Water chemistry – is this a problem?

[trapae]

I’m trying to RDWHAHB, but this is kind of weird to me so I thought I would ask the question. This is my first time after 15 years of Brewing getting into water chemistry And using my tapwater instead of store-bought spring water since I got a new water filter at my home.. Got a Ward labs report, and put it into Bru’n water for my house porter and brewed today. I didn’t actually do that much additions: 2.4 g calcium chloride added to the mash water, and 1.5 g calcium chloride added to the sparge water. In addition, I added 24.3 mL of 10% phosphoric acid to the sprage water as dictated in the spreadsheet. That’s all. The weird thing is after I added the calcium chloride and phosphoric acid to the sparge water and it was heating up, it turned milky opaque and after I ran it out of the hot liquor tank, there was a bunch of white sediment on the hot liquor tank and heating element. It did not happen with the mash water. I’m assuming it has something to do with the acid. Did I calculate wrong or do something else incorrect that caused The precipitate? Will it affect the final beer? Also kind of weird today that my buckets of starsan to sanitize my conical we’re kind of cloudy as well. Any input. Thanks. Just for reference, this is the ward labs report. By the way, I hit 5.55 pH in my mash which is pretty much what I was going for. Thanks in advance.

Ph 8.3
TDS est, ppm 311
Electrical conductivity, mmho/cm 0.52
Cation/Anion me/L 5.3/4.9

ppm
Na. 48
K. 2
Ca. 49
Mg. 8
Total Hardness, CaCO3 156
Nitrate. 0.2 SAFE
Sulfate. 21
Cl. 30
CO3. 1.8
Bicarbonate, HCO3. 163
Total Alkalinity, CaCO3. 136
Total P. 0.02
Total Fe. <0.01

 

[day_trippr]

Star San will turn cloudy when it's mixed with carbonates. But as long as the net pH is below 3 it should still be effective.
I'm betting the same thing happened when you mixed the PA in with your brewing liquors.

Your water isn't bad. The residual alkalinity is in the area where acid is needed to knock it out as Bru'n Water indicated, and the sodium is kinda high, but otherwise it's fine...

Cheers!

 

[mabrungard]

Two things at work there. First, most water that has alkalinity tends to turn cloudy when the water temperature gets above 185F. That’s the dissolved CO2 coming out of solution.

The second thing is the reaction of the water alkalinity with the acid addition. That also releases CO2 which tends to cloud the water.

The presence of white sediment should be no surprise in moderately hard water. The other thing causing sediment could be undissolved mineral additions. Hopefully you stirred the water pretty well after adding the minerals since they will just fall to the bottom and sit there if you don’t give them a decent chance to dissolve with the stirring.

 

[trapae]

OK that’s interesting. Because The sparge water was right at 185°. I did stir well. So can I assume that all is ok, and the beer will turn out otherwise OK? And I can continue using my tapwater as long as I follow the spreadsheet as needed? thanks

 

[cire]

The white deposit is calcium phosphate, the product when reducing alkalinity in natural water with phosphoric acid.

Your calcium chloride will safely remain in solution, with up to 90% of the calcium Ward's found in your supply being lost in the deposit..

 

[DuncB]

I don't have to add a lot of acid to my dark beers , normally the dark grains get the pH low enough. I assume brunwater takes account of your grain bill for it's calculations.

 

[day_trippr]

[...]I assume brunwater takes account of your grain bill for it's calculations.

It does. And I see that paradigm with every batch of my uber black imperial chocolate stout

Cheers!

 

[mabrungard]

The acid was only added to the sparging water, as appropriate.

 

[DuncB]

Well spotted, comprehension as important as reading.

 

[trapae]

So does that mean I have to overcompensate for calcium when designing the water profile to take into account the calcium lost, especially if I have a recipe where I have to add acid to the mash strike water?

 

[cire]

So does that mean I have to overcompensate for calcium when designing the water profile to take into account the calcium lost, especially if I have a recipe where I have to add acid to the mash strike water?

Well, that depends upon how important you might believe the lost calcium might be.

I'm British, where most ale brewers use their standard water supply for brewing, and most excess alkalinity is removed from mash and sparge liquors with AMS/CRS, a mix of sulfuric and hydrochloric acids, or those acids used individually. None of those leave an insoluble residue.

In UK a Porter would be made with a typical calcium content between 100 and 150 ppm, while in USA that level is often much less with concern over high levels of sulfate and chloride more dominant. What is for sure, the white deposit that remained in your HLT contained calcium that didn't participate in that brewing process for your "House Porter", and your conclusions should take account of this fact.

Calcium phosphate isn't soluble, but magnesium phosphate is and will be present during the sparge. However, if sufficient calcium is present during the boil to produce a good deposit of break material, much of it will remain in the kettle. Any alkalinity neutralized by phosphoric acid is associated with sodium, it should be noted that sodium phosphate is more soluble again and won't deposit with hot break.

Is the figure you give for sulfate, that for sodium? That is the usual format for Ward's reports and by using 63 in place of 21, Ward's anion total is a better match for mine. If that is so, I would consider the drying influence of the sulfate content and contemplate adding extra chloride to compensate.

Best wishes.

 

[mabrungard]

The need for calcium in brewing is hugely overblown. The malt itself, provides ALL the calcium that the yeast need for proper metabolism. So there isn't a critical need for Ca.

However, there are benefits to having adequate dissolved calcium content in the water for a couple of purposes. The first is to aid in the stability and longevity of enzymes in the mash. This isn't typically a serious concern in all malt mashes, but might be a concern if adding adjuncts. The second benefit is that calcium enhances yeast flocculation. If you're relying on an ale to clear quickly, then you'll want to make sure you have at least 50 ppm Ca dissolved in the water. If you're fermenting a lager, premature yeast flocculation can be a hazard and you might not want too much Ca in the water. The third benefit is calcium helps remove oxalate from the mash. Having at least 40 ppm Ca in the water appears to be enough to remove the bulk of oxalate from the mash wort.

The apparent British practice of having higher calcium content in the water is mostly a matter of taste and not a necessary component for good brewing. If you want to chew your beer, go ahead and boost the calcium content. The flavor can become quite minerally, but that can be a nice complement in some styles. However, it's definitely not a complement to all.

 

[cire]

If you want to chew your beer, go ahead and boost the calcium content. The flavor can become quite minerally,

The following is a quote from the Handbook of Brewing, the English language text book in common use around the world in Universities and by Professional brewers alike, but its 900 pages are not out of the way for enthusiastic homebrewers.

Calcium.
Ca2 ions are essentially flavor neutral at the levels found in beer, other than for a slight moderating influence on the sour flavor produced by high levels of Mg2. In other words, calcium has no taste, but in its absence the flavor influence of magnesium is increased.

The chapter on Water is found on pages 91 to 137 where it mentions further benefits...
Calcium.
Ca2+ plays a key role in pH control, especially in mashing. It increases TSN and FAN levels in wort, improves wort runoff, limits extraction of polyphenols and silica, and protects malt a-amylase from heat inhibition. Ca2+ also improves wort clarification and protein coagulation, accentuates yeast flocculation27,29,30 and precipitates oxalate, prevents haze formation and gushing, and stimulates yeast growth.


On page130 we find ............ ... as shown earlier, there is much merit in ensuring adequate Ca2 during mashing for many reasons. German brewers tend to compensate low Ca2 contents by .......



However @trapae , all that aside, I'd like to know if the figure you gave for sulfate was that for sulfur, else I'd have some concern for the accuracy of your water report.


Best wishes.

 

[mabrungard]

Yes, calcium is essentially flavorless. But the anions typically associated with a calcium addition do contribute significant flavor.

 

[bwible]

The need for calcium in brewing is hugely overblown. The malt itself, provides ALL the calcium that the yeast need for proper metabolism. So there isn't a critical need for Ca.

However, there are benefits to having adequate dissolved calcium content in the water for a couple of purposes. The first is to aid in the stability and longevity of enzymes in the mash. This isn't typically a serious concern in all malt mashes, but might be a concern if adding adjuncts. The second benefit is that calcium enhances yeast flocculation. If you're relying on an ale to clear quickly, then you'll want to make sure you have at least 50 ppm Ca dissolved in the water. If you're fermenting a lager, premature yeast flocculation can be a hazard and you might not want too much Ca in the water. The third benefit is calcium helps remove oxalate from the mash. Having at least 40 ppm Ca in the water appears to be enough to remove the bulk of oxalate from the mash wort.

The apparent British practice of having higher calcium content in the water is mostly a matter of taste and not a necessary component for good brewing. If you want to chew your beer, go ahead and boost the calcium content. The flavor can become quite minerally, but that can be a nice complement in some styles. However, it's definitely not a complement to all.

This is great insight, thank you. Not to hijack, but I’m fairly new to adjusting water also. I had seen a bunch of things recommending 100ppm. My water is low in calcium (24) so I was finding 100ppm hard to get to with just gypsum and cacl2. Especially if I diluted it any with distilled water. Some things were saying add chalk for calcium, other things were saying never use chalk. So if I can get to 50ppm most of the time that’s good enough?

I’m reading the biggest thing is the ratio of chloride to sulfate. So OP is not just adding cacl2 to raise calcium, but to adjust that ratio. More chloride for malty beers, more sulfate for hoppy beers. The question is what do you want that ratio to be for a porter in this case. I’m still learning all this.

 

[cire]

A good "one-liner" can sell a worn out banger in a local car lot, but making good beer comes from knowledge and fact.

Chalk and water, like calcium and yeast, can't be summed up properly in a one-liner. Alkalinity in most natural waters comes from chalk or limestone, solubilized by carbonic acid, the combination of water and carbon dioxide, to produce calcium bicarbonate, a substance that does not exist in solid form. Adding chalk to water results in very little going into solution and therefore has limited influence. Adding it to grains has only slightly more influence, but becomes self limiting. When disassociated, calcium ions combine with the overwhelming phosphate present to provide yet another insoluble barrier around the chalk particle.

One advantage of chalk has over sodium based alkaline additions is that it deposits during the boil. Any sodium based additions withstand a boil and as a consequence restrict the reduction of pH usual in this stage, passing this task on to the yeast.

Calcium bicarbonate solution can be made from water, precipitated chalk and CO2 in a larger PET bottle with a wide top. Fit a valve to take CO2 from the source into the cap and three quarter fill the bottle with water and some precipitated chalk. Squeeze the air from the bottle and fit the cap, then gently fill the bottle with CO2 and give it a good shake. Top up with gas and shake as required, when an alkalinity level of circa 400 ppm as CaCO3 can soon be measured using a Salifert KH kit. Decant off the remaining chalk sediment.

Calcium isn't needed by yeast for fermentation, magnesium is demanded, similar to the needs of growing barley, which fails when there is not enough magnesium in the soil. However, when yeast finish their tasks and flocculate, without the presence, or an adequate store, of calcium, their cell walls won't withstand the pressure resulting in cells bursting their contents into the green beer. Yeast cell contents are terribly bitter.


Happy New Year brewing to all.

 

[bwible]

This is really some graduate level stuff to me. I appreciate that we have scientific people here talking about this stuff.

i always said I learned more about world history and geography from the study of beer than I did in all my years of school. Now I guess we’re starting to add chemistry to that.

Cheers!

 

[cire]

This is really some graduate level stuff to me. I appreciate that we have scientific people here talking about this stuff.

i always said I learned more about world history and geography from the study of beer than I did in all my years of school. Now I guess we’re starting to add chemistry to that.

Cheers!

Indeed yes, and you yet might extend your chemistry knowledge beyond under graduate level, while most best beers around the world are made by small concerns from in-house knowledge. Academics seem largely intent to spend their time looking for people to tell whatever right or wrong they were taught, or employed in brewing, tasked to produce insipid beers with the greatest possible consistency lest the drinkers notice a difference.

Certainly there is, and ever will be, a link between brewing and world history and I think it goes both ways. When reading here (and elsewhere) of Paul Kolbach's work post WWII wrt mineral salts and pH, I'm reminded of the similar pre WWII brewing research in Britain while at that same time were negotiations that would cede the Sudetenland to Germany. International Correspondents made many journeys following meetings and the civil unrest that is largely lost to history, but of interest to brewers, the first railway stop from Germany to Prague was Pilsen. Known for its beer of course, but of importance to this story, it was also deemed as part of the Sudetenland. Thus Germany got good beer during the entire war without a fight, until well into 1945 when the war was largely over, except for around Pilsen.

I wonder how the Czechs kept their secrets from the Germans during WWII, but it resulted in Paul Kolbach's later examination of the problem. His explanations were more mathematically precise than the earlier British work at Birmingham University, but perhaps that's its weakness and why algorithms in many software applications are in a state of continuous change?

Beer is a fascinating subject.

 

[The_Antikveik]

The need for calcium in brewing is hugely overblown. The malt itself, provides ALL the calcium that the yeast need for proper metabolism. So there isn't a critical need for Ca.

That’s going against the grain and expresses far too much naivety about how complex biological systems are actually organised. In reality, there’s very little free Ca++, in the context of chemistry textbooks. Clue’s in why endogenous (barley) ions like Ca++ easily end up getting trapped in kettle trub. A malted barley seed inherits all the Ca++ it needs for metabolism until it develops into a seedling mature enough to exploit external Ca++ from its environment. Although it might induce a warm pleasant belief to imagine malted barley seeds are generous and considerate enough to provide brewer’s yeast with all the Ca++ they need to perform so spectacularly in a brewery fermentation, to meet our expectations, it’s just that, a warm pleasant belief. And very easy to confirm, with a little malted barley and some of your finest distilled water, prepped with and without Ca++. Monitor both conversion rate in the mash and yeast performance during fermentation

 

[doug293cz]

That’s going against the grain and expresses far too much naivety about how complex biological systems are actually organised. In reality, there’s very little free Ca++, in the context of chemistry textbooks. Clue’s in why endogenous (barley) ions like Ca++ easily end up getting trapped in kettle trub. A malted barley seed inherits all the Ca++ it needs for metabolism until it develops into a seedling mature enough to exploit external Ca++ from its environment. Although it might induce a warm pleasant belief to imagine malted barley seeds are generous and considerate enough to provide brewer’s yeast with all the Ca++ they need to perform so spectacularly in a brewery fermentation, to meet our expectations, it’s just that, a warm pleasant belief. And very easy to confirm, with a little malted barley and some of your finest distilled water, prepped with and without Ca++. Monitor both conversion rate in the mash and yeast performance during fermentation

References?

Brew on

 

[cire]

References? References?

What do you want? Some YouTube event where two guys half out of heir minds brew two beers on a stove top that look more like chicken soup and taste of something no-one can quite recognize, but when taste tested, 4 out of 5 couldn't tell any difference and the one that could thought that without calcium was the better?

Was there nothing that caught your eyes in the Handbook of Brewing and the 1939 paper that preceded Kolbach's work on mineral influence on brewing referenced earlier?

In 1880 in Britain, tax was removed from malt allowing minerals to be added to brewing liquor.

 

[The_Antikveik]

References?

Brew on

I'm not referring to any references in particular here. What I've described is based more on my knowledge as a biologist with a grasp on how biological systems are organised and function. Of course, you could refer to the literature yourself, if you're interested. But there's an awful lot to cover, to be honest. I imagine an up-to-date text in advanced general biology covers most things, at least as an introduction. Ideally a text that covers fields like molecular biology, cell biology, omics and systems biology, and the ecology of plants, too, if you're interested in barley seeds, etc.

To function effectively, a living biological system must be able to exert complete control over thousands of complicated biochemical reactions simultaneously. Biology isn't a proteinaceous blob sprinkled with free metal ions. That's very messy chemistry not biochemistry. Metal ions, for example, need to be packaged (usually in low molecular weight protein structures) or otherwise partitioned in order to control when, where and what specific ions do in terms of participation in the metabolism of a living biological system. Again, relatively tiny amounts of metal ions (especially trace ions) exist as free ions floating about in the cytoplasm of biological systems. Calcium ions, for example, are mainly associated with a messenger protein called 'calmodulin' in all eukaryotic cells, including barley and yeast. Of course, some of the grist's endogenous calcium ions likely get released as 'free' Ca++ during the brewing (wort making) process and some remain bound to messenger proteins as well as to enzymes, which denature and coagulate at some point in the process, where mass and gravity pull them out of the cooling hopped wort. Either way the calcium ions easily get trapped in kettle trub. The ionic content of brewery wort has been well covered in the literature. I have no interest revisiting it, personally.

I think a more pertinent question is, does malted barley provide brewery yeast with all the Ca++ needed for yeast metabolism? The claim malted barely provides all the Ca++ the yeast need for metabolism is based on what? What's even meant exactly by 'metabolism' here? In the brewing literature there's a huge bias towards research in yeast flocculation, but yeast require Ca++ for hundreds of different biochemical reactions regardless. Do all brewer's yeast have comparable requirements for Ca++, regardless of, e.g., strain or pitching rate? Are all worts comparable in terms of Ca++ content, regardless of water source or water treatment?

Why do some Brewers add Ca++ late in the boil? What I've noticed is some yeast strains flocculate within a day or two of the end of fermentation, if extra Ca++ is added late in the boil, vs a week or two without adding extra Ca++. At least in terms of what I consider desirable, yeast performance wise, it's not true that malted barley (even with British style water treatment!) provides all the Ca++ for yeast metabolism.

I hope this was more interesting than a few references