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Gunshot Residues (GSR) Introduction The first step in the firing of a bullet is the detonation of the primer. When the firing pin of a firearm strikes the back of the cartridge, the shock-sensitive primer is detonated when it is crushed by the force of the firing pin of the firearm. The primer compound ignites, sending a flame into the cartridge case. Gunpowder in the cartridge case deflagrate, causing it to change from a solid material to gas. The ignition of the primer mixture and the propellant occurs in a matter of a few ten thousandths of a second. The ignited propellant decomposes and forms gaseous products. Simultaneously, heat, in enormous quantity, is released by this reaction. The high pressure from the heated gases forces the projectile out of the cartridge casing into the barrel and out of the muzzle of the gun. When the bullet exits the muzzle, pressure within the cartridge case also blows the gunshot residues out of the firearms barrel. The residues are expelled from the barrel in a smoky cone shaped pattern at different velocities. These vaporized materials or plume also escapes from the firearm through any available openings that is not gas tight. These products of firearm discharge can be collectively referred to as gunshot residues (GSR). Gunshot residues have been used in criminalistics to estimate firing distances, identify bullet holes, and most importantly, to determine whether or not a person has discharged a firearm.

As can be seen in the image above, the bullet and the flume (streaks of smoke, burning gunpowder and burnt/unburnt/partially burnt particulates) can be seen exiting the barrel/cylinder gap of the revolver. Gunshot Residues (GSR)

Gunshot residues are defined in the Association of Firearms and Toolmark Examiners (AFTE) Glossary, as The total residues resulting from the discharge of a firearm, it includes both gunpowder and primer residues, plus metallic residues from projectiles, fouling etc. This definition is reasonably understood; however, gunshot residue examinations of primer particles are often confused by most people, with examinations of the remaining elements of gunshot residue. Although the examinations of primer particles and those of gunpowder residues are examinations of gunshot residues, they are examined in very different ways. Primer particle examinations utilize instrumental techniques while gunpowder residues utilize visual and chemical methods. The ability to provide evidence, based on analysis of gunshot residues, that a person has discharged a weapon has been one of the most persistent goals of forensic scientists since the turn of the century. Several factors serve as motivation for this intensity of concern. Crimes associated with firearms are particularly serious and require perhaps the greatest investigative effort. It is often possible to recover spent bullets or cartridge casings and associate them with a particular gun. However, the remaining link in the chain of evidence is to associate a suspect with the firing of the gun in question. Forensic scientists always have report that the finding of GSR cannot indicate the shooter, yet people are usually seemed surprised to learn that. Nevertheless, GSR findings continue to add value simply because numerous population studies have shown that GSR is not normally found on the average person. Gunshot residue evidence that provides proof that an individual has recently fired a gun has been of substantial help in the investigation of many of these cases. I. Source of Gunshot Residues 1. Primers Ammunition primers consist of four basic chemical components: the initiating explosive, oxidizing agent, fuel, and sensitizer. Each component can be expected to contribute gunshot residues after a gun has been fired. The standard explosive initiator in primers is lead styphnate. Oxidizing agents are used in primers to increase the heat of ignition. Barium nitrate is most commonly used in small-arms ammunition. Antimony sulfide is commonly used as fuel in primers. The standard sensitizing material used in small-arm primers is tetracene [1-(5-tetrazolyl)-4guanyltetrazene hydrate]. The GSR originating from the primer components contain elements mainly lead (Pb), barium (Ba), and antimony (Sb). Lead residues will be in a vaporous or particulate form and can come within a discharged cartridge; the most common source is the primer. Additional vaporous lead residues can be produced when the hot gases pushing a lead bullet down a barrel, melt lead from the base of the bullet. A third form of lead residue will be in a particulate form. Particulate lead residue comes from

minute lead particles that are shaved from the sides of a lead bullet as it travels down the barrel. Lead particulate has more mass than vaporous lead and travels greater distances. Also, gunpowder particles can be coated by the vaporous lead residues and leave what appears to be a lead particulate deposit upon striking the target. The amount of lead residue emitted from a gun can vary slightly from shot to shot. Fouling in the barrel from previous shots can slightly increase the amount of lead residue emitted from one shot to the next. 2. Propellants All gunpowders are designed to burn quickly to produce rapid expansion of gas (in an explosion something gets very big very fast) in a confined space. The burning rate of gunpowder can be classified in three categories depending on their morphology: A. Degressive (regressive) burning gunpowder grains formed in flakes, balls, and sticks have a burning surface area that decreases continuously as the grains are consumed. B. Neutral burning gunpowder grains that are single perforated and the burning surface area remains relatively constant. C. Progressive burning gunpowder grains that are multiperforated and rosettes that have a burning surface area that increases continuously as the grains are consumed. A few common types of smokeless powder morphologies can be seen in Figure 1.

Figure 1

The use of black powder as a propellant for bullets has largely been discontinued. Smokeless powders, which are commonly used as propellants, are also described as single-base when the basic ingredient is nitrocellulose and as double-base when there is addition of 1 to 40% nitroglycerine. In some double base powders a portion of nitrocellulose and nitroglycerine has been replaced by nitroguanidine. These are sometimes referred to separately as triple-base powders but they are not commercially available. Typical single based powders are found in rifle cartridges and some rim fire rifle and revolver cartridges, whereas double based powders are used in revolver and pistol as well as shotgun cartridges. Rim fire rifle and revolver cartridges may also be double-based. All smokeless powders, in addition to explosive ingredients, contain a number of additives. These additives fulfill the role as stabilizers, plasticizers, flash inhibitors, coolants, moderants, surface lubricants, and antiwear additives etc. A particular propellant powder will contain one or more of these additives depending on its use. 3. Bullets The bullet in an automatic pistol cartridge contains a lead core that is covered with a full metal jacket of copper alloyed with 5 to 10% zinc. Revolver bullets are generally composed of lead, or lead plated with a thin layer of copper, or the lead is alloyed with antimony or tin, or with both. In some bullets, such as hollow-point and soft-point bullets, a copper jacket covers the base and cylindrical portion, leaving a soft metal at the tip. 4. Other Sources Cartridge cases are usually composed of brass but the brass case may sometimes be coated with nickel which leads to this element being present in some residues. Materials present on the interior surface of a gun barrel can give rise to gunshot residues. Iron and oil as well as rust and fouling from previous shots can be found inside a gun barrel. Bullet lubricants are common in cartridges providing a smooth release of the bullet from the cartridge casing. II. Composition of Gunshot Residues (GSR) Particle Formation Firing a weapon produces GSRs, these particles fall on the fired weapon, anything in the vicinity of the fired weapon, including the skin or clothing of the person who fired the gun, on the bullet hole of the clothing or skin of the entrance wound of a victim, or on any materials at the scene. The discharge of a firearm can deposit residues even to persons at close proximity. Tests show that people standing within 3 feet to the side of a shooter may have GSR on their hands, whereas those standing

10 or more feet in the same direction typically will not, so interpretations as to who fired the weapon should be made with caution. The elemental composition of GSR particles may vary depending upon the type of ammunition used. The method of particle formation is generally accepted in the forensic science community. The heat generated on ignition of the primer causes the inorganic ingredients of the primer mixture to vaporize. Because of supersaturation, these vapors re-condense into droplets, which are further subjected to high pressure and temperature arising from the burning propellant powder. Some of these droplets will grow by coalescence. With the expansion and cooling on leaving the barrel many of these droplets freeze in their existing form. The size of these particles range from large visible particles to a fine dust (typically measure 1 to 10 microns in size, for comparison, a typical human hair is approximately 100 microns in diameter). Inorganic Components Understanding particle formation enables the investigator to differentiate GSR particles from environmental sources of Pb, Sb, and Ba. Most primers produce residue deposits that contain lead (Pb), barium (Ba), or antimony (Sb), usually, all three are present. These elements normally become more abundant on the hand after a handgun is fired. Lead and antimony are potentially present in the form of free metal from the bullet or as chemical compounds formed during combustion. Barium is present in compound form. Less common elements include aluminum (Al), sulfur (S), tin (Sn), calcium (Ca), potassium (K), chlorine (Cl), copper (Cu), strontium (Sr), zinc (Zn), titanium (Ti), or silicon (Si). A mercury-fulminant based primer may be found in ammunition manufactured in Eastern Europe and used in the Middle East. Primer elements may be easier to detect in residues because they do not get as hot as the gunpowder. The so-called lead free ammunition may contain one or more elements including strontium (Sr), zinc (Zn), titanium (Ti), copper (Cu), antimony (Sb), aluminum (Al), or potassium (K). The chemical composition of these compounds can have great influence on both potential residue collection and elemental analysis techniques. However, methods for the determination of inorganic molecular composition are more difficult to apply than those for elemental analysis. It is unlikely that extensive information regarding the molecular composition of inorganic gunshot residues will be available in the near future. Organic Components Earlier gunshot residue detection methods were based on analyses for nitrates and nitrites in the gunpowder combustion products. The exact chemical compositions of the residue materials

responsible for the reactions in these tests are still unknown, although it is likely that unburned gunpowder particles are present in the residues. These particles when large enough to be examined by optical microscopy resemble the larger smokeless powder particles of the unfired ammunition. These particles have been shown to produce the streaking blue reaction used to detect nitrate and nitrite-bearing compounds in the dermal nitrate test. If they are produced from unburned smokeless powder fragments, they may contain substantial amounts of nitrocellulose and nitroglycerine as well as the other constituents of smokeless powders. Modern gunpowder, or smokeless powder, can contain up to 23 organic compounds (in an FBI study). Nitrocellulose is virtually always present, along with other compounds containing nitrate or nitrogen. One of these compounds, diphenylamine (used as a stabilizer in the powder), can be detected using reagents containing sulfuric acid and can be differentiated using a mass spectrometer. III. GSR Deposition The amount of deposition is determined by several factors such as the type and condition of weapon, number of shots fired, the amount of oil, moisture or perspiration material on the deposited surface, and the direction and force of air currents. Deposition on the Target If the muzzle of the discharging firearm is sufficiently close, gunshot residues will deposit on the target in an approximately circular area around the bullet hole. When the muzzle of the firearm is next to or is in contact with the target (contact fire), hot gases escaping from the muzzle at a high velocity will typically rip, tear, shred, and/or melt the material of the target. A very intense deposit of gunshot residues will be found around the margins of a contact or near contact entrance hole. The residues include not only those burned, partially burned and unburned primer and propellant materials ejected forward with the bullet, but also some material ablated from the bullet. It has been reported that when the target is backed with a glass panel, another residue pattern is produced on the reverse side of the target; this may also be true for other material. The deposition of gunshot residues around holes in tissue, clothing, wood, metal, and glass permits identification of the bullet entrance holes and determination of muzzle-to-garment distance. Deposition on Garments/Clothings As described above, gunshot residue can be deposited on articles of clothing when in close proximity to a discharged firearm. But will it stay there? In most cases the answer is yes. The various elements contained in gunshot residue are not readily water soluble and clothing left exposed to the elements will not usually diminish the residue deposits. Other factors such as heavy bleeding and rough

handling of the garment can cover up or dislodge some residues. This has to be taken into consideration when conducting all such examinations. The garments must be promptly collected, allowed to air dry, and packaged in a way that will minimize contamination. The clothing submitted to the laboratory will be examined to determine if a pattern of gunshot residue is present and there are a number of examinations conducted to aid in this determination. The muzzle-to-garment distance can vary considerably depending on the firearm and type of ammunition being used. Short-barreled firearms and lower velocity cartridges will not normally expel residues as far as a high velocity rifle. At shorter distances however, they may deposit greater concentrations of gunshot residues. Also, gunpowder can come in several forms such as ball, flake, disc, and others. Ball powder being spherical in shape is more aerodynamic than say a particle of flake gunpowder and as a result will travel farther. A number of other variables can influence the amount of gunshot residues that may reach a target; therefore, it is essential that the firearm and ammunition used in the shooting incident be recovered. Gunshot residues emitted from the muzzle will travel out to distances of approximately 3 to 5 feet in most firearms but in some cases can travel even greater distances. At the 3 to 5 foot range, the gunshot residues may only consist of a few trace particles and make determining the firing distance difficult if not impossible. As the firearm gets closer to its target the residue concentrations increase and the actual size or diameter to the pattern gets smaller. At around 18 to 24 inches, most firearms will start to deposit considerable concentrations of gunshot residues that may or may not be visible to the eye. At distances of less than 12 inches, heavy concentrations of visible gunshot residues will normally be deposited. Comparison of the residues previously developed on evidence items is made against known standards to determine the distance of a suspect firearm from the target at the time of discharge. Distance determinations based on gunshot residues are not performed in isolation from the rest of the firearmsrelated evidence in a shooting case. If the muzzle of the weapon is in contact with the target or within approximately half an inch, gunshot residues are generally absent. This is due to the lack of space available for expansion which results in penetration of the target through the entrance hole of any gunshot residues. When the muzzle to target distance increases, gunshot residues will disperse and this distribution will permit an assessment of the distance from which the weapon was fired. A more precise assessment can be made from repeated firings at described distances from a target and observation of the spread of the residues. To obtain satisfactory results for comparison, test firings have to be performed with: 1) the suspect weapon;

2) the suspect ammunition or the same type, brand, and year of manufacture; and 3) material of the same nature and quality as the material of the target. Any comparison to be made may relate to the geometric area and the concentration of residue. A study using porcine flesh as target material demonstrated that the three elements antimony, barium, and lead were deposited on the target up to 4 feet from a pistol and 3 feet from a .38 caliber revolver. Deposition on the Firer 1. Handguns During discharge, revolvers and pistols leak residues from parts of the gun near the firing hand. There are three sources of deposit: 1) Leakage from gaps in the firing mechanism. Revolvers have a small gap between the cylinder and the rear end of the barrel. Some gunshot residues are leaked from this gap and deposited on the firer during discharge. 2) Emission at ejection of the cartridge case. In semiautomatic pistols, as the bullet moves out of the barrel, another mechanism opens the breech and ejects the spent cartridge case. During this process, some gunshot residues are released and deposited on the firer. 3) Blowback from the muzzle cloud. The major portion of gunshot residues is emitted from the muzzle of the weapon and some of these residues may flash back and be deposited on the firer. Pistols and revolvers deposit more residues on the firing hand compared to the non-firing hand, but this may not always be the case because the concentration and/or location of the residue depends on the shooting stance and grip used. Generally for this type of weapon, the larger the caliber, the larger is the likely amount of gunshot residue to be deposited on the hand. The gunshot residues on the firing hand are mostly deposited in the web area. This is the V-shaped part of the hand between the thumb and forefinger facing upward when the handgun is fired and is the area in closest contact to gases escaping along the side or back of the gun during discharge. Residues may also be deposited on the forearm or sleeves and the front of the chest from both revolvers and pistols. Other skin surfaces such as face and neck have also been reported to be useful sources of gunshot residues. Mere handling or loading of a firearm, as opposed to firing, is inferred from the detection of gunshot residues on the inside of the hand.

2. Long Guns After firing some shotguns and rifles, gunshot residues can be detected on the hands and cheek of the firer but the amount of the residues is usually less than that of common handguns. When both hands are used to fire the long guns, because the non-firing hand is much closer to the muzzle than the firing hand, then more gunshot residues, due to flash back, may be deposited on the non-firing hand than the firing hand. The shorter the barrel, the closer the non-firing hand is to the muzzle. Hence, more gunshot residues may be deposited on the non-firing hand in the case of shotguns and rifles. IV. Persistence of Gunshot Residues Gunshot residues deposited on a person are continuously lost; it is difficult to generalize as to the period over which the residues would be retained. Rates of loss can vary with the type of gun and ammunition, number of shots fired, and the environment of the shooting and activity of the subject. Particles may be removed from a shooters hands within 4 to 5 hours after a shooting event. They can also transfer from a surface or person to another individual; the amount depends on the number of GSR particles on the contaminated surface (e.g., a persons clothing or hands) and likely will be a small percentage of the total number of particles present. However, the length of time during which gunshot residues remain on hands and clothing of a firer is an important factor in evaluating evidence. If the residues are retained over a period of days, then gunshot residues found on a persons hands or clothing might have resulted from a firing several days prior to the incident under investigation. In a study on the effect of hand activity and time on the persistence of gunshot residues found on the hands of persons who test-fired guns; their hands examined for antimony and barium at various timed intervals after shooting. The shooters activity was unrestricted after firing, except that hand washing was forbidden. This study led to the conclusion that two (2) hours after firing, substantial amounts of antimony and barium were removed. Importantly, no evidence of gunshot residue deposition remaining on the hands of a shooter after the hands were washed with soap and water and then dried with paper towels. Other activities shown to remove substantial amounts of antimony and barium include rinsing the hands under low-pressure aerated water for three (3) seconds, wiping the hands on clothing, and placing the hands in pockets three (3) times (a significant amount of primer residue still remained on the hands of the shooter after placing their hands in their pockets three times). A transfer of antimony and barium from the shooting hand to the non-shooting hand was noted when hands were wiped with towels following a shooting and when the shooter was handcuffed with his hands behind his back and then transported in an automobile.

It has also been reported that nitroglycerine residues on the shooters face, throat, and hands may be retained up to seven (7) hours. For unwashed hands of suicides, deposits may be present for 48 hours and perhaps for a much longer period. But in another study, no nitroglycerine was detected on shooters hands 30 minutes after 11 test firings was carried out with a variety of weapons and ammunition. The persistence of gunshot residues on cloth is much greater than that on skin. In test firings which were carried out with a revolver, nitroglycerine, nitrocellulose, and diphenylamine have been detected on a variety of clothing types, six (6) hours after the firing had taken place. Clothings removed just after firing and stored, undisturbed, was found to retain readily detectable amounts of gunshot residues when examined the following day. No gunshot residues could be detected on the firer after the same time period. This suggests that the loss of gunshot residues is due to physical disturbance rather than any chemical degradation. It is further reported that the residues deposited on a cotton sheet placed one (1) meter from a revolver which fired five shots remained detectable for a period of two months providing the sheet was undisturbed during this period. Nitroglycerine could be detected on garments which were worn with unrestricted activity for as long as 5 days after test firing. The constituents of gunshot residues have been discussed above, the remainder of this section will describe and assess sampling methods, sample pretreatment techniques, and methods for gunshot residue detection. Some of the techniques are no longer in use, but for purposes of completion they have been mentioned. V. Survey of Methods for the Identification/Characterization of GSR Choice of Approach to Gunshot Residue Analysis The identification and characterization of gunshot residues (GSR) has always been of great interest to forensic scientists. The major methods for detection of inorganic primer residues are analytical and qualitative. Which procedure is to be used depends on whether organic residues derived from the propellant or the inorganic residues derived from the primer components of a cartridge, are to be analyzed. When used together the two approaches substantially increase the number of cases in which firearms contact may be substantiated. Surveys revealed that gunshot residue detection methods used by forensic science laboratories in the United States are scanning electron microscopy/energy dispersive X-ray analysis (SEM/EDX), flameless atomic absorption spectroscopy (FAAS), neutron activation analysis (NAA), anodic stripping voltammetry (ASV), and chemical tests.

SEM/EDX, FAAS, NAA, and ASV represent quantitative analyses of the bulk content of Ba, Sb, and Pb collected from specific area of a hand. The amounts of these elements, beyond certain established threshold limits, are considered to be characteristic of gunshot residues. However, the environmental and occupational contributions of these elements to any measured values severely restrict the ability of bulk analysis to conclusively identify gunshot residues. The observation that the quantity of these elements present on skin surface decreases with the lapse of time may also lead to inconclusive results. Analytical methods (separation, identification, and quantification of the chemical components) include atomic absorption spectrophotometry (AAS) and inductively coupled plasmaatomic emission spectrometry (ICP-AES). The sources of gunshot residues include every part of the ammunition used, but the main contribution comes from propellant and primer. In connection with its work on a mass spectrometric approach to the analysis of gunshot residues, the FBI laboratory has compiled a list of 23 organic compounds that may occur in smokeless gunpowders. Nitrocellulose is the main ingredient of all smokeless powders and will invariably occur in GSR. VI. Sampling Methods Considerable effort has been directed toward the development of satisfactory techniques for the collection of gunshot residue samples. For these methods, samples must be obtained from the skin surfaces of a victim at the scene. The decision to collect residues is often made by the arresting officers, who must collect samples immediately after apprehension of a suspect because residue deposits normally wear off within a few hours. Delay in obtaining residues, movement, or washing of the body prior to autopsy will diminish or destroy gunshot residues. Therefore, the collection procedure must be quick and simple, and the possibility of external contamination must be avoided. The current techniques used for organic residue collection, include swabbing and vacuum, and tape lifting. Washing and film lifts are generally used to collect inorganic gunshot residues from hands. The use of human nasal mucus as a media for the recovery of GSR has been reported and successful recovery was achieved 48 hours after the firearm was discharged. Contamination Contamination is the major concern when reporting GSR results. GSR particles are more delicate than the finest talcum powder and they are invisible to the eye. GSR particles can be transferred from surface to surface by contact, air movement, abrasion, and washing. Numerous studies for the presence of GSR particles in police cars, police stations, police equipment, and occupational environments have found that sources of contamination are abundant. To report the finding of a single unique particle of GSR on a person as a positive finding for gunshot residue is akin to reporting that

the finding of a single grain of sand upon a persons shoe is a positive determination that that person had recently been on a beach. Police officers are trained to collect samples as soon as possible after apprehending, a suspect, preferably, before transportation to the police station, and to clean their hands and wear gloves when sampling suspects to prevent contamination. While law enforcement personnel could be a potential source of GSR because they carry guns, studies have shown that few of them have particles on their hands because they clean their hands much more often than they touch their weapons. Nevertheless, police officers should avoid contact with a subjects hands before sampling. If armed officers collect the samples, a disposable lab coat, along with proper hand washing and glove use, can minimize the risk of contamination. As police vehicles and interrogation rooms are potential sources of contamination, investigators should collect GSR samples before transporting subjects in a police car or questioning them at the station. Studies have indicated a low potential for secondary transfer in these areas and that testing them occasionally may help prove the low risk of contamination. During examination, safeguards can ensure that GSR samples remain uncontaminated in the laboratory. Samples for GSR testing never should be exposed to the firearms area of the facility. Additionally, no armed personnel or persons who made contact with the firearms section on the day of analysis should have access to those areas. 1. Swabbing Swabbing is the most common technique used for collecting organic compounds from hands. For swabbing, sampling is conducted by repeatedly scrubbing the appropriate area of skin with certain material. Recommended materials include a ball of cotton, synthetic wool, filter paper, a piece of cloth, filter cloth, or Acrilan fiber. The material used is moistened with an appropriate solvent before swabbing. The typical solvents for organic gunshot residue sampling are acetone, ether, methyl tertbutyl ether, alcohol, isopropanol, and isopropanol/water (8:2 V/V). Whichever solvent is chosen, the aim must be to maximize the transfer of gunshot residues to the swabs using a minimum amount of solvent. A study was done using eight solvent systems for use in the removal of nitroglycerine from hands with 30 mg cotton swabs. The results indicated that ethanol appeared to be the best compromise organic solvent for removing nitroglycerine from hands using cotton swabs. The most common technique used to recover organic residues from the swabs is to leach out the swabs with solvents. In order to avoid problems associated with concentration of the sample, impurities present in the solvent, and loss of the more volatile explosives during concentration, a minimum amount of solvent should be used. The commonly used recovery methods are:

a) Direct extraction: With the help of a glass rod, swabs are extracted by successive washing with small portions of the solvent. b) Constricted tube technique: A test tube is drawn to produce an extension tube with a narrow hole at the bottom. The swabs are compressed into the tube using a glass rod and compounds in the swabs are eluted by repeated washings with a small volume of solvent. c) Squeeze method: Solvent is added to the swab in a storage vial and the swab is squeezed and pressed against the inside wall of the vial using forceps. As much liquid as possible is removed by squeezing the swab on the inside of the vial neck. This solvent is then removed to another vial and the same procedure repeated with further volume of solvent and the extracts pooled. d) Syringe elution: The swabs are compressed into the base of a 5-mL glass syringe and the plunger is pressed down to expel any solvent. A portion of solvent is drawn up into the syringe and forced out through the swabs which are again compressed. This procedure is repeated and the extracts pooled. Centrifugal microfilter extraction: All parts of a microfilter are pre-cleaned by Soxhlet extraction and assembled. The swabs are gently inserted into the sample compartment and centrifuged at 4000 rpm for 5 min to remove as much solvent from the swabs as possible. This is collected as the first fraction. Two or three subsequent centrifuge fractions are collected after adding further quantities of solvent. The constricted tube extraction gives more variable recovery efficiency than other methods because of inconsistency generated in packing the swab. Although efficient extraction can be obtained by every studied technique using the correct manipulation procedure, with the exception of centrifugal microfilter extraction, the final extract volume will be of the order of 3 to 5 mL. The use of centrifugal microfilters gives extraction volume less than 1 mL thereby reducing the amounts of solvent impurities which will be concentrated prior to analysis. The technique will therefore diminish the loss of the more volatile explosives on evaporation. 2. Vacuum Lifting Vacuum lifting is widely used for collecting organic gunshot residues from clothing. Clothing debris is vacuumed on to a filter disc, and then the filter is extracted with solvent to recover the organic gunshot residues. Its main advantages are its ease of operation and the fact that a larger area can be sampled within a short time. In the case of vacuum sampling from hands, a considerable amount of nitroglycerine was detected following a subsequent swabbing. This indicates that nitroglycerine is deposited both as particulate matter and as a condensing vapor. The vacuum lifting technique removes only the particulate matter portion.

3. Tape Lifting For the tape lifting method, sampling is carded out by pressing a single sided adhesive tape or a double sided adhesive tape onto the substrate surface. This technique has mainly been used to sample inorganic residues for micellar electrokinetic capillary electrophoresis (MECE) analysis. Masking tape in 1 in. square sections used to collect the gunshot residues were observed under stereomicroscope and any suspect particles removed with tweezers and placed in a glass microvial. The particles were then extracted with 50 micoliter of ethanol. A second approach made use of a direct ethanol extraction of a 2 cm 2 section from a tape lift in a microvial. A comparative study was done tabulating the advantages and disadvantages of the three sampling techniques, the tape lift procedure being identified as the best. Sample Pretreatment In many chromatographic analyses, the analytical systems are able to detect pure standards of organic gunshot residues down to low nanogram levels but such sensitivity cannot be achieved with extracts from hand swabs or vacuumed clothing samples. This problem arises because such extracts are substantially contaminated with lipids and other co-extracted materials which result in deterioration of the separation column and the detector; clean-up is an essential pretreatment to minimize column deterioration and detection noise, even where the system used possess a high degree of selectivity. VII. Quantitative Analyses Scanning Electron Microscopy/Energy Dispersive X-ray Analysis (SEM/EDX) SEM/EDX is potentially superior because it characterizes individual gunshot residue particles both morphologically and elementally. Highly specific results may be obtained by scanning electron microscopy/energy dispersive X-ray analysis (SEM/EDX) of the inorganic residues. If all the requirements for the SEM/EDX method of identification of inorganic residues are met, the additional contribution towards the evidence of organic residues is relatively small. However, when the inorganic residues have not been recovered, or when their characteristics are poorly specific, evidence may be forthcoming from an examination for organic residues. Furthermore, for unknown reasons, it is found that there is a rough reciprocity between the amounts of inorganic and organic residue detected. That is to say when large amounts of inorganic material are found, organic residues may add little further information but where they are not found or are only found at very low levels, then organic residues may be informative.

A major advantage of this method is that it can reveal the actual surface details of the particles examined, for comparison with known examples of gunshot residue, and pictures can be taken. The large particles of partially burned powder and the spheres of residue can be distinguished from contaminant materials. Its ability to detect as little as a single gunshot residue particle also makes conclusive determination of gunshot residues possible after longer lapses of time. Even the main disadvantage of SEM/ EDX, the excessive time required for search and identification, has been overcome by the advent of automated instruments. SEM/EDX offers many advantages over other methods and is reported to have success rates for homicide/assault cases, suicide/homicide decision, and suicide verification of up to 79%, 89%, and 89% respectively. An important application of this technique to lead free ammunition is the identification of the most important particles arising from Sintox ammunition (titanium and zinc).

Diagram of the SEM-EDX pattern of GSR An X-ray analyzer can be beamed directly onto the particles, so that the energy dispersive pattern (EDX) can be generated, giving the elemental composition of the particles. A computer program to speed up the search for GSR particles by SEM has been described. SEM may also have usefulness for examination of bullets, as embedded materials from the target such as bone fragments may aid in reconstruction of the scene. SEM has been used to study tool marks made by the firing pin impressions in the primers of spent cartridges. Such findings could be useful to determine which gun was used to fire the cartridge. SEM could reveal clearly all surface detail in the impression and that 50% of shotgun impressions and 75% of rifle impressions could be positively identified on the basis of four or more individual characteristics, given similar class characteristics.

For SEM, the method of collection for residue is quite simple and easily carried out in the field. Investigators collect primer GSR with adhesive lifters, sometimes referred to in supply catalogs as dabs or stubs. Several companies sell them, usually as a kit with gloves, instructions, an information form, and tape to seal the kit when finished. The adhesive contains carbon, which colors it black and makes it able to conduct electrons in the SEM. Analysts also can use clear adhesive lifters; however, these require an extra step of carbon coating to prevent charging from the electron beam hitting the sample during analysis. The adhesive is located on an aluminum stub fixed into the cap of a plastic container. Removing the cap exposes the tape, and the sample collection official can press the adhesive, without ever touching it to the sampling surface. The submitting officer completes the information form, which provides collection-site data (e.g., condition of the subjects hands, known activity prior to collection, estimated time of shooting, and exact time of collection), as well as the type of gun and ammunition used in the event, if known. Investigators should use one lifter per collection site. Some kits contain two (left hand and right hand), and others feature four (left back, left palm, right back, and right palm). One lifter can suffice when sampling an entire hand, front and back. Lifters from separate hands can be considered and analyzed as one subjects sample at the laboratory. Finding particles on the left hand versus the right hand or back versus palm holds no significance because analysts do not know the activity of the hands between the time of the shooting and the time of collection and because both hands likely are in the vicinity of the fired weapon. Investigators can press lifters to the face, hair, or clothing if they suspect that the hands have been cleaned between shooting and collection or covered at the time of the event. For sampling inanimate objects, like clothing, investigators employ the same type of adhesive lifters. The areas of the garment for sampling depend on whether the person wearing the clothes was believed to be firing a gun, carrying one in a specific location, or trying to conceal a gun in a particular manner. Analysts usually avoid excessively soiled or bloody areas of clothing as these materials can inhibit the ability to find GSR particles. Laboratory tests have shown that GSR on clothing will last considerably longer than on hands, but exactly how long remains unknown and greatly depends on the activity of the clothing and the type of fabric. Similar to hands, however, washing will remove most, if not all, residue from the clothing. VIII. Analytical Methods Chemical Tests 1. Dermal nitrate test or Paraffin test

The earliest technique used in gunshot residues detection is the well-known dermal nitrate test or paraffin test introduced in 1933 by Teodoro Gonzales of the Criminal Identification Laboratory, Police Headquarters, Mexico City. This test was championed by I. Castellanos of the Cuban National Bureau of Identification who stated in 1941 that the test can be used in determining whether or not a suspected person had fired a short-barreled firearm or in contact with gunshot residues. This test was enthusiastically received by the police community. OHara and Osterburg advised general caution in their 1949 text and in the first edition of Crime Investigation (1953) Kirk states: nitrates or other materials which may give the same chemical reactions may be deposited on the hands from cigarette smoking, handling of fertilizers and other sources [or] the person firing the gun frequently gives a negative dermal nitrate The final nail in the paraffin test coffin may have come from Interpol who stated in 1964: The seminar did not consider the traditional paraffin test to be of any value, neither as evidence to put before the courts, nor even as a sure indication for the police officer The test should no longer be used. Thus the dermal nitrate test is offered as an example of a test championed by police investigators but discarded after critical evaluation by criminalists. The gunpowder residues found on the hands after the firing of a gun become imbedded in the pores of the skin underneath its surface. The hot melted paraffin causes the pores of the skin to open up, mixes with the oil in the pores, and causes the pores to exude the gunpowder residues imbedded therein. Because of the manner in which such residues are imbedded in the skin, no ordinary washing of the hands will remove the imbedded nitrate particles from the pores of the skin. The test is, therefore, quite valuable because the presence of gunpowder residues can still be ascertained despite frequent and vigorous washing of the hands by the suspected person. Moreover, these nitrates may be imbedded in the skin pores for some time after the firing of the gun, possibly for three weeks. Detection is based on the color reaction produced by nitrites and nitrates present in gunshot residues to diphenylamine in sulfuric acid. This diphenylamine reaction is not specific to nitrates and nitrites because other oxidizing agents such as chlorates, dichromates, iodates, bromates, permanganates, higher metal oxides etc. may also cause the reaction and lead to false positive results. For reasons not well understood, negative results can be obtained from the paraffin test, even where it is known that a person has fired a gun and has not subsequently washed his hands. Because of its unreliability, the paraffin test has been abandoned by forensic scientists. White, hot, liquid paraffin is poured over the fingers, hands and wrists of the suspect until a coating of paraffin is built up. Successive layers of cotton or other fabrics are added, with additional paraffin poured on between layers, until a paraffin layer of approximately one half inch or more in thickness is obtained. A paraffin glove is finally molded, which, when cooled, is peeled gently from the hand.

An organic reagent, diphenylamine, in a concentrated solution of sulfuric acid, is added to the paraffin glove drop by drop. A positive reaction indicating the presence of gunpowder residues is indicated by the appearance of dark blue pin-point specks on the inner surface of the cast. Sometimes these specks may not appear until twenty minutes after the application of the reagent. The blue specks are transitory in nature and disappear within a relatively short time. For this reason, the paraffin glove should be photographed immediately upon the appearance of the blue specks, preferably in color, so that the forensic scientist will have some permanent record of the results of the tests. The appearance of the dark blue specks upon the application of the reagent may indicate the presence of gunpowder residues as well as other nitrates and therefore such a result is considered positive. The absence of such specks after the application of the reagent would be considered a negative result, but negative results have been obtained even after it has been established positively that an individual fired a gun just prior to the taking of the test. 2. Modified Griess Test In 1984, the use of a modified Griess reagent for the qualitative and quantitative spectrophotometric determination of nitrites originating from gunshot residues was described. The reagent used was sulfanilamide and N-(1-naphthyl)ethylenediamine dissolved in phosphoric acid. For the qualitative determination of nitrites on cotton swabs, the swab was treated with hydrolysis reagent (8% KOH) at 100~ for 5 minutes and then treated with a modified Griess reagent. The appearance of a pink-violet color indicated the presence of nitrites. For the quantitative determination of nitrites, the acetone extract of a cotton swab was evaporated to dryness and then treated with hydrolysis and modified Griess reagents. The reaction mixture was diluted with de-ionized water and subjected to spectrophotometric determination. The characteristic absorbance of the modified Griess reaction was found to be at 540 nm. The hydrolysis step preceding the application of Griess reagent was crucial for the detection of gunpowder nitrite residues. The detection limit of the modified Griess reagent was found to be 0.1 microgram which was better than that of the classic Griess reagent (0.5 microgram). 3. Sodium rhodizonate Test In 1992, a method for detecting nitrites, lead, and copper from gunshot residues using a single paper lift was proposed. Gunshot residues deposited on cotton denim fabric were transferred to a Whatman filter paper dampened with Griess reagent. After the Griess test, the same paper was sequentially tested for lead using sodium rhodizonate and for copper using ammonia and benzoinoxime solutions. Lead and nitrite from muzzle gases were detected at short range test firings only. At longer ranges, the deposits detected were lead and copper wipe from bullets. The use of lead free ammunition has

demonstrated a requirement for additional chemical screening tests. One such test makes use of zincon reagent to detect copper, zinc, and titanium which occur after the discharge. Chromatography 1. Thin Layer Chromatography Thin layer chromatography (TLC) is one of the simplest and most widely used chromatographic techniques. TLC is simple, rapid, moderately sensitive, and inexpensive. However, it suffers from a number of disadvantages including poor quantification, time consumption in visualization and differentiation, and a relatively large amount of required sample. 2. Gas Liquid Chromatography Gas liquid chromatography (GC) is one of the most extensively used analytical techniques for the separation of complex mixtures. Flame-ionization, electron-capture, and thermal energy analysis (TEA) are the basis of some common detector systems used for gunshot residue analysis. The TEA has been demonstrated to be a very selective detector for explosives. GC is rapid, sensitive, and highly selective especially when TEA is used. It is able to analyze gunshot residues both qualitatively and quantitatively. The separating power of capillary column GC is unparalleled. However, the nitrate esters which are frequently found in gunshot residues are incompatible with the usual GC conditions because of their thermal instability and their tendency to decompose on improperly prepared columns. Furthermore, the main ingredient of smokeless gunpowder, nitrocellulose, is a nonvolatile compound, and cannot therefore be analyzed by GC. 3. High Performance Liquid Chromatography (HPLC)/ Electrochemical Detection In 1981, HPLC with electrochemical detection was used for the analysis of smokeless powders and gunshot residues. This method provided a simple, rapid and inexpensive tool for determining components in explosives and gunshot residues. An advantage of this approach over metal residue analysis was the fewer false positive results arising from the fact that the only alternative source of nitroglycerine is as a pharmaceutical preparation. Detection of nitroglycerine and other components of smokeless powder were therefore indicative of firing a weapon or handling nitroglycerine-based explosive. Other Methods 1. Mass Spectrometric Detection

Mass spectrometry (MS) is a highly specific and sensitive detection method. The combination of HPLC and MS would constitute a powerful technique for the analysis of explosives and explosive residues. 2. Fluorimetric Detection Fluorimetry is one of the most sensitive and selective modes of detection commonly used in HPLC. 3. Capillary Electrophoresis Capillary electrophoresis (CE) is one of the most important analytical techniques that can provide rapid, high-resolution separations of complex mixtures. In CE separation is carried out by the two related electrokinetic effects, electrophoresis, and electroosmosis. Although electrically neutral substances such as organic gunshot residues cannot be separated by conventional CE, micellar electrokinetic capillary electrophoresis (MECE) permits the separation of these neutral substances. Conclusion Although highly specific results may be obtained by the analysis of inorganic gunshot residues using scanning electron microscopy, the analysis of organic residues to provide complementary and additional information is required especially when inorganic residues have not been recovered or their characteristics are nonspecific. The choice of approach for organic residue sampling depends on the substrate, that is the material on which the sampling is to be carried out, and the analytical techniques to be used. Swabbing is the commonest technique used for collecting organic residues from hands, whereas vacuum lifting is widely used in sampling organic residues from clothing. Because the extracts from hand swabs or vacuumed clothing samples are substantially contaminated with lipids and other extraneous materials which result in interference for the detection of analytes and deterioration of the equipment used, a clean-up procedure is an essential pretreatment to preserve the performance of equipment and to enhance sensitivity and selectivity. In addition to the most widely used solid phase extraction techniques, TLC has also been used as a clean-up procedure.