High Alkalinity Water, High Sodium, Only Moderate Water Hardness

[PeeBee]

Here's a fine conundrum. Stumbled on it posting in that "other" forum, but I don't expect anyone there to have the answers?

Water is SE Water responsibility (actually from "Battle" in Kent). They provide a suspect analysis which can be translated as:

Calcium: 30.33ppm
Magnesium: 6.27ppm
Sodium: 50.35ppm
Chloride: 50.19ppm
Sulphate: 38.06ppm
...
Alkalinity: 154.67 ppm as HCO3

What a lot of Sodium! Still, I don't think it's unusual down South. But the important bit is Sodium salts (any mono-valent metal salts) do not create Hardness in water.

So, "Total Hardness" (due to Calcium and Magnesium) is 101.55 ppm as CaCO3. That's okay.

Express the Alkalinity as "CaCO3" and it comes out as 126.78ppm (as CaCO3). That's okay too (convert the "as HCO3" by dividing by 1.22). Alkalinity in these situations is the same as so-called "Temporary Hardness". This is also referred to as "Carbonate Hardness" ("KH").

BUT! ...

Temporary Hardness plus "Permanent Hardness" equals "Total Hardness", therefore Permanent Hardness equals Total Hardness minus Temporary Hardnesss, which is 101.45 - 126.78 = ...

See the problem (negative). Now people who know me can believe it's more evidence for me to argue "Hardness" should be assigned to the scrap heap! But will anyone here support "Hardness"?

[Eric]

Temporary Hardness plus Permanent Hardness equals Total Hardness? Yes.
Alkalinity plus Permanent Hardness equals Total Hardness? Not when the carbonate or bicarbonate is bonded with sodium. The are few places in Britain where such alkalinity exists naturally.

Ion exchange water softeners replace calcium and magnesium with sodium. The water is softened, but alkalinity remains exactly the same when measured as Calcium Carbonate.

Sodium based alkalinity won't be temporary as Sodium Carbonate is soluble in water and will not be removed by boiling.

[PeeBee]

Thanks Eric!

I shouldn't have needed that nudge, but I did need it!

You may not like what I'll do with that information though! I'll use it to drive more nails into a coffin for "hard water", "soft water", "water hardness" generally, and the associated bo11ocks that surrounds it (like "as CaCO3").

That guy in Battle, Kent, was being advised to boil his water to reduce its alkalinity: That isn't going to work very well either! But it'll cost a lot for the power to do it.

And I can believe the "The are few places in Britain where such alkalinity exists naturally" remark as it fits with an earlier remark said of SE Water's published report "the op’s water report is complete crap and unworkable". I can see now that the obvious "crap" is probably down to how SE Water's computer systems interpret the data.


I'll get to work on my "Defuddler" so it handles these situations better (and will work around the World where municipal water softening is common).

[PeeBee]

Here's a harder (related) question?

Salts dissociate into their respective anions and cations when dissolved. I've seen the phrase "fully dissociates". Does that mean some salts only "partially dissociate" when dissolved?

Boiling doesn't cause carbonate ions from sodium carbonate to precipitate out. But what if the water contains gypsum? Now there are Calcium ions that can create calcium carbonate, which precipitates out 'cos it's insoluble (the solution remains in balance because the Sodium can replace the Calcium to potentially bond with Sulphate). Or can that not happen for some reason?


Ooo ... Heeaavy!

[Eric]

I've added milliequivalents to your given ppm values.

Calcium: 30.33ppm (1.51mEq)
Magnesium: 6.27ppm (0.52mEq)
Sodium: 50.35ppm (2.19mEq)
Chloride: 50.19ppm (1.42mEq)
Sulphate: 38.06ppm (0.79mEq)
...
Alkalinity: 154.67 ppm as HCO3 (2.53mEq)

What a lot of Sodium! Still, I don't think it's unusual down South. But the important bit is Sodium salts (any mono-valent metal salts) do not create Hardness in water.

So, "Total Hardness" (due to Calcium and Magnesium) is 101.55 ppm as CaCO3. That's okay.

Express the Alkalinity as "CaCO3" and it comes out as 126.78ppm (as CaCO3) (2.53mEq). That's okay too (convert the "as HCO3" by dividing by 1.22). Alkalinity in these situations is the same as so-called "Temporary Hardness". This is also referred to as "Carbonate Hardness" ("KH").

There is an imbalance between total cations (4.22 mEq) and total anions (4.74 mEq) if my sums are correct. Potentially the given figure for alkalinity might be too high in relation to the other quantities, but that's just a guess as I would suggest missing ions are more likely to be phosphates and nitrates, both anions that would increase the imbalance.

Let us assume that sulphate is present in the form of gypsum, a common mineral and component present in water supplies. 0.79 mEq sulphate requires the same level of calcium, slightly more than half the amount present. Another common mineral in water is common salt, and if all the chloride was bonded to sodium, that would leave 0.77mEq of sodium spare in alkaline form.

It is possible that ion exchange has happened here, but this usually occurs with sodium from sodium chloride replacing calcium and magnesium that then combine with the surplus chloride liberated from salt. In this case we don't have the additional chloride present in that analysis.

I would suggest that this supply is one of the few in Britain where Sodium provides alkalinity. There are many such sources in the world, and in particular where ion exchange softening is used on water supplies.

It isn't the carbonate ions that precipitate, in the case of calcium carbonate, the base used for understanding this subject as a whole, it is calcium carbonate that precipitates. Magnesium carbonate is more soluble than calcium carbonate, so it is more difficult to precipitate in water, although it precipitates better from wort as part of hot break from a vigorous boil. Sodium carbonate, commonly called washing soda, is very soluble and won't normally deposit when boiled. Calcium Bicarbonate in water does not deposit when boiled, as it does not exist in solid form. Calcium bicarbonate doesn't qualify as a component of Total Dissolve Solids (TDS) as it isn't a solid, but deposits as Calcium Carbonate.

[PeeBee]

There is an imbalance between total cations (4.22 mEq) and total anions (4.74 mEq) if my sums are correct. ...

What ...

Oh aye! My own "Defuddler" calculates Bicarbonate as 119.28ppm (1.95mEq). I'd reverted all the values to the SE Water report ... I'd been warned that report was "crap and unworkable"!

Sorry about that. I've also assumed the alkalinity is reported "as HCO3" because all other correspondence I've seen from them says that (their report fails to tell you). Better double check that too. But if "alkalinity" was 154.57 ppm as CaCO3, that would be even worse!

And the only other significant ion was "Nitrate" at 3.51ppm.


Just a note for anyone who was thinking of trying my "Defuddler" and was hoping it was devoid of all that "mEq, etc. business: It is! I'm just talking to Eric about stuff "under-the-hood". (Hood = bonnet ... must be a USA saying?).

[PeeBee]

They report Total Hardness as 37.77ppm as Ca (94.42 ppm as CaCO3). But that was already deemed crap and 101.55 (102) ppm as CaCO3 was being used.

[PeeBee]

***INVALID ... DELETED!***

Sunday 10th September 12:50 - FIXED! I'll repost the fixed version:
->

WaterReportII.jpg (225.3 KiB) Viewed 2143 times

Oh dear, that ain't right is it ... Well, I was warned the SE Water report was crap. Seems Mr Brungard's program (Bru'n Water) agrees.

[WallyBrew]

Check your magnesium and sulphate entries

[PeeBee]

Check your magnesium and sulphate entries

(Grumble, grumble. As if I'd publish duff information! ... okay, go through the motions ... Sulphate as 35.1, originally down as 3...8.1 ... Ooops!)

Okay, head scratching moment!

I'll start by deleting that Bru'n Water snip ...



[EDIT: Extraordinary! I make not one, but two, typing mistakes that together shove a crap report into "okay" territory, so I don't suspect there's anything wrong! I'll need to be more careful!]

[Eric]

Why would Mr Brungard's program determine that all hardness in that water is temporary? It is likely that temporary hardness will be somewhere near half of the total hardness.

The given analysis can't be exact and the figure for alkalinity is a primary suspect. However, sodium sulphate is only rarely present in water supplies and combined with a further improbability of the complete absence of calcium and magnesium salts, alkalinity from sodium is very likely present in this water.

[PeeBee]

Why would Mr Brungard's program determine that all hardness in that water is temporary? ...

I think (eek - that's dangerous!) it's solely to prevent "permanent hardness" becoming negative. Like has been happening in my "Defuddler".

But I've changed it in my spreadsheet so they just disappear (both temporary and permanent). Neither play any useful roles in the calculations so having them just disappear seemed the least work and least controversial.

I am aware that there are people that don't agree with my distaste for the old "Hardness" regimes, but understanding "Hardness" is just a lot of learning for no obvious gain. I don't believe Mr Brungard's program should even mention "hardness". But maybe he thinks he must try to pacify those folk who do believe in it (in which case I can tell him he's wasting his time trying!).


[Right, now am I all secured againt the hail of incoming projectiles I can expect ... ]

[PeeBee]

But ...

the impact of sodium ions on carbonate exiting the water (as insoluble calcium carbonate) is what I'm hoping to understand from this thread.

[Eric]

But ...

the impact of sodium ions on carbonate exiting the water (as insoluble calcium carbonate) is what I'm hoping to understand from this thread.

That shouldn't cause problems, acid can be used to bring alkalinity down to the desired level for the type of beer being brewed. What cannot be done is to lower alkalinity sufficiently by boiling.

Such can be an essential addition when brewing dark beers with soft water, but added only to the mash. Mashing at pH<5.0 can produce wort with low fermentability. Get that bit right and the yeast will bring down pH to the right level.

[PeeBee]

Thanks Eric! That bit "What cannot be done is to lower alkalinity sufficiently by boiling" is exactly what I'm trying to understand. Do you have any irrefutable (or as near as possible!) documentation on that I can quote?

The "Defuddler" is getting a bit of enhancement, like a default source option for some of the "Foetid" stuff is to be calculated from "live data" (the six ions to concentrate on). That way it should be able to flag up errors such as I was getting with the Battle, Kent water report. E.g. A snip from the "Defuggler" loaded with that Battle,Kent stuff gives out:

Snip.jpg (37.89 KiB) Viewed 2087 times

It's grey and unclear 'cos this is the "Foetid Mire"!

The "Live Data" coming from the surface (126.78ppm as CaCO3) is out of balance and probably garbage (as you've concluded further up this thread) and therefore quite different from the calculated (balanced) value coming up from the depths of the "Foetid Mire" (97.77ppm as CaCO3). While I can't use the balanced value (assuming too much) it could provide an automatic warning if I jiggle about with the spreadsheet.

I've got to jiggle about with it anyway to prevent invalid entries for arcane "temporary hardness" creeping in as discussed further back.



Thanks for the comment that calcium bicarbonate can't count towards "TDS" 'cos it isn't a valid "solid": I can't see how, but is this why my "correlation factor" 'tween "TDS" and "Electrical Conductivity" drifts far higher than the suggested default (0.65)? The "Defuddler" won't use TDS and EC for this reason. I haven't read up on what causes the "correlation factor" to drift and perhaps compensate for it.