Trends in Analytical Chemistry, Vol. 26, No.

3, 2007

Trends

Applications of capillary
electrophoresis in forensic
analytical chemistry
C. Cruces-Blanco, L. GamizGracia, A.M. Garca-Campana
In the past decade, capillary-electrophoresis (CE) techniques have been
demonstrated to offer promising, effective and economic approaches for the
separation of a large variety of substances, including those encountered in
forensic analysis. Reliable, automated CE instruments have become commercially available and have advanced methods in forensic sciences. This
article reviews applications of CE in the field of forensic analytical chemistry,
covering the literature since the first publication appeared in the early 1990s
and focusing on two applications: (i) explosive compounds and gunshot
residues; and, (ii) inks and dyes.
2007 Elsevier Ltd. All rights reserved.
Keywords: Capillary electrophoresis; Dye; Explosive; Forensic analysis; Gunshot
residue; Inks

1. Introduction
C. Cruces-Blanco*,
L. GamizGracia,
A.M. Garca-Campana
Department of Analytical
Chemistry,
Faculty of Sciences,
University of Granada,
18071 Granada, Spain

Corresponding author.
Tel.: +34 958 248594;
Fax: +34 958 249510;
E-mail: mcruces@ugr.es

Forensic sciences include a broad, interdisciplinary group of applications of

physical and biological sciences and various technologies applied in civil and
criminal justice to cover areas from psychology, pathology, psychiatry, toxicology,
entomology,
anthropology,
odontology up to pure forensic chemistry
issues [13]. Forensic analytical chemistry
is defined as a discipline applied to crimescene analysis and to law and is one of the
areas of analytical chemistry where
the nature of the sample and the use of the
analytical chemical information play
important roles in selecting and executing
the appropriate chemical-analysis technique. This part of forensic sciences deals
with the characterization and quantitation of chemical substances at trace levels,
which often refer to explosive compounds
and gunshot residues and to inks and
writing materials [4].
Most forensic samples are complex
mixtures for which analysis generally requires separation prior to identification of
chemical species. Thus, the principal tools

0165-9936/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.trac.2006.12.007

of the forensic chemist are the instruments

of analytical chemistry [5], with emphasis
mainly on chromatographic techniques
(e.g., gas chromatography (GC) [68] and
high-performance liquid chromatography
(HPLC) [913]), with the help of many
other analytical techniques (e.g., mass
spectrometry (MS), Fourier transform
infrared spectrometry (FTIR), Raman
spectroscopy, thin-layer chromatography
(TLC), immunoassays, atomic absorption/
atomic emission spectroscopy (AAS/AES),
inductively coupled plasma-AES (ICPAES), ultraviolet/visible spectrometry (UVVis) or scanning electron microscopy
(SEM)).
Among the separation techniques, GC
and especially HPLC [14] provide specific
results of multiple components and are
well-established in forensic laboratories,
but they require extensive sample pretreatment and present problems when
samples are quite complicated, an especially time-consuming issue usually observed in HPLC, or when problems derive
from the behaviour of some analytes in GC
due to their thermal instability. So as to
overcome most of these problems, it is
nowadays more common in forensic laboratories to apply capillary electrophoresis
(CE), which originally appeared in the
early 1980s, and is probably the most
rapidly expanding analytical technique
from the past two decades.
Since the appearance of the first practical CE instrument in 1989, numerous
books have been dedicated to this technique [1521,73]. There have also been
comprehensive reviews on the introduction of CE as an analytical technique from
its beginning until the present day
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Trends in Analytical Chemistry, Vol. 26, No. 3, 2007

[22,23]. Many more reviews and book chapters have

appeared in the literature summarizing the basic
instrumental aspects and separation principles of CE
[2426]. The main features of CE are its versatility of
applications (e.g., inorganic ions, organic molecules and
large biomolecules) using the same instrument and, in
most cases, the same capillary, while changing only the
composition of the running buffer. Also, the resultant
waste, mostly an aqueous buffer, sometimes containing
a small percentage of an organic modifier, is environmentally safe and can generally be discarded without
any danger to the environment. However, among the
cited features, the advantage that has caused the widespread application of CE in the various fields of analytical
chemistry has been the accomplishment of both the
availability of different modes of separation together with
the possibility of interfacing with different detection
systems.
Detection in CE has to face two challenges, namely the
small amounts of analytes to be injected together with
the tiny peak volumes. To date, UV-Vis detectors are by
far the most widely adopted detection devices, despite the
short internal diameter of the capillary limiting the
concentration sensitivity [15]. Laser-induced fluorescence (LIF), allowing high-energy excitation and hence
producing high output of emitted radiation, is more
sensitive but instrumentally more complex and more
expensive, suffering the drawback of limited excitation
wavelengths available from the different commercial
lasers, in relation to the excitation needs dictated by the
fluorophore(s) under investigation [2729]. Because of
the importance of information provided by MS techniques, there have been many efforts to develop interfaces between the CE apparatus and the MS detector
[30,31], electrospray ionization (ESI) being the most
common interface offering sufficient sensitivity and
selectivity for the determination of a wide range of
analytes of clinical and forensic significance [32]. Nevertheless, apart from the detection mode, the major disadvantage of CE lies in its lack of sensitivity when
compared to HPLC. Various approaches to this sensitivity limitation have been developed [33,34], mostly using
pre-concentration devices [35,36], stacking techniques
[3739], or liquid-liquid extraction (LLE) or solid-phase
extraction (SPE) pretreatments.
A variety of other detection techniques have been
applied in CE, including chemiluminescence [4049],
electrochemical detection [50,51] or nuclear magnetic
resonance [52,53]. An overview of the main detection
techniques applied in CE, among which MS is perhaps
the most interesting for forensic purposes, can be found
in the monograph by Li [54]. The various modes of
detection in CE have also been reviewed [55,56].
The versatility of CE, along with the possibility of different detection modes, is derived from its additional
separation modes [15,16]. In its simplest form, CE in216

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volves the separation of charged analytes, based on the

differences in their electrophoretic mobilities, resulting in
different migration velocities. This mode is termed capillary zone electrophoresis (CZE). Another commonly
encountered mode of CE is micellar electrokinetic chromatography (MEKC). This combination of electrophoresis and chromatography allows separation of both
neutral and charged solutes [57,58]. Since the first
commercial CE instrument some 17 years ago, CE
applications have become widespread in many fields
(analysis of foodstuffs [5966], environmental analysis
[6772], pharmaceutical analysis [7380], clinical
chemistry [78,8184], and others [85]).
This article offers a comprehensive review of the
applications of CE techniques employing different modes
of operation and detection in forensic chemistry, based
on the literature that has appeared since the first application in 1991, for two important targets of this
discipline:
(i) explosive compounds and gunshot residues; and,
(ii) inks and writing media.

2. Applications of capillary electrophoresis in

forensic chemistry
Among the applications of the CE technique that have
been growing more rapidly in recent years are forensic
chemistry and toxicology [5,24,86]. In the hands of
forensic toxicologists, CE represents a powerful and relatively new analytical tool, which has proved suitable for
the investigation of a great number of different forensic
samples. The exceptional power of separation and resolution, rapid analysis time, simplicity, versatility, low
mass limits of detection (LODs), economy of reagents,
minimal sample requirements and the possibility of
direct sample injection without complex sample pretreatments make CE an attractive methodology to
forensic scientists [8789] when the sample matrix may
be extremely complicated and contain a number of
endogenous components that have to be resolved from
the solute of interest. However, lack of sensitivity and
maturity mean that CE is not yet very well established
in forensic laboratories as an additional tool.
The first application found in the literature of CE in
forensic analysis was described by Weinberger and Lurie
[90] in 1991. They analyzed illicit drug substances using
MEKC, demonstrating that this mode of operation is
more suitable than CZE for obtaining highly efficient
separations of compounds of forensic interest. The first
review of forensic applications of CE was published by
Northrop et al. [91], which was followed by the paper of
Tagliaro and Smith [92].
Since these first publications, the applications of CE to
forensic analysis have been the subject of numerous
comprehensive textbooks and chapters [9395] and also

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of numerous reviews and comprehensive articles

[22,32,81,96105]. A volume of the Journal of Chromatography B [106] covered the use of CE for forensic
and clinical toxicology. As a result of the important reviews cited and due to the fast development of suitable
instrumentation, the use of CE in clinical and forensic
laboratories has been explored extensively. CE still represents an emerging technology for clinical and forensic
laboratories, but the popularity and the importance of
this analytical tool are steadily increasing.
2.1. Explosive compounds and gunshot residues
Gunshot residues are produced when a firearm is discharged and can be deposited on the hands of the perpetrator. In targets and weapons, these residues

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comprise unburned powder, particles from the primer

and case of the cartridge, and metals from the barrel of
the gun [107,108]. Table 1(A) shows the usual components found in gunshot residues.
The upsurge in terrorist activity has generated tremendous demand for innovative tools capable of
detecting major industrial, military and home-made
explosives. Fast, sensitive and reliable detection of
explosives in the field is a very important issue. The main
purposes of analyzing explosives and gunshot residues
are estimation of firing distances, identification of bullet
holes, and, most important, identification of whether or
not a person has discharged a firearm or been involved
in a terrorist blast. For such reasons, analyses of both
explosives and gunshot residues are amongst the most

Table 1. Main components of (A) gunshot residues and (B) inks with some characteristics and usage (adapted from [129] and [149])
(A) Gunshot residue components

Usage

Organic
Nitroglycerin
Resorcinol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
2,3-Dinitrotoluene
Dimethyl phthalate
Diethyl phthalate
Dibuthyl phthalate
Methyl centralite
Diphenylamine
Ethyl centralite

Propellent
Stabilizer
Flash inhibitor
Flash inhibitor
Flash inhibitor
Plasticizer
Plasticizer
Plasticizer
Stabilizer
Stabilizer
Stabilizer

Inorganic
Antimony
Iron
Barium
Calcium
Magnesium
Aluminium
Nickel
Zinc
Lead
Copper

Fuel
Bullet material
Oxidizing agent
Fuel
Fuel
Fuel
Bullet material
Bullet material
Explosive (lead styphnate)
Bullet material

(B) Ink components

Characteristics

Coloring materials:
Dyes
Pigments

Affect the appearance

Classified as acidic, basic, solvent, etc.
Consist of finely ground multimolecular granules. Insoluble in vehicle.

Vehicle:
Oils

Flow and drying characteristics

Can be linseed, soy, mineral or other type of oil. Classified as drying,
non-drying, or combination, depending on degree of unsaturation of oil
Can be any of several organic solvents, or water. Analyzed in many ink dating procedures
Non-crystalline material of high molecular weight. May be natural or synthetic

Solvents
Resins
Other additives:
Driers
Plasticisers
Surfactants
Waxes

Drying characteristics. Catalyze oxidation of drying oils. Many are inorganic salts.
Reduces brittleness of ink. Consist of solvents with low volatility. Give stability of ink film
Changes surface tension of ink. Typically consist of soaps or detergents. Give wetting ability
Increase flexibility and reduce brittleness. May be hydrocarbon waxes, greases such as petroleum jelly.
Give hardness and/or flexibility

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important tests in forensic sciences. Nevertheless, the

results from such tests have been controversial because
of the lack of specificity by most of the traditional techniques [109,110].
Current methods for the analysis of evidence in clandestine laboratory cases primarily focus on analyzing
organic species using GC-MS and IR techniques. However, techniques to analyze inorganic species in samples
collected from clandestine laboratory cases need to be
able to provide relevant information concerning the
process and materials involved.
Since the work of Harrison and Gilroy [111], gunshot
analysis has been based on the determination of heavy
metals, usually lead, barium and antimony, which originate from the primer of the cartridge. Several techniques
of elemental analysis have been used (e.g., neutron
activation analysis (NAA), electrothermal atomic
absorption spectroscopy (ET-AAS), and inductively
coupled plasma mass spectrometry (ICP-MS) [107109]).
A review on all aspects of analysis associated with
gunshot residues [109] included a summary on the
specific nature of inorganic and organic residues, how
they arise and how they may be collected from a variety
of matrices. The techniques described included scanning
electron microscopy with energy dispersive X-ray analysis (SEMEDX), flameless AAS, NAA, energy dispersive
X-ray fluorescence (EDXRF) for inorganic residues and
GC, HPLC and supercritical fluid chromatography (SFC)
with special detectors, such as MS, for organic residues.
Among all these techniques, the most accepted for the
moment is SEMEDX, which combines morphological
(SEM) and elemental (EDX) identification of the metal
residues [107]. Although it is considered specific, heavymetal analysis offers moderate diagnostic sensitivity,
requires expensive instrumentation and is highly
demanding in terms of professional skills, manpower,
maintenance and service. As a result, its application as a
routine technique is difficult. Besides, it has been recently
found that some particles can be misidentified with
gunshot residues, decreasing the specificity of SEM-EDX
analysis [112]. Additionally, an emerging problem is
given by the modern trend to produce primers free of
heavy metals; this would lead to false negative results
[113].
For the above reasons, there is need for a fast, cheap
and specific technique that can be used routinely in
laboratories with a high workload. Meng and Caddy
[109] suggested that one way to enhance the specificity
of bulk analysis is to look simultaneously for inorganic
and organic gunshot residues, (propellants (e.g., nitroglycerin), stabilizers (e.g., resorcinol and diphenylamine), oxidant agents (e.g., barium), plasticizers
(e.g., diethyl phthalate), fuels (e.g., antimony, calcium,
magnesium and aluminium), bullet materials (e.g.,
nickel, zinc, copper, iron), or explosive lead). In this way,
there have been attempts to analyze separately organic
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residues by LC or GC and inorganic residues by the

techniques mentioned above [114].
Since the pioneering works of Northrop in 1991 [115]
and Hagardon and McCord in 1992 [116], CE has been
applied in trace-analysis in areas (e.g., explosive and
gunshot residues) for either organic or inorganic components. This is especially important in the analysis of
inorganic explosives residues due to its role as a complementary technique to ion chromatography (IC),
allowing separation and analysis of these inorganic
species with important impact in the examination of
many forensic evidence samples, including explosives,
gunshot residues and others [91,117,118]. As it was
pointed out in a review on the recent advances in the
application of CE to forensic sciences in the past four
years [101], CE represents today a sound and widely
accepted technique in forensic analysis and has been
used to analyze explosive compounds and gunshot residues in different types of forensic samples [115], soils
[119], explosives [120], etc. using MEKC and also cation
analysis, usually with a complexing agent [121]. These
types of application are becoming especially important
due to the lack of a sensitive spectroscopic technique for
the detection of ammonium, monomethylamine and the
various anions present in pipe-bomb residues. McCord
and Bender [122] published a review that includes significant detail on the use of CE in explosive analysis.
The mode of separation most widely used for this type
of analysis is MEKC. The separation and identification of
organic gunshot and explosive constituents by MEKC
was first applied by Northrop [115]. The separation was
rapid and efficient providing the separation of 26 organic
gunshot and explosive constituents in less than 10 min,
carried out by selecting different experimental parameters such as SDS concentration, pH, addition of tetraalkylammonium salts, the capillary diameter and the
injection times. CE in the MEKC mode has been applied,
in addition to other techniques (HPLC-UV, GC-MS) to the
monitoring of explosives and their degradation products
in soil, groundwater and plants, in order to study
potential environmental contamination produced by
pollution with these compounds [123].
Another method was developed using MEKC for the
analysis of organic gunshot residues [124]. It described
proper sample collection and preparation before
quantitation. Gunshot residues were collected from the
hands of individuals who had discharged a firearm and
analyzed by MEKC.
The work of MacCrehan et al. [125] also explained the
sampling protocols for the recovery of the organic
components under a variety of sampling conditions to
improve the MEKC analysis. They described the collection of residue samples where external contaminants
(e.g., grease or blood that were present on the residue
substrate) were investigated using protocols for both
tape lifts and solvent swabs. The same group analyzed

Trends in Analytical Chemistry, Vol. 26, No. 3, 2007

organic additives in smokeless gunpowder by MEKC to

evaluate residue contamination from previously fired
ammunition [126].
A protocol was also presented recently for collecting
and analyzing gunshot residues from hair using a finetooth comb [127]. Residues were collected from four
weapons a revolver, a semi-automatic pistol, a rifle and
a shotgun. One characteristic additive, nitroglycerin,
was detected by CE in the majority of the collection
experiments.
In casework, MEKC has also been used to examine
characteristic organic gunpowder components (e.g.,
nitroglycerin, diphenylamine, and ethylcentralite)
[128,129]. The first study compared the results of
MEKC analysis of the organic gunshot residues from
firing-range samples with SEM results for inorganic
residues, indicating that this methodology is a potentially valuable tool in the examination of gunshot-residue evidence for characteristic organic gunpowder
compounds. Due to the numerous experimental and
instrumental variables to be optimized in the development of a MEKC methodology, Casamento et al. [130]
used artificial neural networks to optimize variables to
separate 12 explosives. Also, a work based on
comparing MEKC employing SDS and gradient reversephase HPLC, separated 14 organic explosive constituents of gun powders [131], concluding that, using

Trends

diode-array UV detection, CE is more feasible than

gradient HPLC.
Cyclodextrins have also been used to enhance selectivity in analyzing explosives by CE. Groom et al. [132]
employed sulfobutyl ether-b-CD to separate cyclic nitramine explosives (e.g., 2,4,6,8,10,12-hexanitro-2,4,6,8,
10,12-hexaaza-isowurtzitane (CL-20), octahydro-1,3,5,
7-tetranitro-1,3,5,7-tetrazocine (HMX), hexahydro-1,3,
5-trinitro-1,3,5-triazine (RDX)) and their related degradation intermediates.
In order to separate inorganic and organic gunshot
residues, a CE method was developed [133]. Pre-capillary complexation-agent diaminocyclohexane tetraacetic
acid (CDTA) was used, since it forms stable anionic
complexes with 10 inorganic components of different
gunshot residues. Thus, in order to separate 11 organic
residues, it was necessary to add a micellar phase to the
background electrolyte because almost all of the organic
residues lacked any acid-base properties. Fig. 1 shows
the corresponding electropherogram for the simultaneous separation of these organic and inorganic gunshot
residues under optimal conditions. To test the possibility
of applying the method developed to real cases, residues
from shot samples from different firearms were analyzed
and their results compared with those obtained with ETAAS, the conclusion being that there was good agreement between both techniques. The method was tested

Figure 1. Simultaneous separation of organic and inorganic gunshot residues under optimal conditions. Electrolyte: 40 mM borate buffer, 16 mM
SDS, 0.5 mM diaminocyclohexane tetraacetic acid (CDTA), capillary: 79.2 cm (69.2 cm detection length) 75 lm i.d. Hydrodynamic injection:
0.5 psi for 5 s at 25C, UV detection at 200 nm. (1) Sb (30), (2) resorcinol (11.1), (3) 2,4-dinitrotoluene (10.93), (4) 2,6-dinitrotoluene (14.57), (5)
Fe (10), (6) 2,3-dinitrotoluene (18.2), (7) dimethyl phthalate (6.0), (8) Ba (30), (9) Ca (20), (10) Mg (20), (11) Al (20), (12) Ni (20), (13) Zn (10), (14)
Pb (10), (15) Cu (20), (16) diethyl phthalate (17.8), (17) diphenylamine (16.9), (18) methyl centralite (14.4), (19) ethyl centralite (22.6), (20) dibutyl
phthalate (10). Standard concentrations in parentheses in mg/l (adapted from [133]).

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on real samples collected from weapons and from hands

after firing.
Inorganic ion analysis is also fundamental in the
investigation of low levels of explosives and post-blast
and gunshot residues. For this type of analysis, CZE
methodology has become really important because it is
possible to perform anion and cation determinations
using separate buffers for each analysis. When only one
CE system is available, the capillary and the buffer
system must be changed and re-equilibrated in order to
switch between anion and cation analysis. This process
is often time-consuming and laborious. One way to
eliminate this problem is to perform simultaneous analysis, but this requires extensive modification to the
instrumentation [134,135].
Johns et al. [136] reviewed the different simultaneous
ion-analysis techniques. An anion buffer is used with
ethylenediaminetetraacetic acid (EDTA) in simultaneously running anions and chelated cations. The
problem with this method of analysis is that the primary
cations of importance in detecting explosives residues
(e.g., potassium, ammonium, and sodium) do not form
stable complexes with EDTA [137].
Another approach using a high-magnitude electroosmotic flow (EOF) detected three anions and six cations
from the same injection end. However, this method did
not use an anionic probe, and that limited the detection
of many anions [136].
An alternative to this technique is the simultaneous
injection into both sides of a single capillary with the
detector placed in the centre [134,138]. This is called
dual-opposite injection. However, the problem is that
most standard CE instruments are not configured in this
way [135].
CZE has also been employed for analyzing inorganic
ions present in smokeless and muzzle-loading powders,
which are formed during powder production, and those
formed after deflagration [139]. Anion and cation
analysis used indirect and direct UV detection with different electrolyte composition for each type of analysis.
Recently, a novel electrolyte was developed for the
simultaneous separation of cations and anions in low
levels of explosives residues, this being the first report on
simultaneous detection of both anions and cations using
CZE in this application [140]. This electrolyte contained
15 mM a-hydroxyisobutyric acid (HIBA) as the buffer,
6 mM imidazole as the cation chromophore, 3 mM
1,3,6-naphthalenentrisulfonic acid (NTS) as the anion
chromophore, 4 mM 18-crown-6 ether as a cation
selectivity modifier, and 5% (v/v) acetonitrile as an
organic modifier. The pH was adjusted to 6.5 using tetramethyl ammonium hydroxide (TMAOH), an EOF
modifier. The results provided a simultaneous indirect
photometric analysis of both anions and cations with
LODs in the range 0.55 ppm for anions and 1015 ppm
for cations with a total run time of under 7 min. The
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method has been applied to the analysis of different

deflagrated explosives.
Nitrite and nitrate determinations can be used as
screening tools for investigating residues of firearm discharge due to the fact that these ions are major inorganic components of gunshot residues. It has been
demonstrated that use of CE allows rapid determination
of these two anions, offering a quantitative, selective
alternative to the traditional paraffin test (dermal
nitrate test) [141], being simpler, cheaper, and faster
than the modern approaches. The gunshot-residue
analysis is based on the determination of barium, lead
and antimony by flameless absorption spectrometry,
ICP-MS or SEM. The analysis was carried out in a bare
fused-silica capillary (75-lm inner diameter) with a
100-mM borate buffer (pH 9.24). The detection was
by UV absorption at 214 nm using reverse voltage of
15 kV. Sensitivity was about 1 mM for both nitrite and
nitrate. Hair and skin samples from a victim shot in the
head were successfully analyzed for the presence of
nitrite and nitrate.
The growing need for fast, portable instrumentation to
determine the presence of explosive-compound residues
in forensic applications has revealed that CE on a
microchip is emerging as a separation technique that is
attracting wide attention and gaining considerable
popularity. Because of miniaturization of the separation
format, CE on chips typically offers shorter analysis times
and lower reagent consumption with the potential for
developing portable analytical instrumentation. Several
papers have demonstrated the feasibility of microchip CE
for this purpose [142145]. Recently, Vladislav and
Shaorong [146] reviewed the applications of microchip
CE, focussing on many different samples, including
explosives residues and warfare agents. Most of these
applications use electrochemical detection (ECD) because
nitroaromatic explosives possess good redox properties.
Among these works, a contactless conductivity detector
is noticeable for the analysis of low-energy ionic explosives and nerve-agent degradation products [147] and
an amperometric detector for the analysis of nitroaromatic explosives, organophosphate nerve agents and
phenols [148]. Also, analysis of a mixture of four
explosives (TNT; 2,4-TNT; 2,6-TNT; and, 2,3-DNT) was
carried out in less than 130 s, using an SDS/borate
buffer at a detection potential of 0.8 V vs. Ag/AgCl
[143].
Wallenborg and Bailey [145] suggested indirect laserinduced fluorescence (LIF) detection for separation and
detection of different explosives on a microchip using
MEKC. To achieve indirect fluorescence detection, 5 lM
of cyanine derivative (Cy7) was added to the background
electrolyte, the excitation being provided by a near-IR
diode laser operating at 750 nm. EPA 8339 mixture
containing 14 explosives could be analyzed at the ppm
level in less than 1 min in a 65-mm long capillary. They

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obtained 10 peaks corresponding to trinitrobenzene,

dinitrobenzene, trinitrotoluene, tetryl, 2,4-DNT, 2,6DNT, 2-amino-4,6-DNT, and 4-amino-2,6-DNT, when
2-, 3- and 4-nitrotoluene were not resolved, and nitramines HMX and RDX showed rather high LODs.
Microchip CE has also been tested for the measurement of nitroaromatic explosives with a simple interface
that permitted sample introduction directly on the separation channel through a sharp inlet tip placed in the
sample vial, and the reproducibility was acceptable
[149].
All of these methods have demonstrated that rapid,
reproducible assays for the analysis of explosives and
gunshot residues can be provided in a variety of applications, in a single run.
2.2. Inks and dyes
Verification and authentication of printed documents
just from the inks that have been used has long been a
major problem for forensic scientists, customs officials
and historians.
The ability to differentiate between inks is of great
interest in forensic science because it allows evaluation
of the authenticity of a suspicious document [150], for
which inks are considered a class of evidence in forensic
cases, the manufacture involving large-scale blending of
chemicals [151]; also, the dating of ink has been of scientific interest for many years [152].
Modern demands for specialized writing and printing
instruments have resulted in an explosion of ink formulations, each of which may contain dozens of chemical
components (e.g., acid or basic dyes, organic or inorganic
colour pigments, surfactants, antioxidants, viscosity
adjusters, resins, glycol and glycerol, waxes, oils, and
pigments) [153,154]. Table 1 (B) shows the main components of inks together with their characteristics. The
wide array of materials used in inks, coupled with the
possibility of contamination from the writing surface, as
well as chemical changes as ink ages, make separation
techniques a requisite for the analysis of such complex
mixtures. As may be deduced, forensic ink chemists face a
very complex, challenging analytical problem in carrying
out this type of analysis, as sophisticated writing instruments and printing technologies have emerged.
There are two major categories of pens: ballpoint and
non-ballpoint. However, the former account for more
than 80% of the cases requiring ink analysis. Both
chemical and physical examinations have used numerous techniques that can also be differentiated into nondestructive and destructive. Prior to 1950, the nondestructive techniques (e.g., infrared spectroscopy (IR)
[155157], UV-Visible and fluorescence detection
[158,159]) were the most widely employed together
with other techniques, in which the document examiners relied on filter photography, alternate light sources
and chemical spot tests, to differentiate ink samples.

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Evidence from handwritten notes has been a hallmark

of crime detection for a long time, and forensic technology needs to develop the use of more sophisticated
techniques to solve the problems. Separation methods
provide compositional information rarely available
through the use of non-destructive techniques. For this
reason, after 1950, chromatographic techniques to
analyze inks started with paper chromatography
[160,161]. Although it remained a popular method for
discriminating inks in the 1960s, paper chromatography was effectively replaced by thin-layer
chromatography (TLC) [150,158,162,172], because the
latter had superior resolution. Though TLC has been
widely used for the analysis of inks due to its ease of use
and low cost, its resolution was limited, so it is powerless
in differentiating between formulations or distinguishing
between different branches of ink having the same
general formula.
For this reason, both paper chromatography and TLC
have been been substituted by HPLC [153,163167].
From a forensic perspective, although HPLC is a destructive method, it offers detailed information regarding the
concentration of the different components of inks.
Recently, research has evaluated and compared the
application of a destructive technique (e.g., HPLC) with a
non-destructive technique (e.g., IR) for characterizing
blue-ballpoint-pen inks [168]. This study concluded that
HPLC of pen inks, coupled with chemometrics, is a more
powerful discriminating tool for the forensic chemist than
chemometric analysis of IR data collected using nondestructive methods.
Among the different chromatographic techniques, GC
has known limited applications in the field of ink analysis
because most visible components of inks are virtually
non-volatile; applications have primarily focussed on
dating of inks by analyzing volatile components that
comprise the vehicle, especially for photocopy toners
[169] rather than inks [170].
As can be seen from the literature, HPLC is still the
most widely used separation technique for analyzing
inks, but it requires greater technical skill on the part of
the operator, a large ink sample, and greater costs than
the chromatographic techniques used before HPLC.
Nevertheless, although it is a relatively new analytical
technique, CE has already found several applications in
forensic sciences due to the many advantages it offers
over traditional modes of separation. Unlike many other
analytical methods, the basic hardware typical for CE
instrumentation can be adapted to suit a wide variety of
analytes without substantial costs or difficulties. This is
really important in ink analysis because different ink
types contain materials with widely varying properties,
making their identification difficult based on a single
separation method suitable for all components of a single
ink, not to mention the development of a general method
suitable for all types of inks.
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For the forensic scientist, perhaps the most important

characteristic of CE is the extraordinarily small sample
requirement (nanoliters), which is often advantageous in
minimizing the destruction of the document being tested.
Usually, UV-Vis photodiode-array detection (190600
nm) is used to detect most of the ink components. The
process is automated and fast, and results can be stored
electronically, allowing the development of a searchable
reference library. The process is not limited to pen inks,
as it can also be applied to food dyes, textile dyes and inkjet dyes. Further, it detects non-dye ink additives that
could be used as identifiers.
Compared to HPLC, electrophoretic techniques have
not yet been extensively applied to analyze inks, despite
the fact that they are characterized by high resolving
power and are inherently suitable to separate charged
compounds (e.g., most of the acid and basic dye components of inks). Recently, Aginsky [171] summarized
the different techniques (chromatographic and electrophoretic) that can be employed for analyzing inks and,
especially, ink dating.
In 1991, Fanalli and Schudel [172] reported the first
CE method for analyzing inks. They described a series of
liquid black inks and red water-soluble fibre-tipped pen
inks that were quantitatively distinguishable. They
found clear differences between the electrophoretic patterns from different felt-tip-pen inks using a mixture of
0.1 M ammonium acetate (pH 4.5) in presence of
methanol (3:1) as running buffer, and a coated capillary
(20 cm 25 lm I.D.) with UV detection at 206 nm.
They observed excellent peak shape and resolution of the
ink components. They extracted dye spots separated by
TLC and added them to the same ink sample to check by
analyte addition the identity of the well-resolved, but
individually unknown, CZE peaks. Since this first application, CE has been applied to all different types of pen
inks going from fountain-pen inks [151,173176],
water-soluble inks [177179], ballpoint-pen inks
[180182] and red- and blue-pen inks and dyes [179].
One study focussed on separating blue and black fountain-pen inks in the original liquid form and dried on different substrate materials [173]. After optimizing the
conditions of separation, diode-array UV-Vis and LIF
detection were employed. In addition, non-destructive
proton-induced X-ray emission (PIXE) spectrometry was
used to characterize the elemental composition of dried
inks on different substrate materials, concluding that,
despite the fact that the CE technique for ink analysis has
demonstrated successful applications, further efforts need
to be directed towards stacking to preconcentrate ink extracts and eliminate dye signals for substrate materials.
Rohde et al. [174] demonstrated that CE separation
was reproducible and led to baseline resolution of almost
all components of 15 blue and black fountain-pen inks of
various manufacturers and countries of origin, showing
patterns that, in most cases, distinctly differed from each
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other. Another work on these types of inks used CZE

with UV/Vis absorbance and LIF detection [151]. Good
results for the separation of 17 blue and black fountainpen inks were obtained.
UV/Vis scans can be used to compare spectra of the
separated main and trace components of inks. Fluorescence detection at different excitation and emission
wavelengths was more sensitive, but added to the complexity of the electropherograms due to the excitation of
co-extracted fluorescing paper components. The resolving power of CE combined with the information content
provided by these two detection modes proved CE to be a
powerful tool for identifying fountain-pen inks used on
paper documents.
McManus et al. [178] used CE in analyzing watersoluble inks of fountain and felt-tip pens, when the best
results were obtained using MEKC in the presence of
mixed micelles of sodium dodecyl sulphate (SDS) and Brij
35. The separation was reproducible and led to baseline
resolution of most of the components. Inks of different
manufacturers yielded electropherograms with distinctly
different patterns, and the authors concluded that CE is a
potentially powerful tool for identifying water-soluble
writing inks of marker pens (e.g., felt-tip, fibre-tip, plastic
tip and metal-tips) and roller-ball pens [177].
The effectiveness and the limitations of HPLC were
compared with CE for discriminating red- and blue-pen
inks [179]. CE is more useful than reversed-phase HPLC
in discriminating between aqueous pen inks that contain
ionic dyestuffs. CE using 15-mM borate buffer (pH 8.8)
gives significant differences in the electropherogram to
22 out of 26 red roller-ball and marker-pen inks. To
distinguish 22 inks, CE of aqueous blue-pen inks containing basic dyestuffs required addition of b-cyclodextrin and ethanol to the carrier electrolyte.
Ballpoint-pen inks contain a variety of components,
including dyes, additives and solvents. Some attempts
have been made to separate and determine these components using CE. In comparison to water-soluble
fountain-pen inks, ballpoint-pen inks are less soluble or
insoluble in water, and contain only few components. A
CE method with UV/Vis absorbance and LIF detection
optimized separation of ink extracts from paper material
[180]. For this method, different buffers, organic modifiers and surfactants were tested. Good results were obtained with a 50-mM borate buffer (pH 9.0) containing
50% acetonitrile. Reproducible extraction procedures as
well as separations were able to quantitate the ink peaks
within 18% standard deviation. Electropherograms of
20 inks of various origins showed patterns that, in most
cases, distinctly differed from each other.
MEKC was also applied to the separation of dyes in
black ball-point-pen inks [181]. Analysis used standard
mixtures (methyl violet B, Victoria blue B and solvent
black 3) and sample requirements were evaluated for a
black ballpoint-pen ink extracted from paper.

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Zlotnick and Smith [182] also utilized MEKC for

analyzing 10 liquid black roller-ball-pen inks with UVabsorption diode-array detection at 214 nm. The back-

Trends

ground electrolyte (BGE) was 100-mM borate buffer (pH

9.5) with 25-mM SDS at 25C and 30 kV. This yielded a
distinct electropherogram for most pens and an analysis

Figure 2. Electropherogram of different black roller-ball pens using 100 mM borate-25 mM SDS buffer (pH 9.5) run at 30 kV and 25C:
(A) Faber-Castell fine metal point (Japan); (B) Micro Fashion Roller (Korea); (C) Pilot Precise V5 extra fine point (Japan); (D) Tombo roll
pen (Japan); (E) Sanford Uniball Vision micro waterproof/fadeproof (Japan); (F) Sanford Uniball fine (Japan) (adapted from [182]).

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time of less than 15 min, yielding individual fingerprints of different inks that allowed their recognition.
The different electropherograms for each liquid rollerball pen are shown in Fig. 2. The results demonstrated
the potential of CE for analyzing such samples and the
advantage that small sample sizes can be used in this
technique. The same authors also published a review of
different approaches to ink analysis that includes a discussion of CE methods [153].
One of the most challenging investigations is the
dating of entries. If a document was written by a
mechanical device (e.g., typewriter, inkjet printer, laser
printer, or photocopier), a maximum age may be determined from the date that the technique or the type of ink
was introduced into the market. In the case of handwritten entries, this method is valid for very old documents only [183]. In the past, different research
initiatives have studied the degradation process of ballpoint-pen-ink dyes [159,184,185].
Despite the importance of these publications, future
research should include:
 analyses of ink samples extracted from different types
of papers;
 reproducibility studies to determine the relative standard deviations of the retention times and peak areas
to quantify the reliability of each method; and,
perhaps,
 most importantly, the application to ink dating
[171,186,187].
The exact determination of the absolute age of a
document by examining the ink has been the subject of
several studies in the past 30 years [188]. The ability to
determine the date when a document was written
would therefore be a major breakthrough in forensic
sciences.
Another problem is the dramatic increase in the use of
photocopiers and laser printers over the last 20 years
[189]. Because of the speed, simplicity and accessibility
of photocopying, forensic examiners increasingly
encounter photocopies as documents to be examined.
Among other criminal activities, photocopied documents
are involved in counterfeiting, false documentation,
fraud, confidential material, and terrorism. Because of
the large number of manufacturers producing photocopiers and toners, it is not easy for the forensic scientist
to identify the possible source of photocopied documents.
Until now, we have not found any work applying CE to
toner inks, which would undoubtedly be a really
important future challenge for this technique.
Also, paints and coatings are frequently encountered
as materials submitted to forensic science laboratories as
a result of trace-evidence transfers at crime scenes, most
often in cases of automobile hit-and-runs. For these
reasons, characterization of paint samples, including
identification of, e.g., polymer type and colours, is also
really important in forensic analysis. In the literature, we
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have not so far found any application of CE for this type

of analysis, so that opens a new line of research for the
future.
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