Calcium Beyond Mash pH

[gitchegumee]

HeyGabe! I agree that over-calcification is usually not a problem. However, quoting DeClerck,
"If the liquor must be corrected by the addition of gypsum, then precautions must be taken to see that adequate amounts of phosphates are present for fermentation, and if necessary extra phosphates should be added to the wort."

To me, using soft water and rice adjuncts in a thin mash, it sounds like I should NOT be using CaCl2 as the only means of reducing pH. Nor should I be using Ca as the only mineral addition. Or what? All of these "homebrewing" references just mimic other cities' water supplies without a specific requirement based on brewing mechanics. I'd like to know what specific quantities of minerals are essential for proper mash, boil, fermentation, and shelf life. Not just the broad strokes "Sulphate accentuates the hop bitterness". That I already know. I'm particularly keen to know the relationship between Ca and packaged beer stability.

Beerking1, non-chill haze could definitely be due to low mash Ca./high mash pH due to lower degree of protein breakdown and higher degree of polyphenol extraction both in the mash and the boil. Just a guess, but it's consistent with what I've read. And as Dick pointed out, it could be oxalate haze as well. What is your pH for a pale beer made with 60 ppm total Ca?

[sbradt]

What about the kettle?

This is a very interesting thread. A topic that no one has mentioned is additions of calcium post mash. We initially used calcium as a buffer in the mash for pH control. We had a good pH range in the kettle ( one side or the other of 5.25) but always had final beer pH lower than desired (3.85-4.0). After trying a variety of things to no effect, I started adding Ca salts to the kettle as well. This has had a buffering effect on the wort in fermentation and we immediately saw an increase in the final beer pH. It's been a while but I think that I got the idea from either DeClerck or Kunz.

[beerking1]

Dick, Thanks for the info on oxalate haze. Although I do not use lactic acid (lowering mash pH is no problem for me, I frequently have to raise it for amber or darker beers.), that sounds like the most likely source of my problem. I will go for a Ca of closer to 100 ppm than the 60 ppm that I have been working to. Not sure how to go about measuring the Ca level in the finished beer though.

Gitchegumee, I don't think pH or polyphenols are the issue here, but I will check finished beer pH after work today (I brew part-time. Keeps the wife happy by letting her eat on a regular basis. I don't know how the rest of you guys do it!). You say you are using CaCl2 to reduce pH. I think you might try using a combination of CaCl2 and CaSO4, since it is the BALANCE between Chloride and Sulfate that impacts the hops/malt character. Yes, it is a homebrew reference, but John Palmer takes a VERY technical approach, and his Mash pH section of "How to Brew" is pretty darned good. The first edition of the book is entirely online: http://www.howtobrew.com/section3/chapter15-3.html His approach is a combination of Residual Alkalinity for the SRM of the finished beer, and Chloride to Sulfate ratio. Other than my clarity issue, I have been using this on beers I have made since about Feb this year, and it has improved flavor quite a bit. I have mostly used it on dark beers, since that is where my flavor issue was, so I don't really know how much it impacted the clarity issue, but it sure improved my Porter!
Here is the direct link to Palmer's spreadsheet for water. Read sheet one, the instructions. LOTS of good info there.

http://howtobrew.com/section3/Palmers_Mash_RA_ver2d.xls

Wired and sbradt, I have read in a few places that chalk should only be added to 2 places, due to lack of ability to dissolve: in the mash (acids and phosphates from the malt help dissolve the chalk), and in the kettle (lower pH and heat help it dissolve). You add enough chalk for your mash liqour to the mash, and enough for your sparge water to the kettle.

Great thread guys, and HUGE amounts of great information here. ProBrewer ROCKS!!

[Gregg]

I really don't understand how clear beer (e.g. some pilseners) can be produced with water with Ca in the low tens of ppm

I would hazard a guess that this is due to the cooler fermentation and lagering process allowing these to precipitate out before racking off.

[dick murton]

That is the only thing I can think of.

I really must get in touch with my contact about this

[Moonlight]

And longer aging time. I use a Pilsner water and don't have clarity issues, nor do I filter. I don't rush the beer out, though. It could be that my copper kettle has a reducing effect on haze as well.
I would also expect that the Ca/Mg ratio-regardless of being in small absolute numbers, still influences not only flavor but precipitations. I know the ratio can seriously affect beerstone production.

[gitchegumee]

OK, this is where I wanted to go with this. Moonlight; you mention Mg/Ca ratios affecting flavor. I haven't read this anywhere--where can I find information about water chemistry affecting mash mechanics beyond pH? Beerking1; your reference is indeed very informative and I did learn something from it. I've never added CaCO3 to beers, but maybe I should. My water is very soft and I add minerals for pH. I'm sure that the mineral profile goes beyond pH but I'm having trouble finding this information. Again, my literature research doesn't go much beyond adjusting for pH and the obligatory "sulphate accentuates hops" and "Pilsen water/Burton water/Dortmund water" statements.

[liammckenna]

beer pH of 4.5 is too acidic??? pH of 4.15 is sour? Huh?

pH 3.9-4.25 is where we're at on a regular basis, all ales (depending on the style, water treatment, etc.) I would think that at 4.5, the hop character would present as bitterly astringent - 'oily' is a term I've heard to describe the taste/mouth feel - not 'oily' in a good way either.

Perhaps I'm wrong.

A minimum of 100 ppm Ca in the mash water is what we use. It can be a lot more than that depending on the style we are trying to present.

There are other divalent cations which can also influence a lot of biochemical processes in brewing (flocculation, oxalate precipitation, enzyme chemistry, pH dynamics etc) - . Zinc, Magnesium, copper etc.


Pax.

Liam

[wiredgourmet]

Regarding Philip's main question, I have tried but remain unable to find related information I would call reliable. Mostly I see it addressed in homebrew-oriented material.

Perhaps my Google-fu is weaker than I thought, but I'm disappointed in the quality of the information I've encountered. I found this on line, for example: "Increasing calcium values to 200 mg/l has been shown to increase run off from the mash tun, improve extraction and also increase free amino nitrogen..."

Citations desperately needed. "Has been shown" indeed. By whom? where? when? Is there a report? Was the research done in a lab under conditions likely or not likely to be encountered in a brewery? Have the researchers got an interest in the outcome (i.e., is there a handy process aid that the data suggest using)? Like most people, I have little use for information that I can't evaluate.

There are so many variables affecting the process, and so much information of unknown provenance floating about, I think all one can do is experiment and see what works best, and/or consult other brewers, as we do here, who can say, 'yes, I tried this in a brewery (not a lab, not quoting from a chemistry textbook) and I observed that'.

Regarding process variables: Calcium improves yeast flocculation. Does it indeed? I sense that yeast genetics and condition are far more powerful factors. There are strains that will floc in a low-calcium environment (which I know from experience), as I'm sure there are strains that wouldn't floc decently with a huge dose of calcium.

Just because something is shown to have an effect doesn't mean it's important; several other factors might have immensely more potent effects.

Oxalate precipitation via calcium oxalate seems more certain; at least I haven't heard of another way it's likely to occur. But how much calcium really is needed? 4.5 x the oxalate present is what I've read (Handbook of Brewing, Hardwick). How much is that, really? What factors affect the presence of oxalate? Can it be altered by adjusting common brewing process variables and barley varieties and malt processing methods? Perhaps there's more to the Pilsen clarity issue than lagering alone. Perhaps, for several reasons, not much calcium is required.

beer pH of 4.5 is too acidic??? pH of 4.15 is sour? Huh? pH 3.9-4.25 is where we're at on a regular basis

Are you serious? My *soured* wort doesn't fall much below 3.5 (brett will usually stabilise at around 3.4; lacto at around 3.7).

[liammckenna]

Some info on Calcium and yeast flocc. dynamics.

here,
here,
here,
and a good one here

Pax.

Liam

[gitchegumee]

Great references Liam! Maybe I'm making much ado about nothing, and perhaps I should have titled the thread "Mineral salt additions beyond mash pH" because I'd like to know the important mash, boil and fermentation mechanics of the major water-borne minerals/ions. I have nearly distilled water--a "small" rainwater reservoir that's settled and chlorinated before municipal distribution--and our #1 selling beer is brewed with 20% rice and stands at 5% ABV. My references don't address brewing waters with no significant mineral profile. Most advocate Ca addition for mash pH and assume that the other trace minerals are there. That's why I'm asking here. I use CaCl2 exclusively in our Light beer to get mash pH where it should be, and add a bit of yeast nutrient to the whirlpool to assure zinc levels are adequate. I may need to consider adding more/different salts than just the mash, boil, & finished beer pH dictate. Most references specify a range of minerals-and I'm sure they're there for more than just pH--like oxalate reduction, yeast nutrition, flocculation and shelf stability. So, besides my own empirical results, what do I use to guide my salt additions? As Beerking1 noted, the ratio of certain ions may lead to differing flavor perceptions (BTW, I didn't read that in chapter 15 of Palmer's on-line book--where is it discussed?). With our Light beer, small changes in anything make big differences in flavor. So apparently I should be adding a small amount of Mg and SO4 to the mix if none currently exist in my brewing water?
And should I add CaCO3 to our Amber beers? As was already noted on another thread, many brewers find that CaCO3 adds a malty smoothness to dark beers. Does this hold for Amber beers when the brewing liquor has no bicarbonates?
And one related question: I add all minerals directly to the mash. Does anyone know why this would NOT be the best practice?
Thanks for the patience shown in this thread. I should know this better than I do!

[gabewilson50]

And one related question: I add all minerals directly to the mash. Does anyone know why this would NOT be the best practice?

I only add minerals to the mash that will directly affect the mash, anything that I think will aide fermentation or hop utilization is added to the boil. Adding anything to the mash is fairly inefficient, so I feel that adding to the boil helps to ensure that I get what I want in the fermenter.

[gitchegumee]

Well to clarify, I do add "Yeastex" at whirlpool in my Light beer. My Yeastex label shows Biotin, Folic acid, Inositol, Pantothenic acid, Pyridoxin, Riboflavin, Thiamine, Ammonium salts, Amino acids, lower Peptides, Proteins & Proteolipids, Calcium, Magnesium, Manganese, Potassium, Zinc, and Phosphate. Wow--So do I really need anything in my mash beyond correcting for pH? What about oxalate reduction, flocculation, and shelf stability, among other issues? Better in the kettle? What are those minerals, and how much do I use? Where can I learn about this?

[Moonlight]

Relax, don't worry, have a Palaubrew! If you like the beer and everything works, could there really be any reason to change it?

Consider that 99% of the brewing research is done by the major breweries-not with the intention of making the most delightful beer- but trying to make the fastest, cheapest beer possible. Nothing wrong with that, but in context it may mean that to get a lauter out 1.5 minutes sooner will save AB-InBev a million dollars (Euro?) per year. Do you really need that kind of micro-management?

If the beer you make is tasty and the yeast is happy, then you know what you need to know. Keep it simple.

Trying to make a London-style Porter or an Oktoberfest-style in Palau sounds incongruous. Do people there eat kidney pie or saurbraten? I believe that the more you mess with your water away from what your local water tastes like, some desirability will be lost to the local consumers...although the net effect could still be an improvement.

Adding minerals to the mash will make them available to affect mash performance, but they may get lost in the mash, especially if not dissolved well. They can get chemically caught up with the activities there and not make it into the kettle where coagulation and flocculation may use them. Often breweries separately add minerals to the boil for the purpose of supplementing what remains from the mash/lauter to either help flocculation or feed the yeast. The yeast will suck up quite a bit which won't be left for the final beer flavor influence. If you want to explore other mineral flavor actions, I have found it useful to add drops of very diluted minerals to a glass of beer to see how flavor is affected. Every malt, lauter screen, boil dynamic and yeast will have different behavior and what you do may not need what someone else's situation will.

So basically, the over-complicated thought is to add whatever minerals you need for whichever purposes you need, where needed to supplement...or NOT! All this is folly and overkill if what is in your water gives you beer you are happy with! I believe there is absolutely no need to give a dang about what any textbook says is ideal.

[Gregg]

Thanks for those links Liam - interesting reading. If I may present a summary : "It depends." A useful reminder that all yeasts are different, which explains why there is such diversity of opinion and experience.

An excellent thread, rounded off by a good dose of pragmatism from Moonlight.