Experimental evaluation of rigor mortis IX. The influence of the breaking (mechanical solution) on the development of rigor mortis

In criminal proceedings involving illegally manufactured substances, evidence demonstrating the manufacture is required for successful prosecution. In many circumstances the presence of manufacturing equipment and 'recipes' are clear indicators. However establishing chemical links between starting materials and products would be beneficial additional evidence in such circumstances. Isotope analysis is becoming more commonly employed in disputes over authenticity and provenance of materials such as food stuffs or pharmaceuticals [S. Benson, C. Lennard, P. Maynard, C. Roux, Forensic applications of isotope ratio mass spectrometry--a review, Forensic Sci. Int., 157 (2006) 1-22]. We report here the results of an isotope study investigating a link between hexamine used as a starting material and the product explosive RDX, manufactured using the Woolwich process. Isotopic composition of hexamine and RDX was analysed by stable isotope ratio mass spectrometry. Five different hexamine samples were selected from a group of eleven for use in this study. One of the five hexamine samples was used twice, providing data on the reproducibility of the synthesis. Carbon and nitrogen isotope analysis of the hexamine starting material and RDX products reveals a reproducible relationship between reactant and product.     

The Effects of Household Corrosive Chemicals on Human Dentition*

Abstract: There is a gap in the literature concerning the chemical effects that household products may produce on human remains. The present study examines the effects of household chemical products on teeth. A total of eight chemicals were utilized for this experiment. The corrosive chemical categories include: hydrochloric acid, sulfuric acid, phosphoric acid, and sodium hydroxide. Two products with each chemical were used, each representing varying concentrations of the corrosive product. Two human teeth were allocated for emergence in the chemical throughout a 24‐h period of exposure. Results demonstrate hydrochloric acid as the most detrimental chemical to the dental samples. Sulfuric acid enacted minimal alterations to the teeth, although some etching and discoloration were noticeable. Phosphoric acid resulted in variable changes of the organic and inorganic contents of teeth. Lastly, exposure of sodium hydroxide resulted in little to no change. As hypothesized, distinct effects are observable of each chemical.     

Trace element fingerprinting of Australian ocher using laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) for the provenance establishment and authentication of indigenous art

The expansion of indigenous art and the interest it has generated both at a domestic and international level means large monetary transactions are taking place between art galleries or centers and purchasers. As such, an accurate and conclusive method for provenance determination of traditional indigenous artistic materials must be established that can, if necessary, be used to assist in authentication of artworks. Laser ablation inductively coupled plasma mass spectrometry was utilized for elemental differentiation and provenance establishment of ocher samples. This research was used to develop a robust scientific protocol which facilitates definitive and accurate determination of provenance of Australian ochers and the artworks created using them. Analysis of the results obtained through this study show that the trace metal distribution patterns alone appear to be sufficient evidence to establish provenance of specific ochers, although additional differentiation between ocher samples, using major element distribution patterns, was achieved through the utilization of X-ray analytical techniques.     

Provenance determination of oriental porcelain using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS)

The sale of fraudulent oriental ceramics constitutes a large proportion of the illegal artifact and antique trade and threatens to undermine the legitimate international market. The sophistication and skill of forgers has reached a level where, using traditional appraisal by eye and hand, even the most experienced specialist is often unable to distinguish between a genuine and fraudulent piece. In addition, current provenancing techniques such as energy-dispersive X-ray fluorescence (EDXRF) spectrometry and thermoluminescence (TL) dating can result in significant damage to the artifact itself. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), a relatively nondestructive analytical technique, has been used for the provenance determination of materials based on geographical origin. The technique requires the production of a laser crater, c. 100 microm in diameter, which is essentially invisible to the naked eye. Debris from this crater is analyzed using ICP-MS, with the results forming the basis of the provenance establishment protocol. Chinese, Japanese, and English porcelain shards have been analyzed using this protocol and generic isotopic distribution patterns have been produced that enable the provenance establishment of porcelain artifacts to their country of production. Minor variations between elemental fingerprints of artifacts produced in the same country also indicate that it may be possible to further provenance oriental ceramics to a specific production region or kiln site.     

The sensitivity and specificity of red-starch paper for the detection of saliva.

The detection of saliva in forensic casework is extremely important in many types of cases. This study describes a relatively sensitive method, based on a red dye bound to starch, for the detection of amylase. The sensitivity and specificity of the method has been examined by testing over 50 household products, various body fluids and five laboratory chemicals. This study demonstrated for the first time that positive results can be obtained from certain washing powders as well as other household products. As well as detecting amylase in saliva, positive Red-Starch results were obtained from faeces and urine. The method was found to be suitable for the detection of mixtures of saliva and semen in conjunction with the Brentamine test for the detection of acid phosphatase.     

The National Partnership for Environmental Priorities Program

The National Partnership for Environmental Priorities (NPEP) program was created by the U.S. Environmental Protection Agency (USEPA) to reduce or eliminate the nation's production of hazardous wastes and products. The NPEP is a voluntary program that provides incentives to public, private, and federal organizations that minimize their use and generation of thirty-one priority chemicals. These chemicals are considered to be persistent, bioaccumulative, and toxic in the environment and present health risks to human and ecological receptors. The USEPA estimates that 90 percent of priority chemicals are used or produced during manufacturing of various household and industrial products and, as a result, end up in municipal and industrial waste streams. Ultimately, these chemicals find their way back into the environment through wastewater discharges, incineration, or other disposal practices. The NPEP program supports the goals of the National Waste Minimalization Program by encouraging simple waste minimalization solutions such as recycling, replacement, or elimination of wastes or products that contain priority chemicals, and cradle-to-cradle management of waste. Although the USEPA does not limit waste minimalization practices to only the priority chemicals, the program has set specific goals to track the elimination of these thirty-one chemicals to the environment on an annual basis.     

Particle size analysis of sediments, soils and related particulate materials for forensic purposes using laser granulometry

Particle size is a fundamental property of any sediment, soil or dust deposit which can provide important clues to nature and provenance. For forensic work, the particle size distribution of sometimes very small samples requires precise determination using a rapid and reliable method with a high resolution. The Coulter trade mark LS230 laser granulometer offers rapid and accurate sizing of particles in the range 0.04-2000 microm for a variety of sample types, including soils, unconsolidated sediments, dusts, powders and other particulate materials. Reliable results are possible for sample weights of just 50 mg. Discrimination between samples is performed on the basis of the shape of the particle size curves and statistical measures of the size distributions. In routine forensic work laser granulometry data can rarely be used in isolation and should be considered in combination with results from other techniques to reach an overall conclusion.     

Illicitly imported heroin products: some physical and chemical features indicative of their origin

Samples taken from over 200 seizures of imported illicit heroin preparations of known geographical origin have been examined by gas liquid chromatography (GLC). The chromatographic characteristics were considered in conjunction with the physical appearance of the materials and it was found possible in many instances to discriminate between samples of different origin. Thus by carrying out GLC and HPLC and a visual inspection on a sample of unknown provenance, it may be possible to give an opinion as to its geographical origin.     

The petroleum-laced background

Using passive headspace concentration (ASTM E-1412) and gas chromatographic/mass spectrometric (GC/MS) analysis as described in ASTM E-1618, the authors have studied the volatile components detectable in several kinds of otherwise uncontaminated substrata, including clothing, shoes, household products, building materials, paper products, cardboard, and adhesives. Due to the use of petroleum-derived liquids in the manufacture of these materials, it is frequently possible to detect the liquids, even when the products are several years old. These results point out the need for the use of comparison samples whenever possible.     

Novel technique for the combined recovery, extraction and clean-up of forensic organic and inorganic trace explosives samples.

This paper describes a simple processing and analysis scheme for explosives trace swab samples which deals both with organic and inorganic materials. Swabs, wetted with ethanol or ethanol/water mixture, were extracted with ethanol/water mixture. The extract was passed directly through a simple column containing an acrylonitrile/styrene copolymer adsorbent. The adsorbent retained common organic explosives, which were recovered with an efficiency of 30-50% as a relatively clean ethyl acetate solution. The concentrated ethyl acetate eluate was analysed using gas chromatography with chemiluminescence or mass spectrometric detection. The unretained inorganic ions and sugars, which were recovered with generally high efficiency as an ethanol/water solution, could be directly analysed using ion chromatography and/or capillary electrophoresis. Minor difficulties encountered in the analysis of sugars, fluoride and phosphate were examined.     

An environmental survey relating to improvised and emulsion/gel explosives

The detection and identification of traces of inorganic ions and sugars can play a major role in the forensic investigation of an explosives related incident. This survey investigated the background levels of these substances in the general environment. Six sampling locations were selected from around the mainland of the United Kingdom, representing urban and rural sites. Swab and vacuum samples were collected from different locations within each site including motor vehicles, private houses, hotels, the exterior of buildings, road surfaces, and street signs. Sampling was carried out in summer and winter to investigate changes in the levels of the target species due to seasonal factors such as road treatments or weather. The samples were extracted with water and analyzed for a range of inorganic anions, cations, and sugars using ion chromatography. Most of the target anions were found to be common to all locations. Chloride, sulphate, nitrate, and phosphate were found to be the most common and the most abundant. Chlorate was found at a low level in some external samples. Perchlorate and thiocyanate were not detected in any samples. There was a marked increase in the quantity of sodium and chloride detected in samples collected during the winter. Sodium and calcium were detected in most samples. Potassium and magnesium were detected in approximately half of the samples. Ammonium was less common but detected at significant levels in wall samples. Glucose, fructose, and sucrose were detected in the vacuum samples from the interior surfaces of houses, hotels, and cars.     

The GC/MS analysis of some commonly used non-steriodal anti-inflammatory drugs (NSAIDs) in pharmaceutical dosage forms and in urine

All the commonly used non-steriodal anti-inflammatory drugs (NSAIDs), except mefenamic acid, when extracted from the pharmaceutical dosage forms or the urines of users, and derivatized by silylation and then analysed by GC/MS, gave the mono- or the di-trimethylsilyl derivatives (depending on the number of derivatized groups in the drug) as the sole products. Mefenamic acid gave a mixture of products. When extracted from pharmaceutical dosage froms or from the urines of users, and analysed by GC/MS without derivatization, some of the NSAIDs were separated and detected as the unchanged molecules as the sole products, while others were separated and detected in altered forms as sole products or mixtures, depending on: (a) the solvent in which the extract was dissolved for injection into GC/MS, (b) the chemical structure of the drug, and (c) specifically for diflunisal, the presence or absence of potential methylating and/or acetylating agents on the GC column and/or septum. The main thermally-induced reactions of the underivatized NSAIDs included (i) methyl ester formation at the COOH group when the extract was dissolved in methanol, (ii) decarboxylation (i.e., loss of CO2), (iii) dehydration (i.e., loss of H2O) when the chemical structure permitted, such as for diclofenac, and (iv) cleavage at a carbon-heterocyclic nitrogen bond when one is present in an NSAID. Heating the urine in approximately 2 M HCl at 100 degrees C for 30 min, has been found to be a satisfactory means for effecting hydrolysis of the NSAIDs glucuronide conjugates. No metabolites, resulting from aromatic-ring hydroxylation, have been detected in urine for any of the NSAIDs studied.     

Discrimination of pencil markings on paper using elemental analysis: an initial investigation

The characterisation and comparison of pencil markings on paper is an area of questioned document analysis that has previously not received much attention. Despite this, there would be value in an examiner being able to analyse two pencil markings and coming to a conclusion about whether they were from a similar or different source. Previous studies have analysed raw materials and bulk pencil cores for purposes of characterisation and differentiation, but to date, no studies have successfully analysed pencil markings non-destructively off a paper substrate. In this work, pencils from a number of manufacturers were analysed by inductively coupled plasma mass spectrometry (ICP-MS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Analysis of data using multivariate techniques (principal component analysis), showed that ToF-SIMS can successfully be used to analyse such pencil markings to deduce whether two markings can be differentiated, in terms of inorganic elemental composition. It was possible to discriminate between pencil markings from different manufacturers, and it was also indicated that pencils from the same manufacturer, but discrete batches, can be significantly different.     

Identification of Different Forms of Cocaine and Substances Used in Adulteration Using Near‐infrared Raman Spectroscopy and Infrared Absorption Spectroscopy

Identification of cocaine and subsequent quantification immediately after seizure are problems for the police in developing countries such as Brazil. This work proposes a comparison between the Raman and FT‐IR techniques as methods to identify cocaine, the adulterants used to increase volume, and possible degradation products in samples seized by the police. Near‐infrared Raman spectra (785 nm excitation, 10 sec exposure time) and FT‐IR‐ATR spectra were obtained from different samples of street cocaine and some substances commonly used as adulterants. Freebase powder, hydrochloride powder, and crack rock can be distinguished by both Raman and FT‐IR spectroscopies, revealing differences in their chemical structure. Most of the samples showed characteristic peaks of degradation products such as benzoylecgonine and benzoic acid, and some presented evidence of adulteration with aluminum sulfate and sodium carbonate. Raman spectroscopy is better than FT‐IR for identifying benzoic acid and inorganic adulterants in cocaine.     

Automated extraction of DNA from reference samples from various types of biological materials on the Qiagen BioRobot EZ1 Workstation

We have validated and implemented a protocol for DNA extraction from various types of biological materials using a Qiagen BioRobot EZ1 Workstation. The sample materials included whole blood, blood from deceased, buccal cells on Omni swabs and FTA Cards, blood on FTA Cards and cotton swabs, and muscle biopsies. The DNA extraction was validated according to EN/ISO 17025 for the STR kits AmpF?STR^® Identifiler^® and AmpF?STR^® Yfiler^® (Applied Biosystems). Of 298 samples extracted, 11 (4%) did not yield acceptable results. In conclusion, we have demonstrated that extraction of DNA from various types of biological material can be performed quickly and without the use of hazardous chemicals, and that the DNA may be successfully STR typed according to the requirements of forensic genetic investigations accredited according to EN/ISO 17025.     

Potential and pitfalls in establishing the provenance of Earth-related samples in forensic investigations

Earth scientists are often asked to establish or constrain the likely provenance of very small quantities of earth-related material as part of a forensic investigation. We tested the independent and collective interpretations of four experts with differing analytical skills in the prediction of sample provenance for three samples from different environmental settings. The methods used were X-ray diffraction, scanning electron microscopy, the assessment of pollen assemblages, and structural characterization of organic matter at the molecular level. Independent interpretations were less accurate than those where multiple techniques were combined. Collective interpretation was very effective in the assessment of provenance for two of the three sites where the mineralogy and plant communities were distinctive. At the other site, although the mineralogical analysis correctly identified the Triassic mudstone soil parent material, Carboniferous spores from domestic coal were initially interpreted as deriving directly from bedrock. Such an interpretation could be a common pitfall owing to anthropogenic redistribution of material such as coal.     

Determination of Inorganic Ion Profiles of Illicit Drugs by Capillary Electrophoresis

A portable capillary electrophoresis instrument with dual capacitively coupled contactless conductivity detection (C⁴D) was used to determine the inorganic ionic profiles of three pharmaceutical samples and precursors of two illicit drugs (contemporary samples of methylone and para‐methoxymethamphetamine). The LODs ranged from 0.10 μmol/L to 1.25 μmol/L for the 10 selected cations, and from 0.13 μmol/L to 1.03 μmol/L for the eight selected anions. All separations were performed in less than 6 min with migration times and peak area RSD values ranging from 2 to 7%. The results demonstrate the potential of the analysis of inorganic ionic species to aid in the identification and/or differentiation of unknown tablets, and real samples found in illicit drug manufacture scenarios. From the resulting ionic fingerprint, the unknown tablets and samples can be further classified.     

In Vitro Effects of Household Products on Calliphoridae Larvae Development: Implication for Forensic Entomology

Several parameters can delay the first arrival of flies on a corpse and the subsequent development of the larvae. This study focuses on the development of Lucilia sericata (Diptera: Calliphoridae) (Meigen, 1826) on household chemical‐contaminated substrates. bleach, perfume, hydrochloric acid, caustic soda, insecticide, mosquito repellent, and gasoline in quantities consistent with an amount that could possibly be spilled on a corpse were mixed with beef liver to simulate contaminated fleshes. Larvae were bred at 25°C on these media until emergence. Four developmental parameters were followed: survival rates, development times, sex ratios, and adult sizes. Hydrochloric acid, insecticide, and gasoline killed all larvae. In low quantities, caustic soda and mosquito repellent increased the development time and decreased the adult size. However, high quantities of these chemicals killed all larvae. Lastly, bleach and perfume did not affect the survival rate and barely impacted the development time or adult size. These results demonstrate common household products spilled on a corpse can strongly affect the development of Calliphoridae larvae. The effects of such products should be considered in forensic entomology cases.     

Determination of race and sex of the human skull by discriminant function analysis of linear and angular dimensions

The race and sex of the human skull can be determined by craniometry. In this paper we suggest that a large number of craniometric measurements does not necessarily give the best possible discrimination for race and test the performance of subsets of variables drawn from various skull regions, or extracted mathematically on the basis of their discriminatory power. We also suggest that the best discriminators for race are not necessarily the best for sex, and that skulls of unknown provenance are best tested first for race and then for sex, using different variables for each purpose.