So, the answer was copper

Distillation methods and improvements.

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rubelstrudel
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Re: So, the answer was copper

Post by rubelstrudel »

I for one am very glad you resurrected the thread CatCrap. Otherwise I would not have found it. This is important stuff.
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Re: So, the answer was copper

Post by Bagasso »

CatCrap wrote:I wonder if it can be found somewhere for purchase? Other than having to attend MU for some exorbitant sum.
I think you can buy the chemicals of interest from a chemical supply store. Probably expensive but no doubt cheaper than MU.
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Re: So, the answer was copper

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Very true. I'm sure if i dug around i could compline a list of all the specific elements that make up a distillation run. I think there may even be a list on the parent sight, which lists the different boiling points. That would be a good starting point. Good idea to check out chemical supply. Maybe they would sell in the quantities needed? (we're talking one ounce jars, tops. That's all you need for a smell or observation). Although i wonder if some of those chems are hard to track down or strictly control. Not sure.

Good thread Bagasso. And good to see you're still around! Are you still following this practice or having any issues with sulfur aromas? Seems like this could be a very significant point that we don't discuss in much detail.

"You should have copper in the vapor path. The more the better" Well.. how much is enough? Where in the vapor path? Does it help to use it in other areas like fermenting, low wines, the down path the up path etc. etc. Very interesting topic.
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Re: So, the answer was copper

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CatCrap wrote:Very true. I'm sure if i dug around i could compline a list of all the specific elements that make up a distillation run. I think there may even be a list on the parent sight, which lists the different boiling points. That would be a good starting point. Good idea to check out chemical supply. Maybe they would sell in the quantities needed? (we're talking one ounce jars, tops. That's all you need for a smell or observation). Although i wonder if some of those chems are hard to track down or strictly control. Not sure.
I would think that the main ones would be the faults. I remember seeing a pdf on whiskey congeners and there were more than a hundred but I doubt one would need all of them. I am not sure about control issues but I doubt the main faults would have much control. They are just too basic, IMO.

ETA: Another thing is that a wine fault kit could also be useful since many wine faults would also be considered distillate faults.
Good thread Bagasso. And good to see you're still around! Are you still following this practice or having any issues with sulfur aromas? Seems like this could be a very significant point that we don't discuss in much detail.
I do still use it. A foot of 1/2" copper tube in my 20 L ferementer once the wash has stopped. It stays in there at least a day.

Currently I am having trouble with something. I don't know if it is sulfur related but they say that you want to catch and treat sulfur problems with copper as soon as possible and I can't think of anything sooner than before pitching the yeast. The only fear was that it would kill the yeast. I really have no way of knowing what it is but it is musty. I placed a 6" piece of tube in 2.5 L of sugar water for 2hrs 20min. I placed 1.5 tsp of dry yeast and at first the yeast dove to the bottom and stayed there overnight with no activity. I thought they were dead but after 48 hours things were bubbling away.
"You should have copper in the vapor path. The more the better" Well.. how much is enough? Where in the vapor path? Does it help to use it in other areas like fermenting, low wines, the down path the up path etc. etc. Very interesting topic.
Wine makers correct sulfur problems directly in the wine. They first test to see if it makes a difference and then carefully measure their dose because after they place it in the wine it is part of it and there are limits but we are distilling so that lets us be less precise since copper sulfate is denser than table salt and remains in the boiler which is why I just decided to drop it in the wash.

The musty problem that I described got me thinking, what if heat is reverting the copper treatment. It could also be something else but since I have no way of knowing it is bugging me. I think the norm, when things work out, is that everyone ends up with a nice smelling wash. After using copper I have a very clean smelling wash. I would say that it smells like a rather uninteresting white wine, neutral except for the sense of acidity and a hint of yeast.

What is also the norm is that if you do a stripping run everyone ends up with stinky low wines and foul backset. I seem to be getting the same but if you have a good smelling wash, where is all that stink coming from?
Last edited by Bagasso on Sat Jun 16, 2018 9:42 pm, edited 1 time in total.
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Re: So, the answer was copper

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I just did a UJ stripping run. Probably around 10th or so generation. The low wines smell fantastic, and i find the backset pleasant too. Now.. when i say pleasant, i mean it's kind of an acquired taste (or smell). It is a very very strong aroma, and i guess you could call it stinky or funky, but it has this very complex, sour corn smell and taste. If it wasn't in any way pleasant, I wouldn't use it for my next ferment(sour mashing method.) Now as for the low wines, i'd say,they only "stink" because they are not cut. They are a combination of Fores, Heads, Hearts and Tails. So, yes, during the strip, the "heart" portion has the more pleasant smell and taste, but everything ends up in the same carboy, so the accumulation in my opinion doesn't smell bad. If it smells bad.. to that i would say.. how can you expect to get a nice spirit run and spirit, if the product you're using isn't nice? I don't think there is magic happening, that second distillation of a poor quality spirit (low wines) will result in a high quality spirit (final spirit, from the second run). Now, i should mention, that the way i strip (and i assume most do) is at full speed. As fast and hard as my power source allows and condenser can keep up with. So, there is significant smearing going on. that meaning that there is poor separation of fractions. So, in a strip, in my low wines, the first part of the run, the "heads" is going to have plenty of hearts and tails, and the same for the other fractions.

i'm farrrrrrr from an expert or knowledgeable mr. bagasso.. but my suggestion or assessments of your issues.. is that it must come down to either your fermentables or your water source. If you're using the same corn, sugar, etc whatever as most of us are, then it must be your water source. Where do you get your water, and do you treat it in any way? I think we've already covered the yeast you use and fermentation temperatures, and it doesn't sound like you're having infection or bacteria issues. So, the H20 must be the culprit.

Just my 2 cents, man. It's incredibly difficult to diagnose anyone else's difficulties through the forum. But... that's what this board is all about, right?
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Re: So, the answer was copper

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CatCrap wrote:I just did a UJ stripping run. Probably around 10th or so generation. The low wines smell fantastic, and i find the backset pleasant too. Now.. when i say pleasant, i mean it's kind of an acquired taste (or smell). It is a very very strong aroma, and i guess you could call it stinky or funky, but it has this very complex, sour corn smell and taste. If it wasn't in any way pleasant, I wouldn't use it for my next ferment(sour mashing method.) Now as for the low wines, i'd say,they only "stink" because they are not cut. They are a combination of Fores, Heads, Hearts and Tails. So, yes, during the strip, the "heart" portion has the more pleasant smell and taste, but everything ends up in the same carboy, so the accumulation in my opinion doesn't smell bad. If it smells bad.. to that i would say.. how can you expect to get a nice spirit run and spirit, if the product you're using isn't nice? I don't think there is magic happening, that second distillation of a poor quality spirit (low wines) will result in a high quality spirit (final spirit, from the second run). Now, i should mention, that the way i strip (and i assume most do) is at full speed. As fast and hard as my power source allows and condenser can keep up with. So, there is significant smearing going on. that meaning that there is poor separation of fractions. So, in a strip, in my low wines, the first part of the run, the "heads" is going to have plenty of hearts and tails, and the same for the other fractions.

i'm farrrrrrr from an expert or knowledgeable mr. bagasso.. but my suggestion or assessments of your issues.. is that it must come down to either your fermentables or your water source. If you're using the same corn, sugar, etc whatever as most of us are, then it must be your water source. Where do you get your water, and do you treat it in any way? I think we've already covered the yeast you use and fermentation temperatures, and it doesn't sound like you're having infection or bacteria issues. So, the H20 must be the culprit.

Just my 2 cents, man. It's incredibly difficult to diagnose anyone else's difficulties through the forum. But... that's what this board is all about, right?
Good post & yes that is exactly what a forum is all about. :clap:
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Re: So, the answer was copper

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CatCrap wrote:I just did a UJ stripping run. Probably around 10th or so generation. The low wines smell fantastic, and i find the backset pleasant too. Now.. when i say pleasant, i mean it's kind of an acquired taste (or smell). It is a very very strong aroma, and i guess you could call it stinky or funky, but it has this very complex, sour corn smell and taste.
Nothing wrong with that. Sour mash seems to be magical in that way, also dunder pits, and maybe I should have narrowed the scope to plain sugar washes.
Now as for the low wines, i'd say,they only "stink" because they are not cut. They are a combination of Fores, Heads, Hearts and Tails.
This is closer to my point. Nice smelling wash, strong but interesting backset, stinky low wines. Where is it coming from? Don't get me wrong I get that everything is concentrated and smeared. That is the point. Fast and dirty. Say 20L at 10% with 2KW down to 10% coming off the condenser at cut off would leave you, according to the pot still calc on the parent site, with 30% low wines. In simplified theory you have concentrated the ethanol and other chemicals 3X in the low wines but you still have a lot of smell in the backset and a lot in the low wines. Much of it of course is due to esterification and other chemical processes going on in the boiler.

Maybe I was wrong in saying I was getting the norm but I feel like this almost bland wash ends up with a lot more smell both in the low wines and the backset, individually, than what was in the wash to begin with. In my case it is a bad smell.
i'm farrrrrrr from an expert or knowledgeable mr. bagasso.. but my suggestion or assessments of your issues.. is that it must come down to either your fermentables or your water source. If you're using the same corn, sugar, etc whatever as most of us are, then it must be your water source. Where do you get your water, and do you treat it in any way? I think we've already covered the yeast you use and fermentation temperatures, and it doesn't sound like you're having infection or bacteria issues. So, the H20 must be the culprit.

Just my 2 cents, man. It's incredibly difficult to diagnose anyone else's difficulties through the forum. But... that's what this board is all about, right?
Thanks for your thoughts but I must admit that at this point this "obsession" of mine is purely pighead...uhm scientific curiosity. My original post seemed to imply that I had it licked and in a way I did. I would normally smell my wash and sense something meaty or savory in it that is gone after treating it with copper. In theory I should be able to cut out a closer to normal hearts fraction but my mind drifted to "If copper made a better wash, could I treat the wash so that I could do a stripping run, catch all or most of the etho and have it be acceptable". The answer may very well be no but I guess I just wouldn't be happy until I tried.

I have tried different water, different wells, and even RO and distilled water. My sugar is sandy in color, sometimes lighter and sometimes darker but never white and always lighter than light brown sugar. I posted in another thread that I found out that sulfur dioxide is a common chemical used in processing sugar which might be the culprit behind what people have described as sugar-bite although nobody can say what causes it other than "sugar".

Of course, this other problem in no way adds or takes away from the original observation that copper in the wash makes a difference.
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Re: So, the answer was copper

Post by rubelstrudel »

If I could just chime in here with my anecdotes. I've been reading up on all the things I could do to improve my washes and product since I joined here some months ago. And this thread about copper I found just a couple of weeks ago. On Bagassos' advice I dumped a copper spiral in my boiler when doing my spirit run, and that made a huge difference from my previous runs.

I used to have wet cardboard smells in just about everything. But when I rose the pH to about 8 in the low wines, and 2m of copper pipe in the boiler, and with some more copper scrubbers in the vapour path that almost completely went away. I had to dig deep into the tails to get a whiff of wet cardboard now. When I dumped my old feints into the boiler to see if I could clean them up a bit at the end of my spirit run - it was almost magical. What had previously smelld like a mixture of wet dog and sour socks came out almost as clean as my main run product.

So one thing is for sure - that copper pipe stays in the boiler in all future spirit runs.
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Re: So, the answer was copper

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der wo wrote:Bagasso and me...now adding copper in the boiler or...between distillations has become a regular part of our process.

Can you quantify? I tried to read every post, but fail to grasp your conclusions..

eg I produce 25l low wines and store for a few months till I make another batch. I also store 25l high wines a few months till the spirit run.
So do I add 25g CuSO4 plus 25g Na2Co3 to the low wines, or to both?
Or a "handful" of copper shards/cuttings instead?
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Re: So, the answer was copper

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casper the Irish wrote:
der wo wrote:Bagasso and me...now adding copper in the boiler or...between distillations has become a regular part of our process.

Can you quantify? I tried to read every post, but fail to grasp your conclusions..

eg I produce 25l low wines and store for a few months till I make another batch. I also store 25l high wines a few months till the spirit run.
So do I add 25g CuSO4 plus 25g Na2Co3 to the low wines, or to both?
Or a "handful" of copper shards/cuttings instead?
I have a small amount copper carbonate at home. A pinch per 10l wash or 5l low wines? This amount helps, but I don't know if it is the optimal dosage. I don't think it's bad to overdose copper ions. But your amounts sound like a huge wasting.

When I will running out the carbonate, I will either buy copper oxide or perhaps file away some from an oxidized copper pipe.
It solves fast in a wash/mash, but slower in low wines, because low wines aren't acidic normally. Of course you could add an acid to the low wines. Then it solves fast. But acidifying will have an influence on the flavor, definetely not recommended for neutral alcohol, probably nice for Whisky or Rum, for brandy I am unsure.

Why Na2CO3? You mean to get copper carbonate like I did? You have to produce it before using it. There are many youtube videos about how to produce copper carbonate from CuSO4 and Na2CO3. But actually I am not sure if it is needed. Perhaps using the CuSO4 is all fine. Perhaps better, because it solves better in low wines?
I would beging with oxidized copper cuttings in your wash or low wines. If it helps, you can think about something more convenient for future like a powder.
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Re: So, the answer was copper

Post by Kareltje »

Dissolving copper in a bit of car battery acid, would that work? Or is there lead in a fresh bought bottle?
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Re: So, the answer was copper

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Kareltje wrote:Dissolving copper in a bit of car battery acid, would that work? Or is there lead in a fresh bought bottle?
Kareltje , I can only assume that you are talking here about making Copper Sulfate by dissolving copper in Sulfuric acid . Yes Sulfuric acid is used in Lead acid car batteries and and a bottle of acid sold for topping up batteries is Usually Sulfuric acid .

If some cheap skate dick head was to pour some out of a Car battery , then yes , as you suggest there would be a ridiculously high level of Lead Sulfate in it .
If you want Sulfuric acid Buy it from a Chemical supply store in its pure form .

If Derwo uses Copper carbonate and you choose to try it , Go Buy some , its not expensive . Neither is Copper Sulfate , hell , I can buy a 1kg bag from my rural store for $20 that would last me hundreds of washes .....if I chose to try it

The whole point is we are getting way off topic here talking about synthesizing Chemicals and its associated dangers and potential for a cock up . Handling Concentrated acids and knowing how to safely dilute them is not to be taken lightly . If you are not 100% sure what you are doing ....DON"T .
And while Acids are considered dangerous , Don't kid yourself that using Caustic Soda ( Sodium Hydroxide ) and Hydrated Lime ( Calcium Hydroxide ) are child's play either , get some of that in your eyes and you probably won't see again .

Copper Carbonate and Copper Sulfate are fairly safe Chemicals ....if you want to experiment with them , Buy them .....DON"T make them :crazy:
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Re: So, the answer was copper

Post by Bagasso »

Yummyrum wrote:Copper Carbonate and Copper Sulfate are fairly safe Chemicals ....if you want to experiment with them , Buy them .....DON"T make them :crazy:
Good advice and I would add that if you are unsure about buying something just to try then just add copper bits to your wash, low wines and/or boiler. It should give you an idea if there is room for improvement. If you don't notice a difference then there is no point in buying any other form of copper.

The penny/wine test I mentioned a couple pages back is the simplest thing. Take a clean sample of your wash, 1 ounce, and drop a small piece of clean copper in it, swirl and cover. Wait 10-15 minutes and then check it. If it is improved then you have two options 1) go buy some copper carbonate or copper sulfate, 2) use plain copper in the different stages mentioned above and see which works better for you.
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Re: So, the answer was copper

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Kareltje wrote:Dissolving copper in a bit of car battery acid, would that work? Or is there lead in a fresh bought bottle?
I don't think it works. The acid will only solve the copper oxide. Like any acid, you also could use the much less dangerous citric acid for this. If you want to dissolve copper you have to oxidize it first. For example oxidizing with H²O² and dissolving with citric acid will give you copper citrate. I did this on page 4. Or with electrolyse, there are many youtube videos, you need sulphuric acid (diluted), copper and electricity.
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Re: So, the answer was copper

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I fully agree with yummyrum here. Safety first!!! While I believe that all of those participating in this discussion are experienced (some more than other) distillers, It's important to keep in mind that this is a public forum, and any knucklehead can come here and read this stuff. I'm probably the least knowledgeable about all these chemicals (maybe chemicals in general) So I would be best advised to take YummyRum and other's advice... If i don't know wtf i'm doing, don't experiment with this stuff. It's an easy way to

Hurt yourself or others
Fuck up your wash
Poison or burn yourself
Be counterproductive

So, personally I don't have any issues with funky washes. I have smelt some sulfur aromas from a couple of ferments i've done (one of them was a Birdwatchers when i first started distilling. I tried one of the packs of "48-Hr Turbo Yeast) that came with the fermenter kit i bought from Brewhaus. That was the first, only, and last time i've used Turbo yeast. This batch of birdwatchers had a strong sulfur aroma, and my house did as well for 3 days. Pretty stinky rotten egg smell. However, the smell went away and did not carry over to distillation, that being said it wasn't a great neutral for sure. I didn't attempt to make a ridiculously high ABV(i probably shot for around 10%), but just goes to show you the quality of some turbo yeasts. ( I don't mean to go off on that tangent and down that rabbit hole.. as I know Turbo has been discussed at length here ad nauseum) If i get a sulfur aroma from a wash, then it's usually at the beginning, it's a high temp ferment, and i expect it to go away. If it does not go away by the end of the ferment i know there is slight cause for concern. I'd probably add some extra copper mesh to column when i did the stripping run. I could try the techniques mentioned above.

So, for me, and for anyone who is new to distilling, or unsure of how to use any of the techniques or chemicals above, I would STRONGLY suggest the only method you attempt to use is to add some copper bits (oxidized, right? So that just means they aren't shiny and new like?) to either the completed or nearly (right? not before the yeast has had a chance to do most of it's work?) wash, or to the Low wines as they sit, before the spirit run, OR, it sounds like perhaps you could add them to the boiler with the low wines when doing a spirit run... I'm only repeating what i've read from some others here in posts above. I am not speaking from first hand experience, so i can't Personally vouch for the efficacy of any of these methods.

So, to be clear, i am commenting and posting on this topic from the perspective of someone who does NOT know much about this. I am not saying I am knowledgeable at all about these chemicals methods or techniques, I am trying to say the opposite. If you're like me, be smart, don't try messing around with potentially dangerous chemicals, and absolutely, DO not attempt to make, create, synthesize, whatever these chemicals. This is not something you want to take chances on. There are sooooo many other fun, exciting, and tasty washes and recipes we have at our disposal here. Just pick something else to work on, as there is no shortage of outstanding tried and true recipes on our forum.

Don't be hard headed or a knucklehead. Know yourself and your limitations. I am not trying to Fear-Monger, or scare anyone. I just wanted to take an opportunity to advocate for our number one attribute here. Safety!! If you are well versed with chemistry and have a great knowledge of the additives discussed in this thread, please ignore what i have said, although it is always wise to proceed with care and caution. But if you're new to distillation and all the myriad of things that go along with it (it's a very simple process, that can have infinite complications and variations, which i absolutely love) please be careful!! I'd hate for anyone to have any sort of incident. Take care!!

Perhaps one of you fine gentlemen would, if you think it prudent, be able to post a link or two, perhaps discussing more about the processes and chemicals discussed here, or maybe even a link to where one could buy them if so inclined.

Thanks, Y'all

CC
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Re: So, the answer was copper

Post by Bagasso »

CatCrap wrote:So, for me, and for anyone who is new to distilling, or unsure of how to use any of the techniques or chemicals above, I would STRONGLY suggest the only method you attempt to use is to add some copper bits (oxidized, right? So that just means they aren't shiny and new like?)
Every mention of the copper penny test that I have seen mentions clean copper. It makes sense if you think about it. Copper is reactive but once the patina forms it shields the layer below it, like aluminum and SS. It makes no difference in a wash because the wash is acidic and it will clean the patina off and expose clean copper.

Here is a link that talks about the process a bit: Copper additions to wine

One thing that always seemed counter intuitive to me was the addition of copper sulfate. The copper makes sense but sulfate seems to be adding what we want to remove. The link above states
Copper is (almost always) added to wine in the form of Copper Sulfate pentahydrate (CuSO4 • 5H2O), a blue crystalline powder. The active ingredient in Copper Sulfate is the copper ion (the rest is just along for the ride).
Turns out sulfate is a salt, that is filtered/fined out in wine and to our advantage has a boiling point of 1,429 °C.

It can be found on amazon or where pool supplies are sold because it is used as an algaecide.
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Re: So, the answer was copper

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I found a couple articles that were pretty interesting. Predominantly dealing with wine. But interesting nonetheless. and hence by my name I found them interesting cuz it also deals with wine. Wine beer wash all kind of the same.

Copper additions to wine
Copper is (almost always) added to wine in the form of Copper Sulfate pentahydrate (CuSO4 • 5H2O), a blue crystalline powder. The active ingredient in Copper Sulfate is the copper ion (the rest is just along for the ride).

The addition calculations on this site all assume you're using Copper Sulfate pentahydrate, as opposed to metallic copper or straight Copper Sulfate (the green stuff).

So when people talk about a copper addition rate or copper solution they are talking about the rate of the copper ion (Cu+2), not the entire CuSO4 molecule. CuSO4 is about 25% copper by weight, which is why you have to add about 0.4 ppm of CuSO4 to get 0.1 ppm of Cu+2.

Why add copper?
Copper Sulfate (CuSO4) reacts with sulfur compounds such as Hydrogen Sulfide (rotten egg smell) and mercaptans (burnt match, rubber, cooked cabbage, canned corn, etc.) These aromas can arise during fermentation due to nutrient limitations and they can come about also throughout the aging process through breakdowns of sulfur-containing amino acids.

Dealing with these objectionable aromas early, either by adding CuSO4 or by nutrient supplements during fermentation, is important to minimize the amount of intervention required to fix the wine. Sulfides left untreated can form disulfides which not only sound twice as bad but are not eliminated by CuSO4 treatment alone.

Splashing wine to eliminate sulfide aromas can encourage the formation of disulfides, which have a lower sensory threshold than sulfides (so the wine will not smell as bad as before). These disulfides can serve as a reservoir of stink from which sulfides can be re-formed under reductive conditions, bringing you back to square one.

If your wine stinks you should do a copper trial to find the right treatment, then add CuSO4.

Add copper »
Why bother with copper solutions?
Copper solutions are a great way to add copper to barrels or to lab samples.

Typical addition rates for copper are below 0.5 ppm, which makes for a minute amount of CuSO4 to weight out for a lab sample, and a tedious chore for a barrel group.

Also, having a stock copper solution on hand makes it easy to diagnose sulfide problems and determine the correct treatment level with a lab trial.

And, if you're really into solving winemaking problems you can keep this solution on you in the event you're served a stinky wine at a party or restaurant.

Note: Copper solution calculations on WineAdds are in terms of copper ion concentration (Cu+2), not CuSO4 concentration.

Make a copper solution »
Why bother with copper trials?
Lab trials are always a good idea before making additions to production lots. This is especially true with copper additions as you want to make sure your addition is going to have the desired effect.

Foul-smelling sulfur compounds can be either sulfides or disulfides, and copper alone is only effective against sulfides. If you prepare a copper trial and you don't see any improvement, then your wine has a disulfide problem and you'll need to add Ascorbic acid with your copper and wait several months for the stink to go away.

If you see your copper trial improving the wine, then you have caught your sulfide problem in time and you should pat yourself on the back. Just determine which treatment gives you the required result and is legal wherever you're making wine, and pull the trigger.
http://www.wineadds.com/faq/copper" onclick="window.open(this.href);return false;" rel="nofollow
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Re: So, the answer was copper

Post by iwine »

How Copper Fooled Us All
BY PIERO SPADA · MAY 1, 2017

Piero is a Midwest vineyard and winery consultant specializing in cool-climate and cold-climate grape & wine production. He can be reached via email at pierospada.com
Intro — Part i

Got a hint of burnt rubber smell in that St. Pepin that’s sitting idly in tank? No problem, a judicious dose of Copper Sulfate will correct that. Following a quick and easy tank addition, according to protocol, you filter your wine after treatment and Wham-Bam, Ding-a-Ling-a, Ding-Dam – problem fixed“at least for the time being.

You bottle, and after several months, proudly unveil your beloved creation to a room full of your friends, only to realize that the nefarious burnt rubber smell is back. An odor, your neighbor Ned was quick to point out reminds him of being at a racecar track. Who invited that big mouth in the first place?

What the H*%# happened? Well, unbeknownst to you a ticking time bomb went off and it’s in large part because you added Copper to your wine!

How’s that possible? Copper is the tried-and-true fix for treating Reductive aromas, or more precisely put, Sulfur-like Off odor (SLOs) in wine.

And you’re right, traditionally, copper has been used to correct these types of wine faults (open any Enology or Winemaking text book). Heck, I’ve even suggested this correction in previous protocols and articles.

But that was then and this is now. So, buckle up and sit tight – what we’re about to cover in the this article is research that has taken place in the past 5 years that refutes just about everything we think we know about SLO treatment.
Abbreviation Key
Abbreviation Key
Current use of copper in Wine

For those, looking for the basics on SLOs, please read my 2014 MWP article (Back to Basics: Preventing Rotten Eggs). This article assumes you are familiar with the basic nomenclature of different SLOs.

SLO formation during fermentation is pretty well characterized. However, what is poorly understood is post-fermentation SLO formation either during tank storage or in bottle (herein referred to as latent H2S formation). I personally lament latent H2S formation especially as it relates to wine sitting idly in tank (typically a white or rosé) because the exact cause of formation is rather difficult to identify.

Regardless of when SLO formation occurs (assuming it’s not already in bottle), the winemaker will often carry out bench trials to better pinpoint what concentration of Copper is needed to correct the SLO problem at hand — assuming SLO is H2S or a MeSH stock to a Glass of Wine.

Unequivocally, what is not being refuted here is the notion that Copper will complex with the stinky sulfide molecule and form Copper Sulfide (CuS). With little doubt, this chemical reaction occurs rapidly in wine2.

Traditionally, CuS has been said to be insoluble in wine, leading to formation of a black precipitate that over time settles to the bottom of the tank. To ensure CuS does not release H2S over time, after CuS settling, a simple racking and/or filtration has been the standard protocol. One major problem with the current protocol, does anyone actually ever see this precipitate?! Personally, I’ve never seen it before and I’d be willing to bet you haven’t either.

Why is that? A Look at Modern Research

In short, it appears that there are two leading theories as to why the CuS precipitate is never observed: 1) CuS forms nanoparticles ranging in size from 1-1000 nm (for comparison a bacteria cell is roughly 1000 nm) and therefore is not visible to naked eye1, and/or 2) CuS doesn’t precipitate and binds with other wine components (hold your horses on this one).2,3

First things first. In the former experiment1, the authors acknowledged that a precipitate was never visually observed. However, one of the aims of the study was to access the efficacy in removing CuS in wine after Copper treatment. Here the authors assessed the effects of racking, settling (1 vs. 5 days) and sterile filtration (at 0.45 or 0.2 μm). Surprisingly for commercial wines after settling or filtering treatments, negligible amounts of Copper was removed.1 Highlighting the fact that despite your best efforts to remove CuS from wine, it is likely still there after treatment!

As this result significantly differed from that of prior model wine experiments (a model wine is a ‘bare bones” wine comprised of a diluted ethanol solution set at a specific pH), where sterile filtration was indeed able to decrease residual copper levels, the authors theorized that something in commercial wines must be binding up CuS. In a subsequent experiment, that something turned out to be tartaric acid. This piece of evidence suggests for us in cool and cold climate country, where our wines contain elevated organic acid levels (both malic and tartaric acid alike) the wines maybe really good at binding up CuS – making it really hard to remove CuS from wines using conventional methods.

Ah Binders of CuS, this brings us to the latter experiment. Not only can CuS be bound up in wine but it now appears evident that the reductive notes themselves, specifically H2S and MeSH, can also bind (or be trapped) with other wine components — with or without Copper Treatment!2 This new binding mechanism, has lead researchers to segregate and characterize SLOs (for H2S or MeSH) either on bound or free form basis. For example, if H2S is in its free form, it is odor active and you can detect its presence with your nose (assuming it’s concentration is greater than the odor detection threshold). And when H2S is in bound form, it is not odor active. As previously discussed, an example of bound H2S is CuS interacting with tartaric acid. And similar to SO2 wine chemistry, Free H2S + Bound H2S = Total H2S (the same equation works for MeSH).

What is really interesting is that on average, most H2S (80 — 95% of total) in white, rosé, or red wine is in the bound form!2,3 Meaning that most of the H2S in wine isn’t even detectable by the human nose, even though a significant portion might be present! What binds with H2S (and MeSH) in wine and the mode of action, is an area of active research by multiple teams.

As previously mentioned, tartaric acid has already been implicated as one source of bound H2S (trapping CuS) and currently other forms are being explored (see Sulfur Residues and Post-Bottling Formation of Hydrogen Sulfide for more info). What is clear is that this mechanism is multifaceted, with many moving parts, and as of right now poorly characterized.

If the newfound understanding that there is a difference between Free vs. Bound SLOs wasn’t enough, a single research group is also strongly arguing that H2S and MeSH do not precipitate with metals such as Copper in wine at all!2 This notion, runs counter to what has been preached by Wine experts (myself included) and texts for decades.

According to the researchers data set, additions of Copper as high as 2 mg/L (ppm) have not yielded a visual precipitate and upon further analysis, the CuS complex remained in solution (wine). While this notion is still up for academic debate, pairing this data point with winemakers’ observation of never seeing a black precipitate strongly suggests that CuS may not precipitate at all. Lastly, according to this same research group, these H2S metal-complexes (e.g. CuS) are completely soluble, stable, and more importantly reversible…

Part ii — Triggers of Bound H2S Release — A ticking time Bomb

Yes, you read that correctly, bound H2S (or MeSH) formation is reversible! Meaning that a Copper treated wine that forces H2S into a bound state (recall CuS association with tartaric acid), can also release sulfide (at a later time) to reform odor active Free H2S. In this sense, CuS acts as a type of chameleon, tricking you to believe that the issue at hand has been corrected, when in reality it is sitting there in wine, hidden and bound to other wine constituents in its non-odor active form, idly waiting for the right moment and time to resurface!

This new latent H2S release mechanism begs the questions as to how this occurs and more practically when does this release occur, herein called a trigger?

The most well studied triggers of latent H2S release comes from bottled wine studies.4,5 After addition of Copper to a bottled wine, anoxia (or a lack of Oxygen) in bottle is the best characterized trigger to latent H2S release.4 Taking this research a step further, under similar anoxic bottle conditions, a follow-up research group discovered that wines with last minute copper and SO2 additions pre-bottling were more susceptible to have latent H2S issues in bottle than wines treated solely with Copper.5

Coming full circle on our St. Pepin story, this mechanism is the exact mechanism in which the dreaded latent H2S reappeared in your bottle. Because you added Copper pre-bottling and were extremely careful to keep the Dissovled Oxygen (DO) in your wine low (< 0.5 ppm), sparged your bottles with inert gas before filling, purged the bottle headspace with inert gas before closing, and chose a screw cap closure you may have unknowingly accelerated the chemical means to force latent H2S release in bottle.

How and why this happening is not yet fully understood. And there are likely to more triggers / mechanisms to be discovered.

For now, it is interesting to note that anoxic conditions seem to force latent H2S release, especially when considering that the hot topic du jour in wine publications relates to Total Package Oxygen (TPO) in bottle. TPO is the cumulative amount of oxygen exposed to wine in bottle over time, typically measured by taking into consideration dissolved oxygen in wine plus headspace oxygen, and sometimes includes the OTR of the bottle closure overtime. Having high TPO forces premature loss of SO2 and thus premature oxidation mechanisms in to occur in bottle. Therefore, in order to increase the shelf life of a wine, the current recommendation is to minimize TPO as much as possible during bottling. But here, if a wine has been previously exposed to Copper treatment, this deliberately low TPO may in fact be the trigger to latent H2S formation in bottle!

As with most winemaking practices, walking the tight rope of this balancing act is a must — having too much oxygen can predispose your wine to premature oxidation and having too little oxygen may trigger H2S release (if copper has been previously used). Talk about the art of intelligent compromise. On this note, the silver lining as to why more wines treated with Copper haven’t released H2S is because of the OTR of the bottle closure used. Preliminary reports have shown, that higher oxygen permeability in a closure is likely beneficial in minimizing Free Forms of H2S emerging from bound forms.2 Meaning that a higher rate of oxygen diffusion into the wine, either from the closure and/or through the closure, is beneficial to prevent a latent H2S release.

Although not firmly cemented in research, this finding might lend credence as to why screw cap closures have been linked to higher rates of reductive wine faults.6 Before the advent of the more oxygen permeable Saranex liners, screw caps have (and are) notoriously low in OTRs.6 And this property could inadvertently trigger latent H2S release in bottle — especially if the wine had previously been treated with copper. On this premise, for a reductive wine that has been previously treated with Copper, it may be in your best interest to bottle wine with a closure that allows a higher OTR.

So where does this leave us?

Regardless if copper has been added or not, we now understand that the bulk of H2S produced may not be aromatically detectable (in bound form), if we do treat an H2S flaw with Copper, we may never be able to remove CuS; thus leaving our wines open to latent H2S release — especially under anoxic bottle conditions.

So what can we do about this problem?

First and foremost, in terms of treating post-fermentation H2S or MeSH, Copper (hopefully for obvious reasons) is probably not the best choice. For now, two alternatives remain viable alternatives: Reduless and Kupzit. Reduless is a proprietary inactivated yeast product from Lallemand that contains biologically bound Copper. Meaning, when used according to protocol, the maximum residual copper left in wine is 0.02 ppm. Similarly, Kupzit, is propriety product from Erbslöh and contains 2% Copper Citrate encapsulated in Bentonite. Both products work by using embedded Copper to pull H2S or MeSH out of solution and trap Sulfide within the solid phase. After treatment, a simple racking and/or filtration after settling is all that is needed to remove the SLO from wine.

More recently, a winemaker-friendly analytical test has been developed by Dr. Gavin Sacks lab group at Cornell University. 3 This test can help quantify both Free H2S and bound H2S through the use of a Gas Detection Tube (GDT). Note, a similar test was developed by this same group to quantify elemental Sulfur residues on grapes that can also lead to H2S formation (see video here). This test consists of using a GDT, originally developed for the mining industry more than 75 years ago, and a chemical solution (a brine, or other reducing agents) to force the release of bound H2S.

Despite having an inexpensive and accurate test to quantify for possible formation of latent H2S, the challenge here seems to be what to make of the quantified number. Think about it, just because the test can force most of the bound H2S into a detectable free form doesn’t necessarily mean this is what is going to happen in bottle. Recall, there are multiple triggers that favor this release in wine, so there is no guarantee that what has been quantified predisposes the wine to future latent H2S release in bottle (or in tank). Therefore, from a sensory standpoint, any link to current or future detectable amounts of H2S hasn’t been made yet. So unless you’re doing your own R&D, for now, this test may serve more as of academic exercise than a true risk assessment.

In conclusion, if you can’t tell by now, it appears that Enology chapters dealing with Reductive Aromas will be re-written after this research has concluded. There’s much more to discuss with ongoing research efforts but that will have to be for another day. For now, the best strategy is to avoid SLO formation altogether, but that is not always feasible given the number of unknowns for post-fermentation SLO formation. So if you do need to treat, look to the alternatives mentioned above. And if a wine does need treatment, choosing a closure with higher OTRs may be a wise choice in this scenario.

Because if you don’t, well, then I’m sure your beloved neighbor Ned will be there to remind you of your mess-up once again and nobody wants that.

https://midwestwinepress.com/2017/05/01 ... ed-us-all/" onclick="window.open(this.href);return false;" rel="nofollow
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Re: So, the answer was copper

Post by Bagasso »

iwine wrote: Yes, you read that correctly, bound H2S (or MeSH) formation is reversible! Meaning that a Copper treated wine that forces H2S into a bound state (recall CuS association with tartaric acid), can also release sulfide (at a later time) to reform odor active Free H2S.
Thank you for these articles. This quoted part was what I was thinking when I posted this in the post linked below:
The musty problem that I described got me thinking, what if heat is reverting the copper treatment. It could also be something else but since I have no way of knowing it is bugging me.
viewtopic.php?f=1&t=63358&start=150#p7529030

Nice to have some info backing up what I was observing, even if it only offers 2 "kind of expensive" solutions. I mean, they may be worth it for saving an otherwise nice wine but all the ingredients in a sugar wash probably cost less than these fixes and that doesn't include shipping for those of us outside countries with brew-shops.

I have not run anything for a while because the drinking part of the hobby was getting a little out of hand and cutting off the supply seemed like a good first step in getting things under control, but I have to say that this new info has got me in R&D mode. Maybe just 1L batches? For science of course.
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Re: So, the answer was copper

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The only Distillate that I seem to have issues with off taste as my hook rum recipe. I just pulled off a modified version of hook rum and I tried carbon filtering which did clean it up a lot but there is still something weird.For some reason in my rum batches I seem to get what I think is Tails almost threw out the Run.
So after reading this copper thread and doing a lot of reading about copper being used in wines and beers .
After reading this thread. so I thought it was time to do a quick Side by side test.I don't know if this all amount to much but I have the same batch of rum and two jars one with a piece of copper and the other without as my control . I have no idea how long to keep this copper in the jar so I'll taste it tomorrow to see if I see a difference. any advice is welcome. Here are the pics.
copper test40.jpg
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Re: So, the answer was copper

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iwine wrote:For some reason in my rum batches I seem to get what I think is Tails almost threw out the Run.
I know the feel. I remember posting here a long time ago that it seemed like I had tails in my heads and they lasted for the rest of the run.

As for advice on your test, over night should be good. I noticed in my experiments, with wash, that at around 6 hours things had cleaned up as much as they would with little difference after that.

The problem, if I'm remembering my own research into copper correctly, is that copper only works on H2S and doesn't help with things like DMS and other disulfides, so adding copper at that stage might not do any good.

My mind keeps going back to bowl centrifuging to get the CuS out after copper treating the wash and before loading the boiler.
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Re: So, the answer was copper

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The way it was distilled was a strip run then a Spirit Run, and run through carbon filtration before I did this test..
First test initial observation after 24 hours of a piece of copper in the jar.
the first thing that we noticed and I was surprised quite noticeable is the jar with the copper was crystal clear In the second jar compared to the first
it was actually my girlfriend that had noticed the clarity of it.
Our observations were left to right.The right one has the copper in it.
We did to tests First one at Cask strength 50% ABV
and a second test diluted with distilled water at about 30% ABV

Jar 1 she thought there was a taste of paper in it with a hint of molasses smell.
Jar 2 She thought that the paper smell had gone. but also the smell of molasses has diminished and she thought it seemed to be a little sharper.She did like it better she said it was cleaner

my observation
Jar 1 I thought there was a wet paper taste to it and I did smell the molasses It definitely doesn't smell as clean as my birdwatchers
Jar 2 The first thing that I noticed when I smelled it. is that it Smelled sweeter and cleaner.
I noticed the taste and smell, that most of the musty / paper was mostly gone. I did notice that the taste of the molasses did diminish And did create a cleaner drop.

conclusion of this test
is that there was an improvement overall to the flavor and Aromas( except for the taste of the Molasses diminishing) which surprised me.

my next step I decided to leave the little piece of copper in for another 24 hours and rerun the test( oh darn) That will be hard to take.
Because of the improvements I'm going to continue playing around with this over my next few runs
If my observations are different and smell or taste in the next 24 hours I will write about them.

I do have another batch of rum that I'm doing the cuts on tonight the difference between this batch and the one above is that I used my pot and Thumper I will rerun the tests on that one also but I will put the copper in before I run it through carbon filtering if I do. I will keep you up-to-date on my results. Comments and questions are more than welcome
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Re: So, the answer was copper

Post by Bagasso »

iwine wrote:Comments and questions are more than welcome
I think you should do a search for Ethyl carbamate on the site. It is a source of many heated debates but the Cliffs Notes version is that copper acts as a catalyst in the formation of Ethyl carbamate, which is a carcinogen. You don't want to be drinking hooch right off of a copper treatment for this reason.

It is resolved by another run but then you might run into what I observed, nice smelling copper treated wash or low wines went back to having an off smell and/or flavor after their trip through the still (similar to what the second article you posted was talking about).
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Re: So, the answer was copper

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Worth putting a little molasses in the finished product?
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Re: So, the answer was copper

Post by Bagasso »

The Baker wrote:Worth putting a little molasses in the finished product?
Have you seen the essential oils sub-forum?

You take a still place a chamber for plant matter on the up side and the steam carries over big fat oil molecules. Makes me think the old school ideas of how distillation works might have been off in a few spots.

Seems like a good way to add back some molasses or other flavor. The new MO might be stripping run > spirit run > flavoring run. Although, we have to figure out how to make the copper treatment part stick, if running through the rig undoes the magic.
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Re: So, the answer was copper

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https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4609976/" onclick="window.open(this.href);return false;" rel="nofollow
Sorry but this might be slightly off topic for this
it's too long to post. Its a scientific paper about Ethyl carbamate in Fermented drinks and food products From around the world..
The title is "Determination of Ethyl Carbamate in Alcoholic Beverages and Fermented Foods Sold in Korea"
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Re: So, the answer was copper

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iwine wrote:Sorry but this might be slightly off topic for this
I think the mention of copper as a catalyst in the formation of ethyl carbamate means it is on topic.

Here is a paper on ethyl carbamate in pot stilled whisky: ETHYL CARBAMATE FORMATION IN THE PRODUCTION OF POT STILL WHISKY

And one about it in sugar cane products: Ethyl carbamate kinetics in double distillation of sugar cane spirit
Double distillation decreased the ethyl carbamate content in the sugar cane spirit by 97%.
Ethyl carbamate has a boiling point of 182°C. In theory there shouldn't be any coming over but, as essential oil distillation shows, the idea that boiling points are cold hard indicators might not always hold true.
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Re: So, the answer was copper

Post by The Baker »

Bagasso wrote:
The Baker wrote:Worth putting a little molasses in the finished product?
Have you seen the essential oils sub-forum?

You take a still place a chamber for plant matter on the up side and the steam carries over big fat oil molecules. Makes me think the old school ideas of how distillation works might have been off in a few spots.

Seems like a good way to add back some molasses or other flavor. The new MO might be stripping run > spirit run > flavoring run. Although, we have to figure out how to make the copper treatment part stick, if running through the rig undoes the magic.
Thanks, Bagasso.
Actually I just thought of a really tiny amount of molasses 'stirred into' the final product.
Of course you would have to make sure it was clean and clear but a little jar of molasses from the supermarket or a catering supplier should be fine to use...
Just a thought.

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Re: So, the answer was copper

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The Baker wrote:Actually I just thought of a really tiny amount of molasses 'stirred into' the final product.
I know that was what you meant but if memory serves me right, and it probably doesn't, a really tiny amount might not be enough of the flavor rum fans are after and the more you add the sweeter it would get. It would definitely a personal preference thing.

It would be worth trying because it is what we do but then you have the thing about storing or rerunning and having the funk come back and the ethyl carbamate issue.
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Re: So, the answer was copper

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I kind of feel the EC issue has been done to death but if we are going to reanimate this zombie horse for one more whipping let's simplify it. EC can with the right precursors during fermentation or distilling or even while aging as a finished product be formed. Small amounts of this compound can form and is present in many food and beverage products. There are a number of steps we can take to limit the production and or remove it. Urea is a major precursor so avoid it and products that contain it, copper is a known catalyst for said precursors (urea and ethanol) so if you have a copper column or copper in the ascending path it will form there and is unlikely to carry over which will mitigate it forming in the finished product and if double distilled with copper present it will catalyse during the first distillation and due to the high boiling point remain in the stillage, the same principle would also be valid for thumpers and plated columns. The real danger as I see it would be the formation in new make ran in say glass or stainless stills and particularly in single runs.
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Reason: Spelling errors or more to the point spell check changing words :p
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