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Received: 28 January 2014 Revised: 3 March 2014 Accepted: 5 March 2014 Published online in Wiley Online Library
Keywords: mass spectrometry; document examination; erasable ink; electrospray-assisted laser desorption ionization; forensic science
Introduction examine finer details (i.e. indentations in the paper, ink striations,
line crossings) of strokes made with erasable pens. In addition,
The introduction of erasable pens in the late 1970s has made the application of lycode powders on paper surfaces allowed the
correction of written errors easier.[1–4] Based on differences in powders to adhere to erasable ink lines so that the erased writing
vanishing mechanisms, erasable inks are divided into two catego- became visible.
ries. The first type comprises of the inks that are contained in However, spectroscopic approaches fail to reveal the erased
rubber cement during production. The cement facilitates ink ink lines, while the optical property of the erasable ink com-
adsorption on paper surfaces while preventing ink absorption pounds is similar to the paper materials. In these cases, other
by the paper fibers.[4,5] These inks can be rubbed off paper analytical tools must be used to characterize the ink compounds
surfaces with a rubber eraser in a manner similar to remove on the paper. Mass spectrometry (MS), an extremely sensitive
writing made with a graphite pencil; however, the hardening of tool for determining the organic compounds, has been used to
the rubber cement over time will consequently increase the diffi- characterize the organic components in ink.[13–15] Laser desorp-
culty of removing these inks from paper surfaces. On the other tion ionization MS (LDI-MS) and matrix-assisted laser desorption
hand, the second type comprises of thermochromic inks that ionization MS (MALDI-MS) provide the feature of directly
are visible from 10 °C to 60 °C and become invisible at temper- detecting analytes on solid surface, which have been used to
atures higher than 60 °C.[4,6,7] These reversible thermochromic characterize dyes and pigments in inks. Nevertheless, the
processes, modulated via temperature change, are due to elec- document has to be folded up or cut into small pieces to fit in
tron transfers between electron-donating color compounds and the vacuum chamber of the ionization sources of LDI-MS and
electron-accepting compounds in the inks.[7] Regardless of MALDI-MS instruments. In addition, the application of organic
erasable ink type, a hard plastic eraser and freezer are usually MALDI matrix solution on the sample surface usually results in
used to heat and cool the inks, respectively.
Even though erasable pens are convenient for correcting
handwriting, they have been used for criminal purposes such as * Correspondence to: Jentaie Shiea, Department of Chemistry, National Sun
forgeries of checks and wills. Typically, writings made with Yat-Sen University, Kaohsiung, 804 Taiwan. E-mail: jetea@mail.nsysu.edu.tw
erasable pens are rubbed off the surface of a check, after which * Correspondence to: Hsiu-O Ho, College of Pharmacy, Taipei Medical
a normal pen is used to write over the invisible ink lines. Optical University, Taipei, Taiwan. E-mail: hsiuoho@tmu.edu.tw
techniques such as microscope, ultraviolet (UV), infrared, Raman a College of Pharmacy, Taipei Medical University, Taipei, Taiwan
and X-ray spectroscopy are commonly used to examine the
spectral properties of trace ink compounds in the erased ink line b Investigation Bureau, Ministry of Justice, New Taipei City, Taiwan
without damaging documents.[4,8–13] For example, UV–vis and
c Department of Chemistry, National SunYat-Sen University, Kaohsiung, Taiwan
infrared spectroscopy were used to examine the erased charac-
ters after sample temperatures were raised using an eraser, d Department of Medicinal and Applied Chemistry, Kaohsiung Medical
445
laundry iron or hair dryer.[4] A stereomicroscope was used to University, Kaohsiung, Taiwan
J. Mass Spectrom. 2014, 49, 445–451 Copyright © 2014 John Wiley & Sons, Ltd.
Y.-Y. Kao et al
lateral diffusion of ink pigments on the paper.[13,15–20] Chromato- A detailed configuration of the ELDI source can be found in our
graphic and electrophoretic methods, such as thin-layer chroma- previous publications.[29,34,35] A stainless steel plate or a sheet of
tography, gas chromatography, liquid chromatography and paper was placed on an acrylic plate set on an XYZ stage. The ink
capillary electrophoresis, are commonly combined with MS for lines on the plate or paper were positioned in front of the mass
trace ink analysis; however, such analysis requires tedious sample spectrometer inlet (Fig. 1). A pulsed Nd:YAG laser beam (MINILITE
pretreatment that also damages the sample document.[20–25] I, Continuum Electro-Optics Inc., USA) was focused with micro-
Recently, several ambient ionization techniques such as de- scopic objective lens to irradiate the sample surface at an inci-
sorption electrospray ionization, easy ambient sonic-spray ioniza- dent angle of 45°; the laser was operated at a wavelength of
tion, direct analysis in real time and low temperature plasma 1064 nm, a repetition rate of 5 Hz, a pulse duration of 5 ns and
coupled with MS have been used to rapidly characterize inks on a pulse energy of 2 mJ. The spot size of laser beam was approxi-
paper surfaces without sample pretreatment.[26–32] Electrospray- mately 20–50 μm in diameter. An ESI emitter was aligned parallel
assisted laser desorption ionization/MS (ELDI/MS) combines laser to the sample plate and directed toward the MS inlet to generate
desorption and ESI to desorb, ionize and detect analytes in their charged solvent species for post-ionization of the laser-desorbed
native environments.[33–39] The extremely high spatial resolution ink molecules. The distance between the ESI capillary and the
and desorption energy characteristic of the pulsed laser beam sample spot was approximately 3 mm. A potential of 4.5 kV was
makes ELDI/MS a useful tool to characterize the chemical com- applied to the acidic methanol solution (50% methanol solution
pounds adsorbed over a very small area in the paper fiber. In this with 0.1% acetic acid, 150 μl/h) to produce an ESI plume at the
study, two erasable pens each containing ink rubber cement and tip of a fused silica capillary (100 μm, i.d.). Mass spectra were
thermochromic ink were used to draw the characters on paper recorded from m/z 100 to 1200 with a scan rate of 0.5 Hz. The
for test, ELDI/MS was then applied to characterize trace ink presenting mass spectra were the average of six scans. The ELDI
compounds before and after erasable ink markings were mass spectra were exported from DataAnalysis (Version 4.0, Bruker
rubbed off. The ink compounds written over the erased ink line Daltonics) and then further analyzed using Polytools (Version 1.18,
were characterized. Bruker Daltonics) to diagnose the detected polymer ions.
wileyonlinelibrary.com/journal/jms Copyright © 2014 John Wiley & Sons, Ltd. J. Mass Spectrom. 2014, 49, 445–451
ELDI/MS to detect erased ink lines
damage to the sample documents. Figure 1(b) and (c) displays spectroscopy. Even though the vanished ink line made with
photographs of a letter ‘I’ before and after ELDI/MS scanning thermochromic ink can be re-visualized after cooling the docu-
analysis, only an extremely small damage sampling region across ment in a freezer, this test will be performed only on the sus-
the center of the letter ‘I’ was observed in Fig. 1(c). picious case, not routinely. In general cases, the investigators
The ink lines drawn on paper surfaces with erasable pens could do not know what they meet; therefore, a technique capable
be rendered invisible either by rubbing the lines with an eraser or of rapidly telling the writing history of the paper will be useful
heating the paper with a hair dryer. Figure 2(a) and (b) shows the in investigation. To overcome the problem, ESI/MS and ELDI/MS
photographs of the blue ink lines drawn on a copy and a printing were used to characterize trace ink compounds in the erased
paper with Signo and Pilot Frixion erasable pens, respectively. ink lines.
After rubbing the lines with an eraser, both ink lines vanished The ESI/MS was first used to determine the chemical composi-
(Fig. 2(c) and (d)). The possible reasons for the disappearance of tion of the erasable inks. The sample solution was prepared by
the ink lines are as follows: (1) heat was generated at the paper dissolving the ink in the acidic methanol solution. The ESI mass
surface during rubbing, thus turning the thermochromic ink spectra of the Signo ink showed predominant polymeric ions –
transparent, or (2) the ink/cement was simply rubbed off the i.e. six series of ions at m/z 279 + 22n (□), 315 + 22n (▽),
paper surface. To determine which erasable pen contained 348 + 22n (○), 400 + 22n (△), 580 + 44n (●) and 585 + 44n (■) (Fig. 3
thermochromic ink, the paper with ink lines drawn by two (a) and Table 1). Because the mass difference (Δm) between the
erasable pens was placed in an oven for 10 min (80 °C). After neighboring peaks of the polymeric ion series is 44 for singly
heating, the ink lines made by the Pilot Frixion pen turned charged ions and 22 for doubly charged ions, the detected ions
transparent, while those drawn with the Signo pen did not. The are suggested to be either polyethylene glycol (PEG) or com-
eraser-rubbed papers were then placed in a freezer ( 80 °C) for pounds with PEG side chains. PEG is a common additive in the
10 min; the ink lines drawn with the Pilot Frixion pen became ink. The ion series were tentatively assigned as protonated and
visible, while those drawn with the Signo pen did not. The sodiated PEG ions: (M + H)+ for m/z 580 + 44n, (M + 2Na)2+ for
results indicated that Pilot Frixion pen contained thermochro- m/z 400 + 22n, (M + H + Na)2+ for m/z 279 + 22n; and (M′ + H)+
mic ink and Singo pen contained rubber cement ink, which is for m/z 585 + 44n, (M′ + 2Na)2+ for m/z 315 + 22n, (M′ + H + Na)2+
consistent with the previous reports and the statement from for m/z 348 + 22n. Further analysis by using high resolution MS
the manufacture.[4–7] The papers with erased ink lines were must be performed so the identity of these polymer molecules
further examined by UV illumination under a 254 nm light. can be confirmed.
The copy paper displayed a fluorescence emission, but the Figure 3(b) displays the ELDI mass spectra for the ink lines
erased ink lines and the printing paper were not. Thus, the drawn with a Signo pen on a sheet of copy paper. The PEG-like
erased ink lines on a copy paper were visualized, while those ions detected by ELDI/MS on the surface of the copy paper are
on a printing paper were not observed (Fig. 2(e) and (f)). The similar to those detected by ESI/MS; however, the ion series at
results indicated that if the ink compounds have the same m/z 585 + 44n, one of the predominant ion series on the ESI mass
fluorescent property as that of printing paper, after being spectrum, has lower intensities on the ELDI mass spectrum. The
erased, it is impossible to trace the writing history with UV similar type and mass range of the ions detected by ESI/MS and
Figure 2. Photographs of the ink lines on copy paper (left) and printing paper (right): (a and b) before rubbing by an eraser, (c and d) after rubbing by
447
J. Mass Spectrom. 2014, 49, 445–451 Copyright © 2014 John Wiley & Sons, Ltd. wileyonlinelibrary.com/journal/jms
Y.-Y. Kao et al
712.4
x104
756.4
668.4
(a)
800.5
0.8
Ink dissolved in
411.2
455.2
624.4
433.2
477.2
389.2
499.2
844.5
ESI solution
367.2
580.3
521.3
345.2
888.5
0.4
651.4
563.3
543.3
607.3
323.1
932.5
301.1
279.1
1020.6
976.6
0.0
411.2
712.4
433.2
x104
455.2
668.4
389.2
(b)
477.2
367.2
756.4
624.4
Ink on paper
345.2
499.2
800.5
521.3
1.0
319.1
301.1
Absolute Intensity
580.3
543.3
844.5
563.3
279.1
607.3
651.4
888.5
932.6
0.0
411.2
433.2
x103
712.4
(c)
389.2
668.4
455.2
367.2
477.2
756.4
Ink on paper
624.4
4.0
345.2
499.2
800.5
-wiped
521.3
323.1
580.3
844.5
563.3
607.3
543.3
301.1
651.4
2.0
888.5
279.1
932.5
0.0
x104
712.4
433.2
411.2
455.2
(d)
756.5
668.4
389.2
1.0
367.2
477.3
Ink on paper
624.4
800.5
499.3
345.2
844.5
519.3
0.5
323.2
543.3
733.4
777.4
821.4
888.6
689.4
301.1
645.3
0.0
200 300 400 500 600 700 800 900 1000 m/z
Figure 3. (a) ESI (+) mass spectra of the ink in uni-ball Signo erasable pen. (b) ELDI (+) mass spectra of ink line drawn on a copy paper. (c) The ink line of
(b) was wiped by an eraser and then characterized by ELDI/MS. (d) The ink line of (b) was characterized by ELDI/MS 4 months later (□, m/z 279 + 22n ion
series; ▽, m/z 315 + 22n ion series; ○, m/z 348 + 22n ion series; △, m/z 400 + 22n in series; ●, m/z 580 + 44n ion series and ■, m/z 585 + 44n ion series).
Table 1. The polymer ions detected in erasable and gel pens’ inks
Pens Ion series Ions
Uni-ball Singo erasable pen 279 + 22n 279, 301, 323, 345, 367, 389, 411, 433, 455, 477, 499, 521, 543
315 + 22n 315, 337, 359, 381, 403, 425, 447, 469, 491, 513
348 + 22n 348, 370, 392, 414, 436, 458, 480, 502, 524
400 + 22n 400, 422, 444, 466, 488, 510, 532
580 + 44n 580, 624, 668, 712, 756, 800, 844, 888, 932, 976, 1020
585 + 44n 585, 629, 673, 717, 761, 805, 849, 893, 937, 981
Pilot Frixion erasable pen 223 + 111n 223, 334, 445, 556
242 + 111n 242, 353, 464, 575
245 + 111n 245, 356, 467, 578
261 + 111n 261, 372, 483
297 + 111n 297, 408, 519
321 + 111n 321, 432, 543
SKB V6 gel pen 261 + 44n 261, 305, 349, 393, 437, 481
283 + 44n 283, 327, 371, 415, 459, 503
344 + 44n 344, 388, 432, 476, 520, 564
ELDI/MS indicate the usability of ELDI/MS for directly characteriz- the paper. This will be particularly useful in preventing document
ing ink compounds from handwritings. Although a blue color or check forgery. However, proper energy (such as that from a
precipitate was formed after centrifuging the erasable ink pulsed laser beam) must be applied on the paper so the ink
solution, indicating that the erasable ink contained blue color compounds adsorbed in the paper fibers can be efficiently
pigments, no obvious pigment ion signals was detected on the desorbed and ionized. Figure 3(c) shows the ELDI mass spectrum
ESI and ELDI mass spectra. The absence or low intensity of recorded from erased ink lines, which reveals PEG ion series with
pigment ion signals detected in the ink lines may be due to the similar mass range but lower ion intensities as those before the
ion suppression effect from PEG ions. ink lines were rubbed off (Fig. 3(b)). The ink lines drawn on other
Even though the cement facilitates ink adsorption on paper surfaces such as a printing paper and stainless steel plate were
surfaces, trace ink compounds will still be adsorbed by the paper also studied by ELDI/MS. It was found that the type and mass
fibers. Detection of these remaining ink compounds in the erased range of ink ions detected from these two materials were similar
448
ink lines will be helpful in understanding the written history of to those from copy paper (data not shown). The results indicated
wileyonlinelibrary.com/journal/jms Copyright © 2014 John Wiley & Sons, Ltd. J. Mass Spectrom. 2014, 49, 445–451
ELDI/MS to detect erased ink lines
the ELDI mass spectra of ink lines did not change with the lines reappeared, and the PVP ion series were still detected by
surfaces. Figure 3(d) displays the ELDI mass spectrum of the ELDI/MS (data not shown). The thermochromic ink line was also
Singo ink line 4 months later, showing PEG ion series with similar analyzed after saving the paper in a drawer for 4 months,
mass ranges and relative ion intensities as those of fresh ink line displaying PVP ion series with similar mass ranges but lower ion
(Fig. 3(b)). intensities as those in the fresh thermochromic ink line (Fig. 4
We repeated the experiments with the erasable pen con- (b) and (d)). The results indicated that the PEG and PVP com-
taining thermochromic ink – Pilot Frixion pen. Figure 4(a) displays pounds did not undergo obvious change, while the documents
the ESI mass spectrum of Pilot Frixion ink dissolved in the acidic were stored in the dark without excessive handing.
methanol solution. Five series of singly charged polymeric ions The ELDI/MS was also used to examine the ink compounds
with a mass range from m/z 100 to 600 were detected (Table 1). in both visible and invisible ink lines drawn to simulate forg-
Because Δm between neighboring peaks of polymer ion series is ery. A letter ‘A’ was written on a sheet of copy paper with a
111, the detected polymer ion signals [m/z 223 + 111n (□), Pilot Frixion erasable pen; after 5 min, the letter was wiped
242 + 111n (○), 245 + 111n (▽), 261 + 111n (■) and 297 + 111n off with an eraser; a ballpoint pen was used to write a letter
(●)] are tentatively assigned as polyvinylpyrrolidone (PVP) or ‘C’ over the invisible ‘A’. ELDI/MS was used to characterize
polymers with a PVP branch chain, a common aromatic additive the chemical compounds in the visible and invisible lines on
in ink (by Polytools software). the letters. Figure 5(a) shows the points where the pulsed la-
The ELDI/MS was used to analyze lines drawn with Pilot Frixion ser was focused for sampling. These sampling points included
pen on the copy paper. The results showed that the ELDI mass (1) the point on the visible ink line drawn with a ballpoint
spectrum was similar to the ESI spectrum (compare Fig. 4(a) pen (labeled as ‘b’), (2) the crossing point of the writing made
and (b)), which indicated that the degradation of thermochromic with both ballpoint and Pilot Frixion pen (labeled as ‘c’) and
ink by the irradiation of pulsed laser beam was not occurred. In (3) the point on the invisible ink line drawn with a Pilot
addition, there is no obvious difference among the ELDI mass Frixion pen (labeled as ‘d’).
spectra recorded from the copy paper, printing paper and Ion signals of m/z 344, 358, 372 and 470 (▼) were detected at
stainless steel plate (data not shown). However, the absolute point ‘b’ drawn with a blue ballpoint pen (Fig. 5(b)). These ions
intensity of the ions detected in the erased ink line was lower than were tentatively assigned as methyl violet (m/z 358 and 372)
that before wiped (Fig. 4(b) and (c)). Interestingly, a PVP ion series and basic blue 26 (m/z 470).[27,29] Ion signals of m/z 344 and
(m/z 321 + 111n) was prominent on ELDI mass spectrum for erased 358 might be the degradation products of methyl violet.[14]
thermochromic ink line. It seems that this PVP ion series has stron- Figure 5(d) shows partial ELDI mass spectrum recorded at point
ger interaction with the paper materials than others and is difficult ‘d’. As it can be seen, even though the ink line was erased, three
to be erased through mechanical action. These PVP ions, especially series of PVP ions ( ⃟, m/z 242 + 111n, 297 + 111n and 321 + 111n)
m/z 321, were potentially useful for ELDI imaging to monitor the were still detected. Figure 5(c) shows partial ELDI mass spectrum
distribution of erased writing on paper (Fig. 4(c)). recorded at point ‘c’, which had inks from both pens, and the
The ELDI mass spectra recorded from the erased ink line is ion signals originating from ballpoint pen (m/z 358, 372 and
nearly identical as that of unerased ink line. After the sheet of 470) and Pilot Frixion pen (m/z 242 + 111n, 297 + 111n and
copy paper was cooled at 80 °C in a freezer for 10 min, the ink 321 + 111n) were detected.
(a)
353.2
150.1
297.7
356.2
x105
242.1
408.7
334.2
445.3
4
164.1
solution
467.3
556.4
464.3
223.2
138.1
275.2
195.6
578.4
519.8
306.7
2
372.2
575.4
261.2
483.3
0
251.1
x104 (b)
195.6
297.7
353.2
Ink on paper
211.1
408.7
164.1
Absolute Intensity
306.7
5
138.1
334.2
464.3
223.2
556.4
275.2
519.8
578.4
0
321.1
x104 (c)
249.2
445.3
297.7
Ink on paper
334.2
353.2
223.1
556.3
-wiped
432.2
408.7
1
195.6
306.7
543.2
464.2
164.1
150.1
519.8
138.1
578.4
0
249.2
(d)
x104
Ink on paper
334.2
356.2
306.7
445.3
417.7
467.3
2
297.7
556.4
528.8
195.6
164.1
578.3
223.2
519.8
138.1
0
100 200 300 400 500 600 m/z
Figure 4. (a) ESI (+) mass spectra of the ink in Pilot Frixion erasable pen. (b) ELDI (+) mass spectra of ink line drawn on a copy paper. (c) The ink line of
(b) was wiped by an eraser and then characterized by ELDI/MS. (d) The ink line of (b) was characterized by ELDI/MS 4 months later (□, m/z 223 + 111n ion
449
series; ○, m/z 242 + 111n ion series; ▽, m/z 245 + 111n ion series; ■, m/z 261 + 111n ion series and ●, m/z 297 + 111n ion series).
J. Mass Spectrom. 2014, 49, 445–451 Copyright © 2014 John Wiley & Sons, Ltd. wileyonlinelibrary.com/journal/jms
Y.-Y. Kao et al
c (a) (e)
f
b
g
d h
x104
372.2
x104
327.2
358.2
(b) (f)
ballpoint gel-ink
371.2
0.8
470.2
2
283.2
415.3
432.3
305.2
388.3
349.2
0.4
476.3
261.1
1
393.2
253.0
459.3
520.4
344.2
437.3
564.4
344.2
0 0.0
321.1
x104
327.2
(c) x104 (g)
411.2
Absolute Intensity
389.2
433.2
367.2
6 ballpoint gel-ink
251.1
455.3
0.8
& Pilot & Singo
283.2
345.2
372.2
297.6
477.3
353.2
4
481.2
499.3
580.4
432.2
408.7
0.4
242.2
301.2
521.3
305.2
563.4
2
445.3
543.2
519.8
572.9
0 0.0
321.1
411.2
389.2
x104 (d) x104 (h)
433.2
367.2
6 Pilot Signo
455.3
345.2
477.3
392.2
414.2
251.1
1.0 370.2
323.2
436.2
499.3
297.6
353.2
348.2
458.2
275.0
301.2
580.4
242.2
432.2
521.3
279.1
408.7
0.5
257.1
326.2
563.4
481.2
2
543.2
464.2
519.8
0 0.0
200 300 400 500 m/z 200 300 400 500 m/z
Figure 5. (a and e) Forgery simulations by writing a ‘C’ character with ball point pen (left) or a gel ink pen (right) on erased ‘A’ character made with a Pilot
Frixion (left) or a uni-ball Singo (right) erasable pens. ELDI (+) mass spectra of (b and f) the ‘C’ character, (c and g) a crossing line point and (d and h) the erased
‘A’ character (ion signals originating from the ballpoint pen, Pilot Frixion pen, gel ink pen and uni-ball Singo pen are marked as ▼, ⃟, ● and □ individually).
A gel pen and Signo pen were used to repeat the study (Fig. 5 wills. The experimental results indicate that ELDI/MS is capable
(e)). Three series of PEG ions (m/z 261 + 44n, 283 + 44n and to characterize trace ink compounds remaining in the erased
344 + 44n) were detected at the point drawn with a gel pen (Fig. 5 ink lines. Signals for polymeric ions comprised the major ion peaks
(f) and Table 1). Because the mass difference (Δm) between adja- on the ELDI mass spectra for erasable inks and were distinguishable
cent ion peaks of m/z 261 + 44n and 283 + 44n is 22, the two ion by differences in mass and mass range. The document with a size
series were tentatively assigned as protonated (M+H)+ and as large as an A4 paper can be analyzed without being cut or
sodiated (M+Na)+ PEG molecules. Figure 5(g) shows the partial folded. Because of the high spatial resolution of the laser beam,
ELDI mass spectrum recorded at point ‘g’, where ink lines made ELDI/MS analysis resulted in minimal damage to the sample docu-
with Signo and gel pens come into contact. Again, the ion signals ments. Although the optical properties of thermochromic inks
for the inks from both pens were detected on the ELDI mass changed depending on the applied temperature, the ELDI mass
spectrum (Fig. 5(f) and (h)). The results indicate that the written spectra for these ink compounds were not affected by the
history of a sample paper can be traced by using ELDI/MS to de- temperature change. The results obtained in this study have
tect residual ink compounds in the writing. demonstrated that ELDI/MS is useful for identifying forged doc-
uments, finding concealed handwriting and differentiating ink
lines drawn with different writing tools. In the future, ELDI imag-
Conclusion ing analysis can be performed to reveal the concealed words,
signatures and writings on document; this will make the tech-
The ELDI/MS has proven to be useful in characterizing chemical nique even more useful in forensic document examination. In
compounds on different surfaces. This technique can be applied addition, because ‘aging study’ (in normal or accelerated speed)
in forensic examinations to screen and characterize visible and in- is an important topic for document examination, this study
450
visible ink lines in questioned documents such as checks and should be conducted as well.
wileyonlinelibrary.com/journal/jms Copyright © 2014 John Wiley & Sons, Ltd. J. Mass Spectrom. 2014, 49, 445–451
ELDI/MS to detect erased ink lines
J. Mass Spectrom. 2014, 49, 445–451 Copyright © 2014 John Wiley & Sons, Ltd. wileyonlinelibrary.com/journal/jms