When Good Pyrocat goes Bad

[esearing]

Has anyone ever gotten pink negatives from Pyrocat HD? FP4+ and Delta 100

I don't think I cross contaminated my A and B containers but yesterdays developing left me with some thin negatives that were stained pink/magenta instead of tan. I ran them through a fresh batch of fixer just to make sure it wasn't film dye.
I scanned them with an Iphone app and there is some detail there but the negs are very thin.

the Pyrocat HD is about 8 months old and stored indoors around 70-74 degrees. It did seem more "foamy" than usual so wondering if there was contamination from the tanks previous run still containing some fixer, but I wash the film in the tank for at least 10 minutes.
I have not used photo-flo in a while so no foam from there unless it really sticks to the plastics.

Fortunately I have some of the stock in separate containers so I can test with that before losing any more "important" shots.

[koraks]

1: pink hues, especially if not proportional to image density, are antihalation dyes. Pyrocat stain is never pink, not even when the Pyrocat is old. Particularly in films like delta, the pink stain of antihalation dyes can be persistent and in some cases, even 10 minutes of fixing in fresh 1+4 fixer does not entirely eliminate it.
2: thin negatives can certainly be the result of oxidized Pyrocat. What color is your concentrate? Mine is usually pink or yellow when fresh, tending to red or tan when it is older. Fully oxidized Pyrocat should be very dark brown/black and virtually opaque. If yours is light in color, it is unlikely to be very bad and a mixing or development timing/agitation or exposure error is more probable.
3. Foaming is not a sign of developer age and in my experience Pyrocat, old or fresh, does not cause foaming. Remnants of a surfactant or soap on a container is a more likely cause, but you seem to have (partly) ruled that out. However, surfactants are known to adhere to plastics quite well over time. I understand soaking tanks in a water with a denture cleaning tablet can help clean them.

If you can, post a pic of your negatives, it'll make the issue clearer.

[Andrew Tymon]

I always develop a small one inch piece of film in 200 ml of pyrocat while I'm setting up. I like to check it builds density and compare it to a piece I developed when the developer was fresh. It only takes ten minutes whilst getting everything ready. I spend hours making negatives and hate to waste the effort. Was the pyrocat in glycol?

Andy

[Alan9940]

I've had Pyrocat-HD die on me in <1 year, though everyone always says that it lasts for years; even when mixed in distilled water. Negatives came out thin, as you report, but never pink. I suspect the pink color is anti-halation dye, as others have already said. Occasionally, I have to resort to a hypo clear solution to fully remove the dye.

[esearing]

I always develop a small one inch piece of film in 200 ml of pyrocat while I'm setting up. I like to check it builds density and compare it to a piece I developed when the developer was fresh. It only takes ten minutes whilst getting everything ready. I spend hours making negatives and hate to waste the effort. Was the pyrocat in glycol?

Andy

Great Idea Andrew. I always test my fixer that way so might as well check the whole process.

so I ran a fully exposed sliver of film through the process and it is dark brown/grey as expected.

I then ran a test properly exposed negative with the original stock containers and got the same result. I washed all syringes, tank parts, and mixing vessels before starting.
The Pyrocat HD in Glycol is what is foaming. Fresh water in the tank shaken does not foam. Fixer in the tank is not foaming.
No amount of fix time will reduce the pink cast with even fresh fixers so not an anti-halation dye issue. I cleared an unprocessed piece of film in about 20 seconds.

Looks like I have to order more to be sure. But I am throwing away more than half full 500ml bottles if the chemistry is the problem. I would expect it to last at least a year.

[Andrew Tymon]

Do you pre-soak your film? I noticed when I processed some FP4+ the pre-soak was a little frothy, I never use photo-flo in my unicolor drum. If your negative you did a test with developed normally, then you Pyrocat should be fine.

[esearing]

Here is an example. Left negative processed a few days ago and is a little thin but similar in color to prior negatives. the middle is an N-1 processed Negative (shortened development time) and the right is a normal process. I took a slice from the first image so you could see the color shift so even if my monitor or yours are not color correct, the difference is obvious.

182063

Bostick and Sullivan has a 15% off sale through Labor day

[Mark Sampson]

The pink cast is almost certainly retained anti-halation dye. Fresh fixer, hypo-clearing agent, and a longer wash will eliminate that. This was first seen as a problem when the Kodak T-Max films were new; luckily the pink stain has little or no effect on print quality, and can be easily removed by the above procedure (if desired).
Your negatives don't look too under-developed to me; the center one looks underexposed, and there's what appears to be full density in the right-hand image. Of course I can't really tell from your scan, your contact proofs will tell the story.
I use Pyrocat-HD (in glycol) and it has 'gone bad' on me once. However I can't document the exact circumstances so don't put too much weight on that.

[richydicky]

I don't think I cross contaminated my A and B containers but yesterdays developing left me with some thin negatives that were stained pink/magenta instead of tan. I ran them through a fresh batch of fixer just to make sure it wasn't film dye.
I scanned them with an Iphone app and there is some detail there but the negs are very thin.


I had exactly the same happen to me testing for the first time with FP4 4x5. I had been using it for 8x10 sheets of X-ray film and FP4/HP5 all coming out fine but though I noted that last X-ray sheet I processed after the FP4 4x5 came out a bit thin so I will re-test it before using again. Mine is about 9 months old.

[esearing]

I let the pinkest of the bunch sit in fresh fixer 1:4 for an hour with some agitation, then washed it for 30 minutes with 5 mins in washaid. Its still pink.
Its as if the dye hardened into the emulsion. I know what an under fixed image looks like. This ain't that.
When I get my new batch of developer I may bleach and redevelop to see if anything changes.

Note my working stock (small bottle) and my storage stock (big bottle) are both exhibiting this issue. Something just reached the end of its shelf life.
Both A and B yield a clear to light tan liquid once mixed.

To answer the question above - I do presoak for 5-6 minutes with some minimal agitation at 70 degrees same as my working temp for Pyrocat. FP4 yields a nice dark blue water when dumped. Delta 100 was not as noticeable.

[Andrew Tymon]

It does look like something is wrong with it. Have you thought about buying the dry chemicals and mixing your own?You would definitely know how old your stock solution is and you could make it in smaller batches and not waste as much if and when it goes bad.

[Drew Wiley]

Alkaline fixer like TF4 works best for removing the residual pink. But FP4 nevers clears completely of it like TMax, at least until there's either a period of years or strong UV fading due to enlargement. No big deal unless you're trying to factor in exact color printing parameters. I've often used FP4 for unsharp masking of color images, so am quite aware of the .02 to .04 remaining pink magenta density. It's almost undetectable on briefly washed TMax after an alkaline fix.

[Corran]

Eric, I haven't had Pyrocat go bad on me, in Glycol. The foaminess though, I get all the time, with mixed solution. I don't think that's an issue. Hoping some of those images came out - I see the old mill and stump in the river there from Sweetwater :).

[domaz]

Pyrocat can go bad with very little warning in my experience. One subtle clue seems to be the solution color when mixed with water. If it's clearish it should be fine. Very light brown is ok, as it gets darker it can still work but caution should be taken. I could be totally off, but this seems to be the pattern for me at least.

[esearing]

The foaminess is an issue with the SP445 tank if you fill it to about 480mls. The foam seems to limit the agitation flow of the developer, at least I don't get the feeling of the fluid moving inside the tank.

The images are thin and "scanable" with my iphone app but I can tell they are underdeveloped as shadow detail is missing in the zone 3 and possibly zone 4 areas. IE the bricks in the mill on the darkest sides.

I have had a couple of folks email and confirm that the Pyrocat HD in Glycol goes bad suddenly rather than aging to a dark brown.

[Ray Van Nes]

I have had similar issues and it has shaken my confidence in this developer. When it works, it is brilliant but it very upsetting when you lose negatives that are important.

[Jim Noel]

I have been mixing my own Pyrocat in glycol since Sandy's first article about it. Sometimes the "A" solution lasts well over a year prior to use. No problems result. I have had the "B" solution get weak, but I haven't worried about it enough to test. I just throw it out and make more. Foaming is not a problem for me because I don't use any tanks other than JObo Expert occasionally. FP4+ clears well for me in Ryuji's fixer.

[Steve Goldstein]

The A solution of standard Pyrocat-HD has a little bit of water in it, and I understand that this can limit the shelf life. Because I'm not a huge-volume user I've started using the Pyrocat-HDC, which contains no water at all in A (B is the same).

[koraks]

The A solution does not necessarily contain water. The ingredients can directly be mixed in glycol, which is not extremely hygroscopic either. However, both the phenidone and the catechol will oxidize due to the traces of oxygen in the solution, which are added every time you stick a pipette into it or shake/stir the bottle. It is also possible that a manufacturer uses a stock solution of phenidone in alcohol to make the comcentrate; however, in any appreciable volume operation (anything from a liter or more) this would be in my mind unnecessary, and in practice unlikely, and thus hypothetical. Even then, the small amount of alcohol and the water that will invariably be part of it (4% of the alcohol volume) would be quite minimal. A stock solution that is light coloured has not oxidized appreciably, as a significantly oxidized stock solution will be extremely dark.
The B solution going bad is virtually impossible; this is potassium carbonate in an aqaeous solution, which is about as stable as it gets. It'll last years without any change, won't grow mold, etc.

[Andrew O'Neill]

Been using Pyrocat-HD for 16 years. Never had a problem. I just developed a couple of sheets from solutions mixed back in January. Both A and B are mixed from scratch using distilled water. Stored in brown bellows bottles, in a cupboard that is never higher than 20C.

[John Layton]

I must say that I'm suspicious also. I've been using Pyrocat HD in glycol for years with great success...but the most recent batch exhibited foaming upon mixing (1:1:100 from liquid stock), which I'd never noticed before - and my negatives appeared thin and a bit mottled. I always mix from stock using distilled water and must say I have my process down pat...so I do not share this lightly and am frankly distressed.

[Gary Samson]

I have never had a failure with Pyrocat, but I use the Pyrocat M version and mix the A and B solutions from scratch myself using distilled water and storing the solutions in wine bottles with air tight stoppers.

[sanking]

I doubt very much that pink negatives has anything to do with Pyrocat going bad. I have personally never observed any condition in which any of the Pyrocat variations produced a pink color.

On the other hand, if the developer has degraded to the point where it has very little energy one would expect that the pink color of the anti-halation backing would be even more prominent since there would be little image formation and the fixer would then remove the remaining silver.

As for the developer going bad prematurely, I have never observed that except in cases where there was cross-contamination. Pyrocat HD solution mixed in water should be good for at least 6-9 months even in partially full bottles, mixed in glycol the solution should be good for several years.

Foaming is something I have never seen and so far as I can determine there is nothing in the Pyrocat chemicals or glycol that should cause foaming. It is possible that the stock solution was mixed incorrectly, by either the user or a third party. Places like B&S and the Formulary probably keep a record of the production batch and would know that if there have been complaints about the batch.

Sandy

[Peter Lewin]

Marginally off topic, but proof how threads can be useful on related topics. Was mixing up a working solution of PMK this afternoon, and saw that the “A” stock solution was dark brown-red, clearly oxidized as mentioned earlier in this thread for Pyrocat “A.” So, back on topic, I used my good Pyrocat developer instead!

[IanBarber]

The foaminess is an issue with the SP445 tank if you fill it to about 480mls. The foam seems to limit the agitation flow of the developer, at least I don't get the feeling of the fluid moving inside the tank.

I always fill to about this limit, would you suggest lowering the amount we put into the SP445?

[esearing]

I always fill to about this limit, would you suggest lowering the amount we put into the SP445?

Ian , You need some air in the tank for the fluids to move easily or you have to be a bit more aggressive when inverting. There is a tab that sticks out into the fill area, that is fill limit and still allows the squeeze to create vacuum. I only use one holder which creates a bit more space.

I sent a request to Bud at PF for info about batch age and his thoughts on the shelf life. Last year my February purchased batch went bad in October. So I am guessing 9 months if not refrigerated.

[Corran]

Eric - I was curious so I looked up when I ordered my 50L kit, in Glycol. I received it in early December last year. Still working fine. I am getting low, and so I am going to put the rest of the chemicals in the smaller 10L kit bottles I kept from my previous order, for less oxidation. Do you decant your larger kits into smaller bottles ever?

[Andrew Tymon]

I like to decant my pyrocat into small bottles of type 1 plastic that I repurposed, usually medicine or supplement bottles. A pharmacy may sell you some and they come in various sizes. I liked the Target pharmacy bottles as they were a deep red color and some came with a insert for a syringe, which I thought was a smart idea.

[esearing]

So according to Bud at PF my batch #188 was mixed in 2013 (Purchased December 2017). They have newer batches mixed since then, but due to low demand it hangs around. Y'all need to order more!!!

Corran, I did pour some of the 500ML into a 100ML bottle that I work from to prevent the cross contamination. I use the old marbles trick to keep the original bottle close to full. That is why I was disappointed my original nearly full bottle failed too.
I estimate I used about 200mls of Part A of the 500ml. So economically I might do better to buy a 100ML bottle every 6 months since I use it very dilute for one sheet at a time.

I needed some other stuff from elsewhere so placed another order of the non glycol Pyrocat HD version. In theory, I should at least be able to see a color shift as it goes bad.

[Steven Ruttenberg]

I always fill to about this limit, would you suggest lowering the amount we put into the SP445?

Haven't used Pyrocat yet, but I fill to 450ml. I find if I go much more, it will leak out of the caps.

[esearing]

Haven't used Pyrocat yet, but I fill to 450ml. I find if I go much more, it will leak out of the caps.

off topic -- but here are my tips for the sp445 tank; lightly coat the o-ring with silicone or vaseline., squeeze sides to create a slight vacuum when tightening the caps. don't over tighten.

[Corran]

So according to Bud at PF my batch #188 was mixed in 2013 (Purchased December 2017). They have newer batches mixed since then, but due to low demand it hangs around.

Wow, that's pretty bad. So really, the issue is that you were using 5-year-old Pyrocat. I hope they pulled back the amount they mix so that they have fresher stock.

[Doremus Scudder]

Try soaking the negatives in a weak sodium carbonate solution and see if that removes the pink. I have had a similar problem with TMY retaining a lot (a lot more than your negs) of the pink/magenta sensitizing dyes at the end of normal processing. I need an after-bath in the sodium carbonate to eliminate the pink. My problem negs actually start out with a dark blue "veil" which turns to pink/magenta and then clears in the carbonate bath.

Best,

Doremus

[esearing]

New batch of Pyrocat HD non-glycol from B&S and all is right with the world. Nice tan negatives and no more pink. I did have a scare though, the first sheet I developed was blank. Must have forgot to pull the slide.
I may need to retest for time again but my Normal and N- are close for scenes with broad contrast range, but perhaps a tad over. I can see white clouds on blue sky with contrast and plenty of shadow detail.

Note: The Bostick & Sullivan mix comes dry in 500ml bottle for part A, but mixed for Part B in 500ML bottle.

[Andrew Tymon]

Are you going to decant part A into smaller bottles?