• Bulletin of the Korean Chemical Society
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• v.34 no.7
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• pp.1967-1971
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• 2013

Aim of our study is finding adsorbents suitable for pre-concentration of chemical warfare agents (CWAs). We considered Tenax, bare silica and polydimethylsiloxane (PDMS)-coated silica as adsorbents for dimethyl methylphosphonate (DMMP) and dipropylene glycol methyl ether (DPGME). Tenax showed lower thermal stability, and therefore, desorption of CWA simulants and decomposition of Tenax took place simultaneously. Silica-based adsorbents showed higher thermal stabilities than Tenax. A drawback of silica was that adsorption of CWA simulant (DMMP) was significantly reduced by pre-treatment of the adsorbents with humid air. In the case of PDMS-coated silica, influence of humidity for CWA simulant adsorption was less pronounced due to the hydrophobic nature of PDMS-coating. We propose that PDMS-coated silica can be of potential importance as adsorbent of CWAs for their pre-concentration, which can facilitate detection of these CWAs.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.148.2-148.2
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• 2013

We prepared hydrophobic PDMS-coated porous silica as pre-concentration adsorbent for chemical warfare agents (CWAs). Since CWAs can be harmful to human even with a small amount, detecting low-concentration CWAs has been attracting attention in defense development. Porous silica is one of the promising candidates for CWAs pre-concentration adsorbent since it is thermally stable and its surface area is sufficiently high. A drawback of silica is that adsorption of CWAs can be significantly reduced due to competitive adsorption with water molecule in air since silica is quite hydrophilic. In order to solve this problem, hydrophobic polydimethylsiloxane (PDMS) thin film was deposited on silica. Adsorption and desorption of chemical warfare agent (CWA) simulants (Dimethylmethylphosphonate, DMMP and Dipropylene Glycol Methyl Ether, DPGEM) on bare and PDMS-coated silica were studied using temperature programed desorption (TPD) with and without co-exposing of water vapor. Without exposure of water vapor, desorbed amount of DMMP from PDMS-coated silica was twice larger than that from bare silica. When the samples were exposed to DMMP and water vapor at the same time, no DMMP was desorbed from bare silica due to competitive adsorption with water. On the other hand, desorbed DMMP was detected from PDMS-coated silica with reduced amount compared to that from the sample without water vapor exposure. Adsorption and desorption of DPGME with and without water vapor exposing was also investigated. In case of bare silica, all the adsorbed DPGME was decomposed during the heating process whereas molecular DPGME was observed on PDMS-coated silica. In summary, we showed that hydrophobic PDMS-coating can enhance the adsorption selectivity toward DMMP under humid condition and PDMS-coating also can have positive effect on molecular desorption of DPGME. Therefore we propose PDMS-coated silica could be an adequate adsorbent for CWAs pre-concentration under practical condition.

• Bulletin of the Korean Chemical Society
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• v.30 no.1
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• pp.49-52
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• 2009

Single-drop microextraction (SDME) is an extraction methodology where the drop plays an essential role as extracts. It was evaluated for the GC-MS determination of nerve agents, one class of the chemical warfare agents (CWAs). Since these nerve agents are highly toxic, it is important to detect the nerve agents in the environmental samples. Several affecting factors including extraction solvents, stirring rate, extraction time, and amounts of salt were optimized. The limit of detections (LODs) were 0.1 - 10 ng/mL and the relative standard deviations (RSDs%, n=5) were in the range of 6.3% to 9.0% for four nerve agents. Without pretreatment of the environmental samples, 5-103 fold enrichments and 48-100% recovery were accomplished. These results demonstrated the feasibility of this method for on-site and off-site analysis of water sample collected from suspicious CWAs site.

• Applied Chemistry for Engineering
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• v.26 no.1
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• pp.17-22
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• 2015

International interests in chemical warfare agents (CWAs) have been increased recently because of the use of sarin (GB) in Syrian civil war which caused around 1,300 casualties in 2013. After exposing to natural environments, CWAs undergo hydrolysis or photodegrade to non-toxic degradation byproducts. Generally, CWAs and their degradation byproducts are present at very low concentration (e.g. several ppb), thus pretreatment processes including separation, extraction and concentration are required prior to any analyses. Liquid-liquid extraction and solid-phase extraction (SPE) are common techniques to pretreat environmental samples. Recently, a novel pretreatment method, liquid phase miecoextraction (LPME), has been applied to CWAs analysis, which could reduce amounts of solvent used but promote analytical efficiencies. Fundamental backgrounds of LPME and its application to CWAs analysis were reviewed.

• Journal of Soil and Groundwater Environment
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• v.26 no.1
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• pp.54-64
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• 2021

The chemical warfare agents (CWAs) have been developed for offensive or defensive purposes and used as chemical weapons in war and terrorism. The CWAs are exposed to the natural environment, transported through the water system and then eventually contaminate soil and groundwater. Therefore, effective decontamination technology to remediate CWAs are needed. The CWAs are extremely dangerous and prodution is strictly prohibited, therefore, it is difficult to use CWAs even in experimental purpose. In this study, 2,4-dichlorophenoxyacetic acid (2,4-D) was chosen as a model representative CWA because it is a simulant of anti-plant CWAs and one of the major component of agent orange. The optimum degradation conditions such as oxidant:activator ratio were determined. The effects of hydroxylamine and chelating agents such as citric acid (CA), oxalic acid (OA), malic acid (MA), and EDTA addition to increase Fe2+ activation were also investigated. Scavenger experiments using tert-butyl alcohol (TBA) and ethanol confirmed that although both sulfate (SO4•-) and hydroxyl radical (•OH) existed in Fe2+-persulfate system, sulfate radical was the predominant radical. To promote the Fe2+ activator effect, the effect of hydroxylamine as a reducing agent was investigated. In chelating agents assisted Fe2+-persulfate oxidation, the addition of 2 mM of CA and MA enhanced 2,4-D degradation. In contrast, EDTA and OA inhibited the 2,4-D removal due to steric hindrance effect.

• Journal of the Korea Institute of Military Science and Technology
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• v.24 no.4
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• pp.374-381
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• 2021

Raman spectrometers are studied and developed for the military purposes because of their nondestructive inspection capability to capture unique spectral features induced by molecular structures of colorless and odorless chemical warfare agents(CWAs) in any phase. Raman spectrometers often suffer from random noise caused by their detector inherent noise, background signal, etc. Thus, reducing the random noise in a measured Raman spectrum can help detection algorithms to find spectral features of CWAs and effectively detect them. In this paper, we propose a denoising autoencoder for Raman spectra with a loss function for sample efficient learning using noisy dataset. We conduct experiments to compare its effect on the measured spectra and detection performance with several existing noise reduction algorithms. The experimental results show that the denoising autoencoder is the most effective noise reduction algorithm among existing noise reduction algorithms for Raman spectrum based standoff detection of CWAs.

• Journal of Sensor Science and Technology
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• v.28 no.3
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• pp.139-145
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• 2019

Precautionary detection of chemical warfare agents (CWAs) has been an important global issue mainly owing to their toxicity. To achieve proper detection, many studies have been conducted to develop sensitive gas sensors for CWAs. In particular, metal-oxide semi-conductors (MOS) have been investigated as promising sensing materials owing to their abundance in nature and excellent sensitivity. In this review, we mainly focus on various MOS-based gas sensors that have been fabricated for the detection of two specific CWA simulants, 2-chloroethyl ethyl sulfide (2-CEES) and dimethyl methyl phosphonate (DMMP), which are simulants of sulfur mustard and sarin, respectively. In the case of 2-CEES, we mainly discuss $CdSnO_3-$ and ZnO-based sensors and their reaction mechanisms. In addition, a method to improve the selectivity of ZnO-based sensors is mentioned. Various sensors and their sensing mechanisms have been introduced for the detection of DMMP. As the reaction with DMMP may directly affect the sensing properties of MOS, this paper includes previous studies on its poisoning effect. Finally, promising sensing materials for both gases are proposed.

• Journal of the Korea Institute of Military Science and Technology
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• v.18 no.5
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• pp.612-620
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• 2015

Short-range detection of chemical agents deposited on ground surface using a standoff Raman system employing a pulsed laser at 248 nm is described. Mounted in a vehicle such as an NBC reconnaissance vehicle, the system is protected against toxic chemicals. As most chemicals including chemical warfare agents have unique Raman spectra, the spectra can be used for detecting toxic chemicals contaminated on the ground. This article describes the design of the Raman spectroscopic system and its performance on several chemicals contaminated on asphalt, concrete, sand, etc.