Apr 5, 2014

Hexamine Again

If this is your first time here, I recommend starting from the conclusion page.

Dan Kaszeta has published another piece that claims hexamine proves the Syrian government is behind the August 21st attack. Most of these points were refuted here and here, but there are a few new claims which will be addressed here.
  1. For the first time, Dan attempts to address the issue of samples that contained hexamine but no sarin. As detailed in the previous posts here, this is one of the indications that hexamine could have come from many sources and is therefore not a "smoking gun".
    Dan dismisses it by saying: "this is a logical state of affairs as hexamine does not evaporate like Sarin does".
    This, however, fails to explain why none of the stable sarin degradation products (which were found elsewhere) are absent from these samples.
  2. Dan brings up sample 25 from the UN report, which shows hexamine in one of the rocket's bolts. He claims this proves hexamine findings were not a result of environmental contamination.
    This sample is originally described by the UN as "Metal bolt removed from rocket head combined with paint rust scratched from the surface surrounding the bolt", which provides a good clue to the source of hexamine in this sample: One of hexamine's numerous uses in chemistry is in paints.
  3. Dan claims "the UN firmly concluded that the 8/21 Sarin came from Syrian government stockpiles".
    The original quote: "The evidence available concerning the nature, quality and quantity of the agents used on 21 August indicated that the perpetrators likely had access to the chemical weapons stockpile of the Syrian military".
    Besides the misquote - as discussed in detail here, this UN statement is probably not significant.
Dan concludes with the following logical equation:

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

To sum up the weaknesses of this line of reasoning:

  1. There is no indication hexamine was used in production of sarin, rather than another agent, or for another use completely (e.g. safe neutralization of by-products).
  2. Syria has specifically declared Isopropylamine in its stockpiles, which is the standard amine used in binary sarin. Furthermore, the amount of Isopropylamine reported matched the amounts of other reported chemicals, making hexamine redundant.
  3. Hexamine is a very common agent in chemical processes, and there is nothing that associates the hexamine field samples with sarin. More specifically, we have hexamine samples that have no trace of sarin, and we have samples showing explosive traces (hexamine is also used in explosives).
  4. There are no traces of hexamine salts in the field samples, which is a strong indication that hexamine was not present in sarin. If hexamine was indeed intended to react with the HCl created in the sarin binary process, then where are the products of this reaction? (credit to Paveway).
  5. Even if we were to accept this far-fetched connection between the hexamine in the field and the hexamine in the stockpiles, and assuming Syria did make this amazing break-through in sarin production, there is still no way to know that this information was not leaked to the opposition (e.g. by one of the many defectors).


All in all, the fact that this weak circumstantial evidence is still claimed to be a "smoking gun", is mostly a testament to the weakness of the other evidence for a regime attack. And once again: So far no one was able to provide a regime-attack scenario that is consistent with the evidence!

39 comments:

  1. Credit to my grumpy old and occasionally sober ex-Navy EOD pal. We are still banned from the Salty Duck outside of Eglin. I believe it was in effect for several lifetimes, but we're somewhat hazy about the details.

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    1. this comment required me to do way too many google searches.

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    2. Next time try the "little known (at least anymore)" Matador Club in Valparaiso, you can see the EOD School House from the front door. It is almost impossible to get banned from that great institution but it has been made off-limits by the Base Commander a few times.

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    3. Sorry Sasa: Eglin = Eglin Air Force Base in Florida. My work brought me there on occasion a few decades ago. The U.S. Navy has - or at least had - a pretty top-notch Explosives Ordinance Disposal school on the base.

      The old Salty Dog was one of the many local smelly, dumpy off-base bars favored by base personnel, the odd left-over hippie or two and bikers. It had all the elegance one would expect for a bar that served beer in a plastic cup and a duct-tape repaired bar mirror. Plus they had free peanuts.

      Jody - I have not been anywhere near Eglin since the early 80's. I'm sure my buddy would know the place.

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    4. It's ok - I eventually managed to figure all these references out...

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  3. I see Seymour Hersh has written an even more explicit piece on the Ghouta chemicals, blaming the Turks for orchestrating it

    http://www.lrb.co.uk/2014/04/06/seymour-m-hersh/the-red-line-and-the-rat-line

    Eliot Higgins has got extremely exercised about this with three attack pieces in a day including one in Turkish!

    Trusting there will be the usual reasoned and polite article on this soon here.

    TTFN

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  4. Maybe Seymour Hersh and Elliot Higgins are the same person. I have never seen both of them in the same place at the same time.

    Where's that 'Curveball' fellow when you need him?

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  5. http://www.lrb.co.uk/v36/n08/seymour-m-hersh/the-red-line-and-the-rat-line

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  6. There is corroboration for some of the material in Hersh's story:-

    1. the dropping of charges against the JAN group arrested with a sarin shopping list indicates that the Turkish state has something to hide.

    2. the story about analysis of sarin samples at Porton Down indicating that the sarin could not have come from Syrian military stocks is consistent with what this blog has concluded from the OPCW lab findings

    3. Hersh reports a meeting on 16 May between Erdogan and Obama. "Erdoğan had sought the meeting to demonstrate to Obama that the red line had been crossed, and had brought Fidan along to state the case." This was a few days after the French and UK governments had announced that blood samples from victims of the Saraqeb incident on 29 April had tested positive for sarin. I suggested in an earlier thread that the most likely explanation for the bizarre sequence of events in Saraqeb was that the objective was to get sarin-exposed individuals to Turkey for blood tests. This appears to have been timed so that the results would be ready before Erdogan's meeting with Obama.

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    1. 1. I'm not aware of the charges being dropped. Do you have a source? It is however weird that they are not currently under arrest.

      3. Interesting idea.

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    2. My mistake: the Syrian national Hytham Qassap was released on 30 October 2013 but the charges weren't dropped. (http://www.aydinlikdaily.com/Al-Nusra-Militants-Free-in-Adana-%E2%80%98Sarin%E2%80%99-Trial-1119). Qassap was the only one of those arrested who had been charged with anything related to chemical weapons and the only one still in custody by then. The opposition deputy Hurşit Güneş alleged that there had been pressure on the court by the AKP and promised to keep following the case, However I can't find any reports of further developments

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    3. The initial arrests and mention of Sarin came from local officials and local police. They didn't conclude it was Sarin from lab or M8 paper tests - the JAN guys they arrested TOLD them it was Sarin. The details were kind of confusing, but initial translations suggested they were carrying the main binary precursor (DF or DC+DF), not actual Sarin. Early reports said the reason the police even showed up was because they were told these guys had Sarin and one of their rumored targets was Incirlik AFB in Turkey. This was from the initial Turkish media reports published on the internet in Turkish. The on-line translators suck at Turkish. Bloggers and such that were trying to translate them were having all kinds of trouble because the source Turkish on-line versions kept getting edited into simpler, more dumbed-down versions or just outright disappearing.

      The few source articles in Turkish left out there today have all been scrubbed of meaningful detail. Western media never reported the Incirlik detail or the earlier busts. The few western reports have also been 'sanitized' since then. Obviously, Turkey didn't want the world to know about the (by then) out-of-control arms smuggling. Besides, they were making a fortune from their cut. They had no problem helping rebels with obtaining and transporting bulk precursors through Turkey, but they panicked when DC and DF started showing up in the rat lines. One can imagine the U.S. didn't care to have anything about the consequences of their stupid schemes known either.

      There were other similar briefly-covered incidents before this one in Turkey in 2012. They involved airline passengers smuggling a liter or two at a time on flights supposedly originating in Libya. This would have been after the CIA and MI6 lost their exclusive arms-supplier business in Benghazi to Ansar al Sharia militia, who figured they should be enjoying Libyan arms trafficking profits. They appreciated that Petraeus was courteous enough to set up the shop and rat lines and all, but the spoils of the Libyan revolution really belonged to Libyans like Ansar al Sharia.

      Ansar al Sharia is one of those loose coalitions of salafists like the Syrian rebel groups. The individual members are loyal to their own groups. They just call themselves Ansar al Sharia. The member groups that run the arms business have no problems selling anything and everything to their pals in JAN. They are more alike than different (but still - cash only, please...)

      The few early, small CW attacks attributed to Assad's forces only required a few kg of Sarin. Even if JAN was in the process of converting one of the many chemical manufacturing plants in and around Aleppo, they probably were not to the point of manufacturing yet. Early attacks may have used Sarin mixed right before use from a binary precursor smuggled through Turkey, not from locally-brewed Sarin made from scratch.

      All hearsay of course. It's ridiculous to think SAA attacks against and the opposition's particularly vigorous defense of the TAMECO pharmaceutical complex in East Ghouta could have EVER been related to JAN's interests in setting up a few CW shops. That's just crazy talk.

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  7. Very recent interview with Hersh in Turkey

    http://www.diken.com.tr/english/seymour-hersh-in-an-interview-with-diken-claims-that-turkish-intelligence-and-military-were-behind-the-sarin-gas-attack-in-syria/

    Definitely names names. For instance

    "Look! So, I do not know anything about Higgins. All he talks about is volcanos."

    "Higgins repeats the same thing because he doesn’t change his opinion. And I know he had private communication with Postol and man named David Lloyd or something… In which he sort of acknowledged that maybe he isn’t right. But he cant undo it. He is defending the base too. Higgins is a bit like the White House to me.. Once I said something, I m not gonna change it."

    "American intelligence has concluded that Turkish intelligence, MIT, by the way, MIT doesn’t do hands-on… Technical stuff. But they do thinking, strategic staff. Turkish gendarme are the people actually trucked the stuff in. So, materials trucked from Turkey into Syria and Aleppo. Including chemical to make up nerve gas… When they melted together, and they became something different. There is an intelligence report to that effect. That’s what I have written."

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  8. Pmr9,

    More corroboration for Hersh story through his interview (http://www.diken.com.tr/english/seymour-hersh-in-an-interview-with-diken-claims-that-turkish-intelligence-and-military-were-behind-the-sarin-gas-attack-in-syria/)

    - Hersh claims the actual Sarin production was in Allepo (with Turkish chemicals and logistic support)
    - Through Vandyke leaks (http://leaks.sea.sy/vandyke-leaks/#KnewRebels) we know that Vandyke knew where the building was where rebels "acquired Sarin" from. That was in May 2013. Vandyke talked about small quantities then, I guess by August, quantities might have become bigger.

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  9. Pmr9,

    Addition to my previous post: Vandyke knows of a building IN ALLEPO, corroborating what Hersh says.

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  10. It's likely that insurgents planning to make Sarin would have chosen Aleppo: large industrial areas, secure insurgent control, easily supplied from Turkey. The chemical waste from manufacturing several hundred kg of sarin would be hard to get rid of. If so, there's a high chance that the sarin plant will be identified as the SAA gains full control of the industrial areas. Can we make a list of the most likely sites, and what the Syrians should look for?

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  12. Higher-purity Sarin might be produced by exploiting a certain properties of hexamine despite absence of any mention of this in available material. Syria may have determined some practical method using hexamine and used that in their DF-based Sarin production.

    Historical descriptions of the relevant binary Sarin formula describe Methylisopropylamine (MIPA) as the acid scavenger used in the OPA-half of a DF+OPA binary Sarin formula. MIPA would be replaced by hexamine as the amine in the alcohol+amine OPA mixture. For batch mixing, they do not necessarily have to prepare the OPA side independently. A binary shell uses one compartment for OPA. Batch mixing in special-purpose vessels only requires the amine to eventually scavenge all the HF. That eliminates any limitations on how well or how much hexamine dissolves in the alcohol ahead of time. In the OPA component of a binary shell, there is no option - you must be able to dissolve all the required amine in the alcohol first and it must stay in solution for a long time in the OPA compartment during storage. The US had that specific requirement and references to MIPA seem to originate from that use. There are no accounts of a military procedure or preferred formula for batch-converting DF to Sarin prior to use, so there's no certainty that the amine scavenger is limited to the in-shell binary formula using MIPA.

    1. Isn't MIPA the only thing that would work?
    Not necessarily. It's just the only one that was documented of actually being used in CW programs decades ago.

    2. Why not just keep using MIPA?
    From historical material: The MIPA-based DF + OPA process produces an end-product that's roughly only one-half to three-quarters pure Sarin; the rest is some form of a fluorine-amine waste product. MIPA works, but something else might work better.

    3. Why not concentrate on a way to purify MIPA-scavenged Sarin?
    Removing HF during the final step of *any* Sarin production method is extremely difficult according to attempts described in historical accounts. There is no evidence that the fluorine-amine waste in the DF+OPA process is any different or that *anyone* has ever figured out an easy way to purify it.

    4. So hexamine produces superior Sarin than MIPA? No - the Sarin molecules are the same, and using either amine results in Sarin diluted with waste. Hexamine may even leave you with more waste in the Sarin than MIPA. The properties of each waste type are different. MIPA waste can't be removed easily. This might be possible with for hexamine waste.

    How, exactly? Why hasn't anyone heard about it? Involves too much speculation. It would be something *like* a way to precipitate and filter out the waste or separate the Sarin from waste based on density. If someone did figure out this or any another method, they're not going to brag about their discovery in an academic paper. CW program information is secret, whether the program ever used it or not. It's almost an accident that we even know about the US using MIPA in their DF binary artillery shells.

    5. Why isn't anyone else using hexamine in DF if it's this easy?
    Someone might be. If they were not up until now, then they're certainly looking into it.

    6. This should be a secret - you're helping terrorists!
    The OPCW and UN chose to make information on hexamine public when they could have easily kept it internal. They take great pains otherwise to obscure information that might be helpful to CW manufacturers. They've already made the purification connection - I'm certainly not figuring it out for them here.

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  13. 7. How does this prove Syria used it? You're making assumptions to justify the evidence!
    Syria had enough inventory for either method. Setting aside the 'This proves Assad did it' wars for a moment, is there any logical reason why Syria or anyone else would *ever* use hexamine over the known MIPA formula? 'Highly purified Sarin' is a reasonable answer. The contrary argument is that no scientist in Syria was ever clever enough to figure out anything better than the MIPA formula over the last few decades, therefore it must have been used.

    8. Why would Syria have both MIPA and hexamine if they only needed one or the other?
    Consider that if the Syrian CW program discovered a way to use hexamine in last few years, the they would have had a existing full stock of the MIPA and would have gradually added a new stock of hexamine. Why be in a hurry to get rid of the high-grade MIPA? 'Syria switched at some point to hexamine' is plausible and explains both stockpiles.They wouldn't have accumulated both if they knew about hexamine from the very beginning of their Sarin program.

    9. Prove Syria couldn't have used MIPA
    I can't, conversely nobody can prove Syria did use it. There was just good rationale for assuming MIPA at the time and really nothing specific in favor of hexamine. If hexamine might work better than MIPA and Syria had it, then it's at least as plausible as MIPA. If you consider the way they may have used hexamine, then both the inconsistent hexamine findings are explained as well as the lack of huge quantities of pure and spent hexamine residue. That lack of residue alone suggested that Syria was using Sarin of far more purity that the known DF+OPA concentrations. DF+OPA should have produced some traces of the several kg of waste products (or their subsequent degredation products) resulting from using MIPA.

    10. How does this prove Syria used hexamine?
    It doesn't. It's offered because it provides much stronger rationale for the possibility of Syria using hexamine. In addition, there is no satisfactory expiation (my estimation) for either Syria's stock or specific findings of hexamine by the UN. It's reasonable to think that Syria would use whatever method produced the best results, and that method may not be the same as the one used thirty years ago in a binary artillery shell.

    11. You're just blaming Assad by making up theories.
    Not necessarily. The possibility can't automatically be dismissed or dismissed with weak reasoning because it doesn't support an existing conclusion. 'Syria used hexamine; the UN found hexamine' doesn't prove anything either way, it only adds complexity that may always have been there. At the same time, this may actually provide some support for opposition use relative to other existing evidence (not discussed here).


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  14. Vs. reasoning against the existing discussion: Hexamine is not the smoking gun

    Dan's first four points (from the five point summary) are consistent with this alternative

    "5. It is unlikely the opposition will choose the same HF binding chemical as the government, implying government culpability."

    Under a false-flag scenario, the perpetrator has to know and use the same binding agent as the government, period. If the OPCW inspectors' samples showed a different binding agent, it would suggest Assad wasn't responsible.

    Under any other rebel use scenario, they would use whatever they had or could use. If they were in control of most of the raw material factories (at one time or another), then they would have used what they found in their own CW effort. Between defecting military units and factory workers friendly to the opposition, the hexamine trick could have been discovered. Maybe it was known through sources outside Syria because other countries are using it. If you don't have access to quantities of pure MIPA, then pure hexamine may just have been easier to acquire. Especially if you were occupying the facilities that made Assad's hexamine.

    Justification offered against Syrian hexamine:

    1. MIPA known previously used. True decades ago as used in the unique environmental requirements of two-compartment artillery shell and true if nothing better ever applied / later discovered for a batch prep like Syria used.

    2. Mustard (not a gas) - Syria used something in their mustard, but it is already in their finished inventory. 80mt of hexamine only makes sense if they planned on making several thousand tonnes of new mustard and were too lazy to distill it properly like the old stuff. Possible, but 80mt is what they would need for listed DF and listed isopropyl alcohol. Too much of a coincidence to go with the ghetto mustard. A clandestine lab would have more incentive to manufacture a small batch of crude mustard and toss in a stabilizer for immediate use rather than messing around with distillation.

    3. Other sources of hexamine: there may be detectable amounts in undetonated, low-quality explosives. Finding minute traces of it among the detonation products of a regular military shell would need some seriously sensitive analysis. That kind of analysis should also produce a laundry list of other chemicals in the residue. On top of that, the hexamine itself is subject to conditions that almost guarantee it's destruction in the detonation. Seems implausible.

    The finished Sarin could still have residual unreacted hexamine in solution. When that Sarin evaporates, particles of unreacted hexamine are formed. Detecting one or the other or both depends on what you sampled. There's a possibility of any combination in an individual sample. If the hexamine particles fell out of the air from evaporating Sarin mist, then you many find hexamine traces and not Sarin. If they had 500 samples from each location, then total absence of one or the other in every sample is significant. If you're looking at five samples - I'm not so sure.

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    1. Paveway,
      You provide some very strong points. Here are some follow up questions:
      1. Hexamine seems like a very arbitrary amine for this purpose. Choosing a solid for scavenging in liquids seems weird to me.
      2. I assume it is no coincidence an amine of isopropanol was used to be mixed with isopropanol... This must have some advantage like creating a stable uniform mix, or perhaps releasing isopropanol that can then be used to react with DF.
      3. We're still left with the question of where are the Hexamine salts.
      4. You say you'd expect more explosive traces to be found - Note that we do have those in the samples.

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    2. 1. Agree about the seeming arbitrary choice, but I'm not an organic chemist. I don't know specifics on why the US went with MIPA, either. Hexamine is unexpected, and has all the extra baggage of ulterior motives, alternative sources, etc. Its easy to dismiss in this context and that was my initial reaction. I was only considering it as an equal alternative, not as a potentially (but speculative) superior alternative.

      Regarding hexamine's solid form: organic chemists would know hexamine dissolves in isopropyl alcohol so (I assume) the issue wouldn't concern them. If an industrial engineer was given the choice between two equal alternatives in Sarin production, than the liquid seems like a better choice. In this scenario, Syria presumably did start with MIPA and was compelled to switch to hexamine at some point because of the purification discovery and benefits.

      Syria's rationale may not apply in a broader context: would anyone planning on mixing DF-based binary Sarin for any use see the same trade-off? I doubt some guy in a tunnel would want to screw around with powder if he can't easily exploit the separation aspect. If CW programs focused on producing finished Sarin and putting it in long-term storage used the DF-based binary Sarin (no idea if that makes sense) then they may know of some other compound - amide or liquid or neither - that has some benefit.

      2. I agree about being a good choice for a stable uniform mix. That's a requirement for the OPA compartment in a binary shell. I don't know if that's as much of a concern if everything is going into a closed corrosion-resistant vat in bulk for mixing.

      They may be able to dissolve enough hexamine in either the alcohol or the DF before hand anyway, so it may all be in liquid form during the reaction. You also have the luxury of time with the proper mixing vessel. HF-scavenging might be slower with particles of hexamine, but you're not worried about the finished product visiting your shoes in seven seconds. Would they care if they had to mechanically stir when mixing, wait a few more minutes for the HF to be bound and add a filter downstream for dispensing? That seems like a reasonable set of disadvantages to accept if the end result was higher-purity Sarin.

      The 'releasing isopropanol' reason is important in an artillery shell - it makes sense if you're trying to limit weight and volume.No alcohol is released when HF binds to hexamine, so you would compensate by adding more alcohol in your ingredients. The additional weight and volume wouldn't be a big deal when loading a batch reactor with precursors. It would only be a serious disadvantage if the resulting waste couldn't be separated from the Sarin.

      The unseparated resulting mix would probably be both heavier and more dilute than a MIPA formula. If you couldn't remove the waste, then those are two perfectly good reasons to reject hexamine over MIPA if you plan on filling warheads with the resulting Sarin.

      3. In hexamine's case, the waste is a compound, not a salt. Charles Wood referred to it as hexamine(HF) where the HF is qualified with 1 - 4 depending on how many HF molecules are bound to it.

      The entire rationale for suggesting hexamine is the assumption that Syria can be removed from the finished Sarin in their process. In this scenario, it's in the bottom of the mixing vat, not in the Sarin siphoned off for use. If the Sarin was purified of hexamine(HF) by-products, then there shouldn't be any detectable deposits of it at the impact sites.

      Ideally, Syria wouldn't want much hexamine left in the finished Sarin, but may want a little to scavenge the stray HF. Alternatively, they may not have an easy way to remove the unused hexamine. A few grams of leftover hexamine is less consequential than tens of kilograms of leftover hexamine(HF).

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    3. cfr 3.
      Why would´t hexamine and HF not form a salt? Hexamine is a base, HF is an acid, the combination is a salt.(http://etheses.dur.ac.uk/6562/1/6562_3865.PDF?UkUDh:CyT p18-19)

      Assume Sarin is very pure due to revolutionary new DK procedure: After being used, Sarin will start to decompose rapidly resulting in binding of HF with hexamine. No reason to find unreacted hexamine and not its salts...

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    4. I'm just a Google chemist, not a real one Veritas. Dan Kaszeta also called it a salt, too. A paper I found made that distinction for fluorine saying that it didn't react with hexamine like other halogens. I may just be making an ass out of myself because I misunderstood what was being explained. So assume it's "hexamine salt" when I blather about a hexamine compound.

      "Assume Sarin is very pure due to revolutionary new DK procedure:..."

      I don't know how much Syria is able to remove - I'm only saying it was some amount to make it worth the bother. Maybe Syria's 55% Sarin could be made to 98% Sarin by switching to hexamine. Maybe Syria's MIPA version was 75% Sarin and the hexamine version 79% It only had to be 'better' enough to Syrian's chemical guys to switch.

      "No reason to find unreacted hexamine and not its salts.."

      I didn't want to get off on this tangent, but it's a reasonable question someone would ask. The answer - like everything else related to organic chemistry - is way over my head. As much as I can tell from the books, it's easier to add the first HF to hexamine than it is to add the last one. If you have 100 liters of the right proportions of both molecules and start the reaction, the HF will find plenty of 'empty' hexamine molecules and bind instantly. By the end of the reaction, a HF molecule has a hard time finding a hexamine with an opening among all the full ones. The overall reaction slows down towards the end. That's my caveman understanding of chemist's accounts. I don't know if that would mean waiting five minutes or five days for 100% in a vat of Sarin. Tossing in some extra hexamine means 100% of the HF is bound faster than it would be using the 'exact' amount. There's some rationale why they would even do this.

      If unreacted hexamine does not sink to the bottom of the vat, then it's not going to be removed with the salt. I don't know. In a big vat, there might be hundreds of kilograms of hexamine salt that settle out. Adding an extra few hundred grams of hexamine up front may be worth it even if it never settles out and remains in your finished Sarin.

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    5. Hexamine binds in a complex with HF and holds one to four HF atoms.

      I'm not enough of a chemist to know if a complex is a lesser beast than a salt, but I'd expect that the binding is more complex (ha ha) than a pure acid-base reaction

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    6. Something else just occurred to me. As far as we know, Syria had a binary warhead program, not a pre-mix binary program like Iraq. This would make Hexamine an even weirder choice.

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    7. Paveway,
      about your hexamine explanation. HF is a strong acid, no reason (IF the scavenging reaction takes place and not something else with the other chemicals..) for the reaction not to be complete in direction of hexamine.HF salt.
      Additionally when Sarin is used, it starts to decompose almost immediately, freeing HF again. If there would be a stray hexamine somewhere, it would immediately be bounded.
      We indeed need a real chemist to make a reasonable prediction (and even he won´t be sure until trying some things out). But because these chemists don´t seem to contribute to this blog, we try to make do we internet-info... (Where is DDTea????).
      Hexamine used or not, something else or nothing, the produced HF at decomposition of Sarin will react with stuff. And apparently not much has been found...
      Now what does HF do to sand (SiO2). HF is an etching liquid. Apparently it dissolves SiO2 and I can´t imagine it not leaving a trace at the impact crater. Neither do we see any trace of any produced salts from whatever reaction. I still think that is highly suspicious.

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    8. I don't think they had a binary warheads at all, Sasa. At least for Sarin.

      The 1,230 warheads were described as empty in press accounts (for what that's worth). The Times used the phrase 'ready for filling'.

      Setting aside the hexamine issue, I think the CWC declaration details provide some solid evidence for Syria relying exclusively on batch-mixing process for Sarin, i.e., not for use in a binary warhead. The same details don't apply regarding Vx or VM. Both complete binary precursors were stocked, so they could have been used in a binary warhead if they had any.

      Consider this: the CWC declaration showed that Syria did not hold any kind of premixed OPA precursor in stock. None was declared and no indication of it appears on the UN Call for Proposal under the container descriptions. The entire MIPA and hexamine inventory are listed in their individual containers so could not be part of an OPA mixture.

      We don't know what motivated the UN weirdness about arbitrarily moving isopropyl alcohol and then hexamine out of Syria's initial Schedule 1 classification, but Syria insisted both were, in fact, Schedule 1 on their declaration and wouldn't back down. The UN Guide for the Schedule of Chemicals are pretty unambiguous. Under Schedule 1, section 1(b):
      "(iii) It may be used as a precursor in the final single technological stage of production of a toxic chemical listed in Schedule 1, regardless of whether this stage takes place in facilities, in munitions or elsewhere"

      Isopropyl alcohol was eventually removed from the chemicals that need transportation and destruction on the initial tender. Cost is an obvious issue if they need to treat it as Schedule 1. I'm only drawing attention to Syria's insistence that they were using it as a direct precursor. So, not in a binary warhead, but in a batch reaction before filling a warhead.

      If Syria was batch mixing DF-based Sarin, then they didn't need to premix OPA first even if we observe that DF-based binary Sarin is 'usually' mixed that way. All the chemicals ended up in the vat for the final reaction and constituted the final technological step to Syria.

      Would that make it trinary Sarin?

      In any case, I think this all supports an argument that Syria was batch-mixing all their Sarin. It was either the way they always did it or a change made to exploit the hexamine method.

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    9. Hexamine isn't just tossed out here for academic reasons. It brings up an interesting set of conditions that must be met by a false flag: the perpetrator needs to use the exact type of Sarin Syria would use, the scavenger would have to be the same and it would have to be partially purified just like Syria's batch-produced Sarin.

      Example: Chlorine smells were reported at Khan al Assad in the attack. If a Di-Di form of binary Sarin (chlorine from initial reaction) was used in a poorly-engineered weapon, then it probably wasn't Assads - they didn't make that type. Furthermore, there's no way JAN would have produced the most technically challenging form of Sarin in their initial manufacturing. You couldn't blame Di-di Sarin on rogue jihadists, al Qaeda or otherwise.

      Di-di produced Sarin would have to be acquired from one of the few countries that have any. The US, for instance, has over 300 tons of Di-di based binary Sarin-filled shells left to destroy in Kentucky. It would be most inconvenient if samples from Khan al Assad proved to match the chemical profiles of that US binary Sarin. The US is just used as an example. It would have come from somewhere else (maybe through Turkey) and the ultimate source wouldn't care to be identified.

      All the above only makes for a great conspiracy theory, not evidence. I'm reluctant to dismiss it outright because it potentially explains so much irrational reaction by the US around certain events - Khan al Assad is the most striking example.

      Hexamine isn't suggested *in order to* support any alternative scenario. It stands on it's own. Evidence either supports Syria's use of hexamine or it does not, or it doesn't matter either way. Existing and alternative scenarios have to conform to the accepted evidence, not the other way around.

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  15. Paveway,

    I don't follow your logic on the batch mixing.

    From the definition:

    "regardless of whether this stage takes place in facilities, in munitions or elsewhere"

    Which definitely includes an in-munition binary process.

    My understanding is that a batch mixing process will include an HF absorber to make handling easier before filling weapons. I'm also guessing that in both batch mixing and in-munition mixing there is a problem with HF gas pressure as well as corrosion so the absorber is used to limit this.

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  16. I'm not sure I understand what part you're asking about, Charles.

    Either batch-mixing or in-flight mixing would require them to use some kind of HF absorber. In either case, the absorber would be part of the final step and must be reported as Schedule 1.

    Batch-mixing here refers to the final Sarin-producing step done in a smaller batch reactor vessel right at the mix/fill facilities, not any of the earlier process steps done at the main manufacturing plant. The mix/fill facilities (bunkers) would only have stocks of the final-step precursors. For Sarin, those precursors would be DF, isopropyl alcohol and hexamine.

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  17. Mimi Al-Laham has just made a rather interesting observation. Hexamine solubility in isopropanol is 0.6% by weight. This means there is no way that it could be used as an in-flight or immediate pre-launch HF absorber and it would be wildly impractical to use in a manufacturing process.

    https://twitter.com/Partisangirl/status/478933065134137344/photo/1

    This has resulted in a lot of hand-waving and wild-ass guesses by the usual suspects. This includes some process whereby the sarin is made with hexamine (how?) and then the Hexamine-HF complex somehow filtered enough that no trace of Hexamine-HF complex is detectable in an atomic spectrometer.

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    1. Interesting. I had the impression it was much more soluble, but probably misunderstood the kind of alcohol they were talking about. In any case, that would rule out hexamine's usefulness for in-flight mixing inside a binary warhead.

      If you were doing a just-in-time mix in a small batch reactor right at the fill sight, then HMTA's solubility in isopropanol *may* not matter. It seems (Google chemist wild-assed guess warning) to me that the HF would find it's way to the HMTA whether or not the HMTA was in solution or was just suspended. In fact, HMTA's low solubility might mean you can filter out both the excess, unreacted HMTA particles as well as the wast fluorinated compound/salts when transferring the produced Sarin out to a warhead.

      So a mix/fill site would have some kind of appropriate teflon or glass-lined reactor vessel with a small capacity - maybe fifty liters or so. Fill with some amount of isopropanol and hexamine, start stirring, then slowly pump in the appropriate amount of DF. After some length of time and chemical magic, you have your lethal brew of fresh Sarin with some quantity of left-over HTMA particles and some quantity of HTMA salts. Pump the hellish mess through particulate filters before filling unary warheads.

      Is that even possible? I don't know. But Syria didn't have any OPA in bulk or in any binary warhead cannisters according to the OPCW info, so they evidently didn't plan on deploying Sarin in the known DF+OPA two-compartment binary warhead inflight-mixing method.

      If they were pre-mixing prior to filling, then they had enough of either the HTMA or the MIPA to use as the amine (provided HTMA would even work as speculated). You have to add yet another degree of uncertainty to the HTMA option because it also depends on another unknown property - the ability to filter most or nearly all of it and the resulting fluorinated compounds out of the final Sarin produced.

      Possible? I don't know.

      Some other party staging a false flag *for* the OPCW to investigate would have to use whatever Sarin prep method Syria had. If Syria's procedure used hexamine (I don't know) then the actual perpetrator might think there needs to be some hexamine for the OPCW to find. That's why finding any is little proof either way - we have no idea what Syria's actual method was or if *any* unreacted hexamine residue is even a possibility.

      The OPCW's job isn't to explain anything to us peons, and they do a damn good job of it.

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    2. I would, of course, defer to anyone more knowledgeable about chemical process than me. That would probably include Partisangirl back when she was in the eighth grade.

      It would be interesting to hear a conversation on this among people that are knowledgeable about such things. Unfortunately, I can't imagine the unwelcome attention that any CW discussion would draw to a Syrian national. There has to be a permanent NSA 'selector' or whatever they're called in their internet spyware for that.

      Considering my Google searches on the topic, I probably already have a set of shackles with my name on them hanging in a railroad boxcar. All ready for my totally-free DHS-sponsored railroad ride to a quiet FEMA internment camp somewhere in the middle of Montana. No cell phone service, and the WiFi is pretty spotty there. The Twitter device I've imbedded in my skull for such emergencies will be virtually useless.

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    3. For your expected long sojourn in Montana, may I recommend you take along some light reading published 23 June 2014 that never once mentions Hexamine...

      http://strongpointsecurity.co.uk/site/wp-content/uploads/2014/06/What-we-are-talking-about-when-we-talk-about-binaries1.pdf

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  18. Chemical weapons are for old school psychopaths.

    Genocide via biological weapons are cheap and easy. Destroy water and sanitary sewer infrastructure, cut the water supplies, restrict chlorine. Millions become easy prey for whatever bugs you develop - waterborne or not. Blame? Sure - for whoever you set up via a false flag. Nobody will ever be able to prove anything.

    It worked in Acre, and it will work Syria and Iraq.

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  19. It looks like some stakes need to be sharpened to permanently still this undead monster

    http://ciceromagazine.com/features/the-chemical-fingerprint-of-assads-war-crimes/

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