Rosalind Wolstenholme

Study of latent fingermarks by matrix-assisted laser desorption/ionisation mass spectrometry imaging of endogenous lipids.

Identification of suspects via fingermark analysis is one of the mainstays of forensic science. The success in matching fingermarks, using conventional fingermark scanning and database searching, strongly relies on the enhancement method adopted for fingermark recovery; this in turn depends on the components present in the fingermarks, which will change over time. This work aims to develop a robust methodology for improved analytical detection of the fingermark components. For the first time, matrix-assisted laser desorption/ionisation mass spectrometry imaging (MALDI-MSI) has been used to image endogenous lipids from fresh and aged, groomed and ungroomed fingermarks. The methodology was initially developed using oleic acid which was detected along with its degradation products over a 7-day period, at three different temperatures in a time-course experiment. The optimised methodology was then transferred to the imaging analysis of real fingermark samples. Fingermark patterns were reconstructed by retrieving the m/z values of oleic acid and its degradation products. This allowed the three aged fingermarks to be distinguished. In order to prove that MALDI-MSI can be used in a non-destructive way, a simple washing protocol was adopted which returned a fingermark that could be further investigated with classical forensic approaches. The work reported here proves the potential and the feasibility of MALDI-MSI for the forensic analysis of fingermarks, thus making it competitive with other MSI techniques such as desorption electrospray ionisation (DESI)-MS. The feasibility of using MALDI-MSI in fingermark ageing studies is also demonstrated along with the potential to be integrated into routine fingermark forensic analysis.

A novel matrix‐assisted laser desorption/ionisation mass spectrometry imaging based methodology for the identification of sexual assault suspects

An increase in the use of condoms by sexual offenders has been observed. This is likely to be due both to the risk of sexually transmitted diseases and to prevent the transfer of DNA evidence. In this scenario the detection of condom lubricants at a crime scene could aid in proving corpus delicti. Here we show a novel application of Matrix-Assisted Laser Desorption/Ionisation Mass Spectrometry Imaging (MALDI MSI) for mapping the fingermark ridge pattern simultaneously to the detection of the condom lubricant within the fingermark itself. Two condom brands have been investigated to prove the concept. Condoms were handled producing lubricant-contaminated fingermarks. Images of the ridge pattern were obtained simultaneously to the detection of two lubricants, even several weeks after the fingermark deposition. The results therefore show the potential of MALDI MSI to link the suspect (identification through fingermark ridge pattern) to the crime (detection of condom lubricant) in one analysis. This would enable forensic scientists to provide evidence with stronger support in alleged cases of sexual assault.

Beyond the ridge pattern: multi-informative analysis of latent fingermarks by MALDI mass spectrometry

After over a century, fingerprints are still one of the most powerful means of biometric identification. The conventional forensic workflow for suspect identification consists of (i) recovering latent marks from crime scenes using the appropriate enhancement technique and (ii) obtaining an image of the mark to compare either against known suspect prints and/or to search in a Fingerprint Database. The suspect is identified through matching the ridge pattern and local characteristics of the ridge pattern (minutiae). However successful, there are a number of scenarios in which this process may fail; they include the recovery of partial, distorted or smudged marks, poor quality of the image resulting from inadequacy of the enhancement technique applied, extensive scarring/abrasion of the fingertips or absence of suspects fingerprint records in the database. In all of these instances it would be very desirable to have a technology able to provide additional information from a fingermark exploiting its endogenous and exogenous chemical content. This opportunity could potentially provide new investigative leads, especially when the fingermark comparison and match process fails. We have demonstrated that Matrix Assisted Laser Desorption Ionisation Mass Spectrometry and Mass Spectrometry Imaging (MALDI MSI) can provide multiple images of the same fingermark in one analysis simultaneous with additional intelligence. Here, a review on the pioneering use and development of MALDI MSI for the analysis of latent fingermarks is presented along with the latest achievements on the forensic intelligence retrievable.

Direct detection of peptides and small proteins in fingermarks and determination of sex by MALDI mass spectrometry profiling

Matrix Assisted Laser Desorption Ionisation Mass Spectrometry (MALDI MS) can detect and image a variety of endogenous and exogenous compounds from latent fingermarks. This opportunity potentially provides investigators with both an image for suspect identification and chemical information to be used as additional intelligence. The latter becomes particularly important when the fingermark is distorted or smudged or when the suspect is not a previously convicted offender and therefore their fingerprints are not present in the National Fingerprint Database. One of the desirable pieces of intelligence would be the sex of the suspect from the chemical composition of a fingermark. In this study we show that the direct detection of peptides and proteins from fingermarks by MALDI MS Profiling (MALDI MSP), along with the multivariate modeling of the spectra, enables the determination of sex with 85% accuracy. The chemical analysis of the fingermark composition is expected to additionally provide information on traits such as nutritional habits, drug use or hormonal status.

Chemical Characterization of Latent Fingerprints by Matrix-Assisted Laser Desorption Ionization, Time-of-Flight Secondary Ion Mass Spectrometry, Mega Electron Volt Secondary Mass Spectrometry, Gas Chromatography/Mass Spectrometry, X-ray Photoelectron Spectroscopy, and Attenuated Total Reflection Fourier Transform Infrared Spectroscopic Imaging: An Intercomparison

The first analytical intercomparison of fingerprint residue using equivalent samples of latent fingerprint residue and characterized by a suite of relevant techniques is presented. This work has never been undertaken, presumably due to the perishable nature of fingerprint residue, the lack of fingerprint standards, and the intradonor variability, which impacts sample reproducibility. For the first time, time-of-flight secondary ion mass spectrometry, high-energy secondary ion mass spectrometry, and X-ray photoelectron spectroscopy are used to target endogenous compounds in fingerprints and a method is presented for establishing their relative abundance in fingerprint residue. Comparison of the newer techniques with the more established gas chromatography/mass spectrometry and attenuated total reflection Fourier transform infrared spectroscopic imaging shows good agreement between the methods, with each method detecting repeatable differences between the donors, with the exception of matrix-assisted laser desorption ionization, for which quantitative analysis has not yet been established. We further comment on the sensitivity, selectivity, and practicability of each of the methods for use in future police casework or academic research.

Separation of overlapping fingermarks by Matrix Assisted Laser Desorption Ionisation Mass Spectrometry Imaging

Latent fingermarks are impressions of the skin ridge pattern that are transferred by the accidental contact of fingertips with a deposition surface. The ability to enhance, lift and produce an image of a latent fingermark, for comparison and suspect match against a central fingerprint database, provides forensic investigators with what is still considered one of the most powerful means of biometric identification to date. Identification relies on the recovery, visualisation, extraction and comparison of local characteristics of the ridge pattern (minutiae) that are unique to individuals. Therefore, both for manual inspection of the minutiae and using automated ridge extraction algorithms, the clearer the ridge details, the more reliable and successful the match. Overlapping fingermarks pose a remarkable challenge in this context and are often encountered when developing marks from crime scenes. Here we propose the use of Matrix Assisted Laser Desorption Ionisation Mass Spectrometry Imaging (MALDI MSI) to separate overlapping fingermarks using ion signals that are characteristic of each fingermark and that may be endogenous or exogenous in nature. In this work we show that the methodology works in a number of different scenarios both using manual inspection of the spectrum profile or a much quicker multivariate statistical analysis.