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Thread: Using CaCO3

  1. #1
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    Using CaCO3

    I was wondering who uses chalk in brewing? I was talking with another brewer and they have used CaCO3 to raise the pH on a dark beer to aid in maltyness.They were very pleased with the enhanced chocolate flavor. I am in the process of re-evaluating my recipes for water additions. Just wondered how chalk would help or hinder. I only use Acid, Gypsum and CaCl. I guess I want to fool around with chemistry. Any thaughts? Thanks

  2. #2
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    Whether or not you use chalk depends on your water chemistry and your mash pH. If your water has sufficient calcium, you may not wish to bother. Ditto if you have a pH in the right range. Measure your pH from mash-in, all the way through the brewing, and fermenting processes. Most brewers find that they need to lower their mash pH. Hence the acid, CaCl, & CaSO4.
    Phillip Kelm--Palau Brewing Company Manager--

  3. #3
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    I'm also a big user of CaCl2, CaSO4, and acid for most beers.

    For darker beers (brown ales and darker) I generally don't treat the water at all.

    For our stout, I find the pH sinks too low, typically around 5.0. I've tried chalk to raise it, but have a lot of trouble getting it to dissolve. CaOH (slaked lime) is a little easier but still not great, and I can't find a cheap source of it.

    I'm wondering about your original point though: does a higher mash pH (say over 5.4) really add to maltiness? Can you explain that a little further?

  4. #4
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    CaCO3

    What you add is all about what you have to start with in terms of water profile.

    Carbonates are a substantial factor in our water profile in the midwest, as we sit on a giant limestone aquifer. I can't attest to maltiness, but I can tell you that it does screw with our pH pretty well, which has been know to wreck our brewhouse yield. Check DeClerk for the chemistry behind the water, but it seems to me that if you're trying to dissolve CaCO3 into hot liquor, you're just going to get a cloudy paste. Calcium doesn't dissolve well in pH neutral cold water, and generally dissolves worse in hot water (I don't know why; ask your chemist friends). The reason that it gets into the water at all has something to do with bacteria and carbonic acid.

    Calculate the necessary additions, and then add it to your mash and pH it after about 5 minutes or so. For us, that seems to be the requisite amount of time for any mineral additions to dissolve in the naturally acidic mash and make any change on the pH.

    The Lewis and Young book also has a good section on water profiles. There might be something in there about flavor profiles and mineral content, but I don't remember. Maybe it said that increased hop flavor is associated with the SO4++ ion, a la Burton-on-Trent. One way or the other, it's confusing.

    Good luck,
    Bill

  5. #5
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    Chalk solubility is all about the water's carbonic system (carbonate, bicarbonate and carbonic acid) reaching equilibrium with atmospheric CO2. Ground water typically has too much chalk in it, so it'll precipitate out - heat simply speeds up the process. Getting chalk to dissolve beyond its equilibrium requires acid, which can be accomplished by bubbling CO2 through the water. Mash acidity will help to some degree, but you won't get as much chalk to dissolve as most calculations suggest. Maybe about half, but I'm not positive about that.

    For a ton of great info on water chemistry, download some of the files on A.J. DeLange's website here:

    http://ajdel.wetnewf.org:81/

    The articles on alkalinity are a great place to start.

    Joe

  6. #6
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    That's the question. My friends at a local micro neeeded to raise the pH on a stout. The outcome was a very chocolate enhanced beer after addition of chalk. That sounded interesting to me. I can not imagine why CaCO3 will not go into solution at higher temps? I wonder what you could add to get the ions? Acid? Now this is too much chemistry. I really just want to round out my beers. Looking for more malt and smoothness. Mash temps are where they should be so that's why I'm looking into water.

  7. #7
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    Iron Content

    How's the iron level in your water? That could be affecting the malt profile...

    As to the chalk in the stout, the only thing that I can think is that, by affecting the pH balance, it changed the flavor profile. Ray Daniels did some research on final pH and flavor profiles, and I think that he found that stouts with low pH are rather lifeless. This could be what happened in your friend's brewhouse.

    Unless (and this is a wild-ass guess) there is a causal relationship between CO3++ and malt flavor. Bear with me on this one, but it seems that many of the malt driven beers in historical brewing regions of Europe came from areas where CaCO3 levels were high. There's your correlation to malt flavor. Now, there is evidence saying that CO3++ causes astringency in hop profiles, but is it also possible that it plays some role in accentuating malt? I have a feeling that I'm blowing smoke right now, but maybe there's something to it. I'm not sure there's anyplace where we can make the jump from correlation to causation. So I'm sticking with the bit about pH, with the iron comment to cover myself.

    Happy Brewing,
    Bill

  8. #8
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    If not chalk, what?

    I would like to know more about this flavour issue, as I have been considering using CaCO3 in stout to enable me to experiment with adding soured wort. Mash pH is fine, but it does fall too far after fermentation to take it any farther. I had thought of adding some to the boil.

    I wonder if anyone can tell me: is this "lifeless" quality strictly a function of a higher pH, or could it be an unfortunate flavour contribution from the chalk? For example, I've found that NaHCO3 will add an unpleasant flavour of its own.

    As for clarity: is it not true that the chalk will react with acids (losing its opacity), while the portion that does not react will simply settle out? Or is it likely that the milkiness will remain?

    And if chalk doesn't work well, what does? How can one raise beer pH without affecting flavour (except by virtue of raising the pH), or clarity. There are numerous "de-acidifying" potions used in the wine industry; has anyone tried them in beer? Any luck with them?

    Inquiring minds want to know.

  9. #9
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    I would guess that in most cases, beers brewed with mash pHs of 5.5-5.8 (once cooled to room temperature) will taste pleasant - provided nothing else is wrong with them . Dark malts release more acid into the mash than pale malts, so extra carbonates are necessary just to accomplish a proper mash pH. That's why Dublin brewers made stout, Burton brewers made pale ales, etc. Adding unbalanced salt additions will throw things off, though. I try to keep both my chloride and sulfate concentrations below 150 ppm, but I'd rather have high chloride than sulfate (especially for malty beers). Phosphoric acid and slaked lime both reduce the calcium concentration as they remove carbonates, so be careful with those.

    jjs: I'd just add a small amount of chalk to your mash - maybe 10 g per barrel - and check the pH after the mash is well-mixed. If the beer tastes better and the pH is in the right range, try a little more the next time!

    wiredgourmet: If there's a milky portion that doesn't dissolve, I think it'll settle out. The settling tendency of undissolved chalk is the basis for pre-boiling, slaked lime treatment, and improving the vocabularies of brewers as they clean their hot liquor tanks. I'd be more concerned about adding too much chalk and having it successfully dissolve because that would probably make your beer taste "minerally" (think Dortmunder Export). Maybe your pH drop is a buffering issue, i.e. the boil uses up the water's remaining buffering capacity. I'd bet that you could correct your fermenter pH while keeping your mash pH in the proper range by adding a little bit of chalk (or slightly reducing any acid/gypsum/CaCl2 additions) to your mash - especially if you shoot for the high side of the acceptable mash pH range.

    Joe
    Last edited by jwalts; 06-23-2009 at 05:54 PM.

  10. #10
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    Joe, I was about to try the chalk, until I read this thread and got scared Yes, my water has low alkalinity so the only pH reducer I use is the patent, with the blondest malts I can reasonably use. It's a struggle to keep the mash pH from falling below spec even with that arrangement. (yes, I could cut back on the patent; come to think of it, I could get away with increasing the water:grist ratio a bit as well)

    Unfortunately, most of the literature is focused on getting the mash pH low enough, which seems to bedevil most brewers. I have the opposite problem. Mash pH for me will usually run 5.18 - 5.21. Post ferm, 4.42 - 4.44. Ok, not an actual problem, but there's no margin for soured wort, and that's something I really want to play with.

    Thanks for the reply; I will give the chalk a go and post in a few weeks if it accomplishes anything exceptionally good or exceptionally bad.

  11. #11
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    Wired, you speak of two different goals here:
    1. Possibility of adding chalk to get your pH right.
    2. Water additions to increase malt perception in your finished beer.

    As for #1, chalk can be used to increase the pH of your mash. Unless your water is quite soft, you are not likely to need this. In the case where you have soft water, making a dark beer without adjusting the water will lend an acrid flavor to your beer, and the addition of chalk will reduce or eliminate it, leaving the impression that you have added a chocolatey-malt character, when all you have really done is remove the acrid character.
    I have VERY soft water here in VA (damn near Pilsen water!), and had trouble brewing dark beers until I learned this. (The water makes GREAT pale beers, BTW)
    Chalk, when used, is best added to the mash itself. I add it with the grains. The reason for this is that the acid nature of the mash will enable the chalk to dissolve more. Any that does not dissolve will readily precipitate out in the boil, and very quickly settle in your fermenter. Adding chalk raises pH by adding more carbonates to the water.
    I find the best way to balance my water is through a comparison between the beer's SRM and residual alkalinity. John Palmer has an excellent, very well researched explanation of this at:
    http://www.howtobrew.com/section3/chapter15-3.html
    The whole chapter is quite good.
    It is a homebrewing book, but I find it to be a great explanation, and the spreadsheet he posted has been quite useful to me. (I have yet to devote the time to studying DeClerk, although I do own a set and it is on my list.)

    As for the way to increase the malt perception in your beer, what you want is to increase the chloride to sulfate ratio. Chlorides will increase perception of malt, and sulfates will increase perception of hops. The real key, and one that some people miss, is the ratio. You can add a lot of chlorides, but if the ratio with sulfates is not right, it will still leave you with enhanced bitterness over maltiness. Again, Palmer explains this pretty well, and his spreadsheet is useful for this.
    So your next question is probably how to add the chloride. There are basically 2 ways: CaCl or NaCl (table salt). If you have water that results in a reasonably high mash pH (or is well buffered), and you are low in Ca, I would go with the CaCl. This will tend to lower mash pH, but if your water is well buffered it should be all right. The reason it lowers mash pH is not because of the Ca directly, but because some of the Ca binds with carbonates already in the water. Test the pH with a test strip to be sure.
    The other way is to add table salt. Make sure you use Kosher salt, because of the iodine and other additives to regular salt. Be aware that higher sodium levels can give your beer an unpleasant sour character, so check how much is already there.
    I spoke with Colin Kaminski of Downtown Joe's last week at the homebrewer's conference (he did a talk on water chemistry), and he agrees with me that you could probably add MgCl instead if your Ca and Na was high enough for concern, but check the existing level of Mg in your water first...you would not want Milk of Magnesia stout! (Note: neither Colin or I have tried this).
    HTH!
    -Lyle C. Brown
    Brewer
    Camelot Brewing Co.

  12. #12
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    Thanks, nice work. OK I have been working on Palmer's spread sheet. But what I don't get is how color of malt, pH and residual Alkalinity relates to beer specific water chemistry for beer styles. The only thing I found interesting about chalk is that it enhanced the chocolate flavor in stouts. Back to residual alkalinity, how are famous beer city waters (stylres) relate to ra? Thanks

  13. #13
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    Beerking1, thanks for that. Adding chalk to the mash makes sense as probably more effective than adding to the boil, and I can get away with it. Will see how it goes.

    As for getting a maltier flavour profile (posed by jjs, actually), it makes sense to me that salts would have a lot more impact than pH per se.

    I would add the caveat that if one's water has adequate Mg, one should take care with MgCl when also using yeast nutrients, as these will likely supply even more. I should think that combining CaCl, NaCl and MgCl (minus any one you have good reason to withhold) would make it possible to increase chloride a bit without inviting the negative impact of relying on any one salt.

    Also, look for MgCl labelled USP (BP over my way), as some of it is meant strictly for external use and may be impure. Phrases like "food grade" are not really regulated and are about as meaningful as other commercial slogans like "all natural", "digitally remastered", etc.

  14. #14
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    jjs: residual alkalinity is defined as [alkalinity - calcium /3.5 - magnesium/7]. The equation works as long as all three variables are in the same units. What it illustrates is that alkalinity raises residual alkalinity, but calcium and magnesium decrease it. It also shows that alkalinity is the strongest factor, followed by calcium and finally magnesium. You can think of alkalinity and bicarbonate as the same thing because the two concentrations are often very close for water supplies that are suitable for brewing (alkalinity is technically carbonate + bicarbonate + carbonic acid). Anyway, residual alkalinity and mash pH move in the same direction. The lower the residual alkalinity, the lower the mash pH. Dark malts also lower mash pH because they release more acid into the mash than pale malts. In other words, dark malts counteract residual alkalinity. That's why breweries in places with high RA water historically brewed dark beers. Before brewers in such places knew how to treat their water supplies, dark beers simply turned out the best. You can download chart of classic brewing waters and their residual alkalinities from A.J. DeLange's website (http://ajdel.wetnewf.org:81/) - it's just called 'Residual Alkalinity Chart'.

    John Palmer's book is great. However, I think the ion contributions he gives for calcium carbonate are oversimplified. They may hit their marks for some water supplies/mashes but not others, as there are a lot of complicated interactions that aren't accounted for. The good news is that they're conservative, so you probably won't overshoot your mash pH by following his advice. Good luck with your chalk additions, all!

    Joe
    Last edited by jwalts; 06-25-2009 at 06:31 PM.

  15. #15
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    Thanks so much.
    Last edited by jjs; 06-26-2009 at 01:43 PM.

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