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  • #31
    Originally posted by gitchegumee
    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."
    -Lyle C. Brown
    Brewer
    Camelot Brewing Co.

    Comment


    • #32
      Originally posted by Moonlight
      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.

      Originally posted by liammckenna
      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.

      Comment


      • #33
        Professional Sources: Calcium Requirements in Brewing

        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
        Last edited by Ipscman; 10-18-2009, 10:34 AM.

        Comment


        • #34
          Originally posted by wiredgourmet
          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
          Liam McKenna
          www.yellowbellybrewery.com

          Comment


          • #35
            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?

            Comment


            • #36
              Calcium and Flocculation

              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

              Comment


              • #37
                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.

                Comment


                • #38
                  Water Profile Mythology

                  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
                  Last edited by Ipscman; 10-02-2009, 01:11 PM.

                  Comment


                  • #39
                    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
                    dick

                    Comment


                    • #40
                      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!

                      Comment


                      • #41
                        Mandatory minimums

                        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
                        Last edited by Ipscman; 07-18-2011, 05:23 PM.

                        Comment


                        • #42
                          Measuring pH

                          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°C (standard temp and pressure, 20° 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+?
                          Steve Bradt
                          Regional Sales Manager
                          Micro-Matic Packaging Division
                          Eastern United States and Canada
                          sbradt@micro-matic.com
                          785-766-1921

                          Comment


                          • #43
                            pH recommendations

                            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

                            Comment


                            • #44
                              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).

                              Comment


                              • #45
                                Originally posted by WaterEng
                                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.

                                Originally posted by WaterEng
                                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.

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