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  • Calcium Beyond Mash pH

    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!
    Phillip Kelm--Palau Brewing Company Manager--

  • #2
    A lot of references I have found, forgive me but I don't have any on hand right now, suggest a minimum of 50ppm.

    Comment


    • #3
      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:

      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
      Last edited by beerking1; 09-15-2009, 06:44 AM.
      -Lyle C. Brown
      Brewer
      Camelot Brewing Co.

      Comment


      • #4
        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.

        Comment


        • #5
          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

          Comment


          • #6
            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.)
            -Lyle C. Brown
            Brewer
            Camelot Brewing Co.

            Comment


            • #7
              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.

              Comment


              • #8
                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.
                -Lyle C. Brown
                Brewer
                Camelot Brewing Co.

                Comment


                • #9
                  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).

                  Comment


                  • #10
                    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.)

                    Comment


                    • #11
                      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.

                      THE BREWING NETWORKPODCASTS Your multimedia resource for beer and brewing, the Brewing Network is here to provide you with shows that span the spectrum ofRead more

                      THE BREWING NETWORKPODCASTS Your multimedia resource for beer and brewing, the Brewing Network is here to provide you with shows that span the spectrum ofRead more

                      THE BREWING NETWORKPODCASTS Your multimedia resource for beer and brewing, the Brewing Network is here to provide you with shows that span the spectrum ofRead more

                      THE BREWING NETWORKPODCASTS Your multimedia resource for beer and brewing, the Brewing Network is here to provide you with shows that span the spectrum ofRead more


                      Hope this helps.
                      --
                      Brandon Overstreet
                      President, Co-Founder
                      Swing Tree Brewing Company
                      300 E. Hersey St. #7
                      Ashland OR, 97520
                      c. 541-591-8584
                      boverstreet at swingtreebrewing.com
                      www.SwingTreeBrewing.com

                      Comment


                      • #12
                        acidic?

                        @ 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.

                        Comment


                        • #13
                          Originally posted by Brancid
                          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.

                          THE BREWING NETWORKPODCASTS Your multimedia resource for beer and brewing, the Brewing Network is here to provide you with shows that span the spectrum ofRead more

                          THE BREWING NETWORKPODCASTS Your multimedia resource for beer and brewing, the Brewing Network is here to provide you with shows that span the spectrum ofRead more

                          THE BREWING NETWORKPODCASTS Your multimedia resource for beer and brewing, the Brewing Network is here to provide you with shows that span the spectrum ofRead more

                          THE BREWING NETWORKPODCASTS Your multimedia resource for beer and brewing, the Brewing Network is here to provide you with shows that span the spectrum ofRead more


                          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.
                          -Lyle C. Brown
                          Brewer
                          Camelot Brewing Co.

                          Comment


                          • #14
                            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.

                            Comment


                            • #15
                              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
                              dick

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