Film processing silver recovery - practical or not for home processing?

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PhilBurton

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The big sticky thread on Silver Recovery has 176 (!!) posts, but the last is dated 2017. I just checked, and silver now sells for US $10 per "Troy ounce." (approx 31 gms.) If I expect to process about 50-100 rolls a year, is it economical at all to set up some kind of silver recovery system? Are there designs for low-cost home made recovery systems? Steel wool? Something else?

If it matters, I have lots of extra 5V and 12V DC output chargers from various consumer electronics and computer devices.
 

MattKing

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Reach out to John (jnantz).
His Silver Magnet units are aimed at the moderate user.
 

mshchem

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The big sticky thread on Silver Recovery has 176 (!!) posts, but the last is dated 2017. I just checked, and silver now sells for US $10 per "Troy ounce." (approx 31 gms.) If I expect to process about 50-100 rolls a year, is it economical at all to set up some kind of silver recovery system? Are there designs for low-cost home made recovery systems? Steel wool? Something else?

If it matters, I have lots of extra 5V and 12V DC output chargers from various consumer electronics and computer devices.
Silver "good for delivery" bars are 99.9% pure, and nominally 1000 oz troy. This is what you see quoted as spot silver. Right now spot silver is at $17.50 / ozt. Right now to buy 1 -10 oz generic bullion silver, ie a Silvertowne bar you will be paying a premium of about $3/ozt over spot.

Silver recovery from small volumes can be fun, but is not practical for commercial purposes. When you send silver scrap to a refinery there's an assay fee. If you are a scrap buyer and you send say 20-30 pounds of sterling silver (typically flat ware, spoons, tea pots etc) and you have a history of sending real sterling 0.925, the refiner will melt your lot and assay it, there's an assay fee, for something like sterling in excess of 100 ozt the fees are 35-40 dollars, and you get paid 90-95% of the silver spot price.

Dillon Gage and Silvertowne are 2 of the biggest refineries. But there's a lot of good refineries out there.
I'm attaching a pdf, basically what you get from electrolytic recovery is high grade sludge that requires more complicated refining.

A local photo shop (University Camera )sent in sludge a few years back, several years of high-volume RA4, and C41 printing. They used a nice commercial electrolytic recovery unit. They got several thousand dollars, the price of silver was twice what it is today (2011-12?)

I made my own silver nitrate a couple years back. I bought a pure silver token, boiled it in nitric acid, (you absolutely need a fume hood) I got beautiful crystals of silver nitrate. I didn't really have much use for them so I gave them to a friend who does "salt prints"

Some refining processes are very efficient, but involve the use of sodium cyanide, I wouldn't go anywhere near something like that.
 

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Jim70

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A number of years ago, my son & I ran a small commercial film processing lab. We put expired fixed into a plastic jug with 000 steel wool.. After some time, the iron had replaced the silver in solution and we decanted the liquid. we sun dried the sludge. The I washed the sludge with muriatic acid and let it sit in the acid for a few weeks. We decanted the solution and sun dried the sludge. again. we washed the sludge with water, dried it again and sent it for recovery. As I recall, we had about 12 lbs of a silver/iron mix and I believe we got about $90. We probably spent about $5 on the steel wool and $6 on the muriatic acid, so it was somewhat profitable.
Not very economical but kind of fun and we kept that silver out of the environment.
 

Mr Bill

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If I expect to process about 50-100 rolls a year, is it economical at all to set up some kind of silver recovery system?

Well, there's not all that much silver in 50-100 rolls; as a rough number I'm guessing about $10, give or take a factor of two.

The prices mshchem is giving you sound about right but there's a catch. You're not gonna have enough silver for your own refining batch. So what's a refiner gonna do? Unless it's really clean electrolytic flake they have no idea what you've got. I have no idea what they'll do, but they don't really want to risk coming out on the short end of the stick.

If you're gonna be doing this beyond a few years it may be worth going for a "silver magnet" via John Nanian. One of the advantages, in my view, is that the units are supplied by the refiner, so they know exactly what it is and are willing to deal with it. (You could potentially do this sort of thing with other refiners, but I don't know of any with an inexpensive electrolytic unit; if you go for some sort of metallic replacement (aka steel wool, etc., cartridge) you're gonna get, unreliably, some sort of sludge that may well cost more to refine than the silver in it. These cartridges are sort of ok if you can keep a somewhat continuous flow going through them, and IF you periodically test the output for silver "leakage." If they're gonna have extended periods of time without something going through them they may essentially "rust" internally and stop removing silver. I don't think you have anywhere near enough volume to support one of these cartridges.
 

foc

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In my opinion, the 50 to 100 films a year is too low a volume for silver recovery. Of course I stand to be corrected, but when I ran a silver recover machine in my mini lab, we were putting 15-20 Lt of waste a day and it would take 6-8 months for the recovery cartridge to be ready to be sent away.
 

mshchem

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Labs are required to treat waste effluent to keep silver out of the environment.

The good old days, Xray and graphic arts labs produced huge amounts of waste, recycling the silver from mountains of old Xray films was a viable business, especially in large cities.

Color films are left without any silver, one can only imagine what was recovered from processing movie prints for distribution.
 
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PhilBurton

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Labs are required to treat waste effluent to keep silver out of the environment.

The good old days, Xray and graphic arts labs produced huge amounts of waste, recycling the silver from mountains of old Xray films was a viable business, especially in large cities.

Color films are left without any silver, one can only imagine what was recovered from processing movie prints for distribution.
Guys, Thanks. It sounds like I should save the used fixer, and take it to a Hazardous Waste Facility, IF they will even accept soda bottles with used fixer.
I appreciate all this feedback. Very helpful. In "my time" as a teenager doing home development, we just dumped the user fixer down the drain.
 

removed account4

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Hi PhilBurton

If you decide you are interested in a Silver Magnet let me know I will be happy to supply you with the information you will need to decide if it is right for you. I also sell trickle tank systems which have the ability to extract most of your silver from your spent fixer and wash water. The difference between the two is the magnet requires your fixer to be spent ( 2x original clear time with clip text ) a trickle system, anything can go through, and the magnet will leave you with silver still in your fixer because it can't extract below about 50p/million the trickle tank can. The magnet is affordable and you can hang on to the cathodes until you have a few of then to refine and make a little bit of cash ( they hold about 30-32 troy oz on them ) the trickle tank is a little more expensive, and unless you hold on the the media buckets and bring a few down at once a refiner usually charges you some $$ to take it off your hands, unless you live in Canada then ECScares will pay for the freight to get it to them and they will pay you for it as well.
I've been selling silver recovery stuff for quite some time, and did it back in the 1980s too for a while, if I can't answer your questions I will ask the manufacturer.

Best of luck !

John
 
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Mr Bill

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In my opinion, the 50 to 100 films a year is too low a volume for silver recovery.

Hi, well sure, if you're talking about the "metallic replacement" (steel/iron wool) cartridges, yeah, this would be a problem for them.

The silver magnet is different, though. It's basically a very-low current electrolytic unit that electroplates the silver on its inside. With something like this you should be able to turn it on and off at will, use it whenever you feel like it, etc., with no detriment. The only real problem is collecting enough silver to pay for it. Not that IT has a problem recovering silver; it's just that the photographer has to shoot enough film to "feed it" the silver.

One has to decide for themselves what's worth it to them. My understanding is that the community hazardous waste materials are incinerated. Presumably the residual silver goes into a landfill. If one uses a silver magnet, at least there is a chance of it being recycled. (Whatever is collected inside is metallic silver that doesn't disappear; it's just a matter of getting enough to be worth the refining fees.)
 

Adrian Bacon

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Labs are required to treat waste effluent to keep silver out of the environment.

The good old days, Xray and graphic arts labs produced huge amounts of waste, recycling the silver from mountains of old Xray films was a viable business, especially in large cities.

Color films are left without any silver, one can only imagine what was recovered from processing movie prints for distribution.

That is correct. I don't try to recover my waste. I put into a disposal barrel that I got from SafetyKleen and whenever it's full, they come take it away and give me a new empty one. It does cost money, but it saves me more time than what I'd get out of it if I tried to recover it, and I just build that cost into the cost of processing a roll. I replenish my fix so my per roll waste is pretty low.
 

removed account4

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Hi, well sure, if you're talking about the "metallic replacement" (steel/iron wool) cartridges, yeah, this would be a problem for them.

The silver magnet is different, though. It's basically a very-low current electrolytic unit that electroplates the silver on its inside. With something like this you should be able to turn it on and off at will, use it whenever you feel like it, etc., with no detriment. The only real problem is collecting enough silver to pay for it. Not that IT has a problem recovering silver; it's just that the photographer has to shoot enough film to "feed it" the silver.

One has to decide for themselves what's worth it to them. My understanding is that the community hazardous waste materials are incinerated. Presumably the residual silver goes into a landfill. If one uses a silver magnet, at least there is a chance of it being recycled. (Whatever is collected inside is metallic silver that doesn't disappear; it's just a matter of getting enough to be worth the refining fees.)

exactly
It’s just something to do to reduce your chemical waste footprint. I don’t want my photochemistry incinerated and entering the water system or the air I breathe. And I live coastal so I don’t want it to enter my local ground water or my garden or be problematic for the treatment plant whose operators have told me that it screws stuff at their end. And the water they flow their tanks into is 80% them in the dry season.
Is it worth it for me, sure even as a low volume producer it’s not too $$ and I know I am doing something positive, am I going to be rich from it.. nope. Is it right for everyone, who knows I’m not everyone, but if everyone e wanted one I- be happy to sell them one.
 

Mr Bill

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Labs are required to treat waste effluent to keep silver out of the environment.

That is correct. I don't try to recover my waste. I put into a disposal barrel that I got from SafetyKleen and whenever it's full, they come take it away and give me a new empty one. It does cost money, but it saves me more time than what I'd get out of it if I tried to recover it, and I just build that cost into the cost of processing a roll. I replenish my fix so my per roll waste is pretty low.

It's been that way in the US, lab effluents being regulated, for about 35+ years now. So nothing too new; just not well-known to people outside of commercial labs.

Something else not well-known is how nutty some of the regulated standards are. In the US each municipality makes its own laws about what will be accepted into its own "POTW," the publicly owned treatment works, aka "the sewer." The outfit where I worked once owned a large chain of one-hour labs. I was not part of that division but did see some of the effluent regulations. And I like to grouse about it once in while, which is what this post is.

Since Adrian has brought up the situation of his lab, which I presume is also in Petaluma, California, I looked online for their effluent limits. There is a page giving "discharge limits" for silver at 0.10 mg/L, that is, milligrams of silver per liter. To put this in perspective it is roughly the same ratio as if someone had tried to control the population of metro Los Angeles, about 13 million people, to within a bit over one person. It's an unusually stringent limit. (I've designed some large-lab effluent control systems that ran below 0.20 mg/L silver so I know how difficult this is.)

The Petaluma web site gives some other discharge limits: arsenic, at 0.20 mg/L, can be discharged at twice the limit of silver. Cyanide is similar, being limited to 0.26 mg/L. One might think that oh, silver DOES need to be limited that stringently, but... if one looks at EPA drinking water standards, silver is treated as a secondary pollutant with a guideline limit of 0.1 mg/L. In other words, the Petaluma discharge limit for silver is the same as the EPA drinking water standard! Imagine if they treated ALL pollutants the same, essentially you would not be able to discharge anything to the sewer unless it was safe to drink.

But back to photo processing - what does it take to meet a silver limit of 0.10 mg/L? Well, I would say it's not achievable by a normal photographer. Even taking fixer to a hazardous waste facility is not enough. Let me use C-41 processing as an example. But first let me say that effluent regulations don't allow dilution as a means of controlling pollution. So what IS dilution in the case of C-41 processing? In my view, any wash water usage beyond that specified in Kodak's Z-131 process manual can be seen as dilution. If one uses a single wash tank (as opposed to multi-stage washing with counter-current water flow) Z-131 specs about 3.3 liters of water per nominal roll.

So how does this wash water limit affect silver concentration in the effluent? Well the way that silver gets into wash water is by being carried over from a fix tank - the "dirty" film gets some of the wash water dirty. Z-131 lists some typical carry-out amounts for a processor with "efficient squeegees;" it's about 7 ml per roll. Now when one processes by hand, or in a Jobo processor for that matter, they are not generally using a squeegee after the fixer. I would estimate that the fixer carryover is roughly double the squeegeed rate, perhaps 14 ml per roll. This is disregarding what the reel carries over. Let's say that you use your fixer lightly, only letting the silver concentration rise to about 1/2 g/l. Now there is enough information to calculate the silver concentration in the wash water. It's about 2 mg/l, roughly 20 times higher than the allowable discharge limit to the Petaluma sewer system. (The calculation is to take the total amount of silver carried over, about 1/2 gram/1000 ml x 14 ml, and then divide that by the total wash water, about 3.3 liters. This calculation gives GRAMS of silver per, remember that the discharge limits are in milligrams, so multiply by 1,000.)

Thanks for bearing with me on my little rant. Perhaps it'll help explain part of the reason why there are so few smaller labs around nowadays. The expertise needed to deal with these issues can be costly for a small operation. This sort of thing is a major reason why so-called washless systems were developed. They didn't need a permit cuz there was no sewer connection. The low wash volume made it feasible to have all the waste hauled offsite by a licensed waste disposal outfit.
 
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On a cruise to Alaska around 30 years ago, I panned for gold and found a very small amount that I Scotched taped into the photo album of the trip. Back then the guy said it was worth about 75 cents. So it must be worth a few dollars around now due to inflation. I'm rich!
 

Roger Thoms

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On a cruise to Alaska around 30 years ago, I panned for gold and found a very small amount that I Scotched taped into the photo album of the trip. Back then the guy said it was worth about 75 cents. So it must be worth a few dollars around now due to inflation. I'm rich!

Just make sure your heirs know that “there’s gold in that thar album”, I would hate to see them just throw it out. :D
 

mshchem

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It's been that way in the US, lab effluents being regulated, for about 35+ years now. So nothing too new; just not well-known to people outside of commercial labs.

Something else not well-known is how nutty some of the regulated standards are. In the US each municipality makes its own laws about what will be accepted into its own "POTW," the publicly owned treatment works, aka "the sewer." The outfit where I worked once owned a large chain of one-hour labs. I was not part of that division but did see some of the effluent regulations. And I like to grouse about it once in while, which is what this post is.

Since Adrian has brought up the situation of his lab, which I presume is also in Petaluma, California, I looked online for their effluent limits. There is a page giving "discharge limits" for silver at 0.10 mg/L, that is, milligrams of silver per liter. To put this in perspective it is roughly the same ratio as if someone had tried to control the population of metro Los Angeles, about 13 million people, to within a bit over one person. It's an unusually stringent limit. (I've designed some large-lab effluent control systems that ran below 0.20 mg/L silver so I know how difficult this is.)

The Petaluma web site gives some other discharge limits: arsenic, at 0.20 mg/L, can be discharged at twice the limit of silver. Cyanide is similar, being limited to 0.26 mg/L. One might think that oh, silver DOES need to be limited that stringently, but... if one looks at EPA drinking water standards, silver is treated as a secondary pollutant with a guideline limit of 0.1 mg/L. In other words, the Petaluma discharge limit for silver is the same as the EPA drinking water standard! Imagine if they treated ALL pollutants the same, essentially you would not be able to discharge anything to the sewer unless it was safe to drink.

But back to photo processing - what does it take to meet a silver limit of 0.10 mg/L? Well, I would say it's not achievable by a normal photographer. Even taking fixer to a hazardous waste facility is not enough. Let me use C-41 processing as an example. But first let me say that effluent regulations don't allow dilution as a means of controlling pollution. So what IS dilution in the case of C-41 processing? In my view, any wash water usage beyond that specified in Kodak's Z-131 process manual can be seen as dilution. If one uses a single wash tank (as opposed to multi-stage washing with counter-current water flow) Z-131 specs about 3.3 liters of water per nominal roll.

So how does this wash water limit affect silver concentration in the effluent? Well the way that silver gets into wash water is by being carried over from a fix tank - the "dirty" film gets some of the wash water dirty. Z-131 lists some typical carry-out amounts for a processor with "efficient squeegees;" it's about 7 ml per roll. Now when one processes by hand, or in a Jobo processor for that matter, they are not generally using a squeegee after the fixer. I would estimate that the fixer carryover is roughly double the squeegeed rate, perhaps 14 ml per roll. This is disregarding what the reel carries over. Let's say that you use your fixer lightly, only letting the silver concentration rise to about 1/2 g/l. Now there is enough information to calculate the silver concentration in the wash water. It's about 2 mg/l, roughly 20 times higher than the allowable discharge limit to the Petaluma sewer system. (The calculation is to take the total amount of silver carried over, about 1/2 gram/1000 ml x 14 ml, and then divide that by the total wash water, about 3.3 liters. This calculation gives GRAMS of silver per, remember that the discharge limits are in milligrams, so multiply by 1,000.)

Thanks for bearing with me on my little rant. Perhaps it'll help explain part of the reason why there are so few smaller labs around nowadays. The expertise needed to deal with these issues can be costly for a small operation. This sort of thing is a major reason why so-called washless systems were developed. They didn't need a permit cuz there was no sewer connection. The low wash volume made it feasible to have all the waste hauled offsite by a licensed waste disposal outfit.

Here's a little known tidbit. I used to work in the home appliance industry. I was involved with the roll out of refrigerator water filters. The US companies I worked for wanted NSF certification. There's several different certifications, taste and odor, health effects, etc.
Cryptosporidium made big news when people with compromised immune systems got very ill, some died. These are easy to filter out. One other concern is Lead. So the most common way to get rid of small amounts of lead in drinking water is ion exchange, which 20 years ago was by exchange of lead with silver. So for each Pb ion (+2, or +4) removed from the water you would be putting back silver. This was done with carbon block filters compounded with an organometallic silver compound. So having a 2 mg/L, 2 microgram per milliliter Ag limit in waste water is nuts.
Arsenic is abundant in shell fish, lobster etc. Might explain the tolerance for this. :smile:.

For me a non professional, but fanatic I am careful not to put anything in the water or ground that I wouldn't in my backyard.

One thing that is nice is an electrolytic silver recovery unit can produce very high quality silver. Makes nice silver nitrate.
 

mshchem

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I found these listed on Ebay as "darkroom chemicals " some thrift shop had no idea. I told them to get these to the municipal authorities. There was a big ancient bottle of Calcium Carbide listed too. God forbid that get on a plane.
s-l500 (5).jpg
 

Mr Bill

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One other concern is Lead. So the most common way to get rid of small amounts of lead in drinking water is ion exchange, which 20 years ago was by exchange of lead with silver. So for each Pb ion (+2, or +4) removed from the water you would be putting back silver. This was done with carbon block filters compounded with an organometallic silver compound. So having a 2 mg/L, 2 microgram per milliliter Ag limit in waste water is nuts.

That's interesting.

Here's a bit from the (US) EPA site regarding silver in drinking water.
Skin discoloration is a cosmetic effect related to silver ingestion. This effect, called argyria, does not impair body function. It has never been found to be caused by drinking water in the United States. A standard has been set, however, because silver is used as an antibacterial agent in many home water treatment devices and so presents a potential problem which deserves attention.

With respect to municipal limitations for silver going into the sewage system one of our environmental people had asked around a bit, back in our minilab period, through the end of the 1990s. It turned out that the people setting the regulated limits, for the most part, didn't really know what they were doing. So what they did was to mostly copy the limits from another municipality - one they believed to be more knowledgeable than they themselves were. They would modify limits, as needed, to deal with local industries or special problems. But aside from that, I guess they get cast in stone.
 
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