A case study: Possible hydrogen fluoride exposure

How would you have handled this situation?

Three chemists in a small laboratory were moving some old chemicals to a staging area prior to disposal. Many of the chemicals were simply unopened expired reagents, while others had been previously opened and used. After perhaps a half hour of moving chemicals, one of the workers complained of a severe burning sensation on the palm of his hand. When he removed his latex glove, his hand had some minor swelling and redness but no outward sign of burning. His pain quickly became worse.

A quick examination of the chemicals he had been handling showed that most were fairly innocuous, but one was a gallon container of waste labeled “HNO3, H2SO4, and HF.” The immediate suspicion was that some of the hydrofluoric acid had somehow leached out of the bottle or been spilled, depositing residues on the outside. The waste container was a glass bottle, and no HF has been used in this particular laboratory for approximately 20 years. Of the other chemicals the worker handled, the only one with known skin irritant properties was osmium tetroxide. There was no evidence to suggest significant exposure, since the OsO4 bottles were all contained in a box and had not been handled directly.

So what to do? The decision was made to take a conservative approach and treat the hand with calcium gluconate. A tube of 2.5% gel was located fairly quickly. The gel was dated “1993” and had partially separated but appeared to still be viable. The hand was treated heavily with the gel, and a latex glove was then placed over the entire hand. This is all consistent with recommended practice for treating HF burns.

The chemist’s pain persisted after treatment, so as a precaution he was taken to an emergency room about five minutes away. The first two medical professionals attending in the emergency room, a registered nurse and a physician’s assistant, were unfamiliar with HF. The workers didn’t bring a material safety data sheet because there was no way to to be sure of the source of the problem, since the suspect container was a mixture of acids. The physician who eventually arrived was well familiar with HF and the appropriate treatment. Since the hand had already been treated appropriately, she prescribed Benadryl (diphenhydramine) to treat possible allergic or sensitivity symptoms and sent the patient on his way. Later in the day, the chemist reported that the pain had subsided and he had no apparent ongoing effects.

So… what might we have done differently?

Author: Russ Phifer

Russ is a professional volunteer, active in ACS since 1982. He is the only History major (College of Wooster, 1974) to Chair an ACS Committee (Chemical Safety), Technical Division (CHAS), and Task Force (Laboratory Chemical & Waste Management). In his spare time he is Executive Director of the National Registry of Certified Chemists (NRCC), EH&S Manager for a printing plant (Chiyoda America, Morgantown, PA), and run his own environmental health & safety consulting and training firm (WC Environmental, LLC). Also active in local politics, he nonetheless enjoys spending time with his wife Molly and their five children.

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  1. I think this situation was handled extremely well, but if it is necessary to cover the hand after the gel was applied, perhaps another kind of glove (nitrile? butyl rubber?) would be more suitable? Latex is such a poor general use glove, especially for solvents other than water. I would expect the gel to partially dissolve the latex and increase the *latex* exposure.

  2. I think the wrong type of glove was used by the chemists. In a document on HF safety (http://web.utk.edu/~ehss/pdf/has.pdf) Pam Koontz said that whn applying calcium gluconate from an HF exposure kit, 22-mil nitrile or neoprene gloves should be used and that latex gloves are not effective against HF.

  3. The gloves. Disposal of unknown chemicals would warrant substantially thicker gloves than latex gloves (I’m assuming exam gloves).

  4. “So… what might we have done differently?”

    Used a different type of gloves. Latex gloves are close to useless for everything but very dilute aqueous solutions.

  5. When I’m handling extremely toxic or unknown chemicals I sometimes put on a pair of latex gloves over the nitrile ones I usually wear.

    Our health and safety always advises us that if we don’t know what the chemical is, we should call the disposal unit.

    Preventative measures could have been done. For example cleaning up waste promptly, keeping unexpired calcium gluconate etc.

  6. Thanks for commenting and sorry for the moderation hang-ups, everyone!

  7. The points regarding the advisability of using better gloves, neoprene, for example, are well taken. However, this is primarily a microscopy laboratory, and there was no reason to believe when the collection of waste was begun that latex gloves would be sufficient. Lessons learned!

  8. sorry, no reason NOT to believe latex gloves would be insufficient.

  9. Oh well… I think you know what I mean.

  10. I have been burned exactly this way.
    But I always have a 100g bottle of solid calcium gluconate in the lab. Treat quickly and continue until the pain subsides.

    The wrong gloves are more dangerous than no gloves!

  11. The only additional precaution when handling someone else’s leftovers is to check the labels and make a list before moving the containers. Then you can make sure appropriate precautions are in place.
    Sue (who is responsible this sort of clean up)

  12. There are certainly lessons learned here! The laboratory will only be using nitrile or neoprene gloves from now on when moving waste or unknown containers. Thanks for all the comments, they were all helpful!

  13. It sounds as if the need for improvement in waste disposal procedures should be another take away here. If the lab hadn’t used HF in 20 years, then the bottle in question should have been disposed of 20 years ago. Labeling a hazardous waste with chemical formula abbreviations is also not allowed, and is particularly bad given the degree of hazard in this case.

  14. I cannot believe no one has mentioned: “A quick examination of the chemicals he had been handling showed that most were fairly innocuous, but one was a gallon container of waste labeled “HNO3, H2SO4, and HF.” ”

    READ WHAT YOU ARE HANDLING BEFORE YOU HANDLE IT. You can be damn sure if I am even handling a closed bottle of HF that I will check and make sure there is no outside contamination.

    I use HF often, and no matter what, I wash my hands with Ca-gluconate or another calcium salt solution after use. Just in case. This should be common practice however it is not.

    Disagree with Chris neal about needing to dispose old HF. That is a waste. The stuff will not go bad, and it is far better for the environment to use old stock than do dispose of and buy new reagents. I used 40 year old 70% perchloric acid that had an obscene number of 9s in the decimal point after the purity. The cost of that today would be excessive. Worked like a charm.