Dynamics and mechanism of the physical developer process for visualization of latent fingerprints on paper.

We present a detailed mechanistic study of the PD process, focused on the nucleation and growth dynamics of silver particles on fingermarks deposited on a paper surface, from macroscopic (whole fingermark) and microscopic (particle level) perspectives. Conceptually, we separate the outcomes into aspects that precede exposure of the exhibit (relating to the reagent formulation), that relate to the development of the fingermark during immersion in the PD formulation, and that characterise the fully developed mark subsequent to immersion. Initially, dynamic light scattering shows the silver particles in solution to be relatively monodisperse, with a peak particle size of 880 nm. In the second instance, the issue is whether the particles grow to final size in solution then deposit on the surface or deposit as relatively small particles then grow on the surface. To the naked eye, silver deposition is evident after 2 min; corresponding optical profilometry images show evidence of surface-bound particles (mean diameter 2.13 µm) after 30 s. Across the development time (15 min) the particle population density (2.36 ( ± 0.52) x 105 cm-2), is independent of time. During this time, the mean particle diameter increases with the square root of development time to 16.09 µm. The dynamics suggest essentially instantaneous (shorter than observation time) nucleation and diffusionally controlled growth. Surface analysis (EDS) shows the expected high (low) levels of silver on ridge detail (in furrows) but no evidence of iron (from the redox component of the formulation) entrapment at any point on the surface.

The effect of corrosive substances on fingermark recovery: A pilot study.

Corrosive substance attacks have become a growing issue within the UK. Although most commonly occurring in gang-related offences, there are high profile instances where this type of attack has been used to attack women to disfigure and destroy livelihoods. Despite the increase in such attacks, there has been very little published research into the recovery of forensic evidence from items used in these crimes. The effect of corrosive substances on the recovery of different types of forensic evidence is unknown, and there is no guidance for laboratories processing exhibits contaminated with corrosive substances regarding optimum treatments. This pilot study focused on establishing the effectiveness of a range of fingermark visualisation processes in recovering fingermarks on surfaces exposed to concentrated sulfuric acid (acid) and potassium hydroxide (alkali). Results indicate that on non-porous surfaces vacuum metal deposition and powder suspensions remain effective, and on porous surfaces fingermarks could still be visualised with physical developer. Alkalis were found to be more detrimental than acid environments in this limited study. The results demonstrate that fingermark recovery is still feasible on surfaces exposed to corrosive substances and provides encouragement that treatment protocols could be developed for this type of exhibit.

Replacing Synperonic® N in the physical developer fingermark visualisation process: Pseudo-operational trial and parameter studies.

A reformulated physical developer (PD) solution has been devised to replace the use of Synperonic® N for environmental reasons. The performance of the replacement solution has proved promising in laboratory trials using planted fingermarks [1] however; this may not always represent how a reagent works on real world samples. This paper therefore explores the effectiveness of the decaethylene glycol monododecyl ether (DGME)-based PD formulation through a pseudo-operational trial. A range of naturally handled, porous substrates were processed, which totalled over 600 samples that had been previously treated with amino acid reagents (1,2-indandione (IND) or 1,8-diazafluoren-9-one (DFO) and ninhydrin). The trial was representative of the operational use of PD at the end of a processing sequence for porous exhibits. The results from the trial establish that DGME is an effective replacement detergent for Synperonic® N in PD solutions and demonstrated the added benefit of using PD as a sequential treatment. Planted mark studies to assess the parameters of the DGME-based PD formulation are also included in this paper. These studies explored the preparation, processing and storage temperature required for the solution as well as the shelf life. The effectiveness of DGME-based PD on items that have been previously wetted was also investigated. These studies show the formulation is suitable for use in an operational laboratory and is therefore an effective replacement formulation for the Synperonic® N-based PD.

An evaluation of the effect of incorporating metal salts into 1,8 diazafluoren-9-one (DFO) formulations for fingermark enhancement.

A study into the modification of 1,8-diazafluoren-9-one (DFO) formulations by the additions of metal salts into the working solution is reported. Similar additions have been found to increase the fluorescence of marks developed using other amino acid reagents including 1,2-indandione and the ninhydrin analogue 5-methylthioninhydrin. It was found that adding zinc chloride to give a 1:1 ratio of zinc ions:DFO molecules gave optimum fluorescence, and improvements in performance over the standard DFO formulation were achieved. Attempts to produce equivalent formulations with iron, nickel and palladium chlorides were unsuccessful. In a comparative trial with a 1,2-indandione-zinc formulation on brown paper and cardboard substrates, 1,2-indandione-zinc gave superior results and it was decided to focus further research on this reagent instead of DFO-zinc.

Visualisation of latent fingermarks on polymer banknotes using copper vacuum metal deposition: A preliminary study.

The UK's recent move to polymer banknotes has seen some of the currently used fingermark enhancement techniques for currency potentially become redundant, due to the surface characteristics of the polymer substrates. Possessing a non-porous surface with some semi-porous properties, alternate processes are required for polymer banknotes. This preliminary investigation explored the recovery of fingermarks from polymer notes via vacuum metal deposition using elemental copper. The study successfully demonstrated that fresh latent fingermarks, from an individual donor, could be clearly developed and imaged in the near infrared. By varying the deposition thickness of the copper, the contrast between the fingermark minutiae and the substrate could be readily optimised. Where the deposition thickness was thin enough to be visually indistinguishable, forensic gelatin lifters could be used to lift the fingermarks. These lifts could then be treated with rubeanic acid to produce a visually distinguishable mark. The technique has shown enough promise that it could be effectively utilised on other semi- and non-porous substrates.

Fingerprint composition and aging: A literature review.

Fingerprints have a key role in criminal investigations and are the most commonly used form of evidence worldwide. Significant gaps remain however, in the understanding of fingerprint chemistry, including enhancement reaction mechanisms and the effect of environmental variables and time on composition. Determining the age of a fingerprint is also a relatively unexplored area. A successful method, with reliable and quantitative estimates, would have numerous advantages. Previous unreliable methods have predominantly focused on enhancement success based on physical and chemical changes. This review explores variations in composition due to donor characteristics and environmental variables, and identifies gaps for further research. We also present a qualitative and quantitative summary of the effect of time on composition. Kinetics are presented where known, with summary schematics for reaction mechanisms. Previous studies exploring methods for determining the age of a fingerprint are also discussed, including their advantages and disadvantages. Lastly we propose a potentially more accurate and reliable methodology for determining fingerprint age based on quantitative kinetic changes to the composition of a fingerprint over time.

A comparison of the use of vacuum metal deposition versus cyanoacrylate fuming for visualisation of fingermarks and grab impressions on fabrics.

Both vacuum metal deposition (VMD) and cyanoacrylate fuming (CAF) are techniques used to visualise latent fingermarks on smooth non-porous surfaces such as plastic and glass. VMD was initially investigated in the 1970s as to its effectiveness for visualising prints on fabrics, but was abandoned when radioactive sulphur dioxide was found to be more effective. However, interest in VMD was resurrected in the 1990s when CAF was also used routinely. We now report on studies to determine whether VMD or CAF is the more effective technique for the detection of marks on fabrics. Four different fabrics, nylon, polyester, polycotton and cotton, were utilised during this study, along with 15 donors who ranged in their age and ability to leave fingermarks, from good to medium to poor, thus reflecting the general population. Once samples were collected they were kept for a determined time (1, 2, 3, 4, 5, 6, 7, 14, 21 or 28 days) and then treated using either the gold and zinc metal VMD process or standard cyanoacrylate fuming. The smoother fabrics, such as nylon, consistently produced greater ridge detail whereas duller fabrics, like cotton tended only to show empty prints and impressions of where the fabric had been touched, rather than any ridge details. The majority of fabrics did however allow the development of touch marks that could be targeted for DNA taping which potentially could lead to a DNA profile. Of the two techniques VMD was around 5 times more effective than CAF, producing a greater amount of ridge detail, palmar flexion creases and target areas on more samples and fabrics.

Latent fingerprint visualization using a scanning Kelvin probe in conjunction with vacuum metal deposition.

The application of vacuum metal deposition before scanning Kelvin probe visualization of fingerprints is investigated. The potential contrast between fingerprint ridges and furrows is maximized by the use of silver deposition for non-noble metals and gold-zinc deposition for noble metals. The higher susceptibility of eccrine fingerprints to vacuum metal overdeposition is confirmed. Additionally, fingerprints are best developed individually and by building the metal deposition slowly to protect against overdevelopment and variation in the rate of metal condensation. The progress of the metal deposition can be monitored using the scanning Kelvin probe by reference to the change in potential and continuity of the new potential on the surface. The use of acetic acid solution for the recovery of overVMD-developed samples is shown not to be useful. Applying the metal deposition has the additional prospect of increasing surface conductivity and homogeneity and both can aid fingerprint visualization using the scanning Kelvin probe.

Towards the integration of matrix assisted laser desorption ionisation mass spectrometry imaging into the current fingermark examination workflow.

A wide range of fingermark enhancement techniques (FET) is currently employed to visualise latent fingermarks at crime scenes. However, if smudged, partial, distorted or absent in the National Fingerprint Database, crime scene marks may be not useful for identification purposes. In these circumstances, a technology enabling chemical imaging of both endogenous and exogenous species contained within the fingermark could provide additional and associative investigative information, to profile the suspect's activities prior to the crime. Matrix Assisted Laser Desorption Ionisation Mass Spectrometry Imaging (MALDI MSI) has proven to be such a technique, enabling investigative information to be gathered, for example, on what substances the donor has come in contact with and what they have ingested. Nonetheless, to be employed, MALDI MSI has to be validated and its compatibility with FET tested for integration into the standard fingermark examination workflow. For the first time, a direct comparison has been made between the efficiency of a range of FET and MALDI MSI under different conditions. This information will build towards validation of the technology. Also, for the first time, MALDI MSI has been successfully employed as a sequential step following fingermark enhancement using many of the currently employed FET. Additionally, known enhancers have been "re-visited" by combining them with a MALDI matrix, providing both improved fingermark development and chemical species detection via MALDI MSI. The result reported here are good indication in favour of the integration of MALDI MSI into the current fingermark examination workflow for gathering additional investigative information.

Visualisation of fingermarks and grab impressions on dark fabrics using silver vacuum metal deposition.

Vacuum metal deposition (VMD) involves the thermal evaporation of metal (silver) in a vacuum, resulting in a uniform layer being deposited on the specimen being treated. This paper examines the use of silver on dark fabrics, thus offering a simpler operation and more obvious colouration to that of the traditional use of gold and zinc metals which must be evaporated separately. The aim of this study was to investigate the effect of fabric type, donor, mark age and method of fingermark deposition on the quality of marks visualised using silver VMD. This was achieved by collecting fingermark deposits from fifteen donors, of both sexes and various ages, by a grab or a press method. Four different fabrics: satin, polyester, polycotton and cotton were studied over a 10day timeline of 1, 2, 3, 4, 5, 6, 7, 14, 21 and 28+ days. It was found that satin and polyester gave the most positive results, with polyester often producing excellent ridge detail. Cotton and polycotton were less successful with no ridge detail being observed. The donors also had an observable effect on the results obtained probably due to variations in secretions produced or pressures applied during specimen collection. The age of the mark or the method of mark deposition had little influence on the results obtained. Silver VMD is a viable process for visualising marks on certain dark fabrics and has the advantage over gold/zinc VMD in that the marks visualised are light in colour which contrasts well against the dark background.

Chemical changes exhibited by latent fingerprints after exposure to vacuum conditions.

The effect of vacuum exposure on latent fingerprint chemistry has been evaluated. Fingerprints were analysed using a quartz crystal microbalance to measure changes in mass, gas chromatography mass spectrometry to measure changes in lipid composition and attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) to determine changes in the content of water, fatty acids and their esters after exposure to vacuum. The results are compared with samples aged under ambient conditions. It was found that fingerprints lose around 26% of their mass when exposed to vacuum conditions, equivalent to around 5 weeks ageing under ambient conditions. Further exposure to vacuum causes a significant reduction in the lipid composition of a fingerprint, in particular with the loss of tetradecanoic and pentadecanoic acid, that was not observed in ambient aged samples. There are therefore implications for sequence in which fingerprint development procedures (for example vacuum metal deposition) are carried out, as well as the use of vacuum based methods such as secondary ion mass spectrometry (SIMS) and matrix-assisted laser desorption ionisation (MALDI) in the study of fingerprint chemistry.

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.

Determination of the deposition order of overlapping latent fingerprints and inks using secondary ion mass spectrometry.

A new protocol using time-of-flight secondary ion mass spectrometry (ToF-SIMS) has been developed to identify the deposition order of a fingerprint overlapping an ink line on paper. By taking line scans of fragment ions characteristic of the ink molecules (m/z 358.2 and 372.2) where the fingerprint and ink overlap and by calculating the normalized standard deviation of the intensity variation across the line scan, it is possible to determine whether or not a fingerprint is above ink on a paper substrate. The protocol adopted works for a selection of fingerprints from four donors tested here and for a fingerprint that was aged for six months; for one donor, the very faint fingerprints could not be visualized using either standard procedures (ninhydrin development) or SIMS, and therefore the protocol correctly gives an inconclusive result.

An assessment of the effectiveness of 5-methylthioninhydrin within dual action reagents for latent fingerprint development on paper substrates.

A critical investigation of 5-methylthioninhydrin (5MTN) is presented as a 'dual action' formulation component for the development of latent finger marks on paper substrates. Preparation of a dual action reagent was performed by combining proportions of 5MTN and zinc chloride (ZnCl(2)) in a pre-mixed solution. Developed prints (deposited on filter paper substrates) could be subsequently visualised in both colour and fluorescence modes. Finger mark quality was graded using a quartered print approach for a number of reagent compositions to deliver an optimised formulation recipe. To fully appraise 5MTN in comparison to currently employed chemistries, this reagent was evaluated against three alternative amino acid selective reagents, ninhydrin, 1,8-diazafluorenone (DFO) and 1,2-indandione/ZnCl(2). Six common paper types were used for this purpose and split depletion finger marks from six donors were collected. Finger mark sets were also left for two days or two weeks to show the effect of ageing on development quality. For the first time, it was shown that 5MTN/ZnCl(2) is effective as a 'dual action' reagent under the United Kingdom climate conditions. However, results presented herein show that the existing recommended chemistries and the 1,2 indandione/ZnCl(2) process are all more effective than this new latent finger mark enhancement reagent. In a preliminary sequencing study, we show the effectiveness of the existing DFO-ninhydrin sequence over dual action reagents.

The recovery of latent text from thermal paper using a simple iodine treatment procedure.

Faded, or actively removed text on thermally printed paper samples may be enhanced and retrieved through the use of a simple iodine fuming procedure. The recovery of printed documentation evidence in this fashion is neither affected by prior fingerprint enhancement techniques (such as ninhydrin or DFO), nor by sample age. This method allows, for the first time, evidence to be obtained from completely faded thermal paper samples (receipts, for example) as well as allowing deliberately removed printed text (a consequence of solvent washing pre-treatment in latent fingerprint enhancement procedures) to be recovered.

Visualisation of fingermarks and grab impressions on fabrics. Part 1: gold/zinc vacuum metal deposition.

Vacuum metal deposition (VMD) is a highly sensitive technique originally introduced for detecting latent fingermarks on smooth non-porous surfaces such as carrier bags, plastics and glass. The current study explores whether VMD can be used in the examination of clothing from physical and sexual assault cases in order to visualise identifiable fingermark ridge detail and/or palmar flexion crease detail, thus allowing potential areas to be indicated for DNA swabbing and/or to determine the sequence of events. Four different fabrics were utilised during this study - nylon, polyester, polycotton and cotton, along with 15 donors who ranged in their age and propensity to leave fingermarks, from good to medium to poor as determined by results obtained from test runs using paper and plastic carrier bags processed with VMD. Once samples were collected they were kept for a determined time (1, 2, 3, 4, 5, 6, 7, 14, 21 or 28 days) and then treated using the gold/zinc metal VMD process. From the results, it appears that greater ridge detail is visible on the smoother non-porous fabrics, such as nylon whereas on rougher porous fabrics, such as cotton, only empty prints and impressions, rather than any ridge details, were visible. All fabrics did however allow the development of touch marks that could be targeted for DNA taping thus potentially leading to a DNA profile and possible identification of a suspect.