Search Results (13)

Organophosphorus chemical warfare agents such as sarin (GB), soman (GD), and cyclosarin (GF) rank among the most toxic substances known, making trace-level detection critical for public and military safety. In this study, we compared the sensitivity of two analytical techniques for determining these nerve agents: gas chromatography with flame-photometric detection (GC-FPD) and gas chromatography coupled to inductively coupled plasma mass spectrometry (GC-ICP-MS). Diluted samples of sarin, soman, and cyclosarin were prepared under controlled laboratory conditions and then analyzed by both methods. Limits of detection, calibration linearity, and selectivity of the two approaches were evaluated. It was shown that GC-ICP-MS enabled detection of sarin, soman, and cyclosarin at ≈0.12–0.14 ng/mL (LOD), whereas GC-FPD achieved LODs of ≈0.36–0.43 ng/mL. The obtained results confirm that GC-ICP-MS exhibits significantly higher sensitivity than GC-FPD in the analysis of the chemical warfare agents under study. This advantage indicates strong application potential of GC-ICP-MS as a technique for ultra-sensitive detection of trace amounts of chemical warfare agents (CWAs) in environmental samples and in confirmatory testing for compliance with the CWC, while simultaneously employing GC-FPD for rapid preliminary monitoring. Full article

In this manuscript, we present in detail the design and implementation of the hardware and software to produce a standalone wireless sensor node, called SensorQ system, for the detection of a toxic chemical agent. The proposed wireless sensor node prototype is composed of a micro-controller unit (MCU), a radio frequency (RF) transceiver, a dual-band antenna, a rechargeable battery, a voltage regulator, and four integrated sensing devices, all of them integrated in a package with final dimensions and weight of 200 × 80 × 60 mm and 0.422 kg, respectively. The proposed SensorQ prototype operates using the Long-Range (LoRa) wireless communication protocol at 2.4 GHz, with a sensor head implemented on a hetero-core fiber optic structure supporting the surface plasmon resonance (SPR) phenomenon with a sensing section (L = 10 mm) coated with titanium/gold/titanium and a chemically sensitive material (zinc oxide) for the detection of Di-Methyl Methyl Phosphonate (DMMP) vapor in the air, a simulant of the toxic nerve agent Sarin. The transmitted spectra with respect to different concentrations of DMMP vapor in the air were recorded, and then the transmitted power for these concentrations was calculated at a wavelength of 750 nm. The experimental results indicate the feasibility of detecting DMMP vapor in air using the proposed optical sensor head, with DMMP concentrations in the air of 10, 150, and 150 ppm in this proof of concept. We expect that the sensor and wireless sensor node presented herein are promising candidates for integration into a wireless sensor network (WSN) for chemical warfare agent (CWA) detection and contaminated site monitoring without exposure of armed forces. Full article

In the present study, we used two popular radio communication SAW resonators as a base for gas sensors and tested their performance. Taking into account issues related to sensor sensitivity, the possibility of applying a sensor layer, the availability of devices, and other related issues, we selected two popular single-port resonators with center frequencies of 315 and 433 MHz (models R315 and R433, respectively) for testing purposes. Both resonators were equipped with a sensitive film of hexafluoroisopropanol-substituted polydimethylsiloxane, a material that selectively absorbs molecules with a high ability to form basic hydrogen bonds. Fabricated sensors were used to detect trace amounts of dimethyl methylphosphonate (DMMP) vapor, which has often been used in similar studies as a nerve chemical warfare agent simulant. Sensors using both devices loaded with sensor layers of an optimal thickness rapidly reacted to a gas containing DMMP at a concentration of 3 mg/m³, generating a stable analytical signal ranging from several to several dozen kilohertz. In the case of R433, the frequency signal was 20.5 kHz at 1 min from the beginning of exposure to DMMP. The obtained results showed that the used transducers exhibited good performance as a base for gas sensors. Finally, their suitability for sensing applications was confirmed by a comparison with the results obtained in previous similar studies. Full article

The latest trends in the field of the on-site detection of chemical warfare agents (CWAs) involve increasing the availability of point detectors to enhance the operational awareness of commanders and soldiers. Among the intensively developed concepts aimed at meeting these requirements, wearable detectors, gas analyzers as equipment for micro- and mini-class unmanned aerial vehicles (UAVs), and distributed sensor networks can be mentioned. One of the analytical techniques well suited for use in this field is surface acoustic wave sensors, which can be utilized to construct lightweight, inexpensive, and undemanding gas analyzers for detecting CWAs. This review focuses on the intensively researched and developed variant of this technique, utilizing absorptive sensor layers dedicated for nerve CWAs’ detection. The paper describes the mechanism of the specific interaction occurring between the target analyte and the sensing layer, which serves as the foundation for their selective detection. The main section of this paper includes a chronological review of individual achievements in the field, largely based on the peer-reviewed scientific literature dating back to the mid-1980s to the present day. The final section presents conclusions regarding the prospects for the development of this analytical technique in the targeted application. Full article

A dire need for real-time detection of toxic chemical compounds exists in both civilian and military spheres. In this paper, we demonstrate that inexpensive, commercially available Fe₂O₃ nanoparticles are capable of selective sensing of chemical warfare agents (CWAs) using frequency-dependent impedance spectroscopy, with additional potential as an orthogonal magnetic sensor. X-ray magnetic circular dichroism analysis shows that Fe₂O₃ nanoparticles possess moderately lowered moment upon exposure to 2-chloroethyl ethyl sulfide (2-CEES) and diisopropyl methylphosphonate (DIMP) and significantly lowered moment upon exposure to dimethyl methylphosphonate (DMMP) and dimethyl chlorophosphate (DMCP). Associated X-ray absorption spectra confirm a redox reaction in the Fe₂O₃ nanoparticles due to CWA structural analog exposure, with differentiable energy-dependent features that suggest selective sensing is possible, given the correct method. Impedance spectroscopy performed on samples dosed with DMMP, DMCP, and tabun (GA, chemical warfare nerve agent) showed strong, differentiable, frequency-dependent responses. The frequency profiles provide unique “shift fingerprints” with which high specificity can be determined, even amongst similar analytes. The results suggest that frequency-dependent impedance fingerprinting using commercially available Fe₂O₃ nanoparticles as a sensor material is a feasible route to selective detection. Full article

Novichok-like or fourth-generation agents (FGAs) are chemical warfare agents (CWAs) which have been gaining attention since their use in assassination attempts on Sergei Skripal and Alexei Navalny. Due to their physicochemical properties, these substances are difficult to detect by implemented technologies, resulting in massive response efforts if their occurrence is suspected in a civilian environment. In this work, an approach is presented that uses handheld forensic light sources to visually detect surfaces contaminated with Novichok. More than 100 different wavelength combinations were applied to seven substances chosen to represent the newly listed schedule 1 subgroups in the Annex on Chemicals of the Chemical Weapons Convention. One waveband was identified as promising, which allowed the optical detection of all tested substances. Several surfaces, which could be affected in case of a possible attack using novichok-like nerve agents, were also successfully evaluated. The proposed procedure could be implemented for CBRN responders and security agencies to significantly reduce response efforts, thereby diminishing the overall threat posed by this group of chemicals (FGAs). This procedure was also extended to carbamates and CWAs. Full article

A colorless, odorless G nerve agent, a type of chemical transfer agent (CWA) that causes significant loss of life, is being studied for quick and accurate detection. In this study, detection materials with different functional groups were synthesized based on thiourea (TU)-decorated polyhedral oligomeric silsesquioxane (POSS) to study the most suitable material for the detection of dimethyl methylphosphonate (DMMP), a simulant of neural agents. The sensing material was coated on a SAW sensor with a resonance frequency of 250 MHz based on ST-quartz, the DMMP exposure experiment was conducted, and the performance of the sensing material was compared through frequency shift before and after exposure. Coating materials with excellent reactivity with DMMP and appropriate coating concentration for each material were identified at a concentration of 10 ppm. Among them, POSS-TU with 3,5-bis(trifluoromethyl)phenyl as a functional group showed the largest frequency shift characteristics, and it was used in low concentration (1, 5, and 10 ppm) DMMP detection experiments to confirm linear frequency shift characteristics according to low concentration. Finally, through a selectivity experiment with other gases, it was confirmed that the amount of frequency shift in other gases except DMMP was small, making it an excellent DMMP sensing material. Full article

Chemical warfare agents (CWAs) have been threatening human civilization and its existence because of their rapid response, toxic, and irreversible nature. The hybrid nanostructured composites were synthesized by the hydrothermal process to detect the dimethyl methyl phosphonate (DMMP), a simulant of G-series nerve agents, especially sarin. Cellulose (CE), manganese oxide cellulose (MnO₂@CE), and MnO₂@CE/polypyrrole (PPy) exhibited a frequency shift of 0.4, 4.8, and 8.9 Hz, respectively, for a DMMP concentration of 25 ppm in the quartz crystal microbalance (QCM). In surface acoustic wave (SAW) sensor, they exhibited 187 Hz, 276 Hz, and 78 Hz, respectively. A comparison between CE, MnO₂@CE, and MnO₂@CE/PPy demonstrated that MnO₂@CE/PPy possesses excellent linearity with a coefficient of determination (COD or R²) of 0.992 and 0.9547 in the QCM and SAW sensor. The hybrid composite materials showed a reversible adsorption and desorption phenomenon in the reproducibility test. The response and recovery times indicated that MnO₂@CE/PPy showed the shortest response (~23 s) and recovery times (~42 s) in the case of the QCM sensor. Hence, the pristine CE and its nanostructured composites were compared to analyze the sensing performance based on sensitivity, selectivity, linearity, reproducibility, and response and recovery times to detect the simulant of nerve agents. Full article

On-site detection and initial identification of chemical warfare agents (CWAs) remain difficult despite the many available devices designed for this type of analysis. Devices using well-established analytical techniques such as ion mobility spectrometry, gas chromatography coupled with mass spectrometry, or flame photometry, in addition to unquestionable advantages, also have some limitations (complexity, high unit cost, lack of selectivity). One of the emerging techniques of CWA detection is based on acoustic wave sensors, among which surface acoustic wave (SAW) devices and quartz crystal microbalances (QCM) are of particular importance. These devices allow for the construction of undemanding and affordable gas sensors whose selectivity, sensitivity, and other metrological parameters can be tailored by application of particular coating material. This review article presents the current state of knowledge and achievements in the field of SAW and QCM-based gas sensors used for the detection of blister agents as well as simulants of these substances. The scope of the review covers the detection of blister agents and their simulants only, as in the available literature no similar paper was found, in contrast to the detection of nerve agents. The article includes description of the principles of operation of acoustic wave sensors, a critical review of individual studies and solutions, and discusses development prospects of this analytical technique in the field of blister agent detection. Full article

The field of gas chromatography-mass spectrometry (GC-MS) in the analysis of chemical warfare agents (CWAs), specifically those involving the organophosphorus-based nerve agents (OPNAs), is a continually evolving and dynamic area of research. The ever-present interest in this field within analytical chemistry is driven by the constant threat posed by these lethal CWAs, highlighted by their use during the Tokyo subway attack in 1995, their deliberate use on civilians in Syria in 2013, and their use in the poisoning of Sergei and Yulia Skripal in Great Britain in 2018 and Alexei Navalny in 2020. These events coupled with their potential for mass destruction only serve to stress the importance of developing methods for their rapid and unambiguous detection. Although the direct detection of OPNAs is possible by GC-MS, in most instances, the analytical chemist must rely on the detection of the products arising from their degradation. To this end, derivatization reactions mainly in the form of silylations and alkylations employing a vast array of reagents have played a pivotal role in the efficient detection of these products that can be used retrospectively to identify the original OPNA. Full article

G nerve agents are colorless, odorless, and lethal chemical warfare agents (CWAs). The threat of CWAs, which cause critical damage to humans, continues to exist, e.g., in warfare or terrorist attacks. Therefore, it is important to be able to detect these agents rapidly and with a high degree of sensitivity. In this study, a surface acoustic wave (SAW) array device with three SAW sensors coated with different sensing materials and one uncoated sensor was tested to determine the most suitable material for the detection of nerve agents and related simulants. The three materials used were polyhedral oligomeric silsesquioxane (POSS), 1-benzyl-3-phenylthiourea (TU-1), and 1-ethyl-3-(4-fluorobenzyl) thiourea (TU-2). The SAW sensor coated with the POSS-based polymer showed the highest sensitivity and the fastest response time at concentrations below the median lethal concentration (LCt₅₀) for tabun (GA) and sarin (GB). Also, it maintained good performance over the 180 days of exposure tests for dimethyl methylphosphonate (DMMP). A comparison of the sensitivities of analyte vapors also confirmed that the sensitivity for DMMP was similar to that for GB. Considering that DMMP is a simulant which physically and chemically resembles GB, the sensitivity to a real agent of the sensor coated with POSS could be predicted. Therefore, POSS, which has strong hydrogen bond acid properties and which showed similar reaction characteristics between the simulant and the nerve agent, can be considered a suitable material for nerve agent detection. Full article

The paper presents the results of the study of the possibilities of using color metal complexes to detect the presence of chemical warfare agents (CWA) in liquid or aerosol form. Aluminon/Fe³⁺ and Eriochrome Cyanine R/Cu²⁺ coordination complexes and their ability to detect CWA in liquid phase are discussed. Detection systems have been demonstrated on instances of simple detection papers exposed to drops of real CWAs. Detection papers showed a positive response to G-series nerve agents and vesicant lewisite. Other liquid CWA do not interfere and the systems are also resistant to common organic solvents and a wide range of industrial chemicals. Full article

Chemical warfare agents (CWA) continue to present a threat to civilian populations and military personnel in operational areas all over the world. Reliable measurements of CWAs are critical to contamination detection, avoidance, and remediation. The current deployed systems in United States and foreign militaries, as well as those in the private sector offer accurate detection of CWAs, but are still limited by size, portability and fabrication cost. Herein, we report a chemiresistive CWA sensor using single-walled carbon nanotubes (SWCNTs) wrapped with poly(3,4-ethylenedioxythiophene) (PEDOT) derivatives. We demonstrate that a pendant hexafluoroisopropanol group on the polymer that enhances sensitivity to a nerve agent mimic, dimethyl methylphosphonate, in both nitrogen and air environments to concentrations as low as 5 ppm and 11 ppm, respectively. Additionally, these PEDOT/SWCNT derivative sensor systems experience negligible device performance over the course of two weeks under ambient conditions. Full article