PAPER

J Forensic Sci, January 2016, Vol. 61, No. 1

doi: 10.1111/1556-4029.12881
Available online at: onlinelibrary.wiley.com

CRIMINALISTICS
Seth R. Hogg,1,2 Ph.D.; Brian C. Hunter,3 M.D.; and Ruth Waddell Smith,2 Ph.D.

Elemental Characterization and Discrimination

of Nontoxic Ammunition Using Scanning
Electron Microscopy with Energy Dispersive
X-Ray Analysis and Principal Components
Analysis*

ABSTRACT: Concerns over the toxic by-products produced by traditional ammunition have led to an increase in popularity of nontoxic
ammunition. In this work, the chemical composition of six brands of nontoxic ammunition was investigated and compared to that of a road
flare, which served as an environmental source with similar composition. Five rounds of each brand were fired while a further five were disassembled and the primer alone was fired. Particles collected from all samples, including the road flare, were analyzed by scanning electron
microscopy with energy dispersive X-ray analysis. Common elements among the different ammunition brands included aluminum, potassium,
silicon, calcium, and strontium. Spectra were then subjected to principal components analysis in which association of the primer to the intact
ammunition sample was generally possible, with distinction among brands and from the road flare sample. Further, PCA loadings plots indicated the elements responsible for the association and discrimination observed.

KEYWORDS: forensic science, nontoxic ammunition, scanning electron microscopy/energy dispersive X-ray analysis, element composition,
principal components analysis

Currently, the method of choice for gunshot residue (GSR)

analysis is scanning electron microscopy with energy dispersive
X-ray analysis (SEM-EDS). Using this technique, GSR particles
are identified based on morphology and elemental composition.
That is, GSR particles typically have a spherical morphology,
with particle diameter ranging from 0.5 to 5 lm and are composed of lead, barium, and antimony (1).
In traditional ammunitions, lead is a major component of both
the projectile and the primer. Lead readily enters the blood
stream through airborne exposure and may lead to negative
health effects (2,3). Concerns over the toxic by-products produced by traditional ammunition formulations resulted in the
development of nontoxic compositions. Among the first of these
was the Sintox brand, which was commercially available in
1980, and was designed specifically to restrict the use of heavy
metals (4). New primer formulations removed the use of the
traditional lead styphnate, replacing it with a wide variety of ele-

1
Department of Chemistry, Michigan State University, East Lansing, MI
48824.
2
Forensic Science Program, School of Criminal Justice, Michigan State
University, East Lansing, MI 48824.
3
Genesee County Medical Examiners Office, 630 S Saginaw Street, Flint,
MI 48502.
*Presented at the 65th Annual Meeting of the American Academy of
Forensic Sciences, February 1823, 2013, in Washington DC.
Received 18 Aug. 2014; and in revised form 4 Dec. 2014; accepted 17
Dec. 2014.

2015 American Academy of Forensic Sciences

ments such as strontium, potassium, silicon, and titanium. Nontoxic ammunitions also contain projectiles either formulated
without lead or with a lead core that is completely coated in a
nontoxic metal such as copper (5). The new formulations are
also manufacturer specific resulting in greater compositional
variability than is typically observed among traditional ammunitions.
The introduction and increasing use of nontoxic ammunition
provides further challenges for identifying GSR and distinguishing these GSR particles from environmental particles with similar elemental composition. Sintox ammunition was previously
studied and found to contain particles of titanium and zinc with
spherical morphologies (6). Only the unique spherical morphology of these particles that result from condensation of the gases
released upon discharging a firearm allowed distinction from
similar nonspherical particles common to paints (6,7). Similarly,
CCI Blazer ammunition was found to contain primarily strontium, a known major component of road flares and fireworks
(8). While nontoxic ammunition generally produced fewer spherical particles than traditional ammunition, Magtech Cleanrange only produced irregularly shaped particles, thus
complicating GSR analysis (9). With the continuing addition of
nontoxic ammunition to the market, further analysis of environmental sources of similar particles is also necessary to assign
appropriate evidentiary value in cases where nontoxic ammunition is used (5).
Since the 2009, National Research Council of the National Academy of Sciences reports that detailed suggested improvements in
35

36

JOURNAL OF FORENSIC SCIENCES

forensic science practices, there has been increasing interest in statistical evaluation of forensic data (10). Lednev and coworkers have
demonstrated the ability to statistically assess GSR data collected
using Fourier transform infrared spectroscopy with attenuated total
reflectance (ATR-FTIR) and Raman spectroscopy (1113). In these
studies, the collected data are analyzed using partial least squares
discriminant analysis and the ability to distinguish particles originating from different caliber ammunitions has been demonstrated.
While the work by Lednev et al. has focused on more traditional
ammunition, neither of the analytical techniques used rely on the
detection of antimony, barium, and lead (1113). Hence, these techniques certainly have potential for future applications in GSR analysis.
Only a single paper to date discusses statistical treatment of
GSR particles analyzed by SEM-EDS, which is the more conventional method currently used in forensic science laboratories
(14). Both traditional and nontoxic ammunitions were included
in the study, and the resulting EDS spectra were subjected to
fast Fourier transformation to reduce the large number of X-ray
energy counts according to their importance in each spectrum.
Regularized discriminant analysis was then used to classify individual GSR particles to brand. For the seven brands of nontoxic
ammunition, classification was based on 10 elements (silicon,
potassium, calcium, antimony, barium, strontium, zinc, titanium,
copper, and tin) and >90% correct classification was achieved in
all cases (14). However, by reducing the number of data points
through the fast Fourier transformation, the largest peaks contributed most to particle differentiation and smaller peaks were
excluded. Furthermore, there was no attempt to distinguish GSR
particles from environmental sources, such as cartridge fired
welding tools, road flares, or fireworks.
The work reported herein investigates the potential to distinguish among different brands of nontoxic ammunition, as well
as from an environmental source, based on elemental composition determined by SEM-EDS. Six nontoxic ammunitions were
obtained and five rounds from each manufacturer were disassembled to remove the projectile and propellant, leaving only the
cartridge case containing the primer intact. As SEM-EDS only
studies inorganic particles, the most significant contributors to
GSR are the primer and the projectile (15). Removing the projectile and firing only the primers allowed an investigation of
the elemental composition of the primer alone. The intact ammunitions were also discharged, and a road flare was burned to provide an environmental source of particles that may be
chemically and physically similar to strontium-based nontoxic
GSR particles. Collected particles were analyzed by SEM-EDS
to determine the elemental composition, and principal components analysis (PCA) was performed to investigate the differentiation of nontoxic ammunition according to manufacturer and
from an environmental source, based on the primer only, as well
as the intact ammunition.

Materials and Methods

Primer Samples
Six different nontoxic ammunitions were purchased from local
stores and online suppliers. Purchased ammunition consisted of
Remington UMC LeadlessTM 9 mm Luger 147 grain Flat Nose
Enclosed Base (Lonoke, AR), Winchester Super Clean NT
9 mm Luger 105 grain Jacketed Soft Point (East Alton, IL),
Winchester WinClean 9 mm Luger 147 grain Brass Enclosed
Base (East Alton, IL), Magtech Cleanrange 9 mm Luger 115

grain Fully Encapsulated Bullet (Lino Lakes, MN), Blazer

Clean-Fire 9 mm Luger 124 grain Totally Metal Jacketed, and
Sellier & Bellot Nontox 9 mm Luger 115 grain Totally Full
Metal Jacketed (Lewiston, ID).
Under the supervision of firearms personnel at the Michigan
State Police Forensic Science Division, five rounds of each type
of ammunition were disassembled using a kinetic bullet pulling
system to dislodge the projectile from the shell casing. The propellant powder was then removed from each casing to leave only
the intact sealed primer cup and shell case behind. The slide and
barrel from a decommissioned Glock G17 high-capacity pistol
(Glock Inc., Smyrna, GA) were cut to remove the length of the
barrel and leave only the portion required to hold the cartridge
case containing the primer (Figure S1A). The barrel length was
removed to avoid any contamination from the barrel in the primer composition studies.
Five primer samples from each of the ammunition types were
placed in the shortened barrel chamber and aimed downrange
toward two 12-mm adhesive carbon tabs (Ted Pella Inc., Redding, CA) suitable for direct SEM imaging. The tabs were
placed 15 cm downrange from the barrel and aligned perpendicular to the path of ejected primer particles, following a similar
experimental set up described in the literature (5,14). Perpendicular placement of the tabs attempted to achieve maximum particle recovery by exposing the discharged particles to the highest
surface area possible.
The five rounds of ammunition of each type were fired by
pulling back the firing pin present in the slide and allowing it to
strike the primer cup seated within the chamber. After each firing, two new conductive tabs were placed in the holder to collect particles from the next sample. Each set of conductive tabs
was stored in sealed plastic petri dishes to avoid extraneous particle contamination. After firing all five rounds from a particular
ammunition type, the exhaust fan in the firing range was
switched on to remove any remaining air-borne particles and
avoid cross-contamination between samples. During the entire
time the firing range was in operation for this study, separate
conductive tabs were left exposed to the air. These tabs were
used as controls and were used to investigate the possibility of
particle carryover or contamination from the range.
Intact Ammunition Samples
Five rounds of ammunition of each type were fired by firearms personnel at the Michigan State Police Forensic Science
Division using a Ruger KP95DC 9 mm pistol (Sturm, Ruger &
Co., Southport, CT) that was supported on a firing stand. Two
12-mm conductive carbon tabs (Ted Pella Inc.) were placed
15 cm downrange, with one parallel and one perpendicular to
the projectile trajectory (Figure S1B). An additional carbon tab
was placed 10 cm downrange parallel to the projectile trajectory
(Figure S1C). In this study, the extra force present from the propellant may lead to particles discharged at higher velocities that
could penetrate deep into the adhesive coating of the carbon tab.
Therefore, the tabs were positioned parallel to the projectile trajectory to ensure recovered particles were present on the surface
of the adhesive rather than buried within it.
After each fired shot, all three carbon tabs (two parallel and
one perpendicular) were placed into a sealed petri dish to avoid
contamination and new tabs were positioned prior to the next
shot. After all five rounds were fired for each ammunition type,
the exhaust fan over the range was again switched on to remove
any remaining air-borne GSR particles. As before, during the

HOGG ET AL.

entire time the firing range was in operation for this study, separate conductive tabs were left exposed to the air and were used
as control tabs.
Road Safety Flare
An Orion road flare (Orion Safety Products, Easton, MD) was
purchased from a local vendor and burned outdoors in an open
fire pit. Multiple carbon tabs (Ted Pella Inc.) were held 10 cm
above the burning flare for 1 min to capture discharged particles.
All tabs were stored in a petri dish until analysis by SEM-EDS.
SEM-EDS Analysis of GSR Particles
All carbon tabs were analyzed without any further processing
or surface treatments. For SEM-EDS analysis, a Hitachi S4700II field emission SEM (Hitachi High Technologies America,
Schaumburg, IL) equipped with a EDAX Phoenix EDS system
(EDAX, Mahwah, NJ) containing a Sapphire Si(Li) detector was
used. Samples were manually scanned in secondary electron
mode at 5009 magnification using an accelerating voltage of
20 keV and a working distance of 12 mm.
Samples were initially scanned for the presence of small
(150 lm in diameter), spherical particles indicative of GSR. An
elemental profile was obtained for any particles meeting these
criteria using the EDS system with a live time of 8 s. If the element profile of the particle was found to differ from the background, the visible area was labeled a region of interest and
all other potential GSR particles within view were analyzed by
EDS to record their individual elemental compositions. Carbon
tabs corresponding to all samples (primer only, intact ammunition, and road flare) were searched for particles in a serpentine
pattern until a total of 30 regions of interest were designated,
which was deemed suitable for further statistical analysis of the
data.
Data Processing
The EDS spectra were individually opened in the EDAX
Spectrum Viewer software (version 4.0, EDAX) and the counts
for each energy channel were exported to Microsoft Excel (2010
version, Microsoft Corp., Redmond, WA). In all spectra, the
most significant X-ray emission peaks occurred at energies
<5 keV and, to avoid incorporating small differences from noise
and baseline fluctuations into the subsequent statistical analysis,
the spectra were truncated at 5 keV. In addition, nearly every
spectrum included carbon and oxygen peaks resulting from the
carbon tab. While these elements may be contained within GSR
particles, EDS is unable to distinguish the source of each elemental contribution. Hence, carbon and oxygen were excluded
from the spectra by beginning each spectrum at 0.7 keV.
After truncating, all spectra from the 30 regions of interest for
a single firing were consolidated into one Excel file. This was
repeated for the five firings of each primer sample and the five
firings of each intact ammunition samples, producing a total of
60 files. Copper was a common component of all ammunitions
tested, present as either a component in the projectile jacket
material or in the cartridge case. Hence, copper is not unique to
any of the ammunitions and spectra consisting primarily of this
element were excluded from this initial study.
Particles from a single firing produced spectra with a wide
variety of compositions and this high variability may be identified as a major source of variance in subsequent PCA. To

37

DISCRIMINATION OF NON-TOXIC AMMUNITION

overcome this, the EDS spectra for all particles observed during
a single firing event were averaged to obtain a single spectrum
representative of that firing event. For each firing, the number of
particles documented in this study ranged from 12 up to 100
with an average of 50 particles for all firings. The resulting spectra were then normalized to the maximum energy in the spectrum prior to statistical analysis.
Principal Components Analysis
PCA was first performed on a dataset containing the average
spectra for each of the five firings of the six primer samples and
the road flare sample using commercially available software
(The Unscrambler X, version 10.1; CAMO, Woodbridge, NJ).
Scores plots were generated in Excel (Microsoft Corp.) with
PC1 plotted on the x-axis and PC2 plotted on the y-axis. Corresponding loadings plots were also plotted in Excel to assess the
variables (i.e., elements) contributing to the variance described
by the principal components of interest.
PCA was repeated in a similar manner using a dataset consisting of the average spectra of each of the five firings for the
intact ammunition samples and the road flare sample and then
again using the full dataset (i.e., primer and intact ammunition
samples). Scores and loadings plots were again used to investigate both underlying differences and similarities among different
ammunition types, as well as between primer and intact ammunition of the same type.

Results
Particle Deposition Observations
Notable differences were observed in the number of GSR particles deposited among samples from different manufacturers,
and clear trends were evident (Table 1). For both the primer and
the intact ammunition samples, the Magtech (MAG) Cleanrange and Blazer (BLZ) Clean-Fire produced a relatively
large number of detectable particles compared to the other
brands under investigation. Remington (REM) UMC LeadlessTM
produced nearly twice as many particles when studied as a
primer sample alone compared to the intact ammunition.
TABLE 1Gunshot residue (GSR) particle counts for each of five replicates
for six different intact ammunition and primer samples.
Number of GSR Particles
Firing 1
Primer samples
REM
70
WWC
38
WSC
43
MAG
58
BLZ
98
SBN
53
Intact ammunition
REM
44
WWC
28
WSC
34
MAG
60
BLZ
87
SBN
27

Firing 2

Firing 3

Firing 4

Firing 5

Average

63
36
40
87
73
37

86
70
42
67
63
35

100
47
47
87
67
35

90
46
44
72
51
35

82
47
43
74
70
39








15
14
3
13
17
8

45
12
23
63
54
34

42
27
32
44
77
22

52
28
26
63
61
28

48
26
20
36
66
24

46
24
27
53
69
27








4
7
6
12
13
5

Error on the average is reported as 1 standard deviation.

REM, Remington; MAG, Magtech; BLZ, Blazer; WWC, Winchester
WinClean; WSC, Winchester Super Clean; SBN, Sellier & Bellot.

38

JOURNAL OF FORENSIC SCIENCES

Meanwhile, both Winchester WinClean (WWC) and Winchester Super Clean (WSC) NT along with Sellier & Bellot
Nontox (SBN) consistently produced fewer particles.
It should be noted that the particle counts in Table 1 do not
include particles found to consist primarily of copper (based on
maximum characteristic X-ray emission) as these particles were
excluded from this initial study. Particles primarily consisting of
copper accounted for more than 40% of those observed for both
the WWC and WSC samples. Surprisingly, copper particles were
generally <20% of the particles observed for those ammunition
brands with a higher particle count (i.e., MAG and BLZ). On
the one hand, the disparity in the percentage of particles comprised primarily of copper between manufacturers suggests the
exclusion of copper as a characteristic element may reduce the
ability to discriminate samples. Yet, the presence of copper particles in samples from all manufacturers indicates that copper may
be too common an ingredient in many ammunition components
to be useful for association and discrimination of samples.
For most ammunition types, the number of particles detected in
the intact ammunition was 5175% less than the number of particles detected in the primer samples. The exception to this was the
BLZ ammunition, in which a similar number of particles were
detected in both the primer and intact samples. The overall greater
number of particles in the primer studies is likely due to the lower
force ejecting the GSR from the barrel. While primers are explosive, they are designed to ignite the propellant to provide the energy
required to eject the projectile. Thus, the average particle number is
expected to be lower in the intact ammunition samples as the higher
velocity of the discharged particles allows the particles to travel
distances beyond the target designed to catch the particles. The
higher velocity may also lead to particle penetration deep into
adhesive films within the carbon tabs used for particle collection.

FIG. 1EDS spectra for five replicate firings of (A) Remington (REM)
UMC LeadlessTM primers and (B) the corresponding intact ammunition,
showing an elemental composition of Al, Si, and K, with Al as the dominant
peak.

Elemental Composition of Nontoxic Ammunition

Spectra of all primer samples, intact ammunition samples, and
the road flare are given in Figures S2S7. As an example, the
EDS spectra for the REM samples indicated that particles primarily consist of aluminum (Al) with some potassium (K) and a
small amount of silicon (Si) (Fig. 1). Despite being the major
element present, Al is not listed as a component of REM ammunition according to the associated material safety data sheet
(MSDS). However, Oomen and Pierce previously analyzed REM
ammunition and reported primer particles consisted of Al, Si, K,
sodium (Na), calcium (Ca), and magnesium (Mg), which is in
agreement with our conclusions (5). In comparing the EDS spectra from the primer only and the intact ammunition, the average
count was lower for the intact studies but general spectral trends
and peak ratios were conserved, indicating that the propellant
and projectile do not contribute meaningfully to the elemental
GSR analysis. This is particularly true in this study as contributions from copper (Cu), which originates primarily from the projectile, were not included in the analysis.
The EDS spectra of the WWC samples indicated that the primer samples primarily consist of K (Figure S2). For the intact
ammunition, Si was detected at higher intensity on average than
K and small peaks corresponding to Na, Mg, Al, sulfur (S), and
Ca were also observed. The differences in element composition
between the primer and intact ammunition samples suggest that,
in this case, the propellant and projectile have some influence on
the particle composition, which again is in agreement with the
work of Oomen and Pierce (5) In their experiments, direct
ignition of primers produced spectra dominated by K with traces

of Al, Si, Ca, and S present, among other elements. Similar to

the REM samples, K is not listed as a component on the MSDS
for the WWC samples.
Many similarities were apparent when spectra from the WWC
samples were compared to spectra from the WSC samples (Figure S3). For the latter, the primer-only sample consisted almost
entirely of K, with a slight trace of Si. The intact ammunition
consisted primarily of K with traces of Mg, Al, Si, S, and Ca,
which is similar to the element composition observed in the
WWC samples. It is not surprising that the composition of GSR
from two different ammunitions produced by the same company
would be similar as many components are likely used in both
products. The MSDS provided by the manufacturer lists tin (Sn),
zinc (Zn), and Cu as the inorganic components but does not list
those elements observed by EDS.
The MAG ammunition contained primarily Al and Si with a
minor amount of K and trace Ca based on the EDS spectra for
the primer samples (Figure S4). Interestingly, there are relatively
few differences between the primer and intact ammunition samples. However, in the primer samples, Si is the dominant peak,
while in the intact ammunition, Al is dominant. In 2007, Steffen
et al. (14) demonstrated that on average, MAG ammunition was
comprised of strontium (Sr) and hence was similar in elemental
composition to road flares. The results obtained in this study do
not support the same conclusion as not even trace levels of Sr
were detected in the MAG samples. This difference in composition may be due to formulation changes that have occurred in
the past 7 years since the study by Steffen et al.

HOGG ET AL.

Unlike the other ammunitions tested, BLZ primarily contained

Sr, with some contribution from Al in both the primer and the
intact ammunition samples (Figure S5). This finding is in agreement with the work by Steffen et al. (14) which indicated that
BLZ ammunition is primarily composed of Sr. The major difference between the primer samples and the intact ammunition
samples is the ratio of Sr and Al as the intact ammunition contains Al at higher intensity. The cartridge cases for BLZ are
manufactured from Al so the increased pressure and temperature
present upon firing the intact ammunition should vaporize more
Al leading to the higher concentration of Al in the GSR particles.
Primer samples from SBN ammunition primarily contained Si,
with trace K present (Figure S6). Intact ammunition samples had
a similar composition except with additional trace amounts of Al
and Ca present. The high concentration of Si in GSR from SBN
is expected due to the presence of glass in the primer along with
a potassium salt. As before, the elemental composition of SBN
in this study is generally in agreement with the results of Steffen
et al., with the exception of the trace amount of Al found in this
study but not reported by Steffen et al. (14).
The EDS spectra of the road flare sample revealed a composition similar to BLZ with Sr as the primary element with traces
of S, chlorine (Cl), and K (Figure S7). Each of these elements is
in agreement with the MSDS for the flare, which reported Sr, K,
S, and Cl in the form of perchlorate and chlorate.
When visually comparing EDS spectra of the ammunition and
road flare, the intensity of the X-ray is not considered important
as the intensity is related to the size of the particle. For smaller
particles, more background is sampled by the EDS and incorporated into the resulting spectrum. Conversely, larger particles
occupy a greater portion of the EDS analysis area which results
in higher X-ray counts for the elements present in GSR. Thus,
the energy of the X-ray, rather than the intensity, is of greater
importance when comparing these spectra.
Based on a visual comparison of overlaid spectra, REM,
WWC, and WSC lack any peaks in the vicinity of Sr and are
therefore easily distinguished from the road flare sample. In
addition, spectra for WWC and WSC contain a small peak corresponding to Ca and REM primarily consists of Al, neither of
which is present in the road flare sample.
Spectra for MAG and SBN have strong peaks corresponding
to Si that overlap with the peak arising from Sr in the road flare.
These two ammunition types also have a similar ratio of K and
Si, making distinction based on visual comparison of the spectra
difficult. However, as spectra for both ammunition types lack a
peak corresponding to Sr, distinction from the road flare sample
is possible. The most challenging sample to distinguish from the
road flare is the BLZ ammunition as spectra for both BLZ and
the flare contain Sr as the primary peak. However, the additional
presence of S, Cl, and K in the road flare can be used to distinguish this sample from the BLZ ammunition.
PCA of Primer Samples
Discrimination of the nontoxic ammunition and road flare
sample was possible based on differences in elemental composition observed in the EDS spectra. However, the ability to use
PCA to identify underlying differences and similarities among
the samples provides a more objective method to associate and
discriminate samples.
PCA was initially performed on a dataset containing EDS
spectra of the primer samples and the road flare. The resulting

DISCRIMINATION OF NON-TOXIC AMMUNITION

39

FIG. 2Principal components analysis of primer samples and road flare

(A) scores plot, (B) PC1 loadings plot, and (C) PC2 loadings plot.

scores and loadings plots are shown in Fig. 2. The first two principal components accounted for 78% of the variance in the dataset and discrimination of the primer samples from the road flare
was possible. Replicate firings of each primer were closely clustered with the exception of the REM samples. In this case, EDS
spectra indicated slight differences in chemical composition
among the five firings. From the scores plot, distinction among
the different primer samples was possible, with the exception of
WWC and WSC primers, which were overlaid in the scores plot.
This is expected as the EDS spectra showed high similarity in
chemical composition between these two samples (Figures S2
and S3).
The positioning of the samples on the scores plot can be
explained with reference to the loadings plots (Fig. 2B,C). The
PC1 loadings plot indicated that Si and Sr were weighted positively so primers that contained these elements (i.e., MAG, BLZ,

40

JOURNAL OF FORENSIC SCIENCES

SBN), as well as the road flare sample, were positioned positively on PC1 in the scores plot (Fig. 2A). Similarly, as K was
weighted negatively on PC1, primer samples containing K as the
primary component (i.e., WWC and WSC) were positioned negatively in the scores plot (Fig. 2A). Further, as there was only a
small, positive contribution from Al on PC1, replicates of the
REM primer samples were positioned close to zero on this PC
in the scores plot. There was also spread among the five firings
of the REM primer, with one sample positioned negatively on
PC1 and the remaining samples positioned positively. From the
normalized EDS spectra for this primer, the elevated X-ray
counts from K in the fifth firing resulted in a more negative
weighting on PC1 and hence a more negative position on PC1
than the other replicates in the scores plot.
The positioning of the samples on PC2 was explained in a
similar manner, with reference to the PC2 loadings plot
(Fig. 2C). That is, Si and K were weighted positively in the PC2
loadings plot with the result that primer samples containing these
elements were positioned positively on PC2 in the scores plot.
As Al and Sr were weighted negatively in PC2, primer samples
containing these two elements were positioned negatively on
PC2 in the scores plot.
The road flare sample and the MAG and SBN primer samples
had similar scores on PC1 such that differentiation based on this
PC alone was not possible. Spectra for the two primer samples
contained intense peaks for Si while the road flare spectrum contained an intense peak for Sr. Due to the similar X-ray energies
for these two elements, the two peaks were combined into a single variable during PCA, as observed in the PC1 loadings plot
(Fig. 2B). This combined variable resulted in similar scores for
the primer samples and road flare on the first principal component. However, from the PC2 loadings plot, Si was weighted
positively while Sr was weighted negatively, and therefore, distinction of the MAG and SBN primer samples and road flare
sample was possible on the second principal component.
The BLZ primer samples were positioned most closely to the
road flare sample in the scores plot (Fig. 2A), which was
expected as both contained Sr as the primary peak. However,
the Al present in the BLZ primer samples led to a slight increase
in positive positioning on PC1 and negative positioning on PC2
relative to the road flare. The small K peak present in the road
flare also led to a slightly more negative positioning on PC1 and
more positive positioning on PC2 compared to the BLZ primer
samples. Thus, with the assistance of the two smaller peaks present in the spectra, the BLZ primer and road flare samples were
distinguished in the scores plot.
PCA of Intact Ammunition Samples
The scores plot following PCA of the intact ammunition samples and road flare sample is shown in Fig. 3A in which the first
two principal components accounted for 69% of the variance in
the dataset. As before, the positioning of the samples in the
scores plot could be explained with reference to the loadings
plots. The loadings plot for PC1 indicated that Al and Sr were
weighted positively, while Si, S, and K were weighted negatively (Fig. 3B). Meanwhile, Al and K were weighted positively
on PC2, and a combination peak from Si and Sr was weighted
negatively (Fig. 3C).
Firings from the same ammunition were positioned closely on
the scores plot, with the exception of the WWC and WSC samples for which there was spread on both PC1 and PC2. This
increased spread resulted from differences in the intensity of Na,

FIG. 3Principal components analysis of intact ammunition samples and

road flare (A) scores plot, (B) PC1 loadings plot, and (C) PC2 loadings
plot.

Mg, Al, S, and Ca, which were present at trace levels in these
two samples.
The high intensity of Sr and Al in the BLZ ammunition led to
the positive positioning on PC1, while the excess Sr content led
to negative positioning on PC2 in the scores plot. The SBN
ammunition contained Si as the major component; however, this
element did not contribute substantially to the PC1 loadings
which resulted in the SBN samples being positioned close to
zero on PC1 in the scores plot. In contrast, Si was weighted negatively on PC2 in the loadings plot, which resulted in the negative positioning of the SBN samples on PC2 in the scores plot.
The Sr and K present in the road flare sample led to the positive
positioning on PC1, while the excess Sr present in this sample
resulted in the negative positioning on PC2. While the road flare
had a similar score on PC1 as the REM and MAG samples, the

HOGG ET AL.

DISCRIMINATION OF NON-TOXIC AMMUNITION

41

In the scores plot, firings of each primer sample cluster closely, following trends described previously (Fig. 4A). Further,
the intact ammunition samples of REM, MAG, BLZ, and SBN
were positioned closely to the corresponding primer sample.
However, there was substantial spread in the intact ammunition
firings for both WWC and WSC, both in PC1 and PC2. As a
result of this spread, some of the intact ammunition samples
were not positioned sufficiently close to the corresponding primer to afford association. In fact, a firing of the WWC intact
ammunition overlapped with firings of the MAG primer samples.
Further, one firing of MAG primer was positioned more negatively on both PC1 and PC2 compared to the other firings and
actually overlapped with the road flare sample, hindering discrimination. The MAG primer and intact ammunition samples
were positioned similarly on PC1, but were distinguished on
PC2 as the primer samples were positioned positively and the
intact ammunition samples were positioned negatively (Fig. 4A).
This difference in positioning was due to the differences in the
major elements present in the samples: in the primer samples,
the dominant peak was Si, while in the intact ammunition, the
dominant peak was Al (Figure S3). From the PC2 loadings plot
(Fig. 4C), Si was weighted positively while Al was weighted
negatively resulting in the difference in position of the MAG primer and intact ammunition samples.
Discussion

FIG. 4Principal components analysis of primer samples, intact ammunition, and road flare (A) scores plot, (B) PC1 loadings plot, and (C) PC2
loadings plot.

negative positioning on PC2 distinguished the road flare from

these two ammunition samples. Further, the road flare sample
was positioned sufficiently negatively on PC2 to allow distinction from the remaining ammunition samples.
PCA of Primer and Intact Ammunition Samples
The scores plot following PCA of the full dataset (primer,
intact ammunition, and road flare) is shown in Fig. 4A. The
first two principal components accounted for 67% of the variance in the dataset. The loadings plot for PC1 indicated that
K was weighted positively, while Al, Si, and Sr were
weighted negatively (Fig. 4B). On PC2, Si, K, and Ca were
all weighted positively, while Al was weighted negatively
(Fig. 4C).

This work demonstrated the ability to associate and discriminate a selection of nontoxic ammunition based on visual assessment of EDS spectra and subsequent PCA. Most ammunition
types were successfully distinguished from each other, as well as
from a road flare sample, based on element composition. However, the MAG and SBN ammunitions shared highly similar elemental profiles that complicated visual differentiation between
the two. Further, the BLZ ammunition and the road flare sample
had similar EDS spectra, again making distinction more challenging.
PCA was used to provide a more objective method to associate
and distinguish the primer samples, intact ammunition samples,
and road flare sample. When only the primer samples were considered, distinction among brands, as well as from the road flare sample, was possible. However, when intact ammunition was also
included, increased spread among replicate firings made association to the corresponding primer more difficult for the WWC and
WSC ammunition. Further, a difference in the dominant peak in
the EDS spectra for the MAG primer and intact ammunition samples was sufficient to distinguish these two in the PCA scores plot.
In general, distinction of the ammunition from the road flare was
possible based on visual examination of the scores plot, although
there was an anomaly as one firing of the MAG primer sample
could not be distinguished from the road flare.
This work has demonstrated the potential of elemental profiles
and PCA for the analysis and distinction of nontoxic ammunition
from different brands. Based on these results, additional element
combinations (e.g., AlSrKSi) could be added to a laboratorys list of elements to be considered in the protocol for GSR
identification. However, additional work is certainly necessary to
investigate and analyze particles originating from additional
sources that have similar chemical composition as nontoxic
ammunition. Further, this work focused only on particles directly
collected on discharge of the firearm. For greater utility, residue
from nontoxic ammunition recovered from a suspects hand

42

JOURNAL OF FORENSIC SCIENCES

should also be considered to assess the effect of surface contamination on the recovered residue.
Acknowledgments
Lt. Ron Crichton of the Michigan State Police is gratefully
acknowledged for all his help in obtaining the samples necessary
for this study. Dr. Baokang Bi is also acknowledged for assistance with the use of the SEM-EDS system.
References
1. Schwoeble AJ, Exline DL. Current methods in forensic gunshot residue
analysis. Boca Raton, FL: CRC Press, 2000.
2. Landrigan PJ, McKinney AS, Hopkins LC, Rhodes WW, Price WA,
Cox DH. Chronic lead absorption result of poor ventilation in an
indoor pistol range. JAMA 1975;234:3947.
3. Robbins SK, Blehm KD, Buchan RM. Controlling airborne lead in
indoor firing ranges. Appl Occup Environ Hyg 1995;5:4359.
4. Romolo FS, Margot P. Identification of gunshot residue: a critical
review. Forensic Sci Int 2001;119:195211.
5. Oommen Z, Pierce SM. Lead-free primer residues: a qualitative characterization of Winchester WincleanTM, Remington/UMC LeadlessTM, Federal BallisticleanTM, and Speer Lawman CleanfireTM handgun ammunition.
J Forensic Sci 2006;51:50919.
6. Gunaratnam L, Himberg K. The identification of gunshot residue particles from lead-free Sintox ammunition. J Forensic Sci 1994;39:5326.
7. Scientific Working Group for Gunshot Residue (SWGGSR). Guide for
primer gunshot residue analysis by scanning electron microscopy/energy
dispersive x-ray spectrometry. 2011; http://swggsr.org/FINAL%20GUIDE
%2011-29-11.pdf (accessed November 10, 2014).
8. Harris A. Analysis of primer residue from CCI Blazer lead-free ammunition by scanning electron-microscopy energy-dispersive x-ray. J Forensic Sci 1995;40:2730.
9. Martiny A, Campos APC, Sader MS, Pinto MAL. SEM/EDS analysis
and characterization of gunshot residues from brazilian lead-free ammunition. Forensic Sci Int 2008;177:E917.
10. National Research Council. Strengthening forensic science in the United
States: a path forward. Washington, DC: The National Academies Press,
2009.
11. Bueno J, Sikirzhytski V, Lednev IK. Attenuated total reflectance-FT-IR
spectroscopy for gunshot residue analysis: potential for ammunition
determination. Anal Chem 2013;85:728794.
12. Bueno J, Lednev IK. Advanced statistical analysis and discrimination of
gunshot residue implementing combined Raman and FT-IR data. Anal
Methods 2013;5:62926.
13. Bueno J, Lednev IK. Raman microspectroscopic chemical mapping and
chemometric classification for the identification of gunshot residue on
adhesive tape. Anal Bioanal Chem 2014;406:45959.
14. Steffen S, Otto M, Niewoehner L, Barth M, Brozek-Mucha Z, Blegstraaten J, et al. Chemometric classification of gunshot residues based on
energy dispersive x-ray microanalysis and inductively coupled plasma

analysis with mass-spectrometric detection. Spectrochim Acta Part B At

Spectrosc 2007;62:102836.
15. Wallace JS. Chemical analysis of firearms, ammunition, and gunshot
residue. Boca Raton, FL: CRC Press, 2008.
Additional information and reprint requests:
Ruth Waddell Smith, Ph.D.
Forensic Science Program, School of Criminal Justice
Michigan State University
655 Auditorium Road, Rm 560 Baker Hall
East Lansing, MI 48824
E-mail: rwsmith@msu.edu

Supporting Information
Additional Supporting Information may be found in the online
version of this article:
Figure S1. Experimental setup (A) Glock G17 high-capacity
pistol after removing barrel length (top) compared to an unmodified Glock G17 (bottom), (B) downrange view from barrel
showing adhesive tabs positioned perpendicular and parallel to
barrel and (C) overhead view showing two carbon tabs (one parallel, one perpendicular) positioned 15 cm downrange and a
third carbon tab (parallel) positioned 10 cm downrange.
Figure S2. EDS spectra for five replicate firings of (A)
Winchester WinClean (WWC) primers and (B) the corresponding intact ammunition, showing an elemental composition of K
and Si, K with traces of Na, Mg, Al, S, and Ca.
Figure S3. EDS spectra for five replicate firings of (A)
Winchester Super Clean (WSC) NT primers and (B) the corresponding intact ammunition, showing an elemental composition
of K and Si with traces of Mg, Al, S, and Ca.
Figure S4. EDS spectra for five replicate firings of (A)
Magtech (MAG) Cleanrange primers and (B) the corresponding intact ammunition, showing an elemental composition of Al
and Si with traces of K and Ca.
Figure S5. EDS spectra for five replicate firings of (A) Blazer
(BLZ) Clean-Fire primers and (B) the corresponding intact
ammunition, showing an elemental composition of Sr and Al.
Figure S6. EDS spectra for five replicate firings of (A) Sellier
& Bellot (SBN) Nontox primers and (B) the corresponding intact
ammunition, showing an elemental composition of Si with traces
of Al, K, and Ca.
Figure S7. EDS spectrum for the particles resulting from
burning an Orion road flare showing an elemental composition
of Sr and S with traces of Cl and K.