Need water guru for an unusual project

[antisoshal]

Disclaimer: I've done very little water chemistry myself as our municipal water is pretty good and is used out of the tap by dozens of breweries already. That said, Im opening a small "boutique" brewery where a reasonably well known historic brewery operated in the the late 1800's. They bragged about using mineral water from local springs and had national distribution for some of their beer, but have disappeared entirely since prohibition. The springs have long since stopped flowing, but I have the mineral analysis from the 8 local springs operating back around 1865-1885. Because there were operated as "health springs" with hotels and amenities, the analysis is in depth, more so than basic hardness and ion count that brewers focus on now. The water is significantly alkali and I believe the flavor of the water itself was as much a component of the beer as it was to the health of the yeast, so Id like to try and mimic that to the best degree possible. All of the 8 springs vary significantly in some salts but have a few common trends, the biggest being a large bicarbonate of lime and bicarbonate of magnesia count.

Anyone feel up to helping figure out what witches brew of salts I will need to approximate this? We know he bought water from several springs based on availability and price, so rather than emulate one, I'm going to try and work up a profile that would approximate what you'd get if you mixed them, as he likely did. I also suspect he diluted it with well water because it all looks pretty hard and alkali to be used as it came out of the ground. I'm at work right now but I can post some the exact numbers tonight if someone wants to help me down this rabbit hole. Theres a lot of them.

 

[antisoshal]

The following is a weighted mean/average of all of the springs that were in use when this brewery operated. I say weighted because in some cases the measurement wasnt made for a certain spring, but all the others had a significant amount, so I assumed that spring would be similar.

Chloride of Sodium 15.5ppm
chloride of magnesium 8ppm
Sulphate of soda 35.3ppm
Sulphate of potassium 4.5ppm
Sulphate of lime 54ppm
Bicarbonate of lime 265ppm
Bicarbonate of magnesia 208
Sulphate of magnesia 44pm
Bicarbonate of iron 2ppm
Oxide of iron and alumina 1.5ppm
Bicarbonate of soda 93ppm
Silica 13.8ppm
Alumina 2.1ppm
Chloride of Calcium 50.3ppm

So the magic question is how do I translate these adjuncts I can acquire, and what will the magic formula of said adjuncts be.

 

[Vale71]

They bragged about using mineral water from local springs and had national distribution for some of their beer, but have disappeared entirely since prohibition. .

There's a very good chance bragging was all it was. Strongly mineralized water is not really suitable for brewing, both from a mash chemistry standpoint and from a taste standpoint. Even if they did use such water the resulting beer would probably be considered undrinkable by today's average drinker as tastes have evolved somewhat since the 1800's.

 

[Silver_Is_Money]

You're looking at a ballpark of about 570 ppm of totaled bicarbonate, or a ballparked alkalinity of about 467 ppm. No one I can think of would ever want to brew with water that alkaline.

I wonder how they managed to determined the ppm of chloride and sulfate and bicarbonate anions which came from the various cations. That would be one absolutely amazing trick, seeing as how for ions which are dissociated in naturally sourced water there is no telling where they originally hailed from.

The all important calcium and magnesium ppm's are missing from your report. It's wildly possible that they may be derived though. For example, if you know that ~50.3 ppm of chloride came from calcium (presumably as calcium chloride), then the calcium is ~28.4 ppm from that source.

 

[Silver_Is_Money]

Of course this could wildly be construed to be a water recipe:

Chloride of Sodium 15.5ppm = Sodium Chloride at 15.5 mg/L
chloride of magnesium 8ppm = Magnesium Chloride at 8 mg/L
Sulphate of soda 35.3ppm = Na2SO4 at 35.3 mg/L
Sulphate of potassium 4.5ppm = K2SO4 at 4.5 mg/L
Sulphate of lime 54ppm = Calcium Sulfate at 54 mg/L
Bicarbonate of lime 265ppm = Calcium Bicarbonate, or Ca(HCO3)2, at 265 mg/L
Bicarbonate of magnesia 208 = Magnesium Bicarbonate, or Mg(HCO3)2, at 208 mg/L
Sulphate of magnesia 44pm = MgSO4 at 44 mg/L
Bicarbonate of soda 93ppm = Baking Soda at 93 mg/L
Chloride of Calcium 50.3ppm = Calcium Chloride at 50.3 mg/L

Just add the above milligrams of each chemical to a liter of water and you have it. Don't ask me (or anyone else) to drink it though.

Chemistry was in its infancy back then, so who knows what you really have there.

 

[antisoshal]

There's a very good chance bragging was all it was. Strongly mineralized water is not really suitable for brewing, both from a mash chemistry standpoint and from a taste standpoint. Even if they did use such water the resulting beer would probably be considered undrinkable by today's average drinker as tastes have evolved somewhat since the 1800's.

Yeah I'm almost positive they diluted it at the very least, but I have positive confirmation they bought the water from some springs to augment the supply from the spring they were next to. Interestingly, one of the springs was used to make soda in the 20th century and they definitely just used the spring water. The spring itself dried up in the 60's but the soda kept going on municipal water until the late 1970s.

 

[antisoshal]

Of course this could wildly be construed to be a water recipe:

Chloride of Sodium 15.5ppm = Sodium Chloride at 15 mg/L
chloride of magnesium 8ppm = Magnesium Chloride at 8 mg/L
Sulphate of soda 35.3ppm = Na2SO4 at 35.3 mg/L
Sulphate of potassium 4.5ppm = K2SO4 at 4.5 mg/L
Sulphate of lime 54ppm = Calcium Sulfate at 54 mg/L
Bicarbonate of lime 265ppm = Calcium Bicarbonate, or Ca(HCO3)2, at 265 mg/L
Bicarbonate of magnesia 208 = Magnesium Bicarbonate, or Mg(HCO3)2, at 208 mg/L
Sulphate of magnesia 44pm = MgSO4 at 44 mg/L
Bicarbonate of soda 93ppm = Baking Soda at 93 mg/L
Chloride of Calcium 50.3ppm = Calcium Chloride at 50.3 mg/L

Just add the above milligrams of each chemical to a liter of water and you have it. Don't ask me (or anyone else) to drink it though.

Chemistry was in its infancy back then, so who knows what you really have there.

It seems to be a pretty standard format for analyzing "therapeutic" mineral springs. One set of values I have is from an entire book of analysis of mineral springs and there are several hundred from across the country. I honestly wondered myself how they got some of the readings. Everything was in "grains" which translated to grains per gallon> I asked someone in the hot springs industry how they achieved sourcing ions like you mentioned. Apparently the test involved a reagent that would react and precipitate a detectable byproduct when the gallon evaporated. My chemistry is fairly rudimentary so I can't really get deeper than that. This is from a travel book for the midwest. Glen Flora is one of the springs my predecessor got water from, and Bethesda is a mineral spring in Wisconsin that was famous at the time for its "health benefits".

The others I found in other travel logs, advertisements and historical material.

 

[Silver_Is_Money]

17.1 * Grains = ppm = mg/L

 

[antisoshal]

17.1 * Grains = ppm = mg/L

Thats the math I did, but I used a few more decimal points. =8)

 

[Silver_Is_Money]

Or it could be that:

1 gram = 15.43236 grains

I'm voting for this one, and for these being duplication recipes. Scaled (it appears) in grains per US gallon.

 

[Silver_Is_Money]

7,000 grains = 1 Lb. (Avoirdupois)

Or if you go back far enough in time, 7,000 kernels of barley = 1 Lb. (Avoirdupois)
(Wherein 1 'nominal' kernel of barley literally defines the weight of 1 "grain")

and:

5,760 grains (or nominally sized kernels of barley) = 1 Lb. (Troy)

 

[antisoshal]

Is there any place where I can get all of those different salts other than a chemical supply house? They tend to charge an insane amount for lab grade reagents.

 

[Silver_Is_Money]

Is there any place where I can get all of those different salts other than a chemical supply house? They tend to charge an insane amount for lab grade reagents.

If someone is going to drink beer made from it, the chemicals need to go beyond reagent grade and be certified as food grade.

 

[antisoshal]

If someone is going to drink beer made from it, the chemicals need to go beyond reagent grade and be certified as food grade.

Yup. but things made food grade are generally also made in larger quantities and sold cheaper than reagents at online chemical sources.

 

[Silver_Is_Money]

What does your nominal mineralization look like of you go with grains per gallon and convert from there into grams per gallon and then lastly into mg/L (or ppm)? Using 15.43236 grains = 1 gram (or 1 grain = 0.064798903 grams)

It may look much better overall with respect to the ppm of bicarbonate concentration via this method. Be sure to balance out the bicarb as merely a percentage of the molecular weight for each mineral with a bicarb component. That alone will make it look much better.

 

[antisoshal]

What does your nominal mineralization look like of you go with grains per gallon and convert from there into grams per gallon and then lastly into mg/L (or ppm)? Using 15.43236 grains = 1 gram (or 1 grain = 0.064798903 grams)

It may look much better overall with respect to the ppm of bicarbonate concentration via this method. Be sure to balance out the bicarb as merely a percentage of the molecular weight for each mineral with a bicarb component. That alone will make it look much better.

I have all the raw numbers at home in a spreadsheet so I will try that pathway when I get home and post results. I also think that by making an average, I may have elevated the overall alkalinity because most of the springs had one or more component lower than others, but by averaging them I may have escalated to total. I need to ponder my model.

 

[antisoshal]

This is an excerpt from The History Of Chicago published 1883

 

[Silver_Is_Money]

I have all the raw numbers at home in a spreadsheet so I will try that pathway when I get home and post results. I also think that by making an average, I may have elevated the overall alkalinity because most of the springs had one or more component lower than others, but by averaging them I may have escalated to total. I need to ponder my model.

There is another issue at stake when averaging waters. In the real world cation and anion balance must be strictly maintained. When waters are averaged, the positive ion (cation) and negative ion (anion) charge balance of "real" water is typically broken.

 

[antisoshal]

There is another issue at stake when averaging waters. In the real world cation and anion balance must be strictly maintained. When waters are averaged, the positive ion (cation) and negative ion (anion) charge balance of "real" water is typically broken.

This is why I asked for an expert. This is important info. Maybe what I will do is make a spreadsheet page for each of the 8 springs individually. I think maybe I will just use the one that was closes to the largest phase of brewing as I know it was used.

So what happens if you mix different spring waters with different mineral contents? do they precipitate out something to resolve the natural balance?

 

[antisoshal]

So here is the individual analysis for the spring that was closes to the final production brewery (The original brewery was closer to another thats actually 5 springs in a group). Using your math I took the grains per gallon and multiplied by 64.8 to get mg/G then divided by 3.785 to get mg/L

chloride of Sodium 45.02615588 mg/L
suphate of potassium 4.58821664 mg/L
sulphate of lime 215.28665786 mg/L
bicarbonate of lime 138.34842801 mg/L
bicarbonate of magnesia 342.18166446 mg/L
bicarbonate of iron 1.50657860 mg/L
silica 15.57939234 mg/L
alumina 2.56803170 mg/L
Chloride of Calcium 50.17933950 mg/L

does this look better?

 

[antisoshal]

I also notice in the above translation you made to modern chemical salt nomenclature, you ignored the silica, alumina and iron components. Can these not be translated?

 

[Silver_Is_Money]

I also notice in the above translation you made to modern chemical salt nomenclature, you ignored the silica, alumina and iron components. Can these not be translated?

You are not concerned with these minerals (and many others) for beer brewing water. Ignore them. They will only bring along with them flavor degradation. You are only truly concerned with these ions: calcium, magnesium, sodium, chloride, sulfate, and alkalinity (bicarbonate is an example of this). You will also want a very minute amount of zinc (typically from zinc sulfate solution, totaling to about 4 mg maximum Zn in 5 gallons of water) for proper yeast health, so they do not get stressed.

To answer your question regarding blended waters, they both have charge neutrality alone, so they will both have charge neutrality when combined.

But it is possible (rather easy in fact) to fabricate on paper a water that can't possibly exist in nature. Here is one:

Ca++, 50 ppm
Mg++, 7 ppm
Na+, 12 ppm
Cl-, 45 ppm
SO4--, 32 ppm
HCO3-, 150 ppm

mEq/L cations = 3.59, and mEq/L anions = 4.40
The charges do not balance, so this water is impossible.

As long as you are adding minerals which contain both an anion and a cation component (as in Calcium Chloride for example) you will automatically make real water with full cation/anion balance, since every individual component is in itself inherently so balanced. But if you are merely mentally fabricating (dreaming up) brewing water from ions alone (as for my example above, and for the examples of waters likely to be dreamed up by most home brewers, or those who use ion blended waters) it is far/far easier to guess and make impossible water than to guess and make water that can actually exist in the real world. In your case, you will always make real water. And I probably should not have brought this up to confuse you.

The main components you will need for fabricating brewing water are:
Calcium Chloride (Pickle Crisp ®)
Calcium Sulfate (Gypsum)
Magnesium Sulfate (Epsom Salt)
Sodium Bicarbonate (Baking Soda)
Sodium Chloride (table salt, iodine free)
Zinc Sulfate (perhaps, see below)
(most home brewers ignore the last one, but yeast need a very small amount of zinc and it is not present in RO or distilled water, or in most yeast nutrients (with the single exception of Servomyces). More than a small amount (more than around 1 mg in a gallon of water) and you will be throwing the beer away as undrinkable due to the horrible taste of zinc). Either use Servomyces yeast nutrient (the easiest way to go), or add a very small quantity of Zinc Sulfate.

Some others that may be of help (though most of us do not ever use them to build water) are:
Calcium Carbonate (this one is nigh on impossible to dissolve in water without taking extraneous measures)
Magnesium Chloride
Calcium Hydroxide (Slaked Lime or Pickling Lime)
Potassium Chloride
Potassium Bicarbonate

You really don't want to add much potassium, if any. It is generally to be considered on the ignore list. Only consider it if it is the only way to tweak a water into conformance with matching a water. And only use it in small amounts.

 

[Silver_Is_Money]

So here is the individual analysis for the spring that was closes to the final production brewery (The original brewery was closer to another thats actually 5 springs in a group). Using your math I took the grains per gallon and multiplied by 64.8 to get mg/G then divided by 3.785 to get mg/L

chloride of Sodium 45.02615588 mg/L
suphate of potassium 4.58821664 mg/L
sulphate of lime 215.28665786 mg/L
bicarbonate of lime 138.34842801 mg/L
bicarbonate of magnesia 342.18166446 mg/L
bicarbonate of iron 1.50657860 mg/L
silica 15.57939234 mg/L
alumina 2.56803170 mg/L
Chloride of Calcium 50.17933950 mg/L

does this look better?

I have no idea if it looks better. How does it compare with 17.1 x grains? The problem here is that I can't read the mind of an 1880's era chemist to determine what he intended by units of "grains".

The main killer of lighter colored beers (ales/lagers) in particular is bicarbonate. For lighter colored beers it needs to be addressed (eliminated, and then some) via acidification. Only darker beers such as Stouts/Porters can (perhaps) benefit from bicarbonate in water. Do you know the beer styles that were being brewed with this high alkalinity water?

 

[antisoshal]

I have no idea if it looks better. How does it compare with 17.1 x grains? The problem here is that I can't read the mind of an 1880's era chemist to determine what he intended by units of "grains".

The main killer of lighter colored beers (ales/lagers) in particular is bicarbonate. For lighter colored beers it needs to be addressed (eliminated, and then some) via acidification. Only darker beers such as Stouts/Porters can (perhaps) benefit from bicarbonate in water. Do you know the beer styles that were being brewed with this high alkalinity water?

His most popular and well known product was indeed a porter, but my understanding of his brewing techniques leads me to believe I wont be emulating the exact recipe even if I had it. English porters of his day were typically aged up to 18 months and "infected" with Brett as a result. He did make a full line of beer including a Lager eventually.

 

[Northern_Brewer]

Chemistry was in its infancy back then, so who knows what you really have there.

Actually the chemistry of water, and how it related to brewing, was pretty well understood by the late 19th century, our ancestors were rather more sophisticated than you give them credit for. And the above format was a pretty standard one for reporting brewing water.

Compare this water with these analyses of perhaps the world's most famous brewing water, Burton, reported in 1852, 1889 and 1893, the last with a comparison to the less mineralised water in Leeds :

http://barclayperkins.blogspot.com/2011/01/burton-water-part-four.html
http://barclayperkins.blogspot.com/2018/04/the-salts-of-brewing-waters.html

Note that these will be for Imperial gallons (20% bigger than US gallons). This was the water used by the most famous beers of the time and was notoriously sulphate-heavy, but just goes to show that you can make great beer with heavily mineralised water. Presumably US brewers would have sought out sources of mineralised water to better mimic the famous beers of Burton, I can imagine it would be a real selling point.

 

[ajdelange]

The key to brewing water and mash chemistry is the Henderson Hasselbalch equation and the key to that is the concept of pH. These were both conceived around 1908 - 1909. Before that I don't think we could say the chemistry was well understood.

 

[Northern_Brewer]

You don't need the full theoretical framework to develop a practical understanding of what works (and I'd put a shout in for Arrhenius in the 1880s). Burton's secret sauce had been known about for a long time - see James Sheridan Muspratt from 1860 when it was so famous as to barely be worth mentioning :
"The Editor does not deem it necessary to give a long dissertation upon this liquid, as nearly every one at all acquainted with brewing knows, that water which contains a large quantity of gypsum - sulphate of lime - earthy carbonates and no organic matter, is best adapted for his purpose."
As an aside, following pages go into quite a lot of detail about hops and the brewing process, it's the sort of thing that brewers in the (ex-)colonies would have followed if they didn't have previous experience of brewing.

Brewers of pale ales were encouraged to make their water as much like Burton water (at ~70 grains of solids per imperial gallon, although the likes of Bass had even more) as possible. A typical instruction from the Brewer's Guardian of 1891 used Hooper's Burton mix of 4:3:1 gypsum:sodium chloride:Epsom salts which at 1 ounce per UK barrel gave 12 grains per imperial gallon. So people were typically adding 4oz per barrel to soft water, or just under half an ounce of salts in 5 US gallons (more if you're starting with RO).

They'd had the basics down for a long time before that - if you were presented with two samples of water, one of which made "good" beer and the other not so good, you could get a pretty good handle on them using the techniques in Henry's book of 1808 - litmus, dropping out sulphates with barium chloride and so on.

But to get back on-topic, the above gives some context for the OP - the general public would have been dimly aware that the best beer was made with heavily mineralised water, so it might be something to advertise even if (as here) it was the "wrong" sort of mineralisation in the form of bicarbonate. It's pretty horrible water, a bit like London water but more concentrated, although most of that bicarbonate will decompose on boiling (precipitating out "limescale" ie chalk). Once the bicarbonate has gone it's not so bad. But as I say, if they were aspiring to make Burton-style pale ales then they would have been adding a lot of salts to match the Burton water profile - many breweries at the time had a dedicated gypsum tank for dissolving it.

 

[ajdelange]

You don't need the full theoretical framework to develop a practical understanding of what works

No you don't but the full theoretical framework represents the sophistication you referred to earlier whereas the "I don't know why it works - it just works" approach does not.