Gas chromatography-mass spectrometry GC-MS , being a well proven analytical method of determining the qualitative composition of multi-component systems, is effective for the analysis of inks, most of which are complex mixtures of chemical compounds. A combination of thin-layer chromatography TLC , which analyzes ink colored components, and GC-MS, which analyzes ink noncolored components, demonstrates high discriminating power with regard to writing inks that can be distinguished neither by nondestructive techniques nor by TLC. Case examples are considered in which coupling of TLC and GC-MS allowed one to discriminate between ink indistinguishable by TLC and to determine that the inks on questioned documents came from the same manufacturing batch. Introduction Writing inks are multi-component mixtures of various organic substances such as dyes, solvents, resins, modifiers, lubricants, thickeners, antiseptics, surfactants, and byproducts , most of which can be separated and characterized by chromatographic techniques. Chromatography was discovered in when a Russian botanist and biochemist, Michael S. Tswett, separated pigments from chlorophyll using self-made chromatographic columns packed with various adsorbents.
Chromatography was discovered in when a Russian botanist and biochemist, Michael S. Tswett, separated pigments from chlorophyll using self-made chromatographic columns packed with various adsorbents.
This fundamental discovery marked a milestone in the development of chromatographic separation techniques that led to Nobel prizes in chemistry. Today, chromatography has become the main analytical method in the pharmaceutical industry, food analysis, petrochemical analysis e.
Thinlayer chromatography TLC and gas chromatography-mass spectrometry GC-MS are 2 chromatographic methods that are most widely used in analytical and forensic science laboratories all over the world. There are numerous publications describing various procedures for the TLC analysis of writing inks on documents.
TLC has been the principal analytical method employed by most laboratories in forensic ink analysis. The reason for this is that this method is comparatively simple, rapid, and cost efficient.
Also, for comparing inks, TLC allows the examiner to evaluate visually the qualitative and semi-quantitative composition of ink dye components separated on the TLC plate. Though TLC is an excellent method for discriminating between similarly colored inks that have been made using different dyes, the reported capabilities of this method for the identification of ink formula and for the determination of whether 2 or more entries were written with an ink of the same formula or batch are often over amplified.
For example, Brunelle and Crawford recently wrote: "To identify the manufacturer and specific formulation of questioned inks, you must compare standard inks of known manufacturer and formulation simultaneous with the questioned inks using the same procedures TLC and TLC densitometry While the above procedures are most commonly used and have withstood the test of the courts for the comparison and identification of inks, other methods may sometimes be helpful.
If an ink does not contain a unique component such as a date tag, then, as a rule, the results of the TLC analysis of an ink will not be sufficient for the reliable identification of the ink formulation or for determining that the compared entries were written with an ink of the same formulation. It is well known that ink dyes constitute only a part of ink composition.
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Thus, for ballpoint inks, colorants ink dyes never represent more than a quarter of the ink composition. Many of these substances can be analyzed by GC-MS, which is a well proven analytical method of determining the qualitative composition of multicomponent systems. One of the reasons for this may be that some ink chemists believe that after about 1 year of being placed on paper, ballpoint inks will no longer contain any ingredient that could be detected and identified by GC-MS.
Even very old ballpoint inks contain the residues of their volatile components phenoxyethanol or similar high boiling solvents in amounts sufficient for their GC-MS detection and identification Aginsky, ; Gaudreau and Luc Brazeau ; La Porte, Wilson, Cantu, Mancke, and Fortunato In other words, many ink noncolored components, which are either solids or high boiling viscous liquids, are vaporizable at high temperatures used in the injectors of gas chromatographs; therefore, these substances can be easily separated and characterized by GC-MS Aginsky Generally, the GC-MS analysis of noncolored ink components provides much more information on individualizing ballpoint ink composition than the TLC analysis of the ink's dye components.
First, this occurs because the number of noncolored ink components that can be separated and characterized identified by GC-MS is usually significantly greater than the number of colored ink components analyzed by TLC.
Methods and Materials. The Pilot inks used. Figure 1. The thin-layer chromatogram obtained for the 9 red ballpoint inks analyzed shows there are 2 groups of inks that the brand cannot be discriminated by TLC.
The amount of dye components in the analyzed inks varies from 1 orange dye in the Bic USA and Pilot, up to 5 dye components of orange, pink, yellow 2 dyesand brown minor component colors, in 3 Pilot inks manufactured in, and respectively. The Pen tel inks were manufactured in and The Zebra ink was manufactured in Sampling Devices Harris 0. The bored-out ink samples are removed with a plunger.
TLC Materials and Procedure The inks sampled from paper 2 to 4 micro plugs were extracted in chloroform 5 microlitersand the colored extracts were applied on the high performance HPJ TLC silica gel F 10 x 10 em precoated glass plates Merck, Germany. Results and Discussion In the thin-layer chromatogratn obtained for 9 red ballpoint inks Figure 1the eluting solvent was efficient and selective to completely separate all dye components present in the inks analyzed.
The amount of dye components in the analyzed inks varies from 1 orange dye in the Bic USA and Pilot, up to 5 dye components of orange, pink, yellow 2 dyesand brown minor component colors, in 3 Pilot inks manufactured in, an respectively. For example, the Pilot red ballpoint ink manufactured in contains only 1 dye, while each of the Pilot red ballpoint inks manufactured in, and contains a mixture of the same 5 dye components. Among the 9 inks analyzed, the brand of 2 groups of inks could not be discriminated by TLC.
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Given that, within each group, the inks contain the same dyes: 1 group comprises the Bic USA and Pilot inks that contain 1 and the same orange dye; and the other group includes the Pentel, Pentel, Bic Franceand Zebra inks that contain the same 2 dyes of orange and yellow colors. It is a well known fact that there is a small number of commercially available dyes that are often used by different ink manufacturers. For this reason, compared inks of different formulations that contain the same dyes may easily be misidentified as the inks of the same formulation.
In this connection, it becomes evident that when an examiner tries to determine whether 2 or more entries were written with the ink of the same formula or identify a questioned ink formulation and determine the year when this formulation first came into existencethe chemical analysis should not be restricted by the TLC analysis of ink colored components and fluorescing components.
GC-MS may establish that. Thus, all different ink formulations in the above mentioned 2 groups of the red ballpoint ink brands that could not be discriminated by TLC because the inks contain the same dyes were reliably differentiated by GC-MS. The Pilot and Pilot inks contain the same liquid components: the residue of benzyl alcohol and phenoxyethanol Figure 2.
However, the ink manufacturer used different solid components: the Pilot ink contains diphenoxyethane, and the Pilot ink contains N-butylbenzenesulfonamide. The difference in the qualitative composition of solid noncolored components of the inks indicates that probably different resins were used in the manufacturing of these 2 inks.
Comparing the results of the TLC and GCMS analyses of the Pilot and Pilot inks, one can conclude that these inks represent either 2 manufacturing batches of the same ink formulation or 2 different formulations in which the same dyes and solvents were used. Case Example 1 One of the key issues in a civil case was whether 2 documents dated in and were indeed signed in and or were these documents signed simultaneously and several years after The expert retained by the plaintiff compared the blue ballpoint inks on the questioned documents using TLC and came to a conclusion that the similarity of ink formulation used in the documents dated in and was an indication of simultaneous preparation of the documents.
This author, retained by the defendant, conducted the TLC and GC-MS analyses of the same blue ballpoint inks used to produce the signatures on the and documents. The TLC analysis showed similarity of the dye compositions in the inks. The GC-MS analysis, however, showed significant differences in the compositions of the inks' noncolored components Figure 3.
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The ink on the document contains only 1 solvent phenoxyethanolwhile the ink on the document contains 3 solvents: unidentified aliphatic alcohol component "C". Figure 2. Total ion chromatograms of the Pilot red ballpoint inks manufactured in upper chromatogram and lower chromatogra1n. Figure 3. Total ion chromatograms of the blue ballpoint inks used to produce the signatures on the and documents. The upper chromatogram is for the document showing A 1-isocyanatomethylbenzene and B 2-methylbenzeneamine.
The lower chromatogram is for the document showing C an unidentified aliphatic alcohol, D 2,4-dimethylbenzeneamine, and E 2,4-dimethylphenyl isocyanate. Figure 4. Total ion chromatograms of the blue ballpoint ink used to produce the "X" mark upper chromatogram and the remainder of the writing lower chromatogram on the questioned document. The GC-MS analysis showed that the compared inks have the same unique composition of noncolored components.
This evidence was used to show that the high priest added an entry to his diary. Unsuccessful Daubert Challenge in Illinois Court to accelerated aging, Ink Dating, and statistical analysis with well spelled out reasoning by judge.
Dr. Aginsky has developed the SET as a result of many years of research of the ink aging methodology developed and published by Dr. Antonio A. Cantu in the s. To date, the SET is the only ink aging method that has shown its reliability through outside proficiency testing using "blind" samples (outside proficiency tests in , , and ). Artificial aging of ink on documents, carried out to accelerate the processes, is known to be used for three main reasons: hiding a backdating fraud by making the document look older than it really is, studying the natural aging of ink by simulating different environmental conditions in a controlled way, dating an ink by provoking aging in order to calculate a small portion of aging curve. Ink dating is a highly specialized forensic examination and considered to be one of the most accurate and reliable methods to help determine the age of a document. Ink Dating and Ink Aging. An ink formulation can be identified to a specific manufacturer to ascertain the first date of commercial availability. If an entry is dated in , but.
Testimony was presented and accepted. Daubert challenge in Federal Court to Ink Dating and Accelerated Aging Evidence was admitted and formed a partial basis for summary judgment. Testimony was allowed and presented resulting in a defense verdict.
Speckin Forensics is retained by attorney Neil Namaroff to assist in the admission of Ink Dating testing and results by another expert in light of a Daubert challenge by the Government. The court denies Daubert objection by defendants.
Speckin Forensics is retained to assist attorney with a daubert challenge to ink dating methodology. The challenge was denied, the testimony was admitted and the case settled very quickly thereafter.
Erich Speckin testified and was accepted as an expert in ink dating and accelerating aging in Supreme Court in Vancouver British Columbia Canada. This was the first time that ink dating methodology to determine relative ink age was admitted into evidence in Canada.
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Mike Sinke of Speckin Forensic Laboratories testified and showed the LIP Print Identification was not reliable under frye and that the expert from the State Laboratory had missed differences that should have excluded the suspect. The court agreed with Mr. Post trial reversal was granted and the suspect was eventually released from prison.
Forgery and forged documents: methods, types. Signature forgery and its examination
Another expert testified against their findings. The judge agreed with the Speckin Forensic Laboratories examiners and ruled in favor of our client. Johnston, December Robert Kullman testifies successfully in what is probably the first Daubert hearing on Handwriting Analysis in the State of Michigan. Bob first testified and was excepted as an expert in Handwriting Analysis.
After passing the Daubert challenge, he testified to his opinion of authorship of the signatures to the jury.
If you are a lawyer and need consulting in the area of forensics, contact us for a quote. Speckin Erich J. Speckin Richard L. Brunelle Roger J. Kullman Michael Sinke Dr.
Thomas K. Huard Ph. Jay A. Siegel Ph. Laurence Robert Simson, Jr. Robert Cilwa Dr. Julie Howenstine George F. Jackson Ph. Smith Terrell Nadeau Anthony Milone.
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Court Opinions. James P. Gierczyk VS Paul D. Oselka A lawsuit involving allegations of forgery and whether a party had signed a release. Unsuccessful opposing expert: Dr.
Aginsky added that 'Both techniques (i.e., named here as methods 1 and 2) described have been used numerously in actual cases involving tax evasion, medical malpractice, altered wills, contractual disputes, rackets, corruption and organized crime, and many times the conclusions stated on the basis of the results of the ink dating examinations (accepted as conclusive by the courts of law in Russia) directly Cited by: Forensic Chemist / Ink and Document Dating Specialist Aginsky Forensic Document Dating Laboratory, Inc. East Lansing, Michigan Ph.D. Analytical Chemistry - Military Academy of Chemical Defense (formerly known as the Chemical Faculty ofthe Institute of Mechanical Engineering prior to ), Moscow, USSR M.S. Analytical Chemistry - Some of the actual cases in which Aginsky Forensic Document Dating Laboratory has provided expert services included the following types of examinations: Dating of documents Dating of ink on documents (see Ink Dating).
Warner Bros. Entertainment, Inc.
Stephen Slessinger vs. The Walt Disney Corp.
Using TLC and GC-MS to Determine Whether Inks Came from the Same Manufacturing Batch Valery N Aginsky Forensic Ink Chemist and Document Dating Specialist, Riley, Welch & Aginsky . The ink dating of a document was at issue in the patent case in Texas. The ink dating tests showed the documents to be genuine. After a deposition, the Judge ruled the testimony by Erich Speckin and results we admissible. The case settled before a trial testimony was . Aginsky, Dating ink extractability as a function of age-why the relative References aging approach is unreliable and why it is more correct to measure ink volatile components dating dyes, International Journal of Forensic Document Examiners 4 3 -.
Irish Carbonic Company vs. Archer - Daniels - Midland Company Et. Jose Hiquera M. Soka Trial Court in Tokyo Japan accepts evidence from Erich Speckin involving sequence of writing and ink lines with convexities.