Un Burnet Propellant PDF

THE ANALYSIS
OF
UNFIRED PROPELLANT PARTICLES
BY
GAS CHROMATOGRAPHY –
MASS SPECTROMETRY:
A
FORENSIC APPROACH
A thesis presented to the

Queensland University of Technology
in fulfilment of the requirements for the degree of

Masters of Applied Science (Research)
by
Shiona Croft
Bachelor of Applied Science
Under the Supervision of:

Dr John Bartley
School of Physical and Chemical Sciences

Queensland University of Technology
April 2008
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In Australia, the 0.22 calibre ammunition is the most encountered ammunition type
found at a crime scene [1]. Previous analysis of gun shot residue (GSR) and unfired
propellant has involved studying the inorganic constituents by Scanning Electron
Microscopy or similar technique. However, due to the heavy metal build up that
comes with some ammunition types, manufacturing companies are now making
propellant that is safer to use. Therefore, it has become appropriate to study and
analyse unfired propellant by other means. One such technique is unfired propellant
analysis by gas chromatography – mass spectrometry (GC-MS). This technique
focuses on the organic constituent make up of the propellant paying particular
attention to diphenylamine, ethyl centralite and dibutyl phthalate. It was proposed
that different batches of ammunition could be discriminated or matched to each other
by using this technique. However, since the main constituents of unfired propellant
are highly reactive, it was not possible to accomplish batch determination of
ammunition. However, by improving extraction techniques and by removing oxygen
(a catalyst for the degradation of diphenylamine) a superior method was established
to help in the analysis of unfired propellant. Furthermore, it was shown that whilst
differentiating batches of the same ammunition was not possible, the improved
methods have helped identify different types of the same brand of ammunition. With
the aid of future studies to fully explore this avenue, the analysis of unfired
propellant could one day become an integral part of forensic science.
The Analysis of Unfired Propellant Particles by Gas Chromatography-Mass Spectrometry: A Forensic Approach
Shiona Croft
ii
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The work contained in this thesis has not been previously submitted to meet
requirements for an award at this or any other higher education institution. To the
best of my knowledge and belief, the thesis contains no material previously
published or written by another person except where due reference is made.
Shiona Croft Date
Shiona Croft
iii
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I wish to thank all those people who over the past years have seen me through my
best and my worst….
Firstly, to my supervisor Dr John Bartley (QUT) for your advise, patience and
support throughout my research. Your expert knowledge and direction was greatly
appreciated. In particular, your considerable experience with mass spectrometry and
research methodologies. Also, for your endless endurance, patience and guidance
with regards to the thesis write up. For all your help, I thank you.
To the Queensland Police Service (Mr Gary Asmussen and the members of the
Analytical Services Unit) for allowing me to take up this research but for also giving
me the freedom to explore this project in the direction I thought most appropriate.
Thank you.
To my colleague and friend Dr Helen Panayiotou, thank you for your words of
wisdom. Your encouragement and valuable direction when I felt lost was appreciated
greatly.
To my mum and dad who has been supportive from day one. Your support,
enthusiasm and confidence in my abilities allowed me to have courage in my work.
Thank you for never allowing me to give up – although I am too stubborn to do so!
To my dear Chris, who everyday told me how proud of me he was. Thank you for
putting up with the late nights and the stress. For your love, friendship and strength –
I honestly could not have done this without you. You mean everything to me.
To my brother Kevin, who I know is very proud of me. Thanks for your support
Kev!
Shiona Croft
iv
To my Ouma and Grandad, Connie and Gerald Campbell, I wish you could be here
but you are always in my thoughts. Thank you for your support and interest in my
thesis. It means so much to me that even though you are far away your love and
encouragement is not forgotten. I miss you.
To my very much loved group of friends; Scott, Niki, Amy, Mick, Nikki and
everyone else who has been there for me. Some of you have been around for more
than a decade and your love, encouragement and support is never forgotten. You all
mean the world to me and thank you for giving me the strength to go on.
Finally, to all the post graduate students whom I may not have seen as much as I
would have liked (since being off campus) but to my friend Dr Sarah Ede in
particular, who constantly inspired me and who I always knew would do great things.
Thank you.
Shiona Croft
v
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1.1 BACKGROUND .......................................................................................... 1

1.2 THE 0.22 CALIBRE AMMUNITION .............................................................. 1
1.2.1 The Cartridge ................................................................................... 2
1.2.2 The Projectile.................................................................................... 2
1.2.3 The Propellant .................................................................................. 3
1.2.4 The Primer........................................................................................ 3
1.3 PREVIOUS WORK RELATED TO ORGANIC GUN SHOT RESIDUE OR UNFIRED
PROPELLANT ANALYSIS ........................................................................................ 4
(;3(5,0(17$/ ......................................................................... 18
2.1 MATERIALS ............................................................................................ 18

2.2 INSTRUMENTATION ................................................................................ 18
2.3 STANDARD PREPARATION ....................................................................... 19
2.4 ETHYL ACETATE ALONE PROCEDURE ..................................................... 19
2.5 ETHYL ACETATE/DICHLOROMETHANE PROCEDURE ............................... 19
2.6 CONSISTENCY OF PROPELLANT COMPOSITION EXPERIMENT ................. 20
2.7 EXCLUSION OF OXYGEN EXPERIMENT .................................................... 20
2.8 TYPE DETERMINATION OF WINCHESTER AMMUNITION ......................... 20
5(68/76$1'',6&866,21 .................................................. 22
3.1 MASS SPECTRA OF UNFIRED PROPELLANT COMPONENTS ....................... 22
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3.1.1 Diphenylamine (C12H11N) ............................................................... 22
3.1.2 Ethyl centralite (C17H20N2O) ........................................................... 24
3.1.3 Dibutyl phthalate (C16H22O4) .......................................................... 26
3.2 CONTROLLED STANDARDS ..................................................................... 28
3.2.1 Diphenylamine, ethyl centralite and dibutyl phthalate variation...... 29
3.3 THE ANALYSIS OF PROPELLANT USING ETHYL ACETATE ALONE ........... 30
3.4 REMOVAL OF THE NITROCELLULOSE COMPONENT OF PROPELLANT USING
ETHYL ACETATE AND DICHLOROMETHANE ........................................................ 44
3.5 CONSISTENCY OF PROPELLANT COMPOSITION FROM A SINGLE

BOX/BATCH OF AMMUNITION ............................................................................. 53
3.6 THE EFFECTS OF EXCLUDING OXYGEN ................................................... 58

3.7 TYPE DETERMINATION OF WINCHESTER AMMUNITION ......................... 65
3.7.1 Winchester Laser LR HP 2DRM41.................................................. 65
3.7.2 Winchester Expert 23DLH02........................................................... 66
3.7.3 Winchester Winner IDKE52 ............................................................ 66
3.7.4 Winchester Subsonic LR Rim fire AED1FH31 ................................. 67
3.7.5 Winchester Superspeed LR HV solid SDSB51.................................. 68
3.7.6 Winchester Superspeed LR HV hollow point 2DRL62...................... 69
&21&/86,216$1')8785(:25. ................................. 72
4.1 CONCLUSIONS ........................................................................................ 72

4.2 FUTURE WORK....................................................................................... 73
$33(1',; ............................................................................................... 74
Ethyl Centralite standard ............................................................................... 74

Dibutyl phthalate standard ............................................................................. 75
Diphenylamine standard................................................................................. 76
Winchester Laser Long Rifle Hollow point 2DRM41 ...................................... 77
Winchester Expert 23DLH02 .......................................................................... 78
Winchester Winner IDKE52 ........................................................................... 79
Winchester Subsonic Long rifle Rim fire AED1FH31...................................... 80
Winchester Superspeed Long Rifle High velocity solid 2DSB51...................... 80
Winchester Superspeed long rifle high velocity hollow point 2DRL62............. 81
5()(5(1&(6 ......................................................................................... 82
Shiona Croft
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Figure 1.1: Dissected view of the case [8] ................................................................ 2
Table 1.1: Elution order for constituents using HPLC-MS[29] ................................. 6
Figure 1.2 Degradation of DPA [10,11].................................................................... 7
Table 1.2: Results from Northrop[46,47] ................................................................ 15
Table 3.1: Selected target compounds (from NIST library)..................................... 22
Figure 3.1 Mass spectrum of diphenylamine........................................................... 24
Figure 3.2 Chemical structure of diphenylamine and m/z = 77 fragment ion (C6H5)
.......................................................................................................... 24
Figure 3.3: Ethyl Centralite .................................................................................... 25
Figure 3.4: Mass spectrum of ethyl centralite ......................................................... 25
Figure 3.5: Fragmentation ions of ethyl centralite................................................... 25
Figure 3.6: Fragment A = m/z 120 and Fragment B = m/z 148 ............................... 26
Figure 3.7: General structure of phthalate esters where R, R’ = CnH2n+1; n=4-
15[50] ............................................................................................... 26
Figure 3.8: Characteristic fragmentation ions of butyl phthalate esters [51] ............ 27
Figure 3.9: Mass spectrum and chemical structure of dibutyl phthalate................... 28
Table 3.2 DPA, EC and DBPH standard variation .................................................. 29
Table 3.3 Variation in peak area of DPA between three random propellant samples
and variation observed between the three samples ............................. 31
Figure 3.10: Diphenylamine degradation over time ................................................ 31
Figure 3.11: Sample 1 - diphenylamine degradation ............................................... 32
Figure 3.14: 2-nitro-diphenylamine amounts detected (three random samples) –
Extrapolated to time zero to give appreciation of initial amounts of 2-
nitro-DPA in each sample.................................................................. 34
Figure 3.15: Mechanisms of N-Nitroso-DPA in the presence of NO2 and O2 [16] ... 36
Figure 3.16: Lussier and Gagnon [14]: Concentration of DPA and its derivatives as a
function of added nitrogen dioxide .................................................... 37
Shiona Croft
viii
Figure 3.17: Effect of storage on diphenylamine concentration (sample one and two)
.......................................................................................................... 38
Figure 3.18: Sample 1 - Effect of storage on diphenylamine (triplicate).................. 39
Figure 3.19: Sample 1 - The effect of storage on 2- nitro-diphenylamine (analysed
three times) ....................................................................................... 40
Figure 3.20: Sample one and two analysed each three times (average): comparison
between stored samples and samples left in solution for one week..... 41
Figure 3.21: The effect of leaving propellant in solution over one week (2-nitro-DPA
average – each sample analysed three times) ..................................... 42
Figure 3.22: Diphenylamine response (EtAc/Ch2Cl2 procedure) ............................. 45
Figure 3.23: Comparison between EtAc alone and EtAc/CH2Cl2 on DPA (average)
.......................................................................................................... 46
Figure 3.24: Comparison of EtAc alone and EtAc/CH2Cl2 procedures - 2-nitro-dpa
(average: each sample analysed three times)...................................... 47
Figure 3.25: 2-nitro-dpa levels - sample 1: comparison between EtAc alone and
EtAc/CH2Cl2 procedures ................................................................... 48
Figure 3.26: Comparison between EtAc alone and EtAc/CH2Cl2 procedures (ethyl
centralite average) ............................................................................. 50
Figure 3.27: Dibutyl phthalate – comparison between EtAc alone and EtAc/CH2Cl2
procedures......................................................................................... 51
Table 3.4: Relationship between sample size and population size ........................... 53
Table 3.5: Masses from ten random samples from one box of ammunition ............. 53
Figure 3.28: Levels of diphenylamine of ten (10) random samples of propellant from
the one box of ammunition ................................................................ 55
Figure 3.29: Levels of dibutyl phthalate detected of ten (10) random samples of
propellant from the one box of ammunition ....................................... 55
Table 3.6: Ratios (peak area) of main constituents from one box of ammunition .... 56
Figure 3.30 Inert gas procedure consequences on the main constituents of unfired
propellant particles ............................................................................ 58
Figure 3.31: Inert gas procedure (dibutyl phthalate)................................................ 60
Figure 3.32: The effects of leaving propellant in solution under an inert atmosphere
.......................................................................................................... 61
Shiona Croft
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Figures 3.33: Re-analysis of samples A-D 24 hours later (individually separated for
visual clarity) .................................................................................... 63
Figure 3.34: Winchester Laser LR HP 2DRM41 .................................................... 65
Figure 3.35: Winchester Expert 23DLH02 ............................................................. 66
Figure 3.36: Winchester Winner IDKE52............................................................... 67
Figure 3.37: Winchester Subsonic LR Rim fire AED1FH31................................... 68
Figure 3.38: Winchester Superspeed LR HV solid 2DSB51 ................................... 69
Figure 3.39: Winchester Superspeed LR HV hollow point 2DRL62 ....................... 70
Table 3.7: Type determination of Winchester ammunition...................................... 71
Shiona Croft
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CH2Cl2: Dichloromethane
DBPH: Dibutyl phthalate
DEPH: Diethyl phthalate
DNT: 2,4-dinitrotoluene
DPA: Diphenylamine
EC: Ethyl centralite
EtAc: Ethyl Acetate
GC-MS: Gas chromatography – mass spectrometry
GSR: Gun shot residue
HP: Hollow Point
HPLC: High performance liquid chromatography
HV: High Velocity
LC: Liquid chromatography
LR: Long Rifle
MC: Methyl centralite
NC: Nitrocellulose
NG: Nitro-glycerine
N-nitroso-DPA: N-nitroso-diphenylamine
OGSR: Organic gun shot residue
SEM: Scanning electron microscopy
THC: Tetrahydrocannabinol
THC acid: Tetrahydrocannabinol acid
TLC: Thin layer chromatography
TNT: Trinitrotoluene
2-nitro-DPA: 2-nitro diphenylamine
4-nitro-DPA: 4-nitro diphenylamine
Shiona Croft
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Gun shot residue analysis has evolved into a significant, integral part of forensic
science today. Increased research into methodology, detection and subsequent
examination of the gunshot residue has allowed this type of evidence to be used more
effectively by analysts for the purpose of solving crime.
One area of research that has been explored is investigating the organic constituents
of unfired propellant to identify their key role in ammunition make up and functions.
It is widely known that the inorganic components of gunshot residue are readily
analysed by the scanning electron microscope to identify lead, barium and antimony
and other key ingredients[2-5]. However, the potential health risks associated with
heavy metal build up, have led to heavy metal free ammunition being introduced [6].
In this situation, organic analysis of the residue or propellant is required and
subsequently, analysts have demonstrated that this is possible. There are some
discrepancies though with which constituents are unique to smokeless powders,
which will aid in the identification of the ammunition.
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In Australia, the use of 0.22 calibre ammunition is wide spread[1] and so,
investigative forces are mostly concerned with this type of ammunition. To fully
appreciate the diversity of the 0.22 calibre projectile some background information
will be given about the physical make up of ammunition itself, including: the
cartridge and cartridge case, projectile, propellant; and primer and their roles in the
organic make-up of the ammunition[1,7].
Shiona Croft
1
1.2.1 The Cartridge
The calibre of the ammunition refers to the diameter of the bore inside the firearm. A
typical cartridge will contain the case, primer, propellant and projectile. The
ammunition can either be rim fire or centre fire. In rim fire ammunition, the priming
materials are concentrated around the outer edge of the base of the cartridge making
the rim the most susceptible to detonation. Conversely, centre fire concentrates the
priming material into the centre of the base of the cartridge leading to this centre
being the most susceptible to ignition.
This figure is not available online.

Please consult the hardcopy thesis
available from the QUT Library
Figure 1.1: Dissected view of the case [8]
1.2.2 The Projectile
Lands and grooves are often marked onto fired projectiles as they spiral out of the
muzzle of the firearm. These physical striations can help in the physical
characterisation of the projectile through the use of a comparison microscope. The
shape, cannelures, dimensions of the hollow point and coating can all be
discriminating identifiers of the projectile origin. It is known that the inorganic
composition of the projectile is usually lead, or lead with antimony added as a
hardener[2,4,5,9].
Shiona Croft
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1.2.3 The Propellant
The most important part of the ammunition in relation to analysis is the propellant.
The propellant occupies considerable space inside the cartridge case and contains
various compounds. For 0.22 calibre ammunitions, smokeless powders are the
propellant of choice[1]. These powders come in two varieties, single and double
based. Single based powders are those that contain nitrocellulose (NC) as the main
explosive material whereas double based powders contain both NC and nitro-
glycerine (NG). The addition of NG increases the hydrophobic tendencies of the
powder, raises the energy content and softens the powder. The stabilizers ethyl and
methyl centralite behave in a chemically similar way however, only one compound is
used in the ammunition make up, never both. The role of these compounds is to
remove oxides formed by the decomposition of NG and NC. If these oxides are not
removed, they behave as catalysts and are involved in further decomposition, which
will shorten the shelf life of the ammunition. It has also been stated that self-ignition
may occur from the increased degradation due to the auto-catalysis[10-17] of the
ammunition. Ethyl centralite (EC) removes oxides by acting as a weak base and
reacts with the decomposition products to form nitro and nitroso derivates.
Diphenylamine (DPA) is another stabilizer commonly seen in single based powders.
Its usual concentration is only 1% and it is common to see both EC and DPA in
ammunition types. Its function is similar to that of EC, as its main function is to
absorb the free nitrates that have derived from the nitrocellulose. Its degradation and
the subsequent derivatives that are formed will be discussed later in the chapter.
Plasticizers are also found in propellants and work to convert NC from its natural
fibrous state into a gel state. Dibutyl phthalate, diethyl phthalate, dioctyl phthalate,
and glycerol triacetate are common plasticizers found in ammunition today[9,18].
These compounds can also function as burning modifiers which reduce the initial
burning rate of the propellant grains and increase pressure and efficiency[19].
1.2.4 The Primer
Shiona Croft
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Most primers have explosive and oxidizing properties. Many of the compounds
found in primers can be multi or mono functional. Organic compounds with nitro
functional groups are often used as primers. Such compounds include Trinitrotoluene
(TNT) or derivatives thereof. In addition to these organic compounds mentioned,
primers are also comprised of inorganic elements such as barium, lead and antimony.
These elements play key roles; for instance, an initiator (lead styphnate), an oxidiser
(barium nitrate) and a fuel source (antimony sulphide)[2,5,9,18,20].
The primer is ignited when hit by the firing pin of the weapon which results in hot
gases and temperatures being created. The ignited primer now decomposes and the
enormous pressure and energy build up consequently causes the projectile to be
expelled from the chamber of the firearm. Lead, Antimony and barium are converted
into a gas during this process which in turn condenses into tiny spheres or droplets of
residue. These spheres can range in size from 0.5 to 10 microns, making them a
valuable tool in forensic science.
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The use of Gas Chromatography-Mass Spectrometry (GC-MS) as a method for
analysing organic compounds in the forensic field is well established in areas such as
drug analysis, which suggests it could be extended to GSR research. Aebi et al[21]
has stated that GC coupled with dual MS and a Nitrogen-Phosphorous Detector
(NPD) is a powerful tool for forensic analysis. Their study concentrated on
identifying masked pharmacologically active compounds via this method and noting
its advantages over other detection systems. However, they observed that not all
pharmacologically active compounds contain nitrogen and phosphorous. Their
LQYHVWLJDWLRQRI – tetrahydrocannabinol and its metabolites (THC acid) show this.
This compound is the active component in marijuana or cannabis, is non volatile and
therefore Liquid Chromatography (LC) is often used to establish the concentration of
THC in a particular sample. The reason for this is because with higher temperatures
often used within a GC system, THC acid is decarboxylated to THC. This
subsequently results in an inaccurate estimation of the total concentration of THC in
Shiona Croft
4
the sample. This is of significance as a small amount of THC acid decarboxylating to
THC in this process has a dramatic effect on the amount of THC detected. In their
study, while not covering a large number of compounds, did show the possible
advantages of using GC-MS in organic studies of this nature. GC allows for rapid
and sensitive separation of compounds while MS provides identification of the
resulting peaks from the chromatogram. By using mass spectral libraries, unknown
substances can usually be identified. This in turn has allowed GC-MS to be a
valuable tool in forensic analysis and will continue to do so in the future, with many
studies utilising this analytical technique[22-25].
Within the field of unfired propellant analysis, the organic compounds used for
identification have not changed significantly over the years, however, major
discrepancies exist over which of these organic compounds are totally ‘unique’ to
smokeless powders.
Mach undertook two studies in 1977[26] and 1978[27] of 33 different kinds of

ammunition to determine the feasibility of identifying gunshot residue via its organic
constituents using GC-MS. From their earlier study[26] they were not able to predict
the composition of the powder just by its brand and type. Their later study[27] agreed
with Wu et al[28,29] that the main characteristic compound is ethyl centralite but it
is present in comparatively small amounts. Mach’s work did not extend to
discriminating different batches of ammunition. Their main focus was on comparing
the unburnt particles to burnt ones. The results indicated the components detected
were of varying concentrations. It could have been useful, therefore, to establish a
database of the concentrations of the various components detected. Unknown
samples could have been compared to this database to establish whether it had
similar properties to the samples of known origin in the database (i.e. a profiling
method). Interestingly, their results showed that diphenylamine was the most
common additive, and while this is not a new discovery, the lack of investigation into
other organic compounds in the samples would indicate their method is in need of
further exploration. Dibutyl phthalate was seen in about half of their samples but
nitro-glycerine was seen in a substantial number of samples, which suggests that
their work was paving the way for further investigations into this area.
Shiona Croft
5
Wu et al[29] used a tandem mass spectrometry system (MS-MS) to show that the
organic components of GSR are more characteristic than their inorganic counterparts.
MS-MS has the added advantage of being more selective in that molecular ions are
separated by the first mass spectrometer, and these subsequent selected ions are
reanalysed by a second mass spectrometer to give a more specific pattern. It was
stated that the main components of the gunshot residue are NG, trinitrotoluene
(TNT), 2, 4-dinitrotoluene (DNT), DPA and methyl centralite (MC). In their research
they were able to separate the main components of the gunshot residue by High
Performance Liquid Chromatography (HPLC) and observe the molecular ions of the
main stabilizer methyl centralite, which are said to be the most characteristic
compounds of gunshot residue[28]. The components were analysed by HPLC-MS
and the compounds eluted in the following order (table 1.1):
Table 1.1: Elution order for constituents using HPLC-MS[29]
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This table is not available online.

When the compounds were then subjected to MS, characteristic ions were seen. This
however, was done using negative ion mass spectrometry which is not the usual
methodology. The Molecular ion (M-H)- at m/z 226 was seen with fragmentation
ions: (M-HNO3)- at m/z 163 and (NO3)- at m/z 62. These ions are said to be
characteristic of NG[29]. The characteristic molecular ion of MC was seen at m/z
241 and the fragmentation ions at m/z 134, 106, 77, 51. While it has been suggested
that the various components of the smokeless powder do have other origins, MC and
EC are thought to be characteristic of smokeless powders especially when seen with
NG[28]. These two compounds are uncommon in other industries. NC, on the other
hand, is used in lacquers, varnishes, printing and in the pharmaceutical industries
while DPA is used in rubber preparations and in the food industry. NG has uses in
the explosive and pharmaceutical industries[28].
Shiona Croft
6
Wu et al [29] did however suggest that by focusing their studies on methyl centralite
and using concentrated sample volumes, the level of contamination of the injector
contributed to lower than expected detection levels. Several cleaning methods did not
help the situation and so, they adopted a 100 fold dilution of the samples with
methanol to avoid further contamination. Once this method was adopted, they were
able to successfully discriminate 10 persons who had recently fired a revolver, from
10 persons who had not fired a gun. Further experiments could adequately identify
MC on a person who had fired a pistol eight hours earlier and on the hand of an
individual who had washed their hands after firing a pistol. Both tests showed a
positive correlation and they argued that their work could be used in criminal
investigations when an offender managed to escape after firing a firearm, but was
caught several hours later. They proposed that even if the offender washed their
hands with water, detectable amounts of MC could be identified using this method.
This method was found to be sensitive and selective when using Multiple Reaction
Monitoring (MRM) mode, which used ions of m/z 241 as precursor ions and ions of
m/z 134 as product ions, and while their method mainly focused on methyl centralite,
it could be adapted to identify other components, and therefore is a promising
technique.
While Wu et al [29] concentrated on MC as the most characteristic compound for the

identification of smokeless powders; DPA and its derivates have received wide
attention. It is known to decompose substantially[10-17,30-35] and Tong et al[17]
suggested that the ‘detection of DPA may be taken as evidence’ as many gun
powders do not contain the stabilizers methyl or ethyl centralite. However, it should
be noted that DPA is also found in the rubber and food industry.
[2-nitro-DPA]
[DPA] [N-nitroso-DPA]
[4-nitro-DPA]
Figure 1.2 Degradation of DPA [10,11]
Shiona Croft
7
Bergens and Danielsson[10,11] investigated the degradation mechanism of DPA and
their results are shown above in figure 1.2, however, this is in contradiction to the
report of Lussier[14] who suggested other reaction mechanisms. Bergens and
Danielsson concentrated on monitoring the DPA at a temperature of 85ÛC to note the
breakdown products achieved. The conclusion was after analysis by LC, only a small
percentage of the DPA is converted to 2-nitro-DPA and 4-nitro-DPA. Conversely, N-
nitroso DPA corresponds to the largest breakdown product produced, which in turn is
responsible for further interaction with the NC degradation products. After 15 days
of storage at this temperature, the concentration of the 4-nitro-DPA is about twice as
much as 2-nitro-DPA which is supported by the work by Lussier and Gagnon[14].
The concentration-time curves further support the idea that the DPA is rapidly
degraded into these products when introduced to a NC matrix.
Concentration anomalies of DPA were observed in another study[14] which

encountered difficulties during extraction stages; however in the study, critical
evaluation of their extraction and solvent techniques have rendered the paper quite
useful. The cause of the significant DPA loss was not fully explained, and while it is
of extreme importance to understand the chemistry of the reactions, the authors have
suggested that the interaction between the NC matrix and DPA has produced a
compound not amenable to extraction techniques. Methylene chloride was used
suggesting that most of the NC matrix should have been removed during the
extraction stage. It does then beg the question of what DPA is reacting with to create
degradation products. The authors gave many possible explanations including the
interaction with nitrate esters, causing cleavage to leave alkoxy radicals, which are
said to be responsible for rupture of the cellulose chain. Furthermore, the NC-DPA
structure that is then formed could react with nitrous oxides and N-nitroso-DPA, with
2 and 4-nitro-DPA possibly being by-products of this interaction. In part 2 of the
study[10] it was suggested that spectroscopic techniques be employed to determine
whether or not the DPA has been incorporated into the NC matrix. While more
complex reasons were suggested for the DPA degradation, it is important to note the
possible interaction with oxygen as a degradation source[11]. The authors did not
give reasons behind the reaction between DPA and oxygen nor its interaction with
Shiona Croft
8
light. It may be worth investigating these two physical properties on the
decomposition of DPA.
Mathis et al [36] further highlighted the importance of developing an analytical tool

for the characterisation of GSR. Their study involved seven compounds; DPA, N-
nitroso-DPA, MC, EC, dimethylphalate, diethylphthalate and dibutylphthalate
(DBPH). Mathis et al understood the necessity of producing a chemical profile that
allows for determination of distinguishable characteristics. While they acknowledged
the use of GC as a tool for the analysis of GSR, the study involved the use of
gradient reversed phase liquid chromatography as it was felt that the nitro
compounds were susceptible to thermal degradation by GC-MS. This contrasts with
the work of Burns et al[22] who used GC-MS to analyse and characterise NG based
explosives. Burns et al successfully identified nitro esters and nitro aromatic
compounds from the samples and undertook the important task of examining any
batch-to-batch differences between commercial explosives. Determination of the
sample’s total DNT content allowed for further discrimination of the ammunition
type. This information was compared to the manufacturer’s specifications, which
enabled the explosive batch number to be established.
Despite the contradiction, Mathis et al were able to quantify several organic

constituents such as centralites, phthalates and diphenylamine by gradient reversed
phase LC. This phase was chosen due to the spread in polarities of the main
constituents. Coupled with MS, this technique is very powerful in both separating
and identifying capabilities. The separation method was further developed by
Wissinger et al in 2002[37] however slight changes were made to accommodate
Mathis’ study. Ammonium acetate (CH3COONH4) was used to assist the ionisation
process. Methylene chloride as a an extraction solvent was also used as its
application is well documented in OGSR[10,11,25,37]. Its role is to keep the NG
insoluble, which enables ease of removal upon reconstitution. The LC conditions
were modified compared to those used by Wissinger by using a lower flow rate,
smaller column and by adding ammonium acetate to the mobile phase to help in the
ionization stage. The study was significant to GSR analysis as it successfully
discriminated characteristic organic compounds; however, the ambiguity of the
Shiona Croft
9
conclusions reduces the overall value of the work. Wissinger did comment on the
power of GC-MS, particularly with respect to the analysis of phthalates which may
have been missed by LC-MS.
In 1989, Keto et al[18] compared smokeless powders using Pyrolysis Capillary Gas
Chromatography. This method was chosen since there is no sample preparation
involved and consequently any error associated is eliminated. The authors also
argued that by using the capillary column, the better separation would increase the
analytical benefit. Meng et al [20]agreed with this statement by saying that the
‘separating power of the capillary column in the GC is unparalleled’. However, by
using statistical measurements, the amount of detectable difference between
manufacturers was shown to be very small, rendering this method limited in source
identification. This is a situation where the use of MS could be of significance to
properly identify the peaks in the chromatogram. While no real differences seen
between different manufacturers, close examination of the results showed different
levels of peak intensity, which was not appropriately recognised in the paper. The
size of the study was limited to only three samples: Hercules Red Dot; Winchester-
Western 540; and Dupont Hi-Skor 700x brands. This factor could be the reason for
their poor results. Many brands and types of ammunition should have been included,
especially when their statistical method of validation is a chemometric method,
which requires a large sample population.
In a survey of GSR analysis by Meng et al[9], efforts were made to compare the
various techniques available for the study of GSR. They incorporated both inorganic
and organic analysis. From this report, it is clear that there is a variety of techniques
available for analysis of the organic components, whereas in inorganic analysis there
are only four main instruments of choice: Atomic Absorption Spectrometry (AAS);
Anodic Stripping Voltammetry (ASV); Neutron Activation analysis (NAA); and
Scanning Electron Microscopy coupled with the Energy Dispersive X-Ray detector
(SEM/EDX). When analysing the organic components, there is a greater variety of
methods to choose from. Such techniques include Thin Layer Chromatography
(TLC); Gas Chromatography (GC); Infrared Spectroscopy (IR); High Performance
Liquid Chromatography (HPLC); Mass Spectrometry (MS); Fluorometric detection;
Shiona Croft
10
Supercritical Fluid Chromatography (SFC) and Capillary Electrophoresis (CE). The
use of Raman Microscopy has also been noted in Organic GSR analysis[38]. More
recently, the use of time-of-flight secondary ion mass spectrometry (TOF-SIMS) has
been noted in the study and characterisation of propellant samples[39,40]. This
analytical technique has the advantage of obtaining elemental and molecular
information from surface samples with a particularly low level of detection. It can
also capture molecular images which may be useful for investigating distribution of
additives and explosives constituents of the powder.
TLC has the advantage of being simple, rapid, moderately sensitive and relatively
cheap. However, it has poor quantification capabilities and requires a large amount
of sample. Infrared Spectroscopy (IR) has been successfully used to determine the
presence of nitrocellulose in samples[41]. However, it was not as successful in
determining the other minor components present at low concentration, but which are
equally important in function. Such components include the stabilizers in the
propellant grains, which may be used as characteristic compounds of GSR.
Furthermore, the fact that only NC (not being totally unique to GSR) was accurately
detected in this study may render this technique unsuitable for the analysis of GSR,
as there are many other vital components, which have been overlooked. It may be
useful for the confirmation of substances when a positive result using another
method such as HPLC, has been obtained.
HPLC can be used for the analysis of organic compounds and has the added
advantage of being able to separate ionic compounds, polymeric materials and poly-
functional compounds of high molecular weight. Also, HPLC is not limited by
thermal stability of the compounds. Due to the higher temperatures in the GC
instrument, some compounds cannot be adequately analysed as they may undergo
decomposition during injection.
The MS system is a highly specific and sensitive method and has previously been
shown to be a powerful tool in analysing explosive compound[28,29]. Mass
Spectrometry is an excellent analytical system which is best coupled with the GC or
HPLC systems to give both separation and identification of the compounds in a
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mixture. It has been proposed that the coupling of MS with GC will render the best
results since both operate in the gaseous phase and the separated components can
sequentially flow to the MS detector where the individual mass spectra can be
obtained[21]. Most investigations into the organic compounds of GSR have coupled
the MS with HPLC but the use of GC is equally as valid.
Fluorometric detection has been noted as a sensitive and selective mode of detecting
organic components when using HPLC. Meng et al[20] in 1996 investigated the
detection of ethyl centralite and 2-4 DNT in GSR after derivatisation with 9-
fluorenylmethylchlorformate. Their method used a fluorometric detection which they
claimed to be a more sensitive and selective method for the detection of organic
GSR. EC was first hydrolysed to N-ethylaniline (NEA), which was further
derivatised with dansyl chloride (DNS-Cl). The end product was a fluorescent
compound that could be separated using TLC or reversed phase HPLC. While the
authors claim that fluorometric detection is sensitive and selective, their analysis
revealed that only three out of eleven kinds of ammunition contained EC. They
analysed three other compounds recommended as characteristic compounds[35].
These were 2,4 DNT, 2–nitro diphenylamine, and 4–nitro diphenylamine. It is
suggested that they can be reduced to their aromatic amines which then allows for
derivatisation using the labelling agents such as 9-fluorenylmethylchloroformate
(FMOC). Interestingly, the use of diphenylamine derivatives is in complete
contradiction to their previous statement in 1994[42] where they stated that, ‘DPA
has been regarded as an evidentially irrelevant compound’. The authors were able to
achieve good detection levels (1 pg levels) which is lower than their previous
detection limits of 60pg using DNS-Cl[42]. However, only six out of eleven samples
were shown to contain EC or 2, 4-DNT or a combination thereof. Their method
failed to detect the other two compounds previously mentioned to be more
characteristic than EC and DNT. The authors suggested that while the method may
be sensitive, further analysis of the reduction, hydrolysis, derivatisation and
fluorescent steps could ultimately improve the technique.
The use of Supercritical Fluid Chromatography (SFC) has not been extensive in the
area of organic gunshot residue analysis; however it has been reported that its
Shiona Croft
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application is suitable for thermally labile or non-volatile substances. An advantage
of SFC is that it is compatible with virtually all detectors used in established
chromatographic techniques such as GC and HPLC. In a study by Munder et al,
smokeless powders were analysed using this technique and while they were able to
detect several minor constituents such as ethyl centralite, diphenylamine,
dinitrotoluenes and dibutyl phthalate, they were not able to distinguish between
different brands. The possibility then of classifying smokeless powders by
manufacturer using this technique is low.
An interesting example of characterising black powders is the study by MacCrehan

et al in 2002[43] who looked at associating gun powders and residues by
compositional analysis. They identified the main constituents of the powder to be
nitrocellulose, nitro-glycerine, diphenylamine and ethyl centralite. Characterisation
of the ammunition type was achieved by calculating a propellant to stabiliser ratio
(P/S ratio) developed by Reardon et al which is a simple method to use and interpret.
The study collected 7 brands with only 50 rounds in each. Each of the cartridges
were assigned numbers from 1 – 50 and the, numbers 1, 10, 20, 30, 40, 50 were
assigned codes. The powder was removed from the cartridge and placed in a vial
which could only be traced back to this code. This method then allowed for a random
choice for the order of analysis. Ultrasonic Solvent Extraction/Capillary
Electrophoresis was their method of choice and while it was adequate for detection
of certain compounds, some brands were shown to contain diphenylamine only. This
observation is unusual as powders are comprised of various substances such as
propellants, hardeners, stabilisers and so on and therefore detection of these would be
expected. To fully appreciate the characteristic associations, a more sensitive and
selective analytical procedure should be adopted so that a characteristic profile for
each cartridge could have been developed. Furthermore, as suggested by Smith et
al[44], electrophoresis should only be a complementary tool as results can vary
according to different parameters. The study however shows promise in selectivity
and sensitivity but compared to other analytical techniques, it appears that this
method is somewhat lacking. MacCrehan’s study is an example however, of how
important it is to characterise and discriminate powders from each other. This can
Shiona Croft
13
only be of benefit for investigating authorities who rely on validated databases with
which to compare their unknown samples.
Furthermore, in an important recent study by MacCrehan[45] an attempt was made to

create a smokeless powder reference material for laboratories undertaking explosive
and propellant analysis. The aim was to characterise the organic additives commonly
found in smokeless powders such as nitroglycerin, ethyl centralite, diphenylamine
and the nitration product N-nitrosodiphenylamine. This would be achieved using the
analytical techniques Micellar capillary electrophoresis (CE) and Liquid
Chromatography (LC). Three candidate smokeless powders were studied. Powder 1
was Hi Skor 700X (an NG containing powder stabilized with EC). Powder 2 was
Winchester 231 (an NG powder stabilized with DPA) and handgun reloading
smokeless powders purchased from a local gun shop. Powders 1 and 2 became the
inter laboratory comparisons of smokeless powders analysis and measurement and
interestingly, MacCrehan noted a number of inconsistencies from the 20 participants.
Many laboratories reported surprising results with some identifying EC in powder 2
which was stabilized by DPA. They report that manufacturers often use recycled
surplus of materials and this material may have different compositions than intended.
These trace compounds and inhomogeneity of the propellant lead to uncertainty of
the true make up and chemical composition of the smokeless powder. For this
reason, the commercial powders were deemed unsuitable for reference materials.
However, the use of Powder 3 (the handgun reloading smokeless powder) was
explored and through a series of experiments and involving thermal stability and
homogeneity, it was deemed that Powder 3 was suitable for reference materials with
the use of LC. The testing revealed that storage at room temperature or below was
acceptable and sampling sizes should be 20 mg or greater. These conclusions were
supported by the fact that relative uncertainties for the additives were much smaller
with room temperature stored samples and of sizes 20mg or greater. The study was
able to provide a reference material from Powder 3 with a level of uncertainty <5%.
As this is a relatively new study, further follow up inter laboratory analysis and
testing should be carried out to support the long term use of such reference material.
Shiona Croft
14
Electrophoresis also has been applied to organic gunshot residue analysis [44-47].
Northrop completed a two part study[46,47] which concentrated on 13 compounds
including derivatives of the main organic constituents. This work was an extension of
previous work undertaken in 1992[48] which examined sampling protocol for
Micellar Electrokinetic Capillary Electrophoresis (MECE). Results are shown in
Table 1.2.
Table 1.2: Results from Northrop[46,47]
Compound Detection Levels (pg)
2,4 DNT 1.1

2,6-DNT 1.2
3,4-DNT 1
2,3-DNT 1.3
Diphenylamine 0.9
2-Nitrodiphenylamine 1.9
4-Nitrodiphenylamine 2.1
N-nitroso-diphenylamine 1
Dibutyl Phthalate 2.6
Diethyl Phthalate 2.2
Ethyl centralite 1.8
Methyl centralite 1.1
Nitro-glycerine 3.8
Zeichner et al[25] argued that MECE with diode array UV detector is not sensitive
enough for crime scene comparison however Northrop used this tool to develop a
method for separating organic constituents of gunpowder. Northrop argued that the
phthalate esters commonly seen in OGSR analysis are not unique to gunpowder and
have not been included in his study. While this may be the case, the detection of
phthalate esters is a confirmatory tool in the identification of smokeless powders and
their inclusion is both important and significant to the ammunition makeup. Part two
of the study[46] concentrated more on the direct examination and characterisation of
the main organic compounds of GSR. 16 out of 26 samples taken from the back of
the right hand after firing under controlled conditions, showed no detectable GSR.
The other samples were found to contain mostly nitro-glycerine, diphenylamine, and
N-nitroso diphenylamine. Two samples were shown to contain ethyl centralite and
only one sample was shown to contain all components (nitro-glycerine,
diphenylamine, N-nitroso diphenylamine, 2-nitrodiphenylamine, 4-
nitrodiphenylamine and ethyl centralite). When a 0.22 calibre weapon was used, no
Shiona Croft
15
detectable OGSR was found. It was suggested that re-testing of other 0.22 weapons
would be of use to determine whether the lack of OGSR is due to the size of the
weapon or ammunition, or because of the configuration of the weapon. This
assumption is flawed as no attempt was made to discover if the analytical techniques
and recovery procedures played a significant role here. Furthermore, it was suggested
that it may be possible for OGSR not to be deposited on skin surfaces, or that the
weapon characteristics prevent detectable OGSR from being deposited after each
firing. Further investigations into more reliable techniques could dramatically
improve the research. However, this study has demonstrated its limited use in
forensic casework which relies on validated analytical procedures for reliable
conclusions.
The important paper by Wrobel et al[1] emphasizes the necessity for a method that
combines all information pertaining to the organic make up of smokeless powders.
Their work indicated that 0.22 calibre ammunition is the most commonly
encountered projectile in Australia and it appears that this trend has not altered. The
identification of the ammunition was carried out using both physical and chemical
characteristics, which generally were from an inorganic source. A database was
created that consisted mainly of SEM/EDX spectra, which can be compared directly
from materials gathered from a crime scene. The database was useful in identifying
the cartridges from crime scenes, since physical characteristics were being included
into the database. However, the conclusions were limited due to the project
consisting mainly of inorganic substituents which unfortunately do not vary
substantially between types.
A database consisting of organic substituents could in fact be beneficial to

investigating personnel. By combining the powerful separating and identification
qualities that GC-MS possess, a database of considerable importance could be
created which ultimately should be able to differentiate the type of ammunition by
the type and quantity of organic matter present. It is vital that even though a database
could be implemented, it must be constantly reviewed with the changing times and
possible new ingredients. This idea is supported in the study by Collins et al[49]
where recent research has shown that glass containing particles in gunshot residue
Shiona Croft
16
can be analysed and characterised. Even though their study concentrated on the
inorganic components of GSR, it does raise the important point that new discoveries
are constant and analysts need to be aware of this.
Organic constituents can be more characteristic and by using GC-MS, reproducible

and repeatable results can be obtained. Due to the lack of validated GC-MS
methodology, this work will focus on establishing a tool for the forensic
investigation of gunshot residue. Previous studies have shown that GC will not be the
ideal instrumentation to analyse non-volatile substances. However, this can be
overcome by ignoring the major nitrocellulose matrix and maintaining lower port
temperatures. By doing this, it can determine the presence of the major organic
compounds by a sensitive and selective analytical tool. An instrument such as GC-
MS readily fits this description. It is important to distinguish which compounds are
unique to smokeless powders and by intercalating the literature assessed in this
survey, decisions about these compounds can be made.
As previously mentioned, the 0.22 calibre ammunition is the most commonly

encountered ammunition type recovered at a crime scene. This study will therefore
focus on using this type of ammunition. Furthermore, investigations into proper
solvent choice, developing an extraction technique to remove the nitrocellulose
matrix, will be established. To fully appreciate the possibility of matching or
discriminating propellant to a box or batch of ammunition, it is imperative that the
propellant is examined for homogeneity. Also, as previous papers have indicated,
oxygen plays a significant role in the degradation of diphenylamine, it may therefore
be important to investigate the effects of removing oxygen from the experiments.
The ultimate aim will be to determine whether it is possible to match a propellant
sample back to its batch of manufacture.
Shiona Croft
17
([SHULPHQWDO
0DWHULDOV
The standard compounds DPA (99% purity), EC (98% purity) and DBPH (99%
purity) were obtained from Sigma-Aldrich (USA). HPLC-grade ethyl acetate and
dichloromethane (DCM) were obtained from Selby (Brisbane, Australia). The
propellant samples were obtained from the Ballistics section of the Queensland
Police Service (Brisbane, Australia). The GC vials and 300µL glass inserts were
obtained from Biolab (Brisbane, Australia).
,QVWUXPHQWDWLRQ
The GC-MS consisted of a Hewlett Packard HP6890 Series GC system and 5973
Series Mass Selective Detector (Agilent Technologies) equipped with an auto
sampler and injector. Chromatography was achieved using a DB-1 capillary column
(0.25mm x 30m x 0.25µm) using a pulsed splitless injection technique at one ml/min.
The oven initial temperature was set at 50 degrees for one minute with an
equilibration time of 0.2 minutes. A rate of six degrees per minute was selected to
reach a maximum of 270 degrees. The front inlet had a temperature of 250 degrees
with a pulse pressure of 40 psi. The MSD transfer line heater was set at 280 degrees.
1µL of sample was injected into the GC with a total run time for each sample being
45.7 minutes. EI was used over a mass range of 29-300 amu and an operating voltage
of 70eV. MS Chemstation software (Hewlett Packard) was used for automation and
data analysis. Each sample was analysed under these conditions and was used for the
detection of all compounds except nitro-glycerine. Unless stated otherwise, NIST
library was used for compound identification.
To analyse nitro-glycerine, another pulsed split-less technique was used. The same
operating parameters as previously described were used; however, the initial front
inlet temperature was set at 150 degrees and a sampling volume of 2µL was used. As
Shiona Croft
18
all samples analysed in this study were double based in nature (i.e. it contained both
NG and NC), it was decided that analysis of NG would not be efficient.
6WDQGDUGSUHSDUDWLRQ
To gain an understanding of the instrumental variation, standard solutions for DPA,

EC and DBPH were made. This was done by dissolving in volumetric flasks 5mg in
50 ml ethyl acetate (0.01% w/v) for DPA and 100mg in 100ml ethyl acetate (0.1%
w/v) for EC and DBPH. Three stock solutions containing DPA was made and ten
stock solutions for EC and DBPH were made. An aliquot from each stock solution
was taken and analysed. Due to limited availability of DPA, three stock solutions
could only be made.
(WK\ODFHWDWHDORQHSURFHGXUH
Three random rounds of ammunition were obtained from Winchester 0.22 Expediter
with batch number ADD1BGH2. 50mg of the propellant from each projectile was
accurately weighed and dissolved into three separate volumetric flasks with 5ml of
ethyl acetate in each. An aliquot from each volumetric flask was taken and placed in
a 2ml GC vial labelled sample 1, 2 and 3. Each of the vials was analysed three times
to gain an understanding of the variation caused by this dissolution method.
(WK\ODFHWDWHGLFKORURPHWKDQH
SURFHGXUH
One random projectile was obtained from the same batch of ammunition as
previously stated. 50mg of the propellant was accurately weighed and dissolved into
a 5 ml volumetric flask with 5ml of ethyl acetate. Three separate aliquots of 0.3ml
were taken and placed into three separate GC vials labelled 1, 2 and 3. Each vial was
evaporated to dryness with an inert gas (nitrogen) and then reconstituted in 0.3ml of
dichloromethane. The reconstituted samples were then placed in a new GC vials with
a 300µL glass inserts. Each of the vials were analysed three times to gain an
understanding of the variation caused by the extraction technique.
Shiona Croft
19
&RQVLVWHQF\RISURSHOODQW
FRPSRVLWLRQH[SHULPHQW
Ten random projectiles were obtained from Winchester Superspeed 0.22 with batch
number 2DSM92. 50mg of the propellant was accurately weighed and dissolved into
a volumetric flask with 5ml of ethyl acetate. An aliquot of 0.3ml was taken and
placed into a separate GC vial. The vial was brought to dryness with an inert gas
(nitrogen) and then reconstituted in 0.3ml of dichloromethane. The reconstituted
sample was then placed in a new GC vials with a 300µL glass inserts. Each of the ten
samples were made and analysed one at a time to reduce any effect caused by oxygen
and light on the degradation of the propellant.
([FOXVLRQRIR[\JHQH[SHULPHQW
Five random projectiles were again obtained from the same batch of ammunition as
previously stated. 50mg of the propellant was accurately weighed and dissolved into
a volumetric flask with 5ml of ethyl acetate. Each of the five samples were made and
analysed one at a time. All manipulations were carried out in a nitrogen filled glove
box which had been allowed to flush to remove oxygen for 24 hours. During the
experiment, the N2 flow was maintained at 2ml/min.
7\SHGHWHUPLQDWLRQRI:LQFKHVWHU
DPPXQLWLRQ
Six different types of Winchester brand 0.22 ammunition were selected; (1)
Winchester laser Long Rifle High Performance with batch number 2DRM41, (2)
Winchester Expert with batch number 23DLH02, (3) Winchester winner with batch
number IDKE52, (4) Winchester subsonic long rifle rim fire with batch number
AED1FH31, (5) Winchester super speed long rifle high velocity solid with batch
number 2DSB51 and (6) Winchester super speed long rifle high velocity high
performance with batch number 2DLRL62. From each type of ammunition listed two
projectiles were randomly selected from each and analysed as per conditions
described in the extraction procedure.
Shiona Croft
20
Shiona Croft
21
5HVXOWVDQG'LVFXVVLRQ
0DVVVSHFWUDRIXQILUHGSURSHOODQW
FRPSRQHQWV
In order to monitor any changes between unfired propellant particles, it is vital to
initially determine the constituent compounds. This was done with GC-MS, which
allowed for the peak identification through comparison with standards and mass
spectral library matching.
The selected target compounds are listed in table 3.1, with their major ions. These
compounds were diphenylamine (DPA), N,N-Diethylcarbanilide (Ethyl centralite,
EC) and dibutyl phthalate (DBPH). Due to the fact some components are rare, and/or
are explosive in nature with associated health and safety issues, nitro-glycerine and
nitrated derivatives of DPA could not be obtained commercially. As a consequence,
analysis was concentrated on DPA, EC and DBPH.
Table 3.1: Selected target compounds (from NIST library)

Major ion data for standard compounds
Compound Major ions (m/z)
DPA 169,77
EC 120,148
DBPH 149
3.1.1 Diphenylamine (C12H11N)
Diphenylamine (which is used as a stabilizer in propellant) is classed as a secondary

aromatic amine which is a group of basic organic compounds derived from the
ammonia (NH3) group by replacing two hydrogen atoms by alkyl, aryl groups or
Shiona Croft
22
organic radicals. Amines, like ammonia, are weak bases because the unshared
electron pair of the nitrogen atom can form a coordinate bond with a proton. Amides
can be produced by reacting amines with acids anhydrides or esters. Furthermore,
amines react with acids to give salts or reaction with halogenated alkanes can occur
to form longer chains.
Many amines are not only bases but also nucleophiles that form a variety of
substituted compounds. Due to their basic chemical functionality, they are important
intermediates for chemical syntheses with substitution occurring at the nitrogen
atom.
Aromatic amines also exist, such as phenylamine and benzylamine, which dissociate
in water (some very weakly). Aromatic amines are much weaker bases than
aliphatics. The term benzyl describes the radical, ion or functional group C6H5CH2-,
derived by the methyl group of toluene losing one hydrogen atom. Phenyl on the
other hand is the term for the monovalent radical C6H5-, derived by the removal of a
hydrogen atom from a benzene ring. One of the most important aromatic amines is
aniline, a primary aromatic amine replaced by one hydrogen atom of a benzene
molecule with an amino group.
Diphenylamine or N-phenyl aniline is a highly reactive secondary aromatic amine

which undergoes electrophilic aromatic substitution (for example in the presence of
nitrogen oxides) which is heavily activated by the amino function (which is an
otho/para director) and the electron rich benzene ring.
The mass spectrum for commercially available diphenylamine is shown in figure 3.1.
Shiona Croft
23
Figure 3.1 Mass spectrum of diphenylamine
The mass spectrum of DPA is identifiable by the characteristic m/z 169 ion which is
the molecular weight of DPA. The next major ion is m/z 77 which relates to the
aromatic residue found in DPA (C6H5 = m/z 77).
Figure 3.2 Chemical structure of diphenylamine and m/z = 77 fragment ion (C6H5)
3.1.2 Ethyl centralite (C17H20N2O)
Ethyl centralite or its synonyms N,N-Diethylcarbanilide and N,N-diphenyl urea is a

white to grey crystalline powder which is commonly used as a burning modifier and
stabilizer in propellant manufacture. It serves a similar purpose in ammunition to
diphenylamine however its molecular weight is substantially larger than that of
diphenylamine. The chemical structure of ethyl centralite is presented in figure 3.3.
Shiona Croft
24
Figure 3.3: Ethyl Centralite
Figure 3.4: Mass spectrum of ethyl centralite
The mass spectrum (figure 3.4) of ethyl centralite shows a characteristic ion at m/z
268 which corresponds to the molecular ion. Again, m/z 77 ion is observed which is
indicative of the phenyl ring. The m/z ions of 148 and 120 indicate a cleaved bond
between carbon and nitrogen to form radical ions. This is illustrated in figures 3.5
and 3.6.
N C N
C2H5 C2H5
Figure 3.5: Fragmentation ions of ethyl centralite
Shiona Croft
25
O
N C N
C2 H5 C2H5
A B
Figure 3.6: Fragment A = m/z 120 and Fragment B = m/z 148
3.1.3 Dibutyl phthalate (C16H22O4)
Dibutyl phthalate is a compound within a group called phthalate esters. Phthalate

esters exhibit similar chemical properties to each other with a general structure of the
group shown in figure 3.7.
2
& 5
2
2
& 5C
2
Figure 3.7: General structure of phthalate esters where R, R’ = CnH2n+1; n=4-15[50]
Phthalate esters are a group of plasticizers which are made by the reaction of alcohol
with phthalic anhydride which results in a stable compound. Its use in propellant is
primarily to convert NC from its natural fibrous state into a gel (treated with solvent
first which is later evaporated). Furthermore it provides flexibility to the powder
grains.
Phthalate esters not only exhibit similar chemical properties, the mass spectra for this
group of compounds is remarkably similar, with the indicative ion m/z 149
displayed. Diagnostic ions are shown in figure 3.8 which show the chemical
fragmentation of butyl phthalate esters.
Shiona Croft
26
O O O
OH
C C C OR C OH
OH O C4H9
C C C OR‘ C OC4H9
O O O O
m/z = 149 m/z = 205 m/z = 222 (where R and R‘ = butyl) m/z = 223
Figure 3.8: Characteristic fragmentation ions of butyl phthalate esters [51]
As previously stated, the characterization of phthalate esters is usually relied upon

the identification of m/z 149. However, for this reason it is imperative that correct
identification of each phthalate ester occurs. In the instance of dibutyl phthalate, it is
important to consider the higher mass range ions which are usually low in abundance
and readily overlooked. Dibutyl phthalate has two indicative ions in the higher mass
region; being m/z 205 and m/z 223[50]. Figure 3.9 shows the mass spectrum of
dibutyl phthalate and its chemical structure.
Shiona Croft
27
O
Figure 3.9: Mass spectrum and chemical structure of dibutyl phthalate
&RQWUROOHG6WDQGDUGV
To gain a preliminary understanding of instrumental variation with respect to each of
the previous compounds listed, standard stock solutions of each were made and
analysed using methodology described in chapter 2.
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28
3.2.1 Diphenylamine, ethyl centralite
and dibutyl phthalate variation
Table 3.2 DPA, EC and DBPH standard variation
DPA EC DBPH
1 14531326 6890266 16237299
2 15203256 6933313 16767661
3 15408997 6918529 16640942
4 6914442 16798652
5 6993372 16629834
6 7055142 16418809
7 7010126 16677736
8 7042268 16643994
9 7058014 16369011
10 7008347 16577326
Average 15047860 6982382 16576126

% Variation 3% 1% 1%
Each solution was analysed as discussed in chapter 2. The results in table 3.2 show a
satisfactory variation of 1-3% for the components.
Shiona Croft
29
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Current methods involve the dissolution of the propellant into an organic solvent and
analysis by various techniques such as electrophoresis, HPLC or the GC-mass
spectrometer. Acetonitrile and methanol are commonly used as extraction solvents
however the toxic nature of these solvents makes them undesirable to work with. A
small scale investigation into the extraction efficiency of different solvents was
performed and ethyl acetate has been chosen for this experiment because it is has
similar solvent properties to other commonly used chemicals but with less toxicity.
From the standards preparation, optimal weights of the propellant were determined.
This was carried out by using a single point calibration and ensuring that the signals
obtained for each of the analytes DPA, EC and DBPH in the standard preparation
were not overloaded during the GC-MS analysis. From this it was determined that
50mg of propellant to 5ml of ethyl acetate would be adequate in achieving this. Since
the GC-MS methodology had been previously established by the Queensland Police
Service, chapter two explains the instrument parameters used. However, from the
standard preparations it was shown that good peak separation and shape was
occurring (see appendix).
To determine the variation caused by using ethyl acetate extraction, three random
projectiles were opened and the propellant extracted. The propellant was dissolved
using methods already discussed and triplicate samples were analysed.
Unfortunately, samples cannot be analysed simultaneously. The second sample

cannot be injected until the chromatography of the first sample is complete and the
injection of the third sample is delayed even longer. Hence there is an unavoidable
time delay between the analysis of each sample. Any changes which occur during
this time delay could clearly influence the outcome of the analysis.
From the results shown below in table 3.3, a significant variation in DPA response
can be seen. There are many possible reasons for this variation. For example, the
variation could be due to the variation in propellant composition, decomposition or
Shiona Croft
30
reactions occurring in solution. The later is a likely cause as the literature contains
several reports on the nitrated derivatives of gun shot residue. This will be discussed
later.
Table 3.3 Variation in peak area of DPA between three random propellant samples and
variation observed between the three samples
Sample one 1048904
Sample one 979882 Average 950110
Sample one 821543 % Variation 12%
Standard deviation 125511
Sample two 950589 Average 858474
Sample two 824614 Average 832339 % Variation 15%
Sample two 721814 % Variation 14%
Sample three 919557 Average 792973

Sample three 794653 % Variation 16%
Sample three 664709
Diphenylamine degradation
1200000
1100000
Sample 1
1000000
Sample 1
Sample 2
Peak Area
Sample 3
900000
Sample 2 Sample 1
800000 Sample 3
Sample 2
700000
Sample 3
600000
0 50 100 150 200 250 300 350 400
Time (mins)
Figure 3.10: Diphenylamine degradation over time
It can be seen from figure 3.10 that the amount of diphenylamine detected drops
significantly over the 360 minute analysis time. When each individual sample is
observed more closely, the true effect of degradation can be more easily seen. This is
illustrated in figures 3.11 - 3.13.
Shiona Croft
31
The variation levels of over 16% are evident in the figures, indicating a great
degradation of diphenylamine over the course of analysis. Variation due to
instrumentation has been established at approximately 6%, which is a lot less then
the actual variation observed in this study. Another 10% variation therefore has been
likely observed in the propellant sample.
Sample 1: Diphenylamine degradation
1200000
1100000
Sample 1
1000000
Sample 1
Peak Area
900000
Sample 1
800000
700000
600000
0 50 100 150 200 250 300
Time (mins)
Figure 3.11: Sample 1 - diphenylamine degradation
Shiona Croft
32
1100000
1050000
1000000
950000 Sample 2
Peak Area
900000
850000
Sample 2
800000
750000
Sample 2
700000
650000
0 50 100 150 200 250 300 350
Time (mins)
1050000
950000
Sample 3
850000
Sample 3
Peak Area
750000
Sample 3
650000
550000
450000
0 50 100 150 200 250 300 350 400
Time (mins)
Shiona Croft
33
It has been extensively reported in the literature that decomposition of diphenylamine
occurs in nitrocellulose based propellants. Nitrocellulose and nitro-glycerine (both
commonly found in 0.22 calibre double based smokeless powders) break down to
form nitrogen oxides which are highly reactive. If these decomposition products are
not removed from the propellant, they serve as a catalyst for further reaction and the
shelf life of propellant samples can be shortened. Furthermore, self-ignition of the
propellants is possible, thus making this situation highly dangerous.
The downward trend of the amount of diphenylamine detected could therefore be

attributed to the creation of nitrated diphenylamine decomposition products.
2-nitro-DPA
30000
28000
Sample 1, 270
26000
24000 Sample 2, 315

Sample 1, 135
22000
Sample 3, 360
Sample 2, 180
20000
Sample 1, 0 Sample 3, 225
18000 Sample 2, 45
Peak area
16000 Sample 3, 90
14000
12000
10000
8000
6000
4000
2000
0
0 50 100 150 200 250 300 350 400
Time (mins)
Figure 3.14: 2-nitro-diphenylamine amounts detected (three random samples) – Extrapolated to

time zero to give appreciation of initial amounts of 2-nitro-DPA in each sample
This is confirmed in figure 3.14 which demonstrates the presence of 2-nitro-

diphenylamine in the propellant samples. Each of the three samples show an increase
in the amount of nitrated derivative detected over time. As the samples remain in
solution on the auto sampler for extended periods of time, reactions occur resulting
in the increased concentration of this nitrated derivative. The results shown in figure
3.14 complement the results shown in figure 3.10; since as the amount of
diphenylamine decreases the concentration of nitrated diphenylamine derivative
Shiona Croft
34
increases. Interestingly, since the rate of increase appears to be linear, extrapolation
to time zero provides an estimate of 2-nitro-DPA present initially in each cartridge.
The results are consistent with the initial DPA concentrations. Sample one (with the
largest initial DPA response) also gave the largest 2-nitro-DPA response. This is also
observed with samples two and three.
Furthermore, it is interesting to observe that the three random samples taken for this
experiment, yield different amounts of not only diphenylamine but also its nitrated
derivative. The rise in the mono-nitrated derivative can be explained by the fact that
by 360 minutes, DPA has had the longest time to react with any breakdown products
of nitrocellulose. However, it should be pointed out that a variation in levels of
diphenylamine could be attributed to differing amounts of diphenylamine in each
individual projectile. This proposal will be explored further later.
For Sample one DPA concentration fell by 28% in 270 minutes while 2-nitro-DPA
increased by 26% during the same time. The equivalent numbers for sample 2 were
32% and 22% and for sample three, 38% and 25%.
The production of nitrated derivates can be rationalized as follows: the breakdown of

nitrocellulose yields NO2 radicals[10,11,13-17,30,32]. In the presence of
diphenylamine, N-nitroso-diphenylamine (N-NO-DPA), a highly reactive weak
stabilizer nitrosamine, is produced. Moriarty et al [16] investigated the role of N-
nitroso-diphenylamine as a stabilizer in cellulose matrices. In the presence of NO2,
N-nitroso-DPA can react to give 2-nitro-DPA and 4-nitro-DPA + NO (nitric oxide).
In the presence of oxygen, nitric oxide will be converted into nitrogen dioxide again,
and hence the cycle will continue until complete nitration occurs to give 4,4-diNO2-
DPA, 2,2-diNO2-DPA, 2,4-diNO2DPA or other derivatives. The mechanisms for
these reactions can be seen below in figure 3.15.
Shiona Croft
35
Figure 3.15: Mechanisms of N-Nitroso-DPA in the presence of NO2 and O2 [16]
It is important to note however that the degradation mechanisms of nitrocellulose are

still not definitely known, nor exactly how the nitration of the diphenylamine occurs.
The above mechanism is one proposed reaction sequence to explain the
phenomenon.
Although, Lussier et al[14] studied chemical reactions of diphenylamine with

nitrogen dioxide and report that diphenylamine does react with NO2 radicals to give
N-nitroso-DPA. Interestingly, as more NO2 was added to diphenylamine, a
distinctive trend was observed. This is illustrated in figure 3.16.
Shiona Croft
36
Figure 3.16: Lussier and Gagnon [14]: Concentration of DPA and its derivatives as a function of
added nitrogen dioxide
As the concentration of NO2 increases, the level of DPA decreases, probably caused
by nitration. This is supported by the fact that the amount of N-nitroso-DPA
increases at the same time. Interestingly, the amount of N-nitroso-DPA falls further
as the other nitrated derivatives begin to increase. It could be proposed that N-
nitroso-DPA is responsible for the further nitration of diphenylamine or its mono-
nitrated derivatives to give fully nitrated derivates (2 or 4-NO2-N-NO-DPA).
While these theories have been put forward, the loss of diphenylamine could simply
be the result of nitrocellulose matrix and diphenylamine interacting to form a
compound not amendable to extraction techniques.
The reasons for the loss of diphenylamine and consequent detection of mono-nitrated
derivates are therefore supported by the literature. However, as the experiments were
carried out in an oxygen rich environment, oxygen may function as a catalyst for the
reactions.
Shiona Croft
37
While the heavily saturated nitrated derivatives such as 2 and 4-NO2-N-NO-DPA
were not observed, this could be due to thermal decomposition in the GC inlet or to
insufficient time in the methodology for further reactions to occur.
To support the theory that oxygen, storage and light play a role in the decomposition
of the propellant, an opened cartridge case was placed in a screw capped vial and left
for two weeks in low light and adequate oxygen before analysis. In order to minimize
variation, the same box of ammunition previously studied was used. The results can
be seen in figure 3.17.
Effect of storage on Diphenylamine amounts detected
1000000
Sample 2
Sample 1
900000
800000
700000
Sample 1
600000
Peak Area
Sample 2
500000
400000
300000
200000
100000
0
Stored Fresh
Average response (triplicate)
Figure 3.17: Effect of storage on diphenylamine concentration (sample one and two)
Shiona Croft
38
Sample 1: The effect of storage on Diphenylamine
1200000
Fresh
1000000
Fresh
Fresh
800000
Stored
Peak Area
Stored
600000
Stored
400000
200000
0
0 20 40 60 80 100 120 140 160 180 200
Time (minutes)
Figure 3.18: Sample 1 - Effect of storage on diphenylamine (triplicate)
Figure 3.17 shows the effect of leaving the propellant in an oxygen rich environment.
Over the course of two weeks, the amount of diphenylamine in the samples has
decreased quite significantly. Again, the downward trend for the fresh and stored
samples could now be attributed to the compounds being in solution and reactions
occurring via mechanisms previously discussed. Figure 3.18 allows a closer
examination of sample one. An average decrease of 21% is observed which supports
previous observations which indicated that leaving diphenylamine in solution over a
period of time is not recommended.
Observation of the levels of nitrated derivates further explains these reactions.
Shiona Croft
39
Sample 1: The effect of storage on 2-nitro-diphenylamine amounts detected
30000
270 min
25000
135 min
0 min
20000
Peak Area
15000
10000
5000
0
0 135 270
fresh 20078 23528 27276
stored 11111 18336 20276
Time (minutes)
Figure 3.19: Sample 1 - The effect of storage on 2- nitro-diphenylamine (analysed three times)
Figure 3.19, shows a significant increase of nitrated derivates with time. Figure 3.19
shows a triplicate analysis of sample one and the trends previously observed are
evident here also. Bergens et al[10,11] proposed that after day 20 of propellant
storage, mono nitrated derivatives are at their maximum which coincides with DPA
being at its lowest. This could explain why the amounts of 2-nitro-DPA in stored
samples are relatively high. An increase of 45% was observed over the period of
analysis (180 minutes). This indicates that the stored samples are significantly more
reactive than the freshly analysed samples. The freshly prepared samples showed an
increase of 26% over the period of analysis (180 minutes). Whilst it is clear that the
stored samples actually yielded lower detectable concentrations of nitrated DPA
derivatives, this could be due to the fact that the diphenylamine concentrations
decreased in the samples exposed to oxygen for extended periods of time. Or
possibly, it could be due to further reactions to give di-NO2 species. To fully
understand the mechanisms that differ between the fresh and opened samples, a more
comprehensive study would need to be done.
Shiona Croft
40
In order to establish the effect of leaving propellant in solution the same samples that
were stored in low light were left in solution for one week. Figure 3.20 illustrates the
effect this had on diphenylamine concentration.
The effect of leaving propellant in solution for one week on diphenylamine
30000
Sample 2
25000
Sample 2
20000
Sample 1
Peak Area
15000
Sample 1
10000
5000
0
Stored Solution
Sample (analysis average)
Figure 3.20: Sample one and two analysed each three times (average): comparison between
stored samples and samples left in solution for one week.
It is evident that leaving propellant in solution affects the concentration of

diphenylamine, and again reinforces the consequences of leaving the samples in
solution for long periods of time.
For sample one DPA concentration fell by 28% in 270 minutes. For sample two in
the same time, DPA fell by 15%.
The variation in concentrations of DPA between sample one and two is further
suggests that individual rounds of ammunition may contain differing concentrations
of the main constituents. This will be investigated further later. However, from the
results above, it is clear that leaving propellant samples in solution for extended
periods of time has detrimental effects on the quantifiable amounts of
diphenylamine. As the scope of the project was to ‘match’ batches of ammunition,
Shiona Croft
41
the fact that diphenylamine is reactive and unstable may suggest that this is not
possible.
A solution to the phenomenon would be to extract the propellant at the time of the
analysis (see later).
Furthermore, the concentration of the mono nitrated derivate (figure 3.21) also
suffers a 20% reduction in levels.
The effect of leaving propellant in solution over one week on 2-nitro DPA
30000
Sample 2
25000
Sample 2
20000
Sample 1
Peak Area
15000
Sample 1
10000
5000
0
Stored Solution
Sample (analysis average)
Figure 3.21: The effect of leaving propellant in solution over one week (2-nitro-DPA average –
each sample analysed three times)
For sample one 2-nitro-DPA concentration fell by 27% and sample two fell by 13%
in the same time.
It has been demonstrated that the use of ethyl acetate as a solvent is adequate to
dissolve the propellant, however, leaving propellant in solution in the auto sampler
and the removing of the propellant from its cartridge case all contribute to a
significant variation in amounts of diphenylamine and its mono nitrated derivatives.
The degree of variation observed compromises the aim of matching a cartridge case
Shiona Croft
42
found at a scene to a box of ammunition. It appears that once the propellant is
exposed to oxygen or placed in solution, reactions degrade the propellant and make it
more difficult to quantify the amount of compounds present. Especially when left it
solution, the reaction with free nitrogen oxides present from the breakdown of
nitrocellulose, make the task of discriminating or matching propellant samples
almost impossible. To alleviate this situation, it is proposed that an extraction
technique to remove the nitrocellulose matrix from the sample be developed. This
would eliminate the source of the free nitrogen oxides.
Shiona Croft
43
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FRPSRQHQWRISURSHOODQWXVLQJ
HWK\ODFHWDWHDQGGLFKORURPHWKDQH
Optimizing the extraction procedure that will help minimize the effect of free
nitrogen dioxides in solution is of importance to the study of unfired propellant.
Otherwise the variations in the levels of DPA have been shown to be unacceptable.
The extraction technique used by Mathis et al[36] used methylene chloride as the
propellant solvent. A known mass of propellant was dissolved in methylene chloride
and an aliquot taken. This aliquot was dried with nitrogen gas and the samples
reconstituted in methanol. It was claimed that by doing this, nitro-glycerine and
nitrocellulose would remain insoluble and be removed as a source for further
nitration of diphenylamine.
Whilst the study made no attempt to establish whether discriminating or matching

propellants from the same case could be achieved, the benefits of removing the
nitrocellulose matrix are clear.
Based on this observation, samples were dissolved in ethyl acetate (EtAc) as before.
However, an aliquot was transferred to a vial and evaporated to dryness with an inert
gas (nitrogen). A globular mixture was left behind which was not analysed. The
sample was then reconstituted in dichloromethane (CH2Cl2) and left to stand for a
period of time to ensure that the globular nitrocellulose was properly removed. The
reconstituted sample was then analysed using parameters previously discussed.
Triplicates of three random samples were analysed. Results are shown in figure 3.22.
Shiona Croft
44
Ethyl acetate/dichloromethane procedure (DPA detected)
1400000
1300000
sample 1 sample 2
1200000
sample 1
sample 2
1100000 sample 3
sample 1
Peak Area
sample 3 sample 2 sample 1

1000000 sample 2
sample 3
sample 3
900000
800000
700000
600000
0 50 100 150 200 250 300 350 400
Time (minutes)
Figure 3.22: Diphenylamine response (EtAc/Ch2Cl2 procedure)
It can be seen that a downward trend is still observed. This could be an indication
that not all of nitrocellulose could be completely removed when reconstituted in
dichloromethane. As a consequence, free nitrogen oxides could still be present in
solution, albeit at a lower concentration than previously. To establish the effect of the
EtAc/CH2Cl2 procedure, it must be compared to the previous dissolution method of
using only ethyl acetate.
Shiona Croft
45
Comparison between ethy acetate alone and ethyl acetate/dichloromethane procedures (DPA)
1400000
EtAc/CH2Cl2, sample 1
1200000 EtAc/CH2Cl2, sample 2
EtAc, sample 1
1000000
EtAc, sample 2
800000 EtAc, sample 3

Peak Area
600000
400000
200000
0
EtAc/CH2Cl2 1162287 1130223 1022974
EtAc 973017 866383 736022
Sample average: each analysed three times
Figure 3.23: Comparison between EtAc alone and EtAc/CH2Cl2 on DPA (average)
When the EtAc/CH2Cl2 procedure is compared to using ethyl acetate alone, a clear
difference is observed.
For sample one DPA concentration fell by 16% between the combined EtAC/CH2Cl2
procedure and using EtAc alone. For sample two and three, a decrease of 23% and
28% respectively was observed.
The variation between samples is further evidence that the samples should not be left
in solution for extended periods of time. Sample three had the greatest variation of
diphenylamine concentration since the time prior to analysis was longer.
Interestingly, the differences in DPA yield between the two procedures revealed that
the EtAc/CH2Cl2 procedure had an overall variation of 12% whereas the ethyl acetate
alone method revealed an overall difference of 24%. This is a significant difference
between the two methods; and it indicates that the EtAc/CH2Cl2 procedure is
preferred.
Shiona Croft
46
As previously established, it is the breakdown of nitrocellulose that gives the free
nitrogen oxides responsible for the nitration of diphenylamine, thus reducing the
possibility of matching or discriminating propellant based on the diphenylamine
levels. As shown in figure 3.23, while it is evident that diphenylamine is reacting
with nitrogen oxides and thus, yielding the downward trend of diphenylamine
amounts, the amount of diphenylamine degradation appears to have reduced. To
confirm this, the efficiency of this extraction technique was investigated by
examining the amount of mono-nitrated derivatives that were produced.
Comparison between ethyl acetate alone and ethyl acetate/dichlormethane procedures

(2-nitro DPA)
25000
EtAc, sample 1
EtAc, sample 2
EtAc/CH2Cl2, sample 1 EtAc, sample 3

20000
15000
Peak area
10000
5000
0
EtAc/CH2Cl2 19800 17718 15641
EtAc 23627 21702 19862
Sample (average)
Figure 3.24: Comparison of EtAc alone and EtAc/CH2Cl2 procedures - 2-nitro-dpa (average:
each sample analysed three times)
Figure 3.24, shows the ethyl acetate alone procedure produces significantly more
nitrated derivatives of DPA, than the EtAc/CH2Cl2 procedure. The amount of nitrated
derivatives formed in sample 1, was reduced by 19% when using the EtAc/CH2Cl2
procedure; sample 2 by 22% and sample 3 by 27%. This suggest that the
EtAc/CH2Cl2 procedure is desirable when analysing propellant samples as it has
assisted in slowing or diminishing the amount of nitrated derivatives formed over
long periods of time.
Shiona Croft
47
To gain a better illustration exactly what is happening, a more thorough analysis of
sample one is shown below.
Sample 1: Comparison between EtAc alone and EtAc/CH2Cl2 procedures (2-nitro DPA)
30000
EtAc, 270
25000 EtAc, 135
EtAc/CH2Cl2, 0 EtAc/CH2Cl2, 135

EtAc, 0
20000 EtAc/CH2Cl2, 270

Peak Area
15000
10000
5000
0
0 135 270
EtAc/CH2Cl2 20084 21319 17998
EtAc 20078 23528 27276
Time (minutes)
Figure 3.25: 2-nitro-dpa levels - sample 1: comparison between EtAc alone and EtAc/CH2Cl2
procedures
From figure 3.25, the differences in levels of 2-nitro-DPA are clear. The
EtAc/CH2Cl2 technique has slowed the production of 2-nitro-DPA. Compared with
the EtAc alone procedure which appears to produce higher amounts of 2-nitro-dpa as
the analysis progresses (EtAc alone procedure resulted in an increase in production
of 2-nitro-DPA of 27% compared to the EtAc/CH2Cl2 procedure which saw a
decrease in 2-nitro-DPA production of 12%). It is suggested that a reason for this
phenomenon is that when the propellant is in solution with ethyl acetate, the
concentration of free nitrogen oxides is much higher than when extracted using
dichloromethane. The higher concentration of free nitrogen oxides present in solution
could be responsible for the greater amount of nitration that is evident as the analysis
progresses. Conversely, when the propellant is in solution with dichloromethane, the
Shiona Croft
48
concentration of nitrogen oxides is much lower as it was proposed that the
EtAC/CH2Cl2 extraction technique should remove the source of these oxides. This
would indicate that 2-nitro-DPA is less likely to be produced.
It has been shown that the combined EtAc/CH2Cl2 technique has provided an
environment less susceptible to nitrocellulose breakdown, thus reducing the amount
of mono-nitrated derivatives being formed in solution. This is of importance as the
degree of nitration can interfere with observed diphenylamine and consequently, the
levels.
While attention has been concentrated on diphenylamine, it is important to establish

whether the EtAc/CH2Cl2 technique was suitable for the other components of unfired
propellant; ethyl centralite and dibutyl phthalate. Firstly, a comparative diagram is
shown in figure 3.26 which indicates that while similar amounts of ethyl centralite
were detected, a higher level of ethyl centralite was observed using the EtAc/CH2Cl2
technique. This provides further evidence to support the proposal that the
EtAc/CH2Cl2 technique will be a better method for unfired propellant analysis.
Shiona Croft
49
Comparison between EtAc alone and EtAc/CH2Cl2 procedures (Ethyl Centralite)
6000000 EtAc/CH2Cl2
EtAc/CH2Cl2 EtAc/CH2Cl2
EtAc EtAc
EtAc
5000000
4000000
Peak Area
3000000
2000000
1000000
0
EtAc/CH2Cl2 5511039 5511129 5488933
EtAc 5173739 5056856 4972894
Sample (average)
Figure 3.26: Comparison between EtAc alone and EtAc/CH2Cl2 procedures (ethyl centralite
average)
The degree of variation of EC between the two methodologies is not as great as for
DPA. For sample one, the use of the extraction procedure increased the yield of EC
by 6%. For sample two, an increase of 8% and for sample 3 an increase of 9%. This
is an overall average of 8% increase. The degree of variation in the concentrations of
EC between samples could be attributed to varying amounts of EC within the
propellant.
Furthermore, as shown in figure 3.27 the effect of reconstituting dibutyl phthalate in

dichloromethane as opposed to ethyl acetate, seems to have no significant bearing on
the amount detected. This compound did however show a decrease in level for the
three samples when using the extraction procedure (sample 1: -6%, sample 2: -2%
and sample 3: -1%). Whilst the decrease cannot be fully explained, it is likely that
solubility is the major cause for this situation.
Shiona Croft
50
Comparison between Ethyl acetate alone and ethyl acetate/dichlormethane procedures
(dibutyl phthalate)
1400000
EtAc
EtAc/CH2Cl2 EtAc
EtAc/CH2Cl2
EtAc/CH2Cl2 EtAc
1200000
1000000
800000
Peak Area
600000
400000
200000
0
EtAc/CH2Cl2 1238280 1230035 1189287
EtAc 1315107 1255621 1204949
Sample (average)
Figure 3.27: Dibutyl phthalate – comparison between EtAc alone and EtAc/CH2Cl2 procedures
In contrast to the results reported previously, Bergens et al[10,11] used

dichloromethane to extract the analytes and they compared this new solvent to
acetonitrile. No significant differences in the level of diphenylamine were detected
between the two solvents. They were unable to explain the losses of diphenylamine
over time, and suggested that the losses of diphenylamine using acetonitrile were due
to poor extraction techniques. It is more likely however, that while the extraction
technique has removed most of the nitrocellulose and nitro-glycerine matrix, some of
it may have been left behind, leaving a possible source of free nitrogen oxides once
more.
In this project, a higher level of diphenylamine was detected. The discrepancy

between this result and that of Bergens et al[10,11] could be explained by the
following reasons; (1) the propellant in this study was fresher or closer to the time of
manufacture and had less time to decompose inside the cartridge case. (2) Their
extraction technique did not involve evaporation and so the solution was more
susceptible to possible nitration. (3) Perhaps the interaction between diphenylamine
Shiona Croft
51
and nitrocellulose produces a product that may be susceptible to extraction
depending on the amount of nitrocellulose or diphenylamine concentrations in the
propellant.
The act of reconstituting the mixture in dichloromethane appears to have a positive

effect not only on the level of the main constituents of unfired propellant, but it also
slows down the effect of nitration by removing most of the nitrocellulose matrix. As
a consequence, it is desirable to use this method for the analysis of unfired propellant
and to determine whether matching or discriminating propellant is possible.
Before exploring this it is necessary to establish whether the propellant within a

single batch is consistent.
Shiona Croft
52
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ER[EDWFKRIDPPXQLWLRQ
Establishing the consistency of propellant composition from a single batch of

ammunition is of great importance to the success of the project. This clearly
influences the possibility for matching or discriminating propellant.
Statistics is needed to establish a population size for sampling. A population analysis

by definition will include samples from a global population; however, in the case of
ammunition studies it would be impossible to sample every 0.22 ammunition type
available. For this reason, a sampling size of ten bullets was deemed to be suitable as
it is shown statistically to represent 0.989 of the population.
Table 3.4: Relationship between sample size and population size
Relationship between sample size and population size

sample size n population size N sampling fraction ¥{N-n)/N}
10 50 0.9990
10 500 0.9899
10 5000 0.8944
Using the EtAc/CH2Cl2 technique previously developed, investigation of the

chemical constituents from ten (10) random propellant samples was carried out.
Each propellant sample was weighed to establish the variation in the amount used in
a particular brand of ammunition. Interestingly, from the ten random samples
analysed, a variation in mass was observed. The masses of the ten samples can be
viewed in table 3.5.
Table 3.5: Masses from ten random samples from one box of ammunition
Masses from ten random samples from one box of ammunition (mg)
Sample Sample Sample Sample Sample Sample Sample Sample Sample Sample
A B C D E F G H I J
94.9 100.2 96.5 96.2 96.3 95.9 96.8 99.9 96.7 96.1
Shiona Croft
53
The average across the ten samples is 96.9mg with a standard deviation of 1.7 and a
percentage variation of 1.7%, which is not significantly high.
Ammunition relies on a particular barrel pressure of the cartridge to reduce any

possibility of back-fire or loss of velocity of the ammunition once it has left the
barrel of the weapon. In order to maintain quality control of the ammunition, it is the
barrel pressure of the ammunition that is tested, not the exact weight of the
propellant. Therefore, this could include changing the weight of the propellant
slightly in order to maintain the ammunition performance. Barrel pressure should lie
within certain predetermined specifications within any given batch. It is unclear from
the manufactures information whether the same material is used for a single batch.
However, this work showed a variation in the amount of propellant within one batch.
Management of Winchester, Geelong stated that a batch of ammunition referred to
all boxes made on the same day by the same machine. It is also interesting to note
that the propellant (while traceable) was left to stand in the open air for hours even
days at a time. This would undoubtedly have an effect on the degradation of the main
constituents, particularly diphenylamine. Furthermore, Winchester do not
manufacture their own propellant, rather it is outsourced to other companies from
overseas. All these issues indicate the possibility of the propellant being inconsistent
in both amount and composition.
Shiona Croft
54
DPA: Amounts detected from ten (10) random propellant samples
250000
200000
150000
Peak area
100000
50000
0
A B C D E F G H I J
DPA 200936 155303 109123 105767 83675 68655 84550 51156 52088 41490
Sample No.
Figure 3.28: Levels of diphenylamine of ten (10) random samples of propellant from the one box
of ammunition
DBPH: Amounts detected from ten (10) random propellant samples
250000
200000
150000
Peak area
100000
50000
0
A B C D E F G H I J
DBPH 205462 143263 148343 128776 126006 111910 111315 121002 90854 97238
Sample No.
Figure 3.29: Levels of dibutyl phthalate detected of ten (10) random samples of propellant from
the one box of ammunition
Shiona Croft
55
It can be seen from figures 3.28 and 3.29 that a large variation is observed in the
concentration of each constituent (variation equated to 53% for DPA). It should be
noted that all analyses were performed under the same conditions as previously
discussed, and to help eliminate the effect of propellant remaining in solution and
exposed to oxygen, all samples were made freshly one at a time and analysed
immediately. The instrument was tuned at the start of the experiment and found to
be working satisfactorily. It can therefore be assumed that the instrument was
correctly functioning at the time of each sample analysis.
MacChrehan et al[52,53] established a propellant (p) to stabilizer (s) ratio as a

parameter to explain any variation. Ammunition relies on nitro-cellulose as its
explosive source. While a method was established to detect and quantify nitro-
glycerine in this project, nitro-glycerine was often not analysed as it was assumed
that all ammunition was double based. This means testing for nitro-glycerine was not
carried out in all experiments. However, other ratios could be used to explain
variations that may be evident. By comparing ethyl centralite, diphenylamine and
dibutyl phthalate, a different perspective can be obtained for the differences between
the samples. The results are shown in table 3.6.
Table 3.6: Ratios (peak area) of main constituents from one box of ammunition
Ratio A B C D E F G H I J
DPA/EC 27.6 46.2 32.6 32.6 27.6 30.7 33.4 22.0 36.7 24.8
EC/DBPH 0.035 0.023 0.022 0.025 0.024 0.020 0.022 0.019 0.016 0.017
DPA/DBPH 0.97 1.08 0.74 0.82 0.66 0.61 0.76 0.42 0.57 0.43
Standard %
Average Deviation Variation
DPA/EC 31.5 6.79 21.5

EC/DBPH 0.023 0.0055 24.3
DPA/DBPH 0.71 0.22 30.5
It can be seen from table 3.6 that the variation between the ten random samples is
significant and indicates that the propellant is not consistent in composition. It would
Shiona Croft
56
be expected that the variation in the ratios containing diphenylamine would be high
for reasons previously discussed, however, when ethyl centralite and dibutyl
phthalate were compared, the variation is still around 25%.
In a situation where only three major components (DPA, EC and DBPH) are found in
the propellant it is questionable whether the use of ratios will successfully
discriminate between propellant samples. Considering that diphenylamine is reactive
it is appropriate to question whether this component should in fact be used in a ratio
to explain variation. This only leaves two components (EC and DBPH) left for
comparison and determining that any two samples are from the same source or are in
fact different may be difficult.
It should be noted however that only one brand of ammunition has been tested and to
establish whether this is true for all ammunition types, a more comprehensive study
would need to be carried out. Not only are there different calibres of ammunition, but
different brands, types and batches. Furthermore, any discrepancies discovered could
be a result of the storage of the propellant before being placed into the cartridge case.
As the manufacturers of the propellant exercise proprietary over their details of the
propellant it is difficult to establish the exact nature and ingredients of the propellant
before Winchester use this to engineer their products.
The variation is over 30% (ratio) and 50% (peak area) which is well beyond
instrumental variation of 1-3% or the EtAc/CH2Cl2 procedure variation of 9%. This
indicates that the source of the variation is the propellant itself, not the conditions
under which it was analysed.
To further establish whether the propellant composition variation is coming from the
propellant itself or from other sources (e.g. oxygen), an experiment was designed in
which the propellant was manipulated in an inert atmosphere.
Shiona Croft
57
7KHHIIHFWVRIH[FOXGLQJR[\JHQ
The effect of oxygen on the degradation of diphenylamine has been widely accepted
[10-12,14,16,22,30,33,35]. It has been proposed that oxygen provides a catalytic
effect, resulting in the nitrated derivative by-products. Therefore, it could help to
perform all manipulations under an inert atmosphere.
Five (5) random samples were chosen from the same batch of ammunition and
prepared as previously. However, all manipulations were done in a nitrogen filled
glove box. The glove box was allowed to flush for 24 hours before use to eliminate
all traces of oxygen. Samples were again dissolved one at a time and analysed
immediately. The results are tabulated in figure 3.30.
Inert gas procedure: Main constituents
1400000
DBPH
1200000 DBPH
DBPH
DBPH DBPH
1000000
800000
Peak Area
600000
400000
200000 DPA DPA DPA

DPA EC DPA
EC EC EC EC
0
A B C D E
DPA 107617 155900 173591 156886 125608
EC 86859 80196 90023 90767 87273
DBPH 1156875 1062508 1079445 1181054 1126170
Sample No.
Figure 3.30 Inert gas procedure consequences on the main constituents of unfired propellant
particles
It is evident from figure 3.30 that variation still exists between the five random
samples. DPA shows a percentage variation of 19%. EC displays a percentage
variation of 5% and DBPH a percentage variation of 4%. This not only indicates that
performing the analysis under an inert atmosphere dramatically affects the degree of
Shiona Croft
58
variation between samples, but it reinforces the impact that storage has on the
ammunition itself. However, the results could also indicate the actual degree of
variation between propellant samples within a box of ammunition. Whilst the
variation for EC and DBPH is respectable at less than 5%, the degree of variation for
DPA at 18% is too high for batch comparison to be accurately performed.
The variation between samples in an oxygenated environment was as high as 25-30%

for DPA. The EtAc/CH2Cl2 extraction technique showed a variation of
approximately 12% for DPA and the inert gas procedure showed a variation of
approximately 18%. This indicates a real variation in DPA levels which is
independent to methodology.
To further explore the variation of the propellant make-up, it may be beneficial to

examine the degree of variation for dibutyl phthalate, a plasticizer and therefore a
more stable compound. Figure 3.30, shows the variation of propellant composition.
Whilst it was previously suggested that storage of the propellant plays a significant
role in accelerated decomposition of the nitrocellulose, the levels of dibutyl phthalate
should not be affected by storage and so any variation suggests an inconsistency in
propellant composition.
Shiona Croft
59
Inert gas procedure: DBPH (5 random propellant samples)
1200000
1000000
800000
Peak Area
600000
400000
200000
0
A B C D E
DBPH 1156875 1062508 1079445 1181054 1126170
Sample No.
Figure 3.31: Inert gas procedure (dibutyl phthalate)
The variation of DBPH in an oxygenated environment was 4%. The variation of

DBPH observed here is difficult to explain.
It is shown in figures 3.30 and 3.31 that no downward trend has occurred using the
inert gas procedure. The downward trend was attributed to the length of time each
sample waited to be analysed and this direct correlation with diphenylamine in
solution. However it may be possible to leave samples in the auto-sampler for long
periods of time under a nitrogen atmosphere provided the seal has not been
perforated. This possibility was explored further.
Another five (5) random samples were dissolved and manipulated in the inert
atmosphere. When the samples were left in the auto sampler, the nitrogen filled GC
vial has prevented any further reaction that would have occurred if oxygen was
present.
Shiona Croft
60
The effects of leaving propellant in solution on five (5) random samples
350000
dbph
300000 dbph
dbph
dbph
250000
dbph
200000
Peak Area
150000
dpa dpa dpa

100000 dpa
dpa
50000
ec ec ec ec
ec
0
sample f sample g sample h sample i sample j
dpa 72050 87269 101338 97371 94718
ec 17943 23275 22465 25304 27766
dbph 213869 269585 263629 289639 314656
Sample No.
Figure 3.32: The effects of leaving propellant in solution under an inert atmosphere
In this series of experiments the levels of concentration variation of each component

were in the vicinity of 13% (DPA 13%, EC 15% and DBPH 14%). The results
further support the idea that the concentration of each constituent is different within a
batch of ammunition. In the presence of oxygen, the variation observed was DPA
18%, EC 5% and DBPH 4%. However, the main point is that the concentration of the
constituents is scattered and not in a downward trend shown when dissolution in
ethyl acetate alone was used. It appears that with the lack of oxygen, no catalytic
effect is present and a true representation of the constituent concentrations is
observed.
While this may be the case, the importance of leaving samples in the auto sampler is
evident. In a busy laboratory, time is important and bulk sample preparation is more
efficient. While the use of inert gas glove boxes is appropriate in studying the origin
of variation, it could also be incorporated into regular forensic testing.
The effect of leaving the sample in solution is further explored by re-analysis of

previous samples A-D 24 hours later. A new screw capped vial lid with septa was the
Shiona Croft
61
only change that occurred to these samples and the results are shown as below in
figure 3.33.
Re-analysis 24 hours later - the effect of time on Diphenylamine
200000
180000
160000
140000
120000
Peak Area
DPA
100000
DPA (+24 Hours)
80000
60000
40000
20000
0
A B C D
Sample No.
Re-analysis 24 hours later - the effect of time on Ethyl Centralite
95000
90000
85000
Peak Area
EC
EC (+24 Hours)
80000
75000
70000
A B C D
Sample No.
Shiona Croft
62
Re-analysis 24 hours later - the effect of time on Dibutyl phthalate
1250000
1200000
1150000
Peak Area
DBPH
1100000
DBPH (+24 Hours)
1050000
1000000
950000
A B C D
Sample No.
Figures 3.33: Re-analysis of samples A-D 24 hours later (individually separated for visual
clarity)
As shown in figures 3.33 the changes are significantly different from leaving the
solution in an oxygen fuelled environment. DPA concentration has changed by 15%
over 24 hours, EC by 1% and DBPH by 1%. Interestingly, in the case of EC and
DBPH, an increase in the amount detected of these additives has been observed. This
differs from the oxygen rich environment where a 30% variation for DPA was
observed over 360 minutes. It is clear that the effect of manipulating samples in an
inert atmosphere has slowed down the catalysis by oxygen, and thus the amount of
the constituents has not altered greatly. In a real life situation, the sample at a crime
scene would have been exposed to oxygen until police or crime scene examiners can
collect the evidence. Since oxygen plays a significant and detrimental effect on
quantifying diphenylamine, the possibility of matching any crime scene evidence to a
box or batch of ammunition would be almost impossible. To overcome this it may be
possible to develop inert atmosphere sampling bags to minimise the effects that
oxygen has on the propellant. It has so far been shown that the propellant is
susceptible to chemical reactions both in solution and on storage. Furthermore, the
total mass of the charge within individual cartridges also varies. This suggests that
Shiona Croft
63
the possibility of matching a sample to its original box is unlikely. Nevertheless it
may be possible to match ammunition to a particular brand since different
manufacturers may have their own unique propellant composition.
Shiona Croft
64
7\SHGHWHUPLQDWLRQRI:LQFKHVWHU
$PPXQLWLRQ
Matching a projectile to a batch of ammunition is not possible however, it may be

possible to determine the type or brand of ammunition. To explore this suggestion, a
small study was carried out using six different types of ammunition selected from the
Winchester brand with two projectiles from each type analysed. Ammunition types
included Long rifle (LR), Hollow Point (HP) and High velocity (HV) varieties.
3.7.1 Winchester Laser LR HP 2DRM41
This type of ammunition was found to contain the following constituents; Diethyl
phthalate (DEPH), DPA, EC, DBPH and 2-nitro-DPA. The concentration of DEPH
was found to vary by 77% between the two samples from this batch. This is a
significant variation. DPA was found to have a variation of 2%, EC of 13%, DBPH
of 4% and 2-nitro-DPA of 12%. This is shown in figure 3.34.
Winchester Laser Long Rifle Hollow Point D2RM41
14000000
12367704
12090531
12000000
10000000
8000000
Peak Area
Laser 1
6050093 Laser 2
5839487
6000000
4000000
2000000
399766 452139
0 0 113537 25910 69363 77941
0
2,4 DNT DEPH DPA EC DBPH 2-Nitro DPA
Component
Figure 3.34: Winchester Laser LR HP 2DRM41
Shiona Croft
65
3.7.2 Winchester Expert 23DLH02
Interestingly, this Winchester ammunition type was found to contain an extra

constituent; 2, 4-dinitrotoluene (DNT). It was also found to contain DEPH, DPA,
EC, DBPH and 2-nitro-DPA, similar to Winchester Laser as shown before. The
variation in DNT concentration between the two samples was found to be 53%.
DEPH was found to have 75% variation, DPA showed 13.9% variation, EC showed
19% variation, DBPH showed 15% variation and 2-nitro-DPA showed 40%
variation. This is shown in figure 3.35.
Winchester Expert 23DLH02
14000000
13018543
12000000
11199852
10000000
7817919
8000000
Peak Area
Expert 1
6645549
Expert 2
6000000
4000000
2000000
472540 381547
62202 29428 14066 24596 109952 66117
0
Component
Figure 3.35: Winchester Expert 23DLH02
3.7.3 Winchester Winner IDKE52
The level of variation between the two samples is significant for this type of
ammunition. Whilst in one propellant sample, DNT was detected in the other it was
not. The same observation applies to DEPH and 2-nitro-DPA. The level of variation
Shiona Croft
66
for all constituent concentrations was over 90%. This could indicate propellant make
up differences, human or random error. This is shown in figure 3.36.
Winchester Winner IDKE52
14000000
12412663
12000000
10000000
8228937
8000000
Peak Area
Winner 1
Winner 2
6000000
4000000
2000000
750668 654262
411209
67272 0 34122 0 34599 72620 0
0
Component
Figure 3.36: Winchester Winner IDKE52
3.7.4 Winchester Subsonic LR Rim fire

AED1FH31
The number of constituents detected for this type of ammunition was significantly
lower than previous ammunition types. DPA, EC and DBPH were the only
constituents detected. The level of variation for DPA had dropped significantly to
0.6%. EC and DBPH showed a variation of 18% and 11% respectively. No DNT,
DEPH or 2-nitro-DPA were detected indicating that this type of ammunition is
chemically different to other types of Winchester ammunition. This is shown in
figure 3.37.
Shiona Croft
67
Winchester Subsonic Long Rifle Rimfire AED1FH31
600000
526481 523411
500000
400000
Peak Area
Subsonic 1
300000
277880 Subsonic 2
246360
200000
100000
34122 38872 31802
0 0 0 0 0
0
Component
Figure 3.37: Winchester Subsonic LR Rim fire AED1FH31
3.7.5 Winchester Superspeed LR HV

solid SDSB51
Again, this ammunition type was found to contain only three main constituents;
DPA, EC and DBPH. The level of variation between each of the constituents was
found to be: DPA (11%), EC (20%) and DBPH (11%). Again, no DNT, DEPH or 2-
nitro-DPA was detected in either Superspeed sample. It is interesting to note the
larger response for DBPH as opposed to that of DPA in this ammunition type,
compared to the subsonic samples previously. Figure 3.38 shows the results.
Shiona Croft
68
Winchester Superspeed Long Rifle High Velocity solid 2DSB51
1000000
894639
900000
808693
800000
722919
700000
641360
600000
Peak Area
Solid 1
500000
Solid 2
400000
300000
200000
100000
35690 42846
0 0 0 0 0 0
0
Component
Figure 3.38: Winchester Superspeed LR HV solid 2DSB51
3.7.6 Winchester Superspeed LR HV

hollow point 2DRL62
The chemical make up of this type of ammunition is very similar to the solid
propellant type described previously. Three main constituents were again detected;
DPA, EC and DBPH. However, in this instance the Superspeed hollow point
propellant showed greater amounts detected of DPA as opposed to the Superspeed
solid propellant. The level of variation between the two samples of Superspeed
hollow point propellant samples was found to be 15% (DPA), 20% (EC) and 30%
(DBPH). Figure 3.39 shows these results.
Shiona Croft
69
Winchester Superspeed Long Rifle High Velocity Hollow Point 2DRL62
1200000
1044449
1000000
906741
800000
Peak Area
Super 1
600000
520898 Super 2
401057
400000
200000
46743 55838
0 0 0 0 0 0
0
Component
Figure 3.39: Winchester Superspeed LR HV hollow point 2DRL62
Table 3.7 shows the peak areas for the six different Winchester types. Significant
variation for each type was observed between the two propellant samples. This
complements the earlier results suggesting that batch determination is not possible
due to the constituent concentration variation within each batch of ammunition and
sample degradation by oxygen and auto-catalytic reactions. However, while it is the
case that batch determination is not possible, from table 3.7 it is clear that significant
difference exists between different types of ammunition. One of the types contained
five constituents (Laser type), two types contained six constituents (Expert and
Winner types) whilst the other types studied contained three constituents (Subsonic,
Superspeed solid and Superspeed Hollow point).
Shiona Croft
70
Table 3.7: Type determination of Winchester ammunition
TYPE DETERMINATION OF WINCHESTER AMMUNITION

2,4
DNT DEPH DPA EC DBPH 2-nitro-DPA
LASER 1 0 113537 12090531 399766 5839487 69363
LASER 2 0 25910 12367704 452139 6050093 77941
EXPERT 1 62202 14066 13018543 472540 7817919 109952
EXPERT 2 29428 24596 11199852 381547 6645549 66117
WINNER 1 67272 34122 12412663 411209 8228937 72620
WINNER 2 0 0 750668 34599 654262 0
SUBSONIC
1 0 0 526481 38872 277880 0
SUBSONIC
2 0 0 523411 31802 246360 0
SOLID 1 0 0 722919 35690 808693 0
SOLID 2 0 0 641360 42846 894639 0
SUPER 1 0 0 906741 46743 401057 0
SUPER 2 0 0 1044449 55838 520898 0
It is not recommended to discriminate these types of ammunitions based on the

quantity of each constituent as it varies between rounds of ammunition.
Discrimination could be performed on the basis of constituents in each type of
ammunition. For example, Expert type ammunition could be discriminated from
Laser type ammunitions based on the presence of DNT. It may be possible to
distinguish between ammunition based on the concentrations of DPA, EC and
DBPH. In a crime scene scenario, it would be recommended to analyse more than
two controls to gain a better measure of the variation found within that box of
ammunition. In that way, an average or range of DPA, EC and DBPH concentrations
could be obtained for that particular box of ammunition and the recovered propellant
sample could then be compared to the average or range.
Shiona Croft
71
&RQFOXVLRQVDQG)XWXUH:RUN
&RQFOXVLRQV
The possibility of discriminating batches of ammunition based on their organic
composition has been deemed to be difficult. The chemical nature of some of the
compounds present in the propellant means that they are reactive compounds.
Therefore, to match propellant samples back to a known source is impossible. For
example, it has been mentioned that diphenylamine is a propellant stabilizer and is
present to react with free nitrogen oxides to prevent auto ignition of the propellant.
As a consequence, diphenylamine is a reactive compound and is not a suitable
analyte to use for batch discrimination. The compound ethyl centralite is quite
similar in chemical function and therefore is also reactive and unstable. The only
stable organic compounds present in propellant are the phthalates or plasticizers. It
could be argued that ammunition from different sources could be differentiated based
on the concentration of the phthalates present, even on the different types of
phthalates present. However, the variations within the same batch of ammunition
would need to be further explored. Conversely, it may be argued that due to the
abundance of phthalates in our everyday lives, discriminating ammunition using this
common compound may not be valid. Furthermore, the exact chemical make up of
propellant and smokeless powders remains unclear [45]. My own observations of the
manufacturing process support this claim.
Throughout the project, the effects of oxygen are apparent. Removing oxygen from
the samples did play a significant role in preserving the representative chemical
make up of the propellant. Furthermore, extracting the nitrocellulose component
from the propellant extract did benefit the project in that it removed the source of
further nitration and reactions. However, it was shown that the homogeneity of the
propellant could not be established as varying concentrations of propellant are placed
Shiona Croft
72
randomly in each cartridge case. Manufacturing companies are interested in barrel
pressure of the ammunition, not the mass of the charge.
Even though the possibility of batch determination could not be carried out, new
extraction techniques and improved methodologies have been established that could
benefit the study of unfired propellants and organic gun shot residue. Furthermore it
is suggested that brand determination of the ammunition may be a possibility.
)XWXUH:RUN
Future studies should be carried out, however, the focus of these studies should be on
brand and types of ammunitions as opposed to batches. It was shown that different
types of ammunition have different chemical compositions and therefore could be
discriminated based on this characteristic. A more comprehensive study of different
Winchester ammunition types could reveal chemical differences and therefore could
be useful to law enforcing agencies. Furthermore, studies of different brands of
ammunition could also reveal diverse chemical compositions. A database could be
created to indicate whether a propellant sample recovered from a crime scene, could
be similar in chemical composition to different brands of ammunition found in
Australia and overseas. Another study which could explore the possibility of
handling the propellant under nitrogen includes opening a cartridge case under
nitrogen and collecting the propellant sample. Half of the sample could be stored
under nitrogen for a set period of time whilst the other is subjected to open air for the
same period of time. The subsequent extraction and analysis of the two separated
propellant samples could provide a direct comparison between the storage and
manipulation methods.
Whilst batch matching may not be a possibility, unfired propellant analysis may be
able to give the police useful information into the likely sources of the recovered
propellant sample. Therefore this type of analysis could play an integral role in the
field of forensic science.
Shiona Croft
73
$33(1',;
Ethyl Centralite standard
Shiona Croft
74
Dibutyl phthalate standard
Shiona Croft
75
Diphenylamine standard

Shiona Croft
76

Winchester Laser Long Rifle Hollow point 2DRM41
(A – Diethylphthalate; B – Diphenylamine; C –N, N diphenylformamide; D – Ethyl

Centralite; E – Dibutyl phthalate; F: 2-nitro-diphenylamine)
Shiona Croft
77
Winchester Expert 23DLH02
(A – 2,4 Dinitrotoluene; B – Diethylphthalate; C – Diphenylamine; D – N,N-

diphenylformamide; E – Ethyl centralite; F – Dibutyl phthalate; G – 2-nitro
diphenylamine)
Shiona Croft
78

Winchester Winner IDKE52
(A – 2,4 Dinitrotoluene; B – Diethylphthalate; C – Diphenylamine; D – N,N

Diphenylformamide; E – Ethyl Centralite; F – Dibutyl phthalate; G – 2-nitro
diphenylamine)
Shiona Croft
79

Winchester Subsonic Long rifle Rim fire AED1FH31
(A – Diphenylamine; B – Ethyl centralite; C – Dibutyl phthalate)
Winchester Superspeed Long Rifle High velocity solid 2DSB51
(A –Diphenylamine; B – Ethyl Centralite; C – Dibutyl phthalate)
Shiona Croft
80
Winchester Superspeed long rifle high velocity hollow point
2DRL62
(A – Diphenylamine; B – Ethyl centralite; C – Dibutyl phthalate)
Shiona Croft
81
5()(5(1&(6
1 Wrobel, H., Kijek, M, Millar, J (1998) Identification of Ammunition from
gunshot residues and other cartridge related materials - A preliminary model
using 0.22 caliber rimfire ammunition. Journal of Forensic Sciences 43 (2),
324-328
2 D’Uffizi, M., Falso, G, Ingo, G, Padeletti, G. (2002) Microchemical and
micromorphological features of gunshot residue observed by combined use of
AFM, SA-XPS and SEM + EDS. Surface and interface analysis 34, 52-506
3 Garofano, L., Capra, M, Ferrari, F, Bizzaro, G, Di Tullio, D, Dell’Olio, M,
Ghitti, A. (1999) Gunshot residue further studies on particles of
environmental and occupational origin. Forensic Science International 103,
1-21
4 Romolo, F., Margot, P. (2001) Identification of gunshot residue: a critical
review. Forensic Science International 119, 195-211
5 Singer, R., Davis, D, Houck, M. (1996) A survey of gunshot residue analysis
methods. Journal of Forensic Sciences 41 (2), 195-198
6 Bull, S., Roux, C, Dawson, M, Lennard, C. (2001) Organic propellant and
explosives analysis by LC/MS/MS. 13th Interpol Forensic Science
Symposium, Lyon, France
7 Krcma, V. (1996) Fluted and annular grooved barrel chambers in firearms.
Journal of Forensic Sciences 41 (3), 407-417
8 Corporation, M. (2001) How stuff is Made: The modern bullet cartridge (Vol.
2008), Windows Live
9 Meng, H., Caddy, B. (1997) Gunshot residue analysis - A review. Journal of
Forensic Sciences 42 (4), 553-570
10 Bergens, A., Danielsson, R (1995) Decomposition of diphenylamine in
nitrocellulose based propellants - II. Application of a numerical model to
concentration-time data determined by liquid chromatography and dual-
wavelength detection. Talanta 42 (2), 185-196
11 Bergens, A., Danielsson, R. (1995) Decomposition of diphenylamine in
nitrocellulose based propellants - I. Optimization of a numerical model to
concentration-time data for diphenylamine and its primary degradation
products determined by liquid chromatography with dual-amperometric
detection. Talanta 42 (2), 171-183
12 Bohn, M., Vok,F. (1992) Aging behaviour of propellants investigated by heat
generation, stabilizer consumption and molar mass degradation. Propellants,
Explosives, Pyrotechnics 17, 171-178
13 Elliot, M., Smith, F. (2000) Synthetic procedures yielding targeted nitro and
nitroso derivatives of the propellant stabilizer diphenylamine, N-Methyl-4-
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THE ANALYSIS

A thesis presented to the

in fulfilment of the requirements for the degree of

Under the Supervision of:

School of Physical and Chemical Sciences

Shiona Croft Date

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1.1 BACKGROUND .......................................................................................... 1

2.1 MATERIALS ............................................................................................ 18

3.1 MASS SPECTRA OF UNFIRED PROPELLANT COMPONENTS ....................... 22

3.5 CONSISTENCY OF PROPELLANT COMPOSITION FROM A SINGLE

3.6 THE EFFECTS OF EXCLUDING OXYGEN ................................................... 58

4.1 CONCLUSIONS ........................................................................................ 72

Ethyl Centralite standard ............................................................................... 74

This figure is not available online.

Figure 1.1: Dissected view of the case [8]

1.2.2 The Projectile

1.2.4 The Primer

Mach undertook two studies in 1977[26] and 1978[27] of 33 different kinds of

Table 1.1: Elution order for constituents using HPLC-MS[29]

This table is not available online.

While Wu et al [29] concentrated on MC as the most characteristic compound for the

Concentration anomalies of DPA were observed in another study[14] which

Mathis et al [36] further highlighted the importance of developing an analytical tool

Despite the contradiction, Mathis et al were able to quantify several organic

An interesting example of characterising black powders is the study by MacCrehan

Furthermore, in an important recent study by MacCrehan[45] an attempt was made to

Table 1.2: Results from Northrop[46,47]

Compound Detection Levels (pg)

2,4 DNT 1.1

A database consisting of organic substituents could in fact be beneficial to

Organic constituents can be more characteristic and by using GC-MS, reproducible

As previously mentioned, the 0.22 calibre ammunition is the most commonly

To gain an understanding of the instrumental variation, standard solutions for DPA,

Table 3.1: Selected target compounds (from NIST library)

3.1.1 Diphenylamine (C12H11N)

Diphenylamine (which is used as a stabilizer in propellant) is classed as a secondary

Diphenylamine or N-phenyl aniline is a highly reactive secondary aromatic amine

3.1.2 Ethyl centralite (C17H20N2O)

Ethyl centralite or its synonyms N,N-Diethylcarbanilide and N,N-diphenyl urea is a

Figure 3.4: Mass spectrum of ethyl centralite

Figure 3.5: Fragmentation ions of ethyl centralite

3.1.3 Dibutyl phthalate (C16H22O4)

Dibutyl phthalate is a compound within a group called phthalate esters. Phthalate

Figure 3.8: Characteristic fragmentation ions of butyl phthalate esters [51]

As previously stated, the characterization of phthalate esters is usually relied upon

Figure 3.9: Mass spectrum and chemical structure of dibutyl phthalate

Table 3.2 DPA, EC and DBPH standard variation

Average 15047860 6982382 16576126

Unfortunately, samples cannot be analysed simultaneously. The second sample

Sample three 919557 Average 792973

Figure 3.10: Diphenylamine degradation over time

Sample 1: Diphenylamine degradation

Figure 3.11: Sample 1 - diphenylamine degradation

Figure 3.12: Sample 2 - diphenylamine degradation

Sample 3: Diphenylamine degradation

Figure 3.13: Sample 3 - diphenylamine degradation

The downward trend of the amount of diphenylamine detected could therefore be

24000 Sample 2, 315

Figure 3.14: 2-nitro-diphenylamine amounts detected (three random samples) – Extrapolated to

This is confirmed in figure 3.14 which demonstrates the presence of 2-nitro-

The production of nitrated derivates can be rationalized as follows: the breakdown of

Figure 3.15: Mechanisms of N-Nitroso-DPA in the presence of NO2 and O2 [16]

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