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gitchegumee
09-14-2009, 11:09 PM
I searched through old threads and didn't find an answer, so I'm posting here. I've been reading through some of my technical references and cannot find specific Ca recommendations beyond those that influence mash pH.
As we all know, pH is indeed very important, but Ca takes part in and influences many other mechanisms in brewing. Numerous experiments where the pH was held steady show that BEYOND using Ca salts to hit a target pH, Ca also influences the following: activity & stability of many enzymes; extraction of vitamins & minerals; fermentability of wort; hop utilization; precipitation of oxalate & phosphates. I'm sure there are more.
Most of my technical references advise to add Ca until the pH is correct without a mention of specific targets to get the Ca correct for these other mechanisms. DeClerck specifically warns against overuse of Ca due to overprecipitation of phosphates which are required for proper fermentation.
I am fortunate to have very soft water. My beers are very good, but could always get better. I'm concerned that by only adding Ca in the form of CaCl to establish a pH of 3.4, I may be missing some other critical Ca parameter, or possibly another vital mineral entirely. Can someone please point me to specific recommendations for Ca beyond those required for proper mash pH? Thanks in advance!

kai
09-15-2009, 03:49 AM
A lot of references I have found, forgive me but I don't have any on hand right now, suggest a minimum of 50ppm.

beerking1
09-15-2009, 05:39 AM
Well, most of the references I have read are at home, and while I won a set last year, I have not read DeClerk yet. Also, I did not mean to imply I thought 80-100 ppm was a problem, I was wondering if I need to get higher than the 50-60 ppm I have been working with.
Searching web, I found the following:

Calcium (Ca): Aids in extraction of fine bittering principles from hops. Enhances protein coagulation (hot and cold break). Beneficial to yeast. Aids shelf life. 50 - 200 ppm is typical. - http://brewery.org/library/wchmprimer.html

Recommended mineral ranges:

Name Symbol Ideal Range* Metro Water*
Bicarbonate HCO3-- 0-250 ppm 61 ppm
Sulfate SO4-- <150 ppm 44 ppm
Chloride Cl- <200 ppm 8 ppm
Sodium Na+ <150 ppm 5.3 ppm
Magnesium Mg++ 10-15 ppm 5.3 ppm
Calcium Ca++ 50-100 ppm 29.6 ppm
Required for mash enzyme stabilization and a yeast nutrient. Higher levels increase hot break of boil and clarity of finished beer.
- http://www.antiochsudsuckers.com/tom/brewingwater.htm

Calcium (Ca+2)
Atomic Weight = 40.0
Equivalent Weight = 20.0
Brewing Range = 50-150 ppm.
- http://www.howtobrew.com/section3/chapter15-1.html

The older references (I am talking more than 5 years, this is fairly recent, or so it would appear) talk to achieving the right levels of each mineral the brewer is concerned with, and hitting the right pH for the mash. The newer references, such as John Palmer's "How to Brew" talk to adjusting for the proper residual alkalinity, which, IMHO is more useful and probably more accurate for what we are trying to do with our brewing water. (I also like the use of Chloride to Sulfate RATIO instead of the old "raise sulfate for hoppy beers and raise chloride for malty beers" direction.)

John Palmer gives a good explanation of this at:
http://www.howtobrew.com/section3/chapter15-3.html
and also in his spreadsheet for water calculations:
- http://howtobrew.com/section3/Palmers_Mash_RA_ver2d.xls


Of note, Ray Daniels backs up your number, Gitchegumee:
"Ca: Calcium. Primary contributor to hardness of water. Also plays critical role in mashing and brewing chemistry and therefore is required for successful brewing. For flavor purposes, acceptable levels 5 to 200 ppm. The usual goal is 80 to 100 ppm for mash and sparge water."
- http://www.allaboutbeer.com/homebrew/water3.html

wiredgourmet
09-15-2009, 06:24 AM
I doubt that any well-controlled studies exist. Much of this is a lot of anecdotal information and hypothetical reasoning combined, digested and regurgitated through myriad sources.

Look at it this way: they make perfectly good beer in Pilsen, and in Burton-on-Trent.

Calcium is crucial for a good break? How do they get one in Pilsen, then? I'd be tempted to guess that it's not really crucial; it's a factor (perhaps more in theory than in practice), and the quality of the boil is the one that makes the real, practical difference. Ditto for yeast performance. Yeast strain, health, pitch rates, temperature control, essential nutrients, etc, probably account for most of the real difference.

How much of what we read about water chemistry has actually been proved systematically? How much of it just "makes sense"?

I suspect that buffering capacity and essential yeast nutrients are the really important issues. Beyond that, I'd be (pleasantly) surprised if there is much that simple water chemistry within tolerable bounds can do that wouldn't turn out negligible in comparison with the effects of good practice, good ingredients, and good recipes.

jwalts
09-15-2009, 06:57 AM
I've wondered the same thing, but I haven't found any answers. I think the critical question of "how much calcium remains after the mash and boil?" is largely unknown, unless it's been hoarded as a trade secret by a select few breweries, because of its dependence on a huge number of variables. I don't recall any quantification of post-boil calcium in any of Michael Lewis or Charlie Bamforth's books that I've read, and UC Davis does (did?) a lot of AB's research. Due the lack of information or my laziness at finding it, I just shoot for 100 ppm of calcium in my water and add more if I need it to lower the mash pH.

Joe

beerking1
09-15-2009, 07:48 AM
Slight side note here, in answer to Wired's comments.

I have tried a Porter without any water adjustments (5 gallon homebrew batch) to see what would happen. Remember, I have EXTREMELY soft water, almost as soft as Pilsen. Na is <10, Ca is ~40, etc. ALL minerals are low.

The beer came out acrid and harsh, as the books suggest. It smoothed over time (6 months, not a couple of weeks), but never fully lost the acrid, somewhat acidic character.

Shortly afterward, I brewed the same recipe, but used Palmer's RA spreadsheet, and a little of my own experience to tweak the results. The beer turned out GREAT. Wonderful chocolatey, roasted character, it seemed fuller in body, and was a big hit with friends. I used the same yeast strain, same mash profile and same fermentation profile. As much as I could on my home system, I kept all variables other than water the same.

I have to conclude that water chemistry does make a difference, and that if your water is on the end of the scale (either end), that difference can be significant. (BTW, my water makes great pale lagers without any additions, including an awesome Rauch-Helles. I do have to add sulfates for hoppier beers like Pale Ales though.)

wiredgourmet
09-15-2009, 09:50 AM
Beerking1, I was a bit pressed for time earlier. Yes, you absolutely need adequate buffering for dark malts. But if your buffering capacity is reasonable, then I think you are looking at more flavour issues than performance ones when you adjust water chemistry. I really only meant to say that basic performance (outside of buffering) is more affected by other factors.

I have incredibly soft water too, and like to work with black malts. I know that alkalinity is a major issue in flavour since my beer is on the acidic side (final pH is around 4.5). I also find that sulphate is good for enhancing the acrid flavour in Irish stout/porter.

I have been playing with calcium carbonate and it has helped keep the final pH a bit higher. But I have not seen improved yeast performance, breaks, extract efficiency, etc. That's pretty much what I was questioning, not the impact on flavour (that seems self-evident if you are going to do some water alchemy). I think there is probably a lot that can be done in terms of subtle flavour adjustments.

beerking1
09-15-2009, 10:31 AM
Wired, perhaps you can answer a question I have about soft water and performance.
When I adjust my water, I usually work my Ca into the ~60 ppm region (extra 10 ppm for margin of error), and while it has worked flavor wise, I have noticed that my pale beers tend to have a non-chill related haze in them. This haze settles out, but it takes a couple of months. In paler beers, I can usually get away with zero salt additions (Ca is ~40 ppm, highest of any mineral in my water), and I am wondering if the haze I see is just some yeast not flocculating well because the Ca is so low.

On pH side of things, I have had dark beers mash in as low as 4.6 until I add the salts, whereas my pale beers invariably stay in the 5.2-5.5 range. The nice part is, that I have never needed any 5.2 or any other buffer mixes. I tried 5.2 for a while, but couldn't taste or see any difference.

gabewilson50
09-15-2009, 03:39 PM
I don't think that over-calcification is usually a problem, it's the other ions that come along for the ride. Calcium generally comes in beneficial forms as CaCl2 or CaSO4, and the disadvantages of too much Cl2 or SO4 come at much lower concentrations than those of Ca. I don't have exact ranges at hand, but I think they can be found in Hough, Briggs, Stevens & Young's "Malting & Brewing Science" (again, not at the brewery right now, so working off of failing memory).

wiredgourmet
09-15-2009, 04:29 PM
Beerking1, I have not had a similar haze problem with soft water, so I'm afraid I have no insights to share. My chief problem has been a final pH lower than I consider ideal. Beyond that I have no complaints.

Someone else perhaps can comment on your haze problem. You've eliminated chill haze, so that's a start. But there are so many other possible factors it hurts my head to contemplate them :)

Certainly there's no reason why you shouldn't experiment with Ca levels. If it works, you've found a very inexpensive solution to your problem. You were talking about doing homebrew batches to experiment, but one thing you should keep in mind is, that won't really scale in several areas. So you might crack it, only to find that the lesson doesn't apply in the brewery. Also, quite often you will encounter a problem in a homebrew situation that simply is not present in a production environment because of superior kit/processes. (But my hat is off to anyone here who brews at home: I confess that's about the last thing I want to do or even think about around the house.)

Brancid
09-15-2009, 09:52 PM
I'm thinking of starting an extensive water chem research project myself. I know a bit, but not enough to experiment on the house beers. I feel dangerous.

I found a good primer and learned a bit from these podcasts.

http://thebrewingnetwork.com/shows/497
http://thebrewingnetwork.com/shows/500
http://thebrewingnetwork.com/shows/508
http://thebrewingnetwork.com/shows/513

Hope this helps.

Sulfur
09-16-2009, 05:01 AM
@ wired, you say your beer is too acidic at pH 4.5. That to me is an optimal pH for a finished beer. In fact anywhere between 4.3 and 4.6 is what I target.

beerking1
09-16-2009, 07:08 AM
I'm thinking of starting an extensive water chem research project myself. I know a bit, but not enough to experiment on the house beers. I feel dangerous.

I found a good primer and learned a bit from these podcasts.

http://thebrewingnetwork.com/shows/497
http://thebrewingnetwork.com/shows/500
http://thebrewingnetwork.com/shows/508
http://thebrewingnetwork.com/shows/513

Hope this helps.

Yup. Listened to all 3 of these, twice. The BN is a great place for info. I enjoyed the old Jamil show, where each episode went in depth for a specific style (BJCP style, not GABF style). He did the entire guidelines. I won't necessarily follow his exact recipe, but his insights into the important characteristics of each style, and how to achieve them are pretty good education. He has some good ideas there. Now that he is doing "Can you brew it" I find it less interesting. I very rarely want to copy another brewer's exact beer.

The Brew Strong show is probably the most helpful, probably because it is the most technical. They often have very knowledgeable guests on. Face it, if they can get Charlie Bamforth to come on the show and talk technically about one topic or another...it's worth listening to, IMHO. They have had other well known experts as well, and frequently have a brewer from a well respected brewery.

wiredgourmet
09-16-2009, 08:29 AM
Hey Sulphur, Actually, it's a bit more complicated than that. I'm trying to increase buffering capacity so that I can blend pasteurised wort, soured with a blend of lacto and brett, with dark beer for a sort of old-style porter. I absolutely love the flavour, nice fruity hints and mysterious undertones and so on, but this drives the pH down to around 4.15 and, man, is it sour! It gives me heartburn after one pint. Tasters have told me about the same, lovely flavour, but way too crazy in the sour department.

I've got no background in chemistry, so playing with water is like a game of whack-a-mole for someone like me: bring one thing into spec, something else goes out... Therefore I fool around with water as little as possible.

I've been experimenting with CaCO3 and so far the results have been "encouraging". I've added chalk at 30g/hL, which I calculated would put the beer's post-ferm pH in the right range for later treatment with acidic wort. It seemed like a lot to me and I was concerned. Not all of it dissolved, but I was betting that any undissolved portion would settle out in the FV, which it seems to have done. The water looked like bathwater! Totally not something you would brew with or even touch if you didn't know it was all right :)

Anyway, I'm not ready to say much more at this point, but I will post about it once I get it dialed in. When you get close to your ideal balance, very minor influences can upset it quite a bit, so this is obviously going to take a while to perfect. If it's even possible, which I'm not yet convinced it is. But I really do want to make this work if I can.

dick murton
09-16-2009, 12:45 PM
A couple of thoughts

One is that 4.5 pH is actually on the high side. I've brewed a number of different lagers at different sites, and 4.5 has been absolute top whack, most of them have had specs lower than that. And ales have been in the range 3.8 to 4.25 top whack - so 4.5 is certainly not acidic

Re the haze, there is just a possibility this is an oxalate haze, produced as a result of too little Ca in the mash. Using lactic acid to reduce the mash pH will not remove oxalate. To ensure no oxalate hazes we looked for 25 ppm absolute minimum of Ca in the final beer. What that requires in the mash will be determined by the mash conditions, amount and type of yeast, fermentation conditions and so on, but probably 100 ppm is a good starting point. I have to say though, having experienced oxalate hazes, with the solution as mentioned above, 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

gitchegumee
09-16-2009, 06:56 PM
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
09-17-2009, 04:04 AM
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
09-17-2009, 07:29 AM
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!! :D

Gregg
09-25-2009, 02:06 AM
I really don't understand how clear beer (e.g. some pilseners) can be produced with water with Ca in the low tens of ppmI 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
09-25-2009, 12:41 PM
That is the only thing I can think of.

I really must get in touch with my contact about this

Moonlight
09-26-2009, 09:34 AM
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
09-27-2009, 06:07 PM
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
09-28-2009, 07:44 AM
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
09-28-2009, 04:33 PM
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
09-29-2009, 12:24 PM
Some info on Calcium and yeast flocc. dynamics.

here, (http://aem.asm.org/cgi/reprint/61/2/718.pdf)
here, (http://aem.asm.org/cgi/reprint/58/11/3709.pdf)
here, (http://www.springerlink.com/content/gv3107258516t883/)
and a good one here (http://en.wikipedia.org/wiki/Yeast_flocculation)

Pax.

Liam

gitchegumee
09-29-2009, 06:42 PM
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
09-29-2009, 08:39 PM
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
09-30-2009, 12:30 AM
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
09-30-2009, 01:53 AM
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
09-30-2009, 02:50 AM
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.

beerking1
09-30-2009, 07:50 AM
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?).

I must have read it in the 3rd edition (only the 1st edition is online). It is referenced in the instructions of the spreadsheet:
"Step 5, Salt Additions: Add salts (in grams) to build the RA and flavor profile that you want for the beer. You may want to trade off between different calcium salts to balance the anion content. For example, if the sulfate level gets too high from adding gypsum, use some calcium chloride instead. If the alkalinity is not high enough for a dark beer, try adding a combination of sodium bicarbonate and calcium carbonate.

Here is where the chloride to sulfate ratio is useful to help choose which salts to use in adjusting the RA. If you are intending to brew a hoppy beer, use sulfate salts to move the balance Bitter or Very Bitter. If you are intending to brew a malt dominated beer, then use chloride salts to move the balance to Malty or Very Malty. Alternatively, you can use a combination of chloride and sulfate salts to keep the character Balanced."

wiredgourmet
09-30-2009, 10:13 AM
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...

I love you.


Some info on Calcium and yeast flocc. dynamics.

Liam, nice finds, well worth reading -- and thanks very much for the contribution, by the way -- but I'm still pestered by the same question: whether an effect demonstrated in a lab is at all important under real-world conditions.

Let's look at the study methods: Paper #1 is quite interesting, but I wonder about its practical relevance.

1. "Cells were plated in a petri dish on solid medium (1% [wt/vol] yeast extract, 3% [wt/vol] glucose, 2.5% [wt/vol] agar) and incubated at 30C for 3 days."

2. "Cells of the exponential growth phase were harvested after 10h and 2 days of culture for the top and the bottom strains, respectively; cells of the stationary growth phase were harvested after 24h for the top strain and after 5 days for the bottom strain. The cells were harvested by centrifugation and washed twice with cold distilled water."

3. "Flocculation test. The compounds of interest (CaCl2, MgCl2, NaCl, ethanol or other organic compounds, and sugars) were introduced in test tubes. [...] Flocculation was quantified by measuring the residual absorbance of a yeast suspension after agitation and subsequent undisturbed standing to allow floc settling. [...] The tubes were agitated upside down at 25 rpm for 15 min and allowed to stand undisturbed for 15 min."

This seems good for understanding yeast *outside* the brewery. In a practical sense, I think the best thing you could do with a study like this is use it to compare the relative flocculence of one strain to another.

Paper #2 notes that: "Data on determinants of flocculation are scattered and conflicting in the literature and concern different strains, treatments, and growth conditions." I couldn't agree more. It also uses a medium more like wort than #1. But again, the samples are washed and allowed to settle in a clear, pure medium that facilitates examination (obviously a necessity in a lab). I have to think that relative flocculation is all one could measure confidently by such means.

Paper #3 is an abstract. No doubt interesting, but I have to wonder about the data's practical relevance here as well. However, since I was unable to read the paper, I obviously can't comment on that.

Ipscman
10-02-2009, 12:57 AM
First off, we hope you and your family are all well in the midst of the sunami. I assume you will get back to beer and brewing at some point, thus this response.

I too have very soft water (like Pilzen) with only 10 ppm calcium. Here is what I found. In a nutshell you have to have 75-80 ppm calcium in the mash, and 100 in the boil. However, due to the chemical reactions what you start with in the mash is severely reduced before your wort gets into the boil kettle so you will probably add more in the kettle.

First off, here are some of the benefits of calcium in adequate amounts listed above (cf. Briggs, 113-116; Priest, 107-118)

- Mixing with phosphates from malt to acidify wort and help aadjust pH, reducing temporary hardness from bicarbonate

- Calcium ions directly stimulate amylolytic and proteolytic enzyme activities during wort production.

- CA ions protect malt a-amylase activity against inhibition by heat when you add strike water

- this leads to increases in extract

- can lead to an increase of endopeptidase activity at lower temperatures

- wort runoff rate can be significantly increased as a direct cconsequence of increased CA ions during mashing

- increased TSN

- increased FAN

- lower coloring effects during boil

- precipitates oxalate in wort so you don't have beerstone build-up later in process

- improved yeast flocculation

- Can lead to improved wort clarification, during maturation, leading to enhanced haze stability.

- Improved hop utilization

-------------------------------------------------------

You will notice from the Munich water profiles that they too have low calcium. So what do the Germans do?

1. Priest, Handbook of Brewing, 2006, p. 130 "German brewers tend to compensate low calcium contents by additions to water postdealkalization treatment..." So should we if our calcium is low.

CALCIUM DERIVED FROM THE MALT:
Priest, p. 108: In 1.048 all malt wort using demineralized water, there was 35 ppm calcium. I.e., this calcium came from the malt itself. "It is important to note that, in addition to brewing water and any salts added by way of liquor treatment or ionic adjustment, the contribution from malts, adjuncts and hops should be taken into account."

Bamforth, Lewis, p. 72: "Malt also contributes to wort magnesium, sulfate, calcium and chloride ions but it is usual to consider these ions as arising from brew water."

CALCIUM NEEDS IN THE MASH:
2. Priest, p. 113, "It is recommended that 70-80 mg/l CA ions should be present during mashing to eliminate excess oxalate during beer storage."

He lists many other benefits but that is the ppm given.

CALCIUM LOST IN THE MASH:
NOW IT GETS A LITTLE COMPLICATED. Any calcium added to the mash is reduced by two processes:

a) Removal of bicarbonates resulting in acidification of wort and lowered pH: “Note that it takes a single calcium ion to remove two bicarbonate ions, and remember that you want to have 50-100 ppm calcium remaining in your water for mash activity.”
…[to precipitate bicarbonate with calcium] and its removal will encourage the reaction to continue until either the bicarbonate or the calcium is consumed."Zymurgy article, special GRAIN issue, 1995, p. 35 - by Ginger Wotring – author of the BJCB Water section to prep for the BJCB exam)

So whatever your bicarbonate level is, it begins getting precipitated in the mash by calcium mixing with phosphates from the mash at about 158*F. This doesn't take very long and could be accomplished in 10-15 minutes. So, if you have 100 ppm bicarbonate you will 'consume' 50 ppm calcium while precipitating out the bicarbonate.

In addition, you lose 50-60% of the calcium in the spent grains when you sparge. "Because of the precipitation of CA in these pH control reactions, there is a considerable reduction in the calcium ion concentration during wort production; about 50-60% of the CA ions present during mashing (either present in mashing liquor, or as added salts, or derived from grist materials) will be lost with spent grains and trub." Priest, p. 116

So say you started with 100 ppm calcium in the mash (35 from the malt and 65 by salt additions (calcium sulfate or calcium chloride, e.g.). You then subtract 1/2 of whatever your bicarbonate level is, say 50, leaving you with a residual of 75 ppm calcium. Then you lose say 55% of that in the spent grains. Now you have 34 ppm surviving into the boil kettle.

CALCIUM NEEDS IN THE BOIL KETTLE/FERMENTER
"It has been estimated that a minimum level of 100 mg/l CA ions is required for good quality protein break formation." Priest, p. 113

"Yeast flocculation is improved by calcium; most yeast strains require at least 50 mg/l for good flocculation..." Priest, p. 113.


SO, you need 75-80 in the mash; and a net of 100 in the boil which also addresses the yeast needs in fermentation.

"Another recommendation is that calcium should be in the range of 20-150 ml/l depending on the beer that is being made." Briggs, p. 65

CONCLUSIONS:
George Fix: "instead of using historical examples as a guide, the best strategy is to first make sure the technical requirements of the mash are met [i.e., a proper pH and calcium requirements met] and then to adjust the mineral content by using the finished beer's flavors as the guide." p. 15.

So,
IN THE MASH
1. Adjust your pH with acid or calcium, etc.
2. Factor in the calcium losses due to precipitation with bicarbonates
3. Factor in the calcium losses in the spent grains.

IN THE BOIL KETTLE:
4. Add enough calcium in addition to the residual from the mash to total at least 100 ppm. This should meet the needs of the boil and the fermentation processes.

In regards to your original concern about loss of phosphates (I use DeClerck too but his work dates back to the 40's, almost 60 years ago and I tend to rely on more recent sources if there is a contradiction).

POSSIBLE LOSS OF PHOSPHATES FROM USING TOO MUCH CALCIUM:
Briggs, P. 116, Table 4.13 shows gypsum added up to 1140 mg/l and the reduction in phosphate went down from 68 ppm (when no calcium was added) to 50 when that outrageous amount was added. "Additions of calcium ions to the mash reduce the quanititiies of phosphates in solution but apparently not to undesirable extents."

Lots of information to wade through. At least, that is what I understand at this point. Hope this helps.

Mark W., Oregon
Hidden Well Brewery

General References:
Priest, Handbook of Brewing, 2006
Briggs, Brewing: Science and Practice, 2004
Bamforth, Lewis: Essays in Brewing Science, 2006
Fix, Principles of Brewing Science, 1999
Various Zymurgy, Brewing Techniques, BYO issues addressing water modification

liammckenna
10-02-2009, 02:33 AM
whether an effect demonstrated in a lab is at all important under real-world conditions.


Usually, or almost always, given well constructed experimental design.

All of those papers concluded that Ca++ was required for flocculation. That was the point of sharing them. The final paper (although just an abstract) also indicates this. From it's use of proteinase enzymes, it also confirms that flocculation is a cell wall dependent, calcium mediated mechanism.

Excellent summary Mark.

Pax.

Liam

wiredgourmet
10-02-2009, 09:56 AM
That all sounds great, except for one thing. My water supplies a mere 20 ppm calcium. I have no idea how much makes it to the FV, but I know it has to be less than that. Magnesium is also implicated in flocculation, and there again, I have a mere 2 ppm. Still, I have no problem: beer drops bright without auxiliary finings and the sediment is firm.

While my yeast are probably Mg and Ca-starved, yeast genetics and wort gravity appear to be overriding factors. A stack of lab studies as tall as a skyscraper, however well designed, telling me that my yeast aren't floccing isn't going to persuade me to ignore what my own senses report.

Liam, let me ask you this: if lab studies are "usually, or almost always, given well constructed experimental design," relevant to the real world, why on Earth do the FDA and EMEA require clinical trials? Would you say that they are just a lot of stodgy, obstructionist skeptics and nay-sayers (like me)? Or do you think they might have good reason to believe that an effect isn't significant until we see what actually happens under real-world conditions?

Ipscman
10-02-2009, 11:29 AM
Very interesting report from Dublin. I'm both fascinated and confused.

1. My own experience is that I have not been experiencing good hot break. Once I added calcium that changed. So my situation seems to validate the general consensus about the need for calcium.

2. I have seen a number of sources that supposedly indicate what the water profile for Dublin is, e.g. below:

FAMOUS BREWING WATERS
SOURCE Ca Mg Na CO3 SO4 Cl
Antwerp [DeKonick] 90 11 37 76 84 57
Beerse region [Westmalle]41 8 16 91 62 26
Brugse [Brugs Tarwebier] 132 13 20 326 99 38
Brussels region 100 11 18 250 70 41
Burton-upon-Trent 1 268 62 - 280 638 36
Burton-upon-Trent 2 270 60 30 200 640 40
Burton-upon-Trent 3 295 45 55 300 725 25
Burton-upon-Trent 4 268 62 54 200 638 36
Chico [Sierra Nevada] 16-50 10-32 8-34 100est. 0-19 0-37
Dortmund 1 225 40 60 180 120 60
Dortmund 2 250 25 70 550 280 100
Dublin 1 119 4 12 156 53 19
Dublin 2 118 4 12 319 54 19

If these are correct then Dublin water is plenty high in calcium although it would precipiate out with the carbonate almost equally. Are you getting your numbers from a local water company?

In addition, there is definitely some calcium in the malt itself. The example I quoted in the above post indicated 35 mg/l in one example. The calcium in the ground varies and depending on where the barley was grown this is probably quite variable.

Very interesting, Wired. What are you brewing? Grain bill, adjuncts?

Mark

wiredgourmet
10-02-2009, 11:42 AM
My numbers come from the local water authority. There are three treatment facilities serving the Dublin area: Leixlip, Ballymore Eustace (mine), and Ballyboden.

None of them delivers water even remotely resembling the published profiles.

These standard profiles are truly mythological. I don't know who started it, but they have been copied and regurgitated endlessly in books, articles, and brewing software and have become Gospel because "experts" have reproduced them without actually checking their accuracy. Always consult your local authority.

Ipscman
10-02-2009, 11:58 AM
THAT is very helpful information, Wired. I've always been suspect of these profiles. They really do seem bogus oftimes and how people bend over backwards to demonstrate how a given profile works for a given beer seems to challenge reality at times.

THANK you so much for your input on this subject.

Mark

dick murton
10-02-2009, 12:24 PM
Don't forget that it might be gased on a brewery that uses deep, or even shallow well water, not municipal water, so the mineral content of the well water may be slightly, or even vastly different from the local surface water

Moonlight
10-02-2009, 03:06 PM
I must ask that the "required amounts" of anything in beer be taken with a grain of...
well, let's just ask what would happen if there was less in your water? As in could it even still make beer? or would it just mean longer settling time of the yeast, or less efficient mash extraction, or less quick break or yeast flocculation? As in, I refuse to blindly accept any "minimum" number unless it says "minimum for a 3 day yeast settling with x strain of yeast", or "minimum for our brewery to keep production up at the speed the accountants want to crank the stuff out in..." (First let's kill all the accountants!)

However, the more understanding any brewer can get as to WHY and HOW any mineral has an effect, the better that brewer will be prepared to make the decisions he/she needs to make the beer desired within the parameters of the front office and the folks in the pub. I am very grateful for the links below and fascinated by how all this stuff potentially fits together. We each must take in all the potential relevant science and apply it as is appropriate. I just prefer to brew a bit on the fringe and after enough decades at this, have learned that so much that I have been taught is mindlessly oversimplified or irrelevant to my styles or methods of brewing. Viva la difference!

Ipscman
10-02-2009, 04:04 PM
VERY GOOD POINTS! As Palmer is want to say, "Brewing is a very robust system." Another source said, "Malt wants to become beer." With our access to thermometers, hydrometers, stir-plates, access to the best raw materials from all over the world, great yeast, etc., we are probably making the best beer in history. How lucky are we!

DeClerck said, "A distinction is frequently drawn in the industry between the theoretical man who tries to explain everything from a scientific point of view, and the practical man who relies on empirical knowledge and experience. A good brewer should be able to steer a middle course between these two."

I have over 130 books on brewing science. But I've brewed 34 different style batches this year testing many things.

We all bring something to the party as we learn together. I've learned today from this forum. That means it's a good day. I think I'll go back to stepping-up a yeast starter on the old stir-plate, continue listening to DeLange's 4-hour talk on water in brewing and open a bottle of home made beer.

Cheers!
Mark
http://www.hiddenwellbrewery.com

sbradt
06-23-2011, 01:02 PM
Time to give this thread another kick. Recently our water quality has changed a bit and I've been going through the tortuous process of refreshing myself on the ins and out of water chemistry. I ran into something in Palmers writing and then again in another reference regarding measuring pH at room vs process temperature. Years ago (like 15 or 20) i was told by someone whose opinion I held pretty high regard for (still do) that I should perform all pH measurements at room temperature. He explained the different reading you get at higher and lower temperatures but said that all the reference material out there regarding pH limits were based on the lab standard of 20&#176;C (standard temp and pressure, 20&#176; C at 1 atmoshere). Now I'm seeing references that indicate that it is the pH at mash temperature that I should be looking at, which would make my readings all much lower than what I had understood. Anyone have any knowledge to share?

What I can find for reference to the pH and temperature phenomenon indicates that the pH IS actually different at different temperatures (not that it just measures differently). So, does that mean that as long as I don't exceed a pH of 5.7-5.8 - at mash temperature- at the end of my sparge, I'm ok even though this would put the room temp pH at 6+?

Ipscman
07-01-2011, 10:46 PM
The professional books (Kunze, Briggs, Noonan, Priest, Ockert, DeClerck, Lewis, Moll, etc.) generally recommend a mash temp of 5.2-5.4, which is 5.5 - 5.7 at 20*c/68*F.

Mark
Hidden Well Brewery

Woolsocks
07-02-2011, 02:25 PM
Agree on the recommended pH range of 5.2-5.4.

pH *is* different at different temperatures. ALSO, having the sample temperature hotter or colder than the meter is designed to read at will make the reading incorrect.

Best bet is to get a meter that has temperature correction. These have thermometers incorporated into, or in addition to, the electrode and the pH reading will be accurate regardless of the sample temperature. That said, the pH of the sample will change with its temperature, so measure your mash pH at mash temperature (I just stick the electrode directly into the mash).

Woolsocks
07-05-2011, 01:01 PM
Very...very...bad idea. The temperature correction feature on pH meters is only to account for the variation in the way the meter reads due to its idiosyncracies. It does not correct for the very real variation of pH in the mash that occurs with differing temperature.


Agreed. I meant to convey that in my original post.



In addition, the very thin glass membrane IS stressed more from the thermal shock of going from room temp to mash temp repeatedly. If you value your equipment and the measurements they provide, ALWAYS cool your wort samples to a consistent (and modest) temperature before inserting your pH probe.


Hmm... how, then, to know what the actual pH of your mash is? If you cool down the sample, its pH changes before you have a chance to measure what it was, yes? For that reason, I'm willing to live with shortened electrode life.

pbutlert
01-30-2013, 11:18 AM
How far into the boil do you add minerals?

gointomexico
02-25-2013, 10:30 PM
How far into the boil do you add minerals?

I personally add them at the beginning of the boil. A head brewer from another brewery came by and said that I should add ca in the mash instead of the boil to increase my extract. I did that, and it did go up, but i don't feel that I got a good hot break (ordinary bitter). My mash ph was 5.2 (room temp) and I didn't check the boil ph. Ill check the ph of the finished beer and see how i did. In the future, I will split my ca additions between the mash and boil.

I do notice the thiness of the choc. milk stout I did, and i am wondering if it is because of the cacl i added to accentuate the malt profile. I add gypsum or cacl to my boil to accentuate hop bitterness or maltyness. I plan on changing my procedure to get the hot break i expect and raise the ph to 5.3 where i feel most comfortable. I think the ph was a bit low on the choc. milk stout, ill have to check that too.

brendanbrewer
02-06-2017, 02:41 PM
Make sure you have 80-120 ppm in the mash tun. Half of you calcium will be lost in the mash. Recommended levels are 40-60 ppm in the finished beer.

Brendan
Lb. Brewing Co.
Hays, KS

brain medicine
03-09-2017, 05:35 PM
so i dont think i saw the answer to this, maybe i missed it. if half your Ca ions are lost when you separate the grains from the wort, does that go for your negative ions as well? sulfate/chloride/etc?

mmussen
03-09-2017, 05:39 PM
I don't think you're loosing any negative ions while the Ca come out of solution.
The Ca is falling out of solution because its binding to free phosphates and oxilates from the malt. Those won't bind negative ions being negative themselves.