Sodium Sulfite undoes Sulfide toning- puzzled.

I made a first attempt at sulfide toning the other day. As a sulfide toner 'stop bath' I used a sodium sulfite solution (~1 tablespoon/litre). To my unpleasant surprise the stop bath reversed the print to the state before sulfide toning. This shouldn't happen should it?

My workflow:
- Adox MCC 110, neutral developer, acid stop bath, fresh fixer,
- 5 min water wash,
- selenium tone 1+19 for 2-3 minutes (noticeable discolouration),
- 30 min water wash,
- sulfide tone (Agfa Viradon New) 1+24 for 8 minutes,
- water wash ~1 minute,
- sodium sulfite solution wash for 5 min,
- final wash.

Could it be that Adox MCC simply does not respond to sulfide toner in the first place, and that the sulfide toning that I think I'm seeing (before applying the sodium sulfite stop bath) is just the colour of the sulfide toner absorbed into the paper? But then, no rinsing with water manages to remove this sulfide stain (or what it should be called), while the sodium sulfite stop bath does the (unwanted) trick in a couple of minutes.

What am I doing wrong?

Thanks for any help,
Sander

Where is the bleach?

I don't believe this is a bleach and redevelop toner, but a single solution one. Is this similar to Kodak brown toner? I use the Freestyle brand of brown toner.

I have not tried it with Adox MCC 110, however. I love it with Ilford MGWT FB (which responds rapidly and intensely, very easy to over tone.)

I HAVE used brown toner with Freestyle's Private Reserve RC, which I and most people believe to be re-branded MCP, 312 (pearl) in my case. It works fine, but gives, naturally enough, a considerably cooler brown than the rich warm ones of the MGWT, and takes a LOT longer. But I didn't dual tone with selenium and I didn't use sulfite so I really can't answer the question here. However, if the fiber based MCC 110 (I do use that paper and like it a lot, just haven't tried brown toning it) responds to Viardon anything like the MCP 312 responds to Legacy Pro (aka Kodak formula) brown toner, any kind of "stop bath" for the toner is totally un-needed. I toned for 10 full minutes in full strength toner to get a good result. Toning is quite slow so I think a water rinse should do fine.

But I realize that's an awfully lot of "buts" - if a different (but similar) paper responds to a different (and maybe similar) toner in a similar way, after toning with selenium... Not much help I'm afraid.

Couple of things....

You said "noticeable discoloration" during selenium toning. What kind of discoloration? Any stain like mark usually means insufficient fixing and washing. That maybe where your problems are starting.

I don't know Adox but some paper do not respond to toning all that well. Ilford MGIV is one of them. But, it won't stain like you are saying. The silver part gets slight tinge of brown/purple kind of color. White stays white.

Because you kept calling it stain, I'm guessing white part is discolored. That is likely caused by insufficient fix/wash in the first stage.

Sodium Sulfite stop bath needs to be MUCH stronger, like 10% for it to work. (I just learned this myself) So take 100grams of Sodium Sulfite and dissolve it into 1000cc of water. What you have is more less HCA strength. In that dilution, it will have the opposite effect. Strange enough, when polysulfide toner is diluted to certain degree, it speeds up. I used to see my toning do very little and as soon as I soak it in water bath, it goes BOOM!

@cliveh: Viradon new is/was a direct toner.

tkamiya said:

You said "noticeable discoloration" during selenium toning. What kind of discoloration? Any stain like mark usually means insufficient fixing and washing. That maybe where your problems are starting.

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"Stain" is obviously not the word I should have chosen. The toning (selenium and sulfide) looks perfectly homogeneous, definitely no problems with improper fixing or washing, sure of that.

tkamiya said:

I don't know Adox but some paper do not respond to toning all that well. Ilford MGIV is one of them.

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I suspect this is the problem: Adox MCC simply doesn't tone well in sulfide, and all i'm seeing is the yellow/orange colour of the toner absorbed in the paper base, until being washed off by the sodium sulfite solution (suspiciously quickly though).

tkamiya said:

Sodium Sulfite stop bath needs to be MUCH stronger, like 10% for it to work. (I just learned this myself) So take 100grams of Sodium Sulfite and dissolve it into 1000cc of water. What you have is more less HCA strength. In that dilution, it will have the opposite effect.

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What do you mean with "the opposite effect"? Sorry, just not following you here.

Roger Cole said:

Is this similar to Kodak brown toner? I use the Freestyle brand of brown toner.

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Probably quite similar yeah, but I only ever tried "Viradon New". It's a direct toner without selenium.

Roger Cole said:

I have not tried it with Adox MCC 110, however.

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Anybody who has first hand experience with (direct) sulfide toning Adox MCC? I did a search but couldn't make sense out of the results. Should I expect Adox MCC to tone at all (in sulfide)?

Roger Cole said:

However, if the fiber based MCC 110 (I do use that paper and like it a lot, just haven't tried brown toning it) responds to Viardon anything like the MCP 312 responds to Legacy Pro (aka Kodak formula) brown toner, any kind of "stop bath" for the toner is totally un-needed. I toned for 10 full minutes in full strength toner to get a good result. Toning is quite slow so I think a water rinse should do fine.

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Roger, would you have any idea why my sodium sulfite seems to undo (not just stopping it) the sulfide toning?

Roger Cole said:

Not much help I'm afraid.

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You're most welcome, thanks.

I do print on MCC 110, and I do use the (apparently similar?) brown toner, I just haven't tried them together. When an image calls for a warm tone result I usually print on MGWT which responds beautifully to the toner. I use MCC 110 for neutral tones. It DOES respond in selenium, but if I let it go as far as a noticeable color change I don't care for the purple color. I stop just short of that with a slight cooling (to neutral from very slightly warm - as someone, I think Drew, commented here and I have found to be true, it doesn't seem to really be capable of a true cold tone.) I've never tried to split tone it either.

But I do plan/hope to be doing quite a bit of printing in the next several days, some of it on MCC 110 and some on MGWT that will be destined for brown toner. If I get a chance I'll try it out and report back. I'm curious myself now. I've no idea about the sulfite.

sandermarijn said:

What do you mean with "the opposite effect"? Sorry, just not following you here.

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Most toners work faster and deeper when they are more concentrated. Polysulfide toner is an exception. As weird as it may seem, this is documented in books that most consider authoritative, including one from Tim Rudman. I saw this with my own eyes, too.

Say you have a polysulfide (one step brown) toner diluted per specification. You put your print in it to tone. It starts to tone. Say stop at a half way point then put the paper in water or HCA which is basically a weak solution of sodium sulfite. The rate of toning speed picks up. In my own experience, I had a print that toned for 4.5 minutes. In wash water, it actually toned to completion in just a minute or two. If I wanted to do the same level of toning in polysurfide step, it took more than 32 minutes. (my toning test ended at 32 minutes) So this is more than the usual toning with remaining toner in paper situation. The rate itself goes faster.

I wanted to stop the process on a dime, so I had to make a much stronger solution of sodium sulfite, 10%. In this solution, I observed the toning to stop on contact. In fact, to my eyes, it looked like it undid about 30 second to a minute worth of toning already done. I tried this which HCA because it's basically a weaker solution of sodium sulfite. It didn't work. The process sped up like I explained in previous paragraph. I was told by few here that at less than 5% concentration, stopping effect won't take place.

Roger and I had a discussion about this a while back. It's true there has to be a point where this weaker-the-faster holds true. Otherwise, a drop of toner in an ocean can tone everything in sight. He uses his toner much weaker to begin with and doesn't observe this phenomenon. I use mine at the dilution on the bottle. I see it every time.

Thanks tkamiya for your excellent elaboration, I understand what you mean now. Odd sodium sulfite behaviour indeed. Perhaps the weaker-the-faster rule is, in its opposite incarnation, indeed responsible for the undoing of the sulfide toning that I observed with MCC 110. But I've decided to chuck the sodium sulfite altogether and just go with water instead.

Also, after seeing what sulfide does to Ilford MGWT I don't think I will bother using sulfide with MCC anymore. Ilford MGWT seems made for sulfide toning. MCC pales in comparison (not literally though).

I like your drop-in-the-ocean reasoning, quite elegant and very understandable. Sounds like you and Roger will have some more pondering and debating ahead of you .

Roger Cole said:

I do print on MCC 110, and I do use the (apparently similar?) brown toner, I just haven't tried them together. When an image calls for a warm tone result I usually print on MGWT which responds beautifully to the toner. I use MCC 110 for neutral tones. It DOES respond in selenium, but if I let it go as far as a noticeable color change I don't care for the purple color. I stop just short of that with a slight cooling (to neutral from very slightly warm - as someone, I think Drew, commented here and I have found to be true, it doesn't seem to really be capable of a true cold tone.) I've never tried to split tone it either.

But I do plan/hope to be doing quite a bit of printing in the next several days, some of it on MCC 110 and some on MGWT that will be destined for brown toner. If I get a chance I'll try it out and report back. I'm curious myself now. I've no idea about the sulfite.

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Funny, I just ran to the store this morning and got 10 sheets of Ilford MGWT (ouch said wallet). I printed the same negative as yesterday's, but this time on MGWT. Then toned it in selenium and sulfide (with all the appropriate steps in between). WHOW, what a response this MGWT gives to sulfide. After two minutes in Viradon 1+24 it had turned chocolate/red already. I washed with water (no sodium sulfite stop) and it's drying now. It looks, well, unique.

I completely agree with you Roger, that MCC 110 is probably best reserved for neutral prints (it does respond well to selenium though, like you say; I see a change towards red-purple and extra blackening of the blacks and darker greys).

MGWT is really the way to go for sulfide toning. I will have to play around with smaller Viradon dilutions (1+50, 1+100, perhaps even 1+200?) for a better controlable and thereby more subtle browning of the image.

Seems like we're on the same track. Have fun experimenting, I definitely will.

To clarify (and the drop in the ocean was an elaboration of the exchange we had earlier where I said there had to be a limit or else we could put one drop of toner in 10 gallons of water and tone to completion instantly ) ...

The reason I use it that way (with MGWT) was just that Drew Wiley in another thread here recommended it at 1/4 strength for MGWT. I followed his process and loved the results. That included using a water bath, toning for no more than 20 seconds and then dumping the print into the water bath with no drain time (which will cause streaking, it's so fast with MGWT.) Done this way it does continue to tone a while in the water, which is one reason to stop before it's where you want it. But it doesn't bloom or boom or whatever (greatly speed up etc.) It just continues a bit then stops, or almost stops as it will tone a bit more during washing. If it isn't enough, back in the toner with it. I modified this on my own, not having Rudman's book or reading of this "works faster when more dilute" thing, because it was hard to control with such short times. If nothing else, sometimes the print will stick or something and it will take a bit to get the tongs on it. Do not try to grab it with your hands, with or without gloves - heat speeds up the toning drastically and your hands, even through gloves, are warm and will leave fingerprints. Don't ask me how I know. So I went to 1/8th strength dilution and that certainly is slower than 1/4 strength. I make no claims (with MGWT, more on this...) about the speed of 1/4 versus full, which may be faster. I don't know. But I do know that 1/8th strength is about half as fast as 1/4 strength so I at least seem to be hitting that diminish effects point.

I just toned an 11x14. A friend, and very good digital photographer, greatly admired one of my toned, mounted 11x14s, so I offered him a copy - he's moving away, and it's a moving away present, in part. Before he left he gave my wife and me his very first darkroom print from the days when he did darkroom. Anyway, I needed to duplicate the earlier print, which I had toned for approximately 45 seconds at 1/4 strength. In 1/8th strength toner I got a pretty good match for it with two minutes of toning, which I find much more controllable.

I did mix full strength toner to try with Arista Private Reserve RC Pearl, aka (most people think anyway) Adox MCP 312. It responded in the weak toner but I didn't like it. It was an odd reddish brown that I didn't care for, and took a lot longer than MGWT. I think anything takes a lot longer than MGWT. I mixed full strength and got a pretty nice chocolate brown with 10 minutes of toning. I can scan that if anyone is interested. It's a cooler brown than you'll get on a warm tone paper like MGWT. The red tone I didn't like I got after several minutes in the very dilute toner. When I mixed it full strength I just put the same print in for another 10 minutes so it's hard to say if it's faster with one or the other. It's different, though.

Here's what my toning looks like on MGWT with 50 seconds in the 1/8th strength toner, for a light toning effect I like very much:

Dead Link Removed
Dead Link Removed by Roger Cole, on Flickr

Here's the same paper, otherwise same processing, but toned for 40 seconds in 1/4 strength. Considerably more toning than the 50 seconds at 1/8th:

New Orleans Courtyard - Toned by Roger Cole, on Flickr

And another, my now wife then fiance, also 40 seconds at 1/4 strength:

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Dead Link Removed by Roger Cole, on Flickr

Those 40 second results look good for some images but were just too strong for others, and really short times like 20 seconds were just too hard to control. So for this particular paper I like the weak toner.

One thing though - it doesn't last very long after mixing. At these weak strengths it is noticeably weaker the next day, and almost useless a week later. Tkamiya says his full strength toner lasts for a very long time. I did have that full strength toner mixed, but when I got no response at all out of Arista Silver Artist after 10 minutes I mixed a fresh batch - which gave no change at all after another 10 minutes. Now there's a paper that resists sulfide toning. Otherwise I haven't kept full strength toner enough to know.

I like your examples Roger. Although they all look quite different in terms of toning, they do share the same understatedness.

My two prints from today (12x16", too large to scan) are way way overdone compared to yours. I will take your 1/8-dilution, twice-the-time method as a starting point for further play; will have to start somewhere anyway.

Back to the original question. I take the remark "noticeable discoloration" as saying that the selenium toning did not go well either. If that is the case, the paper may just not do well with direct toners. You should, however, try making another print and toning it only with Viradon New. Sulfite solution should have no effect on a silver sulfide image, but I would rinse the toned print briefly in plain water before putting it in the sulfite. If direct toning doesn't work, you could try a bleach redevelop toner. Those toners tend to give a more yellow shade, but a highly alkaline thiocarbamide redeveloper would probably come close to the polysulfide toner shade.

Cole's wonderful examples show how effective toning can be. I especially like his ability to match the subject to the tone.

MCC 110 does fine with selenium. I routinely selenium tone all my MCC 110 prints. But I've never followed it with another toner. As I mentioned, 5 minutes starts to go noticeably purple in a color I'm not really after, so I stop after 4 minutes at 1+19, which yields a slightly cooler (neutral, not really cold) tone and slightly increased d-max. It doesn't change much compared to other papers, but it does change usefully.

Thanks for the compliments on the brown toned images.

nworth said:

Back to the original question. I take the remark "noticeable discoloration" as saying that the selenium toning did not go well either.

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Clumsy wording of me. "Noticeable discoloration" actually meant to say that MCC 110 reacts well to selenium (change in colour as well as darkening of darks).

Thanks for the other suggestions. I was also given some (well, enough for 5 litres) slightly out-of-date indirect sulfide (I think) toner. This is a three bath kit, consisting of bleach and a two-part toner. The ratio of the toner parts sets the colour after bleach, from yellow to something on the other end.

So lots of combos of paper and toners to try- could fill the rest of my life.

I may try MCC 110 with only sulfide also, even though I don't expect much of it. But maybe "not much" is exactly the subtle result Roger seems good at, and his stuff is excellent like you say.

I was in fact looking for a fairly subtle effect. I don't like the slight green cast of un-toned warm tone papers. I wanted something warmer for some subjects, but far short of full on sepia toning. I find strong toning, while occasionally useful, to more often just look overdone. This is entirely my artistic judgment and taste and need not be anyone else's.

The New Orleans courtyard scene is actually an "overtoned" one that resulted in my trying the 1/8th strength in an attempt to gain more control and prevent accidentally toning more than I intend. I meant it to be far more subtle, and have a more subtle one on my wall. But that's about 10x11 or so (slight crop from a 6x6 negative) on 11x14 paper and I couldn't scan it, so I made an 8xwhatever one that I could, and it got away from me a bit and became a lot more toned than the one on the wall. I sent that one away on a print exchange over on FADU. Most people seem to like it this way, though, so I left it in on my Flickr page.

For the shot of my wife I wanted more full toning. The combination of evening sun and the wood of the park bench I thought would work well with a warmer look.

Roger Cole said:

I don't like the slight green cast of un-toned warm tone papers.

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Not limited to warm tone papers, this green cast. It wasn't until I started selenium toning my Kentmere fibre papers that I noticed the green cast of untoned Kentmere. Then I saw the green cast in 'old' Agfa FB papers. I can't stand the green anymore and tone (nearly) all papers by default. Couldn't go back to a life without selenium.

sandermarijn said:

Sounds like you and Roger will have some more pondering and debating ahead of you .

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No, not really. We both have a method that works well for each of us. That's what's important.

Mmm maybe one of you could help me out, I started a thread somewhere else (there was a url link here which no longer exists)
In the past I never had a problem with toner darkening in my wash using Kentmere paper, now with Ilford paper my prints are all going yellow.
It may be that I did not wash my prints properly, since I did them at night, was tired and possible made a mistake.
Just thinking what if one uses a stop bath made of stop to halt the toning. Aren`t direct sulfite toners alcaline? Just wondering if the low PH of a stop bath would stop the toning?!?

Are you seeing yellowing in wash water or later? If you are seeing this yellowing thing during wash... read on...

If you are using direct sulfide toner using manufacturer's recommended dilutions, curious things happen. It will tone in the toner bath. When you *think* you are done and put it in wash water, it speeds up and moves toward more toning effect. It may look like yellowing but it's actually toning more and more from black into light brown.

To stop this, you don't do acid/alkaline thing. You make a 10% solution of sodium sulfite (aka strong HCA) and dip the print after toning is done to your liking. That'll stop it right way. This is the method I use when I want a precise control.

Roger (who posted above) have a different method. He uses much weaker solution to tone then washes it after it's done. He has his system calibrated so that this toning faster in water effect does not happen.

Again, PH has nothing to do with it and it is unlike developer where acid will stop the action.

I have seen yellowing after toning and washing with Ilford MGWT FB and direct sulfide toning. It was definitely yellowing, not toning, as the white borders were very obviously affected. What was puzzling is that sometimes it did, sometimes it didn't. Turned out that the process seems very sensitive to fixer exhaustion. Fixer that tested fine with hypo check but had been used a bit, but not overused according to my past experience, would result in this yellowing. Fresh fixer did not.

The good news is that re-fixing and washing seems to remove the yellow, but doesn't affect the toning.

I now limit fixer use to no more than 15 sheets of 8x10 per quart of film strength (no hardener) Rapid Fixer. I began to see this yellowing at about 20 8x10s.

Roger Cole said:

I have seen yellowing after toning and washing with Ilford MGWT FB and direct sulfide toning. It was definitely yellowing, not toning, as the white borders were very obviously affected. What was puzzling is that sometimes it did, sometimes it didn't. Turned out that the process seems very sensitive to fixer exhaustion. Fixer that tested fine with hypo check but had been used a bit, but not overused according to my past experience, would result in this yellowing. Fresh fixer did not.

The good news is that re-fixing and washing seems to remove the yellow, but doesn't affect the toning.

I now limit fixer use to no more than 15 sheets of 8x10 per quart of film strength (no hardener) Rapid Fixer. I began to see this yellowing at about 20 8x10s.

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Refixing removes the yellow?? Really, if that works that would make me a happy man. Since I have a few "yellow" prints now.

AndreasT said:

Refixing removes the yellow?? Really, if that works that would make me a happy man. Since I have a few "yellow" prints now.

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Well, it did with MINE. Worth a try anyway. Your yellowing might not be the same as what I saw, but not much to lose other than a tiny bit of fixer capacity and some time.

tkamiya said:

Are you seeing yellowing in wash water or later? If you are seeing this yellowing thing during wash... read on...

If you are using direct sulfide toner using manufacturer's recommended dilutions, curious things happen. It will tone in the toner bath. When you *think* you are done and put it in wash water, it speeds up and moves toward more toning effect. It may look like yellowing but it's actually toning more and more from black into light brown.

To stop this, you don't do acid/alkaline thing. You make a 10% solution of sodium sulfite (aka strong HCA) and dip the print after toning is done to your liking. That'll stop it right way. This is the method I use when I want a precise control.

Roger (who posted above) have a different method. He uses much weaker solution to tone then washes it after it's done. He has his system calibrated so that this toning faster in water effect does not happen.

Again, PH has nothing to do with it and it is unlike developer where acid will stop the action.

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Thank you, how long does sodium sulfite last? Not that long if I recall. I actually use a very weak toner solution 1+100 and tone very short. I like the idea of only having a hint of colour. Then again maybe that strengthens the idea of toning in the wash. I will try some things tomorrow. I have to get to the bottom of this. I have used this toner for a while now and this is a first for me so really a bother.