Forensic applications of chemical imaging: latent fingerprint detection using visible absorption and luminescence

Chemical imaging technology is a rapid examination technique that combines molecular spectroscopy and digital imaging, providing information on morphology, composition, structure, and concentration of a material. Among many other applications, chemical imaging offers an array of novel analytical testing methods, which limits sample preparation and provides high-quality imaging data essential in the detection of latent fingerprints. Luminescence chemical imaging and visible absorbance chemical imaging have been successfully applied to ninhydrin, DFO, cyanoacrylate, and luminescent dye-treated latent fingerprints, demonstrating the potential of this technology to aid forensic investigations. In addition, visible absorption chemical imaging has been applied successfully to visualize untreated latent fingerprints.     

The application of infrared chemical imaging to the detection and enhancement of latent fingerprints: method optimization and further findings

Fourier transform infrared (FTIR) chemical imaging allows the collection of fingerprint images from backgrounds that have traditionally posed problems for conventional fingerprint detection methods. In this work, the suitability of this technique for the imaging of fingerprints on a wider range of difficult surfaces (including polymer banknotes, various types of paper, and aluminum drink cans) has been tested. For each new surface, a systematic methodology was employed to optimize settings such as spectral resolution, number of scans, and pixel aggregation in order to reduce collection time and file-size without compromising spatial resolution and the quality of the final fingerprint image. The imaging of cyanoacrylate-fumed fingerprints on polymer banknotes has been improved, with shorter collection times for larger image areas. One-month-old fingerprints on polymer banknotes have been successfully fumed and imaged. It was also found that FTIR chemical imaging gives high quality images of cyanoacrylate-fumed fingerprints on aluminum drink cans, regardless of the printed background. Although visible and UV light sources do not yield fingerprint images of the same quality on difficult, nonporous backgrounds, in many cases they can be used to locate a fingerprint prior to higher quality imaging by the FTIR technique. Attempts to acquire FTIR images of fingerprints on paper-based porous surfaces that had been treated with established reagents such as ninhydrin were all unsuccessful due to the swamping effect of the cellulose constituents of the paper.     

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.     

Detection of visible and latent fingerprints using micro-X-ray fluorescence elemental imaging

Using micro-X-ray fluorescence (MXRF), a novel means of detecting fingerprints was examined in which the prints were imaged based on their elemental composition. MXRF is a nondestructive technique. Although this method requires a priori knowledge about the approximate location of a print, it offers a new and complementary means for detecting fingerprints that are also left pristine for further analysis (including potential DNA extraction) or archiving purposes. Sebaceous fingerprints and those made after perspiring were detected based on elements such as potassium and chlorine present in the print residue. Unique prints were also detected including those containing lotion, saliva, banana, or sunscreen. This proof-of-concept study demonstrates the potential for visualizing fingerprints by MXRF on surfaces that can be problematic using current methods.     

应用红外化学成像技术显现潜在的指印

目的应用红外化学（光谱）成像技术显现潜在指纹。方法采用这种新技术进行显现潜在指印的初步实验。结果显示了其对复杂图案背景上指印突出的显现能力。该成像技术具有物质形态特征检验和物质成分检验双重分析能力，在法庭科学领域具有重要的应用价值。     

Infrared spectroscopic imaging for noninvasive detection of latent fingerprints

The capability of Fourier transform infrared (FTIR) spectroscopic imaging to provide detailed images of unprocessed latent fingerprints while also preserving important trace evidence is demonstrated. Unprocessed fingerprints were developed on various porous and nonporous substrates. Data-processing methods used to extract the latent fingerprint ridge pattern from the background material included basic infrared spectroscopic band intensities, addition and subtraction of band intensity measurements, principal components analysis (PCA) and calculation of second derivative band intensities, as well as combinations of these various techniques. Additionally, trace evidence within the fingerprints was recovered and identified.     

Comparative study of electrochromic enhancement of latent fingerprints with existing development techniques

To address the challenge of capturing latent fingerprint evidence from metal surfaces, a new method of latent fingerprint enhancement based on electrochromic polymer films has recently been developed. Here, we present a study comparing the development and visualization of nonvisible fingerprints on stainless steel substrates using this electrochromic enhancement approach with three classical methods (dusting, wet powder, and cyanoacrylate fuming). Two variants of the electrochromic enhancement method were utilized with polyaniline and poly(3,4-ethylenedioxythiophene) as the electrochromic materials. Fingerprint samples were taken from different donors (varying in age and gender) and were exposed to different environments for systematically varied periods of time (up to 28 days). The environments represent plausible evidential scenarios: left under ambient conditions, washed with aqueous soap solution, washed with acetone, submerged in water, and maintained at elevated temperature. The electrochromic enhancement procedure frequently outperformed the traditional methods, particularly for samples exposed to more challenging histories.     

A novel chitosan/tripolyphosphate/L‐lysine conjugates for latent fingerprints detection and enhancement

Most chemical and physical methods employed in visualizing latent marks have shown detrimental effects on human health and, therefore, some research groups have directed their attention to the utilization of various (bio)polymers with the aforementioned purpose. Although chitosan is widely used in medicine, pharmacy, food, and drug delivery systems, there are very few studies that address this biopolymer utilization in forensic applications, such as the detection of latent fingerprints. We used chitosan crosslinked with sodium tripolyphosphate and conjugated with L‐lysine to enhance the visualization of latent fingerprints, due to its ability to interact with fingerprint sweat residues. These conjugates were prepared using different (w/w) amounts of chitosan and tripolyphosphate (6/1; 4/1; 1/1; 1/4; and 1/6), and those with the most promising results (i.e., 6/1 formulation) were investigated in detail. Fourier transform infrared (FT‐IR) spectroscopy confirmed interactions between components of the systems. Optical microscopy and scanning electron microscope (SEM) analysis showed that prepared powder formulations were uniform in size and confirmed that chitosan/tripolyphosphate/lysine conjugates bind easily to the sweat and lipid residues present in the latent fingerprints. The testing of prepared conjugates demonstrated the potential of these systems as bio‐based powder substitution for commercially available powders.     

On the detection of fingerprints by laser excited luminescence

Two surveys were carried out to determine the percentage of latent fingerprints detectable by their inherent luminescence under laser illumination. Less than one-fifth of 240 samples each containing four prints on paper gave luminescent prints. The luminescence from these was weak and only detectable under close scrutiny. Similar results were obtained for 120 samples each containing one print on glass. Forty-one of the samples showing no luminescence were sprayed, approximately one month after deposition, with a solution containing the fluorescent tagging agent 7-chloro-4-nitrobenzo-2-oxa-1,3-diazole (NBD chloride). After treatment with NBD chloride, 37 of these samples gave luminescent prints, many of which were intensely luminescent and contained good ridge detail.     

Sensitivity enhancement of ninhydrin-treated latent fingerprints by enzymes and metal salts

Lyophilized Sigma Type III trypsin has been applied to latent prints two weeks to two months old. This trypsin preparation eliminates the background problems that had been encountered with old prints in a previous study. Zinc chloride treatment of latent prints previously exposed to ninhydrin enhances their detectability upon laser examination. However, it has been reported that the zinc chloride reaction occasionally fails to occur. Accordingly, we have investigated the optimization of this reaction. We find that high humidity and elevated temperature, particularly the former, are needed. Cadmium nitrate, although it produces weaker fluorescence than zinc chloride, may at times be useful. Reaction conditions are much the same as those for zinc chloride.     

Visualization of latent fingerprints using fluorescence lifetime imaging on paper emitting strong fluorescence

Latent fingerprints were successfully visualized using fluorescence lifetime imaging (FLIM) on paper which emits strong fluorescence with a lifetime close to that of fingerprints and thus from which it is difficult for time-resolved spectroscopy to visualize fingerprints. Latent fingerprint samples on paper were excited using a 450 nm or 532 nm nanosecond pulsed-laser, and time-resolved fluorescence images were obtained at a delay time of 6–16 ns in intervals of 1 ns, to the excitation pulse. The excitation beam was expanded using a lens, and the fluorescence from the fingerprints was captured using an intensified CCD camera. Because of the large fluorescence intensity of the background paper of approximately two to four orders of magnitude larger than that of the fingerprint, the fingerprint was not visualized on each fluorescence image by time-resolved spectroscopy. However, the fingerprint was visualized in a FLIM image constructed using a series of the fluorescence images for the case with the fluorescence intensity of the background paper being four orders of magnitude larger than that of the fingerprint. The difference in fluorescence lifetime in the FLIM image of the visualized fingerprint and background paper was in the order of 0.1 ns, which was an order of magnitude smaller than the inherent fluorescence lifetime of a few nanoseconds for the fingerprints and paper. It was demonstrated that, at a background fluorescence intensity with a certain order of magnitude larger than that of fingerprints, FLIM has the potential to visualize latent fingerprints which cannot be visualized by time-resolved spectroscopy.     

Extension of the color suite available for chemical enhancement of fingerprints in blood

The use of ortho- and para-phenylenediamine (OPD & PPD respectively) for the enhancement of fingerprints in blood has been investigated. Optimal pH conditions and H2O2 concentrations have been determined using UV/Vis spectroscopy. Both OPD and PPD are effective and less hazardous alternatives to the presently used 3,3'-diaminobenzidine (DAB) for the development of blood fingerprints, especially on porous surfaces. The orange color of OPD and the purple color of PPD offer alternative colors to the brown color of DAB and the light green color of ABTS for standing out against particular backgrounds. Both OPD and PPD can be used after ninhydrin treatment, but the reverse is not the case.     

Determining the order of deposition of natural latent fingerprints and laser printed ink using chemical mapping with secondary ion mass spectrometry

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) chemical mapping was used to investigate the order of deposition of natural latent fingerprints and laser printed ink on paper. This feasibility study shows that sodium, potassium and C₃H₅ positive ions were particularly abundant endogenous components of the natural fingerprints and also present in the paper examined, but were mostly absent in the laser printed ink. Mapping of these ions enables the observation of friction ridges from latent prints on the ink surface, only when a fingerprint was deposited above the layer of ink. As a demonstration of proof of concept, blind testing of 21 samples from three donors resulted in a 100% success rate. The sensitivity of this technique was investigated within this trial through the examination of up to fifth depletion fingerprints and ageing of up to 28 days. Migration of fingerprint and paper components to the ink surface, although observed with increased ageing time, was not found to compromise determination of the deposition sequence.     

A mechanistic model for the superglue fuming of latent fingerprints

The use of superglue vapors to detect latent fingerprints, known as superglue fuming, is a chemical process that has not been fully described. The role of the fingerprint material in the process, leading to formation of methyl cyanoacrylate polymer at the site of the fingerprint, remains to be established. Films of liquid alkanes respond similarly to actual fingerprints in the fuming experiment. Their responses depended on the hydrocarbon used, viscosity, and film thickness. Aspects such as film thickness appear to be relevant for actual fingerprints as well. A model was proposed in light of these observations. The model compares the process with gas chromatography, in which molecules partition between the gas phase and a stationary phase. Aspects such as accumulation of superglue monomers by partitioning into a thin film (or wax) are consistent with the preferential response of fingerprints on surfaces relative to the background.     

Processes involved in the development of latent fingerprints using the cyanoacrylate fuming method

Chemical processes involved in the development of latent fingerprints using the cyanoacrylate fuming method have been studied. Two major types of latent prints have been investigated-clean and oily prints. Scanning electron microscopy (SEM) has been used as a tool for determining the morphology of the polymer developed separately on clean and oily prints after cyanoacrylate fuming. A correlation between the chemical composition of an aged latent fingerprint, prior to development, and the quality of a developed fingerprint has been observed in the morphology. The moisture in the print prior to fuming has been found to be more important than the moisture in the air during fuming for the development of a useful latent print. In addition, the amount of time required to develop a high quality latent print has been found to be within 2 min. The cyanoacrylate polymerization process is extremely rapid. When heat is used to accelerate the fuming process, typically a period of 2 min is required to develop the print. The optimum development time depends upon the concentration of cyanoacrylate vapors within the enclosure.     

8种方法显现的汗潜指印STR分型研究

目的研究常见指印显现方法对指印STR检验的影响。方法采用Invisorb spin forensic试剂盒提取纯化人汗潜指印DNA,低拷贝模板(LCN)STR复合扩增,荧光电泳检验。结果用铜粉、铝粉、荧光粉、黑磁粉、"502"胶、茚三酮、磺酸双三嗪荧光显色液显现的玻片、纸张和胶带纸粘面上的汗潜指印可成功进行STR分型。结论常见指印显现方法不影响指印STR检验。     

油红O显现热敏纸上潜在手印研究

目的建立了一种油红O显现热敏纸上客体表面的潜手印的新方法。方法将检材浸泡在配制好的油红O的显现试剂中,油红可将指纹中遗留的油脂染色从而显现出手印纹线。结果显现出手印纹线为红色,纹线连贯,反差明显。结论油红O能够有效地显现出热敏纸上潜手印。     

Reagents for the chemical development of latent fingerprints: scope and limitations of benzo[f]ninhydrin in comparison to ninhydrin

Benzo[f]ninhydrin was compared to ninhydrin for fingerprint development on paper. Overall, the performance of ninhydrin on exhibits was slightly better than that of benzo[f]ninhydrin. The significant advantages of the benzo[f]ninhydrin over ninhydrin were the much stronger fluorescence it gave after treatment with zinc salts and a slightly quicker reaction under ambient conditions. This fluorescence is, however, similar to that obtained with other reagents, such as DFO or ninhydrin analogs. These advantages apparently are not sufficient to justify regular usage of benzo[f]ninhydrin, especially when one considers its low solubility and high cost.     

Use of styryl 11 and STaR 11 for the luminescence enhancement of cyanoacrylate-developed fingermarks in the visible and near-infrared regions

In current casework, most post-cyanoacrylate stains rely on luminescence emission in the visible region (400-700 nm). While traditional stains such as rhodamine 6G work well under most circumstances, some surfaces may generate background luminescence under the same conditions. Detection in the near-infrared region (NIR > 700 nm) has shown to be effective in minimizing the interferences from such surfaces. The laser dye styryl 11 generated strongly luminescent fingermarks when applied after cyanoacrylate fuming on all surfaces tested. When compared to rhodamine 6G, the dye was superior only when viewed in the NIR. Styryl 11 was subsequently combined with rhodamine 6G, and the mixed stain formulation (named StaR 11 by the authors) induced stronger luminescence compared with styryl 11 alone with an ability to visualize in both the visible and NIR regions. Reliable and consistent results were obtained when using either styryl 11 alone or the STaR 11 mixture. The enhancement achieved did not otherwise vary depending on the source of the fingermark secretions. With visualization possible in both the visible and NIR regions, the styryl 11/rhodamine 6G mixture showed significant potential as a post-cyanoacrylate stain.