Yellowish base after selenium toning

[jose angel]

I notice a yellow cast on the base of my MG IV FB papers after the Se toning process. I`m using a very old Selenium Toner solution by Kodak.

Is it normal? Maybe it`s due to remaining fixer particles, or a bad washing procedure... I really don`t know. What do you think?

Sadly, it is "ruining" two of my three "finished" prints, which I prefer with the original clear white base. No problem with the purplish Se tone in the blacks. Is there any method to recover the original white base?

Any help is welcomed, thanks.

[MIke Sherck]

What is your fixing and, particularly, washing process?

Mike

[jose angel]

This time I fixed the prints for two minutes in Ilford rapid fixer, after that a wash on a tray, with running water, for around 20 minutes or maybe more. Then dry.
Twenty-four hours later, a second wash about fiveteen minutes, then 5 minutes in "old" Se toner, and a final wash on a big Nova slot washer for half an hour.
A bit of a hurry on process, I know. The still untoned print looks great, the toned ones are ugly, absolutely yellowish in the highlights and borders.

[Andrew O'Neill]

I have an old bottle of KRST (about 6 years old) and never had yellowing on MG IV fibre. What's your dilution? I dilute 1+9 with water. After fixing (I use the same fixer as you) and before toning the print gets a good rinse in water, followed by HCA, then a final rinse. How fresh is your fixer? Is your paper newish? Maybe it's time to buy a new bottle of KRST.

[ROL]

I am not aware that Se Toner can go 'bad'. One of the great bonuses of Se toning all your prints, whether to completion or not, is that it will indicate, pretty much as you have described, if they have been fixed properly. You should consider re-fixing any remaining prints before toning. The toner didn't ruin your prints, your fixing procedure and/or washing may have – it was actually more of an early warning system. I couldn't say whether you might recover whites by re-fixing after toning.

[Mark Sampson]

ROL is essentially correct. I'll add that sometime around 2001 or so I found a quart bottle of KRST; from the label design it was made before 1971. I tried it and it worked identically to the new bottle I had on hand. Whichever prints I toned with that old stuff still look good.. but in those days I double-fixed in F-6 non-hardening fixer, too.

[MIke Sherck]

I suspect insufficient fixing but I don't know. You fixed two minutes in Ilford Rapid Fixer; was that freshly mixed, at 1 part fixer to 4 parts water?

Mike

[Bill Burk]

I had the exact same thing happen to me when I fixed in a fresh single bath fixer and only rinsed prior to Selenium toning. Since I don't have the same problem when I wash for at least 2 hours prior to toning, that's what I've gone back to.

I know it's a sickening feeling when perfectly good prints turn brown. Good luck solving your problem.

[jose angel]

Yes, I tend to think it was a bad fixing&washing procedure. I also think the KRST "never" go bad.

Mike, the fixer dilution was 1+4, too. I think the KRST is 1:19, not sure. The fixer may be good (I actually don`t take control of the number of sheets, but I think it was not so used), but the short rinse could be the culprit. At that time I hadn`t any Hypo Clearing Agent at hand, so probably it was a too much brief rinse. There must be fixer still on the fiber base.

BTW, I have been looking at "The Toning Book", searching for the topic, and it was mentioned the staining problem with Se toners, due to poor fixing and washing process. But I wonder if it can be considered "staining"... there are not marks or spots. Just a yellowish base, specially at the emulsion side.

I don`t want to reprint the same pic again... argh! Too much stuff to print. And with burnings&dodgings... I`ll try to refix and to wash using HCA, hope it works. If not, I`ll have to make a new print.

Thank you all very much.

[IanG]

It's residual silver left in the paper causing the staining, it's a mix of silver/thiousulphite complexes that aren't fully soluble. Fixing is a complex sequence of equilibrium reactions and if the fixing bath is part used some of these complexes form weak bonds with the cellulose in the fibre based paper so won't wash out, with selenium toning you get a yellow stain.

Simplest solution is to use two bath fixing, it actually works out being more economic, the fresher fresh fixer in the second bath with a low silver level completes the equilibrium processes and leaves no insoluble silver/thiosulphate complexes.

It's highly unlikely you'll remove the stain now.

Ian

[jose angel]

Thanks Ian. I have been always thinking about the convenience of a two bath fixing, I have used it a couple times in the past, so I`ll start with the habit right now.

[Doremus Scudder]

It's residual silver left in the paper causing the staining, it's a mix of silver/thiousulphite complexes that aren't fully soluble. Fixing is a complex sequence of equilibrium reactions and if the fixing bath is part used some of these complexes form weak bonds with the cellulose in the fibre based paper so won't wash out, with selenium toning you get a yellow stain.

Simplest solution is to use two bath fixing, it actually works out being more economic, the fresher fresh fixer in the second bath with a low silver level completes the equilibrium processes and leaves no insoluble silver/thiosulphate complexes.

It's highly unlikely you'll remove the stain now.

Ian

Ian has your answer.

I'll add that I use Ilford Rapid Fix or Hypam at the 1+9 dilution. I transfer prints directly from the second fixing bath to the toner without any staining. No intermediate rinse means a large savings in time. Two-bath fixation is much more efficient and secure than single bath.

There is absolutely no benefit to using your fixer at the stronger 1+4 dilution and then fixing for two minutes. It is simply wasteful. The whole point of the Ilford recommendation to use "film-strength" fixer for fiber-base prints is to reduce fixing times to one minute, which prevents the fixer from soaking fully into the paper base thus reducing washing time and efficiency. At two minutes you are simply defeating the purpose; the paper base is saturated and longer wash times are required.

FWIW, many, including me, are skeptical of the Ilford fixing sequence; it was tested only on Ilford products and reduces the fixer capacity to just a few prints if you want optimum permanence. A two-bath method with fixer diluted 1+9 uses the same amount of fixer and has a much greater (3x or more!) capacity. It does require longer wash times, but you need these anyway with your two-minute fixing time.

And, do replenish, filter and reuse your selenium toner! Just add a bit of stock when the toning times get too long. Use coffee filters before and after use. You will never have to discard expensive and dangerous selenium again.

Best,

Doremus

[hmf]

I have had this same problem when fixing with an older,, though sealed, bottle of Ilford Rapid Fix that I got as a part of a larger purchase. I always use a two bath fix. The problem went away when I use hypo as the second bath.

[Jim Noel]

It's residual silver left in the paper causing the staining, it's a mix of silver/thiousulphite complexes that aren't fully soluble. Fixing is a complex sequence of equilibrium reactions and if the fixing bath is part used some of these complexes form weak bonds with the cellulose in the fibre based paper so won't wash out, with selenium toning you get a yellow stain.

Simplest solution is to use two bath fixing, it actually works out being more economic, the fresher fresh fixer in the second bath with a low silver level completes the equilibrium processes and leaves no insoluble silver/thiosulphate complexes.

It's highly unlikely you'll remove the stain now.

Ian

By all means two fixing baths and either tone directly after fixing, or after a complete washing cycle. Have you aver tested your prints for residual thiosulfate after your wash cycle? If not, you might learn something by doing so.

[ROL]

I transfer prints directly from the second fixing bath to the toner without any staining. No intermediate rinse means a large savings in time. Two-bath fixation is much more efficient and secure than single bath.

I do much the same with a few variants. Since I always tone at the end of a printing session, I go from holding water bath, after single rapid fix (TF4) – then a final thorough washing. I don't bother toning prints that don't make through the fix to fine art status – I feed them to my ravenous rubbish can. It is impossible for me to use two fixes for mural prints, even in my 20' sink. I figure it ultimately saves time and handling difficulties to incorporate toning into the single session workflow. I "know" right away whether fixing is sufficient. Never any problems with inadequate fixation after 15 years of my present workflow, +35 in total, even with GSPs receiving direct partial seasonal sun.

[mike rosenlof]

if you read the ingredients of KRST, (bottle? or maybe MSDS) you'll see that amonium thiosulfate (rapid fixer) is one of the components. Probably no need to wash all of the fixer out before toning. You do want the prints to be completely fixed.

[ROL]

if you read the ingredients of KRST, (bottle? or maybe MSDS) you'll see that amonium thiosulfate (rapid fixer) is one of the components. Probably no need to wash all of the fixer out before toning. You do want the prints to be completely fixed.

Since that follows my post without quote, I assume that was intended for me, not Jose. To clarify, I tone after holding bath, then wash. What you want, ideally, is complete fixation followed by complete removal of hypo.

[matthew blais]

I also use a fresh fix/hypo then straight into SE toner...this is my second fix after washing thoroughly

[jose angel]

Thank you all very much for your help.

Doremus, I get your point, I`ll follow your procedure. Anyway, I think I was wrong, the solution I used was 1+9 not 1+4 (I use to follow the instructions).
---

if you read the ingredients of KRST, (bottle? or maybe MSDS) you'll see that amonium thiosulfate (rapid fixer) is one of the components. Probably no need to wash all of the fixer out before toning. You do want the prints to be completely fixed.
It`s true. So I`d think an improper wash is not the problem. Maybe an improper fix.
---

I have had this same problem when fixing with an older, though sealed, bottle of Ilford Rapid Fix that I got as a part of a larger purchase. I always use a two bath fix. The problem went away when I use hypo as the second bath.
Well, as mentioned, I don`t control the number of sheets I put on the fixer solution but I`d say they were not enough to be replaced. And it was the very first time I buy this fixer, I don`t know how old it could be (it could have been on the store shelve for years!).
---

Have you aver tested your prints for residual thiosulfate after your wash cycle? If not, you might learn something by doing so.
Jim, I`ll look how to do it. Thanks.

FWIW, I finally gave to one of the yellowish prints an "extra treatment"; I placed it directly (no prewet) into a fresh hypo clearing tray for 15 minutes, with continuous agitation, then into the NOVA slot washer for one hour.
The yellowish cast has partially gone, it is now in a middle point between the pure white of the untoned sample and the yellow from the toned one. Maybe a bit closer to the clear one, but still with a very slight grey cast. From an aesthetic point of view, the print is "usable", although not perfect. From an "archival" point of view, I don`t know.

As I still have the other yellow one, I don`t know if it makes too much sense, but I`m planning to re-fix it right now, then to the hypo tray, ending with the same one hour wash. I`ll tell you the results.

[jose angel]

Update; the second yellowish print has been processed as mentioned above, with the very same results as the first one. Still to complete drying, but it looks also slightly clearer, not as yellow, but still not white.

[ROL]

Well, as mentioned, I don`t control the number of sheets I put on the fixer solution but I`d say they were not enough to be replaced.

:eek:. Jose, you must count prints (failing any other method), per square unit area, given the fix manufacturer's recommendations. This is fairly easy to do once you figure out the area of your sheets, and you are working by yourself. Just take before and after counts of the paper in your used boxes. Any exposed paper not ending up fixed will simply build in a safety factor. This is the safest and easiest way not to exhaust the fix. I replace fix long before I bump up against manufacturer capacity.

[Doremus Scudder]

:eek:. Jose, you must count prints (failing any other method), per square unit area, given the fix manufacturer's recommendations. This is fairly easy to do once you figure out the area of your sheets, and you are working by yourself. Just take before and after counts of the paper in your used boxes. Any exposed paper not ending up fixed will simply build in a safety factor. This is the safest and easiest way not to exhaust the fix. I replace fix long before I bump up against manufacturer capacity.

Jose,

Yes indeed! As ROL mentioned earlier, your selenium toning step can be viewed as a kind of residual silver test: if your prints turn yellow, your fixing has been inadequate (or the print was too acidic when introduced into the toner). You need to refine your workflow.

You should refix any prints in the batch that turned yellow in fresh fix before trying to tone again!

Counting prints is really easy: I use 36 8x10 prints per liter of bath 1 and bath 2 (slightly less than the manufacturer's recommendation, but exactly three washer batches for my 12-print washers). When you reach that number, replace bath 1 with bath 2 and mix a new bath 2. Don't forget to count test strips and prints as well. Err on the side of too few.

Best,

Doremus

[jose angel]

Well, looks like I`m a bit abandoned in my procedures... Never thought in this counting method, good idea. I like to refill my 25 sheet empty envelops (I use to buy 100 sheet boxes), so I`ll simply put the number of sheets needed to know that an empty envelop means fixer replacement. Thanks for the tips.

I`ve just refixed some other prints I had awaiting for Se toning, and -all- came out -perfect-. Looks like the problem actually was on my bad fixing procedure.

BTW, I don't want to take advantage of your kindness... but I wonder about your tray lines; maybe dev-stop-1st fix-water rinse-2nd fix-hold water bath? (six trays) Do you use an hypo tray instead in the same line, or maybe you prefer to do the work in two stages? I see ROL mentioned the lack of space with mural prints, but, out of curiosity, what about "normal" sized prints? Thanks.

[ROL]

BTW, I don't want to take advantage of your kindness... but I wonder about your tray lines; maybe dev-stop-1st fix-water rinse-2nd fix-hold water bath? (six trays) Do you use an hypo tray instead in the same line, or maybe you prefer to do the work in two stages? I see ROL mentioned the lack of space with mural prints, but, out of curiosity, what about "normal" sized prints? Thanks.

I always enjoy helping well mannered people who don't throw well intended offerings in my face. I suspect most here feel the same. I write basic technique articles (http://www.rangeoflightphotography.com/pages/techniques) and produce videos for my site from time to time, in large part to assist others in common classical photography.

My "mural" reference is indeed more than it first appears. My DR is designed with the ultimate goal in mind of GSP enlarging to a normal maximum of 40". That means a tight fit for my mural sized trays, no more than 5 at a time in my nearly 20' long sink (see A Darkroom Portrait (http://www.rangeoflightphotography.com/pages/a-darkroom-portrait) – btw, those trays in the sink are my normal size trays, not the mural trays). My normal basic processing workflow is:


developer –> stop/rinse (water) –> fix (TF4) –> water holding bath –> Se toning –> hypo clear (PermaWash) –> wash


Print/film washing normally happens in a separate sink with dedicated washers, However, mural prints must, because of their size, be processed entirely within the main sink, including washing. 34"x42" trays are unwieldy enough when empty – when filled with 2 to 3 gallons of chemistry they are impossible to relocate. For murals, this reduces the number of process workflow stations in the main sink to 4. One of those remaining holds the toner, resulting in only 3 available spots for developer, stop/rinse, and (one) fix.

It should be obvious from general workflow above that there is not enough space for complete processing as the number of stations exceeds 5. I normally reconfigure the tray stations after all the printing and basic processing (up to fixing) is done in order to begin toning. The water stop is emptied and rinsed, and clean water is added to become another holding tray to which all prints are transferred to await toning. A holding tray is replaced with PemaWash. Secondary processing then occurs:


water holding bath –> Se toning –> hypo clear (PermaWash) –> wash
(4 trays ;))

My decision to use a well tested and regarded single rapid fix for all print processing is based on two rationales. Firstly, that the less hypo introduced into the print (fiber) once fixing is complete, the less there will be to wash out, and thus less potential damage to any print's substrate or additive whiteners (if any). Over-fixation has its own deleterious issues. Archival processing is, in practice, a balancing act of proper fixing followed by complete washing. I have to rely on the manufacturer's testing of these chemicals and my own experience to arrive at workable decisions in my own DR. That is possibly as good a definition of workflow as I may be able to come up with. Secondly, I am forced to work with some logical limitations on size and from my very personal workflow. I reckon, what's good for expensive, difficult to produce mural sizes is at least as good for normal sheet sizes (e.g., ≤ 20"x24"), and so I also use the same workflow for those, with some variation – and a bit more elbow room!. The complications and difficulties of producing, handling, and presenting (another can of worms!) mural prints is the reason I charge considerably more for them.

Rinsing between the fixes of the two fix process, if that is your pleasure, varies depending on your toning goals. Read Adams' The Print. Doremus is probably the most vocal proponent of that technique on this forum. I believe all classical photography darkroom workers share the same goal of producing archival fine art prints in the constantly shifting terrain of available and affordable resources.

[Doremus Scudder]

... BTW, I don't want to take advantage of your kindness... but I wonder about your tray lines; maybe dev-stop-1st fix-water rinse-2nd fix-hold water bath? (six trays) Do you use an hypo tray instead in the same line, or maybe you prefer to do the work in two stages? I see ROL mentioned the lack of space with mural prints, but, out of curiosity, what about "normal" sized prints? Thanks.


I'm happy to help as well.

My workflow is just a bit different than ROL's. I divide my sessions into a printing session, where I really work on refining one or two prints. I'll print for several days, often straight but sometimes with a day or more between sessions. In the printing sessions I give a generous first fix (one that would be adequate for "commercial" processing standards, but not completely "archival"). Tray set-up is as follows:

Developer(s) (with graded papers I often use both a soft and hard-working developers)
Stop
Fix 1 (usually Hypam or Rapid Fix 1+9 - fixation is 1.5-2 minutes at the above-mentioned 36 8x10s per liter capacity)
Water holding tray
Wash (minimum 60 minutes in an archival washer)
Dry on screens (after squeegeeing, face-up)

I then collect prints until I have enough for a toning session. The number of prints depends on size; for prints on 11x14 and 8x10 paper I like 36 prints, since that fits my washer/drying screen capacity for 11x14s (I don't make lots of 8x10s, just still-lifes and natural details); for 16x20s I can do up to 20 at a time, but usually stop at 14-15; for 20x24s I can only do 10 at a time. At any rate, here is the tray set-up for toning:

Water soak (5 minutes)
Fix 2 (always with freshly-mixed fixer. I usually use Ilford Hypam or Rapid fix at 1+9 and keep the capacity to 36 8x10/liter or less)
Selenium toner trays (I often have two trays, one a relatively strong solution, one weaker; some papers tone faster than others. As mentioned, I transfer directly from the fixer 2 to the toner with no intermediate water bath. This has worked fine for me for years. I also save and replenish toner, more below)
Wash aid (I skip the water rinse due to space limitations and just use my homemade wash aid to a smaller capacity. I mix my own wash aid from sodium sulfite and bisulfite and follow the Kodak capacity recommendations for their Hypo Clearing Agent. I do, however, collect the prints in the wash-aid tray. They get a minimum of 10 minutes wash aid, but often up to 45 minutes or so.
Wash in an archival washer for a minimum of 60 minutes and often twice that or longer. I test the last print through the fixer/washer for both residual hypo and residual silver to check my fixing and washing; no problems for years now)
Stabilizer (after washing I give the prints the recommended time in Sistan or equivalent; they come out of the washer, into the Sistan and then get squeegeed and
Dried (on screens, face-up - I've had screen marks on prints dried face-down)

I clean up between putting the last batch of prints into the washer and the stabilizer step so I have room. This means filtering and returning the toner baths to their jugs, saving the fixer for bath one for a printing session if I plan on printing in the next couple of days, dumping the wash-aid, scrubbing the sink, etc. By the time I've got the last print on the drying screens, everything is spic-and-span.

Replenishing and reusing toner:
This is one of my pet topics, so bear with me :) Selenium toner will last practically forever if you simply filter it before and after use with a coffee filter or the like. When toning times become too long, add a bit of stock toner to your working solution; an ounce or less per liter is a good starting point. If the activity is still too slow, add more; if it is too fast, dilute your toner a bit. It doesn't take too long to get the hang of this. As mentioned above, I keep two different dilutions, marked simply "strong" and "weak" for papers that tone at different rates. Some tone way too fast in the stronger solution. I don't even know the real dilutions anymore.

Replenishing and reusing toner is both more economical and eco-friendly. You never have to discard toner again. Plus, the toner quickly loses the unpleasant ammonia odor and is a lot more pleasant to work with. I often tone two batches of 36 prints without needing to replenish (just extending the time somewhat).

This method requires that you tone visually, i.e., pull the print from the toner when it has changed to the tone you desire. IMO, toning with weak dilutions and a set time is basically useless. There is no real archival advantage to "barely" or partially toning. Toning is for aesthetic reasons; there is no significant protection of the print unless it is toned pretty much to completion, which practically no one does.

Every print through the toner weakens it somewhat, so there is zero chance that the last print of a batch toned at all the same time will have the same amount of toning as the first. Plus, different papers and subjects all need different amounts of toning. Keep an untoned print handy for comparison and pull the print when it reaches the amount of toning you desire; from enhancement of the low values to a real tone change. If you can't see any difference, toning isn't doing anything for you... you might as well save your time.

Hope this helps,

Doremus

[jose angel]

Very interesting. It`s great to know how you experienced printers like to work, I`m a somewhat "lone printer" and autodidact, so I use to live with many vices and faults...

ROL, your system seem based on effectiveness and accuracy, I have read anywhere from Ilford literature the idea of the shortest effective fixing times... I try to remember that they even proposed a fixing solution to work effectively in no more than 30 seconds.

I never figured to place the toning tray directly after the fixer... if it works there is no reason to avoid this way. Your ideas are so useful. BTW, I have sent the links to my iPad, so I`ll have today much fun reading your site... :)

Funny, yesterday I had to be out all day, and I took The Print to refresh on the free hours. So yes, I read Adams` method with a "secure" fixing procedure and "thorough rinse", about the alkalinity, etc. Actually his books are like a bible.

Doremus, my darkroom procedure is "closer" to yours, as I also print in low quantities and use to leave the toning stage for a "toning day". But I was currently missing the second fixer in the toning process; as mentioned, I have tested that my other prints became perfect following your procedure. So I have just started new habits...

I`m actually a long time printer, but I know I have loads of things to improve. Funny that after many years printing in any way, I`m becoming more and more excited in the darkroom... LOVE this kind of art.

Well, your help is so valuable. Thank you very much.

[Doremus Scudder]

My pleasure.

[Bill Burk]

Note the important difference in the choice of chemistry. ROL is using an alkaline fixer and Doremus (you and I too) are using acid fixer.

So if you choose to change your process steps, verify they are valid for your chemicals.

[jose angel]

Thanks Bill. I have also read something about acidity/alkalinity on The Print. Right now I`m buying the Ilford fixer, so no problem at all.