Organisation For Prohibition Of Chemical Weapons Research Articles

Selective Colorimetric Detection of Novichok Agents with Hydrazone Chemosensors.

Novichok is a recently identified class of neurotoxic organophosphorus compounds that have subsequently been banned by the Organization for Prohibition of Chemical Weapons (OPCW) as chemical warfare agents. Selective, rapid detection of Novichok remains a challenge. Several colorimetric paper-based detection devices have recently been developed for the rapid and selective detection of sarin, VX, and sulfur mustard. In this article, we present a similar colorimetric device designed specifically for the detection of Novichok, based on hydrazone derivatives from 2,4-dinitrophenylhydrazine (2,4-DNPH) impregnated on a glass fiber substrate. Results show that these compounds rapidly and selectively reveal the presence of Novichok agents to the naked eye. The low cost, ease of use, portability, and high selectivity to Novichok of this device complete the detection range of colorimetric paper-based sensors for chemical warfare agents.

Verification of Exposure to Novichok Nerve Agents Utilizing a Semitargeted Human Butyrylcholinesterase Nonapeptide Assay

Novichok (NV) nerve agents were recently added to the list of Schedule 1 chemicals of the Chemical Weapons Convention. There is a well-accepted method for assessment of nerve agent exposure based on mass spectrometric analysis of a nonapeptide with the serine-198 residue modified by the nerve agent, but this approach has not yet been reported for the class of NV agents and requires the availability of reference standards, which may be a limitation for NV agent exposure assessment. Thus, a goal of this study was to first verify the utility of the nonapeptide method for the characterization of human plasma samples exposed in vitro to the NV agents A-230, A-232, and A-234. A second aim was to evaluate the possibility of identifying unknown exposures by applying precursor ion scanning in combination with high resolution mass spectrometry (HRMS). Thus, precursor ion scanning, with a generic fragment ion (m/z 778) of the nonapeptide, was used to pinpoint any modified nonapeptide, while HRMS was used for structural elucidation of the adduct moiety. By this approach, use of HRMS enabled differentiation between adducts of agents with similar molecular masses. A new unique feature that could be exploited for NV nonapeptide analysis was that the modification was released from the peptide during fragmentation in the mass spectrometer and was detected in the low-mass region of the mass spectrum. This low-mass region was extremely informative and contributed to the assignment of the structure of the particular agent used, which is especially important in case no reference materials are available. The presented method is important for verification purposes by the Organisation for Prohibition of Chemical Weapons (OPCW), e.g., in case of investigations of alleged use of NV agents, and for regular forensic investigations.

Tools and Incentives for Implementing Codes of Ethics to Help Prevent the Reemergence of Chemical Weapons

Since 1997, when the Chemical Weapons Convention (CWC) entered into force and the Organisation for Prohibition of Chemical Weapons (OPCW) was established, >97% of the world’s declared stockpile, comprising 70,372 t of chemical warfare agents, has been destroyed. Despite this notable progress, advances in chemical synthesis bring new challenges to preventing chemical weapons production. The development of ethical codes or guidelines such as The Hague Ethical Guidelines and the Global Chemists’ Code of Ethics (GCCE) and their voluntary adoption by chemical practitioners worldwide are important steps in strengthening international nonproliferation efforts through their potential to impact the intent of the individual by normalizing ethical behavior. However, the simple act of adopting a code or implementing Responsible Care initiatives does not guarantee ethical behavior. Individuals’ decisions often contribute to the seriousness of chemical incidents and accidents, even if the root causes are shortfalls in safety and/or security. History is replete with accounts of chemical incidents that were made worse due to ethics failures at the individual and/or corporate level. The cost associated with response and root cause investigations for such incidents can be massive, but knee-jerk reactions to push for more regulation or to establish more oversight mechanisms following the immediate impact and initial cleanup may require significantly more resources to execute. At their core, ethics failures often arise, at least partially, due to a lack of shared investment in the company’s mission. When people are guided by a shared mission, they are more likely to bring a sense of professionalism to their work and to hold each other accountable for ethical behavior. Scenario-based training can provide new employees opportunities to practice acting ethically, but it takes time and money to organize in-person training events. Careful implementation of scenario-based e-learning to teach behavioral expectations that compel trainees to practice and discuss ethics, however, can provide a meaningful way to ensure employees are provided the necessary opportunities to rehearse ethical behavior, regardless of where they are physically located. As individuals become comfortable identifying and standing up for what is right, they strengthen their resolve to act when issues arise in the future. Company managers and university professors alike have a duty to educate others on the importance of ethical behavior, capitalize on teachable moments to help others understand the principles behind the desired behaviors, encourage others to speak up and act when they see something wrong, and model the behaviors they seek. In so doing, they may actively participate in making the world a better place and minimize the potential for the reemergence of chemical weapons.

In-situ derivatization and headspace solid-phase microextraction for gas chromatography-mass spectrometry analysis of alkyl methylphosphonic acids following solid-phase extraction using thin film

A headspace solid-phase microextraction (HS-SPME) method, involving solid-phase extraction and in-situ derivatization using polymeric thin film, was developed for the gas chromatography-mass spectrometry (GC–MS) analysis of the degradation products of nerve agents. The solid-phase extraction (SPE) was performed using poly([2-(Methacryloyloxy)ethyl]trimethylammonium chloride) film on a gold plate prepared via surface-initiated polymerization. The extracted analytes were directly derivatized with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) on the plate. Various parameters like fiber type, headspace time, temperature, and amount of BSTFA were optimized. Under the optimized conditions, the relative standard deviations (RSDs) were in the range 7.0–13.1% and the limits of detection (LODs) were measured to be between 10 and 20 pg mL−1. The application of the developed method was tested using the 35th Organization for Prohibition of Chemical Weapons (OPCW) proficiency test sample.

Keeping Momentum up and Looking Forward

Abstract At the beginning of a new biennium, the first thing is always to have a look at what we have accomplished, where we are, and to think about what to do next. I thank the volunteers and the staff of the Union for their excellent work over the last two years. Highlights include the naming of four new elements, progress on the revision of IUPAC’s “color books,” the release of several IUPAC Recommendations, the granting of many awards, the establishment of the Interdivisional Committee on Green Chemistry for Sustainable Development, and strengthened cooperation with other international organizations, including the Organization for Prohibition of Chemical Weapons (OPCW) and the International Younger Chemists Network.

La Organización de Prohibición de Armas Químicas (OPAQ) y su intenso trabajo por la paz y seguridad mundial

La Organización de Prohibición de Armas Químicas (OPAQ) y su intenso trabajo por la paz y seguridad mundial

Single vial sample preparation of markers of nerve agents by dispersive solid-phase extraction using magnetic strong anion exchange resins

A sample preparation method involving extraction, enrichment and derivatization of acidic degradation products of nerve agents was developed using magnetic strong anion exchange resins (MSAX). The method was performed in a single vial involving magnetic dispersive solid phase extraction (MDSPE). Analytes were derivatized with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) in the presence of resins. MSAX were custom synthesized using Fe3O4 nanoparticles as core, 4-vinylpyridine-co-divinylbenzene as polymer shell and quaternary pyridinium function as anion-exchanger. Hydroxide ions were the counter-anions of MSAX to effectively capture the acidic alkyl alkylphosphonic acids (AAPAs) and alkylphosphonic acids (APAs). Quantitative measurements of analytes were performed in the selected ion monitoring mode of GC–MS. Full scan mode of analysis was followed for identifications. Under the optimized conditions analytes were recovered in the range of 39.7–98.8% (n=3, relative standard deviations (RSD) from 0.3 to 6.5%). Limits of detection (LODs) were in the range of 0.1–1.1ngmL−1; and the linear dynamic range was 5–1000ngmL−1 with r2 of 0.9977–0.9769. Applicability of the method was tested with rain-, tap-, muddy-water and Organization for Prohibition of Chemical Weapons (OPCW) Proficiency Test samples.

Identification of N-Methyl Bis(2-(Alkyloxy-Alkylphosphoryloxy)Ethyl) Amines by LC-HRMS/MS

N-Methyl bis(2-(alkyloxy-alkylphosphoryloxy)ethyl)amines, which are abbreviated as PNPs, are a series of new skeleton chemicals belonging to schedule 2.B.04 chemicals of Chemical Weapons Convention (CWC). PNPs are important markers of chemical warfare agents because they are structurally relative to both nerve agents and N-mustards. In this study, fragmentation pathways of the most characteristic fragment ions in Q-TOF mass spectrometry were proposed based on the information from accurate mass and secondary fragmentations of product ions scan experiments. Results indicated that the base ion in LC/HRMS was the quasi-molecular ion [M+H]+. In LC-HRMS/MS, it was [M+H-CnH2n+1P(O)(OH)CmH2m+1O]+ fragment ion which was formed by losing an alkyloxy alkylphosphoryloxy group from the quasi-molecular ion. The diagnostic ion m/z84.0814 was identified as [C5H10N]+, which was the group of (CH2=CH)2N+(H)CH3. PNPs have two protonated centers. One is on the N atom, the other is on the O atom (P=O). O-n-propyl PNPs generally exhibited two fragmentation pathways. Firstly, the quasi-molecular ion [M+H]+ lost a propoxy alkylphosphoryloxy group to produce [R1P(OH+)(O-n-C3H7)OCH2CH2N(CH3)CH=CH2]+, which could be fragmented further to produce [C5H10N]+ ion. Secondly, [R1P(OH+)(O-n-C3H7) OCH=CH2]+ ions were produced from [M+H]+ and fragmented further to produce the abundant ions [R1P(OH+)(OH)OCH =CH2]. However, O-isopropyl PNPs characteristically produced weak fragment ions [M+H-C3H6]+, which were presumably formed via loss of CH3CH=CH2 from [M+H]+. Other PNPs showed similar fragmentation pathways as O-n-propyl PNPs. On the summarization of the MS fragmentation pathways of PNPs, LC-HRMS/MS quantitative and qualitative methods were developed and applied to analyze N-Methyl bis(2-(butoxy-methylphosphoryloxy)ethyl]amine in high background organic samples. The analytical results had successfully supported the sample preparation for the 33rd official proficiency test of Organization for Prohibition of Chemical Weapons (OPCW).

Ion-Pair Single-Drop Microextraction Determinations of Degradation Products of Chemical Warfare Agents in Water

Ion-pair single-drop microextraction (SDME) coupled to gas chromatography–mass spectroscopy (GC–MS) methods for the determination of four degradation products of chemical warfare agents were investigated in water. Acidic analytes were converted into their ion-pair complexes with cation surfactants in aqueous sample and then extracted into the organic single drop containing the derivatising agent. Upon injection, the analytes were derivatised in the GC injection hot port. Parameters, such as type of extraction solvent, ion-pairing (IP) reagent, reagent concentration, salt concentration, stirring speed and pH, were all optimized. This method is reproducible for spiked water sample for four different analytes (RSDs < 9.33 %, n = 5) and linear (r 2 > 0.9945). The limit of detection (LOD) is in the range of 0.08–0.01 ng mL−1 (S/N = 5) under GC–MS selected ion monitoring mode. The method was successfully applied to the proficiency test samples from the Organization for Prohibition of Chemical Weapons (OPCW).

English

The extractability of the O,O'-dialkyl methylphosphonates, (the important markers of nerve agents) included in the schedule 2B4 of the Chemical Weapons Convention (CWC) has been studied by NMR, the aim being the optimisation of extraction protocols routinely used for the identification of Convention-related Chemicals (CRCs) during Official Proficiency Tests (OPTs) conducted by the Organization for Prohibition of Chemical Weapons (OPCW) and for the off-site analysis of real field samples. The technique is easy to optimise, fast, nondestructive, and shows excellent reproducibility. Defence Science Journal, 2010, 60(5), pp.502-506 , DOI:http://dx.doi.org/10.14429/dsj.60.573

Liquid–liquid–liquid microextraction of degradation products of nerve agents followed by liquid chromatography–tandem mass spectrometry

Alkyl alkylphosphonic acids (AAPAs) are important environmental markers of nerve agents. A simple hollow fiber-based liquid–liquid–liquid microextraction (HFLLLME) technique has been developed to enrich the AAPAs from water. AAPAs were extracted from acidified aqueous phase to organic phase present in pores of the hollow fiber, and then back extracted into the alkaline acceptor phase present in the lumen of the hollow fiber. Variables affecting the HFLLLME process were optimized using a Plackett–Burman design and a Doehlert design. Optimal experimental conditions were: organic solvent, 1-octanol; pH of acceptor phase, 14; extraction time, 60 min; pH of donor phase, 1; and NaCl concentration, 10% (w/v). Depending upon the alkyl substituent, lower limits of detection varied from 0.1 to 100 ng mL −1 (S/N ≥ 5). Repeatability of the method was observed with relative standard deviation of 1.49–9.83% ( n = 3). After validation, the method was applied to detect AAPAs present in the water sample provided by the Organization for Prohibition of Chemical Weapons (OPCW) during the 23rd official proficiency test. The added advantage of this method is that several successive extractions of AAPAs from the same water sample can be performed.

Application of cation-exchange solid-phase extraction for the analysis of amino alcohols from water and human plasma for verification of Chemical Weapons Convention

The analysis of nitrogen containing amino alcohols, which are the precursors and degradation products of nitrogen mustards and nerve agent VX, constitutes an important aspect for verifying the compliance to the CWC (Chemical Weapons Convention). This work devotes on the development of solid-phase extraction method using silica- and polymer-based SCX (strong cation-exchange) and MCX (mixed-mode strong cation-exchange) cartridges for N, N-dialkylaminoethane-2-ols and alkyl N, N-diethanolamines, from water. The extracted analytes were analyzed by GC–MS (gas chromatography–mass spectrometry) in the full scan and selected ion monitoring modes. The extraction efficiencies of SCX and MCX cartridges were compared, and results revealed that SCX performed better. Extraction parameters, such as loading capacity, extraction solvent, its volume, and washing solvent were optimized. Best recoveries were obtained using 2 mL methanol containing 10% NH 4OH and limits of detection could be achieved up to 5 × 10 −3 μg mL −1 in the selected ion monitoring mode and 0.01 μg mL −1 in full scan mode. The method was successfully employed for the detection and identification of amino alcohol present in water sample sent by Organization for Prohibition of Chemical Weapons (OPCW) in the official proficiency tests. The method was also applied to extract the analytes from human plasma. The SCX cartridge showed good recoveries of amino alcohols from human plasma after protein precipitation.

Extraction of acidic degradation products of organophosphorus chemical warfare agents: Comparison between silica and mixed-mode strong anion-exchange cartridges

The analysis of alkyl alkylphosphonic acids (AAPAs) and alkylphosphonic acids (APAs), the hydrolyzed products of nerve agents, constitutes an important aspect for verifying the compliance to the Chemical weapons convention (CWC). This work devotes on the development of solid-phase extraction method using polymeric mixed-mode strong anion-exchange (Oasis MAX) cartridges for extraction of AAPAs and APAs from water. The extracted analytes were analyzed by GC–MS under full scan and selected ion monitoring mode. The extraction efficiencies of MAX and silica-based anion-exchange cartridges were compared, and results revealed that MAX sorbents yielded better recoveries. Extraction parameters, such as loading capacity, extraction solvent, its volume, and washing solvent were optimized. Best recoveries were obtained using 1 mL of acidic methanol (0.1 M), and limits of detection could be achieved up to 5 × 10 −4 μg mL −1 (in SIM) and 0.05 μg mL −1 in full scan mode. The method was successfully employed for the detection and identification of alkylphosphonic acids present in soil sample sent by the Organization for Prohibition of Chemical Weapons (OPCW) in the official proficiency tests.

WEAPONS TREATY GROUP MEETS

DELEGATES FROM 151 MEMber states of Organization for Prohibition of Chemical Weapons (OPCW) will meet in Hague this week and next to assess how well 1997 Chemical Weapons Convention is working. treaty calls for a review conference every five years, and this is first to be held. With threat of terrorists using weapons of mass destruction looming large, keeping treaty on track toward total elimination of chemical weapons (CW) and fostering of peaceful uses of chemistry is imperative today. The need to rely upon strength of convention and firm resolve of states' parties has never been greater, OPCW Director-General Rogelio Pfirter says. With Pfirter's words in mind, delegates will take up the timely destruction of all declared CWs, ensure that all states' parties have implemented legislation to make any breach of convention a crime, and consider more resource-efficient means to stem ...