Wednesday, 2 April 2014

Why Nigel Farage Has It All Wrong: Smoking Guns, Hexamine, And Syrian Sarin

A guest post by chemical weapons specialist Dan Kaszeta.

This evening witnessed the odd spectacle  of Mr. Nigel Farage, MEP and head of the rightwing UK Independence Party, giving ventilation to discredited theories.  This is not the first time strange utterances have come from Mr. Farage, but this time he has parked himself squarely in the lane of my expertise. Sadly, he’s placed himself on the side of the brutal Assad dictatorship by repeating conspiracy theories that somehow Syrian rebels perpetrated the 21 August 2013 attacks on themselves.  This canard has been proved to be substantially wrong.   Others address it by means of  analysis  of the rockets used, but I rely on the technical aspects of the chemical weapon that was used.  I am using this particular opportunity to summarize the work myself and many others have done over the last months to get to the bottom of the 8/21 attacks.

The UN Office of the High Commissioner for Human Rights issued a UN report  that confirms what I have known to be the case for some time.  There is evidence tying the Sarin chemical warfare agent used at Ghouta last year to the significant chemical warfare stockpile of the Syrian government.   I originally formulated my ideas in November of last year, and provisionally called them the ‘Hexamine Hypothesis’, a theory which now appears to be vindicated.  Indeed, I believe that the chemical hexamine is a unique link tying the Ghouta war crimes to the Syrian government.  This article explains the what, why, and how of the ‘Hexamine Hypothesis’.

Two general categories of Sarin

To the layman, Sarin is Sarin. But that’s simply not true.  I have spent a lot of time and effort studying the history of Sarin and the particularly obtuse history of industrial efforts to produce Sarin.  There are at least 20 production pathways to Sarin, each of at least 5 steps.   I do not exclude the theoretical possibility of additional pathways to Sarin being developed in a laboratory at some point in the future.  All of these methods rely on one of two reactions to produce Sarin in the final chemical reaction. For the purposes of this discussion, we can divide Sarin into two basic categories, based on the final chemical reaction.  

DF + Isopropanol reaction - The simplest methods react DF and Isopropanol.  Often, online sources, some of which are of dubious provenance, refer exclusively to these methods.  Most of the 20 or so Sarin production pathways use this reaction. This reaction combines DF (methylphosphonyl difluoride) with isopropyl alcohol.  1 mol DF + 1 mol Isopropanol react to create 1 mol Sarin + 1 mol HF (hydrogen fluoride).  By mass, this works out to 140 g of HF for each 1 kg of Sarin produced.  As you probably can understand, this residual HF is highly dangerous and destructive.  It is corrosive to most materials and seriously reduces the shelf-life of the Sarin.  Indeed, this reaction is really only suitable for binary-type weapons, and even then only if you do something about the residual HF acid. (More on this later.) The Japanese Aum Shin Rikyo cult, which used Sarin in 1994-1995 in terrorist attacks in Japan used one of the methods using this step.  If you are making Sarin to keep for a long period of time, production processes that use this reaction are not very useful as it is indeed hard to get rid of this HF.   Saddam Hussein's Iraq discovered this, because they used these methods, and the shelf life of their Sarin could be measured in weeks.  The US military used this method in the M687 binary Sarin artillery shell, and found that, without some method to counteract the HF, the binary Sarin weapon systems barely survived the six to ten seconds time of flight of an artillery shell.
“High quality Sarin” – Some critics have made points about whether or not the 8/21 Sarin was “high quality” or not.  It should be noted that this DF + Isopropanol reaction cannot make “pure” or “high grade Sarin” by definition.  This process produces a cocktail of Sarin and HF.  It produces a mix that is, at best, 50% Sarin by mol or 87% if you go by weight.
The DC+DF reaction (The "di-di" process.) - The US and the Soviet Union both realized that DF+Isopropyl worked, but created Sarin that was not very useful for long-term storage.  Both the US and the Soviet Union wanted to have weapons that could be kept in long-term storage until they were needed, not artillery shells and rockets that had only a few months shelf-life.  In this method, equal parts of DC (methylphosphonic dichloride) and DF are reacted with alcohol to produce Sarin and HCl.  From an economic and industrial viewpoint, these DC+DF methods are more complicated, because they require effectively two parallel production paths, one for DF and one for DC.  The important difference is the residual contaminant in the Sarin. In the di-di process, the residual is hydrogen chloride (HCl) not HF. While being corrosive and dangerous, is not as difficult to deal with the HCl as is the HF in the other methods. More importantly, it is much more possible on an industrial scale to refine this residual HCl out of the Sarin and get a high purity product.  Getting rid of this excess HCl is still not easy and both the US and the Soviet Union had to do a lot of research and spend much time and money to figure out how to do it.  These issues were eventually solved, but the effort to do so was measured in years and millions of dollars. It was a complex industrial process and is still considered a secret.  Indeed, the US had to re-refine its earlier stockpiles of Sarin in order to ensure a long shelf-life for its Sarin. 

Environmental and biomedical samples after 8/21

The joint UN/OPCW mission collected a number of biomedical and environmental samples.  If we delve into the details of both the interim and the final reports as well as various reports and statement made by the OPCW, there are interesting conclusions we can make if we carefully examine the fine details. These are as follows:
  • Sarin was used, not some other chemical.  We know this for the following reasons:
  • Sarin was actually detected in field samples
  • Both unique and generic Sarin decomposition products were detected in field samples
  • Sarin was re-generated out of protein adducts in human blood using a sophisticated method known as fluoride regeneration. 
  • The Sarin was binary, produced from a DF + alcohol method.  We know this for several reasons:
  • The OPCW’s own documents  refer to the Syrian government having binary methods for production of chemical warfare agents. A chemical known as MPFA (methylphosphonofluoridic acid) was found in many of the environmental samples.  This is a hydrolysis product of DF. DF degrades quickly into MPFA in the environment.  This is no smoking gun on its own, as MPFA is also a decomposition product of Sarin under alkaline conditions.  
  • No DF was found. But I would not expect this, as DF is far more volatile than Sarin, and would have either evaporated or degraded. 
  • A DC+DF method requires DC. There is no evidence of DC production, DC precursors, or DC decomposition products.  
  • The chemical hexamine, also known as hexamethylenetetramine, was present in large numbers of the field samples. It would appear that the munitions contained hexamine for some reason.  The significance of this finding was unknown to me at the time.  But with only one exception (a headscarf), hexamine was in every sample that had Sarin or Sarin decomposition products.  There were also many samples that had hexamine, but no Sarin, but this is a logical state of affairs as hexamine does not evaporate like Sarin does. 

The Syrian Regime’s Declared Inventory of Chemicals

An interesting revelation occurred 20 November 2013.  The OPCW issued a document called a “Request for Expression of Interest ” for the disposal of chemicals from Syria.  This document described the OPCW’s requirements to safely get rid of various chemicals from the Syrian government’s chemical weapons program.  The serious high-grade chemicals, such as chemical warfare agents themselves and immediate precursors aren’t listed.  So this document represents an effort to get rid of the various feedstock, additive, and waste chemicals that represent less of a proliferation hazard.  For example, the list contains 30 tons of phosphorous trichloride, which is an early feedstock chemical in many of the production methods for making Sarin.  The list also included 80 tons of hexamine.  This is really interesting.  There’s hexamine all over the battlefield and hexamine in the storage vaults of the Syrian government. 

Knowing how the Chemical Weapons Convention is written and understanding how the OPCW works, one can make several assumptions from this revelation. 
  • Assad’s government admitted to having 80 tons of hexamine. This kind of list would only be made based on declarations by the Syrian government.  The OPCW inspectors did not have the resources or wherewithal to crawl into every nook and cranny of Syria during an active war.  If 80 tons of hexamine are on this list, it is likely because this list was given to the OPCW by the Syrian government
  • The hexamine is for chemical weapons purposes: The OPCW operates within the terms of its mandate. Hexamine isn’t a substance on the various schedules of the CWC.  The OPCW has no remit to deal hexamine for its numerous commercial and industrial uses, including the manufacture of RDX, an explosive.  If it is on this list, it is because either the OPCW believes it has a use in chemical weapons industrial processes, the Syrians said that it was for such processes, or both. 
  • 80 tons ain’t cheap to get rid of: The OPCW is not going to spend money getting rid of 80 tons of a chemical unrelated to either its remit or the problem at hand.  
  • Hexamine would have been easy to deny: If the Assad regime wanted to deny the 8/21 attacks, they would have had ample opportunity to do so by not declaring the hexamine.  As it is not a scheduled chemical under the CWC it would have been quite easy for Syria to not declare it. 
The Hexamine Hypothesis

So, what is the hexamine doing on the list? And why is it all over the battlefield.  There are many commercial and industrial uses of hexamine , as a cooking and heating fuel, as the most common example.  It also has uses as an anti-corrosion aide.  However, it has very little history of use in the history of chemical warfare. Indeed, I researched the subject at some length and the only use I could find was its sporadic use as an anticorrosion additive in the seriously outdated Levinstein Mustard, an older form of Sulfur Mustard (commonly misnamed “Mustard Gas”).  There’s no use for hexamine in Mustard production processes after the 1920s, and it does not occur as a trace content in published specifications for either older or more recent US Mustard, nor does it have any use as a precursor.  

Hexamine’s anti-corrosion properties stem partly or even largely from its ability to bind with acid molecules.  This is where it gets interesting.  The US Army spent a lot of time trying to turn binary Sarin, made by the DF + Isopropanol method into a useful weapon system.  This process, described in detail above, results not in pure Sarin but in a cocktail of Sarin and Hydrogen Fluoride (HF).  When the US tried to make weapons, like the M687 155mm howitzer round, using the binary method, this surplus HF was like a wrecking ball inside the munition.  Most of the information from the M687 program is still not available, but it takes little imagination or technical knowledge to realize that HF, one of the most corrosive chemicals in existence, will have a serious deleterious effect on things like the case of the shell, the fuze, and the conventional explosive bursting charge.   The US military found that the chemical isopropylamine (also noted in the Syrian inventory, by the way) was an isopropanolamine as an additive  to reduce the HF content in Sarin produced by the DF + Isopropanol method.  The US M687 howitzer shell combined a cartridge of DF with a cartridge containing a mix of 72% isopropyl alcohol and 28% isopropylamine, a ratio published in the US Army’s Field Manual 3-9. 

While isopropylamine is the amine compound of record for use in Sarin, other amines are of use for acid scavenging, including hexamine.  I found a dissertation on the usefulness of hexamine specifically as an HF scavenger , noting the ability of one molecule of hexamine to bind up to four molecules of HF.  I consulted 5 chemists and an engineer, all of whom affirmed to me that hexamine’s utility of an acid scavenger.  Hexamine can be used in binary Sarin as an acid scavenger, either on its own or in conjunction with isopropylamine.  Because this is an “off-label” use of hexamine, and one never done before, if hexamine was in the Syrian government recipe (as implied by the inventory) AND in the field samples, it is strong evidence that the 8/21 Sarin came from government inventories and was made using a unique Syrian government process. 

Of particular interest is environmental sample 25, which was taken from the screwthread of a bolt on one of the rockets.  No amount of hexamine in the ambient environment for cooking purposes could explain the presence of hexamine on this component of the actual weapon system.  There's no physical or mechanical mechanism to explain why hexamine elsewhere in the environment would get onto a screw-thread.  Hexamine on the screw thread is consistent with hexamine dissolved in the expected cocktail of substances that result from a binary reaction.

The Hypothesis Confirmed 

After working hard to confirm my suspicions about hexamine as the acid reducer in Sarin, I originally broached this idea in an article in NOW Lebanon  in early December 2013.  Somini Sengupta at the New York Times interviewed me at length, and an appropriate question was put to the OPCW in congressional hearings on 13 December 2013 .  Ms. Sengupta put forward the hexamine hypothesis in the New York Times  on 18 December 2013. I knew I was onto something serious because of the furious onslaught of trolling, threats, and general cyberbullying I received as a result of voicing the hexamine hypothesis.   Ake Sellstrom, Swedish CBRNE expert and head of the UN/OPCW inspection mission, acknowledged the role of hexamine in the following extract from Sellstrom interview  from his interview with CBRNe World magazine:
CBRNe World - Why was hexamine on the list of chemical scheduled to be destroyed - it has many other battlefield uses as well as Sarin? Did you request to put it on the list or had the Syrian’s claimed that they were using it?
Sellstrom - It is in their formula, it is their acid scavenger.
I confirmed the veracity of this statement in an email exchange with Prof. Sellstrom, although he did not provide further elaboration. This is as close as I can ever hope to a confirmation of my hexamine hypothesis, and I believe that this was one of the reasons, if not the strongest reason, that the UN firmly concluded that the 8/21 Sarin came from Syrian government stockpiles. 

The lack of compelling alternative narratives helps to reinforce the conclusion.  Other attempts to come up with a logical explanation for hexamine are based on some combination of wishful thinking, stretches in credibility, and/or faulty chemistry. 

Conclusion:

I believe the regime committed the 8/21 Sarin attack.  The following formula is a useful summation of the evidence:

Nobody’s used hexamine previously as a Sarin additive

+

There’s hexamine in the field samples

+

There’s 80 tons of hexamine in the declared inventory of the Assad Regime

+

The Syrian government’s admission to Sellstrom’s team

EQUALS

The Assad Regime Did the Wicked Deed

About the author: Dan Kaszeta is the author of “CBRN and Hazmat Incidents at Major Public Events: Planning and Response” (Wiley, 2012) as well as a number of magazine articles and conference papers.  He has 23 years of experience in CBRN, having served as an officer in the US Army Chemical Corps, as CBRN advisor for the White House Military Office, and as a specialist in the US Secret Service. He now runs Strongpoint Security, a London-based CBRN and antiterrorism consultancy. Mr. Kaszeta also holds a part-time post as Senior Research Fellow with the International Institute of Nonproliferation Studies and is a contributor to Wikistrat.


15 comments:

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  2. If anyone needs this article as a PDF it is at http://strongpointsecurity.co.uk/site/wp-content/uploads/2013/08/Why-Farage-Has-it-All-Wrong.pdf

    ReplyDelete
  3. I definitely enjoying every little bit of it and I have you bookmarked to check out new
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  4. Why did they admit to having 80 tons of hexamine ? There's no logical reason behind this. Although I agree with the conclusion that the attack was almost certainly perpetrated by Bashar's troops, I don't understand why they would admit to having these chemicals.

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    1. Here's my theory:

      1. At the global diplomatic level, Assad agrees to join the CWC and give up his weapons.
      2. This requires a full declaration.
      3. Order comes from above, from political officials who think Sarin is Sarin and don't know any better, to make a declaration.
      4. Orders from above in the regime are always faithfully obeyed.

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  5. This comment has been removed by the author.

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  6. Thank you for the clear explanation and for following up on your theory. One question that I haven't seen an answer for is whether the sarin samples from the rockets and surrounding environment could be matched to the chemicals that OPCW inspected at sites and are now in the process of being destroyed. Wouldn't the sarin used have unique markers, beyond hexamine, that could provide definitive proof that Syrian government stockpiles were used in Ghouta?

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    1. I could write pages on this (indeed I will at some point), but here is the basic answer. By both the field evidence and the Syrian regime's admissions, they used a binary process to make Sarin. No two batches made by such a method will ever be truly identical.

      But there are things we can look at to help guide us here. First of all, when hexamine reacts with HF, it forms a salt. There's no apparent sign of these salts in the field samples. This leads me to believe that the binary Sarin was mixed prior to use on the battlefield, as the salts are easily removed. One expert tells me that they'll likely form a sludge on the bottom of the reactor vessel.

      So, mixing the isopropyl and DF in a large reaction vessel is not an easy thing. This is not done in the field. It needs to be done in a lab. For the amounts of Sarin for 8/21 we are looking at a factory scale operation. Again, this is a circumstantial indicator, but a strong one. Assad declared large mixing vessels of the correct type in his OPCW declaration. Mixing isopropyl and DF in hundreds of liter quantities isn't something that's going to happen in a shed.

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    2. When hexamine reacts with HF, it forms a liquid compound - perfluoridated HTMA - not a salt. It forms the expected n-chloride salt when it reacts with HCl.

      Does your expert have a reference for perfluoridated HTMA's insolubility in DF / isopropyl? It's somewhat dense, but I've only ever heard of it stratifying in a HF / HTMA synthesis. It's certainly soluble in saline and water - they use it for the oxygen carrier in artificial blood.

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  7. Seriously, Dan...

    "...The lack of compelling alternative narratives helps to reinforce the conclusion..."

    Confirmation bias, much? No - the lack of compelling alternative narratives means you have a reasonably educated guess, but nobody speaking publicly really knows with any certainty. One hopes the OPCW knows, but they apparently have little intention of telling anybody. Their expertise seems to lean more towards bureaucracy, obfuscation and politics nowadays. Then again, maybe they just don't know either. Thank god Assad didn't declare 20000mT of deionized water as a precursor chemical.


    "...Other attempts to come up with a logical explanation for hexamine are based on some combination of wishful thinking, stretches in credibility, and/or faulty chemistry..."

    You speak as if there are several other theories out there - do tell. have not heard of *any* other reasonable explanation. I initially suggested the possibility of acid scavenging in crude sulphur mustard, but that wasn't reasonable. It doesn't nearly explain a stock of 80mT of hexamine given Syria's declared mustard. They simply would never have used that much unless they were producing hundreds of additional tons of new, undistilled mustard for some reason.

    It's even less likely that they would need that much for some mystery Sarin manufacturing process considering the quantity of raw/finished stocks of Sarin they declared. If they were ramping up *new* production facilities, I would expect to see far more and greater quantities of precursors. Hexamine isn't even that difficult to manufacture - there would be no need to stockpile tons of it for a production process 'just in case' when nearly all the other precursors are far more difficult to manufacture or obtain quickly.

    "...Nobody’s used hexamine previously as a Sarin additive..."

    So are you suggesting that 80mT was all for post-production acid scavenging? I could see some intermediate industrial-scale production step potentially using quantities of hexamine, but they are apparently already using the well-known and effective amine as post-production scavenger. Additional hexamine used for some reason post-production would be in the kg range for their Sarin stocks, not in the mT-range. I'm not even sure those quantities would be reasonable if they were using hexamine as a complete replacement scavenger.


    "...There’s hexamine in the field samples..."

    Curious how the OPCW would only call out pure hexamine, when specifying the halogenated compounds found would have been far more informative and incriminating. Didn't the OPCW test for them at all, or are they saying that they only found pure, unreacted hexamine residue that somehow escaped the liters of HF or HCl being produced in the warhead? In fact, I can't think of any reason they would not preferentially announce finding the expected specific hexamine salts rather than pure, unreacted hexamine. How coincidental for the OPCW that they subsequently reveal a great quantity of unexplained, non-scheduled hexamine in the Syrian declaration.

    As a loyal tin-foil hat brigade member, I would guess the hexamine is a red herring by the Syrians or OPCW to obfuscate the identity of a non-scheduled, non-lethal calmative or psycho agent or precursor. Benzodiazepines, BZ or some other weponized anticholinergic or GABA agonist compounds would explain for more of the symptoms and fatalities in East Ghouta than 'just' Sarin. That doesn't explain OPCW's hexamine findings in field samples, but I'm not too inclined to make much of their strangely amateurish public report.

    The Syrian declaration was only a sample of one. I'll hold off pointing my finger at anyone until I see the other half-dozen OTHER parties involved in East Ghouta publish their CW inventory declarations so we can compare them.

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  8. These blogs and articles are fully good enough for me.
    vision spinner rainbow

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  9. Analysis of this post on the WhoGhouta blog:
    http://whoghouta.blogspot.com/2014/04/hexamine-again.html

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  10. NYT Backs Off Its Syria-Sarin Analysis

    http://consortiumnews.com/2013/12/29/nyt-backs-off-its-syria-sarin-analysis/

    This is good article throws doubt on original claim it was regime.

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  11. Information that the rebels not the Syrian govt used Sarin has been in the public domain for a while.( Since December 2013) Curious that the mass media have continued to peddle the untruths and propaganda served up by mainstream politicans. The highly respected author, Seymour Hersh who has serious contacts in the intelligence agencies exposed the truth in his book Whose Sarin? http://www.lrb.co.uk/v35/n24/seymour-m-hersh/whose-sarin

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