Validation of X-ray fluorescence spectrometry for determining osseous or dental origin of unknown material

Forensic anthropological examinations typically involve the analysis of human skeletal remains, but in cases where samples are very small and/or physically compromised, it may first be necessary to determine whether the material is even osseous or dental in origin. X-ray fluorescence spectrometry (XRF) is a technique that reveals the elemental composition of materials and is hypothesized to have utility in such cases. XRF analysis was conducted on a variety of tissues and materials in unaltered and altered (damaged) states. With few exceptions, osseous and dental tissues in unaltered and altered conditions contained characteristic levels of calcium and phosphorus, while other materials did not. Materials could be accurately identified as osseous or dental in origin based on the calcium and phosphorus levels identified by XRF, and we therefore conclude that XRF analysis is a valid and effective means of determining osseous or dental origin of unknown material.     

Classification of counterfeit coins using multivariate analysis with X-ray diffraction and X-ray fluorescence methods

Counterfeit coins (277 samples) were analyzed by both X-ray diffraction (XRD) and X-ray fluorescence (XRF) methods without any pretreatment. The counterfeit coins were clearly classified into two groups using cluster analysis (CA) and principal component analysis (PCA) for XRD peak patterns. One group (250 samples) was made by a pressed method and another one (27 samples) was made by a nickel-plated method. Using four elements (Cu, Ni, Fe and Zn) and obtaining XRF for 257 samples, they could be divided into four groups by CA. On the other hand, they were classified into five groups using their diameter, thickness, weight, density, density/thickness and density/weight. The latter classification method would suggest something of a change in the process of the pressed method.     

Forensic oral imaging quality of hand-held dental X-ray devices: Comparison of two image receptors and two devices

Recently, different portable hand-held and battery-powered dental X-ray units have become available. Especially for forensic odontological purposes, they offer diverse advantages such as for use in disaster areas and crime-scene locations as also in autopsy rooms and mortuaries. For any application, the most important feature of these hand-held devices is the delivered image quality. The aim of this study is to evaluate the radiographic image quality acquired by two portable X-ray devices in combination with two types of image receptors and to compare the findings with the image quality of a standard intra-oral X-ray device.Eleven samples consisting of eight teeth, two dry skeletal specimens and one formalin-fixed mandible part were mounted on blocks for standardised (re)positioning. Radiological images were acquired with two hand-held (AnyRay^® 60 kVp, 0.02–4.00 mAs and NOMAD^® 60 kVp, 0.023–2.277 mAs) and one wall-mounted (MinRay^® 60/70 kVp 0.14–22.4 mAs) X-ray device combined with two image receptor systems (VistaScan^® phosphor storage plate (PSP) and SIGMA^® M CMOS Active Pixel technology sensor). The effect of X-ray source-to-object distance (SOD) was checked at 20 cm in conjunction with object to image receptor distances (OIDs) of 0.8 and 2.5 cm. For each parameter setup, the exposure times were run from low till high. An expert consent statement was achieved by agreement of four expert observers selecting the optimal images based on a developed four point quality rating system. Next, a selection of the images was assembled in a set of 198 observation screens and scored by seven observers. The observation screens were designed to compare observer scores, relations between devices, receptors and OIDs and images obtained from the different devices at equal exposure levels (mAs). All results were statistically analysed.Radiological image quality was significantly higher for phosphor plate compared with the CMOS digital receptor system (p < 0.0001). Furthermore, a significantly superior image quality was obtained for OID = 0.8 than for OID = 2.5 (p = 0.039). A significant difference in image quality between the three devices was also established (p = 0.02). The present study demonstrated the feasibility of portable X-ray systems for forensic odontological applications based on rendering optimal image quality, provided an in vitro guideline of optimal parameter settings and offered a radiological image database usable in further research.     

The determination of toxic metals in simulated stomach contents by energy dispersive X-ray fluorescence analysis and a fatal case of mercury poisoning

Soup is used as a simulated stomach contents matrix to determine the lower level of detection for 16 metals. All of the metals can be detected at the levels which might be expected for acute fatal doses even if the stomach contents are considerably diluted. However where small doses are administered over a prolonged period this method may not be sufficiently sensitive. A case of fatal poisoning by the ingestion of mercuric chloride is described to illustrate the effectiveness of the method. In this case mercury was also detected and determined at highly significant levels in blood and liver by the same technique. This energy dispersive X-ray fluorescence (EDXRF) method is easy to use, rapid and non-destructive.     

黑色墨迹的拉曼光谱分析

目的对常见的黑色墨迹进行初步筛选,为墨迹的进一步检验提供依据。方法依据黑色墨迹的同色异谱特征,利用显微共焦激光拉曼光谱仪对19种黑色墨迹进行分析检验。结果根据不同墨迹的拉曼谱图,19种黑色墨迹可以分为3大类,即:未检出拉曼峰的墨迹,只检出碳物质的墨迹,以及主体色料为染料的墨迹。结论拉曼光谱可用于区分不同种类黑色墨迹,从而为选择合适的方法对黑色墨迹进一步进行检验奠定基础。     

Analysis of primer residue from lead free ammunition by X-ray microfluorescence

In forensic science, the analysis of gunshot residues was traditionally done by the detection of lead (Pb), antimony (Sb) and barium (Ba) usually found in a primer. However, the recent development of lead-free ammunition represents a new challenge for ballistic specialists. This analysis study gunshot residues from primers and ammunitions in the area surrounding bullet holes, a very important tool to determine the shooting distance. The ammunitions used were 9 mm Luger and .38 spl + p calibers, where lead in the primer was replaced with strontium (Sr) and where the lead bullet was plated with copper (Total Metal Jacket). Gunshot analysis results were obtained using an energy dispersive X-ray microfluorescence spectrometer. The method allows the detection and quantification of strontium residues on the target up to a distance of 45 cm.     

诈伤致错误鉴定案件分析

在法医鉴定和审判实践中经常遇到被鉴定人诈伤，他们或故意夸大伤情，将本不是他人所为的损伤说成是他人所为，或采取不就医而加重病情，或请人作伪证、写假病历来编造较重的伤情，或者采取各种化学的、物理的方法加重伤情，甚至造成新的更大的创伤，来达到获取赔偿或惩治对方的目的，有的还真的如愿以偿。诈伤没有被发现，甚至造成案件实体处理错误，最容易引起人们对法医工作的置疑，为此，笔者对诈伤致错误鉴定案件做些分析。     

诈伤致错误鉴定案件分析

在法医鉴定和审判实践中经常遇到被鉴定人诈伤,他们或故意夸大伤情,将本不是他人所为的损伤说成是他人所为,或采取不就医而加重病情,或请人作伪证、写假病历来编造较重的伤情,或者采取各种化学的、物理的方法加重伤情,甚至造成新的更大的创伤,来达到获取赔偿或惩治对方的目的,有的还真的如愿以偿。诈伤没有被发现,甚至造成案件实体处理错误,最容易引起人们对法医工作的置疑,为此,笔者对诈伤致错误鉴定案件做些分析。案例资料本组诈伤致错误鉴定案件共2 4件,均来自法医鉴定实践,有关诈伤及鉴定情况详实可靠。一、一般情况男11人(占46% ) ,女1…     

京尼平显现渗透性客体上潜在手印方法研究

目的介绍一种能够用来显现潜在手印的新型物质—京尼平。方法依据京尼平能和手印遗留物质中的氨基酸或蛋白质发生反应,生成一种有荧光效应的多聚体深蓝色物质,通过自然光或多波段光源下显现观察,并将其与传统的茚三酮、DFO显现进行比较。结果京尼平显现法的显现条件与茚三酮类似,其处理后的潜在手印既在自然光下可见又在多波段光源的激发下有荧光现象。结论京尼平显现法可用于渗透性客体上潜在手印的显现。     

Classification of black powder toners on the basis of integrated analytical information provided by Fourier transform infrared spectrometry and X-ray fluorescence spectrometry

Differentiating between black powder toners used in laser printers and copiers can be challenging for forensic examiners. One hundred and sixty-two samples from 82 different types of cartridges produced by 21 manufacturers that are currently available on the Polish market were studied using Fourier transform infrared spectrometry (FT-IR) and energy-dispersive X-ray fluorescence spectrometry (XRF). The spectra obtained by these two methods were classified into 14 groups and 28 groups using FT-IR and XRF, respectively. These classifications served as a basis for the development of an analytical scheme for differentiating black powder toners. This scheme can be used with any two methods that supply different information about an examined sample. The research will show that if two samples are similar in polymer composition (e.g., FT-IR spectra), additional quantitative elemental composition from XRF analyses may provide more discrimination. It was possible to differentiate 82.5% pairs of examined samples using only FT-IR, 90.8% pairs of examined samples using only XRF, and 95.8% pairs of examined samples using these two methods. Obtained spectra and all the available information could be used to create/build a database. The results obtained confirm the multiplicity and compatibility of toners. Additionally, it was stated that not all the samples were original (OEM).     

Identification through X-ray fluorescence analysis of dental restorative resin materials: a comprehensive study of noncremated, cremated, and processed-cremated individuals

Tooth-colored restorative materials are increasingly being placed in the practice of modern dentistry, replacing traditional materials such as amalgam. Many restorative resins have distinct elemental compositions that allow identification of brand. Not only are resins classifiable by elemental content, but they also survive extreme conditions such as cremation. This is of significance to the forensic odontologist because resin uniqueness adds another level of certainty in victim identification, especially when traditional means are exhausted. In this three-part study, unique combinations of resins were placed in six human cadavers (total 70 restorations). Simulated ante-mortem dental records were created. In a blind experiment, a portable X-ray fluorescence (XRF) unit was used to locate and identify the resin brands placed in the dentition. The technique was successful in location and brand identification of 53 of the restorations, which was sufficient to enable positive victim identification among the study group. This part of the experiment demonstrated the utility of portable XRF in detection and analysis of restorative materials for victim identification in field or morgue settings. Identification of individuals after cremation is a more difficult task, as the dentition is altered by shrinkage and fragmentation, and may not be comparable with a dental chart. Identification of processed cremains is a much greater challenge, as comminution obliterates all structural relationships. Under both circumstances, it is the nonbiological artifacts that aid in identification. Restorative resin fillings can survive these conditions, and can still be named by brand utilizing elemental analysis. In a continuation of the study, the cadavers were cremated in a cremation retort under standard mortuary conditions. XRF was again used to analyze retrieved resins and to identify the individuals based on restorative materials known to exist from dental records. The cremains were then processed and the analysis was repeated to determine whether restorative resins could be found under this extreme condition. Under both circumstances, sufficient surviving resin material was found to distinguish positively each individual in the study group. This study showed the utility of XRF as an analytical tool for forensic odontology and also the significance of the role of restorative resins in victim identification, even after cremation.     

采集、供应血液、制作、供应血液制品事故罪的客体特征研究

本罪的犯罪客体是复杂客体，即国家对于采集、供应血液、制作、供应血液制品的管理制度和他人的健康权、生命权。     

Trace elemental analysis of drugs of abuse using synchrotron radiation total reflection X-ray fluorescence analysis (SR-TXRF)

Synchrotron radiation total reflection X-ray fluorescence spectroscopy (SR-TXRF) was utilized to analyze various trace elements in small amounts of drugs of abuse. Sample amounts of 1 microL solutions containing 10 microg of drugs (methamphetamine, amphetamine, 3,4-methylenedioxymethamphetamine, cocaine, and heroin) were spotted on silicon wafers for direct analysis. In addition, a leaflet of marijuana was set directly on a silicon wafer, and opium in the form of a soft lump was smeared on another silicon wafer for analysis. In these experiments, about 10 pg of contaminant elements could be detected. For example, in a seized methamphetamine sample, iodine was found, which could be indicative of synthetic route. In seized 3,4-methylenedioxymethamphetamine samples, variable amounts of phosphorus, calcium, sulfur, and potassium were found, which could not be detected in a control 3,4-methylenedioxymethamphetamine sample. For marijuana and opium, two spectral patterns were obtained that were far different from each other and could be easily discriminated. Using SR-TXRF, pg amounts of each trace element in 10 microg of various drugs can be easily detected, which is not the case either for a standard TXRF experimental system or for other elemental analysis techniques.     

Defining the quantity and sequence of impacts by craniogram in blunt object injuries

A possibility was studied to determine the quantity and sequence of traumatic impacts by using the craniogram; an error was calculated for measurements of injuries registered in craniograms with respect to their real sizes in the skull base bones.     

青少年骨发育X线分级方法

目的 利用青少年骨关节x线影像变化规律制定青少年骨发育X线分级标准.方法 参照国内外权威学者关于不同部位关节骨骼发育分级的研究成果,以骺软骨发育组织学分层(区)为理论支撑、以骨发育X线影像特征为基础的分级原理.横向和纵向观察我国河南、海南、浙江三个省份300名11～20周岁男、女性青少年双侧锁骨胸骨端及左侧肩、肘、腕、髋、膝、踝关节骨发育X线影像特征,选取与年龄变化关系密切的24项骨骼发育指标.结果 根据不同部位关节骨骺生长变化规律,将24项骨骼发育指标分为2级至8级不等.研究显示,各单一关节组成诸骨发育指标的分级基本相同或接近.单一关节内不同的骨骺发育变化具有同步性.结论 本分级标准涉及骨骼发育指标广、适用年龄范围宽、可操作性强,为我国法医学活体骨骼年龄推断建立了良好的基础平台.     

Gunshot residue testing in suicides: Part I: Analysis by scanning electron microscopy with energy-dispersive X-ray

Several different methods can be employed to test for gunshot residue (GSR) on a deceased person's hands, including scanning electron microscopy with energy-dispersive x-ray spectroscopy (SEM-EDX) and inductively coupled plasma-atomic emission spectrometry (ICP-AES). Each of these techniques has been extensively studied, especially on living individuals. The current studies (Part I and Part II) were designed to compare the use and utility of the different GSR testing techniques in a medical examiner setting. In Part I, the hands of deceased persons who died from undisputed suicidal handgun wounds were tested for GSR by SEM-EDX over a 4-year period. A total of 116 cases were studied and analyzed for caliber of weapon, proximity of wound, and results of GSR testing, including spatial deposition upon the hands. It was found that in only 50% of cases with a known self-inflicted gunshot wound was SEM-EDX positive for at least 1 specific particle for GSR. In 18% of the cases there was a discernible pattern (spatial distribution) of the particles on the hand such that the manner in which the weapon was held could be determined. Since only 50% of cases where the person is known to have fired a weapon immediately prior to death were positive for GSR by SEM-EDX, this test should not be relied upon to determine whether a deceased individual has discharged a firearm. Furthermore, in only 18% of cases was a discernible pattern present indicating how the firearm was held. The low sensitivity, along with the low percentage of cases with a discernible pattern, limits the usefulness of GSR test results by SEM-EDX in differentiating self-inflicted from non-self-inflicted wounds.     

Identification of unknown dead bodies by X-ray image comparison of the skull using the X-ray simulation program FoXSIS

The aim of the study was to improve the objectivity of X-ray image comparison for the identification of unknown dead individuals. CT-data were collected for 30 macerated skulls. An already presented computer program which uses CT data to establish virtual X-ray images was used to obtain X-rays with different beam angulations simulating rotation, dorsal flexion, and ventral flexion. Specific parameters were measured on the simulated images. The frontal sinus reveals the highest variability not only between the individual skulls but also within an individual skull in different positions. The most consistent parameters with respect to different positions were the skull breadth, the biorbital breadth and the bizygomatic breadth. In a blind study, three out of 24 skulls could clearly be identified just by measured distances although the positions were different and unknown to the investigator. The dimensions of the frontal sinus do not correlate with the other skull parameters (analysis of covariance). Based on the presented results, we propose a method that will calculate the probability of identity. The presented results demonstrate that the comparison of X-ray images can be undertaken in an objective way by quantifying the probability of identity even when the comparative images were made under different conditions.     

Trace analysis of urea nitrate by liquid chromatography-UV/fluorescence

In this paper we have adapted a technique, previously used to determine the presence of urea in aqueous samples of wine and urine, to detect trace levels of urea nitrate explosives. The procedure involves the reaction of the uronium ion (protonated urea) with a fluorophore, xanthydrol. By modification of the procedure to utilize non-aqueous reagents, in neutral conditions, it can be made specific to the presence of the urea nitrate ion pair. The procedure includes selective detection of derivatization products by UV and fluorescence following separation by High-Performance Liquid Chromatography (HPLC). Analytical method development included optimization of HPLC conditions (solvent, gradient), UV and fluorescence wavelengths, and derivatization parameters (xanthydrol amount, reaction times, temperature). The extraction of urea nitrate from surfaces was also investigated and optimized. For best quantification, it was shown that an internal standard was required; this resulted in a quantification limit around 0.17mM (21mg/L). The entire procedure could be performed in less than 30min per sample and potential interferences such as ammonium, nitrate, and urea did not produce a response under standard conditions.     

Forensic analysis of bioagents by X-ray and TOF-SIMS hyperspectral imaging

Hyperspectral imaging combined with multivariate statistics is an approach to microanalysis that makes the maximum use of the large amount of data potentially collected in forensics analysis. This study examines the efficacy of using hyperspectral imaging-enabled microscopies to identify chemical signatures in simulated bioagent materials. This approach allowed for the ready discrimination between all samples in the test. In particular, the hyperspectral imaging approach allowed for the identification of particles with trace elements that would have been missed with a more traditional approach to forensic microanalysis. The importance of combining signals from multiple length scales and analytical sensitivities is discussed.