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....... LTéRARY
Michigan State
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This is to certify that the
thesis entitled

THE ANALYSIS OF EXTRACTABLE VOLATILES
IN CHARCOAL FROM BLACK POWDER

presented by

Melinda Kay Ferguson

has been accepted towards fulfillment
of the requirements for

M.S. degree inQLiminalJustice

 

 

 

I Maj¢ pro§sor /

I /
Date b/L/ 0‘

0-7639 MS U is an Affirmative Action/Equal Opportunity Institution

 

 

 

 

 

PLACE IN RETURN BOX to remove this checkout from your record.
To AVOID FINES return on or before date due.
MAY BE RECALLED with earlier due date if requested.

 

DATE DUE DATE DUE DATE DUE

 

 

 

 

 

 

 

 

 

 

 

 

 

 

6/01 cJClFlC/DateDuepss-pJ 5

 

THE ANALYSIS OF EXTRACT ABLE VOLATILES
IN CHARCOAL FROM BLACK POWDER

By

Melinda Kay Ferguson

A THESIS
Submitted to
Michigan State University
in partial fulfillment of the requirements
for the degree of
MASTER OF SCIENCE

School of Criminal Justice

200 1

ABSTRACT

THE ANALYSIS OF EXTRACTABLE VOLATILES
IN CHARCOAL FROM BLACK POWDER

By

Melinda Kay Ferguson

Forensic scientists have a vested interested in the analysis and identification of
black powder to ensure that criminals are brought to trial and that justice is served.
Powder comparisons and characterizations could have probative value in a court of law.
However, little research has been done to this end.

Of the three components of black powder, potassium nitrate and sulfur are
reproducible ingredients and provide little potential for the discrimination of black
powder samples. The type of charcoal used, however, varies by each manufacturer.
Thus, the chemical components of charcoal were further examined by this study to
determine their propensity to distinguish samples of black powder.

The volatile examination study looks at eight brands of black powder and within
each brand, between one and eleven lots were analyzed via gas chromatography/mass
spectrometry (GC/MS), both qualitatively and quantitatively. Black powder samples
weighing six grams each were ground and subsequent addition of ethyl acetate extracted
the targeted volatiles from the sample. Results indicate that domestic and foreign made

black powders can be distinguished based upon the type of charcoal that is incorporated

into the three component mixture.

ACKNOWLEDGEMENTS

For the opportunity to observe, assist and perform research at the National
Laboratory Center in Rockville, Maryland, I would like to acknowledge the Bureau of
Alcohol, Tobacco and Firearms (ATF). Furthermore, I would like to acknowledge the
scientists of ATF for their patience, support and guidance. Throughout this study,
scientist Edward Bender was willing to share his vast knowledge and his insight proved
most helpful; for that I am grateful. I would also like to recognize the camaraderie of
scientists Douglas Klapec and Gregory Czarnopys for making my time at ATF most
enjoyable.

In addition, I would like to recognize the guidance given me, while at Michigan
State University, by the director of the forensic science program, Dr. Jay Siege]. With his
guidance and wisdom, many new doors have been opened. I am forever indebted.

Most importantly, I would like to recognize the continued encouragement of
family and friends. I would like to thank my parents, Jack and Kathy, my sister, Sarah,

my dear Joshua and my cherished friends for their support.

iii

TABLE OF CONTENTS

LIST OF TABLES

LIST OF FIGURES

1. INTRODUCTION

1.1 Black Powder

1.2 The Forensic Value of Black Powder

1.3 Preceding Black Powder and Charcoal Analyses

1.4 The Analysis of Extractable Volatiles in Charcoal from Black Powder

2. METHODS

2.1 Chemicals

2.2 Sampling Procedure of Charcoal

2.3 Sampling Procedure of Black Powder

2.4 Gas Chromatography/Mass Spectrometry of Charcoal Extractions

2.5 Gas Chromatography/Mass Spectrometry of Black Powder Extractions

3. RESULTS AND DISCUSSION

3.1 Charcoal Extractions

3.2 Black Powder Extractions Examined by GC-MSD for Reproducibility Study
3.3 Black Powder Extractions Examined by GC-MSD for Discrimination Study
4. CONCLUSIONS AND FUTURE RESEARCH

APPENDIX A, “Total Ion Chromatograms of Charcoal Samples”

APPENDIX B, “Total Ion Chromatograms of Black Powder Samples

in Reproducibility Study”

APPENDIX C, "Total Ion Chromatograms of Thirty-two Black Powder Samples”

APPENDIX D, “Total Ion Chromatograms of Black Powder Samples

in Sensitivity Study"

vi

\l MWNH

\OOOOOQQ

10
14
22
33

38

45

62

95

APPENDIX E, “Selected Extracted Ion Chromatograms of Black Powder Samples” 100

WORKS CITED

ADDITIONAL WORKS CONSULTED

iv

122

122

LIST OF TABLES

TABLE 1: Standard Deviation and Relative Stande Deviation of
Target Ion Abundance and Ion Abundance Relative to Abudance
of Ion 192

21

LIST OF FIGURES
FIGURE 1: Abundance of Target Ions in Five Charcoal Samples

FIGURE 2: Abundance of Target Ions in Five Charcoal Samples
Relative to Ion 192, Pyrazole

FIGURE 3: Abundance of Target Ions in Five Samples of
GOEX 3Fg 03-05 92JU6B

FIGURE 4: Abundance of Target Ions in Five Samples of
GOEX 4Fg 04-23 850C058

FIGURE 5: Abundance of Target Ions in Five Samples of
Elephant 4F g 52-93 Lot. No. 151

FIGURE 6: Abundance of Target Ions in Five Samples of
GOEX 3F g 03-05 92JU6B Relative to Abundance of Ion 192,

3-(p-chlorophenyl)-5-methyl-pyrazole

FIGURE 7: Abundance of Target Ions in Five Samples of
GOEX 4Fg 04-23 850C058 Relative to Abundance of Ion I92,

3-(p-chlorophenyl)-5-methyl-pyrazole

FIGURE 8: Abundance of Target Ions in Five Samples of
Elephant 4Fg 52-93 Lot. No. 151 Relative to Abundance of Ion 192,

3-(p~chlor0phenyl)-5-methyl-pyrazole

FIGURE 10: Abundance of Target Ions in One Austin Black Powder
Sample Relative to Abundance of Ion 192,
3-(p-chlorophenyl)-5-methyl-pyrazole

FIGURE 11: Abundance of Target Ions in Two DuPont Black Powder
SamplesRelative to Abundance of Ion 192,

3-(p-chlorophenyl)-5-methyl-pyrazole

FIGURE 12: Abundance of Target Ions in Eight Elephant Black Powder
SamplesRelative to Abundance of Ion 192,

3-(p-chlorophenyl)-5-methyl-pyrazole

FIGURE 13: Abundance of Target Ions in Two “Debarked” Elephant Black
Powder Samples Relative to Abundance of Ion 192,

3-(p-chlorophenyl)-5-methyl-pyrazole

vi

12

13

15

16

17

18

19

20

24

25

26

27

FIGURE 14: Abundance of Target Ions in Eight Gearhart-Owen Black
Powder Samples Relative to Abundance of Ion 192,

3-(p-chlorophenyl)-5-methyl-pyrazole

FIGURE 15: Abundance of Target Ions in Two Hodgen Black Powder
Samples Relative to Abundance of Ion 192,
3-(p-chlorophenyl)-5-methyl-pyrazole

FIGURE 16: Abundance of Target Ions in Two Meteor Black Powder
Samples Relative to Abundance of Ion 192,
3-(p-chlorophenyl)-5-methyl-pyrazole

FIGURE 17: Abundance of Target Ions in Four Swiss Black Powder
Samples Relative to Abundance of Ion 192,
3-(p-chlorophenyl)-5-methyl-pyrazole

FIGURE 18: Abundance of Target Ions in Three Wano Black Powder
Samples Relative to Abundance of Ion 192,
3—(p-chlorophenyl)-5-methyl-pyrazole

FIGURE 19: Total Ion Chromatogram of ethyl acetate control (SmL
concentrated), 19 to 25 minutes

FIGURE 20: Total Ion Chromatogram of GOEX charcoal, as used by the
Gearhart-Owen Explosives Company (1 gram/SmL ethyl acetate),

19 to 25 minutes

FIGURE 21: Total Ion Chromatogram of Roseville charcoal, as used by the
Gearhart-Owen Explosives Company (1 gram/SmL ethyl acetate),

18 to 25 minutes

FIGURE 22: Total Ion Chromatogram of “Debarked” Umbauba charcoal,
as used by the Pemambuco Powder Company
(lgram/SmL ethyl acetate), 18 to 25 minutes

FIGURE 23: Total Ion Chromatogram of Pinus charcoal, obtained from the
Pemambuco Powder Company (1 gram/SmL ethyl acetate),
18 to 25 minutes

FIGURE 24: Total Ion Chromatogram of Umbauba charcoal, as used by the

Pemambuco Powder Company in Elephant Black Powder prior
to the year 2000 (lgram/5mL ethyl acetate), 19 to 25 minutes

FIGURE 25: Total Ion Chromatogram of ethyl acetate control (10mL
concentrated), 19 to 25 minutes

vii

28

29

3O

31

32

38

39

40

41

42

43

45

FIGURE 26: Total Ion Chromatogram of GOEX 3Fg 03-05 92.IU6B,
sample 1, (6gram/lOmL ethyl acetate), 19 to 25 minutes

FIGURE 27: Total Ion Chromatogram of GOEX 3Fg 03-05 921U6B,
sample 2, (6gram/10mL ethyl acetate), 19 to 25 minutes

FIGURE 28: Total Ion Chromatogram of GOEX 3F g 03-05 9ZJU6B,
sample 3, (6gram/10mL ethyl acetate), 19 to 25 minutes

FIGURE 29: Total Ion Chromatogram of GOEX 3Fg 03-05 921U6B,
sample 4, (6gram/10mL ethyl acetate), 19 to 25 minutes

FIGURE 30: Total Ion Chromatogram of GOEX 3Fg 03-05 921U6B,
sample 5, (6gram/10mL ethyl acetate), 19 to 25 minutes

FIGURE 31: Total Ion Chromatogram of GOEX 4Fg 04-23 850C058,
sample 1, (6gram/10mL ethyl acetate), 19 to 25 minutes

FIGURE 32: Total Ion Chromatogram of GOEX 4Fg 04-23 850C058,
sample 2, (6gram/10mL ethyl acetate), 19 to 25 minutes

FIGURE 33: Total Ion Chromatogram of GOEX 4Fg 04-23 850C058,
sample 3, (6gram/10mL ethyl acetate), 19 to 25 minutes

FIGURE 34: Total Ion Chromatogram of GOEX 4Fg 04-23 850C058,
sample 4, (6gram/10mL ethyl acetate), 19 to 25 minutes

FIGURE 35: Total Ion Chromatogram of GOEX 4Fg 04-23 850C058,
sample 5, (6gram/10mL ethyl acetate), 19 to 25 minutes

FIGURE 36: Total Ion Chromatogram of Elephant 4Fg 52-93 Lot#151,
sample 1, (6gram/10mL ethyl acetate), 18 to 25 minutes

FIGURE 37: Total Ion Chromatogram of Elephant 4F g 52-93 Lot#151,
sample 2, (6gram/10mL ethyl acetate), 19 to 25 minutes

FIGURE 38: Total Ion Chromatogram of Elephant 4F g 52-93 Lot#151,
sample 3, (6gram/10mL ethyl acetate), 19 to 25 minutes

FIGURE 39: Total Ion Chromatogram of Elephant 4Fg 52-93 Lot#151,
sample 4, (6gram/10mL ethyl acetate), 19 to 25 minutes

FIGURE 40: Total Ion Chromatogram of Elephant 4F g 52—93 Lot#151,
sample 5, (6gram/10mL ethyl acetate), 19 to 25 minutes

viii

46

47

48

49

50

51

52

53

54

55

56

57

58

59

FIGURE 41: Total Ion Chromatogram of Austin Black Powder 09627
(6gram/10mL ethyl acetate), 18 to 25 minutes

FIGURE 42: Total Ion Chromatogram of DuPont Black Powder
2Fg Lot. No. 02-82 (6gram/10mL ethyl acetate), 18 to 25 minutes

FIGURE 43: Total Ion Chromatogram of DuPont Black Powder
2Fg LC (6gram/10mL ethyl acetate), 19 to 25 minutes

FIGURE 44: Total Ion Chromatogram of Elephant Black Powder
4Fg 52-93 Lot#151 (6gram/10mL ethyl acetate), 18 to 25 minutes

FIGURE 45: Total Ion Chromatogram of Elephant Black Powder
2Fg 08/1998 391 (6gram/lOmL ethyl acetate), 19 to 25 minutes

FIGURE 46: Total Ion Chromatogram of Elephant Black Powder
SFg 251/93 Lot. No. 146 (6gram/10mL ethyl acetate),
19 to 25 minutes

FIGURE 47: Total Ion Chromatogram of Elephant Black Powder Cannon
264/93 Lot. No. 117 (6gram/10mL ethyl acetate), 19 to 25 minutes

FIGURE 48: Total Ion Chromatogram of Elephant Black Powder
Fg 258/93 Lot. No. 134 (6gram/10mL ethyl acetate),
19 to 25 minutes

FIGURE 49: Total Ion Chromatogram of Elephant Black Powder
2Fg 10/94 Lot. No. 160 (6gram/10mL ethyl acetate),
19 to 25 minutes

FIGURE 50: Total Ion Chromatogram of Elephant Black Powder
3Fg 6/24/96 PAD/NLC (6gram/10mL ethyl acetate),
19 to 25 minutes

FIGURE 51: Total Ion Chromatogram of Elephant Black Powder
3Fg 6/24/95 PAD/NLC (6gram/10mL ethyl acetate),
19 to 25 minutes

FIGURE 52: Total Ion Chromatogram of Elephant “debarked” Black Powder

3Fg S-10 22/00 (6gram/10mL ethyl acetate), 19 to 25 minutes

FIGURE 53: Total Ion Chromatogram of Elephant “debarked” Black Powder

2Fg S-09 22/00 (6gram/10mL ethyl acetate), 19 to 25 minutes

ix

62

63

64

65

66

67

68

69

70

71

72

73

74

FIGURE 54: Total Ion Chromatogram of GOEX Black Powder
3Fg 03-76 99SE10B (6gram/10mL ethyl acetate), 19 to 25 minutes

FIGURE 55: Total Ion Chromatogram of GOEX Black Powder
4Fg 04-16 39MA04B (6gram/lOmL ethyl acetate), 19 to 25 minutes

FIGURE 56: Total Ion Chromatogram of GOEX Black Powder
3Fg 03-0592JU6B (6grarn/10mL ethyl acetate), 19 to 25 minutes

FIGURE 57: Total Ion Chromatogram of GOEX Black Powder
4Fg 04-23 850C058 (6gram/10mL ethyl acetate), 19 to 25 minutes

FIGURE 58: Total Ion Chromatogram of GOEX Black Powder
2Fg 02-15 94JA31C (6gram/10mL ethyl acetate), 19 to 25 minutes

FIGURE 59: Total Ion Chromatogram of GOEX Black Powder
2Fg 81JU23B 02-91 (6gram/lOmL ethyl acetate), 19 to 25 minutes

FIGURE 60: Total Ion Chromatogram of GOEX Black Powder
4F g 04-75 81MA03B (6gram/10mL ethyl acetate), 19 to 25 minutes

FIGURE 61: Total Ion Chromatogram of GOEX Black Powder
3Fg 81] A12A 03-95 (6gram/10mL ethyl acetate), 19 to 25 minutes

FIGURE 62: Total Ion Chromatogram of Hodgen Black Powder
3Fg (6gram/10mL ethyl acetate), 19 to 25 minutes

FIGURE 63: Total Ion Chromatogram of Hodgen Black Powder
2Fg (6gram/10mL ethyl acetate), 19 to 25 minutes

FIGURE 64: Total Ion Chromatogram of Meteor Black Powder
3Fg 73 AP 1510 S2 (6gram/10mL ethyl acetate), 19 to 25 minutes

FIGURE 65: Total Ion Chromatogram of Meteor Black Powder
3Fg NC (6gram/10mL ethyl acetate), 19 to 25 minutes

FIGURE 66: Total Ion Chromatogram of Swiss Black Powder
1.5Fg Lot. No. 001 #310100 (6gram/10mL ethyl acetate),
19 to 25 minutes

FIGURE 67: Total Ion Chromatogram of Swiss Black Powder
Fg Lot. No. 001 #041.199 (6gram/10mL ethyl acetate),
19 to 25 minutes

FIGURE 68: Total Ion Chromatogram of Swiss Black Powder
3Fg 02-01 00FE15C (6gram/lOmL ethyl acetate), 19 to 25 minutes

75

76

77

78

8O

81

82

83

84

85

86

87

88

89

 

 

FIGURE 69: Total Ion Chromatogram of Swiss Black Powder
4Fg 00FE29B (6gram/10mL ethyl acetate), 19 to 25 minutes

FIGURE 70: Total Ion Chromatogram of Wano Black Powder
3Fg Oct.l 1992 0,2-0,7mm (6gram/10mL ethyl acetate),

18 to 25 minutes

FIGURE 71: Total Ion Chromatogram of Wano Black Powder
PP Oct.1 1992 0,7-0,9mm (6gram/10mL ethyl acetate),

18 to 25 minutes

FIGURE 72: Total Ion Chromatogram of Wano Black Powder
3Fg 0,2-0,7mm (6gram/10mL ethyl acetate), 18 to 25 minutes

FIGURE 73: Total Ion Chromatogram Using the Splitless Mode of
GOEX Black Powder 4Fg 04-23 850C058
(6gram/5mL ethyl acetate), 18 to 25 minutes

FIGURE 74: Total Ion Chromatogram Using the Splitless Mode of
GOEX Black Powder 4Fg 04-23 850C058
(.Sgram/SmL ethyl acetate), 18 to 25 minutes

FIGURE 75: Total Ion Chromatogram Using the Splitless Mode of
GOEX Black Powder 4Fg 04-23 850C058
(.1 gram/SmL ethyl acetate), 18 to 25 minutes

FIGURE 76: Total Ion Chromatogram Using the Splitless Mode of
GOEX Black Powder 4Fg 04-23 850C058
(.05gram/5mL ethyl acetate), 18 to 25 minutes

FIGURE 77: Extracted Ion Chromatogram, Ion 121, of
GOEX Black Powder 3Fg 03-05 92JU6B
(6gram/10mL ethyl acetate), 18 to 25 minutes

FIGURE 78: Extracted Ion Chromatogram, Ions 151 and 152, of
GOEX Black Powder 3Fg 03-05 92JU6B
(6gram/10mL ethyl acetate), 19 to 25 minutes

FIGURE 79: Extracted Ion Chromatogram, Ion 168, of
GOEX Black Powder 3Fg 03-05 921U6B
(6gram/10mL ethyl acetate), 19 to 25 minutes

FIGURE 80: Extracted Ion Chromatogram, Ion 170, of

GOEX Black Powder 3Fg 03-05 92JU6B
(6gram/10mL ethyl acetate), 19 to 25 minutes

xi

90

91

92

93

95

96

97

98

100

101

102

103

FIGURE 81: Extracted Ion Chromatogram, Ions 180 and 181, of
GOEX Black Powder 3Fg 03-05 92JU6B
(6gram/10mL ethyl acetate), 19 to 25 minutes 104

FIGURE 82: Extracted Ion Chromatogram, Ion 192, of
GOEX Black Powder 3Fg 03-05 92.IU6B
(6gram/10mL ethyl acetate), 19 to 25 minutes 105

FIGURE 83: Extracted Ion Chromatogram, Ion 196, of
GOEX Black Powder 3Fg 03-05 921U6B
(6gram/10mL ethyl acetate), 19 to 25 minutes 106

FIGURE 84: Extracted Ion Chromatogram, Ion 121, of
GOEX Black Powder 4Fg 04-23 850C058
(6gram/10mL ethyl acetate), 18 to 25 minutes 107

FIGURE 85: Extracted Ion Chromatogram, Ions 151 and 152, of
GOEX Black Powder 4Fg 04-23 850C058
(6gram/10mL ethyl acetate), 19 to 25 minutes 108

FIGURE 86: Extracted Ion Chromatogram, Ion 168, of
GOEX Black Powder 4Fg 04-23 850C058
(6gram/10mL ethyl acetate), 19 to 25 minutes 109

FIGURE 87: Extracted Ion Chromatogram, Ion 170, of
GOEX Black Powder 4Fg 04-23 850C058
(6gram/10mL ethyl acetate), 19 to 25 minutes 110

FIGURE 88: Extracted Ion Chromatogram, Ions 181 and 182, of
GOEX Black Powder 4F g 04-23 850C058
(6gram/10mL ethyl acetate), 19 to 25 minutes 111

FIGURE 89: Extracted Ion Chromatogram, Ion 192, of
GOEX Black Powder 4Fg 04-23 850C058
(6gram/10mL ethyl acetate), 19 to 25 minutes 112

FIGURE 90: Extracted Ion Chromatogram, Ion 196, of
GOEX Black Powder 4Fg 04-23 850C058
(6gram/10mL ethyl. acetate), 19 to 25 minutes 113

FIGURE 91: Extracted Ion Chromatogram, Ion 121, of

Elephant Black Powder 4Fg 52-93 Lot#151
(6gram/10mL ethyl acetate), 18 to 25 minutes 114

xii

FIGURE 92: Extracted Ion Chromatogram, Ions 151 and 152, of
Elephant Black Powder 4F g 52-93 Lot#151
(6gram/10mL ethyl acetate), 19 to 25 minutes 115

FIGURE 93: Extracted Ion Chromatogram, Ionl68, of
Elephant Black Powder 4Fg 52-93 Lot#151
(6gram/10mL ethyl acetate), 19 to 25 minutes 116

FIGURE 94: Extracted Ion Chromatogram, Ion 170, of
Elephant Black Powder 4F g 52-93 Lot#151
(6gram/10mL ethyl acetate), 19 to 25 minutes 1 17

FIGURE 95: Extracted Ion Chromatogram, Ions 181 and 182, of
Elephant Black Powder 4Fg 52-93 Lot#151
(6gram/10mL ethyl acetate), 19 to 25 minutes 118

FIGURE 96: Extracted Ion Chromatogram, Ion 192, of
Elephant Black Powder 4Fg 52-93 Lot#151
(6gram/10mL ethyl acetate), 19 to 25 minutes 119

FIGURE 97: Extracted Ion Chromatogram, Ion 196, of

Elephant Black Powder 4Fg 52-93 Lot#151
(6gram/10mL ethyl acetate), 19 to 25 minutes 120

xiii

1. INTRODUCTION

1.1 Black Powder

Throughout the ages, numerous cultures have made assertions, claiming to be the
first to discover black powder. Chinese, Hindus, Greeks, Arabs, the English and
Germans all assert that they were the first to combine sulfur, charcoal, and potassium
nitrate into the explosive mixture known as black powder. While the first historically
sound documents detailing experimentation and fabrication of black powder date from
the mid-thirteenth to early fourteenth centuries, the emergence of black powder in
America can be traced to around 1675 and the founding of Milton Mill in Massachusetts.

At its inception, black powder was used primarily for domicile tasks, such as
reloading of ammunition for hunting and blasting for mining and excavation purposes.
As time past and the American Revolution commenced, black powder production
increased, as it was needed for use in battle. Powder-mills became a permanent fixture in
America. Although only one domestic manufacturer of black powder, Gearhart-Owen
Explosives, is currently in existence, its historical presence is still felt. Black powder
continues to be imported into the country from manufacturers in Europe and South
America. Instances of homemade black powder mixtures have also been encountered
and while its use is still somewhat limited in the general public, black powder is still used
by individuals for reloading of ammunition and for use in muzzle-loading weapons. On a
larger scale, the military uses black powder for certain exercises and it is still used on a
limited basis for excavation purposes. Black powder has also been used illegitimately in

the manufacture of improvised explosive devices (IEDs).

1.2 The Forensic Value of Black Powder

According to the Bureau of Alcohol, Tobacco and Firearms (ATF), from 1992-
1996, black powder was the filler material of choice used in roughly thirteen percent of
the bombings reported in the United States. With this statistic in mind, the proper
analysis, identification and possible brand determination of black powder takes on a role
of utmost importance to the forensic science community.

To the trained eye conducting a physical examination, the black, glazed, irregular
shaped grains that constitute black powder are readily identifiable. According to
Bender‘, the stande protocol for the analytical identification of black powders involves
the use of X-ray Powder Diffraction (XRPD), or a combination of Fourier Transform
Infrared Spectroscopy (FT IR) and Scanning Electron Microscopy/Energy Dispersive X-
ray analysis (SEM/EDX). Ion chromatography is also used to identify nitrate and
potassium ions. As standard protocols indicate, once the three elements of black powder,
namely sulfur, charcoal, and potassium nitrate, have been identified, the substance can
then be characterized as black powder.

In the past, these methods and criteria have been sufficient; however,
technological advances and the heightened sophistication of criminals have forced the
forensic science community to evaluate their analytical methods. The characterization of
substances, such as black powder, can be a positive step in the detection of illegal
behavior. With Gearhart-Owen Explosives being the one domestic brand of black
powder currently in production, and with there being only three other major imported
brands of black powder currently in production, Elephant, Swiss and Wano,

characterization will not serve to uniquely identify a sample. Classification of black

 

powder samples based upon the charcoal component will, however, serve to narrow the
scope of possible sources of a given sample. Whether a sample is determined to be a
homemade mixture, Elephant, Gearhart-Owen, or Dupont, a parent company no longer in
business, the probative information provided with respect to this type of evidence will
undoubtedly prove useful in a court of law.

1.3 Preceding Black Powder and Charcoal Analyses

A literature review indicates that only limited research and written work exist
pertaining to this topic. Of the work inquiring into the behavior of volatiles contained in
black powder, little mention is made with regards to type differentiation.

In the attempt to identify characteristics of charcoal which prove to be important
in the manufacture of a high quality black powder, Marsh and Gray2 conducted a series of
analytical tests. Using elemental analysis, differential thermal analysis, scanning electron
microscopy (SEM), porosimetry and rnicrostrength analyses, the researchers compared
charcoals from four different types of woods. Based upon physical structure, elemental
content, surface area, and physical strength of the charcoals examined, a recommendation
was given that alder buckthom or alder woods be used to generate charcoals employed in
the production of black powder.

Similarly, Sasse3 evaluated the use of maple charcoal used in black powder
fabrication. His conclusions were that the characteristics of charcoal vary not only by
type, but intra-variations within charcoal types are also present.

Gray, Marsh, and Mclaren4 also performed a similar study with the aim of
replacing charcoal with a more easily reproduced synthetic material. Three types of

charcoal: Rhamnus frangula (alder buckthom), Alnus gultinosa (common alder), and

 

 

Fagus sylvatica (common beech) were examined and it was determined that of the three,
Rhamnusfrangula (alder buckthom), having the lowest spontaneous ignition temperature
and highest porosity, would be best suited for use in gunpowder.

Roses, under supervision of the Department of the Navy, examined the effects of
properties of charcoal on black powder as well. After an explosion closed the DuPont
owned Belin Powder Works in Moosic, Pennsylvania, Gearhart-Owen took over
ownership of the property and plant. Civilian reports indicated that the quality of the
black powder produced there declined between pre- and post-explosion samples. This
concern prompted the Navy to further explore the effects of charcoal on the ballistic
properties of black powder. Rose determined from closed-bomb analysis and other
laboratory analyses, including chemical analysis, heat of explosion, density and ignition
temperature, that differences noted by civilian consumers could be a result of variation in
charcoal ingredients.

Kirshenbaum6 further addressed the issue of carbon usage as it pertains to ignition
temperature and activation energy of black powder. Differential thermal analysis and
therrnogravimetric analysis yielded data demonstrating that the varying carbon types can
alter the decomposition and reaction characteristics of black powder. It was also shown
that while sulfur does not affect the ignition temperature, it does affect the pre-ignition
reaction.

Hussain andRees7 utilized FT emission spectroscopy to examine the combustion
of black powder and subsequent products. Samples of black powder were ignited by a
hot wire and the spectra collected were examined for combustion products, as well as

compounds present in the atmosphere. The researchers determined that a mixture of

gases (C02, CO, N2) and solid products (K2804, K2CO3, K28, KNO3) were produced as a
result of combustion and that a portion of the carbon dioxide present could be attributed
to the atmosphere.

1.4 The Analysis of Extractable Volatiles in Charcoal from Black Powder

While these studies have addressed the charcoal characteristics necessary for
effective, efficient use in black powder, namely the volatile content, and the products
formed from the combustion of black powder, they have failed to focus on the possible
uses of the extractable volatiles. Approximately twenty-five percent of the weight of
charcoal is comprised of volatiles and of this twenty-five percent, only one to two percent
is extractable. This research project will look specifically at these extractable compounds
and their potential for distinguishing and identifying samples of black powder. Although
homemade mixtures may be encountered by the forensic community, for ease of analysis,
this study will focus only on commercially available brands of black powder; though, the
technique presented may be applied to any type of black powder sample.

There are several aims of this project. Samples of domestic and foreign black
powder, as well as their corresponding charcoal must be obtained. An efficient method
must be established that adequately extracts the maximum number of volatiles from the
charcoal and black powder samples. When collecting items of evidentiary value at the
scene of an explosion, not only are explosive residues present, but often unburned
particles of the filler material used are also apparent. Because this study is exploratory in
nature, it focuses on particulate matter and not residual materials. Therefore, once an

efficient extraction procedure has been established, samples of charcoal will be analyzed

by gas chromatography/mass spectrometry (GC/MS) to detect the presence of any target
compounds.

Upon completion of the preliminary charcoal analysis and the identification of
target ions, actual samples of black powder will be analyzed. The extraction of the
volatiles from black powder is difficult, as it requires the elimination of the sulfur
component of the original sample. If this is not accomplished, the sulfur will overwhelm
the targeted volatiles in the output of the GC/MS and the data will be rendered useless.
With the targeted compounds appropriately isolated from the sulfur, instrumental
examination can commence. Prior to this examination, however, the reproducibility of
the extraction and analytical procedures must be assessed. Ultimately, the major goal of
this project is to compare the extractable volatiles present and the abundance of the
targeted compounds existent among the thirty-two samples analyzed. The varying levels
of extracted volatile compounds among the samples will serve to distinguish the black
powder samples.

Working in conjunction with Michigan State University and the Bureau of
Alcohol, Tobacco, and Firearms, this study was carried out at the National Laboratory
Center (ATF) in Rockville, Maryland. Spanning the months of May, June, July, and
August of 2000, this study focused on the sequential analysis of charcoal and black

powder samples and the subsequent analysis of the data collected.

2. Experimental Methods

2.1 Chemicals

Representatives from Gearhart-Owen Explosives Company (GOEX) and
Pemambuco Powder Company, manufacturers of Elephant brand black powder, were
contacted and requested to send samples of charcoal for preliminary analyses. Five
samples of charcoal were obtained: Roseville Charcoal, used by GOEX, a generically
labeled sample obtained from GOEX, Umbauba charcoal, used by the Pemambuco
Powder Company prior to the year 2000, experimental “debarked” Umbauba charcoal,
used by Pemambuco Powder Company, and Pinus Charcoal. The ATF explosives library
contained twenty-six black powder samples and an additional six samples were obtained
from the Pemambuco Powder Company. Collectively, eight different brands and
numerous lots were represented. I-IPLC grade ethyl acetate was used for the extractions
of both charcoal and black powder samples, as well as the blanks run between each
sample. Dicholoromethane and acetone, being less polar than ethyl acetate, were found
to be less effective at extracting the targeted volatile compounds, while extracting only
minimal amounts of sulfur from the black powder sarnples. Thus, ethyl acetate was the
solvent utilized in this study.
2.2 Sampling Procedure of Charcoal

One gram of each of the charcoal samples (unground) was placed in a separate
vial and SmL of ethyl acetate was added. The vials were shaken by hand for
approximately one minute and then refined using a .45p.m filter. The samples were
further concentrated under a Nitrogen stream to a volume of approximately 250uL and

then analyzed.

2.3 Sampling Procedure of Black Powder

Because the extractable volatile content of the black powder is much smaller than
that of the charcoal, as charcoal comprises only roughly 10% of the mixture, larger
sample sizes were used. Six grams of each black powder, in small allotments, were
ground by hand using a mortar and pestle. This was done under stringent safety

conditions due to the sensitivity of black powder to friction. These samples were placed

in separate vials and 10mL of the HPLC grade ethyl acetate were added. As with the
charcoal samples, the vials were shaken for one minute, filtered and concentrated using a
nitrogen stream to a volume of 2501LL.

Three powders were selected for a reproducibility study: GOEX 4Fg 04-23

850C058, GOEX 3Fg 03-05 9ZJU6B, and Elephant 4Fg 52 93 Lot. No. 151. Five

samples of each of the three powders were prepared, as indicated previously.

When reproducibility was verified, the additional twenty-nine samples, consisting

of Austin, DuPont, Elephant, Gearhart-Owen, Hodgen, Meteor, Wano, and Swiss black

powders, were prepared as above.

Preliminary experimentation was done to detemiine sensitivity levels of the

technique used. Using GOEX 4Fg 04—23 850C0858, .05 g, .1 g and .Sg samples were

prepared.
2.4 Gas Chroma tographyMass Spectrometry of Charcoal Extractions

Gas Chromatograms and mass spectra of the charcoal extracts were obtained with
an HP 5973 GC-MSD. The 2501uL autosampler vials were filled with the concentrated
samples and I 11L injections were used employing a 20:1 split. Ethyl acetate was run as a

blank between each sample. Additional parameters are as follows:

GC:

MSD:

Hewlett-Packard 6890 Series Gas Chromatograph
Column: Hewlett-Packard I-IP-l (methyl siloxane)
Length: 30 meters
I.D.: 0.20mm
Film thickness: 0.33pm
Injection Source: ALS - luL
Split: 20:1
Temperature Program: Inlet Temperature: 250°C
Transfer Line Temperature: 280°C

Initial Oven Temperature: 60°C
(hold time) (3 minutes)
Temperature Ramp: 5°C/min
Temperature (hold time): 120°C (0 minutes)
Temperature Ramp: 12°C/minute
Final Oven Temperature: 300°C (5 minutes)
Column Head Pressure: 10.65psi, Helium
Hewlett-Packard 5973 Series Mass Selective Detector

M/Z range: 33-300amu

2.5 Gas Chromatography/Mass Spectrometry of Black Powder Extractions

Gas Chromatograms and mass spectra of the black powder extracts were obtained

in the same manner as above.

The sensitivity study samples were prepared in the same manner as the other

black powder samples, however, they were analyzed using the Splitless mode and ions

with a mass-to-charge ratio of 121, 151, 152, 168, 1170, 181, 182, 192 or 196 were

targeted, increasing the sensitivity of detection.

3. Results and Discussion

3.1 Charcoal Extractions

The chromatograrns and mass spectra of the charcoal were analyzed to determine
which, if any, ions would be of assistance in differentiating the various samples. The
majority of ions, not associated with the solvent, were detected between nineteen and
twenty-five minutes in the thirty-five minute analysis time. Therefore, this six minute
segment was focused on. Nine ions were selected for further evaluation, namely 4-
hydroxybenzaldehyde (121 amu), vanillin ( 151/ 152 amu), 2-(4,5-dihydro-2-oxazolyl)-
N ,N-diethyl-ethenamine (168 amu), 2,3,6-trimethyl-napthalenr (170 amu), 4-hydroxy-
3,5-dimethoxy-benzaldehyde (182 amu), 3-(p-chlorophenyl)-5-methyl-pyrazole (192
amu), and 1-(4-hydroxy—3,5-dimethoxyphenyl)-ethanone (196 amu).

It was surmised that these relatively large ions could be fragments of the lignin
molecules found in the bark, heartwood and trunk exudates of trees. Li gnin, which is
closely correlated with cellulose, is the principal constituent of the woody structure of
many plants. Its purpose is to bind the matrix of cellulose fibers together. While the

exact molecular structure of lignin is not known, it has been determined that lignin
content is established by the species of the plant, the growing conditions to which the
plant was subjected and the geographical location from which a plant sample is taken.

Furthermore, the composition and properties of lignin molecules are also dependant upon

the method of isolation. Consequently, the nine ion fragments selected were analyzed to

determine if they were capable of distinguishing the charcoal component of the black

powder samples.

10

Extracted ion profiles were obtained using the system software for each of the
charcoal samples. The subsequent peaks were integrated using the following parameters:

Initial Area Reject: 0

Initial Peak Width: 0.028

Shoulder Detection: OFF

Initial Threshold: 8
Using the corrected peak areas of the 100% peaks from the nine extracted ion
Chromatograms of each charcoal sample, the abundance levels of the nine ions were
determined. For ease of comparison, these values were then ratioed to the abundance
level of the ion with a mass-to-charge ratio of 192 amu, 3-(p-chlorophenyl)-5-methyl-
pyrazole, which was found to be present in each sample. The results of the relative
abundance calculations are summarized in Figures 1 and 2 (note the varying abundance
scales).

Based upon these data, it is evident that the different types of charcoal contain

different levels of the target ions.

11

  

 

70000

W m

8CCEB<

'Debarked' Umbauba

Roseville

  

170

Ion Mass Number

168

Figure 1: Abundance of Target Ions in Five Charcoal Samples

12

 

 

Figure 2: Abundance of Target Ions in Five Charcoal Samples
Relative to Abundance of Ion 192, 3-(p-chlorophenyl)-5-methyl-pyrazole

3.2 Black Powder Extractions Examined by GC-MSD for Reproducibility Study

After analysis by the GC-MSD, the chromatograms and mass spectra of the three
black powders, selected to study the reproducibility of the extraction technique, were
examined. The five samples of GOEX 4Fg 04-23 850C058, GOEX 3Fg 03-05 92JU6B,
and Elephant 4Fg 52 93 Lot. No. 151 were evaluated to determine which, if any, of the
target ions were present and to what degree. Extracted ion profiles were obtained using
the same parameters employed in the analysis of the charcoal samples. Using the
corrected peak areas of the 100% peaks from the nine extracted ion chromatograms of
each of the fifteen black powder samples, the abundance levels of the nine ions were
determined. The results of the ion abundance figures are summarized in Figures 3, 4, and
5 and the deviations are reported in Table 1.

Analysis of the data indicates that though the abundance levels are not precisely
exact from sample to sample and standard deviations are quite large, the trends are the
same for each grouping. The Gearhart-Owen sample 3Fg 03-05 92.IU6B has low
abundance levels for ions 121 and 151/ 152. The abundance values increase slightly for
ions 168 and 170 and then steadily rise as the mass-to-charge ratio of the ion increases
from 181 to 192, falling abruptly off at ion 196. This same general trend applies to the
second Gearhart-Owen sample 4Fg 04-23 850C058. The abundance levels increase as
ion mass-to-charge value increases and then decline in ions 192 and 196. The overall
abundances, however, for this second Gearhart-Owen sample are higher than that of the
first sample. The Elephant black powder sample, on the other hand, offered relatively low
abundance levels of all the target ions with the exception of ion 192. The variation in

abundance levels and overall high deviation levels may be attributed to the initial

14

 

 

lon Mus Number 132

Figure 3: Abundance of Target Ions in Five Samples of
GOEX 3Fg 03-05 92IU6B

Abundance

 

 

Figure 4: Abundance of Target Ions in Five Samples of
GOEX 4Fg 04-23 850C058

 

 

 

Samples of

in Five
No. 151

Abundance of Target Ions
Elephant 4Fg 52—93 Lot.

5

gure

Fi

17

Rom Abundance

 

121 151 152 168 170 181 1& 192 196
loan-u Number

Figure 6: Abundance of Target Ions in Five Samples of
GOEX 3Fg 03-05 92JU6B Relative to Abundance of Ion 192,
3-(p-chlorophenyl)-5-methyl-pyrazole

Relatlve Abundance

 

 

 

 

   

 

 

 

 

 

 

 

 

 

 

 

 

g; g » " {Samples
'- ' "’ ~ VSamplet
121 151 152 168 170 181 182 192 196
' loanNumbor

Figure 7: Abundance of Target Ions in Five Samples of
GOEX 4Fg 04-23 850C058 Relative to Abundance of Ion 192,
3-(p-chlorophenyl)-5-methyl-pyrazole

19

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Sample 4
O 1 Sample 3
Sample 2
o 3 Sample 1
l i l . , l
121 151 152 168 170 181 182 192 1%
Ion I‘m Number

Figure 8: Abundance of Target Ions in Five Samples of
Elephant 4Fg 52-93 Lot. No. 151 Relative to Abundance of Ion 192,
3-(p-chlorophenyl)-5-methyl-pyrazole

20

“Ab-ammunit-
hMusN—br . , -
mm moo I 151.00L15200 I 163.00 T17000 131.00 I 132.00 I 192.00 [196.00 I
cor-25133 4323.32 P133322] 33937921040414 I 63730.36 156655.13T 263067.79 I 71636.37 I 21957.76 I
cor-2x“: 4047.03] 31579.33 L29341.75I 40030.74J 35265.03 139726.26 I 236579.211 261622.54I20350.01_I
41-' 0.001 5069.071 5215.97 I 9581.84D69830 10401.75 I 16913.74] 130612.3fl 5536.451

 

 

 

 

 

 

 

MMMJI‘AW

IuMmN-hr ,. , , _ g ,
menu: I_121.00T151.00 I 152.00 I 163.00 L170.00 [131.00 L132.00 I 192.00 I 196.00 I
. 0035131»: I144.37I 100.69 I 100.42 L75.12 L106.61f 91.91 I 91.45 I 31.05 F9201J
may I 23.91 L 25.31 I 25.33 I 40.13 I 41.00 I 27.20 I 27.63 I 35.35 I 23.43 I
(M 0001 103.43 J 133.46 I105.49 L92.” I 123.65 T11319j 61.32 f7929 J

 

WWdI-mmbmdbm
il-Mu-N—bor 7
“Powder 121.001 151.00 I 152.00

1
. 002x333 I_0.021 0211 0.20 I
l

168.00I 170.00 I 131.00 [ 132.00 L192.00 I 196.0U
0.24 I 0.32 I 0.30 I 1.341 0.00 r 0.11_I
coaxmgj 0.03] 0.29 I 023 0.17 I 0.271 1.17 I 1.93 I 0.00 1 0.17 I
. M1 0.00 I 0.02 I 0.03 0.01 I 0.02 L005 I 0.03 1 0.00 I 001—I

wwmaummumah 192
Jenkins-Nutcr-

 

 

 

 

 

uruanizmoI 151.00 152.00] 16300 I 170.00 00[ 131.00 I 132.00 I 192.00 I 196.00 I
‘ 003x335 I159.09 I 109.20 I 103.96I33 35] 11224 I 101.10 I 100.56 I 0.00 I 101.02 I
‘ 005x01 I 52.71] 52.36 I 52.79 [40.76] 64.61 I 51.37 I 51.93 I 0.00 I 5359—]
,Mom 1 115.43 I 144.49] 5554 I 102.971 135.33 I 126.61 I 0.00 I 45.511

 

 

Table 1: Standard Deviation and Relative Standard Deviation of
Target Ion Abundance and Ion Abundance Relative to Abudance of Ion 192

21

granular size of the black powder particles and the sample preparation technique. The
4Fg particles, being smaller and easier to pulverize, may yield more extractable volatiles
than the larger 3Fg, which were not as conducive to the milling phase of the sample
preparation. Furthermore, grinding and shaking the samples by hand undoubtedly
contributed to the large deviations. However, after conducting the reproducibility tests
and evaluating the resulting data, it can be concluded that the general trends of ion
abundance levels can be useful in distinguishing differing samples of black powder.

3.3 Black Powder Extractions Examined by GC-MSD for Discrimination Study
Prior to analysis on the GC-MSD, the visual examination of the prepared
extractions indicated that sample distinction was possible. The basic mixture of seventy-
five percent potassium nitrate, fifteen percent charcoal and ten percent sulfur is relatively

constant between manufacturers of black powder. As the samples were prepared,
however, the color of the extractions varied between brands, indicating that varying
levels of sulfur were being extracted. For example, Gearhart-Owen black powder had a
much darker yellow color than did Elephant black powder. This observation, in addition,
to instrumental data, demonstrated the capability to discriminate between black powder
samples.

The data generated from the additional twenty-nine samples of black powder were
assessed in the same manner as the charcoal samples. For ease of comparison, the
abundance levels of the target ions were ratioed to the abundance level of 3-(p—
chlorophenyl)-5-methyl-pyrazole. The thirty-two powder sample set is distinguished by
brand and the relative abundance figures are displayed in Figures 6, 7, 8, 9, 10, 11, 12,

and 13 (note the varying scale on figure 10).

22

This data shows that an increased number of the target extractable volatiles,
compared to the level of 3-(p—chlorophenyl)-5—methyl-pyrazole, are detected in the
majority of the Gearhart—Owen and Swiss samples. Meteor black powder yielded slightly
lower relative abundance levels. Austin, DuPont, Elephant, “Debarked” Elephant,
Hodgen, and Wano samples all yielded similar results. In these samples, the relative
abundance levels of the target ions compared to 3-(p-chlorophenyl)-5-methyl-pyrazole

were much lower than the other three brands.

23

 

Figure 10: Abundance of Target Ions in One Austin Black Powder Sample
Relative to Abundance of Ion 192, 3-(p-chlorophenyl)-5-methyl-pyrazole

  

 

 

h .-.< _ I, ‘1
. .

- l

Dqul 2Fg
Dqul 2Fg LotNo.0232

»

I:

  

16° 170

.4

Ion Mus Number

Figure 11: Abundance of Target Ions in Two DuPont Black Powder
Samples Relative to Abundance of Ion 192, 3-(p-chlorophenyl)-5-methyl-
pyrazole

25

 
 
  
  
 
 
 
 
 
 
   

Elephant 3Fg 6/24/95

ElephamaFg 6/24/96

ElephantZFg 10/94 Lot.No.160

Elephant F9 258/93 LotNo.134

Eepham cannon 26093 Lot.No.117

Elephant ng 251/93 Lot.No.146

2 Elephant 2Fg 08/1998 391
Elephant4Fg 52/93 Lot.No.151

Figure 12: Abundance of Target Ions in Eight Elephant Black Powder
Samples Relative to Abundance of Ion 192, 3-(p-chlorophenyl)-5-methyl-
pyrazole

26

Relative W

  
   

Elephant 'debarked' 2Fg S—09 22/00
Elephant 'debarked' 3Fg 5-10 22/00

 
   

lon Mus Number 192

Figure 13: Abundance of Target Ions in Two “Debarked” Elephant Black Powder
Samples Relative to Abundance of Ion 192, 3-(p-chlorophenyl)-5-methyl-
pyrazole

27

 

  
 
   
 
 
 
 
 
 
 
 
 
 

GOEX 3Fg 311141273 03-95
GOEX 4Fg 04-75 3114143033
GOEX 2Fg 81JU238 02-91
GOEX 2Fg 02-15 94.1mm
GOEX 4Fg 04-23 350c063
GOEX 3Fg 0305 92JU68
GOEX 4Fg owe 99MB
GOEX 3Fg 03-76 995E108

 

Figure 14: Abundance of Target Ions in Eight Gearhart-Owen Explosives Black
Powder Samples Relative to Abundance of Ion 192,
3-(p-chlorophenyl)-5-methyl-pyrazole

28

lon Mus Number

 

Figure 15: Abundance of Target Ions in Two Hodgen Owen Black Powder
Samples Relative to Abundance of Ion 192, 3-(p—chlorophenyl)-5-methyl-
pyrazole

29

Relative Mme.

 

 

 

-»> ’ . «4 Meteor 3Fg
Meteor 3Fg 73AP1510$2

Figure 16: Abundance of Target Ions in Two Meteor Black Powder
Samples Relative to Abundance of Ion 192, 3-(p—chlorophenyl)-5-methyl-
pyrazole

30

Relative Abundance

 

 

 

 

 

 

 

 

 

 

 

  
  
  
   

Swiss 4Fg 01-01 00FE293

' Swiss 3Fg 0201 005156
Swiss F9 Lot.No.0010041.199
Swiss 1.5Fg Lot.No.m20310.100

Figure 17: Abundance of Target Ions in Four Swiss Black Powder
Samples Relative to Abundance of Ion 192, 3-(p-chlorophenyl)-5-methyl-
pyrazole

31

WM“

  
 
 
   

 

Wano 3Fg 0.2-0.7 Oc111992 PB
Wano PP Oc1119920.7-O.93mn
Wano 3Fg 01111992 02-0.7mrn

Ion 1.1-u Number ‘32 192

Figure 18: Abundance of Target Ions in Three Wano Black Powder
Samples Relative to Abundance of Ion 192, 3-(p-chlorophenyl)-5-methyl-
pyrazole

32

4. CONCLUSIONS AND FUTURE RESEARCH

The evidentiary value of explosives in criminal investigations, particularly those
involving IEDs, is very great. An abundance of analytical techniques, such as XRPD,
FI‘IR, or SEM/EDX, can be used to identify components of various explosives; yet, the
focus of these techniques is component identification and not brand identification.

Presently, the protocol for examination of black powder includes the
identification of its three integral parts: sulfur, charcoal and potassium nitrate. This study
has gone one step further and explored the brand identification, or type characterization,
of black powder utilizing the inherit differences in the charcoal component.

The use of GC/MS as an analytical tool serves the purpose of this study quite
well. The specificity and sensitivity of the instrumentation allow minute quantities of
sample to be accurately analyzed.

Using ethyl acetate as a solvent, extraction of the volatile components of the
charcoal proved to be an effective means of characterization. The total ion
chromatograms of the five charcoal samples studied appear different. Upon closer
examination of the mass spectra, the abundance and relative abundance of nine select
ions are able to quantitatively characterize the samples.

The extraction technique also proved effective in the analysis of black powder
samples. Because charcoal comprises only ten percent of black powder, larger samples
were used so greater volumes of the extractable volatiles could be analyzed. Again the
total ion chromatograms for different brands of black powder showed unique patterns.
There were also distinct trends of ion abundance and relative abundance levels between

black powder brands, particularly GOEX and Elephant black powders. While several of

33

the brands that are not currently in production yielded similar results, the major brands

currently in production were indeed distinguishable.

The reproducibility study showed that while there are distinct trends, the sampling
procedures must be evaluated and improved as the standard deviations and relative
standard deviations are rather high. The sample preparation procedures developed were
highly based upon time and material constraints. Pulverizing the samples allows for ease
of extracting volatile material. However, because some brands are more difficult to
pulverize than others, grinding samples by hands with a mortar and pestle does not yield
readily reproducible results. In the future, a more uniform means of grinding the black
powder samples must be developed. However, a liquid phase extraction with a hot
solvent, such as a Soxleth extraction, may eliminate the need for pulverizing the sample.
Apart from ethyl acetate, other solvents may be more efficient in the extraction of volatile
compounds. Solvent selection is crucial, as a solvent must be chosen that will be as, or
more, effective than ethyl acetate at eliminating the sulfur component of the black
powder.

The sensitivity study suggested that there may be limits to the size of the sample
that can be used in this type of analysis. If a more efficient means of extracting the
volatile compounds were developed, perhaps the size of the sample necessary for analysis
would decrease. This would prove useful to forensic examiners, as the amount of
evidentiary materials in the majority of cases is rather limited.

Furthermore, if additional target ions could be shown to differentiate samples, the

sensitivity of the method would improve.

34

Provided that a more efficient sample preparation method is developed, work may
also be continued in the area of black powder residue characterization.

Although the ion abundance and relative abundance levels were not reproducible
to the degree desired, this study has uncovered a new area in explosives analysis. The
brand identification and characterization of black powder will no doubt aid criminal
investigations as the sample extraction techniques are perfected. The sensitivity provided
by GC/MS provides an efficient means to analyze the small quantities of extracted
volatiles and the abundance and relative abundance values provide an acceptable means
of sample characterization. Thus, this study and future work perfecting sampling

techniques will serve to better the analytical characterization of black powder.

35

APPENDICES

36

APPENDDI A

Total Ion Chromatograms
of Charcoal Samples

37

 

333

0
d

 

TIC: EACNTRLD

 

1

fl

 

 

11.33333

I V

Irjji' ‘ V V

"II’T'V‘V'IW VIfiVrVIVVVIIfV‘VIIIVVI‘YV—rjl'VYvT—V’r
19.50 420.00 $.50 21!!) 2130 2200 22.50 23.!!! 23.50 24.1!) 24.§0

——__

Figure 19: Total Ion Chromatogram of ethyl acetate control
(SmL concentrated), 19 to 25 minutes

38

 

 

 

.e .e-ea
.e
.3§§§§§§§§§§§§

 

m

 

 

 

VVVVVVVV

'VVT—f‘ vvvvvvvvvvvv
W4 20'50 21.'00 21.30 m 2230 ”.'00 m 24'00 24'30

 

 

Figure 20: Total Ion Chromatogram of GOEX charcoal, as used by the
Gearhart-Owen Explosives Company
(1 gram/SmL ethyl acetate), 19 to 25 minutes

39

 

Vr

 

“0sz0

13333331331}

 

 

e
vvvvvvvvvvvvvv

 

 

1r VVVVVVVV

 

 

“1m1m 10350 20.00 2050 21.00 21.50 22'00 22'50 23.!!! 23h) 21$ 2433111

 

Figure 21: Total Ion Chromatogram of Roseville charcoal, as used by the
Gearhart-Owen Explosives Company
(lgram/SmL ethyl acetate), 18 to 25 minutes

40

 

 

W r10: mom—100

1311100
130000
140000

1211100

 

 

 

Al I - 4 -1 J-LILMEI’Iw,

fivvv'vvvavvyr'vv'VIV YI'VVY'IYV‘I W'V‘V [VIVIVT
.50 E 21.50 2.50 23 23.50 24.00 24.50

 

 

 

Figure 22: Total Ion Chromatogram of “Debarked” Umbauba charcoal, as used by the
Pemambuco Powder Company
(lgram/SmL ethyl acetate), 18 to 25 minutes

41

 

 

 

 

 

 

 

1.1..

1 1350 2000 20 21.00 21 2230 3.50 24130

Figure 23: Total Ion Chromatogram of Pinus charcoal, obtained from the
Pemambuco Powder Company
(1 gram/SmL ethyl acetate), 18 to 25 minutes

42

 

 

 

 

 

 

 

 

rWu Wt)
140000
120000
100000
30000
30000
40000
20000
c‘ L. fl .....,.A."..,-;..,.. LJ.JI.,...-: LAM
rm.» 1050 20.00 m 21g 21.30 m 22.50 M 2350 3100 24.50 ,

 

 

 

Figure 24: Total Ion Chromatogram of Umbauba charcoal, as used by the
Pemambuco Powder Company in Elephant Black Powder prior to the year 2000
(1 gram/SmL ethyl acetate), 19 to 25 minutes

43

APPENDIX B

Total Ion Chromatograms
of Black Powder Samples in Reproducibility Study

 

 

m
m
1m
1

1m

 

 

 

 

 

 

 

Figure 25: Total Ion Chromatogram of ethyl acetate control
(10mL concentrated), 19 to 25 minutes

45

 

311

150000

100000

 

Ween

 

'11 JILL LIAM-n“

 

 

Tune»

'ITVT'vvvr'TTf‘V‘I V—7 W".

v V V V I v I V ‘ Y Y I V r Y Y ' V I V I I V V V I Y V V ‘v r'fi
1 no 2150 00 2250 00 23 24.1!) 24.50

Figure 26: Total Ion Chromatogram of GOEX 3Fg 03-05 92.1U6B,
sample 1, (6gram/10mL ethyl acetate), 19 to 25 minutes

 

 

 

TIC: GOEX3FG‘12.D

 

 

 

 

 

tmfi
m
m
411m
A LA. jean A LJJ
nu...» "1'”2000 '11 00 mm'rgoé'3250'n'hn'""."F'24.'50'fi1

 

 

Figure 27: Total Ion Chromatogram of GOEX 3F g 03-05 92.1U6B,
sample 2, (6gram/10mL ethyl acetate), 19 to 25 minutes

47

 

 

 

TIC: GONG“)

 

 

 

13:10 am 230 21.00 2150 w m m 3g 240,0

'LHHHHI

Figure 28: Total Ion Chromatogram of GOEX 3F g 03-05 921U6B,
sample 3, (6gram/10mL ethyl acetate), 19 to 25 minutes

48

ML

243-10

 

 

333313333331

 

 

1WD

 

 

 

 

 

 

 

 

 

 

 

Figure 29: Total Ion Chromatogram of GOEX 3Fg 03-05 9211163,
sample 4, (6gram/l OmL ethyl acetate), 19 to 25 mmutes

49

 

 

A E. mean

 

 

 

 

 

 

 

 

 

 

 

Figure 30: Total Ion Chromatogram of GOEX 3F g 03-05 92.1U6B,
sample 5, (6gram/10mL ethyl acetate), 19 to 25 minutes

50

 

.1?

5

EL

 

 

 

 

 

 

m
m
m
v...,firrTTJ-¥:r‘;-44. ..-r,‘.:f.J;—.?A.'.,..r.r....,..-.,....,....,
rim.» 1;; 103 20.30 21 00 2250 23.00 23.50 24.00 24L

 

 

 

 

Figure 31: Total Ion Chromatogram of GOEX 4Fg 04-23 850C058,
sample 1, (6gram/10mL ethyl acetate), 19 to 25 minutes

51

 

 

 

W

 

 

 

 

 

Figure 32: Total Ion Chromatogram of GOEX 4Fg 04-23 850C058,
sample 2, (6gram/10mL ethyl acetate), 19 to 25 minutes

‘52

 

 

 

TIC: W631)

I

‘
E

 

UBLEEUS?

 

 

 

 

 

 

 

Figure 33: Total Ion Chromatogram of GOEX 4F g 04-23 850C058,
sample 3, (6grarn/10mL ethyl acetate), 19 to 25 minutes

53

 

Ft“ no: em
1111000

 

 

 

 

 

 

21300 @190 2100 21:90 22'00 2250 zr'oo 23'50 240) 24;

Figure 34: Total Ion Chromatogram of GOEX 4F g 04-23 850C058,
sample 4, (6gram/10mL ethyl acetate), 19 to 25 minutes

54

 

 

 

W 11112009143050

140000

120000:

 

 

 

 

 

0
Mum 19,39 20.00 20.30 2100 2150 gm 22.50 2100 2350 24.00 24110

Figure 35: Total Ion Chromatogram of GOEX 4F g 04-23 850C058,
sample 5, (6gram/10mL ethyl acetate), 19 to 25 minutes

55

 

 

 

 

TIC: ELE4FGBD

 

AL H AIL AI- 4 .__.-v~:-:'

 

 

VVVVVVVVVVVVVVVVVVV fiTT'V'VVY: ‘11"7"1"""—r"r71_ 1

I T I r v v v v I v v
19.m 19.50 20.00 24m 24.50

Figure 36: Total Ion Chromatogram of Elephant 4F g 52—93 Lot#151,
sample 1, (6gram/10mL ethyl acetate), 18 to 25 minutes

56

 

 

3.31

‘
g

 

 

13333333333

75: ELE4l-‘GZD

 

moo 21.“) 2200 2300 23 .00 24.50

Figure 37: Total Ion Chromatogram of Elephant 4Fg 52-93 Lot#151,
sample 2, (6gram/10mL ethyl acetate), 19 to 25 minutes

57

 

 

 

 

8 83851

 

m: 21.543030

 

 

 

 

Figure 38: Total Ion Chromatogram of Elephant 4F g 52-93 Lot#151,
sample 3, (6gram/10mL ethyl acetate), 19 to 25 minutes

58

 

33131

-.

 

 

Tim-J 10.00 1!.50 420100

 

 

 

TIC: EWD

 

ALA A.qu
V V Vfi

2.50 23.00 3.30 24.00 24'110

 

 

 

Figure 39: Total Ion Chromatogram of Elephant 4F g 52-93 Lot#151,
sample 4, (6gram/ 10mL ethyl acetate), 19 to 25 minutes

59

 

 

 

 

'rlc: era'ow

 

 

 

 

 

 

Figure 40: Total Ion Chromatogram of Elephant 4F g 52-93 Lot#151,
sample 5, (6gram/10mL ethyl acetate), 19 to 25 minutes

 

APPENDIX C

Total Ion Chromatograms
of Thirty-two Black Powder Samples

61

 

33333 31

 

DOW

 

 

 

 

VVVW—Vvvv T‘r vvvvv

1 1 1 fI—r r 1 1 1 1 r
"II—’1lm 1 19.00 11% .m 20.50 21.” 5 am 23.00 2350 24.50

 

Figure 41: Total Ion Chromatogram of Austin Black Powder 09627
(6gram/10mL ethyl acetate), 18 to 25 minutes

62

 

 

 

116W

3?

130000

1011:»

 

 

 

 

 

Figure 42: Total Ion Chromatogram of DuPont Black Powder 2F g Lot. No. 02-82
(6gram/10mL ethyl acetate), 18 to 25 minutes

63

 

 

 

TIC: WD

 

 

43333313331

 

 

 

 

 

 

 

Figure 43: Total Ion Chromatogram of DuPont Black Powder 2Fg LC
(6gram/10mL ethyl acetate), 19 to 25 minutes

 

 

 

TIC: ELEdFGBD

 

 

40000
m ‘ IL
- .L AIAJJ
................ ,

T r 1 r 1 1 1 r 1
tin» 19.00 13.50 20.00 2150 2400 24;

 

 

 

 

 

Figure 44: Total Ion Chromatogram of Elephant Black Powder 4Fg 52-93 Lot#151
(6gram/10mL ethyl acetate), 18 to 25 minutes

65

 

 

 

 

 

 

 

 

Womb

05000
30000
33000
30000
43000
40000
a
30000
13000
10000
3000

.. - L M

Le» " "'1'3'3011m""'2030 '31' m""21.'60"m""'22'50"23100"23;-9——14'00"24'§6""

 

 

 

Figure 45: Total Ion Chromatogram of Elephant Black Powder 2Fg 08/1998 391
(6gram/10mL ethyl acetate), 19 to 25 minutes

 

 

 

I E: ELE5FGD

 

 

 

 

 

 

 

Figure 46: Total Ion Chromatogram of Elephant Black Powder 5Fg 251/93 Lot. No. 146
(6gram/10mL ethyl acetate), 19 to 25 minutes

67

 

 

 

 

 

 

 

Figure 47: Total Ion Chromato
gram of Elephant Black Powder Cannon
264/93 Lot. No. 117 (6gram/10mL ethyl acetate), 19 to 25 minutes

68

 

 

 

 

 

 

 

 

 

 

IL- -1. J-

f'vvvv VVVY VV‘V '1‘!

1950 20110 ' 21'50 ' 22330Hé'00'n'30'124301'in24'

 

 

1133333333333.

Figure 48: Total Ion Chromatogram of Elephant Black Powder Fg 258/93 Lot. No. 134
(6gram/10mL ethyl acetate), 19 to 25 minutes

69

 

 

TIC: more!)

 

 

 

 

 

 

 

 

 

 

10000

3000

3000

4000

2000 M
nap; "'10'30"""'20.'50'121' $122300"""'"'T'.'30"24.'"'2'4.'30'1'

Figure 49: Total Ion Chromatogram of Elephant Black Powder 2Fg 10/94 Lot. No. 160
(6gram/10mL ethyl acetate), 19 to 25 minutes

70

 

fir-lie: 11mm

13000

 

 

 

 

__A AAA A”
O'I' vmrv'YVfivjfijvv'rvv V'v

'l'V'V'V'V'Ij I'YIVTVII'YYVITYYV‘V‘UV"
T!” 1200 20.00 00 21. 2200 2:00 23.50 241:: 24.50

 

 

 

Figure 50: Total Ion Chromatogram of Elephant Black Powder 3F g 6/24/96 PAD/NLC
(6gram/10mL ethyl acetate), 19 to 25 minutes

71

 

W TIC: 5390941020

9'1

 

 

 

 

. JILL _.

Vm'jfi'VIV—fvvflHerI17:117110V7j1'1filvTfi—7'I11"
Lug-o 1000 J00 2051 21.00 3100 2200 g 2300 3300 24.00 M

 

 

11

 

 

 

Figure 51: Total Ion Chromatogram of Elephant Black Powder 3F g 6/24/95 PAD/NLC
(6gram/ 10mL ethyl acetate), 19 to 25 minutes

72

 

 

 

 

 

 

 

 

 

 

 

Figure 52: Total Ion Chromatogram of Elephant “debarked” Black Powder
3F g S-lO 22/00 (6gram/10mL ethyl acetate), 19 to 25 minutes

73

 

 

 

TD: ELDEB2FOD

 

 

 

 

‘

"'1' 'l""l' n r 1
19.” .113 mm 21 .50 23.00 23.50 24

 

Figure 5 3: Total Ion Chromatogram of Elephant “debarked” Black Powder
2F g S-09 22/00 (6gram/10mL ethyl acetate), 19 to 25 minutes

74

 

 

 

 

 

 

 

 

 

mt WED

m
m
m
m
m
m
m

A A A A A I

v vvvvvv I VVVVVVVVVVV I VVVVVVVV I r V V V 1 V V ’Y—r ' V V V V I V V I V l ' I V ' I

The-o 19.50 21 m 21 x 2.50 3.“) 3.5) 24.”

Figure 54: Total Ion Chromatogram of GOEX Black Powder 3F g 03-76 99SE10B
(6gram/10mL ethyl acetate), 19 to 25 minutes

75

 

TIC: GOMFWD

 

 

 

1“

MI

W

- A _LII L .. A J. 11 A W
rm""1'3""'.' 21350"2100"2100"2200"2250"2300"2350H'244g3"2400"1'

 

 

 

Figure 55: Total Ion Chromatogram of GOEX Black Powder 4F g 04-16 39MA04B
(6gram/10mL ethyl acetate), 19 to 25 minutes

76

 

 

100351..
210000]

100000

100000

“I

 

 

['12:

10.80

 

IE: WORD

 

W

§.m flfi 21m 21 .50 goo 250 E00 3% 24.“) 24.50

 

 

Figure 56: Total Ion Chromatogram of GOEX Black Powder 3F g 03—05 92.TU6B
(6gram/10mL ethyl acetate), 19 to 25 minutes

77

 

 

 

I E: GOEXAFGBD

 

 

 

 

 

 

Figure 57: Total Ion Chromatogram of GOEX Black Powder 4Fg 04-23 850C058
(6gram/10mL ethyl acetate), 19 to 25 minutes

78

 

 

ii: WMD

 

 

 

 

 

 

 

 

 

Figure 58: Total Ion Chromatogram of GOEX Black Powder 2F g 02-15 94JA31C
(6gram/10mL ethyl acetate), 19 to 25 minutes

79

 

 

 

 

 

 

 

 

 

F ' -
rgure 59. Total Ion Chromatogram of GOEX Black Powder 2F g 81JU23B 02-91
(6gram/10mL ethyl acetate), 19 to 25 minutes

80

 

 

TIC: 0021434730

I

 

 

 

 

120000
110000
100000
00000
30000
70000
30000
30000
40000
30000
20000
10000,
mJ 10.30 am Q50 21L 2130 22.30 20.00 2400 2430

 

Figure 60: Total Ion Chromatogram of GOEX Black Powder 4Fg 04-75 81MA03B
(6gram/10mL ethyl acetate), 19 to 25 minutes

81

 

 

 

TB: 00101313310

3 31

.
g
f

5318

 

 

 

 

Figure 61: Total Ion Chromatogram of GOEX Black Powder 3Fg 811A12A 03-95
(6gram/10mL ethyl acetate), 19 to 25 minutes

82

 

 

TIC: HODGENBD

 

 

 

 

 

 

 

Figure 62: Total Ion Chromatogram of Hodgen Black Powder 3Fg
(6gram/ 10mL ethyl acetate), 19 to 25 mmutes

83

 

——

 

 

 

9

 

TIC: HODGEN2FD

 

 

21.00 21.50 20.00 23 24.00 2430

Figure 63: Total Ion Chromatogram of Hodgen Black Powder 2F g
(6gram/10mL ethyl acetate), 19 to 25 minutes

 

 

 

 

TIC: METEORBD

“i

 

 

 

fine—'4 1000 2000 2000 21.09 21.00 3.00 Q00 2300 2000 24.00 24.00

 

 

 

Figure 64: Total Ion Chromatogram of Meteor Black Powder 3F g 73 AP 1510 82
(6gram/10mL ethyl acetate), 19 to 25 minutes

85

 

 

 

W

 

 

 

 

 

Figure 65: Total Ion Chromatogram of Meteor Black Powder 3F g NC
(Ggram/ 10mL ethyl acetate), 19 to 25 minutes

 

 

 

? W

Figure 66: Total Ion Chromatogram of Swiss Black Powder 1.5F g Lot. No. 001 #310.100
(6gram/10mL ethyl acetate), 19 to 25 minutes

 

 

 

 

 

 

 

 

 

 

 

 

 

 

87

 

 

TIC: SWSFWD

HE?

 

 

 

 

 

 

 

 

Figure 67: Total Ion Chromatogram of Swiss Black Powder Fg Lot. No. 001 #041.l99
(6gram/10mL ethyl acetate), 19 to 25 minutes

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Figure 68: Total Ion Chromatogram of Swiss Black Powder 3Fg 02-01 00FE15C
(6gram/ 10mL ethyl acetate), 19 to 25 minutes

89

 

 

 

 

 

 

 

 

 

 

 

Figure 69: Total Ion Chromatogram of Swiss Black Powder 4F g 01-01 00FE29B
(6gram/ 10mL ethyl acetate), 19 to 25 minutes

 

 

TIC: WANOPPBD

 

 

 

 

 

 

Figure 70: Total Ion Chromatogram of Wano Black Powder 3Fg Oct] 1992 0,2-0,7mm
(6gram/10mL ethyl acetate), 18 to 25 minutes

91

 

 

TB: WANO3FGBD

 

 

 

 

 

 

Figure 71: Total Ion Chromatogram of Wano Black Powder PP Oct.1 1992 0,7-0,9mm
(6gram/10mL ethyl acetate), 18 to 25 minutes

 

 

m: WANOPBD

 

 

flasflguaasii

%
,1
18‘
8
,-
IB
8
E
f
8
fl
8

 

 

 

 

 

 

Figure 72: Total Ion Chromatogram of Wano Black Powder 3F g 0,2-0,7mm
(6gram/10mL ethyl acetate), 18 to 25 minutes

93

APPENDIX D

Total Ion Chromatograms
of Black Powder Samples in Sensitivity Study

94

 

 

 

 

 

 

 

 

 

 

VVTTW" T71

fitfiv"rf"'r" '1 *T l I
21.00 Wm 21.50 24:2 24L

 

 

m w
. L 1,1111.”
" m‘fm r IIIIIIIIIIII

  

 

Figure 73: Total Ion Chromatogram Using the Splitless Mode
of GOEX Black Powder 4F g 04-23 850C058
(6gram/5mL ethyl acetate), 18 to 25 minutes

95

Hg]

 

 

Flt“ W0
4000
3000
3000
2000
m

 

 

 

 

 

 

 

 

 

Figure 74: Total Ion Chromatogram Using the Splitless Mode
of GOEX Black Powder 4Fg 04-23 850C058

(.5gram/5mL ethyl acetate), 18 to 25 minutes

 

El

 

 

 

303031513?

 

 

 

 

 

 

 

vvvvvvvvvvvvvvvvvv j—v—

YIIVVIw1fi'

...-,....,....,....,.-..,
1050 20.00 2050 21.00 2200 2250 2100 211-50 «.'00 353*

Figure 75: Total Ion Chromatogram Using the Splitless Mode
of GOEX Black Powder 4F g 04-23 850C058
(. lgram/SmL ethyl acetate), 18 to 25 minutes

97

 

 

 

TIC: WSID

 

 

 

 

L
*vr‘v‘v IIIIIII 'vvvv'VVVT

fi'V'vivvlfifi'VITvvv v—rir WIvv vvvv
Win-Ham 1050 31.00 2050 21.’00 21110 mica £50 3:00 2130 24.00 m

 

Figure 76: Total Ion Chromatogram Using the Splitless Mode
of GOEX Black Powder 4F g 04-23 850C058
(.05gram/5mL ethyl acetate), 18 to 25 minutes

98

APPENDIX E

Select Extracted Ion Chromatograms
of Black Powder Samples

W lMivN i. Niw411mim11iqlflmui Mi- W. Iqm. 11%!in .m-l.jiml.lfiimwidifliflllm 11%..“
. ..... .m

 

 

 

\
II! 12100 (12070 b 121.70): GOEXIIFGBD

 

Luggage?

fi

 

 

 

 

 

 

F igure 77: Extracted Ion Chromatogram, Ion 121, of GOEX Black Powder
3F g 03-05 921U6B (6gram/10mL ethyl acetate), 18 to 25 minutes

100

 

 

 

PM Im 151.00 (150.70 b 151.70): WOOD

1400
11D

1M

 

 

 

 

 

v vv vvvv v vv'vvv jvvt V v m

I v I Y V V I V V V '7' ' V V V T r V V V I I V V Y Y I V V T I
21.00 21.50 2200 22.50 goo 23.50 24.00 24.50
M 152.00 (151.70Io 152.70): GOEXSFGBD

 

 

 

 

 

 

 

 

 

 

1200
1000
000
000
"I'-v-ywfi.,.fi71v11v1....1....I.vv.,v..v,.v..r..y.,..17.
run.) 1900 200042050 21.00 3130 22.00 2250 2:100 2150 2400 __24f.00

 

 

Figure 78: Extracted Ion Chromatogram, Ions 151 and 152, of GOEX Black Powder
3Fg 03-05 921U6B (6gram/10mL ethyl acetate), 19 to 25 minutes

101

mm m WI mimia -

 

 

 

N
HI 1000011071010 168.70): WOOD

 

 

 

 

i§g§§§j§§LL§§§§§§Jj

 

 

 

 

vvvvvvvvvvvvvvvvvvvvvvvvvvvvvvv '

v'vvfi—I'V'VIVVTV VVVY
“In; 1950 20g fig gig 31 Q‘ 22700 2250 m' £50 21100 2430

 

 

Figure 79: Extracted Ion Chromatogram, Ion 168, of GOEX Black Powder
3F g 03-05 921U6B (6gram/10mL ethyl acetate), 19 to 25 minutes

102

 

 

 

Lfi

 

 

FR” III 110.00 (1 ”.70 b 170.70): GOEXSFGBD

1500
1400
1300
1”

11m

 

1000

 

 

 

 

 

 

 

 

 

vvvv' vvvvvvvv 'I‘VTT YV'II""" '1 ”I“ at” I 2‘?”
Tm» 10 2000 20.50 50 non 2250

Figure 80: Extracted Ion Chromatogram, Ion 170, of GOEX Black Powder
3Fg 03-05 9ZJU6B (6gram/10mL ethyl acetate), 19 to 25 minutes

103

Fl

Sliiil

IE

(:9

 

 

 

Im 101001111701010110): 009139000

“‘
3‘3

 

Efiéflfifiéfi

 

 

 

1000 L A
E’vrvv'vvvv'vvvv'rrvv'vvv‘vIvv‘vvrvvvr'Avavrllvnvvvafi-rvv'1vvr'
1950 ”I” 20.50 21 .00 21 50 ”In 2250 23m 23.”
Inn 18200 (101101010270): coexasoan

    

     

 

3

 

L A ‘ "V1Ivvv'

'firlvvr' "" IVY—T Tfivv TY‘I[I'It'v'vv'vtvv'vvvyvyv
\IN‘M 215L213!) n00 22.50 2100 2150 2400 24.50

 

 

.3353

 

 

 

Figure 81: Extracted Ion Chromatogram, Ions 180 and 181, of com Black Powder
3F g 03-05 921U6B (6gram/10mL ethyl acetate), 19 to 25 mmutes

104

 

 

Ian 19.001191.7010102.70):Goex31=ca.0 ,

 

 

 

 

 

 

 

#gsgssagggseaagagaé

 

 

V'vv",,fi"""" VfrvvrvIvvrvivvrvIvaT'vvvv'
ED; 10.00 20.00 20; am 2150 .00 2200 2000 3,00 m 24.00 ,

Figure 82: Extracted Ion Chromatogram, Ion 192, of GOEX Black Powder
3Fg 03-05 921U6B (6gram/10mL ethyl acetate), 19 to 25 minutes

105

m - .
”Wumiwiml mil-mljiw1im1iflimli 0-110 vim 11miiw m mimiww. MM\ PM.

 

 

 

 

 

 

 

lon 100.00 (15.70 b 18.70): GOEX3FGB.0

 

 

0000000000000000‘

 

 

 

 

 

 

 

 

 

 

 

 

 

Figure 83: Extracted Ion Chromatogram, Ion 196, of GOEX Black Powder
3Fg 03-05 921U6B (6gram/10mL ethyl acetate), 19 to 25 minutes

106

.A

 

 

W M1210 (1U.70b121.fizm

 

 

 

 

 

 

 

 

 

 

 

Figure 84: Extracted Ion Chromatogram, Ion 121, of GOEX Black 32d“
4Fg 04-23 850C058 (6gram/lOmL ethyl acetate), 18 to 25 mm

107

 

 

 

 

 

F... 10111010000070 10101.70); 009140000

 

 

 

 

 

 

 

 

 

 

 

 

 

 

000 R
- ' ' ' r ' ' 'fiF‘I V ' ' '1' Y v—fi ' I v v v rfiru I v 0 VA 1 v v v v "vlv v riflv v VTn"
I'm-e 10.00 2000 2000 00 21 200 2200 2_000 2000 2400 2400

 

 

 

 

 

Figure 85: Extracted Ion Chromatogram, Ions 151 and 152, of GOEX Black Powder
4F g 04-23 850C058 (6gram/10mL ethyl acetate), 19 to 25 minutes

108

 

 

10.1100001107701010070): GOEX4FGBD

 

 

 

 

 

 

 

 

 

Figure 86: Extracted Ion Chromatogram, Ion 168, of GOEX Black Powder
4Fg 04-23 850C058 (6gram/10mL ethyl acetate), 19 to 25 minutes

109

 

 

 

 

FIT-— 101“ “170001100770" '0' '1'\70.71»:ooex4r000

 

 

 

 

 

 

 

 

 

 

 

Figure 87: Extracted Ion Chromatogram, Ion 170, of GOEX Black Powder
4Fg 04-23 850C058 (6gram/10mL ethyl acetate), 19 to 25 minutes

110

 

 

 

 

 

 

 

 

 

 

 

FIN-u lon 181.W(WGBD
55000
50000
451m
4m
05000
00000
25000
20000
15000
10000
” L
L
rm...» 0 ' ”1'0350' '20300fi20f50' '21'00 ' ' ' rfl 22:00 2250 20_@_. v.50'E 2400 24.50 ;

 

 

 

 

hi102M(101.70to182.:70) GOEX4FGB—- 0

 

 

 

M588”

1L AL -.

v'vv 'YV‘AM

""0155‘2000 2000 21.00 2100 2200____2250 ’1‘” ”5° “0° 245°

Tine-5 1

 

Figure 88: Extracted Ion Chromatogram, Ions 181 and 182, of GOEXOBlack Powder
4Fg 04.23 ssocoss (6gram/10mL ethyl acetate), 19 to 25 mmutes

lll

 

 

10111020009110 b19270): GOEX4FGB.D

335?

10000

17000

15000

 

 

 

 

 

 

 

Jeueugnseagn

 

Figure 89: Extracted Ion Chromatogram, Ion 192, of GOEX Blac.k Powder
4Fg 04-23 850C058 (6gram/ 10mL ethyl acetate), 19 to 25 mmutes

112

 

 

 

ll'l 195.00 (195.7010 Ifim GOEXAFGBD

-_§_§§§§§§§§§§§?

§§§§

g

 

 

 

 

 

 

 

 

 

GOEX Black Powder
4F 3 04-23 850C058 (6gram/10mL ethyl acetate), 19 to 25 minutes

Figure 90: Extracted Ion Chromatogram, Ion 196, of

113

 

 

”Mamflzxmmztm m fl

”J

 

B

15

1O

 

L'V'V'fil'VVVrVY’v—vtvvvv'vvvv'rfifvvvvvaVVVVIVIVV[IVYTY'VVVIVVVVIVVVfi
Manna 1 1100 1 20.00 20.50 21.50 non 24

Figure 91: Extracted Ion Chromatogram, Ion 121, of Elephant Black Powder
4Fg 52-93 Lot#151 (6gram/ 10mL ethyl acetate), 18 to 25 minutes

 

 

114

 

 

 

if
m

1:1ng

 

 

 

 

Ian 151.00 (19an 151.70): euwcao

J

150

"W

 

 

 

 

   

p
' IVT—V'Ttv‘vvv—ijvvvlv—v—IU'vvvrj—v—uvvlvvvv'Iv—vv'vvv

2250 23.00 23.50
1m 1520:) (151.70!) 1&70): ELE4FGB.D

      
 

150

100

9%

r"V'Y—T’IT'Ivvvljrvvlyrv’VII‘vv'IVtV'VVIVI'VIV'I'V'IfIY‘IVV
mem 19m 2000 20.50 gg 2150 2200 22.50 23m 2350 24.00 2453

 

 

 

' Y]

 

 

 

 

Figure 92: Extracted Ion Chromatogram, Ions 151 and 152, of Elephaat Black Powder
4Fg 52-93 Lot#151 (63mm! 10mL ethyl acetate), 19 to 25 mmutes

115

 

 

 

\
En Inn 10100 (107.70» 10070): euwcao

 

 

 

 

 

 

almanac 10750 2d 20.30 .00 21130 00 22300

Figure 93: Extracted Ion Chromatogram, Ionl68, of Elephant Black Powder
4F g 52-93 Lot#151 (6gram/ 10mL ethyl acetate), 19 to 25 minutes

116

 

 

 

 

W Ian 1' 70.00 (1' 00' '.'70" '1o' 170.70): 51.547000

1”
150
140
1”
120

110

 

3M8

8

 

 

 

 

 

 

 

Figure 94: Extracted Ion Chromatogram, Ion 170, of Elephant Black Powder
4Fg 52-93 Lot#151 (6gram/10mL ethyl acetate), 19 to 25 minutes

117

 

 

 

I

 

 

 

 

Inn 181.!!! (100.70 111101.70): ELE4FGBD

 

 

 

l

 

 

 

 

 
  

 

 

150

 

 

 

"'.v ' '51750' 'az'oo . '22'g' ' vision '2'330' '2'4.'oo' '2'4556 ' m
Inn 10200 (101.70 to 102.70}: ELE4FGBD

 

'Vfifi

 

 

 

 

' v I I v r I V V T I v I v f l I V
9.50 2000 fl.” 2100

{Tho-o 1‘31“! 7 '1

‘v'rvvrti'vv'vaIIVWTVIVVYI'v'vt
2150 2200 2250 20.00 23.50 24.00 24.50

F igure 95: Extracted Ion Chromatogram, Ions 181 and 182, of Elephant Black Powder

4F g 52-93 Lot#151 (6gram/ 10mL ethyl acetate), 19 to 25 minutes

118

 

 

\
rill-nun, Inn 10200 (191.70 10 19270): ELE4FGBD

 

 

 

 

 

 

 

 

 

 

 

Figure 96: Extracted Ion Chromatogram, Ion 192, of Elephant Black Powder
4Fg 52-93 Lot#151 (6gram/10mL ethyl acetate), 19 to 25 minutes

119

 

, J

150

100

 

lon 100.00 (1%.70 b 13.70): ELE4FGBD

 

 

r I V 'jfij

 

 

Figure 97: Extracted Ion Chromatogram, Ion 196, of Elephant Black Powder

r V V

‘ v IvaTvvvv vvvl 'I'V'YI'fiVIV' '
20.00 20. 21.50 2200 2:100 23.50 2100 24

4Fg 52-93 Lot#151 (6gram/ 10mL ethyl acetate), 19 to 25 minutes

120

 

WORKS CITED

121

WORKS CITED

. Bender. “Analysis of Low Explosives.” Forensic Investigation of Explosives. Taylor
& Francis Ltd. Bristol, PA: 1998.

. Gray and Marsh. “Physical Characteristics of Charcoal for Use in Gunpowder.”
Journal of Materials Science 1985, 20: 597-611.

. Sasse. “The Influence of Physical Pr0perties of Black Powder on Burning Rate.”
ARBRTL-TR-O2308, Ballistic Research Laboratory, USA-ARRADCOM, Aberdeen

Proving Ground, MD: 1981 (ADA100273).

. Gray, Marsh, and McLaren. “Review A Short History of Gunpowder and the Role of
Charcoal in its Manufacture.” Journal of Materials Science 1982, 17: 3385-3400.

. Rose. “Investigation on Black Powder and Charcoal.” IHTR-433, Naval Ordinance
Station, Indian Head, MD: 1975.

. Kirshenbaum. “Effect of Different Carbons on Ignition Temperature and Activation
Energy of Black Powder.” Thermochimica Acta 1977, 18: 113-123.

. Hussain and Rees. “Combustion of Black Powder. Part II: PT IR Emission
Spectroscopic Studies.” Propellants, Explosives, Pyrotechnics I991, 16: 6-11.

ADDITIONAL WORKS CONSULTED

Baker. “Charcoal Industry in the USA.” Forest Products Laboratory, Madison, WI.

Bowland and Lu. “Combustion Characteristics of Single Granules of Black Powder.”
Development Center, USA ARRADCOM, Dover, NJ.

Davis. The Chemistry of Powder and Explosives. Angriff Press. Hollywood, CA: 1972.

Johnstone and Gore. “The Manufacture of Industrial Grade Charcoal in Armco Robson
Kilns.” Charcoal Section, National Timber Research Institute, Pretoria, Republic of South

Africa.

Sasse. “A Comprehensive Review of Black Powder.” Ballistic Research Laboratory,

USA ARRADCOM, Aberdeen Proving Ground, MD: 1985.

122

ADDITIONAL WORKS CON SULTED

Sasse. “Characterization of Charcoal Used to Make Black Powder.” Ballistic Research
Laboratory, USA ARRADCOM, Aberdeen Proving Ground, MD.

Sasse. “Characterization of Maple Charcoal Used to Make Black Powder.” ARBRL-TR-
0332, Ballistic Research Laboratory, USA ARRADCOM, Aberdeen Proving Ground,

MD: 1983 (AD A136513).

Sasse and Rose. “Comparison of Spherical and Ellipsoidal Form Functions for Evaluating
Black Powder.” Ballistic Research Laboratory, USA ARRADCOM, Aberdeen Proving

Ground, MD.

Urbanski. “On Charcoal as an Ingredient of Black Powder and Some Pyrotechnic
Mixtures.” Explosivstofle 1963, 9: 200.

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