Safety correction in JACS

JACS logoA few weeks ago, “Kenrod” left this comment on my post about the new safety policy for ACS journals:

So check out the Experimental in the Supporting Information of this Communication in the very first JACS issue of 2017: J. Am. Chem. Soc., 2017, 139 (1), 19; http://pubs.acs.org/doi/full/10.1021/jacs.6b09889
The first two procedures describe the prepn of trinitroaniline (TNA) and triaminotrinitrobenzene (TATB). Both are known explosives. No hazard warnings whatsoever, not even a peep.

The paper was reviewed and published before the new policy went into effect. Nevertheless, I contacted JACS editor Peter Stang to ask him about it–in particular, how he’d like to see these sort of safety hazards addressed in JACS in the future.

Stang first noted that he did not handle this particular paper, because it was authored some of his colleagues at the University of Utah.

That acknowledged, “Clearly safety is an absolutely critical issue, and it’s also a very complex issue,” he said. He pointed to one source of complexity as quantity, because there may be different safety concerns depending on whether you’re making a few milligrams, a few grams, or several kilograms of a particular compound. Another source of complexity is that toxicity is difficult to determine when a brand new compound is synthesized. “To do toxicity tests on every new compound made is not feasible,” Stang said.

However, when there are known safety issues, such as in the above paper, “we will require authors to provide a warning, even if they don’t know the full details or extent of toxicity, explosiveness, or other properties,” Stang said.

And to that end, JACS has now issued a correction to the paper that adds this to the materials and experimental methods sections of the supporting information:

Warning: 2,4,6-Trinitroaniline (TNA) and 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) are very
sensitive and highly explosive. They should be handled with extreme caution.

Author: Jyllian Kemsley

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6 Comments

  1. Did you even research these materials before pushing this agenda?

    Check wikipedia for TATB: https://en.wikipedia.org/wiki/TATB

    “TATB is a powerful explosive (somewhat less powerful than RDX, but more than TNT), but it is extremely insensitive to shock, vibration, fire, or impact. Because it is so difficult to detonate by accident, even under severe conditions, it has become preferred for applications where extreme safety is required, such as the explosives used in nuclear weapons, where accidental detonation during an airplane crash or rocket misfiring would present extreme dangers.”

    Now you cheapen a major journal by having them lie about the property of these materials. TATB is not highly sensitive.

  2. @this name is fake: So you don’t think TATB needs to be handled with caution?

    For the record, I did not suggest any wording to JACS. That was determined solely by the authors and journal editor.

    Also, I caution against using Wikipedia as a sole source for chemical information: Glaring Chemical Errors Persist for Years on Wikipedia

  3. While calling out hazards is commendable, JACS should really strive for warnings that are going to be more useful than this. “They should be handled with extreme caution” is so general as to have no practical value. Are you supposed to worry more on your way back from the balance? Maybe duck a little before snatching a TLC sample? Add an additional 7mg of caution to the flask at the outset?

    How about,”limit standard glassware manipulations to milligram quantities, as gram quantities can detonate with violent force, and should be handled behind blast shielding” or “compounds are shock sensitive, avoid scraping residue with spatulas, storing in screw-cap enclosures or otherwise exposing isolated solids to mechanical force”

    I don’t know what the appropriate version of the above warnings are, but the author and editor ought to be able to come up with something more useful than “be careful.”

    -t

  4. What “@this name is fake” is so clearly illustrating is a systemic misunderstanding of the fundamental difference between hazard and risk.

    Hydrochloric acid is corrosive = Hazard

    6M Hydrochloric acid is *more likely* to cause serious harm than 0.1M Hydrochloric acid = Risk

    My experience suggests this nuance is lost and not clearly explained, which ultimately leads to misguided and uninformed outbursts like the one above.

    I for one am happy to see the ACS set make a positive change and setting the example by requiring at least brief hazard statements in their publications.

  5. Jyllian, I have personally tried to make TATB detonate with a hammer and anvil. Won’t happen. 0 lab risk. (unless you store your reagents with detonators in the bottle)
    (or maybe I need to go to the gym more)

    Furthermore, “very sensitive” has a specific meaning in explosives chemistry and the UN transport of dangerous goods regulations.

    Classification: impact sensitivity
    Insensitive: greater than 40J
    Less sensitive: 35-40J
    Sensitive: 4-34J
    Very sensitive: less than 4J

    Classification: Friction sensitivity
    Insensitive: greater than 360N
    Less Sensitive: 360N
    Sensitive: 80-360N
    very sensitive: 10-80N
    Extremely sensitive: less than 10N

    TATB is greater than 40 J impact and greater than 360N friction

    TATB needs more caution for its high toxicity as a nitroaromatic than it needs as an explosive for lab scale quantities.

    (had to repost, use of greater and less than signs killed formatting and deleted text)

  6. Hi, “Kenrod” here. A couple of points come to my mind, for what they’re worth:

    I emailed the PI the same day I wrote the post above, voicing my concern. She responded quickly.

    The revision is unsatisfactory, largely for the reasons cited above (and especially Ted’s). My interpretation, based on zero evidence, is that there were no safety precautions taken in the lab and the revision statement amounts to a flippant afterthought. I may very well be overstating things – apologies if I am – but that is how it feels. If they had taken further precautions, had set mitigation procedures, had studied and known the literature, and already had that in hand when I wrote them then I can’t imagine they would not have included it in the correction (or, for that matter, the original manuscript).

    From the little bit of reading I’ve done, these molecules are not particularly shock sensitive. They absolutely are explosive, however. They are, depending on the property you look at, pretty similar to TNT and picric acid (no surprise). Those properties may not look similar to someone who is an explosive expert working in a lab or facility devoted to such chemistry, but to a lab full of undergraduate/graduate/postdoctoral students with no such experience they are not so dissimilar. SOME sort of procedure should have been in place. Any experienced organic chemist worth his or her salt should have been able to look at those structures and know immediately that this might be an issue that needed to be addressed, especially in the hands of the inexperienced.

    The previous posts discuss TATB exclusively. Note that the paper also reports the preparation of 2,4,6-trinitroaniline (TNA, picramide), which is significantly more shock sensitive than TATB and nearly equal to TNT.

    Finally, it is not clear to me what is new about this policy at ACS that just took effect. It has been longstanding policy in ACS journals that authors are supposed to call out particular experimental hazards, and reviewers are responsible for checking that it is done. Statements to those effects have been in the Instructions to Authors and the Reviewers Guidelines for a very, very long time.

    Regards,

    Kenrod

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