Pilsner and acid adjustment

[manticle]

Martin - do you have some sources I can look at for this info on calcium? I'd like to amend my water chem document and it would be great to read and find out more.
Cheers.

 

[Mardoo]

Second that. I'd love to do some more research.

 

[TheWiggman]

Excellent post Martin, thanks for sharing your expert opinion. The water profile for Pilsen is almost devoid of minerals so it makes sense to me that if one is trying to emulate the water to replicate the style, minimising minerals is key. In addition, wessmith posted this -

"It starts with the brewing liquor - it MUST be low in minerals, no bicarb hardness at all and have a pH factor around 7.0 or slightly less."

My water has slight bicarb hardness of about 54 which is not ideal. This of course has a negative impact on mash pH. Without adding extra mineral additions, the only way I can see that I can address the mash pH is through lactic acid or similar. I'll never get it perfect but hopefully this will be a good starting point.
Cash is tight at present so can't afford ingredients, but will hopefully put the brew together at the end of the month. Being a lager, expect feedback mid-year.

 

[mabrungard]

Here is the reference list for the upcoming article that will be published by the Brewers Association in the AHA magazine "Zymurgy" and the BA magazine "New Brewer". Many of these are available on the web.

1Bertoft E, C Andtfolk, and SE Kulp, Effect of pH, Temperature, and Calcium Ions on Barley Malt Alpha-Amylase Isoenzymes, Journal of the Institute of Brewing, Sep-Oct 1984, Vol 90, pp 298-302.

2Birch RM, A Dumont, and GM Walker, The Role of Magnesium and Calcium in Governing Yeast Agglomeration, Food Technology and Biotechnology, Vol 40, pp 199-205, 2002.

3Briggs DE, JS Hough, R Stevens, and TW Young, Malting and Brewing Science, 2nd Ed, Chapman and Hall, 1981.

4Bromberg SK, PA Bower, GR Duncombe, J Fehring, LA Gerber, VK Lau, and M Tata, Requirements for Zinc, Manganese, Calcium, and Magnesium in Wort, Journal of the American Society of Brewing Chemists, Vol 55, pp 123-128, 1997.

5Brungard MA, Brewing Water Series: Bavaria, Zymurgy-The Journal of the American Homebrewers Association, Mar/Apr 2014.

6Bush DS, L Sticher, R vanHuystee, D Wagner, and RL Jones, The Calcium Requirement for Stability and Enzymatic Activity of Two Isoforms of Barley Aleurone Alpha-Amylase, The Journal of Biological Chemistry, Vol 264, No. 32, Nov 1989.

7Dengis PB, LR Nelissen, and PG Rouxhet, Mechanisms of Yeast Flocculation: Comparison of Top- and Bottom-Fermenting Strains, Applied and Environmental Microbiology, Feb 1995, pp 718-728.

8Forsen S and J Kordel, Calcium in Biological Systems, Bioinorganic Chemistry, University Science Books, 1994.

9Fulmer EI, The Acclimatization of Yeast to Ammonium Fluoride and its Reversion in Wort, Journal of Physical Chemistry, 1921.

10Kontkanen D, DL Inglis, GJ Pickering, and A Reynolds, Effect of Yeast Inoculation Rate, Acclimatization, and Nutrient Addition on Icewine Fermentations, American Journal of Enology and Viticulture, Vol 55, 2004.

11Kumari A, T Rosenkranz, AM Kayastha, and J Fitter, The Effect of Calcium Binding on the Unfolding Barrier: A Kinetic Study on Homologous Alpha-Amylases. Biophysical Chemistry, Sept 2010, pp 54-60.

12Liu DJ, Y Pomeranz, and GS Robbins, Mineral Content of Developing and Malted Barley, American Association of Cereal Chemists, Sep-Oct 1975.

13MacWilliams IC, Wort Composition – A Review, Journal of Institute of Brewing, Vol 74-1, 1968.

14Nielsen AD, CC Fuglsang, and P Westh, Effect of Calcium Ions on the Irreversible Denaturation of Recombinant Bacillus Halmapalus Alpha-Amylase: a Calorimetric Investigation, Biochemical Journal, Vol 373, pp 337-343, 2003.

15Rees E and G Stewart, The Effects of Increased Magnesium and Calcium Concentrations on Yeast Fermentation Performance in High Gravity Worts, Journal of Institute of Brewing, Vol 103, pp 287-291, Sep-Oct 1997.

16Rees E and G Stewart, Effects of Magnesium, Calcium, and Wort Oxygenation on the Fermentative Performance of Ale and Lager Strains Fermenting Normal and High Gravity Worts, Journal of Institute of Brewing, Vol 105, No 4, 1999.

17Saltukoglu A and JC Slaughter, The Effect of Magnesium and Calcium on Yeast Growth, Journal of Institute of Brewing, Vol 89, pp 81-83, Mar-Apr 1983.

18Smith GD and GM Walker, Fermentation Performance of Mg-preconditioned Yeast, In: Brewing Yeast Fermentation Performance, KA Smart, Ed., Oxford, 2000, pp 92-95.

19Stratford M, Yeast Flocculation: Calcium Specificity, Yeast, Vol 5, Issue 6, Nov/Dec 1989.

20Walker GM, The Roles of Magnesium in Biotechnology, Critical Reviews in Biotechnology, pp 311-354, 1994.

21Walker GM and JH Duffus, Magnesium Ions and the Control of the Cell Cycle in Yeast, Journal of Cell Science, Vol 42, pp 329-356, 1980.

22Walker GM, R DeNicola, S Anthony, and R Learmouth, Yeast-Metal interactions: Impact on Brewing and Distilling Fermentations, Institute of Brewing and Distilling Asia-Pacific Section Convention, Hobart, Australia, 2006.

23Udeh, HO and TE Kgatla, Role of Magnesium Ions and Yeast Performance during Very High Gravity Fermentation, Journal of Brewing and Distilling, Vol 4, pp 19-45, Sep 2013.

24Verstrepen KJ, G Derdelinckx, H Verachtert, FR Delvaux, Yeast flocculation: What Brewers Should Know, Applied Microbiology and Biotechnology, Vol 61, pp 197-205, 2003.

 

[Mardoo]

Wow. Thank you SOOOOOOOO much. What a list! Your input and work are always very much appreciated Martin.

 

[manticle]

Cheers Martin.

 

[Online Brewing Supplies]

There goes my Friday night.
Nev

 

[kevin_smevin]

Well, even myself and John Palmer were taken in by the myth that brewing water HAS to include at least 50 ppm calcium. There are a number factors that are cited and yeast health and flocculation are primary. Apparently, nobody ever really did the research to confirm those factors. It turns out that there is ample research in a variety of scientific journals that completely refute the need for brewing water to include calcium for yeast health. In fact, the research goes further and points out that high calcium in the absence of magnesium can actually harm yeast health.

Fortunately, typical barley and wheat malt provide magnesium and calcium to wort in the proper ratio. Not surprisingly, yeast have evolved to prefer the high magnesium content and relatively low calcium content of typical wort. The Mg to Ca ratio of typical wort is between 2 and 6 parts Mg to 1 part Ca. This is without the additional Mg or Ca that may be supplied by the water.

It also turns out that Ca has the ability to strip Mg from yeast cells. That is a bad thing since yeast need Mg more than they need Ca. In fact, if the yeast become Mg deficient, than can lose the ability to ferment maltose and maltotriose. Lager yeast are particularly susceptible to this, while ale yeast is not.

But this not to say that calcium has no place in brewing water. It turns out that calcium's role in flocculation is very real. In addition, it has a real role in reducing beerstone in the brewery by precipitating out the calcium oxalate from the wort in the tun. For ale brewing, calcium is necessary. The 50 ppm minimum Ca is a reasonable target for ales. But the picture changes for lagers. Since they rely more on long lagering, they are far less dependent on flocculation than an ale is. So they can be brewed with low calcium water. That is one reason why you often hear that the megabrewers use water with very little mineralization. They don't need calcium and as pointed out above, adding calcium could make the yeast Mg deficient and this may create fermentation problems for the lager yeast.

So, the water that the OP listed above should be fine for lager brewing. No need to add calcium unless you want the flavor ions that are attached to the calcium or want to reduce beerstone problems in your brewing. There is no detriment to yeast health when brewing with low calcium water!

It is true that yeast require only small amounts of Ca for proper function, and that too high levels of Ca can adversely effect fermentation performance by antagonising Mg uptake.

Dont forget however, that Ca is very important for wort production - thermal protection of alpha amylase during mashing, ph regulation, oxalate precipitation, enhanced protein precipitation and a number of other things. 50-100ppm Ca is recommended for wort production. You would get about 30ppm from you malt alone.

I have read the majority of articles you sited in a later post and none of them suggest that Ca is not needed. The fact is that it is needed for mashing and boiling to produce the best quality wort. Yeast need only very small amounts for normal fermentation but absolutely require it for flocculation. The adverse affect of Ca on fermentation (namely lag time, sugar uptake and attenuation) was observed at Ca levels over 800ppm - at least 8 times higher then you would find in any wort. None of the studies suggested that Ca at levels typically seen in wort adversely affect fermentation. It would appear that yeast require Mg to be at higher levels than Ca, this is the norm anyway - for 1.048 OG all grain wort without salt additions, Mg = 106ppm, Ca = 35ppm. All texts i have read say that a finished beer must contain 40-50ppm Ca. Considering the amount of precipitation you get in the boil, you would be very safe to have 100ppm Ca during wort boiling.

So for all of you brewers out there who have read this thread, and are now thinking that you do not need to add Ca to you mash or kettle, dont. This is wrong. Unless you are adding huge amounts of Ca, you will not affect fermentation performance. Not adding Ca however will reduced your mash efficiency, wort clarity and flocculation.

 

[mabrungard]

Dont forget however, that Ca is very important for wort production - thermal protection of alpha amylase during mashing, ph regulation, oxalate precipitation, enhanced protein precipitation and a number of other things. 50-100ppm Ca is recommended for wort production. You would get about 30ppm from you malt alone.

Unfortunately, that listing of references doesn't put the whole story together. Those forum members that are members of the Brewers Association or American Homebrewers Association will get to read the whole story in the July/Aug issues of Zymurgy and New Brewer.

While the thermal protection of alpha amylase (AA) is a welcome feature of calcium addition, its effect is almost negligible at the calcium content we typically employ in brewing. The reference that confirms that alpha amylase is indeed thermally protected by calcium addition, only conducted that evaluation at 400 ppm calcium. Using another reference, I was able to confirm that the thermal protective response of calcium addition is generally proportional to calcium content. Since the thermal stability of AA is enhanced by roughly 50% at 400 ppm Ca, Its fairly easy to back calculate that the effect is almost negligible at 50 to 100 ppm. In addition, that thermal stability research was performed at 70C. While some brewers do conduct mashes at that temp, many brewers find that better results are produced with slightly lower mashing temperatures. AA thermal stability is greatly enhanced by minor temperature reduction. The advantage presented by elevating the water's calcium content is therefore, further muted.

I had not heard of calcium's role in pH regulation. However I have heard of its role in mash pH reduction via its reaction with malt phytins. Perhaps that was what you were implying? While calcium's ability to reduce mash pH is well known, it is not the only way to achieve pH reduction. Acid addition is substantially more effective than calcium's effect, but its effect comes along with an anion that may or may not be desirable in the finished beer. Calcium addition also comes with this bonus or detriment of an anion addition. Since this is essentially a wash, adding calcium for its pH reducing effect is neither a plus or minus.

Oxalate reduction IS an important feature of calcium addition. The opportunity to precipitate oxalates in the mash instead of beerstone throughout your brewery or equipment is an important advantage. I find that about 40 ppm is the minimum calcium needed in the brewing water to provide adequate oxalate reduction. However, there are hundreds of breweries that routinely brew with far less calcium in their water. All it means is that a brewer will have to contend with the additional problems that beerstone presents for maintenance and operation. Again, calcium is desirable, but not required.

Typical barley or wheat produces wort with a bit more calcium than mentioned above. 60 ppm Ca is easily achieved in typical 1.045 gravity wort using distilled water. All that calcium comes directly from the malt. That calcium content is more than needed for the nutritional needs of yeast (which are about 10 to 20 ppm Ca). So it is not necessary to supplement the water for that reason.

So I reiterate: Calcium is NOT REQUIRED in brewing water. However, there are reasons to include it in some cases. The oxalate reduction is a good reason and for ale yeast, the ability to flocculate well is another. There is little reason beyond that to target a certain calcium content. I find that an important reason to add calcium is to obtain those anions that generally regard as desirable for flavor (chloride and sulfate). With all this said, ale brewers should still target a calcium level in the 40 to 150 ppm range for a variety of reasons. However, lager brewers should not target similar levels. Lager yeast can be adversely affected by high calcium levels unless the yeast have been pre-acclimated to high calcium levels. In the case of many lager strains, you are better off targeting much lower calcium levels than suggested for ale yeasts.

The point of my original post was to alert brewers that the 50 ppm calcium target is not necessary or desirable for lager brewing and might be ignored for some ale brewing.

Enjoy!

 

[wessmith]

Thankyou Martin.

Wes

 

[kevin_smevin]

Unfortunately, that listing of references doesn't put the whole story together. Those forum members that are members of the Brewers Association or American Homebrewers Association will get to read the whole story in the July/Aug issues of Zymurgy and New Brewer.

While the thermal protection of alpha amylase (AA) is a welcome feature of calcium addition, its effect is almost negligible at the calcium content we typically employ in brewing. The reference that confirms that alpha amylase is indeed thermally protected by calcium addition, only conducted that evaluation at 400 ppm calcium. Using another reference, I was able to confirm that the thermal protective response of calcium addition is generally proportional to calcium content. Since the thermal stability of AA is enhanced by roughly 50% at 400 ppm Ca, Its fairly easy to back calculate that the effect is almost negligible at 50 to 100 ppm. In addition, that thermal stability research was performed at 70C. While some brewers do conduct mashes at that temp, many brewers find that better results are produced with slightly lower mashing temperatures. AA thermal stability is greatly enhanced by minor temperature reduction. The advantage presented by elevating the water's calcium content is therefore, further muted.

I had not heard of calcium's role in pH regulation. However I have heard of its role in mash pH reduction via its reaction with malt phytins. Perhaps that was what you were implying? While calcium's ability to reduce mash pH is well known, it is not the only way to achieve pH reduction. Acid addition is substantially more effective than calcium's effect, but its effect comes along with an anion that may or may not be desirable in the finished beer. Calcium addition also comes with this bonus or detriment of an anion addition. Since this is essentially a wash, adding calcium for its pH reducing effect is neither a plus or minus.

Oxalate reduction IS an important feature of calcium addition. The opportunity to precipitate oxalates in the mash instead of beerstone throughout your brewery or equipment is an important advantage. I find that about 40 ppm is the minimum calcium needed in the brewing water to provide adequate oxalate reduction. However, there are hundreds of breweries that routinely brew with far less calcium in their water. All it means is that a brewer will have to contend with the additional problems that beerstone presents for maintenance and operation. Again, calcium is desirable, but not required.


Typical barley or wheat produces wort with a bit more calcium than mentioned above. 60 ppm Ca is easily achieved in typical 1.045 gravity wort using distilled water. All that calcium comes directly from the malt. That calcium content is more than needed for the nutritional needs of yeast (which are about 10 to 20 ppm Ca). So it is not necessary to supplement the water for that reason.

So I reiterate: Calcium is NOT REQUIRED in brewing water. However, there are reasons to include it in some cases. The oxalate reduction is a good reason and for ale yeast, the ability to flocculate well is another. There is little reason beyond that to target a certain calcium content. I find that an important reason to add calcium is to obtain those anions that generally regard as desirable for flavor (chloride and sulfate). With all this said, ale brewers should still target a calcium level in the 40 to 150 ppm range for a variety of reasons. However, lager brewers should not target similar levels. Lager yeast can be adversely affected by high calcium levels unless the yeast have been pre-acclimated to high calcium levels. In the case of many lager strains, you are better off targeting much lower calcium levels than suggested for ale yeasts.

The point of my original post was to alert brewers that the 50 ppm calcium target is not necessary or desirable for lager brewing and might be ignored for some ale brewing.

Enjoy!

Ca has a number of beneficial roles that are separate to its role in pH reduction (yes, this is what I was referring to when I said pH regulation). You most certainly can reduce pH by simple acid addition, nothing wrong with that.

The main reason for removal of oxalic acid is to prevent haze formation and potential gushing

Other non pH related roles of Ca include improved protein coagulation during boil, restricting colour formation during boil - important for a nice pale lager. It also stimulates proteolytic enzyme activity.

In most of these, Ca would play a very small role. The big one is improved wort clarity, and therefore beer clarity by aiding in precipitation of oxalic acid and protein during boil, and aiding in yeast flocculation.

The suggestion that lager breweries rely on long lagering times so don't need the flocculation benefit is far away from the commercial reality of a large brewery. The fact is that a large brewery will do everything in its power to speed up maturation times and decrease the load on the filter.

Text books and research papers aside, my personal experience with Ca, Dosing 100ppm to the mash and 50ppm to sparge liquor resulted in a huge improvement in hot break formation and resulting clear wort, and a step change in efficiency - 75% pre calcium to 90-95% post calcium. This change may be due to PH reduction alone, I don't know?

In the end, there are many ways to skin a cat. If you want clear/bright beer, I would keep adding Ca. Otherwise you might be waiting a very long time for your beer to clear up. If you have a good clean ferment, lagering will not improve flavour, just clarity. In fact, the longer beer is stored, the more aged and oxidised it will become

 

[Dunkelbrau]

In the end, there are many ways to skin a cat. If you want clear/bright beer, I would keep adding Ca. Otherwise you might be waiting a very long time for your beer to clear up. If you have a good clean ferment, lagering will not improve flavour, just clarity. In fact, the longer beer is stored, the more aged and oxidised it will become

Firstly, the "fact" is incorrect.. Lagering actually reduces oxidation by allowing the yeast to clean up not only off flavours, but residual oxygen and other imperfections, and improves beer stability over longer time frames.

Lets look to history.. In Bavaria, Germany 1553 it was once not permitted to brew in summer. .. here is a snippet

"In 1553, summer brewing was outlawed altogether in Bavaria. By then the authorities--always worried about the supply of healthy summer beer--had obviously learned that cold fermentation yielded a purer beer with better keeping qualities than possessed by those unwittingly brewed and probably bacterially infected top-fermented beers of summer. The official brewing season was, therefore, restricted to between St. Michael's Day (September 29) and St. George's Day (April 23)."

This means that the summer stock of beer had to be brewed during the permitted brewing season! Thats at least 5 months of age if the beer is brewed in the final days of April.

If thats the case, they drank old, infected, bad tasting, oxidized beer.. the exact reason they outlawed summer brewing in the first place (and inadvertently, Ale brewing).

Regarding commercial clarifying, big commercial breweries use something called a centrifuge, this pre clears the beer before filtration, where they add a pile of antioxidants and stabilizers to ensure good shelf live and reduce risk of oxidation in the bottle..

 

[manticle]

Yyy said the longer beer is stored (not lagered) the more it is prone to staling. What happened in 1553 doesn't negate that.
His argument was that with insufficient Ca, lagering periods would be extended considerably in order to achieve the same levels of flocculation.
Staling reactions occur as early as mash and even malting from memory - chemical pathways that are often irreversible which have a variety of effects on flavour - some desirable (beer dependent) others not so. Active yeast may retard some of the negative effects and stave off other oxidation reactions but its efficacy is not permanent or immortal.

 

[TheWiggman]

I should apologise that I haven't brewed my Bohemian Pilsner because I put my order through MHB at the wrong time. Haven't ordered grain from someone who has lactic acid, so it's off the cards 'til I get my other brews out of the way.
Still looking forward to it though and have received a lot of good advice from this thread.

 

[Muscovy_333]

Cracking discussion!
Taking notes...

 

[antiphile]

If you're willing to sit thru a 30 minute video, is full of really good tips as well as some in-depth chemistry.

 

[Dunkelbrau]

Yyy said the longer beer is stored (not lagered) the more it is prone to staling. What happened in 1553 doesn't negate that.
His argument was that with insufficient Ca, lagering periods would be extended considerably in order to achieve the same levels of flocculation.
Staling reactions occur as early as mash and even malting from memory - chemical pathways that are often irreversible which have a variety of effects on flavour - some desirable (beer dependent) others not so. Active yeast may retard some of the negative effects and stave off other oxidation reactions but its efficacy is not permanent or immortal.

The way yyy worded the text I quoted was to allude that lagering for longer periods doesn't mature the beer, but negatively impacts it instead. To which I referred to a centuries old observation in which that isn't the case.

If that is not the case, then it should be stated more plainly.

I'll shoot you a PM Wiggman

 

[TheWiggman]

I've got tomorrow off and finally decided to brew this. I managed to get hold of some WLP800 pilsner yeast so rather than do a Bohemian pilsner, I'm going for a Czech Pilsner.
I bought a pH test kit today to find my water is 7.6 pH. Higher than expected.
I used Brun Water to calculate my required acid additions and also added 1.5% acidulated malt.

View attachment Brun Water - Czech Pilsner.xls

Adjustments using 80% lactic acid were -

• 1.9 ml to sparge to achieve pH 6.5
• 5.3 ml to mash (15l total for a 3:1 water:grain ratio)

I created these adjustments to target the figures from this post from Wessmith.

After adjustments, I tested the sparge water and it was pH 6.5 - perfect.
I can't test the mash water as my kit doesn't go down that far, but I tasted it with 4.5ml of lactic acid and I could definitely taste it. I wouldn't want to have a glass of it if I was thirsty.

My concern is even if I follow the pH and mash guidelines that I'm going to taste the sourness of the lactic acid in the final product. In this case, I'm not going to bother going to the effort. Will this sourness be obvious and detrimental to the final product?

 

[Black n Tan]

The kaiser did a lactic acid taste threshold test and concluded the following, so I don't think you will have a problem:

"It was surprisingly difficult for panelists to pick out beers that had lactate added even at levels that correspond to an equivalent acidulated malt use of 13% and higher. Note that the acidity of the lactic acid was neutralized with slaked lime. A general recommendation for home brewers is to keep the use of acidulated malt below 5%, which corresponds to a level of 264 mg/l added lactate in a 12 Plato beer with 85% efficiency into kettle. Many of the panelists were not able to pick up the added lactate at a level of about 400 mg/l which corresponds to about 7.5% acidulated malt. Based on that we can safely say that even 8% acidulated malt won't ruin a beer if that amount is needed to counteract water alkalinity." http://braukaiser.com/wiki/index.php?title=Lactate_Taste_Threshold_experiment

 

[Online Brewing Supplies]

My next venture is a Bohemian pilsner. I now have my system under control and have the luxury of temp control. The venture into the subtle style of pilsner though has identified the biggest weakness in my system to tackle this - water.

I've enjoyed reading through this thread with some clearly very experienced an knowledgeable brewers. Below is a picture of the tap water I have on hand, which I got tested privately recently -

Metals - tested to CA14106. If not listed, concentration is <0.01mg/l

Calcium 9.9 mg/l
Copper 0.02 mg/l
Magnesium 7.1 mg/l
Potassium 3 mg/l
Silica (Si02) 4.9 mg/l
Sodium 10 mg/l
Zinc 0.03 mg/l
Total hardness: 54.0 mg\l

Anions - test method CA15000

Chloride (Cl) 14 mg/l
Sulfate (SO4) 4 mg/l

Alkalinity - test method CA12121

Total alkalinity (CaCO3) 53 mg/l
Phenolphthalein alkalinity (CaCO3) <25 mg/l

pH @ 25°C 7.4

Overall it's good and very low in minerals, but I've noticed that due to the slight hardness and measured alkalinity, the mash pH is too high. To do a pilsener properly I need it to get down to the low 5's.
There are a few ways I can see I can do this -

1. Adding some acidulated malt (2% max recommend to minimise minerals)
2. Treating with calcium chloride
3. Treating with lactic acid

The issue as I see it is mainly the total carbonate (bicarb + carb) content. Using a calculator, it's around 64 ppm. If I use CaCl this will up the bicarbonate and minerals but reduce the pH.
If I use lactic acid though I can get it as far down as I want, but I'm concerned 4ml of lactic acid (some for the sparge, some for mash) will contribute too much to flavour/sourness and will again have a negative impact. In either case I will need to add some some I can fly sparge at 85°C.

Any suggestions? I have a feeling lactic acid is simply 'too easy' and if it was the be-all and end-all of pH issues it'd be a stable mention for any home brewer. And no, I don't have access to RO water and due to cost I want to avoid distilled. I've attached the Brunwater spreadsheet for those interested.

First port of call Acidulated malt, the rest of your chems aint that bad.
Don't over complicate it , suck it and see.
Nev