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DATE DUE DATE DUE DATE DUE 6/01 cJCIRC/DateDuepss-p. 15 TH THE CHEMICAL COMPOSITION OF BLACK POWDER SUBSTITUTES By Jennifer Marie Yezek A THESIS Submitted to Michigan State University in partial fiilfillment of the requirements for the degree of MASTER OF SCIENCE Department of Criminal Justice 2000 T destructi used in t ponder. lower ign prOdUCIlO determine ““151 be k1 “Vera! tec ABSTRACT THE CHEMICAL COMPOSITION OF BLACK POWDER SUBSTITUTES By Jennifer Marie Yezek The challenge at a bombing or other explosion scene is to determine the type of destructive device and filler used. A strong percentage of improvised explosive devices used in bombings in the United States incorporate the use of the low explosive, black powder. Unfortunately, there are many problems with using black powder due to its lower ignition temperature, its poor efficiency, and its tirne-consuming and dangerous production. Thus, black powder substitutes are also being used as fillers. In order to determine the existence of black powder substitutes in evidence, their chemical properties must be known. This chemical characterization can be successfully completed using several techniques on both the intact powder and the residue. The useful characterization steps are x-ray diffraction (XRD), spot tests, ion chromatography (1C), capillary ion analysis (CIA), and high performance liquid chromatography (HPLC). These tests will be run on Golden Powder, Black Canyon Powder, Black Mag Powder, and Clean Shot Powder. Black Powder and PyrodoxR will also be tested for confirmation and comparison purposes. After determining the compositions of the black powder substitutes, analysts will be able to use the information to eliminate certain sources and identify possible sources in low explosive cases. LIST OF 1 LIST OF T BTRODL BACKGRi Bla BLT Bla Cle C Is Go! P}TI EXPERIM: X-r: Spo Ion TABLE OF CONTENTS LIST OF TABLES ............................................................................................................... v LIST OF FIGURES ............................................................................................................ vi INTRODUCTION ............................................................................................................... 1 BACKGROUND INFORMATION Black Powder ........................................................................................................... 2 Black Canyon Powder .............................................................................................. 6 Black Mag Powder ................................................................................................... 7 Clean Shot Powder ................................................................................................... 7 Clear Shot Powder ................................................................................................... 7 Golden Powder ......................................................................................................... 8 Pyrodcx .................................................................................................................... 8 EXPERIMENTAL X-ray Diffraction (XRD) ....................................................................................... 10 Spot Tests ............................................................................................................... 10 Ion Chromatography (IC) ...................................................................................... 12 Capillary Ion Analysis (CIA) ................................................................................. 14 High Performance Liquid Chromatography (HPLC) ............................................ 15 RESULTS X-ray Diffraction ................................................................................................... 17 Spot Tests ............................................................................................................... l7 Ion Chromatography .............................................................................................. 20 Capillary Ion Analysis ........................................................................................... 21 Comparison of IC & CIA ....................................................................................... 22 High Performance Liquid Chromatography .......................................................... 23 DISCUSSION X-ray Diffraction ................................................................................................... 23 Spot Tests ............................................................................................................... 26 Chromatographic Methods ..................................................................................... 29 High Performance Liquid Chromatography .......................................................... 37 CONCLUSION .................................................................................................................. 39 APPENDIX I Analytical Results .................................................................................................. 44 Compilation of Analysis Results ........................................................................... 47 Photographs ............................................................................................................ 50 APPENDIX Spot APPENDI X XRT APPENDIX IC R APPENDI) HPI REFEREN APPENDIX II Spot Test Results ................................................................................................... 52 APPENDIX III XRD Results .......................................................................................................... 65 APPENDIX IV [C Results ............................................................................................................... 72 APPENDIX V HPLC Results ...................................................................................................... 139 REFERENCES ................................................................................................................ 143 Percentage Bumed Bla. Analnical i Description Major Anio Major Anio Intact Com] RCSICIUC C0 LIST OF TABLES Percentage of Black Powder Used as Filler ........................................................................ l Burned Black Powder Composition .................................................................................... 3 Analytical Capillary Ion Analyzer Paramaters .................................................................. 15 Description of Black Powder and its Substitutes ............................................................... 17 Major Anionic and Cationic Species in Intact Powders .................................................... 22 Major Anionic and Cationic Species in Residue Powders ................................................. 22 Intact Composition of Powders .......................................................................................... 41 Residue Composition of Powders ...................................................................................... 42 Schematic l 1 Schematic . l Schematic l LIST OF FIGURES Schematic of Ion Chromatograph for Cation Analysis ...................................................... 13 Schematic of Capillary Ion Analyzer ................................................................................. 15 Schematic of High Performance Liquid Chromatograph .................................................. 16 vi Tl Introdut whether I} determine ( improvise IOW explt‘ the Burea themest r dexices a: ( Pen The Chemical Characterization of Black Powder Substitutes Introduction The primary challenge at a bombing or other explosion scene is to determine whether the act was accidental or intentional. If the latter, the examiner must then try to determine the type of destructive device and filler used. A significant percentage of improvised explosive devices used in bombings in the United States incorporate fillers of low explosives such as black powder.l According to prior and recent statistics outlined in the Bureau of Alcohol, Tobacco, and Fiream’s Arson and Explosives Incidents Report, the most recent yearly percentages for usage of black powder as a filler in destructive devices are as follows: Table 1. Percentage of Black Powder Used as Filler2 (Percentages adjusted to include only destructive devices and to avoid duplicate recordings) YEAR % Black Powder 1993 27 1994 35 1995 23 1996 20 1997 19 Due to the knowledge of the products and reactants of black powder, trained laboratory personnel and investigators can and do determine the nature of the explosive(s) used in the device(s) at bombing scenes. However, there is not an abundance of information available on black powder substitutes. The scant information found was obtained from gun magazines, which are concerned mostly with the ability of forensic c As users t tum to bl. aVailahle bombs. m that these filIUI'e plp Ti PIOpem'eS COmPOSII I4 Subgthme. intact pofi Backgr Black P ODS K\‘( has no, ch DroduCeS black powder substitutes to perform in hunting and competitive shooting situations. There was even less information found about the chemical composition and properties of the substitutes in the few relevant academic papers. Despite the shortage of available information, there is a definite need for the forensic community to understand the chemical composition of black powder substitutes. As users of black powder become more irritated with its shortcomings, they will begin to turn to black powder substitutes. These substitutes will then become more readily available on the market. Since the majority of cases received at ATF labs are pipe bombs, many of which contain black powder or PyrodexR, there is a distinct possibility that these same black powder substitutes used in muzzle-loading firearms will appear in future pipe bombs as well. To determine the existence of fillers in arson and explosive cases, their chemical properties must be known. There is virtually no literature on either the chemical composition of the pure black powder substitutes or their residues. None of the literature individually or collectively serves to provide a justifiable chemical characterization of the substitutes. Thus, it is extremely beneficial to perform various chemical tests on both the intact powders and their combustion residues in order to characterize the powders. Background Information Black Powder Originally used in simple blasting operations, black powder is a ternary mixture of 75 KNO3: 15 charcoal/carbon black: 10 sulfur. This approximate 6:1:1 composition has not changed drastically since 1781.3 Deviating considerably from this formula produces burning that is much slower and much less vigorous. Potassium nitrate serves Enron chdor black to ; fi’om the 5 white smt burned pt as the oxidizer, while charcoal and sulfur serve as the combustible materials, or firels. The color of black powder is initially dark gray. When tumbled with graphite, or carbon black, to glaze the surface, it becomes black. Black powder is non-porous and burns from the surface, which becomes progressively smaller as the burning continues. The white smoke contains small, solid particles. Although the percent composition of the burned powder by volume varies from source to source, general guidelines are as follows: Table 2. Burned black powder composition3 Gaseous Products % Solid Products °/o Carbon dioxide 49.29 Potassium carbonate 61.03 Carbon monoxide 12.47 Potassium sulfate 15.10 Nitrogen 32.90 Potassium sulfide 14.45 Hydrogen sulfide 2.65 Potassium thiocyanate 0.22 Methane 0.43 Potassium nitrate 0.27 Hydrogen 2.19 Ammonium carbonate 0.08 Carbon 8.74 Sulfur 0.08 The chemical reactions that occur during combustion are complex These reactions have been extensively studied with sometimes unequivocal results."8 Since the major products result from the oxidation of sulfirr and charcoal, the extent of this oxidation influences the variety and intensity of intermediate products observed. The extent of the oxidation is itself influenced by the combustion or explosion conditions. Tenny L. Davis, in his chapter on black powder in the book, Chemistry of Powder and Explosives, states the uses of black powder as the following: It is used in petards, as a base charge or expelling charge for shrapnel shells, in saluting and blank fire charges, as the bursting charge of practice shells and bombs, as a propelling charge in certain pyrotechnic pieces, and, either with or without the admixture of other substances which modify the rate of burning, in the time-train rings and in «he parts of titses.3 It supplant; ballistic functiom smokele R closer Iar hunting ii retailers a hunting 5 31061! Po Field an, l black p0 impact 5 ha? alst Shots, 0r Add it im high am “Please experlSit flame- In this country, the use of black powder as a blasting powder has been supplanted by blasting powders containing sodium nitrate. With this shifi in function, the ballistic effects of black powder have become even more important. Black powder functions as the propellant in muzzle-loading firearms. Due to dangerous pressures, smokeless powders carmot be substituted for the propellant. Recently, black powder firearms have become more popular. They require a closer range for hunters. This closer range expands hunting opportunities for ethically hunting most game in North America. Due to this renewed popularity of black powder, retailers are offering more muzzle-loading products and states are offering special hunting seasons. There are also several magazines devoted to black powder, such as Black Powder Cartridge News and Black Powder Journal. Other magazines, such as Field and Stream and Handloader, regularly cover black powder shooting and hunting. Unfortunately, there have been many claims about problems encountered with black powder. With its lower ignition temperature of 300°C, it is extremely sensitive to impact friction. Thus, handling and storage procedures must be strictly observed. There have also been concerns over the ability of black powder to build up residue between shots, or fouling. Other claims cite the presence of observable corrosive material. Additionally, black powder combustion products are 56 percent solid materials.9 This high amount of solid combustion products results in poor efliciency and huge amounts of unpleasant smoke. Finally, the manufacture of black powder requires heavy and expensive material as well as being time-consuming and dangerous. Throughout recent history, improvements have been sought for a cleaner, flashless, smokeless, and noiseless powder. Although smokeless powder is safer to handle a: isused. ' powder a the fires COmposit presence :8» 5' .' handle and store, it can produce dangerously high pressure levels if too much propellant is used. Thus, the invention of a product with the low pressure characteristics of black powder and the safer characteristics of smokeless powder would be greatly appreciated in the firearms community. Since the 1970s, there have been many patents dealing with new methods and 9-11 compositions of explosives. These altered compositions suggest an emergence in the presence of black powder substitutes. For example, Patent USO4497676 states: A gunpowder substitute whidi is capable of also being molded into a consumable cartridge or cartridge case comprising between 50% to 75% by weight of an inorganic nitrate and between 25% to 30% by weight of an organic acid including ascorbic acid, erythorbic acid and mixtures thereof. Or similarly: A pyrotechnic composition useful for gunpowder, propellant or explosive purposes, which comprises an organic acid such as ascorbic or erythorbic acid, a nitrate salt oxidizer, and about 6- 15% of potassium perchlorate, has improved properties including reduced residue.11 The basic principle in developing a black powder substitute is mixing an oxidizing salt with a combustible material. One black powder substitute, PyrodexR, is a commercial success patented by the Hodgdon Powder Company. It claims to burn cleaner and alleviate the fouling and clean-up procedures between shots necessary with black powder. It also claims to provide more consistent pressure and velocity as well as being less sensitive to ignition.12 With its success and the recurring inconveniences of black powder, it is highly probable that other black powder substitutes will appear on the explosives market as long as funds are available for the necessary research and development. Currently, both information and availability of black powder substitutes are extremely scarce. An exhaustive search for more information on these substitutes was only slightly productive. Besides the commercially successful Pyrodcx“, there is no mention of the chemical composition of the other black powder substitutes in any of the examine. obsenatj Powder. The resp I h as An C‘m'd'. successft phone nt Block P Manufar Claim; } equll‘aler Observarr Veloclllet, (Om-"m bms IS It be loader: only One examined literary materials. Thus, the only available information relies on the observations and claims of effectiveness listed in the following section. Attempts to contact the manufacturers were fi'uitless. For Black Canyon, Golden Powder, and thk Mag there was no response to phone calls, letters, or e-mail inquiries. The response to an e-mail for more information on Clean Shot read as follows: Unforttmately, we can not release the ingredients in our product and the percentages for a study to be published as a thesis. We only release this information after we have obtained a confidentiality agreement from the person, organization, or government agency to which we release the information. Our patent application for this product has not been granted yet and for that reason we do no disclose this information without the confidentiality agreement. Our confidentiality agreement specifically states that any information that is released can not be published or used in any way that would cause harm to our organization. We hope that you understand that this precaution is taken because of the significant amount of money that went into developing om' formulation and how releasing this information could harm our company. An e-mail from Clear Shot related the same information. Although there was no successful avenue for obtaining information fiom any manufacturer, the addresses and phone numbers used for contact purposes are listed below. Black Powder Substitutes 1. Black Canyon Powge 3'" Manufacturer: Legend Products Corporation; Las Vegas, NV 89125; 702-593-6722 Claims: heavy compression necessary in order to work properly; sweet, non-toxic taste; equivalent weight to black powder Observations: no staining, leading, or fouling afler 25 Shots; consistent, slightly higher velocities; moisture resistant; more complete burn due to higher burning rate Concerns: problems with clean-up and storage; green and blue oxidation formed when brass is left uncleaned; film of orange dust formed at the breech end of the rifling; must be loaded by weight, not volume; only comes in one granulation; extremely hydrophylic; only one granulation available 2. Black Mann/at Claims: _ fouling: 5 Observar patches: Concern 2. Black Mag Powder” Manufacturer: Arco Company; PO. Box 101, Mayor, FL 32066; 904-294-3882 Claim: moisture resistance; faster ignition; consistent velocity; non-corrosive; non- fouling; safe; non-toxic; and clean Observations: lower peak pressure; no noticeable residue afier swabbing with two patches; quick and dependable ignition; no signs of rust formation; slower burn Concerns: $25.00 per pound; very difficult to find 3. Clean Shot Powder’“7 Manufacturer: Clean Shot Technologies, Inc.; 21218 St. Andrew’s Boulevard, Suite 504, Boca Raton, FL 33433; 888-886-2532; www.cleanshots.com/product.htm Claims: no nitrocellulose; no sulfur fouling, corrosion, or odor; no cleaning necessary between shots; safer than black powder; similar ballistic pressure curves to black powder Observations: no fouling build-up; less cleaning time; accurate; no swelling of cases Concerns: indeterminable “shelf-life”; overloading creates dangerous pressures; sensitive to moisture and humidity; threatening ignition and combustion problems 4. Clear Shot Powder" ‘ Manufacturer: Goex; PO. Box 659; Doyline, LA 71023-0659; 318-382-9300 Claims: contains no ascorbic acids or perchlorates; clean burning; non-corrosive; not hygroscopic; indefinite shelf life; consistent velocities; low pressures; easy clean-up Observations: none Concerns: impossible to find despite claims of its availability in 1999 5. Golda. Menu/a B.C., C 3' Claims: applicati Observe. Conant Mimi Manufa. 66201; 9 Uremic? dici'andi Oaths: Clean bet black p0 Observm Concern Experl Bth M AICOhO L 5. Golden Powde ’-" Manufacturer: Golden Powder International; 701 -1470 Pcnnyfarthing Drive, Vancouver, BC, Canada V6J4Y2; 604-731-4637 Claims: even burn rate; able to be compressed, formed, and handled lead to various applications; non-corrosive Observations: lab reports show it will perform; black stuff in bore was wiped out Concerns: difficult to obtain; no performance figures 6. flrodcxn’” Manufacturer: Hodgdon Powder Company; P.O. Box 2932, Shawnee Mission, KS 66201; 913-362-9455 Chemical Composition: potassium nitrate, potassium perchlorate, sodium benzoate, and dicyandiamine Claims: more shots per pound; cleaner burn which alleviates fouling and the need to clean between shots; consistent pressures and velocities; performance comparable to black powder; safer alternative to black powder; less sensitive to ignition Observations: much less fouling than black powder Concerns: still some fouling; no significant improved performance over black powder Experimental Samples of Goex Black Powder FFFg, Pyrodcx RS, Clean Shot Powder, and Black Mag Powder were obtained fi'om the low explosive collection at the Bureau of Alcohol, Tobacco, and Firearm’s National Laboratory Center in Rockville, Maryland. Samples of Golden Powder and Black Canyon Powder were obtained from reference samples in a collection compiled by Charles Midkiff, a senior forensic chemist at the ATF National Laboratory Center. Samples of all six powders were burned in open air and atmospheric pressure conditions. In order to obtain burned residue from the powders, .05 g of each substitute powder was placed in the bottom of a clean crucible. Once the crucible was placed in a hood, a wooden stick was lit and quickly placed in the powder. The residue was recovered fi'om the crucible by using approximately 10-20 mL deionized (DI) water. This mixture was then filtered for purity and the filtrate was diluted to suitable concentrations for analysis. Five different analyses were performed on the six powders and are outlined below. Each analysis was performed on both the intact powder and the burned residue with the exception of x-ray diffraction and capillary ion analysis. These two tests were only run on the intact powder. In the case of x-ray diffraction, there was an insufficient amount of residue from the powder combustion for analysis. In the case of capillary ion analysis, there was a limited amount of personnel knowledgeable in the operation of the instrument and its intracacies. Additionally, several physical properties of the intact powder particles were observed visually. Since this observation was done only with the naked eye and a low- power (12X), binocular laboratory microscope, its findings will be recorded in the results section without further discussion. X—ray Difii'action (MD) The original samples of the intact powder were crushed using a mortar and pestle. The sample was then placed evenly in the well of a slide. The analyses were performed using a Scintillation Phillips 3100 X-ray Generator (XRG) and a Long Fine Focus Cu Anode X—ray tube. 45 volts and 35 amps were applied to each powdered sample. Each sample was then measured from an angle of 5 degrees to an angle of 60 degrees.21 The approximate run time was 30 minutes. Spot Tests Ammonium IonI Nitrate, NitriteI OxillggrI Perchlorate, and Ibiggzanatc Tests 2-3 drops of the reagent were added to 4-5 drops of the sample powder in a white spot plate using a disposable pasteur pipette. Charles Midkiff prepared the reagents listed below: Ammonium Ion T est) 2 I. Nessler ’s Reagent- A.P.H.A. (Fisher SO-N-16 or equivalent) Nitrate and Nitrite Tests22 1. Sulfanilic Acid Solution- 1g ACS Reagant Grade Sulfinilic Acid by warming in 100 mL of 30% acetic acid (aqueous) 2. N-I-mphtlwlethylemediamine dihydrochloride Solution- 1g of ACS Reagent Grade in 100 mL of 70/30 ethanol/acetic acid solution. 3. Zinc Powder- fine 10 Oxidizer Test” 1. Sulfirric Acid-18M- ACS Reagent Grade 2. Diphenylamine- 1 g in 100 mL concentrated sulfuric acid Perchlorate T est] 3 I. Methylene Blue- 0.03-0.05% aqueous solution Thiogzanate Test” 1. Ferric Chloride Solution- 1 g ACS Reagent Grade Fer in 10 mL high resistance deionized water, 10% aqueous Chlorate and Sgltule: Tess Afier acidifying 34 drops of the sample powder with 1-2 drops of 6N nitric acid, 2-3 drops of the reagent were added to the acidic sample in a small glass vial using a disposable pasteur pipette. Charles Midkiff prepared the reagents listed below. 1. Silver Nitrate Solution— 1 g ACS Reagent Grade AgNO; in 100 mL of high resistance deionized water, 1% aqueous 2. Nitric Acid- 20 mL ACS Reagent grade HNO3 to 50 mL high resistance deionized water, 6N same Test” After acidifying 3-4 drops of sample powder with 1-2 drops of hydrochloric acid, 2-3 drops of the reagent were added to the acidic sample in a small glass vial using a disposable pasteur pipette. Charles Midkifi‘ prepared the reagents listed below. I. Barium Chloride Solution- 5g ACS Reagent Grade BaClz in 100 mL high resistance deionized water, 5% aqueous ll Dl Wale Dig-ital arrange Sampk ChymT anda‘ Sulfate COhIn 2. Hydrochloric Acid- 25 mL ACS Reagent Grade HCl in 50 mL high resistance deionized water, 6N Sultur Tes?‘ Afier weighing several grains of the sample and a piece of filter paper, the sample is rinsed with approximately 10-20 mL of hot water. After allowing the filter paper to dry and re-weighing it, the sample is then rinsed with approximately 10-20 mL of pyridine. Finally, the filter paper is dried and re-weighed one final time. The loss in weight is recorded. Ion Chromatography (I C) The original samples of the intact powder and burned residues were diluted with DI water until they produced a reading of approximately 50 ppm on a Fisher Scientific Digital Conductivity Meter. The samples were then placed in individual 0.5 mL vials and arranged into a cassette. This cassette was mounted in a Dionex AS40 Automated Sampler connected to the IC. The analysis was performed on a Dionex CX 500 Ion Chromatograph equipped with a 25 pl injection loop, a DS-3 Conductivity Cell Detector, and a ASRS-ULTRA Auto Self-Regenerating Suppressor. The analytical separation of chlorate, nitrite, chlorate, nitrate, phosphate, and sulfate were performed with Dionex columns: Dionex 4 mm ASll Ion Pac Analytical Column, Dionex 4 x 50mm AGll Ion Pac Guard column, and an Anion Trap Cartridge (ATC). The eluent was sodium carbonate. The analysis time was 22 minutes. 12 column 50mm . 60mM runata Dionex usedIS. forasc Inja For the analytical separation of thiocyanate and perchlorate, the following Dionex columns were used: Dionex 4 x 250mm ASl6 Ion Pac Analytical Column, Dionex 4 x 50mm A616 Ion Pac Guard column, and an Anion Trap Cartridge (ATC). The eluent is 60mM KOH which flowed at a rate of 1.0 ml/min. The analysis time was 15 minutes and run at a temperature of 30 degrees Celsius. Cation separation was also performed using the following Dionex columns: Dionex 4mm C812 and Dionex 4 x 50mm CG12 Guard Column. The isocratic system used lSmM Methanesulfonilic Acid (MSA) as its mobile phase. Please refer to Figure 2 for a schematic diagram of the IC instrumentation used in the tests. Eluent Electro- Su Conduc- R Pump chemical pm: ”my coast-er Cell sor Cell ° Injection Port Re- Reeorder +— U V Cell la Waste corder Figure 2. Schematic of Ion Chromatograph for cation analysis.” For cation analysis, the suppressor column contains a strongly basic exchange resin in the hydroxide form. This basic exchange resin is necessary for two important conversions. First, the conductive species hydrochloric acid is converted into water as seen in reaction 1 below. Second, the cations present in the sample (W) are converted into their 13 correspc reaction: 1. Resin- 2. Resin- 1 resin in 1 importar sodium 1 Reactior acidic fc I. Resir 2. Resir Capillt; prOdUCe COndqu Sample i Placed i. Capillar A Schei': corresponding bases, which are free to migrate through the column. The illustrative reactions are listed below. 26 1. Resin-N+OH' + I-FCI' -———> Resin-N+Cl' + H20 2. Resin-N+OH' + Y+Cl' ——> Resin-N+Cl' + TOH‘ For anion analysis, the suppressor column contains a strongly acidic exchange resin in the hydrogen form. This acidic exchange resin is again necessary for two important conversions. Reaction 1 diagrams the conversion of the conductive species sodium bicarbonate into carbonic acid, which dissociates into water and carbon dioxide. Reaction 2 diagrams the conversion of the anions present in the sample (X') into their acidic forms.26 I. Resin-803'}? + Na+I-ICO3 ———+ Resin-SO3'Na+ + H2CO3 2. Resin-SO3'H+ + Na+X' —_" Resin-SO;'Na+ + HTX‘ Capillary Ion Analysis (CIA) The original samples of the intact powder were diluted with DI water until they produced a reading of approximately 15 ppm on the Fisher Scientific Digital Conductivity Meter. After 1 drop of the internal standard is added to the bottom of a sample vial, 0.5 mL of the sample is placed in the vial. The sample vials were then placed in a carousel in the autosampler. The analysis was performed on a WatersTM Capillary Ion Analyzer. Analytical parameters appear in Table 3 on the following page. A schematic diagram of CIA also appears as Figure 3 on the following page. 14 Electrolj l I l Capillarj ; Power l Supply 5 Applied i Voltage E 1 Internal M : DClettioc \ 2T7 F r ”-53,: Per Table 3. Analytical Capillary lon Analyzer Parameters Electrolyte 4.3 mM sodium Waters IonSelectTM Low chromate, 0.48 mM mobility Cation TTAB, pH8 Electrolyte (2- Hydroxyisobutyric acid, 4-methylbenzylamine, and l8-crown-6 ether) Capillary 60 cm x 75 pm fused 60 cm x 75 pm fused silica silica Power Positive Voltage Negative Voltage Supply Applied 20 KV 15 KV Voltag Internal Cesium Barium Standard Detection Indirect UV at 214 nm Indirect UV at 254 nm Electrodes Detector tics Capillary Op \ Capillary ._ Positive ‘ High Voltage Power Supply Electrolytic Vial, Electrolyte Electrolytic Vial, ' Sample Side Receiving Side Figure 3. Schematic of Capillary [on Analyzer". High Performance Liquid Chromatography (HPLC) The HPLC used to detect benzoic acid and/or dicyandiamide (DCDA) consisted of a Waters 6000A pump (Waters Associates, Milford, MA) and a Waters model 441 absorbance (UV) detector. The column used was a Polypore H', 4.6mm x 100 mm. manufactured by the Pierce Chemical Company (Rockville, 1L). All solvents were HPLC grade. The chromatograms were recorded on a Hewlett-Packard HP3396 Series II Integrator. The mobile phase was 10% methanol in .OlN sulfuric acid. The eluent was pumped through the column at 1.0 mL/min and was monitored by the UV detector at 230 nm. Each sample was approximately 50 ppm with an injection volume of 5 pl. This procedure was used on the powder extracts and residues. Please see Figure 4 below. Solvent Supply Solvent lflleCllon Delivery System System Column Souvent Waste Detecto: Figure 4. Schematic of High Performance Liquid Chromatogram Results Visual Analysis The results of this section were done quickly. The color was solely determined by the human eye. whereas the shape and texture of the particles were determined with the aid of a microscope. General results appear in the table on the following page. Please 1 Black 5 photogl Please refer to the last page of Appendix I for photographs of all the powders except Black Mag. There was not a sufficient amount of this substitute powder for a suitable photograph Table 4. Description of Black Powders and its substitutes Color Shapefl‘exture Black Powder Black Pyramidal slabs Pyrodcx Dark Gray Stony, rounder Golden Powder Golden Irregular, jagged Black Canyon Light brown Stony, smoother Black Mag Tan Stony Clean Shot Gray Stony, blotched X-ray Difihaction Analysis If a crystalline material is present, x-ray diffraction can serve to characterize the compounds present. Due to the repetitive arrangement of atoms in a crystal lattice, the x- rays directed at these regions will diffract at a given wavelength to form a characteristic pattern. This analysis revealed several of the powders to be similar in composition. Potassium nitrate was present in all six powders. Both Golden Powder and Black Canyon powder also contained ascorbic acid. Clean Shot Powder and Black Mag Powder contained ascorbic acid and potassium perchlorate as well. The formula of Pyrodcx“ is patented and contains sulfilr, sodium benzoate, potassium nitrate, and potassium perchlorate. Black powder’s composition has been known for several centuries to be potassium nitrate, sulfur, and charcoal. Please see Appendix II for relevant data. 17 Spot 7t their re- color 0.? anions 1 plates 3 solutior results = “lien t red pret only p0 LOW Ct‘ PreCipi Clean. Spot Tests These tests are an initial screening technique for suspected intact explosives and their residue. When a known reagent reacts with an unknown solution, a characteristic color or precipitate is formed. This result is then used for further identification of the anions and/or cations present. These tests are simple, requiring only disposable spot plates and pipettes, glass well slides, test reagent solutions, known anion and cation test solutions, and drops of the unknown solution. Please see Appendix III for complete results and observations. When the ammonium ion is present in a strongly basic solution, NH3 is liberated. When the Nessler’s reagent, a mixture of KI and Hglz, is mixed with ammonia, an orange red precipitate, HgIz'HgNHzl, is formed.22 This color is indicative of ammonia salt. The only positive result for this test was the black canyon residue. In an acidic solution, the chloride ion, a Group 1 anion, reacts with silver nitrate. Low concentrations produce turbidity while higher concentrations produce a white precipitate. The significant, positive results for this test were the residues of PyrodexR, Clean Shot, and Black Mag. In a mildly acidic solution, nitrites react with primary amines to form diazonium cations, which result in highly colored azo dyes in further reactions.22 The dyes produce an intense red color that is readily observable at low concentrations. This analysis is known as the Greiss Spot Test. The residues for all six of the powders tested were significantly positive. Unlike nitrites, nitrates do not react with primary amines to form diazonium cations or colored azo dyes. However, when a reducing agent is added, nitrates can be 18 reduced to nitrites and will then react to form the azo dyes.22 Significant positive results for this spot test, coined the Modified Griess test, included all six of the powder extracts and powder residues. The extracts formed more intense colors than the residues. Oxidizers can be detected by color formation when in the presence of diphenylamine in concentrated sulfuric acid.22 This test is a preliminary screening analysis for the presence of nitrate, nitrite, and chlorate. Nitrate forms an immediate and permanent ultramarine. Both nitrite and chlorate form a dark blue color. However, this blue color fades to a yellow green in the presence of nitrites. Positive results indicative of nitrites were found in the residues for Pyrodcx“, Clean Shot, and Black Mag powders. In the presence of the methylene blue cations, perchlorates form violet precipitates23 This positive reaction was seen strongly in the water extracts of PyrodexR, Clean Shot, and Black Mag and less strongly in their residues. When sulfates are placed in an acidic solution with barium chloride, turbidity ensues at lower concentrations and a white precipitate forms at higher concentrations.” Significant, positive results were obtained in the residues of black powder and PyrodexR. Trace amounts were observable in the residues of Black Canyon, Golden Powder, and Black Mag. However, these results may be attributed to the use of a black powder- containing fuse for initiation. The detection of thiocyanate is obtained by reacting it with ferric chloride in an acidic solution.24 In this acidic solution, a blood red color is indicative of thiocyanate. Positive results were seen with black powder, Pyrodcx“, and Clean Shot residues. The presence of sulfur in a black powder formulation can be determined. Once the potassium nitrate is dissolved in hot water and filtered out of the solution, pyridine is 19 then ac equal 1 Canyo: black r be scra Ion Ci: capable nitrite. I analysi ammor minute- IEprodL deteCta' exPlosi a gradie for r€le A "01,118 i , Worm, CleanS then added. After the filter paper is dried, it is re-weighed. The difference in weight is equal to the amount of sulfur present. For Golden Powder, Clean Shot, and Black Canyon, the weight differences were all .01 g. Thus, there was no sulfur present. The black material left on the filter paper was indicative of charcoal. However, it could not be scraped from the filter paper and thus not ignited for further confirmation. [on Chromatography The ion chromatography system used in the ATP National Laboratory Center is capable of running anion and cation analysis simultaneously. The anion run for chlorate, nitrite, chlorate, nitrate, phosphate and sulfate is completed in 22 minutes while the anion analysis for thiocyanate and perchlorate is 15 minutes. Cation analysis for sodium, ammonium, potassium, magnesium, calcium, strontium, and barium is complete in 16 minutes. With the installation of the autosampler, the time in between runs becomes reproducible and appears to improve reproducibility of the final, analytical results. The detectable anions and cations included in the standard are those ions characteristic of low explosives and their residues. Two separate anion analyses are used to prevent the use of a gradient system that can present many operational problems. Please see Appendix IV for relevant chromatograms. Analysis of Anions by [C As evident in Table l, nitrate was present in the extracts of all six of the powders examined. Perchlorate was also evident in the extracts of Pyrodcx“, Black Mag, and Clean Shot. 20 In the residues of all six of the powders, nitrate was present. Additionally, black powder and PyrodexR residues indicated the presence of the thiocyanate and sulfate ions. Finally, PyrodexR, Black Mag, and Clean Shot residues also showed the presence of chloride and small traces of perchlorate. Analysis of Cations by [C The major cations detected in the extracts of the six powders were sodium and potassium. To a lesser extent, calcium was detected in each sample. The ammonium ion was also present in the residues of Pyrodcx, Golden Powder, Black Canyon, and Clear Shot. Traces of magnesium were also found in Clear Shot and Black Canyon. Capillary Ion Analysis This system achieves separation by applying a high-voltage potential across 3 60cm x 75pm uncoated fused silica capillary with each end inserted in an electrolyte reservoir. The ions present in the sample migrate according to their electrolytic conductivity relative to the electrolyte solution. This solution contains a UV-absorbing species and samples are detected by absorbance loss as they displace the buffer in the detector’s light path. Careful maintenance of the electroosmotic flow rate, pH, and the age of the buffer solution are necessary to obtain reliability in this method. This technique helps confirm IC peaks by serving as a complement to it. It is more sensitive; a typical separation efficiency is 70,000 plates as opposed to 3,000 for IC. The cation standard was identical to the IC standard. The anion standard also included the carbonate anion. 21 Analysis of A nions by CIA The anions present in all six of the powder extracts were nitrate and carbonate. Perchlorate was indicated in the extracts of PyrodexR, Black Mag, and Clean Shot. Analysis of Cations by CIA The cations found in the sample powders were much more consistent. Significant amounts of potassium, calcium, and sodium ions were found in all of the extracts along with a smaller amount of magnesium. The fact that the potassium peaks were the largest is not surprising since potassium nitrate is the primary oxidizer in each. Comparison of 1C, ICA, and Spot Test Results According to the analyses listed above and Appendix I, the major anionic and cationic species in the extracts of the powders and residues are listed below: Table 5. Major anionic and cationic species in intact powders ANIONS CATIONS Black Powder Nitrate, sulfate Sodium, potassium, calcium Pyrodcx Nitrate, sulfate, perchlorate Sodium, potassium, calcium Black Canyon Nitrate Sodium, potassium, calcium Golden Powder Nitrate Sodium, potassium, calcium Black Mag Nitrate, perchlorate Sodium, potassium, calcium Clean Shot Nitrate, perchlorate Sodium, potassium, calcium Table 6. Major anionic and cationic species in residue powders ANIONS CATIONS Black Powder Nitrite, nitrate, thiocyante, sulfate Sodium, potassium Pyrodcx Chloride, nitrite, sulfate, chlorate, Sodium, potassium, calcium, thiocyanate, perchlorate ammonium Black Canyon Nitrite, nitrate Sodium, potassium, ammonium Golden Powder Nitrate, nitrate Sodium, potassium, ammonium Black Mag Chloride, nitrite, nitrate, chlorate, Sodium, potassium, calcium perchlorate Clean Shot Chloride, nitrite, nitrate, chlorate, Sodium, potassium, calcium, thiocyanate, perchlorate ammonium 22 reVeal ; comm High Performance Liquid Chromatography Analysis Although black powder, PyrodexR, and black powder substitutes share some common chemical components, PyrodexR also contains sodium benzoate and dicyandiamide.29 It is much easier to differentiate between residues if unique species are present in a powder. After applying every powder, both extract and residue, to the appropriate solvent system and method to detect benzoic acid and DCDA, PyrodcxR remained the only powder of the six to contain these two chemical species. Please refer to Appendix V for relevant data. Discussion X -ray Difii'action Due to the almost unique crystalline structure of materials, identifying materials by the shape of their crystals is a useful method. The external shape of a crystal is a reflection of its interior and the external faces of the crystal are parallel to the lattice planes. The lattice planes are characteristic of a crystal. The powder diffraction method involves X-ray beams striking the crystal whose lattice planes then diffi'act the beam and produce a line. From this line, corresponding interplanar spacings are calculated. The spacings calculated from the three most intense lines are then used to identify the crystal and its materials.21 Although similar crystal patterns may appear, the actual components of the crystal influence the intensities of the lines of the powder pattern. Identification of these materials involves recognizing their patterns. X-ray diffraction offers several advantages. Unlike chromatography methods that reveal the ions present, x-ray diffi'action reveals their combinations; it will identify the compounds in a sample. It is also capable of differentiating between several crystalline 23 forms of the same compound as well as identifying various hydrates. Second, the method is non-destructive and requires only a small sample volume for accurate and rapid results. However, there are correlating disadvantages as well. The sample must be in the powdered form. Although sometimes this involves only crushing a solid sample, other times this may involve an attempt to recover a solution, which is a tenuous situation in many instances. Additionally, if a material represents only a few percent of the total sample, its presence may not be recorded. Finally, the materials in the sample will only be identified if the known material is included in the database searched by the sofiware used for analysis. The x-ray diffraction patterns were measured from five degrees to sixty degrees in increments of 0.02. The analysis and identification of the peaks were completed using JADE for Windows software.30 This software uses powerful computerized techniques to automatically find and characterize peaks. All samples were searched for inorganic peaks first. If peaks remained, a search of organic materials ensued. Black powder revealed the compounds it is known to contain, i.e. potassium nitrate and sulfur. The charcoal does not have a crystalline form and is therefore not observed. This x-ray pattern has remained relatively unchanged for over 100 years.3 ' PyrodcxR also revealed no surprises in its composition. Like black powder, it contains potassium nitrate and smaller amounts of sulfur. It also contains the stabilizer sodium benzoate and the additional oxidizer potassium perchlorate.9 Because one objective of black powder substitutes may be to remove sulfur and its disagreeable effects, it was no surprise that none of the diffraction patterns of four of 24 the substitute powders revealed the presence of sulfur. Golden Powder, Black Canyon, Black Mag, and Clean Shot Powder all contained potassium nitrate and ascorbic acid. Ascorbic acid, C6H306, or Vitamin C, has known antioxidant and food preservative properties. In the past ten years, ascorbic acid has also been studied as an additive in explosive compositions. Since it is less susceptible to ignition by friction and can sustain pressure for higher periods of time, compositions that contain it are only classified as flammable solids.32 When combined with sources of nitrate, these compositions have been observed to fimction as gunpowder substitutes, explosives, and propellants. The products are stable in air and do not detonate easily, if at all. As a powder, they can be used in propellant applications or as a viable black powder substitute. In replacing sulfur as an additional fuel, the presence of ascorbic acid appears to lower both the corrosivity upon contact with metal and smoke evolution. Compared to known explosive powders, these substitute powders have a higher explosive power, distinctly lower hygroscopicity, and better stability.10 Additionally, the absence ofsulfur leads to less fouling and less emission of its characteristic distasteful odor. The composition of Black Mag and Clean Shot Powder also include potassium perchlorate. One of the major claims stated explicitly in the PyrodcxR patent is that it is safer to handle.9 This additional safety comes from a slightly higher ignition point that may be the result of the potassium perchlorate. Since the alkali metal perchlorates themselves are readily available, inexpensive, stable, and safe to handle, it is justifiable to extend this claim to the materials in which they are included, such as PyrodcxR and the black powder substitutes incorporating perchlorate. 25 There are numerous patents on substitute black powder compositions that include potassium perchlorate and/or ascorbic acid. One patent limits the amount of potassium perchlorate to between 6 and 15 percent while not limiting the amount of ascorbic acid.11 Another patent’s limits only dictate the presence of an inorganic nitrate and ascorbic acid with percentages of 50 to 75 and 25 to 50 respectively.10 It is therefore no surprise the x- ray diffraction revealed compositions that included the same materials mentioned in the patents. Whereas Black Mag and Clean Shot Powder both contain the same components, the difference lies in the percentages of each and their corresponding ratios. However, since no quantitative studies were undertaken in this project, no estimates can be offered as to the approximate percentages of each component in a specific powder. Due to the scant product and manufacturing information, future quantitative studies determining exact concentrations of materials would be beneficial. Spot Tests Spot tests are qualitative analyses used to identify components of a sample. When a specific reaction occurs, a spot test is capable of indicating the presence of a certain element even in the presence of a large excess of other substances. Although spot tests make no claims to uncover the percent composition or molecular weight of an unknown material, they are often capable of revealing physical and chemical properties, the presence of functional groups, and general classes of substances.23 In simplest terms, a drop of the test solution is mixed with a drop of the liquid, or infrequently, solid reagent. This addition then provokes a physical, observable reaction. In terms of material and time, spot tests require only minimum levels of both. The levels of detection are inherently small but due to a distinct possibility of interfering elements, 26 they sometimes provide false information. Thus, being absolutely certain of the identity of an element in the presence of large amounts of other materials is not impossible, but it is indeed rare.23 However, spot tests do serve as an important preliminary technique for anion and cation detection that can be confirmed by further analysis. In this project, they were performed first in the scheme of analysis on the liquid extracts and residues. The results were assumptions and only confirmed by further chromatographic methods. As tests yielding purely preliminary results, the spot tests were indeed accurate in the sense that they were confirmed by other methods as will be discussed later. All of the powder extracts produced the deep red ring indicative of a positive result for the nitrate spot test, or Modified Greiss Test. However, when performing the Greiss Test on the residues, the results sometimes interfered with the Modified Greiss Test on the residues. The ring forming around the zinc powder could not always be observed due to the deep red color already present from the Greiss test for nitrites. When this interference happened, no result could be observed and N/A was recorded. This problem occurred only with the residues since they contain high amounts of nitrites and much decreased levels of nitrates compared to the original formulation. When this problem is encountered, both the nitrite ion and excess azide can be removed; sodium azide under acidic conditions decomposes the nitrite ion and heating the sample to near boiling removes the excess azide. Although it is highly probably that the residues in which the interference occurred did contain smaller amounts of nitrates due to powder that remained intact after combustion, they cannot alone characterize low explosive residue.8 Thus, firrther removal was not completed and seen as unnecessary. 27 Originally, two tests for perchlorate were performed that involved methylene blue. The results of the spot test were easily observed. However, the microcrystal test was more difficult to perform and observe. Therefore, only the methylene blue spot test was used on subsequent samples.23 Black Mag, Clean Shot, and PyrodexR showed positive results with the perchlorate spot test by fading to a lighter blue and forming a dark precipitate after a period of time. The positive results for the residues were more varied. Since perchlorate is more concentrated in the intact powder before combustion, results were harder to determine in the residues. Of the powders that contain perchlorate, the residues of PyrodcxR and Black Mag had slight positive results. The residue for Clean Shot powder, whose composition includes perchlorate, had a negative result. The amount of perchlorate left after combustion must have been below the level of detection for the spot test, which is approximately 500 ppm.23 This illustration of the problem with levels of detection for spot tests is definitely incentive to use them only as a preliminary technique in a scheme of analysis. The chloride spot test produced turbidity, which is indicative of a positive result, only in the residues of the powders containing perchlorate, i.e. Pyrodcx“, Black Mag, and Clean Shot powder. The thiocyanate spot test was only positive for samples that included sulfur in their composition; a rose color developed in the residues of black powder and Pyrodcx“. The test for oxidizers is a general screening technique for oxidative species such as NO;', NO3‘, and ClO3’. The permanent ultramarine color indicative of the presence of nitrate was never observed. The blue color that does not tide and is indicative of chlorate 28 was observed only with the Black Mag Residue. The remainder of the positive results, the residues of the other five powders, turned blue and then faded to a yellow-green color. This coloration is indicative of the presence of nitrite. It is highly possible that the other samples that include perchlorate in their composition could also include chlorate; chlorate is one of the combustion products of perchlorate. The sulfide spot test is the only test that could not be confirmed by fiJl'thCl' analysis. Thus, its results were record only as a possibility of being present. This test was only positive for the residues of Pyrodcx“ and black powder. Since these two powders do contain sulfur, sulfide is a likely combustion product. However, their presence cannot be confirmed unless a sulfide standard is included in IC or CIA analysis in the future. The sulfur spot test was completed to see if any sulfur could be detected in low part per million quantities. A positive result would negate the nmnufacturer’s claims that their products contain no sulfur. The negative results for the residues of Golden Powder, Black Canyon, and Clear Shot, however, reveal that there is no detectable sulfur in the chemical compositions of these powders. However, the dark material lelt on the filter paper after the sulfur was removed is indicative of clmrcoaL It is likely that a small amount of charcoal is used in these substitute powders as an additional fuel, complementing ascorbic acid. Chromatographic Methods Major criteria for effective chromatographic analysis is the ability of the method to separate the species of interest, to reproduce retention times, and to minimize interferences. For many years, ion chromatography (IC) has been employed by the 29 forensic chemist to determine the ionic species in explosive residues."33’34 Since explosive residues are water soluble, IC is an efficient technique. Employing ion exchange resins, IC has a well-known ability to provide excellent separations of ionic species. Developed in the early 19705, the high sensitivity and qualitative accuracy of IC led to many applications. One such application involved its adaptation for the analysis of ions of interest in explosive scenes. In 1975, Small, Stevens, and Bauman solved the problem of neutralizing the conductivity of the background electrolyte.” By employing a combination of resins that neutralize these background ions, the sample ions are left as the only major conducting species in the effluent. In 1980, it was implemented in the FBI laboratory.34 The ATF followed suit several years later. With the number of pipe bomb cases exploding, IC ins become an important tool for analyzing these residues. Both anion and cation analysis were completed on the intact powder and their residues. The ATF recemly formulated both the anion and cation systems to be isocractic systems. Since an isocratic system is inherently easier to run than a gradient system, run times and operational problems were reduced. With the installation of autosamplers, the analyses became even less tedious. After preparing the eluent and preparing the samples, the autosampler takes care of the injection. For both cation and anion analysis, two standards were run in between two water blanks. Water blanks were also run in between each individual sample. In each instance that either the anion or cation systems were run, the water blanks indicated no contamination before, after, or in between samples Although initially it took up to an hour to settle the conductivity into an appropriate range, neither the conductivity nor the pump created any problems during the actual cation and anion analysis. The cation analysis did not reveal anything 30 discerning.” Every sample, both intact powder and residue, contained potassium and sodium in relatively large amounts. Smaller amounts of calcitun and ammonium were found in almost all of the samples as well. It is worthy to note that the calcium in the extracts of Clean Shot and Black Mag were in a much higher quantity than the other powders. In fhct, the existence of calcium in the extracts and residues of black powder, Pyrodcx“, Golden powder, and Black Canyon powder could not be considered significant. The high amount of potassium can be contributed to the major ingredient, potassium nitrate, in each of the samples. The sodium and calcium present in each sample is harder to explain. Their existence can only be a conjecture. Their most likely source is as an environmental contaminant. However, if a manufacturer is able to obtain contaminated potassium nitrate that is cheaper and functions equally or with no significant disadvantage to a pure lot, then the contaminated lot may be used. Since an efficient business operates under the precepts of price and availability, the lots contaminated with calcium and sodium may indeed be prevalent. Although sodium nitrate has a greater hydroscopicity and oxidizer containment, its presence has been noted in black powder compositions.” The presence of the ammonium ion in the Pyrodcx“, Black Canyon, Clear Shot, and Golden Powder residues can only be a conjecture as well. Earlier research that revealed the ammonium ion attributes its existence to soil contamination.35 Although that is not the case in this particular study, it is a verifiable conclusion. Instead, it is more likely that ammonium nitrate could have been substituted for potassium nitrate to some degree. Another speculation involves its existence as a reduction product of nitrite that appears after combustion. Since ascorbic acid is a strong reducing agent, it is possible 31 that the nitrate was reduced to ammonium, which would involve a transfer of three electrons. If this reduction process was the explanation, further qualitative tests need to be performed to see if there is a specific ratio formulation for the different chemical species in the powders that enhance the reduction process. Further studies would also be beneficial in order to determine if the ammonium nitrate is characteristic of the powder in general or of the specific lot used in this study. The anion amlysis and interpretation involved more species of interest. The extracts were relatively simple. The major identified anionic species in the extracts of black powder, Golden Powder, and Black Canyon was nitrate. These results agreed with earlier published work on black powder and Golden Powder.36 This nitrate obviously was due to the potassium nitrate in their compositions. The major identified anionic species in the extracts of Pyrodcx“, Black Mag, and Clean Shot Powder were nitrate and perchlorate. The nitrate was again from the potassium nitrate while the perchlorate was from the potassium perchlorate in their compositions. Finally, chloride was also present in Pyrodcx“, Black Mag, and Clean Shot Powder in low levels. Chloride is a minor by- product in the commercial production of perchlorate. However, the residues of the powders provided greater variation. Significant amounts of nitrite were found in each residue due to the reduction of nitrate upon combustion.37 Smaller amounts of nitrate not affected by reduction were evident as well in the residues. The three sample powders that have potassium perchlorate, i.e. PyrodexR, Black Mag, and Clean Shot Powder, had slight traces of perchlorate left over in their residues. However, perchlorate undergoes a reduction when combusted. 32 Below is the characteristic reaction equation. ClO4' —> ClO3'—-> C1' The most significant peaks were those of chloride, which is the main reduction product of perchlorate.” To a lesser extent, chlorate peaks were observed in the residues as well. Finally, due to the sulfur content in black powder and PyrodexR, these species also included the sulfate and thiocyanate ions in their residues. One interpretation problem was apparent in the residues. In each of the substitute black powder residues, there is a tiny trace of the sulfate ion. The sulfate ion is understandable in the residues of black powder and PyrodcxR because their compositions contain sulfur and thus the peak is of a significant size. Alternately, the size of the sulfate peaks in the substitute powders is insignificant when compared to the size of the sulfate peaks in black powder and Pyrodcx“. The presence of a sulfate peak in the substitute powders is puzzling. One very hypothetical explanation could be attributed to the charcoal that was evidenced by black material remaining on the filter paper after the sulfur spot test. Perhaps this charcoal was wood charcoal containing a small of sulfur. Whatever the case, it is important to note that the sulfate was only picked up by the IC, which has an extremely high level of detection. The sulfur was not in a high enough concentration to be detected by either the sulfate or sulfur spot test. Thus, the miniscule amount of sulfur detected is not a major species in the black powder substitute compositions in any way. Another possible explanation involves the instrumentation itself. The only species the IC detects are those that are present in the standard. It is therefore possible that there is a species that elutes around the same time as sulfate but is not sulfate. 33 Further tests would be needed to determine if there is an additional species and its identity. As evidenced by earlier discussion, it is very difficult to manufacture a mass- market gunpowder product completely fi'ee of contaminants and minor species. There were also slight traces of chloride in the Black Canyon and Golden Powder residues. Although they do not contain potassium perchlorate and the presence of chloride cannot be attributed to the reduction products of it, chloride is a widespread environmental contaminant. It is on streets, on walls, and other obvious places inhabited by human beings and their daily efforts. This, of course, includes the forensic laboratory in which these tests were conducted. i No sample powder had significantly different IC results than those of other powders. However, the presence of perchlorate in Black Mag and Clean Shot Powder does differentiate them from Black Canyon and Golden Powder. Black Powder and Pyrodcx“ can be differentiated from all four of the substitute black powders due to the presence of significant sulfate and thiocyanate peaks. Obviously, black powder substitute manufacturers are most concerned with eliminating the sulfur and its ensuing problems fiom their products. The second chronmtographic, or separation, method used was capillary ion analysis. This is a variation of capillary electrophoresis. As an analytical method, it is rapid, simple, and has the potential for excellent separation. In general, the principle of capillary electrophoresis involves applying voltage to cause differential migration of charged sample components.38 These separated analytes are then passed through a detector. Several factors influence electrophoretic separation including size, shape, charge, mass, and interaction with the carrier electrolyte. The overall mobility is also 34 influenced by electroosmotic mobility, which involves loosely charged cations associating with the negatively charged interior of the capillary wall. To analyze ions with small molecular weights, capillary ion analysis is employed. In this method, analytes always migrate in the same direction as the electroosmotic flow (EOF). While cation analysis involves both an analyte and a pH-controlled EOF that travel in the same direction, anion analysis requires a reversal of the EOF by an electrolyte modifier that coats the inner wall of the capillary.38 The preferred method of detection is by indirect ultraviolet (UV) detection. Capillary ion electrophoresis is best viewed as a complementary technique to ion chromatography. Despite having shorter run times and a slightly heightened sensitivity, it is a much newer method. As such, it has not been as extensively studied or used in the field of forensic science. However, there is positive data when IC and CE are used in tandem for explosive residue analysis.33 These two techniques were complementary in this project. The CE available at the ATF is newer than the IC and has not had much time or effort dedicated to its use. Melinda Ferguson, an intern at the ATF, was responsible for its upkeep and use. She delivered a talk at the end of her internship stating that not enough tests lmve been done on the CE to include it in routine explosive analysis. The major problem she encountered was co-elution, especially if the sample was too concentrated. Although the software facilitated the interpretation of the chromatograms, it contributed to the problem of co-eluted peaks. For anion analysis, the samples were around 30 ppm and for cation analysis, the samples were around 10 ppm With the time already devoted to learning and running the IC already, it was not efficient for me to learn the care and use of the CE. Since the data 35 was only seen as complementary to IC and was not proof in itself of the presence of a certain ionic species, Melinda ran the prepared samples. The cations present in the extracts of the six powders included significant amounts of potassium and sodium and less significant amounts of calcium and magnesium. The calcium was again more significant in the extracts of Black Mag and Clean Shot Powder. In general, these results were compatible with the results of the IC. However, the detection of magnesium is due to the more sensitive nature of the CIA. Only minute amounts of magnesium were found and are most likely attributed to environmental contamination that is not a major species in the sample composition. The major anion present in the extract was nitrate. PyrodexR, Black Mag, and Clean Shot also contained perchlorate. These results are analogous to those obtained from the IC. For the same reasons as outlined above, these are the major anionic species that are expected to be detected in the powder samples. After performing the two chronntographic methods IC and CIA, it indeed does seem that they are complementary in nature. There were no significant differences in the results for the powder extracts. Although CIA may seem faster as well as more sensitive and efficient, it is less thoroughly researched and cannot stand alone as an analytical confirmation. Additionally, the IC is a finicky instrument whose standards can be difi'lcult to reproduce. Due to the inherent deficiencies in both, it is conducive to the scientist to perform both methods for confirmation purposes. Used in tandem, these two methods are capable of detecting the presence of the ions most characteristic of explosive materials. 36 High Performance Liquid Chromatography Liquid chromatography is a separation technique that relies on specific interactions between the sample molecules and those of the stationary and mobile phases. This technique can be extremely advantageous. First, it is not limited by sample volatility or thermal stability. Second, it can achieve difficult separations due to its reliance on two chromatographic phases and low separation temperatures. Finally, there are an abundance of useful column packings, stationary phases, and detectors that are available and effective for this technique.28 One specific application of this technique is in the area of explosives. Reported in 1989 by Edward Bender of the Materials Analysis Unit in the FBI Laboratory, this application is specific in detecting the presence of Pyrodcx“.29 By using specific solvents, optimum separation is achieved for two stabilizing materials. Besides potassium nitrate and potassium perchlorate, PyrodcxR also contains sodium benzoate and dicyandiamide (DCDA). These two materials are unique to Pyrodcx“. Although black powder, PyrodexR, and the black powder substitutes look different before combustion, these differences become less significant after combustion. Thus, chemical analysis is required to characterize the residue. The process for detecting the two stabilizers mentiomd above, sodium benzoate and DCDA, is capable of distinguishing PyrodcxR residue fiom the residue of black powder and its substitutes. Therefore, the sensitivity and selectivity of this application of HPLC is important in determining the residues specific to PyrodexR. When this application of HPLC was applied to the extracts of the six powders, only PyrodexR revealed the elution of two peaks at the times that are characteristic of 37 benzoic acid and DCDA. No qualitative determination was undertaken, although previous work has been done to show that the concentration of sodium benzoate and DCDA in PyrodexRRS to be 6 and 12 percent respectively.” In the residues, the two compounds again only appeared in PyrodexR. This result supports the earlier finding that these two compounds survive combustion. Sodium benzoate and DCDA continue to be evidence of the presence of PyrodcxR since no black powder substitute shows evidence of their existence. However, this statement can only be generalized to include the four black powder substitutes tested in this study. It is interesting to note that no other black powder substitute contains these stabilizers. One can only conjecture as to why their presence is not more ubiquitous in low explosive compositions. PyrodcxR received its patent in 1978.9 One stipulation of the patent is that it contain “approximately 14.5-45 parts by weight of an organic carboxylic acid or oxidizable derivative thereof. . .2” Further, it emphasizes the effectiveness of sodium benzoate in terms of cost, availability, and inhibition of corrosion and specifically claims: 1. In a deflagrating gas generation composition for producing controlled gas pressure which imparts high velocity to projectiles at relatively low peak pressure, the improvement which comprises employing, a the essential gas-producing elements, approximately 82.5-30 parts by weight of an oxidizing agent selected from the group consisting of ammounium, alkali metal, and alkaline earth nitrates, chlorates and perchlorates; approximately 14.5-45 parts by weight of an oxidizable derivative of an organic carboxylic acid selected from the group consisting of ammonium and alkali metal salts of aromatic carboxylic acids; and approximately 25-l.0 parts by weight of water. 6. A composition according to claim 1 which consists of from 20 to 50 paeent of the composition claimed therein admixed with from 80 to 50 percent of the components of black powder. 7. A composition according to claim 6 which consists of 45 parts of potassium nitrate, 9 parts of charcoal, 6 parts of sulfur, 19 parts of potassium perchlorate, 11 parts of sodium benzoate, 6 parts of dicyandiamide and from 1 to 4 parts of water. Perhaps the limits that the patent sets on the amounts of sodium benzoate and dicyandiamide are the specific formulation needed for maximum effectiveness. Or 38 did his ill: Wit Pu we] HOB: perhaps it is in combination with the other mixture of materials specific to PyrodcxR which necessitate the need for the added stability gained from the presence of these two materials. Whatever the case, sodium benzoate and DCDA remain characteristic of only PyrodcxR in this study. Conclusion After extensive study on several analytical instruments, the chemical composition of the water extracts and combustion of residues of Black Canyon, Golden Powder, Black Canyon, and Clean Shot Powder have been determined. A referral to Appendix I-V allows the chemist to compare an unknown sample to known specimens of each powder using several analytical techniques. X-ray diffiaction allows compounds in only the intact material to be compared while spot tests, IC, and CIA allow for the comparison of characteristic ions in the intact material and its residues. Although this study did not discover an ionic species capable of differentiating black powder substitutes individually or collectively, several groupings can be made. The two major groups include those substitute compositions with perchlorate and those without. If the perchlorate ion is found either in the extract or residue, it is fair to say that the powder is not black powder, Black Canyon, or Golden Powder. Black powder substitutes as a whole can be distinguished fi‘om black powder and Pyrodcx“ by sulfur alone. It is fair to say that if sulfur or any of its combustion products such as thiocyanate and sulfate are present, it is not a black powder substitute tested in this study. Alternately, ascorbic acid is only characteristic of black powder substitutes. However, since it does not seem to form any different ionic species, this observation is 39 only helpful if the intact powder is recovered. Perhaps fiirther quantitative studies will reveal that its presence impacts the detected amount of a certain ion. Additionally, these studies could reveal a characterizing relationship between the amount of certain ions detected in the residues of black powder substitutes. One final conclusion concerns nitrates and nitrites. The presence of nitrates in extracts and the presence of nitrites in residues are ubiquitous amongst the powders tested in this study. Nitrates are a powerful oxidizer whose effectiveness in black powder and PyrodexR has not been altered significantly in substitute compositions. Whether or not this is due to a lack of study on alternative oxidizers is not known. The small amount of information available today on black powder substitutes is geared toward a shooting audience. Although sport shooting is a safe recreational activity, another more dangerous activity involving the use of black powder substitutes includes the creation of destructive devices such as pipe bombs. As the number of pipe bomb cases increase and black powder substitutes become more readily available on the market, forensic scientists may be faced with compositions other than those typical of black powder and Pyrodcx“. Consulting this study may help these professionals generate comparisons and conclusions. And perhaps the manufacturers of the black powder substitutes in this study and others not studied will become more liberal with necessary information on the composition of their products. A final compilation of their compositions as determined by this study is listed on the final, following pages. 40 Table 7. Intact composition of powders Black Pyrodcx Black Extracts Powder Canyon Potassium, Potassium, Ascorbic Nitrate, Nitrate, Acid, Intact Sulfate Potassium Potassium Materials Perchlorate, Nitrate Sodium Benzoate Nitrate Nitrate Nitrate Anions Chlorate Perchlorate Sodium Sodium Sodium Cations Potassium Potassium Potassium Calcium Calcium Calcium Golden Black Mag Clean Shot Extracts Powder Ascorbic Ascorbic Ascorbic Acid, Acid, Acid, Intact Potassium Potassium Potassium Materials Nitrate Nitrate, Nitrate, Potassium Potassium Perchlorate Perchlorate Nitrate Nitrate Nitrate Anions Perchlorate Perchlorate Sodium Sodium Sodium Cations Potassium Potassium Potassium Calcium Calcium Calcium 41 Table 8. Residue composition of powders Black Pyrodcx Black Residues Powder Canyon Nitrite Chloride Nitrite Nitrate Nitrite Nitrate Anions Sulfate Nitrate Thiocyanate Chlorate Thiocyanate Perchlorate Sodium Sodium Sodium Cations Potassium Potassium Potassium Calcium Ammonium Ammonium Calcium Calcium Golden Black Mag Clean Shot Residues Powder Nitrite Chloride Chloride Nitrate Nitrite Nitrite Anions Nitrate Nitrate Perchlorate Chlorate Perchlorate Sodium Sodium Sodium Potassium Potassium Potassium Cations Ammonium Calcium Ammonium Calcium Calcium 42 APPENDIX I Analytical Results Compilation of Analysis Results Photographs 43 rClE a a a E a a a E E Ethane..-\..\-.\-C1-C;\\ X-RAY flFERACTlQN ESULTS Black Black Golden Black Clean Powder Pyrodcx Canyon Powder Mag Shot Ascorbic Acid X X X X Potassium Nitrate X X X X X X Potassium Perchlorate X X X Sodium Benzoete X Sulfur X X ION CHRflA TQQRAPHY RE§QL l§ Black Black Golden Black Clean Anions In Water Extract Powder Pyrodcx Canyon Powder Mag Shot Chloride- Cl Nitrite- N02 Nitrate- NO3 X X X X X X Chlorate- ClO3 X Sulfate- $04 Thiocyanate- SCN Perchlorate- ClO4 X X X Cations In Water Extract Sodium- Na X X X X X X Ammonium- NH4 Potassium- K X X X X X X Magnesium- Mg 1: Calcium- Ca x x x x X X Strontium- Sr Barium- Ba Anions In Residue Chloride- Cl X x X X Nitrite- NOZ x X X X X X Nitrate- NO3 x X X X X X Chlorate- Cl03 x Sulfate- 304 X X x x x Thiocyanate- SCN x X Perchlorate- C104 x X X Cations In Residue Sodium- Ne X X X X X X Ammonium- NM x x x Potassium- K X X X X X X Magnesium Mg X x Calcium- Ca x X x x X X Strontium- Sr Barium- Ba CAPILLARY ION ANALYSIS MSULTS Black Black Golden Black Clean Anions In Water Extract Powder Pyrodcx Canyon Powder Mag Shot Chloride- Cl Sulfate- $04 Nitrite- N02 Nitrate- NO3 X X X X X X Chlorate- ClO3 Thiocyanate SCN Perchlorate- ClO-t X X X Carbonate- CO3 X X X X X X Cations In Water Extract Ammonium- NHl Potasium- K X X X X X X Calcium- Ca X X x x X X Sodium- Na X X X X x X Magnesium- Mg x x x X X x Strontium- Sr Barium- Ba HIGH PERFORMANCE Ll UID CHROMATOGRAPHY RESULTS Black Black Golden Black Clean Water Extracts Powder Pyrodcx Canyon Powder Mag Shot Dicyandiamlne (DCDA) X Benzolc Acid X Residues Dicyandlamine (DCDA) X Benzoic Acid X 45 EFT. :1 are; ELIFLLNIEWNE SPOT TEST RESULTS Black Black Golden Black Clean Water Extracts Powder Pyrodcx Canyon Powder Mag Shot Ammonium lon Neg Neg Neg Neg Neg Neg Chloride Ion Neg Neg Neg Neg Neg Neg Nitrate Ion Poa Poe Poe Poe Poe Poo Nitrite Ion N09 N09 N09 N09 N09 N09 Oxidizer Neg Poo Neg Neg Nag Neg Perchlorate Ion Neg Poe Neg Neg Neg Poe Perchlorate lon- Crystals Neg NIA Neg NIA NIA Poe Sulfate lon Neg Neg Neg Neg Neg Neg Sulfide Ion Neg Neg Neg Neg Neg Neg Thiocyanate Ion N09 N09 N99 N09 N09 N09 Residues Ammonium ion Neg Neg Low Poe Neg Neg Neg Chloride Ion Neg Poa Neg Neg Low Pee Pee Nitrate ion Poe Poe Low Poe Poe NIA NlA Nitrite Ion Poe Poe Poe Poe Poe Poe Oxidizer Poe Poe Poe Poe Poe Poe Perchlorate Ion Neg Low Poe Neg Neg Low Poe Neg Perchlorate lon- Crystais NIA NIA NIA NIA NIA NIA Sulfate lon Poe Poa Neg Neg Neg Neg Sulfide Ion Poe Poe Neg Neg NIA Neg Thiocyanate Ion Poe Poe Neg Neg Neg Neg 46 COMPILATION OF ANALYSIS RESULTS I Black Powder I Anions IC Extract CE Extract Spot Tests Ic Residue Spot Tests Chloride- Cl Nitrite- N02 Nitrate- N03 Chlorate- ClO3 Sulfate- $04 Thiocyanate- SCN Perchlorate- Cl04 Cations Sodum- Na Ammonlum- NH-t Potasslum- K Magnesium- Mg Calclum- Ca Strontium- Sr Barium- Ba [ Pyrodcx ] Anlons to Extract CE Extract Spot Tests lC Resldue Spot Tests Chloride- Cl x x Nitrite- N02 Nitrate- NO3 x Chlorate- 6103 Sulfate- 804 x Thiocyanate- SCN Perchlorate- ClOl Cations Sodum- Na Ammonium- NM Potassium- K Magnesium- Mg Calcium- Ca Strontlum- Sr Barlum- Ba 47 COMPILATIQN OF ANALYSI§ RESULTS Black Canyon AnIons lC Extract CE Extract Spot Tests lC Residue Spot Tests Chloride- 0 Nitrite- N02 X Nitrate- N03 Chlorate- 003 Sulfate- $04 Thiocyanate- SCN Perchlorate- 004 Cations Sodum- Na Ammonium- Ni-i4 Potassium- K Magnesium- Mg Calcium- Ca Stontlum- Sr Barium- Ba | Golden Powder ] Anions lC Extract CE Extract Spot Tests lC Residue Spot Tests Chloride- Ci x Nitrite- N02 X X Nitrate- N03 x x Chlorate- 003 Sulfate- $04 Thiocyanate- SCN Perchlorate- 004 Cations Sodum- Na Ammonium- NH4 Potassium- K Magneslum- Mg Calcium- Ca Strondum- Sr Barium- Ba 48 COMPILATION OF ANALYSIS RESULTS I Clean Shot J Anions iC Extract CE Extract Spot Tests rc Residue Spot rm Chioride- or x mum- N02 x Nltrate- N03 x Chlorate- cros Sulfate- $04 Thiocyanate- SCN Perchlorate- 004 Cations Sodum- Na Ammonium- Nl-l4 Potassium- K Magnesium- Mg Calcium- Ca Stontlum- Sr Barium- Ba [ Black Mag | Anions lC Extract CE Extract Spot Tests lC Residue Spot Tests Chloride- 0 x Nitrite- N02 x Nitrate- N03 x Chlorate- 003 Sulfate- 804 Thiocyanate- SCN Perchlorate- 004 Cations Sodium- Na Ammonium- Nl-i4 Potassium- K Atagneslum- Mg Calcium- Ca Strontium- Sr Barium- Ba 49 From left to right starring in top row, Goex thk Powder FFFG. Pyrodcx RS. Golden Powder, Black Canyon Powder. Clean Shot Powder APPENDIX II Spot Test Results 51 Chemical Sgot Tests Powder Name: Black Powder Extract Ioan est Type Observations Result Ammonium Pale Yellow Negative Chloride No turbidity Negative Nitrate Rose Ring Positive Nitrite Brown Negative Oxidizer No change Negative Chlorate No change Negative Chlorate No crystals Negative Sulfate Slow precipitate Positive Sulfur No change Negative Thiocyanate Tums orange Negative Analyst: JMY Date: 7/22/99 52 Chemical Spot Tests Powder Name: Black Powder Residue Ioanest Type Observations Result Ammonium No change Negative Chloride Dark, no Negative precipitate Nitrate Rose Ring Positive Nitrite Rose Positive Oxidizer Blue, fade to Positive yellovggraen Chlorate Slight change Negative Sulfate Slow precipitate Positive Sulfur Dark, no Positive precipitate Thiocyanate Darker Low positive Analyst: JMY Date: 7i22/99 53 Chemical Spot Tests Powder Name: Pyrodcx Extract loni'l’ est Type Observations Result Ammonium Pale Yellow Negative Chloride No change Negative Nitrate Rose Ring Positive Nitrite Brown Negative Oxidizer Blue fade to light Positive yellow Chlorate Fades, precipitate Positive Sulfate Slow precipitate Positive Sulfur No change Negative Thiocyanate Stayed yellow Negative Analyst: JMY Date: 7l22/99 Chemical Smt Tests Powder Name: Pyrodcx Residue Ion/T est Type Observations Result Ammonium No change Negative Chloride Dark precipitate Positive Nitrate Rose Ring Positive Nitrite Rose Positive Oxidizer Blue fades to Positive yellow-green Chlorate Fade slightly Low positive Sulfate Slow precipitate Positive Sulfur Dark, precipitate Positive Thiocyanate Red color Positive Analyst: JMY Date: 7I22l99 55 Chemical Smt Tests Powder Name: Black Canyon Extract lonl'l' est Type Observations Result Ammonium Brown, muddy Negative Chloride No change Negative Nitrate Rose Ring Positive Nitrite Bmwn Negative Oxidizer No change Negative Chlorate No change Negative Chlorate No crystals Negative Sulfate No change Negative Sulfur No change Negative Thiocyanate No change Negative Analyst: JMY Date: 7l27/99 Chemical Spot Tests Powder Name: Black Canyon Residue Ionl'l' est Type Observations Result Ammonium Darker, precipitate Positive Chloride No change Negative Nitrate Rose Ring Low positive Nitrite Rose Positive Oxidizer Blue fades to Positive yellow-green Chlorate No change Negative Sulfate No change Negative Sulfur No change Negative Thiocyanate No change Negative Analyst: JMY Date: 7l27/99 57 Chemical Smt Tests Powder Name: Golden Powder Extract lonll’ est Type Observations Result Ammonium Darker Negative Chloride No change Negative Nitrate Rose Ring Positive Nitrite Brown Negative Oxidizer No change Negative Chlorate No change Negative Sulfate No change Negative Sulfur No change Negative Thiocyanate No change Negative Analyst: JMY Date: 7/27/99 Chemical Spot Tests Powder Name: Golden Powder Residue lonl'l’ est Type Observations Result Ammonium No change Negative Chloride No change Negative Nitrate Rose Ring Positive Nitrite Rose Positive Oxidizer Blue fades to Positive yellow-green Chlorate Slight change Negative Sulfate No change Negative Sulfur No change Negative Thiocyanate No change Negative Analyst: JMY Date: 7/27I99 59 Chemical Smt Tests Powder Name: Black Mag Extract Ioan est Type Observations Result Ammonium No change Negative Chloride No change Negative Nitrate Rose Ring Positive Nitrite No change Negative Oxidizer No change Negative Chlorate No change Negative Sulfate No change Negatvie Sulfur No change Negative Thiocyanate No change Negative Analyst: JMY Date: 7I27l99 Chemical Spot Tests Powder Name: Black Mag Residue loan est Type Observations Result Ammonium No change Negative Chloride Turbidity Low positive Nitrate Too dark to tell N/A Nitrite Deep red Positive Oxidizer Deep blue Positive Chlorate Slight change Low positive Sulfate No change Negative Sulfur Dark precipitate MA with heat Thiocyanate No change Negative Analyst: JMY Date: 7I27l99 61 Powder Name: Clean Shot Extract Chemical Spot Tests Ionl'l'est Type Observations Result Ammonium Darker Negative Chloride No change Negative Nitrate Rose Ring Positive Nitrite Brown Negative Oxidizer No change Negative Chlorate Lavender needles Positive Chlorate White precipitate Positive Chlorate White precipitate Positive Sulfate No change Negative Sulfur No change Negative Thiocyanate No change Negative Analyst: JMY Data: 7I22IQQ Chemical Spot Tests Powder Name: Clean Shot Residue loan est Type Observations Result Ammonium No change Negative Chloride Brown precipitate, Positive white ppt with heat Nitrate Too dark to tell N/A Nitrite Rose Positive Oxidizer Blue fades to Positive yellow-green Chlorate No change Negative Sulfate No change Negative Sulfur No change Negative Thiocyanate Darker Negative Analyst: JMY Date: 7I27l99 63 APPENDIX III XRD Results 3389:." S on . an we 3. 1 a1 ‘43 4.. .J‘.‘l~s:ls p4 .3114“... 7.91‘51. — p b ) fi:...-¢ e e p p . r .q .l A. em" 8m .93. , :8— i 8 a . - . R a 2 __.!~.:....._....... *4 .. ._ . _ .i .. r. 1.. .3 . _ .. . .r r! 6 m. A m m S" m u m can emu flea—2v 28:2 52.9.8.2. -820. Anna _-:.v ABEZV m .9? 5:5 Anvmoécv .325.— xoa-m— 8: — 65 e . emu 68 r ea. 58. I bl b L °IN b D b n— D l c— D b c a _ la A _ All 8" .8» e an» coazv 5:6 .3 A2: iv Aaazv 222.6 eases. +0.8. A. .84.? ,8... toazv 2.5.2 52328 -822 can _ .:.v m Aaazv 038:3 .558 -Noaanb $8.? 5.5.: (euanumrnI 66 3.3835 8n _ I u a m. a m m n u N San i g... 1 8m _ ABE—av Eo< 03.33 602:5 noon 7va domes—v 2952 82329. .nozx Aamn ..:.v .363...— flow-emu 67 Amoesofie com com (stumow!sueiu1 "" can Asa—av 826. as .32 $8-ch oaezv 22 2e§< -8350 a: _ .NV _ SE5 :3:— 8n— 68 mm 9332;." a. , cm 6? mm 1.13.." c ‘3‘. 5.13.311 1. . .54. 3.- r._.a‘. J —. , q pg .p .6 ,3." :8 SP ,8... I n . a plow . . . . -mm ‘ cm 2 a m m = . fisfi. 2.111... w: i‘firfifi. ..J‘.. . .4. . .11. «1:43-31‘ 2. .3 as? . 11.. Y: “a! , V m . , u _ m .. 4 :2 gen :85 Aaazv 2225 55.8 -548. A335? .82 Asa—av 22 03.83 68:8 $8.-va Aaazv 22.2 59.58 -826. Ann EV we: :3:— 69 an 9.333...." cm we as doazv 22 05.83 6828 Sen 78v coma—2v 282.6 5.8%.. +0.8. A. .8-ch Aaazv 25:2 5328 -826. ASN-2» mm «cam use—U an" E — é (am-09mins"! § an“. 70 APPENDIX IV IC Results 71 33...: F2 cm; a w. c 2 cm. are ole cm was- Jul 3 j . _\r\>...i......,m o _ _ _ r”, . h c _ . . A, o m w v m A 1:“ o6 _ . T T. T. I III -3: N 333.3% zeteb grl SAMPLE ANALYSIS REPORT Sample Name: Cation Standard for Extracts Peak ii Component Retention Amount Peak Area Peak Height Name Time 1 2.88 0.00 76562 844 2 Na 3.68 0.00 634865 70663 3 NH4 4.25 0.00 315169 16613 4 K 5.35 0.00 372645 22008 5 Mg 6.98 0.00 724728 18651 6 Ca 8.63 0.00 604574 13113 7 Sr 10.13 0.00 599446 ’ 10676 8 Ba 15.33 0.00 102042 2333 73 wees-.2 38 fit em. 3. 9.: me am MN o 3. 1.? w H. c _ was N 1. _ 11,, 3: _ H. m H . rmo m— 13.8 m. «6.633%. 282‘ srt 74 SAMPLE ANALYSIS REPORT Sample Name: Anion Standard for Extracts Peak # Component Retention Amount Peak Area Peak Name Time (ppm) [fight 1 Cl 3 .77 0.00 799257 87504 2 N02 4.65 9.61 414703 37527 3 N03 7.97 0.00 499891 82661 4 C103 8.18 3.31 129776 21196 5 804 11.10 2.55 547312 95330 6 SCN 14.32 8.64 337864 25353 7 C104 17.27 9.54 87879 7795 75 megs—=2 Spar 8.6. 8H. , - 180. r , 8,2 - 8... Se 8.. com com. > 1” Z .. o . . 1. _ _ H a tad ~_. _ _ H _ v n rcr ca. 6 M Z 1;, c6 _ H a W _ +3. ~ U. roe. . Been—3m c230 sri 76 Sample Name: Cation Standard for Residues SAMPLE ANALYSIS REPORT Peak # Component Retention Peak Area Peak Area/Height Name Time Height Ratio 1 2.63 583 52 1 1.16 2 Na 3 .90 669028 77654 8.62 3 NH4 4.52 313656 25429 12.33 4 K 5.72 390974 26086 14.99 5 Mg 6.87 1115834 61582 18.12 6 Ca 8.48 734476 33288 22.06 7 Sr 10.05 623817 23035 27.08 8 Ba 15.16 381525 8849 43.12 77 coda 833.2 . ant, 8...... cm. - 8“... 8. b 8n 8..” o 8..- < 2 1.2. 8.. _ H _ n u. n .m 8N _ Hf o M 1.186 _ _ H v 3 _ i 86 “fl _ -- 8.“ N 93285 Sfl 78 SAMPLE ANALYSIS REPORT Sample Name: Anion Standard for Residues Peak # Component Retention Peak Area Peak Area/Height Name Time Height Ratio 1 Cl 4.73 247572 32795 7.55 2 N02 6.05 4493 73 45374 9.90 3 C103 8.88 131277 8946 14.67 4 N03 9.72 4741 16 30648 15.47 5 P04 12.37 288817 12485 23.13 6 S04 16.15 550364 19563 28.13 79 noun-Ia: -8“- SN 1‘ Em 880220; 1% ('3— ‘ l .63 .8...” ffT T86 Sod srt 80 PERCHLORATEIT HIOCYAN ATE REPORT Sample Name: Perchlorate Standard Peak # Component Retention Peak Area Peak Area/Height Name Time Height Ratio 1 1.35 1813 185 9.77 2 2.87 7121 859 8.29 3 3.10 57502 7964 7.22 4 3.50 6567 952 6.90 5 5.85 4753 547 8.69 6 6.87 19221 4786 4.02 7 SCN 8.70 472264 34837 13.56 8 C104 10.57 265523 16104 16.49 81 ed— ,3; c."— c.6— 8.3.2 cw» 1.. 0 v AJJAA V1,.v O. co I II 533 83$ «83 82 CATION ANALYSIS REPORT OF EXTRACT Sample Name: Black Powder Extract Peak # Component Retention Amount Peak Area Peak Height Name Time 1 2.80 0.00 53881 851 2 Na 3.68 0.00 205175 18998 3 K 5.28 0.00 960008 66172 4 Ca 8.73 0.00 17533 678 83 ~33 newest «33 98 m.— cfi flu 92 S. cm MN cow- “3 4 J- o . ”I _ I _ 156 m “L :2 _ .. N 8.2 AHedn I I II IE II 311 84 ANION ANALYSIS REPORT OF EXTRACT Sample Name: Black Powder Extract Peak # Component Retention Amount Peak Area Peak Name Time (ppm) Height 1 3.07 0.09 14444 2385 2 N03 7.20 0.00 1241461 102771 3 S04 10.93 0.07 15147 2152 85 8.2:: . +9.: 92 fi: qr» awe ow on” 83. Q I 41 a _ J I v _ _ fem m I lacé _ .36 I N n we.” I I I T. IT. I .3: 3.3.32 «whack «85m 86 CATION ANALYSIS REPORT OF EXTRACT Sample Name: Black Powder Residue Peak # Component Retention Amount Peak Area Peak Height Name Time 1 2.87 0.00 71091 896 2 Na 3.70 0.00 555840 58733 3 K 5.32 0.00 25021 1 16408 4 Ca 8.75 0.00 3229 169 87 8.39.2 9.18 at .i an". 3: mm. o.“ Wm can. I. 1 1 I o . _ m e an _ I” . a b Aflom I69 .L o 138.2 I I II II Ti I m 3.” 3.33: $3: .33 88 ANION ANALYSIS REPORT OF RESIDUE Sample Name: Black Powder Residue Peak # Component Retention Amount Peak Area Peak Name Time (ppm) Height 1 3.28 0.00 10182 1828 2 N02 4.02 0.59 25291 3407 3 4.33 0.00 14461 1881 4 N03 7.62 0.00 31484 4854 5 10.38 0.00 2649 2421 6 804 11.17 2.94 631081 96104 7 SCN 14.28 0.26 9971 1 165 8 14.97 0.24 40660 3428 89 3: 3.1 gm. 3: cw owe ow. cm can- 4 . ; I... v . $3 _ we... N n me.» i We... r UH3: T. T. I T. ITT. 8.3.5 385 Sn CATION ANALYSIS REPORT OF EXTRACT Sample Name: Pyrodcx Extract Peak # Component Retention Amount Peak Area Peak Height Name Time 1 3.20 0.00 169339 2234 2 Na 3.68 0.00 499108 36866 3 K 5.28 0.00 1357698 92478 4 Ca 8.68 0.00 1687 175 91 98 3.. o.“ _ 83...: mun. cw... II 883 §§Eb~ 92 ANION ANALYSIS REPORT OF EXTRACT Sample Name: Pyrodcx Extract Peak # Component Retention Amount Peak Area Peak Name Time (ppm) Height 1 3.10 0.07 11175 1894 2 N03 7.27 0.00 1629629 132734 3 C103 8.27 4.89 191845 18296 4 S04 10.95 0.22 46307 1584 5 C104 16.68 30.65 282433 15504 93 8h» ., 8.0— Ji- 85...: 8h: 8.: 8.2 8... *r 26qu 5.55a— All A A A v I ON 1 c6 1 ed .8... LL A A A v v ..o.o. Sl‘l 94 CATION ANALYSIS REPORT OF RESIDUE Sample Name: Pyrodcx Residue Peak # Component Retention Peak Area Peak Area/Height Name Time Height Ratio 1 2.62 1382 83 16.69 2 Na 3.88 416629 47608 8.75 3 N114 4.50 187528 16095 1 1.65 4 K 5.67 811753 56461 14.38 5 Ca 8.50 15241 751 20.28 95 8.9m on: .m 8 4L new—=32 own. ,8“... A LL A v v v 2.28»— .835 A 1 A A A A l A A A A v v v V V V § 5!! 96 ANION ANALYSIS REPORT OF RESIDUE Sample Name: Pyrodcx Residue Peak # Component Retention Peak Area Peak Area/Height Name Time Height Ratio 1 Cl 4.70 436808 58188 7.51 2 N02 6.00 18581 1615 11.51 3 N03 9.62 430144 1968 15.32 4 804 16.20 344236 12418 27.72 97 8.5.: 8.". 8.2 8... 8... .835. A-.. A L 98 srt A l A A l PERCHLORATE/T HIOCYAN ATE REPORT Sample Name: Pyrodcx Residue Peak # Component Retention Peak Area Peak Height Area/Height Name Time Ratio 1 2.93 5718 751 7.61 2 3.15 1449592 179448 8.08 3 3.52 105385 16242 6.49 4 3.83 55384 5373 10.31 5 4.63 3285 340 9.68 6 6.03 1136 251 4.52 7 SCN 8.83 233250 16433 14.19 8 9.72 3162 587 5.38 9 C104 10.75 19739 1214 16.26 99 .‘ r-__~_._.x 83...: 9.: 9.2 3: 9.. one 3. cm a .2- h? UHo _ . _ a _ _ A” a a m N . 3N _ U. o _ H 1.. .V m .c _ mod 4 AZ... ....o.c. .8th we: «85 511 100 CATION ANALYSIS REPORT OF EXTRACT Sample Name: Black Mag Extract Peak # Component Retention Amount Peak Area Peak Height Name Time 1 2.02 0.00 6884 1912 2 2.53 0.00 44230 1193 3 Na 3.67 0.00 30291 1 31345 4 K 5.25 0.00 851674 60035 5 Mg 6.65 0.00 1867 282 6 Ca 8.30 0.00 693786 19318 7 12.85 0.00 1315 231 8 14.07 0.00 1278 191 9 14.77 0.00 1754 206 101 a 83...: 9R 9.: 9.2 9m. 92 ms om mm 89m- A... we a 9.: $9“. 5.8 83.9 mm: «8.9 stt 102 ANION ANALYSIS REPORT OF EXTRACT Sample Name: Black Mag Extract Peak # Component Retention Amount Peak Area Peak Name Time (ppm) Hejght 1 Cl 3.82 0.00 11531 1819 2 N03 8.02 9.70 380416 66272 3 10.18 0.00 1606 1590 4 $04 1 1.42 0.48 103217 9057 103 83...: 9w: 9.: 9w cm... 81.» 3.4 9H - ow o9”- _ _ _ A \ j _ H. o : o. a _ . “A . i: a N. no... 9. 9.: case: we: «8... 104 $11 CATION ANALYSIS REPORT OF EXTRACT Sample Name: Black Mag Residue Peak # Component Retention Amount Peak Area Peak Height Name Time 1 0.77 0.00 1471 177 2 1.83 0.00 12758 908 3 2.03 0.00 9906 2360 4 2.43 0.00 86941 2792 5 3.05 0.00 42214 1603 6 Na 3 .65 0.00 280054 26449 7 K 5.22 0.00 1036904 73850 8 Ca 8.28 0.00 376372 11016 9 1 1.50 0.00 1259 227 10 13.10 0.00 2611 258 1 1 14.35 0.00 2963 274 105 1198 1.9.: 9.2+ 9w. 9.: M» 9m 9w 89m- E is < 37 He 5.. n v . m9. ,....,9.: .fi «92 H L.98 25.8% we: «.83 Sfl 106 ANION ANALYSIS REPORT OF RESIDUE Sample Name: Black Mag Residue Peak # Component Retention Amount Peak Area Peak Name Time (ppm) Height 1 Cl 3.67 0.00 74202 10286 2 N02 4.53 0.91 39187 4798 3 4.88 0.00 20934 2310 4 N03 7.95 0.00 113201 19286 5 10.37 0.00 31511 1357 6 11.18 0.00 13305 2164 7 S04 1 1.45 0.14 31085 5220 107 83...: 9.2 9+: 9m. 92 9.. 9o 94 9.. o 9N- 1 1 r 111,, H. c _ a J a _ H. v . U. . i. N .mcé _ 9.. N 8.. l I T. T. .1. IT. I 9.: 29.5.55 8.28% .8309 311 108 CATION ANALYSIS REPORT OF EXTRACT Sample Name: Golden Powder Extract Peak # Component Retention Amount Peak Area Peak Height Name Time 1 2.68 0.00 39226 560 2 Na 3.68 0.00 603999 61985 3 K 5.25 0.00 1650608 1 17988 4 Ca 8.75 0.00 23434 734 109 .‘n.__.-_ mil. 9: 82.3.2 9m. 9m: 9.. o 9 V5 I VVW'IV'Vj'V—fTVWjfivvv'fiv II I: Bfiha BOE§AN ENEAVG 0 °. in °. 0 fl °. m .- odu sfl 110 ANION ANALYSIS OF EXTRACT Sample Name: Golden Powder Extract Peak # Component Retention Amount Peak Area Peak Height Name Time (ppm) 1 3.20 0.00 18682 2957 2 N03 7.40 0.00 1309077 125326 3 9.97 0.00 72683 5358 4 S04 10.75 0.30 64786 5511 5 11.18 7.06 331586 25007 111 8“... 8.0— P 1 8.2.: wow. 8.". 8.2 8... 8... D h 1 1 4 0 2.28..— .536.— .5280 112 Sample Name: Golden Powder Residue CATION ANALYSIS REPORT OF RESIDUE Peak # Component Retention Peak Area Peak Area/Height Name Time Height Ratio 1 2.51 3627 248 14.63 2 Na 3.90 235142 27789 8.46 3 N114 4.50 236907 1999 1 1.85 4 K 5.67 701437 48673 14.41 5 Ca 8.52 11194 652 17.16 113 2.23% .833.— con—o0 1 SN sfl 114 Sample Name: Golden Powder Residue ANION ANALYSIS REPORT OF RESIDUE Peak # Component Retention Peak Area Peak Area/Height Name Time Height Ratio 1 3.17 17440 2633 6.62 2 Cl 4.70 41957 4904 8.56 3 N02 6.00 951 15 9521 9.99 4 N03 9.62 436596 28321 15.42 5 16.17 29922 1119 26.73 115 «Oval—z 8.: 8d— 8.2 8 a 8.0 8 v God a . 0 0 o p u 1 - o x . CO v. A. o _v H . m .H. 00 —. H 1.- CON H 1... cod If m8... A. -59.. .836.— .5280 srt 116 Sample Name: Golden Powder Residue PERCHLORATE/T HIOCYAN ATE REPORT Peak # Component Retention Peak Area Peak Height Area/Height Name Time Ratio 1 2.87 207295 32897 6.30 2 3.23 657067 57088 11.51 3 3.52 1146162 184473 6.21 4 5.52 5391 633 8.52 5 5.75 41878 2501 16.75 6 7.62 4359 790 5.52 117 8:- In: . +9.2 9m. 92 9... 9.. 3 9m 8 9N- . A. _ . J. n w. v .9. #9.. M woe $9.. _ .. - m H 92 T. T. T I T T. 8.355 SASS «.393 $11 118 CATION ANALYSIS REPORT OF EXTRACT Sample Name: Black Canyon Extract Peak # Component Retention Amount Peak Area Peak Height Name Time 1 2.73 0.00 49960 782 2 Na 3.70 0.00 491495 50325 3 K 5.28 0.00 1 139858 80472 4 Ca 8.70 0.00 53130 1433 119 91m. mfi— 8.3.: 5W— mS II 1 3.52M 99......9 «2.3 ¢ °. tn S‘l’l 120 ANION ANALYSIS REPORT OF EXTRACT Sample Name: Black Canyon Extract Peak # Component Retention Amount Peak Area Peak Name Time (ppm) Height 1 N03 7.62 0.00 669807 84317 2 10.15 1.02 43977 2921 3 11.42 0.81 174778 13514 121 ‘n‘ ‘2 .. I .i..‘l .. .i 8.2:: 8“: - 18E. - 7 .831. , 8w. 8““: r3.» 8.0- 18... -Lfifl - - ecu. . J . ..... - . - . . . . . 1 - .. > .o < _ A 4 Z _ on _ m _ _ .H n :3 o H LS. A” hoe _ U N . . 11cm “2 1.5.2 2.23m coma—«U xuflm s'd 122 CATION ANALYSIS REPORT OF RESIDUE Sample Name: Black Canyon Residue Peak # Component Retention Peak Area Peak Area/Height Name Time He'ght Ratio 1 2.47 659 103 6.43 2 Na 3.90 538069 63261 8.51 3 N114 4.50 92716 6112 15.17 4 K 5.60 3179898 215864 14.73 5 Mg 6.88 79429 3840 20.68 6 Ca 8.50 199314 9533 20.91 123 Show cm: 8...».— 88...: 8m. 8%.: o2. 8.“ can #4 2: 2.28% :9980 x85 124 ANION ANALYSIS REPORT OF RESIDUE Sample Name: Black Canyon Residue Peak # Component Retention Peak Area Peak Area/Height Name Time Height Ratio 1 Cl 4.70 112315 14710 7.62 2 N02 6.00 352680 35377 9.97 3 6.47 99434 8923 1 1.14 4 N03 9.63 92382 5729 16.13 6 16.17 66263 2314 28.63 125 Hi .1....... . _._..1‘:-'fl 85...: cacao gun—m l ..,-. o 0. P L L A Y A J A A l A v v Vi v 1 1 o Q V [4.4 A A Y V V sri 126 PERCHLORATE/T HIOCYAN ATE REPORT Sample Name: Black Canyon Residue Peak # Component Retention Peak Area Peak Height Area/Height Name Time Ratio 1 2.87 12524 1641 7.63 2 3.17 1539251 175179 8.79 3 3.50 289557 34651 8.36 4 4.88 7646 1464 5.22 5 5.52 1508 251 6.00 6 C104 10.62 7210 437 16.51 7 14.83 801 131 6.10 127 —...u......¥111. -. . at»... 8.252 90— c..: 9N— cd— emu omc 9v chm c 9N- L A 4 A v v v m. N. Z c. a as. _ l1. 'V'VY O <- l _A A A l A A A A v v v v v v .. 3: 8.5 .2... =85 $11 128 CATION ANALYSIS REPORT OF EXTRACT Sample Name: Clean Shot Extract Peak # Component Retention Amount Peak Area Peak Height Name Time 1 2.00 0.00 7604 1549 2 2.45 0.00 23042 854 3 3.33 0.00 1225 195 4 Na 3.65 0.00 149532 15529 5 K 5.17 0.00 1657572 122569 6 Ca 8.27 0.00 334829 9703 7 10.45 0.00 2637 244 8 10.75 0.00 1384 218 9 12.20 0.00 2834 317 10 12.87 0.00 2001 208 1 1 13.53 0.00 2240 230 12 14.20 0.00 1343 235 13 15.65 0.00 6694 239 129 n “K‘ 82.1.2 .33 3.31 .339 3% £1. 3... MN. 3: mm. .Mm mw a 9n- _ _ m who.“ . .. A." . Mac O— . u” N 1... .3. r E I I I in I 3.. gr! 130 ANION ANALYSIS REPORT OF EXTRACT Sample Name: Clean Shot Extract Peak # Component Retention Amount Peak Area Peak Name Time (ppm) Height 1 3.22 0.00 . 13924 2545 2 N03 7.37 0.00 1421300 123763 3 10.18 0.00 75069 14552 4 S04 1 1.45 3 .21 689331 40913 5 C104 16.70 34.98 322359 18336 131 .1. a . . . “M ‘l A‘.‘ till. .1... «383—2 8%. 8...: 8.: , 8%. cm... 3.» 3... 3.41 3N o 9N- ) H < .2 z _ A. _ M _ _ .. m 11 . 0 .. O N A... 3 . .. N U. 1-90 .H 11 Gd .. 1.5.2 02...»... .95 5.1.6 sfl 132 CATION ANALYSIS REPORT OF RESIDUE Sample Name: Clean Shot Residue Peak # Component Retention Peak Area Peak Area/Height Name Time Height Ratio 1 2.47 2141 238 8.98 2 Na 3.90 355563 41897 8.49 3 NH. 4.50 93413 6217 15.02 4 K 5.60 3190576 217325 14.68 5 Mg 6.90 73812 3660 20.16 6 Ca 8.50 208327 9921 21.00 133 “151 'u- [—4- _ A “f. .7. “I“ III. . .. c— o‘- 328... .25 52o .. A l A A A V v 7 v v v v .118... .fi . . 1. 8 n 511 134 ANION ANALYSIS REPORT OF RESIDUE Sample Name: Clean Shot Residue Peak # Component Retention Peak Area Peak Area/Height Name Time Height Ratio 1 3.17 2511 255 9.85 2 Cl 4.72 587058 79284 7.40 3 N02 6.02 48948 5001 9.79 4 6.70 1142 151 7.57 5 C103 8.85 23742 1428 16.63 6 N03 9.67 198273 12757 15.54 7 11.55 2035 198 10.28 8 12.57 717 114 6.28 9 16.18 35651 1169 30.51 10 18.70 1956 153 12.77 135 .11: am {A 1 ll 83...: .95 50.0 3r! 136 PERCHLORATE/T HIOCYAN ATE REPORT Sample Name: Clean Shot Residue Peak # Component Retention Peak Area Peak Height Area/Height Name Time Ratio 1 1 .02 2649 406 6.53 2 2.87 59332 10309 5.76 3 3.10 1290051 190735 6.76 4 3 .50 499143 72055 6.93 5 4.23 1928 221 8.74 6 5.37 9296 938 9.91 7 C104 10.58 296327 17830 16.62 137 (3‘4 “an 3.1.! APPENDIX V HPLC Results 138 ——L ' 0.500 F Black Powder Extract x 0.525 Black Powder Residue 0.500 4.019 L 2:- 5.962 Pyrodcx Standard .1 i. 0.515 C ::_________ 4.052 C 3 6.033 r... 1 ‘ 5.836 ‘ Pyrodcx Extract 139 fi fi 0.500 3.948 ww ’1 1 Golden Powder Extract 052‘ —°__L f Golden Powder Residue 0-545 1 1 ‘1 “‘1 fr 1 0.531 1’ Black Canyon Extract 1 ‘r 1 i. 0.545 Black Canyon Residue 140 0.495 Black Mag Extract 1 0.526 {1 Black Mag Residue 1 1 —_1____ 0.500 Clean Shot Extract 1F 0.520 Clean Shot Residue 141 REFERENCES 142 REFERENCES lRudoph, T. L. “The Characterization of Some Low Explosive Residue By Ion Chromatography,” Proceedings of the International Symposium on the Analysis and Detection of Explosives, FBI Academy, Quantico, VA, 29-31 March 1983, 213-219. 2Bureau of Alcohol, Tobacco, and Firearms Arson and Explosives Programs Division, National Repository Branch, Arson and Explosives Incident Report, 1997. 3Davis, T. L. 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(1975) U.S. Patent 4,128,443. l0Karl, E. F. (1985) US. Patent 4,497,676. ”Ciofi‘e, A. (1997) US. Patent 5,663,476. 12Yard, E. M. “Blackpowder Could have been White or Yellow. . .or Pink!” The Gun Digest, 43, 161-164 (1989). l3Lanara, D. A. “Black Canyon Powder,” Black Powder Cartridge News, 9, 12-13 (1995). ”Ozzie, “A Guide to Muzzle Loading Accuracy,” The Black Powder Journal, 2, 2-3 (1997). 143 lsKindig, R. “Product Review: Black Mag Powder,” The Black Powder Journal, 1, 3-6 (1996). 16Miller, A. “Clean Shot- A Black Powder Substitute,” Handloader Magazine, 6-12, (1999). ””Clean Shot Power Data Sheet” from www.cleanshot.com 18”Clear Shot” from WWW-gOCXQOWder-Com l9Anonymous, “Black Powder Substitute,” Explosives Engineering, 4, 7 (1987). 20”Pyrodcx” from w .pyrodex . co m 21Willard, H. H., Merritt, L. L., Dean, J. A. Instrumental Methods of Analysis, D. Van Norstrand Company, Inc., Princeton, New Jersey, 1958. 22Feigl, F. and Anger V. Spot Tests in Inorganic Analysis. 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A. and McCord, B.R. “Explosive residue analysis by capillary electrophoresis and ion chromatography,” Journal 0 f Chromatography, 602, 241-247 (1992). 34Reutter, D. J.; Buechele, R. C. and Rudolph, T. L. . “Ion Chromatography in Bombing Investigations,” Analytical Chemistry, 55, 1468A-1472A (1983). 3"’Hall, K. E. and McCord, B. R. “The Analysis of Mono- and Divalent Cations Present in Explosive Residues Using Ion Chromatography with Conductivity Detection,” Journal of Forensic Sciences, 38, 928-934 (1993). 36Bender, E. C. “Indirect Photometric Detection of Anions for the Analysis of Low Explosives,” Crime Laboratory Digest, 16, 78-83 (1989). 37Beveridge, A. D.; Green, W. R. A.; and Shaddick, R. C. “Identification of Reaction Products in Residues fi’om Explosives,” Proceedings of the International Symposium on the Analysis and Detection of Explosives, FBI Academy, Quantico, VA, 29-31 March, 1983, pp. 53-58. 38McCord, B. R.; Hargadon, K. A.; Hall, K E. and Burmeister, S. 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