Influence of Chlorinating Agents on the Formation of Stable Biomarkers in Hair for the Retrospective Verification of Exposure.

Chlorine, as a dual-use chemical, is an essential industrial chemical which has been used as a chemical weapon in the past due to its toxicity and availability. The retrospective verification of chlorine intoxication is often especially challenging, and unambiguous markers are still missing. In this study, the effects of different chlorinating and oxidizing agents on human hair were investigated. Samples were exposed to a variety of chlorinating chemicals for a short time and then completely hydrolyzed by a HBr solution to break down their keratin proteins into individual amino acids. After derivatization and targeted liquid chromatography-mass spectrometry analysis, 3-chlorotyrosine and 3,5-dichlorotyrosine were unambiguously identified from human hair exposed to chlorine, hypochlorite, and sulfuryl chloride. Our results show long-term stability of these markers in the biological matrix, as the chlorotyrosines can still be found 10 months post-exposure at the same levels. Finally, an untargeted analysis was able to discriminate between some of the different intoxicants.

Effects of chemical warfare agent decontaminants on trace survival: Impact on fingermarks deposited on glass.

Following a chemical incident involving chemical warfare agents or more broadly, chemical weapons, there are two possible approaches in dealing with the traditional forensic analysis of contaminated exhibits. The first is to analyze the contaminated items under safe conditions (i.e. in laboratories dedicated to the handling of such substances), while the second relies on item decontamination prior to processing them in traditional forensic laboratories. One of the main limitations of the latter is the possible degradation or destruction of traces caused by the decontamination process. Hence, it is crucial to have as much information as possible on the impact of different decontamination agents and procedures on traces. This research presents experimental results on the recovery of fingermarks on glass after the application of decontaminants typically used in case of chemical incidents. The impact of 11 decontaminants on fingermarks deposited on glass and on the subsequent enhancement with cyanoacrylate and Small Particle Reagent (SPR) was evaluated (by visual examination) by four evaluators. The results of the study demonstrated that the persistence of fingermarks on glass is highly dependent on the type of decontaminant used. Decontamination agents based on the principle of nucleophilic substitution to neutralize toxic chemicals allowed good subsequent development of fingermarks with SPR. Powdered decontaminants did not show any indication of alteration of fingermarks, whereas decontamination with oxidants leads to variable results.

A Rapid, Highly Sensitive and Selective Phosgene Sensor Based on 5,6-Pinenepyridine.

The toxicity of phosgene (COCl2 ) combined with its extensive use as a reactant and building block in the chemical industry make its fast and accurate detection a prerequisite. We have developed a carboxylic derivative of 5,6-pinenepyridine which is able to act as colorimetric and fluorimetric sensor for phosgene in air and solution. For the first time, the formation of a pyrido-[2,1-a]isoindolone was used for this purpose. In solution, the sensing reaction is extremely fast (under 5 s), selective and highly sensitive, with a limit of detection (LOD) of 9.7 nM/0.8 ppb. When fixed on a solid support, the sensor is able to detect the presence of gaseous phosgene down to concentrations of 0.1 ppm, one of the lowest values reported to date.

Advice on assistance and protection provided by the Scientific Advisory Board of the Organisation for the Prohibition of Chemical Weapons: Part 3. On medical care and treatment of injuries from sulfur mustard.

Blister agents damage the skin, eyes, mucous membranes and subcutaneous tissues. Other toxic effects may occur after absorption. The response of the Scientific Advisory Board (SAB) of the Organisation for the Prohibition of Chemical Weapons (OPCW) to a request from the OPCW Director-General in 2013 on the status of medical countermeasures and treatments to blister agents is updated through the incorporation of the latest information. The physical and toxicological properties of sulfur mustard and clinical effects and treatments are summarised. The information should assist medics and emergency responders who may be unfamiliar with the toxidrome of sulfur mustard and its treatment.

Qualitative colorimetric analysis of a Ir(iii)/Eu(iii) dyad in the presence of chemical warfare agents and simulants on a paper matrix.

The addition of G- and V-series organophosphorus chemical warfare agents and simulants to a paper-based assay of a dual-luminescent Ir(iii)/Eu(iii) dyad generated different emissive responses between the classes and compound types. The emission responses are complex and based not only on altering the balance between red Eu(iii)-based and blue Ir(iii)-based luminescent components, but also incorporate other factors such as analyte volatility, concentration and UV absorption. The extent of this emission colour change was analysed colorimetrically and related to the change in RGB output over time.

Advice on chemical weapons sample stability and storage provided by the Scientific Advisory Board of the Organisation for the Prohibition of Chemical Weapons to increase investigative capabilities worldwide.

The Scientific Advisory Board (SAB) of the Organisation for the Prohibition of Chemical Weapons (OPCW) has provided advice on the long-term storage and stability of samples collected in the context of chemical weapons investigations. The information they compiled and reviewed is beneficial to all laboratories that carry out analysis of samples related to chemical warfare agents and is described herein. The preparation of this report was undertaken on request from the OPCW Director-General. The main degradation products for chemicals on the Schedules in the Annex on Chemicals of the Chemical Weapons Convention are tabulated. The expertise of the 25 scientists comprising the SAB, a review of the scientific literature on environmental and biomedical sample analysis, and answers to a questionnaire from chemists of nine OPCW Designated Laboratories, were drawn upon to provide the advice. Ten recommendations to ensure the long-term storage and stability of samples collected in relation to the potential use of chemical weapons were provided and are repeated here for the consideration of all laboratories worldwide.

Synthesis of different glutathione-sulfur mustard adducts of verified and potential biomarkers.

Sulfur Mustard (SM) is a blistering agent used as a chemical weapon. Glutathione (GSH) is involved in the ß-lyase degradation pathway of SM and recently, bioadducts between SM and GSH were observed in vitro. While these bioadducts have never been isolated from in vivo tests or real poisoning with SM, they could be of interest as potential future biomarkers for the retrospective validation of exposure. We herein report the synthesis of different observed and new potential GSH-SM bioadducts as reference materials for analytical investigation. Two distinct approaches were investigated: a building-block pathway and the direct reaction with GSH. The availability of these references will aid future studies and may lead to the discovery of new GSH-SM biomarkers.

Advice from the Scientific Advisory Board of the Organisation for the Prohibition of Chemical Weapons on riot control agents in connection to the Chemical Weapons Convention.

Compounds that cause powerful sensory irritation to humans were reviewed by the Scientific Advisory Board (SAB) of the Organisation for the Prohibition of Chemical Weapons (OPCW) in response to requests in 2014 and 2017 by the OPCW Director-General to advise which riot control agents (RCAs) might be subject to declaration under the Chemical Weapons Convention (the "Convention"). The chemical and toxicological properties of 60 chemicals identified from a survey by the OPCW of RCAs that had been researched or were available for purchase, and additional chemicals recognised by the SAB as having potential RCA applications, were considered. Only 17 of the 60 chemicals met the definition of a RCA under the Convention. These findings were provided to the States Parties of the Convention to inform the implementation of obligations pertaining to RCAs under this international chemical disarmament and non-proliferation treaty.