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  1. #1
    AndreasT's Avatar
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    Print wipe off panic

    Hallo band,
    I am just busy finishing off some prints for someone. After wiping off the prints I have some reddish scum on my sponge. What is this? I used Selenium toner with these prints. Is it Selenium?
    The funny thing is there are about 10-12 prints and it is only showing up now with the last few prints.
    I have had this years ago where there was a lot of reddish scum on prints. Since then I have never had this again till now.
    This is making me a bit nervous because I have to handover the prints tomorrow and I am worried that I have possibly not washed the prints properly.
    Any ideas?

  2. #2

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    Yes, it sounds like elemental selenium.

    The following article may be useful, http://www.heylloyd.com/technicl/seuse.htm
    A rock pile ceases to be a rock pile the moment a single man contemplates it, bearing within him the image of a cathedral.

    ~Antoine de Saint-Exupery

  3. #3
    AndreasT's Avatar
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    Thanks for the link very interesting.
    Maybe I need glasses but I saw nothing about elemental selenium. Is that the precipitant? Because that is not the problem. I filtered the toner beforehand.

  4. #4

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    Selenium is in the same family of the periodic table as sulfur. Just as exhausted fixer throws down a precipitate of elemental sulfur so does selenium toner throw down elemental selenium. Even though you filter beforehand the precipitate can occur during toning. Any acid trace in a print from an acid stopbath to an acid fixer can cause this problem to occur. The only thing you can do now is to gently wipe off the prints. Anything that would dissolve the selenium would destroy the print.

    I think Kodak used to recommend soaking prints in a 1% to 2% solution of Kodalk before toning to neutralize any residual acid in the paper.
    A rock pile ceases to be a rock pile the moment a single man contemplates it, bearing within him the image of a cathedral.

    ~Antoine de Saint-Exupery

  5. #5

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    Lloyd's article is good and covers a lot of ground. I'd like to add my experience to his. I've expounded this a time or two here at APUG and elsewhere, but it seems appropriate to reassert it again now, and in a bit more detail, especially since I have just finished a rather large run of prints, all selenium toned.

    Acid fixers (and anything else acidic) used immediately before selenium toning will cause problems such as yellow overall staining, mottling and the selenium precipitate that is the topic of this thread. The obvious solution is to not use anything too acidic before toning. Fortunately, that includes all alkaline fixers, plain fixers and even Ilford Rapid Fix and Hypam in the 1+9 dilution (this latter is what I use; directly from fix 2 to toner-never any problems).

    Many use a wash between second fix and the toner. If this is done, and the fixer is acidic, the wash must be thorough or mottling may still occur. Twenty minutes for fiber-base prints is safe. I prefer (as does Lloyd) to use a less acidic fix and move prints directly from the second fix to the toner after a good drain.

    Inadequate fixing is your enemy, and shows up even sooner when toning. Prints that are not properly fixed will stain in the toner. It is difficult to tell from the staining whether it is caused by a too acid environment immediately prior to toning or whether there are still unfixed (or complex undissolvable) silver halide compounds in the emulsion. If you are getting stains and are sure that your fixer (or whatever comes before toning) is not too acidic, then your prints are simply not fixed properly. One can think of selenium toning as a poor-man's residual silver test (in fact, some recommend using a drop of the selenium toner concentrate for just this purpose). I tend to think that staining during toning is most often due to inadequate fixing than to other reasons. With fiber-base papers, two-bath fixing is a must. Don't exceed capacities and you'll be fine.

    At this juncture, I must point out that I normally divide my printing and toning sessions. Printing goes through fix one and then the prints are washed and dried. At times I have printed and toned on the same day, but the prints always get at least a twenty minute wash before (yes before) the second fix. This gets all developer residue out of the print before toning. I do not know if the intermediate wash is necessary for good toning results. I kind of doubt it. I use it simply because it is more convenient for my work flow. For what it's worth, I use a standard acetic acid stop bath, and have never had problems due to acidity from the stop carrying over.

    I am an advocate of replenishing and reusing selenium toner. Lloyd's article mentions this, but also mentioned that he has not tried it. I have. I have two gallon jugs of diluted toning solution that have been going strong for well over eight years (more like 10 or 12 now that I think back...). Used toning solution forms a black precipitate/sludge that needs to be filtered out. This I do before and after toning sessions, using coffee filters as Lloyd describes. I have, on rare occasion, observed a white organic sludge, usually floating, that I take to be a mold or bacterial slime. This filters out easily as well, with no ill effects on the the toner or the print.

    When I began replenishing and reusing toner, I was concerned that by-products of some kind (undissolvable sivler halides) would build up in the toning solution and be harmful to the print. I then began more rigorous testing for residual silver and hypo. I have never detected too-high levels of either using this toning method, even after the ten or more years of using the same solutions. I'm fairly sure that whatever carried-over silver compounds end up in the toner are bound by the selenium and precipitated out, which makes the toning solution self-cleaning. Whatever the mechanism, my prints, after a treatment in wash-aid and an hour minumum wash time show zero stain with the HT-2 test and no residual hypo whatsoever. I am confident that the replenished toner is not adversely affecting the prints in any way.

    My toning solutions need replenishing only occasionally. I tone for just a bit of image-color change; I like a hint of deep eggplant color, reminiscent of 19th-century printing-out-papers for some images, just a bit of d-max intensification for others. I often tone 50-100 11x14 prints in toner that hasn't been replenished in more that a year. The toning action is just fine. I only replenish when toning times get too long for comfort, which for me, is longer than five or six minutes. Then, I add approximately 25ml of toner concentrate per liter of toning solution and see how this affects the toning times. Usually this is fine. If times are still too long, I'll add another 25ml/liter. It is obvious from this that I am never really sure of the exact dilution of my toning solutions; for me, it has to be strong enough to give me the results I want in a comfortable time.

    Different papers tone at different rates and with more or less image-color change. I keep two solutions, one labeled weak, the other strong, and tone the paper I am using in the appropriate solution. In a typical toning session, I tone about 36 prints (three washer loads and my fixer and drying screen capacity). These are often on many different papers, so I set up two toning trays, one strong, one weak. Workflow is as follows: Soak -- Fix 2 -- Toner -- Wash Aid -- Wash (min. 1hr.) -- Stabilizer (Sistan) -- Squeegee -- Dry face-up on screens.

    I never discard selenium toner. The tiny bit I replenish is balanced by carry-over and I rarely even top-up my gallon jugs. I believe this is the most economical and eco-friendly way to deal with selenium. Heavy metals, like silver and selenium, are not removed in water-treatment plants. They concentrate in the sludge and find their way onto farm fields, etc. I'd rather not contribute.

    If you must dispose of selenium toner, then a responsible way to do so is to use the toning solution till toning times become rather long, say 8-10 minutes to reduce the selenium concentration. Then toss in a few scrap prints and let them soak overnight. This will further reduce the amount of selenium in solution. Then you can dispose of small amounts into the municipal sewer system (ref: Kodak Tech-Pub J-300). I have seen someone say that selenium toner is exhausted when you can no longer smell the ammonia. This is patently false. My toning solutions never smell of ammonia except for a short time after replenishing. They work just fine with no smell. I recently toned over 100 prints (three toning sessions of 36 prints each) in toner that had been replenished more than nine months earlier and had been sitting in jugs for that time. The toner poured out fairly clear, and toned all the prints perfectly with no odor whatsoever and no need for further replenishing. Only during the fourth session did I need to replenish one of the solutions and put up with the ammonia smell for a few minutes. If you discard toner when the smell disappears, you are wasting money and being environmentally irresponsible. Just don't do it.

    I hope the above augments Lloyd Erlick's article and that together with that, we have a fairly comprehensive primer on selenium toning.

    Best,

    Doremus

    www.DoremusScudder.com

  6. #6
    AndreasT's Avatar
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    Thanks for the replies.
    Just to state a few facts and a few view points. I do replenish my selen toner from time to time and I filter as well. I only use alkaline fixer which I prefer. I use two fixer bath straight after each other and the prints where all washed to completion. The decision to give them a selen toning was only decided later.
    I have inspected the prints now that they are dry and I see so reddish scum or anything else on them.
    When I tone the temperature of the toner is at about 24°. I have read a few times that the toner should be warmer than the wash water afterwards otherwise a bit will be washed off. Since some selen combines permantly with the silver and some of it is just attached / sitting on the silver. If this is true then one would actually be able to wipe it off??
    Thanks for all the information because it is rather difficult to get information about selenium toner seeing that it is used a lot.

  7. #7

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    Quote Originally Posted by AndreasT View Post
    Thanks for the replies.
    Just to state a few facts and a few view points. I do replenish my selen toner from time to time and I filter as well. I only use alkaline fixer which I prefer. I use two fixer bath straight after each other and the prints where all washed to completion. The decision to give them a selen toning was only decided later.
    I have inspected the prints now that they are dry and I see so reddish scum or anything else on them.
    When I tone the temperature of the toner is at about 24°. I have read a few times that the toner should be warmer than the wash water afterwards otherwise a bit will be washed off. Since some selen combines permantly with the silver and some of it is just attached / sitting on the silver. If this is true then one would actually be able to wipe it off??
    Andreas,

    Your technique sounds good and, if your are not exceeding fixer capacities, you should have no problems toning. What brand of toner are you using?

    Your idea that you are wiping off some of the toning from the print sounds reasonable. I, however, have never had any red anything wipe off my prints after toning them (I use the Kodak toner). That said, I don't use sponges, rather a squeegee (windshield wiper, actually) to remove excess water before drying prints. I could be that you are wiping some of the toning from the print... Are you perhaps wiping to hard?

    I'll have to try wiping a scrap print after toning it to see if I can repeat your results. Unfortunately, I won't be able to do that for some time, since I'm away from my darkroom.

    Anyone else willing to selenium tone a scrap print, wash it and then wipe it vigorously with a cloth or sponge and see if they can get some selenium color to wipe off the toned print? And report back here? I'd be interested to know.

    Best,

    Doremus

    www.DoremusScudder.com

  8. #8
    AndreasT's Avatar
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    I do not use Kadak Selen Toner, here in Germany it is not available because something is missing on the label so by law it is not allowed to be sold here since a few years.
    I use the Adox Selenium Toner sold by Fotoimpex. Like stated earlier I do not have this thing happen normally, but I will keep my eyes open.
    It may be that I did wipe too hard, since I place my prints on glass and wipe them off. Since glass is hard the paper has no buffer to give way when wipping it. Maybe.

  9. #9
    AndreasT's Avatar
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    OK, I think I know what the problem was. A day or two ago my water was turned off in my street because they were working on the piping I presume. As a result when the water is turned on again there is a lot of junk in the water. I had a print which I washed but did not wipe off and it had reddish brown streaks on the surface and when I washed it again and wiped it off the print was clean.

  10. #10

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    Quote Originally Posted by AndreasT View Post
    OK, I think I know what the problem was. A day or two ago my water was turned off in my street because they were working on the piping I presume. As a result when the water is turned on again there is a lot of junk in the water. I had a print which I washed but did not wipe off and it had reddish brown streaks on the surface and when I washed it again and wiped it off the print was clean.
    Hi Andreas,

    If dirt from your water was indeed the problem, you might want to re-wash all the prints you washed in the dirty water, even if you did wipe them off, especially if you used fiber-base paper.

    Re-washing will not hurt and you want to make sure all the dirt is removed. Wiping gently with your viscose sponge with the print submerged in a tray of water and rinsing will remove surface dirt.

    Best,

    Doremus

    BTW: Did you get my return e-mail? I'm having a bit of trouble sending messages through my website account these days.

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