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J Forensic Sci, 2019

doi: 10.1111/1556-4029.13984
TECHNICAL NOTE Available online at: onlinelibrary.wiley.com

CRIMINALISTICS

Nadia Geusens, B.Sc.; Bart Nys, Ph.D.; and Sebastien Charles, Ph.D.

Implementation and Optimization of the


Sodium-Rhodizonate Method for
Chemographic Shooting Distance Estimation†

ABSTRACT: In shooting incident investigations where it is important to estimate the shooting distance, the sodium-rhodizonate coloring
method has been used for the visualization of GSR patterns extensively. This publication describes the optimization of this method by the use
of a heated press for the transfer of GSR traces on garments, as well as variation of a number of other important process parameters. Our final
aim for this project was to prepare a formal validation of the coloring method as prerequisite for its inclusion into the scope of ISO17025-certi-
fied methods in the GSR Laboratory. A number of important factors and process parameters were identified, such as buffer composition and
pH, type of textile used as a substrate and resolution of the documentation of the results. Results were tested using a synthetic proficiency test.
Our optimized method has been found to be a very effective technique for visualization of macroscopic GSR traces.

KEYWORDS: forensic science, gunshot residue analysis, shooting distance determination, sodium-rhodizonate test, gunshot residue pattern
visualization, optimization of laboratory method, implementation of a hot press

When a cartridge of “classic” (i.e., lead-containing primer) of acetic acid. The filter paper and garment were covered with
ammunition is fired at short range, small lead particles and other extra sheets of absorbent paper to form a sandwich. This sand-
primer residues are deposited around the bullet hole in a specific wich was finally pressed with a hot iron (1,2) until completely
pattern. These patterns are produced by the cloud of the expand- dry. Next, a freshly prepared saturated solution of sodium-rhodi-
ing gases which deposit the small lead particles on the victim’s zonate in distilled water was sprayed onto the dry filter paper,
clothing. The source of the lead particles can be from the surface forming the pink lead-rhodizonate spots. Finally, a 2.8 pH tar-
of a lead bullet, the core of a jacketed bullet, or lead compounds taric buffer solution was sprayed on the filter paper to stabilize
in the priming mixture itself. The size and density of the pattern the formed complexes.
form the basis for estimating the distance between muzzle and A Canon Ixus 285 HS with 20.1 MP was used to take a pho-
victim/target at het time of discharge. For this purpose, a series tograph of the filter paper with the gunshot residue pattern to
of test firings is performed at various known distances on a ser- document the result, as the color of the complex fades rapidly
ies of white cotton cloth targets preferably using the litigious by hydrolysis and photolysis.
firearm and ammunition to maximize reproducibility. The purpose of this article is to present a revised procedure for
The sodium-rhodizonate test (1,2) is used afterward to visual- the sodium-rhodizonate test solely. The modified Griess test has
ize the lead particles by forming a lead–rhodizonate complex not been used in our laboratory for many years, because after years
which is colored pink. Once the gunshot residue patterns on of executing it in the past, we found almost never a valuable con-
these targets have been revealed using this method, an estimation tribution of this test to the outcome of the distance estimation.
of the probable firing distance can be made by comparison with Therefore, this test has been excluded from further exploration.
results of the reference shots at known shot ranges. We have optimized the transfer efficacy by replacing the hot iron
In our laboratory, the method used previously to this study that was previously used, as well as the quality of documentation
consisted of transferring the pattern from the clothing to a chro- of the pattern. We also adapted the preparation of the rhodizonate
matographic filter paper, previously sprayed with a 15% solution solution by dissolving it directly in the buffer solution (3).

Materials and Methods


1
National Institute for Criminalistics and Criminology-Criminalistics,
Vilvoordsesteenweg, 100 1120 Neder-over-heembeek, Brussels, Belgium. The victim’s clothing is examined visually for the presence of
Corresponding author: Nadia Geusens, B.Sc. E-mail: nadia.geusens@just. suspected ballistic entrance hole(s). A square of approximately
fgov.be 30 9 30 cm is subsequently cut out of the garment, centered

Presented in part at the 24th Annual Meeting of the ENFSI Firearms/ around the hole. This is then laid upon a piece of paper a bit lar-
GSR Working Group, October 11-13, 2017, in Espoo, Finland; and at the
Project Home/2011/ISEC/AG/4000002489 Final Meeting of ENFSI Firearms/
ger than the target to support it. A WhatmanTM filter paper type
GSR Working Group April 13-15, 2016, in Dresden, Germany. 5 (GE Healthcare Life Sciences HQ 100 Results Way, Marlbor-
Received 26 July 2018; and in revised form 9 Nov. 2018; accepted 29 ough, MA 01752, USA) is placed upon the target material. The
Nov. 2018. exact position of the entrance hole is marked on the filter paper.

© 2019 American Academy of Forensic Sciences 1


2 JOURNAL OF FORENSIC SCIENCES

A 15% acetic acid solution is sprayed on the filter paper until


moist. The filter paper is then covered with two more sheets of
WhatmanTM filter paper type 595, cut to a dimension slightly lar-
ger than the circle of the filter paper which has a diameter of
24 cm, to form a sandwich. The whole package is placed inside
a Stahls’ Hotronixâ Sprintâ Mag Digital 40 9 50 cm press
(Stahls HQ 6353 14 Mile Road Sterling Heights, MI 48312
USA).
The optimal settings of the press for bloody garments, as
determined during the validation of the chemographic method,
are selected. Typical pressing conditions are as follows: tempera-
ture 76°C, pressure setting “2,” and pressing time 60 sec (Note:
blood-free clothing can be treated at a higher temperature:
110°C is found to be ideal).
After the transfer phase, the filter paper is sprayed with a
freshly prepared saturated sodium rhodizonate/buffer solution (3)
(buffer composition: 4.75 g sodium bitartrate monohydrate +
3.75 g tartaric acid in 250 mL H2Odest).
The result is finally scanned at 600 DPI using a Plustek Optic-
Slim 1180 flatbed scanner (Plustek HQ 13F-1, No.3, Yuan Qu FIG. 2––Previous method transfer using a hot clothing iron.
St., 115 Nankang Taipei, Taiwan R.O.C). During the scanning
phase, a transparent plastic pocket holding the filter paper pro-
tects the scan bed.
depending on their thickness and composition. There is however,
Results and Discussion one shortcoming with the use of this type of press in that the
pressure appeared not to be completely homogeneous over the
The sodium-rhodizonate method has been optimized with the entire surface. This was discovered when performing a test using
introduction of a Stahls’ Hotronixâ Sprintâ press (4) (Fig. 1) to a synthetic resolution test sample (S1959R-1 PLANOTEC
improve the transfer of the gunshot residue patterns as compared chemographical test for homogeneity and resolution for filter
to the use of the hot clothing iron (Fig. 2). By applying a repro- paper) (5) (Fig. 3). This sample was developed as part of the
ducible pressure and temperature, a controlled environment is EU project (6,7) (D. Neimke, personal communication, April
assured and the transfer process is more effective and repro- 13–15, 2016) (LH. Niewoehner, personal communication, Oct
ducible. This has the advantage that all the reference targets can 11–13, 2017): “Proficiency test on shooting distance determina-
be treated in the same circumstances as the victim’s clothing (or tion” (With support of the Prevention of and Fight against Crime
other items of evidence). Another advantage is that the amount Programme European Commission—Directorate General Home
of pressure exerted on the reference target surfaces is adjustable, Affairs Project Home/2011/ISEC/AG/2489), of which the goal

FIG. 3––Resolution test developed in the course of the ISEC project: “Pro-
FIG. 1––Stahls’ Hotronixâ Sprintâ Mag Digital 40x50 cm press used in ficiency test on shooting distance determination.”
the transfer phase.
GEUSENS ET AL. . OPTIMIZED SHOOTING DISTANCE ESTIMATION 3

FIG. 6––Digital Scan performed at 600 DPI.

FIG. 4––Homogeneity test developed in the course of the ISEC project:


“Proficiency test on shooting distance determination.” sprayed onto the filter paper is obviously smaller than when two
separate solutions are used consecutively. This renders the scan-
ning of the filter paper easier, as it is not too wet when scanned.
Note that when working at a temperature of 110°C, the filter paper
was the improvement of quality in chemo graphic GSR investi- is still hot when sprayed and most of the liquid quickly evapo-
gations. In fact, the resolution and homogeneity (Fig. 4) over rates, leaving the filter paper dry to be scanned. The confirmation
one half of the pressed surface was very good, whereas the reso-
lution over the other half was questionable. This resolution test
was unfortunately only performed once, because at that time
these testing materials were not yet commercialized and only
one project prototype was available in the laboratory. Since then,
however, the synthetic reference materials are being commercial-
ized by PLANO (PLANO GmbH; Ernst-Befort-Str. 12; 35578
Wetzlar; Germany) and testing is continuing using higher pres-
sure settings. These synthetic reference samples have therefore
proven to be indispensable in the context of the validation pro-
cess of the method.
Further, the chemical phase of the procedure was improved by
adding the sodium-rhodizonate powder directly to the buffer solu-
tion (3). By using this combined solution, the amount of liquid

FIG. 5––Plustek OpticSlim 1180 flatbed scanner. FIG. 7––Digital photograph taken with Canon Ixus 285 HS with 20.1 MP.
4 JOURNAL OF FORENSIC SCIENCES

of lead with HCl is not performed in our laboratory because the 2. Dillon JH. The sodium rhodizonate test: a chemically specific
selectivity of the rhodizonate reaction for lead and barium has chromophoric test for lead in gunshot residues. AFTE J 1990;22(3):
251–6.
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A. Brouwer-Stamouli, personal communication, April, 2007). sodium rhodizonate test for the detection of lead originating from firearm
Finally, a Plustek OpticSlim 1180 flatbed scanner (8) (Fig. 5) discharges. J Forensic Sci 1996;41(6):1046–51.
was used to document the residue pattern at 600 DPI resolution 4. Stahls’ International. Hotronixâ Sprintâ Press; http://www.stahlsinter
national.com/eng/p-hotronix-auto-open.php (accessed July 24, 2018).
(Fig. 6). This yields a much more satisfactory result in display-
5. Planotec Chemographic Test Sample S1959R-1 Homogeneity and Resolu-
ing details as compared to the digital photographs that were tion for Filter Paper; -https://www.plano-em.de/katalog/eichstandards-und-
taken previously with the Canon Ixus 285 HS with 20.1 MP testobjekte/planotec-gsr-partikelanalyse-kalibrierkit-und-chemographie-te
(Fig. 7). For particles of even smaller dimensions, the resolution stprobe/#cid2244 (accessed July 24, 2018).
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Development, design, and realization of a proficiency test for the forensic
The validation process of this method has been terminated determination of shooting distances - FDSD 2015. Forensic Chem
and will be the subject of the next articles that are currently 2016;1:22–30.
under redaction: “Validation and Optimization of the Sodium 7. Niewoehner LH, Neimke D, Barth M. Final report on the FDSD2015 pro-
Rhodizonate Method Part I and Part II.” ficiency test on shooting distance determination, 2017; https://www.resea
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References 2018).
8. Plustek. Plustek OpticSlim 1180 flatbed scanner; http://plustek.com/ne
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