The Perils of Pyro???

Discussion in 'B&W: Film, Paper, Chemistry' started by jovo, Jun 5, 2004.

  1. jovo

    jovo Membership Council Council

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    On a rainy Saturday, it's my family's custom to hie ourselves to a Barnes and Noble about 20 miles from our home to drink coffee and read. (The seven year old happily curls up in the children's section...but has no coffee that we know of.) I like to catch up on all the photography magazines to which I don't subscribe and will usually buy the ones that offer something worth taking home.

    Today, in the May/June issue of Phototechniques, I came across an exceedingly forthright essay by Howard Bond titled: "Pyro Investigation: Pyro's Benefits May Not Be Worth Its Costs" in which he compares the results of several negatives of the same subject developed in D76 and PMK Pyro and the consequent prints including one coupled with an unsharp mask. His conclusion seems to be that the "meager benefits" that might be detected by use of pyro are significantly compromised by it's inherent health hazards, and certainly don't hold a candle to the benefits of unsharp masking in terms of sharpness. He writes: "A biochemist friend told me that the pyro molecule is similar to the pesticide molecule that has been giving Canadian farmers Parkinson's disease (not proof, but a red flag). Anecdotes don't prove anything, but it is interesting that the most famous pyro user, Edward Weston, died of Parkinson's disease." He further states in a subsequent paragraph: "Granted, I am not aware of any proof that long-term low-level exposure to pyro causes a specific health problem. On the other hand, the only evidence a pyro enthusiast can offer for the safety of its use is "Nothing has happened to me yet."

    So...though I've bought the "Book of Pyro" and the PMK kit that comes from Bostick and Sullivan, it shall remain unopened until I am sure beyond any reasonable doubt that it is safe...including the remote consequences of inadvertant exposure by accident.

    Many on this site seem to be enamored of the stuff. I'd like to suggest a discussion that offers an alternative view or corroborates Howard Bond's assesment.
     
  2. Deniz

    Deniz Member

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    see, I am a Rodinal user. It is extremely easy to mix and cheap!
    I just don't see the point of having to mix all the chemicals for the pyro formulas.

    Also, Rodinal has been around quite a long time and doesn't seem to have ill effects on anybody.

    so for me its Yay for rodinal... :smile:
     
  3. noblebeast

    noblebeast Member

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    This was already discussed a month or so ago. Maybe try a search of the archives - I'm too lazy to do it myself.(At least I think it was here. It might have been over at photo.net now that I think about it) One thing someone in that thread pointed out was that Bond was comparing the developers with TMax, and that the T-grained films, TMax in particular, tend to be the least suitable for pyro developers. It also discussed that all chemical formulas are toxic in the right circumstances, and that most modern pyro formulas are so dilute that while the wearing of rubber gloves is recommended, the same could be said for pretty much all photo chemicals.
     
  4. Ka

    Ka Member

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    Being rather impulsive and impetuous, and always wanting to try new THINGS, I do appreciate your note, John, which presents a warning toward another view. So thanks, 'cause I too like to frequent the coffee shoppes with my 4 1/2 and 6 year old wee ones. And, I'd like to continue doing so.

    Cheers,
    Karen
     
  5. Jorge

    Jorge Inactive

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    I believe there is very through discussion at the LF forum about this. The article is nothing more than another pitch for unsharp masking by Howard Bond. There are many things in the article that are if not inaccurate they are at least biased. For one, he used PMK with tmx 100, a film that most everybody that uses PMK knows it does not stain as well as most other developer.

    As to the toxicity, Bond cites the book by Susan Shaw, a book that is full of errors and is nothing more than a compilation of MSDSs or toxicity data, without any regard to the use and method of use of the chemicals and certainly without any intelligent analysis.

    To judge toxicity you need to look at 3 important factors. Chemical concentration, length of time exposed to the chemical and route of entry into the system.

    Lets start with the concentration. I dont recall exactly the LD50 of pyro, but I remember is somewhere around 250 mg/kg. With PMK you start with a 10% stock solution, so if we fudge a little and set the density of this solution to 1, you have in the stock solution 100,000 mg/kg. To use it you then dissolve the stock solution a 100 fold, leaving you with approximately 1000 mg/kg. Now, lets say the average person who uses this developer is 176 pounds or 80 Kg. If you multiply 80 x 250 mg/kg, you find that a dose that would be harmful to you would be around 20,000 mg/kg. IOW 20 times more than what you use for developing and twice as much than what is contained in the stock solution.
    Lets move on to the length of exposure time. The LD50 doses are arrived by feeding the subject big amounts of the chemical on a daily basis until 50% of the subjects die. This can take days, weeks or months, depending on the chemical. Unless you plan to add 20 grams of pyro to your diet on a daily basis, the chances that you will be exposed to pyro long enough to cause you harm are close to infinitesimal.
    Now, finally we move on to the route of entry. Lets say you decide to develop with PMK and you put your hands in the developer without gloves. Lets further assume that you absorb all of the pyro through your skin (clearly impossible, the pyro would be gone and you would not have a developing action). At this time you have been exposed to a dose that is 20 times lower than the one determined to be harmful and if you stop developing, you have only been exposed for a small amount of time.

    Of course, if you develop everyday, take no precautions and eat, drink and smoke in your darkroom, well then yes your chances of getting sick are greater, but it might not be only because of the pyro.

    Now, the sentence about the pesticide. First, pyro is used in hair dye, I dont see people dropping off like flies after getting their hair tinted. Second, just because it is similar, does not mean it is the same, nor that it has the same effects on the body. Funny thing is, D76 has a developing compound that is very similar to pyro, yet we dont see Bond making any objections to it.

    The Parkinson's statement is so ridiculous it chaps my hide. For one, Weston also used amidol, another benzene derivative, for another, there are millions of people who get Parkinson's without ever coming within 50 miles of pyro. His statement that people say "well nothing has happen to me" as proof of safety should not even be written, since he only offers the case of one person who happened to use pyro and get Parkinson's. How stupid is this?

    Bottom line John, the article is a self serving ad for his unsharp mask and his workshops, he wrote about things about which he has no knowledge based on the flawed and alarmist research of a woman whose only merit was to read MSDS sheets and write about them on a terrible book.

    It is unfortunate that people like him write these things and they become part of the "truths" of photography, just because Bond said it.

    I cannot guarantee you 100% that nothing will happen to you, but with a little bit of care, good laboratory practices and a little bit of common sense I can guarantee you that if a drop falls on your arm, your gonads are not going to shrivel. All this based on careful analysis of the evidence, not on some hear say, or faulty information from from a woman that was too lazy to think.
     
  6. jovo

    jovo Membership Council Council

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    No, Noblebeast (that's fun to type) the article from Phototechniques is not the one to which you refer. Nor was it a topic here in the time I've been a habitue...(February). I suspect Mr. Bond..... Howard Bond (that's fun to type too) is on a bit of a crusade and may be so in several forums. I think if someone suggested leprechaun sweat was a magic elixer of photoformulary, someone else would be happy to debunk it. But in this case, aside from the, as he put it, "meager benefits" the safety concerns are the secondary but more critical issue.

    When I first began to read this forum I was new to the term "pyro-cat" and laughed out loud at the notion that 'Garfield' had a cousin who shared my passion for analog photography. It's easy to be swept up in the tsunami of ULF and arcane materials as grails seeking questers (or are they questors). But, health issues are no joke. I still invite those who are practicioners to hold forth...or at least make a credible case.
     
  7. jovo

    jovo Membership Council Council

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    I seem to have been typing when Jorge was....sorry about that.
     
  8. Tom Hoskinson

    Tom Hoskinson Member

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    IMO Howard Bond didn't research the subject very well and produced a very biased report.

    The World Health Organization has some very good literature on this subject. The Benzene Ring compounds used for photographic developing are all toxic and pyrogallol, pyrocatechol and hydroquinone all occur in nature. However, these chemicals all oxidize and break down very quickly in nature - unless there is a massive contamination event (like the massive dumping of Pyrocatechol in China).

    These Benzine Ring compounds all represent a health threat if their dust is inhaled, if they are ingested, or if they are absorbed through the skin. Reasonable safety precautions (like Nitrile gloves, masks, etc.) can reduce or eliminate these risks.

    If you are a tobacco smoker, you have taken a fair amount of Pyrocatechol and other related Benzene Ring compounds into your respiratory system already (and this is not a good thing).

    Hydroquinone has the same molecular formula and weight as Pyrocatechol, with the Hydroxyl attached to a different site on the Benzene Ring. Hydroquinone is a major component in both D-76, HC-110 and Dektol to name just a few developers. Hydroquinone requires the same safety/handling precautions as Pyrogallol and Pyrocatechol.

    Arguably, the safest and least toxic developers are the Phenidone/Ascorbic Acid developers - like Pat Gainer's brews - but you really don't want to drink them, either.
     
  9. Jorge

    Jorge Inactive

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    No problem John, I could go on and on about what all is wrong with the article, but I did not want to bore people and my answer was long enough as it is.
     
  10. garryl

    garryl Member

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    Well if your that conserned about Pyro, what about DiHydrogen Monoxide? It been involve in more deaths than Pyro, and is use to compound every formula I know about. It's been found in every
    cancer tumor study. It can burn you in it's gasious state and can
    cause death if your lungs become saturated with it. Yet every
    photochemical manufacturer still uses it!
     
  11. Jim Chinn

    Jim Chinn Member

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    The article doesn't mention the many photographers who used pyro for years and did not get Parkinsons. To make such a broad generalization with regard to one individual (E Weston) is totally irresponsible.

    His claims are what is known as junk science. Junk science is speculation that has no basis in hard evidence or scientific research. Jorge presented hard data. If there is a research study somewhere that quantifies the death rate for photographers that use Pyro or similar compounds is higher than other photographers, that is hard science.
     
  12. Jim Chinn

    Jim Chinn Member

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    Garryl,

    I saw that report on the internet. I do not understand why the EPA and the FDA do not restrict its use. The only answer can be a conspiracy. A conspiracy so big that both John Kerry and G W Bush are covering it up.

    I have seen reports on the net that they both take very large contributions from the spigot of the DiHydorgen Monoxide corporate interests. It might even be part of the agenda of the Tri-Lateral Comission.

    The facts were pretty surprising to me. I mean I used to literally bath myself in the stuff in the darkroom. The most frightening thing is my oldest daughter dropped a tray containing some and was doused from head to toe. If I would have known then what I know now we would have gone straight to the emergency room.
     
  13. chrisg

    chrisg Member

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    I read Bond's article awhile back. It never should have made it into print. His methodology was poor. He failed to present scientific justification to back his technical arguments - heresay is not evidence. He did the community a disservice by publishing the piece.

    When you work with chemicals, wear personal protective equipment: gloves and safety glasses. Also get fresh air flowing through your workspace so you're not inhaling nasty fumes. Very simple steps can go a long way to mitigating risk. Weston (and many others) practically took baths in pyro and amidol. Not smart. We know they're bad enough that bathing in them is a very bad idea. But wear gloves and you've likely dropped your exposure level by a few thousand over not doing so. Hazardous chemicals only make you ill if you're exposed to them.

    I'd argue that the relevant figure-of-merit for expose is not LD50 but OSHA's specified 8 hour maximum permissible exposure level. EPA often offers a max exposure level of their own. The LD50 is the "lethal dose" at which 50% of those exposed die. The maximum permissible exposure level is usually much, much lower. That said, often times OSHA and EPA don't have enough data to make particularly scientific estimates of their max exposure numbers, so take them with a grain of salt.

    Wear gloves. Wear safety glasses. Put a fan in your darkroom. You do those things and you've probably got more to fear from meeting your end in a traffic accident than by being done in by Pyro.

    Chris
     
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  15. Aggie

    Aggie Member

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    lol@dihydro mono oxide....or water! another product that contains pyrogollic acid that was not mentioned is topical medicinal ointments. Err on the side of caution and wear gloves. examination gloves are fine. If not your fingernails begin to turn brown from dyes. By the time you have processed your film the PMK has oxidized completely. Another thing. Gordon Hutchings who developed the formula, has been using the stuff without the gloves for a very long time well over 20 years. The harm from pyrogolic acid comes when it crosses the blood brain barrier. That happencs only when inhaled and quickly goes into the blood stream. Even at that it would take a large amount to do damage.

    I read the article. Funny how he didn't have an unsharp mask of the PMK negative to compare it to the unsharp mask of the Kodak one. As far as I remember you do tests that compare two items doing the same thing, except of one item of that process. In this case the change would only have been what developer and it's attendant processing that was used. All other variables should be exactly the same.

    BTW I want to thank the computer gods that with a new reformat of our main computer got rid of a gemlin preventing me from posting. Sean I don't know what it was, but it is gone now.
     
  16. Jorge

    Jorge Inactive

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    Not in this case Chris. While PELs are a safer guide for people who are in constant contact with toxic material, for the purpose of examining the maximum possible dose when exposed for short periods of times the LD50 is better, since we are looking for doses that are big enough to cause acute harm in a short period of time. This is an important distinction for those of us who develop infrequently but perhaps do it for longer than the 8 hour period used by OSHA.

    IOW, you can feed an animal 250 mg/kg of pyro for 1 month and kill it, or you can feed it 5 mg/kg for one year and kill it. You need to pick the appropriate dose for the appropriate length of time exposed.
     
  17. Flotsam

    Flotsam Member

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    I wonder if it is worse than some of the nasty chems in the E-6 process? Or C-41 for that matter? These are used regularly in both home and commercial labs.
     
  18. Jorge

    Jorge Inactive

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    Certainly not, color processes contain aldehydes to aid in the process and prevent mold and bacteria formation.
     
  19. john_s

    john_s Subscriber

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    A useful document about the toxicity of pyrogallol is at:

    http://ntp-
    server.niehs.nih.gov/htdocs/Chem_Background/ExecSumm/Pyrogallol.html#humanexp

    I hope the line break does not break the url.

    Pyrogallol is clearly one of the things that you should protect yourself from, along with many other substances in the environment, our food, our workshops etc. A small amount of common sense is in order.
     
  20. john_s

    john_s Subscriber

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    And I'd rather use PMK than make an unsharp mask for every negative. Call me lazy if you want.

    I've been a loyal reader (and buyer) of Photo Techniques for years, but I'm reviewing the situation.
     
  21. RAP

    RAP Member

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    I have been printing for my 2006 calendar and was working on a negative, developed in HC110, because I needed a N+2 contrast. (N+2 in PMK is not recommemded) It is a mountain scene with white puffy clouds. Suffice it to say, the PMK negatives printed so much easier; better contrast control, tones, feel of substance. The HC110 negatives were much more diffucult to print. To try to get the feeling of puffy clouds was very diffucult with HC110. I will probably never develope cloudscapes in HC110 again. I used almost half the paper with PMK negatives and almost half the time.

    Right now, my favorite combo is TRI-X in PMK. I get far better results for extreme contrast reduction, N-3 in PMK, then I do with compensating development in HC110.

    BTW, I just tested the new TRI-X sheet film, with PMK, nothing has changed for me, same personal ASA and same development time.
     
  22. jovo

    jovo Membership Council Council

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    Alistair Inglis finally got a website. I looked into the feasability of using his unsharp mask products. HOLY SPIT!!! That stuff is EXPENSIVE!!!
    And probably unnecessary too...if digital unsharp mask is any indication, it's way too easy to over sharpen, although some is necessary for the miserably low resolution of web presentation. I've never felt sharpness was an issue in any of the work I've ever done except when I've clearly made errors in depth of field or plane of focus settings, and nothing will make those mistakes go away. So I'll save the bucks that might have gone into USM and direct them to another lens for my 4x5, which I can't get enough of it seems.

    In any case, thank you all for your input on this. It's very reassuring to hear the drawbacks of pyro put in perspective. I agree with those who've declared his column irresponsible and needlessly alarmist after offering a larger, rational view of the subject. I'll get some gloves and use a dustmask when mixing the stuff.
     
  23. c6h6o3

    c6h6o3 Member

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    Weston put his ungloved hands into both pyro and amidol working solutions on a daily basis for decades. Since none of it has ever touched my skin, I'm hardly worried.

    On the other hand, I am personally acquainted with one photographer whose lungs are quite damaged from having breathed pyrogallol powder. Good respirators are the better part of valor. We should be very careful when mixing stock solutions.

    Another great photographer who died with Parkinson's disease was Margaret Bourke-White. I do not know what her level of exposure was to any photographic reducing agents.
     
  24. steve simmons

    steve simmons Inactive

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    Bond's articl;e was stupid and irresponsible. No magazne should ever have pulished it. As stated abve he used T-Max whih is the worst choice for any pyro develper. he cited innuendo and rumor in his claims about Weston, and he was pitching his unsharp maskng and promising to reveal the secrets ofhis msking techniques in a future article and possibly if you take a workshop. Of course he would not fid a developr he has refused to try for 20+ years any good as he would be afraid it might sully his previous print sales.

    Whenyou read anysuch article by a name photographer one should as the follwing questions

    have they been given free equipment that they are now promotng?
    have they been given free supplies or been put on a retainer by any companies currently or in the past and are they promoting those products?
    Do they have any axes to grind,?
    Is there any self promotion going on for future articles, workshops, etc.

    Unfortunately this type of artcle just creates unneccessary scare and does nothing to promote photography.

    steve simmons
     
  25. Tom Hoskinson

    Tom Hoskinson Member

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    Steve,

    Hydroquinone is a member of the "Pyro Family" of the hydroxybenzene ring reducing agents. It is one of the reducing agents in D-76 (Howard Bond's comparison developer). When used in low sulfite or sulfite free developer recipes, hydroquinone produces a proportionally stained and tanned image, very similar to those produced by pyrogallol and pyrocatechol.

    Hydroquinone (p-Dihydroxybenzene) has the same molecular formula and molecular weight as Pyrocatechol (o-Dihydroxybenzene). Pyrogallol is 1,2,3 Trihydroxybenzene.

    All three of these hydroxybenzene reducing agents (hydroquinone, pyrocatechol and pyrogallol) are capable of producing excellent results with both TMX and TMY. This is from my direct personal experience, which includes controlled comparative testing.
     
  26. L Gebhardt

    L Gebhardt Subscriber

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    For the users of Pyrocat and PMK what is a good film to test with, if one wants to redo Bond's test? I will be testing Pyrocat with TriX, HP5+, and FP4+. Do these stain well and show the benefits of pyro? Once I determine my development times I plan on shooting the same images and using different developers in my Jobo then printing them each on the same paper as my test.