Refining Fingermark Development using Diacetylene Copolymers on Difficult Surfaces,

In further work investigating the intriguing application of diacetylene copolymers in fingermark detection, methods were developed to control (inhibit or enhance) the diacetylene polymerization reaction in fingermarks treated with a mixture of the monomers 2,4‐hexadiyne‐1,6‐bis‐(phenylurethane) (HDDPU) and 2,4‐hexadiyne‐1,6‐bis(p‐chlorophenylurethane) (HDDCPU) in acetone solution. These methods included the use of a humidity chamber to reduce the amount of background development while promoting development on the fingermark, subjecting developed fingermarks to freezing temperatures and using a solvent to remove unreacted monomer in order to inhibit the polymerization reaction. Developed fingermarks were enhanced by conventional lighting (white light, filtered light) and fast Raman mapping, which was shown to be advantageous over FTIR imaging. This study also demonstrated the applicability of diacetylene copolymer solutions in the covert detection of fingermarks on difficult surfaces. Furthermore, fingermarks were successfully developed with good ridge detail on pig skin (used as a model for human skin, a notoriously difficult surface on which to develop fingermarks).     

Four novel alkyl 2-cyanoacylate monomers and their use in latent fingermark detection by mid-infrared spectral imaging

Four novel alkyl 2-cyanoacrylate monomers (alkyl=1-cyanoethyl, 2-cyanoethyl, trideuteromethyl and pentadeuteroethyl) have been tested for their ability to develop latent fingermarks that can then be visualized using mid-infrared spectral (chemical) imaging. Each of the four monomers was chosen for its potential to produce a strong, isolated infrared spectral band in its corresponding polymer (to provide spectral contrast against most backgrounds), as well as for its potential ability to be fumed onto fingermarks in the manner of conventional ethyl 2-cyanoacrylate (superglue). With the exception of the 2-cyanoethyl 2-cyanoacrylate, which had to be fumed under reduced pressure, all of the monomers were found to be sufficiently volatile to be fumed in a conventional fuming cabinet. All four monomers polymerized selectively on fingermark ridges on a variety of non-porous and semi-porous surfaces, leading to excellent development of the fingermarks. Unfortunately, although high quality mid-infrared spectral images of the fingermarks could be formed for all of the polymers at various frequencies, the new CN or CD stretching vibrations did not give rise to strong enough absorption intensities for good contrast on difficult backgrounds such as polymer banknotes. However, in the 1-cyanoethyl 2-cyanoacrylate polymer, the presence of the additional nitrile group had the unintended but desirable effect of shifting the strong CO absorption to higher frequencies, moving it away from interfering banknote absorptions. This enabled fingermark contrast to be achieved even against the intaglio printing on the banknotes.     

Studies into exfoliation and coating of Egyptian blue in methanol for application to the detection of latent fingermarks

We have recently demonstrated that coated exfoliated Egyptian blue powder is effective for detecting latent fingermarks on a range of highly-patterned non-porous and semi-porous surfaces. In this extension of that work, we present our studies into an alternative approach to prepare exfoliated Egyptian blue coated with cetrimonium bromide and Tween® 20 using a simpler technique. The quality of the latent fingermarks developed with these exfoliated powders and the commercial powder were compared in a comprehensive study. Depletion series of natural fingermarks from a wide range of donors (12 males and females) deposited on non-porous (glass slides) and semi-porous (Australian banknotes) surfaces were used in this study. Enhancement in the performance of the coated exfoliated particles compared to the commercial powder was observed, particularly in the case of aged fingermarks and polymer banknotes as challenging substrates.     

Fingermark detection on non-porous and semi-porous surfaces using NaYF4:Er,Yb up-converter particles

This article describes the first use of an anti-Stokes material, or up-converter, for the development of latent fingermarks on a range of non-porous surfaces. Anti-Stokes materials can absorb long-wavelength light and emit light at a shorter wavelength. This property is unusual in both natural and artificial materials and so fingermark detection techniques based on anti-Stokes luminescence are potentially sensitive and selective. Latent fingermarks on luminescent and non-luminescent substrates, including Australian polymer banknotes (a well-known 'difficult' surface), were developed with sodium yttrium tetrafluoride doped with erbium and ytterbium (NaYF(4):Er,Yb) by dry powder, wet powder, and cyanoacrylate staining techniques. This study illustrates the potential of up-converter phosphors for the detection of latent fingermarks.     

Fingermark detection on non-porous and semi-porous surfaces using YVO4:Er,Yb luminescent upconverting particles

This article describes the use of an anti-Stokes luminescent material (upconverter), yttrium vanadate doped with ytterbium and erbium (YVO(4):Er,Yb), for the development of latent fingermarks on a range of non-porous surfaces. Anti-Stokes luminescent materials emit light at shorter wavelengths than the excitation wavelength. This property is unusual in both natural and artificial materials commonly found as exhibits in forensic science casework. As a result, fingermark detection techniques based on anti-Stokes luminescence are potentially extremely sensitive and selective. Latent fingermarks on non-luminescent and inherently luminescent substrates, including Australian polymer banknotes (a well-known 'difficult' surface), were developed with YVO(4):Er,Yb by dry powder and wet powder techniques. The effectiveness of YVO(4):Er,Yb for fingermark detection was compared with that of cyanoacrylate fuming and of sodium yttrium tetrafluoride doped with ytterbium and erbium (NaYF(4):Er,Yb). The results illustrate some benefit of luminescent up-converting phosphors over traditional luminescence techniques for the detection of latent fingermarks.     

Preliminary studies into fluorescent semiconductor nanorods for the detection of latent fingermarks: Size matters,shape matters

The effect of the shape of semiconductor nanocrystals on their performance for visualising latent fingermarks was investigated for the first time. Highly luminescent CdSe/CdS core/shell nanocrystals in rod and spherical shapes were synthesised in organic solvent and transferred to aqueous solution using ligand exchange. The 3-mercaptopropionic acid coated nanorods and nanospheres were characterised using electron microscopy and UV-visible absorbance and luminescence spectrophotometry. A simple and rapid development of fresh to less than a week-old natural fingermarks from 4 donors (male and female) on non-porous surfaces including glass slides, aluminium foil and germanium disks using both CdSe/CdS core/shell nanorods and spherical dots was achieved, wherein nanorods demonstrated an enhanced development of ridge details in comparison to the spherical dots.     

Photoluminescence of blood by acidic hydrogen peroxide—A preliminary test

In this study, the authors found that treating blood with 1 M HCl and 2% (w/v) 5-sulfosalicylic acid (SSA) in 1% (v/v) hydrogen peroxide mixture can produce photoluminescence of blood. SSA was added as a blood fixer. The photoluminescence was induced by irradiation of a forensic light source at 505 nm, which was detected using a 550 nm barrier filter. In this experiment, various level of acid and hydrogen peroxide were tested to find the optimal formulation of reagents, spot tests were conducted with diluted blood to test the sensitivity of this reagent, and impressions in blood left on porous/nonporous surfaces were enhanced. The sensitivity of this solution was slightly lower than Bluestar and was similar to leucocrystal violet or leucomalachite green on both porous/non-porous surfaces. The photoluminescence of blood treated with this reagent has been observed over 2 months. Using this reagent, it was possible to observe fingermarks or footwear impressions in blood on a black porous/non-porous surface. Through this, it was found that using this reagent could enhance bloodstains regardless of the porosity or color of the surface.     

The detection and enhancement of latent fingermarks using infrared chemical imaging

The use of a new technique, Fourier transform infrared (FTIR) chemical imaging, has been demonstrated for the enhancement of latent fingermarks on a number of surfaces. Images of untreated fingermarks on glass backgrounds with excellent ridge detail were acquired using infrared chemical imaging. High quality fingermarks on glass backgrounds were also developed using ethyl cyanoacrylate (super glue) fuming and subsequent infrared chemical imaging. This new method allows the collection of images from backgrounds that traditionally pose problems for current fingermark detection methods. The background may, for example, be highly colored, have a complex pattern, or possess other pattern or image characteristics that make it difficult to separate fingermark ridges using traditional optical or luminescent visualization. One background that has proven to be a challenging surface for the development of latent fingermarks is the Australian polymer banknote. To demonstrate the power and applicability of infrared chemical imaging, fingermarks fumed with ethyl cyanoacrylate were successfully imaged from Australian polymer banknotes.     

A preliminary investigation into the use of alginates for the lifting and enhancement of fingermarks in blood

Recent studies have reported the use of alginate in the lifting and subsequent enhancement of footwear marks in blood. A study was set up to assess the use of such a method in the treatment of fingermarks in blood on a variety of porous, non-porous and semi-porous surfaces. Other variables included ageing of the fingermarks in blood and the application of chemicals prior to or post-alginate lifting. All different variations were compared to direct chemical treatment of the substrate. The results demonstrated that alginate is not compatible with certain substrates (e.g. glass and tile). On substrates that were compatible with alginate (e.g. fabric and paper), the enhanced fingermarks on the alginate cast and the enhanced fingermarks on the post-alginate substrates appeared, overall, inferior compared to direct chemical enhancement without the use of alginate. A further variation using water-based protein stains directly mixed with the alginate appeared to provide enhancement directly on the substrate as well as simultaneous lifting and enhancing the fingermarks in blood on the alginate cast.     

Use of gold nanoparticles as molecular intermediates for the detection of fingermarks

Among the numerous methods dedicated to the detection of latent fingermarks, the MultiMetal Deposition (MMD) offers, as a main advantage, the ability to be applied on a great number of porous and non-porous surfaces, e.g., paper, plastic, glass, latex, and polystyrene, even if wetted. While considered as a powerful and sensitive technique, MMD is often neglected, mainly because of operational limitations (siliconized vessels, restrictive pH domain, numerous immersion baths, ...). In this contribution, we propose a modification of the standard MMD method so that the procedure is simplified with a number of baths reduced to a minimum. To reach this goal, it was necessary to obtain a fully operable solution which could detect fingermarks in a single step. We chose to take advantage of the molecular recognition mechanisms by functionalizing the gold nanoparticles with a molecular host able to bind itself to gold while keeping the ability to trap molecules in solution. Cyclodextrins were chosen as they can be easily chemically modified to offer gold-binding abilities. Moreover, they are widely used as hosts for various molecular guests (dyes, luminescent molecules, ...). This new formulation has been tested on three different surfaces to attest the feasibility of this strategy. Successful results were obtained with detailed fingermarks offering a good contrast to allow their identification without the need to enhance the results (such as with a physical developer). If the new formulation behaves very similarly to the old one, in terms of experimental conditions, it offers the additional advantage to develop fingermarks after immersing them in only one bath. The goal is thus reached.     

Nanoscale analysis of the interaction between cyanoacrylate and vacuum metal deposition in the development of latent fingermarks on low-density polyethylene

Vacuum metal deposition (VMD) has been previously demonstrated as an effective development technique for latent fingermarks and in some cases has been shown to enhance prints developed with cyanoacrylate (CA) (superglue) fuming. This work utilizes scanning electron microscopy (SEM) to investigate the interactions of the two development techniques when applied to latent fingermarks on low-density polyethylene. CA is shown to act principally on the eccrine deposits around sweat pores, where polymerization results in long polymer fibrils a few 100 nm in width. Subsequent VMD processing results in additional areas of development, for example, between pores. However, the primary mode of deposition of zinc is by interaction with the polymerized CA, the fibrils of which become decorated with zinc nanoparticles. Areas with limited CA deposition and no significant polymerization are also enhanced with the VMD process, resulting in increased print development.     

Single-metal deposition (SMD) as a latent fingermark enhancement technique: an alternative to multimetal deposition (MMD)

This paper proposes an alternative solution to multimetal deposition (MMD) for the development of latent fingermarks on non-porous and porous surfaces. MMD offers a good sensitivity, however it is very time-consuming and requires many reagents to be carried out. Single-metal deposition (SMD) replaces the silver enhancement of the gold colloids by a gold enhancement procedure. This reduces the number of baths by one as well as the number of reagents and their cost, utilizes reagents with a longer shelf life, and most importantly reduces the labor-intensity of the procedure. It offers quasi-identical results to MMD and thus makes a very attractive alternative.     

Fingermark detection based on the in situ growth of luminescent nanoparticles--towards a new generation of multimetal deposition

The in situ deposition of zinc oxide on gold nanoparticles in aqueous solution has been here successfully applied in the field of fingermark detection on various non-porous surfaces. In this article, we present the improvement of the multimetal deposition, an existing technique limited up to now to non-luminescent results, by obtaining luminescent fingermarks with very good contrast and details. This is seen as a major improvement in the field in terms of selectivity and sensitivity of detection, especially on black surfaces.     

The effect of chlorine and hydrogen chloride on latent fingermark evidence

Exposure of forensic evidence to either hydrogen chloride or chlorine can result in acidification to such an extent that enhancement of fingermarks with ninhydrin or cyanoacrylate is inhibited. Under these circumstances, pretreatment of samples with volatile bases such as triethylamine or ethanolamine prior to using these enhancement techniques can lead to successful visualization of fingermarks. Alternatively, physical enhancement techniques such as powder dusting or small particle reagent can be used on acidified non-porous substrates, although the former technique is subject to increased background under such conditions.     

The effectiveness of strong afterglow phosphor powder in the detection of fingermarks

There are numerous types of fluorescent fingermark powders or reagents used with the visualization of latent fingermarks deposited on multicolored substrate surfaces that can present a contrast problem if developed with regular fingermark powders. The developed fingermarks can show bright fluorescence upon exposure to laser, ultraviolet light and other light sources. These kinds of methods share a common concern, where surfaces and other substrates may fluoresce also. To overcome this concern, we have developed a phosphor powder which offers a strong afterglow effect which aid in the establishment of better fingermark detection. With the advent of a phosphor powder no special devices are required and the results obtained from fresh or a few days aged latent fingermarks left on: non-porous; semi-porous and also on some porous surfaces have been good. The strong afterglow effect offered by phosphor powder is also applicable for cyanoacrylate fumed fingermarks. Lift off and photography procedures of the developed fingermarks are incorporated in this paper.     

Latent fingermark visualisation using reduced-pressure sublimation of copper phthalocyanine

The sublimation of copper phthalocyanine (CuPc) at a temperature of 400°C under conditions of reduced pressure is shown to be an effective method of developing latent fingermarks on certain types of surface. Preliminary experiments on a limited selection of surfaces including paper, plastic and ceramic tiles were carried out using a simple apparatus consisting of a vacuum desiccator and a resistive heater. CuPc from the gas phase condenses preferentially on fingermark deposits, revealing deep blue patterns with excellent ridge detail clarity on light coloured surfaces. The technique is shown to be most effective on porous surfaces such as paper, but relatively ineffective on non-porous ceramic and plastic surfaces.     

The effect of household corrosive substances on latent fingermark development in the context of deliberate corrosive substance attacks

Corrosive substance attacks (CSA) are a prevalent issue in the UK with 525 offenses involving a corrosive substance reported to the police in the year ending March 2022. Easy availability, low cost, and concealability in public are common reasons for choosing a corrosive substance as a weapon. The Metropolitan Police revealed that 68% of 1849 CSA cases resulted in no suspect identified or evidential difficulties. There is limited research into the effect of corrosive substances on latent fingermarks. This study aimed to determine the potential for fingermarks to be recovered from surfaces exposed to a household corrosive substance within the context of a deliberate CSA. Natural and sebaceous-loaded fingermarks were exposed to Domestos bleach, Harpic limescale remover (hydrochloric acid-based) and lemon juice. Harpic limescale remover had the most detrimental effect, with only 7.1% of fingermarks (n = 378) exposed being identifiable (defined as sufficient clear ridge detail for identification) after enhancement, followed by bleach with only 10.3% of fingermarks (n = 378) identifiable. Lemon juice had the least detrimental effect on fingermarks, with 40.5% fingermarks (n = 378) identifiable compared to 53.4% for the controls (not exposed to any substance; n = 378). Throughout the study, fewer natural fingermarks were identifiable after exposure to corrosive substances compared to sebaceous fingermarks which was as expected. Overall, this study demonstrated that there is potential to recover latent fingermarks, depending on their composition, following exposure to a household corrosive substance. This area warrants further research to establish best practice to maximize the potential to recover identifiable fingermarks.     

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.     

Degradation of polymer banknotes through handling,and effect on fingermark visualisation

The surface structure of mint (as-issued) and handled polymer five pounds sterling banknotes was studied by atomic force microscopy and laser scanning confocal microscopy. A total of 1856 fingermarks on mint and handled banknotes from four different issuing banks (Bank of England, Bank of Scotland, Royal Bank of Scotland and Clydesdale Bank) were visualised with Vacuum Metal Deposition (VMD), Cyanoacrylate Fuming (CAF) and, on Clydesdale Bank notes, magnetic fluorescent powder. VMD was significantly more effective in developing fingermarks on handled banknotes, across all the banks studied, although effectiveness varied with issuing bank. For example, on handled Bank of England notes 45% of marks showed ridge detail with VMD development and 28% with CAF; for Bank of Scotland handled notes success rates were 17% with VMD and 1% with CAF. Microscopy of degraded banknotes showed the loss of intaglio printing and the formation of a cracked surface structure in the handled notes. These features can lead to the trapping of powder, or contaminants, increasing quantity of development agent in fingermark background between the ridges, decreasing contrast and decreasing performance of powder-based fingermark development techniques. These same features can restrict the migration of components of the fingermark, preventing fingermarks degrading through spread of material and thus reducing potential formation of empty prints, so that VMD development is not adversely affected.     

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.