B3 85C ........................................ 29
Figure 8: PDA printout for ink sample Staedtler B3 84C ....................................... 30
Figure 9: HPLC report for ink sample Pilot B103D (1St time run) ............................ 31
Figure 10: HPLC report for ink sample Q6B (Pilot B103 3rd time run) ...................... 33
Figure llePLC report for ink sample Fisher B65D ........................................... 35
Figure 12: HPLC report for ink sample Fisher B65D (own library) ......................... 37
Figure 13: HPLC report for ink sample Staedtler B384D ..................................... 39
Figure 14: HPLC report for ink sample Staedtler B3 84D (own library) ..................... 41

Figure 15: Thin layer chromatography plate for similar blue ballpoint PDA samples. . .. 44
Figure 15A: Thin layer chromatography plate for similar blue ballpoint PDA samples...45

Figure 16: Thin layer chromatography plate for similar black ballpoint PDA samples. . .46

Figure 17: HPLC report for ink sample Russian Ink B426D ................................... 73
Figure 18: HPLC report for ink sample Cross B164D ......................................... 75
Figure 19: HPLC report for ink sample Papermate 622D ..................................... 77
Figure 20: HPLC report for ink sample Inoxcrom B10D ...................................... 79
Figure 21: HPLC report for ink sample Mont Blanc B106D ................................... 81

vi

Figure 22:
Figure 23:
Figure 24:
Figure 25:
Figure 26:
Figure 27:
Figure 28:
Figure 29:
Figure 30:
Figure 31:
Figure 32:
Figure 33:
Figure 34:
Figure 35:
Figure 36:
Figure 37:
Figure 38:
Figure 39:
Figure 40:
Figure 41:
Figure 42:
Figure 43:

Figure 44:

HPLC report for ink sample Bic B162D ............................................ 83
HPLC report for ink sample Dupont B102D ........................................ 85
HPLC report for ink sample F ormulabs B517D ................................... 87

HPLC report for ink sample Fisher B4D ............................................ 89
HPLC report for ink sample Formulabs B519D ................................... 91

HPLC report for ink sample Pilot B 103D ........................................... 94
HPLC report for ink sample Mitsubishi B395D ................................... 96
HPLC report for ink sample Parker Bl76D ........................................ 98
HPLC report for ink sample Papermate B225D ................................... 100
HPLC report for ink sample Papermate B376D ................................... 102
HPLC report for ink sample Cross B164G ........................................ 105

HPLC report for ink sample Itoya B194D ........................................ 107
HPLC report for ink sample Sheaffer B166D .............. _ ....................... l 09
HPLC report for ink sample Mitsubishi B394D .................................. 111

HPLC report for ink sample Papermate B3 760 ................................... 1 l3
HPLC report for ink sample Tombo B535G ...................................... 115
HPLC report for ink sample Dupont B102G ...................................... 117

HPLC report for ink sample QIB (New Bic) ...................................... 120
HPLC report for ink sample Q2B (Bic B162) ..................................... 122
HPLC report for ink sample Q3B (Papermate B376) ............................ 124
HPLC report for ink sample QSB (Formulabs 8517) ............................ 126
HPLC report for ink sample Q6B (Pilot B103) ................................... 128
HPLC report for ink sample Q7B (Papermate 622) .............................. 130

vii

Figure 45:
Figure 46:
Figure 47:
Figure 48:
Figure 49:
Figure 50:
Figure 51:
Figure 52:
Figure 53:
Figure 54:
Figure 55:
Figure 56:
Figure 57:
Figure 58:
Figure 59:
Figure 60:
Figure 61:
Figure 62:
Figure 63:
Figure 64:
Figure 65:
Figure 66:

Figure 67:

HPLC report for ink sample Lindy B159D ........................................ 135

HPLC report for ink sample Cross B13D ......................................... 137
HPLC report for ink sample Parker B174D. .................................... 139
HPLC report for ink sample Eversharp 657: ...................................... 142
HPLC report for ink sample Staedtler B391D .................................... 144
HPLC report for ink sample Papermate B183D ................................... 146
HPLC report for ink sample Zebra B7D ........................................... 149
HPLC report for ink sample Parker B45 8D ....................................... 151
HPLC report for ink sample Q4B (Pentel 623) ................................... 154
HPLC report for ink sample Q8B (Bic B396) ..................................... 156
HPLC report for ink sample Q9B (Cross B13) ................................... 158
HPLC report for ink sample Pentel 623D ......................................... 160
HPLC report for ink sample Bic B396D ................... p ........................ 162
HPLC report for ink sample Fisher B536G ........................................ 164
HPLC report for ink sample Staedtler B387D .................................... 166
HPLC report for ink sample Bic B197D ........................................... 171
HPLC report for ink sample Senator B385D ..................................... 173
HPLC report for ink sample New Bic D ........................................... 175
HPLC report for ink sample Staedtler B384D .................................... 178
HPLC report for ink sample Bic B388D ........................................... 180
HPLC report for ink sample Fisher B50D ......................................... 182
HPLC report for ink sample Tombo B535D ...................................... 184
HPLC report for ink sample Fisher B65D ......................................... 187

viii

Figure 68:
Figure 69:
Figure 70:
Figure 71:
Figure 72:
Figure 73:
Figure 74:
Figure 75:
Figure 76:
Figure 77:
Figure 78:
Figure 79:
Figure 80:
Figure 81:
Figure 82:
Figure 83:
Figure 84:
Figure 85:
Figure 86:
Figure 87:
Figure 88:
Figure 89:

Figure 90:

HPLC report for ink sample Papermate B68D .................................... 189
HPLC report for ink sample Fisher B77D ......................................... 191
HPLC report for ink sample Fisher B11 1D... ..................................... 196
HPLC report for ink sample DupontB113D ...................................... 198
HPLC report for ink sample Pilot Bl 15D ......................................... 200
HPLC report for ink sample Pilot B 103D ......................................... 205
HPLC report for ink sample Bic B197D (own library) .......................... 210
HPLC report for ink sample Senator B385D (own library) ..................... 212
HPLC report for ink sample New Bic D (own library) .......................... 214
HPLC report for ink sample Staedtler B3 84D (own library) ................... 217
HPLC report for ink sample Bic B3 88D (own library) .......................... 219
HPLC report for ink sample Fisher BSOD (own library) ........................ 221

HPLC report for ink sample Mitsubishi B395D (own library) ................. 223
HPLC report for ink sample Parker B176D (own library) ....................... 225
HPLC report for ink sample Tombo BS35D (own library) ...................... 227
HPLC report for ink sample Papermate B68D (own library) ................... 230

HPLC report for ink sample Pilot BlO3D (2“d run, own library) ............... 232
HPLC report for ink sample Fisher B65D (own library) ........................ 234
HPLC report for ink sample Fisher B77D (own library) ........................ 236
HPLC report for ink sample Dupont Bl 13D (own library) ..................... 241

HPLC report for ink sample Eversharp 657 (own library) ....................... 243
HPLC report for ink sample Fisher Bl 1 1D (own library) ...................... 245

HPLC report for ink sample Pilot B115D (own library) ......................... 247

ix

1. INTRODUCTION

The forensic examination of ink has been used extensively over the years for the
detection of various crimes and resolution of civil matters. For example, people attempt
to back-date, alter or forge tax forms, wills, letters of authentication, mortgages, pre-
nuptial agreements and other forms of legal documentation, and might very well succeed
at their fraudulent acts were ink analysis not available. There are several ways inks can
be analyzed varying from ink dating procedures to the detection of fluorescent date tags.
The form of ink analysis focused on in this research, however, is that of ink
identification; that is, the determination of the manufacturer and the formulation of a
questioned ink.

In this research project, a variety of ballpoint pen inks were analyzed by high
performance liquid chromatography (HPLC). A protocol already developed for the
purpose of ink comparisons (determining if questioned ink “matches” ink from a suspect
pen) was used to run known samples of forty-four ballpoint pen inks. These inks were
either blue or black and represented twenty-one pen manufacturers. A processing method
was created on the HPLC software to objectively analyze the ink samples by such
parameters as peak retention time and peak area. Within each sample run, a library of the
resulting spectra was then created and the processing method was used to process
questioned samples and run them against the library in order to identify the questioned
ink.

1.1 The Ballpoint Pen
Although the first patent for the ballpoint pen was obtained in 1888, it did not

become popular until the late 19305.1 The ballpoint pen was presented to the American

public in the mid-19403 and was received with a great deal of enthusiasm. The pen of the
19408, however, had several imperfections such as leaving large ink deposits on the paper
and problems of skipping and directionality. By 1950, the majority of the imperfections
had been resolved.1
1.2 Ink

Inks used in pre-l950 ballpoint pens were oil-based, using solvents such as
mineral oil, linseed oil, recinoleic acid, methyl and ethyl esters of recinoleic acid,
glycerine, monolicinoleate, coconut fatty acids, sorbital derivatives, and plasticizers.1 The
type of ink developed in 1950 by the Hungarian chemist Fran Seec created the new trend
which has carried on into the formulas of today: glycol-based inks. Examples of
solvents commonly used in glycol-based inks include ethylene glycol, 1,2-propylene
glycol, 1,3-butylene glycol, hexylene glycol, octylene glycol, di and tri ethylene glycol,
di propylene glycol, glycerin, phenoxyethylene glycols, benzyl alcohol, ethylene glycol
monomethylether, and diethylene glycol monomethylether.l

Also included in the formulas of “modern” ballpoint inks are the dyes. Dyes
based on copper phthalocyanine are popular since they are readily soluble and do not fade
when exposed to light. The basic dyes used in the oil-based inks, methyl violet, Victoria
blue, rhodamine red, Victoria green, and ausamine, are also popular for use in glycol-
based inks; however, they must first be made into organic salts that are soluble in
glycols.l

Additional ingredients are included in an ink’s formula in order to impart desired
characteristics. They include resins, acidic materials, surface active agents and viscosity

adjusters. The resins, which can be either natural or synthetic, adjust the viscosity of the

ink, act as a ball lubricant, and have an effect on several physical properties of the ink
including adhesiveness and elasticity. The acidic materials, typically fatty acids, serve a
variety of functions including acting as a lubricant for the ball of the pen and in
neutralizing the dyes. The wetting characteristics of an ink are adjusted by the surface
active agents present. Also, other organic substances can be added to inhibit corrosion or
aid in improving a dye’s solubility in different solvents.l
1.3 The Value of Ink as Forensic Evidence

As stated earlier, ink can be a crucial part of a forensic document examination.
Ink identifications, highlighted here since that is the focus of this research can be used as
a portion of an ink analysis or can constitute the examination itself. In the first case, ink
identification can be used as a step in a relative ink age determination. To determine the
age of an ink using this technique, the sample of questioned age is compared to a sample
of known age. One way this can be done is by identifying an entry on the same page as
the questioned entry whose authenticity is unquestioned and is of the same formulation as
the questioned entry. The second option is obtaining a sample of ink whose age is known
by identifying the manufacturer and formulation of the questioned ink. A new mark is
then made on the paper on which the questioned entry is written by a pen identified as
having the same ink formulation as the questioned entry. Therefore, in cases where a
lone ink entry on a page is to be dated using the relative ink age technique, it is
imperative to identify the ink so a new mark can be made to which the questioned entry
can be compared.

Also, ink identification can be used to determine the outcome of certain cases by

itself. For example, if a questioned entry is made with an ink that was not commercially

available at the time the document was purportedly signed, it is clear that the document is
not authentic. A slight variation to this use of ink identification is if an ink is identified
as that produced by one of the manufacturers who participated in the fluorescent ink
tagging program between the years 1975-1994. If that is the case, an additional

procedure can be performed to see if any tags are indeed present.1 (”mm “WM“ “‘3‘ " and“

i“ 1994) The presence of a tag would determine the earliest year that document could have
been prepared by determining the year of production of the ink that was used to make the
questioned entry.

Thus the identification of an ink can and does play a crucial role in the forensic
examination of a questioned document. Therefore, a quick and reliable method for ink
identification is necessary.

1.4 Established Methods for Ink Identification

In the 1950s when analysis of ballpoint pen ink was in its infancy, Brown and
Kirk experimented with horizontal paper chromatography for the purposes of ink
identification. The researchers observed separation of dye components but only to the
extent that the inks could be classified into broad groups, not individually identified.2

Brown and Kirk then tried paper electrophoresis in an attempt to distinguish inks from
one another for the purpose of ink identification. This method was able to further
separate ink components that paper chromatography was unable to separate.2

In the 19605, thin layer chromatography (TLC) was applied to ink analysis. It
was determined that this method provided separation of dyes and other ink components
far superior to that provided by paper chromatography.3’ 4 Thin layer chromatography is

the method primarily used for ink identifications by forensic ink examiners today.

To identify an ink using the TLC method, a small sample of the questioned ink
(approximately four microplugs of ink ‘/2 mm in diameter) is extracted using a strong
solvent, typically pyridine for ballpoint inks. This questioned ink extract is then spotted
onto a low-resolution, silica-coated chromatography sheet such as the plastic
chromatography sheets produced by Eastman Kodak. After the strong solvent has
evaporated, the sheet is developed in Solvent System 1 (ethyl acetate: ethanol: distilled
water, 70:35:30). This results in a non-specific chromatogram that is compared against a
library of low-resolution chromatograms of known inks. Any possible match to the
questioned ink’s chromatogram is identified and the known ink sample is obtained.

Samples are then taken from the possible known ink matches and their extracts
are spotted alongside the questioned ink sample’s extract on a glass-backed, silica-coated
high performance thin layer chromatography plate (HPTLC). In this way many
environmental factors that may cause differences in the final chromatogram are
eliminated by running all of the samples on one plate. The HPTLC plate differs from the
low-resolution plate by having a much smaller particle size of the stationary phase.
Consequently, the resolution of the different components is much greater allowing for
better separation of closely related compounds‘. In addition, the smaller particle size of
the stationary phase provided by HPTLC plates allows for smaller sample sizes to be
utilized owing to the greater sensitivity of the technique.

This HPT LC plate is then developed in Solvent System 1. If necessary, an
additional analysis can be performed to substantiate the results from the Solvent System I

development by spotting an additional HPTLC plate with the known and questioned

samples’ extracts and developing the plate in Solvent System 2 (n-butanol: ethanol:
distilled water, 50:10: 15) " 3’ 4- 5

Finally, if the previously mentioned HPTLC techniques are not able to eliminate
all but one standard ink sample, spectrophotometry can be utilized. Using a
spectrophotometer equipped to scan spots on TLC plates, the inks are scanned in the
visible region at 550 nm with a xenon light source. The percent transmission of light
through each band is recorded and compared relative to respective bands of the other
samples. In other words, dye-ratios are calculated for the bands present and compared to
the bands of the other like samples. 1’3’5
1.5 High Performance Liquid Chromatography in Ink Analysis

In 1977, Colwell and Karger utilized normal phase HPLC to examine ballpoint
inks. It was determined that since HPLC was more sensitive compared to other
chromatography techniques used, it provides greater selectivity in distinguishing among
different inks. They found that out of twenty-five blue ballpoint inks sampled,
differences in dye components were distinguished in all samples.

Ratios were found to be useful in ink comparisons. In the visible region, HPLC
could discriminate between dyes based on relative peak heights. Furthermore, if an
ultraviolet detector were used, the vehicle components of the ink could also be analyzed
by comparing the ratio of the UV-absorbent vehicle components to the dye components.6

Lyter disagreed with the latter analysis of Colwell and Karger. 7 He had
performed his own experiments of ink analysis using the HPLC and arrived at different
conclusions. Lyter utilized reversed phase chromatography but had limited his

experiments to analyzing the dye components of the ink and their qualitative and

quantitative differences.8 He claimed that the resins and organic acids present in the ink
could not be analyzed since they could not be detected in concentrations corresponding to
their amounts in the ink.8 This fact could be explained by his determination of the
following: while the paper type did not affect the characteristics of the resultant
chromatogram, the paper type did affect the extractability of the ink.7' 8 Thus, he felt
Colwell and Karger’s analysis of vehicle components was not reproducible since, owing
to the differences in paper type extractability, false results could unwittingly be obtained.
Also, since the vehicle components elute as unretained peaks, they are not specific
enough to use in ratio comparisons and could lead to false results. Finally, dye
components can also elute at 254 nm (the wavelength used by Colwell and Karger to
analyze the vehicle components) and could thus interfere with the ratio calculations.7

Lyter’s analysis of the dyes by HPLC permitted both qualitative and quantitative
differences to be detected in the ten ink formulations he examined. Theoretically, pens
from the same box of ink should contain identical ink formulations. There are instances,
however, when slight differences occur between batches of ink of the same ink
formulation. Demonstrating the specificity of the HPLC technique, Lyter was able to
recognize quantitative differences between four different batches of the same ink
formulation.8

The most recent research performed on ballpoint inks using the HPLC does not
involve differentiating among different ink formulations. Instead, it involves the changes
that ink undergoes as it ages that can be detected by HPLC. Andrasko has illustrated that
certain non-lightfast dye components of ink, such as methyl violet and Victoria blue,

decompose over time. These decomposition byproducts appear as separate peaks in

chromatograms at 540nm that change quantitatively as the inks age or are exposed to
light. In other words, the original component’s peak gets smaller while the byproducts’
peaks increase in size. These changes in components’ concentrations can be depicted on
ternary diagrams in which the percentages of components and byproducts are plotted with
respect to one another.9' ‘0

The effect of Andrasko’s research on ink differentiation and identification by
HPLC is that an analyst must recognize the fact that some components of the ink will
change with time and/or light exposure which may affect the HPLC chromatogram both
qualitatively and quantitatively. With knowledge of this alteration process, however,
such differences may be noted and dealt with accordingly during ink identifications.

1.6 Why Use the HPLC for Ink Identifications?

Although the current method of ink identification works acceptably, there are a
few advantages to using the HPLC for ink identifications. For example, as noted by
several authors of articles regarding HPLC and ink analysis, HPLC is a more specific
method of ink identification with the ability to distinguish between those inks with
similar TLC chromatograms and even different batches of the same ink formulation." 4’ 8
As with other forensic analyses such as drug identification, it is suggested that different
forms of analyses be utilized for the preliminary screening steps and the identification
step. Using normal phase TLC for both the preliminary screening step and the final
identification step obviously works, but adding reversed phase HPLC as the alternative
final step allows the ink to be subjected to an alternative environment, therefore

providing results not as closely related to the screening step.

Furthermore, as also noted in previous research, HPLC can be used to determine
quantitative differences between ink samples. Also of great importance is the fact that by
using a computer program to search an ink library of the possible ink matches, a
quantitative measurement of the degree of fit between the known and questioned ink
samples is provided. There is no such measurement when identifying inks using the TLC

method.

2. METHODS AND MATERIALS
2.1 Chemicals

The mobile phase in this project was 80:20 acetonitrile:water with an ion pairing
reagent (Waters Pic® B-7 Low UV reagent, containing water, methanol, heptane sulfonic
acid and phosphoric acid). Both the water and acetonitrile were HPLC grade. The
mobile phase was degassed by vacuum filtration using a 0.50 um-pore, 47 mm-diameter
filter (Alltech). The ion pairing reagent was utilized so that the ionic species of interest
within the ink samples could be bound to counter ions to produce ion-pairs that were able
to be analyzed.

2.2 Ink Samples

Ink samples for this research project were obtained from the ink library of
Speckin Forensic Laboratories (Okemos, M1). N0 ink samples from outside the library
were utilized since the goal of this research was to create a library of documented known
inks. The ink samples from this library were all on white copy paper since colored paper
would introduce additional dyes into the analysis.

F orty-four ballpoint inks (29 blue, 15 black) were selected from the SF L library
and run in duplicate. Fourteen microplugs of each sample were taken and extracted into
25 microliters of mobile phase (80:20 acetonitrile:water with ion-pairing reagent as noted
above). The samples were sonicated for thirty minutes to insure complete extraction of
the ink into the mobile phase prior to analysis.

2.3 High Performance Liquid Chromatography
The samples were analyzed by a Waters HPLC system consisting of a Waters 600

Controller, gradient pump, WatersTM 717 Plus autosampler, and a Waters 996 Photodiode

Array Detector. The mobile phase was sparged with nitrogen twenty percent of the time.
The reversed-phase column was manufactured by Waters (N ovaPac® C13, 3.9 x 150mm,
4 um spherical particles, 60 A pore size). The samples were run using the “inkrev2”
method (see Appendix A for details).

2.4 Processing Data with Waters Empower Software

In order to create an ink library, a processing method must first be developed.
However, before developing a processing method, one must first derive a chromatogram.
The manufacturers of the software recommend that a Max Plot chromatogram be derived
as opposed to a chromatogram from a specific wavelength so that all the chromatographic
peaks in the sample are viewed. The Max Plot chromatogram plots the maximum
spectral absorbance at each time point. See Appendix Bl for details on creating the Max
Plot chromatogram.

Using the Max Plot chromatogram, a processing method was then created. This
processing method was used to process the ink samples and identify specific peaks in
each sample based on such criteria as peak area and peak retention time. See Appendix
B2 for details on creating a processing method using the Empower software.

Following processing of the ink samples by the processing method described
above, the resulting spectra were added to libraries. See Appendix B3 for details on
creating libraries and adding and matching spectra to existing libraries. Libraries were
created of known inks by separating them into their respective runs. For example, the
thirteen blue inks that were in the first run on January 16, 2003 were entered into one

library and the three black inks from the first run were entered into another library. This

11

was repeated for each of the four runs performed, resulting in four separate blue ballpoint
libraries and four separate black ballpoint libraries.

Those samples that were not identified to a satisfactory standard with this
technique had an additional library created. In these cases, one sample was processed
with the processing method and a library was created with its spectrum. The duplicate
sample was then processed and run against the library with only its counterpart as a
choice. This enabled a quantitative measure of how well the peaks measured against one
another alone.

Reports were generated for the results of the library matching. The images in this
thesis are presented in color. See Appendix B4 for how to create and print reports.

2.5 Thin Layer Chromatography

Thin layer chromatography was performed on the samples that were both not
identified to a reasonable degree of certainty by HPLC and had similar photodiode array
printouts as other ink samples. Five microplugs of each known ink were extracted with
six microliters of pyridine. Four microliters of the extracted ink were spotted using a
Camag Nanomat mechanical spotter onto a glass-backed, silica-coated, high resolution
thin layer chromatography plate such as those manufactured by Merck. The pyridine was
evaporated off by placing the plate in an 80’ C oven for approximately thirty minutes.
The plate was allowed to return to room temperature. The plate was then developed in

Solvent System 1 (ethyl acetate: ethanol: distilled water, 70:35:30) for fifteen minutes.

12

3. RESULTS AND DISCUSSION
3.1 High Performance Liquid Chromatography

The majority of the inks (18 of 29 blue inks and 12 of 15 black inks) were
correctly identified as the other sample of the duplicate sample pair when compared
against the created library within their respective sample runs. Examples of this form of
identification are shown in Figures 1 and 2.

There were some inks (10 of the remaining 11 blue inks and 3 of the remaining 3
black inks) that were identified, but not to any reasonable degree of certainty because,
although the correct ink was listed as a possible match, too many other possible matches
were proposed during the library search. An example of this form of identification is
shown in Figure 3. In this situation, the examiner would have to further look at the three-
dimensional photo diode array (PDA) printout and compare it to the other PDA printouts
within that sample run before a positive identification could be made. Indeed, when the
PDA printouts were compared for samples that fit into this category, inks that were
identified but not to any reasonable degree of certainty, a positive identification was
easily made in all but two cases, Senator B385 and Staedtler B384, which will be
discussed below.

Finally there was the ink sample that was not able to be identified by the library
search. An example of this lack of identification by library matching is shown in Figure
4. Again, in this case the examiner would have to compare the questioned PDA printout
against the other known PDA printouts from that sample run.

9 There are several possible reasons for the weak identifications or lack of an

identification by the library matching method. The most probable explanation is that the

13

software, in creating the library, identifies each individual peak within a sample. For
example, in Figure 1, Bic 3162 has seven peaks found against which the library is
searched. The software does not recognize the PDA as a whole; instead it is broken up
into individual pieces and the whole picture is never considered when library matching is
performed. Furthermore, only the best fit for each individual peak is listed in the results
of the matching. How this can cause problems in identifying inks is clear: there are often
identical components of inks produced by different manufacturers. Methyl violet, for
example, will theoretically appear the same in a HPLC chromatogram whether it is
produced by Bic, Fisher, or another ink manufacturer. Therefore, the same peak will
appear in similar locations in the chromatograms of different inks and could easily lead to
misidentifications. Figure 5 illustrates the case of Papermate B68, an example of
misidentification due to identifying individual peaks instead of the entire PDA as a
whole. The ink composition of Papermate B68 is virtually identical to that of Papermate
B376 (Figure 6), with the exception of the farthest peak to the right which is absent in
Papermate B376. Three of the four peaks to which a match was made for Papermate B68
were misidentified as belonging to Papermate B376; the fourth, although labeled as
Fisher B65, is correct as it was later shown by thin layer chromatography that Papermate
B68 and Fisher B65 have identical ink compositions (see Section 3.2). However, if one
were to examine the PDAs of Papermate B68 and Papermate B376, it would be readily
obvious that the two inks are not the same.

Another explanation for the poor identification of select inks is the lack of
retention of copper phthalocyanine in the HPLC environment used in this research. Per a

conversation with Dr. Albert Lyter III who has previously conducted research on HPLC

14

analysis of ballpoint inks (references 7 and 8), it was learned that copper phthalocyanine
either gets trapped in the reversed phase column (if a guard column is not present), or
elutes too rapidly for detection. Therefore, as was the case with Senator B3 85 and
Staedtler B3 84 (Figures 7 and 8), inks that differ only in the presence or absence of
copper phthalocyanine will not be able to be distinguished with this library searching
method, nor by the examination of the PDA printouts for each ink. Thin layer
chromatography, however, will still be able to distinguish between the two inks (see
Section 3.2).

There were also a few inks run multiple times with varying success rates in the
library matching method. For example in Figures 4, 9, and 10, Pilot B103 was run three
separate times with two different results: twice it was identified to a reasonably certain
degree, and the third time it was misidentified (Pilot B 103 wasn’t listed as a possible
match for any peak). Furthermore, when run against only its counterpartduplicate
sample, no peak was identified. This last result is rather perplexing, as pictorially the
PDAs of the duplicate samples look similar. However, the intensity of the peaks in the
two samples (absorbance unit value) differs drastically. One possible explanation for this
difference in intensity could be the weak extraction that was noted for this certain ink
sample. It is noted that at its strongest peak, the absorbance value is a mere 0.04.
Perhaps a small increase in extraction of one of the duplicate weak samples as compared
to the other would create relatively large differences in peak area that could lead to
misidentification or non-identification. New Bic and Tombo B-535 also were poorly

identified in one run, and identified to a reasonably certain degree in another run.

15

In other samples that were not identified to a satisfactory degree, but that could be
identified from the list of possible matches presented by the library search by comparing
PDA printouts, the “questioned” sample was run against a library containing only its
duplicate sample counterpart. This was done to gain a quantitative measure of the degree
of fit for the peaks present in the samples. In the majority of cases, the number of peaks
correctly identified increased when other inks with possible similar components were
removed from the library and the resultant quantitative measurements indicated a good
match. Figures 11 and 12 representing the ink Fisher B65 are illustrations of this marked
improvement in identification and subsequent quantitative measurements. However, there
were some cases in which the number of peaks identified as the correct ink increased but
the quantitative measure of fit did not improve when the other samples were removed.
Figures 13 and 14 representing Staedtler B384 illustrates this observation.

One other possible source of confusion when utilizing this library search method,
which would be inherent in any type of ink identification process, is the fact that several
of the pen manufacturers buy ink from either a general ink manufacturer or from other
pen companies. This results in several pens from different pen manufacturers being filled
with ink with identical composition. This would not lessen the ink library matching
effectiveness, but would provide a source of concern as the ink could appear to be
misidentified when it in fact is being correctly identified. This occurred during this
research with numerous samples and is explained in Section 3.2.

Furthermore, a different sort of confusion could arise when an ink manufacturer
maintains the same formula for their inks, but purchases the dyes from different

suppliers. This could cause inks of the same formulation to appear spectrally different.

16

Figure 1: HPLC report for ink sample Bic Bl62D

SampleName Bic 31620 Date Acquired 1/17/2003 2:37:08 AM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name man'lyn 11603 Channel Name MaxPlo1250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

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Sample Name Bic B162D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.108 242620 20.01 18984
2 PDA MaxPlot (250nm-550nm) 1.499 317561 26.19 21382
3 PDA MaxPlot (250nm-550nm) 1.625 166238 13.71 17119
4 PDA MaxPlot (250nm-550nm) 2.302 23931 1.97 2271
5 PDA MaxPlot (250nm-550nm) 2.577 40485 3.34 3918
6 PDA MaxPlot (250nm-550nm 5.046 276767 22.83 13481
7 PDA MaxPlot (250nm-550nm) 8.06] 144942 11.95 6974
PDA Result Table
Name RT Purity l Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name AngLe Threshold

1 1.108 Bic 8162-] 0.768 1.150
2 1.499 Bic Bl62-2 0.424 1.123
3 1.625 Bic Bl62-3 0.896 1.155
4 2.302
5 2.577 Bic Bl62-5 3.984 2.083
6 5.046 Bic Bl62-6 0.998 1.514
7 8.061 Bic Bl62-7 0.601 1.647

 

l8

 

 

Figure 2: HPLC report for ink sample Zebra B7D

SampleName Zebra B7D
Injection Volume 10.00 ul
Run Time 20.00 Minutes

Sample Set Name man'lyn 11903

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

Date Acquired 1/19/2003 7:53:29 PM
Acq Method Set inkrev2 method set
Processing Method Marilyn library 2103

Channel Name MaxP101250_550

 

 

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Sample Name Zebra B7D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.189 681911 36.42 89772
2 PDA MaxPlot (250nm-550nm) 1.438 174379 9.31 19592
3 PDA MaxPlot (250nm-550nmL 1.815 107240 5.73 11068
4 PDA MaxPlot (250nm-550nm) 2.118 38864 2.08 4600
5 PDA MaxPlot (250nm-550nm) 2.238 28850 1.54 4653
6 PDA MaxPlot (250nm-550nm) 2.618 207498 11.08 17203
7 PDA MaxPlot (250nm-550nm) 3.381 367958 19.65 26256
8 PDA MaxPlot (250nm~550nm) 4.553 237240 12.67 12789
9 PDA MaxPlot (250nm-550nm) 7.485 28556 1.53 1630
PDA Result Table
Name RT Purity l Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angle Threshold
1 1.189 Zebra B7-1 1.743 1.051
2 1.438 Zebra B7—2 0.617 1.152
3 1.815 Zebra B7-3 2.396 1.356
4 2.118 Zebra B7-4 2.243 2.378
5 2.238 Zebra B7-5 1.953 2.014
6 2.618 Zebra B7-6 0.529 1.444
7 3.381 Zebra B7-7 0.220 1.292
8 4.553 Zebra B7-8 0.405 1.519
9 7.485 Zebra B7-9 2.238 4.044

 

20

 

 

Figure 3: HPLC report for ink sample Bic B388D

SampleName Bic 33880
Injection Volume 10.00 uI
Run Time 20.00 Minutes

Sample Set Name marilyn 11703

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

Date Acquired 1/17/2003 9:55:49 PM
Acq Method Set inkrev2 method set
Processing Method Marilyn library 2103

Channel Name MaxPlot250_550

 

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Sample Name Bic B388D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.117 410689 31.11 36415
2 PDA MaxPlot (250nm-550nm) 1.471 487187 36.90 32523
3 PDA MaxPlot (250nm-550nm) 1.862 45310 3.43 4383
4 PDA MaxPlot (250nm-550nm) 2.530 27470 2.08 2348
S PDA MaxPlot (250nm-550nm) 3.404 62555 4.74 4776
6 PDA MaxPlot (250nm—550nm) 4.661 286934 21.74 15171
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name AngLe Threshold
1 1.117 Bic 8388-1 6.390 1.080
2 1.471 Bic B388-3 4.730 1.091
3 1.862 Tombo 3535-1 8.032 1.445
4 2.530 Bic B388-5 7.737 2.789
5 3.404 Fisher 350-4 1.307 1.849
6 4.661 Papermate B376-7 0.655 1.389

 

22

 

Figure 4: HPLC report for ink sample Pilot BlO3D (2nd time run)

SampleName Pilot 81030 Date Acquired 1/19/2003 9:18:17 PM

Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name marilyn 11903 Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

 

 

 

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Sample Name Pilot 8103D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.129 147918 18.14 11291
2 PDA MaxPlot (250nm-550nm) 1.444 145228 17.81 13083
3 PDA MaxPlot (250nm-550nm) 1.809 33125 - 4.06 2496
4 PDA MaxPlot (250nm-550nm) 2.022 25226 3.09 1758
5 PDA MaxPlot (250nm-550nm) 2.579 84761 10.40 5556
6 PDA MaxPlot (250nm-550nm) 3.342 144555 17.73 10024
7 PDA MaxPlot (250nm-550nm) 4.510 105909 12.99 6226
8 PDA MaxPlot (250nm-550nm) 10.963 128521 15.76 3858
PDA Result Table
Name RT Purity Purity 1 Match 1 Spect. Match 1 Match 1
1 Threshold Name Angle Threshold
Angle
1 1.129
2 1.444 Itoya 8194-2 7.514 12.038
3 1.809
4 2.022
5 2.579
6 3.342 Cross Bl64E-6 6.422 17.963
7 4.510
8 10.963

 

24

 

 

Figure 5: HPLC report for ink sample Papermate B68D

SampleName Papermate 8680 Date Acquired 1/19/2003 6:49:53 PM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name marilyn 11903 Channel Name MaxP101250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

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25

Sample Name Papermate B68D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area "/11 Area Height
(min)
1 PDA MaxP10t(250nm-550nm) 1.231 208327 10.98 13409
2 PDA MaxPlot (250nm-550nm) 1.529 375218 19.78 36998
3 PDA MaxPlot (250nm-550nm) 1.870 72332 3.81 5519
4 PDA MaxPlot (250nm-550nmL 2.028 49920 2.63 3793
5 PDA MaxPlot (250nm-550nm) 2.476 64856 3.42 7553
6 PDA MaxPlot (250nm-550nm) 2.609 44550 2.35 5639
7 PDA MaxPlot (250nm—550nm) 3.374 279426 14.73 20739
8 PDA MaxPlot (250nm-550nm) 4.538 384641 20.28 20485
9 PDA MaxPlot (250nm-550nm) 5.241 54236 2.86 2576
10 PDA MaxPlot (250nm-550nm) 6.512 35392 1.87 616
11 PDA MaxPlot (250nm-550nm) 10.698 327674 17.26 9284
PDA Result Table
Name RT Purity Purity 1 Match 1 Spect. Match Match 1
1 Threshold Name 1 Threshold
Angle Angle

1 1.231 Fisher B65-l 6.695 14.586
2 1.529 Papermate B376E-2 3.862 6.086
3 1.870
4 2.028
5 2.476
6 2.609
7 3.374 Papennate B376E-6 6.450 16.903
8 4.538 Papermate B376E—7 8.108 21.963
9 5.241
10 6.512
11 10.698

 

26

 

Figure 6: HPLC report for ink sample Papermate B3 76G

SampleName Papermate 83766 Date Acquired 1/20/2003 3:18:48 AM

Injection Volume 10.00 01 Acq Method Set inkrev2 method set

Run Time 20.00 Minutes Processing Method Marilyn library 2103

Sample Set Name marilyn 11903 Channel Name MaxP101250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

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Sample Name Papermate B376G

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.193 299484 13.25 24172
2 PDA MaxPlot (250nm-550nm) 1.541 620990 27.47 68619
3 PDA MaxPlotiZSOnm-SSOnm) 1.923 33024 1.46 3992
4 PDA MaxPlothSOnm-SSOnm) 2.229 21558 0.95 2390
5 PDA MaxPlot (250nm-550nm) 2.591 140236 6.20 12278
6 PDA MaxPlot (250nm-550nm) 3.331 483771 21.40 35065
7 PDA MaxPlot (250nm-550nm) 4.456 588343 26.02 30968
8 PDA MaxPlot (250nm-550nm) 5.360 23559 1.04 1657
9 PDA MaxPlot(250nm-550nm) 7.524 49874 2.21 2596
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match Match 1
Angle Threshold Name 1 Angle Threshold
1 1.193 Papermate B376E-1 3.587 1.163
2 1.541 Papermate B376E-2 0.201 1.035
3 1.923 Papermate B376E-3 5.868 2.054
4 2.229 Papermate B376E-4 2.071 2.601
5 2.591 Papermate B376E-5 0.981 1.890
6 3.331 Papermate B376E-6 0.622 1.320
7 4.456 Papermate B376E—7 0.419 1.350
8 5.360 Papermate B376E-8 3.490 5.328
9 7.524 Itoya Bl94-10 1.326 2.340

 

28

 

 

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SampleName Senator B3850; Vial 4; Injection 1; Date Acquired 1/16/2003 8:36:40 PM

Figure 7: PDA printout for ink sample Senator B385C

2 9

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SampleName Stuttler 33046; W14; Injection 1; Date Acquired “1712003 8:52:13 PM

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Figure 9: HPLC report for ink sample Pilot B103D(l“timc run)

SampleName Pllot 81030 Date Acquired 1/17/2003 8:31:01 PM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name marilyn 11703 Channel Name MaxP101250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

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Sample Name Pilot BlO3D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.133 340040 44.90 26933
2 PDA MaxPlot (250nm-550nm) 1.406 238185 31.45 14835
3 PDA MaxPlot (250nm-550nm) 2.564 45586 6.02 3819
4 PDA MaxPlot (250nm-550nm) 3.401 83479 11.02 6376
5 PDA MaxPlot (250nm-550nm) 4.695 49986 6.60 3351
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Argfle Threshold

1 1.133 Pilot B103-l 1.947 2.794
2 1.406 Pilot B 103-2 3.799 5.318
3 2.564
4 3.401 Papermate B376-6 5.369 11.318
5 4.695

 

32

 

Figure 10: HPLC report for ink sample Q68 (Pilot 8103 3"d time run)

Date Acquired 1/22/2003 1:22:21 AM

SampleName QBB

Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name marilyn 12103 Channel Name MaxP101250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

.107
,/ I . I
,- 24.---.- a - ,m , 7 W , 2 2 - - - {0.030
1
1 I
i #0020 a
1
1‘ L
1 I ~0010
1 I
1 j .. i :_o.ooo
g" I 1 J
371/ 1 .é .. _
z ' 500.00

‘ A; r ‘ T ,7, ’1" rrv" ’ *‘fi‘r'fi—fi' *vrr'vrf'r ~ * .,v,r-._, *ve -v V-.. .r...
2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00
Mnutes

Auto-Scaled Chromatog ram

 

0
IO
. N. I
0008 a? m 1
‘ ‘ :25 1 g 1
t-I N M
30006 1‘“. $1. 4' g l
°- 18. ‘ '7
7' 2 '
0002 ‘ i g '
, I , 1

 

.. f: fiv—r . . . .,‘—I_.liiiyql l—
2.00 4.00 600 0.00 03038 12100 14.00 16.00 18.00 20.00

Sample Name Q6B (Pilot 8103)

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.151 112454 19.73 8365
2 PDA MaxPlothSOnm-SSOnm) 1.440 112723 19.78 10246
3 PDA MaxPlot (250nm-550nm) 1.869 18896 3.32 1533
4 PDA MaxPlot Q50nm-550nm) 2.522 41748 7.32 3778
5 PDA MaxPlot (250nm-550nm) 3.250 101534 17.81 7285
6 PDA MaxPlot (250nm-550nm) 4.362 77805 13.65 4611
7 PDA MaxPlot (250nm-550nm) 6.270 18281 3.21 444
8 PDA MaxPlot (250nm-550nm) 10.489 86526 15.18 2861
PDA Result Table
Name RT Purity Purity 1 Match 1 Spect. Match Match 1
1 Threshold Name 1 Threshold
Angle Angle

1 1.151 Pilot B103G-1 4.509 10.549
2 1.440 Pilot BlO3G-2 6.030 12.799
3 1.869

4 2.522

5 3.250 Papermate B376E-6 6.804 17.102
6 4.362

7 6.270

8 10.489

 

34

 

 

Figure 11: HPLC report for ink sample Fisher B65D

SampleName Fisher 3650
Injection Volume 10.00 111
Run Time 20.00 Minutes

Sample Set Name marilyn 11903

Processed Channel Descr. PDA MaxPlot

(250.0 nm to 550.0 nm)

Date Acquired 1/19/2003 6:07:29 PM
Acq Method Set inkrev2 method set
Processing Method Marilyn library 21 03

Channel Name MaxP101250_550

 

 

 

 

 

 

 

 

/ ' £0.12
_/ " fi /. / E 0.10
l.
I I 0.08
1 :>
0.06 <
I 0.04
I
I1 1 I I 0.02
‘ ’1 I ‘ 1
A1... ‘ ‘ ‘ 0.00
. 1 2
I1 r j .
H / 1 :77 .
L ~~ . . J . 500.00
2.00 4.00 6.00 3.00 10.100 12.00 14.00 16.00 18.00 20.00
Mnutes
Auto-Scaled Chromatogram
1” —‘ I
I 1 I
0.020. 3 1 I
. n ‘ ‘
. a g I
0.0155 g1 E . I
‘ F.‘ I 01' 1
a . T . I
0.01o--_ IL I 3 8 I
11 *Q o. 1
. Bfil .. ,C 1
_ . CD
0005 N M T or 1
. I 1‘ :‘3 I
I 1. g ‘ :
0000‘1 J 7"7 . . — .. _ i
I I . . I I I . . I I I I I I . I I I . I I I iiAI'WT—I '77:.17 I I
2.00 4.00 6.00 8.00 910019111 12.00 14.00 16.00 10.00 20.00

35

Sample Name Fisher B65D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxP1ot(250nm-55011m) 1.199 145522 10.75 10224
2 PDA MaxPlot (250nm-550nm) 1.559 375771 27.76 22000
3 PDA MaxPlot (250nm-550nm) 2.074 31508 2.33 2091
4 PDA MaxPlot (250nm-550nm) 2.511 19000 1.40 2301
5 PDA MaxPlot (250nm-550nm) 2.658 42557 3.14 4286
6 PDA MaxPlot (2500m-550nm) 3.447 244771 18.08 17468
7 PDA MaxPlot (250nm-550nm) 4.607 348524 25.75 19485
8 PDA MaxPlot (250nm-550nm) 11.000 126719 9.36 3430
9 PDA MaxPlot (ZSOnm-SSOnm) 16.267 19335 1.43 330
PDA Result Table
Name RT Purity Purity 1 Match 1 Spect. Match 1 Match 1
1 Threshold Name Angle Threshold
Angle
1 1.199 Fisher B65-1 3.973 10.182
2 1.559 Fisher B65-2 2.664 7.676
3 2.074
4 2.511
5 2.658
6 3.447 Cross Bl64E-6 3.875 9.588
7 4.607 Dupont BlOZE-6 5.618 10.838
8 11.000
9 16.267

 

36

 

Figure 12: HPLC report for ink sample Fisher B65D (own library)

SampleName Fisher B65D Date Acquired 1/19/2003 6:07:29 PM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name marilyn 11903 Channel Name MaxP101250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

 

 

. 0.12
0.10
. 0.08
I :
f0.06 <
I i
1 f'0.04
1| 0.02
. 3' 0.00
I
1. .
I ‘ 500.00
14%;;rr—r77—v—afi..- ~ «fi—Hvemr -~ ~77.” if" T-.. . 2* . . I
2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 1800 20.00
Mnutes
Auto-Scaled Chromatogram
* 1 *-————*” (fl
0020 fi 1 1
. 1 N I
f? I
. I" § I
0.015— 3. 3 . '
'11 m‘ I
3 ‘—‘ 1 ‘ 1
<0.01 1“ oo o 1
11! I ' . O,
l 1 ‘- 1
0.005 I I ‘ I ‘1- .

« 16267

 

I I j . . . I . . , . I T—.'"— , % ._,’ .
8.00 hx000 12.00 14.00 16.00 18.00 20.00
"U108

Sample Name Fisher B65D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
Lmin)
1 PDA MaxPlot (250nm-550nm) 1.199 145522 10.75 10224
2 PDA MaxPlot (250nm-550nml 1.559 375771 27.76 22000
3 PDA MaxPlot (250nm-550nm) 2.074 31508 2.33 2091
4 PDA MaxPlot (250nm-550nm) 2.511 19000 1.40 2301
5 PDA MaxPlot (250nm-550nm) 2.658 42557 3.14 4286
6 PDA MaxPlot (250nm-550nm) 3.447 244771 18.08 17468
7 PDA MaxPlot (250nm-550nm) 4.607 348524 25.75 19485
8 PDA MaxPlot (250nm-5500m) 11.000 126719 9.36 3430
9 PDA MaxPlot (250nm-550nm) 12.267 19335 1.43 330
PDA Result Table
Name RT Purity Purity 1 Match 1 Spect. Match 1 Match 1
1 Threshold Name Angle Threshold
Angle
1 1.199 Fisher 65-1 3.973 10.182
2 1.559 Fisher 65-2 2.664 7.676
3 2.074
4 2.511
5 2.658
6 3.447 Fisher 65-6 4.263 12.280
7 4.607 Fisher 65-7 6.454 14.078
8 11.000
9 12.267

 

38

 

Figure 13: HPLC report for ink sample Staedtler B384D

SampleName Staettler B3840
Injection Volume 10.00 ul
Run TIme 20.00 Minutes

Sample Set Name man'lyn 11703

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

Date Acquired 1/17/2003 9:13:25 PM
Acq Method Set inkrev2 method set
Processing Method Marilyn library 2103

Channel Name MaxP|01250_550

 

 

 

I i 0.08
l
7 __1,- 4’ 7* 7 fl _. i 7 7 I
1 . 0.06
1 .i a
1 I 1'0.04
I I I 1
I I
1 1 1 1 L 002
. 1 1'1 I .. .
1 1 I f 1 I
I". l
1 ‘I‘ 0.00
"/ ,I 1
f I . . I - A
1 I . ' 500.00
a... 7 . -.;.-....I .. .. I- .j..... - .---....fii
2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00
Mnutes
Auto-Scaled Chromatogram
$1 I: i
0.020 n t" is. I
I e ‘3 I
0.0154 .—' 3 I
D ‘0 I
< 1 121 hi I
00104 "II"; .
FIN. I aa‘ 1 8 {7, 1
1 1- II I g It) 1‘ 1
0.005 I. I - no
o.oooi__r ‘5‘ .3 j " I
. 1 I I ' I . I I~—.-- f— I I I I I I I I I IV I I I I I I I I I I "Vii—"i
2.00 4.00 6.00 3.00 0.00 12.00 14.00 16.00 18.00 20.00

nutes

39

Sample Name Staedtler B384D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.176 84794 6.13 6772
2 PDA MaxPlot (250nm-5500m) 1.423 149196 10.78 12421
3 PDA MaxPlot (250nm-550nm) 1.787 82627 5.97 4018
4 PDA MaxPlot (2500m-550nm) 2.514 36908 2.67 3422
5 PDA MaxPlot (250nm-5500m) 2.698 87798 6.34 8783
6 PDA MaxPlot (250nm-550nm) 3.524 356502 25.76 25487
7 PDA MaxPlot QSOnm-SSOnm) 4.359 18803 1.36 1355
8 PDA MaxPlot (250nm-550nm) 4.777 463155 33.46 23895
9 PDA MaxPlot (250nm-550nm) 5.593 54418 3.93 2580
10 PDA MaxPlot (250nm-550nm) 7.737 49882 3.60 2519
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Aggle Threshold Angle Threshold
1 1.176 Staettler B384-l 9.989 1.324
2 1.423 Tombo 8535-2 3.839 1.363
3 1.787 Staettler B384-3 4.566 1.896
4 2.514
5 2.698 Fisher B50-3 2.439 1.799
6 3.524 Fisher 850-4 0.589 1.289
7 4.359 ‘
8 4.777 Parker 8176-9 3.105 2.292
9 5.593 Staettler B384-8 3.803 2.190
10 7.737 Papermate B376-8 4.937 7.106

 

40

 

 

Figure 14: HPLC report for ink sample Staedtler B384D (own library)

SampleName Staettler 8384D Date Acquired 1/17/2003 9:13:25 PM
Injection Volume 10.00 111 Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
3801910 Set Name "HWY" 11703 Channel Name MaxP101250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

5, “A , _ , a ,
. I000
4_,—_—1_.._.¥—¥ ,.¥.,. #7 ,2 \ in 7 7 if i f I
1 1 1 1006
I 1 1
I . I
. I . :(3
1 I I I ‘r 0.04
1 I I I
I I
. I r
I I I
I '11 ’I I I :002
I / .1 1 i
I .
I 0.00
/ I g r
I 50000
“CC. I ‘

 

10:00 12100 14.00 16:00 18:00 20.00
Mnutea

mI—Im—I’ I 7 ""‘ r 1* r"?
2.00 4.00 8.00 8.00

Auto-Scaled Chromatogram

 

0.025I
1

A 3.524:—

4.777 ——

0.020%

1 .423

0015—1
3
<

0.010

‘-‘- 1.787

0.005

*I 251‘- 2.698
' » 7.737

 

0.000 31 ‘ . .,
I 1 F 1 l I I l I I ' 7 ‘ l I I I I I if I I I I 1 I I l
2.00 4.00 6.00 8.00 11°00 12.00 14.00 16.00 13.00 20.00
nutea

 

 

41

Sample Name Staedtler B384D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time ‘Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.176 84794 6.13 6772
2 PDA MaxPlot (250nm-550nm) 1.423 149196 10.78 12421
3 PDA MaxPlot QSOnm-SSOnm) 1.787 82627 5.97 4018
4 PDA MaxPlot (250nm-550nm) 2.514 36908 2.67 3422
S PDA MaxPlot (250nm-550nm) 2.698 87798 6.34 8783
6 PDA MaxPlot (250nm-550nm) 3.524 356502 25.76 25487
7 PDA MaxPlot (250nm-550nm) 4.359 18803 1.36 1355
8 PDA MaxPlotQSOnm-SSOnm) 4.777 463155 33.46 23895
9 PDA MaxPlot (250nm—550nm) 5.593 54418 3.93 2580
10 PDA MaxPlot (250nm-550nm) 7.737 49882 3.60 2519
PDA Result Table
Name RT Purity l Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angle Threshold
1 1.176 Staettler B384-l 9.989 1.324
2 1.423 Staettler B384-2 4.225 1.330
3 1.787 Staettler B384-3 4.566 1.896
4 2.514
5 2.698 Staettler B384-S 6.830 1.659
6 3.524 Staettler B384-6 1.715 1.229
7 4.359 ‘
8 4.777
9 5.593 Staettler B384-8 3.803 2.190
10 7.737

 

 

 

 

 

 

 

 

 

 

42

3.2 Thin Layer Chromatography

Those inks that were not able to be identified to a reasonable degree of certainty
and whose PDAs showed great resemblance to others in their respective sample runs
were run on a high resolution thin layer chromatography plate for comparison purposes.
It was determined that Papermate B68, Fisher B65, Fisher B77 and Fisher B4
all had identical ink compositions. Mitsubishi B384 and Mitsubishi B385 were also
shown to have identical ink compositions. Cross B164, Parker B176 and Formulabs
8517 also have the same ink composition as one another. Finally, Bic Bl62, Bic B197
and Bic B388 were shown to share the same ink composition as one another.
Furthermore, Senator B3 85 and Staedtler B3 84 whose PDAs were remarkably similar
were shown to differ only by the presence of copper phthalocyanine in Staedtler B3 84
and its absence in Senator B385. See Figure 15 and Figure 15A. None of the black ball
point inks that had similar PDA printouts were shown to have the same ink composition.

See Figure 16.

43

 

 

 

H. ween—.598 wan
N. man—.2. wau

u. wwcowasa 8.3
A. Ea Ema

u. nan—.2. um:

mam—:6 Hm“

a. woe—8.. Emu

q. @8252. gas
a. 2:855: 83
o. 35:—.55 Sou
5. 03% .33

:. wan—8.. ”flag

5. mic—.3593 um:
nu. 33.2. a:

ma. mam—5.. 2

mm. 5.3 mag

5:: :42. «33:-£3363. E»? 3.. emu—=3. Sea 3:63.: a; 2.3—=8.

 

 

o . ..«H- “A

 

a. Ea wan n. Ea ~33 u. Ea wumm

39.3 5? H5: .35.. 93.335063. Ea? m3. «mu—=3. Sea 99:53:“ a?» 2.5—=8.

45

 

1r" “'

 

—. $2.8. Sm w. @3252. mu: m. @5853 3..
N. 5.18.. an: A. 5.62: an; a. 5.3 an;

ENE... 3. HE: .36.. 2.3338365. 3:8 3.. 33...... 2.8.. 9.5.3.: 3; 2.528.

46

4. CONCLUSIONS AND FUTURE DIRECTION

The use of high performance liquid chromatography (HPLC) as the final step in ink
identifications has been shown through this research to be ”highly effective. As stated
earlier, the use of a reversed phase examination as the final step in the ink identification
as opposed to an additional normal phase process provides much needed variation in the
techniques utilized to produce the ink identification. Furthermore, both the increased
specificity of the HPLC as compared to HPTLC and the quantitative measure of degree
of fit provided by the library matching software allow for a more objective analysis and
conclusion to be performed and attained.

Alterations to this technique, however, could drastically improve the results. For
example, if software were developed to not only look at only the individual peaks in a
chromatogram, but instead to examine the entire chromatogram, several
misidentifications that occurred could be avoided. Also, if a HPLC environment were
identified that would allow for the examination of copper phthalocyanine, a common
ingredient in inks, a more inclusive analysis of the inks would be able to be performed
and much confusion, and possible misidentification, could be eliminated.

Ink identifications are crucial to many questioned document cases. It is therefore
imperative that a reproducible, reliable, and highly efficient technique be available.
HPTLC and HPLC have been shown to meet these standards, and there are other
techniques currently being developed that will further the science of ink identification.
Capillary electrophoresis (CE) is a technique that is gaining popularity in the field of
forensic science owing to its great versatility. The ability to easily alter the

instrumentation and analysis environment on the CE greatly facilitates the analysis of

47

different kinds of ink (i.e. rollerball ink, ballpoint ink, felt tip ink) which are composed of
vastly different components requiring different analytical techniques.” In addition, CE
has been found to be more discriminating than either HPTLC or HPLC in the analysis of
ink and provides greater resolving power than those techniques as well.12 Furthermore,
CE typically requires a much smaller sample size than HPTLC or HPLC. For example,
using capillary zone capillary electrophoresis, Whiting was able to obtain consistent
results differentiating between four ballpoint inks with sample sizes as small as 5mm of
an ink line.”

Other forms of capillary electrophoresis have also been utilized in ballpoint ink
analysis. Micellar electrokinetic capillary chromatography (MECC) was used by a group
in the Netherlands to differentiate ballpoint inks that were indistinguishable by HPLC or
HPTLC.12 Capillary electrophoresis has also been paired with particle induced x-ray
emission (PIXE) to obtain favorable results. Ballpoint ink samples that were not able to
be differentiated by the capillary electrophoresis were shown by PIXE to possess a
different copper: zinc ratio or additional metals not present in the other inks. Conversely,
those samples that were not able to be differentiated by PIXE analysis exhibited different
peak patterns in their electropherograms. ‘3

Another method of ink differentiation analysis currently being pursued is that of
field desorption mass spectrometry (FDMS). This method, too, uses a much smaller ink
sample size than either HPLC or HPTLC: 1mm of an ink line. FDMS is a simple, quick
method that has been shown to differentiate ballpoint inks by the identification and

comparison of the basic dyes present in the inks. One notable disadvantage to this

48

technique, however, is that it is unable to differentiate between different dyes with
identical molecular weights.14

As is obvious from the amount of research being pursued with the various
techniques discussed, ballpoint ink differentiation and identification are extremely timely
topics of research. With the HPLC method proposed by this research and the results it
has provided, this author hopes to provide yet another building block on which improved

methods of ballpoint ink identification analysis can be constructed.

49

APPENDICES

50

APPENDIX A

51

APPENDIX A

Instrument Method for inkrev 2

52

Instrument Method: inkrev2 instrument method
Stored: 2/25/2002 10:42:53 AM

 

Method Information
Comments
Modified User System
Locked No
Method Id 5296
Method Version 12
Edit User

996 PDA Instrument Setup
Type 996 PDA
Instrument Status On
Channel Name 996

 

 

 

Start Wavelength 208.0
End Wavelength 800.0
Sampling Rate 1.0
Resolution 1.2
Auto Exposure Yes
Lamp On Yes
lnterpolate 656 nm Yes
Channel1 Enable Off
Channel 2 Enable Off
Exposure Time 15.00
Filter Response 1
Digital Filter Response 1.0
Channel 1 Mode Off
Channel1 Bandwidth 4.8
Channel 1 Wavelength 254.0
Channel 1 Offset 0.000

996 PDA Event Table

 

Time EvontOutNumbor Event Comments

 

 

 

 

 

 

1 22.00 Event Lamb Olf

 

 

Channel1 Ratio Wavelength 254.0

Channel 1 Threshold

Channel 1 Minimum Ratio
Channel 1 Maximum Ratio

Channel 1 Filter Type

Channel 1 Filter Response

Channel 2 Mode
Channel 2 Bandwidth
Channel 2 Wavelength
Channel 2 Offset

Channel 2 Ratio Wavelength

Channel 2 Threshold

Channel 2 Minimum Ratio
Channel 2 Maximum Ratio

Channel 2 Filter Type

Channel 2 Filter Response

Event Enable

53

0.001
0.001
100.000
Hamming
0

Off

4.8

254.0
0.000
254.0
0.001
0.001
100.000
Hamming
0

On

 

W600 Instrument Setup

 

Ty pe W600
Instrument Status On
Channel Name 600 PRESS
Description

Use channel monitor Off
Monitor parameter Pressure
Chart Parameter 96A

 

 

Head Volume 100
Pump Type 800E
Pump Mode lsocratic
Flow 1.00
%A 100.0
968 0.0
%C 0.0
%D 0.0
High Limit 4000
Low Limit 0
Sparge Rate 20
Sparge A On
Sparge 8 Off
Sparge C Off
Sparge D Off
Setpoint 0.0
High temp limit 25.0
Silk On Off
Vacuum Degas On Off
Switch 1 Off
Switch 2 Off
Switch 3 Off
Switch 4 Off
Use Events Off
Solvent A 80:20 acetonitrile: H20 .005 heptanesulfonlc acid + 0.025 acetic
acid
Solvent 8
Solvent C
Solvent 0
W717 Instrument Setup
Type W717
Instrument Status On
Use Temp No
Setup 4.0

Heater Cooler Not Installed

54

Channel 2 Wavelength

Channel 2 Offset

Channel 2 Ratio Wavelength

Channel 2 Threshold

Channel 2 Minimum Ratio
Channel 2 Maximum Ratio

Channel 2 Filter Type

254.0
0.000
254.0
0.001
0.001
100.000
Hamming

Channel 2 Filter Response 0

 

 

 

 

 

 

 

 

 

 

 

Event Enable On
896 PDA Event Table
Tlme EventOut Number Ewnt Comments
1 22.00 Event Lamp Off
W600 Instrument Setup
Type W600
Instrument Status On
Channel Name 600 PRESS
Description
Use channel monitor Off
Monitor parameter Pressure
Chart Parameter %A
Head Volume 100
Pump Ty pe 600E
Pump Mode lsocratic
Flow 1.00
%A 100.0
968 0.0
%C 0.0
%D 0.0
High Limit 4000
Low Limit 0
Sparge Rate 20
Sparge A On
Sparge B Off
Sparge C Off
Sparge D Off
Setpoint 0.0
High temp limit 25.0
Silk On Off
Vacuum Degas On Off
Switch 1 Off
Switch 2 Off
Switch 3 Off
Switch 4 Off
Use Events Off

55

APPENDIX B

56

APPENDIX B

Processing Data with Waters Empower Software

57

 

APPENDIX 8.]

Deriving a Max Plot Chromatogram

58

To Derive a Max Plot Chromatogram:

1.

Open the Project window

0 At the main menu, right click on the Review Data box.

0 Select Review from the context menu.

0 Select Channels from the cascade menu.

Select (double click) the sample you wish to build the processing method with. It

is advantageous to select one with numerous peaks. If one of the samples run has

an upward sloping baseline, select that sample with which to build the processing
method.

0 It is necessary to use the sample with the high baseline, if present, because if
you utilize a spectrum that does not have a high baseline to create a processing
method and then try to utilize the processing method on a spectrum that does
have a high baseline, the method will find a reduced number or no peaks.
However if the reverse is done, creating the processing method with the high
baseline spectrum and then analyzing samples without the high baseline, there
are no adverse effects noted.

0 The numerous peaks characteristic is advantageous in that it provides a large
variety of peaks from which to select a “narrowest peak” (a later step in
building the processing method).

In the Review Main window, click the Method Set tool in the tool bar to bring

the Method Set Editor into view.

Right click on the Method Set tree (in the window on the left of the screen);

select New from the context menu and Derived Channel from the cascade menu.

59

From the Channel tab, select PDA: Max Plot from the drop-down menu.

Enter 250 for the start wavelength and 550 for the end wavelength in their

respective text boxes.

0 This span was selected owing to previous research that illustrated the greatest
diversity between ball point inks to occur at the wavelengths of 254 nm and
546 nm.7 It is suggested by the software manufacturer to keep the wavelength
range as small as possible, thus explaining the precise numbers selected here.

Click OK after the correct wavelength range has been selected.

Enter a name for the new derived channel in the dialog box which appears (for

example, MaxPlot250_550), and click OK.

60

APPENDIX B.2

Building a PDA Processing Method

61

To Build a PDA Processing Method:

1.

2.

Click on the Processing Method Wizard icon in the tool bar.

Select PDA from the Processing Type drop-down menu, and click OK. The Peak
Detection 1 page will appear.

On the Integration - Peak Detection 1 page, select the narrowest peak of interest;
click Next.

Do not select the smallest, narrowest peak present in the spectrum; instead, select
a peak that is of decent height (somewhat of a judgement call) and is slightly
wider than the narrowest peak. This will allow the processing method to be more
discriminatory in the peaks it identifies.

The peak width selected here was 30.00 seconds.

The Integration - Peak Detection 2 page appears next. This page allows you to set
the peak threshold by selecting a portion of the baseline that has representative
noise.

This is where the high baseline is a factor.

Zoom in on an area of the baseline that does not have peaks, but that is sloping
upwards (if applicable, towards the right hand side of the spectrum). It may be
necessary to zoom in several times to ensure that the baseline is indeed free of
peaks.

The threshold selected in this case was 60.00 uV/sec.

Click Next.

The Integration - Peak Detection 3 page appears next. In this page, you are to

select the portion of the chromatogram over which you would like the integration

62

performed. Using the mouse, select the entire chromatogram; dragging the box
within the x- and y-axes. Click Next.

The Integration - Peak Detection 4 page appears next. This page allows you to
discard peaks that are not of interest.

Click in the middle of the peak of interest; select either the Minimum Height or
Minimum Area box. This sets the Minimum Area or Minimum Height to 95%
of the smallest peak of interest.

A peak of area 18,000 uV*sec. was selected

Click Next.

The Calibration — General page appears next. Click Next on the following pages
until you reach the PDA Purity/Matching page.

To the question: “Do you wish to perform peak purity testing on all peaks?”,
answer No.

To the question: “Do you wish to match spectra against PDA library spectra?”,
answer Yes.

The Processing Method Name page appears. In the Method Name text box, type
the desired name, in this case “Marilyn library 2103”. Click Finish.

It is also necessary to save the Method Set in which the Processing Method
functions. To do this, simply go to Save As, select Method Set from the drop

down window, and type in the desired name.

63

APPENDIX B.3

Creating a Library; Adding and Matching Spectra to an Existing Library

To Create and Add Spectra to the Library:

1.

Return to the Project window (Step 1 under “To Derive a Max Plot
Chromatogram”), and select the spectra you desire to have in your library. You
may start with as many or few as you choose; you can always add more at later
times. To select more than one, you must hold down the Shift key on the
keyboard when clicking on the spectra name with the mouse. Click the Review
tool.

Click the 3D Channels tab at the bottom of the Review Main window.

Select Open from the File menu, and then select Method Set.

Select the desired method set (Marilyn library 2103); click Open.

The method set should automatically be applied to the sample. If not, click on the
Apply Method Set tool in the upper tool bar.

Select Library from the Spectrum Review menu; select New Library from the
cascade menu.

Name the new library; click on the Create button.

Again, select the Library option from the Spectrum Review menu; select Add to
library __ from the cascade menu.

The Add Spectrum to Library dialog box then appears.

In the Name text box enter the desired name of the identified peak. Each peak
within the sample will be identified and will subsequently need some sort of label.
For example, if it were the first peak identified from the sample Tombo B-535, I
would name the peak “Tombo B-535-1”, then “T ombo B-535-2”, and so on.

Click OK.

65

After all peaks from one sample are named, go to the 3D Channels table and
select the next spectrum to be processed. Repeat steps 8 through 10.
Continue entering spectra into the library until finished.

Select Exit from the File menu.

To Match Spectra to an Existing Library:

1.

Again, open the Project window (Step 1 under “To Derive a Max Plot
Chromatogram”).

Click on the “Method” tab that will then display all processing methods and
method sets in the computer’s memory. Click on the processing method that was
used to create the library, and that will be used to process the unknown sample.
In the library matching area, check the empty box next to the library created for
this questioned sample. Ensure that no other box is checked.

Save these changes to the processing method.

Return to the Channels tab.

Select the spectrum you would like matched against the existing library. Click
Review.

At the bottom of the Review Main window, click on the 3D Channels tab.
Select Open from the File menu, and then Method Set from the cascade menu.
Select Marilyn library 2103 from the menu of existing method sets. Click

Open.

66

10.

Again, the processing method should automatically be applied to the sample.

However, if it is not, click on the Apply Method Set tool. This will extract and

process a Max Plot chromatogram for the spectrum selected.

Scroll the menu where 3D Channels is initially highlighted until you reach a tab

entitled Peaks. This will display a table where the calculated values for the

library matching are listed.

0 The Match Angle should be less than the Match Threshold to indicate a good
match.

Save the results so that they can be printed in a report.

0 Select Save from the File menu, then All.

67

APPENDIX 3.4

Creating and Printing Reports

68

To Create and Print Reports:

1.

Return to the Project window (Step 1 under “To Derive 3 Max Plot
Chromatogram”).

Click the Results tab.

Select the data you wish to print; click Preview/Report Publisher under the
Tools menu.

In the Open Report Method dialog box, create your report. A report for individual
samples was created in this case by adding the following items to a blank report
template: sample name, injection volume, run time, sample set name, processed
channel description, date acquired, acquiring method set, processing method,
channel name, 3D plot, auto-scaled chromatogram, peak results table, and PDA
result table.

Save the result method.

After the Report Method has been saved, click the Print tool.

69

APPENDIX C

70

APPENDIX C

HPLC Reports for Blue Ball Point Inks That Were Identified to a Reasonable
Degree of Certainty by Library Matching

7l

APPENDIX C.l

HPLC Reports for Blue Ball Point Inks That Were Identified to a Reasonable
Degree of Certainty by Library Matching

Sample Run 1

72

Figure 17: HPLC report for ink sample Russian Ink B426D

SampleName Russian Ink 34260 Date Acquired 1/16/2003 9:40:16 PM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name marilyn 11603 Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

 

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nutes

73

Sample Name Russian Ink B426D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time ' Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.212 73523 7.73 5964
2 PDA MaxPlot (250nm-550nm) 1.486 449822 47.27 57074
3 PDA MaxPlot (250nm-550nm) 1.895 72834 7.65 8299
4 PDA MaxPlot (250nm-550nm) 2.212 57234 6.02 4790
5 PDA MaxPlot (250nm-550nrr9 2.441 33250 3.49 2591
6 PDA MaxPlot (250nm-550nm) 2.805 107663 11.31 9212
7 PDA MaxPlot (250nm-550nm) 3.715 117534 12.35 8087
8 PDA MaxPlot (250nm-550nm) 5.113 39656 4.17 2165
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Ange Threshold Name Angle Threshold

1 1.212 Russian Ink 3426-] 0.440 1.224
2 1.486 Russian Ink 8426-2 0.178 1.022
3 1.895 Russian Ink 8426-3 1.006 1.103
4 2.212 Russian Ink B426-4 2.604 1.581
5 2.441 Russian Ink 8426-5 8.371 1.827
6 2.805 Senator 3385-4 2.980 1.940
7 3.715 Senator B385-5 0.888 1.493
8 5.113 Formulabs 3517-11 1.988 2.479

 

 

 

 

 

 

 

 

 

 

74

Figure 18: HPLC report for ink sample Cross Bl64D

SampleName Cross B1640
Injection Volume 10.00 ul
Run Time 20.00 Minutes

Sample Set Name marilyn 11603

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

Date Acquired 1/16/2003 10:43:52 PM
Acq Method Set inkrev2 method set
Processing Method Marilyn library 2103

Channel Name MaxP101250_550

 

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Sample Name Cross B164D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.108 249857 19.91 28649
2 PDA MaxPlot (250nm-550nm) 1.517 357626 28.50 21975
3 PDA MaxPlot (250nm-550nm) 1.628 119216 9.50 19312
4 PDA MaxPlot (250nm-550nm) 1.828 43258 3.45 6288
S PDA MaxPlot (250nm-550nm) 2.801 24924 1.99 2669
6 PDA MaxPlot (250nm-550nm) 3.703 151753 12.09 10480
7 PDA MaxPlot (250nm-550nm) 5.068 308162 24.56 15073
PDA Result Table
Name RT Purity l Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angle Threshold
1 1.108 Cross 8164-] 0.778 1.111
2 1.517 Cross Bl64-2 0.481 1.186
3 1.628 Cross Bl64-3 0.431 1.197
4 1.828 Cross B164-3 5.016 1.498
5 2.801 Cross 3164-4 2.380 3.185
6 3.703 Cross B164-5 4.567 1.528
7 5.068 Fisher B4-6 0.889 1.461

 

76

 

 

Figure 19: HPLC report for ink sample Papermate 622D

SampleName Papermate 6220 Date Acquired 1/16/2003 11:26:16 PM

Injection Volume 10.00 uI Acq Method Set inkrev2 method set

Run Time 20.00 Minutes Processing Method Marilyn library 2103

Sample Set Name marilyn 11503 Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

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- - .7..-.—.p—' ‘
I

 

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2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 2000
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77

Sample Name Papermate 622D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time ' Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.163 68832 16.70 5963
2 PDA MaxPlot (250nm-550nm) 1.482 69720 16.92 6857
3 PDA MaxPlot (250nm-550nm) 11.915 273590 66.38 6407
PDA Result Table
Name RT Purity l Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angle Threshold
1 1.163 Papermate 622-1 6.074 12.567
2 1.482 Papermate 622-2 8.116 18.857
3 11.915

 

78

 

 

SampleName Inoxcrom B100
Injection Volume 10.00 ul
Run Time 20.00 Minutes

Sample Set Name marilyn 11603

Figure 20: HPLC report for ink sample Inoxcrom BlOD

Acq Method Set inkrev2 method set

Date Acquired 1/17/2003 12:08:41 AM

Processing Method Marilyn library 2103

Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot

(250.0 nm to 550.0 nm)

 

 

 

 

 

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79

Sample Name Inoxcrom B10D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.187 168135 29.30 14719
2 PDA MaxPlot (250nm-550nm) 1.429 91873 16.01 6593
3 PDA MaxPlot (250nm-550nm) 8.088 42559 7.42 2608
4 PDA MaxPlot (250nm-550nm) 8.449 69907 12.18 2728
5 PDA MaxPlot (250nm-550nm) 11.977 201402 35.10 4886
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Arrgle Threshold

1 1.187 Inoxcrom B 10-1 3.035 6.057
2 1.429 Inoxcrom B 10-2 6.002 12.691
3 8.088
4 8.449
5 11.977

 

80

 

 

Figure 2]: HPLC report for ink sample Mont Blanc B 106D

SampleName Mont Blanc 81060 Date Acquired 1/17/2003 1:12:19 AM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name marilyn 11603 Channel Name MaxP101250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

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Sample Name Mont Blanc Blo6D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.140 566640 54.90 68190
2 PDA MaxPlot (250nm-550nm) 1.437 66273 6.42 7190
3 PDA MaxPlot (250nm-550nm) 8.461 44523 4.31 1803
4 PDA MaxPlot (250nm-550nm 11.974 157890 15.30 3885
5 PDA MaxPlot (250nm-550nm) 12.915 196829 19.07 4640
PDA Result Table
Name RT Purity l Purity 1 Match 1 Spect. Match Match 1
Angle Threshold Name 1 Aflle Threshold

1 1.140 Mont Blanc B106-1 1.034 1.329
2 1.437 Mont Blanc B106-2 5.972 11.291
3 8.461
4 11.974
5 12.915 Formulabs BS 19-11 3.897 7.760

 

82

 

Figure 22: HPLC report for ink sample Bic Bl62D

SampleName Bic 81620 Date Acquired 1/17/2003 2:37:08 AM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name marilyn 11603 Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

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83

Sample Name Bic Bl62D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.108 242620 20.01 18984
2 PDA MaxPlot (250nm-550nm) 1.499 317561 26.19 21382
3 PDA MaxPlot (250nm-550nm) 1.625 166238 13.71 17119
4 PDA MaxPlot (250nm-550nm) 2.302 23931 1.97 2271
5 PDA MaxPlot (250nm-550nm) 2.577 40485 3.34 3918
6 PDA MaxPlot (250nm-550nm) 5.046 276767 22.83 13481
7 PDA MaxPlot (250nm-550nm) 8.061 144942 11.95 6974
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angle Threshold

1 1.108 Bic 8162-] 0.768 1.150
2 1.499 Bic 8162-2 0.424 1.123
3 1.625 Bic Bl62-3 0.896 1.155
4 2.302
5 2.577 Bic Bl62-5 3.984 2.083
6 5.046 Bic Bl62-6 0.998 1.514
7 8.061 Bic Bl62-7 0.601 1.647

 

84

 

 

Figure 23: HPLC report for ink sample Dupont B102D

SampleName Dupont B1020
Injection Volume 10.00 ul
Run Time 20.00 Minutes

Sample Set Name marilyn 11603

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

Date Acquired 1/17/2003 3:40:47 AM
Acq Method Set inkrev2 method set
Processing Method Marilyn library 2103

Channel Name MaxPlot250_550

 

 

 

 

 

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Sample Name Dupont B102D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
Quin)
l PDA MaxPlot (250nm-550nm) 1.133 156928 14.62 11398
2 PDA MaxPlot (250nm-550nm) 1.49] 185793 17.31 8881
3 PDA MaxPlot (250nm-550nm) 1.960 20893 1.95 2166
4 PDA MaxPlot (250nm-550nm) 2.332 21025 1.96 1483
5 PDA MaxPlot (250nm-550nm) 2.585 20716 1.93 2334
6 PDA MaxPlot (250nm-550nm) 3.688 117297 10.93 8182
7 PDA MaxPlot (250nm-550n@ 5.059 193387 18.02 9417
8 PDA MaxPlot (250nm-550nm) 16.924 128039 11.93 3661
9 PDA MaxPlot (250nm-550nm) 19.096 228953 21.34 4413
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Argle Threshold
1 1.133 Dumnt B102-1 3.406 1.325
2 1.491 Dupont B 102-2 0.838 1.377
3 1.960 Dupont 8102-2 7.951 2.242
4 2.332 Bic Bl62-4 6.054 2.001
5 2.585 Fisher B4-3 6.795 4.063
6 3.688 Dupont 8102-5 0.795 1.774
7 5.059 Dupont B 102-6 0.765 1.591
8 16.924 Dupont 3102-7 1.048 2.181
9 19.096 Dupont B 102-8 0.806 1 .865

 

86

 

Figure 24: HPLC report for ink sample F ormulabs BSl7D

SampleName Formulabs 85170 Date Acquired 1117/2003 4:23:11 AM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name marilyn 11603 Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

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Sample Name Formulabs B517D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
4min)
1 PDA MaxPlot (250nm-550nm) 1.231 75589 2.85 6331
2 PDA MaxPlot (250nm-550nm) 1.581 343716 12.95 23669
3 PDA MaxPlot (250nm-550nm) 1.779 128449 4.84 8876
4 PDA MaxPlot QSOnm-SSOnm) 2.206 48294 1.82 3585
5 PDA MaxPlot (250nm-550nm) 2.454 36387 1.37 3263
6 PDA MaxPlot (250nm-550nm) 2.784 189057 7.12 16060
7 PDA MaxPlot (250nm-550nm) 3.074 20007 0.75 2489
8 PDA MaxPlot (250nm-550nm) 3.376 142441 5.37 11959
9 PDA MaxPlot (250nm-550nm) 3.665 443863 16.72 29224
10 PDA MaxPlot (250nm-550nm) 4.027 22556 0.85 2464
11 PDA MaxPlot (250nm-550nm) 5.037 338763 12.76 16448
12 PDA MaxP10t(250nm-550nm) 7.646 718598 27.07 28404
13 PDA MaxPlot (250nm-550nm) 7.957 147252 5.55 14658
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match Match 1
Angle Threshold Name 1 Threshold
Angle
1 1.231 Formulabs BS 17-1 1.304 1.953
2 1.581 Formulabs BSl7-2 0.412 1.257
3 1.779 7.368 2.191
4 2.206 Formulabs 8517-4 1.738 2.948
5 2.454 Formulabs B517-5 2.125 3.391
6 2.784 Formulabs BS 17-6 2.401 1.448
7 3.074 Formulabs BSl7-7 3.140 4.220
8 3.376 Formulabs BS 17-8 0.928 1.819
9 3.665 Formulabs B5 17-9 0.340 1.349
10 4.027 Formulabs BSl7-10 2.811 4.330
11 5.037 Formulabs BSl7-11 0.407 1.557
12 7.646 Formulabs BS 17-12 0.199 1.226
13 7.957 Formulabs 8517-13 0.365 1.491

 

 

 

 

 

 

 

 

 

 

88

Figure 25: HPLC report for ink sample Fisher B4D

SampleName Fisher B40 Date Acquired 1/17/2003 5:26:50 AM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name marilyn 11603 Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

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Mnutes

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nutes

Sample Name Fisher B4D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time ' Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.188 122811 13.53 9173
2 PDA MaxPlot (250nm-550nm) 1.576 274622 30.25 15733
3 PDA MaxPlot (250nm-550nm) 2.776 29909 3.29 3212
4 PDA MaxPlot (250nm-550nm) 3.664 175068 19.29 11965
5 PDA MaxPlot (250nm-550nm) 5.023 236983 26.11 11965
6 PDA MaxPlot (250nm-550nm) 8.121 18988 2.09 1087
7 PDA MaxPlot (250nm—550nml 12.832 49355 5.44 1561
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match Match 1
Aug: Threshold Name 1 Anfl Threshold

1 1.188 Fisher B4-1 1.001 1.466
2 1.576 Fisher B4-2 0.519 1.396
3 2.776 Fisher B4-4 1.745 3.345
4 3.664 Fisher B4-5 0.551 1.539
5 5.023 Fisher B4-6 1.478 1.533
6 8.121
7 12.832 Formulabs BS 19-11 1.665 2.902

 

90

 

Figure 26: HPLC report for ink sample Formulabs BS 19D

SampleName Formulabs 85190
Injection Volume 10.00 ul
Run Time 20.00 Minutes

Sample Set Name marilyn 11603

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

Date Acquired 1/17/2003 6:09:14 AM
Acq Method Set inkrev2 method set
Processing Method Marilyn library 2103

Channel Name MaxPlot250_550

 

2.00 4.00 6,00
Mnutes

Auto-Scaled Chromatog ram

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91

AU

12.692 ,.

 

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0.00 12:00
nutes

Sample Name Formulabs BSl9D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm—550nm) 1.447 290390 13.87 15197
2 PDA MaxPlot (250nm-550nm) 1.643 135034 6.45 14326
3 PDA MaxPlot (250nm—550w 1.875 183769 8.78 13534
4 PDA MaxPlot (250nm-550nm) 2.145 79438 3.79 7531
5 PDA MaxPlot (250nm-550nm) 2.308 76328 3.64 6149
6 PDA MaxPlot (250nm-550nm) 2.569 36924 1.76 4090
7 PDA MaxPlot (250nm-550nm) 2.774 73556 3.51 7847
8 PDA MaxPlot (250nm-550nm) 3.674 194483 9.29 12657
9 PDA MaxPlot (250nm-550nm) 5.041 26322 1.26 2097
10 PDA MaxPlot (250nm-550nm) 5.733 92609 4.42 5484
11 PDA MaxPlot (250nm-550nm) 7.357 197550 9.43 8537
12 PDA MaxPlot (250nm-550nm) 12.692 707718 33.80 16521
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match Match 1
Angle Threshold Name 1 Angle Threshold
1 1.447 Formulabs BS 19-2 3.912 2.052
2 1.643 Formulabs B519-3 1.201 2.187
3 1.875 Formulabs BS 19-4 8.933 2.151
4 2.145 Formulabs B519-5 3.958 2.717
5 2.308 Formulabs BS 19-6 2.313 2.942
6 2.569 Formulabs BS 19-6 8.270 3.719
7 2.774 Formulabs BS 19-7 2.320 3.835
8 3.674 Formulabs BS 19-8 3.356 2.794
9 5.041 Bic Bl62-6 9.046 9.568
10 5.733 Formulabs BS 19-9 3.874 4.388
11 7.357 Formulabs BS 19-10 2.178 4.028
12 12.692 Formulabs BS 19-11 1.012 2.270

 

92

 

APPENDIX C.2

HPLC Reports for Blue Ball Point Inks That Were Identified to a Reasonable
Degree of Certainty by Library Matching

Sample Run 2

93

Figure 27: HPLC report for ink sample Pilot BlO3D

SampleName Pllot 31030 Date Acquired 1/17/2003 8:31:01 PM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name marilyn 11703 Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

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2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 13.00 20.00
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Auto-Scaled Chromatogram
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2.00 4.00 6N 8.00 A10.00 12.00 14.00 16.00 18.00 20.00
nutes

Sample Name Pilot BlO3D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time ' Area % Area Height
1min)
1 PDA MaxPlot (250nm-550nm) 1.133 340040 44.90 26933
2 PDA MaxPlot (250nm-550nm) 1.406 238185 31.45 14835
3 PDA MaxPlot (250nm-550nm) 2.564 45586 6.02 3819
4 PDA MaxPlot QSOnm-SSOnm 3.401 83479 11.02 6376
5 PDA MaxPlot (250nm-550nm) 4.695 49986 6.60 3351
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angle Threshold

1 1.133 Pilot B103-1 1.947 2.794
2 1.406 Pilot B 103-2 3.799 5.318
3 2.564
4 3.401 marinate B376-6 5.369 11.318
5 4.695

 

95

 

 

Figure 28: HPLC report for ink sample Mitsubishi B395D

SampleName Mitsubishi 83950 Date Acquired 1/18/2003 1:27:49 AM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name marilyn 11703 Channel Name MaxP101250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

 

 

 

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2.00 4.00 6.00 800 10.00 12.00 14.00 16.00 13.00 20.00
Mnutes
Auto-Scaled Chromatogram
‘I '_"”“—""“W ' " ’7’ "l
1 l I
006—I 8 I
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96

Sample Name Mitsubishi B395D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.200 649939 21.33 67929
2 PDA MaxPlot (250nm-550nm) 1.426 149438 4.90 26159
3 PDA MaxPlot (250nm-550nm) 1.539 187495 6.15 17756
4 PDA MaxPlot (250nm-550nm) 1.799 124620 4.09 9432
s PDA MaxPlot (250nm-550nng 2.053 39185 1.29 5035
6 PDA MaxPlot (250nm-550nm) 2.251 92729 3.04 7383
7 PDA MaxPlot (250nm-550nm) 2.518 60956 2.00 5940
8 PDA MaxPlot (250nm-550nm) 2.696 87300 2.86 7686
9 PDA MaxPlot (250nm-550nm) 3.101 60233 1.98 4262
10 PDA MaxPlot (250nm-550nm) 3.523 200338 6.57 13053
11 PDA MaxPlot (250nm-550nm) 4.374 32902 1.08 1911
12 PDA MaxPlot QSOnm-SSOnmL 4.644 118270 3.88 11411
13 PDA MaxPlot (250nm-550nm) 4.807 132572 4.35 7440
14 PDA MaxPlot (250nm-550nm) 5.633 44531 1.46 2267
15 PDA MaxPlot (250nm-550nm) 7.865 315483 10.35 11010
16 PDA MaxPlot (250nm-550nm) 9.411 27096 0.89 1263
17 PDA MaxPlot QSOnm-SSOnm) 11.011 676972 22.22 16633
18 PDA MaxPlot Q50nm-550nm) 16.757 47216 1.55 1469
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Algle Threshold Angle Threshold
1 1.200 Mitsubishi B395-l 2.928 3.388
2 1.426 Mitsubishi B395-2 6.281 6.222
3 1.539
4 1.799 Mitsubishi B395-3 7.083 8.091
5 2.053 Fisher 850-] 9.224 7.704
6 2.251 Mitsubishi B395-3 9.995 7.801
7 2.518
8 2.696
9 3.101 Mitsubishi B395-3 8.618 10.005
10 3.523
11 4.374
12 4.644 Mitsubishi B395-5 2.803 5.31 1
13 4.807
14 5.633
15 7.865
16 9.411
17 11.01
1
18 16.75
7

 

97

 

Figure 29: HPLC report for ink sample Parker Bl76D

SampleName Parker B176D Date Acquired 1/18/2003 3:56:16 AM

Injection Volume 10.00 111 Acq Method Set inkrev2 method set

Run Tlme 20.00 Minutes Processing Method Marilyn library 2103

Sample Set Name marilyn 11703 Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

 

 

 

 

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2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 13.00 20.00
Mnutes
Auto-Scaled Chromatogram
r N l
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0.020-I 1.4 3 I;
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2.00 4.00 6.00 8.00 “1.0.00 12.00 14.00 16.00 18.00 20.00
nutes

98

Sample Name Parker Bl76D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(mil!)
1 PDA MaxPlot (250nm-550nm) 1.192 279003 13.20 20140
2 PDA MaxPlot (250nm-550nm) 1.544 433846 20.52 25406
3 PDA MaxPlot (250nm-550nm) 1.757 132631 6.27 12023
4 PDA MaxPlot (250nm-550nm) 2.233 46426 2.20 4010
5 PDA MaxPlot (250nm-550nm) 2.524 51119 2.42 5657
6 PDA MaxPlot (250nm-550nm) 2.658 131991 6.24 13841
7 PDA MaxPlot (250nm-550nm) 3.236 84894 4.02 7251
8 PDA MaxPlot (250nm-550nm) 3.525 163404 7.73 10786
9 PDA MaxPlot (250nm-550nm) 4.376 22068 1.04 1220
10 PDA MaxPlot (250nm-550nm) 4.801 171581 8.12 9098
11 PDA MaxPlot (250nm-550nm) 7.147 354430 16.76 17969
12 PDA MaxPlot (250nm-550nm) 7.391 242926 11.49 13463
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angle Threshold

1 1.192 Parker B176-1 6.865 1.321
2 1.544 Parker B 176-2 8.502 1.434
3 1.757 Parker Bl76—3 8.115 1.793
4 2.233 Parker 8176-4 4.454 2.754
5 2.524 Parker B 176-5 4.3142 2.972
6 2.658 Parker B176—6 2.201 1.428
7 3.236 Parker Bl76-7 2.326 2.762
8 3.525 Staettler B384-6 3.820 1.806
9 4.376
10 4.801 Bic B388-7 3.481 2.006
11 7.147 Parker Bl76-10 0.830 1.519
12 7.391

 

99

 

Figure 30: HPLC report for ink sample Papermate B225D

SampleName Papermate 8225D ‘ Date Acquired 1/18/2003 8:53:14 AM
Injection Volume 10.00 111 Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name man'lyn 11703 Channel Name MaxP101250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

5
2
AU

 

2.00 4.00 6.00 8.00 10.00 12.00 14.00 16:00 18:00 20.00
Mnutes

A11to$caled Chromatog ram

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11053

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7.874

 

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2.00 4.00 6.00 8.00 0100 12.00 14.00 16.00 18.00 20.00

100

Sample Name Papermate B225D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.174 112295 19.78 10398
2 PDA MaxPlot (250nm-550nm) 1.466 137537 24.22 12647
3 PDA MaxPlot (250nm-550nm) 7.874 53151 9.36 2035
4 PDA MaxPlot (250nm-550nm) 11.053 264809 46.64 6751
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Ange Threshold Name Angle Threshold

1 1.174 Papermate B225-1 5.529 5.550
2 1.466
3 7.874
4 11.053

 

 

 

 

 

 

 

101

 

 

 

 

Figure 3]: HPLC report for ink sample Papermate B376D

SampleName Papermate B3760 Date Acquired 1/18/2003 9:35:38 AM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run T1me 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name marilyn 11703 Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

 

 

 

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2.00 400 6,00 3.00 10.00 12.00 14.00 1600 1800 20.00
Mnutes
Auto-Scaled Chromatogram
0001—};— H‘” —‘— —_—~ ' i’ —— A“;
l
1 W 1
0.04
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nutes

Sample Name Papermate B376D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.220 645246 32.77 44778
2 PDA MaxPlot (250nm-550nm) 1.476 629640 31.97 58379
3 PDA MaxPlot (250nm-550nm) 2.259 30799 1.56 2973
4 PDA MaxPlot (250nm-550nm) 2.599 80827 4.10 6744
5 PDA MaxPlot (250nm-550nmj 3.426 263243 13.37 19478
6 PDA MaxPlot (250nm-550nm) 4.710 293050 14.88 15658
7 PDA MaxPlot (250nm-550nm) 7.893 26406 1.34 1465
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angle Threshold
1 1.220 Papermate B376-1 1.059 1.084
2 1.476 Papermate B376-2 0.699 1.041
3 2.259 Papermate B376-4 1.749 2.337
4 2.599 Papermate B376-5 2.447 1.881
5 3.426 Staettler B384-6 0.986 1.310
6 4.710 Papermate B376-7 1.553 1.431
7 7.893 ngermate 8376-8 4.232 6.474

 

103

 

 

APPENDIX C.3

HPLC Reports for Blue Ball Point Inks That Were Identified to a Reasonable
Degree of Certainty by Library Matching

Sample Run 3

104

Figure 32: HPLC report for ink sample Cross Bl64G

SampleName Cross 81646 Date Acquired 1/19/2003 5:25:05 PM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name man'lyn 11903 Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

.0
8
AU

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2.00 400 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00
Mnutes

AutoScaled Chromatogram

 

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3‘ 3 l E- 1
0.0204 1n, 0» a, ,5} 1
l 8" 9'1. ‘13 «5‘ E
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nutes

105

Sample Name Cross Bl64G

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.202 179373 8.22 12999
2 PDA MaxPlot (250nm-550nm) 1.519 450222 20.62 23485
3 PDA MaxPlot (250nm-5500m) 2.227 31413 1.44 2892
4 PDA MaxPlot (250nm-550nm) 2.648 156582 7.17 9732
5 PDA MaxPlot (250nm-550nm) 3.143 86181 3.95 8262
6 PDA MaxPlot (250nm-550nm) 3.429 307701 14.09 21016
7 PDA MaxPlot (250nm-550nm) 4.629 247632 11.34 13305
8 PDA MaxPlot (250nm-550nm) 6.757 405324 18.57 22484
9 PDA MaxPlot (250nm-550nm) 7.012 278548 12.76 18191
10 PDA MaxPlot (2500m-550nm) 7.530 40231 1.84 2184
PDA Result Table
L Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angle Threshold
L 1 1.202 Sheaffer B 166-1 3.745 1.433
[_2 1.519 Cross Bl64E 1.423 1.295
L 3 2.227 Cross 816413 3.341 2.710
4 2.648 Cross 316413 1.487 1.617
5 3.143 Cross Bl64E 1.911 2.032
6 3.429 Cross B 16413 0.607 1.436
‘7 4.629 Cross Bl64E 0.840 1.622
8 6.757 Cross B1645 0.448 1.264
#9 7.012 Cross Bl64E 0.916 1.332
1 0 7.530 Cross Bl64E 5.143 4.580

 

106

 

Figure 33: H PLC report for ink sample Itoya Bl94D

SampleName Itoya B1940 Date Acquired 1/19/2003 8:35:53 PM
Injection Volume 10.00 111 Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name marilyn 11903 Channel Name MaxP101250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

AU

 

2.00 4.00 6.00 8.00 10.00 12.00 14.00 16100 18.00 20.00
Mnute:

Auto-Scaled Chromatogram

 

 

 

l
0.06 3‘ §
: E!" T
0.04- T
3 * 1 ‘9
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I 200 400 eloo 000' 000 12100 ' 1400 I 16i00‘ 18i00 12000

nutes

107

Sample Name Itoya Bl94D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.174 355916 13.74 35381
2 PDA MaxPlot (250nm-550nml 1.447 835779 32.26 63734
3 PDA MaxPlot Q50nm-550nm) 1.858 87323 3.37 7455
4 PDA MaxPlot (250nm-550nm) 2.194 33460 1.29 3545
5 PDA MaxPlot (250nm-550nmj 2.453 54295 2.10 6989
6 PDA MaxPlot (250nm-550nm) 2.583 62742 2.42 8783
7 PDA MaxPlot (250nm-550nm) 3.343 240929 9.30 18537
8 PDA MaxPlot (250nm-550nm) 4.495 229238 8.85 13299
9 PDA MaxPlot (250nm-550nm) 5.189 283711 10.95 15140
10 PDA MaxPlot (250nm-550nm) 7.375 380960 14.70 18274
11 PDA MaxPlofiZSOnm-SSOnm) 8.219 26781 1.03 1375
PDA Result Table
L Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Aggle Threshold Name Angle Threshold
L 1 1.174 ItoyaBl94-1 1.851 1.167
2 1.447 Itoya B 1942 2.974 1.118
3 1.858 Itoya B 194-3 2.284 1.948
4 2.194 Itoya B 194-4 2.908 3.164
5 2.453 Itoya B 194-5 2.587 2.711
6 2.583 @a B 194-6 2.167 2.873
‘7' 3.343 Itoya Bl94-7 0.908 1.957
8 4.495 Itoya Bl94-8 1.533 2.397
9 5.189 Itoya Bl94-9 0.959 1.499
1 0 7.375 Itoya Bl94-10 0.377 1.466
1 l 1 8.219 Tombo B535E-9 3.440 4.648

 

 

 

 

 

 

 

 

 

108

 

SampleName Sheaffer B1680

Figure 34: HPLC report for ink sample Sheaffer Bl66D

Date Acquired 1/19/2003 10:21:54 PM

Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Tlme 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name marilyn 11903 Channel Name MaxPlolzso_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

 

 

 

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l ‘1 T 1 L030
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2.00 4.00 6.00 0.00 10.00 12.00 14.00 16.00 18.00 20.00
M as
Autoslzaled Chromatogram
f (O ’N W W 1
0.040: N V 1
. O Q '0. ‘
' to <0 ‘91
1 .' eel lg
0030‘ ,.._ 3 0 ‘d b
1 "1* l" S l
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2.00 4.00 6.00 8.00 9119123 12.00 14.00 16100 18.00 20.00

109

Sample Name Sheaffer Bl66D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
1min)
l PDA MaxPlot (250nm-550nm) 1.176 279115 7.60 23225
2 PDA MaxPlot QSOnm-SSOnm) 1.522 419308 11.42 42092
3 PDA MaxPlot (250nm-550nm) 1.751 149424 4.07 8414
4 PDA MaxPlot (250nm-550nn3 2.203 58192 1.59 5601
5 PDA MaxPlot (250nm-550nm) 2.580 284517 7.75 27585
6 PDA MaxPlot (250nm-550nm) 2.886 32410 0.88 4651
7 PDA MaxPlot (250nm-550nm) 3.055 230052 6.27 22267
8 PDA MaxPlot QSOnm-SSOnm) 3.323 484834 13.21 32072
9 PDA MaxPloQZSOnm-SSOnm) 4.476 374220 10.20 18778
10 PDA MaxPlot (250nm-550nrn) 6.542 649799 17.70 32567
11 PDA MaxPlot (250nm-550nm) 6.953 644405 17.56 36207
12 PDA MaxPlot (250nm-550nm) 7.427 64075 1.75 3624
PDA Result Table
Name RT Purity l Purity 1 Match 1 Spect. Match Match 1
Angle Threshold Name 1 Angle Threshold

1 1.176 Sheaffer B 166-1 1.451 1.563
2 1.522 Sheaffer B 166-2 2.253 1.326
3 1.751 Sheaffer B 166-3 2.748 2.287
4 2.203 Sheaffer 8166-4 2.587 3.067
5 2.580 Sheaffer B 166-5 0.640 1.382
6 2.886

7 3.055 Sheaffer B 166-6 2.478 2.282
8 3.323 Tombo BS35E-6 1.998 1.941
9 4.476 Papermate B376E-7 2.623 2.086
10 6.542 Sheaffer B 166-9 0.883 1.721
11 6.953 Sheaffer B 166-10 1.658 1.818
12 7.427 Cross Bl64E-10 5.205 5.537

 

110

 

 

AU

Figure 35: HPLC report for ink sample Mitsubishi B394D

SampleName Mitsubishi 8394D Date Acquired 1/19/2003 11:04:18 PM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name marilyn 11903 Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

 

 

 

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2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00
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Auto-Scaled Chromatog ram
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1 ‘L 1
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111

Sample Name Mitsubishi B394D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.216 383612 19.68 37602
2 PDA MaxPlot (250nm-550nm) 1.428 216732 11.12 25678
3 PDA MaxPlot (250nm-550nmL 1.558 74578 3.83 13701
4 PDA MaxPlot (250nm-550nm) 1.789 111319 5.71 6907
S PDA MaxPlot (250nm-550nml 2.225 61164 3.14 6556
6 PDA MaxPlot (250nm-550nm) 2.482 37938 1.95 4176
7 PDA MaxPlot (250nm-550nm) 2.593 59219 3.04 5539
8 PDA MaxPlot (250nm-550nm) 3.028 28148 1.44 2384
9 PDA MaxPlot (250nm-550nm) 3.353 136777 7.02 10409
10 PDA MaxPlot (250nm-550nm) 4.502 142804 7.33 8846
11 PDA MaxPlot (250nm-550nm) 5.242 18556 0.95 988
12 PDA MaxPlot (250nm-550nm) 7.242 169654 8.70 6488
13 PDA MaxPlot (250nm-550nm) 10.046 423380 21.72 11805
14 PDA MaxPlot L250nm-550nmL 15.922 85428 4.38 2565
PDA Result Table
Name RT Purity l Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angle Threshold

1 1.216 Mitsubishi 8394-1 0.583 1.660
2 1.428 Mitsubishi 8394-2 2.443 3.343
3 1.558 Mitsubishi B394-3 2.186 4.858
4 1.789 Mitsubishi B394-4 4.001 4.800
5 2.225 Mitsubishi B394-5 1.919 4.066
6 2.482
7 2.593 Mitsubishi B394-6 7.631 14.221
8 3.028 Mitsubishi 8394-7 5.600 10.272
9 3.353
10 4.502 Mitsubishi 8394-9 1.372 3.426
11 5.242
12 7.242
13 10.046
14 15.922

 

112

 

Figure 36: HPLC report for ink sample Papermate B376G

SampleName Papermate 33766 Date Acquired 1/20/2003 3:18:48 AM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Tlme 20.00 Mnutes Processing Method Marilyn library 2103
Sample Set Name marilyn 11903 Channel Name MaxP101250__550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

 

 

 

 

 

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2 43 '‘060
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} PO20
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2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00
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Alto-Scaled Chromatog ram

 

 

 

 

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num

113

Sample Name Papermate B376G

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.193 299484 13.25 24172
2 PDA MaxPlot (250nm-550nm) 1.541 620990 27.47 68619
3 PDA MaxPlot (250nm-550nm) 1.923 33024 1.46 3992
4 PDA MaxPlot (250nm-550nm) 2.229 21558 0.95 2390
5 PDA MaxPlot QSOnm-SSOnm) 2.591 140236 6.20 12278
6 PDA MaxPlot (250nm-550nm1 3.331 483771 21.40 35065
7 PDA MaxPlot (250nm-550nml 4.456 588343 26.02 30968
8 PDA MaxPlot (250nm—550nm) 5.360 23559 1.04 1657
9 PDA MaxPlot (250nm-550nm) 7.524 49874 2.21 2596
PDA Result Table
Name RT Purity l Purity 1 Match 1 Spect. Match Match 1
Angle Threshold Name 1 Agle Threshold
1 1.193 Papermate B376E-1 3.587 1.163
2 1.541 Papermate B376E-2 0.201 1.035
3 1.923 Papermate B376E-3 5.868 2.054
4 2.229 Papermate B376E-4 2.071 2.601
5 2.591 Papermate B376E-5 0.981 1.890
6 3.331 Papermate B376E-6 0.622 1.320
7 4.456 Papermate B376E-7 0.419 1.350
8 5.360 Papermate B376E-8 3.490 5.328
9 7.524 Itoya B 194-10 1.326 2.340

 

1

14

 

Figure 37: HPLC report for ink sample Tombo 85350

SampleName Tombo 85356 Date Acquired 1/20/2003 2:36:24 AM

Injection Volume 10.00 111 Acq Method Set inkrev2 method set

Run Time 20.00 Minutes Processing Method Marilyn library 2103

Sample Set Name marilyn 11903 Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

l I

U

} 0.020 <

l . L L 0010

~ I" l
I‘rl‘ ' I

_Ll’ l" .y . i i 1 ‘ ‘7 A
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2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00
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Auto-Scaled Chromatog ram

 

 

 

 

 

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0.006“ a- 8 L_ "N33
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0.002—l 1
1
0.0004 - AV ' e -,
l“'l“‘ ‘!"'l“'l*'
. .00 12.00 14.00 16.00 18.00 20.00

115

Sample Name Tombo B535G

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
1min)
1 PDA MaxPlot (250nm-550nm) 1.188 47232 9.10 5389
2 PDA MaxPlot (250nm-550nm) 1.448 48795 9.40 6672
3 PDA MaxPlot (250nm-550nm) 1.865 39874 7.68 5132
4 PDA MaxPlot £250nm-550nm) 2.253 19045 3.67 2495
5 PDA MaxPlot (250nm-550nm) 2.609 52663 10.15 4356
6 PDA MaxPlot (250nm-550nm) 3.366 103405 19.92 6812
7 PDA MaxPlot (250nm-550nm) 4.521 79855 15.39 4344
8 PDA MaxPlot (250nm-550nm) 5.215 88438 17.04 4685
9 PDA MaxPlot (250nm-550nm) 8.351 39697 7.65 2014
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match Match 1
Angle Threshold 1 Threshold
Angle
1 1.188 Peak 1 2.983 1.724
2 1.448 Tombo BS35E-1 0.784 1.492
3 1.865 Tombo BS35E-3 0.621 1.413
4 2.253 Tombo BS35E-4 3.473 3.040
5 2.609 Tombo BS35E-5 3.120 2.607
6 3.366 Tombo BS35E-6 1.702 2.000
7 4.521 Papermate B376E-7 2.446 2.297
8 5.215 Tombo BS35E-8 0.724 1.665
9 8.351 Tombo B535E-9 2.807 4.218

 

1

16

 

 

Figure 38: HPLC report for ink sample Dupont BlOZG

SampleName Dupont B1026 Date Acquired 1/20/2003 1:32:45 AM
Injection Volume 10.00 111 Acq Method Set inkrev2 method set
Run Tlme 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name marilyn 11903 Channel Name MaxP101250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

1. (”#0040
I /,//

 

 

# —w—1~ “ / 0.030
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1 ° 1 l
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.L- ,. VLL-C,1
2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00

Mnutea

AutoScaled Chromatogram

0.00843 L

1 l 1 “ii? a

I L . N 1‘
(«‘- 05 3 i l
a 1 ‘ y l 1 I
<0.0041 l
l
l I
00024 L
1 r l
l L. L I
0.0001” ’ g _ v1
1

..’. L .. —-fi T‘Tfl—lLT.1
2.00 4.00 6.00 8.00 “282 12.00 14.00 16.00 18.00 20.00

117

Sample Name Dupont BlOZG

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time ‘ Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.167 108751 15.32 6944
2 PDA MaxPlot (250nm-550nm) 1.487 79850 11.25 5536
3 PDA MaxPlot L250nm-550nm) 3.352 87449 12.32 6555
4 PDA MaxPlot (250nm-550nm) 4.513 146442 20.63 7988
5 FDA MaxPlot (250nm-550nml 14.542 122686 17.28 3800
6 PDA MaxPlot (250nm-550nm) 15.702 164661 23.20 3890
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Alfie Threshold Name Angle Threshold

1 1 . 167 Dupont B 102E-l 1.093 1.238
2 1.487 Dupont B 102E-2 0.970 1.284
3 3.352 Dupont BlOZE-S 1.514 1.815
4 4.513 Dupont B 102E-6 1.768 1.622
5 14.542 Dmnt BlOZE-7 2.545 2.059
6 15.702 Dupont BlOZE-S 2.711 1.795

 

 

 

 

 

 

 

 

 

 

118

APPENDIX C.4

HPLC Reports for Blue Ball Point Inks That Were Identified to a Reasonable
Degree of Certainty by Library Matching

Sample Run 4

119

Figure 39: HPLC report for ink sample QIB (New Bic)

SampleName Q1B
Injection Volume 10.00 ul
Run Time 20.00 Minutes

Sample Set Name marilyn 12103

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

Date Acquired 1/21/2003 9:29:08 PM
Acq Method Set inkrev2 method set
Processing Method Marilyn library 2103

Channel Name MaxPlot250_550

 

 

 

M nutes

. 7 , A .

We'efiAfiTvy ‘ 7 +,,§;,,a+,%fiz;.’ ‘
2‘00 400 6.00 5.00 10.00 12.00 14.00 16.00 18.00 200

g
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120

l"‘|“‘l"‘l‘
00120014001600

‘ 1 , t
8.00 0
“nutes

13.00 20.00

Sample Name QlB (New Bic)

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time ‘ Area % Area Height
(min)
1 PDA MaxP10t(250nm-550nm) 1.195 203290 11.60 12908
2 PDA MaxPlot QSOnm-SSOnm) 1.488 21634 1.23 5135
3 PDA MaxPlot (250nm-550nm) 1.695 129633 7.40 11991
4 PDA MaxPlot (250nm-550nm) 2.091 31917 1.82 3437
5 PDA MaxPlot QSOnm-SSOnm) 2.571 179184 10.22 16265
6 PDA MaxPlot QSOnm-SSOnm) 3.302 593831 33.88 43109
7 PDA MaxPlot (250nm-550nm) 4.415 593338 33.85 32360
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match Match 1
Angle Threshold Name 1 Threshold
Angle

1 1.195 Papermate B376E-1 5.044 1.225

2 1.488 New Bic C-2 4.908 1.409

3 1.695 New Bic 03 0.507 1.129
4 2.091

5 2.571 New Bic C-4 1.448 1.588

6 3.302 New Bic 05 0.340 1.230

7 4.415 New Bic C-6 0.490 1.273

 

1

21

 

 

Figure 40: HPLC report for ink sample Q2B (Bic Bl62)

SampleName 028 Date Acquired 1/21/2003 10:11:33 PM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Trrne 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name marilyn 12103 Channel Name MaxP101250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

 

w r
i . [/1, tL020
F l f l 1...
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Auto-Scaled Chromatog ram

 

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0.0404 1
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2.00 4.00 8.1!) 8.00 0.00 12.00 14.00 16.00 18.00 20.00

122

Sample Name Q2B (Bic B162)

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(mini
1 PDA MaxPlot (250nm-550nm) 1.099 394274 18.41 38403
2 PDA MaxPlot (250nm-550nm) 1.480 780040 36.42 40931
3 PDA MaxPlot (250nm-550nm) 1.895 52151 2.44 6325
4 PDA MaxPlot (250nm-550nm) 2.200 37548 1.75 3466
5 PDA MaxPlot (250nm-550nm) 2.458 72539 3.39 6650
6 PDA MaxPlot (250nm-550nm) 2.804 28458 1.33 1547
7 PDA MaxPlot (250nm-550nmL 3.259 25221 1.18 2236
8 PDA MaxPlot Q50nm-550nm) 4.327 501659 23.42 27990
9 PDA MaxPlot (250nm-550nm) 7.395 249688 11.66 12048
PDA Result Table
Name RT Purity l Purity 1 Match 1 Spect. Match Match 1
Angle Threshold Name 1 Threshold
Angle

1 1.099 Bic Bl62E-1 0.866 1.167
2 1.480 Bic B162E-2 0.293 1.128
3 1.895
4 2.200 Bic Bl62E-3 1.581 3.021
5 2.458 Bic Bl62E-4 0.834 2.405
6 2.804 Bic Bl62E-5 2.633 5.526
7 3.259 Formulabs BSl7E-8 5.845 4.654
8 4.327 Papermate B376E-7 1.519 1.563
9 7.395 Bic Bl62E-7 0.561 1.755

 

1

23

 

 

Figure 41: HPLC report for ink sample Q3B (Papermate B376)

SampleName 038 Date Acquired 1/21/2003 10:53:57 PM

Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103

Sample Set Name marilyn 12103 Channel Name MaxPIorzso_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

 

 

 

 

,2 7* raiam 7* ri—gr 4» ,,i,,,i_ 7— 77 mi 7 7~ ~ 0.60
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1 1 ‘ L
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2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00
Mnutea
Auto-Scaled Chromatogram
r__fl__._,_.__ i
0.064, “1) 1
1 v- 31 1
4 N. 3 I
J 8, a) (‘3
3 004—1 ,3 1 1 Q l
< ‘ F1 1
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2.00 400 600 000 911323 1200 14.00 16.00 1800 2000

124

Sample Name Q3B (Papermate B376)

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time ' Area % Area Height
(minL

1 PDA MaxPlot (250nm-550nm) 1.188 383343 15.69 28882
2 PDA MaxPlot (250nm-550nm) 1.516 601483 24.62 72390
3 PDA MaxPlot (250nm-550mn) 1.865 78944 3.23 5733

4 PDA MaxPlot (250nm-550nm) 2.208 32812 1.34 3261

5 PDA MaxPlot (250nm-550nm) 2.527 179074 7.33 14563
6 PDA MaxPlot (250nm-550nm) 3.242 532268 21.78 38871
7 PDA MaxP10t(250nm-550nm) 4.328 609957 24.96 33643
8 PDA MaxPlot (250nm-550nm) 7.521 25644 1.05 1778

PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match Match 1
Angle Threshold Name 1 Threshold
Angle

1 1.188 Papermate B376 E- 1.019 1.180
2 1.516 Papermate B376 E- 0.243 1.053
3 1.865 Papermate B376 E- 2.843 2.209
4 2.208 Papermate B376 13- 6.571 3.113
5 2.527 Papermate B376 E- 7.260 2.161
6 3.242 Formulabs BS l7E-8 1.546 1.296
7 4.328 Formulabs BSl7E-10 1.100 1.415
8 7.521 Bic Bl62E-7 ' 2.240 3.072

 

 

 

 

 

 

 

 

 

 

125

Figure 42: HPLC report for ink sample QSB (Formulabs 8517)

SampleName 053 Date Acquired 1/22/2003 12:39:57 AM

Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103

Sample Set Name marilyn 12103 Channel Name MaxP101250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

1 1 0.15
.17 ,_L.,_.,,_C ailf~i7i~—-iii L
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V .. , ._ 9:;7‘ L'":':: , '
1 .-, '1 .- r ; , ;1 500.00
3.-;,,,._ff:-+3;:; ',.—...i1;-;fi;.1.-...-h 7W??? - ; ' 71¥a}—+~;f 7'
2.00 4.00 6.00 8.00 10 00 1200 14 00 16.00 18.00 20 00
Mnutes
Auto-Scaled Chromatogram
1 ’ #1
1 § 1 “l, 1
1
1 1 co m 0'" a 1
1 1 9M ' a 1
0020 No: 1 q
3 1 1 a; N
( D
‘- w . 1
J P. w ,,
00101 a” 1 °
1 1 B. 1 1h. 1
1 .N , n 1
T 1 , 1. 1
V 1 , . ,‘ ’Afi”? ' —_——’—————,——’—‘ . . .,
2.00 4.00 600 8.00 M000 12.00 14.00 16.00 18.00 20.00
nutes

126

Sample Name QSB (Formulabs B517)

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time ' Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.211 94603 3.34 7931
2 PDA MaxPlot (250nm-550nm) 1.524 393821 13.89 26542
3 PDA MaxPlot (250nm-550nm) 1.840 76243 2.69 8837
4 PDA MaxPlot (250nm-550nm) 2.050 29043 1.02 3708
5 PDA MaxPlot (250nm-550nm) 2.526 201856 7.12 17201
6 PDA MaxPlot (250nm-550nm) 2.658 28305 1.00 9135
7 PDA MaxPlot (250nm-550nm) 2.995 134415 4.74 13654
8 PDA MaxPlot (250nm-550nm) 3.237 468295 16.52 33708
9 PDA MaxPlot (250nm-550nm) 3.750 34345 1.21 2984
10 PDA MaxPlot (250nm-550nm) 4.322 360564 12.72 20331
11 PDA MaxPlot (250nm-550nm) 6.316 728628 25.70 33765
12 PDA MaxPlot (250nm-550nm) 7.022 285321 10.06 15506
PDA Result Table
Name RT Purity l Purity 1 Match 1 Spect. Match Match 1
Angle Threshold Name 1 Threshold
Algle

1 1.211 Papermate B376E-l 1.770 1.471
2 1.524 Formulabs B517E-2 0.723 1.242
3 1.840 Formulabs B517E-3 1.399 1.545
4 2.050 Formulabs B517E-4 3.278 2.703
5 2.526 Formulabs B517E-6 1.389 1.529
6 2.658

7 2.995 Formulabs BS 1713-? 1.179 1.615
8 3.237 Formulabs BS l7E-8 0.402 1.280
9 3.750 Formulabs B517E-9 2.740 3.684
10 4.322 Formulabs BS 1713-10 0.479 1.452
11 6.316 Formulabs B5 l7E-12 0.192 1.182
12 7.022 Formulabs 851713-13 0.551 1.573

 

127

 

 

Figure 43: HPLC report for ink sample Q6B (Pilot B 103)

SampleName 068 Date Acquired 1/22/2003 1:22:21 AM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 “nutes Processing Method Marlyn library 2103
Sample Set Name marilyn 12103 Channel Name MaxP101250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

 

1111r1111111'11111111'1111111111111/
2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00
Mnutes

Auto-Scaled Chromatog ram

 

—— 3.250

‘ ——4.362

-—— 10.489

1 1 1 1 1 1 1 l 1 1 1 1 1 1 1 1 ' 1 1 1 1 1 -
8.00 0.00 12.00 14.00 16.00 18.00 20.00
um

 

 

 

128

Sample Name Q6B (Pilot B103)

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Tlme ' Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.151 112454 19.73 8365
2 PDA MaxPlot (250nm-550nm) 1.440 112723 19.78 10246
3 PDA MaxPlot (250nm-550nm) 1.869 18896 3.32 1533
4 PDA MaxPlot (250nm-550nm) 2.522 41748 7.32 3778
5 PDA MaxPlot (250nm-550nmL 3.250 101534 17.81 7285
6 PDA MaxPlotQSOnm-SSOnm) 4.362 77805 13.65 4611
7 PDA MaxPlot (250nm-550nm) 6.270 18281 3.21 444
8 PDA MaxPlot (250nm-550nm) 10.489 86526 15.18 2861
PDA Result Table
Name RT Purity Purity 1 Match 1 Spect. Match Match 1
1 Threshold Name 1 Threshold
Angle Angle
1 1.151 Pilot B103G-1 4.509 10.549
2 1.440 Pilot B 1036-2 6.030 12.799
3 1.869
4 2.522
5 3.250 Papermate B376E-6 6.804 17.102
6 4.362
7 6.270
8 10.489

 

129

 

 

Figure 44: HPLC report for ink sample Q7B (Papermate 622)

SampleName 078 Date Acquired 1/22/2003 2:26:00 AM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name "1811131" 12103 Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

11- ‘) 1 . -~ ",1 1- ;;_ _: : 212.7,“,

1%
l

 

-. 0.00

l

. " 500.00

2.00 4.00 6000 8.00 10100 12.00 14.00 16.00 18:00 20.00

Mnutea

AutoScaled Chromatog ram

 

i
0.010 1,
1 1%
0.0081 :5»
Y.

‘ 9596*

A-

~ 7.000

0.0021

0.00011“;

2.00 4.00 6.00 8.00 0.00 12.00 14.00

nutes

I30

16l00 18l00 20.00

Sample Name Q7B (Papermate 622)

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention T lme ' Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.149 91998 16.16 8719
2 PDA MaxPlot (250nm-550nm) 1.434 87424 15.36 9394
3 PDA MaxPlot (250nm-550nm) 7.000 18057 3.17 915
4 PDA MaxPlot Q50nm-550nm) 9.696 371865 65.31 10666
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angle Threshold

1 1.149 Papermate 62213-1 3.418 5.993
2 1.434 Pamermate 62213-2 8.581 1 1.427
3 7.000
4 9.696

 

131

 

 

APPENDIX D

132

APPENDIX D

HPLC Reports for Black Ball Point Inks That Were Identified to a Reasonable
Degree of Certainty by Library Matching

133

APPENDIX D.l

HPLC Reports for Black Ball Point Inks That Were Identified to a Reasonable
Degree of Certainty by Library Matching

Sample Run 1

134

Figure 45: HPLC report for ink sample Lindy BlS9D

SampleName Lindy B1590
Injection Volume 10.00 ul
Run Time 20.00 Minutes

Sample Set Name marilyn 11603

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

Date Acquired 1/17/2003 1:54:43 AM
Acq Method Set inkrev2 method set
Processing Method Marilyn library 2103

Channel Name MaxPlot250_550

 

 

 

 

 

 

 

' l
r //
///’ ,
// I ‘ ‘ / ”0.08
|r1 1 1 7‘—+— l—~—— MAD~ —~———7‘¥ 7 1 -
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2.00 4.00 6.00 3.00 10.00 12.00 14.00 16.00 18.00 20.00
M as
Auto-Scaled Chromatogram
§
us a
l 0°.
‘1 T
1 | 1 1 1 . 1| 1 1 | 1 1 1 l 1 1 1 | 1 '
6.00 8.00 “000 12 00 14.00 16.00 18 00 20.00
nutes

 

135

Sample Name Lindy BlS9D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time ' Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.185 179268 22.80 16075
2 PDA MaxPlot (250nm-550nm) 1.441 125523 15.96 18270
3 PDA MaxPlot (250nm-550nm) 1.611 77756 9.89 11241
4 PDA MaxPlot (250nm-550nm) 2.596 23117 2.94 2812
5 PDA MaxPlot (250nm-550nm) 2.736 53176 6.76 6079
6 PDA MaxPlot (250nm-550nm) 3.307 44433 5.65 3648
7 PDA MaxPlot (250nm-550nm) 3.682 99890 12.70 7980
8 PDA MaxPlot (250nm-550nm) 5.060 104263 13.26 5550
9 PDA MaxPlot (250nm-550nm) 7.922 78862 10.03 3309
PDA Result Table
Name RT Purity l Purity 1 Match 1 Spect. Match 1 Match 1
Ar@ Threshold Name Angle Threshold

1 1.185 Lindy 8159-1 1.145 1.479
2 1.441 Lindy B159-2 0.604 1.484
3 1.611 Lindy 3159-3 2.020 2.201

4 2.596 Lindy B159-4 9.426 5.254
5 2.736 Lindy 8159-5 1.395 1.814
6 3.307

7 3.682 Lindy 8159-7 0.930 1.852
8 5.060 Lindy B159-8 0.987 2.073
9 7.922 Lindy 8159-8 8.151 4.022

 

1

36

 

 

Figure 46: HPLC report for ink sample Cross B 13D

SampleName Cross B130
Injection Volume 10.00 ul
Run Time 20.00 Minutes

Sample Set Name marilyn 11603

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

Date Acquired 1/17/2003 6:51:38 AM
Acq Method Set inkrev2 method set
Processing Method Marilyn library 2103

Channel Name MaxPlot250_550

 

 

 

'5 0.050
,7 *‘ 1 ‘_7 ,
‘1 : 0.040
P 0.030 3
; ‘ l
l ; 0.020
1‘ s -;
11 ,1 r 0.010
.1 ,1 l' '
1. ~ . i 0.000
'V' "T ' f ‘ 50000
L - ~ -- 1 *- f ~ ** 1 r r' 1 ‘1 ca ’fi ‘fi 1*1 1*?“ *1 w - 11-1 1 1' ~* ~rri'11vfl
2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 10.00 20.00
Mnutea
Auto-Scaled Chromatogram
0.0144. . ~-~- --— -~ 7 ‘
0.012%
.' -' 1 ID
0010—; ._ 1..., g l
j Fin 0 g 'n ‘
0008‘: l ‘0‘! co m l 1
< 0.0061 1. l T 1 . l
4 . l ‘ ‘— i
0004—: ‘ 1 11 8 I
2 r<
0.002 l i
0.000} f ‘ ‘ g i
' ’ ' l ' I ‘ ‘ | ‘ ' | ‘ ' l ‘ ' l ' ‘ l ' ' ' l ‘ ‘ l ‘ ‘
2.00 4.00 6.00 8.00 11°00 12.00 14.00 16.00 18.00 2000
nutes

137

Sample Name Cross B13D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time ' Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.136 100075 14.56 7708
2 PDA MaxPlot (250nm-550nm) 1.442 75637 11.00 12521
3 PDA MaxPlot Q50nm-550nm) 1.566 101159 14.71 8676
4 PDA MaxPlot (250nm-550nm) 1.835 41577 6.05 4892
5 PDA MaxPlot (250nm-550nm) 2.780 45535 6.62 4560
6 PDA MaxPlot (250nm-550nm) 3.669 148477 21.60 10116
7 PDA MaxPlot (250nm-550nm) 5.045 144653 21.04 7238
8 PDA MaxPlot (250nm-550nm) 7.961 30344 4.41 1137
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Agle Threshold Name Agle Threshold
1 1.136 Cross Bl3-1 2.550 1.375
2 1.442 Cross Bl3-2 1.662 1.257
3 1.566 Cross Bl3-3 2.167 1.389
4 1.835 Cross B13-4 1.770 2.306
5 2.780 Cross Bl3-5 4.347 2.237
6 3.369 Cross B13—6 0.556 1.554
7 5.045 Cross B13-7 0.600 1.712
8 7.961 Cross B13-8 3.099 4.272

 

1

38

 

 

Figure 47: HPLC report for ink sample Parker B l 74D

SampleName Parker 31740 Date Acquired 1/17/2003 7:55:20 AM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name "131W" 11603 Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

.: f l 90.02

.4

1’ 0.00

. 7‘ I ”V- . . ’ L .J
l J ,‘ ' '2. ”’..‘.;. ,>
r .1 . ._/"1 . .'::" ,,:‘“/ ‘. _...-1 ' .'
l

H: ' ' -.... ' " 3‘ '1 '7‘ 50000

“ ’ l‘ "* r
2.00 400 6,00 8.00 10.00 12.00 14.00 16.00 1800 2000
Mnutes

Auto-Scaled Chromatog ram

0.0304 g
~—

0. 020—1

0.0103
0.000J

-1 5.020

D
<

’- 3.671

1 - mam

~— 2.326
'+ 2 780

1L_.-v, w

‘ . . r l i . I . r . 1 i i I r r r 1

2.00 4.00 6.00 6.00 0.323 12.00 14.00 16.00 13.00 20.00

139

AU

Sample Name Parker B174D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time ' Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.213 223270 23.62 30118
2 PDA MaxPlot Q50nm-550nm) 1.439 158544 16.77 26713
3 PDA MaxPlot (250nm-550nm) 1.601 49848 5.27 5958
4 PDA MaxPlot (250nm-550nmL 1.830 26707 2.82 2558
5 PDA MaxPlot (250nm-550nm) 2.326 20592 2.18 1657
6 PDA MaxPlot (250nm-550nm) 2.780 20337 2.15 1772
7 PDA MaxPlot (250nm-550nml 3.671 141576 14.98 9656
8 PDA MaxPlot (250nm-550nm) 5.020 304532 32.21 14696
PDA Result Table
Name RT Purity l Purity 1 Match 1 Spect. Match 1 Match 1
AngLe Threshold Name Argle Threshold
1 1.213 Parker Bl74-l 1.503 1.115
2 1.439 Parker Bl74-2 0.380 1.055
3 1.601 Parker Bl74-3 0.485 1.317
4 1.830 Parker Bl74-4 3.554 1.747
5 2.326 Parker B 174-5 0.526 1.527
6 2.780 Parker Bl74-6 7.126 3.904
7 3.671 Parker Bl74-7 0.687 1.536
8 5.020 Parker B 1 74-8 0.420 1.340

 

140

 

 

APPENDIX D.2

HPLC Reports for Black Ball Point Inks That Were Identified to a Reasonable
Degree of Certainty by Library Matching

Sample Run 2

141

Figure 48: HPLC report for ink sample Eversharp 657

SampleName Eversharp 657 Date Acquired 1/18/2003 5:21:05 AM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample 361 Name marilyn 11703 Channel Name MaxP101250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

 

 

 

T l /’
/1 1 ,1 / E0050
- ,-- 7 LL-ifi! -__-l -‘ - - - - - - ‘
5 [—0.040
. l
P0030 3
150.020
1
l l" 10.010
. l
‘ .I 7 . _ _ . ,, _ 1| .4. fro-000
j --1 .. :11: 1.1 V A, - 1.1 , . , . ,,.I _ ' 50000
2.00 4.00 6.00 6.00 10.00 12100 14.00 16.00 18.00 20.00
Mnutes
Auto-Scaled Chromatogram
00201 i 1
0.015- “3 l
1 3 1
'1" 0°.
3 0.010-l| ‘ 1; st :
. N v l
('3
l r: l g 1
0,005 f‘.’ i
o.ooo1_._ .1
‘ 1 ‘ l l 1 ‘ I ' ' ' l ' ' | ' r ‘ ‘ ‘ 1
2.00 400 6.00 800 10.00 1200 14.00 16.00 18.00 20.00
Mnutes

142

Sample Name Eversharp 657

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time ' Area % Area Height
1min)
1 PDA MaxPlot (250nm-550nm) 1.216 154977 28.05 20152
2 PDA MaxPlotQSOnm-SSOnm) 1.437 69934 12.66 12154
3 PDA MaxPlot (250nm-550nm) 1.674 23002 4.16 2811
4 PDA MaxPlotQSOnm-SSOnm) 2.775 88678 16.05 6796
5 PDA MaxPlot (250nm-550nm) 3.534 56970 10.31 3935
6 PDA MaxPlot (250nm-550nm) 4.802 158858 28.76 8222
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angle Threshold
1 1.216 Eversharp 657-1 7.499 1.180
2 1.437 Eversharp 657-2 1.015 1.176
3 1.674 Staettler B391-2 4.144 1.863
4 2.775 Eversharp 657-3 8.421 2.752
5 3.534 Eversharp 657-4 2.046 2.529
6 4.802 Everslgp 657-5 0.620 1.687

 

 

 

 

 

 

 

 

 

 

143

Figure 49: HPLC

SampleName Staettler 83910
Injection Volume 10.00 ul

Run Time 20.00 Minutes

report for ink sample Staedtler B391 D

Date Acquired 1/18/2003 6:24:44 AM
Acq Method Set inkrev2 method set

Processing Method Marilyn library 2103

Sample Set Name marilyn 11703 Channel Name MaxPlot250_550

Processed Channel Descr. PDA
(250.0 nm to 550.0 nm)

MaxPlot

 

 

L- ., —. ..-. .3--

.o
8
AU

. '50000
1 .

7 '77 7‘ 7'7 . 1"V7'7'77‘ '7" ‘1""I"7.
2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00

nutes

Auto-Scaled Chromatog ram

 

 

 

 

 

0.030—
1 r 2
ID
0)
0.020- 1‘”
'5,
I) 1 -
< . O In
4 as. a.
0.0101 $1 v a)
, 1:.
1 1~ .,
. .l |
00004 -1 ‘7: 11~

144

Sample Name Staedtler B391D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time ' Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.438 202988 18.07 26970
2 PDA MaxPlot (250nm-550nml 1.678 164266 14.62 13351
3 PDA MaxPlot (250nm-550nm) 2.260 35656 3.17 4614
4 PDA MaxPlot (250nm-550nm) 2.502 26642 2.37 2169
5 PDA MaxPlotQSOnm-SSOnm) 2.700 69143 6.15 6661
6 PDA MaxPlot (250nm-550nm) 3.519 442257 39.36 30338
7 PDA MaxPlot (250nm-550nm) 4.815 135952 12.10 6912
s PDA MaxPlot (250nm-550nm) 5.443 27436 2.44 1998
9 PDA MaxPlot (250nm-550nm) 7.809 19265 1.71 917
PDA Result Table
Name RT Purity l Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angle Threshold
1 1.438 Staettler B391-1 0.321 1.140
2 1.678 Staettler B391-2 0.790 1.322
3 2.260 Staettler B391-3 1.651 1.955
4 2.502 Staettler B391-4 2.523 3.585
5 2.700 Staettler B391-5 0.774 2.014
6 3.519 Eversharp 657-4 1.074 2.001
7 4.815 Staettler B391-7 2.509 1.791
8 5.443 Staettler B391-8 2.876 3.854
9 7.809 Papermate B183-9 6.565 7.333

 

145

 

Figure 50: HPLC report for ink sample Papermate B183D

SampleName Papermate B1830
Injection Volume 10.00 ul
Run Time 20.00 Minutes

Sample Set Name marilyn 11703

Date Acquired 1/18/2003 7:49:32 AM
Acq Method Set inkrev2 method set

Processing Method Marilyn library 2103

Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

AU

\
\
‘\
.
U"
o
.0
o
o

, 'V
8.00 10.00 12.00 14.00 16.00 18.00 20.
Mnutes

 

Auto-Scaled C h romatog ram

~— 3.547

+‘4.816

+ 7.771

 

 

0.000-Ly“ ‘ *1 ' ,
7"7 ,‘_‘.'". I”Ti.‘. ‘

¥ A“‘l"‘l"l"'l"|“
2.00 4.00 6.00 8.00 (3.323 12.00 14.00 16.00 18.00 20.00

146

Sample Name Papermate 8183D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.1 13 590592 22.37 52810
2 PDA MaxPlot 1250nm-550nm) 1.446 245010 9.28 36126
3 PDA MaxPlot (250nm-550nmL 1.558 406411 15.40 50957
4 PDA MaxPlot (250nm-550nm) 1.799 141233 5.35 10137
5 PDA MaxPlot (250nm-550nm) 2.276 164345 6.23 15950
6 PDA MaxPlot (250nm-550nm) 2.538 65908 2.50 6593
7 PDA MaxPlot (250nm-550nm) 2.717 116309 4.41 8176
8 PDA MaxPlot (250nm-550nm) 3.547 361851 13.71 24892
9 PDA MaxPlot (250nm-550nm) 4.816 390313 14.79 19675
10 PDA MaxPlot (250nm-550nm 7.771 157660 5.97 7588
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angle Threshold
1 1.113 Papermate 8183-1 8.517 1.167
2 1.446 Papermate 8183-2 1.468 1.092
3 1.558 Papermate 8183-3 2.427 1.061
4 1.799 Papermate 8183-4 6.129 1.420
5 2.276 Papermate 8183-5 2.644 1.498
6 2.538 Fisher 8111-5 6.299 2.460
7 2.717 Pilot 8113-3 ‘ 9.942 2.179
8 3.547 Eversharp 657-4 2.774 2.052
9 4.816 Eversharp 657-5 6.216 1.646
10 7.771 Papermate 8183-9 0.470 1.583

 

147

 

 

APPENDIX D.3

HPLC Reports for Black Ball Point Inks That Were Identified to a Reasonable
Degree of Certainty by Library Matching

Sample Run 3

148

Figure 51: HPLC report for ink sample Zebra B7D

SampleName Zebra 870 Date Acquired 1/19/2003 7:53:29 PM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 M‘nutes Processing Method Marilyn library 2103
Sample Set Name marilyn 11903 Channel Name MaxP101250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

~0.12

.r'____—1—————__.————J)’—_—i-.—_Vi ‘ ‘
l
i f0.10
l
I . 0.08

AU

 

 
     

/

.111/
18.00 20.00

 

+74% , fie II. 1'. . : I ;—1;-
4.00 6.00 3.09 10.00 12.00 14.00 16.00
Mnutea

 

 

 

2.00

Auto-Scaled Chromatog ram

 

 

 

 

177T '
0.08! 3
. v-
,.'
0.06-
3 1 .-
o.o4— 3 In 8
2 no " "’ "’
< H" °' l "-3.
0.024 1%? T g
. . t
1 “11' v-
down—”M 7 2,- 1
. . I I . .

1' I I I . I I I . I . . . I . . . I I . I I . I . I . .
2.00 4.00 6.00 8.00 “0.00 12.00 14.00 16.00 18.00 20.00
nutes

149

Sample Name Zebra B7D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.189 68191 1 36.42 89772
2 PDA MaxPlot (250nm-550nm) 1.438 174379 9.31 19592
3 PDA MaxPlot (250nm-550nm) 1.815 107240 5.73 11068
4 PDA MaxPlot QSOnm-SSOnm) 2.118 38864 2.08 4600
5 PDA MaxPlot (250nm-550nm) 2.238 28850 1.54 4653
6 PDA MaxPlot QSOnm-SSOnm) 2.618 207498 11.08 17203
7 PDA MaxPlot (250nm-550nm) 3.381 367958 19.65 26256
8 PDA MaxPlotQSOnm—SSOnm) 4.553 237240 12.67 12789
9 PDA MaxPlot (250nm-550nm) 7.485 28556 1.53 1630
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angle Threshold
1 1.189 Zebra 87-1 1.743 1.051
2 1.438 Zebra 87-2 0.617 1.152
3 1.815 Zebra B7-3 2.396 1.356
4 2.118 Zebra 87-4 2.243 2.378
5 2.238 Zebra 87-5 1.953 2.014
6 2.618 Zebra 87-6 0.529 1.444
7 3.381 Zebra B7-7 0.220 1.292
8 4.553 Zebra 87-8 ‘ 0.405 1.519
9 7.485 Zebra B7-9 2.238 4.044

 

150

 

 

Figure 52: HPLC report for ink sample Parker 8458D

SampleName Parker 34580 Date Acquired 1/19/2003 11:46:42 PM

Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample 381 Name marilyn 11903 Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

5 10.60

 

r—. .
.‘ A-

" " ' ' _:i,'i/--*7soooo
:7

2.00 400 6.00 800 10.00 12.00 14.00 1600 18.00 20.00
Mnutes

 

Auto-Scaled Chromatog ram

. AAA—— 4.393

10.767

 

l 4- 5.308

———+-:, ,1 1 ,7;

‘ ' . "'7 I . I I . . I . . ' 1 . . . . . I I
2 00 4 00 600 8.00 h10.00 12.00 14.00 16.00 18.00 20.00
nutes

 

151

Sample Name Parker B458D

Processed Channel: PDA MaxP10t(250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Height
(min) Area
1 PDA MaxPlot (250nm-550nm) 1.218 804147 19.70 114338
2 PDA MaxPlot (250nm-550nm) 1.429 838305 20.54 133745
3 PDA MaxPlog250nm-550nm) 1.839 174386 4.27 24796
4 PDA MaxPlot (250nm-550nm) 2.120 212519 5.21 19787
' 5 PDA MaxPlot (250nm-550nm) 2.651 30401 0.74 2401
6 PDA MaxPlot (250nm-550nm) 2.841 18817 0.46 2150
7 PDA MaxPlot (250nm-550nm) 3.022 27098 0.66 2485
8 PDA MaxPlot (250nm-550nm) 3.327 111092 2.72 6946
9 PDA MaxPlot (250nm-550nm) 4.393 1808874 44.32 94129
10 PDA MaxPlot (250nm-550nm) 5.308 32211 0.79 2547
11 PDA MaxPlot (250nm-550nm) 10.767 23656 0.58 290
PDA Result Table
Name RT Purity Purity 1 Match 1 Spect. Match 1 Match 1
1 Angle Threshold Name Angle Threshold
1 1.218 Parker 8458-1 0.343 1.066
2 1.429 Parker 8458-2 1.179 1.049
3 1.839 Parker B458-3 0.864 1.180
4 2.120 Parker B458-4 3.304 1.664
5 2.651 Parker B458-5 6.494 4.897
6 2.841 '
' 7 3.022
8 3.327 Parker B458-4 4.330 2.484
9 4.393 Parker 8458-7 0.424 1.164
10 5.308 Parker 8458-8 3.778 5.377
11 10.767

 

152

 

 

APPENDIX D.4

HPLC Reports for Black Ball Point Inks That Were Identified to a Reasonable
Degree of Certainty by Library Matching

Sample Run 4

153

Figure 53: HPLC report for ink sample Q48 (Pentel 623)

SampleName 048 Date Acquired 1/21/2003 11:57:33 PM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name man'lyn 12103 Channel Name MaxP101250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

 

AU

vr‘fi‘

' ' ‘rf- . ' I ' r . T—v—m—r—fi 'é 3.1;; --.V4
2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00
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1:}3236

 

 

 

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2.00 400 600 8.00 011.10; 12.00 14.00 1600 18.00 20.00

154

Sample Name Q4B (Pentel 623)

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.190 488134 22.38 73361
2 PDA MaxPlot (250nm-550nm) 1.436 179132 8.21 30790
3 PDA MaxPlot (250nm-550nm) 1.610 24138 1.11 4499
4 PDA MaxPlot (250nm-550nm) 1.794 214850 9.85 27598
5 PDA MaxPlot (250nm-550nm) 2.231 36563 1.68 5592
6 PDA MaxPlot (250nm-550nm) 2.528 118513 5.43 10503
7 PDA MaxPlot (250nm-550nm) 3.236 652532 29.92 48034
8 PDA MaxPlot (250nm-550nm) 4.327 466783 21.41 26156
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angle Threshold
1 1.190 Pentel 6238-1 0.246 1.077
2 1.436 Pentel 623-2 0.210 1.103
3 1.610 Pentel 623-3 3.003 2.200
4 1.794 Pentel 623-4 1.043 1.269
5 2.231 Pentel 623-5 1 .297 1.940
6 2.528 Pentel 623-6 0.835 1.906
7 3.236 Pente1623-7 0.218 1.208
8 4.327 Pentel 623-8 0.297 1.356

 

155

 

 

Figure 54: HPLC report for ink sample Q88 (Bic 8396)

SampleName 088 Date Acquirea 1/22/2003 3:08:24 AM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run 'fime 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name marilyn 12103 Channel Name MaxP101250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

 

 

 

 

 

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2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00
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Auto-Scaled Chromatogram
0151 no 03‘
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2.00 4.00 600 800 111000 1200 14.00 16.00 1800 20.00
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156

Sample Name Q88 (Bic B396)

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Height
(min) Area
1 PDA MaxPlot (250nm-550nm) 1.088 771538 16.31 103742
2 PDA MaxPlot (250nm-550nml 1.434 750879 15.87 55265
3 PDA MaxPlot (250nm-550nm) 2.182 85257 1.80 5752
4 PDA MaxPlot (250nm-550nm1 2.484 39086 0.83 3523
5 PDA MaxPlot (250nm-550nm) 2.785 148917 3.15 15073
6 PDA MaxPlot (250nm-550nm) 3.136 2172813 45.93 189366
7 PDA MaxPlot (250nm-550nm) 3.751 23257 0.49 1725
8 PDA MaxPlot QSOnm-SSOnm) 6.234 31544 0.67 1788
9 PDA MaxPlot (250nm-550nm) 7.109 23628 0.50 1312
10 PDA MaxPlot (250nm-550nm) 7.527 37623 0.80 1927
11 PDA MaxPlot (250nm-550nm) 10.379 646388 13.66 18869
PDA Result Table
Name RT Purity Purity 1 Match 1 Spect. Match 1 Match 1
1 Threshold Name Angle Threshold
Angle

1 1.088 810 83968-1 0.175 1.199
2 1.434 Bic 8396-2 3.768 8.997
3 2.182
4 2.484
5 2.785 Bic B396E-6 8.833 31.699
6 3.136 Bic 8396-7 0.774 3.553
7 3.751
8 6.234
9 7.109
10 7.527
11 10.379

 

 

 

 

 

 

 

 

 

 

157

Figure 55: HPLC report for ink sample Q9B (Cross 813)

SampleName 098 Date Acquired 1/22/2003 3:50:48 AM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Tlme 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name mafilyn 12103 Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

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158

Sample Name Q9B (Cross Bl3)

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
Quin)
l PDA MaxPlot (250nm-550nm) 1.132 123385 21.45 11237
2 PDA MaxPlot (250nm-550nm) 1.431 141086 24.53 10472
3 PDA MaxPlot (250nm-550nm) 1.795 52840 9.19 4239
4 PDA MaxPlot (250nm-550nm) 2.518 40694 7.07 3875
5 PDA MaxPlot (250nm-550nm) 3.233 107940 18.77 8187
6 PDA MaxPlot (250nm-550nm) 4.332 109241 18.99 6087
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angle Threshold
1 1.132 Cross 8138-1 2.117 1.199
2 1.431 Cross Bl3E-2 0.527 1.149
3 1.795 Cross Bl3E-3 1.670 1.456
4 2.518 Cross 81313-4 7.327 2.132
5 3.233 Pentel 6238-6 4.238 1.622
6 4.332 Staettler 8387-10 5.561 1.861

 

 

 

 

 

 

 

 

 

 

159

Figure 56: HPLC report for ink sample Pentel 623D

SampleName Pentel 623D
lnjectiodVolume 10.00 ul
Run Time 20.00 Minutes

Sample Set Name marilyn 12103

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

Date Acquired 1/22/2003 5:36:51 AM
Acq Method Set inkrev2 method set
Processing Method Marilyn library 2103

Channel Name MaxPlot250_550

 

 

 

 

 

 

 

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2.00 4,00 6.00 8.00 10.00 12.00 14.00 16 00 18,00 20,00
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Auto-Scaled Chromatogram
0.081 g
81 rs
0.06‘ «- fl
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a 1 a.
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2.00 4,00 6.00 8.60 2'32: 12.00 14.00 16.00 18.00 20.00

160

Sample Name Pentel 623D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(mm
1 PDA MaxPlot (250nm-550nm) 1.221 518598 23.50 77552
2 PDA MaxPlot (250nm-550nm) 1.471 137948 6.25 23209
3 PDA MaxPlot Q50nm-550nm) 1.647 30759 1.39 5278
4 PDA MaxPlot (250nm-550nm) 1.838 222835 10.10 28542
5 PDA MaxPlot (250nm-550nm) 2.107 23945 1.08 2945
6 PDA MaxPlot (250nm-550nm) 2.287 32114 1.46 5022
7 PDA MaxPlot (250nm-550nm) 2.583 136362 6.18 11827
8 PDA MaxPlot (250nm-550nm 3.297 656373 29.74 48298
9 PDA MaxPlot (250nm-550nm) 4.393 448068 20.30 25181
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angle Threshold

1 1.221 Pentel 623-1 1.085 1.054

2 1.471 Staettler B387-1 4.986 1.102

3 1.647 Pentel 623-3 2.668 1.980

4 1.838 Pentel 6234 0.641 1.251

5 2.107

6 2.287 Pentel 623-5 1.830 1.895

7 2.583 Pentel 623-6 0.906 1.604
8 3.297 Pentel 623-7 ‘ 0.178 1.141

9 4.393 Pentel 623-8 0.208 1.240

 

161

 

 

Figure 57: HPLC report for ink sample Bic B396D

SampleName Bic B3960 Date Acquired 1/22/2003 6:19:15 AM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name mafilyn 12103 Channel Name MaxP101250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

AU

1 .‘,.1 , ~.

 

AutoScaled Chromatogram

 

 

 

Tfi~fi_ ,
0.204 $
1 g m
0.15? q
'- I
2 1 1
0.10 13
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1: n1 2
0.05 1.1 339:! " ‘3‘“ ‘5
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2.00 4.00 6.00 8.00 11°00 12.00 14.00 16.00 18.00 20.00

162

Sample Name Bic B396D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Height
(min) Area
1 PDA MaxPlot (250nm-550nm) 1.080 873841 15.74 118574
2 PDA MaxPlot (250nm-550nm) 1.486 817377 14.72 53492
3 PDA MaxPlot (250nm-550nm) 2.052 39574 0.71 5094
4 PDA MaxPlot (250nm-550nm) 2.167 55616 1.00 6274
5 PDA MaxPlot (250nm-550nm) 2.467 43401 0.78 3872
6 PDA MaxPlot (250nm-550nm) 2.763 176928 3.19 18291
7 PDA MaxPlot (250nm-550nm) 3.108 2619713 47.18 229896
8 PDA MaxPlot (250nm-550nm) 3.712 27542 0.50 2064
9 PDA MaxPlot £250nm-550nm) 6.161 37420 0.67 2077
10 PDA MaxPlot (250nm-550nm) 7.049 27044 0.49 1537
11 PDA MaxPlot (250nm-550nm) 7.472 51151 0.74 2078
12 PDA MaxPlot (250nm-550nm) 10.336 792415 14.27 22905
PDA Result Table
Name RT Purity Purity 1 Match 1 Spect. Match 1 Match 1
1 Threshold Name Angle Threshold
Aggle

1 1.080 Bic BB96E—l 0.191 1.208
2 1.486 Bic B396E-2 3.681 11.206
3 2.052
4 2.167
5 2.467
6 2.763 Peak 7 8.093 30.798
7 3.108 Bic B396-7 0.746 3.531
8 3.712
9 6.161
10 7.049
11 7.472
12 10.336 Bic B396-13 8.626 39.332

 

163

 

Figure 58: HPLC report for ink sample Fisher BS36G

SampleName Fisher 85366
Injection Volume 10.00 ul

Run Time 20.00 Minutes

Sample Set Name marilyn 12103

Processed Channel Descr. PDA MaxPlot

(250.0 nm to 550.0 nm)

Date Acquired 1/22/2003 8:05:16 AM
Acq Method Set inkrev2 method set
Processing Method Marilyn library 2103

Channel Name MaxP101250_550

 

 

 

 

 

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200 400 600 8.00 10.00 1200 1400 1600 1800 2000
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1 ” ”“‘ ‘
0.10‘ $ 5
1 .- 1
0.084
3006‘ !
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I64

Sample Name Fisher B536G

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.190 40753 3.55 4525
2 PDA MaxPlot (250nm-550nm) 1.423 656150 57.12 111907
3 PDA MaxPlot (250nm-550nm) 1.833 136486 11.88 18302
4 PDA MaxPlot (250nm—550nny 2.340 22044 1.92 1823
5 PDA MaxPloflZSOnm-SSOnm) 2.953 161623 14.07 7972
6 PDA MaxPlot (250nm-550nmL 3.501 51862 4.52 3904
7 PDA MaxPlot (250nm-550nm) 5.801 79724 6.94 3747
PDA Result Table
Name RT Purity l Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angle Threshold
1 1.190 Fisher BS36E-l 3.529 1.742
2 1.423 Fisher BS36E-2 0.061 1.025
3 1.833 Fisher BS36E-3 0.358 1.098
4 2.340 Fisher 853613-4 2.544 3.590
5 2.953 Fisher BS36E-5 1.073 2.171
6 3.501 Fisher 85365-6 1.028 2.298
7 5.801 Fisher B536E-7 1.473 2.433

 

1

65

 

Figure 59: HPLC report for ink sample Staedtler B387D

SampleName Staettler 83870

Injection Volume 10.00 ul

Run Time 20.00 Minutes

Sample Set Name marilyn 12103

Date Acquired 1/22/2003 8:47:40 AM

Acq Method Set inkrev2 method set

Processing Method Marilyn library 2103

Channel Name MaxP101250_550

Processed Channel Descr. PDA MaxPlot

(250.0 nm to 550.0 nm)

 

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16.00 18.00 20.00

Sample Name Staedtler B387D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(mm
1 PDA MaxPlot (250nm-550nm) 1.435 517034 22.84 44503
2 PDA MaxPlot (250nm-550nm) 1.812 160525 7.09 8963
3 PDA MaxPlot (250nm-550nm) 2.247 72431 3.20 5323
4 PDA MaxPlot (250nm-550nm) 2.498 69741 3.08 6067
5 PDA MaxPlot (250nm-550nm) 2.759 28240 1.25 3054
6 PDA MaxPlot (250nm-550nm) 2.960 144105 6.37 13535
7 PDA MaxPlot (250nm-550nm) 3.257 163372 7.22 10500
8 PDA MaxPlot (250nm-550nm) 3.911 709575 31.35 47016
9 PDA MaxPlot (250nm-550nm) 4.395 323022 14.27 17861
10 PDA MaxPlot (250nm-550nm) 5.589 38342 1.69 2634
11 PDA MaxPlot (250nm-550nm) 7.626 36991 1.63 1945
PDA Result Table
Name RT Purity l Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angle Threshold
1 1.435 Staettler B387-1 1.882 1.116
2 1.812 Staettler B387-2 1.632 1.568
3 2.247 Staettler B387-3 2.624 2.004
4 2.498 Staettler 8387-5 2.709 2.102
5 2.759 Staettler B387-6 3.545 2.432
6 2.960 Staettler B387-7 3.424 1.899
7 3.257 Staettler B387-8 4.240 2.317
8 3.911 Staettler 8387-9 1.073 1.374
9 4.395 Staettler B387-10 2.316 1.853
10 5.589 Staettler 8387-1 1 2.962 4.189
11 7.626 Cross B 1313-8 3.046 4.295

 

167

 

 

APPENDIX E

168

APPENDIX E

HPLC Reports for Blue Ball Point Inks That Were Not Identified to a Reasonable
Degree of Certainty, but Were Listed as Possible Matches by Library Matching

169

APPENDIX E]

HPLC Reports for Blue Ball Point Inks That Were Not Identified to a Reasonable
Degree of Certainty, but Were Listed as Possible Matches by Library Matching

Sample Run 1

170

Figure 60: HPLC report for ink sample Bic Bl97D

SampleName Bic B197D
injection Volume 10.00 ul
Run Time 20.00 Minutes

Sample Set Name marilyn 11

Date Acquired 1/16/2003 8:15:28 PM
Acq Method Set inkrev2 method set
Processing Method Marilyn library 2103

603 Channel Name MaxP101250_550

Processed Channel Descr. PDA MaxPlot

(250.0 nm to 550.0 nm)

 

l

 

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10.00 12100 14.00 16.00 1800 20.00

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171

Sample Name Bic Bl97D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.125 576098 33.82 46081
2 PDA MaxPlot (250nm-550nm) 1.470 858272 50.39 49519
3 PDA MaxPlot (250nm-550nm) 1.941 76902 4.52 6110
4 PDA MaxPlot (250nm-550nm) 2.300 25314 1.49 2597
5 PDA MaxPlot (250nm-550nm) 2.597 50281 2.95 5175
6 PDA MaxPlot (250nm-550nm) 5.037 116381 6.83 6650
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match Match 1
Angle Threshold Name 1 Threshold
Angle

1 1.125 Bic 8162-] 4.472 1.137
2 1.470 Bic B197-2 1.929 1.042
3 1.941
4 2.300
5 2.597
6 5.037 Formulabs B517-1l 3.438 1.693

 

172

 

Figure 61: HPLC report for ink sample Senator B385D

SampleName Senator 3385D Date Acquired 1/18/2003 8:57:52 PM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marily 11 library 2103
Sample Set Name marilyn 11503 Channel Name MaxP101250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

AU

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, » 7.... ..3 .

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2.00 4.00 6.00 8.00 10:00 12.00 14.00 16.00 18:00
Mnutes

20.00

Auto-Scaled Chromatog ram
0.0143
0.0121
0.010 V
3 0.008
«1
0.006
0.004

0.002%

 

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0000.17 “' ' 7‘ .. W We *7 7' ' 1 ' - i

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2.00 4.00 6.00 8.00 “10.00 12.00 14.00 16.00 18.00 20.00
nutes

173

Sample Name Senator B385D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.189 125509 18.12 10175
2 PDA MaxPlot (250nm-550nm) 1.500 109170 15.76 6425
3 PDA MaxPlot (250nm-550nm) 1.851 51310 7.41 4099
4 PDA MaxPlot (250nm-550nm) 2.434 18309 2.64 1511
5 PDA MaxPlot (250nm-550nm 2.596 30675 4.43 3616
6 PDA MaxPlot (250nm-550nm) 2.818 43361 6.26 4097
7 PDA MaxPlotiZSOnm-SSOnm) 3.721 206095 29.76 13869
8 PDA MaxPlot (250nm-550nm) 5.130 72381 10.45 3624
9 PDA MaxPlot (250nm-550nm) 6.018 35689 5.15 1760
PDA Result Table
Name RT Purity l Purity 1 Match 1 Spect. Match Match 1
Angle Threshold Name 1 Threshold
Angle

1 1.189 Senator B385-l 3.221 1.344

2 1.500 Dupont B 102-2 6.866 1.594

3 1.851 Cross Bl64-3 9.074 1.755
4 2.434

5 2.596 Bic 8162-5 7.553 2.474
6 2.818 Russian Ink 8426-6 2.728 2.127
7 3.721 Dupont B 102-5 0.858 1.642

8 5.130

9 6.018 Senator B385-7 2.150 2.397

 

174

 

 

Figure 62:

SampleName New Bic 0
Injection Volume 10.00 ul

Run Time 20.00 Minutes

HPLC report for ink sample New Bic D

Date Acquired 1/17/2003 8:37:44 AM
Acq Method Set inkrev2 method set

Processing Method Marilyn library 2103

Sample Set Name marilyn 11603 Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot

(250.0 nm to 550.0 nm)

 

2.00 4.00 6.00 800

AU

10.00 12.00 14.00 1600 1800 20.00
Mnutes

Auto-Scaled Chromatog ram

 

. l .n
0040 Q § §
,_ ..
0030- ‘ l
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l l n l
. ° '5
(0.0204 “75.001
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6.00 8.00 “0.00 12.00 14.00 16.00 18.00 20.00

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I75

Sample Name New Bic D

Processed Channel: PDA MaxP10t(250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.172 428371 19.70 29372
2 PDA MaxPlot (250nm-550nm) 1.748 163091 7.50 13234
3 PDA MaxPlot (250nm-550nmL 2.212 23031 1.06 3629
4 PDA MaxPlot (250nm-550nm 2.335 68283 3.14 8679
5 PDA MaxPlot (250nm-550nm) 2.780 196164 9.02 16963
6 PDA MaxPlot (250nm-550nm) 3.652 647928 29.80 43722
7 PDA MaxPlot (250nm-550nm) 4.995 647286 29.77 31824
PDA Result Table
Name RT Purity l Purity 1 Match 1 Spect. Match Match 1
Angle Threshold Name 1 Threshold
Angle

1 1.172 New Bic-1 4.751 1.202

2 1.748 New Bic-2 1.190 1.124

3 2.212

4 2.335 Bic B162-4 7.499 1.355

5 2.780 Senator B385-4 3.052 1.885

6 3.652 Formulabs 8517-9 0.597 1.278

7 4.995 Formulabs 8517-11 1.072 1.423

 

176

 

 

APPENDIX E.2

HPLC Reports for Blue Ball Point Inks That Were Not Identified to a Reasonable
Degree of Certainty, but Were Listed as Possible Matches by Library Matching

Sample Run 2

177

Figure 63: HPLC report for ink sample Staedtler B384D

SampleName Staettler 83840
Injection Volume 10.00 ul
Run Time 20.00 Mnutes

Sample Set Name marilyn 11703

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

Date Acquired 1/17/2003 9:13:25 PM
Acq Method Set inkrev2 method set
Processing Method Marilyn library 2103

Channel Name MaxPlot250_550

 

 

 

‘

 

008

AU

0.04
0 02

4
l
l

0.00
. (4" t,
.9 500.00

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8.00 10.00 12.00 14.00 18.00 18.00 20.00
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Auto-Scaled Chromatog ram

 

 

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1 i
0.025-
: a l
. IQ R
0.020—j 0° r~_
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l l I l l I I I | | 1 l l l l 1 l l I I | > I I | I l
8.00 0.00 12. 14.00 . . .
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Sample Name Staedtler B384D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.176 84794 6.13 6772
2 PDA MaxPlot (250nm-550nm) 1.423 149196 10.78 12421
3 PDA MaxPlot (250nm-550nm) 1.787 82627 5.97 4018
4 PDA MaxPlot (250nm-550nm) 2.514 36908 2.67 3422
5 PDA MaxPlot (250nm-550nm) 2.698 87798 6.34 8783
6 PDA MaxPlot (250nm-550nm) 3.524 356502 25.76 25487
7 PDA MaxPlot (250nm-550nn9 4.359 18803 1.36 1355
8 PDA MaxPlot (250nm-550nm) 4.777 463155 33.46 23895
9 PDA MaxPlot (250nm-550nm) 5.593 54418 3.93 2580
10 PDA MaxPlot (250nm-550nm) 7.737 49882 3.60 2519
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angle Threshold

1 1.176 Staettler B384-1 9.989 1.324
2 1.423 Tombo 8535-2 3.839 1.363
3 1.787 Staettler B384-3 4.566 1.896
4 2.514
5 2.698 Fisher 850-3 2.439 1.799
6 3.524 Fisher 850-4 0.589 1.289
7 4.359
8 4.777 Parker B176-9 3.105 2.292
9 5.593 Staettler B384-8 3.803 2.190
10 7.737 Papermate B376-8 4.937 7.106

 

179

 

 

Figure 64: HPLC report for ink sample Bic B388D

SampleName Bic B388D Date Acquir9d 1/17/2003 9:55:49 PM
injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name marilyn 11703 Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

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2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00
‘ Mnutea
Alto-Scaled Chromatogram
2- _ ._ _. _j
1 l
1 :1
0.030-4 '“e-
. .1;
"' v-
0.020§ 8.
D
< : T
I 1N 3
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2.00 4.00 6.00 8.00 “0.00 12.00 14.00 16.00 18.00 20300
nutes

180

Sample Name Bic B388D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(will)
1 PDA MaxPlot (250nm-550nm) 1.117 410689 31.11 36415
2 PDA MaxPlot (250nm-550nm) 1.471 487187 36.90 32523
3 PDA MaxPlot (250nm-550nm) 1.862 45310 3.43 4383
4 PDA MaxPlotQSOnm-SSOnm) 2.530 27470 2.08 2348
5 PDA MaxPlot (250nm-550nm) 3.404 62555 4.74 4776
6 PDA MaxPlot QSOnm-SSOnml 4.661 286934 21.74 15171
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angle Threshold
1 1.117 Bic B388-1 6.390 1.080
2 1.471 Bic 8388-3 4.730 1.091
3 1.862 Tombo B535-1 8.032 1.445
4 2.530 Bic 8388-5 7.737 2.789
5 3.404 Fisher B50-4 1.307 1.849
6 4.661 Papermate B376-7 0.655 1.389

 

181

 

Figure 65: HPLC report for ink sample Fisher BSOD

SampleName Fisher BSOD Date Acquired 1/17/2003 10:59:25 PM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name marilyn 11703 Channel Name MaxP101250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

/./ .‘ ,7 / / 10.10

 

~' 0.08

0.06

AU

’ l 10.04

1 , #000
l, _
- l L 50000
WW W .44 171W~ Wr * -44 - WWWWW
2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00
Mnutea

Auto-Scaled Chromatog ram

 

0.0154 1
i
l 1 a,
0.010: a- L;
1 H. ‘0' 3
3 1 1‘ ‘0 l f‘
. 3 3‘ V
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2.00 4.00 6.00 8.00 911%:12'00 14.00 16.00 18.00 20.00

182

Sample Name Fisher 850D

Processed Channel: PDA MaxP10t(250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
Lmin)
l PDA MaxPlot (250nm-550nm) 1.183 196708 35.19 14572
2 PDA MaxPlot (250nm-550nm) 1.503 133772 23.93 12215
3 PDA MaxPlot (250nm-550nm) 2.643 33519 6.00 3183
4 PDA MaxPlot (250nm-550nmL 3.479 104058 18.62 7172
5 PDA MaxPlot (250nm-550nm) 4.765 90881 16.26 4841
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angle Threshold
1 1.183 Fisher 850-1 1.844 1.139
2 1.503 Papermate B376-2 0.948 1.054
3 2.643 Tombo B535-3 3.370 3.303
4 3.479 Papermate B376-6 0.818 1.585
5 4.765 Parker B176-9 2.848 2.552

 

183

 

Figure 66: HPLC report for ink sample Tombo BS35D

SampleName Tombo 85350
injection Volume 10.00 ul
Run Time 20.00 Minutes

Sample Set Name marilyn 11703

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

.1 1" A~~11

1
/

 

,1. w“,

M "0128

Auto-Scaled Chromatog ram

Date Acquired 1/18/2003 2:10:14 AM
Acq Method Set inkrev2 method set
Processing Method Marilyn library 2103

Channel Name MaxPlot250_550

 

'mf rr'mr‘rr r—mfimm‘r—n fir?" “'7— ' "r *1 ___ a
2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00

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184

 

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8.00 “0.00 12.00 14.00 16.00 18.00 20.00
nutes

Sample Name Tombo 85350

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.188 83179 25.80 7765
2 PDA MaxPlot (250nm-550nm) 1.431 52016 16.13 6099
3 PDA MaxPlot (250nm-550nm) 1.863 25488 7.91 3355
4 PDA MaxPlot (250nm-550nm) 2.569 27121 8.41 2650
5 PDA MaxPlot (250nm-550nm) 3.400 55410 17.19 3958
6 PDA MaxPlot (250nm-550nm) 4.694 41071 12.74 2344
7 PDA MaxPlot (250nm-550nm) 5.480 38114 11.82 2139
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Age Threshold

1 1.188 Tombo 8535-1 1.283 1.286
2 1.431 Tombo 8535-2 0.500 1.288
3 1.863 Bic B388-4 9.933 1.497
4 2.569 Fisher 850-3 4.761 2.719
5 3.400 Fisher 850-4 0.995 1.994
6 4.694 Staettler 8384-7 2.391 2.616
7 5.480 Staettler B384-8 6.135 2.222

 

185

 

 

APPENDIX B.3

HPLC Reports for Blue Ball Point Inks That Were Not Identified to a Reasonable
Degree of Certainty, but Were Listed as Possible Matches by Library Matching

Sample Run 3

186

Figure 67: HPLC report for ink sample Fisher B65D

SampleName Fisher 865D Date Acquired 1/19/2003 6:07:29 PM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marily n library 2103
Sample Set Name marilyn 11903 Channel Name MaxP101250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

/"/ "—0.12

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AU

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0.00

 

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2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.1!) 18.00 20.00
Mnutea

Auto-Scaled Chromatogram

 

 

 

 

J
- l
0.020J 8'5 1
: m. l h
. ‘— §
0015-: g 3 C
. F. 06
:> ‘7 ‘ ‘
< .
0.010— 1 co 1
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0.0051 T? ‘ T g
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. ' 1 I 1 1 ‘

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2.00 4.00 6.1!) 8.00 Joioo 12.00 14.00 16.00 18.00 20.00
nutes

187

Sample Name Fisher 865D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.199 145522 10.75 10224
2 PDA MaxPlot (250nm-550nm) 1.559 375771 27.76 22000
3 PDA MaxPlot (250nm-550nm) 2.074 31508 2.33 2091
4 PDA MaxPlot £250nm-550nm) 2.511 19000 1.40 2301
s PDA MaxPlot (250nm-550nm) 2.658 42557 3.14 4286
6 PDA MaxPloflSOnm-SSOnm) 3.447 244771 18.08 17468
7 PDA MaxPlot (250nm-550nm) 4.607 348524 25.75 19485
8 PDA MaxPlot QSOnm-SSOnm) 11.000 126719 9.36 3430
9 PDA MaxPlot (250nm-550nm) 16.267 19335 1.43 330
PDA Result Table
Name RT Purity Purity 1 Match 1 Spect. Match 1 Match 1
1 Threshold Name Angle Threshold
Angle

1 1.199 Fisher B65-1 3.973 10.182
2 1.559 Fisher B65-2 2.664 7.676
3 2.074
4 2.511
5 2.658
6 3.447 Cross 81648-6 3.875 9.588
7 4.607 Dupont 81028-6 5.618 10.838
8 11.000
9 16.267

 

188

 

Figure 68: HPLC report for ink sample Papemiate B68D

SampleName Papermate 868D
Injection Volume 10.00 111
Run Time 20.00 Mnutes

Sample Set Name marilyn 11903

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

Date Acquired 1/19/2003 6:49:53 PM
Acq Method Set inkrev2 method set
Processing Method Marilyn library 2103

Channel Name MaxPl01250__550

 

 

 

 

 

 

 

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2.00 400 6.00 8.00 10.00 12100 14.00 16:00 13.00 20.00
Mnutee
Auto-Scaled Chromatogram
0an ‘32- 1-
1 ‘- «'72 §
“3 11
:0 §l I 1 o
< Pi! O l 8
1‘: ég 3
0.01 In ‘ 1
1:1

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Sample Name Papermate B68D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
4min)
l PDA MaxPlot (250nm-550nm) 1.231 208327 10.98 13409
2 PDA MaxPlot QSOnm-550nm) 1.529 375218 19.78 36998
3 PDA MaxPlot (250nm-550nm) 1.870 72332 3.81 5519
4 PDA MaxPlot (250nm-550nm) 2.028 49920 2.63 3793
5 PDA MaxPlot (250nm-550nm) 2.476 64856 3.42 7553
6 PDA MaxPlot (250nm-550nm) 2.609 44550 2.35 5639
7 PDA MaxPlot (250nm-550nm) 3.374 279426 14.73 20739
8 PDA MaxPlot (ZSOnm-SSOnm) 4.538 384641 20.28 20485
9 PDA MaxPlot (250nm-550nm) 5.24] 54236 2.86 2576
10 PDA MaxPlot (250nm-550nm) 6.512 35392 1.87 616
11 PDA MaxPlot (250nm-550nm) 10.698 327674 17.26 9284
PDA Result Table
Name RT Purity Purity 1 Match 1 Spect. Match Match 1
1 Threshold Name 1 Threshold
Angle Angle

1 1.231 Fisher B65-l 6.695 14.586
2 1.529 Papermate BB76E-2 3.862 6.086
3 1.870
4 2.028
5 2.476
6 2.609
7 3.374 Papermate BB76E-6 6.450 16.903
8 4.538 Papermate B376E-7 8.108 21.963
9 5.241
10 6.512
11 10.698

 

190

 

Figure 69: HPLC report for ink sample Fisher B77D

SampleName Fisher 3770
Injection Volume 10.00 ul
Run Time 20.00 Minutes

Sample Set Name marilyn 11903

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

Acq Method Set inkrev2 method set

Channel Name MaxPlot250_550

 

    

 

Date Acquired 1/20/2003 12:50:22 AM

Processing Method Marilyn library 2103

 

 

 

 

 

 

 

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2100 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00
Mnutes
AutoScaled Chromatogram
0.030 I
g V §
Eli ' l
30.02041 ‘1”, 11‘ ‘
< Fl °° ll ' no
i‘ . vs 1., a 1
1" 3 ‘1 1‘ 8.
0010; 91‘ l‘” ‘1 ' 3 °
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2.00 4.00 6.00 8.00 M91190 12.00 14.00 16.00 18.00 20.00

ta 8

I91

Sample Name Fisher B77D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.171 206145 9.63 14843
2 PDA MaxPlot (250nm-550nm) 1.525 556938 26.02 34595
3 PDA MaxPlot (250nm-550nm) 2.049 41924 1.96 2863
4 PDA MaxPlot (250nm-550nml 2.578 97976 4.58 7955
5 PDA MaxPlot (250nm-550nm) 3.324 405089 18.92 29548
6 PDA MaxPlot (250nm-550nm) 4.449 621606 29.04 31789
7 PDA MaxPlot (250nm-550nrr3 10.868 211009 9.86 6169
PDA Result Table
Name RT Purity Purity 1 Match 1 Spect. Match Match 1
1 Threshold 1 Threshold
Ange Alfie

1 1.171 Fisher B77-l 4.063 9.483

2 1.525 Fisher B77-2 3.634 8.161

3 2.049

4 2.578 Papermate 33765-5 9.436 23.794
5 3.324 Papermate BB76E-6 3.670 9.017
6 4.449 Papermate BB76E-7 3.762 10.347
7 10.868

 

192

 

 

APPENDIX F

193

APPENDIX F

HPLC Reports for Black Ball Point Inks That Were Not Identified to a Reasonable
Degree of Certainty, but Were Listed as Possible. Matches by Library Matching

194

APPENDIX E]

HPLC Reports for Black Ball Point Inks That Were Not Identified to a Reasonable
Degree of Certainty, but Were Listed as Possible. Matches by Library Matching

Sample Run 2

195

Figure 70: HPLC report for ink sample Fisher B11 1D

SampleName Fisher B111D Date Acquired 1/17/2003 11:41:49 PM

injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103

Sample SE3t Name marilyn 11703 Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

1
$0.000

l
E . ,-
» $ w. 500.00

 

200 4.00 6.00 800 10100 12.00 1400 16.00 1800 20.00
Mnutes

AutoScaled Chromatog ram

.‘;“»3.190
. +6474

.1. 4.862

I 7' 7‘ '1 ' , ' 1 . > 1 | v - ' l . 1 ' l ' . 1 l ‘ ‘ ' I 1 ' '
2.00 4.00 6.00 8.00 Bx000 12.00 14.00 16.00 18.00 20.00
nutes

196

Sample Name Fisher BlllD

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(mm
1 PDA MaxPlot (250nm-550nm) 1.129 95159 20.00 7272
2 PDA MaxPlot (250nm-550nm) 1.432 94941 19.96 14284
3 PDA MaxPlot (250nm—550nm) 1.597 86408 18.16 12448
4 PDA MaxPlot (250nm-550nm) 1.825 70535 14.83 6490
5 PDA MaxPlot (250nm-550nfl 2.533 20793 4.37 2518
6 PDA MaxPlot {250nm-550nm) 3.190 34877 7.33 2833
7 PDA MaxPlot (250nm-550nm) 3.862 18140 3.81 1359
8 PDA MaxPlot (250nm-550nm) 6.474 54917 11.54 2733
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angli Threshold

1 1.129 Fisher Bl 1 1-1 4.729 1.506

2 1.432 Pilot 8115-2 2.001 1.218

3 1.597 Fisher B1 1 1-3 6.968 1.654
4 1.825 Fisher B1 1 1-4 4.735 1.702

5 2.533 Dupont 8113-4 8.305 3.573

6 3.190

7 3.862

8 6.474

 

197

 

 

Figure 71: HPLC report for ink sample Dupont B1 13D

SampleName Dupont B1130 Date Acquired 1/18/2003 12:24:13 AM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name marilyn 11703 Channel Name MaxPlotZ50_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

AU

1 ' l,

,.» 7 'i',.‘5oooo

LCEXLCXLWWCLC--_WLLX-. .. .W . : ‘
2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00

nutes

Auto-Scaled Chromatog ram

 

H 15.535

J
1

 

 

7 ’ 7 ' V" . l ‘ . ' l v ‘ ' 1 ' ' ' l ' ' ' l
6.00 8.00 0.00 12.00 14.00 16.00 18.00 20.00
111.1193

 

198

Sample Name Dupont Bl 13D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.093 245392 17.50 20568
2 PDA MaxPlot @0nm-550nm) 1.444 292630 20.87 19792
3 PDA MaxPlot (250nm-550nm) 1.814 114477 8.17 12124
4 PDA MaxPlot (250nm-550nm) 2.530 25106 1.79 3123
5 PDA MaxPlot (250nm-550nm) 2.678 29771 2.12 3563
6 PDA MaxPlot (250nm-550nm) 3.504 245604 17.52 17247
7 PDA MaxPlot (250nm-550nm 4.755 420049 29.96 21525
8 PDA MaxPlot (250nm-550nm) 15.535 28919 2.06 926
PDA Result Table
Name RT Purity Purity 1 Match 1 Spect. Match 1 Match 1
1 Threshold Name Angle Threshold
AnLle
1 1.093 Dupont Bl 13-1 1.575 1.155
2 1.444 Dupont Bl 13-2 0.613 1.163
3 1.814 Fisher B111-4 7.075 1.571
4 2.530 Dupont Bl 13-4 7.095 3.225
5 2.678 Staettler B391-5 5.649 2.405
6 3.504 Dupont Bl 13-6 0.360 1.395
7 4.755 Pilot B115-8 . 0.450 1.298
8 15.535 Dupont Bl 13-8 4.877 6.942

 

199

 

Figure 72: HPLC report for ink sample Pilot Bl 15D

SampleName Pilot 81150
Injection Volume 10.00 ul
Run Time 20.00 Minutes

Sample Set Name marilyn 11703

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

Date Acquired 1/18/2003 4:38:41 AM
Acq Method Set inkrev2 method set
Processing Method Marilyn library 2103

Channel Name MaxPlot250_550

‘T’fi . ——,—.— MT—r—r Cf...
AU

 

 

 

 

0.02
1 ‘1 l l
~ I .V.'/\ 1| 0.00
. 1 g
12”“ 500.00
.32 .2. LEMMA ,# ,....- .3‘
2.00 4.00 600 800 10.00 1200 1400 1600 1800 2000
S
Auto-Scaled Chromatogram
006T$
0.04 1‘
:1 ‘ I!)
< “ (0
H In. *0
002 E “2’” 8'
N v N l. T
‘ {‘FN
. 1 l:
°~°°‘Li"_;;- LIST. 1 I 7.." _ "
‘ | " "“‘l" “‘l"‘|"‘l"‘l
200 4.00 6.00 0.00 0.00 12.00 14.00 16.00 18.00 20.00

200

Sample Name Pilot Bl 15D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.182 491082 36.00 62020
2 PDA MaxPlot (250nm-550nm) 1.437 79131 5.80 8951
3 PDA MaxPlot (250nm-550nm) 1.834 53327 3.91 4632
4 PDA MaxPlot (250nm—550nm) 2.170 43203 3.17 3489
S PDA MaxPlot (250nm-550nm) 2.705 148292 10.87 11655
6 PDA MaxPlot (250nm-550nm) 3.535 276129 20.24 18809
7 PDA MaxPlotiZSOnm-SSOnm) 4.805 272802 20.00 13914
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angle Threshold
1 1.182 Pilot B115-1 1.737 1.057
2 1.437 Pilot Bl 15-2 1.224 1.208
3 1.834 Pilot Bl 15-3 4.981 1.647
4 2.170 Pilot Bl 15-3 2.293 2.473
5 2.705 Pilot Bl 15-5 1.052 1.478
6 3.535 DupontB113-6 0.561 1.352
7 4.805 DupontB113-7 0.378 1.356

 

201

 

 

APPENDIX C

202

APPENDIX G

HPLC Reports for Blue Ball Point Inks That Were Not Identified

203

APPENDIX G.1
HPLC Reports for Blue Ball Point Inks That Were Not Identified

Sample Run 3 i

204

Figure 73: HPLC report for ink sample Pilot B 103D

SampleName Pilot B1030
Injection Volume 10.00 ul
Run Time 20.00 Mnutes

Sample Set Name marilyn 11903

Processed Channel Descr. PDA MaxPlot

(250.0 nm to 550.0 nm)

Date Acquired 1/19/2003 9:18:17 PM
Acq Method Set inkrev2 method set
Processing Method Marilyn library 2103

Channel Name MaxP101250_550

 

 

 

 

/ j / ;0040
l / I
4" i-
_—0.030
1 Z
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—o.020 <
f , _—o.o1o
‘\ /, \ ;0.ooo
“ ' __- ‘1/‘50000

 

 

 

V v I 1 v v r v I v i r ‘r I 1 I I I t Y Y I 7’ Y ‘ V v V 7 v r I ‘1 ‘7 Y ‘ ‘
2.00 4.00 6.00 8.00 10.“) 12.00 14.00 16.00 18.00 20.00
Mm

Auto-Scaled Chromatogram

 

—— 3.342

——4.510

 

—10.963

 

 

,1..,.......,...
0.00 12.00 14.00 18.00 iefoo 20.00
nub:

Sample Name Pilot BlO3D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.129 147918 18.14 11291
2 PDA MaxPlot QSOnm-SSOnm) 1.444 145228 17.81 13083
3 PDA MaxPlot (250nm-550nm) 1.809 33125 4.06 2496
4 PDA MaxPlot (250nm-550nm) 2.022 25226 3.09 1758
5 PDA MaxPlot (250nm-550nmL 2.579 84761 10.40 5556
6 PDA MaxPlotQSOnm-SSWm) 3.342 144555 17.73 10024
7 PDA MaxPlot (250nm-550nm) 4.510 105909 12.99 6226
8 PDA MaxPlot (250nm-550nm) 10.963 128521 15.76 3858
PDA Result Table
Name RT Purity Purity 1 Match 1 Spect. Match 1 Match 1
1 Threshold Name Angle Threshold
Angle
1 1.129
2 1.444 Itoya 8194-2 7.514 12.038
3 1.809
4 2.022
5 2.579
6 3.342 Cross Bl64E-6 6.422 17.963
7 4.510
8 10.963

 

206

 

APPENDIX H

207

APPENDIX H

HPLC Reports for Blue Ball Point Inks That Were Run Against Only Their
Counterparts in a Library

208

APPENDIX H.1

HPLC Reports for Blue Ball Point Inks That Were Run Against Only Their
Counterparts in a Library

Sample Run 1

209

Figure 74: HPLC report for ink sample Bic Bl97D (own library)

SampleName Bic 81970
injection Volume 10.00 ul
Run Time 20.00 Minutes

Sample Set Name marilyn 11603

Processed Channel Descr. PDA MaxPlot

(250.0 nm to 550.0 nm)

Date Acquired 1/16/2003 8:15:28 PM
Acq Method Set inkrev2 method set
Processing Method Marilyn library 2103

Channel Name MaxPlot250_550

 

 

 

: o 25
f , ”"7: ’* , , , fl , - 1020
l
‘ l
: 015 :2
(
010
l/ ‘
0 05
N 000
,., . -1...-2---_m
, l’ , '
, , ,‘ . , .
1 g . 50000
2.00 4.00 6.00 8.00 10.00 12.00 14.00 16 00 18 oo 20 oo
Mnutes
AutoScaled Chromatogram
0050—11 i ' ‘ ”*1
J 1% l
0.040-j
F."
j a 1
0.030 I ‘1 l
3 h l
< ‘ |
0.020 1
1 1 He 5:- I
0.010 1 “an 1
'N l [
1 il ' i
0M1 ' "I ' ’ ~ I
"F ‘ ’I—V 1 ' l ' ‘ I 1 ' I ‘ ' ‘ . * 1 I ‘ ' ' I ‘ ' ‘ l 1 ' - I 1 I
2.00 4.00 6.00 8.00 91111.23 12.00 14.00 16.00 18.00 20.00

210

Sample Name Bic B197D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.125 576098 33.82 46081
2 PDA MaxPlot (250nm-550nm) 1.470 858272 50.39 49519
3 PDA MaxPlot (250nm-550nm) 1.941 76902 4.52 6110
4 PDA MaxPlot (250nm-550nm) 2.300 25314 1.49 2597
5 PDA MaxPlot QSOnm-SSOnm) 2.597 50281 2.95 5175
6 PDA MaxPlot QSOnm-SSOnm) 5.037 116381 6.83 6650
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angle Threshold

1 1.125 Bic Bl97—l 9.750 1.059
2 1.470 Bic Bl97-2 1.929 1.042
3 1.941
4 2.300
5 2.597
6 5.037 Bic Bl97-3 6.379 2.262

 

 

 

 

 

 

 

 

 

 

211

Figure 75: HPLC report for ink sample Senator B385D (own library)

SampleName Senator 83850 Date Acquired 1/16/2003 8:57:52 PM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample 581 Name marilyn 11503 Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

AU

1'" 0.02

I

I .
i ...

l .

1 ,73
2,00 4.00 6.00 8.00 10.00 1200 14.00 16.00 1800 20 00
Mnutes

Auto-Scaled Chromatog ram

 

 

 

. ’ ‘7 ' r ‘ ‘ ‘ ‘ ‘ ‘ ‘ ‘ | ‘
2.00 4.00 6.00 8.00 “9119129 12.00 14.00 16m 18.00 20.00

0.01431 I
3 a
0012« E I~"~
. 4 «Ii
0.010 c
[O
0008 ‘m'
3 ' 13$ 11 8
0.006 1 - - A .—
“1‘- i 1 1 '0 3
0.004 ‘ I Ii 3 I I g
1 1 11511 1‘ I
0.002 1 1 II 1
I 1 11“ ., ., .
0.0004 "” "175;. 2 ..
' I ' ' ‘ I

212

Sample Name Senator B385D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.189 125509 18.12 10175
2 PDA MaxPlot (250nm-550nm1 1.500 109170 15.76 6425
3 PDA MaxPlot (250nm-550nm) 1.851 51310 7.41 4099
4 PDA MaxPlotiZSOnm-SSOnm) 2.434 18309 2.64 1511
S PDA MaxPlot (250nm-550nm) 2.596 30675 4.43 3616
6 PDA MaxPlot (250nm-550nm) 2.818 43361 6.26 4097
7 PDA MaxPlot (250nm-550nng 3.721 206095 29.76 13869
8 PDA MaxPlot (250nm-550nm) 5.130 72381 10.45 3624
9 PDA MaxPlot (250nm-550nm) 6.018 35689 5.15 1760
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Anfi Threshold Name Angle Threshold

1 1.189 Senator B385-1 3.221 1.344
2 1.500
3 1.851
4 2.434
5 2.596
6 2.818 Senator B385-4 3.081 2.362
7 3.721 Senator B385-5 0.982 1.337
8 5.130
9 6.018 Senator B385-7 2.150 2.397

 

213

 

 

Figure 76: HPLC report for ink sample New Bic D (own library)

SampleName New Bic D Date Acquired 1/17/2003 8:37:44 AM

Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name marilyn 11603 Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

 

 

 

 

L020
[7 ‘ ‘i7 g 7’ if if 7 7 7 ..
I ‘ p
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1 $0.15
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I . ‘50000
L... 1.1 . 13-...fisfifl 1 . . Mv. .............-.I’c'
2.00 400 6.00 800 10.00 1200 14.00 16.00 1800 2000
Mnutes
Auto-Scaled Chromatogram
00401; "L 3
v'. ,5 1'
I " ‘1 I
0-030-I i
I “ ° “
ll 0
:> “ co I5
(00204 11.11,,“
1‘ PM!
1 ‘fll I
1I ' I
0.010J 1 21111
I IV” ‘ ‘
o-mo‘LV"—'.—I4»iflfi‘> ‘7l ‘ ‘ ‘ I ' ‘ |,_., """ | V W—V" ’ ' ' l—H—‘—1
2.00 4.00 6.00 8.00 911912: 12.00 14.00 16.00 16.00 20.00

214

Sample Name New Bic D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(minL
l PDA MaxPlot (250nm-550nm) 1.172 428371 19.70 29372
2 PDA MaxPlot (250nm-550nm 1.748 163091 7.50 13234
3 PDA MaxPlot (250nm-550nm) 2.212 23031 1.06 3629
4 PDA MaxPlot (250nm-550nm) 2.335 68283 3.14 8679
5 PDA MaxPlot QSOnm-SSOnm) 2.780 196164 9.02 16963
6 PDA MaxPlot (250nm-550nm 3.652 647928 29.80 43722
7 PDA MaxPlot (250nm-550nm) 4.995 647286 29.77 31824
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Aflle Threshold

1 1.172 New Bic-1 4.751 1.202
2 1.748 New Bic-2 1.190 1.124
3 2.212
4 2.335
5 2.780
6 3.652 New Bic-4 0.844 1.252
7 4.995 New Bic-5 1.773 1.324

 

215

 

 

APPENDIX H.2

HPLC Reports for Blue Ball Point Inks That Were Run Against Only Their
Counterparts in a Library

Sample Run 2

216

Figure 77: HPLC report for ink sample Staedtler B384D (own library)

SampleName Staettler 83840
Injection Volume 10.00 ul
Run Tlme 20.00 “nutes

Sample Set Name marilyn 11703

Processed Channel Descr. PDA Maxle
(250.0 nm to 550.0 nm)

Date Acquired 1/1 712003 9:13:25 PM
Acq Method Set inkrev2 method set
Processing Method Marilyn library 2103

Channel Name MaxPlot250_550

 

F008
I.

 

 

 

MM”

f‘Y—Wfi—Yfifi—V—Y—fi—T—T—Y‘Y‘T—‘YT‘F‘Y—Yfi—I/
2.00 4.00 6.“) 8.00 10.“) 12.00 14.00 16.00 18.00 20.00

AU

' 0.04

F 0.02

 

I— 0.00

 

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0.02;; I
: . p
0920—: '1” b.
1 g ‘-
30.015: .—' g
( - OI 0.
: h N
0.010— "- F ‘
: I 1,- N g m. 2
o.ooo—:_~' ‘ ‘ ' -

217

. 1 1 I 1 1 . I 1 . 1 I . . 1 I 1 1 . I . . 1 I 1 . 1
8.00 0. 1 . 1 . . . .
“n& 200 400 16m 1800 2000

Sample Name Staedtler B384D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.176 84794 6.13 6772
2 PDA MaxPlot (250nm-550nm) 1.423 149196 10.78 12421
3 PDA MaxPlot (250nm-550nm) 1.787 82627 5.97 4018
4 PDA MaxPlot (250nm-550nm) 2.514 36908 2.67 3422
5 PDA MaxPlot (250nm-550nm) 2.698 87798 6.34 8783
6 PDA MaxPlot QSOnm-SSOnm) 3.524 356502 25.76 25487
7 PDA MaxPlot (250nm-550nm) 4.359 18803 1.36 1355
8 PDA MaxPlot QSOnm-SSOnml 4.777 463155 33.46 23895
9 PDA MaxPlot (250nm-550nm) 5.593 54418 3.93 2580
10 PDA MaxPlot (250nm-550nm) 7.737 49882 3.60 2519
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angle Threshold

1 1.176 Staettler 3384-] 9.989 1.324
2 1.423 Staettler B384-2 4.225 1.330
3 1.787 Staettler B384-3 4.566 1.896
4 2.514
5 2.698 Staettler B384-5 6.830 1.659
6 3.524 Staettler B384-6 1.715 1.229
7 4.359
8 4.777
9 5.593 Staettler B384-8 3.803 2.190
10 7.737

 

218

 

Figure 78: HPLC report for ink sample Bic B388D (own library)

SampleName Bic 83880
Injection Volume 10.00 ul
Run Time 20.00 Minutes

Sample Set Name marilyn 11703

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

Date Acquired 1/17/2003 9:55:49 PM
Acq Method Set inkrev2 method set
Processing Method Marilyn library 2103

Channel Name MaxPlot250_550

 

 

 

 

I—"r—* er ,
1‘ Inc
I 0.15
I I
1 1 I)
l 1 I 010 “
I - 1
1' E005
‘ 1 .i 0.00
I A 7f" 50000
’iérwfir v ,,,r,,, 'A—a—I—F" 7;va -rv~~—~~ 4-I74— i773 - ~- ~- ~ 'vfigfi—r—Q’
200 4.00 600 800 10.00 12.00 14.00 1600 18.00 20 oo
Mnutes
AutoScaled Chromatogram
oesoi :4:
. ‘1'.
‘ ‘1'17 ‘-
30.020— 1 8
< - I1 T
. 1 I
IN '
. I ~ 0
0.010— ‘ '53 8 V,
‘ 1 I.—' In. <0
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00001 «I ,,

 

219

1 1 I I . . 1 l 1 . 1 I 1 1 . . . I 1 I 1 I I 1 1 l
8.00 0.00 12.00 14.00 16.00 18.00 20.00
nutes

Sample Name Bic B388D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.117 410689 31.11 36415
2 PDA MaxPlot (250nm-550nm) 1.471 487187 36.90 32523
3 PDA MaxPlot (250nm-550nm) 1.862 45310 3.43 4383
4 PDA MaxPlot (250nm-550nm) 2.530 27470 2.08 2348
5 PDA MaxPlot (250nm-550nm) 3.404 62555 4.74 4776
6 PDA MaxPlot (250nm-550nm) 4.661 286934 21.74 15171
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Alfie Threshold Name Angle Threshold

1 1.117 Bic B388-l 6.390 1.080
2 1.471 Bic B388-3 4.730 1.091
3 1.862
4 2.530 Bic B388-5 7.737 2.789
5 3.404 Bic B388-6 1.313 2.061
6 4.661

 

220

 

Figure 79: HPLC report for ink sample Fisher BSOD (own library)

SampleName Fisher 8500 Date Acquired 1/17/2003 10:59:25 PM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marily n library 2103
Sample Set Name marilyn 11703 Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

 

AU

I I

,,,«

500,00

 

I
I
7' ‘r—r-‘r—Y' -1—fiI¥ v 77 w y afar fi—vw 1 ~« 1 ,. r'w- rh‘LJAV—r x _,_.;,+ .—~<IH‘
2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00
Mnutes

Auto-Scaled Chromatog ram

 

0.015«_ I
‘ 8
V’.
"% 2
0.010— 1?- t
‘ ‘1 (0 In
D I I 0
< II n 1 N.
. ‘ a I: V
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4 I I I I ‘ 1
0.00m:

 

 

 

I 1 I I - I I 1 . 1 1 I I 1 1 1 1 . I I 1 . I I I . 1
2.00 4.00 6.00 8.00 “0.00 12.00 14.00 16.00 18.00 20.00
nutes

Sample Name Fisher 350D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.183 196708 35.19 14572
2 PDA MaxPlot (250nm-550nm) 1.503 133772 23.93 12215
3 PDA MaxPlot (250nm-550nm) 2.643 33519 6.00 3183
4 PDA MaxPlot (250nm-550nm) 3.479 104058 18.62 7172
5 PDA MaxPlot QSOnm-SSOnm) 4.765 90881 16.26 4841
PDA Result Table
Name RT Purity l Purity 1 Match 1 Spect. Match 1 Match 1
Alfie Threshold Name Aggie Threshold

1 1.183 Fisher BSO-l 1.844 1.139
2 1.503 Fisher B50-2 0.950 1.072
3 2.643 Fisher BSD-3 8.136 2.317
4 3.479 Fisher 850-4 0.832 1.573
5 4.765

 

222

 

Figure 80: HPLC report for ink sample Mitsubishi B395D (own library)

SampleName Mitsubishi B3950
Injection Volume 10.00 ul
Run Time 20.00 Minutes

Sample Set Name marilyn 11703

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

Date Acquired 1/18/2003 1:27:49 AM
Acq Method Set inkrev2 method set
Processing Method Marilyn library 2103

Channel Name MaxPlot250_550

 

6.00 10.00 12.00
Mnutea

600

4.00

AU

I”

14.00 16.00 18.00 20100

Autoscaled Chromatog ram

 

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223

 

_ —16.757

 

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12.00 14.00 16.00 18.00 20.00

Sample Name Mitsubishi B395D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.200 649939 21.33 67929
2 PDA MaxPlot (250nm-550nm) 1.426 149438 4.90 26159
3 PDA MaxPlot (250nm-550nm) 1.539 187495 6.15 17756
4 PDA MaxPlot (250nm-550nm) 1.799 124620 4.09 9432
5 PDA MaxPlot (250nm-550nm) 2.053 39185 1.29 5035
6 PDA MaxPlot (250nm-550nm) 2.251 92729 3.04 7383
7 PDA MaxPlot (250nm-550nm) 2.518 60956 2.00 5940
8 PDA MaxPlot (250nm-550nm) 2.696 87300 2.86 7686
9 PDA MaxPlot (250nm-550nm) 3.101 60233 1.98 4262
10 PDA MaxPlot (250nm-550nm) 3.523 200338 6.57 13053
11 PDA MaxPlot (250nm-550nm) 4.374 32902 1.08 191 l
12 PDA MaxPlot (250nm-550nm) 4.644 118270 3.88 11411
13 PDA MaxPlot (250nm—550nm) 4.807 132572 4.35 7440
14 PDA MaxPlot (250nm-550nm) 5.633 44531 1.46 2267
15 PDA MaxPlot (250nm-550nm) 7.865 315483 10.35 11010
16 PDA MaxPlot (250nm-550nm) 9.411 27096 0.89 1263
17 PDA MaxPlot (250nm-550nm) 11.011 676972 22.22 16633
18 PDA MaxPlot (250nm-550nm) 16.757 47216 1.55 1469
PDA Result Table
Name RT Purity Purity 1 Match 1 Spect. Match 1 Match 1
1 Threshold Name Angle Threshold
Angle

1 1.200 Mitsubishi B395-l 2.928 3.3 88
2 1.426 Mitsubishi B395-2 6.281 6.222
3 1.539
4 1.799 Mitsubishi 8395-3 7.083 8.091
5 2.053 Mitsubishi 8395-1 9.317 9.180
6 2.251 Mitsubishi B395-3 9.995 7.801
7 2.518
8 2.696
9 3.101 Mitsubishi B395-3 8.618 10.005
10 3.523
11 4.374
12 4.644 Mitsubishi B395-4 2.803 5.311
13 4.807
14 5.633
15 7.865
16 9.411
17 11.011
18 16.757

 

224

 

 

Figure 81: HPLC report for ink sample Parker Bl76D (own library)

SampleName Parker 81760 Date Acquired 1/18/2003 3:56:16 AM

Injection Volume 10.00 ul Acq Method Set inkrev2 method set

Run Time 20.00 Minutes Processing Method Man'Iy n library 2103

Sample Set Name marilyn 11703 Channel Name MaxPlot250__550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

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Sample Name Parker Bl76D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.192 279003 13.20 20140
2 PDA MaxPlofiZSOnm-SSOnm) 1.544 433846 20.52 25406
3 PDA MaxPlot (250nm-550nm) 1.757 132631 6.27 12023
4 PDA MaxPlot (250nm-550nm) 2.233 46426 2.20 4010
5 PDA MaxPlot (250nm-550nm) 2.524 51119 2.42 5657
6 PDA MaxPlot QSOnm-SSOnm) 2.658 131991 6.24 13841
7 PDA MaxPlot (250nm-550nm) 3.236 84894 4.02 7251
8 PDA MaxPlot (250nm-550nm) 3.525 163404 7.73 10786
9 PDA MaxPlot (250nm-550nm) 4.376 22068 1.04 1220
10 PDA MaxPlot (250nm-550nrm 4.801 171581 8.12 9098
11 PDA MaxPlot (250nm-550nm) 7.147 354430 16.76 17969
12 PDA MaxPlot (250nm-550nm) 7.391 242926 11.49 13463
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Aug Threshold Name Angle Threshold

1 1.192 Parker Bl76-1 6.865 1.321
2 1.544 Parker 8176-2 8.502 1.434
3 1.757 Parker 8176-3 8.115 1.793
4 2.233 Parker 8176-4 4.454 2.754
5 2.524 Parker 8176-5 4.342 2.972
6 2.658 Parker 8176-6 2.201 1.428
7 3.236 Parker B176-7 2.326 2.762
8 3.525 Parker Bl76-8 4.120 2.424
9 4.376
10 4.801 Parker 3176-9 5.112 2.633
11 7.147 Parker B176-10 0.830 1.519
12 7.391

 

226

 

 

Figure 82: HPLC report for ink sample Tombo BS35D (own library)

SampleName Tombo 35350
Injection Volume 10.00 ul
Run Time 2000 Minutes

Sample Set Name marilyn 11703

Date Acquired 1/18/2003 2:10:14 AM
Acq Method Set inkrev2 method set
Processing Method Marilyn library 2103

Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot

(250.0 nm to 550.0 nm)

 

 

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227

Sample Name Tombo BS35D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.188 83179 25.80 7765
2 PDA MaxPlot (250nm-550nm) 1.431 52016 16.13 6099
3 PDA MaxPlot (250nm-550nm) 1.863 25488 7.91 3355
4 PDA MaxPlot (250nm-550nm) 2.569 27121 8.41 2650
5 PDA MaxPlot (250nm-550nm) 3.400 55410 17.19 3958
6 PDA MaxPlot (250nm-550nm) 4.694 41071 12.74 2344
7 PDA MaxPlot (250nm-550nm) 5.480 38114 11.82 2139
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Angle Threshold
1 1.188 Tombo 8535-1 1.283 1.286
2 1.431 Tombo 8535-2 0.500 1.288
3 1.863
4 2.569 Tombo 8535-3 8.908 3.571
5 3.400 Tombo 8535-4 3.929 2.651
6 4.694 Tombo 8535-5 5.776 3.842
7 5.480

 

228

 

 

APPENDIX H.3

HPLC Reports for Blue Ball Point Inks That Were Run Against Only Their
Counterparts in a Library

Sample Run 3

229

Figure 83: HPLC report for ink sample Papermate B68D

SampleName Papermate 8680 Date Acquired 1/19/2003 6:49:53 PM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name marilyn 11903 Channel Name MaxPlot250_550

Processed-Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

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230

Sample Name Papermate B68D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.231 208327 10.98 13409
2 PDA MaxPlot (250nm-550nm) 1.529 375218 19.78 36998
3 PDA MaxPlot (250nm-550nm) 1.870 72332 3.81 5519
4 PDA MaxPlot (250nm-550nm) 2.028 49920 2.63 3793
5 PDA MaxPlot (250nm-550nm) 2.476 64856 3.42 7553
6 PDA MaxPlot (250nm-550nm) 2.609 44550 2.35 5639
7 PDA MaxPlot (250nm-550nm) 3.374 279426 14.73 20739
8 PDA MaxPlot (250nm-550nm) 4.538 38464] 20.28 20485
9 PDA MaxPlot (250nm-550nm) 5.241 54236 2.86 2576
10 PDA MaxPlot (250nm-550nm) 6.512 35392 1.87 616
11 PDA MaxPlot (250nm-550nm) 10.968 327674 17.28 9284
PDA Result Table
Name RT Purity Purity 1 Match 1 Spect. Match 1 Match 1
1 Threshold Name Angle Threshold
Angle

1 1.231
2 1.529 Papermate B68-2 3.95] 8.519
3 1.870
4 2.028
5 2.476
6 2.609
7 3.374 Papermate B68-7 7.816 25.703
8 4.538
9 5.241
10 6.512
11 10.968

 

231

 

Figure 84: HPLC report for ink sample Pilot BlO3D (2"‘1 run, own library)

SampleName Pilot 81030 Date Acquired 1/19/2003 9:18:17 PM

Injection Volume 10.00 ul Acq Method Set inkrev2 method set

Run Time 20.00 Minutes Processing Method Marilyn library 2103

Sample Set Name marilyn 11903 Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

0.040

 

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232

Sample Name Pilot B1030

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.129 147918 18.14 11291
2 PDA MaxPlot (250nm-550nm) 1.444 145228 17.81 13093
3 PDA MaxPlot (250nm-550nm) 1.809 33125 4.06 2496
4 PDA MaxPlot (250nm-550nm) 2.022 25226 3.09 1758
5 PDA MaxPlot (250nm-550rm 2.579 84761 10.40 5556
6 PDA MaxPlot (250nm-550nm) 3.342 144555 17.73 10024
7 PDA MaxPlot (250nm-550nm) 4.510 105909 12.99 6226
8 PDA MaxPlot (250nm-550nm) 10.963 128521 15.76 3858
PDA Result Table
Name RT Purity Purity 1 Match 1 Spect. Match 1 Match 1
1 Threshold Name Angle Threshold
Angle
1 1.129
2 1.444
3 1.809
4 2.022
5 2.579
6 3.342
7 4.510
8 10.963

 

233

 

Figure 85: HPLC report for ink sample Fisher B65D (own library)

SampleName Fisher 8650 Date Acquired 1/19/2003 6:07:29 PM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Mnutes Processing Method Marilyn library 2103

Sample Set Name marilyn 11903 Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

 

 

 

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nutes

234

Sample Name Fisher B65D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.199 145522 10.75 10224
2 PDA MaxPlot (ZSOnm-SSOnm) 1.559 375771 27.76 22000
3 PDA MaxPlot (250nm-550nm) 2.074 31508 2.33 2091
4 PDA MaxPlot (250nm-550nm) 2.511 19000 1.40 2301
5 PDA MaxPlot QSOnm-SSOnm) 2.658 42557 3.14 4286
6 PDA MaxPlot (250nm-550nm) 3.447 244771 18.08 17468
7 PDA MaxPlot (250nm-550nm) 4.607 348524 25.75 19485
a PDA MaxPlot (250nm-550nm) 11.000 126719 9.36 3430
9 PDA MaxPlot (ZSOnm-SSOnm) 12.267 19335 1.43 330
PDA Result Table
Name RT Purity Purity 1 Match 1 Spect. Match 1 Match 1
1 Threshold Name Angle Threshold
Angle

1 1.199 Fisher 65-1 3.973 10.182
2 1.559 Fisher 65-2 2.664 7.676
3 2.074
4 2.511
5 2.658
6 3.447 Fisher 65-6 4.263 12.280
7 4.607 Fisher 65-7 6.454 14.078
8 11.000
9 12.267

 

235

 

Figure 86: HPLC report for ink sample Fisher B77D (own library)

SampleName Fisher 8770
Injection Volume 10.00 at

Run Time 20.00 Minutes

Sample Set Name marilyn 11903

Date Acquired 1/20/2003 12:50:22 AM
Acq Method Set inkrev2 method set
Processing Method Marilyn library 2103

Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot

(250.0 nm to 550.0 nm)

 

 

 

 

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236

Sample Name Fisher B77D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.171 206145 9.63 14843
2 PDA MaxPlot (250nm-550nm) 1.525 556938 26.02 34595
3 PDA MaxPlot (250nm-550nm) 2.049 41924 1.96 2863
4 PDA MaxPlot (250nm-550nm) 2.578 97976 4.58 7955
5 PDA MaxPlot (250nm-550nm) 3.324 405089 18.92 29548
6 PDA MaxPlot (250nm-550nm) 4.449 621606 29.04 31789
7 PDA MaxPlot (250nm-550nm) 10.868 211009 9.86 6169
PDA Result Table
Name RT Purity Purity 1 Match 1 Spect. Match 1 Match 1
1 Threshold Name Angle Threshold
Angle

1 1.171 Fisher B77-l 4.063 9.483
2 1.525 Fisher B77-2 3.634 8.161
3 2.049
4 2.578
5 3.324 Fisher B77-5 4.854 12.056
6 4.449 Fisher B77-6 5.990 14.129
7 10.868

 

237

 

 

APPENDIX I

238

APPENDIX 1

HPLC Reports for Black Ball Point Inks That Were Run Against Only Their
Counterparts in a Library

239

APPENDIX 1.1

HPLC Reports for Black Ball Point Inks That Were Run Against Only Their
Counterparts in a Library

Sample Run 2

240

Figure 87: HPLC report for ink sample Dupont Bl 13D (own library)

SampleName Dupont B1130
Injection Volume 10.00 111
Run Time 20.00 Minutes

Sample Set Name man'lyn 11703

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

Date Acquired 1/18/2003 12:24:13 AM
Acq Method Set inkrev2 method set
Processing Method Marilyn library 2103

Channel Name MaxPlot250_550

 

 

AU

 

8.00 10.00 12.00 14.00 16.00 1800 2000
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8.00 “000 12.00 14.00 16 00 16 00 20.00
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Sample Name Dupont 113D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.093 245392 17.50 20568
2 PDA MaxPlotLZSOnm-SSOnm) 1.444 292630 20.87 19792
3 PDA MaxPlot (250nm-550nm) 1.814 114477 8.17 12124
4 PDA MaxPlot (250nm-550nm) 2.530 25106 1.79 3123
5 PDA MaxPlot (250nm-550nm) 2.678 29771 2.12 3563
6 PDA MaxPlot (250nm-550nm) 3.504 245604 17.52 17247
7 PDA MaxPlotQSOnm-SSOnm) 4.755 420049 29.96 21525
8 PDA MaxPlot (250nm-550nm) 15.535 28919 2.06 926
PDA Result Table
Name RT Purity Purity 1 Match 1 Spect. Match 1 Match 1
1 Threshold Name Angle Threshold
Angle
1 1.093 Dupont Bl 13-1 1.575 1.155
2 1.444 Dupont Bl 13-2 0.613 1.163
3 1.814 Dupont Bl 13-3 7.306 1.465
4 2.530 Dupont Bl 13-4 7.095 3.225
5 2.678 Dupont Bl 13-5 5.870 2.769
6 3.504 Dupont Bl 13-6 0.360 1.395
7 4.755 Dupont Bl 13-7 1.670 1.297
8 15.535 Dupont Bl 13-8 4.877 6.942

 

242

 

Figure 88: HPLC report for ink sample Eversharp 657

SampleName Ev ersharp 657 Date Acquired 1/18/2003 5:21:05 AM
Injection Volume 10.00 ul Acq Method Set inkrev2 method set
Run Time 20.00 Minutes Processing Method Marilyn library 2103
Sample Set Name marilyn 11703 Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

l
l
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2.00 400 600 8.00 10.00 1200 14,00 16 00 1800 20.00
Mnutes

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< or
0.0157 '3.
I '— N I
a ‘ “l :2 8. I
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.00 4.00 6.00 8.00 IIx000 12 00 14 00 16.00 18.00 2000
nutes

243

Sample Name Eversharp 657

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.216 154977 28.05 20152
2 PDA MaxPlot (250nm-550nm) 1.437 69934 12.66 12154
3 PDA MaxPlot (250nm-550nm) 1.674 23002 4.16 2811
4 PDA MaxPlot (250nm-550nm) 2.775 88678 16.05 6796
5 PDA MaxPlot (250nm-550nm) 3.534 56970 10.31 3935
6 PDA MaxPlot (250nm-550nm) 4.802 158858 28.76 8222
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
Agle Threshold Name Angle Threshold

1 1.216 Eversharp 657-1 7.499 1.180
2 1.437 Eversharp 657-2 1.015 1.176
3 1.674
4 2.775 Eversharp 657-3 8.421 2.752
5 3.534 Eversharp 657-4 2.046 2.529
6 4.802 Eversharp 657-5 0.620 1.687

 

 

244

 

 

SampleName Fisher B111D
Injection Volume 10.00 ul
Run Time 20.00 Minutes

Sample Set Name marilyn 11703

Figure 89: HPLC report for ink sample Fisher B11 10 (own library)

Date Acquired 1/17/2003 11:41:49 PM
Acq Method Set inkrev2 method set
Processing Method Marilyn library 2103

Channel Name MaxP101250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

 

&- 0.050

i— 0.040

570.010

,1 0.000

400 6,00 6.00 10.00 12.00 14.00 16.00 18.00 20.00
nutes

Autoécaled Chromatogram

 

 

 

 

 

245

Sample Name Fisher B111D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Time Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.129 95159 20.00 7272
2 PDA MaxPlot (250nm-550nmL 1.432 94941 19.96 14284
3 FDA MaxPlot (250nm-550nm) 1.597 86408 18.16 12448
4 PDA MaxPlot (250nm-550nm) 1.825 70535 14.83 6490
s PDA MaxPlot (250nm-550nm) 2.533 20793 4.37 2518
6 PDA MaxPlot QSOnm-SSOnm) 3.190 34877 7.33 2833
7 PDA MaxPlot (250nm-550nm) 3.862 18140 3.81 1359
8 PDA MaxP10t(250nm-550nm) 6.474 54917 11.54 2733
PDA Result Table
Name RT Purity l Purity 1 Match 1 Spect. Match 1 Match 1
Angle Threshold Name Angle Threshold

1 1.129 Fisher Bl 1 1-1 4.729 1.506
2 1.432 Fisher Bl 1 1-2 4.756 1.221
3 1.597 Fisher Bl 1 1-3 6.968 1.654
4 1.825 Fisher Bl 11-4 4.735 1.702
5 2.533
6 3.190
7 3.862
8 6.474

 

246

 

 

Figure 90: HPLC report for ink sample Pilot Bl 15D (own library)

SampleName Pilot B1150
Injection Volume 10.00 ul
Run Time 20.00 Minutes

Sample Set Name marilyn 11703

Date Acquired 1/18/2003 4:38:41 AM
Acq Method Set inkrev2 method set
Processing Method Marilyn library 2103

Channel Name MaxPlot250_550

Processed Channel Descr. PDA MaxPlot
(250.0 nm to 550.0 nm)

 

 

 

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8

7. 77.7. .7. 7 , .fi_7777 ,7 7Y ,7

2.00 4.00 6.00 8.00 10.00 1200 14.00 16.00 1800 000
Mnutea

Auto-Scaled Chromatogram

 

+— 4.805

 

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8.00 0.00 12.00 14.00 16f00 18.00 20.00

247

Sample Name Pilot B115D

Processed Channel: PDA MaxPlot (250.0 nm to 550.0 nm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Processed Channel Retention Tlme Area % Area Height
(min)
1 PDA MaxPlot (250nm-550nm) 1.182 491082 36.00 62020
2 PDA MaxPlot (250nm-550nm) 1.437 7913] 5.80 8951
3 PDA MaxPlot (250nm-550nm) 1.834 53327 3.91 4632
4 PDA MaxPlot (250nm-550nm) 2.170 43203 3.17 3489
5 PDA MaxPlot (250nm-550nm) 2.705 148292 10.87 11655
6 PDA MaxPlot (250nm-550nm) 3.535 276129 20.24 18809
7 PDA MuPMZSOnm-SSOm) 4.805 272802 20.00 13914
PDA Result Table
Name RT Purity 1 Purity 1 Match 1 Spect. Match 1 Match 1
A318 Threshold Name Angle Threshold
1 1.182 Pilot Bl 15-1 1.737 1.057
2 1.437 Pilot B 1 15-2 1.224 1.208
3 1.834 Pilot Bl 15-3 4.98] 1.647
4 2.170 Pilot 8115—4 2.293 2.473
5 2.705 Pilot Bl 15-5 1.052 1.478
6 3.535 Pilot Bl 15-6 0.576 1.286
7 4.805 Pilot Bl 15-7 2.920 1.353

 

248

 

 

10.

11.

List of References

Brunelle, Richard L. and Reed, Robert W., Forensic Examination of Ink and
Paper, Charles C. Thomas: Springfield, Illinois, 1984.

Brown, Charlotte and Kirk, Paul L., “Horizontal Paper Chromatography In the
Identification of Ball Point Pen Inks”, Journal of Criminal Law, Criminology,
and Police Science, v. 45, May 1954-April 1955 pp. 334-339.

Brunelle, Richard L. and Pro, Maynard J ., “A Systematic Approach to Ink
Identifcation,” Journal of the AOA C, v. 55, No. 4, 1972, pp.823-826.

Tebbett, I.R., “Chromatographic Analysis of Inks for Forensic Science
Applications”, Forensic Science Review, v. 3, No. 2, December 1991, pp.72-82.

Cantu, Antonio A. and Kelly, Jerry D., “Proposed Standard Methods for Ink
Identification,” Journal of the AOAC, v. 58, No. 1, 1975, pp. 122-125.

Colwell, Lawrence F. and Karger, Barry L., “Ball-Point Pen Ink Examination by
High Pressure Liquid Chromatography,” Journal of the AOA C, v. 60, No. 3, 1977,
pp. 613-618.

Lyter, Albert H. 111, Analysis of Writing Inks by High Performance Liquid
Chromatography,” in High Performance Liquid Chromatography in Forensic
Chemisg, Lurie, Ira S. and Wittwer, John D. (Eds), Marcel Decker: New York,
NY, pp. 399-418, 1983.

Lyter, A.H., III, “Examination of Ball Pen Ink by High Pressure Liquid

Chromatography,” Journal of Forensic Sciences, v. 27, No. 1, Jan. 1982, pp. 154-
160.

Andrasko, J ., “HPLC Analysis of Ballpoint Pen Inks Stored at Different Light
Conditions,” Journal of Forensic Sciences, v. 46, No. l, 2001, pp. 21-30.

Andrasko, J ., “Changes in Composition of Ballpoint Pen Inks on Aging in
Darkness,” Journal of Forensic Sciences, v. 47, No. 2, 2001 , pp. 324-327.

Zlotnick, J. A., Smith, F. P., “Chromatographic and Electrophoretic Approaches
in Ink Analysis”, Journal of Chromatography B, v. 733, 1999, pp. 265-272.

249

12.

13.

14.

Brunelle, Richard L. and Crawford, Kenneth R., Advances in the Foren§i_c
fllvsis and Dating of Writing Ink, Charles C. Thomas: Springfield, IL, 2003.

Vogt, C., Becker, A., Vogt, 1., “Investigation of Ball Point Pen Inks by Capillary
Electrophoresis (CE) with UVN is Absorbance and Laser Induced Fluorescence
Detection and Particle Induced X-Ray Emission (PIXE)”, Journal of Forensic
Sciences, v. 44, No. 4, 1999, pp. 819-831.

Sakayanagi, M., Komuro, J ., Konda, Y., Watanabe, K., Harigaya, Y., “Analysis of

Ballpoint Pen Inks by Field Desorption Mass Spectrometry”, Journal of Forensic
Sciences, v. 44, No. 6, 1999, pp. 1204-1214.

250

 

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