GSR2005—Continuity of the ENFSI Proficiency Test on Identification of GSR by SEM/EDX

Abstract:  Within the framework of the ENFSI Expert Working Group "Firearms" a proficiency test on the detection and identification of GSR by energy-dispersive scanning electron microanalysis (SEM/EDX) is carried out in a 2 years term. The latest test was performed in 2005/2006 and was denoted as GSR2005 . Seventy-five laboratories from 28 countries participated in this proficiency test and submitted in total 83 independent data-sets. The participating laboratories were requested to determine the total number of PbSbBa containing particles on a synthetic test sample following their own laboratory specific methods of automated GSR particle search and detection by SEM/EDX. Furthermore size and position of the detected particles had to be reported by the laboratories and were evaluated statistically. The results were compiled by means of z -scores according to the IUPAC and EURACHEM guidelines—assessing individual laboratory achievements (inter-laboratory) as well as intra-laboratory performance—and were compared to the results of the previous proficiency test run GSR2003 ( 1 ). The comparison shows that there is a noticeable improvement in the method's detection capability.     

Characterization of Printing Inks Using DART‐Q‐TOF‐MS and Attenuated Total Reflectance (ATR) FTIR

The rise in improved and widely accessible printing technology has resulted in an interest to develop rapid and minimally destructive chemical analytical techniques that can characterize printing inks for forensic document analysis. Chemical characterization of printing inks allows for both discrimination of inks originating from different sources and the association of inks originating from the same source. Direct analysis in real‐time mass spectrometry (DART‐MS) and attenuated total reflectance Fourier transform infrared spectroscopy (ATR‐FTIR) were used in tandem to analyze four different classes of printing inks: inkjets, toners, offset, and intaglio. A total of 319 samples or ~ 80 samples from each class were analyzed directly on a paper substrate using the two methods. DART‐MS was found to characterize the semi‐volatile polymeric vehicle components, while ATR‐FTIR provided chemical information associated with the bulk components of these inks. Complimentary data results in improved discrimination when both techniques are used in succession resulting in >96% discrimination for all toners, 95% for all inkjets, >92% for all offset, and >54% for all intaglio inks.     

根据霰弹丸分布图形推断射击距离的实验研究

目的 建立推断制式霰弹猎枪射击距离的数学计算公式和方法。方法 选用国产制式12号及16号猎枪,配用1号及3号猎枪弹,以1至12m距离射击实验靶纸,获得霰弹分布图形360例,将图形测量数据与实验距离进行数学理论分析。结果 建立6种不同枪弹种类推断射击距离d的计算公式,分别为12-1型(缩口)ss=-0.2+0.44d;12-1型(无缩口)ss=-0.94+0.63d;12-3型(缩口)ss=-0.59+0.52d;12-3型(无缩口)ss=-0.36+0.34d;16-1型s=-0.37+0.30d;16-3型s=-0.16+0.23d,并用Visual Basic5.0软件编制通用程序汇总软件。结论 本研究建立的方法简单实用,误差较小,可以用于推断制式猎枪的射击距离。     

红外光谱微量水平衰减全反射技术检验常见胶水的应用研究

目的建立无损快速检验胶水红外光谱法。方法利用红外光谱衰减全反射技术（ATR）对8种常见胶水样品进行光谱分析,根据出峰位置差异,对8种胶水样品进行鉴别,并建立相应的红外光谱数据库。结果不同类型的胶水其红外图谱有明显差异,而同一类胶水在某些波数区间也存在着一定的差异。结论利用红外光谱衰减全反射技术可以快速、准确、无损的检验鉴别胶水样品。     

基于化学计量法的FTIR鉴别心源性猝死

目的联合应用傅里叶变换红外光谱技术及化学计量法对心源性猝死的大鼠进行鉴别分析。方法注射药物或空气分别诱导大鼠的心源性猝死及空气栓塞死亡模型。应用Nicolet i Z10 FTIR光谱仪采集血清样本的红外光谱,联合OMNIC及Unscrambler软件,基于光谱不同分子吸收区间建立偏最小二乘回归模型。结果基于指纹区(1 200~900cm-1)建立PLS模型,均方根误差和决定系数分别是0.068 3、0.981 3,预测均方根偏差和预测决定系数分别是0.104 8、0.956 1;基于蛋白质酰胺区间(1 720~1 480cm-1)建立PLS模型,RMSE和R2分别是0.058 6,0.986 2,RMSEP和预测R~2分别是0.079 4、0.974 7。综合分析两种模型,蛋白质酰胺区间的RMSEP更小,且预测R2更大,提示其预测效果略好于指纹区间。结论联合FTIR及化学计量法,基于蛋白质及指纹区的分子特征均可有效鉴别大鼠的心源性猝死,其中两种不同死因引起的蛋白质差异更为显著。     

Rapid presumptive "fingerprinting" of body fluids and materials by ATR FT-IR spectroscopy

Human body fluids and materials were evaluated using attenuated total reflectance Fourier transform infrared spectroscopy. Purified proteins, cosmetics, and foodstuffs were also assayed with the method. The results of this study show that the sampled fluids and materials vary in the fingerprint region and locations of the amide I peaks because of the secondary structure of the composite proteins although the C = O stretch is always present. The distinct 1016 cm(-1) peak serves as a signature for semen. The lipid-containing materials (e.g., fingerprints, earwax, tears, and skin) can also be easily separated from the aqueous materials because of the strong CH(3) asymmetric stretch of the former. Blood-saliva and blood-urine mixtures were also successfully differentiated using combinations of peaks. Crime scene investigators employing rapid, portable, or handheld infrared spectroscopic instruments may be able to reduce their need for invasive, destructive, and consumptive presumptive test reagents in evaluating trace evidence.     

Estimating Projectile Perpendicular Impact Velocity on Metal Sheet Targets from the Shape of the Target Hole

Abstract:  The correlation between bullet hole shapes in metal and projectile impact velocity was examined. A series of shots were fired from an M-16A1 assault rifle of 5.56 mm caliber toward a 1-mm thick metal target. All shots were fired at a perpendicular angle to the metal sheets, and the velocity was measured just before the projectile hit the target. Velocities ranged between 400 and 900 m/sec. From the replica of the shooting hole, a perpendicular plane was created, showing the symmetrical properties of the hole. The best mathematical equation describing the shape of the entrance hole was the exponential function in the form:
The empirical equation of the hole defined using the regression method is:
This equation describes the general shape of shooting holes created by velocities ranging from 440 to 750 m/sec. From this equation, one can estimate the bullet velocity when it hits the target.     

TOF‐SIMS Analysis of Red Color Inks of Writing and Printing Tools on Questioned Documents

Time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS) is a well‐established surface technique that provides both elemental and molecular information from several monolayers of a sample surface while also allowing depth profiling or image mapping to be performed. Static TOF‐SIMS with improved performances has expanded the application of TOF‐SIMS to the study of a variety of organic, polymeric, biological, archaeological, and forensic materials. In forensic investigation, the use of a minimal sample for the analysis is preferable. Although the TOF‐SIMS technique is destructive, the probing beams have microsized diameters so that only small portion of the questioned sample is necessary for the analysis, leaving the rest available for other analyses. In this study, TOF‐SIMS and attenuated total reflectance Fourier transform infrared (ATR‐FTIR) were applied to the analysis of several different pen inks, red sealing inks, and printed patterns on paper. The overlapping areas of ballpoint pen writing, red seal stamping, and laser printing in a document were investigated to identify the sequence of recording. The sequence relations for various cases were determined from the TOF‐SIMS mapping image and the depth profile. TOF‐SIMS images were also used to investigate numbers or characters altered with two different red pens. TOF‐SIMS was successfully used to determine the sequence of intersecting lines and the forged numbers on the paper.     

根据创口射击残留物推断“5.4”式手枪射击距离的研究

目的利用环境控制扫描电镜/能谱仪（SEM/EDX）研究枪弹创射入口周围射击残留物与射击距离的关系,探讨其能否用于射击距离的判断。方法采用＂＂5.4＂＂式手枪分别在5、10、15、20、30、40、50、60、70、80、90、120cm处射击乳猪皮肤,利用SEM/EDX观察创口周围GSR的分布和成分,并建立回归方程。结果射击距离和GSR颗粒数量之间总体表现为直线关系,并建立了相应的回归方程。当射击距离为10~90cm时,用该方程推断射击距离效果较好。结论检测创口周围GSR可望用于判断“5.4”式手枪的射击距离。     

FTIR法检验海洛因中的淀粉、葡萄糖、蔗糖

目的建立检验掺有淀粉、葡萄糖、蔗糖的海洛因的新方法。方法红外光谱。结果给出了用FTIR检验掺有淀粉、葡萄糖、蔗糖的海洛因的判据。结论用红外光谱法可以准确、无损鉴定掺杂淀粉、葡萄糖、蔗糖的海洛因。     

The Differentiation of Menstrual from Venous Blood and Other Body Fluids on Various Substrates Using ATR FT‐IR Spectroscopy

Crime scene investigators and laboratory analysts use chemical tests to detect and differentiate body fluids. Testing often requires a sample of the stain, and the chemicals may cause degradation of the fluid or interfere with subsequent tests. Colorimetric chemical tests do not differentiate between different types of the same fluid, such as venous and menstrual blood, and there is no presumptive test available to simultaneously differentiate several body fluids. In this study, we recorded ATR FT ‐IR spectra of venous and menstrual blood, semen, saliva, and breastmilk. Neat and simulated casework body fluid samples were analyzed on cotton, nylon, wood, paper, and glass substrates. Differences in fluid composition, including proteins and small molecules, resulted in spectral differences. Venous and menstrual blood is differentiated by the peak at 1039 cm^?1 attributed to phosphoric acid found in menstrual blood. Peak intensity is influenced by the porosity and weave of the substrate fabric.     

Determination of firing distance. Lead analysis on the target by atomic absorption spectroscopy (AAS)

This paper reports a method for the determination of the firing distance. Atomic absorption spectroscopy (AAS) was used to determine the lead (Pb) pattern around bullet holes produced by shots on test targets from the gun. Test shots were made with a Colt 38 Special at 5, 10, 20, 25, 30, 35, 40, 45, 50, 60, 80, and 100 cm target distance. The target was created with sheets of Whatman no. 1 paper on a polystyrene support. The target was subdivided into three carefully cut out rings (1, 2, and 3; with external diameters of 1.4 cm; 5 cm; 10.2 cm, respectively). Each sample was analyzed with graphite furnace AAS. Lead values analysis performed for each ring yielded a linear relation between the firing distance (cm) and the logarithm of lead amounts (microg/cm(2)) in definite target areas (areas 2 + 3): [ln dPb(2+3) = a(0) + a(1)l]; where dPb(2+3) = lead microg/cm(2) of area 2 + 3; a(0) and a(1) are experimentally calculated; l = distance in cm.     

Forensic analysis of bicomponent fibers using infrared chemical imaging

The application of infrared chemical imaging to the analysis of bicomponent fibers was evaluated. Eleven nominally bicomponent fibers were examined either side-on or in cross-section. In six of the 11 samples, infrared chemical imaging was able to spatially resolve two spectroscopically distinct regions when the fibers were examined side-on. As well as yielding characteristic infrared spectra of each component, the technique also provided images that clearly illustrated the side-by-side configuration of these components in the fiber. In one case it was possible to prepare and image a cross-section of the fiber, but in general the preparation of fiber cross-sections proved very difficult. In five of the 11 samples, the infrared spectra could be used to identify the overall chemical composition of the fibers, according to a published classification scheme, but the fiber components could not be spatially resolved. Difficulties that are inherent to conventional "single-point" infrared spectroscopy, such as interference fringing and sloping baselines, particularly when analyzing acrylic type fibers, were also encountered in the infrared chemical image analysis of bicomponent fibers. A number of infrared sampling techniques were investigated to overcome these problems, and recommendations for the best sampling technique are given. Chemical imaging results were compared with those obtained using conventional fiber microscopy techniques.     

Age estimation by pulp/tooth ratio in canines by mesial and vestibular peri-apical X-rays

Changes in the size of the pulp canal, caused by apposition of secondary dentine, are the best morphometric parameters for estimating age by X-rays. The apposition of secondary dentine is the most frequently used method for age estimation in adult subjects. In two previous papers, we studied the application of the pulp/tooth area ratio by peri-apical X-rays as an indicator of age at death. The aim of the present study was to test the accuracy of age evaluation by combined analysis of labio-lingual and mesial peri-apical X-rays of lower and upper canines. A total of 200 such X-rays were assembled from 57 male and 43 female skeletons of Caucasian origin, aged between 20 and 79 years. For each skeleton, dental maturity was evaluated by measuring the pulp/tooth area ratio according to labio-lingual and mesial X-rays on upper (x(1), x(2)) and lower (x(3), x(4)) canines. Very good agreement was found between intra-observer measurements. Statistical analysis showed that all variables x(1), x(2), x(3), and x(4) and the first-order interaction between x(1) and x(3) contributed significantly to the fit, so that they were included in the regression model, yielding the following regression formula: Age = 120.737 - 337.112x(1) - 79.709x(2) - 364.534x(3) - 65.655x(4) + 1531.918x(1)x(3) . The residual standard error of estimated ages was 3.62 years, with 94 degrees of freedom, and the median of the residuals was -0.155 years, with an interquartile range of 4.96 years. The accuracy of the method was ME = 2.8 years, where ME is the mean prediction error. The model also explained 94% of total variance (R(2) = 0.94).     

A detailed mechanistic fragmentation analysis of methamphetamine and select regioisomers by GC/MS

A novel ring-substituted methamphetamine regioisomer, N,alpha,4-trimethyl phenmethylamine, was synthesized in order to study the validity of proposed structures for various mass spectrometry (MS)-derived peaks in a methamphetamine fragmentation pattern. While other research efforts have studied aspects of methamphetamine in detail, a full fragmentation study has not been reported previously. In addition to showing molecular structures represented by fragment peaks, mechanisms for selected processes are detailed. An empirically derived procedure to easily determine by simple spectral peak pattern recognition the geometry of dimethyl- or ethyl-substituted immonium ions (RRC = N+ RR) where m/z = 58 is outlined. These results are platform independent for electron ionization (EI) instruments, but have also proven to be helpful in explaining spectral peaks observed in spectra from ion trap systems. The spectrum for the synthesized methamphetamine regioisomer was accurately predicted using this methodology. While this approach is useful in some casework, the converse may be more useful: when an unexpected or unusual peak pattern arises in a spectrum, being able to analyze it to determine the structure of the molecule. This paper gives an analyst the means to begin such retro-synthetic analyses.     

92式手枪射入口形态特征与射击距离的关系

目的研究手枪射入口形态特征与射击距离的关系,为射击距离的推断提供依据。方法选择92式手枪,在带皮的猪肉上覆盖白色棉布,设计了0m,0.1m,0.2m,0.5m1.0m,1.5m,3.0m,5.0m,10m,15.0m,20.0m,25.0m共12个射击距离,对白棉布和肉皮上的弹孔进行拍照,对比研究不同射击距离的射入口形态特征,并利用Autocad软件对射入口的面积进行计算。结果白棉布和肉皮上射入口的形态特征与射击距离有一定的相关性。结论根据射入口的形态特征,能够对射击距离进行推断,对涉枪案件中射击距离的判断有参考价值。     

Age estimation by pulp/tooth ratio in canines by peri-apical X-rays

Estimation of age in individuals has received considerable attention in forensic science, in which it is a widely used method for individual identification, together with paleo-demographic analyses to establish mortality patterns in past populations. The present investigation, which is a continuation of a previously published pilot study, was conducted to examine the possible application of the pulp/tooth area ratio by peri-apical images as an indicator of age at death. A total of 200 peri-apical X-rays of upper and lower canines were assembled from 57 male and 43 female skeletons of Caucasian origin, aged between 20 and 79 years. They belong to the Frassetto osteological collection of Sassari (Sardinia) and are housed in the Museum of Anthropology, Department of Experimental and Evolutionistic Biology, University of Bologna. For each skeleton, dental maturity was evaluated by measuring the pulp/tooth area ratio on upper (x(1)) and lower (x(2)) canines. Very good agreement was found between intraobserver measurements. Statistical analysis was performed in order to obtain multiple regression formulae for dental age calculation, with chronological age as dependent variable, and gender, and upper and lower canines as independent variables. Stepwise regression analysis showed that gender did not contribute significantly to the fit (p=0.881) whereas variables x(1) and x(2) and the first-order interaction between them did. These two variables explained 92.5% of variations in estimated chronological age and the residual standard error was 4.06 years. Lastly, two simple linear regression equations were obtained for age estimation using canines from the maxilla and mandible separately. Both models explained 86% of variations in estimated chronological age and allowed an age-at-death estimate with a residual standard error of about 5.4 years.     

Analytical survey of restorative resins by SEM/EDS and XRF: databases for forensic purposes

Frequently in forensic cases, unknown substances must be identified. Automated databases can ease the burden of comparison as materials may be compared against many known standards in a relatively short period of time. It has been shown that dental resins can be named according to brand or brand group even in conditions as harsh as cremation. Databases are already in use for many materials, but no such database exists for dental resins. Thus, two databases were generated. One utilized a laboratory-based method, scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDS), in conjunction with the Spectral Library Identification and Classification Explorer (SLICE) software. The other was based on portable X-ray fluorescence (XRF). The ability to perform database comparison with portable instrumentation can thus be brought directly to the field. Both the SLICE and XRF databases were evaluated by testing unknown resins. EDS is a well-established technique and the SLICE program was demonstrated to be a good tool for unknown resin identification. Portable XRF is a relatively new instrument in this regard and its databases have been constructed mostly for metal alloy comparison and environmental soil testing. However, by creation of a custom spectral library, it was possible to distinguish resin brand and bone and tooth from other substances.     

Rapid and non-destructive differentiation of Shahtoosh from Pashmina/Cashmere wool using ATR FT-IR spectroscopy

Shahtoosh, the most expensive and sought-after wool in the illegal wildlife trade is obtained from the underfur of a critically endangered species-the Tibetan Antelope (Pantholops hodgsonii). It is often adulterated or mixed with the wool of Pashmina goat (Capra aegagrus hircus) for making shawls, scarves and other woolen articles to maximize the profit. The comparable fineness, color and texture, makes it a challenging task in wildlife forensics to differentiate them. In this study, an attempt has been made to differentiate 50 reference unprocessed underfur hairs from five individuals of each species using ATR FT-IR spectroscopy in combination with chemometric tools such as PCA, and PLS-DA. Results of PCA model demonstrated slight overlap and thus failed to distinguish hairs of these two species. Subsequently, PLS-DA model was employed, and also validation tests (external and blind testing) were carried out to ensure the predictive ability of the model, which resulted in 100% accuracy. The results of PLS-DA model exhibited complete differentiation between Shahtoosh, Pashmina and Angora (Oryctolagus cuniculus domesticus) wool used for external validation study with highly significant predictive ability (R-square value 0.99). This proof-of-concept study illustrates the potential of ATR FT-IR spectroscopy to complement current forensic microscopic and DNA based technique to analyze hair evidence in wildlife investigations owing to its rapid and non-destructive nature with high degree of confidence, and its ease-of-use with minimal to no sample preparation.