Time since discharge of rifles

The estimation of time since the latest discharge of rifles has been achieved by the SPME sampling technique and the GC-TEA analytical system. An unidentified compound, designated as the TEA2 compound, was detected in all the rifles investigated. The same compound was observed in shotguns and spent cartridges in our previous work. This compound escapes rapidly from the inside of rifle barrels, but can still be detected there one to two months after the shooting. The decrease of the TEA2 peak with time after shooting is non-exponential, and the curve-fitting procedure proposed for the estimation of time since discharge of shotguns can be applied also for rifles.     

Time since discharge of pistols and revolvers

The estimation of time since the latest discharge of pistols and revolvers has been achieved by the Solid Phase Microextraction (SPME) sampling technique and the GC/TEA analytical system. The TEA2 compound, which in our previous work (1) was observed in barrels of shotguns and rifles as well as inside spent cartridges, was also detected in pistols and revolvers. The amount of this compound was very low in short-barreled small arms and its escape from the barrel could generally be measured for only a few days or up to two weeks after the latest discharge. To improve the detection of TEA2 compound, the SPME sampling time was prolonged and fibers coated by Carboxen/polydimethylsiloxane were used. The decrease of the TEA2 peak with time after shooting from pistols is nonexponential but the curve-fitting procedure proposed for the estimation of time since discharge of shotguns and rifles is difficult to apply as the decay is very rapid. Therefore, the detection of TEA2 compounds in small arms should be interpreted that the firearm had been used very recently. The amount of volatile decomposition products of smokeless powder increased significantly with the length of the barrel when firearms of the same caliber, but with different barrel lengths were investigated.     

Estimating the time since discharge of spent cartridges: A logical approach for interpreting the evidence

Estimating the time since discharge of a spent cartridge or a firearm can be useful in criminal situations involving firearms. The analysis of volatile gunshot residue remaining after shooting using solid-phase microextraction (SPME) followed by gas chromatography (GC) was proposed to meet this objective. However, current interpretative models suffer from several conceptual drawbacks which render them inadequate to assess the evidential value of a given measurement. This paper aims to fill this gap by proposing a logical approach based on the assessment of likelihood ratios. A probabilistic model was thus developed and applied to a hypothetical scenario where alternative hypotheses about the discharge time of a spent cartridge found on a crime scene were forwarded. In order to estimate the parameters required to implement this solution, a non-linear regression model was proposed and applied to real published data. The proposed approach proved to be a valuable method for interpreting aging-related data.     

Pellet embolization to the right atrium following double shotgun injury

A 28-year-old man sustained two shotgun injuries of the left inguinal region from a distance of about 1.5 m by simultaneous discharge of both shells from a sawn-off double-barrelled 16-bore shotgun (diameter of the lead pellets, 4 mm). The first X-ray examination carried out soon after hospital admission showed a single embolized pellet near the right margin of the cardiac silhouette. Eight months later, the man committed suicide by drug intoxication. At autopsy, the embolized pellet was found embedded between the pectinate muscles of the right atrium. On the basis of the reported case and with reference to the pertinent literature, the paper points out the medico-legal aspects of venous bullet/pellet embolism and the risk of lead poisoning after shotgun injury.     

Study of the Behaviors of Gunshot Residues from Spent Cartridges by Headspace Solid‐Phase Microextraction–Gas Chromatographic Techniques

Gunshot residues, produced after shooting activity, have acquired their importance in analysis due to the notoriety of firearms‐related crimes. In this study, solid‐phase microextraction was performed to extract the headspace composition of spent cartridges using 85‐μm polyacrylate fiber at 66°C for 21 min. Organic compounds, that is, naphthalene, 2,6‐dinitrotoluene, 2,4‐dinitrotoluene, diphenylamine, and dibutyl phthalate were detected and analyzed by gas chromatography‐flame ionization detection technique. Evaluation of chromatograms for diphenylamine, dibutyl phthalate, and naphthalene indicates the period after a gunshot was discharged, whether it was 1 days, 2–4 days, <5 days, 10 days, 20 days, or more than 30 days ago. This study revealed the potential effects of environmental factors such as occasional wind blow and direct sunlight on the estimation of time after spent cartridges were discharged. In conclusion, we proposed reliable alternative in analyzing the headspace composition of spent cartridges in a simulated crime scene.     

Single wound produced by simultaneous discharge of both shells from a double-barrel shotgun

We present the case of a man who was killed by simultaneous discharge of both barrels of a double-barrel shotgun. Externally, there was a single wound simulating a wound made by a discharge of a single barrel. Test-firing of the shotgun against cloth, paper, and naugahyde targets revealed defects similar in shape to the wound in the victim. Simultaneous discharge of both barrels from a double-barrel shotgun may simulate the wound made by discharge of a single barrel.     

The detection and analysis of ignitable liquid residues extracted from human skin using SPME/GC

A simple, fast, inexpensive, and sensitive technique for the detection and identification of flammable or combustible liquid residues on the skin of arson suspects is presented. The use of solid phase microextraction (SPME) for the analysis of ignitable liquid residues has been demonstrated and it is shown in this work that this technique is effective in extracting these liquid residues at extremely low quantities. Microliter quantities of controlled spikes of gasoline, diesel fuel, and charcoal lighter fluid were deposited on the hands of a volunteer and extracted after several time intervals. The SPME technique can recover very small amounts of liquid deposits on skin up to 3.5 h after exposure, depending on the class of the ignitable liquid residue used.     

Optimization of solid-phase microextraction (SPME) for the recovery of explosives from aqueous and post-explosion debris followed by gas and liquid chromatographic analysis

Solid-phase microextraction (SPME) has been evaluated for the recovery of explosives residues from aqueous samples and real post-explosion solid debris samples and optimized using gas chromatography with an electron capture detector (GC-ECD) and high-performance liquid chromatography with ultraviolet detection (HPLC-UV). A modified SPME/HPLC interface utilizing dual six-port valves allowed for independent optimization of SPME desorption and injection variables that provided improved chromatographic resolution and sensitivity. A unique combination of cyano and octadecyl columns resulted in the complete separation of the 14 explosives in EPA method 8330 mixture using HPLC with good quantitative results. At the optimum SPME conditions, the limits of detection (LOD) were found to be of 5 ng/mL to 16 ng/mL of explosives in water and 10 microg/kg to 40 microg/kg of explosives from soil. The technique has been successfully applied to the analysis of real post-explosion debris and can be adapted for use in the field utilizing portable chromatographic instruments.     

Firing distance estimates with pellet dispersion from shotgun with various chokes: an experimental, comparative study

There are several studies suggesting models for firing distance estimation due to pellet dispersion, but few of them consider the degree of choke of a shotgun. The purpose of this research is to suggest some models for estimation of the firing distance for choked and cylinder bore shotguns. Twelve gauge with full chokes, and 12 and 16 gauge with cylinder bore shotguns were fired with #2 and #5 shots from 75, 100, 300, 500, and 1000 cm distances. Statistically significant pellet dispersion values were found for each shotgun by using #2 and #5 shots for different firing distances. All the data obtained were analyzed with linear regression and four models were constituted. Investigators should use special formulae for each shotgun, degree of choke, and pellet type while determining the firing distance. Therefore, more experimental and comparative studies should be designed for each type.     

Determining an Optimal Sequence for Chemical Development of Latent Prints on Cartridge Casings and Shotgun Shells*,†

Abstract: In developing latent prints on cartridge casings and shotgun shells, multiple chemical processes should be used in order to obtain the best results. In Phase I, this study established an optimal chemical sequence for both Brass and Nickel cartridge casings based on six sequences involving four chemicals: Cyanoacrylate, Black Powder, Rhodamine 6G and Acidified Hydrogen Peroxide. Phase II was a validation study of Phase I involving a random sample of both Brass and Nickel cartridge casings, which were processed according to the determined optimal sequences. In addition, ribbed shotgun shells were processed under Phase I results and determined to be dependent upon the utilization of a CrimeScope at 515 nm. Consideration should be given to the type of cartridge case being examined. Although limitations exist, some chemical sequences undeniably work better than others. All photographs were manipulated with Adobe^® Photoshop^®. All results were verified by a senior latent print examiner.     

Detection of trace drugs of abuse in baby formula using solid‐phase microextraction direct analysis in real‐time mass spectrometry (SPME‐DART‐MS)

The intentional or unintentional adulteration of baby formula with drugs of abuse is one of the many increasingly complex samples forensic chemists may have to analyze. This sample type presents a challenge because of a complex matrix that can mask the detection of trace drug residues. To enable screening of baby formula for trace levels of drugs, the use of solid‐phase microextraction (SPME) coupled with direct analysis in real‐time mass spectrometry (DART‐MS) was investigated. A suite of five drugs was used as adulterants and spiked into baby formula. Samples were then extracted using SPME fibers which were analyzed by DART‐MS. Development of a proof‐of‐concept method was completed by investigating the effects of the DART gas stream temperature and the linear speed of the sample holder. Optimal values of 350°C and 0.2 mm/s were found. Once the method was established, representative responses and sensitivities for the five drugs were measured and found to be in the range of single ng/mL to hundreds ng/mL. Additional studies found that the presence of the baby formula matrix increased analyte signal (relative to methanolic solutions) by greater than 200%. Comparison of the SPME‐DART‐MS method to a traditional DART‐MS method for trace drug detection found at least a factor of 13 improvement in signal for the drugs investigated. This work demonstrates that SPME‐DART‐MS is a viable technique for the screening of complex matrices, such as baby formula, for trace drug residues and that development of a comprehensive method is warranted.     

SPME-GC\NPD法快速分析尿液中苯丙胺类化合物

建立了ＳＰＭＥ－ＧＣ／ＮＰＤ法同时分析尿液中九种苯丙胺类化合物的方法。取１ｍｌ尿样以４－苯基丁胺为内标,在碱性条件下,将１００μｍＰＤＭＳ纤维头浸入尿液中２０ｍｉｎ,气相色谱进样后热解吸３ｍｉｎ,用ＧＣ／ＮＰＤ进行测定。九种苯丙胺类化合物及内标完全分离,五种苯丙胺类化合物分别在０．０５～１５、０．１～１５、０．２～１５μｇ／ｍｌ浓度范围内线性良好,ｒ为０．９９２８～０．９９９５,变异系数均小于１０％。方法简便、快速、准确,可用于尿液中苯丙胺类违禁药物的检测     

A preliminary study of changes in scalp impedance during the early post-mortem period in rats.

An accurate and reproducible technique was used for estimation of scalp impedance (1 kHz) in each of eight rat cadavers, maintained at 9.0 +/- 0.7 degrees C, during the 1 to 144 hour post-mortem period. Scalp impedance increased non-linearly, and in a bimodal manner, between 24 and 144 hours post-mortem. The relationship between scalp impedance and post-mortem interval, and the degree of individual variation in the time course of impedance change, were such that scalp impedance is unlikely to be a suitable tool for estimation of time since death.     

Cross-examination of liquid-liquid extraction (LLE) and solid-phase microextraction (SPME) methods for impurity profiling of methamphetamine

Impurities in 48 methamphetamine (MA) samples were analyzed by liquid-liquid extraction (LLE) and headspace solid-phase microextraction (HS-SPME) methods. MPS-2 autosampler was used to improve reproducibility of SPME method, and nonadecane (C(19)) diluted with potassium bromide (KBr) powder was used as an internal standard for standardizing retention time. Impurities identified by SPME method showed different patterns compared with LLE method. Non-volatile impurities like methamphetamine dimer were not identified by SPME method, but some volatile impurities like diphenylketone, caprolactam and lots of unknowns were identified only by SPME method. 1-Phenyl-2-propanone (P2P), 1-phenyl-2-propanol and benzylcyanide peaks could be discriminated clearly by SPME method without interference of amphetamine, an artifact originates from MA degradation. Differences in the impurity patterns resulted in different clustering results. When 48 MA samples were classified into 5 LLE and 5 SPME clusters, cross-matching of the clusters resulted in 8 sub-clusters. It shows that combination of the different extraction methods can distinguish the differences which cannot be distinguished by LLE or SPME method alone, and can improve reliability of the profiling results.     

GC-MS of ignitable liquids using solvent-desorbed SPME for automated analysis

Solid-phase microextraction (SPME) is well documented with respect to its convenience and applicability to sampling volatiles. Nonetheless, fire debris analysts have yet to widely adopt SPME as a viable extraction technique, although several fire debris studies have demonstrated the utility of SPME coupled with gas chromatography-mass spectrometry (GC-MS) to identify ignitable liquids. This work considers the expansion of SPME sampling from the customary thermal desorption mode to solvent-based analyte desorption for the analysis of ignitable residues. SPME extraction fibers are desorbed in 30 microL of nonaqueous solvent to yield a solution amenable to conventional GC-MS analysis with standard autosampler apparatus. This approach retains the advantages of convenience and sampling time associated with thermal desorption while simultaneously improving the flexibility and throughput of the method. Based on sampling results for three ignitable liquids (gasoline, kerosene, anddiesel fuel) in direct comparisons with the widely used activated charcoal strip (ACS) method this methodology appears to be a viable alternative to the routinely used ACS method.     

Solid phase micro extraction coupled with on-column GC/ECD for the post-blast analysis of organic explosives

Gas chromatographic analysis with electron capture detection is very sensitive to post-blast residues and useful for the determination of organic explosive molecules. But many compounds extracted from the matrices may interfere with the explosives. Using SPME, most interfering compounds are eliminated so the identification is easier. Another advantage of the technique is a low limit of detection. In this study, four different SPME fibers were tested to analyze the most common encountered organic explosives including nitro aromatics, nitramines and nitro-esters. Different parameters were tested (desorption time, agitation, ...) and a special device has been created to optimize the agitation. Direct desorption effect of the SPME fiber on the column compared to normal split-splitless injection is shown. In this way, the degradation of the most sensitive molecules is decreased. An application to a real case is also described in this paper.     

Aqueous phase hexylchloroformate derivatization and solid phase microextraction: determination of benzoylecgonine in urine by gas chromatography-quadrupole ion trap mass spectrometry.

A derivatization/solid phase microextraction (SPME) method for the determination of benzoylecgonine in urine was developed. The derivatization is conducted directly in 1 mL of urine while sonicating for 3 min with 12 microL of hexyl chloroformate and 70 microL of a mixture containing acetonitrile:water:hexanol:2-dimethylaminopyridine (5:2:2:1 v/v), yielding benzoylecgonine hexyl ester (BHE) as the product. After the 3 min period, an aliquot of 250 microL is transferred to a vial for SPME. After the desired extraction time the 100 microns polydimethylsiloxane SPME fiber was transferred to the GC-MS for separation and analysis with a quadrupole ion trap mass spectrometer. The hexyl chloroformate derivatization and SPME procedures were optimized for compatibility and sensitivity. The method was found linear for 0.10 to 20.0 micrograms/mL (r2 = 0.999) of benzoylecgonine in urine using benzoylecgonine-d3 as an internal standard (1.5 micrograms/mL). Intra-day precisions were 8.8 and 6.8% RSD for 0.30 microgram/mL and 17 micrograms/mL benzoylecgonine standards in urine (n = 6), respectively. Inter-day precision (n = 3) were < or = 3.3% RSD, indicating good reproducibility. A detection limit of 0.03 microgram/mL (S/N = 3) was achieved, thus making the SPME method a simplified alternative to SPE for GC-MS confirmation after EMIT tests for benzoylecgonine which have a cutoff of 0.30 microgram/mL. Quantitative results by SPME and SPE of two clinical urine specimens known positive for cocaine by EMIT were in excellent agreement. Benzoylecgonine was detected by the derivatization/SPME method in 22 out of 22 other urine specimens known positive for cocaine.     

Application of solid-phase microextraction to the profiling of an illicit drug: manufacturing impurities in illicit 4-methoxyamphetamine

This article describes the application of solid-phase microextraction (SPME) to the recovery of manufacturing by-products and impurities from an illicit drug seizure. The preparation chosen for examination using this technique contained 4-methoxyamphetamine, an hallucinogenic amphetamine that has been encountered frequently in South Australia. Compounds found in the PMA preparation included 4-methoxyphenol, 4-methoxybenzaldehyde, 4-methoxyphenyl-2-propanone, 4-methoxyphenyl-2-propanol, 4-methoxyphenyl-propene, and (tentatively) 4-methyl-5-(4'-methoxyphenyl) pyrimidine. The presence of these compounds suggests that the active drug was prepared from 4-methoxybenzaldehyde via 4-methoxyphenyl-2-propanone using a Leuckardt reductive amination. In this instance, SPME was found to be a simple, rapid, and non-destructive recovery technique that gave results complementary to those provided by conventional liquid-liquid extraction. There is an indication that SPME might find application in profiling of illicit drugs.     

A simple microthermal desorption device

A new method for thermal desorption of small samples is presented. The method uses a solid phase microextraction (SPME) holder with the fiber removed. The sample-for example, an ink sample on paper-is simply placed inside the needle of the holder, where normally an SPME fiber is positioned. The thermal desorption is then performed on any kind of gas chromatograph in a manner similar to that for SPME analysis. The needle of the SPME holder penetrates the injector septum; the temperature of the thermal desorption is simply the temperature of the injector. No solvents or liquid nitrogen cooling are used. The paper sample is kept inside the holder needle during the analysis. After the analysis is completed, the sample is removed from the needle by pushing forward the steel wire inside the needle in the way normally used to perform sampling with the SPME fiber. The desorbed compounds were analyzed by gas chromatography with a flame ionization detector or by gas chromatography-mass spectrometry. The optimum temperature for desorption of ink samples on paper was 200 degrees C. The influence of the paper matrix is negligible at that temperature. Laboratories lacking the commercial device for thermal desorption can use this cheap device for the analysis of, for example, writing ink, printing ink, and inkjet ink samples on paper. Other types of samples can be investigated but the size of samples suitable for analysis is limited.     

Pump-gun as a weapon. Type of injuries, prohibition of weapons

Pumpguns are shotguns with pump action whose injuries and wound mechanisms have several special features: extremely high kinetic energy of the shot (2500 to 3500 J) frequent cases of "Kr?nlein shots" (exenteration of the brain) punchmark/imprint immediately adjacent to the entrance wound from the front of the pipe magazine exit wounds from buckshot may be similar to pellet entrance injuries from a distant shotgun discharge the use of various shotgun cartridges (plastic ammunition, slug bullet, various lead pellets) within the same weapon. The change in the Austrian gun law and the banning of the pumpgun in 1995 is also discussed in the article.