* INK: In the hundreds of pages of handwritten exemplars taken from Dr. Bruce Ivins’ home and office, FBI Laboratory Experts determined that there was not a single exemplar written by him in which the distinctive “fluid-like” ink used on the envelope was a match. FBI should produce the laboratory reports to GAO on the ink used in the first mailing (and the different ink used in the second mailing) without further delay.
Posted by DXer on March 8, 2012
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DXer said
The FBI consultant published this article using on stable isotope analysis on ink. The FBI should disclose all documents relating to the ink used.
The potential for application of ink stable isotope analysis in questioned document examination
Lesley A. Chesson, Brett J. Tipple, Janet E. Barnette, Thure E. Cerling, James R. Ehleringer
Received: December 20, 2013; Received in revised form: May 21, 2014; Accepted: May 28, 2014; Published Online: June 16, 2014
DOI: http://dx.doi.org/10.1016/j.scijus.2014.05.010
Publication stage: In Press Corrected Proof
Abstract
Full Text
Images
References
Highlights
•We investigated application of stable isotope analysis to characterize pen ink.
•Inks were analyzed “as is” and following application to paper.
•There was isotope ratio variation among inks of different ages, types, and brands.
•Paper inked with different pens could be distinguished using stable isotope ratios.
•With reductions in sample size, technique could be useful in document examination.
Abstract
We investigated a novel application of stable isotope abundance analysis of nitrogen (15N), carbon (13C), hydrogen (2H), and oxygen (18O) to characterize pen ink. We focused on both ballpoint and gel pen inks. We found that the isotope ratios of ink from pens purchased together in a package were similar and within-package stable isotope ratio variability was not significantly larger than the variability of isotope reference materials used during analysis. In contrast, the isotope ratios of ink from pens of the same brand purchased in three states of the continental USA were significantly different from each other and there was isotope ratio variation among pens of the same brand but different, unknown production periods. The stable isotope ratios of inked paper were statistically distinguishable using measured δ15N values. Paper inked with different gel pens was statistically distinguishable using measured δ2H values. The capacity of stable isotope ratios to differentiate among ballpoint inks as well as gel inks shows that stable isotope analysis may be a useful and quantifiable investigative technique for questioned document examination, although current sample size requirements limit its utility. Application of the technique in casework will require the development of micro-scale sampling and analysis methods.
DXer said
ASTM E1422-05
Withdrawn Standard: ASTM E1422-05 Standard Guide for Test Methods for Forensic Writing Ink Comparison (Withdrawn 2014)
WITHDRAWN, NO REPLACEMENT
Withdrawn Rationale:
This guide is intended to assist forensic examiners comparing writing or marking inks.
Formerly under the jurisdiction of Committee E30 on Forensic Sciences, this guide was withdrawn in January 2014 in accordance with section 10.6.3 of the Regulations Governing ASTM Technical Committees, which requires that standards shall be updated by the end of the eighth year since the last approval date.
1. Scope
1.1 This Guide is intended to assist forensic examiners comparing writing or marking inks. Included in this analysis scheme are the necessary tools and techniques available to reach conclusions as to the common or different origin of two samples of ink.
1.2 Identifying ink formulas as to their manufacturer or time of manufacture as well as performing ink dating examinations are beyond the scope of this guide.
StandardGuide for
Test Methods for Forensic Writing Ink Comparison
This guide is intended to be a general guide for forensic ink examinations, both for the experienced document examiner (Guide E444) and for forensic ink comparison specialists. The aim is to include those techniques that will provide the most information about an ink with the least damage to the document. Therefore, this guide refers to well-reported and thoroughly tested techniques currently in use by document examiners in general practice and dedicated forensic ink comparison facilities.
By following the procedures outlined here, an examiner can accurately discriminate ink formulas
and reduce the possibility of false matches of ink differentiation of ink samples with a common origin
DXer said
Research and Technology
Forensic Analysis of Blue Ballpoint Pen Inks Using Capillary Electrophoresis
Jason D. Brewer
Chemist
Federal Bureau of Investigation
Laboratory
Chemistry Unit
Quantico, Virginia
Kristin A. Hagan
Oak Ridge Institute for Science and Education Visiting Scientist
Federal Bureau of Investigation
Laboratory
Counterterrorism and Forensic Science Research Unit
Quantico, Virginia
James M. Egan
Research Chemist
Federal Bureau of Investigation
Laboratory
Counterterrorism and Forensic Science Research Unit
Quantico, Virginia
http://www.fbi.gov/about-us/lab/forensic-science-communications/fsc/july2005/research/2005_07_research02.htm
DXer said
“Document examination can also be useful in investigations of
material origin, as when the FBI searched for the origins of the 2001 Amerithrax letters [5].”
“The potential for application of ink stable isotope analysis in questioned document examination”
Lesley A. Chesson, Brett J. Tipple, Janet E. Barnette, Thure E. Cerling, James R. Ehleringer
Received: December 20, 2013; Received in revised form: May 21, 2014; Accepted: May 28, 2014; Published Online: June 16, 2014
http://www.scienceandjusticejournal.com/article/S1355-0306(14)00065-3/abstract
Comment:
The GAO should not fall for the spin that there the analysis of the ink and paper did not lead to any probative evidence. Instead, given that it was part of the scientific approaches used by the FBI in Amerithrax, the GAO should delve into and note that it was EXCULPATORY of Dr. Ivins.
Here are a samle of authorities relied upon by the FBI’s expert:
V. Causin, C. Marega, A. Marigo, R. Casamassima, G. Peluso, L. Ripani
Forensic differentiation of paper by X-ray diffraction and infrared spectroscopy
Forensic Sci. Int., 197 (2010), pp. 70–74
M. Manso, M.L. Carvalho
Application of spectroscopic techniques for the study of paper documents: A survey
Spectrochim. Acta B, 64 (2009), pp. 482–490
G.R. Nakamura, S.C. Shimoda
Examination of micro-quantity of ball point inks from documents by thin-layer chromatography
J. Crim. Law Criminol. Police Sci., 56 (1965), pp. 113–118
J.A. Zlotnick, F.P. Smith
Chromatographic and electrophoretic approaches in ink analysis
J. Chromatogr. B, 733 (1999), pp. 265–272
. Denman, W.M. Skinner, K.P. Kirkbride, I.M. Kempson
Organic and inorganic discrimination of ballpoint pen inks by ToF-SIMS and multivariate statistics
Appl. Surf. Sci., 256 (2010), pp. 2155–2163
D.M. Grim, J.A. Siegel, J. Allison
Evaluation of desorption/ionization mass spectrometric methods in the forensic applications of the analysis of inks on paper
J. Forensic Sci., 46 (2001), pp. 1411–1420
Jones, R.B. Cody, J.F. McClelland
Differentiating writing inks using direct analysis in real time mass spectrometry
J. Forensic Sci., 51 (2006), pp. 915–918
J. Coumbaros, K.P. Kirkbride, G. Klass, W. Skinner
Application of time of flight secondary ion mass spectrometry to the in situ analysis of ballpoint pen inks on paper
Forensic Sci. Int., 193 (2009), pp. 42–46
J.D. Kelly, A.A. Cantu
Proposed standard methods for ink identification
J. AOAC Int., 58 (1975), pp. 122–125
JW. Hargett
The International Ink Library
Int. Crim. Police Rev., 45 (1990), pp. 33–34
G.M. LaPorte, M.D. Arredondo, T.S. McConnell, J.C. Stephens, A.A. Cantu, D.K. Shaffer
An evaluation of matching unknown writing inks with the United States International Ink Library
J. Forensic Sci., 51 (2006), pp. 689–692
C. Neumann, R. Ramotowski, T. Genessay
Forensic examination of ink by high-performance thin layer chromatograph—The United States Secret Service Digital Ink Library
J. Chromatogr. A, 1218 (2011), pp. 2793–2811
J.D. Wilson, G.M. LaPorte, A.A. Cantu
Differentiation of black gel inks using optical and chemical techniques
J. Forensic Sci., 49 (2004), pp. 1–7
M.N. Gernandt, J.J. Urlaud
An introduction to the gel pen
J. Forensic Sci., 41 (1996), pp. 503–504
Y. Wu, C.-X. Zhou, J. Yu, H.-L. Liu, M.-X. Xie
Differentiation and dating of gel pen ink entries on paper by laser desorption ionization- and quadruple-time of flight mass spectrometry
Dyes Pigm., 94 (2012), pp. 525–532
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W.D. Mazzella, P. Buzzini
Raman spectroscopy of blue gel pen inks
Forensic Sci. Int., 152 (2005), pp. 241–247
T. Trejos, A. Flores, J.R. Almirall
Micro-spectrochemical analysis of document paper and gel inks by laser ablation inductively coupled plasma mass spectrometry and laser induced breakdown spectroscopy
Spectrochim. Acta B, 65 (2010), pp. 884–895
N.N. Daeid, H.A.S. Buchanan, K. Savage, J.G. Fraser, S.L. Cresswell
Recent advances in the application of stable isotope ratio analysis in forensic chemistry
Aust. J. Chem., 63 (2010), pp. 3–7
J.R. Ehleringer, T.E. Cerling, J.B. West
Forensic science applications of stable isotope ratio analysis
R.D. Blackledge (Ed.), Forensic Analysis on the Cutting Edge: New Methods for Trace Evidence Analysis, John Wiley & Sons, Inc., San Diego, California, USA (2007), pp. 399–422
S.J. Benson, C. Lennard, P. Maynard, C. Roux
Forensic applications of isotope ratio mass spectrometry—A review
Forensic Sci. Int., 157 (2006), pp. 1–22
J.F. Carter, P.L. Grundy, J.C. Hill, N.C. Ronan, E.L. Titterton, R. Sleeman
Forensic isotope ratio mass spectrometry of packaging tapes
Analyst, 129 (2004), pp. 1206–1210
M. Horacek, J.-S. Min, S. Heo, J. Park, W. Papesch
The application of isotope ratio mass spectrometry for discrimination and comparison of adhesive tapes
Rapid Commun. Mass Spectrom., 22 (2008), pp. 1763–1766
richard rowley said
Nice work, DXer!
DXer said
Part of the science in Amerithrax — which has not yet been disclosed — is that none of the hundreds of samples seized by the FBI from Bruce Ivins was a match. The inki was analyzed via solubility and thin-layer chromatography.
In such analyses, ink and dye samples are available from an extensive U.S. Secret Service ink library. It is wrongheaded to selectively disclose science in support of a conclusion. The exculpatory ink analysis should have been disclosed by the FBI to the GAO and now should be made public.
Forensic Analysis of Blue Ballpoint Pen Inks Using Capillary Electrophoresis, July 2005
http://www.fbi.gov/about-us/lab/forensic-science-communications/fsc/july2005/research/2005_07_research02.htm
DXer said
In his new manuscript, Dr. Vahid Majidi writes: “Ink samples from the handwritten addresses on the front of the envelopes were analyzed and the results showed that the type of pen used for the envelopes mailed to Brokaw and the New York Post was likely the same, but different from the one used on other envelopes (i.e.,s two different pens were used by the perpetrator).”
Dr. Majidi, can’t you see the problem here? In this book that you undertook to write (and I’m grateful for all insights and perspectives), you have claimed that all the scientific reports have been produced — and you have described this examination of the ink that was done. Yet neither those reports nor the examination of the ink on the papers written by Dr. Ivins were produced. The FBI — while you were in charge — did not produced the scientific reports even though you in your book have claimed that the FBI did.
In federal court, this would constitute grievous prosecutorial misconduct — but the oversight, no doubt due to innocent human error, can be corrected. Either have your former FBI colleagues produce the reports or correct your misstatement that all the reports have been produced.
Just because you were in charge of non-traditional forensic methods means you can overlook or sweep under the rug — to tidy your conclusion up — the traditional forensic analysis.
DXer said
Among the most downloaded Forensic Science International articles in the last 90 days are a couple regarding mass spectrometry in ink analysis.
http://www.journals.elsevier.com/forensic-science-international/most-downloaded-articles/
19. Analysis of writing inks on paper using direct analysis in real time mass spectrometry
10 September 2013
Roger W. Jones | John F. McClelland
Abstract: Ink analysis is central to questioned document examination. We applied direct analysis in real time mass spectrometry (DART MS) to ballpoint, gel, and fluid writing ink analysis. DART MS acquires the mass spectrum of an ink while it is still on a document without altering the appearance of the document. Spectra were acquired from ink on a variety of papers, and the spectrum of the blank paper could be subtracted out to produce a cleanly isolated ink spectrum in most cases. Only certain heavy or heavily processed papers interfered. The time since an ink is written on paper has a large effect on its spectrum. DART spectra change radically during the first few months after an ink is written as the more volatile components evaporate, but the spectra stabilize after that. A library-search study involving 166 well-aged inks assessed the ability to identify inks from their DART spectra. The aggregate success rate was 92%.
20. Forensic applications of desorption electrospray ionisation mass spectrometry (DESI-MS)
10 March 2013
Marie Morelato | Alison Beavis | Paul Kirkbride | Claude Roux
Abstract: Desorption electrospray ionisation mass spectrometry (DESI-MS) is an emerging analytical technique that enables in situ mass spectrometric analysis of specimens under ambient conditions. It has been successfully applied to a large range of forensically relevant materials. This review assesses and highlights forensic applications of DESI-MS including the analysis and detection of illicit drugs, explosives, chemical warfare agents, inks and documents, fingermarks, gunshot residues and drugs of abuse in urine and plasma specimens. The minimal specimen preparation required for analysis and the sensitivity of detection achieved offer great advantages, especially in the field of forensic science.
DXer said
The FBI is in the process of collecting samples of correspondence that Mr. Paul Kevin Curtis has sent to others to compare aspects of the correspondence to the letters sent containing ricin.
In the Amerithrax case, the FBI never produced the report on the ink used in the anthrax letters showing that Dr. Ivins never used that type of pen.
In its ongoing review of the FBI’s Amerithrax investigation, GAO should insist that the report(s) be provided.
The GAO employees bemoaning the FBI’s slow production should understand that someone involved produces the important stuff (the stuff does not support their position) last.
And they produce it all only if the requestor forcefully insists on it.
Forensic Sci Int. 2013 May 10;228(1-3):1-7. doi: 10.1016/j.forsciint.2013.01.034. Epub 2013 Mar 5.
Forensic discrimination of blue ballpoint pens on documents by laser ablation inductively coupled plasma mass spectrometry and multivariate analysis.
Alamilla F, Calcerrada M, García-Ruiz C, Torre M.
Source
Department of Chemistry and Environmental Sciences, Criminalistics Service, General Direction of Civil Guard, C\Guzmán el Bueno, 110 Madrid, Spain; University Institute of Research in Police Sciences (IUICP), University of Alcalá, Ctra. Madrid-Barcelona km. 33.600, 28871 Alcalá de Henares, Madrid, Spain.
Abstract
The differentiation of blue ballpoint pen inks written on documents through an LA-ICP-MS methodology is proposed. Small common office paperportions containing ink strokes from 21 blue pens of known origin were cut and measured without any sample preparation. In a first step, Mg, Ca and Sr were proposed as internal standards (ISs) and used in order to normalize elemental intensities and subtract background signals from the paper. Then, specific criteria were designed and employed to identify target elements (Li, V, Mn, Co, Ni, Cu, Zn, Zr, Sn, W and Pb) which resulted independent of the IS chosen in a 98% of the cases and allowed a qualitative clustering of the samples. In a second step, an elemental-related ratio (ink ratio) based on the targets previously identified was used to obtain mass independent intensities and perform pairwise comparisons by means of multivariate statistical analyses (MANOVA, Tukey’s HSD and T2 Hotelling). This treatment improved the discrimination power (DP) and provided objective results, achieving a complete differentiation among different brands and a partial differentiation within pen inks from the same brands. The designed data treatment, together with the use of multivariate statistical tools, represents an easy and useful tool for differentiating among blue ballpoint pen inks, with hardly sample destruction and without the need for methodological calibrations, being its use potentially advantageous from aforensic-practice standpoint. To test the procedure, it was applied to analyze real handwritten questioned contracts, previously studied by the Department of Forensic Document Exams of the Criminalistics Service of Civil Guard (Spain). The results showed that all questioned ink entries were clustered in the same group, being those different from the remaining ink on the document.
DXer said
Guang Pu Xue Yu Guang Pu Fen Xi. 2010 Oct;30(10):2816-9.
[Determination of blue ballpoint pen ink by laser ablation inductively coupled plasma mass spectrometry].
[Article in Chinese]
Ma D, Shen M, Luo YW, Bo J, Xu C, Zhuo XY.
Source
Forensic Medicine Department of Shanghai Medical College, Fudan University, Shanghai 200032, China. madong@ssfjd.cn
Abstract
To establish an identification method for the forensic analysis of blue ballpoint ink by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), 95 kinds of blue ballpoint pen from different manufacturers were detected. These blue ballpoint pens were classified into 34 groups according to their metal element components, among which, 26 groups can be directly distinguished according to the types of metal element components contained in the ballpoint pen, the other groups can be distinguished by different element response ratios. Meanwhile the examination result on the papers showed that the papers have no impact on the ink handwriting analysis. Experimental results showed that the method’s reproducibility is good and precision is less than 10%. This method has better identification ability than traditional identification technology for questioned document. Eighty eight kinds of blue ballpoint pen out of the total 95 selected kinds can be distinguished with this method. The established method is simple, rapid, with good precision, and almost has no damage to the sample. It is particularly suitable for the demand of identification of blue ballpoint pen in forensic science.
DXer said
Thin-layer chromatography (TLC) was one of the methods used by the FBI to determine the pen used.
The United States Secret Service has maintained the International Ink Library for many decades. Because manufacturers change their ink formulas slightly from year to year, thin-layer chromatography (TLC) can be used on ink from traditional pens to trace the manufacturer and date of manufacture of most inks.
LaPorte, Gerald; Arredondo, MD; McConnell, TS; Stephens, JC; Cantu, AA; Shaffer, DK (May 2006). “An Evaluation of Matching Unknown Writing Inks with the United States International Ink Library”. Journal of Forensic Science 51 (3): 689. doi:10.1111/j.1556-4029.2006.00144.x.PMID 16696723.
An Evaluation of Matching Unknown Writing Inks with the United States International Ink Library†
Article first published online: 2 MAY 2006
Journal of Forensic Sciences
Volume 51, Issue 3, pages 689–692, May 2006
Additional Information(Show All)
How to CiteAuthor InformationPublication History
• †
ABSTRACT: Utilizing a database of standards for forensic casework is a valuable resource. Undoubtedly, as more standards (and corresponding information about the specimens) are collected, there is a greater certainty of identification when a questioned and a known item cannot be distinguished after a series of analyses. The United States Secret Service and the Internal Revenue Service National Forensic Laboratory jointly maintain the largest known forensic collection of writing inks in the world, which is comprised of over 8500 ink standards collected worldwide, dating back to the 1920s. This study was conducted to evaluate the reliability of matching arbitrarily purchased pens with known inks from a database. One hundred pens were randomly obtained from a variety of sources and their respective ink compositions were compared with standards. Eighty-five of the inks were determined to be suitable for comparison utilizing optical examinations and thin-layer chromatography. Three of the inks did not match any of the specimens on record; one of these inks was similar to an ink from an identical brand of pen that was in the database, but had a modified formulation.
DXer said
The expertise of the Secret Service Forensic Services Division on thin layer chromatography as applied to liquid inks is just a short Metro ride or walk away.
The use of filtered light for the evaluation of writing inks analyzed using thin layer chromatography.
Author
Houlgrave, Stephanie · LaPorte, Gerald M · Stephens, Joseph C
Published online 2011-03-01
Journal Journal of forensic sciences
Thin layer chromatography (TLC) is a scientific methodology that can be used to compare and characterize ink formulations. Occasionally, when evaluating chromatographic profiles on a TLC plate with ambient light, different ink formulations, or the same inks from different batches, may appear indistinguishable. The use of filtered light can be very effective to illuminate characteristics that are not readily apparent with ambient light. There are a diverse number of components commonly found in writing inks, and it may be that some of them respond to particular wavelengths of energy that are not visible to the unaided eye (i.e., colorless). There has been very little information published that addresses the use of filtered light for evaluating TLC plates. Twenty-nine ballpoint writing ink samples were selected for TLC analysis. Further evaluation using an alternate light source, coupled with the appropriate filter, proved to be an effective means for definitive discrimination in some cases.
Stephanie M. Houlgrave, BA*, The George Washington University, 4001 North Ninth Street, #519, Arlington, VA 22203; Gerald M. LaPorte, MSFS, United States Secret Service, Forensic Services Division, 950 H Street, Northwest, Washington, DC 20223; Joseph C. Stephens, MSFS, 950 H Street Northwest, Forensic Services Division, Washington, DC 20223; Vanessa E. Abercrombie, BA, The George Washington University, 1600 South Eads Street #307 North, Arlington, VA 22202; and Justin L. Wilson, West Virginia University, 717 Snider Street, Morgantown, WV 26505
DXer said
For starters, and turning to the reports, how wide was the line?
0.3mm? .4mm? .5mm? .6mm?
http://www.tigerpens.co.uk/acatalog/Pilot_Liquid_Ink_Pens_.html
http://www.tigerpens.co.uk/acatalog/Uni_Liquid_Ink_Rollerball_Pens.html