Organic Gunshot Residues Research Articles

The development of screen-printed electrodes modified with gold and copper nanostructures for analysis of gunshot residue and low explosives

Due to their portability, sensitivity, and ease of use, electrochemical sensors have recently become a popular method for rapid, on-site analysis. This study presents a proof of principle for the application of modified screen-printed carbon electrodes (SPCEs) for the detection of signature metals (Pb, Sb, and Zn) commonly found in gunshot residue (GSR), as well as for the detection of nitrate/nitrite in organic GSR and low explosives. To achieve these two aims, we have examined various electrode surface modifications. For metal detection, SPCEs were modified by electrodeposition of gold to improve sensitivity. GSR samples taken from two types of cartridge cases and shooting-related surfaces were analyzed using the Au-modified SPCEs. For nitrate/nitrite analysis, further electrode surface modifications were carried out by depositing Cu(II) onto the Au-SPCEs to enhance signal through catalytic activity of the copper surfaces. Both unburned and burned forms of black powder samples, as well as burned smokeless powder, were then analyzed using the Cu/Au-SPCEs. In conclusion, due to their low cost and portability, these sensors should prove useful for rapid forensic examination.

Point-and-shoot: portable Raman and SERS detection of organic gunshot residue analytes

Raman spectroscopy is one of many tools available to verify the molecular composition of an analyte. Due to its non-destructive nature and its ability to accurately discern differences in closely related molecular structures, it has become invaluable in many fields, including its potential for forensic gunshot residue detection. Firearm-related fatalities in the United States continue to rise and many of them remain unsolved. This necessitates tools that are better equipped to aid in the investigation of firearm-related crimes, capable of high-throughput analysis yet remaining sensitive to give accurate and valuable information. The comparative downside of Raman spectroscopy to neighboring techniques like mass spectrometry and nuclear magnetic resonance is its lower sensitivity. Surface-enhanced Raman spectroscopy allows for the benefits of Raman spectroscopy alongside the added lower limit of detection with the simple application of nanoparticles, typically gold. Unfortunately, these benefits have seen little on-site application due to the difficulty of translating methods from conventional tabletop Raman spectrometers to point-and-shoot portable Raman spectrometers which have even lower sensitivities (higher limits of detection). Herein, we outline a versatile methodology for the detection of 6 organic gunshot residue components (diphenylamine (DPA), ethyl centralite (EC), 2,4-dinitrotoluene (2,4-DNT), 2-nitrodiphenylamine (2-nDPA), 4-nitrodiphenylamine (4-nDPA), and N-nitrosodiphenylamine (N-nDPA)) in liquid-phase that allows us to detect millimolar concentrations of these analytes. Furthermore, we report calculated vibrational assignments for these 6 analytes in solution, alongside detailed peak-by-peak analyses on a portable instrument. We showed signal enhancement and lower LODs through our data processing as well as a proof-of-concept SERS enhancement in a complex liquid-phase matrix, with an increased sensitivity of 700% when using SERS.

Capabilities and limitations of GC–MS and LC-MS/MS for trace detection of organic gunshot residues from skin specimens

Capabilities and limitations of GC–MS and LC-MS/MS for trace detection of organic gunshot residues from skin specimens

Transfer and persistence studies of inorganic and organic gunshot residues using synthetic skin membranes

The complex nature of gunshot residue (GSR) transfer and persistence introduces challenges and skepticism in its evidential value. Therefore, this work evaluates the behavior and movement of inorganic and organic gunshot residues to assist in the evidence interpretation. The study encompassed over 650 samples, including 247 collections from human skin after firing a gun and 405 synthetic skin and fabric substrates after depositing a characterized pGSR/OGSR standard. Transfer and persistence experiments were evaluated on different substrates (hands, ears, nostrils, forehead, hair, fabrics, and synthetic skin), at different times after firing (0 to 6 h), and common post-shooting activities (rubbing hands, handshaking, running, washing hands and fabrics). Ground truth knowledge of particle counts and analyte concentrations was used to calculate the recovery for inorganic and organic constituents from clothing and a synthetic skin membrane (StratM®). Authentic shooter skin samples were compared to synthetic skin to establish the validity of skin-substitute models. During controlled experiments, inorganic particles persisted longer than OGSR on inactive samples (9% and < 25% loss at 6 hrs, respectively), but inorganic particles were more prone to secondary transfer than OGSR (up to 35% vs. 0% transfer, respectively). High percentages of particles were lost during vigorous activities like washing hands (99% loss) or rubbing hands (55% loss). In comparison, less loss was observed during the same studies for OGSR (<21%). This study offers a deeper understanding of gunshot residue transfer and persistence mechanisms that can assist analysts and investigators in improving sample collection and interpretation of evidence.

Should inorganic or organic gunshot residues be analysed first?

Gunshot residues (GSR) collected during the investigation of firearm-related incidents can provide useful information for the reconstruction of the events. Two main types of GSR traces can be targeted by forensic scientists, the inorganic (IGSR) and the organic GSR (OGSR). Up to now, forensic laboratories have mainly focused on the detection of inorganic particles on the hands and clothes of a person of interest using carbon stubs analysed by scanning electron microscopy coupled with energy dispersive X-ray spectrometry (SEM/EDS). Several approaches have been proposed to also analyse the organic compounds since they might bring additional information for the investigation. However, implementing such approaches might disrupt the detection of IGSR (and vice versa depending on the applied sequence of analysis). In this work, two sequences were compared for the combined detection of both types of residues. One carbon stub was used for collection, and the analysis was performed either by targeting the IGSR or the OGSR first. The aim was to evaluate which one allows maximum recovery of both types of GSR while minimising losses that might occur at different stages of the analysis process. SEM/EDS was used for the detection of IGSR particles while an ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) was used for the analysis of OGSR compounds. Extracting OGSR first required the implementation of an extraction protocol that did not interfere with the IGSR particles present on the stub. Both sequences allowed good recovery of the inorganic particles since no significant difference was observed in the detected concentrations. However, OGSR concentrations were lower after IGSR analysis than before for two compounds (ethyl and methylcentralite). Thus, it is advised to extract rapidly the OGSR before or after IGSR analysis to avoid losses during the storage and analysis processes. The data also indicated that there was a low correlation between IGSR and OGSR highlighting the potential of a combined detection and analysis of both types of GSR.

Identification and highly selective differentiation of organic gunshot residues utilizing their elemental and molecular signatures

Firearm related evidence is of great significance to forensic science. In recent years, many researchers have focused on exploring the probative value of organic gunshot residue (OGSR) evidence, which is often bolstered by many factors including recoverability. In addition, OGSR analysis has shown the potential to achieve differentiation between OGSRs generated from various ammunition brands and/or calibers. Raman spectroscopy is a vibrational spectroscopic technique which has been used in the past for gunshot residue analysis—including OGSR specifically. Raman spectroscopy is a nondestructive, highly-selective, simple, and rapid technique which provides molecular information about samples. LIBS or Laser-Induced Breakdown Spectroscopy is a simple, robust, and rapid analytical method which requires minimal to no sample preparation and a small amount of sample for analysis. LIBS provides information on the elemental compositions of samples.In this study, Raman spectroscopy and LIBS were used together in sequence in an attempt to achieve the specific identification and characterization of OGSR particles from ammunition types which were closely related. The main goal was to determine if this method had the potential to differentiate between various ammunition types of the same caliber and produced by the same manufacturer, and generated under identical firing conditions. High-resolution optical microscopy documented the OGSR particles’ morphologies and Raman spectroscopy was used to identify particles as OGSRs. Finally, LIBS analysis of the OGSR particles was carried out. Advanced chemometric techniques were shown to allow for very successful differentiation between the OGSR samples analyzed.

A feasibility study of direct analysis in real time-mass spectrometry for screening organic gunshot residues from various substrates.

This study reports the use of direct analysis in real time-mass spectrometry (DART-MS) for the detection of organic gunshot residues (OGSR) in a variety of matrices of interest for forensics, customs, and homeland security. Detection limits ranged from (0.075 to 12) ng, with intra- and inter-day reproducibility below 0.0012% CV. The collection of mass spectra at multiple in-source collision-induced dissociation (is-CID) voltages produced distinctive mass spectral signatures with varying levels of fragmentation and allowed differentiation of isomers. To test method performance, a collection of 330 authentic specimens from various substrates were analyzed - (1) neat smokeless powders, (2) spent cartridge cases, (3) burnt particles removed from clothing via carbon stubs or (4) with tweezers, and hand samples from (5) non-shooters, and (6) shooters. A subset of hand specimens (n = 80) was further analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) for confirmation and comparison. Seven types of ammunition from five manufacturers and two calibers were monitored for OGSR profiles with similar compositions observed for paired sets (e.g., unburnt smokeless powder and the respective residues on spent cartridges, clothing, and hands). No false positives were observed across all datasets. A 100% true positive rate (TPR) was observed for all substrates except the shooters' hands. Depending on the ammunition type and classification criteria, the shooters' hands exhibited a TPR ranging from 19% to 73%. The results show that DART-MS is feasible and versatile for fast screening of OGSR across various substrates but may benefit from alternative approaches to improve detection at trace levels.

Hierarchical Modelling of Raman Spectroscopic Data Demonstrates the Potential for Manufacturer and Caliber Differentiation of Smokeless Powders

Gunshot residue (GSR) is an important type of forensic trace evidence produced when a firearm is discharged. Currently, inorganic GSR particles are used for establishing the fact of shooting. The organic gunshot residue (OGSR) has been recently shown to have great potential for providing additional information vital for the crime scene investigation. Smokeless powder is the precursor to OGSR and one of its chemical components. In this study, Raman spectroscopy and chemometric modeling were used to analyze smokeless powder extracted from ammunition cartridge cases. The proposed hierarchical model demonstrated great potential for determining the manufacture and the bullet type based on the analysis of smokeless powder. Expanding the developed approach to the analysis of OGSR will be needed to make it a useful tool for law enforcement agencies.

Oral fluid as a new investigative matrix for the determination of organic gunshot residue exposure

In recent years, increased use of ammunition without lead and heavy metals was observed, leading to a growing interest in the detection of organic gunshot residues (OGSR) as evidence of firearms related crimes. The wide range of compounds belonging to the OGSR class hinders their mass spectrometric detection as different ionization techniques may be needed to obtain good results for all compounds.The purpose of this work was the development of a reliable analytical method by means of UHPLC-HRMS for the determination in oral fluid (OF) of the most common explosives and the most used stabilizers, arising from fire discharge and post-deflagration residues.For this purpose, SPE was used for OF clean-up before UHPLC-HRMS analysis. All target analytes were chromatographically separated by means of a Polar-C18 column. A chlorinated compound was added to the mobile phases in order to promote the formation of chloride adduct ions in the electrospray ion source operating in polarity switching to allow the best conditions for each analyte. The detection was conducted by means of a high-resolution mass spectrometer equipped with Orbitrap technology working in data dependent acquisition mode, in order to detect both the precursor ions and/or the most intense fragments for stabilizers.To verify its potential, the method was tested on real samples: a shooting session was performed in an open shooting range; the shooters fired from 2 to 20 rounds with a 9x21 caliber, thereafter OF was sampled. Samples were analyzed confirming that explosives may be detected in OF; the use of this matrix may be of great interest for investigative purposes as it is less affected by secondary transfer when compared to other commonly sampled matrices. The developed method could be a useful tool for law enforcement authorities for the detection of explosives in forensic potential scenarios, including biological matrices.

LC-MS/MS monitoring for explosives residues and OGSR with diverse ionization temperatures in soil &amp; hands: 30 minutes for extraction + elution

Abstract A fast LC-APCI-MS/MS screening/confirmation method was developed and validated for trace analyses of 18 analytes which are explosives and organic gun shot residues including the challenging ones with diverse ionization conditions, in soil and on hands. (+) and (−) ionization modes were used after a single-step, low-volume solvent extraction procedure developed using methanol. Tape-lifting, stub, alcohol wipes, cotton bud were compared for collecting the residues from hands of a shooter. Tape-lifting and stub gave the highest recoveries and tape-lifting was chosen. Gradient elution system using ammonium chloride:methanol was developed. Whole procedure lasted approximately 30 min, was validated in both matrices, applied to real samples as post-blast residues, smokeless powder and the hands of a shooter, after shooting. Most of the recoveries were &gt;80% and since all the precisions were &lt;15%, quantitation was possible for all. Limit of Detection (LOD) and Limit of Quantification (LOQ) values were: 0.2–54.1 and 0.3–190.0 ngg−1 in soil, and 0.2–132.3 and 1.1–355.0 ngg−1 in tape-lift.

Comparison of portable and benchtop electrochemical instruments for detection of inorganic and organic gunshot residues in authentic shooter samples

Analysis of gunshot residue currently lacks effective screening methods that can be implemented in real time at the crime scene. Historically, SEM-EDS has been the standard for analysis; however, advances in technology have brought portable instrumentation to the forefront of forensic science disciplines, including the screening of GSR. This study proposes electrochemical methods with disposable screen-printed carbon electrodes for GSR screening at the laboratory and points of care due to their rapid, cost-efficient, and compact platform. GSR residues were extracted from typical aluminum/carbon adhesive collection stubs and analyzed via square-wave anodic stripping voltammetry. Benchtop and portable electrochemical instruments were compared for the assessment and classification of authentic shooter samples by monitoring a panel of inorganic and organic GSR elements and compounds including lead, antimony, copper, 2,4-dinitrotoluene, diphenylamine, nitroglycerin, and ethyl centralite. The evaluation included the assessment of figures of merit and performance measures from quality controls, nonshooter, and shooter data sets. Samples collected from the hands of 200 background individuals (nonshooters), and shooters who fired leaded ammunition (100) and lead-free ammunition (50) were analyzed by the benchtop and portable systems with accuracies of 95.7% and 96.5%, respectively. The findings indicate that electrochemical methods are fast, sensitive, and specific for the identification of inorganic and organic gunshot residues. The portable potentiostat provided results comparable with the benchtop system, serving as a proof-of-concept to transition this methodology to crime scenes for a practical and inexpensive GSR screening that could reduce backlogs, improve investigative leads, and increase the impact of gunshot residues in forensic science.

Detection of organic gunshot residues from human hands using direct sample analysis‐time of flight‐mass spectrometry

AbstractThe organic gunshot residues (OGSRs), specifically methyl centralite (MC; 1,3‐dimethyl‐1,3‐diphenylurea), ethyl centralite (EC; 1,3‐diethyl‐1,3‐diphenylurea), 2,4‐DNT (2,4‐dinitrotoluene), and TNT (trinitrotoluene), are characteristic compounds for which forensic analysts test determining if a person has discharged a firearm. A set of 200 samples from 50 shooters were collected as part of the validation study. Pistol 9 mm and special revolver .38 were fired at indoor and outdoor shooting ranges. The development of a methodology based on direct analysis of samples‐time of flight‐mass spectrometry (DSA‐TOF‐MS) made it possible to identify the main components of organic shot residues, which gave the possibility to introduce a new method of analysis of shot residues in the Chilean supply area. The DSA‐TOF‐MS provided extensive information on the composition of the shot residues: MC, EC, 2,4‐DNT, and TNT. Samples taken from the trigger hands required minimal sample preparation that reduced analyses time. With the implementation of new alternative analytical methodologies, a great step would be taken in the analysis of OGSRs, because now there is no such technique for its analysis in Chile, and the results would also complement the existing inorganic elemental analyses generated during a gunshot.

An application example of the likelihood ratio approach to the evaluation of organic gunshot residues using a fictional scenario and recently published data

The analysis of gunshot residues (GSR) can provide important information with regard to the involvement of a person of interest (POI) in a firearm-related incident. Organic gunshot residues (OGSR) have been investigated in order to provide additional and complementary information to the traditional inorganic gunshot residue (IGSR) particles detected by scanning electron microscopy (SEM). Currently, many procedures and analytical methods have been developed to detect OGSR-related compounds collected from the shooter’s hands. However, such studies provide no information regarding the inclusion of such results in an activity level evaluation for discharging a firearm. The aim of this article is to assess the feasibility of using the likelihood ratio (LR) approach as a tool to evaluate OGSR results for activity level propositions. The developed model focuses on the assignment of an LR for several compounds detected in OGSR. A simple worst-case simulation was investigated in order to assess the applicability of the LR approach to evaluate OGSR traces. This simulation highlighted the importance of addressing an appropriate pair of activity level propositions when evaluating the results.

Noninvasive, visual examination for the presence of gunshot residue on human skin.

When a firearm is discharged, the highest concentration of gunshot residue (GSR) is located on a shooter's hands, forearms, and clothing. Currently, collecting GSR from an individual's hands is accomplished with a carbon disk that is submitted for confirmatory analysis in a forensic laboratory. Presumptive chemical tests can be performed in the field, but these tests consume a portion of the GSR particles leaving a reduced amount of evidence available to be collected and sent to a forensic laboratory. An abundance of research exists for detecting GSR particles instantly on different fabrics using an alternate light source (ALS). This study expanded on that research and developed a noninvasive, visual examination to detect GSR on a suspected shooter's hands without destroying or removing any particles prior to collection. The hands of individuals who recently discharged a firearm were examined under a light source between 475 and 530nm and an infrared (IR) camera. The fluorescent particles observed on a shooter's hands under 520nm were similar in size and appearance to GSR particles observed on fabrics under an ALS. The fluorescent particles were collected and analyzed for GSR, and the results indicated that GSR particles were present. More testing needs to be conducted to determine if the fluorescent particles observed are inorganic or organic GSR particles. There is also potential to detect GSR under IR light; however, more research needs to be conducted to determine the composition of the particles observed after image enhancement.

Evaluation of the Simultaneous Analysis of Organic and Inorganic Gunshot Residues Within a Large Population Data Set Using Electrochemical Sensors*, †.

The increasing demand for rapid methods to identify both inorganic and organic gunshot residues (IGSR and OGSR) makes electrochemical methods, an attractive screening tool to modernize current practice. Our research group has previously demonstrated that electrochemical screening of GSR samples delivers a simple, inexpensive, and sensitive analytical solution that is capable of detecting IGSR and OGSR in less than 10min per sample. In this study, we expand our previous work by increasing the number of GSR markers and applying machine learning classifiers to the interpretation of a larger population data set. Utilizing bare screen-printed carbon electrodes, the detection and resolution of seven markers (IGSR; lead, antimony, and copper, and OGSR; nitroglycerin, 2,4-dinitrotoluene, diphenylamine, and ethyl centralite) was achieved with limits of detection (LODs) below 1µg/mL. A large population data set was obtained from 395 authentic shooter samples and 350 background samples. Various statistical methods and machine learning algorithms, including critical thresholds (CT), naïve Bayes (NB), logistic regression (LR), and neural networks (NN), were utilized to calculate the performance and error rates. Neural networks proved to be the best predictor when assessing the dichotomous question of detection of GSR on the hands of shooter versus nonshooter groups. Accuracies for the studied population were 81.8 % (CT), 88.1% (NB), 94.7% (LR), and 95.4% (NN), respectively. The ability to detect both IGSR and OGSR simultaneously provides a selective testing platform for gunshot residues that can provide a powerful field-testing technique and assist with decisions in case management.

Tandem detection of organic and inorganic gunshot residues using LC–MS and SEM-EDS

Gunshot residue (GSR) is a valuable form of forensic trace evidence in the investigation of firearms crime. The current gold-standard approach does not include the analysis of organic components of the residues, which may be a deficiency, particularly in cases where there is little to no inorganic gunshot residue (IGSR) present or its attribution to a firearm source is ambiguous. A solvent extraction method was used for the extraction of organic GSR (OGSR) from the most common sampling device used to collect IGSR (i.e., SEM stubs with double-sided carbon adhesive tape). It was found that extraction did not significantly disturb inorganic GSR present on stubs, which raises the possibility that a valuable, comprehensive tandem analysis of both organic and inorganic GSR may be implemented using a single and commonly used residue collection device.The organic extract was analysed using Ultra High Performance Liquid Chromatography coupled to an Ion Trap Mass Spectrometer using Electrospray Ionisation (UHPLC-ESI-MS/MS), with preliminary results indicating that organic components can be extracted and detected at levels appropriate to casework GSR analysis. Testing of traces collected from the hands of recent shooters showed detection of stabiliser compounds typical of OGSR, which were confirmed to be present in the test ammunition’s propellant. Total analysis time is approximately 30min per specimen, including preparation, instrumental analysis and data review.As the first step in the examination of GSR stubs in relation to a shooting case, extraction of organics and analysing them for the presence of OGSR may bring two operational benefits. First, that approach may be a useful way to determine which stubs warrant priority examination for IGSR, and second, it offers the possibility of providing relatively rapid case information to investigators.

Combined Collection and Analysis of Inorganic and Organic Gunshot Residues.

Gunshot residue (GSR) analysis and their interpretation provide crucial information on a criminal investigation involving the use of firearms. To date, several approaches have been proposed for the implementation of a combined sampling and analysis of inorganic (IGSR) and organic GSR (OGSR). However, it is not clear at this stage if concurrent analyses of both types of residue might be detrimental to the analysis of IGSR currently applied in forensic laboratories. Thus, this work aims to compare and evaluate three different protocols for the combined collection and analysis of IGSR and OGSR. These methods, respectively, involve the use of a modified stub (with two halves, one for the detection of IGSR and the other for the analysis of OGSR); the sequential recovery of GSR with two stubs mounted with different adhesives (double-sided carbon tape and Tesa® TACK) and the sequential analysis of IGSR and OGSR from a single carbon stub following carbon deposition. The detection of IGSR was carried out using SEM-EDX, while OGSR analysis was performed using ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). Obtained results for experiments performed using Geco Sinoxid® ammunition indicated that sequential analysis was the most suitable protocol for the combined collection and analysis of both IGSR and OGSR. A higher number of inorganic (characteristic and consistent) particles and higher concentrations of ethylcentralite, N-nitrosodiphenylamine, diphenylamine, and nitroglycerin were recovered with this method.

Screening of Gunshot Residue in Skin Using Attenuated Total Reflection Fourier Transform Infrared (ATR FT-IR) Hyperspectral Microscopy.

The detection of gunshot residues (GSR) in skin is important in criminal forensic investigations related with firearms. Conventionally, the procedure is based on the detection of metallic or inorganic residues (IGSR). In this work, we propose attenuated total reflectance Fourier transform infrared (ATR FT-IR) hyperspectral microscopy as a complementary and nondestructive technique for detection of organic GSR (OGSR). The spectra were acquired from GSR of three ammunition manufacturers, which were collected from shooter's hands by the tape-lifting method. Before spectroscopic analysis, a Na-Ca bleach solution was added to all GSR samples on the tape for destroying skin debris. Positive detection of OGSR spectra were achieved by ATR FT-IR hyperspectral microscopy. Spectra show characteristic patterns of nitrate ester compounds which agrees with the propellant chemical composition. Characteristic ATR FT-IR spectral patterns of OGSR were measured from visualized GSR particles demonstrating the potential of ATR FT-IR hyperspectral microscopy.

HPLC detection of organic gunshot residues collected with silicone wristbands

An HPLC method was developed for detection of organic gunshot residues extracted from silicone wristbands used as passive sampling devices.

Prevalence of organic gunshot residues in police vehicles

The present study investigated the organic gunshot residue (OGSR) background level of police vehicles in Switzerland. Specimens from 64 vehicles belonging to two regional police services were collected and analysed by LC-MS in positive mode. The driver’s and back seats were sampled separately to monitor potential differences between locations and to assess the risks of a suspect being contaminated by OGSR during transportation to a police station.The results showed that most of the 64 vehicles were uncontaminated (44 driver’s seats and 38 back seats respectively). Up to six of the seven targeted compounds were detected in a single sample, once on a driver’s seat and twice on back seats. The contamination frequency generally decreased as the number of compounds detected together increased. The amounts detected were in the low ng range and less than amounts generally detected just after discharge on a shooter. Our data indicated that detecting a combination of four or more compounds on a police vehicle seat appears to be a relatively rare occurrence. The background contamination observed was most probably due to secondary transfer from police officers (e.g. through recent participation in a shooting session or firearm manipulation) or from firearms stored in the vehicles. The present results might be used as a recommendation to minimize contact of a suspect with contaminated surfaces if OGSR is implemented in routine work in parallel to IGSR analysis.