Replenished XTOL too strong?

ALCON: I've been using an XTOL replenished developer for the past year or so. I generally add 70-75mL of fresh XTOL to every 36 frame roll of 35mm, or per 1 roll of 120. The system had been working fine, whether I was developing several rolls per week, or if it sat for a month or two. I keep both the replenished developer and fresh stock in dark glass bottles filled to the top so that none--or very little--of either is exposed to air. Last week I started noticing that my negatives were coming out overdeveloped. The leaders were much more darker than previous rolls, and images were all darker, quite contrasty, with highlights being blown and/or little shadow detail.

I didn't know if this was a camera metering issue (was using a Minolta X-700), a lens issue or just the developer. So, I ran a series of tests using TRI-X 400, both in the replenished developer and in the fresh stock (1:1). Negatives were still coming out to what appeared to be overdeveloped. So then I tried a second camera (another X-700 that I had), using the same lenses. However, when changing cameras, I forgot to set the ISO dial to 400 (it was set on 800). Wouldn't you know, while the exposed leaders were still a lot darker than normal, the images at EI800 (but developed at 9 minutes XTOL 1:1 for EI400) seemed to be a lot better.

My conclusion is that my fresh XTOL stock is not mixed properly, and is too strong. Or could something have become contaminated? I only have half a liter of that stock left, so was considering just tossing it and remixing another batch of fresh XTOL stock. But I'm also wondering if I should toss out my replenished stock and start over. Or... cut back on developing time and wait for the replenisher to become diluted to the point it was producing acceptable results.

I think you can rule out contamination, but mixing strength/dilution sounds like a good place to start. Happened to me just a couple of weeks ago. I read the formulae CC numbers and when I got to the mixing beaker they had changed. Yes, my brain inverted the numbers. Typically known as an adult "BRAIN FART". I thinks we all has 'em from time to time. JohnW

Oh, I would try to think where I screwed up and then take an educated guess on dilution.

I suggest you reconsider two elements of your technique:

1. Leader density is a poor indicator of film speed or development. Film manufacturers carefully control the manufacturing of film so when it is exposed to a fraction of a meter candle second (MCS) of light then when properly developed it will have a predictable density. Leaders are exposed to tens of orders of magnitude more MCS in a totally uncontrolled manner. Not a reliable measure of photographic performance.

2. Intermittent use of a replenished process with no sensitometric monitoring and no adjustment may or may not approximate a fresh process. With multiple film types, inconsistent times between processing sessions, varying film load, different exposure levels, etc. all add variability to the film development process. It is unlikely a set replenishment rate will accurately compensate for this variability especially over many cycles and a long period of time. Manufacturer's replenished recommendation are best applied to daily use when one or more photographers are exposing and processing film nearly every day. For consistent developing results I suggest one-use of developer solutions and storing the stock solution in full (no air) glass bottles. Use glass marbles to take up the air space. This will yield far more reliable result than replenishment for a modest or no increase in cost.

Just my thoughts based on lots of experience with one-shot and replenished developing systems.

laser said:

1. Leader density is a poor indicator of film speed or development.

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Not going to argue, especially when I don't have any empirical way of measuring. However... when the density of film leaders change from the same film stock and the same developer from batch to batch, I would take that as an indicator that something has changed. Add to that the discernible changes in the negatives themselves.

laser said:

For consistent developing results I suggest one-use of developer solutions and storing the stock solution in full (no air) glass bottles. Use glass marbles to take up the air space.

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Maybe I wasn't clear in my description, but this is exactly how I stored the stock solution. And as I mentioned, there was no change between replenished developer and the 1:1 stock solution in my testing. Only when I accidentally pushed the TRI-X 1 stop, but developed it normal in the stock 1:1, was I able to see that the developer (both the replenished and the stock (which I had recently introduced to the replenished developer)) was too strong. It is for that reason I think my stock XTOL wasn't mixed properly. Nor do I believe there was anything wrong with the replenished developer, other than I had been feeding it improper stock XTOL.

Dont rule out Temperature.
Has something happened to your thermometer?

Duceman said:

my fresh XTOL stock is not mixed properly, and is too strong.

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How can this happen assuming you followed the mixing instructions?

Duceman said:

so was considering just tossing it and remixing another batch of fresh XTOL stock. But I'm also wondering if I should toss out my replenished stock and start over. Or... cut back on developing time and wait for the replenisher to become diluted to the point it was producing acceptable results.

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Up to you. Both approaches will work. I will say though that Xtol-R activity is always fluctuating, after 2 years of frustration I gave up and purchased a densitometer and a roll of control strips. Life is so much simpler once you have your developer activity level expressed as a number and tracked over time in a spreadsheet.

michaelfoto said:

Dont rule out Temperature.
Has something happened to your thermometer?

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Didn't think about that. Was using a digital thermo pen; maybe it's off. Will check it against my old (but trustworthy) thermometer.

There is always the possibility as well that for the films you have been developing and the workflow you have that less than 70 ml per roll is appropriate for you.
Particularly if there are lots of dark and moody subjects in your photography, along with a decent percentage of shorter than 135-36 rolls.
Most likely though that would show itself in a gradual increase in activity.

Is there any possibility this could be from depleted fixer? The negatives aren't milky, but the fixer (Ilford Rapid Fixer diluted from concentrate solution) may be at the end of its useful life.

Duceman said:

Is there any possibility this could be from depleted fixer? The negatives aren't milky, but the fixer (Ilford Rapid Fixer diluted from concentrate solution) may be at the end of its useful life.

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It would be easy to test - refix in fresh fixer.
But I don't think that is the problem.
One quibble about word choice.

Duceman said:

Only when I accidentally pushed the TRI-X 1 stop

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It is a bit of a hobby horse of mine, but "pushing" really only refers to increasing development. A "push" development is increased development - often done to partially compensate for under-exposure. What you were meaning here was that you decreased exposure by one stop - no "pushing" involved. I only bring this up because my initial mis-read of your post had me thinking that you had increased your development time.

Duceman said:

Is there any possibility this could be from depleted fixer? The negatives aren't milky, but the fixer (Ilford Rapid Fixer diluted from concentrate solution) may be at the end of its useful life.

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I'm doubtful, mainly cuz I'd expect that you'd recognize the appearance. But the standard test is to refix in a known good fixer. I realize that you're not sure if it's still good, but you could probably use a piece of fresh leader to see how well it works. If the fixer is at all functional, and assuming the original film IS INCOMPLETELY FIXED, you'd probably see a change on refixing. One way to see this is to clip through the middle of a bad frame. After refixing you can butt the clip up against the original - it will be easy to see any changes.

Duceman said:

My conclusion is that my fresh XTOL stock is not mixed properly, and is too strong. Or could something have become contaminated? I only have half a liter of that stock left, so was considering just tossing it and remixing another batch of fresh XTOL stock. But I'm also wondering if I should toss out my replenished stock and start over.

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I would suggest that you go ahead and mix the fresh batch of Xtol. But... rather than discard the remaining half liter, do a test comparison between the two. That way you'll have a better idea of what went wrong.

If I might make a suggestion for testing... first, set up a test scene to photograph. Shoot an entire roll of that scene with the same exposure (manually set). This is gonna be your test film whenever you wanna verify something. So keep it in a zip lock bag, or the like, along with a label. When you wanna do a test clip off about 2 frames (in the dark, obviously). You can manually develop in the dark, with a small amount of developer in a beaker, or whatever. Where I'm from we used to use disposable plastic forceps (they're self-locking) to hold things like this. If you wanna compare two developers at the same time you could rig up a holder - say two binder clips on an old wooden ruler, etc., then hand develop while using two separate beakers. Being on the same holder means that both will get the same agitation, more or less, so it should be a pretty good comparison. Anyway, having a reference like this might help solve future problems.

If you were to also start keeping a notebook or some other sort of log it might be useful in answering questions. For example, you have some question as to whether you mixed the Xtol properly. If you recorded the details, including "topped up to X volume," and that sort of thing, you wouldn't have to second-guess whether there was a mixing error, etc.

Fwiw forum member laser was also the editor of the chapter on "Processing Methods" in the IS&T Handbook of Photographic Science and Engineering. On that basis alone I'd say that careful consideration should be given to anything he says.

Just a few further thoughts from a guy with pretty substantial process and QC experience. Best of luck.

Mr Bill said:

Fwiw forum member laser was also the editor of the chapter on "Processing Methods" in the IS&T Handbook of Photographic Science and Engineering. On that basis alone I'd say that careful consideration should be given to anything he says.

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I understand that, and like I said, I wasn't about to argue. However, to the extent his comments were directed at the replenished developer, I'm not sure if he understood that my fresh stock of XTOL (at 1:1) was giving me similar results (i.e., the problem appears to be the fresh stock, not the replenished developer).