Help me to understand chloride - sulfate ratio

I use a 14 or so liter kettle on the stove, boil, then rack off with a stainless racking cane. I give it a good stir so the chalk crap settles in the middle, and rack off the side.

See this thread for pics and such:

https://www.homebrewtalk.com/f13/effectiveness-pre-boiling-water-remove-bicarbonate-134108/

I've seen references to John Palmer over and over in this thread. WTF is John Palmer when it comes to homebrewing? He doesn't know any more about it than we do. He's a metallurgist for crissake. He just likes to promote himself and write books for money. If I were wanting info on water chemistry I'd ask a chemist. If I were wanting info on welding, I'd ask John Palmer...........

papaw said:

I've seen references to John Palmer over and over in this thread. WTF is John Palmer when it comes to homebrewing? He doesn't know any more about it than we do. He's a metallurgist for crissake. He just likes to promote himself and write books for money. If I were wanting info on water chemistry I'd ask a chemist. If I were wanting info on welding, I'd ask John Palmer...........

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I'm not sure it works that way. Is metallurgy not a type of chemistry? Besides, by that logic, Jamil Z is full of crap and shouldn't be reliable either.

Here's a link to notes from Palmer's presentation on proteins and head retention at this year's NHC; tell me the person who made this doesn't know anything about homebrewing:
http://www.beertown.org/events/hbc/presentations/2009/John-Palmer-NHC2009-Proteins.pdf

Nattering naybob of negativism!

;-)

Palmer's written some good information on brewing and regularly spends a lot of time trying to help other homebrewers. If he's "one of us", all the better. Don't see any reason to knock him.

Anyway, his spreadsheet works. The proof's in the pudding, er beer.

Ok, let's talk real numbers. I understand what Palmer and others are saying about the sulfate:chloride ratio, but it doesn't make sense when looking at classic brewing cities. If I'm not mistaken, he says balanced between "malty/sweet" and "dry/bitter" is 1:1, or equal quantities of each. So, 30ppm Chloride, 30ppm Sulfate or 150ppm Sulfate; 150ppm Chloride. Correct? Moving on then, looking at "classic" water profiles, I see London as 32ppm:34ppm-essentially 1:1, Pilsen 1:1, and various other less well known Belgian cities (Achouffe, Poperinge, Luik)at even, or slightly tilted to Cl-. And even some cities that have descriptions of being balanced to malty/sweet are still Sulfate balanced i.e.


"Munich

Ca+
109

Mg+
21

HCO3
171

SO4
79

Na+
2

Cl-
36

Oktoberfest
Munich - Although moderate in most minerals, alkalinity from carbonates is high. The smooth flavors of the dunkels, bocks and oktoberfests of the region show the success of using dark malts to balance the carbonates and acidify the mash. The relatively low sulfate content provides for a mellow hop bitterness that lets the malt flavor dominate." -from How to Brew
79:36 essentially 2:1

So what is the actual "balanced' range? What do you like to do? Where can I find good ratios for different styles? Is there really no difference between the same ratio at different levels (within reason), is 10ppm:10ppm really equal 150ppm:150ppm?

First off, speaking as another metallurgist -- inorganic chemistry is a big part of the science, so there's no reason to think Palmer doesn't know what he's talking about. Secondly, regardless of his schooling, the guy has LEARNED more about brewing that most of the rest of us, and he communicates it well.

Secondly, what's everybody's understanding on making additions to the mash vs. the mash and sparge? My water is relatively soft (Denver), with a Cl/SO4 ratio biased toward the bitter side of things. I've been treating my mash water only, but I think that's still leaving me more biased toward chloride than sulfates.

So then, since I have to add hardness for anything darker than about 15 SRM, should I be adding hardness to the mash only and just adjusting sparge water for the Cl/SO4 ratio, or should I treat all the water for hardness too? It seems like the first is the way to go, unless I'm misunderstanding something, right?

Right?

jds said:

Secondly, what's everybody's understanding on making additions to the mash vs. the mash and sparge? My water is relatively soft (Denver), with a Cl/SO4 ratio biased toward the bitter side of things. I've been treating my mash water only, but I think that's still leaving me more biased toward chloride than sulfates.

So then, since I have to add hardness for anything darker than about 15 SRM, should I be adding hardness to the mash only and just adjusting sparge water for the Cl/SO4 ratio, or should I treat all the water for hardness too? It seems like the first is the way to go, unless I'm misunderstanding something, right?

Right?

Click to expand...

You bring up a good point that I have asked in another thread. I've been reading about and making water adjustments since going to all grain a year ago. Now that I'm confident in my consistency, my plan is to make the same recipe and only tweak the water. One of my last batches was Ed Worts Haus Pale. A light APA should be a good starting point plus my wife loves it.

If anyone wants to do the same but with a different style(or same style) we could start a thread and share info. Having more than one palate of reference would be good. For everyone involved we should give our water profile and how we plan to adjust the water. With enough participants we could all do two batches of the same recipe and get a lot of good info.

Ketchepillar said:

So what is the actual "balanced' range? What do you like to do? Where can I find good ratios for different styles? Is there really no difference between the same ratio at different levels (within reason), is 10ppm:10ppm really equal 150ppm:150ppm?

Click to expand...

I'm wondering this also. My water is pretty soft and my chloride to sulfate Ratio favors bitterness.

CL :25
SO: 54
Ratio: .46

If I can add 50 ppm of chloride to achieve a 1:1 balance, would that be identical to a profile with ~300 ppm of each?

The other issue with soft water that I can see is the low levels incresses the potential for error. If my city water report is off by 10 to 20 ppm for either value it could seriously mess up the results. For those who might have have you water tested, was the report similar to the values form the city?

daveotero said:

If I can add 50 ppm of chloride to achieve a 1:1 balance, would that be identical to a profile with ~300 ppm of each?

The other issue with soft water that I can see is the low levels incresses the potential for error. If my city water report is off by 10 to 20 ppm for either value it could seriously mess up the results. For those who might have have you water tested, was the report similar to the values form the city?

Click to expand...

No, once you start to get up that high, you can start to taste the 'minerally' aspect. My water report is a 12-month average from the previous year, but tends to have low levels. I like to bump my numbers up to adjust for the fact that it could off on any given day.

Sudbuster said:

I've seen references to John Palmer over and over in this thread. WTF is John Palmer when it comes to homebrewing? He doesn't know any more about it than we do. He's a metallurgist for crissake. He just likes to promote himself and write books for money. If I were wanting info on water chemistry I'd ask a chemist. If I were wanting info on welding, I'd ask John Palmer...........

Click to expand...

This is such a ridiculous comment, I don't even know how to respond.

I don't hold Palmer or Jamil up at any kind of god status and I'm sure they would humbly agree with that sentiment. However, they have done due research on the topics they write about. Jamil gets respect for the pure fact that he has won Ninkasi and he deserves it. In any case, everyone should question the facts as they are posed in all cases no matter who they originate from. Go ahead and read the references given at the end of How to Brew.

Secondly, what's everybody's understanding on making additions to the mash vs. the mash and sparge? My water is relatively soft (Denver), with a Cl/SO4 ratio biased toward the bitter side of things. I've been treating my mash water only, but I think that's still leaving me more biased toward chloride than sulfates.

Click to expand...

So then, since I have to add hardness for anything darker than about 15 SRM, should I be adding hardness to the mash only and just adjusting sparge water for the Cl/SO4 ratio, or should I treat all the water for hardness too? It seems like the first is the way to go, unless I'm misunderstanding something, right?

Click to expand...

That doesn't really make sense. If anything you'd add alkalinity to your water to make darker brews. You need a higher RA for darker brews and alkalinity increases RA, hardness decreases RA (better for light colored brews).

Some state that you don't need to treat the sparge water unless it's alkaline and you're brewing light-colored beers. I treat all the water for light brews and only treat the mash water for dark brews. But you're on the right track that during the mash it's only the pH we're concerned with (so alkalinity and hardness)...the chloride:sulphate ratio or any additions for flavor can go in later. I just do it all at the beginning.

jds said:

Secondly, what's everybody's understanding on making additions to the mash vs. the mash and sparge?

Click to expand...

I start with RO and add whatever salts are needed. For the mash, the salts are added right with the grain at dough in. For the sparge, I use straight RO water, and then add the salts directly to the boil kettle for the amount of sparge water needed to hit my preboil level. In the end, my mash and sparge water are identical, just as the mash and sparge water has traditionally been identical in the historic brewing cities.
The reason not to add salts to your sparge water is that some of them, calcium carbonate in particular, don't dissolve well into plain water, but will at the pH levels in the kettle.

SpanishCastleAle said:

That doesn't really make sense. If anything you'd add alkalinity to your water to make darker brews. You need a higher RA for darker brews and alkalinity increases RA, hardness decreases RA (better for light colored brews).

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I'm confused by your statement that "hardness decreases RA". Isn't hardness a measure of bicarbonate in the water? Can you have hard water with a low pH?

From my understanding, "permanent" hardness is hardness derived from Calcium and Magnesium, while "temporary" hardness is derived from carbonate. Gypsum and Calcium Chloride lower the pH. Carbonate has the effect of raising it.

SpanishCastleAle said:

If anything you'd add alkalinity to your water to make darker brews. You need a higher RA for darker brews and alkalinity increases RA, hardness decreases RA (better for light colored brews).

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Yeah. Brain fart. Nice catch. I add alkalinity to my water for darker beers.

MattHollingsworth said:

From my understanding, "permanent" hardness is hardness derived from Calcium and Magnesium, while "temporary" hardness is derived from carbonate. Gypsum and Calcium Chloride lower the pH. Carbonate has the effect of raising it.

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I'm not really sure if I'm reading this right, but according to wikipedia, CaCl2 has an acidity of 8-9?

http://en.wikipedia.org/wiki/Calcium_chloride

(under Properties in sidebar on right)
Acidity (pKa)
8-9 (anhydrous)
6.5-8.0 (hexahydrate)

Calcium sulfate (gypsum) has an acidity even higher:

http://en.wikipedia.org/wiki/Calcium_sulfate

Acidity (pKa)
10.4 (anhydrous)
7.3 (dihydrate)

hexmonkey said:

I'm not really sure if I'm reading this right, but according to wikipedia, CaCl2 has an acidity of 8-9?

http://en.wikipedia.org/wiki/Calcium_chloride

(under Properties in sidebar on right)
Acidity (pKa)
8-9 (anhydrous)
6.5-8.0 (hexahydrate)

Calcium sulfate (gypsum) has an acidity even higher:

http://en.wikipedia.org/wiki/Calcium_sulfate

Acidity (pKa)
10.4 (anhydrous)
7.3 (dihydrate)

Click to expand...

Don't think that's important to know, personally. If you get your head around the basic concepts of what's going on, that's good enough.

Alemental said:

I start with RO and add whatever salts are needed. For the mash, the salts are added right with the grain at dough in. For the sparge, I use straight RO water, and then add the salts directly to the boil kettle for the amount of sparge water needed to hit my preboil level. In the end, my mash and sparge water are identical, just as the mash and sparge water has traditionally been identical in the historic brewing cities.
The reason not to add salts to your sparge water is that some of them, calcium carbonate in particular, don't dissolve well into plain water, but will at the pH levels in the kettle.

Click to expand...

Is RO close enough to distilled to not worry about the numbers or does it really need to be tested?

MattHollingsworth said:

Don't think that's important to know, personally. If you get your head around the basic concepts of what's going on, that's good enough.

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I'm not sure how that isn't important. If you're adding something to water that either increases or decreases its pH, shouldn't you know which one it does?

hexmonkey said:

I'm not sure how that isn't important. If you're adding something to water that either increases or decreases its pH, shouldn't you know which one it does?

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I'm not saying it's not important to know what those salts do. I'm saying it's not important that you look up the exact information you posted from WikiPedia. If you can tell me what you're going to do with that information I'd be curious.

The basic stuff to understand has already been posted. Yes, salts lower the pH. I've said that before. Dark grains also lower the pH. Calcium Carbonate will raise it.

But you can also end up reading into this too far and lose sight of the basic idea behind this stuff.

Hermit said:

Is RO close enough to distilled to not worry about the numbers or does it really need to be tested?

Click to expand...

RO is very close to distilled. A little bit of minerals do slip past the filters, but it is very a tiny amount. For brewing purposes they are interchangable.
RO can be a lot cheaper too. The grocery store I go to has a dispensing machine where I can buy refills for $1.49 for 5 gallons. Some pet stores have it in bulk too. People use it to fill aquariums for exotic fish, sometimes a couple of hundred gallons at a time.

Alemental said:

RO is very close to distilled. A little bit of minerals do slip past the filters, but it is very a tiny amount. For brewing purposes they are interchangable.
RO can be a lot cheaper too. The grocery store I go to has a dispensing machine where I can buy refills for $1.49 for 5 gallons. Some pet stores have it in bulk too. People use it to fill aquariums for exotic fish, sometimes a couple of hundred gallons at a time.

Click to expand...

I have RO at my sink. The local water has a web site but it doesn't list much. Just contaminates.....

MattHollingsworth said:

I'm not saying it's not important to know what those salts do. I'm saying it's not important that you look up the exact information you posted from WikiPedia. If you can tell me what you're going to do with that information I'd be curious.

Click to expand...

LOL I just re-read what I posted last night and it doesn't even make sense to me now.

My original question was regarding this statement from earlier in the thread:

SpanishCastleAle said:

alkalinity increases RA, hardness decreases RA

Click to expand...

Based on what I understand of hardness/alkalinity, I interpret that to mean:

Alkalinity increases alkalinity, carbonate decreases alkalinity

Click to expand...

Whereas the first half is self-explanatory, I think the second half is a contradiction. SpanishCastleAle was saying that you need to decrease the RA to make lighter beers. But if you added carbonate, wouldn't that increase the pH and therefore the RA?

Am I totally backwards on this?

No worries.

Simple:

To lower the pH:

Add calcium chloride, gypsum or dark malts. (Or lactic acid or acid malt.)

To raise the pH:

Add calcium carbonate.

The higher the pH, the higher the RA. High RA better for dark beers. Low RA better for pale beers.

In my opinion anything targeted towards homebrewing is going to be empirically stated. Meaning, I don't think anyone has sat down with chemistry equations to understand what is going on it beer. And I don't see why that would ever be considered as necessary. I don't even think Charlie Bamforth could or would do that.

My point is that these are things that have been "measured" through experience. So really the only way to understand it, or to verify it, is to try it yourself. I did for myself out of necessity, and now I can say that I have hard evidence (sitting in bottles) that Palmer's descriptions, at least of chlorides and sulfates, is real.

By the way - when it comes to water profiles, there are two intentions: mash pH, and flavor. The mash pH only applies to AG, but flavor profile applies to any brew method. An incorrect sulfate to chloride ratio can ruin even an extract beer.

Beerrific said:

I think that seems to be the case. I think it is interesting that he chooses "malty" and "bitter" as the descriptors. I am not sure I see those as definatively opposite. I think "bitter" vs. "sweet" might be better. Here is the only other reference to this I have seen:
Handbook of brewing - Google Book Search

I also wonder where this comes in. If it is simply perception only, then one could in theory just add some salt (CaCl2 or CaSO4) to the 2 pours of a beer and compare. I think I am going to try this soon.

Click to expand...

That Handbook link is incredible.... Thank you very very much.

One question I haven't found a solid answer to...

Ignoring all other issues like mash pH and yeast nutrients, can the flavor effects of the chloride to sulfate ratio be adjusted after fermentation? Can I play with these levels in a finished beer?

Only issue I can think of would be possible salt solubility problems due to colder temperatures or beer pH. Precision measurements for only a pint of beer would be impossible on the home brewer scale, but this would be useful for getting a general idea of the flavor changes or adjustment in the keg or bottling bucket.

I'm going to bump this thread because I've been doing a lot of reading on water and its effects on brewing, which as usual, raise more questions.

Facts:

1. I, currently, am an Extract + Steeped grains brewer.

2. Town water is from 3 wells whose average values are as follows:
Ca = 4.87
Mg = 1.29
SO4 = 6.3
Na = 10.5
Cl = 18.4
CaCO3 = 33
Est pH = 5.85
Residual Alkalinity = 28.85

3. After punching these numbers under the "default values" of the calculator at brewer's friend the result is

Chloride to Sulfate Ratio = Highly Malty (18.4 : 6.3) or (2.9 : 1)
Alkalinity = Pale Ale (33)

I can't see a "highly malty" pale ale, unless you guys know of one.

4. Posts here and other places indicate us extract brewers are at the mercy of the water profile of the extract manufacturers.
( I am trying to get Muntons to provide this data)

So..

A. Don't worry, my water is so soft that I can make a pale ale with mild to moderate hoppiness or a great porter.

B. Everything but my Alkalinity is great, but I'm stuck using only distilled water.

C. Dilute my water by as much as 25% per batch, then build it back up by adding salts back in....

D. Use DME instead?

- Chemistry is not my strong suit.

You have lovely water - even the alkalinity is not that bad and that is easily dealt with by dilution with RO.

As an extract brewer you have far fewer concerns as the pH control aspect of water management has been taken care of for you by the extract manufacturer. That leaves flavor and really only one element of that is available to you and that is how much sulfate you use. That will effect the way the hops are perceived. The more sulfate you use the harsher, drier, sharper, coarser the hops bitterness will be. How much of this you want is entirely up to you and I always recommend that people brew the beer with no supplemental sulfate and then brew it again several times incrementally increasing it until they hit the level that gives them the beer they like best.

The chloride/sulfate ratio thing is something that was in a couple of papers written in the UK which found its way into the second edition of Handbook of Brewing. It has been grasped at as a possible way of simplifying brewing calculations and, of course, the relationship between SRM and RA is another. Wouldn't it be great if we could just dial in color, move a slider along a malty/hoppy ruler and come up with a water ion profile? Problem is we can't - you must learn what chloride and sulfate do independently* of one another and set their levels appropriately. Does anyone think that waters with 1 mg/L each sulfate and chloride, 10 mg/L sulfate and chloride and 250 mg/L sulfate and chloride will make beers that are essentially the same? That's what the ratio concept advertises. But common sense, and the experimental data given earlier in this thread show that it isn't that simple.

*They aren't probably completely independent. I don't want to get too hairy here but if we were doing principal components analysis on beer flavor and if the ratio criterion were valid chloride and sulfate would both be aligned with one of the principal components i.e. that PC would be of the form a*p[sulfate] - b*p[chloride]. I doubt very much this would turn out to be the case. OTOH I doubt that one would find one principal component 100% and sulfate and another 100% chloride either (if they were completely independent that would be the case).

Thanks Aj.

Your explanations have been very informative, as well as the rest of this thread.

I am posting the response from Muntons concerning their water report.

"Unfortunately I am unable to provide this information. We use a mix of borehole water, softened water and recycled water but the blend varies depending on usage. The 200g of water per kg of extract used would have little influence on the final beer when it is diluted with 2200g of your own water"

daveotero said:

One question I haven't found a solid answer to...

Ignoring all other issues like mash pH and yeast nutrients, can the flavor effects of the chloride to sulfate ratio be adjusted after fermentation? Can I play with these levels in a finished beer?

Click to expand...

I wasn't aware of this thread until it popped up to the top of the stack yesterday and so have been looking back over it.

It's easy to obtain an answer to this question simply by tasting a beer, shaking a little table salt into it and then tasting it again and repeating with gypsum or epsom salts. I think you will find the answer with respect to chloride is "yes". When I was a kid the blue collar workers in the bars did this as a matter of course with table salt. With the sulfate I don't know (I never saw shakers of gypsum on the bars in the dives I went into) but I expect the answer will be "no" as I think it is in the kettle where sulfate has its effect.

hexmonkey said:

I'm not really sure if I'm reading this right, but according to wikipedia, CaCl2 has an acidity of 8-9?

http://en.wikipedia.org/wiki/Calcium_chloride

(under Properties in sidebar on right)
Acidity (pKa)
8-9 (anhydrous)
6.5-8.0 (hexahydrate)

Calcium sulfate (gypsum) has an acidity even higher:

http://en.wikipedia.org/wiki/Calcium_sulfate

Acidity (pKa)
10.4 (anhydrous)
7.3 (dihydrate)

Click to expand...

Again, posted over a year ago but an interesting observation. Actually, these salts are the salts of a strong acid and a strong base. As such, they should give neutral (pH 7) solutions but that is based on theory that makes lots of assumptions. In fact they give solutions with basic pH but these solutions don't have any buffering capacity. Addition of small amounts of acid or base will cause dramatic changes in pH. The presence of the salt does have an effect but it is a minor one. pKa is an unfortunate choice of symbol for acidity as it is usually used to represent minus the log of the equilibrium constant for the dissociation of an acid e.g. HA + H2O <---> H3O* + A-. Salts separate into their cations and anions when dissolved but salts of strong acids and strong bases disassociate completely at any reasonable pH. One can calculate the theoretical pH of a mixture of an acid (such as hydrochloric acid) and a base (such as calcium hydroxide) from the pKa of the acid and the pKb (dissociation constant of the base) but AFAIK salts don't have pKa's (a real chemist might know). I think what they mean by this is the pH of a solution of the salt in DI water.

Wow, the amount of information in this thread is immense. Thank you very much to all who have contributed.

Regarding chloride to sulfate ratio, my current situation with my local water supply is as such:

15 ppm - Cl
30 ppm - SO4
Cl/SO4 = 0.5

Even at these relatively low levels, is the Chloride to Sulfate ratio just as significant as when the Chloride and Sulfate are at much higher levels (say, for example, five times greater, Cl = 75, SO4 = 150 ppm)?

Sorry if this question was answered earlier.

Thanks in advance,

Jason Smith

Think about this. Common sense is enough to answer the question. Then see #69 in this thread.

I'm simply asking if there are reasonable real-life lower and upper bounds to this ratio. I'm not a chemist, but I am guessing that if you have exceedingly low amounts of chloride & sulfate (e.g. 10 parts per billion), I assume that other elements will render this ratio insignificant. In the other direction, if you have exceedingly high amounts of chloride & sulfate (e.g. 1000 parts per million), I figure the beer may be undrinkable.

Do you not agree?

jsmith32 said:

I'm simply asking if there are reasonable real-life lower and upper bounds to this ratio. I'm not a chemist, but I am guessing that if you have exceedingly low amounts of chloride & sulfate (e.g. 10 parts per billion), I assume that other elements will render this ratio insignificant. In the other direction, if you have exceedingly high amounts of chloride & sulfate (e.g. 1000 parts per million), I figure the beer may be undrinkable.

Do you not agree?

Click to expand...

I absolutely do agree. You don't need to be a chemist or even a brewer to figure this out. Common sense is sufficient as you have demonstrated.

While it is fairly obvious that there are upper and lower limits on the usefulness of the ratio concept, is anyone willing to hazard a guess where the limits begin? That is, at the extreme numbers jsmith threw out there (I assume he said pp billion intentionally) I would agree that it's obvious the ratio is meaningless on the low end and irrelevant at the high end because the beer would be suitable for de-icing sidewalks.

Chemist's experiments described on page 2 suggest 1:1 ratios with 0 ppm were bland, 250 ppm decent (no comment on quality, just that it was balanced), and 500 ppm unpleasant. It would be great if someone could do this with smaller numbers, like 10, 50, and 100 ppm, at Cl:SO4 ratios ranging from .5 to 2.

For my situation, I have been brewing for years with a Cl:SO4 of 1.89, and would like to hold that constant while I experiment with water additions. However, that ratio is built of only 17 ppm Cl to 9 ppm SO4, so I wonder if it really matters much.

The basis for the ratio idea came from some testing done with panels in the UK. The relevant papers are listed in the references for the water chapter in the second edition of Brewing Handbook. I'd try to get copies of those before undertaking tests. Meaningful tests would be difficult for home brewers. We are talking about subjective impressions here and those are very hard to quantify. This makes it hard to design an experiment and beyond that there are the difficulties associated with double blind testing, the size of panels, statistical significance, coefficients of variation, repeatability etc.

Thanks again for your responses.

The reason for my curiosity is because the results of my latest batches of beer were good, but considerably more bitter than I had expected. While there are numerous factors that definitely could have caused this, I'm exploring my chloride/sulfate ratio (which as I mentioned is currently 15/30 = 0.5) as one of the possibilities.

I really don't want to add much in the way of brewing salts, as my tap water is actually pretty decent brewing water, but for my next batch, I'm thinking about adding maybe 40-50 ppm chloride to my water via calcium chloride and using the identical recipe and procedure to see if it makes a huge difference.

Thanks again.

Jason Smith