Evaluation of Raman spectroscopy for the analysis of colored fibers: a collaborative study

A collaborative study on Raman spectroscopy was carried out by members of the ENFSI (European Network of Forensic Science Institutes) European Fibres Group (EFG) on three dyed fibers: two red acrylics and one red wool. Raman instruments from six different manufacturers were tested as well as nine different laser wavelengths ranging from blue (lambda = 458 nm) to near infrared-NIR (lambda = 1064 nm). This represents the largest comparison study of Raman analytical parameters carried out on identical fiber samples. For the chosen fiber and dye samples, red lasers (lambda = 633 and 685 nm) gave the poorest spectral quality whereas blue (458 nm), green (514 nm) and near infrared lasers (785, 830 and 1064 nm) provided average results. Blue (488 nm) and green lasers (532 nm) globally gave the best quality spectra. Fluorescence problems were often encountered with some of the excitation wavelengths and therefore a flexible Raman instrument equipped with different lasers can be recommended to measure forensic fiber samples. The instrument should also be equipped with a Raman microscope in order to be able to focus on a single fiber. This study shows that Raman spectroscopy usually enables the identification of the main dye present in a colored fiber; however, minor dye components are much more difficult to detect. SERRS (Surface Enhanced Resonance Raman Scattering) techniques give an improvement of the dye's spectral intensity but no spectral improvement was observed for the two red acrylic and red wool fibers tested.     

Classification of premium and regular gasoline by gas chromatography/mass spectrometry,principal component analysis and artificial neural networks

Detection and correct classification of gasoline is important for both arson and fuel spill investigation. Principal component analysis (PCA) was used to classify premium and regular gasolines from gas chromatography-mass spectrometry (GC-MS) spectral data obtained from gasoline sold in Canada over one calendar year. Depending upon the dataset used for training and tests, around 80-93% of the samples were correctly classified as either premium or regular gasoline using the Mahalanobis distances calculated from the principal components scores. Only 48-62% of the samples were correctly classified when the premium and regular gasoline samples were divided further into their winter/summer sub-groups. Artificial neural networks (ANNs) were trained to recognise premium and regular gasolines from the same GC-MS data. The best-performing ANN correctly identified all samples as either a premium or regular grade. Approximately 97% of the premium and regular samples were correctly classified according to their winter or summer sub-group.     

The effect of metal salt treatment on the photoluminescence of DFO-treated fingerprints

Ninhydrin developed fingerprints can be enhanced by treatment with a zinc or cadmium salt. The resulting fingerprint luminescence has been attributed to the induced coplanarity of the bicyclic indanedione rings of Ruhemann's purple due to complexation with the metal ions. This paper explores whether this effect also occurs in the 1,8-diaza-9-fluorenone (DFO)-amino acid adduct (1), formed from the reaction of DFO with amino acids. Molecular modeling studies of (1) indicate a relatively small out-of-plane angle of 24 degrees. 1H NMR studies indicate (1) is asymmetric about the C2 axis in contrast to what has been previously reported. Little, if any, enhancement of luminescence was observed with Zn, Cd, Ru or Eu treated DFO developed latent fingerprints. This lack of enhancement was also borne out by solution luminescence studies. Given this lack of enhancement of luminescence, solutions of (1) and the four metal ions above were analyzed by electrospray mass spectrometry (ESMS). This indicated the formation of predominantly 1:1 complexes of (1) with both Zn and Cd, and the 2:1 complex with ruthenium. No evidence of a Eu complex was found by ESMS.     

A protocol for the forensic analysis of condom and personal lubricants found in sexual assault cases.

In sexual assault cases, lubricant trace evidence may supplement biological evidence, or may be the primary physical evidence where biological evidence is unavailable. This study considered a total of 50 lubricants from condoms and personal lubricant products available in Australia. Differentiation of the samples was attempted using fluorescence examination, Fourier transform infrared spectroscopy (DRIFTS), gas chromatography-mass spectrometry, liquid chromatography-tandem mass spectrometry, and pyrolysis gas chromatography-mass spectrometry. Eleven of the samples were uniquely identified by the analysis scheme, while the remainder of the samples were separated into nine groups. As a result of this study, a recommended protocol for the detection and analysis of an "unknown" biological swab was produced.     

Moving into and out of poor urban areas

Newly available geographical information from the Panel Study of Income Dynamics (PSID) is used to estimate a variety of relationships involving high-poverty metropolitan census tracts. The longitudinal data from the PSID show a great deal of geographical mobility even for persistently poor adults, with as many as one fourth of certain groups of these entering and leaving poor urban census tracts in a year. At the same time, solution of the transition matrices for various groups—whites and blacks of various income classes, in families with and without children, living in different types of census tracts—in the early 1980s shows the gradual emptying out of poor urban tracts, particularly of whites and blacks in families without children. As a consequence, despite the great degree of geographical “churning,” poor urban areas gradually become poorer, blacker, and the home of a larger share of black families with children. Some of these aggregate trends had been noticed by researchers comparing these areas in the 1970 and 1980 censuses; our more up-to-date results demonstrate the relationships between the micro and macro data.     

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.