British Waters, Hardness, Alkalinity, TDS and Treatment.

(That's water to the rest of us!) Beer is about 95% water, so if you want to discuss water treatment, filtering etc this is the place to do it!
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Re: British Waters, Hardness, Alkalinity, TDS and Treatment.

Post by Eric » Mon Oct 16, 2023 12:05 am

In early history, beer would be a product of local ingredients. It would vary from place to place and largely be an acquired taste, which frequently prevails to this day. Little record exists of early brewing, and any that might could not be heavily detailed or make much sense in today's technological world. What might be found will likely be recorded by diarists, authors and poets rather than by brewers.

During the 100 years war, 14th and 15th centuries, invading British armies demanded British beer, for while content to pillage French food, they didn't want their drinks. Wars have always had some sort of influence on beer.

From the advent of the industrial revolution, nearly all we do and make has changed, and while many aspects of brewing are radically different, some older aspects can be believed still best, as this offering might testify. Burns died in 1797, but his song describing the creation of floor malted barley was an early one of his works. Six years later Coleridge, with William and Dorothy Wordsworth, set out to tour Scotland and meet Jean Armour, Burns' widow, but she wasn't at home. Later they had an acrimonious split, and Coleridge, alone and on foot, recorded that a bottle of Burton Ale he bought in Tyndrum put bounce in his step to walk over Rannoch Moor to Glencoe. What did those brewers in Burton know about the water used for that beer? It would be 4 years after it was drank before Humphry Davy separated and identified potassium and sodium and another before he did similar for Calcium and Magnesium.

Even when it became understood what minerals water contained, there were restrictions, often due to tax rules that limited what brewers might do. After Napoleon was defeated at Waterloo, Belgium became part of the "United Kingdom of the Netherlands", under the Dutch King Willem and Dutch rules for beer taxation, even after Belgium rebelled and achieved independence in 1839. This was a levy for every brew at a rate dependent upon the volume of the mash tun. This resulted in beer being made with the maximum amount of malted barley the tun would contain, with little space for liquor. The resultant wort was turbid and it was 1885 before brewers could mash as had been done in Britain for many years. The result, Belgian beer drinkers rebelled against the new beers.

Britain had its own problems as until 1880, beer tax was levied on malt and sugar used and any other ingredients, including water treatment would be considered to be tax evasion.

What we might take from what we know is that water treatment wasn't very practical or possible until late in the 19th century.
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Re: British Waters, Hardness, Alkalinity, TDS and Treatment.

Post by Eric » Sun Oct 22, 2023 10:20 pm

The Inland Revenue Act of 1880, so-called Free Mash Tun Act, changed taxation from malt (previously including hops) to the gravity and volume from the mash tun. The act stated that a quarter (336 lbs for malt, other ingredients had their equivalent weights) of average malt was expected to be capable of yielding 4 barrels of wort of specific gravity 1057. That, with current day malts, would be 80% extraction efficiency and changed the way brewers defined extract.

When introduced, Mr. Gladstone said, "The intention of the new law will be to give what may be described as a perfectly free choice of materials for manufacture...outside the use of deleterious materials". Later the Prime Minister would say that "With the exception of the limitation to which reference had been made with regard to things in themselves mischievous, the Bill did not contemplate any limitation whatever on the use of materials which might be thought useful by parties in the production of beer".

In 1814 it was learned that starch infused with malt could form sugar. 19 years later the agent in malt attributed to produce this saccharifying action was named diastase. Some distillers and private breweries had been able to mash with such adjuncts prior the Free Mash Tun Act, so the advantages and potential was already understood. Certainly the larger breweries appear to have taken quickly to the new act as the price of barley, wheat and oats were lower by the following year, and prices of maize and rice increased. However, smaller breweries seem not to respond to the same degree, resulting in higher taxation and production costs, causing some to go out of business. Burton brewers, like Bass and Worthington who employed chemists Cornelius O'Sullivan and Horace Tabberer Brown with others, were well able to deal with all the changes caused by revised taxation. However, it was to be Burton brewing that would endure huge decline, when one by one London brewers returned to treat their water to make paler beers. One exception was Truman's, which in 1873 became the world's largest brewer when buying the Phillips Burton Brewery to add Pale Ale to their production range. Britain's regional beers were under threat.
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Re: British Waters, Hardness, Alkalinity, TDS and Treatment.

Post by Eric » Sun Oct 29, 2023 11:18 pm

From the 1880 Act there would be significant discussion between and research by breweries on all matters, and the following is an extract from a paper read to the Yorkshire Institute of Brewing titled "Notes on the Training of a Brewer" by Frank E Lott, A.R.S.M, F.I.C., etc in February 1895. In that, after a long introduction of what a brewer should learn and know by following his trade, he continued .... and even the most careful and well trained man finds each year new points worth noting and new lessons to be learned in this branch of his business, the science or chemistry of brewing, more perhaps than in any other.

Then he listed seven separate subjects, of which the first was...........
(1.)Water.—Whereas formerly each brewery found a certain quality of water to hand with which the beer had to be brewed, and, as a natural consequence, became more or less noted for that quality of ale for which this water was most suitable for producing, e.g., Burton with its pale and export ales, London and Dublin for stouts, &c.; now it is quite a rarity to find a brewery using only one quality of water for all its beers; either it has what is most to be desired, an ample supply of two qualities of natural water, or, with a soft-water supply, waters of different qualities are prepared as required by means of various hardening mixtures. This of course makes the question of the composition of water and the methods of treatment one with which all brewers ought to be familiar, and although it is hardly necessary that a brewer should be able to analyse water himself, it is undoubtedly an essential part of a thorough knowledge of his business for him to be in a position to fully understand the terms in which water analyses are usually expressed, and not to think, as we once heard in the case of a brewery owner, that quicklime would do just as well as sulphate of lime or gypsum for hardening his water, or he may obtain results of the same alarming nature as those the gentleman in question experienced. In studying this branch of his work, a few practical experiments with hard and soft waters and with artificially hardened water may be tried with advantage, as I believe they will do more to impress on the observer the real value of certain salts occurring in brewing waters than the mere reading of work done by other observers can possibly do.

During the discussion, the Chairman asked if Burton water was best for brewing "all round beers" and bottling beers and were all Burton waters all alike?
Mr. Lott replied that the Burton water was certainly the best for brewing bottled beers if they were matured under the old method of bottling, but not for running beers. Burton brewers have very much the same difficulties of producing running beers as brewers in other parts of the country. Hardly any two Burton waters are alike, although they are all hard gypseous waters specially adapted for brewing pale ales and stock beers if these are allowed to get into condition slowly.
What did that last point exactly refer to? Was that the Burton Union System? Used in Burton by Ind and Coope, potentially the first London brewer to open in Burton, was described by Alfred Barnard from a visit not long after publication of Mr. Lott's paper (See page 53). This was a stage after initial fermentation in larger vessels.

Image

10 years ago I attempted a Pale Ale with a Burton water profile and fermented with a Burton yeast. It was all but finished before it developed even a small amount of character. My notes for that brew included, nothing special, very plain, bland, no great flavours. I fear there is vastly more to brewing a particular beer than just having the precise ingredients.

In the same period as the paper, and when Alfred Barnard visited Dublin and the St James Gate Brewery, the new soft water supply from the Wicklow Mountains for Dublin had been rejected for brewing, preferring the harder supply from the Royal Canal. They preferred the softer water for use in their boilers.

The large population of London demanded large volumes of beer and across time there were several different waters available to its brewers. At one time it was believed that from the Thames was best. King Henry III, 1216-1272 directed a supply of clean water should be piped into London and two centuries later when Henry IV improved the ducting and hence the volume, breweries were soon built nearby to take advantage of better water, and had to be limited. Later in the first Queen Elizabeth's reign there were bans on taking water from the Thames at particular states of the tide, probably for health reasons.
London is built on Clay and as Graham Wheeler oft said, wells in that would produce water with "bugger all" calcium. That said, there were were water courses that had made their way to the Thames from further afield lost under developments that breweries might at times strike when boring deeper wells. It is easy to think one well would suffice, but there was need for other vast volumes of water for purposes like cooling, washing casks, washing floors. sanitising purposes etc, so breweries usually had several wells. Even with the coming of local provision of potable waters, they were not necessarily as suitable as that from a breweries own wells.
The chalk beneath the London Clay is of significant depth holding a large volume of water, some of which is thought to have been there since before the last ice age. It's depth is such for there to be a Redox Boundary, but I don't really know what impacts such would have for brewers. Sixty years ago it was known that too much of that water was being drawn to cause need to draw less, but I'm unsure if that had any impact on London Breweries. Even during the 19th century, some brewers, including Meux of the Porter Flood fame, managed to drill fully through the chalk into underlying sands to take water.
Regardless of the type of London water, it would seem a type of Porter was the best beer that might be produced and further, other water profiles would likely produce better Porters.

All the above happened before Soren Sorensen even became head of the Carlsberg Laboratory to begin his work that eventually introduced the concept of the pH scale and eventually a hand held calibrated meter that today so many take for granted. One existing instrument was the polarimeter, which could in expert hands might give an indication of sugars extracted during a mash if taken after half an hour. Remarkably, when more than 20 years later, an early and bulky thermionic pH meter was taken to Fullers Brewery, mash pH was measured at pH 5.4.

Meanwhile it seemed all liquor research was done for comparison with Burton water. Sorry about the quality of the table that follows, it is from another paper by Mr. Lott and there will be more to say from that later, but it gives an example of the research work that was being examined to hopefully derive a water profile better than that of a typical Burton Brewery. Imitation Burton Water produced the greatest extract and the strongest beer against all other, very basic profiles. 1 grain per gallon is equivalent to 14.25 mg/L.
Burton.jpg
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Re: British Waters, Hardness, Alkalinity, TDS and Treatment.

Post by bellebouche » Mon Oct 30, 2023 3:55 pm

Excellent work, Sir. So much good information.

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Re: British Waters, Hardness, Alkalinity, TDS and Treatment.

Post by Eric » Sun Nov 12, 2023 5:03 pm

bellebouche wrote:
Mon Oct 30, 2023 3:55 pm
Excellent work, Sir. So much good information.
How kind.

Just noticed that I credited Henry IV with the improvements to a water supply into London, which should have been Henry VI. I'm sure there are many more errors that should be corrected.

The previous chart from a paper by Frank E Lott read in Manchester in 1897 contains a vast amount of information. Some perhaps conflicts with what we know today, but many statements are good advice for brewers today. Burton water was still believed as best, titled Class 1 in "A Text Book of the Science of Brewing", and today the term Burtonising is still in use all around the globe.

The paper contains vastly more than warrants a few extracts and is worthy of reading and digesting Grains per gallon multiplied by 14.25 will give ppm. Just one extract for starters......
Brewing Waters.—Whether it be the water used for mashing, sparging, or diluting in copper or hop-back, it is of the greatest importance that it should be the right kind to produce the quality of ale required. Although it is quite possible to brew a passable stout with water which makes excellent pale ale, a great deal of the finest stout is brewed with water which cannot be considered as in any way suitable for the production of pale ales; and, again, a water which may give satisfaction to a brewer whose trade consists entirely of running ales not kept on the market or in the cellars more than a few weeks, may be absolutely useless for the production of stock, pale, or strong ales.

https://onlinelibrary.wiley.com/doi/epd ... .tb00319.x
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Re: British Waters, Hardness, Alkalinity, TDS and Treatment.

Post by PeeBee » Mon Nov 13, 2023 3:26 am

Eeee ... cracking stuff Eric. I've been keeping mum here recently, well you know my opinions of "Hardness", and no-way was I going to turn your essay into a bun fight. But all this talk of Burton-on-Trent did have me remembering being a scruffy urchin looking over the river plains to Burton-on-Trent (dead obvious with its rear-guard sentinel ... Drakelow Power Station!) from our vantage atop our straw bale dens (undoubtably Plumage-Archer or Spratt-Archer straw) in amongst fields and fields of barley being harvested. Only learnt later in life (very recently!) the barley was all destined for Burton-on-Trent and I was in fields growing barley for malting as it had been doing for 400 years, or more?

But back to Burton ... and its water! I know the nearby breweries of Shipston's, Home, and Hardy & Hanson's (and Offiler's, but that had closed before I got chance to try it) did have access to gypseous water (hence "Shippo's gives you the sh**os") and I wondered if it had any connection to Burton and its water? All the Jurassic Mercia Mudstone series, the Tutbury Gypsum, the Fauld crater ... !

That was as far as I got. I'd never heard of the Fauld crater despite being born a few miles from it. 4,000 tons of HE. Crikey, that must have been a big bang. But I did dig this out for later (not vetted by me yet, I have noticed the odd dubious comment in though so careful with it):

The role of geology in the fall and rise of local brewing
Cask-conditioned style ale out of a keg/Cornie (the "treatise"): https://drive.google.com/file/d/0BwzEv5 ... rDKRMjcO1g
Water report demystified (the "Defuddler"; removes the nonsense!): https://drive.google.com/drive/folders/ ... sp=sharing

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Re: British Waters, Hardness, Alkalinity, TDS and Treatment.

Post by Eric » Tue Nov 14, 2023 6:10 pm

Hi PeeBee, you and I can leave hardness where it stands for the moment, there will be times yet to discuss the merits of measurements in various units.

I knew nothing of the Fauld Crater until your post, and as for Burton, only the bits visible from the A38 when travelling to Wales and back have caught my gaze.

As for barley, in days past many breweries malted local barley, which could be mixed with better ones for the mash. Cost has always been a major concern for many breweries.

Burton's water was transported by rail to other breweries, the longest I've read of was to Magee Mashall in Bolton until the fifties.

Thanks for the link, I've briefly read through it, but was starkly pulled up starkly by Table 5. It at least needed a better proof reading, something I'm too frequently very guilty of. Calcium decreases pH, not increase, a major error, and think better wording would reduce the number of misconceptions from assuming its contents are unconditional fact. Calcium protects enzymes and acts as a catalyst in many reactions. It can reduce darkening when boiling wort. I don't think adding calcium will make a beer lighter than its wort. I should say no more at this stage.
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Re: British Waters, Hardness, Alkalinity, TDS and Treatment.

Post by PeeBee » Tue Nov 14, 2023 8:41 pm

Eric wrote:
Tue Nov 14, 2023 6:10 pm
Hi PeeBee, ...
:thumbsup:

"Hardness": I've found evangelising over its deserving demise to be a subject for in another forum, so I'm saving you and most forumites here from all that. It was that Mr Pheonix-Analytical who originally started me off with that!

The Fauld Crater: Scary! I suppose not being in a populous area like the 2020 Lebanese big bang has saved it from notoriety.

Burton misses it's Drakelow power station landmark, but Burton-on-Trent being that bit less visible is a small price for the loss of that eyesore.

Derbyshire was famous for its malt (and ale in 17th C.), and perhaps one of the earliest to turn malting into an industry in its own right supplying breweries over a largish area? Perhaps when the Trent Navigation opened in early 18th C. nearby Derby malt was likely used for the famous "Burton Ale" (the ale that seemed to have eclipsed the "Darbie Ale"). I thought I'd find you a piccie of an ancient malt house that stood in the fields near me ... digging about in such things are dangerous! Heck, it's almost invisible now, and the nearby farm is now a cattery! From Google Maps:
Malthouse, Ockbrook.jpg
Malthouse, Ockbrook.jpg (49.32 KiB) Viewed 17290 times
Anyway, less of that ... Water! The Derby/Nottingham breweries apparently used gypseous water, the "Mersia Mudstones" were certainly there, gypsum is a component, but not the extensive seams of gypsum like near Burton. How much of the East Midlands could have shared with Burton's luck?
Cask-conditioned style ale out of a keg/Cornie (the "treatise"): https://drive.google.com/file/d/0BwzEv5 ... rDKRMjcO1g
Water report demystified (the "Defuddler"; removes the nonsense!): https://drive.google.com/drive/folders/ ... sp=sharing

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Re: British Waters, Hardness, Alkalinity, TDS and Treatment.

Post by Eric » Thu Nov 30, 2023 10:32 pm

:=P Yes PeeBee, gypseous water was for a long time seen by many as the perfect medium for making beer. Graham Wheeler, on several occasions, said he thought sulphate acted to keep beers sanitised as much or more than gypsum as a whole benefitted the brewing process.

In four decades from the introduction of the Mash Tun Act there must have been many changes to both water treatment and ingredients, but I had difficulty finding much constructive information on water treatment. In 1896, during discussions after the reading in the Midlands of a paper by F W Fellowes titled "Facts Fancies and Fallacies", a Mr. Butler asked,
"He should like to know the author's precise opinion as to the value of calcium bicarbonate in brewing waters. Opinions seemed divided as to this."
In reply Mr Fellowes said
..... it was difficult to give a definite reply. If, as had been stated, the opinions of other experts differed on this matter, and, at the same time, did not receive confirmation in practice, an opinion expressed by him would probably be to add but another fancy.
As a practical brewer, he agreed that laboratory results in many cases differed from those obtained in practice; the influence of "mass" was an all-important factor, and must be reckoned with. He hoped very soon to erect a model brewery of sufficient size to enable him to make investigations on a much larger scale than was possible in the ordinary laboratory, and the effect of brewing with different waters was one of the subjects in regard to which he intended to enlarge upon general laboratory experience.
It seems the advice around this time was quite limited. This from 1898 by Thomas Fairley, Vice President of the Institute of Chemistry, "On the Water Supplies of Yorkshire."

For light pale beers hard waters containing much calcium sulphate such as the Burton waters are most appreciated, and for this purpose it has become common to filter softer waters through a layer of calcium sulphate. For darker beers, and for porter, &c., softer waters are used. No doubt they have more powerful solvent properties. In London, alkaline waters pumped from below the chalk are said to be used in the brewing of porter and stout. I am not aware whether any alkaline waters are used for this purpose in Yorkshire.


However, it would seem there was as much, or maybe more, discussion of the increased in duty caused by adding salts. Tax was levied on the gravity of wort, and salts increased that gravity. Data indicating that gravity of worts were increased by the equivalent of one pound of extract per quarter, to negate any achieved increase in extract. A paper read in 1910 was one of several covering this subject.


Another example, but suggesting there may be other benefits to adding salts. This extract is from a 1912 paper by R L Siau titled, "Influence of Mashing Liquor on Extract Yield". A subject that still looms large between British and New World beers.
Taking, as a concrete example, the values obtained in Experiment 2; our malt gave an extract of 97'5 lbs. per quarter when mashed with distilled water, and 100.1 lbs. when mashed with the hardened liquor. Of these 100.1 lbs., only 94.4 lbs. were true malt extract, so that 3.1 lbs. (97.5-94.4) of malt extract were lost per quarter. We can assume that malt extract is worth about 5d. per lb., so that, on this basis, extract to the value of Is.3d. is lost from every quarter of malt mashed. Furthermore, if the brewery is one of those which attain to, or surpass, laboratory extracts, there will be duty to be paid on those 3.1 lbs., or possibly, even, in the limit case, on 5.7 lbs. (100.1-94.4), which, on our present scale of charges, amounts to 14.6 and 26.6 pence respectively. In this presentation of the case, the value of the saline ingredients of the mashing liquor ,as contributing to the flavour, stability, or other desirable attributes of the beer, has been purposely avoided.
This is a question which each one must consider for himself.
Further, in The Discussion, the subject of acidifying the mash by a lactic organism was raised. While the author said he didn't know what effect on the extract might be, but considered that to be a roundabout way, and the judicious addition of a quantity of acid sufficient to stay on the right side of neutral. He said this was common practice in the distilling industry, and this was confirmed by a member. So it is possible the distillers, and potentially the Scots, who were first to recognise the importance of dealing with alkalinity, although I suspect many larger breweries with their own chemists may well have been doing this for a long time, just not telling others.

Other works of possible interest.....

https://onlinelibrary.wiley.com/doi/epd ... .tb00012.x

https://onlinelibrary.wiley.com/doi/epd ... .tb02341.x

But if interested in this era of brewing, perhaps "Reminiscences of Fifty Years' Experience of the Application of Scientific Method to Brewing Practice by Horace Brown should not be omitted.
https://onlinelibrary.wiley.com/doi/epd ... .tb02377.x
He includes Hansen's attempt to persuade Burton brewers to change their yeast strains.

Next post will be about another from the Carlsberg Laboratory.
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Re: British Waters, Hardness, Alkalinity, TDS and Treatment.

Post by Eric » Thu Dec 14, 2023 12:08 am

Litmus was the first colourific indicator, it was first made using mosses about 1300 and would differentiate acids and bases. From the 16th century it would be made from lichen and as chemistry advanced, other indicators were produced that could differentiate other chemicals. Methyl Red test was first described in 1915 and is still commonly used to indicate the end point by titration with acid of alkalinity in water. supplies.

Soren Sorensen was Director at the Carlsberg Laboratory between 1901 and 1938, and when researching the effect of ion concentrations in the analysis of proteins, he opted to determine this by using a galvanometer to measure any change in electrical activity. Normally such measurements were made using indicator solutions to observing colour change, which was difficult and subjective. Sorensen was aware of of an 1884 definition by Svante Arrhenius of an acid was something that dissociates in solution to produce hydrogen ions. Dissociation was understood by some British brewers adding gypsum, found some of its calcium would combine with phosphates from malt and reduce phosphates in beer. The actual equipment used by Sorensen didn't survive, but it would likely be similar to that incorporated in the very early pH meters. It seems Sorensen didn't initially conceive the concept of a scale, but others, and it was the scale that coordinated works, that without might appear unrelated.

A 1923 paper, Fig 1 shows an early pH meter with lots of readings still good today, one hundred years later.
It also contains an explanation of the pH scale.
One answer might be: It is the power of 10 which gives the volume in litres containing 1 gram of hydrogen fully ionised. Pure water is found to have 1 gram of hydrogen ionised in ten million litres. One gram ionised in 10,000,000 litres, i.e., 10^7l itres, so pure water is said to have a pH of 7. This is neutrality. If a test solution has 1 gram ionised in 10^5 litres the pH is 5, the hydrion more concentrated, and the solution more acid than pure water. If an other test solution has 1 gram ionised in 10^9 litres, the pH is 9, the hydrion less concentrated, the solution less acidic than pure water, i.e., more alkaline. It should be clear that 1 in 5 is more concentrated and more acid than 1 in 7, and 1 in 9 is less concentrated, less acid and more alkaline.
https://onlinelibrary.wiley.com/doi/epd ... .tb02620.x

Yet at a similar time to that above, another paper said this about the electronic meter.......
It was a rather difficult method to carry out without a properly equipped laboratory. The colourimetric method now to be described was much simpler and gave results which were sufficiently accurate for most purposes, namely, to pH 0-05.


And who made this easier machine, the Biotech Comparator? Messrs. Murphy and Son.
https://onlinelibrary.wiley.com/doi/epd ... .tb02621.x

Suddenly, by virtue of the scale created from the work by Sorensen for Carlsberg in Copenhagen, brewers could talk in the same mathematical language to compare their work.

Further reading.

https://onlinelibrary.wiley.com/doi/epd ... .tb06672.x

https://onlinelibrary.wiley.com/doi/epd ... .tb04932.x

https://onlinelibrary.wiley.com/doi/epd ... .tb06747.x

https://onlinelibrary.wiley.com/doi/epd ... .tb02576.x

https://onlinelibrary.wiley.com/doi/epd ... .tb02645.x

Lots od data, some that improve some of todays pH spreadsheet calculators.
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