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Journal of Forensic Identification67 (3), 2017 \ 391

Received March 1, 2017; accepted May 20, 2017

Article

Fingerprint Development on Cartridge Cases Through the Electrodeposition of Gun Blue

Aaron DoveForensic Identification Section Royal Canadian Mounted Police Montréal, QC

Abstract: This paper examines whether an electrically stimulated deposition of gun blue is a viable technique for developing fingerprints on cartridge cases. By running an electric current through a cartridge case while it is suspended in a diluted solution of gun blue, sebaceous f ingerprints were quickly, eff iciently, and inexpensively developed to a quality surpassing both the passive deposition of gun blue and the sequential development using cyanoacrylate → brilliant yellow 40.

IntroductionFired car tridge cases are both excellent and problematic

pieces of evidence. Because they are normally an integral part of the crime being committed, the probative value is excel-lent. However, the firing of a bullet tends to have a deleterious effect on any fingerprint evidence that may have existed on the cartridge [1]. To quantify the issue, Bentsen et al. [2] were only able to recover one usable print in 104 operational cases over a period of two years.

Historically, bullet cartridges and other metal exhibits have been treated the same as other nonporous exhibits (i.e., using powders, small particle reagent, and cyanoacrylate fuming). More recently, there have been at tempts to develop other fingerprint visualization techniques, in particular by using the electrochemical properties of the metals, with variable results. Williams and McMurray [3] successfully examined the use of a

Journal of Forensic Identification392 / 67 (3), 2017

scanning Kelvin probe to delineate corrosion caused by the latent fingerprint. Although the technique was robust, it was dependent on equipment that is not accessible to most forensic laboratories. Bond [4] and Wightmann and O’Connor [5] examined heating the cartridge in an attempt to create fingerprint matrix-induced corrosion of the metal. Although the technique could be used on problematic cartridges (e.g., post-firing and arson involved), the stated success rate was only 5% [4]. Bond and Heidel [6] examined creating an electr ic potential on the car tr idge to preferentially attract carbon powder to areas corroded by the fingerprint matrix. Although the technique did generate friction ridges 14 years after the crime, the results were not identif i-able. Jasuja et al. [7] examined placing the cartridge cases in an aqueous solution to etch either the background metal or the f ingerprint ridges into the metal. Although the results were only preliminary and no comparative test was performed, the technique was able to develop high-quality impressions from fresh friction ridge impressions. Further research is required to determine whether the same results could be achieved in operational or aged impressions. Nizam et al. [8] effectively combined Jasuja’s and Bond’s techniques when they attempted to corrode the metal via galvanic corrosion. Although the technique showed some interesting potential, the experiment was noted as being very limited in scope and requiring further research. These purely electrochemical techniques showed either limited efficacy, limited accessibility, or both.

An electrochemically similar but alternative approach by Bersellini et al. [9] examined using the electropolymerization of porphyrins to create an electrochromic contrast of fingerprints on various metals. Rather than inducing corrosion, Bersellini et al. used the insulating properties of the f ingerprint to deposit a f ilm on the substrate and thereby create a negative contrast between the fingerprint and the substrate. Similarly, Beresford and Hillman [10] examined the possibility of electrochromi-cally enhancing fingerprints on steel surfaces using polyaniline. Brown and Hillman [11] examined the same using poly-3, 4-ethylenedioxythiophene. The process they used could also be electrochemically reversed, counteracting overdevelopment. Both techniques were also found to be comparable or better than conventional development techniques, demonstrating that there is potential in electrochromic development. At present, the limit-ing factor for the electrochromic techniques is noted to be a lack of comparative trials with alternative processes [12].


The forensic use of chromic dyes on metallic substrates to create a negative contrast is not new. Long utilized by gunsmiths, gun blue is a product used to protect firearms from rust or corro-sion. “Cold bluing” (i.e., the deposition of a selenium-containing compound at room temperature) has been used in forensics to create negative contrast on metals, par ticularly car tridge cases [13–16]. Of note, Ramotowski and Leben [17] examined the use of gun blue for developing fingerprints as well as developing a technique to reverse any accidental overdevelopment during gun blue treatment. A more recent study by Dominick et al. [18] of the six standard development techniques commonly used to treat cartridge cases found a sequential development process of cyanoacrylate → gun blue → brilliant yellow 40 development was equivalent to cyanoacrylate → palladium and surpassed cyanoacrylate → brilliant yellow 40 development. The results of Dominick et al. are somewhat contradicted by Bhaloo et al. [19] (who found that cyanoacrylate → brilliant yellow 40 and gun blue both surpassed palladium deposition) and Bond and Heidel’s [6] electrostatic recovery technique. The previously mentioned study by Girelli et al. [1], however, showed some slightly different results, with cyanoacrylate development showing the best results on brass discs. Gun blue was specifically noted as sometimes causing irregular development. It may be for reasons such as these that the Fingermark Visualisation Manual notes gun blue development “has not yet been fully evaluated and optimised” [15] and is therefore a category B process instead of a recommended A-level process. The current technique recom-mended by the Fingermark Visualisation Manual is treatment using a sequential cyanoacrylate-f luorescent dye process [20].

Given the reactions involved, this conclusion of “not fully evaluated and optimised” is not surprising. Although Migron and Mandler [21] examined the process and determined the mechanism involves a multistep reaction wherein the copper and selenium are independently reduced but result in a final co-deposition of the two to create a copper selenide film (Figure 1), the precise mechanism of the gun blue deposition is quite variable, depend-ing on the precise substrate and composition of the solution. By varying the conditions during the deposition of copper-selenide layers, Lippkow and Strehblow [22] were able to shift the deposition between the pure Cu3Se2 and pure Cu2Se. In The Fingerprint Sourcebook, Holder et al. [16] describe a theoreti-cal aluminum substrate to demonstrate that a 1:1 Cu-Se alloy is not always formed (depending on the relative kinetics of the competing reactions).


Cu2+ + Zn → Cu + Zn2+ 4H+ + H2SeO3 + 2Zn → 3H2O + Se + 2Zn2

+ Se + Cu → CuSe(black)

Figure 1The redox of the Cu(II) and Se(IV) using a zinc intermediary. In the presence

of zinc, Cu(II) and Se(IV) undergo a redox reaction using the zinc as an intermediary, resulting in the ultimate formation of CuSe. [21]

In theory, the ionic selenium reacts with the metal substrate, forming a thin blue-black f ilm while failing to react with the sebaceous components of the f ingerpr int. In practice, however, this separation is not absolute. As Girelli et al. [1] and Cantu et al. [23] demonstrated, overdevelopment is possible. The precise mechanism by which the development proceeds in, under, or through the sebaceous components is not clear, but the rate of the reaction is much slower than with the surrounding metal. The key to optimizing development should therefore, in theory, be to maximize the differences in the rate of reactiv-ity between the two surfaces. By either increasing the rate of deposition on the metal or decreasing the rate of deposition on the sebaceous components, or both, the contrast, and therefore the precision of the development technique, should be increased.

Using the electrochemical properties of the metal to attract the chromic agents should achieve exactly that. In theory, the metallic ions will be preferentially attracted to the metal substrate at a higher rate than occurs in passive deposition, and the insulated sebaceous components will likewise be propor-tionally less attractive. This may lead to a more controlled and even deposition similar to what was seen in the electrochromic techniques [9–11].

To test this hypothesis, two separate comparisons must be examined. First, how does the electrically stimulated deposi-tion of gun blue compare to the passively deposited gun blue? Second, if the electrically stimulated deposition of gun blue does prove to be better than the passive deposition, how does electrically stimulated deposition compare to a current opera-tional development technique? In this case, the comparison will be made to the current operational recommendation of sequen-tial cyanoacrylate and subsequent f luorescent dye, as per the Fingermark Visualisation Manual. In keeping with previous works [1, 18, 19], the f luorescent dye will be brilliant yellow 40.


The questions posed by this paper are therefore the following: • Will applying a potentiostatic electrodeposition technique to

gun blue deposition have an effect on the fingerprint develop-ment on cartridges cases?

• How will it compare to cyanoacrylate → brilliant yellow 40?

Material and MethodsSpent brass casings (Speer Luger 9 mm brass cartridges,

Lewiston, ID) and spent nickel-plated brass casings (Winchester Luger 9 mm nickel-plated cartridges, East Alton, IL) were recov-ered from the firing range of the Royal Canadian Mounted Police in Montreal, Quebec. Before testing, they were washed in warm, soapy water, rinsed with distilled water, and left to air dry.

The f ingerprint samples were provided by the same donor throughout the experiment, and all sample f ingerprint prints were “loaded” prints (i.e., the donor rubbed his face or neck prior to depositing a print).

The electrochemical cell consisted of 2 mm solid steel wire electrodes powered by a 1.5 V Duracell “C” battery forming a two-electrode system. The cartridge case was held in place from the inside, creating the working electrode, and another section of steel wire was used as the auxiliary electrode (Figure 2).

Figure 2Potentiostatic two-electrode system. Schematic of the set-up used to

perform the electrodeposition of gun blue.


The gun blue solution was “Super Blue Liquid Gun Blue” (Birchwood Casey, Eden Prairie, MN). The active components are listed as 1– 5% selenious acid, 1– 3% cupric sulfate, and 1– 3% cupric phosphate [24]. Any dilutions were performed using distilled water.

After the f ingerprint development was deemed complete, further development was halted by rinsing the cartridge case in distilled water. A GraLab 505 darkroom timer was used for all timing functions.

The quality of the developed fingerprints was graded by three Royal Canadian Mounted Police certified Forensic Identification Specialists (FISs) using the scale found in Table 1.

Grade Criteria

4 Usable third-level details (e.g., pores, ridge edges, minor ridge deviations) are visible. This fingerprint is identifiable (Figure 3).

3 No third-level details, but usable second level details (e.g., bifurcations, ridge endings) are visible. This print is identifiable (Figure 4).

2 No usable second- or third-level details, but first level detail (e.g., ridge f low, pattern) is visible. This fingerprint is not identifiable (Figure 5).

1 No usable details at any level, but indications of matrix are present (e.g., a smudge). This fingerprint is not identifiable (Figure 6)

0 There is no evidence of a fingerprint having been deposited (Figure 7).

Table 1 Quality-based grading scale.

In a print where multiple grades were observed, the grader was requested to choose a grade that best summarized the majority of the print. Given that a blind verification was impos-sible because of the different techniques required to visualize the electrodeposition of gun blue (eGB) and cyanoacrylate → brillant yellow 40 (CA → BY40), multiple examiners were used to minimize any potential bias that may have affected the results.

The cyanoacrylate (Via-Chem, Lasalle, QC) was applied via fuming for 23 minutes in a CA fuming cabinet (noncommercial construction). The brilliant yellow 40 (BY40, Lightning Powder, Salem, OR) was prepared by dissolving 2 grams of BY40 in 1000 mL of ethanol [19]. After treatment in the CA, each sample was suspended in the BY40 solution for 10 seconds and then rinsed using distilled water before being left to dry overnight in a fume hood.


Figure 3Grade 4: Third-level details.

Figure 4Grade 3: Second-level details.

Figure 5Grade 2: First-level details.

Figure 6Grade 1: Contrast, no details.

Figure 7Grade 0: No contrast, no details.


Photos were taken using a digital SLR camera (Nikon 610) equipped with a 60 mm micro lens (Nikko). A stereomicroscope (Bausch & Lomb StereoZoom 7) was used for the micro level photos. The BY40 was photographed using a KV550 camera filter and a 450 nm Polif lare Plus 2 (Rofin) as the light source.

Determining the Optimal Set-UpThe f irst step required determining the proper polarity of

the working electrode. It is known that selenium is a critical component in the process. Migron et al. [14] used only selenium in place of a mixed copper and selenium solution. However, the precise mechanism of the deposition is still unclear. Ramotowski and Leben [17] and Migron et al. [14] state the final deposited f ilm as being copper selenide. Therefore, an initial test was performed in an attempt to clarify whether it was the copper or the selenium initiating the deposition in the mixed copper-selenium compound.

To test this, the electrocell was initially set up with the working electrode as the cathode and the auxiliary as the anode. Using a ~13% by volume (v/v) diluted solution of gun blue, 15 brass samples were treated, and the time to full development was recorded. A sample was deemed to be fully developed if the forensic identification specialist who was observing the develop-ment was of the opinion that any further development would risk overdeveloping the print. Timing was to the nearest second. In total, each FIS observed five developments.

The electrocell was then reversed (working = anode, auxil-iary = cathode), and the test was repeated.

Determining the Optimal ConcentrationAfter determining the optimal set-up, the next step was to

determine the optimal working concentration of the solution. A 5% v/v of gun blue and distilled water was prepared, and a series of 10 brass cartridge cases were treated until deemed fully developed by the FIS. The same was then done with 10%, 15%, 20%, 25%, 30%, 35%, and 40% solutions. Another series of samples were treated passively (i.e., without electric current) at the 5% and 40% concentrations as negative controls. The results can be seen in Table 2.


Time to Complete Development (avg.) STD Dev. % STD Dev.

5% Solution 32.4 seconds 0.74 2.3%10% Solution 23.2 seconds 0.20 0.8%15% Solution 11.2 seconds 0.25 2.3%20% Solution 8.2 seconds 0.24 3.0%25% Solution 5.9 seconds 0.30 5.1%30% Solution 5.0 seconds 0.33 6.6%35% Solution 4.9 seconds 0.36 7.33%40% Solution 4.9 seconds 0.37 7.55%5% (Control) 88.0 seconds 11.02 12.5%

40% (Control) 14.0 seconds 3.01 21.8%

Table 2 Average time to complete development vs concentration of gun blue.

Comparison Versus Sequential Cyanoacrylate Fuming → Brilliant Yellow 40One hundred twenty brass cartridge cases were prepared and

randomly separated into 3 groups of 40 each. The f irst group was treated using the eGB. The second group was treated using cyanoacrylate fuming followed by BY40 staining and visual-ization under a 450 nm light source (CA → BY40). The third group was treated using a passive deposition of gun blue (pGB), prepared as per Bhaloo et al. (1 mL : 40 mL distilled water) [19]. The treated samples were then separated into groups of 40, with each group containing 13 or 14 samples from each development technique. Each treated group was then examined and graded by one of three FISs.

Submersion TestOne of the known advantages of the gun blue, as well as all

other techniques that are based around the sebaceous components of the f ingerprint, is the continued eff icacy of the technique after exposure to water. To confirm this, a test was performed where 20 brass cartridge cases were prepared as per protocol and then left submerged in distilled water for a period of 4 hours before being treated and graded.

Nickel-Plated Brass Cartridge CasesTo determine whether the technique could be applied to metals

other than brass, the eGB set-up was tested on 20 nickel-plated brass cartridge cases, prepared and tested as per the determined protocol.


Results and Discussion

Determining the Initial Set-UpThe results of the initial set-up test are shown in Table 3. The

deposition speed was much faster when the working electrode was the anode, indicating it is possibly the negatively charged selenium ion that is the primary initiator. However, in addition to the time difference, the overall development showed a much clearer contrast between the r idges and substrate when the working electrode was the anode rather than the reverse.

The remainder of the experiment was performed on the basis of these results, with the cartridge case as the anode (Figure 2).

Working = Cathode Working = AnodeFIS #1 Average 28.1 16.3FIS #2 Average 27.3 13.1FIS #3 Average 29.8 14.3

Avg. 28.4 seconds Avg. 14.5 seconds

Table 3Average time to complete development anode vs cathode.

Determining the Optimal ConcentrationThe results of this stage generated several observations of

note. First, at any concentration over 30% v/v, the time to devel-opment appeared to plateau; the time no longer decreased as the concentration of the gun blue increased. This indicates that 30% is the maximum capacity of this system.

Second, although the samples used for the timing portion of the experiment were not graded, the 35% and 40% concen-trations demonstrated a poorer contrast between the substrate and the fingerprints than the lower concentration samples. This could be due to additional passive deposition occurring because of the high concentration. Regardless of the precise reason, this indicates the higher concentrations (above 30%) are unsuitable for this technique.

In the case of the 5% concentration, the positive eGB sample was clearer with greater contrast than the negative pGB controls, where the gun blue started depositing on the ridges. In the case of the 40% concentration, the positive eGB sample was much clearer than the negative pGB controls; the deposition with the pGB was very spotty and negatively affected the ridges. In both cases, the calculated standard deviation was much higher than with the positive samples.


The optimum concentration seemed to be in the 10 to 20%. This concentration range gave a clear, sharp contrast and quick development time while still being low enough to not have the spotty deposition visible at the higher concentrations. It was therefore decided that 15% would be the concentration used in future tests (15% of gun blue translates into a maximum concen-tration of 0.75% selenious acid, 0.45% cupric sulfate, and 0.45% cupric phosphate).

Comparison Versus Sequential Cyanoacrylate Fuming → Brilliant Yellow 40The final results after grading are displayed in Table 4 and

Figure 8. Avg. Grade Std. Dev.

Group 1(eGB) 3.5 0.52

Group 2(CA → BY40) 3.2 0.54

Group 3(pGB) 2.9 0.63

Table 4 CA-BY40 vs eGB

Figure 8Left: Cartridge treated with eGB.

Right: Cartridge treated with CA → BY40.


To test for differences in the response variable (the grade of the fingerprints) between the three development techniques (eGB, CA → BY40, and pGB), a Kruskal-Wallis test was performed. The Kruskal-Wallis test is a nonparametric test that looks for differences in the mean rank of the grades of the techniques. The confidence level was set at 95%, meaning a p value less than 0.05 indicates a significant difference, whereas a p value greater than or equal to 0.05 indicates no significant difference can be concluded.

The Kruskal-Wallis test between the three development techniques produced a p value of <0.0001, confirming that at least one technique appeared to have signif icantly different fingerprint grades from another.

Following the significant response of the Kruskal-Wallis test, multiple Mann-Whitney tests were performed on each pairing of techniques. To maintain a 95% level of confidence for the family of tests, a Bonferroni correction was done; subsequently, a 98.33% level was used for each individual test. This means that a p value less than 0.0167 indicates a significant difference, whereas a p value greater than or equal to 0.0167 indicates that no significant difference can be concluded. The results from the Mann-Whitney tests can be found in Table 5.

Mann-Whitney Test Pairing p valueeGB vs CA → BY40 0.0045

eGB vs pGB <0.0001pGB vs CA → BY40 0.0132

Table 5 Mann-Whitney p values for the comparison test.

Each test produced a result indicating a signif icant differ-ence. Therefore, it can be concluded that each development technique resulted in different fingerprint grades from the other.

A comparison of the results showed eGB developed the highest quality prints, CA → BY40 produced the second highest quality prints, and pGB developed the lowest quality prints.

These results support the results found by Girelli et al. [1] and Dominick et al. [18] (where in both cases, CA → BY40 su r passed pGB). However, these result s cont rad ict the results found by Bhaloo [19] (where pGB was found to have surpassed CA → BY40). Given that the grading system in those experiments measured the amount of clear ridge detail devel-oped whereas this experiment measured the quality of the ridge detail developed, a direct comparison between the experiments may not be accurate.


Submersion Test ResultsThe results of the post-submersion test are displayed in

Table 6 and Figure 9. The results of the eGB samples of the submersion test and

the eGB samples from the comparison test showed vir tually no degradation in post-development print quality. This was confirmed using a Mann-Whitney test with a 95% confidence level. The resulting p value of 0.7197 indicates the fingerprint grades of the varied factor (the pre-treatment submersion in water) were not significantly different from the grades from the eGB samples in the comparison test.

Avg. Grade Std. Dev.eGB 3.4 0.61

Table 6 eGB post-submersion.

Figure 9An example of a cartridge developed using the electrodeposition of

gun blue following submersion in water.


Nickel-Plated Brass Cartridge Case Test ResultsThe results of the test are displayed in Table 7 and Figure 10.The average time for development on the nickel-plated brass

cartridges was 48.3 seconds and the quality of development was much more variable across the surface of the samples. This is likely due to the differential redox potential of the nickel-plating versus the brass. As a result, under normal circumstances, this technique is not recommended over the alternatives on nickel-plated brass cartridges without further optimization.

Avg. Grade Std. Dev.eGB 2.9 0.77

Table 7 eGB nickel-plated cartridges.

Figure 10 An example of electrodeposition of gun blue on a nickel-plated

cartridge case.


Other ObservationsIn addition to the experimental results, two other general

observations were noted. First , the deposit ion across the substrate was much more even when eGB was used than when pGB was used, a problem previously noted by Girelli et al. [1] This variable deposition was very evident during the initial preparation of the experiment. Some of the fired brass cartridge cases collected from the firing range showed evidence of corro-sion. Despite an attempt to screen out these visibly corroded cartridges prior to treatment, some of them were still treated, some using eGB and some using pGB, while determining the initial set up. The presence of the corrosion made little or no difference on the eGB-treated sample, but the corrison had an extremely negative effect on the pGB-treated sample. The samples were not graded at the time, but an example of each can be seen in Figure 11. The eGB sample likely would have been graded a 4; the pGB sample likely would have been graded a 2. Although the results were similar for all the corroded samples, the effective sample size was only nine samples, and the results should therefore be weighed accordingly.

Figure 11Left: Corroded cartridge treated using eGB.

Right: Corroded cartridge treated using passive GB deposition.


Second, this technique is inexpensive, fast, and very acces-sible. The average cost per cartridge treated in this study was estimated at $0.03 CDN (approximately $ 0.0225 USD). The development took about 18 seconds per cartridge. Supplies that can be found in every forensic identification department were used. It requires no additional training for a forensic identifica-tion specialist to use, and the technique could even be performed at a crime scene if necessary.

Future ConsiderationsThe performance does merit further examination for treat-

ing brass car tridge cases and possibly other metal exhibits. An experiment that should be investigated is a comparison against palladium deposition and sequential CA → GB → BY40 techniques, which have performed the best in previous labora-tory studies [1], [18]. An additional consideration is that this experiment was performed with loaded prints and with only one donor. Follow-up experiments should consider an operational or pseudo-operational approach to determine whether this can be applied to less-than-ideal impressions.

Given the negative effects on fingerprints noted by Girelli et al. [1] during the firing of the bullet and the resulting low success rate in operational cases noted by Bentsen et al. [2], a critical follow-up experiment would be to determine whether eGB will show similarly advantageous results on f ired cartridge cases. The author is currently taking steps to perform this experiment.

Conclusion The goal of this experiment was to determine how applying a

potentiostatic electrodeposition technique to gun blue deposition would affect f ingerprint development on cartridges cases and how it would compare to cyanoacrylate → brilliant yellow 40.

The results showed eGB gave a more even distribution across the substrate than did pGB, was more resistant to degradation than pGB when used on corroded cartridge cases, and was more efficient than either of the compared development techniques. The results further showed a submersion of the impressions prior to treatment did not significantly impact its treatment using eGB.

An evaluation of the results showed electrically stimulated deposition of gun blue (eGB) developed signif icantly higher quality prints in a laboratory setting than both the passive gun


blue deposition (pGB) development technique and the sequential cyanoacrylate → brilliant yellow 40 (CA → BY40) development technique.

In summary, the electrically stimulated deposition of gun blue, defined as a potentiostatic 1.5V electrocell with a 15% dilution of gun blue (0.75% selenious acid, 0.45% cupric sulfate, and 0.45% cupric phosphate) installed with the cartridge case as the anode, provided a simple and cost-effective method that gave greater clarity and efficacy than the simple passive deposi-tion of gun blue or treatment using sequential cyanoacrylate → brilliant yellow 40.

AcknowledgmentThe author wishes to acknowledge the assistance of Cst.

Robin Thibault and Cpl. Martin Villeneuve for helping with the firearms, the members of the Montreal Forensic Identification Section for lending their expertise with the grading, and Daniel Hockey for his assistance with the statistical analyses. Finally, the author wishes to acknowledge Sgt. (ret.) Serge Bertrand for his support and mentorship at a time when it was most needed.

For further information, please contact:Aaron DoveMontreal FIS RCMP 4225 Dorchester BoulevardWestmount, QC, H3Z 1V5 [email protected]

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