Tuesday, August 25, 2015

The UC-Berkeley diazonium incident

Also from this week's C&EN, Jyllian Kemsley talks with Professor Dean Toste and the EH&S director of UC-Berkeley on the recent diazonium salt explosion incident:
Earlier this year, a University of California, Berkeley, first-year chemistry graduate student synthesized about 1 g of a diazonium perchlorate compound (R-N2+ClO4) as part of an effort to explore the effect of the perchlorate ion on a reaction. Working at an open bench and wearing regular prescription eyeglasses, he was using a metal spatula to transfer the material out of a porcelain funnel when the compound exploded. 
Porcelain fragments shattered the lenses of his glasses and lacerated his left cornea and his face. The student required surgery on his eye but was not permanently injured and is back in the lab. 
He knew he was working with an explosive and followed appropriate safety measures for most of the experiment, but at the end, “he became a little complacent,” says the student’s adviser, chemistry professor F. Dean Toste. The student should have worn safety glasses and used a nonmetal spatula for the transfer. 
Toste and UC Berkeley Office of Environment, Health & Safety Executive Director Mark Freiberg have worked together in the months following the accident to figure out what to do to try to prevent other similar events. “We look at it as systemic failure,” Freiberg says. “We’ve spent a lot of time with this student and others in the lab, trying to explore this incident and glean from it as much as we can about how our current, fairly extensive efforts to improve safety were ineffective in this instance...."
Back when we discussed this in June, I was a bit confused as to why the graduate student made as much as they did. 1 gram seems like a lot. Doesn't look like we got any answers on that question.

The issue of side-shields on prescription safety glasses seems pretty fundamental, though, and it doesn't seem like much progress has been made there, either:
...Following policies implemented in response to the [CJ's note: UC Regents'/LADA Sangji-related] agreement, the student injured at Berkeley had completed standardized safety training; received personal protective equipment (PPE) appropriate for his research, including eye protection; and signed that he’d read the relevant standard operating procedure (SOP) for the experiment that he was doing.... 
...Wearing regular prescription glasses may give people a sense that their eyes are protected, even when they’re not wearing safety glasses or goggles. To address that issue, the UC Berkeley College of Chemistry will now pay any costs for prescription safety eyewear not covered by a researcher’s insurance company....
There are two separate issues here. First, it's cynically amusing to me to see that the organization has all the paperwork lined up that says "we told you to do it correctly." While UC-Berkeley has been legally protected, somehow the student was still in their lab, using the wrong equipment, wearing the wrong PPE.

(I am beginning to think (only 8 years after the Great Recession) that "systemic failure" is organization-speak for "everyone's at fault, so no one's at fault.")

Secondly, I have a question about the massive, massive problem in both academia and industry of wearing prescription glasses as pseudo-safety glasses in the laboratory.* I bet you that we could walk into any chemistry laboratory within 100 yards to 50 miles of where you are sitting here reading this, and we'd find someone breaking this common sense rule. While I think Berkeley is being very gallant in picking up the difference in costs for prescription safety glasses, I think this is a paper solution, just like the SOPs. What can we do about it? Readers, any suggestions?

*As a young graduate student, I decided to transition from prescription glasses to contacts to avoid the temptation of wearing prescription glasses in the laboratory and thinking "I am still protected here." Any vanity on my part, or that I was single at the time is strictly coincidental. 

33 comments:

  1. "To address that issue, the UC Berkeley College of Chemistry will now pay any costs for prescription safety eyewear not covered by a researcher’s insurance company."

    Um, when I was a graduate student at UC Berkeley, at least 9 years ago, the college of chemistry already did this. Unless they decided to stop for some reason....?

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  2. Speaking of contact lenses, is there a consensus on wearing these in a laboratory environment? I worry about solvent vapours or whatever getting trapped against your eyeball - is this a thing?
    I would prefer to switch to contacts, my script is quite high so to make prescription safety glasses they would literally end up like the bottom of a fishbowl.

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    1. I asked this same question the last time this incident was discussed on CJ. I got some useful replies: http://chemjobber.blogspot.com/2015/06/uc-berkeley-safety-report-student.html?showComment=1433432934455#c6076248767674472259

      The short of it is that it's considered okay to wear contacts in the lab. I don't know if milkshake's caveat about a labmate not realizing that you are wearing contacts while trying to help you was addressed in any studies.

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  3. 1. Contact lenses are not that safe - if you happen to pass out as a result of a splash in your face and someone is washing your eyes without knowing about your contact lenses, and does not remove them, they eye injury could be much worse
    2. Prescription glasses are better than nothing, and many safety glasses are made with poor consideration to ease of use - they are heavy, have side-shields that cause nasty reflections. You get a headache wearing crappy safety glasses and then you take them off when sitting at the bench "just running TLCs". I prefer wearing oversized prescription glasses, even though frames that big that cover you over the eyebrows are problem to buy nowadays (out of fashion)
    3. Why so much diazonium perchlorate: students don't always correctly estimate the risk, and sometimes do a dumb thing - like scaling up hazardous reaction/product without considerations that come from experience. There needs to be a better supervision. Sangji immolated herself because she used very poor technique and did not realize she was handling nasty stuff. Someone should have been watching over her.

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    1. milkshake, your previous warnings about contacts have not gone unheeded and I've done what I can to tell my coworkers/family about them, re: short-term/longer-term damage.

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  4. I wonder why they decided to use the perchlorate salt instead of the much safer tetrafluoroborate? Is there really some special procedure where only the former will get the job done? There must be... but I can't think of one off the top of my head.

    Also, like milkshake said, prescription glasses are some protection at least and they are better than nothing so that has to be recognized. Even if you don't like it, you have to admit that a person wearing them is better protected than a person without glasses not wearing their safety goggles. To an extent. I know people who just wear prescription and then put safety goggles overtop for 'dangerous' procedures, of which this would have been the case here. Obviously this solution wouldn't fly in industry I guess.

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    1. My guess, partially informed by the comment that the student was "[prepared] as part of an effort to explore the effect of the perchlorate ion on a reaction" (end of 1st graf in 1st quotation). It is pretty common to investigate counterion effects, or at least it is in the Toste lab (based on his papers).

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    2. Perchlorate doesn't hydrolyze in water over time to release flouride, while BF4 and PF6 do. This is especially problematic for high temperature work like MOF synthesis or ionic liquid reactions, where you need something you can heat in a bomb for 72hrs but also need non-coordinating anions. Generally, the counteranion progression is Cl, NO3, BF4, PF6, triflate, ClO4, then everything that's not commercially available, like bistriflimide.

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    3. Well, the BF4 salt is usually made in water as the solvent, at least in my procedures. Then I left it in the fridge and it was good for half a year. I seriously doubt that the Toste group was working at high temperatures on MOFs with this stuff. It would have been far easier to make the non-explosive compound, and then add a salt during the reaction to explore counterion effects. These are all non-coordinating anions after all, so it sounds like a safer solution.

      And even if that is not a good solution, exploring counterion effects is not worth it due to the combined danger of these compounds and a first year student. Maybe the boss just didn't know, and this is common as there is a lot of this weird chemistry dangers you have to watch out for that one person cannot possibly keep track of, and the student wasn't good enough at that point to do a good search and read through the articles (some of which explain the dangers) well.

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  5. This was exactly my complaint about the Sheri Sangji situation. Rather than spur people to study what they're using and take appropriate precautions, they simply turned her accident into a box checking exercise. Lab coat? Yup. Gave you an SOP? Yup. We're done here. Even Toste's "solution" to this is a box checking exercise. It says right at the beginning of the article that the student knew he was working with an explosive compound and got complacent about it. How is writing down the hazard number supposed to change that attitude? As long as people keep reducing these accidents to nothing more than a checklist nothing will change.

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    1. What should be done differently? People talk about changing the culture but beyond telling people to be more careful and making an SOP and covering the cost of prescription safety glasses, what should be done?

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    2. So we have all of these graduate students and postdocs who know the proper safety measures and simply do not obey them. I've seen this first-hand every school where I've been. How can you change this? Mind control, I suppose.

      Failing that, you could fire all the people who are unwilling or unable to take the proper precautions. The way I see it, this solution would kill two birds with one stone. You'd end up firing so many chemists that the field would no longer be producing a surplus of PhDs!

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    3. Some of the people I worked with in undergrad organic made me very nervous indeed. Everything on full blast, erroneous calculations, people rushing through procedures so they could get out early and watch their TV shows. It's surprising nothing blew up.

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    4. Wonky and anon, I mentioned in the thread about Sheri's sister that I don't have a good easy solution. I wish I did. Do you agree that the way safety is handled now is ineffective? Because if not then we're at odds right there. If you do agree though, then something fundamentally needs to change.

      Kicking students out of your group for not following safety protocols seems a bit drastic. But is it? According to Toste, this student knew full well what he was working with and how to properly do it, he just got careless at the end. Now if you did this in an industrial job; didn't follow the specific protocol you were given and then caused a major incident, do you think the company would stand by you and let you keep your job? I don't know if this is the best solution to the issue, but I do think it would help. I'm open to hearing any other suggestions people might have though.

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    5. I think the problem is that in industry you're working with people who are supposed to know what they're doing versus people who are doing long term training. Also I would take that "the student knew the proper procedure" with a grain of salt. It's the kind of thing someone would say in the course of an accident investigation.

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    6. Academia isn't industry - it's point is to train people to do research who haven't done it for a living before (which ought to include surviving it). It's possible that the grad student was cavalier or dumb, but he also may not have been trained well or may have had a momentary lapse of reason. Both because of the consequences and because I don't see intent (contrast with Preston Brown, an older grad student disobeying clear lab rules, doing something that seems really dumb, and having a history of doing things with explosives he shouldn't have - here more than enough continuous stupidity to imply danger and intent) I'd be hesitant to hammer the student. (On the other hand, I think I'd want him learning some things before he goes back to lab again.)

      The problem to me is that in academia, I don't think safety is even job three - as the C+E Onion post (http://cenonion.blogspot.com/2015/03/overhaul-in-universitys-eh-policy.html) put it, probably around job four (or lower). It's not supposed to be job one, but if you're training people, then that should take precedence over everything else (if students' primary job is to get results and not train, then perhaps they shouldn't be paid as students?) You get what you reward, and safety (and training, lots of places) doesn't matter. In that environment, you're not going to get people to act carefully, and any rules to try and force people to be safe will be treated as obstacles to doing what they feel is important (just like security in lots of places).

      I'd also wondering where all that overhead goes. If your job is to get grants and cash the checks, then safety policy isn't going to get anywhere either, or it'll the favorite university game, "Blame Someone Else". Since the people with least power get the blame, well, guess who'll get it? (Then we'll hear more about the STEM shortage: "There's clearly a shortage of people willing to get paid crap and work long hours under questionable conditions to be the guy with the short straw in lab. We need people on visas, stat!")

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  6. "To address that issue, the UC Berkeley College of Chemistry will now pay any costs for prescription safety eyewear not covered by a researcher’s insurance company."

    Moreover, isn't this *mandated* by OSHA, let alone the most basic of common sense for the UC system safety police??!!

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  7. I think that part of the problem is the fact that, while in the lab, most grad students are not working alongside highly experienced people. The most senior members of the lab are post-docs with only a few more years of experience than them (unless it's specifically a 1st year working with a 2nd term post doc, and a 1st year that gets complacent with perchlorate salts is far too reckless to be working with them in the first place). You don't really have anyone who has more than 10 years of experience who is 1. In the lab with the students on a regular basis and 2. Has been around long enough to have safety considerations naturally ingrained in their psyche. Combined with the tendency for people in academic labs to focus entirely on what they're doing and not pay attention to their fellow students, this leads to an environment where such complacency goes unnoticed until accidents like this occurs.

    Unfortunately, I don't see this changing anytime soon, and the only way I can see this changing is if academia starts to embrace the idea of a permanent post-doc (and I'm not really sure that I like that idea)

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  8. WileyX - Prescriptions available with high impact rating and pretty good wrap-around for splash protection. Well under $200.

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  9. Re: contact lenses - the concern whether contact lenses accumulate sufficient vapors to damage eye has been debunked. Other organs of the chemist will be damaged by the vapor before the lens can absorb enough to hurt the eye. If the chemist is in an environment where eye irritation is reasonably expected the protocols and engineering need to be adjusted first before removing contact lenses.

    Re: need for better protection - the required order of consideration is: 1. protocol 2. engineering 3. PPE. If an experiment is deemed hazardous enough to require more stringent PPE OSHA mandates re-examination of 1. protocol and 2. engineering.

    Re: more stringent PPE - these things are made mostly for first responders who work in emergency situations where engineering controls have failed. In non-emergency work 1. protocol and 2. engineering must provide sufficient protection to use just the standard PPE.

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  10. Here is a poster showing the effect of using the wrong eye protection on splashes

    http://www.amazon.com/Comparison-Eye-Protection-Options-Poster/dp/B006NYXYAU

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  11. "He knew he was working with an explosive" - prof. Toste needs to re-examine the Fifth Amendment protection against self-incrimination. He just admitted that a student was allowed to work with explosives without any Ex training and in the absence of a Ex work policy at UC Berkeley.

    Reading these excerpts is a jaw-dropping experience. I need to go watch some Schwarzenegger movie with lots of distracting explosions...

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  12. We pride ourselves in my organization on absolutely requiring side shields on lab goggles or safety glasses.

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    1. yeah, but you are a computational guy and experimental design for you involves writing code sitting at the monitor - so you maybe you don't know if your employers pride is misplaced. The problem with heavy-heanded safety is that it prevents accidents by preventing any meaningful work being done, and failing that, it provides ironclad alibi for the management

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    2. I actually don't write any code at all :) For me experimental design involves working with structural biologists and medicinal chemists to understand crystal structures, SAR and synthetic feasibility. On a different note, I am not sure how insisting on side shields can prevent meaningful work - care to elaborate a bit?

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    3. The side shields make the safety glasses cumbersome, narrow the field of vision, and more annoyingly have these weird light reflection that are distracting and can cause headaches. If the protective glasses are not comfortable enough to be worn all day long, the chemists will find excuses not to wear them all they long. Which is a problem in the lab, and imperfect protection is worse than no protection at all.

      Another example: we got very expensive fancy Nomex lab coats after the Sangji death at Scripps. The coats were flame-retardant which should have made them a safer alternative than cotton ones. But it so happens that those coats were heavy and unpleasant to wear in Florida, so some people used to work without lab coats. So in the end, the old lab coats would be fine or even better, and the flame retadrant Nomex stuff could be reserved for synthetic chemists working with pyrophorics or large volumes of flammable solvents.

      I think it is better to be pragmatic and find alternatives that are not too bothersome, rather than heaving one size fits all safety policies starting from maximalist point of view. (For example, the biologists can get away with much less, and in scale up lab you need more), it helps to have informed scientists and a safety officer who is helpful rather than alibistic and high-handed, looking for ways to threaten people with citations. (Because outcome of that is that he will be despised and problems will be covered up and hidden from him.)

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    4. I didn't mind side shields when I had glasses for lab - they didn't seem that onerous, and wearing lab glasses was better than goggles, because they didn't fog up or cut off the circulation around my face. The problem with prescription safety glasses (or nonprescription ones, I guess) is that serious splashes to the face go right around them. (From C+E News: http://cenblog.org/the-safety-zone/2010/06/eyes-in-the-lab/).

      Of course, protection that you don't wear isn't protection.

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  13. correction: I wanted to say that imperfect protection is better than no protection

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  14. This comment from In The Pipeline (http://blogs.sciencemag.org/pipeline/archives/2009/09/18/175_times_and_then_the_catastrophe#comment-22363) on the T2 accident seems relevant, particularly on the lack of safety concern in schools, and the contrast with other labs.

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    1. T2 was a total screwup job waiting to blow up. The two dudes who run the company were not qualified and experienced for a dangerous process done on such a massive scale. They did not understand the self-accelerating runaway possibility due to excursion past a critical temperature, and blindly believed a small burst disk was going to save them. They had no contingency plans or backup for the likely scenario that one day their cooling fails. They did not run any stress tests.

      It wasn't their process - they started actually as a simple fuel blending operation. Their main business partner just handed them a synthetic procedure and urged them to build that thing, and helped them to raise money from investors that he brought in. The whole enterprise was underfunded, cheaply rigged together. There were many close calls suggesting that this thing is eventually going to blow up. Since their initial profit projections were unrealistic, they ended up struggling financially so there was a renewed push to cut corners, so they started loading their poor old reactor to 150% of the initial quantities. And so on. Had their burst disk was set up to to lower pressure, they would still have a flaming inferno of hundreds kilos of molten sodium at 200C rolling all over their yard but at least they would not reach a critical temperature when diglym solvent starts suddenly reacting with Na.

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    2. T2 still gives me nightmares.

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    3. I don't see why. Large-scale reactions with all-at-once addition on 10 kL scale (blocks of sodium? Whee!) scaled up from 1 L without intermediate stages, no thermodynamic or process safety testing (despite the owners being told that they needed it), a thirty-year-old reactor with far-insufficient venting and no backup coolant system, missing emergency procedures (we don't need them!), and ten or so minutes after realizing that you have fatally f%$#d up to come to grips with what is left of your life before being spread across a couple of square blocks? This is not the stuff of nightmares...ok, maybe it is (the only thing left to render it hell is for the whole thing to repeat on an endless loop, or maybe to wake up naked with in the middle of the plant at the beginning of batch 175).

      I don't know why the remaining living owner either has his engineering license or is not in jail. The lesson might be that if you thought killing stupid was hard when it's just stupid, it's much harder when it's stupid and greedy.

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