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Emerging and Re-emerging Chemical Threats (part 2)

Defense General

Chemical Threats on the Battlefield and Home Front

Chemical weapons. Some might read that and think they’re a relic of the past. A technology reserved for history that is buried in books and that has given way to more modern weapons and warfare. In part, that may be because the first use of blister agents in World War I occurred more than 100 years ago, so it seems distant. Soon thereafter, the Geneva Protocol banned the use – but not development or possession – of chemical warfare agents. 

Since then, chemical weapons have been developed, possessed, and used in conflicts around the world. The oft-cited Aum Shinrikyo attacks in the 1990s are well-known for the use of sarin (GB), one of the most dangerous agents due to its volatility. Years later in 2002, the Dubrovka Theater in Moscow was held siege by Chechen terrorists. More than 800 hostages were taken, ending with the death of at least 170 people from exposure to aerosolized opioids. A decade later, the Assad regime used weapons carrying nerve agent sarin into the Ghouta district of Damascus, Syria, killing more than 1,400 people. In 2017, the assassination of Kim Jong-nam, the older half-brother of the incumbent leader of North Korea Kim Jong Un, brought the semi-volatile nerve agent VX into the public eye. Two of the most high-profile recent uses of chemical weapons were the attempted assassinations of Russians Sergei Skripal in 2018 and Alexei Navalny in 2020. In each case, assassins used agents known as Novichok, which are semi-volatile nerve agents. Lastly, one doesn’t have to look hard to find headlines covering deaths related to fentanyl and other potent opioids; while not chemical weapons, these types of substances can be used for nefarious purposes.

Today’s conflicts around the world highlight the current and pressing need for continued research to help ensure the safety of anyone in danger. And though we touched on “Emerging and Re-emerging Chemical Threats” earlier in the year, because emerging and re-emerging chemical threats pose an ever-present challenge to both warfighters and civilians, we are revisiting the topic to share additional expertise. To learn more, we visited with Cristina Youngren and Evan Durnal, subject matter experts in MRIGlobal’s Integrated Defense Solutions division.

How do we know if a chemical weapon has been used?
Identification of exposure to a chemical warfare agent (CWA) or other toxic chemical depends on if the exposure was environmental, for example at a testing site, or if there were people or other living creatures showing symptoms of exposure. In a case of environmental exposure, instrumental analysis methods can detect even trace amounts of CWAs, their precursors, or degradation products present in air, water, soil, sand, or on surfaces. 

Determination of CWA use in exposed victims can be difficult as the onset of symptoms can vary based on the agent used, the concentration of the dose, and the route of exposure. Adequate training of medical professionals to identify probable symptoms of CWA exposure is critical. Once that possibility has been determined, tests exist to verify the presence of nerve agent organophosphates in the body, allowing for rapid use of antidotes such as atropine or oximes to counteract their effect of acetylcholinesterase enzyme inhibition. Although certain CWAs do not have antidotes, early identification can allow for effective treatment to mitigate their effects.

Interested in hearing more? Cristina Youngren joined Dr. Amy Manning-Boğ for a conversation about “Chemical Threats” on this episode of the “Science Diction” podcast from MRIGlobal.

What types of technologies can be used to identify chemical weapons?
CWAs can be found in the form of liquid, gas, or aerosol particles. Numerous instrumental analysis methods can be used to identify the neat (also called concentrated or intact) agents as well as their precursors or degradation products. The metabolites and adducts of CWAs can also be detected in victims through their urine, plasma, tissue, or even hair. In the field, quick qualitative identification methods such as colorimetric sensors or portable miniature detectors are extremely useful to identify whether an agent has been used. 

These most commonly utilized identification methods utilize Raman or FTIR spectroscopy for bulk samples and ion mobility spectrometry for trace samples. While these methods are very helpful for fast identification, they are not always sensitive enough to detect trace amounts of CWAs or selective enough to specifically identify the correct CWA. More advanced quantification methods include gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS), which can be made portable as well. High resolution mass spectrometry can also be combined with chromatography or used as a complementary technology to NMR spectroscopy for CWA characterization.

What does MRIGlobal do to mitigate these threats to warfighters and civilians?
MRIGlobal has a long and successful history providing test and evaluation services related to CWAs. Over the years, MRIGlobal has tested and assessed hundreds of decontamination and detection technologies for chemical agents, toxic industrial chemicals, toxic industrial materials, explosives, bio-threat agents, and nontraditional agents. Our testing and evaluation experience has included sampling, real-time detection, decontamination, chemical detection library development, and bench-top analytical method development. 

Our Chemical Agent Facility and team are fully equipped to perform a wide variety of testing and research activities using neat CWAs including permeation testing, vapor and aerosol generation, purification and synthesis, kinetic determinations, transport and fate determinations, decontamination testing, vapor and contact hazard testing, CWA purity determinations, and evaluations of new and innovative instrumental techniques for detecting CWAs. This capability includes qualitative and quantitative testing of CWAs, their precursors, and degradation products using advanced analytical instrumentation methods. By constantly refining and improving CWA detection and decontamination methods, we contribute to our mission of improving people’s lives through innovative scientific and engineering research.

Once a chemical weapon has been used, can the site be decontaminated?
The short answer is yes, though the decontamination method employed is highly dependent on the specific CWA(s) present and the substrate or environment being decontaminated. An effective decontaminant is one that eliminates the hazard of a CWA quickly and completely without forming any degradation products that are themselves dangerous. 

The earliest CWA decontamination agents were various forms of bleach (either sodium or calcium hypochlorite) used in response to sulfur mustard (HD) exposure in 1915. Bleach is quite corrosive to many surfaces including human skin, requires large amounts to be effective, decreases quickly in efficacy when stored, and while it neutralizes G-series nerve agents, its effectiveness is pH dependent for V-series and other compounds. Modern decontamination methods optimize degradation mechanisms such as nucleophilic neutralization, oxidation, and most often hydrolysis by a variety of physiochemical means. Liquid or powder decontaminants include alkali salts, amino alcohols, imidazoles, potent oxidizers such as Oxone, and deep eutectic solvents. Catalytic methods use enzymes like phosphotriesterase, metals like copper, or combinations of metal-organic frameworks to neutralize agent toxicity.

With the goal of decontaminating toxic materials like TICs and TIMs (toxic industrial chemicals and toxic industrial materials), MRIGlobal researched development and testing of a soap that is safe for skin and surfaces. Established as a broad-spectrum, low-volume decontaminant that shows good reactivity and efficacy against a broad array of chemical and biological warfare agents, Dahlgren Decon is overpowering for many common hazardous materials. Our work examined a reformulated and diluted version of the Dahlgren Decon chemistry known as Dahlgren Decon Skin Soap (DDSS), with a formulation that may provide a decontamination solution for use on a variety of common hazardous threat materials and on surfaces that include human skin. Read more at “Decontaminating Toxic Industrial Chemicals and Materials.” 

Ensuring Accurate Identification of Chemical Agents
To ensure accurate identification of chemical agents, MRIGlobal research scientists developed a new process to generate high-purity vapors of semi-volatile chemical agents. This process has the potential to improve the chemical vapors used in the testing of existing and new technologies to identify chemical agents, resulting in more accurate evaluations. These methods may also be used to help create medical countermeasures or expose materials for subsequent decontamination tests. Read more at “New Generation Method Delivers Clean Vapor Profiles.”

Market Survey Supports First Responders
While not chemical weapons, the accurate detection and identification of fentanyl and other potent opioids is critical. To support his effort, MRIGlobal created a baseline market survey of portable detection equipment capable of identifying these compounds. This effort provides first responders with independent, unbiased, and reliable third-party data to choose the fieldable chemical detection equipment that is right for them. Read more at “Detection Equipment to Address the Drug Crisis.”

Contact MRIGlobal to further understand our work in defense against chemical and biological threats. We work with our clients to test and evaluate current methods to detect, prevent, decontaminate, protect, and destroy these materials.

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