Elemental analysis of human cremains using ICP-OES to classify legitimate and contaminated cremains

The Tri-State Crematory Incident in Nobel, GA (February 2001) revealed limitations in traditional human cremated remains (cremains) analytical methodology. The goal of this study was to develop a method for effectively classifying questionable sets of cremains as legitimate or contaminated. Eighty-eight samples of known human cremains, concrete, mixtures of the two, and questionable sets of cremains were acid digested and analyzed for 21 elements by Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES). Variable cluster and principle component analyses identified the seven elements (Sb, B, Li, Mn, Sr, Tl, and V) used to develop discriminant functions to classify questionable sets into two groups: cremains and concrete. The discriminant analysis shows that at the 0.90 probability level, mixtures of 50% or less human content were classified as concrete. Mixtures with 90% human content classified as cremains. Sixty percent and 75% human content mixtures remained in the questionable classification, but as the concentration of human increased in the mixture, the probability of assignment to the known cremains group increased. Most of the questionable human samples classified as cremains. This is a pilot study and cannot yet satisfy Daubert standards for courtroom admissibility, but it indicates that it is possible to determine the legitimacy of cremains using elemental analysis by ICP-OES coupled with multivariate statistical analysis.     

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.     

Discrimination of arsenous acids with comparison of trace elements contained by using synchrotron X-ray fluorescence spectrometry

In the poisonous incident case occurred in Japan, clarification of the identity between seized poisons and retrieved from crime scene is strictly required from the court. In this case, arsenous acid was used as a poisonous material and, seized one from suspect's house was only twenty particles. The synchrotron X-ray fluorescence spectrometry by comparing the intensity ratios of L(alpha) line of four heavy metal, such as Bi, Sn, Sb, Se to K(beta) line of As was performed to overcome this problem. In this paper, the evaluation of this new method using 13 authentic arsenous acid samples, 4 of 13 were refined by Chinese method, 7 of 13 were refined by Japanese method (Sumitomo mining Co. Ltd. method), 2 of 13 were refined by German and Swiss method. As a result, by the comparison of the ratios of these four elements to As, these 13 samples were clearly classified to three products classes produced by different refining methods.     

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.     

Possibilities for using bedside cards as secondary comparison in trace element studies with the PCR technique]

When fresh blood is not available as a control in stain investigations extracted teeth, hair, preserved tissue samples, histological slides, cigarette butts or used stamps can also be used. This paper reports on a stain investigation performed 7 months after the death of the victim, where a bedside card from the medical records was successfully employed as a control blood sample. In a series of 10 bedside cards up to 9 years old, the investigation with the PCR method showed recognizable patterns in the STR systems SE 33 and TC 11. Matching patterns could be found from the 4 sections of each card (anti A, anti B, anti AB and anti D). A comparison of the oldest card with a fresh blood sample of the patient also showed matching patterns. AMPFLPs were successful with more recent cards. Using the PCR method typing of bedside cards from medical records up to 10 years old can be used in stain investigations.     

Conjunctive use of quantitative and qualitative X-ray diffraction analysis of soils and rocks for forensic analysis

This paper describes a repeatability test, comparing conventional X-ray diffraction (XRD) analyses with the technique of quantitative X-ray diffraction (QXRD) as a determinant of mineral abundance. The conjunctive use of both methods allows specific mineral abundances to be matched between scene of crime (SOC) and suspects where soil or substrate mineralogy is similar. In our test, samples from potential SOC locations were taken from car tyre tracks. A car was driven to one location by an independent person and the car submitted for sampling. The tyre-tread sample showed potential correlation to two locations: one correct and the other incorrect. QXRD showed the mineral proportions of the tyre-tread sample matched only the correct location. However, QXRD did fail to discriminate two locations that XRD did show to be different. Both methods utilise the same sample and X-ray diffractogram, suggesting that their conjunctive use, preceded by standard Earth material forensic study, is recommended.     

Development of heavy mineral and heavy element database of soil sediments in Japan using synchrotron radiation X-ray powder diffraction and high-energy (116 keV) X-ray fluorescence analysis: 1. Case study of Kofu and Chiba region

We have started the construction of a nationwide forensic soil sediment database for Japan based on the heavy mineral and trace heavy element compositions of stream sediments collected at 3024 points all over Japan obtained by high-resolution synchrotron X-ray powder diffraction (SR-XRD) and high-energy synchrotron X-ray fluorescence analysis (HE-SR-XRF). In this study, the performance of both techniques was demonstrated by analyzing soil sediments from two different geological regions, the Kofu and Chiba regions in Kanto province, to construct database that can be applied in the future to provenance analysis of soil evidence from a crime scene. The sediments from the quaternary volcanic lithology of the Chiba region were found to be dominated by heavy minerals of volcanic origin - orthopyroxene, clinopyroxene, and amphibole, and the REEs (rare earth elements) within the region showed similar geochemical behavior. On the other hand, four distinct heavy mineral groups were identified in the sediments of the Kofu region, where there is a great variety of underlying bedrock, and the geochemical behavior of the REEs in the sediments also varied accordingly to their geological origins. As such, our study shows that high-resolution SR-XRD data can provide information on the spatial distribution patterns of heavy minerals in stream sediments, playing an important role in determining their likely geographical origin. Meanwhile, the highly sensitive HE-SR-XRF data allow us to study the geochemical behavior of trace heavy elements, especially the REEs in the sediments, providing additional support to further constrain the likely geographical origin of the sediments determined by heavy minerals.     

Identification of dog bites using a comparative video analysis

Pictures from wounds are identified as bite marks of dogs with help of the video-comparison-technic. It is shown, that two dogs had left bite marks.     

Particle size distribution analysis of soils using laser diffraction

The use of laser diffraction for the particle size distribution analysis of the sub-63 μm fraction of soil samples is described. Each sub-63 μm fraction was obtained from the wet sieving of 1500 mg of whole soil. Using similarity probabilities, the data obtained, when combined with other information from wet sieving and/or organic matter content, will enable the correct identity of a given soil sample with that of an unknown to be made. Although the sub-63 μm fraction can account for 450 mg or more of the total soil content, analyses of this fraction can be conducted on sample sizes as small as 100 mg.     

A re-examination of cremains weight: sex and age variation in a Northern California sample

The reduction of modern commercially cremated remains into a fine powder negates the use of traditional methods of skeletal analysis. The literature on the use of cremains weight for estimating aspects of the biologic profile is limited, often with conflicting results. This study re-evaluates the value of weight in the assessment of biologic parameters from modern cremated remains. A sample of adults was collected in northern California (n = 756), with a cremains weight averaging 2737.1 g. Males were significantly heavier than females (mean = 3233.2 g versus mean = 2238.3 g, respectively; p<0.001). Comparison of this sample with other previously reported samples from southern California, Florida, and Tennessee indicates a consistent sex difference, with the most similar mean values to the Tennessee study. Although cremains weight decreases with age as expected, the relationship is weak; thus, cremains weight cannot accurately predict age-at-death. While sex estimation shows considerable accuracy (86.3% for males and 80.9% for females), sectioning points may be population specific.     

Development of a searchable major and trace element database for use in forensic soil comparisons

Forensic soil comparisons are normally undertaken on the basis of several physical, chemical and biological properties, but in all cases the interpretation of results is dependent on the availability of relevant contextual information. This paper summarises the results of major and trace element analyses performed using inductively coupled plasma atomic emission spectrometry and inductively coupled plasma-mass spectrometry on the < 150 µm size fraction of 1896 soil samples collected in connection with forensic investigations in England and Wales between 1999 and 2007. A number of new methods are described which facilitate inter-sample comparison. Although the available data do not provide uniform geographical coverage they do provide useful information which can assist police search investigations and they provide valuable contextual information which aids the evidential assessment of soil evidence when used in court. There is considerable scope to improve the database by increasing the geographical coverage and increasing the number of soil attributes which are included.     

Clarifying the complex chemistry of cobalt(II) thiocyanate-based tests for cocaine using single-crystal X-ray diffraction and spectroscopic techniques

Cobalt(II) thiocyanate-based tests are routinely used to screen cocaine products, with the formation of a blue species interpreted as a positive response. An array of other organic bases has been identified as false positives – including well-documented cocaine product adulterant lidocaine and its salt. False positives prompt continued test development, though improvements are hindered by unresolved product structures and reaction pathways. Toward greater clarity, cobalt(II) thiocyanate reactions with cocaine hydrochloride, along with lidocaine and its salt, were investigated using multiple analytical techniques. Reactions involving cocaine hydrochloride yielded glassy, amorphous blue material while reactions of lidocaine hydrochloride monohydrate produced larger, needle-like crystals whose structure was determined via single-crystal X-ray diffraction to be an ion pair (Hlidocaine⁺)₂([Co(SCN)₄]²⁻)·H₂O. While the blue precipitate isolated from reactions involving cocaine hydrochloride was unsuitable for crystallographic structure determination, comparative ultraviolet–visible, attenuated total reflectance infrared, and Raman spectroscopic analysis – along with elemental analysis – supports that this solid is comprised of a comparable ion pair (Hcocaine⁺)₂[Co(SCN)₄]²⁻. Pink crystals isolated from lidocaine reaction vessels were identified as coordination compounds cis-[CoL₂(SCN)₂] and trans-[CoL₂(SCN)₂] where L = lidocaine, while pink crystals from both cocaine hydrochloride and lidocaine hydrochloride monohydrate reaction vessels were the coordination polymer trans-[Co(H₂O)₂(SCN)₂]·H₂O. The results presented herein enable reaction optimization to favor a desired product, whether ion pair or coordination species.     

Chronic alcoholic intoxication and the trace element composition of the hair

Chronic alcoholic intoxication was found to result in changes in trace elemental structure of human hair and mongrel white rat hair. Reliable increase of iron, zinc, copper and manganese in hair of alcoholic patients and tendency to increase iron content in rat hair were detected.     

Classification of narcotics in solid mixtures using principal component analysis and Raman spectroscopy

Eighty-five solid samples consisting of illegal narcotics diluted with several different materials were analyzed by near-infrared (785 nm excitation) Raman spectroscopy. Principal Component Analysis (PCA) was employed to classify the samples according to narcotic type. The best sample discrimination was obtained by using the first derivative of the Raman spectra. Furthermore, restricting the spectral variables for PCA to 2 or 3% of the original spectral data according to the most intense peaks in the Raman spectrum of the pure narcotic resulted in a rapid discrimination method for classifying samples according to narcotic type. This method allows for the easy discrimination between cocaine, heroin, and MDMA mixtures even when the Raman spectra are complex or very similar. This approach of restricting the spectral variables also decreases the computational time by a factor of 30 (compared to the complete spectrum), making the methodology attractive for rapid automatic classification and identification of suspect materials.