Fluorescence of 1,2‐Indanedione with Amino Acids Present in the Fingerprint Residue: Application in Gender Determination

1,2‐indanedione is used for latent fingerprint visualization on porous surfaces. In this paper, fluorescence spectra of 1,2‐indanedione after reacting with 21 individual amino acids present in latent fingerprints residue were measured in water‐methanol solutions. The fluorescence intensity depends on the amino acid used, while the fluorescence peak does not change much. The concentration of amino acids in fingerprint residue in females is almost the double of their concentration in males. This property combined with fluorescence of 1,2‐indanedione‐amino acids compounds is used for gender determination, by comparing the fluorescence intensity peaks in the same experimental conditions. In this preliminary study, the fluorescence signal from the samples representing females was almost two times the signal for samples representing males. In addition to the reduction by almost 50% of the number of suspects in a criminal research case, these results could be helpful in gaining some knowledge about the papillary residue composition.     

A Noninvasive and Speculative Method of Visualizing Latent Fingerprint Deposits on Thermal Paper

Latent fingerprint deposits on thermal paper have been visualized noninvasively at visible wavelengths when illuminated with a UV‐A light source (peak 365 nm). A higher intensity UV source (250 W/m² at 0.38 m) gave superior fingerprint visibility when compared with a 60 W/m² (at 0.4 m) source. Removing the visible (blue) component of the light source emission did not adversely affect the visibility of the fingerprint. Sample fingerprints from 100 donors, when examined 24 h after deposition, produced identifiable fingerprints from nearly 34% of fingerprint deposits. A mechanism for the observed visibility is proposed based on low emission of visible wavelengths from areas of thermal paper coincident with the fingerprint deposit, when illuminated with UV. This is likely due to a weak color change in the thermal paper dye arising from protonated amino acid components of the sweat. This effect was not observed on nonthermal paper.     

Development of Latent Fingerprints on Thermal Paper by the Controlled Application of Heat

Apparatus to produce a spatially and temporally uniform heat source is described and this is used to visualize latent fingerprints deposited onto thermal paper by raising the temperature of the paper. Results show an improvement over previous research when fingerprint deposits are aged or the developed fingerprints faint; visualization being enhanced by the use of a blue LED light source of 465 nm peak wavelength. An investigation of the components in fingerprint sweat likely to affect the solubility and hence color change of the dye present in the thermal paper has shown that polar protic solvents able to donate a proton are favored and a polar amino acid found commonly in eccrine fingerprint sweat (lysine) has been shown able to produce the desired color change. Aged fingerprint deposits on thermal paper from a variety of sources up to 4 years old have been visualized with this technique.     

Pyrolysis Products of Linear Alkylbenzenes— Implications in Fire Debris Analysis*

Abstract: In this case report, potential interferences from an improvised fire‐extinguishing agent, a dishwashing liquid, containing linear alkylbenzene sulfonates (LAS), was studied. The presence of linear alkylbenzenes (LABs) in the fire debris sample was identified from the summed ion profile (SIP) analysis. It was found that the LAS from dishwashing liquids produce LABs by thermal degradation. Direct pyrolysis of a LAS‐containing dishwashing liquid at 300°C yielded a distribution of LABs in the SIP. LABs began to break down at pyrolysis temperatures between 450 and 500°C and completely break down by 800°C. Observed pyrolysis breakdown products of LABs included toluene, ethylbenzene, meta‐, para‐, and ortho‐xylenes, propylbenzene, indane, naphthalene, and 1‐ and 2‐methylnaphthalenes. These data suggested the presence of LABs in fire debris evidence might complicate subsequent analysis because their breakdown products contained some of the target compounds common to ignitable liquid identification. Therefore, a positive determination of the presence of foreign ignitable liquids should be carefully evaluated when there is a presence of LABs in the SIP.     

Development of a GC-MS method for the simultaneous analysis of latent fingerprint components

Latent fingerprint residue is a complex mixture of organic and inorganic compounds. A full understanding of the composition of this mixture and how it changes after deposition is lacking. Three solvent systems were compared for the simultaneous extraction and derivatization with ethyl chloroformate of selected amino and fatty acids from a nonporous substrate (Mylar for subsequent analysis by gas chromatography-mass spectrometry. A solvent system comprised of sodium hydroxide, ethanol, and pyridine was found to be the most effective. This method was applied to the analysis of latent fingerprint residue deposited on Mylar and preliminary data are presented. Twelve amino acids (e.g., serine, glycine, and aspartic acid) and 10 fatty acids (e.g., tetradecanoic, hexadecanoic, and octadecanoic acids) were identified. The potential application of this method to further the understanding of latent fingerprint chemistry has been demonstrated.     

The Effect of Temperature and Exposure Time on Stability of Cholesterol and Squalene in Latent Fingermarks Deposited on PVDF Membrane

Cholesterol and squalene are fatty materials of latent fingermarks that can be utilized for dating methodologies and visualization techniques. Previous studies have suggested these compounds undergo degradation in fingermarks as a function of time (days) and light at ambient temperature. However, studies assessing how their composition changes at low and high temperatures over short periods of time (hours) have not been published previously. Here, we performed quantitative analysis of cholesterol and squalene in natural fingermark residue using PVDF membrane, after exposure to a range of temperatures (−20 to 100°C) for 4 and 8 h. We found that levels of both fatty materials remained constant at −20 to 60°C, but both showed significant reduction at 100°C, over short exposure times. These results indicate that cholesterol and squalene are detectable at −20 to 60°C, whereas at 100°C or higher, both are lost due to rapid thermal degradation.     

Scanning Electron Microscopy–Energy‐Dispersive X‐Ray (SEM/EDX): A Rapid Diagnostic Tool to Aid the Identification of Burnt Bone and Contested Cremains

This study investigates the use of Scanning electron microscopy–energy‐dispersive X‐ray (SEM‐EDX) as a diagnostic tool for the determination of the osseous origin of samples subjected to different temperatures. Sheep (Ovis aries) ribs of two experimental groups (fleshed and defleshed) were burned at temperatures of between 100°C and 1100°C in 100°C increments and subsequently analyzed with the SEM‐EDX to determine the atomic percentage of present elements. Three‐factor ANOVA analysis showed that neither the exposure temperature, nor whether the burning occurred with or without soft tissue present had any significant influence on the bone's overall elemental makeup (p > 0.05). The Ca/P ratio remained in the osseous typical range of between 1.6 and 2.58 in all analyzed samples. This demonstrates that even faced with high temperatures, the overall gross elemental content and atomic percentage of elements in bone remain stable, creating a unique “fingerprint” for osseous material, even after exposure to extreme conditions.     

Carbon‐Based Fingerprint Powder as a One‐Step Development and Matrix Application for High‐Resolution Mass Spectrometry Imaging of Latent Fingerprints

Carbon‐based materials are often used as matrices for matrix‐assisted laser desorption/ionization mass spectrometry (MALDI‐MS) and its imaging (MALDI‐MSI). However, researchers have refrained from using carbon‐based fingerprint powder (CFP) as a matrix due to high background and contamination. In this work, the compatibility of CFP is reevaluated with MALDI‐MSI using a high‐resolution mass spectrometer (HRMS) and compared to traditional organic matrices. Relevant fingerprint compounds were easily distinguished from carbon cluster peaks when using HRMS. For fair comparison, half of a fingerprint was dusted with CFP while the other half was dusted with traditional organic matrices. All compounds studied had comparable, or higher, signal‐to‐noise (S/N) ratios when CFP was used as the matrix. Additionally, chemical image qualities closely followed the trend of S/N ratios. CFP proved to be an effective one‐step development and matrix application technique for MALDI‐MSI of latent fingerprints, when carbon cluster peaks are well separated by a HRMS.     

Toward multidimensional information: A derivatization-free UHPLC-QqQ MS/MS method for amino acid components of fingerprint

The analysis of fingerprint chemical composition is a meaningful way to excavate the multidimensional information of fingerprint, including the donor profiling information and the age of a fingerprint, which broadens the evidential values of fingerprint, especially for the partial and distorted fingerprint. But the research remains still in the pilot phases or is ongoing. Amino acids are the dominant organic substances in latent sweat fingerprint and influenced by many donor factors. Hence, their content reflects personal information of donors. Forensic science will be revolutionized if suspects can be individualized by their amino acid content. The diverse nature, distinct physicochemical properties, and ultra-micro levels of amino acids present in fingerprints make it hard to detect. A high sensitivity method for detecting and quantifying multiple amino acid components is required. UHPLC-QqQ MS/MS offers high sensitivity, high separation, simultaneous multicomponents detection, and no derivatization, making it an ideal method for detecting and analyzing amino acids in fingerprints. Therefore, in this study, we propose and validate an efficient UHPLC-QqQ MS/MS method for the extraction and analysis of 13 amino acids from fingerprint. We compared the results of amino acids of 10 different substrates and found that the inherent amino acids in most porous substrates would have been extracted along with the fingerprint amino acids, making them unsuitable for quantitative amino acid analysis. Instead, plastic sheets are ideal substrates for laboratory studies. Then, extensive experiments were conducted among 30 donors for multidimensional information analysis. The type of samples analyzed were eccrine-rich fingerprints. A Binary Logistic Regression (BLR) model was developed, and the female and male donors were successfully differentiated by amino acids in fingerprints. Two other mathematical models were also developed to verify the accuracy, and all three different mathematical models were able to identify donors of different genders with over 90% accuracy. This demonstrates that amino acids have the potential to provide more information for donors as metabolic markers. In the future, we will conduct a series of experiments to analyze more multidimensional information for individual identification by amino acid content in the fingerprint.     

Optimizing Accu Time‐of‐Flight/Direct Analysis in Real Time for Explosive Residue Analysis

The use of a direct analysis in real time (DART) mass spectrometer (MS) instrument was optimized for 22 compounds of organic explosive residues to provide a guide for DART‐MS users in rapid screening of explosive compounds. Samples were introduced as neat solutions and sequential dilutions to determine optimal instrument conditions and lowest concentration detectable. Most compounds were optimized to 250°C in the negative ion mode, and several compounds benefited from the addition of a chloride dopant from methylene chloride (amino‐dinitrotoluenes, RDX, EGDN, and PETN). Few compounds were more sensitive in the positive ion mode (TEGDN, DEGDN, HNS, and DMNB). Mixtures of compounds were detected using clean room wipes, directly from their surfaces and from subsequent extractions. Compounds from the mixtures were also successfully detected in soil and from swipes of spiked surfaces. The instrument showed merit in detection of pg/μL solutions for most of the compounds and among the substrates tested.     

Latent Fingerprint Development on Thermal Paper Using Traditional Ninhydrin and 1,2‐indanedione

Thermal paper poses a significant challenge to latent print development as it tends to change color when traditional fingerprint development formulations are applied to it. In this study, the optimal components of ninhydrin, 1,2‐indanedione, 1,8‐diazafluoren‐9‐one (DFO), and 5‐methylthioninhydrin (5‐MTN) for yielding clear fingerprints on thermal paper were determined by systematically adjusting the relative amounts of the reagents, polar solvents, and the nonpolar diluent petroleum ether, followed by validation on text‐printed thermal paper. Specifically, 3.0% ethyl acetate as the polar solvent in petroleum ether was found to be the optimal combination; the optimal dilution ratios of ninhydrin, DFO, and 5‐MTN original solutions with petroleum ether were 1 to 2, 11, and 7, respectively. The optimal concentration of 1,2‐indanedione in petroleum ether was 0.125 g/L, with a string of 0.5% ethyl acetate in petroleum ether.     

X‐ray Scattering Evaluation of Ultrastructural Changes in Human Dental Tissues with Thermal Treatment

Micro‐ and ultrastructural analysis of burned skeletal remains is crucial for obtaining a reliable estimation of cremation temperature. Earlier studies mainly focused on heat‐induced changes in bone tissue, while this study extends this research to human dental tissues using a novel quantitative analytical approach. Twelve tooth sections were burned at 400–900°C (30‐min exposure, increments of 100°C). Subsequent combined small‐ and wide‐angle X‐ray scattering (SAXS/WAXS) experiments were performed at the Diamond Light Source synchrotron facility, where 28 scattering patterns were collected within each tooth section. In comparison with the control sample, an increase in mean crystal thickness was found in burned dentine (2.8‐fold) and enamel (1.4‐fold), however at a smaller rate than reported earlier for bone tissue (5–10.7‐fold). The results provide a structural reference for traditional X‐ray scattering methods and emphasize the need to investigate bone and dental tissues separately to obtain a reliable estimation of cremation temperature.     

Fingerprint error rate on close non‐matches

The accuracy of fingerprint identifications is critically important to the administration of criminal justice. Accuracy is challenging when two prints from different sources have many common features and few dissimilar features. Such print pairs, known as close non‐matches (CNMs), are increasingly likely to arise as ever‐growing databases are searched with greater frequency. In this study, 125 fingerprint agencies completed a mandatory proficiency test that included two pairs of CNMs. The false‐positive error rates on the two CNMs were 15.9% (17 out of 107, 95% C.I.: 9.5%, 24.2%) and 28.1% (27 out of 96, 95% C.I.: 19.4%, 38.2%), respectively. These CNM error rates are (a) inconsistent with the popular notion that fingerprint evidence is nearly infallible, and (b) larger than error rates reported in leading fingerprint studies. We conclude that, when the risk of CNMs is high, the probative value of a reported fingerprint identification may be severely diminished due to an elevated false‐positive error risk. We call for additional CNM research, including a replication and expansion of the present study using a representative selection of CNMs from database searches.     

Postmortem Blood Concentrations of R‐ and S‐Enantiomers of Methadone and EDDP in Drug Users: Influence of Co‐Medication and P‐glycoprotein Genotype

Abstract: We investigated toxicological and pharmacogenetic factors that could influence methadone toxicity using postmortem samples. R‐ and S‐methadone were measured in femoral blood from 90 postmortem cases, mainly drug users. The R‐enantiomer concentrations significantly exceeded that of the S‐enantiomers (Wilcoxon’s test, p < 0.001). The samples were divided into four groups according to other drugs detected (methadone only, methadone and strong analgesics, methadone and benzodiazepines, or methadone and other drugs). There was no significant difference in any of the R‐methadone/total methadone ratios among the four groups. The median R/S ratio was 1.38, which tends to be higher than that reported for the plasma of living subjects. In addition, we investigated whether small nucleotide polymorphisms in the MDR1 gene that encode the drug transporter P‐glycoprotein were associated with the concentrations of R‐ and S‐methadone and its metabolite 2‐ethylidene‐1,5‐dimethyl‐3,3‐diphenylpyrrolidine. No significant association was detected.     

Thermal degradation analysis of amino acids in fingerprint residue by pyrolysis GC-MS to develop new latent fingerprint developing reagents

Conventional development of latent fingerprints is compromised when the prints are decomposed by extreme temperatures, such as those encountered when a weapon cartridge is fired, an improvised explosive device is detonated, and/or in arson cases. Understanding how these extreme temperatures alter the chemical and physical properties of latent fingerprint residue could aid in the discovery of a reagent that could effectively develop these decomposed fingerprints. To mimic scenarios where fingerprints may be exposed to high heat conditions, standards of the five most abundant amino acids in fingerprint residue as well as extracted fingerprint residue were pyrolized under controlled conditions. Compounds identified as pyrolytic decomposition products were 3,6-dimethylpiperazine-2,5-dione (from alanine), maleimide, and 2,5-furandione (from aspartic acid). The pyrograms and selected ion traces show these products to hold promise as indicators of decomposed fingerprint residues and, therefore, may serve as good candidate substrates for a developing reagent.     

Forensic Comparison of Automotive Aluminum Wheel Fragments Using Synchrotron Radiation X‐ray Fluorescence with 18‐ and 116‐keV Excitation X‐rays

The performance of synchrotron radiation X‐ray fluorescence (SR‐XRF) spectrometry for nondestructive discrimination of small fragments of automotive aluminum wheels was studied. Fragments (< 500 × 500 μm²) of 45 kinds of wheels were first analyzed by scanning electron microscopy–energy dispersive spectroscopy (SEM‐EDS) and then by SR‐XRF. Despite the Mg/Al intensity ratio being a useful identification index, SEM‐EDS was not efficient enough because of the absence of other meaningful indicators of comparison. Conversely, pairwise comparison was conducted and a 92.9% identification was achieved via SR‐XRF using 18‐keV X‐rays. Trace heavy elements in the high‐energy region were detected by SR‐XRF using 116‐keV X‐rays, and an 82.9% identification was obtained. Combined use of 18‐ and 116‐keV X‐rays allowed 98.2% identification. Hence, SR‐XRF is a powerful tool for nondestructive discrimination of automotive aluminum wheels with high precision using trace elements in a wide energy region.     

Surface Modification for the Collection and Identification of Fingerprints and Colorimetric Detection of Urea Nitrate

Glass surfaces were modified with a combination of dyes and reagents to allow for the potential simultaneous recording of a detailed fingerprint and the detection of the explosive urea nitrate (UN), as a proof of principle of surface modification for simultaneous linking of identity to manipulation of explosives. By coating microscope slides with 9,10‐diphenylanthracene (DPA), p‐dimethylaminobenzaldehyde (p‐DMAB) and p‐dimethylaminocinnamaldehyde (p‐DMAC), a colorimetric change was observed in the presence of UN, while revealing a fingerprint with enough resolution to isolate at least 10 minutiae. This is the first step in creating point‐of‐care devices capable of detecting low concentrations of explosives and drug metabolites and connecting them to a fingerprint.     

Discriminating Hodgdon Pyrodex® and Triple Seven® Using Gas Chromatography–Mass Spectrometry

Abstract: Pyrodex ^® and Triple Seven ^® are black powder substitutes that often find use as fillers in improvised explosive devices, such as pipe bombs. These propellants have essentially the same overall appearance and oxidizers, but different fuels. For example, Pyrodex ^® contains sulfur, sodium benzoate, and dicyandiamide (DCDA), whereas Triple Seven ^® lacks sulfur but also contains 3‐nitrobenzoic acid. In this method, intact particles and postblast solid residues were reacted with bis(trimethylsilyl)trifluoroacetamide + 1% trimethylchlorosilane in acetonitrile for 30 min at 60°C. The resultant trimethylsilyl derivatives of the organic fuels were then analyzed by gas chromatography–mass spectrometry. Each derivative was clearly resolved from other components, and high‐quality mass spectra were obtained. In addition, characteristic fragments resulting from loss of a methyl radical from the molecular ion (m/z 163 for sulfur, m/z 171 for DCDA, m/z 179 for benzoic acid, and m/z 224 for nitrobenzoic acid) were able to be monitored.     

Enhancement of Aged and Denatured Fingerprints Using the Cyanoacrylate Fuming Technique Following Dusting with Amino Acid‐Containing Powders

We have carried out experiments to investigate the aging of latent fingerprints deposited on black PVC over a period of 4–15 weeks. A thumbprint was used in each case and before deposition of the print the donor rubbed their thumb around their nose to add sebaceous deposits. We have studied the effect of heat, light, and moisture and we find that moisture is the most significant factor in the degradation of the latent print. We have attempted to enhance these latent prints by dusting with valine powder or powders composed of valine mixed with gold or red fluorescent commercial fingerprint powders. To make a direct comparison between “treated” and “untreated” prints, the prints were cut in half with one‐half being “treated” and one‐half not. Our studies show the best results being obtained when powders of valine and red fluorescent powders are applied prior to cyanoacrylate fuming.