Photo Forum / Film Photography / Darkroom / February 2006
exhausted fixer: what risks?
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Gianni Rondinini - 06 Feb 2006 17:15 GMT i'm reading adam's book "the negative", but i haven't reached the dark room chapters yet. i wouldn't want to jump forward and backward while reading that book, then here i am with this question.
yesterday evening i was in my darkroom to develop some rolls i shot this summer during our holidays in south west usa.
kodak declares that 1 liter of (1+4)-solution of tmax fix can fix 12 rolls. using my deltas, after 8 rolls the fixer began being exhausted, because the rolls remained slightly violet. frames seemed to be ok: contrasty, dense and so on, but the whole stripe was slightly violet. i didn't notice it because the colour was very light, then went on using that fixer for 2 more rolls. the following ones (9th and 10th, say, using that liter of solution) remained very violet-ish. i noticed it as soon as i took them out of the tank: at this point, i trashed the exhausted fixer, immediately prepared a liter of fresh one and then re-fixed the rolls. i, then, used my wetting agent and when i took the rolls out of the reel they were perfectly transparent and with good contrast and density, exactly as i expected them to be. when i hang them to dry, i saw that the previous ones (that had been hang for about one hour) were slightly violet, then i put them back into the fixer bath, then the wetting agent and so on. at these point these 2 rolls seem to be ok, but i'm wondering what may happen to the negatives in this way; i mean: with an uneven or incomplete fixing, can the negatives get damaged? and how long can a negative stay with an incomplete fixing before getting damaged? hours? days? months?
thanks in advance and excuse my newbie questions.
regards,
 Signature Gianni Rondinini (30, tanti, RA) Nikon user - Bmw driver http://bugbarbeq.deviantart.com
Tom Phillips - 06 Feb 2006 22:20 GMT > i'm reading adam's book "the negative", but i haven't reached the dark > room chapters yet. i wouldn't want to jump forward and backward while [quoted text clipped - 25 lines] > > thanks in advance and excuse my newbie questions. One assumes your talking about T-max or some other t-grained film? The purple stain you see is a sensitizing dye. It's normal to have a slight residue after fixing but this should be gone after using a hypo clearing wash agent. If not refix. As far as refixing already washed and dried film, it takes more than a hour for residual silver to affect it. But if there's a purple stain after both fixing and washing the film is either inadequately fixed or you didn't remove all silver thiosulfate complexes by using a hypo clear before washing. Should also wash a good 10 minutes.
Generally as you use a film fixing bath you would need to lengthen the fix time as you approach it's maximum capacity. IOW if you fix the first few rolls for 6-7 minutes you would need to fix the remaining rolls for increasing longer times. Some people recommend using a two bath fixer with t-grain films like tmax, delta etc. to help insure complete fixing and it would also reduce fixer byproducts. Whether you do or not its a good idea to fix these films for 3 times the clearing time instead of the normal recommended 2 times the clearing time for non t-grain films.
Gianni Rondinini - 07 Feb 2006 13:24 GMT >One assumes your talking about T-max or some >other t-grained film? The purple stain you see i'm sorry: i forgot to write that yes, i was talking about ilford delta's, that are t-grained films.
>slight residue after fixing but this should be >gone after using a hypo clearing wash agent. If i've never used hypo clearing wash agent: i'm just using a wetting agent (agepon 1+200).
>not refix. As far as refixing already washed and [...]
>thiosulfate complexes by using a hypo clear before >washing. Should also wash a good 10 minutes. i'm beginning to think that i should consider starting using a hypo clearing...
i think that adding some more info will help you understanding what may be my problem. 1. i develop 2. a couple of rinses with fresh water (no stop bath) 3. fixing (see later for times) 4. inford simplified washing (2 rinses with water, 1 rinse with 5 agitations, 1 rinse with 10 agitations, 1 rinse with 20 agitations); water is very expensive and limited here, this is why i chose this way of washing my films. 5. a couple of minutes in wetting agent, while i wash tank cap and i prepare the developer for next rolls.
>maximum capacity. IOW if you fix the first few rolls >for 6-7 minutes you would need to fix the remaining kodak declares 2-5 minutes for tmax fix, then i usually fix the first films about 3 minutes, the next ones 4 minutes, the following ones 5 minutes. i have seen that after 6 120 rolls of delta's, tmax fix seems to be exhausted, then i'm not going any further than this. *but*, last two rolls already seem to be a little bit violet-ish, sometimes, so i was worried about damages my negatives could get by this.
>you do or not its a good idea to fix these films >for 3 times the clearing time instead of the normal >recommended 2 times the clearing time for non >t-grain films. i'll have a look at their clearing time: i had trusted in fixer sticker instead of checking it by hand.
thanks for your reply.
 Signature Gianni Rondinini (30, tanti, RA) Nikon user - Bmw driver http://bugbarbeq.deviantart.com
Tom Phillips - 08 Feb 2006 00:34 GMT snip..
> i've never used hypo clearing wash agent: i'm just using a wetting > agent (agepon 1+200). [quoted text clipped - 18 lines] > 5. a couple of minutes in wetting agent, while i wash tank cap and i > prepare the developer for next rolls. You should use a stop bath. Using a stop bath for 30-60 seconds (30 seconds minimum to allow the acid solution to soak completely into the emulsion) will prevent any developer carry over which will weaken the fix and shorten it's life/capacity. I also would never use a fixer to exhaustion. And as others have commented fixer isn't particularly toxic to the environment so long as the effluent is treated by your local Sewer/Sanitation District. Most photo chemicals are easily handled by sewage treatment. A good practice is to mix your used developer (alkaline) and fixer (acid) together to neutralize them before dumping.
Also, using a hypo clearing agent will shorten wash times and improve washing efficaciousness. I generally give a 10 minute wash with t-grained films after 2-3 minutes in hypo clear. Your fill and dump w/agitation rinse method is fine, so long as you use enough rinses. But I would test the results using the HT-2 wash/fixer residue test.
> >maximum capacity. IOW if you fix the first few rolls > >for 6-7 minutes you would need to fix the remaining > > kodak declares 2-5 minutes for tmax fix, Not long enough...
then i usually fix the first
> films about 3 minutes, the next ones 4 minutes, the following ones 5 > minutes. i have seen that after 6 120 rolls of delta's, tmax fix seems > to be exhausted, then i'm not going any further than this. > *but*, last two rolls already seem to be a little bit violet-ish, > sometimes, so i was worried about damages my negatives could get by > this. Like I say you can simply refix. The effect unremoved silver halides will have on negatives that are improperly fixed will be more pronounced the longer the time (i.e., days or weeks.)
> >you do or not its a good idea to fix these films > >for 3 times the clearing time instead of the normal [quoted text clipped - 9 lines] > Nikon user - Bmw driver > http://bugbarbeq.deviantart.com dan.c.quinn@att.net - 06 Feb 2006 22:37 GMT I use fresh fix for each roll. Add 20 ml of concentrate to whatever solution volume needed to do one roll. Give 5 minutes with constant agitation and take a look. Give another 2 or 3 minutes if needed. Toss the fix when done. Dan
Peter Irwin - 07 Feb 2006 00:17 GMT > kodak declares that 1 liter of (1+4)-solution of tmax fix can fix 12 > rolls. using my deltas, after 8 rolls the fixer began being exhausted, > because the rolls remained slightly violet. I wouldn't worry too much about a bit of the dye remaining in the film, but I would suggest moving to a two bath system. I'm not an expert, so don't take my opinions as gospel, but I can assure you that using a two bath system is easy and once you get in the habit it is not significantly more work than a single fixing bath.
The big advantage of the two bath system is that you can be sure that you are fixing properly because the second bath is always pretty fresh. You could also use fresh fix every time, which wouldn't be as economical but would give you the same assurance.
Make up two bottles of film strength fixer. Label the bottles "one" and "two." Use the fixer from bottle one for four minutes (if using a rapid fixer, I use Kodak Fixer for six minutes each bath). Pour the fixer back into bottle one, and then use fixer two for another four minutes.
It is safe to inspect film after the first fix, and if the fixer seems to be getting tired then discard the first fixer, pour the second fixer into bottle "one" and make up fresh fixer for bottle "two." After a few cycles you should start over with two fresh baths. I make fresh baths every time I finish a gallon of fixer.
I get around 40 rolls per gallon from Kodak Fixer. I think this is fairly conservative for a two bath system. You should get somewhat more than this from rapid fixer. My bottles hold around 600ml. I get 10-12 rolls from from a fresh first bath, and around 6-8 from a first bath which was formerly a second bath. If I am shooting a lot of Pan-F the fixer capacity seems higher than this, if I am using a lot of Tmax-100 the fixer capacity is less. Fixer is cheap, so if in doubt, change fixing baths.
It may do some good to refix film if it has been less than a couple weeks since they were fixed, but I wouldn't worry too much about a bit of pink dye. It doesn't sound like you have been seriously overworking your fixer.
Peter.
 Signature pirwin@ktb.net
Gianni Rondinini - 07 Feb 2006 13:24 GMT >I wouldn't worry too much about a bit of the dye remaining >in the film, but I would suggest moving to a two bath system. [...]
you're not the first that suggests this, then i'll do it. thanks also for the explanation of what a 2 bath system is: i've read about people that uses it, but never read what it exactly is.
>bath is always pretty fresh. You could also use fresh fix >every time, which wouldn't be as economical but would give >you the same assurance. i try to exhaust the fixer both for a reason of economy and pollution. i mean, if i throw away half a liter of fixer every roll or every 5 rolls, chances are that i pollute less. i feel better with myself in the latter case :)
>"one" and "two." Use the fixer from bottle one for four [...]
ok, i got it.
>I get around 40 rolls per gallon from Kodak Fixer. I think this that's good. with tmax fix i don't get as many. i think i'll go once more with tmax fix because it's easy to find here in italy. an alternative would be ornano st-205 (an italian brand), but i'm never able to use 100% of the bottle because, even if in a tightly closed non-filled bottle, it deposits "salts" at the bottom of the bottle quite quickly.
>somewhat more than this from rapid fixer. My bottles hold >around 600ml. I get 10-12 rolls from from a fresh first bath, mine too. i have 600ml glass bottles that perhaps i'll replace with 600 and 1000ml plastic bottles with wider... ehm... where you remove the cap :) those are far easier to clean and wash after use.
>bath. If I am shooting a lot of Pan-F the fixer capacity seems >higher than this, if I am using a lot of Tmax-100 the fixer >capacity is less. Fixer is cheap, so if in doubt, change fixing good. i use pan-f/fp4+ and delta 100/400, then results should be comparable as numbers.
>It may do some good to refix film if it has been less than >a couple weeks since they were fixed, but I wouldn't worry ok, i may give them another fix, in case. the important is that my negatives didn't get damaged by such a fixing.
>too much about a bit of pink dye. It doesn't sound like >you have been seriously overworking your fixer. ok, thanks. indeed, the pink/violet dye is *very* light, so light that i could notice it only when i took a negative and put it, on a white paper, next to a "perfect" one, which allowed me to see that the other one had this dye.
i'll, perhaps, fix my negatives with longer times and a slightly higher temperature in the future.
regards,
 Signature Gianni Rondinini (30, tanti, RA) Nikon user - Bmw driver http://bugbarbeq.deviantart.com
Lloyd Erlick - 07 Feb 2006 18:09 GMT >i try to exhaust the fixer both for a reason of economy and pollution. >i mean, if i throw away half a liter of fixer every roll or every 5 >rolls, chances are that i pollute less. i feel better with myself in >the latter case :) February 7, 2006, from Lloyd Erlick,
This is not strictly true. Fixer components themselves are not particularly bad substances, so dumping unused fixer would not be much of an environmental problem.
Silver compounds in the fixer are the problem. Thus, the more film or paper that is fixed, the worse the fixer would be as an environmental effluent. The size of the problem of fixer/silver effluent is directly related to the amount of photosensitive material used.
I have a few articles on my website - heylloyd.com - that might be of interest.
regards, --le
 Signature ________________________________ Lloyd Erlick Portraits, Toronto. voice: 416-686-0326 email: portrait@heylloyd.com net: www.heylloyd.com ________________________________
Peter Irwin - 07 Feb 2006 18:20 GMT > you're not the first that suggests this, then i'll do it. > thanks also for the explanation of what a 2 bath system is: i've read > about people that uses it, but never read what it exactly is. I'm glad if my description helped. I've been doing it for the last few years, and it seems natural to me now, but before I started doing it it sounded like a lot of extra work. It isn't.
> i try to exhaust the fixer both for a reason of economy and pollution. > i mean, if i throw away half a liter of fixer every roll or every 5 > rolls, chances are that i pollute less. i feel better with myself in > the latter case :) Fresh fixer by itself is (AFAIK) not particularly toxic or bad for the environment. I wouldn't recommend drinking it without a good medical reason, but from what I understand it would be unlikely to do you lasting harm. Used fixer contains silver which is toxic and an environmental problem. I confess that I pour mine down the drain, and I probably should investigate where to take my spent fixer so that someone can extract the silver for re-use. You might try asking at photographic shops if there is a place for you to take spent fixer.
Severely overworking the first fixing bath is not a good idea because it just shifts most of the work to the second bath and the whole point of the two bath approach is to keep the second bath fairly fresh.
Richard Knoppow has posted the proper way of checking the activity of fixer. Another method which is probably not quite as good is to check the amount of time it takes to "clear" a negative. An unfixed negative has a milky white emulsion which becomes clear in the fixer. Fixing is only half done when the negative clears. To test clearing time with a piece of scrap film you should first soak the film in water for a few minutes, then put the film in the fixer and measure the time until the negative becomes clear. It is important that the film should be wet before it is put in the fixer for testing. Traditionally fixer is said to be exhausted when the clearing time is double what it is in fresh fixer, it is probably better to play it safe and stop using the first bath when clearing time is one and a half times the clearing time for fresh fixer.
Total fixing time should be at least twice the clearing time, and it is probably safer to aim for three times the clearing time. It is possible to "overfix" films and bleach the image, but this seems to take a _very_ long time to happen to any noticeable extent, so it shouldn't be a big worry.
Peter
 Signature pirwin@ktb.net
Ken Hart - 07 Feb 2006 20:01 GMT snip lots
> i'll, perhaps, fix my negatives with longer times and a slightly > higher temperature in the future. Longer times in the fixer is alright, but try to keep all the chemicals close in temperature. Don't develope at 68F and fix at 80F.
 Signature Ken Hart kwhart@aec.nu
Richard Knoppow - 07 Feb 2006 02:13 GMT > i'm reading adam's book "the negative", but i haven't > reached the dark [quoted text clipped - 48 lines] > > regards, Peter Irwin's advice about 2 bath fixing is a very good idea. The capacity of single baths to handle tabular grain films like T-Max is considerably less than for conventional film. Rapid fixer is less sensitive to the residual chemicals that come out in the fixer and lasts longer with these films. Some say that a single bath is sufficient with rapid fixer but I prefer to use a two bath system. It is impossible to give exact capacity for fixer because the capacity depends on how much halide the fixer must remove from the film. Its less where a lot of the halide has been developed into metallic silver. The capacity is also affected by Iodides and other materials which leach out of the film, but its mostly limited by the amount of silver dissolved in the fixer. The effectiveness of the fixer should be tested directly by using a sulfide test on the film or on a sample of paper processed through the system. One can also test for dissolved silver by using a solution of Potassium Iodide. This will precipitate some of the dissolved silver in the hypo sample. If a could forms and does not redissolve in a couple of seconds the fixer should be discarded. The Sulfide test on the emulsion is a better test since it measures the amount of halide left in the emulsion and its possible for the Iodide test to indicate the fixer is still good after its not completely fixing. I will post the formulas for these solutions below. Any unfixed halide, or the intermediate fixing products, begin to change in a couple of weeks. Once this process has begun refixing will not completely remove them. Michael Gudzinowicz posted complete explanations of what goes on in the fixing process to this group some years ago. His posts are still available on Google, a name search in this group will find them. Test for exhausted fixer. Kodak Fixer Test Solution FT-1 Water (at 80F or 27C) 750.0 ml Potassium Iodide 190.0 ml Water to make 1.0 liter
For use, to 5 drops of the test solution add 5 drops of fixing bath and 5 drops of water. If a permanent precipitate forms discard the fixer. This solution will last up to 1 year in a filled, closed bottle. Note: This is a life time supply. I suggest making up 50 or 100 ml.
Residual Silver Halide Test Kodak Residual Silver Test Soluton (Stock) ST-1 Water 100.0 ml Sodium Sulfide, anhydrous (not Sulfite) 2.0 grams
Store in a small stoppered bottle for no more than 3 months.
To use dilute the above solution 1 part to 9 parts water. Place a drop or two in a clear area of the negative or print, preferably outside of the image area. Allow to stand for 2 or 3 minutes and blot off. There should be no visible stain. Note, if not stabilized this solution will eventually cause a yellow stain. This stain is not indicative of the presense of halides. There is a more complex version of this test that stabilizes the test stain so that it can be compared with a standard using a densitometer. This more complex version is not necessary for routine testing. For prints I suggest processing a test strip along with the prints for testing purposes.
I will give in addition the Kodak formula for a wash test. This test indicates residual hypo.
Kodak Residual Hypo Test Solution HT-2
Water (deionized) 750.0 ml 28% Acetic Acid 125.0 ml Silver Nitrate (crystals) 7.5 grams Water to make 1.0 liter
Again, this is a life time supply, make it up in 50 or 100 ml amounts.
Store the solution in an air tight bottle away from light and excessive heat. It will last about 6 months. It will cause black stains on hands or clothes if not removed promptly. To use apply a drop or two on an unexposed section of the film or paper and allow to stand for about 2 minutes. Then rinse the test solution off with water and blot. Even well washed film or prints will leave a slight yellow stain. There is a comparison chart in the Kodak book _The Kodak Black and White Darkroom Dataguide_ Publication R-20 CAT828 9029 I believe this is still available. Kodak also used to publish strips called Kodak Hypo Estimating Strips which had a more complete set of comparison chips. I don't know if this is still available.
A 1:9 dilution of Kodak Rapid Selenium Toner can be used in place of the 2% Sodium Sulfide test or residual silver but is no longer recommended because it fails under some conditions.
 Signature --- Richard Knoppow Los Angeles, CA, USA dickburk@ix.netcom.com
Gianni Rondinini - 07 Feb 2006 10:39 GMT > Peter Irwin's advice about 2 bath fixing is a very good >idea. The capacity of single baths to handle tabular grain [...]
thanks for your long post. i'm going to print it immediately and will read it during lunch pause or this evening.
regards,
 Signature Gianni Rondinini (30, tanti, RA) Nikon user - Bmw driver http://bugbarbeq.deviantart.com
Richard Knoppow - 08 Feb 2006 01:31 GMT >> Peter Irwin's advice about 2 bath fixing is a very good >>idea. The capacity of single baths to handle tabular grain [quoted text clipped - 5 lines] > > regards, A correction: the quantity of Potassium Iodide for the fixer test solution is given in milliliters, it should be in grams.
 Signature --- Richard Knoppow Los Angeles, CA, USA dickburk@ix.netcom.com
Richard Knoppow - 08 Feb 2006 01:47 GMT >> Peter Irwin's advice about 2 bath fixing is a very good >>idea. The capacity of single baths to handle tabular grain [quoted text clipped - 5 lines] > > regards, Oh dear, a couple of other notes. Testing fixer. A very good test for fixer is to measure the clearing time of the film you are using when the fixer is fresh and unused. Then measure it occasionally as its used. A small clip of film is all thats needed. Soak dry film in plain water for about 2 minutes before putting it in the fixer. This is because dry film fixes at a slightly different rate than wetted film. The old rule of thumb was to discard the fixer when the clearing time doubled. This is probably too liberal for a single bath but is probably about right for the first bath of a two bath fixing system. Again, the best test is the residual silver test because this is a direct measure of the completeness of fixing. The rule of thumb for fixing time is twice the clearing time. This is fine where a fresh single bath or a two bath fixer is used. However, as fixer becomes more loaded with dissolved silver there may not be enough free thiosulfate ions to complete the fixing processes in any length of time. For tabular grain films in sodium thiosulfate fixer three times the clearing time may be a better rule but I have not found excessive silver using the sulfide test after double the clearing time. A little extra time will not hurt. For paper there is a danger of slight bleaching of highlights when film strength _acid_ rapid fixer is used. A neutral rapid fixer, as sold for color processing, does not have the bleaching effects. The main reason a weaker dilution of rapid fixer is given for paper is to avoid this problem. Determining fixing time for paper is not so simple as for film because generally clearing can not be seen easily. However, the sulfide test works fine. If you are in doubt about fixing time takes several small test strips of paper, soak them for a few minutes and fix them for various times (mark them on the back). The wash as usual (or use a wash aid and wash as usual). Then test with the sulfide solution. The first strip with no stain will be tell the minimum time.
Another after thought. For a final rinse for film I have been using a solution I first saw suggested by Micheal Gudzinowicz.
Clean water 1.0 liter Isopropyl Alcohol, 70% (rubbing alcohol) 35.0 ml Kodak Photo Flo 2.5 ml
Soak the film in this for 1 or 2 minutes with occasional agitation. Then hang up to dry without squeegeeing. If stronger Isopropyl is used adjust the amount according to the percentage. Use rubbing alcohol that is just alcohol and water, not the kind flavored with oil of wintergreen. The Photo Flo is used at half the strength that would be used alone. The combination of the Photo Flo and alcohol makes a sort of super wetting agent. If you must wash in dirty water this final rinse will wash off any junk on the film when made up with clean water.
 Signature --- Richard Knoppow Los Angeles, CA, USA dickburk@ix.netcom.com
Gianni Rondinini - 08 Feb 2006 10:50 GMT i wanted to thank everybody for all your replies. it will take some hours to read and study them and i'm going to try all of this this friday evening, that is the evening i usually spend in my darkroom.
have a nice day!
 Signature Gianni Rondinini (30, tanti, RA) Nikon user - Bmw driver http://bugbarbeq.deviantart.com
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