Effect of temperature on rectifying Schottky barriers formed from fingerprint sweat corrosion of brass

Corrosive electrochemical processes of brass, including those resulting from fingerprint sweat, continue to be studied because of the widespread industrial use of brass. Here, we examine how increased temperature affects the relative abundance of fingerprint sweat corrosion products and the rectifying Schottky barrier formed between p-type copper (I) oxide corrosion and brass. X-ray photoelectron spectroscopy confirms increasing dezincification with increasing temperature. This leads to n-type zinc oxide replacing copper (I) oxide as the dominant corrosion product, which then forms a rectifying Schottky barrier with the brass, instead of copper oxide, when the temperature reaches c. 600°C. Using X-ray diffraction, resulting diodes show polycrystalline oxides embedded in amorphous oxidation products that have a lower relative abundance than the diode forming oxide. Conventional current/voltage (I/V) characteristics of these diodes show good rectifying qualities. At temperatures between c. 100 and c. 600°C, when neither oxide dominates, the semiconductor/brass contact displays an absence of rectification.     

Effect that the relative abundance of copper oxide and zinc oxide corrosion has on the visualization of fingerprints formed from fingerprint sweat corrosion of brass

From an examination of the fingerprint sweat corrosion of 40 different individuals on α phase brass, we show that an increase in visualization can be achieved by applying a negative potential to the brass followed by the introduction of a conducting powder. Previously, this technique has been demonstrated only for a positive applied potential and a corrosion product that was dominated by p-type copper (I) oxide. X-ray photoelectron and Auger electron spectroscopic analyses of the surface of the corroded brass show that an increase in visualization with a negative applied potential corresponds with an increase in the concentration of n-type zinc oxide relative to p-type copper (I) oxide with the Cu:Zn ratio <0.8:1. Work function conditions for the formation of an n-type zinc oxide/brass rectifying Schottky barrier are fulfilled.     

Effect of chloride ion concentration on the galvanic corrosion of α phase brass by eccrine sweat

Inductively coupled plasma mass spectrometry measurement of the relative concentration of sodium, chloride, calcium, and potassium ions in eccrine sweat deposits from 40 donors revealed positive correlations between chloride and sodium (ρ = 0.684, p < 0.01) and chloride and calcium ions (ρ = 0.91, p < 0.01). Correlations between ion concentration and the corrosion of α phase brass by the donated sweat were investigated by visual grading of the degree of corrosion, by measuring the copper/zinc ratio using energy-dispersive X-ray spectroscopy, and from a measurement of the potential difference between corroded and uncorroded brass when a large potential was applied to the uncorroded brass. An increasing copper/zinc ratio (indicative of dezincification) was found to correlate positively to both chloride ion concentration and visual grading of corrosion, while visual grading gave correlations with potential difference measurements that were indicative of the preferential surface oxidation of zinc rather than copper.     

Visualization of latent fingermark corrosion of brass, climatic influence in a comparison between the U.K. and Iraq

Through a comparison of fingermark sweat corrosion of α phase brass in both the U.K. and Iraq, we show how samples from Iraq have improved fingermark corrosion over U.K. samples that require no additional enhancement prior to visualization. Over 50% of Iraqi samples produced fingermark corrosion with full ridge detail compared with 0% from the U.K. X-ray photoelectron spectroscopy analysis of the fingermark corrosion products showed that Iraqi samples exhibit more dezincification with the Zn:Cu ratio averaging 1:1.82 compared with 1:3.07 for U.K. samples. Auger spectroscopy showed the presence of both zinc oxide and copper (I) oxide. No copper (II) was observed on the surface of the corroded brass. Opportunities to exploit the optical properties of these thin film oxides to enhance the visualization of fingermark corrosion are considered, and the potential to use fingermark corrosion of metal as a means of visualizing fingerprints in war zones is discussed.     

Comparison of metal ions recovered during DNA analysis of brass ammunition and effects of copper and zinc ions on DNA profiling

Analyzing DNA from brass surfaces poses unique challenges that may result from DNA damage and/or PCR inhibition. To examine the relationship between the metal ions present in brass ammunition and the success of Short Tandem Repeat (STR) profiling, six recovery methods were tested to determine the identity and quantity of metal ions co-recovered during DNA sampling. In addition, DNA and metal ion solutions were created at varying concentrations to determine the threshold at which deleterious effects occur. The results of this study show that copper and zinc are recovered in the highest concentrations from both fired and unfired ammunition, but at substantially lower levels than previously published. Furthermore, most metal ions co-recovered with DNA were removed during DNA purification and complete STR profiles were generated when the concentrations of copper and zinc ions were less than 0.1 M and 0.03 M, respectively.     

Can the RUVIS Reflected UV Imaging System Visualize Fingerprint Corrosion on Brass Cartridge Casings Postfiring?

Comparisons are made between the visualization of fingerprint corrosion ridge detail on fired brass cartridge casings, where fingerprint sweat was deposited prefiring, using both ultraviolet (UV) and visible (natural daylight) light sources. A reflected ultraviolet imaging system (RUVIS), normally used for visualizing latent fingerprint sweat deposits, is compared with optical interference and digital color mapping of visible light, the latter using apparatus constructed to easily enable selection of the optimum viewing angle. Results show that reflected UV, with a monochromatic UV source of 254 nm, was unable to visualize fingerprint ridge detail on any of 12 casings analyzed, whereas optical interference and digital color mapping using natural daylight yielded ridge detail on three casings. Reasons for the lack of success with RUVIS are discussed in terms of the variation in thickness of the thin film of metal oxide corrosion and absorption wavelengths for the corrosion products of brass.     

Effect of Temperature on the Visualization by Digital Color Mapping of Latent Fingerprint Deposits on Metal

Visualization of fingerprint deposits by digital color mapping of light reflected from the surface of heated brass, copper, aluminum, and tin has been investigated using Adobe^® Photoshop^®. Metals were heated to a range of temperatures (T) between 50°C and 500°C in 50°C intervals with enhancement being optimal when the metals are heated to 250°C, 350°C, 50°C, and 300°C, respectively, and the hue values adjusted to 247°, 245°, 5°, and 34°, respectively. Fingerprint visualization after color mapping was not degraded by subsequent washing of the metals and color mapping did not compromise the visibility of the fingerprint for all values of T. The optimum value of T for fingerprint visibility is significantly dependent of the standard reduction potential of the metal with Kendall's Tau (τ) = 0.953 (p < 0.001). For brass, this correlation is obtained when considering the standard reduction potential of zinc rather than copper.     

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.     

A Preliminary Study on Vacuum Metal Deposition as a Standalone Method for Enhancement of Fingermarks on Ballistic Brass Materials

In order to assess the efficacy of vacuum metal deposition (VMD) as a technique to develop fingermarks on ballistic metallic surfaces, a preliminary study using six donors (three male & three female) was conducted. Using a sequential metal deposition process, two metal combinations were studied—gold/zinc and silver/zinc. Results indicate the potential of this technique, by developing identifiable fingermarks on brass metal disks aged from a few days up to more than a month old. As the development of fingermarks on fired (brass) cartridge cases is an area of interest, a further study was conducted where a total of 20 fingermarks were deposited on cases. After firing, second level fingermark characteristics were successfully observed on cartridge cases highlighting its potential as a fingermark enhancement method for ballistic brass materials. Further work is required to fully evaluate the VMD process and its reliability as a fingermark enhancing method on ballistic surfaces.     

Visualization of Latent Fingerprint Corrosion of Brass

Abstract:  Visualization of latent fingerprint deposits on metals by enhancing the fingerprint-induced corrosion is now an established technique. However, the corrosion mechanism itself is less well understood. Here, we describe the apparatus constructed to measure the spatial variation (Δ V ) in applied potential ( V ) over the surface of brass disks corroded by latent fingerprint deposits. Measurement of Δ V for potential of 1400 V has enabled visualization of fingerprint ridges and characteristics in terms of this potential difference with Δ V typically of a few volts. This visualization is consistent with the formation of a Schottky barrier at the brass-corrosion product junction. Measurement of the work function of the corroded brass of up to 4.87 ± 0.03 eV supports previous results that suggested that the corrosion product is composed of p-type copper oxides. A model for the galvanic corrosion of brass by ionic salts present in fingerprint deposits is proposed that is consistent with these experimental results.     

1,2,4‐Triazine‐Based Chromogenic Reagents for the Detection of Microtraces of Various Metals Left on Human Skin*

Abstract: This article extends the application of 1,2,4‐triazine‐based chromogenic reagents to the detection of nonferrous metal traces left on contact with canvas and human skin. The possibility of detection of iron traces resulting from contact with objects made of stainless steel was investigated as well. Additionally, the ability of triazines to form chromatic complexes with Zn²⁺, Ni²⁺, Co²⁺, Cu²⁺, Cr³⁺, and Al³⁺ ions was studied spectrophotometrically. Molar absorption coefficients, ranging from 8.8 to 29.9 × 10³/M/cm, provide high sensitivity of 1,2,4‐triazines toward nonferrous ions, thus, enabling the detection at concentrations as low as a few μM. The method was sensitive enough to detect traces resulting from a 1‐min contact with a stainless steel made object, which is commonly considered as a corrosion‐resistant material. The amounts of metal ions transferred to the skin after a 2‐min contact with objects made of brass, zinc, and copper were sufficient to develop chromatic imprints.     

The thermodynamics of latent fingerprint corrosion of metal elements and alloys

Redox reactions taking place between the surface of a metal and fingerprint residue have been expressed thermodynamically in terms of both the Nernst equation for reduction potential and the complexation constant for the formation of complex metal halide ions in aqueous solution. These expressions are used to explain experimental results for the corrosion of 10 different metal elements by fingerprint residue in air at room temperature. Corrosion of noble metals, such as silver and gold, supports the proposition that the degree of metal corrosion is enhanced by the presence of chloride ions in eccrine sweat. Extending the experiments to include 10 metal alloys enabled the construction of a fingerprint corrosion series for 20 different metals. Fingerprint corrosion on metals alloyed with > approximately 40% copper was found to display third level fingerprint detail. A comparison of both conventional ink on paper and digital (Livescan) fingerprinting techniques with fingerprints deposited on 9 Karat gold alloy has shown that gold alloy depositions are least susceptible to third level detail obliteration by poor fingerprint capturing techniques.     

Physical Characterization and Recovery of Corroded Fingerprint Impressions from Postblast Copper Pipe Bomb Fragments

Pipe bombs made from 1 mm thick copper pipe were detonated with a low explosive power powder. Analysis of the physical characteristics of fragments revealed that the copper had undergone work hardening with an increased Vickers Hardness of 107HV1 compared with 80HV1 for unexploded copper pipe. Mean plastic strain prior to fracture was calculated at 0.28 showing evidence of both plastic deformation and wall thinning. An examination of the external surface showed microfractures running parallel with the length of the pipe at approximately 100 μm intervals and 1–2 μm in width. Many larger fragments had folded “inside out” making the original outside surface inaccessible and difficult to fold back through work hardening. A visual examination for fingerprint corrosion revealed ridge details on several fragments that were enhanced by selective digital mapping of colors reflected from the surface of the copper. One of these fingerprints was identified partially to the original donor.     

Corrosion behaviour of four handguns in aqueous environments: Corrosion product characterization and effects on estimating the time since deposition

When a firearm has been disposed of in a body of water and becomes corroded, its appearance is altered and determining a time-since-immersion may be of import to the investigation. Therefore, in this study, the corrosion and mass loss of four handgun slides over a period of 180 days were examined. Solid-state characterization of the metals and their corrosion products via SEM/EDX and powder X-ray Diffraction (pXRD) was performed. The pXRDs were analyzed against the NIST Powder Diffraction Database to determine the crystalline phases. Filings from the SS416 standard, Llama and Ruger handgun slide predominantly consisted of iron alloys. After 180-days in solution, pXRD indicated that the adherent corrosion products consisted of 1) γ-FeOOH and 2) iron oxide (Fe₃O₄ or Fe₂O₃). Additionally, pXRD analysis indicated that the adherent corrosion products of the SS416 standard also consisted of CrO₃. Metal filings from the Raven and Jennings handgun slides were a mixture of iron–nickel–zinc and EDX and pXRD analyses of the corrosion products, when submersed in deionized water, indicated that the products consisted of: 1) γ-FeOOH, 2) iron oxide (Fe₃O₄ or Fe₂O₃), and 3) ZnFe₂O₄ or ZnO; where the Jennings adherent rust contained ZnFe₂O₄ and the Raven adherent rust contained ZnO. Further, pXRD of the corrosion products from these alloys, when submersed in 25 PSU (Practical Salinity Unit) solution, indicated that the products consisted of: 1) ZnO, 2) Zn(OH)₂, 3) α-Ni(OH)₂, and 4) NaCl.The data thus indicated that both metal composition and the presence of chloride ions had significant impacts on rates and products of corrosion and suggest that the presence of Cl^? changes not only the rate of corrosion, but also the corroding species itself. While mechanisms and rates of the chloride driven corrosion processes offer explanations as to the different oxides and hydroxides observed between immersion conditions, they do not offer an explanation for the differences observed between handguns. Therefore, utilizing a general approach where surface area coverage of corrosion products is the sole consideration is not sufficient to determine time-since-immersion. Attempts to determine a time-since-immersion would require a priori knowledge of the mechanism of corrosion for a given metal mixture within a specified environment. The results described herein give indications as to the possible corrosion mechanism driving the process in high and low Cl^? environments and show the necessity of including the metal composition, rust composition and ion concentration in any models that attempt to elucidate the time-since-immersion of handguns for forensic applications.     

High Resolution Imaging of Latent Fingerprints by Localized Corrosion on Brass Surfaces

Abstract:  The Atomic Force Microscope (AFM) is capable of imaging fingerprint ridges on polished brass substrates at an unprecedented level of detail. While exposure to elevated humidity at ambient or slightly raised temperatures does not change the image appreciably, subsequent brief heating in a flame results in complete loss of the sweat deposit and the appearance of pits and trenches. Localized elemental analysis (using EDAX, coupled with SEM imaging) shows the presence of the constituents of salt in the initial deposits. Together with water and atmospheric oxygen—and with thermal enhancement—these are capable of driving a surface corrosion process. This process is sufficiently localized that it has the potential to generate a durable negative topographical image of the fingerprint. AFM examination of surface regions between ridges revealed small deposits (probably microscopic "spatter" of sweat components or transferred particulates) that may ultimately limit the level of ridge detail analysis.     

The Effect of Varying the Composition of Fingerprint Sweat Deposits on the Corrosion of Brass and Fingerprint Visibility

Corrosion of α‐phase brass by sebaceous sweat fingerprint deposits produced identifiable impressions in a majority of samples (n = 40) 4 days after deposition. Combining sebaceous with eccrine sweat yielded a greater percentage of identifiable fingerprint deposits, although this increase was not statistically significant. Production of identifiable fingerprints from eccrine sweat deposits was dependent on the sampling time of year with deposits taken during summer months giving similar percentages of identifiable fingerprints to sebaceous deposits. A statistically significant positive correlation was found between elapsed days after deposition and identifiable eccrine (ρ = 0.787, p < 0.05), sebaceous (ρ = 0.724, p < 0.05), and eccrine/sebaceous mixture (ρ = 0.908, p < 0.01) fingerprints deposited during summer months. The summer increase in the percentage of identifiable eccrine sweat deposits was statistically significant compared to winter eccrine deposits (p < 0.0001). Observations were consistent with results obtained from artificial sebaceous and eccrine sweat.     

The Effect of Light Exposure on the Degradation of Latent Fingerprints on Brass Surfaces: The Use of Silver Electroless Deposition as a Visualization Technique

We have studied the degradation of sebaceous fingerprints on brass surfaces using silver electroless deposition (SED) as a visualization technique. We have stored fingerprints on brass squares either (i) in a locked dark cupboard or (ii) in glass‐filtered natural daylight for periods of 3 h, 24 h, 1 week, 3 weeks, and 6 weeks. We find that fingerprints on brass surfaces degrade much more rapidly when kept in the light than they do under dark conditions with a much higher proportion of high‐quality prints found after 3 or 6 weeks of aging when stored in the dark. This process is more marked than for similar fingerprints on black PVC surfaces. Identifiable prints can be achieved on brass surfaces using both SED and cyanoacrylate fuming (CFM). SED is quick and straightforward to perform. CFM is more time‐consuming but is versatile and can be applied to a wider range of metal surfaces than SED, for example brass surfaces which have been coated by a lacquer.     

Printed artificial sweat as replacement for natural fingermarks: Qualitative and quantitative approach considering an amino acid reagent

The study presented in this paper aims at assessing how printed fingermarks can be used to generate realistic latent marks bearing varying quantities of materials to be detected. Considering dilution series of artificial sweat (eccrine secretion) and 1,2-indanedione/zinc as amino acid reagent, we assessed how printed marks behave in comparison to natural fingermarks provided by a set of 30 donors. The results were assessed in terms of relative intensity (contrast, luminescence) and expert grading (ridge details, overall quality). With regards to the set of 30 donors, this study brought a quantitative look to the influence of intra- and inter-variability on the relative intensity values observed when processing natural fingermarks. This provided new data to further understand the concept of “donorship”. With regards to the use of printed marks, it has been illustrated how dilution series of a concentrated solution allows covering a range of cases: unnatural marks (intensity values well above those obtained with donors), rich marks (corresponding to fingermarks left by good donors), and faint marks (associated with the kind of results observed with poor donors). Such a range of detection performance offers the possibility to generate fine-tuned detection exercises of varying difficulty levels. Printed items made of artificial sweat could hence constitute a valuable alternative to natural secretions in the context of education and proficiency testing.     

Copper-binding protein in acute copper poisoning

This paper presents a suicide case of copper sulfate ingestion. Post-mortem autopsy revealed mucous membrane necrosis of the esophagus and the stomach. Histological examination revealed centrilobular necrosis in the liver and renal insufficiency. The quantitative determination of copper, zinc and cadmium in various tissues showed that the copper concentrations in blood, liver, kidney and lung were 3.5-24-fold higher than those of the normal level, whereas zinc and cadmium concentrations were within normal range. Chromatographical patterns on Sephadex G-75 showed that most of the accumulated copper in the liver and kidney was bound to metallothionein (MT), a low molecular weight protein with high metal binding capacity which plays a role in the detoxification of heavy metals, while no copper bound to MT was found in the lung. These results suggest that the formation of Cu-induced MT in the liver and kidney occurred at the early stage in fatal acute copper poisoning.     

Combined DNA Typing and Protein Identification from Unfired Brass Cartridges,,,

Biological evidence analysis from contact traces is adversely affected by low quantity and quality of DNA. Proteins in these samples contain potentially individualizing information and may be particularly important for difficult surfaces such as brass, where DNA may yield incomplete profiles. In this study, touched unfired brass cartridges were sampled using dry tape or wet swabs and analyzed by separating DNA and protein from the same collected material, thus producing both genomic and proteomic information. DNA recovery was similar for both collection methods, with tape yielding an average of 1.36 ± 1.87 ng and swabs, 1.34 ± 3.04 ng. Analysis by mass spectrometry identified 95 proteins, with the two collection methods showing no significant difference (p = 0.76) in the average number of collected proteins: 44.5 ± 10.9, (tape) versus 47.9 ± 20.4 (swabs). Proteins can be collected from fingerprints at levels necessary to provide identifying information, thus expanding information obtained from challenging evidence.