16 September 2020
- 1 Summary
- 2 Introduction
- 3 Mirzayanov’s story from 1991 to 1995
- 4 The official Russian position
- 5 Uglev’s story: corroboration or rebuttal?
- 6 Fake corroboration: the 2003 Amazon book review
- 7 US studies of the phosphylated amidine compounds identified as Novichoks
- 8 Mirzayanov’s role as a Tatar separatist in 2008-09
- 9 Cases of poisoning with A-234
- 10 Chemical and toxicological properties of A-234 and other A-series compounds
- 11 Discussion
- 12 Acknowledgements
- 13 Conflicts of interest
The poisoning incidents in Salisbury, England in 2018 with an unusual organophosphate compound designated A-234 gave rise to wide coverage of the story that a novel class of nerve agents named “Novichoks” had been discovered in the Soviet Union in the 1980s and that development of these agents as weapons had continued in Russia in violation of bilateral agreements with the US signed in 1989 and 1990. This story, originating with the dissident Russian chemist Vil Mirzayanov, has been accepted by many scientists and officials involved with chemical arms control. Russian officials however have denied that any studies under the name “Novichok” were ever conducted in the USSR or the Russian Federation. Official Russian statements have been supplemented with an unofficial explanation that the Novichoks story originated as a Russian counter-intelligence operation (“canary trap”) to identify Mirzayanov as a leaker, and that he was used (unwittingly) to channel disinformation after he had been identified. This article examines evidence in the public domain that is relevant to evaluating which of these two alternative explanations – chemical weapons programme or canary trap – is correct, based on primary sources.
Mirzayanov reported in 1992 that a new class of binary nerve agents named “Novichoks” had been developed during the 1980s at the GosNIIOKhT laboratories in Moscow, that field tests had shown one of these binary nerve agents to be several times more more effective than VX, and that three of these binary agents had been stockpiled in quantities of several tons from 1989 onwards. To assist Mirzayanov in preparing his defence against prosecution during 1993, he was provided with what were purportedly top secret documents confirming this story, before charges were dropped in 1994.
The only other account from a chemist inside the Soviet chemical weapons programme was provided by Vladimir Uglev, who stated that the compounds alleged to have been developed in binary form as Novichoks during the 1980s had been synthesized in unitary form in the 1970s in quantities of no more than a few kilogrammes, and that no binary formulations had ever been developed. Other information in the public domain rebuts or casts doubt on other key points in Mirzayanov’s story: that these compounds had structures similar to those published in the open Soviet literature as possible pesticides, that their precursors were widely available industrial chemicals, and that standard therapies for nerve agent poisoning were not effective against them. Mirzayanov’s credibility as an independent whistleblower is undermined by his role in a US government-sponsored operation to encourage Tatar separatism, coinciding with the publication of his book in 2008 which gave structures for the compounds allegedly developed as fourth generation nerve agents into the early 1990s.
From information in the public domain it is possible to deduce that the US military knew the phosphylated amidine structures designated as A-232 and A-234 by early 1997 and that by 1998 they had synthesized these compounds, studied their toxicity in vivo, and reported the results publicly. The results of these studies were subsequently removed from public databases, and the toxicity studies remain classified. From in silico predictions and clinical histories it is possible to infer that the low volatility and slow percutaneous absorption of these compounds would have limited their usefulness as chemical weapons.
The evidence that is publicly available thus supports the explanation that the Novichoks story originated as a counter-intelligence operation rather than a real chemical weapons programme. If this was the case, the operation has backfired by creating a situation in which incidents in which these “fourth generation agents” are detected are blamed on Russia. The success of efforts to eliminate the stockpiling of chemical weapons, together with establishment of international mechanisms to detect and report on any use of such weapons, may have had the unintended consequence of facilitating operations that attribute the possession or use of chemical weapons to an adversary.
The poisoning incidents in Salisbury, England in 2018 gave rise to wide coverage of a story originating with the Russian chemist Vil Mirzayanov in 1992 that a novel class of nerve agents named “Novichoks” had been discovered in the Soviet Union in the 1980s and that development of these agents as chemical weapons had continued after Russia had negotiated the Chemical Weapons Convention and signed the Wyoming Agreement in 1990. This story has been accepted by many commentators on chemical weapons and chemical arms control. In contrast, Russian officials have denied that any studies under the name “Novichok” were ever conducted in the USSR or the Russian Federation, and have stated that all chemical weapons programmes were stopped in 1991-92, but have not denied that the chemical compounds purported to be Novichoks were studied at bench scale in Russia. The official Russian version has been supplemented with an unofficial explanation that the Novichoks story originated as a Russian counter-intelligence operation to identify Mirzayanov as a leaker.
For reasons explained below, the possible explanations of the Novichoks story can be reduced to these two alternatives: a chemical weapons programme or a counter-intelligence operation. This article examines evidence in the public domain that is relevant to evaluating which of these alternatives is true. In contrast to other commentaries on the Novichok story that have relied on secondary sources, this review is based strictly on primary sources in the public domain.
3 Mirzayanov’s story from 1991 to 1995
Descriptions of a secret “Novichok” programme were published in the press before Mirzayanov was arrested and charged with revealing state secrets on 22 October 1992. Russian language articles were published on 10 October 1991 in Kuranty, on 16 September 1992 (co-authored with Lev Fedorov) in Moscow News, on 20 October 1992 in Moskovsiye Novosti, and on 22 October 1992 in Novoye Vremya. English-language articles in the Baltimore Sun were published on 16 September 1992 and 18 October 1992. The Baltimore Sun however quoted a sceptical opinion from Lora Lumpe, an arms control researcher at the Federation of American Scientists. The most detailed first-hand version of Mirzayanov’s story was given in an article published in 1995 after he had settled in the US.
Mirzayanov alleged that:
- The Soviet Union had “intensified the development and testing of the most modern class of chemical weapons during the final stages of the CWC’s negotiations”, in violation of two bilateral agreements with the US: the 1989 Wyoming Memorandum of Understanding on bilateral exchanges of information about chemical weapon stockpiles, and the 1990 Moscow Bilateral Destruction agreement. President Gorbachev had been aware of this programme and had secretly awarded decorations to the two officials in charge of it.
- New unitary (that is, not formulated as binary) agents, designated A-230 and A-232 had been developed by GosNIIOKhT (State Union Scientific Research Institute for Organic Chemistry and Technology) in Shikhany, Saratov in a continuation of the programme in which Russian VX (aso known as Substance 33 or VR) was developed.
- A-230 had been tested in 1988, adopted as a chemical weapon in 1990 and produced in “tens of tons”. “A few tons” of A-232 had also been produced. Mirzayanov did not use the term “Novichok” for these unitary agents, and did not mention a compound designated A-234 at this stage.
- A new secret program under the codename “Foliant” began at GosNIIOKhT in Moscow in 1982, leading to the development of a new binary agent named Novichok-5 produced in 1987 and tested in 1989. These tests showed that it “under optimal conditions exceeds the effectiveness of VX by five to eight times”. It was produced in quantities of “a few tons”. Novichok-5 was described by Mirzayanov as a binary version of A-232, or (in apparent contradiction) as “based on A-232” with A-232 as “a Novichok precursor”. Mirzayanov did not mention any field tests of A-232, only of its supposed binary version designated Novichok-5.
- Another binary agent designated Novichok-7 was developed by GosNIIOKhT in Moscow and tested in 1993. It was found to be “approximately ten times more effective than soman” and to have similar volatility. It was produced in “tens of tons”. The information about tests in 1993 must have reached Mirzayanov after he had been charged with revealing state secrets in October 1992.
- “The chemical components or precursors of A-232 and its binary version Novichok-5 are ordinary organophosphates that can be made at commercial chemical companies that manufacture such products as fertilizers and pesticides.”
- Poisoning with Novichok-5 is difficult to treat and causes long-term disability. “If someone is affected by it, even if it only gets on the skin, it is practically impossible to effect a cure. I know people who were subjected in the past to the effects of this toxin. They were all left invalids.”
This last statement would have suggested, to anyone familiar with the toxicology of organophosphates, that the Novichok agents were “delayed neuropathic agents” which bind to the enzyme neuropathy target esterase (NTE) with onset of irreversible paralysis a few weeks after exposure. Although some organophosphates formerly used as pesticides have off-target effects on NTE causing delayed neuropathy, there has been no evidence (other than this element of the Novichok story) of a deliberate attempt to develop such compounds for military use.
In December 2008, some 13 years after he had emigrated to the US, Mirzayanov published an autobiography in which he gave structures for five phosphylated amidines containing P-N=C-N bonds designated A-230, A-232, A-234, A-242 and A-262. A-234 differed from A-232 by the substitution of an ethyl for a methyl group. A synthetic pathway for A-232 was given, in which acetonitrile was a precursor.
Mirzayanov’s story in this book differed from what he had written during 1992 to 1995.
- the term Novichoks was used to to denote the unitary agents discovered in the 1970s, rather than the binary agents supposedly developed in the 1980s.
- it was the unitary agent A-230, rather than the binary version of A-232 designated Novichok-5, that was described was “5 to 8 times more lethal” than VX under field conditions.
- A-232 was described as having “the same toxicity” as Russian VX but was “much more volatile”. Field tests of A-232 were “just as successful” as those for A-230. A programme to develop a binary formulation is mentioned briefly, but no further details are given. The designation Novichok-5 appeared only in the copies of purportedly top secret documents made available to Mirzayanov during 1992-93 to prepare his defence.
3.1 Relevance of binary formulations
Up to the 1980s both the US and the USSR held their stockpiles of chemical weapons in unitary form. Binary formulations, in which precursors were to be combined in a final synthesis step shortly before or after launch, had two advantages: first, the precursors were less toxic than the final agent, making the munitions safer to produce and to handle; second, binary formulations could be used to weaponize compounds that were too unstable for long-term storage. This was especially relevant to the “intermediate volatility agent” studied by the US at Edgewood Arsenal since 1970 under the name EA 5365, and later designated “GV” by the Czech chemists Ivan Masek and Jiri Matousek. This phosphoroamidofluoridate compound was sufficiently volatile to cause an inhalation hazard and had percutaneous toxicity similar to that of the V agents, but its storage stability was too poor for it to be stockpiled as a weapon in unitary form. It might have beoome an important threat agent if a binary formulation had been successfully developed. A story that Russia had succeeded where the US had not in developing a binary agent more effective than VX, and that this agent was resistant to treatment and caused irreversible paralysis, would have evoked serious concern among US chemical defence planners. However it would not have made sense for GosNIIOKhT to attempt development of a binary formulation without testing the unitary agent first, as it is unlikely that a binary formulation would be more effective than its unitary equivalent.
4 The official Russian position
The Russian envoy to the UN, Vasily Nebenzya stated on 15 March 2018 that
No research, development or manufacturing of projects codenamed Novichok has ever been carried out in Russia, all CW programmes were stopped back in 1991-92._
In a television interview the Foreign Ministry spokeswoman Maria Zakharova gave a still more comprehensive denial:-
Never on the territory of the USSR in Soviet times or in the times of the Russian Federation on its territory have there been studies conducted under the code name Novichok. It was neither patented, nor used as a symbol or a code. Once more, as this is the key thing: the word Novichok has never been used in the USSR or in Russia as something related to chemical weapons research.
At a briefing by the Russian Ministry of Foreign Affairs on 21 March 2018, Viktor Kholstov, Director of the Centre for Analytical Research on Chemical and Biological Weapon Conventions under the Russian Ministry of Industry and Trade stated that:
Vil Mirzayanov did not have these formulas in the early 2000s. Trying to earn a living and to improve his finances, Mirzayanov published a new book, probably in cooperation with the Edgewood Arsenal, titled “State secrets: an insider’s chronicle of the Russian chemical weapons programme.” This book included some formulas.
An Aide memoire on enhancement of the Chemical Weapons Convention submitted by the Russian delegation to the Executive Council of the OPCW on 18 April 2018 reiterated that Mirzayanov had not known the chemical structures that he published in his book in 2008 until they were provided to him by the Edgewood Arsenal, and argued that the publication of the structures in Mirzayanov’s book was “indirect transfer of chemical weapons” in violation of the Chemical Weapons Convention.
4.1 Lazarchuk’s story: the unofficial Russian explanation?
In March 2018, the Russian writer Andrey Lazarchuk wrote a post on social media based on an undisclosed source, translated elsewhere to English. He reported that:
- The Soviet army withdrew their chemical weapon stocks to long-term storage in 1983-84.
- Mirzayanov never worked on theoretical developments or practical synthesis.
- In the second half of the 1980s, the KGB undertook a counter-intelligence operation intended both to disinform the other side and to identify channels through which information was being leaked. For this purpose, stories about non-existent projects to develop “a new chemical super-weapon” were composed, and the version with Novichoks was passed to Mirzayanov.
- Mirzayanov was identified immediately as a channel of leakage, removed from all real work in 1990, and allowed to continue (unwittingly) as a channel of disinformation.
The terms “blue dye operation”, “barium meal” or “canary trap” have been used for this type of counter-intelligence operation in which suspects are passed different versions of a story so as to identify which of them is passing information to adversaries.
A passage in Mirzayanov’s 1995 article appears to corroborate Lazarchuk’s story that information about possibly non-existent projects was deliberately passed to him:
More than fifty top secret documents, many of which had not previously been in my possession, somehow appeared among my files at work. For example, though I had never officially had access to the project that developed and tested the Novichok-5 agent, one document detailed my technical assignment to this program
After Mirzayanov had been arrested and charged, additional documents that appeared to confirm his story and were marked top secret were made available to him to prepare his defence, before the case was dropped by the prosecutor on 11 March 1994. In his 1995 article Mirzayanov noted that:
What became clear was that those prosecuting me were less concerned with protecting state secrets than with making an example of me. To wit, as I prepared my defense, I was legally allowed to copy numerous top secret documents – many of which I had never seen before – and distribute them to my attorney, the press and others abroad who were denouncing my persecution.
Four of these documents were reproduced in English translation in Mirzayanov’s autobiography published in 2008. Copies of the Russian originals dating from 1993 exist in the Sussex Harvard Information Bank and for at least one of these there is an contemporary English translation that agrees closely with that given later by Mirzayanov. Excerpts from the versions in Mirzayanov’s book are given below:
- Annex 5 (25 September 1992, marked top secret): Resolution of the Permanent Technical Commission at GosNIIOKhT, chaired by Y I Baranov
Referring to Mirzayanov’s story that a new toxic agent more effective than VX and resistant to treatment had been developed, the document stated:
This information is true. GOSNIIOKhT (currently, GRNIIOKhT) did synthesize, studied, and tested a number of new chemical compounds of different classes that are considerably more potent than the VX gas (the substance that the U.S. is armed with) by a complex of combat characteristics, including difficulties of treatment. According to available information, the armies of the countries that possess chemical weapons are not armed with an equivalent of the above-mentioned agent. Equipping chemical ammunition with such compounds considerably increases its effectiveness.
Referring to Mirzayanov’s story that a binary version had been developed, the document stated:
This is also true. GRNIIOKhT developed its own binary weapons based on the new chemical agent and these weapons are currently being tested.
- Annex 30 (24 February 1993, marked secret): Transcript of the Inspection:
The Inspection established: Case N 73-3, inventory number 6291, in one volume, on 260 numbered pages in the dark-blue cardboard folder. In this case there is a document on pages 160-165 with the title “Technical order for a part of the experimental and design work of “Agent A-232” based on the system of components” and the cipher “Novichok-5,” stamp “Top Secret,” number 2187 ss/khf. The document contains 9 clauses. (Further, all the clauses are enumerated.) [At the bottom of the last page of the original document there is a signature and the date 20 April 1990, in blue ink.] During the inspection, Kuznetsov explained that Agent A-232 mentioned in the technical order was the new chemical agent in its binary version, created at GRNIIOKhT.
- Annex 31: (dated 16 May 1990, marked top secret): Technical order for the compound part of the experimental and design work of “Agent A-232” based on the system of components. (document referred to in Annex 30):
The code “Novichok-5” – The development, manufacture and delivery of bodies of special products (models) of the explosion mode of operation for testing the system of components “A-232”
The development, manufacture and delivery of bodies of the special products (models) of the Explosion Operation Mode for Field Tests of the System of components of the substance “A-232” is being carried out following the resolution of the Authority No 844-186, adopted on 6 October 1989.
Mirzayanov explained that “the Authority” meant the Central Committee of the Communist Party of the Soviet Union, implying a resolution signed by President Gorbachev as General Secretary.
- Annex 34 (16 March 1993, marked top secret: Commission of Experts headed by Y M Karmishin, [Experts’ Report]”:
In GosNIIOKhT a new chemical compound has really been synthesized, studied and tested that significantly surpasses the agent VX by a complex of battle characteristics including difficulties in curing.
the armies of the countries that possess chemical weapons are not armed with any compounds analogous to the above-mentioned compound
GoSNIIOKht has developed experimental batches of binary weapons based on the new chemical agents, which were successfully tested at the test site.
These documents purportedly contained top secret information that confirmed Mirzayanov’s story. If they were true, Mirzayanov’s story was largely true. If they were conveying false information, the only possible explanation is that Mirzyanov was being used to channel disinformation after he had been identified as a leaker. The possible explanations for the Novichoks story can thus be reduced to these two alternatives. A possible motive for passing false information to the US could have been to deter US military adventures with a story of a new super-weapon at a time when Russia’s military capability was weak. The story that between 1966 and 1969 US counter-intelligence mounted a deception operation that misled the Soviet Union into believing that the US had developed a new and highly effective nerve agent may have been a precedent for such a counter-deception operation.
5 Uglev’s story: corroboration or rebuttal?
Vladimir Uglev, who worked from 1975 onwards at the Saratov branch of GosNIIOKhT has been widely quoted as corroborating Mirzayanov’s story. Uglev gave an interview in in February 1993 to Novoye Vremya, in which he was asked about Mirzayanov’s story. Some 25 years later on 20 March 2018, Uglev was interviewed by The Bell, a pro-opposition news outlet. Another article quoting Uglev as a source was published in The Project in September 2018.
Uglev stated that he had worked in a research group led by Pyotr Kirpichev “who in 1973 for the first time was able to obtain a fundamentally new phosphoric toxic agent with a paralytic action on the nerves that subsequently received the name”Novichok.“. In the 1993 interview he stated that five of these compounds went through development to the stage of field testing, and that he had discovered three of them. In the March 2018 interview he gave the code names of four (rather than five) compounds as A-1972, B-1976, C-1976, and D-1980. He stated that he had developed the second and third of these, and added that one of these compounds was used in the Kivelidi poisoning. In the September 2018 article, apparently sourced from Uglev, these four compounds are respectively designated A-230, A-232, A-234 and A-242. Uglev had stated in 1993 that several kilogrammes of”the new substance” were produced, and in 2018 “20 grammes to a few kilos”. Uglev’s story is consistent with Mirzayanov’s in that he states that new unitary agents were discovered in Saratov during the period 1972-1980 and that these agents were not designated Novichoks. He states that the quantities synthesized at this time were no more than a few kilogrammes. If, as Mirzayanov alleged, binary versions of these compounds had been developed in Moscow during the 1980s, tested in Uzbekistan and stockpiled in quantities of several tons, Uglev in Saratov would not necessarily have had first-hand knowledge of these developments.
Prompted in the 1993 interview to confirm Mirzayanov’s story that tests had shown “the new substance” to be 5-8 times more effective than VX, Uglev answered in words that indicated his information was not based on first-hand knowledge: “The military people have whispered to me that it is a minimum of 5-10 times”. Uglev stated that binary agents had been developed but again indicated that this was not based on observation at first-hand:-
- Of the three new toxic substances that Uglev discovered, one was “a basic component of a binary that, according to my information, has gone through successful testing on the range”.
- “I have information on the existence in Russia of a minimum of one kind of binary weapon made on the basis of the so-called Novocheboksarskiy product [Russian VX]”
- “I know about production as well: a certain quantity of components of a binary weapon is now being kept at a secret storage depot”.
In the 2018 interview, Uglev contradicted his own and Mirzayanov’s earlier statements about binary formulations, stating unequivocally that:
No one ever had any binary weapons. I think that several of my colleagues, just like I did, tried to work on this idea, but I don’t know a single binary weapon, not for VX, not for other types of chemical weapons. At least for the period up until 1994.
6 Fake corroboration: the 2003 Amazon book review
On 16 March 2004 an amateur chemist in Baltimore posted on a science forum an edited copy of a book review that had been posted on Amazon on 16 November 2003, but is no longer on that site. This had been posted under the name Anatoly Kuntsevich as a review of the Handbook of Chemical and Biological Warfare Agents by D Hank Ellison. The review contained obviously false information, stating that Ken Alibek (a former Soviet biological warfare expert) was an alias for Vil Mirzayanov. Anatoly Kuntsevich, who had been deputy commander of Soviet chemical forces, had died in 2002.
The review stated that Novichoks belonged to “the class of organophosphate structues containing a dihaloformaldoxime group”, and that the binding of these compounds to their target was resistant to reactivation by oximes such as 2-PAM. These dihaloformaldoxime structures had P-O-N=C-X.Y bonds, where X and Y are halogens. The review included a brief but apparently accurate description of papers on the possible use of dihaloformaldoxime compounds as pesticides, published in the open Soviet literature during the late 1960s and early 1970s, apparently corroborating Mirzayanov’s story that Novichoks had structures similar to those published as possible pesticides.
This posting on the
sciencemadness.org forum in 2004 was the basis (Hoenig, personal communication 2019) for a discussion of the posited structures of Novichok agents in a new edition, published in November 2006, of the Compendium of Chemical Warfare Agents by Steven Hoenig, a forensic chemist who has served as chemical defence specialist with the National Guard in the US. Hoenig emphasized that “these compounds have been subjected to some debate, but very little is known about them in detail”. The discussion in Hoenig’s book was in turn the basis for two more publications that were widely quoted as sources for Novichok structures: the second edition of D Hank Ellison’s Handbook of Chemical and Biological Warfare Agents, published in August 2007, and a patent entitled “Method of treating organophosphorous poisoning”, for which a continuation-in-part was submitted by the University of Maryland and the US Army on 27 August 2008. It appears that the Amazon book review was the primary source for all other publications giving dihaloformaldoxime structures for Novichoks.
7 US studies of the phosphylated amidine compounds identified as Novichoks
A German newspaper reported in May 2018 that the German intelligence service had acquired a sample of what was purported to be a Novichok compound from a scientist in Russia in the 1990s, that this sample was sent to Sweden for analysis, and that the result was shared with US and UK intelligence services. Based on information from the Defence Science and Technology Laboratory at Porton Down, the BBC journalist Mark Urban confirmed this story, reporting that the compound had been identified as A-232 and that Porton Down had analysed it by 1998. If, as this story indicates, obtaining a sample of a purported Novichok agent was a key objective for western defence intelligence agencies in the mid-1990s, this implies that at this time they did not know the structures of these compounds. Urban’s source has thus (perhaps unwittingly) corroborated the statement by Russian officials that Mirzayanov did not know the structures of these compounds when he left Russia.
A 1997 newspaper article with the title “Russia dodges chemical arms ban” quoted a secret report in the Military Intelligence Digest of 24 January 1997 as follows: “By using chemicals not specified in the CWC schedules, the Russians can produce A-232 and its ethyl analog A-234, in unitary and binary forms within several chemical complexes”. One binary formulation was said to use acetonitrile and an organic phosphate compound “that can be disguised as a pesticide precursor”. The mention of A-234 as the ethyl analogue of A-232, and the mention of acetonitrile as a precursor indicates that the structures with these designations that appeared in Mirzayanov’s book in 2008 were known to the US military by early 1997. The article identified the author of the report as James Poarch, then serving as a chemical engineer to the US National Ground Intelligence Center. At this time US Senators were divided on whether to support ratification of the Chemical Weapons Convention. The article quoted an anonymous Pentagon official as commenting that the intelligence report “clearly shows the Russians are circumventing the treaty”.
The head of the Russian chemical weapon detection laboratory revealed on a Russian television programme (at 1:11:53 in the recording) that Edgewood Arsenal had submitted a mass spectrometry profile for a compound named N-(O-ethyl-fluorophosphoryl)-N’N’-diethylacetamidine (corresponding to the structure designated A-234 in Mirzayanov’s book) to the public mass spectrometry database NIST98. The entry in NIST98 cross-referenced an entry in the database RTECS (Registry of Toxic Effects of Chemical Substances), implying that toxicity results had also been submitted. This is consistent with allusions to in vivo toxicity studies in the Chemical Hazards Emergency Medical Management (CHEMM) guide on Fourth Generation Agents issued by the US Department of Health and Human Services in January 2019. On further enquiry, an official of the Department of Health and Human Services has stated (personal communication) that these studies were undertaken by the US Department of Defense “for defense purposes, toward developing countermeasures”.
NIST98 was current from 1998 to 2001. The entry for A-234 in NIST98 was not present in subsequent versions of the NIST mass spectrometry database, and no entry for this compound now exists in RTECS. This establishes that the US Department of Defense was studying these compounds and their toxicity around 1997, and that at some time after this it was decided to remove this information from the public domain.
8 Mirzayanov’s role as a Tatar separatist in 2008-09
A post on the Radio Free Europe / Radio Liberty (RFE/RL) Tatar language website Radio Azatliq on 27 October 2008 had announced that Mirzayanov had been elected the previous day to the “Praesidium of the Milli Mejlis [national parliament]” apparently consisting of ten people including Mirzayanov, whose book was published seven weeks later on 18 December. On 20 December at another meeting of the Milli Mejlis two days after the publication of his book, Mirzayanov signed a Declaration of Independence of Tatarstan, proclaiming himself head of state of a Tatar government in exile. The support of the US government for Mirzayanov’s role in Tatar separatism may explain why subsequent discussions of his book by delegates to OPCW and the Australia Group were closely monitored and discouraged by the US State Department. A Russian view of this attempt to sponsor a Tatar separatist movement was given in an article in Nevismaya Gazeta dated 9 December 2009, translated for a private intelligence report (item 20):
As though in confirmation, the so called “government of Tatarstan in exile” was formed in the United States in December 2008. It is headed by US citizen Vil Mirzayanov, a Russian scientist granted political asylum in the United States. Along with Mirzayanov himself, the alleged government includes two Germans and a Turk. This self-proclaimed government already appealed to the UN to recognize independence of Tatarstan in the manner sovereignty of Kosovo, Abkhazia, and South Ossetia had been. The US-Tatar affair then developed in the following manner. An impressive delegation of US Department of State functionaries visited Tatarstan in March. This visit got scant media coverage. The diplomats meanwhile toured the republic and met with religious celebrities, leaders of national movements, and officials of the republican administration. Before that, the American-Tatar relations had been limited to sporadic contacts with officials of the US Embassy that sponsored all sorts of humanitarian and educational programs (like Tolerant Tatarstan) in the republic. US President Barack Obama mentioned Kazan in his speech before the student body and faculty of the Russian School of Economics this July. Clinton made a visit to Kazan in October. She became the first US state secretary to venture out of Moscow or St.Petersburg while in Russia.
As Tatarstan is in the mid-Volga region far from the Russian borders, Tatar independence would have been possible only in the context of a Yugoslavia-style breakup of the Russian heartland. Tatars have been integrated into the Russian elite, especially the military, since the 18th century. The timing of the publication of Mirzayanov’s book to coincide with a US-government sponsored operation in which he was declared leader of a Tatar government-in-exile strongly suggests that the book itself was part of this operation.
9 Cases of poisoning with A-234
9.1 Moscow 1995: two fatal cases, other non-fatal cases
The deaths of the banker Ivan Kivelidi on 4 August 1995 and his secretary Zara Ismailova the previous day were initially attributed to poisoning with a heavy metal. Only limited information on the clinical histories is available from news reports at the time, but it appears that they both survived long enough to reach hospital and at least for one day more. It was reported that other individuals, including Kivelidi’s bodyguard, cleaners and eight police officers had been affected after visiting Kivelidi’s office. Reports in Novaya Gazeta on 22 March 2018 and 2 April 2018 included copies of material from the investigation including a mass spectrometry profile of the sample recovered from a telephone handset in Kivelidi’s office, acquired on 24 August 1995. This profile matches that submitted by Edgewood to the NIST98 mass spectrometry database for the compound subsequently designated A-234 in Mirzayanov’s 2008 book. The investigation had confirmed that the compound had been synthesized in the GRNIIOKhT laboratory in Saratov and sold to a criminal group.
9.2 Salisbury 2018: five cases
Though neither the UK nor OPCW have officially confirmed the identity of the agent used in the Salisbury poisonings, the compound was named as A-234 by Russian diplomats based on what they were told by the UK Foreign Secretary on 12 March 2018 and by the Russian Foreign Minister on 14 April based on quoting a report from the Swiss Federal Institute for Nuclear, Biological and Chemical Protection. The identity of the compound was confirmed by Mark Urban in October 2018. On 14 January 2019 the OPCW Executive Council recommended adding two families of compounds to Schedule 1 of the Annex on Chemicals to the Chemical Weapons Convention. The statement by the envoy from The Netherlands indicated that the agent used in Salisbury belonged to one of these families, but did not name it. After negotiations, agreement to add generic chemical structures to the Chemical Weapons Convention was reached at the Conference of States Parties on 27 November 2019: an Addendum published on 20 May 2020 lists these structures, one of which is A-234 named as ethyl (1-(diethylamino)ethylidene)phosphoramidofluoridate (CAS registry number 2387496-06-0).
10 Chemical and toxicological properties of A-234 and other A-series compounds
10.1 Physical and chemical properties
From in silico predictions, A-234 is expected to have very low vapour pressure. This is confirmed by the NIH reference guide to fourth generation agents which states that the vapour pressure of these agents is “5 to 10 times lower than VX”. An experimental study from the US Army Combat Capabilities and Development Command Chemical Biological Center reported in 2020 that the rate of hydrolysis at 25oC was 77-fold lower for A-234 than for VX. Ian Boyd, the chief scientific adviser at the Department for Environment, Food and Rural Affairs, was reported to have stated: “The chemical does not degrade quickly. You can assume it is not much different now from the day it was distributed”.
10.2 In vivo studies of toxicity
The Chemical Hazards Emergency Medical Management (CHEMM) guide on Fourth Generation Agents issued by the US Department of Health and Human Services in January 2019 mentions that bronchoconstriction and seizure activity were observed in animal studies, but does not give any other information about these in vivo studies. An official of the Department of Health and Human Services has stated (personal communication) that results of these in vivo toxicity studies are classified by the Department of Defense, and that no further information from them will be released. Guidelines emphasize that the results of experiments on animals should be reported in full so as to prevent unnecessary animal use in the future.
10.3 In silico studies of toxicity
Carlsen (2018) reported in silico predictions of toxicity using several publicly available packages. In comparison with predictions for VX, A-234 was predicted to have a higher LD50 for oral administration and lower skin permeability. An in silico study by Bhakhoa et al (2019) reported that “The current theoretical work could not authenticate the claim made by Mirzayanov on A234 being more potent than VX”.
10.4 Clinical experience of toxicity
The CHEMM guide states that
In general, the latent period between dermal exposure and symptom onset may be longer for [Fourth Generation Agents] than for VX and can be up to 3 days. Inhalational, ingestion, or large dermal exposures will have shorter latent periods.
In contrast a briefing for the NHS prepared by Gent and Winter dated September 2018 stated that “Patients with Novichok poisoning present within hours of exposure, typically less than 6 hours”. Treatment with the oxime AChE reactivator 2-PAM is recommended. There is no suggestion that oximes are less effective against these agents than against other nerve agents. The list of toxic effects does not mention delayed neuropathy, and this has not been reported in the four cases in the UK who survived to leave hospital.
The combination of very low volatility (indexed by the vapour pressure) and very slow absorption through the skin implies that these fourth generation agents would be less effective than VX for military use. This is consistent with the low case fatality rate in Salisbury. This undermines another key element of Mirzayanov’s original story: that Novichoks were more effective than VX in field tests.
It is not disputed that the compounds A-232 and A-234 were studied during the 1970s in Saratov, but there is no evidence to support Mirzayanov’s story that binary formulations of these compounds were developed in Moscow during the 1980s, designated “Novichoks”, found to be more effective than existing agents, and stockpiled in quantities of several tons in violation of bilateral agreements with the US.
This review has shown that all the key points in Mirzayanov’s story are rebutted by other accounts or by information now in the public domain.
- A scientist widely quoted as corroborating the story has stated that the compounds were not designated Novichoks, the quantities produced were no more than a few kilogrammes, and that no binary versions were developed.
- As the compounds appear to be highly stable, binary formulations would not have been necessary for them to be developed as weapons. By 2008 Mirzayanov’s story had substantially changed: the term Novichok was used for the compounds themselves, not the supposed binary formulations.
- The structures of these compounds (phosphylated amidines) are not similar to structures published in the open Soviet literature as possible pesticides.
- The battlefield effectiveness of the compounds designated A-232 and A-234 would have been limited by their low volatility and slow absorption through the skin (inferred from the delayed onset of symptoms in known human cases of exposure and supported by in silico predictions).
- The story that Western chemical defence agencies first learned the structure of these compounds from a sample provided in the mid-1990s is corroborated by records indicating that chemical and toxicological studies of these compounds were undertaken around this time by the US Department of Defense. This in turn corroborates the statements by Russian officials that Mirzayanov did not know the structures of these compounds when he left Russia (as otherwise he would have revealed these structures when he was debriefed), and thus that the US government provided him with the structures that he published in 2008.
- The publication of this book, timed to coincide with Mirzayanov’s role in a US government-sponsored Tatar separatist movement, indicates that by this time the Novichok story was being exploited for foreign policy objectives.
- As the US proceeded to ratify the Chemical Weapons Convention in April 1997, it appears that by this time the US government no longer had any serious concerns about an alleged secret Russian programme.
It is clear that both the US and Russian governments are withholding information about their own studies of these compounds. The US Department of Defense has removed public records that these compounds were studied at Edgewood Arsenal in the mid-1990s, and refuses to reveal the results of in vivo toxicity studies. Russian officials have not denied that these compounds were studied at bench scale, but have not provided any explanation of the purportedly top secret documents made available to Mirzayanov in 1993.
The publication of the structures of A-232 and A-234 in 2008 would have laid the basis for them to be used to lay a trail pointing to Russia, whoever was the perpetrator. If the Novichoks story was originally a disinformation operation, it has backfired some 25 years later to cause serious damage to Russia’s relations with western countries. For Russia to counter this, a first step would be to publish a complete account of Russian research on these compounds, including any in vivo toxicity studies.
I am grateful to the late Julian Perry Robinson for making available material from the Sussex Harvard Information Bank and for detailed comments on an earlier draft of this article. I thank Steven Hoenig for discussions on the sources of published Novichok structures. All other source information used in this article is publicly available. Responsibility for this article is the author’s alone.
13 Conflicts of interest
The author has no conflict of interest to declare.