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The present study aimed to investigate the persistence and existence of chemical warfare agents (CWAs) and related dissipation products in the environment of Sardasht area, Iran. Three types of environmental samples including water, soil, and native local plant materials were collected and analyzed. Gas chromatography-mass spectrometry in the elect...
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Chemical warfare agents (CWAs) are significant threats to human peace and global safety. Most of the personal protective equipment in service used to barrier CWAs is devoid of decontamination activity. Rechargeable N‐halamine‐based detoxifying nanofibers/graphene chemical protective aerogels (HNAs) with ternary pores bearing π‐conjugation galleries...
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... Since soil organisms' populations are linked together, so any adverse impact of CWAs on single species can easily alter the rest of them too. As a result, all these negative impacts can interfere with essential soil processes which have important roles in the flow, regulation, internal cycling of nutrients and carbon, and irreversibly degradation of soil ecosystems (Chmielińska et al., 2019;Kuperman et al., 2014Kuperman et al., , 2007Kuperman et al., , 1998Medvedeva et al., 2008;Vaezihir et al., 2021). For example, mustard gas can significantly impact the micro invertebrate community of soil depending on the soil texture (Certini et al., 2013;Kuperman et al., 2007). ...
... For example, previous studies by investigating the susceptibility of a war impacted area, where mustard gas was used during Iraq-Iran war, to wind erosion found that contaminated particles originating from this contaminated area are affecting both terrestrial and marine environments during both cold and warm periods of a year (Broomandi et al., 2017(Broomandi et al., , 2018(Broomandi et al., , 2021. Therefore, it is important to predict and investigate the changes in soil ecosystem caused by persistent soil contaminants (Chmielińska et al., 2019;Vaezihir et al., 2021). However, ecotoxicological test studies with CWAs are scarce and usually focus only on the impact of CWAs added to a natural soil or artificial soil (e.g., OECD soil), than the use of naturally contaminated soil by CWAs. ...
War and military activities impact soil properties by physical, chemical, and biological disturbances during warfare, terrorist attacks, and military activities. Soil pollution by Potentially Toxic Elements, energetic compounds or organic contaminants have the most significant impacts on soil ecosystems. Among these pollutants, Chemical Warfare Agents (CWAs) are one of the least known and with less information available primarily due to difficulties of access to collect naturally contaminated samples or challenges in determining the contaminants, especially with their distribution in the soil. This chapter summarises existing information about CWAs, focusing on the detection of CWAs and their breakdown products, distribution in the soil profile, bioaccumulation, ecotoxicology and their remediation through physical, chemical and biological methods. We demonstrate a significant scarcity of information about the impact of CWAs on soil ecosystems and their potential risk to human health and biota, such as the no-existence of soil guidelines. More studies are needed covering a range of CWAs and the collaboration between the civilian scientist and military corps are also needed.
... The use of plant evidence has been scarcely examined for the presence of the intact CWAs or associated degradation products. [22][23][24][25][26] In addition, a news article reported that researchers at Lawrence Livermore National Laboratory identied small chlorine biomarkers and protein adducts in grass. 27 However, to our knowledge, no research article has been published that specically targets plant protein adducts to demonstrate CWA exposure. ...
The continuing threats of military conflicts and terrorism may involve the misuse of chemical weapons. The present study aims to use environmental samples to find evidence of the release of such agents at an incident scene. A novel approach was developed for identifying protein adducts in plants. Basil (Ocimum basilicum), bay laurel leaf (Laurus nobilis) and stinging nettle (Urtica dioica) were exposed to 2.5 to 150 mg m-3 sulfur mustard, 2.5 to 250 mg m-3 sarin, and 0.5 to 25 g m-3 chlorine gas. The vapors of the selected chemicals were generated under controlled conditions in a dedicated set-up. After sample preparation and digestion, the samples were analyzed by liquid chromatography tandem mass spectrometry (LC-MS/MS) and liquid chromatography high resolution tandem mass spectrometry (LC-HRMS/MS), respectively. In the case of chlorine exposure, it was found that 3-chloro- and 3,5-dichlorotyrosine adducts were formed. As a result of sarin exposure, the o-isopropyl methylphosphonic acid adduct to tyrosine could be analyzed, and after sulfur mustard exposure the N1- and N3-HETE-histidine adducts were identified. The lowest vapor exposure levels for which these plant adducts could be detected, were 2.5 mg m-3 for sarin, 50 mg m-3 for chlorine and 12.5 mg m-3 for sulfur mustard. Additionally, protein adducts following a liquid exposure of only 2 nmol Novichock A-234, 0.4 nmol sarin and 0.2 nmol sulfur mustard could still be observed. For both vapor and liquid exposure, the amount of adduct formed increased with the level of exposure. In all cases synthetic reference standards were used for unambiguous identification. The window of opportunity for investigation of agent exposure through the analysis of plant material was found to be remarkably long. Even three months after the actual exposure, the biomarkers could still be detected in the living plants, as well as in dried leaves. An important benefit of the current method is that a relatively simple and generic sample work-up procedure can be applied for all agents studied. In conclusion, the presented work clearly demonstrates the possibility of analyzing chemical warfare agent biomarkers in plants, which is useful for forensic reconstructions, including the investigation into alleged use in conflict areas.
Organoarsenicals, such as Lewisite and related chloroarsine, Di-phenyl Chloro Arsine (DPCA), are chemical warfare agents developed during WWI. Stockpiles in Eastern Europe remain a threat to humans. The well-documented effects of cutaneous exposure to these organoarsenicals include skin blisters, painful burns, and life-threatening conditions such as Acute Respiratory Distress Syndrome. In survivors, long-term effects such as the development of respiratory ailments are reported for the organoarsenical sulfur mustard (SM), however no long-term pulmonary effects are documented for lewisite and DPCA. No animal models exist to explore the relationship between skin exposure to arsenicals and constrictive bronchiolitis. We developed and characterized a mouse model to study the long-term effects of cutaneous exposure on the lungs in survivors. We exposed mice to lewisite, DPCA, or a less toxic surrogate organo-arsenic chemical phenyl arsine oxide (PAO) on the skin. The surviving mice were followed for 20 weeks following skin exposure to arsenicals. The lung micro-computed tomography, lung function, and histology demonstrated increased airway resistance, increased thickness of the smooth muscle layer, increased collagen deposition in the sub-epithelium, and l peribronchial lymphocyte infiltration in the mice exposed to arsenical on skin.
The detection of Chemical Weapon Convention (CWC)-related amine compounds including the precursors or degradation products of V-type organophosphorus nerve agent, nitrogen mustard and 3-quinuclidinyl benzilate is an important aspect for verifying their intact chemical warfare agents. This work focuses on the development of a novel formulation for the simultaneous solvent extraction of eleven CWC-related amine compounds, from the four-type soil matrices including environmental standard soil, sand, clay, and loam. Extracts were well separated on the hydrophilic interaction liquid chromatography (HILIC) and then detected by MS/MS multiple reaction monitoring mode. The type and component of solvent mixtures were optimized to cover a wide range of polarity over all eleven amine compounds with high extraction efficiencies. Extraction parameters, such as the proportion of methanol, water and NH4OH, the times and the period of extraction, and volumes of extraction solution were optimized. The results indicated that a mixed solvent of methanol/water (44:53, v/v) in 3.0% NH4OH was the optimal formulation for extraction of all 11 analytes with high mean extraction recoveries (64.4-96.1%). Specificity and sensitivity were well improved by the good separation of 11 analytes from four-type soil matrices using these optimized HILIC parameters. This method was fully validated for each analyte in four soil matrices. The linear range of 11 analytes was 0.50/0.75-500 ng•g⁻¹ with correlation coefficient (R²) ≥0.990, and intra/inter-day accuracies were 70.3-125% with relative standard deviation (RSD) ≤19.3%. Limit of detection (LOD) of 11 analytes ranged from 0.01 to 0.5 ng•g⁻¹, which was far lower than those reported in previous studies. The built method accomplishes simultaneously quantitative and trace measurement of all eleven CWC-related amine compounds within a single solvent extraction and detection. It only takes a small amount of soil samples and possesses the highest sensitivity over all previous methods. This study provides an optional recommended operating procedure for determination of CWC-related amine compounds in four typical types of complex soils during chemical weapons verification.
