An interlaboratory study evaluating the interpretation of forensic glass evidence using refractive index measurements and elemental composition.

Seventeen laboratories participated in three interlaboratory exercises to assess the performance of refractive index, micro X-ray Fluorescence Spectroscopy (µXRF), and Laser Induced Breakdown Spectroscopy (LIBS) data for the forensic comparison of glass samples. Glass fragments from automotive windshields were distributed to the participating labs as blind samples and participants were asked to compare the glass samples (known vs. questioned) and report their findings as they would in casework. For samples that originated from the same source, the overall correct association rate was greater than 92% for each of the three techniques (refractive index, µXRF, and LIBS). For samples that originated from different vehicles, an overall correct exclusion rate of 82%, 96%, and 87% was observed for refractive index, µXRF, and LIBS, respectively. Special attention was given to the reporting language used by practitioners as well as the use of verbal scales and/or databases to assign a significance to the evidence. Wide variations in the reported conclusions exist between different laboratories, demonstrating a need for the standardization of the reporting language used by practitioners. Moreover, few labs used a verbal scale and/or a database to provide a weight to the evidence. It is recommended that forensic practitioners strive to incorporate the use of a verbal scale and/or a background database, if available, to provide a measure of significance to glass forensic evidence (i.e., the strength of an association or exclusion).

Condom evidence: Characterisation, discrimination and classification of pyrolysis-GC-MS profiles.

Analysis of condom evidence commonly focusses on the detection of silicone-based lubricants, such as polydimethylsiloxane (PDMS). Although various instruments are used to analyse silicone lubricants, pyrolysis-gas chromatography coupled to mass spectrometry (py-GC-MS) is one of the few instruments that presents immediate applicability to casework. However, considering that this technique detects silicone-based evidence, it is important to evaluate the discrimination potential of the method when applied to various samples. Examination of the variability within a large sample set from an international market is needed to evaluate the most distinguishing compounds likely to be detected in casework. In this study, 70 condoms, personal hygiene products, and lubricants, were analysed using py-GC-MS. Resulting pyrograms were characterised using published spectral databases. Pyrolysates data were extracted and evaluated using multivariate techniques. Qualitative visual inspection of the data, as well as statistical analysis, revealed at least five groups within the dataset. Discrimination was based on four main oligomers, as well as six minor compounds from siloxane degradation. Condom lubricants were found to present a very regular pattern, allowing for the majority of them to be differentiated from personal lubricants.

A forensic international market survey of condom lubricants and personal hygiene products using ATR-FTIR coupled to chemometrics.

Condom residues may be encountered in forensic investigations as traces in sexual assault or rape cases. Casework studies have shown the value of distinguishing condom residues from other types of personal products used by women. However, up to now, there has been no investigation of their chemical variability within an international context. This work employed attenuated total reflectance Fourier transform infrared spectroscopy with chemometrics to provide objective characterisation of condom lubricants and personal hygiene products from the international market. 166 samples were obtained covering five major classes of products likely to be used by women. Principal component analysis distinguished most major classes based on their spectral profiles, with subsequent support vector machine models yielding discrimination accuracies over 90%. A two-step approach was subsequently developed and enabled both classification and a discrimination accuracy of 100%. This could provide greater confidence in chemical discrimination of residues from these products when conducting investigations and help assess the origin of the chemical profile obtained. Further testing using three validation sets produced an identification accuracy of 100% for generic classes, which may allow investigative leads to be more readily obtained from recovered evidence.

Characterization and classification of water-based compounds in condoms and personal hygiene products using GC-MS.

Analysis of condom evidence commonly focusses on the detection of silicone-based lubricants, such as polydimethylsiloxane. However, water-based compounds such as propylene glycol or glycerin can also be used as condom lubricants and may, therefore, be detected as transferred traces. Evaluation of the variability amongst a large sample set from an international market is needed to determine what are the most likely compounds that may be detected in casework. In this study, 165 condoms, personal hygiene products, lubricants, creams and oils were analysed using gas-chromatography coupled to a mass spectrometer detector (GCMS). The resulting compounds were identified using mass spectral databases, then the data were extracted and evaluated using established multivariate statistical techniques, such as principal component analysis and discriminant analysis. Qualitative visual inspection, as well as statistical analysis, revealed at least twelve different groupings within the dataset. Discrimination was based on variations in the concentration of major compounds, as well as the presence or absence of minor compounds, such as anaesthetics. For the 127 condoms examined, 2 were exclusively water-based lubricated (1.5 %) and 6 contained silicone and water-based components (4.7 %). All the others were only silicone-based (119 condoms, 93.7 %). Strong variation was observed between the different sources of products. Personal hygiene products (PHP), creams, lubricating oils, personal lubricants, and condoms were found to have different chemical compositions. Hence GCMS can be used to assist in the differentiation of water-based residues for investigative purposes.

Persistence of Polydimethylsiloxane Condom Lubricants.

Polydimethylsiloxane (PDMS) is commonly used to lubricate condoms. The detection of PDMS on swabs from complainants can be used to support an allegation of sexual assault. Previous research has focused on establishing analytical techniques for detecting PDMS. This research examined the persistence of PDMS on the penis, in the vagina, in the mouth, and on skin. The longest PDMS detection times were 20 h on the penis, 35 h in the vagina, and 52 h on skin. PDMS was detected up to 4 h in the mouth if the participant did not eat or drink and up to 9 h if the participant slept. PDMS was not detected in the mouth after eating or drinking. The presence of biological fluids had no detrimental effect on the analysis. Aqueous extraction of swabs for DNA did not remove any significant amount of PDMS; hence, swab remains could be subsequently analyzed for PDMS.

Simulating transfer and persistence of a chemical marker powder for Lycopodium clavatum spores.

In this research a chemical marker powder, based on Lycopodium clavatum spores, was studied to determine its transfer and persistence on a T-shirt. Such chemical marker powders are used to provide evidence that a person has handled a covertly marked object, such as a drug package. The powder was found to transfer readily between a marked item and the person handling it. The powder was found to persist on a T-shirt for up to 13h; however, there was only a very small amount of powder remaining at this time. The rate of loss of the L. clavatum spores was found to follow a decay curve. The largest decrease in spores from the T-shirt was seen in the first 2h after the marked item had been handled.

Compositional data analysis for elemental data in forensic science.

Discrimination of material based on elemental composition was achieved within a compositional data (CoDa) analysis framework in a form appropriate for use in forensic science. The methods were carried out on example data from New Zealand nephrite. We have achieved good separation of the in situ outcrops of nephrite from within a well-defined area. The most significant achievement of working within the CoDa analysis framework is that the implications of the constraints on the data are acknowledged and dealt with, not ignored. The full composition was reduced based on collinearity of elements, principal components analysis (PCA) and scalings from a backwards linear discriminant analysis (LDA). Thus, a descriptive subcomposition was used for the final discrimination, using LDA, and proved to be more successful than using the full composition. The classification based on the LDA model showed a mean error rate of 2.9% when validated using a 10 repeat, three-fold cross-validation. The methods presented lend objectivity to the process of interpretation, rather than relying on subjective pattern matching type approaches.

An investigation into the presence of petrol on the clothing and shoes of members of the public.

First, the clothing and shoes from 29 participants who had recently filled their vehicles with petrol were analysed for any traces of petrol. No traces of petrol were found on any of these items. Secondly, the clothing and shoes from 17 participants who had recently used a petrol-powered lawn mower were also analysed for petrol. Petrol was detected on two pairs of shoes from different participants. Components of petrol were detected on a set of clothing from a third participant, however, there were insufficient components present in this sample to confirm the presence of petrol. No traces of petrol were found on the items from the remaining 14 participants. Thirdly, the clothing from a forecourt attendant, a mechanic and a professional lawn mower were analysed at the end of a number of shifts. Petrol was detected on the upper and lower clothing from the forecourt attendant at the end of one shift. No petrol residues were found on the forecourt attendant after a second shift, or on the mechanic's clothing after two separate shifts or on the professional lawn mower's clothing after three separate shifts. These results can be used to assist the forensic analyst in assessing the chance of finding traces of petrol on clothing and shoes after the wearer has performed common activities that involve petrol.

The evidential value of cosmetic foundation smears in forensic casework.

Cosmetic foundation products are easily transferred to clothing and other surfaces as a result of contact with such objects. Examination of past cases involving cosmetics in New Zealand has shown cosmetic foundation to be one of the more common cosmetic products encountered. The aim of this research was to determine the most discriminating method for the comparison of transferred foundation with samples obtained from a known source in forensic casework. Fifty-three foundation samples were analyzed by Fourier transform infrared spectroscopy (FTIR), gas chromatography with a flame ionization detector (GC-FID) and scanning electron microscopy-energy dispersive X-Ray analysis (SEM-EDX). It was found that a 5 mm2 section of a light smearing was enough to provide detectable results. The discriminating powers for FTIR, SEM-EDX and GC-FID were 98.3, 93.8, and 82.0% respectively. A combination of all three techniques provided a discriminating power of 99.7%, meaning that almost complete discrimination was achieved between the foundation samples.