Ceglia v. Zuckerberg et al

Filing 416

DECLARATION signed by Larry Stewart re 348 Order on Motion to Stay, Scheduling Conference, Oral Argument,,,,,,,,,,,, 414 Declaration filed by Paul D. Ceglia Expert Report. (Attachments: # 1 Supplement 46-55, # 2 Supplement 56-66, # 3 Supplement 67-90, # 4 Exhibit p. 1-82, # 5 Exhibit p. 83-167, # 6 Exhibit p. 168-229, # 7 Exhibit p. 230-290)(Boland, Dean)

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Exhibit 14 Declaration of Larry F. Stewart Exhibit 15 Declaration of Larry F. Stewart Lesnovich has implied that there was some change in the pages of the WFH document sometime between his Q1 and Q2 images and his Q3 and Q4 images. Following is an experiment comparing the position of the interlineation writings to the printed document on the best (clearest) sample of each of his two groups. Q1 from Lesnovich. Tif sent by Ceglia to Argentieri 6/27/10. Q3 from Lesnovich. Aginsky scan from 1/13/11 examination. Exhibit 16 Declaration of Larry F. Stewart Comparison of poorly resolved scanned image of the WFH Pg1 to high resolution scanned image taken after forensic testing began and the document was in secure storage: Here we have two images that were simply scanned at different settings creating similar anomalies to what Lesnovich is pointing out. This doesn’t imply wrongdoing, but instead computer scanner setting differences. Lesnovich’s Q1 - Image from Ceglia email to Argentieri 6/27/10 (Note: Poor resolution) High resolution scanned image taken 7/15/11 Look at the difference in thickness within the vertical staff of the printed “P” in the lower right corner. The difference in thickness can cause the letters to merge or appear to close in on each other. Exhibit 17 Declaration of Larry F. Stewart Exhibit 18 Declaration of Larry F. Stewart TEST REPORT December 13, 2011 Page 1 of 2 IPS FI 02956-11 Report to: Larry Stewart Stewart Forensic Consultants 793 A East Foothill Blvd. San Luis Obispo, CA 93405 Sample identification: 2 Vials Date received: November 1, 2011 Test requested: Fiber Identification Purchase Order: Credit Card Report of Fiber Analysis Enclosed are the results of the analysis performed on the sample we received with your Test Services Request Form. If you have any questions concerning this work, please do not hesitate to contact us. Authorized By: ______________ Gregory J. Fox Lab Manager Signed _______________________________ Walter J. Rantanen Technical Leader, Fiber Science (920) 749-3040 Ext. 127 WJR/jml 3211 E. Capitol Drive ~ Appleton, WI 54911 (920) 749-3040 ~ Fax: (920) 749-3046 ~ www.ipstesting.com Report to Stewart Forensic Consultants IPS FI 02956-11 Fiber Identification December 13, 2011 Page 2 of 2 The paper samples did not have any detectable mechanical (high lignin) pulp fibers which would be effected by photodegredation from UV light. There is a strong UV fluorescence in both samples, which indicates optical brightening agents. In the small punch outs, significant fluorescence differences were not detected. It could not be determined if these samples were effected by contact with UV light, but long exposure to UV light has been known to lower the whiteness of paper. A noticeable particulate material was observed on one side of the punch outs. This particulate may also affect the UV fluorescence of paper. The main inorganic substance in these particulates was found to be iron. The EDS spectra are enclosed. The nature of this material implies contact on one surface of the papers. Spot tests show the same consistent reactions for starch and pH levels between the two samples. The fiber content of the two vials is consistent with coming from the same mill and production run. Table 1. Fiber Identification of Vial 7 Hardwood Bleached Kraft – Principally Redgum and Oak with some Blackgum, YellowPoplar, Cherry, Southern Magnolia Softwood Bleached Kraft – Hard Pine (Except Red & Pine) Table 2. Fiber Identification of Vial 9 Hardwood Bleached Kraft – Principally Oak and Redgum with some Yellow-Poplar, Blackgum, Cherry Softwood Bleached Kraft – Hard Pine (Except Red & Pine) Method: TAPPI Test Method T 401 om-03 “Fiber Analysis of Paper and Paperboard.” Analyzed by WJR Quality review by JML, KTM Date(s) of testing November 8, 2011 Notes: These results relate only to the item(s) tested. This test report shall not be reproduced, except in full, without written consent of IPS. See the TAPPI test method(s) cited for estimates of measurement uncertainty. Exhibit 19 Declaration of Larry F. Stewart Lat7 y F. Stewart, 1 M . F . S . Ballpoint Ink Age Determination by Volatile Component Comparison--A Preliminary Study REFERENCE: Stewart, L. F., "BaHpolntInk Age Determination by Volatile Component Comparlson--A PreliminaryStudy," Journal of Forensic Sciences, JFSCA, Vol. 30, No. 2, April 1985, pp. 405-411. ABSTRACT: Ballpoint pen inks consist primarily of a mixture of dyes. resins, and vehicle components. The vehicles are used to solubilize or suspend dyes. resins, and other compoueuts as well as to provide smooth ball movement and flow of ink onto writing surfaces. These vehicles are relatively volatile and make up approximately 50% of the ink by weight. Extraction and fornmlation identification of the questioned ink is performed. Once identified, the volatile components of the ink are measured quantitatively by gas chromatography. PreliminalS stvdies show that the relative proportions of these volatile ingredieuts decrease as the ink ages. How long an ink has been on paper is determined by comparison of the relative concentrations of the volatile components of the questioned ink with those of known inks (age) of the same formulation. The relationship between age of ink. storage conditions, aud paper will also be discussed. KEYWORDS: questioned documents, inks, gas chromatography, pens, age determination The a m o u n t of time an ink has been on a d o c u m e n t has been a question t h a t has plagued many forensic science examiners since writing inks were first introduced. The conventional approach to dating an ink entry has been the identification of certain ink components which may indicate gross formulation changes. Ballpoint pen inks, first developed in the 1930s [1], used oils for the vehicles. It was not until the 1950s that glycol-based inks were widely used [2]. Additions to formulas such as the introduction of copper phthalocyanine dye (1954) in ballpoint pen inks, fluorescent dyes ( 1955 to 1957) in fountain pen inks, and the introduction of entirely new markets, for example, felt and fiber tip pen inks (1961) have aided the forensic science investigator in determining the "age" of an entry. 2 O t h e r methods for dating an ink entry included determining the presence or absence of a dye. for example, the blue dye in blue-black writing inks of the early 1900s 131, and differentiating between the amounts of a c o m p o n e n t extracted from two entries through the use of chemical reagents (for example, oxalic acid) in the 1920s [4]. During the mid-1960s, in an attempt to improve upon the conventional method by increasing the knowledge of known changes in formulations, W e r n e r Hoffman, Zurich Cantonal Police, Zurich, Switzerland, began collecting samples of European ballpoint pen inks. He began comparing questioned inks with his collection for purposes of showing similarities or differences between formulas [5]. In the mid-1960s, Richard Brunelle, Bureau of Alcohol, ToNote: the experimental work for this paper was conducted at the Bureau of Alcohol. Tobacco and Firearms Forensic Science Branch. National Laboratory Center. Rockville, MD. Presented at the 34th Annual Meeting of the American Academy of Forensic Sciences, Orlando, FL. 8-11 Feb. 1982 and the Spring 1982 Joint Meeting of the Mid-Atlantic Association of Forensic Scientists/ Northeast Association of Forensic Scientists. Harrisburg, PA, April 1982. Received for publication 21 May 1984; revised manuscript received 28 June 1984; accepted for publication 29 June 1984. IDocument analyst, United States Secret Service, Washington, DC. 2A. A. Cantu, private communication. 1980. 405 Copyright © 1985 by ASTM International 406 JOURNAL OF FORENSIC SCIENCES bacco & Firearms, National Laboratory Center, Washington, DC, began collecting a library of standard inks from U.S. manufacturers. This library has been maintained and expanded to its present-day status of being the largest single collection of inks in the world consisting of over 4000 domestic and foreign inks. 3 The Bureau of Alcohol, Tobacco and Firearms (ATF) also initiated a national ink tagging program (1971 to 1974) in an effort to determine more closely the age of an entry produced by an ink whose formulation is not often changed by the manufacturer [6]. Even with these technical advances it is often necessary to determine more closely (less than a few years span) the actual age of an entry. This work will address only ballpoint pen inks because of their amenability to drying determinations. Composition of Ballpoint Inks Ballpoint ink is a high viscosity (nonfluid) writing medium. It consists primarily of three components [7]: (1) vehicles, (2) dyes or pigments or both, and (3) resins or polymers. Vehicles Vehicles are added to an ink for purposes of solubilizing(or carrying) the dyes/pigments and for ease of flow over the cartridge ball. Vehicles in ballpoint inks have had only one dramatic formulation change since their inception in the 1930s. Before 1950, inks contained oil as the primary vehicle; after the early 1950s. glycol-based inks were developed and quickly became the favorite among the population. These inks usually contain one or more of the following vehicle solvents: 4 1,3 propylene glycol Diethyl glycol phenyl ether Benzyl alcohol 2 ethyl hexoic acid Ethylene glycol 2,3-butylene glycol Monophenylether 1.2-propylene glycol Ethylene and diethylene glycol monomethyl ether Hexylene glycol Octylene glycol 1.3 butylene glycol Di and triethylene glycol Dipropylene glycol Glycerine Phenoxyethanol Phenoxyethylene glycol The volatile components of the ink make up approximately 50% of its composition. Dyes and Pigments Dyes and pigments are the color giving components of an ink. Some of the more common ones used in ink formulations include:4 Methyl violet Victoria blue Crystal violet Copper pbthalocyanine Nigrosine Solvent fast blue Luxol fast orange Dyes and pigments make up approximately 25% of the ink's composition. 3A. A. Cantu, private communication, 1982. 4Private communicationswith ink manufacturers. 1982. STEWART , BALLPOINT INK AGE DETERMINATION 407 Reshts and Polymers Resins a n d polymers are added to ballpoint inks for purposes of " e x t e n d i n g " the ink (used as a filler) and for thickening the ink. Some resinous components found in writing inks include: 4 Vinsol| Nevillac Hard + Pyrrolidone (PVP) K r u m b h a a r K-1717 ~ Phthalopal SEB ~ Synthetic Resin SK The resinous additives usually make up approximately 25% of the total ink volume. The vehicle components are of primary interest in this work. The ink cartridge is considered a "closed" system; essentially no drying takes place in the cartridge. The ink on the paper surface is an " o p e n " system; the ink drying process begins as soon as the ink is placed on the paper. The vehicles evaporate with time leaving the dyes,, pigments and resins ,'polymers adhering to the writing surface. This work is based on the fact that volatile components evaporate with time. Ballpoint pen inks contain volatile components that begin evaporating when placed on a document. This indicates that the age of a ballpoint pen ink entry stored u n d e r some " c o n s t a n t " conditions could be determined if the a m o u n t of volatile components per weight,volume of ink was measured (see Fig. 1). If the temperature and humidity do not remain constant, then only the "relative" age of an entry as compared to another entry (stored on the same paper) may be determined. Materials and Equipment The materials and e q u i p m e n t used were: 9 Temperature programmable gas chromatograph equipped with a flame ionization detector 9 Stainless steel column 1.8 m (6 ft) packed with 3 % Tenax GC on 60-80 mesh Supelcoport 9 Ten-microlitre syringe 9 Micro vials (0.5 dr tapered) 9 High purity methanol 9 Micro pipets, 10/xL 9 Ice bath 9 High purity vehicle standards 9 • gauge hypodermic needle 9 Plunger 9 Timer "New" Entry 'i" ~as~rlng Apparatus "Old" Entry FIG. l - - Theo O' o/' work. Consists of X + Y % Volatile Conponent s 408 JOURNAL OF FORENSIC SCIENCES Method The first step in determining the age or "relative" age of a ballpoint pen ink entry is the identification of the ink formulation. Identification is necessary so the examiner can determine the quality control from the manufacturer and the "uniqueness" of a formula. The method used involves thin-layer chromatographic comparisons of questioned to known ink samples [5]. The known ink samples used in this work are stored and maintained in the standard ink library at the Bureau of Alcohol, Tobacco & Firearms, National Laboratory Center, Roekville, MD. Once the questioned ink formulation has been identified, the volatile components and percentages present in kr~own "fresh" ink of the same formula are obtained by gas chromatographic analysis. Fresh ink samples of the same formulation were placed on a single sheet of paper on various dates. This sheet was stored under "standard" conditions (that is, room temperature and humidity) in a file drawer. Samples of ink were removed from the paper by a micro-pellet technique. This technique utilizes a blunted 20-gauge hypodermic needle fitted with a shortened "syringe type" plunger. The micro-plugs of ink and paper ( : 15 plugs) are placed in tapered microvials. Approximately 10 to 15 p,L of methanol is slowly added (being careful not to disturb the pellets) by syringe through the capped/stoppered lid of the vial. The vial is placed in an ice bath to minimize "travel" of the methanol up the sides of the tapered vial, The vials remain in the ice bath undisturbed for 5 rain. At the end of the extraction process a 5- to 10-pL aliquot is removed for injection into the gas chromatograph. A gas chromatograph equipped with a flame ionization detector was chosen as the analysis instrument because of the need for reproducible detection and quantitation of micro-amounts of volatile components. Fresh ink samples containing different combinations of volatile components were chromatographed using various extraction methods, gas chromatograph columns, and temperature programs. A suitable method for analysis was obtained. The gas chromatographic conditions chosen are as follows: Temperature programmable gas chromatograph (Perkin-EImer Sigma 3B) Flame ionization detector 3% Tenax GC on 60-80 mesh Supelcoport (stainless steel, 1.8 m [6 ft]) N2 gas flow at 25 cm3/min Initial hold, 0-min 12~ ramp 50 to 280~ Final hold, 10 min Chart speed, 12.7 ram/rain (0.5 in./min) Injections of 5 to 10 #L using methanol as the extracting solvent Attenuation: • K till methanol peak, then • 100 Once a suitable chromatogram was obtained the vehicle peaks were identified by using known standards and formulation information obtained from the ink's manufacturer. An "'aging" curve for each ink was obtained (Fig, 2). This was done by finding two sufficiently resolved vehicle peaks, quantitatively determining the peak areas, and then ratioing one peak to the other. The ratio of Peak A/Peak B is plotted versus actual age (days). This gives the aging curve for that particular ink formulation (Fig. 3). The questioned entry is analyzed in the same way. The peak areas are taken, a ratio is obtained, and, using the previously calculated "aging curve." the age of the Q entry is determined (Fig. 4). This calculated "age" of the Q entry is absolute only if the storage conditions of both the Q and K entries are identical. The storage conditions of the inks used to obtain the aging curve should be equal or better (that is, slower aging process) than those of Q. STEWART 9 BALLPOINT INK AGE DETERMINATION 409 GO COMPARISION OF TWO INKS OF THE SAME FORMULATION WRITTEN AT DIFFERENT TIMES & fresh writing t w o month o I d writing / _~ FIG. 2--Aging curve.for etwh ink. 8.0 7"01 RATIO = (PeakA) / (PeakB) 6.0 5.0 4.O 3.0 2.O I. 0.0 0 10 20 30 40 50 60 70 80 90 lob 110 120 130 1~I0 150 160 FIG. 3--Agblg curve calculated from the ratio of Peak A/Peak B versus actual age. DY AS 410 JOURNAL OF FORENSIC SCIENCES 8.0 7.0 6.0 5.0 4.0 3.0 2,0 5.0 0.0 0 I0 20 30 ~"~ 40 50 60 70 8n 90 Ioo 11F) ]2F) "3,s 130 I~0 ]50 260 DY AS FIG. 4--Aging curve for d w Q ('toO'. Conclusions Ideally at least two inks of the same formula should be compared. They should be on the same paper and stored u n d e r the same conditions. If two inks of the same formulation on the same document have different ratios of the volatile components, then one ink can be determined to be fresher than tile other, that is, (A : first eluting comparison peak) (B : second eluting comparison peak) new > (A) (B) old If two inks of the same formulation are found on different paper, then tile paper type is probably not a factor but storage conditions are. The "willingness" of tile paper to allow these components to be extracted in the same ratio slmuld not be affected by a paper's porosity, thickness, type, or age. However, this must be further tested. Certain ballpoint pen ink formulations were shown to have reproducible aging curves up to one-and-one-half years after placement on paper. Differences in peak ratios for known inks stored under standard conditions were detected over as small a time frame as a few days. Some ink formulations tested have evaporation rates or vehicle components not ameuable to this technique. Ratioing the chromatograph peaks eliminates tile necessity of removing equal masses of "questioned and known age" ink when performing an age comparison. Further work that should be performed includes testing the paper iqdependence theory and developing a laboratory technique for "controlled" artificial aging of ink standards to obtain " i m m e d i a t e " aging curves for known standard inks. STEWART * BALLPOINT INK AGE DETERMINATION 411 Acknowledgments This work was greatly assisted by the knowledge and cooperation of the following: Dr. Antonio A. Cantu, the ink industry, Dr. Phillip M. Daugherty, Richard L, Brunelle, and Connie Lee. References [1] "The Battle of the Bali-Point Pen," Reader's Digest, Dec. 1946, pp. 59-63. [2] Daugherty, P. M.. "Composition of Ball Pen Inks," presented at the First Georgetown University Conference on Surface Analysis. Washington, DC. Oct. 1969. [3] Waters, C. E., "'Blue Dye as Evidence of the Age of Writing," hzdustrialandEngmeering Chemist13,, Vol. 25, No. 9, Sept. 1933. pp. 1034-1035. [4] Mitchell, C. A. and Hepworth, T. C.. "'Inks: Their Composition and Manufacture," 3rd ed., Griffin & Co., London, 1924, p. 181. [5] Crown, D. A., Brunelle, R. L.. and Cantu, A. A., "The Parameters of Ballpen Ink Examinations." JournalqfForensic Sciences. Vot. 21, No. 4, Oct. 1976. pp. 917-922. [6] Brunelle, R. L., Cantu, A. A., and Lyter, A. H., "Current Status of Ink Analysis," presented at the 1975 Annual lnterpol Meeting. St. Cloud. France. [7] Witte, A. H., "The Examination and Identification of Inks." in Methods of Forensic Science, Vol. 2, [nterscience Publishers, London, 1963, p. 35. Address requests for reprints or additional information to Larry F. Stewart United States Secret SeB'ice Forensic Services Division 1800 G St., N.W., Room 929 Washington. DC 20223 Exhibit 20 Declaration of Larry F. Stewart JOURNAL OF CHROMATOGRAPHY A ELSEVIER Journal of Chromatography A, 678 (1994) 119-125 Determination of the age of ballpoint pen ink by gas and densitometric thin-layer chromatography* Valery N. Aginsky Forensic Science Centre, Ministry of the Interior, 22 Raspletina Street, Moscow 123060, Russian Federation (First received October 8th, 1993; revised manuscript received March 31st, 1994) Abstract Two procedures for dating ballpoint inks are considered that use gas chromatography (a combination of the technique for determining the extent of extraction of ink volatile components and of the accelerated ageing technique) and densitometric thin-layer chromatography (separation of ink components and evaluation of the resulting chromatograms using a specially developed mass-independent technique that is also a very effective tool for the comparative TLC examination of similarly coloured inks, paints, fibres and other materials of forensic interest). The procedures have been used in many real case situations and the results of the examinations were accepted as conclusive evidence by courts of law. 1. Introduction Gas chromatography (GC) and densitometric thin-layer chromatography (TLC) have been demonstrated to be useful tools for the solution of many problems frequently encountered in ink analysis, including ink dating problems [l-4]. Recently, five new procedures for dating ballpoint inks have been described [5,6]. Two of them, based on using chromatographic methods, are as follows. (1) A GC method is used to determine the extent of extraction of ink volatile components, which decreases as ink ages on paper. The procedure considered in this paper combines the capabilities of this method and of the accelerated ageing technique. The procedure allows discrimi*Presented in part at the Germany, August 1993. 13th IAFS Meeting, Dtiseldorf, nation between “fresh” (age less than several months) and “old” ballpoint ink entries and it does not need dated reference entries written with ink having the same formula as that of the questioned ink. (2) A TLC method is used for determining age changes in resins and other colourless nonvolatile ballpoint ink components; these changes are detected by observing the resulting thin-layer chromatograms under UV illumination and evaluated by using scanning densitometry. The modified TLC procedure described in this paper includes a new, mass-independent approach to evaluating thin-layer chromatograms that allows one to obtain the values of an “ink ageing parameter” [7] directly proportional to the ratios of the masses of the separated ink components (dyes, resins, etc.). For this reason, the proposed procedure gives more reliable results for ink age determination than those obtainable with the 0021-9673/94/$07.00 0 1994 Elsevier Science B.V. All rights reserved SSDZ 0021-9673(94)00322-Z V.N. Aginsky. 120 I J. Chmmatogr. widely used peak signal-to-peak signal ratio technique. The described approach is also a powerful tool for the comparative examination of similarly coloured inks, paints, fibres and other materials of forensic interest as its discriminating power is much greater than that usually produced by the peak ratioing technique [S-10]. 2. Experimental 2.1. Materials Up to 15year-old entries written with Soyuz ballpoint inks of different colours having similar compositions of colourless components were analysed by GC. Entries of known ages (1 day, 1 month, 1, 2, 3 and 6 years old) written with a Parker blue ballpoint ink were analysed by TLC. Camag N-11 polypropylene micro vials with cone-shaped interiors and a lo-~1 Hamilton syringe were used. 2.2. Gas chromatography A Hewlett-Packard Model 5890 gas chromatograph equipped with a flame ionization detector and an HP split-splitless injection system was used. A SCOT column containing SP-1000 (polyethylene glycol 20M terminated with nitroterephthalic acid) (Supelco) (25 m x 0.5 mm I.D.) was used with nitrogen (4 p.s.i.) as the carrier gas at a flow-rate of 40 mlimin. The column oven temperature was programmed from 50°C (held for 0.5 min) at lO”C/min to 220°C (held for 6 min). The injection volume was 2 ~1 (splitless) at 250°C. A flame ionization detector was used at 250°C. Each sample was obtained by cutting out a ca. l-cm sliver of ink of approximately equal thickness from the paper using a safety razor and placed in a micro vial. A lo-~1 volume of carbon tetrachloride as a “slowly extracting weak solvent”, containing 10 pgiml of benzyl alcohol as an internal stranded (if benzyl alcohol is detected in ink samples in significant amounts, another appropriate substance can be used as an internal A 678 (1994) 119-125 standard) was added and the vial was capped. After 30 min a ca. 2-pl aliquot of each sample was removed and analysed by GC. The samples were removed from the extraction solutions, dried and placed into other micro vials. A second extraction was carried out for 1 min, stirring with a needle, with 10 ~1 of chloroform (“fast-extracting strong solvent”) also containing benzyl alcohol in the same concentration. About 2 ~1 of each extract were removed and analysed by GC. The masses of a vehicle component determined in each of the two extracts analysed (M, and M2 for the first and second extractions, respectively) were calculated by means of the internal standard method. The percentage extraction [l,S], that is, the percentage of the mass of the ink vehicle component, %M, extracted in the “weak” solvent (relative to its total amount contained in the sample analysed), was calculated as follows: %M = [M, /(M, + M2)]. 100 The values of %M obtained analysed were plotted against known ink entries (see Fig. 1). 2.3. for all samples the age of the Thin-layer chromatography To obtain an “ageing curve”, samples as two l-cm slivers of ink of approximately equal thickness were taken from five entries of known ages (X,-X,). Three more samples were taken from a 2-year-old entry that was analysed as a questioned (Q) entry. Each sample was placed in a micro vial and extracted for 2 min with 15 ~1 of chloroform, stirring with a needle. A calibration standard solution was prepared by the treatment of eight l-cm slivers taken from a l-month-old entry with 60 ~1 of chloroform. Volumes of 10 ~1 of the obtained extracts and 5,8,11 and 15 ~1 of the calibration standard solution (calibration standards, S,-S,) were applied to a 20 x 10 cm precoated Merck HPTLC silica gel 60 F,,, plate as X-mm bands by means of a Camag Linomat-3 applicator. One-dimensional ascending development was performed with ethanol-acetone-hex- V.N. Aginsky. I J. Chromatogr. ane (1:5:20, v/v/v). The development distance was 50 mm. The resulting chromatograms contained zones of two ink components, A and B. For five samples, X,-X,, the relative proportion of these components was obviously linked with the age of the ink (see Fig. 2). The chromatograms were scanned densitometrically by reflectance in the absorbance mode for fluorescence quenching at 254 nm using a Camag TLC/HPTLC scanner (with a mercury lamp, monochromator bandwidth 30 nm, slit dimensions 0.3 x 5 mm and scanning speed 1 mm/s) connected to an SP4100 integrator (Spectra-Physics). The densitometric data obtained were evaluated with external standards in the following way. For the calibration standards S,-S,, it was assumed that the contents of components A and B per zone (their real values are unknown, as follows from the procedure used for preparing the calibration standard solution) were equal to the corresponding values of the volumes of the calibration standard solution applied to the plate (see Table 1). For each calibration standard component, A and B, a logarithmic (this function gave the best correlation coefficient in all non-linear calibrations that were tested in the given case) approximated calibration graph was constructed and then the contents C, and C, of components A and B per zone were determined for the chromatograms of the samples taken from the known and Q aged entries. The ratio C, lC, was calculated for each A 678 (1994) 119-125 121 sample. The values obtained were plotted against the actual age of the known ink entries and the age of the Q ink entry was determined (see Table 3 and Fig. 3). 3. Results and discussion 3.1. Gas chromatography Figure 1 shows ageing curves obtained for Soyuz ballpoint inks of different colours having similar compositions of colourless components. The curves show that significant ageing taking place over a period from about 6 months to more than 2 years for different inks. After this period until the age of 15 years the extent of the extraction of the volatile component, phenoxyethanol, from the ink entries remained at about 20? 10%. An explanation of this result characterizing the mechanism of evaporation of volatile compophenoxynents (such as phenoxyethanol, ethoxyethanol and other high-boiling vehicles frequently used as the ingredients of ballpoint inks) from ageing inks has been given previously [5]. It was considered that the evaporation process includes a limiting stage of diffusion of a vehicle from the interior layers of the ink body PERCrn Kx!lmcl!IoN mp1) Table 1 Contents of components A and B in the chromatographic zones of the calibration standards Standard” Volume applied W) Component content (mg per spot) A S, S* S, S, 5 8 11 15 B 5 8 11 15 5 8 11 15 a Extract from the l-month ink entry. Aat CF INK (Years) Fig. 1. Ageing curves obtained for violet, blue, green and black Soyuz ballpoint inks: 1 and 2 relate to the maximum and minimum values of %M obtained for the inks analysed. 122 V.N. Aginsky. I J. Chromatogr. to the surface of the film. For the same vehicle and thickness (depth) of the ink film, the efficiency of the diffusion process is mainly a function of the nature of ingredients of inks such as resins and polymers. Moreover, if the resin is capable of polymerizing, i.e., of cross-linking, the diffusion process slows as an ink ages on paper, and at a certain stage of ageing it can virtually stop. For this reason the remaining ink volatile components can be detected in the ink line even after a long period of time; this is shown in Fig. 1 for up to 15year-old entries written with Soyuz ballpoint inks. In such situations, a “weak” solvent (with regard to hardened ink resins), being unable to penetrate inside an old ink line, extracts the ink volatile components only from its exterior layers. However, the newer the ink, the more exterior layers of the ink become available to the weak solvent, and hence a greater amount of the volatile components is extracted. Fig. 1 is a good illustration of the above observation that the extraction efficiency of a “weak” solvent decreased from about 90% for fresh writings to about 20% for old writings. It should be noted that the proposed method includes also an important stage that is carried out if the values of %M determined for the Q ink entry are larger than cu. 60%. In this event, another sample (l-cm sliver) is taken from the ink entry, heated moderately, e.g., at 80°C for 5 min, and analysed as described under Experimental. The percentage extraction value, %M,, is calculated for the heated sample and compared with the value of %M that was determined for the unheated sample. If the difference between %M and %M, is ca. 10% or larger, it can be concluded that the ink entry analysed is a fresh one. If the difference is less than lo%, it means that a more suitable “weak solvent” should be chosen for a given ink. For example. as a result of studying the ageing process of many ballpoint inks of different formulae by using the proposed method, it has been established that if, for a given ink, the analytical results are %M > 70% and %M then the age of the ink %O”~=XO”C.min > lo%, 5 analysed is less than cu. 6 months (depending on A 678 (1994) 119-125 the ink formula, this value may decrease to cu. 2 months). As an example, Fig. 1 shows the results of the age determination obtained for the Q entry (in fact, it was a 3-month old entry written with a Soyuz blue ballpoint ink) using the proposed method. The method demonstrated high efficiency in many actual case situations when it was necessary to determine whether the age of the Q entry was less than several months or not less than 1 year. Such cases are fairly typical when the investigator suspects that the given entry or signature was made after the time the investigation began. Some similar examples have been presented by Cantu [ 111. 3.2. Thin-layer chromatography Fig. 2 demonstrates the view under UV illumination of the fragment of the thin-layer chromatogram (without the chromatographic zones of the paper’s ingredients) and corresponding densitograms obtained for samples taken from entries written with Parker blue ballpoint ink. A and B represent separated colourless components of interest in the ink analysed. It is clearly seen in Fig. 2 that there is an I W light (254 nm) _______________________-___________ (B ---- _ a_--- I Front 1 Fig. 2. Fragment of the thin-layer chromatogram (UV detection at 254 nm) and corresponding densitograms obtained for Parker blue ballpoint ink entries of different ages. S,-S, are calibration standards: Q relates to an entry of questionable age; X,-X, relate to known ink entries: X, = 1 day, XL = 1 month, X, = 1 year. X, = 3 years, X, = 6 years old. V.N. Aginsky. I J. Chromatogr. A 678 (1994) 119-125 obvious link between the relative proportion of substances A and B and the age of the ink writings examined: the substance A/substance B ratio gradually increases as the ink ages (it is a minimum for a fresh, l-day-old entry, the X, track, and maximum for a 6-year-old entry, the X, track). As a rule, the relative proportions of the components separated by TLC are evaluated by obtaining related densitometric data and further by calculating the ratios of the components’ peak signals [l-3,8,9]. However, this approach has been shown to produce erroneous results because, in densitometric TLC, when chromatograms are scanned by reflectance in ‘the absorbance mode, the relationship between signal output (peak height or peak area) and the content of a separated zone is hardly ever a directly proportionality [ 10,12,13]. In this connection, a more reliable approach is offered here. It can be considered as a version of the external standard method for evaluating thinlayer chromatograms for cases typical in forensic analysis when information on the quantitative and even qualitative composition of samples to be analysed is not available and, therefore, calibration graphs cannot be obtained for the analytes. (Another way to avoid erroneous results produced by the signal-to-signal ratio technique includes the application of the approach based on the mass-independent version of the peak ratioing technique [10,13].) The proposed method allows one to obtain the actual mathematical functions of signal versus content for any two components, A and B, of the materials analysed within a certain calibration range of the contents of these components, This calibration range is formed by Cmin-Cmaxe applying at least four or five calibration standards on a TLC plate as follows. If samples are sprayed on as narrow bands, different volumes of only one standard solution can be applied to form a calibration range, An important characteristic of the ‘min coax. method is that the real values of Cmin and C,,, can be unknown to the examiner: only the values of c max/Cmin and CiI&, (where i relates to a calibration standard characterized by the content 123 of a component per zone that is less than C,,, and larger than Cmin) must be known, as was described under Experimental. If samples are applied as spots, calibration standards should be prepared in different concentrations and spotted as a fixed constant volume: multiple spotting of a single standard solution to generate a calibration graph is not acceptable for accurate quantification as there is no simple correlation between signal response for a constant amount of substance and spot size in scanning densitometry [12]. In this case, the contents of components A and B per zone are assumed to be equal (or directly proportional, if only dilution factors, not real concentrations, are known for the calibration standard solutions) to the corresponding concentrations of the calibration standard solutions. Hence the value of the ratio of the contents of any component in the chromatographic zones corresponding to any two prepared calibration solutions will be equal to the value showing how many times one of these solutions is more (or less) concentrated than the other. Further, for each component A and B, an appropriate approximation function is found and used as a calibration function for calculating the contents, C, and C,, of components A and B per spot of the samples taken from the entries of the known and questionable ages. Although these content values are not real, this is not sufficient for the considered method: the main point is that the ratios of these values, C,IC,, are independent of mass, in contrast to the peak ratioing technique that is based on using the mass-dependent values of signal, /signal, (see Table 2). Tables 2 and 3 show peak-height values calculated by an integrator for the separated components of the Parker ink analysed, PH, (for component A) and PH, (for component B), and the values characterizing the relative proportions of the components A and B calculated by using the peak rationing technique (fourth column) and the proposed “content” ratioing method (last column). Fig. 3 shows ageing curves obtained for the Parker ink by plotting the values of the ratios V.N. Aginsky. 124 Table 2 Data obtained Standard for calibration s, A 678 (1994) 119-12.5 standards reading” PH, 31032 51 716 73 261 88 782 90 99 107 112 506 126 745 056 Mean R.S.D. Ratio of peaks, PH, IPH, Ratio of contentsa. 0.34 0.52 0.68 0.79 1.02 0.98 0.96 1.04 0.58 0.34 Integrator PH, S, S, S, I J. Chromaiogr. 1.00 0.04 C,‘CB a Peak heights, PH, and PH,, were plotted against the contents C, and C, (see Table I). As a result, the following regression equations and correlation coefficients (r”) of the logarithmic calibration graphs were obtained: PH, = -56 496 + 53 529 log C,, (r” = 0.9929) and PH, = 57 816 + 20 258 log C, (r’ = 0.9894). Using these equations, the values of CA and C, were recalculated for each standard, S,-S,, and used for calculating the content ratio values listed in the last column. listed in the last two columns of Table 3 against the actual age of the known ink entries. The results of determining the age of the Q entry (in fact, the age of this entry was 2 years) are also shown in Fig. 3 and presented in Table 3. It is clearly follows from Fig. 3 and the data in Tables 2 and 3 that, in comparison with the peak Table 3 Data obtained Ink entry ratioing technique, the proposed mass-independent content ratioing method gives a significant increase in the accuracy and precision of ink age determination. It should also be noted that this method can be successfully applied to a comparative TLC cxamination of similarly coloured inks, paints, fibres and other materials of forensic interest, as for ink entries Integrator reading PI-I, Xl XZ % X, Xi Q Age determined PH, Ratio of peaks, PH,/PH,, 39 659 64 644 70 73s 84 472 88351 110 334 103 435 94817 94 388 93 093 0.36 0.63 0.84 0.8’) 0.95 0.45 1.01 2.04 2.27 2.60 Xl 887 87 963 SO 168 93 529 96 975 Y3 394 0.88 0.91 0.85 2.26 2.14 2.20 1.3 2.6 4.1 1.4 2.4 3.0 for the Q entry (years) Ratio of contents, c*ic, V.N. Aginsky. I J. Chromatogr. NASS-DEPmwT NASS-INDKPmm NAT10 OF “CONTmrs” MT10 OF PEAK SIGNALS(b) (0) 2.5 1 .o I QL\ 2.0 I .- : lQ / : 0.8 1.5 : 1.0 Ii 0 0.7 I x : AGE OF INK Fig. 3. Ageing curves the content ratioing technique. obtained method (Years) A 678 (1994) 119-125 125 The method using TLC allows the detection of age changes in resins and other non-volatile ink components. It includes a new procedure for evaluating thin-layer chromatograms of separated ink components. Being mass-independent, this procedure gives much more correct results for dating inks than those obtained with the aid of the widely used signal-to-signal ratio technique. Both methods, together and separately, have been used in many actual case situations and the results of the examinations have been accepted as conclusive evidence by courts. Further work is necessary to evaluate the limits of the applicability of the methods to numerous inks that are on the market. for the Parker ink using (a) and (b) the peak ratioing References Cantu and R.S. Prough, J. Forensic Sci., 32 (1987) 1151. PI R.L. Brunelle and A.A. Cantu, J. Forensic Sci., 32 (1987) 1522. [31 R.L. Brunelle, J. Forensic Sci., 37 (1992) 113. [41 L.F. Stewart, J. Forensic Sci., 30 (1985) 405. PI V.N. Aginsky, J. Forensic Sci., 38 (1993) 1134. PI V.N. Aginsky, in Proceedings of the 13th IAFS Meeting, Diisseldorf, Germany, August 1993, in press. 171 A.A. Cantu, J. Forensic Sci., 33 (1988) 744. 181 R.L. Brunelle and H. Lee, J. Forensic Sci., 34 (1989) 1166. [91 G.M. Golding and S. Kokot, J. Forensic Sci., 35 (1990) 1310. 1101 V.N. Aginsky, J. Forensic Sci., 38 (1993) 1111. IllI A.A. Cantu, Anal. Chem., 63 (1991) 847A. 1121 C.F. Poole and S.K. Poole, J. Chromatogr., 492 (1989) 539. u31 V.N. Aginsky, J. Planar Chromatogr., 4 (1991) 167. [II A.A. its discriminating power is much greater than that usually produced by the widely used massdependent signal-to-signal ratio technique. 4. Conclusions Two complementary methods for dating ballpoint inks have been considered. The method using GC allows discrimination between fresh (age not greater than a few months) and old ballpoint inks, including inks with formulae unknown to the examiner. It is effective for analysing ballpoint inks that contain phenoxyethanol, phenoxyethoxyethanol or similar highboiling vehicles. Exhibit 21 Declaration of Larry F. Stewart Exhibit 22 Declaration of Larry F. Stewart Exhibit 23 Declaration of Larry F. Stewart J Forensic Sci, Jan. 2004, Vol. 49, No. 1 Paper ID JFS2003217–491 Available online at: www.astm.org TECHNICAL NOTE Gerald M. LaPorte,1 M.S.F.S.; Jeffrey D. Wilson,3 B.S.; Antonio A. Cantu,2 Ph.D.; S. Amanda Mancke,3 B.S.; and Susan L. Fortunato,1 B.A. The Identification of 2-Phenoxyethanol in Ballpoint Inks Using Gas Chromatography/Mass Spectrometry—Relevance to Ink Dating∗ ABSTRACT: Developing and implementing a generally accepted procedure for the dating of ink found on documents using dynamic approaches has been a very formidable undertaking by forensic document examiners. 2-Phenoxyethanol (PE), a common volatile organic compound found in ballpoint inks, has been recognized for over a decade as a solvent that evaporates as ink ages. More recently, investigations have focused on the solvent loss ratio of PE prior to and after heating. To determine how often PE occurs in ink formulations, the authors analyzed 633 ballpoint inks utilizing a gas chromatograph/mass spectrometer. 2-Phenoxyethanol was identified in 85% (237/279) and 83% (293/354) of black and blue inks, respectively. KEYWORDS: forensic science, questioned documents, phenoxyethanol, ballpoint ink, ink dating, ink aging, GC/MS, volatile analysis, SPME An examination to determine the age of ink on a document can be quite challenging. Cantu (1,2) outlines two approaches to determine the age of ink on a questioned document. The first of these is the static approach, which generally applies to methods based on the comparison of various ink components to a standard reference collection to determine the first date of production. In fact, the United States Secret Service (USSS) and the Internal Revenue Service (IRS) jointly maintain the largest known collection of writing inks from around the world. These inks date back to the 1920s and include over 8000 inks obtained from various manufacturers throughout the world. Annually, contact is made with the pen and ink manufacturers requesting that they send any new formulations of inks, along with appropriate information, so that the submitted standards can be chemically tested and added to the reference collection. Writing pens are also obtained from the open market and compared to the library of standards to verify and identify additional inks. This is a formidable task that obviously requires significant resources and maintenance. Indeed, this is not always a practical solution for every forensic facility to achieve. Ideally, ink tags would be the most reliable method for the dating of inks. Tags can be added to formulations in the form of fluorescent 1 United States Secret Service, Forensic Services Division, Questioned Document Branch, 950 H Street NW, Washington, DC. 2 United States Secret Service, Forensic Services Division, Research Section, 950 H Street NW, Washington, DC. 3 United States Secret Service, Forensic Services Division, Questioned Document, chemist contractor, 950 H Street NW, Washington, DC. ∗ This work was presented, in part, at the Mid-Atlantic Association of Forensic Scientists Annual Meeting, May 8, 2003, Annapolis, MD. All references pertaining to manufacturers and their products do not imply endorsement by the United States Secret Service or the authors. Received 21 June 2003; and in revised form 4 Sept. 2003; accepted for publication 4 Sept. 2003; published 17 Dec. 2003. Copyright C compounds or rare earth elements and were evident in some formulations from about 1970 until 1994. Factors have precluded some ink manufacturers from participating in such a program, including, but not limited to, insufficient resources, low priority, and/or disagreement about the type of tag utilized. This is not to say that a widespread tagging agenda is not achievable. On the contrary, efforts do continue to convince ink companies to add tags to their formulations. As recently as November 2002, a dominant ink manufacturer has begun adding tags to their ink in collaboration with the U.S. Secret Service. With stringent demands from the forensic community to develop and validate scientifically reliable laboratory techniques, implementing other methods for ink dating is an arduous endeavor as well. Such methods include those involving the dynamic approach, which incorporates procedures that measure the physical and/or chemical properties of ink that change with time. The changes that occur over a given period of time can generally be referred to as aging characteristics. Ballpoint inks mainly consist of colorants (dyes and/or pigments) and vehicles (solvents and resins). There is also a wide array of other ingredients, which may include antioxidants, preservatives, and trace elements, but these are typically a small component of the overall ink composition. Nevertheless, the importance of their presence should not be diminished since the combination of all ingredients may play a pivotal role in the aging characteristics of an ink formulation. However, the subject of this paper will focus on the vehicles found in ballpoint inks. More specifically, the authors have chosen to investigate a single volatile compound that has been reported by the industry to be in many formulations of inks. Volatile analysis of ballpoint inks, using GC/MS, for determining the age of inks on paper has been studied and reviewed in the literature for more than a decade (3–8). These authors have laid the 2004 by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. Copyright by ASTM Int'l (all rights reserved); Tue Sep 15 09:34:34 EDT 2009 Downloaded/printed by Tina Tam (Good and Cormier) pursuant to License Agreement. No further reproductions authorized. 1 2 JOURNAL OF FORENSIC SCIENCES FIG. 1—The chemical structure and formula for 2-phenoxyethanol. groundwork for what may be a very promising dynamic approach to the future of ballpoint ink age determination. These works have honed in on the analysis of 2-phenoxyethanol (PE), a common volatile organic compound found in some ballpoint writing inks. 2-Phenoxyethanol, also referred to as ethylene glycol monophenyl ether, 1-hydroxy-2-phenoxyethane, beta-hydroxyethylphenyl ether, Dowanol EP, and Phenyl Cellosolve, is a glycol ether and is used as the principal solvent in many ballpoint ink formulations. It is a colorless, slow evaporating, viscous liquid with a faint aromatic odor and is used in most ballpoint ink formulations because it is stable in the presence of acids and alkalis. It is also nonhygrosopic (does not absorb water, making it amenable to hot, humid climates), nonhazardous, economical, and especially good at solubilizing resins and nigrosine (a common solvent soluble black dye used in the writing ink formulations). It is recognized as Chemical Abstracts Service (CAS) number 122-9-6 and has a molecular weight of 138.17 with a boiling point of 245.2◦ C (9). Figure 1 depicts the chemical formula and structure of PE. Beshanishvily et al. (4) were the first to discuss the identification of PE as it relates to the aging of inks. Since then, Aginsky (5) reported that, “. . . significant aging [takes] place over a period of about 3 months. After this period until the age of 15 years the extent of the extraction of the volatile component (phenoxyethanol) from the ink entries has been kept at a level about 20%.” Aginsky also describes the ink-drying process and surmises that volatile components stop emitting from a dried sample of ink until they are freed by heating or a solvent extraction. More recently, Gaudreau and Brazeau (10) presented their findings on an extensive research effort that focuses on how PE levels change over time following an ink entry placed on paper. They discuss solvent loss and state that the “. . . phenoxyethanol in ink evaporates at a high rate during the first six to eight months following its application on paper. The rate of evaporation stabilizes over a period of six to eighteen months. This process is no longer significant after a period of about two years.” Given the chemical properties of PE, its loss due to evaporation is most affected by heat. With these caveats, they developed a dynamic approach to ink dating that incorporates comparing the PE ratio of an ink prior to and after heating. In addition, Brazeau et al. (11) have experimented with solid phase micro-extraction (SPME), which utilizes a specially coated silica fiber that is mounted in a syringe-like device. A small glass vial is placed over the ink entry with the SPME device inserted in the sealed environment. Volatile solvents that emit from the ink adsorb onto the fiber for a set time, i.e., until an equilibrium is achieved within the system. The fiber is then withdrawn and injected into a gas chromatograph (GC), whereby the volatile components are desorbed due to the high temperature (e.g., 250◦ C) in the injection port. The analytes are then separated in the GC and identified using an appropriate analytical instrument such as a mass spectrometer (MS). SPME has proven to be an efficient and effective method for the extraction of volatile components (12,13) and has been utilized in the authors’ laboratory for the detection of PE in some ballpoint inks. Chemical analysis of writing inks by means of thin layer chromatography (TLC) is viewed by the scientific community as a valid procedure to compare inks (14–18). Since TLC is an effective and efficient method for separating and identifying various colored components such as dyes, and nearly all ink formulations are proprietary, forensic examinations that employ TLC analysis are invaluable. For instance, two or more questioned inks can be compared to determine if they are the same, or questioned inks can be associated to a known standard to determine the age of an ink, i.e., the static approach. With respect to this latter instance, appropriate information and documentation acquired from a manufacturer regarding their ink will allow a forensic document examiner to make significantly reliable conclusions, assuming there is access to a thorough ink collection. Although obtaining a supplemental volatile profile may increase the degree of discrimination, limitations include solvent loss over time or other external factors such as exposure to high temperatures, light, and/or humidity. With the benefit of having a large collection of standards, the authors determined that it would be advantageous to begin conducting volatile profiles of writing inks to investigate the percentage of ballpoint inks that actually contain PE since it is an important compound of interest for the determination of ink age. An extensive search of the literature was conducted, but no studies investigated a large population of inks to determine how often PE is present in ballpoint ink formulations. Thus, the focus of this paper will be on the examination for the presence of 2-phenoxyethanol in 633 ballpoint inks. Materials and Methods Ink Standards As stated, ink standards are received by the USSS from all over the world and date back to the 1920s. As new ink formulations are received, samples of the ink are placed onto WhatmanTM filter paper No. 2 (also referred to as scribble sheets), allowed to air dry, placed in a protective sheet and binder, and finally stored in dark cabinets to ensure minimal degradation due to environmental factors such as light, temperature, and humidity. Many of the ink standards are received as a liquid in a bottle and permanently retained, and others are received in pens, pen refills, or as samples on paper. For this study, whenever possible, ballpoint ink samples in liquid form were analyzed directly from the bottle or pen. Other ink samples were taken off the scribble sheets; however, volatile profiles of scribble sheet samples were closely examined to determine if they were suitable to include in the study since some were over 30 years old. This topic will be discussed under Results and Discussion. A total of 279 black ballpoint inks from 31 companies and 354 blue ballpoint inks from 26 companies were chosen for analysis using a PerkinElmer TurboMassTM gas chromatograph/mass spectrometer. Extraction Liquid inks were sampled utilizing a disposable capillary glass pipette in order to minimize sample handling. The pipette was then placed into a glass vial containing 1 mL of acetonitrile. The ink and solvent were agitated/stirred to ensure a homogenous mixture. Dried ink samples from scribble sheets were sampled using a 5-mm hole punch. The punches were taken from a highly dense area and allowed to extract in a vial with 1 mL of acetonitrile for approximately 1 min. The solvent was decanted and placed into a separate vial. Copyright by ASTM Int'l (all rights reserved); Tue Sep 15 09:34:34 EDT 2009 Downloaded/printed by Tina Tam (Good and Cormier) pursuant to License Agreement. No further reproductions authorized. LAPORTE ET AL. r ANALYSIS OF 2-PHENOXYETHANOL 3 FIG. 2a—The total ion chromatogram for 2-phenoxyethanol standard (J.T. Baker TM product No. T-319-07). Gas Chromatography/Mass Spectrometry (GC/MS) All of the extracted ink samples were analyzed using an auto sampler attached to a PerkinElmer TurbomassTM GC/MS. Onemicroliter samples were injected into the GC. The column used was an HP-5 (30 m × 0.32 mm × 0.25 µL) cross-linked 5% phenylmethylsiloxane. The injector temperature was set to 260◦ C and the flow rate was 1.2 mL/min split mode at 20 mL/min. The temperature program started at 50◦ C for 1 min and increased at a rate of 10◦ C/min to 200◦ C with a 2-min hold. The second rate was 25◦ C/min to 300◦ C with a final 2-min hold. The mass spectrometer detector was set for full scan from 1.8 to 24 min with the 1.8-min delay set to begin following the solvent elution, i.e., solvent delay. The detector was programmed to scan compounds ranging from 28 to 500 atomic mass units (amu). Results and Discussion A review of the standards library indicated that at the inception of this project there were 516 black ballpoint inks from 53 companies and 854 blue ballpoint inks from 65 companies. All the liquid ink samples that were obtained from bottles were extracted and exhibited significant volatile profiles with sufficient peak abundance for accurate integration. In contrast, there were numerous scribble sheet samples that did not produce a significant, or very limited, chromatographic profile. The lowest level of detection for sufficient interpretation was estimated to be 0.1 ppb. It was determined that insignificant peak area was the result of the age of the ink on the scribble sheet (e.g., some scribble sheets were 20 to 30 years old). The results for the samples determined to have poor chromatographic profiles were recorded, but not used to calculate the statistics presented in this paper. A total of 279 black ballpoint inks FIG. 2b—The mass spectrum for Peak 1 at retention time (RT) = 8.79 min. FIG. 2c—The mass spectrum for Peak 2 at RT = 12.45 min. from 31 companies and 354 blue ballpoint inks from 26 companies were determined to have significant chromatographic profiles necessary for peak integration and, hence, accurate identification of chemical composition. 2-Phenoxyethanol was identified in 85% (237/279) and 83% (293/354) of the black and blue inks, respectively. Furthermore, 20 of the 31 companies that have manufactured black ballpoints used PE in the vehicle in 100% of their ballpoint formulations and 11 of the 26 manufacturers incorporated PE in all of their blue ballpoint inks. The 2-phenoxyethanol standard (J.T. Baker product No. T31907, Lot No. N35622) contained two major peaks on the TIC (total ion chromatogram), and the GC/MS results are depicted in Figs. 2a, 2b, and 2c. In addition to the PE at retention time (RT) 8.79 min, Copyright by ASTM Int'l (all rights reserved); Tue Sep 15 09:34:34 EDT 2009 Downloaded/printed by Tina Tam (Good and Cormier) pursuant to License Agreement. No further reproductions authorized. 4 JOURNAL OF FORENSIC SCIENCES 2-(2-phenoxyethoxy)ethanol, also referred to as diethylene glycol phenyl ether (DGPE) or phenyl carbitol, was detected at a RT of 12.45 min. It is identified as CAS number 104-68-7. The SigmaAldrich catalogue (2003-2004) indicates that Dowanol EPH, i.e., PE, can contain up to 10% DGPE. DGPE was detected in 21.5% (60/279) and 12.1% (43/354) of the black and blue ballpoint inks that contained PE, respectively. There was no evidence that the level of DGPE was directly related to the level of PE (e.g., DGPE was occasionally absent in samples with relatively high levels of PE and was present in samples with relatively low levels of PE). However, no further study was conducted to examine if the ratio of PE/DGPE changed with aging. The authors did infer that there may be differences in the composition of 2-phenoxyethanol that may be attributable to a particular chemical manufacturer. Indeed, this information could be utilized to differentiate ink manufacturers depending on their supplier. GC/MS is an obviously powerful analytical tool, not only for the dating of inks, but for the identification of some components of inks. Brunelle and Crawford (19) recently wrote, “GC-MS shows great promise for strengthening ink identifications, because it can be used to identify both volatile and non-volatile ingredients of inks.” Accordingly, the authors were cognizant of this at the outset of the study and maintained data of all the identifiable components in the 633 black and blue ballpoint inks to determine if there are chemical class characteristics specific to a manufacturer. A thorough review of the results and all subsequent conclusions pertaining to the use of GC/MS to profile company ink formulations was considered a secondary objective. The authors determined that this analysis would be better suited in a future work with an extensive and dedicated discussion to the GC/MS analysis of a large population of ballpoint inks. The analysis of volatile components such as PE to determine the age of an ink is promising, especially when using methods that are based on the relative loss of a solvent between heated and unheated samples. There are different scenarios of a document examination that an examiner may encounter that will significantly affect the degree of qualification of a conclusion. For example, an examiner may be requested to compare two or more inks on the same document to determine if they were produced contemporaneously. If prior examinations indicate that the inks are matching formulations, but they are suspected of being made at two different time periods (e.g., several months apart), then factors such as storage conditions, the type of paper, exposure to a variety of environments, and differences in formulation should not preclude a forensic examiner from making conclusions with limited qualifications. It is important to note that the Merck Index (9) indicates that PE is used as a fixative in perfumes, which would require handlers to be cognizant so as not to possibly contaminate a questioned document. As well, the approaches discussed in this paper are not mass independent when sampling the ink; therefore, care and accuracy need to be administered when removing ink plugs for analysis. One final caveat that requires some consideration is the rate of PE migration on paper once an entry is made. Since PE is a liquid solvent, it is feasible to ascertain that it may dissipate through the paper into a questioned entry if ink is present on the reverse side of a page. Ink may also migrate from nearby adjacent entries, but taking blank samples (e.g., samples of the paper with no ink) in close proximity may aid the examiner in understanding the extent of PE migration. Another scenario that may be encountered is the analysis of ink entries on a document that are not of the same formulation. Although one may argue that the document is likely to have been stored under the same conditions, the level of PE may exist in different levels in different formulations from the same manufacturer. Finally, one may be requested to date entries on multiple pages that are part of the same document submission (e.g., multi-page wills or contracts) to determine if they were produced at, or around, the same time. Differences in paper, storage conditions, and how the document is arranged (e.g., the presence of ink solvents on subsequent or overlying pages that transfer to adjacent pages) should be taken into consideration. Indeed, more research and validation into these unknown effects will be fundamental in developing standard allowable variations. Standard error can then be incorporated to account for human error and experimental deviation that are necessary to make qualified conclusions of forensic significance. Conclusion The identification of PE in over 80% of black and blue ballpoint ink formulations has shown that studies investigating PE as it relates to the aging of writing inks have been and continue to be significant. As our field undergoes necessitated scrutiny of forensic examinations, GC/MS is an excellent and well-proven analytical tool for the identification and quantification of chemical compounds. Validation of the instrumentation and the procedures utilized to identify PE should therefore be minimal. This will allow future researchers to concentrate their efforts on the development and implementation of a generally accepted procedure for a dynamic approach to ink dating. Acknowledgments The authors wish to extend their gratitude to Dr. Ben Fabian from Sensient Imaging Technologies for the information he provided regarding the use of 2-phenoxyethanol in the writing ink industry. As well, we wish to thank Mr. Marc Gaudreau and Mr. Luc Brazeau of the Canada Customs Revenue Agency for their efforts to accommodate our many questions regarding the analysis of volatile solvents in ballpoint writing inks. References 1. Cantu AA. A sketch of analytical methods for document dating. Part I: The static approach: determining age independent analytical profiles. Int J Forensic Doc Examiners 1995;1(1):40 –51. 2. Cantu AA. A sketch of analytical methods for document dating. Part II: The dynamic approach: determining age dependent analytical profiles. Int J Forensic Doc Examiners 1996;2(3):192–208. 3. Stewart LF. Ballpoint ink age determination by volatile component comparison—a preliminary study. J Forensic Sci 1985;30(2):405–11. 4. Beshanishvily GS, Trosman EA, Dallakian PB, Voskerchian GP. Ballpoint ink age—a new approach. Proceedings of the 12th International Forensic Scientists Symposium; 1990 Oct 15–19; Adelaide, Australia. 5. Aginsky VN. Some new ideas for dating ballpoint inks—a feasibility study. J Forensic Sci 1993;38(5):134–50. 6. Aginsky VN. Determination of the age of ballpoint ink by gas and densitometric thin-layer chromatography. J Chromatogr A 1994;678:117–25. 7. Aginsky VN. Dating and characterizing writing, stamp pad and jet printer inks by gas chromatography/mass spectrometery. Int J Forensic Doc Examiners 1996;2(2):103–15. 8. Aginsky VN. Measuring ink extractability as a function of age—why the relative aging approach is unreliable and why it is more correct to measure ink volatile components than dyes. Int J Forensic Doc Examiners 1998;4(3):214–30. 9. Budavari S, editor. The merck index: an encyclopedia of chemicals, drugs, and biologicals. 12th ed. Whitehouse Station (NJ): Merck Research Laboratories Division of Merck & Co., Inc., 1996:7410. 10. Gaudreau M, Brazeau L. Ink dating using a solvent loss ratio method. Proceedings of the 60th Annual Conference of the American Society of Questioned Document Examiners; 2002 Aug 14 –18; San Diego (CA). Copyright by ASTM Int'l (all rights reserved); Tue Sep 15 09:34:34 EDT 2009 Downloaded/printed by Tina Tam (Good and Cormier) pursuant to License Agreement. No further reproductions authorized. LAPORTE ET AL. [PubMed] [PubMed] 11. Brazeau L, Chauhan M, Gaudreau M. The use of micro-extraction in the development of a method to determine the aging characteristics of inks. Proceedings of the 58th Annual Conference of the American Society of Questioned Document Examiners; 2000 Aug 24 –29; Ottawa, Ontario. 12. Vu DTT. SPME/GC-MS characterization of volatiles associated with methamphetamine: toward the development of a pseudomethamphetamine training manual. J Forensic Sci 2001;46(5):1014 –24. 13. Vu DTT. Characterization and aging study of currency ink and currency canine training aids using headspace SPME/GC-MS. J Forensic Sci 2003;48(4). 14. Aginsky VN. Forensic examination of “slightly soluble” ink pigments using thin-layer chromatography. J Forensic Sci 1993;38: 1131–3. 15. Brunelle RL, Pro MJ. A systematic approach to ink identification. J AOAC Int 1972;55:823–26. r ANALYSIS OF 2-PHENOXYETHANOL 5 16. Kelly JD, Cantu AA. Proposed standard methods for ink identification. J AOAC Int 1975;58:122–25. 17. The American Society for Testing and Materials (ASTM) E 1422-98: Standard Guide for Test Methods for Forensic Writing Ink Comparison, 1998;530–7. 18. The American Society for Testing and Materials (ASTM) E 1789-96: Standard Guide for Writing Ink Identification, 1996:722– 6. 19. Brunelle RL, Crawford KR. Advances in the forensic analysis and dating of writing ink. Springfield (IL): Charles C. Thomas, 2003;164. Additional information and reprint requests: Gerald M. LaPorte, M.S.F.S. United States Secret Service Forensic Services Division 950 H Street NW Washington, DC 20223 E-mail: gerry.laporte@usss.dhs.gov Copyright by ASTM Int'l (all rights reserved); Tue Sep 15 09:34:34 EDT 2009 Downloaded/printed by Tina Tam (Good and Cormier) pursuant to License Agreement. No further reproductions authorized.

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