Slowing or halting the decline of my negatives

Jarin Blaschke · Aug 7, 2018

Hello.

Sorry, it's a long one:

I just picked up one of my oldest binders of negatives from my father's house to add to my other 13 binders that I have with me at home in Los Angeles, which date to the present. The 35mm, 120 and 4x5 negs in this particular older binder date from 1997-1999. The pages are largely Print File filing pages, with some BesFile pages, within a black, fully closing Besfile binder.

Opening and flipping through memory lane, I was dismayed to find the definite beginnings of silver mirroring throughout the black and white negatives in the binder. On the emulsion side, silver-rich areas sometimes reflect a flat blue, with green and yellow fringes to the affected area. I was somewhat surprised because it's only been 20 years and silver is supposed to last for ages. Photographers and preservationists often print from negatives that are many many years older. Seemingly you can make a gorgeous print of Pepper #30 today, or heck, something 50 years older than that.

After the shock, I realized that I don't quite remember how stringent my fixing and washing was back then, a couple years after high school. I also lived in New York City apartments from 1995-2011 with great seasonal fluctuations in temperature and presumably less than ideal pollution conditions. The negs have been in the same Print File pages since the beginning. The sampling of BesFile negs is much smaller, but none of the clearer, BesFile negs show any of the mirroring.

I haven't yet scrutinized my other binders that post-date the problem group, but I'm alarmed an concerned - around 2000/2001 I finally started to take genuinely GOOD photographs, and regardless I want the preservation of the record of my life as I photographed it, starting in 1994.

I am about to move to northern California, with good air quality (maybe not in fire season however).

---
So, how does one ensure a safe place for the silver (and dye) records to reside for at least the rest of my life, and ideally a couple generations?

Can I virtually halt the decay of negatives that have already started their decline, or are the pollutants hopelessly embedded in the media doing their dastardly work at full speed forever?

Is thee any sense in rewashing important negatives?

Negatives in Print File pages are wonderfully organized, clear, and easy to find, but in reality are they archivally dubious? Do I ditch the binders too? What are the alternatives, and how do you file negatives in a way that you can see and find them easily? For example, filing 35mm negs in 6-frame glassine strips seems horribly opaque, bulky and cluttered.

Is some airflow actually good for negatives?

Are there somewhat affordable, temperature and humidity-controlled vaults for negatives, like those for wine? If so, are they worth it?

Thanks!!

-Jarin

zanxion72 · Aug 7, 2018

That is strange. I store my negatives in folded A4 paper sheets one atop the other to keep them flat. I have negatives from 1993 like this in a carton box and have no problems so far. No airflow, just a couple of silica de-hydrant sacks in the box (have them in there for five years or more, perhaps I should replace them).

Could it be negatives not fixed/washed enough to make the silver and the emulsion side forever stable?

guangong · Aug 7, 2018

I have negatives from beginning of 20th century that my grandmother kept in pasteboard candy box in Southern house with no air conditioning that have suffered no discernible deterioration. Your negatives suffer from incomplete fixing and washing. Most likely you were too eager to “see the results” of your picture taking back then, which was perfectly natural behavior. You could try fixing and washing again.

Agulliver · Aug 7, 2018

I know this is the UK but I have taken responsibility for storage and preservation of prints and negatives for pretty much my whole family. I have boxes of negatives, slides and prints dating back to the 1940s. A few Perutz-Chrome slides have faded such that only monochrome images can be produced....but everything else including the glass plates is fine.

My own B&W processing dates back to 1981 for prints and 1986 for films, and I know that as a child my washing "technique" left much to be desired....but those prints are sitll good and I was making new scans and optical prints from a roll of HP5 I shot in 1986 just last December.

I'd suggest you could try to re-wash some negatives and see if it has any effect? Negatives can be safely cleaned with isopropyl alcohol but it sounds like some sort of chemical reaction has been happening with your negatives....so I'd be careful and try some less important frames first.

DDTJRAC · Aug 7, 2018

Archival Printfile pages turn yellow in 15 to 20 years. Maybe that had something to do with it. Don't know.

Google:

'Just because it is marked archival…it does not mean it IS archival!'

You can see the Printfile page article.

I have had little luck with reprocessing prints or negs that were decomposing due to poor processing. I manage a huge print and film archive. I have negs going way back that have no issues. So yes, your negs should have lasted. Acetate film stock showing signs of vinegar syndrome have to be frozen to halt the decay. They cannot be fixed or reversed. Freezing just halts the decay before they can be digitized. Good luck!

Kino · Aug 7, 2018

Your best resources...

https://www.imagepermanenceinstitut...etter-archive/v12/preserving-film-collections

https://www.archives.gov/preservation/storage/cold-storage-photos.html

https://www.filmpreservation.org/preservation-basics/the-film-preservation-guide-download

Some of these are specifically aimed at motion picture film, but the principals are roughly the same...

pentaxuser · Aug 7, 2018

So is the consensus that if you fail to fix and wash properly during processing and the results of poor processing are seen years later then a fix and a wash is useless or as good as because by then an irreversible process of deterioration has occurred which cannot be stopped?

If this is the case then what is the easiest rescue method for the OP to try?

pentaxuser

Stats · Aug 7, 2018

It has happened to me with some old negatives, which I believe were improperly fixed or washed. I resoaked the negatives in distilled water and carefully wiped them with wet cotton balls.

Paul Howell · Aug 7, 2018

What you don't know is, were the negatives improperly fixed or fixed with depleted fixer or improperly washed? I would buy a Residual Silver Test kit and test the negatives. If a negative tests clear of residual silver I would assume that the problem was in the wash. If you have silver then issue was in the fix. If the problem is that if the negatives were not fixed then you need to re-fix, but you don't know for how long, you don't want to over fix. I would re-fix in standard fix, test with the residual silver kit until clear of silver then wash with a hypo clearing agent step followed by a wetting agent in distilled water. I would hang them to dry. If the issue was too short of a wash, then rewash using a hypo clearing agent step followed by a wetting agent. If you wash in a tray make sure the emulsion side is up so the negative is well washed.

Kino · Aug 7, 2018

pentaxuser said:
So is the consensus that if you fail to fix and wash properly during processing and the results of poor processing are seen years later then a fix and a wash is useless or as good as because by then an irreversible process of deterioration has occurred which cannot be stopped?

If this is the case then what is the easiest rescue method for the OP to try?

pentaxuser

Realistically, to the typical photographer, the only real viable solution is to make high resolution digital scans and migrate them into the future.

You could try a hybrid approach and have the negatives scanned and output on a film recorder back to film, but that's wildly expensive and impractical for most people.

In the motion picture industry, we use an intermediary copy (interpositive) as both a means to preserve and protect the images, but the process would be hard for the typical photographer to emulate without a huge investment in equipment, materials and time.

Rewashing and storage in proper containers, in ideal storage conditions will help extend the life of negatives, but once something like base degradation begins, it's a non-reversible process.

This is why archival processing standards are so important.

martinola · Aug 7, 2018

Years ago Kodak had a publication on conservation of photographic materials. I can't remember the title just now, however I suggest you search on ebay and find a copy. There is a section on what you describe and some suggestions on how to treat it.

There are lots of things that film doesn't like. As others have said; insufficient washing and fixing are two big ones. I know from personal experience that having photos in a room that has strong paint fumes (during renovation) can also do nasty things. Sorry to hear of your troubles and good luck with stopping the damage.

Martin

Sirius Glass · Aug 7, 2018

Refixing, washing, using PhotoFlo or other surfactant, and hanging to dry may stop further degradation but will not reverse any damage. Unfortunately one can only stop the process, not reverse it.

pentaxuser · Aug 7, 2018

Paul Howell said:
What you don't know is, were the negatives improperly fixed or fixed with depleted fixer or improperly washed? I would buy a Residual Silver Test kit and test the negatives. If a negative tests clear of residual silver I would assume that the problem was in the wash. If you have silver then issue was in the fix. If the problem is that if the negatives were not fixed then you need to re-fix, but you don't know for how long, you don't want to over fix. I would re-fix in standard fix, test with the residual silver kit until clear of silver then wash with a hypo clearing agent step followed by a wetting agent in distilled water. I would hang them to dry. If the issue was too short of a wash, then rewash using a hypo clearing agent step followed by a wetting agent. If you wash in a tray make sure the emulsion side is up so the negative is well washed.

I have never used a residual silver test but I looked it up and all it gave me was the Photographer's Formulary Residual Hypo Test which appear to detect silver left behind as a result of poor washing but this does not seem to square with what you describe above. Is there a separate test for underfixing ie. are there two types of tests?.

I think I need help here to fully understand how you determine lack of fixing so the need to re-fix. I think I understand the test for residual fix being left and thus inadequate washing but not the poor as in lack of fixing or exhausted fixer

Thanks

pentaxuser

Paul Howell · Aug 7, 2018

PF sells both a residual silver and residual fixer test kits. You want the silver kit, once you've ruled out excessive silver the only other explanation is improper washing.

Residual Silver Test
RRP:
$12.95
Formulary's Residual Silver Test is used to determine If any silver ions remain in a print or on a film strip after fixing. When the silver test solution is applied to photographic material the sul...

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03-0170 .
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Kino · Aug 7, 2018

The ANSI/ASC PH4.8-1985 "Residual Thiosulfate and Other Chemicals in Films, Plates, and Papers - Determination and Measurement" whitepaper states that Iodine-Amylose, Methylene Blue and Silver Densitometric Methods of testing MUST be performed within 2 weeks of being processed to determine actual levels of residual chemicals.

All testing after 2 weeks can be useful as a indicator of changes in the future, but this appears to be less valuable as a diagnostic tool.

pentaxuser · Aug 7, 2018

Thanks Paul. That clarifies matters. It is still not clear to me in terms of the science of film degradation whether further action in "chemical terms" year later for want of a better phrase will definitely have any effect on even stopping further degradation. It would seem that it may or equally may not stop further degradation.

Digital intervention may prove the best or only solution?

pentaxuser.

RalphLambrecht · Aug 7, 2018

Jarin Blaschke said:
Hello.

Sorry, it's a long one:

I just picked up one of my oldest binders of negatives from my father's house to add to my other 13 binders that I have with me at home in Los Angeles, which date to the present. The 35mm, 120 and 4x5 negs in this particular older binder date from 1997-1999. The pages are largely Print File filing pages, with some BesFile pages, within a black, fully closing Besfile binder.

Opening and flipping through memory lane, I was dismayed to find the definite beginnings of silver mirroring throughout the black and white negatives in the binder. On the emulsion side, silver-rich areas sometimes reflect a flat blue, with green and yellow fringes to the affected area. I was somewhat surprised because it's only been 20 years and silver is supposed to last for ages. Photographers and preservationists often print from negatives that are many many years older. Seemingly you can make a gorgeous print of Pepper #30 today, or heck, something 50 years older than that.

After the shock, I realized that I don't quite remember how stringent my fixing and washing was back then, a couple years after high school. I also lived in New York City apartments from 1995-2011 with great seasonal fluctuations in temperature and presumably less than ideal pollution conditions. The negs have been in the same Print File pages since the beginning. The sampling of BesFile negs is much smaller, but none of the clearer, BesFile negs show any of the mirroring.

I haven't yet scrutinized my other binders that post-date the problem group, but I'm alarmed an concerned - around 2000/2001 I finally started to take genuinely GOOD photographs, and regardless I want the preservation of the record of my life as I photographed it, starting in 1994.

I am about to move to northern California, with good air quality (maybe not in fire season however).

---
So, how does one ensure a safe place for the silver (and dye) records to reside for at least the rest of my life, and ideally a couple generations?

Can I virtually halt the decay of negatives that have already started their decline, or are the pollutants hopelessly embedded in the media doing their dastardly work at full speed forever?

Is thee any sense in rewashing important negatives?

Negatives in Print File pages are wonderfully organized, clear, and easy to find, but in reality are they archivally dubious? Do I ditch the binders too? What are the alternatives, and how do you file negatives in a way that you can see and find them easily? For example, filing 35mm negs in 6-frame glassine strips seems horribly opaque, bulky and cluttered.

Is some airflow actually good for negatives?

Are there somewhat affordable, temperature and humidity-controlled vaults for negatives, like those for wine? If so, are they worth it?
Jarin,most importantly, where was the binder in your father's house?;freshly painted, wooden cabinet in the attic? I recommend not to rewash or reprocess in any way but to store in archival boxes in a cool and dry place to avoid further decay.It's unfortunately unlikely that you will be able to repair the damage but, having them professionally scanned may offer some repair possibilities.
Thanks!!

-Jarin

Paul Howell · Aug 7, 2018

pentaxuser said:
Thanks Paul. That clarifies matters. It is still not clear to me in terms of the science of film degradation whether further action in "chemical terms" year later for want of a better phrase will definitely have any effect on even stopping further degradation. It would seem that it may or equally may not stop further degradation.

Digital intervention may prove the best or only solution?

pentaxuser.

In my way of thinking do both. Scan the negatives then re-fix and wash in attempt to save the negatives. Over they years I've been very lucky, my negatives go back to the mid 60s and so far all are in fine shape. I've had prints go bad, many were printed on GAF VC RC paper from the early 70s which have not held up over the years, and an occasional print was not wash properly, but I still have the negatives and I can reprint, just have to find the right set of negatives.

removed account4 · Aug 7, 2018

you might be able to save your film i had dicrotic fog that sounds like what you might have, IDK ...
i made a batch of farmers reducer and put my film in it for 10-20 seconds and then fixed it.
the negatives are obviously thinner and it saved the film ...
its something i was taught by the founder of sprint photo chemistry before he passed away
he had me use sprint fixer dilute 2:8 ...
not sure how it happened ot you but it happened to me because kodak suggested i use
the wrong tmax developer for sheet film ... should have been tmax RS .. oh well, live and learn !

[ posted later after i saw ic-racer's images ]
oops mine looked nothing like that, i don't think farmer's reducer will help at all
sorry about that .. good luck !

ic-racer · Aug 7, 2018

I had a similar issue with some film from 1988. I do much better processing these days. I don't re-use fixer anymore.

Jarin Blaschke · Aug 8, 2018

ic-racer said:
I had a similar issue with some film from 1988. I do much better processing these days. I don't re-use fixer anymore.
View attachment 205503 View attachment 205504 View attachment 205505

Thank you for these images! This is what the negs look like, but based around high density areas rather than toward the edge. My greatest hope is that the problem lies in my young processing, and that my slightly more experienced self, who made better images next year, also fixed and washed better and my slightly better images survive with much better success. I will check negs from 2000 onward next week. Stay tuned...

Jarin

mnemosyne · Aug 8, 2018

ic-racer said:
I had a similar issue with some film from 1988. I do much better processing these days. I don't re-use fixer anymore.
View attachment 205503 View attachment 205504 View attachment 205505

While mostly dealing with historical glass negatives, according to this dissertation silver mirroring is the result of the emulsions contact with external sources of sulphur (H2S etc) and not a result of poor fixing (which will create different problems). Storage (humidity, ventilation, contact with storage materials) apparently plays a big part and It would be interesting to know how the affected negatives were stored.

"It has been observed that mirroring often does not occur on poorly processed prints. The sulfur from the residual fixer combines with the silver ions to form stable silver sulfide before the silver can travel all the way to the surface."
source: "A Guide to Fiber-Base Gelatin Silver Print Condition and Deterioration" by Gwain Weaver.

martinola · Aug 8, 2018

I don't know if this will help or cause you more problems BUT:
I have heard of a method to reduce the dichroic fog on prints by very, very gently polishing the affected surface with a very fine abrasive. I have tried it with cotton wipes and a tiny amount of white autobody polish. After doing as much as you dare, gently wash in water. Be aware it may result in some (or much) damage, so copy/scan the original to protect what you have. Here's an example of what I did to a family photo of my Grandmother and her daughters.

Martin

pentaxuser · Aug 8, 2018

Martin, that's a pretty good solution, especially if you can easily detect when you start to overdo it. The key ingredient tends to be difficult to find these days when everything has to be easy and quick. It cannot be bought either. It is called patience

pentaxuser

mnemosyne · Aug 9, 2018

What you refer to is not dichroic fog but silver mirroring, a layer of silver sulfide that forms at the surface of the emulsion. This kind of damage is caused by image silver in the emulsion that is oxidized in the presence of other chemical compounds like hydrogen peroxide, then slowly migrates towards the surface of the emulsion where it reacts with environmental sulphur (mostly hydrogen sulfide H2S) to form silver sulfide (Ag2S).

This gives a good summary:
https://archivesandspecialcollectio...of-photographic-degradation-silver-mirroring/

Slowing or halting the decline of my negatives

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