White calcite crudballs on my negs after they're dry!! Ideas?

jimgalli · Jan 8, 2006

We photographers just live to progress to ever better and better problems right?

Lately my negs have been suffering from white calcium deposits on them when dry. At first I thought it was just the ones developed in Rodinal since the bottle dates from about 1976 and has some "interesting stuff" in the bottom. But now my Pyrocat negs are experiencing the same problem.

Today I did a batch of 810's and when I was washing in the JOBO I ran a wash of glacial acetic acid on #5 of the 8 washes. No good. Problem still there.

Anybody else got the crudballs?

Normal procedure: JOBO Rotary

1. Prebath for 1 minute

2. Developer in. 10 1/2 min for pcat hd on efke 100

3. 3 consecutive washes in tap water, I do not stop with glacial acetic acid

4. TF-4 fixer

5. 1st wash 2.5M

6. 2nd wash 2.5M with sodium sulfite bath (teaspoon of ss in liter H2O)

7. 3rd through 8th washes at 2.5M each

8. each sheet gets a bath in distilled water plus nothing in clean tray before hung up to dry.

Welcome your ideas. I use tap water for all but the final rinse just before hanging up to dry. Always have. We have nice H2O here in Tonopah. Like I say, this problem occured after 8 years of processing more or less just as I've stated above.

Donald Qualls · Jan 8, 2006

I'd guess your tap water has changed and you're getting more calcium than you were previously. This could happen if a change in rainfall (increase or decrease), possibly many miles away, changed the level of an aquifer (which would cause you to receive water that passed through different strata in the ground from what you usually get), or (if you don't have your own well) your water supplier tapped a different supply (which often happens in droughts). Given what I've seen on the news about the weather out west, however, I doubt drought is your major problem there in northeastern Nevada.

The crudballs you have might well be calcium sulfite, BTW; it's insoluble in water and forms quickly in the developer if there's significant calcium in the water and no sequestrant present. Acetic acid won't help with calcium sulfite, I don't think; it dissolves calcium carbonate by converting the carbonate to bicarbonate, which is slightly soluble in water, but there's no analogous reaction with the sulfite (and in any case, calcium bisulfite, if it were to form, is no more soluble than calcium sulfite).

Try doing a batch with ion-exchange filtered water (i.e. through a Brita filter or similar) -- but be sure to put that water through a fine particulate filter to remove any stray carbon -- or try distilled water for a batch. If you find you need better water, you can buy a water distiller for (IIRC) a couple hundred dollars that will pay for itself in six months of active use compared to buying distilled water in gallon jugs, or if you're the least bit handy with tools you can make a water still from scrap (which, there, you can probably pick up for free). Do avoid iron or steel (other than high quality 304 or 316 stainless) in the still, if you make one...

eumenius · Jan 8, 2006

Hi Jim,
are you really sure that this is a calcium salt deposit? Is it soluble in acetic acid? If not, it can be powder sulfur from the sulfurized fixer. Is your sodium sulfite clean? Sometimes some Ca/Mg ions can form some sulfites, all looking like white deposits. Nice water can be not co nice sometimes, eslecially when it's taken for the artesian well - the salt content can change rapidly and unexpectedly...

PS. You mention a glacial acetic acid - it can't be the pure thing that you have used, no? You always dilute it to, say, 2% - the straight acid is very very corrosive, so it can damage even plastics!

Cheers, Zhenya

eumenius · Jan 8, 2006

I competely agree with Donalds' reply - that's the more clear description of my view If the deionized water is a problem, you may use a boiled cooled water, filtered well through many layers of muslimgauze or cheesecloth. Or you also can conveniently put some divalent ion sequestrant like Versen (EDTA-2Na, Trilon B) in your sulfite bath - I think that 1 g of sequestrant per liter would effectively prevent formation of any bad sulfites with no adverse effects on film itself.

glbeas · Jan 8, 2006

If it really is from calcium deposits a soak in salt water then a few exchanges of distilled should get rid of the worst of it. Sounds like a water softener is needed for the darkroom.

wfwhitaker · Jan 8, 2006

It's one of the plagues. Divine retribution for having too many lenses. Either that or it's alien space eggs from Area 51.

jimgalli · Jan 8, 2006

wfwhitaker said:
It's one of the plagues. Divine retribution for having too many lenses. Either that or it's alien space eggs from Area 51.

So if I grind a Dagor to dust and sprinkle it as an offering????

BTW, thanks all. I'll try the table salt first

me being the lazy type and that being a painless experiment.

wfwhitaker · Jan 8, 2006

Or you could pulverize a Petzval. But I'd go with the table salt.

noseoil · Jan 9, 2006

Are you reusing your TF4 without filtering it? I use a coffee filter and plastic funnel with mine. I've found that over time, Efke films tend to be a good cleaning agent for TF4. The soft emulsion acts like a magnet for all kinds of good stuff. Distilled water for your photo-flo? The coffee filters tend to help. tim

eclarke · Jan 9, 2006

jimgalli said:
So if I grind a Dagor to dust and sprinkle it as an offering????

BTW, thanks all. I'll try the table salt first me being the lazy type and that being a painless experiment.

Hey, When you get to the grocery store, get a couple gallons of distilled water to mix with..Evan Clarke

Stoo Batchelor · Jan 9, 2006

Sorry to hear your having the same problem i've just battled with. It just crept up on me after a good few years of clean negatives. I would agree with everyone else. Your water is to blame. I used a process of elimination, changing my fixer, wetting agent etc. Then finally arrived on the tap water. I've banished it from my development routine completely now.

I would pop down to your local tropical fish centre. If you have a good one, he will have a reverse osmosis water filter fitted, to sell R.O to his customers, and very cheaply too.

Mine charges me 75 pence for 5 ltrs, and I use 10 ltrs ( 2gals ) per 120 film in a 600mm pot. With that I mix my developer, two pre soaks, 5 water baths for stop bath, my fixer, fixer rinse, 3 standing baths to enhance stain, ilford wash process and final rinse. All that for the price of a bottle of beer!

Hope this helps and good luck.

Stoo

P.S . A good sighn to check if its your water, have a look in the cupboard where you keep your measuring jugs etc, you will probably find a thin layer of white dust, thats whats clinging to your film emulsion!

Thomas Bertilsson · Jan 9, 2006

I've been seing the same problem in my negs. I have a feeling our strange weather lately here in the US upper midwest is causing some strange water qualities.
I used to have slight specks of dust on my negs, since my heating system is a forced air furnace. The dust is inavoidable for me. But yesterday I printed some freshly developed negs of FP4 and Tri-X, and I had these huge blobs of deposits showing up in the prints. Made me very uneasy.
I think I'll go for some destilled water too. Or maybe a water softener. Or maybe I'll take a trip to "A world of fish" and buy some RO treated water.

Is it true to say that this would be more crucial for the rinsing stage rather than mixing developer and fixer?

- Thom

jimgalli · Jan 9, 2006

Hope I don't have to go to 100% distilled. That would get expensive with 8X10 in a big Jobo tank. Like 14 liters all told. I have a small still but it's an overnight process for it to make a gallon. With electricity costs, it might be cheaper at the grocery store. Thanks for all the ideas.

Stoo Batchelor · Jan 9, 2006

huggyviking said:
Is it true to say that this would be more crucial for the rinsing stage rather than mixing developer and fixer?

- Thom

It is crucial at the rinsing stage but that alone didn't work for me Thom. Mind you, they were rather large lumps of crud.

Stoo

Bruce Watson · Jan 9, 2006

I had problems with my city water. I was getting very small translucent stuff on my film that would cluster together. Took forever to spot. I never did figure out what it was (thin iron oxide chips?) - but I did eliminate it.

What I did was to go to steam distilled water. For everything. Mixing (stock, and diluting before use, developer, stop, and fix), washing, final rinse, cleanup. No tap water touches the film or the film side of the equipment. Problem solved.

I'm processing with a JOBO 3010 tank and using the Ilford wash method. Total distilled water per run of 10 5x4 sheets is right at 6 liters, or about $1.50 USD.

I don't know if it will solve your problem, but it's cheap to try. It will tell you right away which side of your darkroom faucets has the problem.

dancqu · Jan 9, 2006

jimgalli said:
Like I say, this problem occured after 8 years of
processing more or less just as I've stated above.

Perhaps it's the more. Perhaps it's the less. Posts of this
sort pop up quite often:
After-years-and-years-of-doing-it-the-same-way ...

If the method and it's execution are the same then it
has to be the materials involved in the process. The more
or the less could make a difference if some other factor or
factors interact in some noticeable manor. Dan

Maine-iac · Jan 12, 2006

jimgalli said:
Lately my negs have been suffering from white calcium deposits on them when dry. At first I thought it was just the ones developed in Rodinal since the bottle dates from about 1976 and has some "interesting stuff" in the bottom. But now my Pyrocat negs are experiencing the same problem.

Today I did a batch of 810's and when I was washing in the JOBO I ran a wash of glacial acetic acid on #5 of the 8 washes. No good. Problem still there.

Anybody else got the crudballs?

If it really is calcium, then a final rinse, just before hanging up to dry in water with some water-softening crystals in it will do the trick. While living in Paris, the tap water had visible crystals of calcium in it, and initially, I was getting globs of the stuff drying onto my film. So after final washing, I simply dunked the reels into a beaker of water with a teaspoon or so of water softening crystals in it, hung it up, and "sqeegeed" it between my forefinger and middle finger (which I had also dipped into the softened water). Eliminated the problem completely. And you can keep re-using the softened water rinse for a long time before needing to replace it. I just kept a beaker of it sitting around with a cover over it to keep dust out.

Larry

jimgalli · Apr 13, 2007

This is an old thread but thought I would update it with the solution I found.

The problem continued for a time until I started introducing Calgon. Calgon is Sodium Hexametaphosphate. You can do searches at Ebay under the chemical name and buy a supply for 50 lifetimes from industrial water treatment sellers. It is the same stuff that makes your wine glasses sparkle in the dishwasher. A water surfactant for hard water which we have out here in the desert. It solved my problem with the negs and also leaves the Jobo tank sparkly clean. I put enough granules to cover 2/3 of a nickel in a liter of water in my final wash. I've never weighed that amount on a scale. 1/4 teaspoon would be close. Hi Aggie!

Donald Miller · Apr 14, 2007

White calcite crudballs on my negs after they're dry!! Ideas?

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