Chemical footprints of sulfur mustard: GC-MS profiling of methylated degradation products.
Sulfur mustard, a Schedule 1 chemical under the Chemical Weapons Convention (CWC), poses a significant threat to human health, animals, plants, and the environment due to its persistent nature. Bis(2-methoxyethylthio)alkanes (compounds 10-14), along with Bis(2-methoxyethyl)sulfide (compound 8) and related disulfide Bis(2-methoxyethyl)disulfide (compound 9), were synthesized and investigated using gas chromatography-mass spectrometry (GC-MS) under both electron ionization (EI) and positive chemical ionization (PCI) conditions. These compounds are structurally analogous to known degradation products of sulfur mustard, such as thiodiglycol and its derivatives, making them of particular interest for environmental analysis and chemical forensics. EI mass spectra revealed consistent fragmentation behavior, including α cleavage and neutral losses. Diagnostic ions at m/z 45 (C₂H₅O+), m/z 59 (C3H7O+), m/z 61 (C2H5S+), and m/z 75 (C3H7S+) were observed across the series. A generalized fragmentation pathway is proposed to support structural elucidation and homologous trend interpretation. PCI with isobutane and ammonia provided molecular ion confirmation via [M+H]+, [M+39]+, and [M+18]+ adducts. Due to their chemical resemblance to vesicant degradation products, these sulfur-containing compounds, along with their comprehensive mass spectral data, contribute to the spectral libraries essential for off-site analysis, substance verification, and participation in official proficiency tests conducted under the framework of the CWC by the Organization for the Prohibition of Chemical Weapons (OPCW).
- Research Article
- 10.1515/pac-2016-1115
- Jan 20, 2017
- Pure and Applied Chemistry
In May and June of 2016 the Organisation for the Prohibition of Chemical Weapons (OPCW), IUPAC and the ACS CHED Committee on Computers in Chemical Education (CCCE) collaboratively ran an online conference hosted with the online ConfChem conference system on “Science, Disarmament and Diplomacy in Chemical Education.” This ConfChem Online Conference was designed to highlight the work of the OPCW and the important contribution of scientists and educators to achieving its goals, the science that underpins the Chemical Weapons Convention, and how scientific and technological advances will help to better implement the Convention in the future. The OPCW is the implementing body for Chemical Weapons Convention, an international disarmament treaty banning chemical weapons. The organisation is now approaching the 20th anniversary of the entry into force of the Chemical Weapons Convention in 1997. Twenty years that have seen the destruction of more than 67 000 metric ton of the world’s declared military stockpiles of chemical weapons and a Nobel Peace Prize in 2013. With 192 States Parties (the governments that have agreed to uphold the norms and obligations required by the treaty), the Chemical Weapons Convention is the most widely subscribed disarmament treaty in history. Despite the aforementioned successes, the OPCW is not widely recognized outside disarmament-focused diplomatic circles. This is in spite of the fact that the science of chemistry played a critical role in informing the negotiations that lead to the signing of the Chemical Weapons Convention, and underpinning the articles of implementation. Science represents an important dimension in international disarmament policy and diplomacy, requiring that organizations like the OPCW interact with the scientific communities – especially in the field of chemistry. In order to achieve its goals in the future, the OPCW will need to reach out to new stakeholders and strengthen its ties with its existing partners. To this end, the OPCW has been placing increasing priority on education and engagement to raise awareness of its work and the contributions both from and to science in chemical disarmament. The objective of this internationally open access ConfChem online conference was to bring forth educational material that could usefully introduce chemistry educators and students to the nexus of science and multilateral diplomacy in chemical disarmament. To this end, we introduce the seven papers of the ConfChem and their authors. We hope you enjoy this collection of papers at the intersection of science and international disarmament policy. A collection that looks to stimulate interest in the role of scientists and educators, especially chemists in making the world a safer place.
- Research Article
3
- 10.1177/1469066719886424
- Nov 7, 2019
- European Journal of Mass Spectrometry
Screening of chemicals related to chemical weapons convention including their all possible degradation and reaction products in environmental samples is important in the organization for prohibition of chemical weapons verification process. Sulfur mustards, commonly known as blistering agents, are included in schedule 1 chemicals of chemical weapons convention. Because of the presence of chlorine atoms in sulfur mustards, they are highly reactive and prone to react with other organic molecules such as phenols to produce corresponding reaction products. Thus, it is important to screen for not only the sulfur mustards but also their reaction products for verification process. The sulfur mustards and their degradation products have been routinely analyzed by gas chromatography/mass spectrometry method, however, the methods are yet to establish for the reaction products. In this study, the reaction products of the sulfur mustards with phenol (compounds 1-7) were studied by gas chromatography/mass spectrometry under electron ionization and chemical ionization conditions. The EI spectra of 1-7 displayed molecular ion and characteristic fragments that provided structure information. Mostly the fragment ions were due to homolytic cleavages involving C-O, C-S, and C-C cleavages. The methane or isobutane CI spectra showed M+., [M + H]+, and [M - H]+ ions including reagent specific adduct ions. The CI spectra also showed other adduct ions formed by association of analyte molecule with its most abundant fragment ion. The gas chromatography/retention index values were also calculated, which support unambiguous identification of targeted molecules in suspected environmental samples. The method was demonstrated for detection of the targeted molecules spiked in soil samples.
- Book Chapter
- 10.1007/1-4020-4170-5_05
- Jan 1, 2006
The Chemical Weapons Convention (CWC) is shortly characterised stressing its main principles, inter alia the General Purpose Criterion. Status of its implementation as of December 2004 shows the main data obligatory declared by already 167 States Parties and main achievements in destruction of Chemical Weapons (CW) stockpiles and destruction / conversion of CW production facilities and the verification efforts. The Organisation for the Prohibition of the Chemical Weapons (OPCW) is briefly presented, results of the 1st Review Conference and future problems of the CWC are analysed. Special emphasis is laid on threats and benefits of the scientific and technological development and potential misuse of toxic chemicals for terrorist purposes. Role of the CWC especially of respective national implementation measures in combating chemical terrorism is analysed stressing the OPCWs expertise including its developed system of assistance and protection under the CWC and enforcement by all countries of the CWCs requirement to make the development, production, stockpiling, transfers and use illegal for anyone. (CWPF), CW destruction, CWPF destruction & conversion, CW non- production, Organisation for the Prohibition of Chemical Weapons (OPCW), First Review Conference, Chemical terrorism .
- Research Article
9
- 10.1351/pac200880010175
- Jan 1, 2008
- Pure and Applied Chemistry
This report summarizes the findings and recommendations of an international workshop that was organized jointly by IUPAC and the Organisation for the Prohibition of Chemical Weapons (OPCW), and held in Zagreb, Croatia, from 22 to 25 April 2007. It was held to assist with preparation for the Second Review Conference of the Chemical Weapons Convention (CWC), which will commence in April 2008. The CWC has been in force since 29 April 1997, and today 182 States have joined the Convention. The CWC aims at the total prohibition of all chemical weapons (CW) and the destruction of all CW stockpiles and production facilities by 2007. Extensions have been agreed upon and, for some CW stockpiles, the deadline is now 2012. This disarmament is subject to strict international verification by the OPCW. The CWC also prohibits the development, production, acquisition, stockpiling, and retention of CW and requires national implementation measures, including legislation, together with the international verification of chemical industry facilities. Furthermore, the CWC aims to strengthen States Parties' capacities in the field of protection against CW, and encourages international cooperation in the peaceful application of chemistry. The CWC requires that reviews of the operation of the Convention are carried out at five-year intervals and specifies that such reviews "shall take into account any relevant scientific and technological developments", so as to ensure the continued effectiveness of the treaty and of its verification and implementation systems. This report has been prepared to assist the parties of the CWC with that review.
- Research Article
- 10.1021/cen-10118-feature1
- Jun 5, 2023
- C&EN Global Enterprise
In 1997, the Chemical Weapons Convention —a first-of-its-kind global disarmament agreement—came into force. The treaty was championed by the Organisation for the Prohibition of Chemical Weapons (OPCW) with the aim of ridding the world of that class of weapons of mass destruction. In World War I alone, chemical weapons injured more than 1.3 million people, and over 100,000 of those died shortly after exposure, according to the OPCW . Now the OPCW is approaching a new milestone: the destruction of all declared stockpiles of chemical weapons by its 193 member states. (Only four countries—Egypt, Israel, North Korea, and South Sudan—aren’t members.) In a few weeks, the destruction of the remaining stockpiles by the US will be completed, according to the OPCW. In Pueblo, Colorado , the US is destroying between 600 and 700 4.2 in (107 mm) mortars containing sulfur mustard, also called mustard gas, a chemical warfare agent that
- Book Chapter
5
- 10.1002/9780470027318.a0405.pub2
- Dec 17, 2012
Mass spectrometry in combination with gas chromatography (GC/MS) is at present the most suitable technique for the analysis of chemicals related to the Chemical Weapons Convention (CWC), as GC/MS is capable of providing the required analytical evidence needed to sustain any claim of noncompliance under the Convention.(1–3) Chemical analysis will be carried out on‐site, during an inspection using mobile GC/MS equipment, or off‐site, in at least two designated laboratories selected by the Organization for the Prohibition of Chemical Weapons (OPCW). GC/MS analysis under the Convention is focused primarily on qualitative analysis (unambiguous identification) rather than on quantitative analysis. Moreover, GC/MS analysis has to be established under a strict quality assurance/quality control (QA/QC) program. The two most applied techniques in verification analysis are low‐resolution electron ionization (EI) and chemical ionization (CI) GC/MS under full scan conditions. EI is the oldest and still most used ionization technique for the analysis of CWC‐related chemicals. Therefore, special attention is paid in this article to the fragmentation under EI conditions of a number of chemicals belonging to the CWC Schedule list. The chemicals placed on this list are the target for verification analysis, especially the Schedule 1 chemicals, which encompass the well‐known chemical warfare agents (CWA) such as the nerve agents sarin (GB), soman (GD), tabun (GA), andO‐ethyl‐S‐2‐diisopropylaminoethyl methylphosphonothiolate (VX) and the vesicants sulfur mustard (HD) and lewisite (L). Sample preparation methods for these chemicals and their degradation products in environmental, synthetic material, and biological sample matrices are described in this article.
- Research Article
- 10.1515/ci.2003.25.1.17a
- Jan 1, 2003
- Chemistry International -- Newsmagazine for IUPAC
This report summarizes the findings and recommendations of an international workshop that was organized jointly by IUPAC and the Organisation for the Prohibition of Chemical Weapons (OPCW), and held in Zagreb, Croatia, from 22 to 25 April 2007. It was held to assist with preparation for the Second Review Conference of the Chemical Weapons Convention (CWC), which will commence in April 2008. The CWC has been in force since 29 April 1997, and today 182 States have joined the Convention. The CWC aims at the total prohibition of all chemical weapons (CW) and the destruction of all CW stockpiles and production facilities by 2007. Extensions have been agreed upon and, for some CW stockpiles, the deadline is now 2012. This disarmament is subject to strict international verification by the OPCW. The CWC also prohibits the development, production, acquisition, stockpiling, and retention of CW and requires national implementation measures, including legislation, together with the international verification of chemical industry facilities. Furthermore, the CWC aims to strengthen States Parties' capacities in the field of protection against CW, and encourages international cooperation in the peaceful application of chemistry. The CWC requires that reviews of the operation of the Convention are carried out at five-year intervals and specifies that such reviews shall take into account any relevant scientific and technological developments, so as to ensure the continued effectiveness of the treaty and of its verification and implementation systems. This report has been prepared to assist the parties of the CWC with that review.
- Research Article
6
- 10.1080/00450618.2018.1559356
- Dec 26, 2018
- Australian Journal of Forensic Sciences
ABSTRACTThe Chemical Weapons Convention (hereinafter ‘the Convention’), an international disarmament and non-proliferation treaty, entered into force in 1997. It prohibits the development, stockpiling, transfer and use of chemical weapons. Today there are 193 nations (‘States Parties’) that are members. The Organization for the Prohibition of Chemical Weapons (OPCW), in The Hague, is the implementing body of the Convention. Herein we outline the verification regime of the Convention and how the work of the OPCW has evolved in recent years in response to the use of chemical warfare agents (CWAs), as well as potential impacts from advances in science and technology (S&T). We describe challenges recognized from recent contingency operations in response to the use of CWAs and how S&T might support the development of safe and effective approaches to verification. The role of OPCW’s Scientific Advisory Board and its Temporary Working Group on Investigative Science and Technology are discussed; specifically, how scientific advice supports the development of the capability for the verification of alleged use of CWAs, as well as informing the decisions made by policymakers. The importance of engagement with forensic agencies for the continuing development of state-of-the-art approaches to verification is highlighted.
- Research Article
- 10.1080/10736700.2020.1878666
- Sep 1, 2020
- The Nonproliferation Review
The 1993 Chemical Weapons Convention (CWC) and the 1972 Biological and Toxin Weapons Convention (BWC) are key components of the international arms-control landscape. Yet the two conventions differ widely, particularly in the ways that are available to treaty parties to resolve any questions about compliance with the treaties. Both contain language concerning consultation and cooperation, but the CWC also has extensive procedures available to investigate allegations of noncompliance. This article reviews these differences in the conventions and explains, in part, how and why they came about. The Organisation for the Prohibition of Chemical Weapons (OPCW) has engaged in several consultations regarding compliance issues, but the OPCW publishes virtually nothing about the topics of the consultations or their frequency, findings, or conclusions. An exception, perhaps, is the OPCW’s work regarding Syrian use of chemical weapons (CW). Moreover, thus far, no treaty party has called for a challenge inspection to officially investigate perhaps the most serious allegations of treaty violations: Syrian and Russian alleged use of CW. The BWC states parties conducted one formal consultation raised by Cuba, alleging that the United States dropped biological agents on the island nation from airplanes to cause an animal epidemic. The consultation reached no official conclusion. The article goes on to praise the work of Raymond Zilinskas debunking the allegations through a careful scientific review of the Cuban claims. The article discusses the consequences of secrecy surrounding the CWC consultation process and laments that the BWC does not have the institutional capacity to carry on the type of analysis that Zilinskas undertook discrediting the Cuban allegations.
- Research Article
9
- 10.1016/j.chroma.2013.02.081
- Mar 4, 2013
- Journal of Chromatography A
Detection and identification of hydrolysis products of sulfur mustards at trace levels in environmental samples using liquid chromatography solid phase extraction combined with off-line nuclear magnetic resonance analysis
- Research Article
- 10.1111/ajes.12530
- Jul 27, 2023
- The American Journal of Economics and Sociology
The Organisation for the Prohibition of Chemical Weapons (OPCW) is a significant component of the global governance structure and considered a gold standard international body with 193 member states and scientific divisions expected to adhere rigorously to objectivity and political neutrality. However, OPCW's reputation has recently been tarnished. Dissenting scientists from within the organization have raised serious questions about the integrity of an OPCW fact‐finding mission (FFM) investigating the alleged chemical attack in Douma, Syria on April 7, 2018. The OPCW FFMs are tainted in three ways: (1) they rely upon information provided via intermediaries connected to states that are belligerents in the war in Syria; (2) the organizational structure of an FFM excludes scientific and verification divisions of the OPCW; and (3) control of FFMs is held by a bureaucratic office staffed by career diplomats who are from states involved with the Syrian war. Furthermore, officials involved with the Douma FFM investigation report the following anomalies: (a) an original interim report was secretly altered in order to make an unsubstantiated suggestion that an alleged attack had occurred; (b) A U.S. delegation was allowed to brief the FFM, an action prohibited by the Chemical Weapons Convention; and (c) formal attempts by the inspectors to obtain transparency and dialog was rejected by the OPCW. Meanwhile, the United States and its allies have dismissed questions as Russian “disinformation” or as a “conspiracy theory.” Overall, analysis of the alleged Douma attack and the OPCW's FFM supports the thesis that key international organizations have been effectively captured, or at the very least heavily influenced, by particular states that assume their own impartiality. This shortcoming poses a risk to international peace and security.
- Research Article
4
- 10.1515/pac-2016-0903
- Nov 9, 2016
- Pure and Applied Chemistry
The Chemical Weapons Convention remains a landmark international treaty. It was the first multilateral agreement to ban an entire class of weapons of mass destruction and include a strict verification regime to monitor compliance. Scientists were not only deeply engaged in the negotiation of the Chemical Weapons Convention, but have been central to the life of the Organization for the Prohibition of Chemical Weapons (OPCW) ever since it came into existence almost 20 years ago. Over that time, during which the OPCW focused primarily on its mission to oversee the destruction of chemical weapons stockpiles, the organization has relied on a very committed core of scientific expertise – from within and outside – to help guide it. As that core task comes to a close, the Organization faces a new challenge: ensuring that chemical weapons do not return. Meeting that challenge will require new approaches to the OPCW’s mission.
- Book Chapter
1
- 10.1163/9789004274587_010
- Jan 1, 2014
The response of the United Nations Security Council and the Executive Council of the Organisation for the Prohibition of Chemical Weapons (OPCW) to the chemical weapons attack in Ghouta in Syria on 21 August 2013, Syria's accession to the Chemical Weapons Convention, and the role of the United Nations in disarmament initially raised a number of issues of international law. This chapter discusses the issues that were at the forefront between 21 August and 15 November 2013. It is irrelevant from an international law perspective. The measures adopted by the Security Council are unequivocally binding for all States and actors concerned and these decisions must be complied with. Before the Executive Council decision, a particularly sensitive discussion was held on the expression 'elimination'. The first draft of the decision contained several references (including in the title) to the elimination of all Syrian chemical weapons. Keywords: Chemical Weapons Convention; Ghouta; international law; OPCW; Syria; United Nations Security Council
- Research Article
- 10.1515/ci-2025-0303
- Jul 1, 2025
- Chemistry International
Even before the Organization for the Prohibition of Chemical Weapons (OPCW) was established and the Chemical Weapons Convention (CWC) entered into force, IUPAC was dealing with chemical challenges related to disarmament and produced several reports on aspects related to chemical-weapon issues. However, as the IUPAC archives reveal, this work was not supported with enthusiasm. This may explain the scepticism that was experienced when IUPAC was approached by OPCW in 2001 and asked to produce a report evaluating the scientific and technological advances that had occurred in the chemical sciences since 1993. Based on documents from the IUPAC archives and my own observations as a member of numerous IUPAC committees, this article gives an account of how difficulties were met and overcome and eventually paved the way for the productive collaboration IUPAC now enjoys with OPCW.
- Research Article
1
- 10.1057/s41311-017-0083-3
- Oct 11, 2017
- International Politics
The presence of an international organisation—the Organisation for the Prohibition of Chemical Weapons (OPCW)—in the chemical weapons (CW) prohibition regime and a large number of norms, rules and procedures contained in the Chemical Weapons Convention (CWC) leads to the preponderance of institutional power in the CW prohibition regime. The paper analyses its manifestation, and contestation by other forms of power, in four key areas of the OPCW’s activities—disarmament, non-proliferation, internalisation of regime provisions, as well as assistance and protection. The subsequent discussion of the Syrian Arab Republic’s accession to the CWC identifies some great power politics, and hence compulsory power, at work. The concluding section raises the question of potentially changing power relationships as the CW prohibition regime transitions to a world in which declared CW stockpiles will have been destroyed and the OPCW increasingly focus on preventing the re-emergence of CW.
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