A solvent-free solid catalyst for the selective and color-indicating ambient-air removal of sulfur mustard

AbstractBis(2-chloroethyl) sulfide or sulfur mustard (HD) is one of the highest-tonnage chemical warfare agents and one that is highly persistent in the environment. For decontamination, selective oxidation of HD to the substantially less toxic sulfoxide is crucial. We report here a solvent-free, solid, robust catalyst comprising hydrophobic salts of tribromide and nitrate, copper(II) nitrate hydrate, and a solid acid (NafionTM) for selective sulfoxidation using only ambient air at room temperature. This system rapidly removes HD as a neat liquid or a vapor. The mechanisms of these aerobic decontamination reactions are complex, and studies confirm reversible formation of a key intermediate, the bromosulfonium ion, and the role of Cu(II). The latter increases the rate four-fold by increasing the equilibrium concentration of bromosulfonium during turnover. Cu(II) also provides a colorimetric detection capability. Without HD, the solid is green, and with HD, it is brown. Bromine K-edge XANES and EXAFS studies confirm regeneration of tribromide under catalytic conditions. Diffuse reflectance infrared Fourier transform spectroscopy shows absorption of HD vapor and selective conversion to the desired sulfoxide, HDO, at the gas–solid interface.

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The Identification of Seven Chemical Warfare Mimics Using a Colorimetric Array

Sensors ◽

10.3390/s18124291 ◽

2018 ◽

Vol 18 (12) ◽

pp. 4291 ◽

Cited By ~ 3

Author(s):

Michael Kangas ◽

Adreanna Ernest ◽

Rachel Lukowicz ◽

Andres Mora ◽

Anais Quossi ◽

...

Keyword(s):

21St Century ◽

Colorimetric Detection ◽

Chemical Warfare Agents ◽

Large Data ◽

Armed Forces ◽

Chemical Warfare ◽

Methylphosphonic Acid ◽

Mustard Gas ◽

Sensor Performance ◽

Warfare Agents

Chemical warfare agents pose significant threats in the 21st century, especially for armed forces. A colorimetric detection array was developed to identify warfare mimics, including mustard gas and nerve agents. In total, 188 sensors were screened to determine the best sensor performance, in order to identify warfare mimics 2-chloro ethyl ethylsulfide, 2-2′-thiodiethanol, trifluoroacetic acid, methylphosphonic acid, dimethylphosphite, diethylcyanophosphonate, and diethyl (methylthiomethyl)phosphonate. The highest loadings in the principle component analysis (PCA) plots were used to identify the sensors that were most effective in analyzing the RGB data to classify the warfare mimics. The dataset was reduced to only twelve sensors, and PCA results gave comparable results as the large data did, demonstrating that only twelve sensors are needed to classify the warfare mimics.

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Air oxidation of sulfur mustard gas simulants using a pyrene-based metal–organic framework photocatalyst

Beilstein Journal of Nanotechnology ◽

10.3762/bjnano.10.232 ◽

2019 ◽

Vol 10 ◽

pp. 2422-2427 ◽

Cited By ~ 3

Author(s):

Ghada Ayoub ◽

Mihails Arhangelskis ◽

Xuan Zhang ◽

Florencia Son ◽

Timur Islamoglu ◽

...

Keyword(s):

Sulfur Mustard ◽

Metal Organic Framework ◽

Oxidative Degradation ◽

Chemical Warfare Agents ◽

Mustard Gas ◽

Air Oxidation ◽

Substitution Pattern ◽

Warfare Agents ◽

Metal Organic ◽

Organic Framework

We demonstrate a microporous metal–organic framework NU-400 based on a 2,7-disubstituted pyrene linker as a highly efficient photosensitizer for generating singlet oxygen and subsequent oxidative degradation of chemical warfare agents (CWAs). The high activity of NU-400 permits photocatalytic conversion of the 2-chloroethyl ethyl sulfide (CEES) mustard gas simulant into a benign sulfoxide derivative, in air, with less than 15 minutes’ half-life. This is a considerable improvement to NU-1000, based on a 1,3,6,8-tetrasubstituted pyrene unit, demonstrating how variation of the substitution pattern of a metal–organic framework linker permits modification of its photoactive behavior.

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Studies on Environmental Effects of Underwater Chemical Munitions in the Southern Adriatic Sea (Mediterranean Sea)

Marine Technology Society Journal ◽

10.4031/mtsj.46.3.5 ◽

2012 ◽

Vol 46 (3) ◽

pp. 10-20 ◽

Cited By ~ 4

Author(s):

Luigi Alcaro ◽

Camilla Della Torre ◽

Tommaso Petochi ◽

Valerio Sammarini ◽

Marco Matiddi ◽

...

Keyword(s):

Reference Site ◽

Adriatic Sea ◽

Sulfur Mustard ◽

Health Assessment ◽

Chemical Warfare Agents ◽

The Body ◽

Assessment Index ◽

Skin Ulcers ◽

Warfare Agents ◽

Helicolenus Dactylopterus

AbstractThe present paper shows the multidisciplinary approach used to assess the ecotoxicity of chemical munitions lying on the seabed in the Southern Adriatic Sea where aerial bombs charged with mustard agent and organoarsenic chemical warfare agents (CWAs) have been dumped.Sampling activities and laboratory analyses have been carried out on two sentinel species, the blackbelly rosefish, Helicolenus dactylopterus, and the European conger, Conger conger, collected in a CWA dumping site 35 nm from the coast of Apulia, Italy, and from a reference site. Fish were analyzed through an ecotoxicological approach, integrating chemical analysis and biological responses.Degradation products of the blister agents bis-(2-chloroethyl)sulphide, commonly known as mustard agent or yperite (also called sulfur or sulfur mustard), were found in sediment samples collected nearby aerial bombs. Although no evidence of these compounds was detected in tissues of either fish, levels of heavy metals (arsenic and mercury), potentially released by rusted chemical weapons, were significantly higher in sediment and fish from the CWA site compared to the reference site. Severe external and internal lesions were observed in fish captured in the CWA site, with congers displaying small to large skin ulcers along the body. Health assessment index (HAI) values, as well as spleen melano-macrophages centres and CYP1A ethoxyresorufin-O-deethylase activity were higher in fish from the CWA site, indicating a chronic state of illness and environment degradation.The working procedures and analyses performed during these surveys could be suitable for future biomonitoring studies in other CWA dumping sites.

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Comparative Toxic Effect of Nitrogen Mustards (HN-1, HN-2, and HN-3) and Sulfur Mustard on Hematological and Biochemical Variables and Their Protection by DRDE-07 and Its Analogues

International Journal of Toxicology ◽

10.1177/1091581810365730 ◽

2010 ◽

Vol 29 (4) ◽

pp. 391-401 ◽

Cited By ~ 12

Author(s):

Manoj Sharma ◽

R. Vijayaraghavan ◽

Om Prakash Agrawal

Keyword(s):

Sulfur Mustard ◽

Protective Efficacy ◽

Lethal Dose ◽

Chemical Warfare Agents ◽

Thiobarbituric Acid ◽

The Body ◽

Spleen Weight ◽

Nitrogen Mustards ◽

Warfare Agents ◽

Wbc Count

The chemical warfare agents sulfur mustard (SM) and nitrogen mustards (HN-1, HN-2, and HN-3) are highly reactive vesicants. The study was planned to investigate the protective efficacy of amifostine, DRDE-07 and their analogues, and few conventional antidotes (30 minutes pretreatment) against dermally applied SM and nitrogen mustards in preventing hematological and biochemical changes in mice. Mustard agents (1.0 median lethal dose [LD50]) induced a significant decrease in the body weight and spleen weight. A significant decrease in the white blood cell (WBC) count and an increase in serum transaminases and alkaline phosphatases (ALPs) were observed. A significant decrease in reduced (GSH) and oxidized glutathione (GSSG) and an increase in thiobarbituric acid reactive substances were also observed. All the mustard agents increased DNA fragmentation. The effects of SM were significantly ameliorated by DRDE-07 analogues, and with nitrogen mustards the protection was partial. Overall, DRDE-30 (propyl analogue) followed by DRDE-35 (butyl analogue) are favored as safer and better compounds.

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Oxidation of Chemical Warfare Agents in Supercritical Water

Advanced Materials Research ◽

10.4028/www.scientific.net/amr.356-360.2610 ◽

2011 ◽

Vol 356-360 ◽

pp. 2610-2615

Author(s):

Lian Yuan Wang ◽

Meng Meng Ma ◽

Xiao Chun Hu ◽

Guo Min Zuo ◽

Hai Yan Zhu ◽

...

Keyword(s):

Reaction Temperature ◽

Supercritical Water ◽

Water Oxidation ◽

Sulfur Mustard ◽

Organic Phosphorus ◽

Batch Reactor ◽

Chemical Warfare Agents ◽

Sulfur Oxidation ◽

Chemical Warfare ◽

Warfare Agents

Oxidation of chemical warfare agents (CWAs) such as Sulfur Oxidation of chemical warfare agents (CWAs) such as Sulfur Mustard (HD) and Soman (GD) and their simulants 2-chloroethyl ethyl sulfide (2-CEES) and dimethyl methylphosphonate (DMMP) in supercritical water were studied by a batch reactor. Results showed that HD, GD and their simulants 2-CEES and DMMP could be effectively destroyed into their corresponding mineral compounds by supercritical water oxidation (SCWO). The mineral ratio was a function of reaction temperature, reaction time and oxidant concentration. But reaction temperature seemed to have more important effect on the mineral ratio than other two factors. Sulfur compounds 2-CEES and HD could easily be mineralized under 475°C and the inorganic products were mainly SO32- and SO42- , while complete oxidation of organic phosphorus reactants GD and DMMP needed a high temperature of >600°C. And under relatively low temperature, DMMP tended to form a white organic phosphorus polymer with P-C and P-O-P bonds. Results also indicated that P-F bond was more easily broken than P-C bond.

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A SERS-BASED ANALYZER FOR POINT AND CONTINUOUS WATER MONITORING OF CHEMICAL AGENTS AND THEIR HYDROLYSIS PRODUCTS

International Journal of High Speed Electronics and Systems ◽

10.1142/s0129156407004928 ◽

2007 ◽

Vol 17 (04) ◽

pp. 719-728 ◽

Cited By ~ 1

Author(s):

STUART FARQUHARSON ◽

FRANK E. INSCORE

Keyword(s):

Sulfur Mustard ◽

Active Material ◽

Hydrolysis Product ◽

Chemical Warfare Agents ◽

Surface Enhanced Raman Spectroscopy ◽

Water Monitoring ◽

Hydrolysis Products ◽

Surface Enhanced ◽

Surface Enhanced Raman ◽

Warfare Agents

Protection of military personnel and civilians from water supplies poisoned by chemical warfare agents (CWAs) requires an analyzer that has sufficient sensitivity (μg/L, ppb), specificity (differentiate the CWA from its hydrolysis products), and speed (less than 10 minutes) to be of value. In an effort to meet these requirements, we have been investigating the ability of surface-enhanced Raman spectroscopy (SERS) to detect cyanide and sulfur mustard in water. In our work, we have developed a novel SERS-active material that consists of a porous glass with trapped metal particles. Previously, we coated the inside walls of glass vials and measured cyanide at 1 mg/L in water in as little as 1 minute. However, measurements of sulfur mustard have only been measured to 10 mg/L. Recently, we filled glass capillaries with the SERS-active material. Here we describe measurements of cyanide, sulfur mustard, and it's hydrolysis product, thiodiglycol, using these capillaries and a portable Raman analyzer suitable for point and continuous water monitoring.

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The U. S. Army Reactive Topical Skin Protectant (rTSP): Challenges and Successes

MRS Proceedings ◽

10.1557/proc-628-cc10.8 ◽

2000 ◽

Vol 628 ◽

Cited By ~ 2

Author(s):

Stephen T. Hobson ◽

Erich K. Lehnert ◽

Ernest H. Braue

Keyword(s):

Composite Materials ◽

Sulfur Mustard ◽

Cell Model ◽

Research Effort ◽

Base Material ◽

Chemical Warfare Agents ◽

Fold Increase ◽

Inorganic Oxides ◽

Warfare Agents

ABSTRACTIn 1994, the U. S. Army initiated a research effort towards an effective material that acts both as a protective barrier and as an active destructive matrix against chemical warfare agents (CWA). We report results on our preparation and evaluation of Reactive Topical Skin Protectants (rTSP's). These creams are composite materials consisting of a base material (TSP) and a reactive moiety. Using an established base of perfluorinated-polyether and perfluoropolyethylene solids we incorporated over 60 reactive components. Classes tested include organic polymers, organic/inorganic hybrid materials, polyoxometallates (POM's), enzymes, inorganic oxides, metal alloys and small molecules. We characterized these materials by light microscopy and FTIR. We determined the efficacy of these materials against both sulfur mustard (HD) and a representative nerve agent, soman (GD), using a penetration cell model coupled to a continuous air monitor and also by in vivo testing. Composite materials with optimum reactive compounds exhibit a 94% reduction of GD vapor break-through after 20 hours (from 9458 ng to 581 ng) and a 3.6 fold increase (from 162 min to 588 min) in the time 1000 ng of GD liquid penetrates through the material. Similar composite materials show a 99% reduction in HD vapor break-through after 20 hours (from 4040 ng to 16 ng), a 2.3 fold increase (from 524 min to >1200 min) in the time 1000 ng of HD vapor penetrates through the material, and an elimination of erythema versus control in an HD vapor challenge. These results indicate that an rTSP that protects against sulfur mustard and nerve agents is within reach.

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