Nanosculptured tungsten oxide: High-efficiency SERS sensor for explosives tracing.

The accurate and rapid identification of explosives and their toxic by-products is an important aspect of safety protocols, forensic investigations and pollution studies. Herein, surface-enhanced Raman scattering (SERS) is used to detect different explosive molecules using an improved substrate design by controllable oxidation of the tungsten surface and deposition of Au layers. The resulting furrow-like morphology formed at the intersection of the tungsten Wulff facets increases nanoroughness and improves the SERS response by over 300 % compared to the untreated surface. The substrate showed excellent reproducibility with a relative standard deviation of less than 15 % and a signal recovery of over 95 % after ultrafast Ar/O2 plasma cleanings. The detection limit for the "dried on a surface" measurement case was better than 10-8 M using the moving scanning regime and an acquisition time of 10 s, while for the "water droplets on a surface" scenario the LoD is 10-7, which is up to 2 orders of magnitude better than the UV-Vis spectroscopy method. The substrates were successfully used to classify the molecular fingerprints of HMX, Tetryl, TNB and TNT, demonstrating the efficiency of a sensor for label-free SERS screening in the practice of monitoring traces of explosives in the water medium.

Rapid sequential determination of the explosives 2,4,6-trinitrotoluene and cyclotrimethylenetrinitramine in forensic samples employing a graphite sheet sensor and cyclic square-wave stripping voltammetry.

The development of a portable analytical procedure is described for rapid sequential detection and quantification of the explosives 2,4,6-trinitrotoluene (TNT) and cyclotrimethylenetrinitramine (RDX) in forensic samples using a graphite sheet (GS). A single GS platform works as a collector of explosive residues and detector after its assembly into a 3D-printed cell. The detection strategy is based on cyclic square-wave stripping voltammetry. The cathodic scan from + 0.1 to -1.0 V with accumulation at 0.0 V enables the TNT detection (three reduction peaks), and the anodic scan from + 0.2 to + 1.55 V with accumulation at -0.9 V provides the RDX detection (two oxidation processes). Low detection limit values (0.1 µmol L-1 for TNT and 2.4 µmol L-1 for RDX) and wide linear ranges (from 1 to 150 µmol L-1 for TNT and from 20 to 300 µmol L-1 for RDX) were obtained. The sensor did not respond to pentaerythritol tetranitrate (PETN), which was evaluated as a potential interferent, because plastic explosives contain mixtures of TNT, RDX, and PETN. The GS electrode was also evaluated as a collector of TNT and RDX residues spread on different surfaces to simulate forensic scenarios. After swiping over different surfaces (metal, granite, wood, cloths, hands, money bills, and cellphone), the GS electrode was assembled in the 3D-printed cell ready to measure both explosives by the proposed method. In all cases, the presence of TNT and RDX was confirmed, attesting the reliability of the proposed device to act as collector and sensor.

Zwitterionic Energetic Materials: Synthesis, Structural Diversity and Energetic Properties.

Zwitterionic compounds are an emergent class of energetic materials and have gained synthetic interest of many in the recent years. Due to their better packing efficiencies and strong inter/intramolecular electrostatic interactions, they often ensue superior energetic properties than their salt analogues. A systematic review from the perspective of design, synthesis, and physicochemical properties evaluation of the zwitterionic energetic materials is presented. Depending on the parent ring(s) used for the synthesis and the type of moieties bearing positive and negative charges, different classes of energetic materials, such as primary explosives, secondary explosives, heat resistant explosives, oxidizers, etc., may result. The properties of some of the energetic zwitterionic compounds are also compared with analogous energetic salts. This review will encourage readers to explore the possibility of designing new zwitterionic energetic materials.

A study into the natural occurrence of inorganic ions relevant to forensic explosives investigations on human hands.

The natural occurrence of 16 inorganic ions relevant to forensic explosives investigations on human hands was studied to support the evaluation of activity-level propositions when such traces are found on the hands or in the fingerprints of a suspect. A total of 594 hand swab extracts from 297 participants throughout Europe and the United States of America were analyzed using Ion Chromatography - Mass Spectrometry. The data provides a reference framework for future covert investigations and forensic casework. The results indicate that thiocyanate, chlorate, nitrite, lithium, strontium, and barium are rarely detected on the hands of individuals who have had no direct contact with explosives (P<0.03) and in quantities below 6 µg. Perchlorate contamination sporadically occurs without deliberately handling perchlorates (P=0.03), albeit at low levels (<12 µg). It also seems that the presence of perchlorate on hands is generally related to professions that involve explosives. Detecting substantial amounts of any of these rare ions on a suspect's hands would require a specific explanation. Because legitimate activities exist that can also result in elevated levels of ions of interest on hands, the context surrounding their presence has to be carefully assessed for each individual case.

Construction and Modification of Nitrogen-Rich Polycyclic Frameworks: A Promising Fused Tricyclic Host-Guest Energetic Material with Heat Resistance, High Energy, and Low Sensitivity.

The construction and modification of novel energetic frameworks to achieve an ideal balance between high energy density and good stability are a continuous pursuit for researchers. In this work, a fused [5,6,5]-tricyclic framework was utilized as the energetic host to encapsulate the oxidant molecules for the first time. A series of new pyridazine-based [5,6] and [5,6,5] fused polycyclic nitrogen-rich skeletons and their derivatives were designed and synthesized. Two strategies, amino oxidation and host-guest inclusion, were used to modify the skeleton in only one step. All compounds exhibit good comprehensive properties (Td (onset) > 200 °C, ρ > 1.85 g cm-3, Dv > 8400 m s-1, IS > 20 J, FS > 360 N). Benefiting from the pyridazine-based fused tricyclic structure with more hydrogen bonding units and larger conjugated systems, the first example of [5,6,5]-tricyclic host-guest energetic material triamino-9H-pyrazolo[3,4-d][1,2,4]triazolo[4,3-b]pyridazine-diperchloric acid (10), shows high decomposition temperature (Td (onset) = 336 °C), high density and heats of formation (ρ = 1.94 g cm-3, ΔHf = 733.4 kJ mol-1), high detonation performance (Dv = 8820 m s-1, P = 36.2 GPa), high specific impulse (Isp = 269 s), and low sensitivity (IS = 30 J, FS > 360 N). The comprehensive performance of 10 is superior to that of high-energy explosive RDX and heat-resistant explosives such as HNS and LLM-105. 10 has the potential to become a comprehensive advanced energetic material that simultaneously satisfies the requirements of high-energy and low-sensitivity explosives, heat-resistant explosives, and solid propellants. This work may give new insights into the construction and modification of a nitrogen-rich polycyclic framework and broaden the applications of fused polycyclic framework for the development of host-guest energetic materials.

Efficient nanostructured Cs2CuBr2Cl2 perovskite as a fluorescent sensor for the selective "Switch Off" detection of nitrobenzene.

Lead halide nanostructured perovskites are well known for their excellent photoluminescence and optoelectronic properties. However, lead toxicity and instability in moisture impedes its suitability for material use. Here we synthesized a highly efficient, lead free, economical, stable Cs2CuBr2Cl2 perovskite nanocrystals (PNCs) via Ligand Assisted Re-Precipitation (LARP) method which is less explored. The sensing application of the synthesized PNCs towards nitro explosives and other small organic compounds were studied. The probe exhibited high selectivity towards nitrobenzene with a lowest detection limit of 57.64 nM. The fluorescent emission intensity was drastically quenched upon the addition of 32 µM nitrobenzene. A Stern-Volmer plot was utilized for the quantification of fluorescence quenching. Further to investigate the quenching mechanism, time correlated single photon counting spectroscopy and other photoluminescence studies were performed pointing out the possibility of fluorescence resonance energy transfer. The work has been further extended to test the capability of the probe to detect nitrobenzene in real water samples and a good recovery percentage ranging from 93-98 % was obtained. Further, a paper strip assay was designed which successfully detected nitrobenzene and can be clearly noticed even with our naked eye making the probe an excellent sensor for nitrobenzene detection.

Sub-PPB Detection with Gas-Phase Multiphoton Electron Extraction Spectroscopy under Ambient Conditions.

Multiphoton electron extraction spectroscopy (MEES) is an advanced analytical technique that has demonstrated exceptional sensitivity and specificity for detecting molecular traces on solid and liquid surfaces. Building upon the solid-state MEES foundations, this study introduces the first application of MEES in the gas phase (gas-phase MEES), specifically designed for quantitative detection of gas traces at sub-part per billion (sub-PPB) concentrations under ambient atmospheric conditions. Our experimental setup utilizes resonant multiphoton ionization processes using ns laser pulses under a high electrical field. The generated photoelectron charges are recorded as a function of the laser's wavelength. This research showcases the high sensitivity of gas-phase MEES, achieving high spectral resolution with resonant peak widths less than 0.02 nm FWHM. We present results from quantitative analysis of benzene and aniline, two industrially and environmentally significant compounds, demonstrating linear responses in the sub-PPM and sub-PPB ranges. The enhanced sensitivity and resolution of gas-phase MEES offer a powerful approach to trace gas analysis, with potential applications in environmental monitoring, industrial safety, security screening, and medical diagnostics. This study confirms the advantages of gas-phase MEES over many traditional optical spectroscopic methods and demonstrates its potential in direct gas-trace sensing in ambient atmosphere.

Estimation of Environmental Effects and Response Time in Gas-Phase Explosives Detection Using Photoluminescence Quenching Method.

Detecting the presence of explosives is important to protect human lives during military conflicts and peacetime. Gas-phase detection of explosives can make use of the change of material properties, which can be sensitive to environmental conditions such as temperature and humidity. This paper describes a remote-controlled automatic shutter method for the environmental impact assessment of photoluminescence (PL) sensors under near-open conditions. Utilizing the remote-sensing method, we obtained environmental effects without being exposed to sensing vapor molecules and explained how PL intensity was influenced by the temperature, humidity, and exposure time. We also developed a theoretical model including the effect of exciton diffusion for PL quenching, which worked well under limited molecular diffusions. Incomplete recovery of PL intensity or the degradation effect was considered as an additional factor in the model.

Study of the relationship between pressure and sensitivity of energetic materials based on first-principles calculation.

CONTEXT: In order to study the relationship between the sensitivity and pressure of energetic materials, six kinds of energetic materials were selected as the research object. The crystal structure, electronic, and phonon properties under hydrostatic pressure of 0 ~ 45 GPa were calculated by first principles. The calculation results show that the lattice parameters and band gap values of these six energetic materials decrease with the increase of pressure. The peak of the density of states decreases and moves to the low energy direction, and the electrons become more active. Meanwhile, the effect of pressure on the sensitivity of the energetic materials is analyzed based on the multi-phonon up-pumping theory. The number of doorway modes and integral of projected phonon density of states under high pressure is calculated. The results show that both of them increase with the increase of pressure. And the smaller the value of the band gap, the larger the number of doorway modes and integral of projected phonon density of states, and the more sensitive the energetic material is. METHODS: All calculations are performed using the Materials Studio software based on density functional theory. The Perdew-Burke-Ernzerhof (PBE) functional of the generalized gradient approximation (GGA) is used to calculate the exchange correlation function, and the Grimme dispersion correction method is used to deal with the weak intermolecular interaction. The structure of the compound was optimized by BFGS algorithm. The linear response is used to calculate the phonon properties of energetic materials. The plane wave cutoff energy was set to 830 eV. The K-point grids of TATB, FOX-7, TNX, RDX, TNT, and HMX were chosen as 2 × 2 × 2, 2 × 2 × 1, 2 × 1 × 1, 1 × 1 × 1, 1 × 2 × 1, and 2 × 1 × 2.

Novel Covalent Bonds and Hydrogen Bonds Linked Porous Organic Frameworks as Chemosensor for Detecting 2,4,6-Trinitrophenol in Water and Soil Samples.

A novel and unconventional structural porous organic framework combined through the synergistic effect of covalent bonds and hydrogen bonds was prepared with the combination of 4,4',4″,4‴-(pyrene-1,3,6,8-tetrayl)tetraaniline (Py) and 5-hydroxyisophthalaldehyde (HP). It was the second example of CHOF until now and had been designated as Py-HP CHOF. The suspension of Py-HP CHOF in various solvents, such as ethanol, CH3CN, and methanol, exhibited a remarkably selective and sensitive "on-off" fluorescence response toward 2,4,6-trinitrophenol (TNP) compared with other explosives, with exceptionally low detection limits. The X-ray diffraction (XRD) spectra confirmed that the framework of Py-HP CHOF collapsed after interaction with TNP and acid, further indicating the existence of hydrogen bonds in the framework of Py-HP CHOF. The fluorescence quenching can be ascribed to the photoinduced electron transfer and the absorption competition quenching, as supported by XRD, X-ray photoelectron spectroscopy results, UV-vis absorption spectra, and density functional theory calculations. Fluorescence channels can be utilized by Py-HP CHOF to function as chemosensor, enabling the identification and detection of TNP in water and soil, and Py-HP CHOF is also the second CHOF example of sensing TNP reported to date. The application of this technique exhibits considerable potential in the analysis and detection of environmental pollutants, thereby presenting substantial practical implications.

Aggregation-induced emission enhancement (AIEE) active bispyrene-based fluorescent probe: "turn-off" fluorescence for the detection of nitroaromatics.

The detection of nitroaromatic explosives in real samples is essential for environmental monitoring because of their strongly powerful nature and wide applications in industries. Aggregation-induced emission enhancement (AIEE) active fluorescent probe has been widely employed to detect nitroaromatic explosives. Hereby, a simple V-shaped bispyrene-based fluorescent probe (called py-o) with AIEE properties was designed and synthesized, which was fully charactered by 1D NMR, ESI, FTIR, and 2D NOESY spectra. The py-o displayed bright blue-green fluorescence excimer emission at 480 nm in DMF/H2O (v/v 1:1). It is observed that the fluorescence excimer emission of py-o at 480 nm was quenched by PA in solution with a quenching constant of 5.45 × 104 M-1, and the limit of detection was approximately 0.139 µM. The details of the sensing mechanism were explained using 1H NMR titrations, Job's plot and Bensi-Hildebrand methods, which revealed a 1:1 binding ratio via the π-π interactions between PA and py-o. Meanwhile, it exhibited outstanding anti-interference ability in the detection of PA when interfering analytes were added under the same conditions. Furthermore, low-cost thin-layer chromatography (TLC) plates coated with py-o were developed as fluorescent tools for naked-eye detection of PA in the solid state. Therefore, this work provides a new method for constructing an AIEE fluorescent probe for the detection of nitroaromatic explosives to utilize in environmental monitoring.

Review of Explosive Contamination and Bioremediation: Insights from Microbial and Bio-Omic Approaches.

Soil pollution by TNT(2,4,6-trinitrotoluene), RDX(hexahydro-1,3,5-trinitro-1,3,5-triazacyclohexane), and HMX(octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), resulting from the use of explosives, poses significant challenges, leading to adverse effects such as toxicity and alteration of microbial communities. Consequently, there is a growing need for effective bioremediation strategies to mitigate this damage. This review focuses on Microbial and Bio-omics perspectives within the realm of soil pollution caused by explosive compounds. A comprehensive analysis was conducted, reviewing 79 articles meeting bibliometric criteria from the Web of Science and Scopus databases from 2013 to 2023. Additionally, relevant patents were scrutinized to establish a comprehensive research database. The synthesis of these findings serves as a critical resource, enhancing our understanding of challenges such as toxicity, soil alterations, and microbial stress, as well as exploring bio-omics techniques like metagenomics, transcriptomics, and proteomics in the context of environmental remediation. The review underscores the importance of exploring various remediation approaches, including mycorrhiza remediation, phytoremediation, bioaugmentation, and biostimulation. Moreover, an examination of patented technologies reveals refined and efficient processes that integrate microorganisms and environmental engineering. Notably, China and the United States are pioneers in this field, based on previous successful bioremediation endeavors. This review underscores research's vital role in soil pollution via innovative, sustainable bioremediation for explosives.

Improved preconcentration workflow for organic explosive traces in aqueous samples using solvent-assisted dispersive solid-phase extraction.

The present study deals with the development of a solvent-assisted dispersive solid phase extraction method for the extraction of HMX, RDX, and TNT from aqueous samples. Benzophenone and methanol were selected as explosives sorbent and dispersive solvent respectively. Extraction parameters like pH, extraction time, amount of sorbent, volume and type of the disperser solvent and centrifuge time were optimized. Dispersion of 0.5 mL dispersive solution (4% (w/v) benzophenone in methanol) was performed by injection into the 5 mL aqueous sample (pH=7) using a 1.0 mL syringe. After centrifuge, the extracted explosives were analyzed by high performance liquid chromatography with ultraviolet detection (HPLC-Uv). The results indicated that the linear ranges with the correlation coefficients of 0.99 ≤ R2 were 1.6-204.6 µg L-1, 1.4-213.7 µg L-1 and 1.3-225.9 µg L-1 for HMX, RDX and TNT respectively. The limit of detection and limit of quantification obtained for each explosive were: 0.3 µg L-1 and 0.8 µg L-1 for HMX, 0.3 µg L-1 and 0.9 µg L-1 for RDX and 0.2 µg L-1 and 0.7 µg L-1 for TNT. Finally, the practical applicability of the developed method was evaluated for the extraction of some organic explosives in water samples followed their determination by HPLC-Uv.

Increased impact sensitivity in ageing high explosives; analysis of Amatol extracted from explosive remnants of war.

Millions of tonnes of explosive remnants of war remain in nature and their volume is continuously growing. The explosive legacy of wars represents an increasing threat to the environment and societal safety and security. As munitions continue to deteriorate, harmful constituents will eventually leak into the environment, poisoning ecological receptors and contaminating the surrounding soil and groundwater. Moreover, munition deterioration due to exposure to various environmental factors may ultimately cause them to become increasingly sensitive to external stimuli and susceptible to accidental detonation. To thoroughly assess how to address these ageing munitions, we must first establish certain threshold values for safe and secure handling and final disposal of the explosive ordnance. One key factor is to establish how the impact sensitivity of the explosives evolves over time. In the present work, we investigated the high-explosive substance Amatol extracted from ageing explosive remnants of war. The results obtained in the analysis indicate that the high explosives in the examined specimens were generally much more sensitive to impact than previously assumed. Furthermore, the analysis revealed that the standardized methodology of impact sensitivity testing was insufficient for estimating the sensitivities in question, and a more careful statistical analysis is required.

Modeling and simulation on spontaneous detonation of ammonium nitrate explosive induced by sulfide ores.

In this work, the characteristics of the exothermic reaction between ammonium nitrate and sulfide ores were explored using COMSOL Multiphysics. This reaction can cause an increase in temperature within the blast holes of sulfide mines and can potentially induce premature explosions of the explosives. Initially, simulations were conducted to observe temperature variations in blast holes before and after the loading of explosives. Then, the impact of blast hole diameter and initial temperature on the thermal environment was assessed. Subsequent analysis focused on the fluid field's dynamics, examining flow rate changes and the concentration of signature gases produced by the reaction. Additionally, the influence of blast hole diameter on these parameters was evaluated. The results show that the blast hole temperature is positively related to its diameter and initial temperature. When the diameter of the blast hole is 120 mm and 165 mm, a significant change in flow rate is observed, with a trend of being rapidly increased and then rapidly decreased. The production of NH3 is always found to be greater than that of the other two gases. As for NO and SO2, their production is characterized by an approximate ratio of 1:2. The numerical simulation results can provide important theoretical guidance for the spontaneous detonation of blast hole in sulfide mines.

Forensic profiling of smokeless powders (SLPs) by gas chromatography-mass spectrometry (GC-MS): a systematic investigation into injector conditions and their effect on the characterisation of samples.

Smokeless powders (SLPs) are composed of a combination of thermolabile and non-thermolabile compounds. When analysed by GC-MS, injection conditions may therefore play a fundamental role on the characterisation of forensic samples. However, no systematic investigations have ever been carried out. This casts doubt on the optimal conditions that should be adopted in advanced profiling applications (e.g. class attribution and source association), especially when a traditional split/splitless (S/SL) injector is used. Herein, a study is reported that specifically focused on the evaluation of the liner type (Ltype) and inlet temperature (Tinj). Results showed that both could affect the exhaustiveness and repeatability of the observed chemical profiles, with Ltype being particularly sensitive despite typically not being clarified in published works. Perhaps as expected, degradation effects were observed for the most thermolabile compounds (e.g. nitroglycerin) at conditions maximising the heat transfer rates (Ltype = packed and Tinj ≥ 200 °C). However, these did not seem to be as influential as, perhaps, suggested in previous studies. Indeed, the harshest injection conditions in terms of heat transfer rate (Ltype = packed and Tinj = 260 °C) were found to lead to better performances (including better overall %RSDs and LODs) compared to the mildest ones. This suggested that implementing conditions minimising heat-induced breakdowns during injection was not necessarily a good strategy for comparison purposes. The reported findings represent a concrete step forward in the field, providing a robust body of data for the development of the next generation of SLP profiling methods.

Biotransformation of 2,4,6-Trinitrotoluene by a cocktail of native laccases from Pycnoporus sanguineus CS43 under oxygenic and non-oxygenic atmospheres.

2,4,6-Trinitrotoluene (TNT) is a highly toxic nitroaromatic explosive known for its environmental consequences, contaminating soil and groundwater throughout its life cycle, from production to disposal. Therefore, the urgency of developing innovative and ecological strategies to remedy the affected areas is recognized. This study reports, for the first time, the enzymatic biotransformation of TNT by a cocktail of native laccases from Pycnoporus sanguineus CS43. The laccases displayed efficient TNT conversion under both oxygenic and non-oxygenic conditions, achieving biotransformation rates of 80% and 87% within 48 h at a temperature of 60 °C and pH 7. Preliminary kinetic constants were calculated with the laccase cocktail, being a Vmax of 1.133 µM min-1 and 0.2984 µM min-1, and the Km values were 1586 µM and 458 µM, in an oxygenic and non-oxygenic atmosphere, respectively. High-performance liquid chromatography-mass spectrometry (HPLC/MS) confirmed the formation of amino dinitrotoluene isomers and hydroxylamine isomers as biotransformation products. In summary, this study suggests the potential application of laccases for the direct biotransformation of recalcitrant compounds like TNT, offering an environmentally friendly approach to address contamination issues.

Advances in ionic liquids as fluorescent sensors.

Ionic liquids (ILs) are a class of liquid salts with characteristics such as a low melting point, an ionic nature, non-volatility, and tunable properties. Because of their adaptability, they have a significant influence in the field of fluorescence. This paper reviews the primary literature on the use of ILs in fluorescence sensing technologies. The kind of target material is utilized to classify the fluorescence sensors made with the use of ILs. They include using ILs as probes for metals, nitro explosives, small organic compounds, anions, and gases. The efficacy of an IL-based fluorescence sensor depends on the precise design to guarantee specificity, sensitivity, and a consistent reaction to the desired analyte. The precise method can differ depending on the chemical properties of the IL, the choice of fluorophore, and the interactions with the analyte. Overall, the viability of the aforementioned materials for chemical analysis is evaluated, and prospective possibilities for further development are identified.

Vapor phase detection of explosives by surface enhanced Raman scattering under ambient conditions with metal nanogap structures.

Non-invasive and passive detection of explosives in the vapor phase is advantageous for military, counter-terrorism, and homeland security applications. Detection of explosives using SERS has been an active research topic. However, the vapor pressures of most explosives are low at room temperature, and consequently, the vapor phase detection by SERS is highly challenging without intentionally heating explosive powder to increase the vapor pressure. In this work, we report the rapid and sensitive detection of 2,4,6-trinitrotoluene (TNT) and 2,4-dinitrotoluene (2,4-DNT) in the vapor phase, using a gold nanogap (AuNG) SERS substrate. The AuNG SERS substrate was fabricated with electron beam evaporation, rapid thermal annealing, and wet etching. SERS measurements were carried out with an incident power as low as 0.56 mW at 785 nm. To prevent the condensation effect, the TNT and 2,4-DNT powders inside the cuvette were taken out before inserting the nanogap substrate. Our SERS results demonstrate the feasibility of the non-invasive detection of vapor phase explosives under ambient conditions.

Screening of volatiles from explosive initiators and plastic-bonded explosives (PBX) using headspace solid-phase microextraction coupled with gas chromatography - mass spectrometry (SPME/GC-MS).

The detection of explosives and explosive devices based on the volatile compounds they emit is a long-standing tool for law enforcement and physical security. Toward that end, solid-phase microextraction (SPME) combined with gas chromatography-mass spectrometry (GC-MS) has become a crucial analytical tool for the identification of volatiles emitted by explosives. Previous SPME studies have identified many volatile compounds emitted by common explosive formulations that serve as the main charge in explosive devices. However, limited research has been conducted on initiators like fuses, detonating cords, and boosters. In this study, a variety of SPME fiber coatings (i.e., polydimethylsiloxane (PDMS), polydimethylsiloxane/divinylbenzene (PDMS/DVB), divinylbenzene/carboxin/polydimethylsiloxane (DVB/CAR/PDMS), and carboxin/polydimethylsiloxane (CAR/PDMS)) were employed for the extraction and analysis of volatiles from Composition C-4 (cyclohexanone, 2-ethyl-1-hexanol, and 2,3-dimethyl-2,3-dinitrobutane (DMNB)) and Red Dot double-base smokeless powder (nitroglycerine, phenylamine). The results revealed that a PDMS/DVB fiber was optimal. Then, an assortment of explosive items (i.e., detonation cord, safety fuse, slip-on booster, and shape charge) were analyzed with a PDMS/DVB fiber. A variety of volatile compounds were identified, including plasticizers (tributyl acetyl citrate, N-butylbenzenesulfonamide), taggants (DMNB), and degradation products (2-ethyl-1-hexanol).