Water chemistry help

[MChopz]

Hi everyone,

I'm attempting to brew an american pale ale and I'm currently using brunwater to help me adjust my water chemistry.

My water is:
Calcium: 30 ppm
Magnesium: 13 ppm
Sodium: 73 ppm
sulfate: 161 ppm
Chloride: 43 ppm
bicarbonate: 73 ppm
pH: 9.5

I'm diluting about 10% with distilled water to reduce the sodium and then adding back 0.5 g/gal of gypsum to raise calcium and sulfates, and then I'm adding about 0.1 g/gal epsom salt to raise magnesium back up a little bit.

I'm adding about 2mL of lactic acid in the mash to bring my mash pH to about 5.3, and then adding 1.5mL to the sparge water to bring that pH to about 5.7

My final water chemistry that brunwater calculated is:
Calcium: 58 ppm
Magnesium: 14 ppm
Sodium: 66 ppm
Sulfate: 229 ppm
Chloride: 39 ppm
Bicrbonate: -27 ppm
pH (mash): 5.3

My concern here is that the bicarbonates is negative after the lactic acid additions. also my total alkalinity becomes negative as well. Does this matter at all? I'm somewhat new with adding salts to the water, so any input on this will be greatly appreciated. I'm really afraid of ending up with salt water or something for brewing.

Also I've never added salts to the sparge water before, but this software incorporates that, so is this just to keep the wort balanced with the minerals after sparging?

Thanks!

 

[mchrispen]

I'm diluting about 10% with distilled water to reduce the sodium and then adding back 0.5 g/gal of gypsum to raise calcium and sulfates, and then I'm adding about 0.1 g/gal epsom salt to raise magnesium back up a little bit.

I would dilute a bit further to get the sodium level under 40, and also skip the epsom and see the mash pH prediction - if it is high - then add a bit more sulfate or chloride to make up the difference in the profile, or use acid. Shoot for 5.3/5.4 - so you are already close. For an IPA or Pale Ale I personally don't like magnesium or sodium in the water at moderate levels.

My concern here is that the bicarbonates is negative after the lactic acid additions. also my total alkalinity becomes negative as well. Does this matter at all?

You can ignore the bicarb and total alkalinity in the prediction - it is simply indicative of the acid additions and mash contributed acids overcoming the residual alkalinity of your water profile, and a hint that alkalinity MIGHT be needed in the mash. When you dilute further, this number will likely decrease a bit (meaning a larger negative number)... and you should need to use less acid - or perhaps add a tiny bit of alkalinity. This depends on where you want to fall for mash pH... 5.4 is a good number, but so is 5.3. YMMV.

Go ahead and add the acid salts to the sparge (never alkaline additions). I would only acidify to 5.8 or 6.0 range to reduce the acid amount. If you dilute by 50%, you will not likely need any acid in the sparge at all.

Please make sure to treat for Chlorine/Chloramine in the tap water, and use a calibrated pH meter throughout the mash if possible.

Best of luck!

 

[MChopz]

Thanks for the input! that was exactly what I needed.

I am also worried that the calcium levels are a little low too. what range would you recommend for calcium?

I want to make a crisp pale ale thats dry hopped and has nice hop bitterness and aroma

 

[Yooper]

Thanks for the input! that was exactly what I needed.

I am also worried that the calcium levels are a little low too. what range would you recommend for calcium?

I want to make a crisp pale ale thats dry hopped and has nice hop bitterness and aroma

50 ppm as a minimum for calcium. No additional magnesium, and a sulfate level at 150 would make a good pale ale.

 

[ajdelange]

... my water chemistry.

My water is:
Calcium: 30 ppm
Magnesium: 13 ppm
Sodium: 73 ppm
sulfate: 161 ppm
Chloride: 43 ppm
bicarbonate: 73 ppm
pH: 9.5

I keep gently encouraging people to think about alkalinity, not bicarbonate. Many of the spreadsheets and calculators use bicarbonate as a proxy for alkalinity justifying this by noting that bicarbonate is the major source of alkalinity in potable water. This works quite well except when the source water pH gets as high as yours at which levels there is appreciable carbonate as well as bicarbonate. To solve problems like these the first thing I have to do is figure the alkalinity from the bicarbonate and pH and then figure the carbonate as well. It is a little easier for me if you give me the alkalinity (actually I can just go into a family of curves in pH and alkalinity to get me what I need. OK - I'm lazy.

Taking you at your word that the bicarbonate is really 73 mg/L this means, at pH 9.5, that your alkalinity would be 78 ppm as CaCO3. It probably isn't because your lab calculates bicarbonate from alkalinity and many labs don't do this right. Another reason that I want alkalinity, not a bicarbonate number.

I'm diluting about 10% with distilled water to reduce the sodium and then adding back 0.5 g/gal of gypsum to raise calcium and sulfates, and then I'm adding about 0.1 g/gal epsom salt to raise magnesium back up a little bit.

Why all the intricate tinkering?

I'm adding about 2mL of lactic acid in the mash to bring my mash pH to about 5.3, and then adding 1.5mL to the sparge water to bring that pH to about 5.7

My final water chemistry that brunwater calculated is:
Calcium: 58 ppm
Magnesium: 14 ppm
Sodium: 66 ppm
Sulfate: 229 ppm
Chloride: 39 ppm
Bicrbonate: -27 ppm
pH (mash): 5.3

My concern here is that the bicarbonates is negative after the lactic acid additions. also my total alkalinity becomes negative as well. Does this matter at all?

Well you should be confused as there is no such thing as negative bicarbonate. This is a consequence of using bicarbonate as a proxy for alkalinity. Most calculators use bicarb = 61*alkalinity/50 and if you do this negative alkalinity, which is possible, will give you negative bicarbonate. But you wouldn't have negative alkalinity here either. Using your supplied bicarbonate and pH numbers and assuming that you added the salts, the 2 mL of 88% lactic acid, and 0.5 gal ofr RO water to 5 gal of tap water the acid will take the mix to pH 5.87 leaving 18 mg/L bicarbonate and positive but small alkalinity of 22 ppm as CaCO3 (over half of which comes from the lactate ions produced when carbonate and bicarbonate in your water neutralized the acid you added). Alkalinity is acid required to move those (and the residual bicarbonate) to the alkalinity titration end point (I used the Ward Labs value of 4.4 in these calculations).

Given that your acid addition won't get the water alone to the desired mash pH (5.3) it is unlikely that it will take the mash (water plus malt) that low. IOW you are going to need more than the 2 mL of lactic unless you have acidic malts in your grist.

I'm somewhat new with adding salts to the water, so any input on this will be greatly appreciated. I'm really afraid of ending up with salt water or something for brewing.

This is why I recommend the KISS approach set out in the Primer until you understand what is really going on. This is quite a complicated subject as this example shows especially when you get into the region where the alkalinity/bicarbonate assumption starts to get shaky. The Primer would have you dilute your water down until the alkalinity is 30 or less and then add back in some calcium chloride and calcium sulfate (if you want it). As the alkalinity is largely defeated by doing this you would need less acid which the primer has you WAG as a sauer malz addition at the level of 2 - 3 % of the grist.

Also I've never added salts to the sparge water before, but this software incorporates that, so is this just to keep the wort balanced with the minerals after sparging?

Your water is fairly (but not terribly) alkaline and so it will pull the pH of the mash high fairly quickly as you sparge with it. The amount of acid to add to prevent this is enough to get the water's pH below 6 which is as high as we generally want runoff pH to go. As we have calculated that 2 mL is enough to bring 5.5 gal of the diluted tap water to pH 5.87 clearly a like amount will do for the sparge water.

 

[mabrungard]

As AJ mentions, those negative alkalinity and bicarbonate values are a result of the calculation methodology. They are OK. In fact, most pale beers need an external acid or elevated hardness to drive the mash pH into a desirable range. Bru'n Water quantifies this effect as a 'negative' bicarbonate value when adding acid. While there is no such thing, it does properly account for the acid contribution.

For those of you with tap water pH below 8.5, you won't need to worry too much about using bicarbonate or alkalinity values in calculations. The error is less than 1.5 percent. But AJ is correct that focusing on the alkalinity value is a safer way to look at this important parameter.

For a more assertive bittering presence, boosting the magnesium and sulfate are fairly important. This is a personal preference aspect of brewing, so the OP's experience and expectations will drive the final water treatment. In my opinion, the proposed water profile is a modest pale ale water and should be acceptable. Do reduce the sodium content when the sulfate content will be boosted since those ions don't play well together on the drinker's palate.

 

[ajdelange]

As AJ mentions, those negative alkalinity and bicarbonate values are a result of the calculation methodology. They are OK. In fact, most pale beers need an external acid or elevated hardness to drive the mash pH into a desirable range. Bru'n Water quantifies this effect as a 'negative' bicarbonate value when adding acid. While there is no such thing, it does properly account for the acid contribution.

Alkalinity answers the question 'How many protons do I need to reach a reference pH?'. Protons are measured in equivalents (units of Avogadro's constant) or, for our purposes, milliequivalents per liter of water, kg of malt etc. Milliequivalents can be expresses 'as Calcium carbonate'. Given that the carbonate ions in 100 mg of calcium carbonate absorb 2 mEq of protons (as its molecular weight is 100) it is clear that 50 mg of CaCO3 requires 1 mEq of protons. For this reason alkalinity is often expressed 'as calcium carbonate' and confuses the hell out of everyone (except chemists in the water industry). My well water has alkalinity of about 1.2 mEq/L. It's alkalinity would usually be stated as being 1.2*50 = 60 mg/L as CaCO3 even though it contains no CO3. You can clearly express alkalinity in terms of any ion or ionic compound you choose. Bicarbonate is under scrutiny here. Sixty one mg of bicarbonate ion will absorb 1 mEq of protons. Hence my water's alkalinity can be stated as 1.2* 61 = 73 mg/L 'as bicarbonate' or 1.2*84= 90.8 mg/L 'as NaHCO3' as the equivalent weights of calcium carbonate, bicarbonate ion and sodium bicarbonate are, respectively, 50, 61 and 84. But why do this? There is, at least, a reason for the water chemists: if you dissolve 100 mg of calcium carbonate in a liter of water using carbon dioxide gas, the way in which nature does it, the alkalinity and hardness of that water will be approximately 100 ppm as CaCO3. Is this worth the confusion the practice causes? Not in the water industry but for brewers the answer is, IMO, 'No.'. In Europe they tend to use the mVal (equal to 1 mEq/L) and avoid all the confusion. So my take here is that ppm as CaCO3 is bad enough but at least it has precedent behind it. 'As bicarbonate' only makes things worse, IMO. This could be ameliorated somewhat if the numbers calculated 'as bicarbonate' were labeled 'Alkalinity as bicarbonate' making it clear that we are talking about an acid amount - not an ion concentration. Now if you are going to say 'Alkalinity as bicarbonate' why not just say 'Alkalinity as CaCO3' or better yet, 'Alkalinity, mEq/L'.

As we are moving towards fuller understanding of what dictates mash pH it seems to speak of alkalinity in its intrinsic units makes more sense. If I say a particular base malt has an alkalinity WRT mash pH of 5 mEq/kg that immediately makes sense and can be used in calculations. If I say it is 250 mg/kg as Calcium Carbonate or 305 mg/kg as bicarbonate it doesn't. The first thing anyone has to do to use that figure is convert back to mEq/kg.

For those of you with tap water pH below 8.5, you won't need to worry too much about using bicarbonate or alkalinity values in calculations. The error is less than 1.5 percent. But AJ is correct that focusing on the alkalinity value is a safer way to look at this important parameter.

The problem I see in this thread is not that alkalinities are expressed 'as bicarbonate' so much as that the calculations done by OP show a negative alkalinity for a given acid addition when in fact adding the amount of acid he proposes will not result in a negative alkalinity unless he has malts with negative alkalinities. This confuses him and causes Matt to conclude that an addition of alkali will/may be needed when in fact it looks as if additional acid will be required. It appears, from looking at OP numbers (and I may not have interpreted what he did exactly right) that most of the positive alkalinity is due to neglecting the alkalinity of lactic ions. Whenever acid anions are added to water those anions contribute alkalinity to the mix. In the OP example, lactate contributes a bit more than half the alkalinity and bicarbonate the rest (ignoring the wee, wee bit more from sulfate). Here the rationale that bicarbonate is the sole source of alkalinity is clearly not justified. There appears to be a problem at the low (near mash) pH end as well.One can dodge that criticism by not using that justification and, instead, making clear that alkalinity, while it is not exclusively associated with bicarbonate, is being expressed 'as bicarbonate'. But this is sort of like doing all your finances in Bahraini Dinar because the Dinar is tied to the dollar.

 

[mchrispen]

AJ, my conclusion is drawn from seeing a negative RA prediction in the spreadsheet that has required me in all but a single case to raise the mash pH. Please note the "might" as a suggestion and not as a pure recommendation. When I see a negative bicarb prediction (common using RO water), then I expect that my water's alkalinity is insufficient to achieve my target pH, but relative to that pH and to the size of the negative number. My thinking, thanks to you and Martin, is that bicarbonate = alkalinity, hence the confusion perhaps. I can strive to be more clear in the future.

The OP was confused by messaging presented by Bru'n Water, and while Martin's Knowledge page is fairly straight forward, it seems few people bother to read it before diving in (guilty as charged myself). The disagreement between Martin's spreadsheet and your spreadsheet calculations remain somewhere around +/- 0.2-0.3 pH, enough to warrant a possible adjustment to mash pH either up or down in practical application. More and more people seem to be punting for a recommendation here, and less willing to do the research and education before hand. If there is a weakness to the otherwise VERY good product (at least proven to me in my brew house) is that it is as easy to screw up additions as it is to get the right ones. But this is true of any tool, and each should be measured and proven to work.

Obviously I am making recommendations without a recipe in hand... and a delta could also be the difference between a pound of crystal or a pound of base malt... the recipe could drive the pH either direction. I have tried to provide options, and hopefully some decent guidance in application of using Bru'n Water, as well as flag my personal preferences appropriately. The better advice, perhaps, would be to read the Primer, and I recommend that regularly.

It should also be noted that the OP posted in different section here the report gleaned from a municipal report that shows wildly variable ion concentrations and those in this post seem to be best guesses. Martin responded to that post already - no need for me to jump in, but this is definitely NOT a lab report and the OP should be aware of that fact, and that his brewing liquor will be subject to seasonal changes throughout the year.

I am also concerned that the OP may NOT be using a calibrated pH meter during mashing and is flying blind.

Why all the intricate tinkering?

While the OP should answer this particular question, I think part of the issue that the current focus on water - through the Palmer/Kandinsky book, as well as articles in Zymurgy (nicely done BTW Martin), have perhaps created the impression that water issues solve all quality issues for brewers, AND that a one-size fits all methodology is simply not practical. I may be a bit caught in this as well - as water management really has made a tremendous difference in my brewing. But it should be noted that it took nearly 2 years of brewing a virtually identical recipe, investment in water treatments, and a modest education in water management to get the beer right. I may need OCD treatment this year. As each new issue comes to the forefront, it is often stated that "no single {issue/process/understanding} can more dramatically affect your brewing" regardless of the role of the procedure and so the elevated attention it receives, which is just not the case overall in most issues. That said - I think we agree that water hardness and alkalinity play a tremendous role in the final quality of our beers.

But this is sort of like doing all your finances in Bahraini Dinar because the Dinar is tied to the dollar.

Obviously I prefer to manage my finances in WW1 era Deutschmarks... doesn't everyone? Nothing like being a fake trillionaire. At least I can make up the conversion and inflation to modern dollars - much like we do today anyway!

 

[ajdelange]

AJ, my conclusion is drawn from seeing a negative RA prediction in the spreadsheet that has required me in all but a single case to raise the mash pH. Please note the "might" as a suggestion and not as a pure recommendation. When I see a negative bicarb prediction (common using RO water), then I expect that my water's alkalinity is insufficient to achieve my target pH, but relative to that pH and to the size of the negative number.

Negative alkalinity with respect to desired mash pH is an indication that alkalinity is insufficient. Negative M alkalinity (what the lab measures) will be an even stronger indicator as protons must be absorbed to get from M (pH 4.3) to mash pH. The problem here is that with respect to the water, at least, the alkalinity is positive, even with the addition of the acid, down to any reference pH as low as 4.4.

My thinking, thanks to you and Martin, is that bicarbonate = alkalinity, hence the confusion perhaps. I can strive to be more clear in the future.

The problem with this is that at higher pH alkalinity ~ bicarbonate + carbonate + water + sulfate + chloride (the last two are unappreciable). And at lower pH where acidification has been done with lactic acid or phosphoric acid it is alkalinity ~ bicarbonate +lactate (or phosphate) + water + sulfate + chloride. But I think I have to take some of the responsibility for giving the impression that it is mostly attributable to bicarbonate because, by and large it is. The business of taking a bottle of 0.1 N acid, ripping off the label and replacing it with one that says 5 g/L CaCO3 has bothered me from day one, however, and I have always been fairly vocal about that.

More and more people seem to be punting for a recommendation here, and less willing to do the research and education before hand.

That's the problem with putting a tool in the hands of an untrained user. I am reminded recently of this in that my walk-in compressor crashed on me Sat. I know enough to be dangerous about refrigeration. I got it fixed but an experienced tech would laugh at how I did it (and, knowing what I know now I would laugh too).

If there is a weakness to the otherwise VERY good product (at least proven to me in my brew house) is that it is as easy to screw up additions as it is to get the right ones. But this is true of any tool, and each should be measured and proven to work.

My reason for all this carrying on about this topic is that I hope the authors of spreadsheets will see how easy it is to make their offerings more robust. Correcting the alkalinity approximation is very easy to do. It is already in any spreadsheet that has a water acidification calculator as many do.

I am also concerned that the OP may NOT be using a calibrated pH meter during mashing and is flying blind.

No calculator will ever replace a pH meter.

While the OP should answer this particular question, I think part of the issue that the current focus on water - through the Palmer/Kandinsky book, as well as articles in Zymurgy (nicely done BTW Martin), have perhaps created the impression that water issues solve all quality issues for brewers, AND that a one-size fits all methodology is simply not practical.

The situation WRT water is asymmetrical. Bad water equals bad beer but not conversely. At the same time you cannot fix a bad beer by 'fixing' the water.

You would hardly expect a couple of guys writing a book about water to promote the 'one size fits all' notion but it is amazing to how great an extent that is true. Get the mash pH right and the rest is 'seasoning'.

But it should be noted that it took nearly 2 years of brewing a virtually identical recipe, investment in water treatments, and a modest education in water management to get the beer right.

I'm all for fine tweaking but that shouldn't be part of the early endeavours. They should be dedicated to getting the pH right and the seasoning ions into broad bands of acceptability. I often note that the senses (light, sound, smell..) respond to the log of the stimulus and that pH and chemical potential are measured on log scales. I suppose that the concentrations of stylistic ions may work in the same way which means that a doubling or halving of an ion concentration is doubtless noticeable but that a 5% change probably isn't.

 

[MChopz]

Thanks for the information guys. I'll be using just gypsum and calcium chloride in small amounts. My predicted alkalinity is 30 ppm. And I will be using a calibrated pH meter, I'm just using the program to know what to expect

 

[mchrispen]

MChopz,

Then you are taking the right steps. While I find Bru'n fairly accurate, it is best to confirm with the meter.

Cheers! And Happy New Year