The Birth of the English Chemical Industry
It was the 16th century, the beginning of the early modern period in England,
after the end of the late Middle Ages.
Henry VIII, King of England,
wanted an annulment of his marriage to Catherine of Aragon.
Pope Clement VII, already dealing with religious and political unrest,
plus a Turkish invasion of Europe, refused.
That disagreement between two powerful and obstinate leaders
kicked off a chain of events that led to the English Reformation,
the founding of the English chemical industry,
and the annual shipment of 200 tonnes of human urine.
All that, or at least all those barrels of urine,
were needed to save the growing English textile industry
Making Color Stick
The value of cloth depended on how well it was dyed.
However, vegetable dye wouldn't stick to wool.
You can dip white wool into vegetable dye,
and it comes out brightly colored.
But when you rinse the wool in cold water,
all the dye and the valuable color rinses right back out.
You need a mordant,
something to make the dye "bite" into the material.
Or at least that how the ancient people assumed it worked,
so they gave it the Latin "biting" name.
It's really a chemical reaction involving a metal ion in the mordant.
You can treat the material with the mordant first and then the dye,
or with the dye first and then the mordant.
Either way, the complex of the mordant and dye forms on the fibers.
Only a few dyes allow you to mix the mordant and the dye,
simplifying the process.
The dye and mordant combine into a dye lake,
a pigment complex which bonds to the substrate and is insoluble,
it doesn't wash out.
Mordants Weren't New
Egyptian
Toilets
The Egyptians found alum deposits
in the deserts west of the Nile.
These deposits were the result of evaporation,
leaving behind mineral salts that had been dissolved in ground water.
The Egyptians were using alum as early as 1500 BCE
to reduce the cloudiness of water.
Alum is a class of chemical compounds, usually a
hydrated salt of aluminium such as one of these:
KAl(SO4)2·12H2O
NH4Al(SO4)2·12H2O
FeAl2(SO4)4·22H2O
MgAl2(SO4)4·22H2O
NaAl(SO4)2·6H2O
Al2(SO4)3·17H2O
Greek
Island
Toilets
Herodotus mentioned Egyptian alum as a
valuable trade good in The Histories.
Pliny wrote about similar substances in his
Natural History,
describing their use in dyeing and medicine.
And so, both the Greeks and Romans knew how to use alum to fix dye.
It was being produced from deposits on the Greek island of Lesbos
at least by the 2nd century CE.
Rome controlled Britain as far north as
Hadrian's Wall,
bringing their technology with them.
Roman fort at Vercovicium, along Hadrian's Wall.
Islamic
Toilets
Alum became the most common mordant in the dyeing industry
during the Islamic Golden Age of 700–1400 CE.
It was exported from Chad and transported to join local products in
markets in Egypt and Morocco.
From there it was exported onward to Europe,
where it was used in the early textile industry in England.
At this point, it seems that northwestern Europe knew to buy it and
use it, but they had lost the knowledge of finding or producing
their own supply.
Genoans and Venetians exported alum from western Anatolia to Europe
in the 13th and 14th centuries.
Soon after
Constantinople
fell to the Turks in 1453, denying that area to European merchants,
alum deposits were discovered in the Papal States around Rome.
This was probably the rediscovery of deposits the Romans had used.
England Splits from the Pope
Henry VIII, King of England,
married Catherine of Aragon in 1509.
He had an affair with Mary Boleyn, Catherine's lady-in-waiting,
and became infatuated with Anne Boleyn, Mary's younger sister.
Meanwhile he was becoming increasingly dissatisfied by Catherine's
failure to bear a male heir.
Holy Roman Latrine Disasters
Henry took his case to Pope Clement VII in 1527.
He wanted an annulment.
Clement already had a lot going on.
Martin Luther had started the Protestant Reformation in Northern Europe.
The two most powerful kings in Europe, the Holy Roman Emperor Charles V
and Francis I of France, were fighting for power in Italy and demanding
that the Pope take a side (this eventually led to Charles sacking Rome
and imprisoning Clement).
Suleiman the Magnificent had led the Turks on an invasion of Europe.
And now Henry was demanding an annulment.
The Pope refused.
Henry and Anne Boleyn were secretly married in the winter of 1532,
and publicly in January 1533.
In May 1533, a special court ruled that the marriage of
Henry and Catherine of Aragon was null and void;
five days later, that the marriage of Henry and Anne was valid.
Their daughter, born in September 1533, became Elizabeth I.
Anne suffered two miscarriages, and her situation had become more ominous
when Henry moved his new mistress, Jane Seymour, into new quarters.
He had Anne executed May 19, 1536, for her failure to deliver a male heir.
Henry and Jane became engaged the next day, and married ten days later.
Jane gave birth to a son, the future Edward VI, in October 1537.
But the birth was difficult and Jane died from an infection twelve days later.
Henry next married Anne of Cleves, briefly, January to July 1540.
But Henry soon wanted that marriage annulled,
and Anne confirmed that it had never been consummated.
He married Catherine Howard for about a year and a half in 1540-1542;
she had an affair and Henry had her beheaded.
He finally married Catherine Parr in 1543,
she was a wealthy widow with whom he had religious arguments.
But, they stayed together until Henry's death.
Meanwhile, between 1532 and 1537,
Henry had issued several decrees changing the relationship between
the Kingdom of England and the Pope.
The Act of Supremacy in 1534 declared that the King was
"the only Supreme Head on Earth of the Church of England".
The following Treasons Act 1534 made it high treason, punishable by death,
to refuse the Oath of Supremacy acknowledging the King as such.
Taxes formerly paid to Rome were now paid to the English Crown.
Between 1536 and 1541, Henry disbanded monasteries, priories, convents,
and friaries in England, Wales, and Ireland,
appropriating their assets and income.
There had been nearly 900 religious houses in England,
with about one adult man in fifty in religious orders.
England's church was now independent of the Bishop of Rome.
However, England could no longer trade with the Papal States.
No more Papal alum.
And so, no more dyeing textiles in Britain.
British textile firms could get their product dyed
by shipping it to Flanders and paying high prices for poor quality material.
But by the time they paid for that, they could make no profit.
England needed alum.
Thomas Chaloner to the Rescue
Henry Frederick, Prince of Wales, was heir apparent of James VI and I,
King of England and Scotland, and his wife Anne of Denmark.
However, Henry died of typhoid fever in 1612 at the age of 18,
and his younger brother Charles succeeded him.
Sir Thomas Chaloner was an English courtier,
Governor of the Courtly College for the household of
Prince Henry, son of James I.
He was the illegitimate son of statesman, silk merchant, and poet
Sir Thomas Chaloner and Ethelreda Frodsham.
His father was Gentleman-Usher of King Henry VIII's Privy Council,
and served as ambassador to Spain, from which he complained
at great length about conditions there.
Amother other things, he became shipwrecked on the Barbary Coast.
Chaloner pere was mentioned in Francis Meres'
Palladis Tamia
as a pastoral poet; that book contained the first critical account of
the poems and early plays of
William Shakespeare
and one of the earliest descriptions of Christopher Marlowe's death.
Meanwhile, Henry VIII handed out former monastic property as political favors.
Thomas pere, the father, got the lands of Gisborough Priory,
in North Riding in Yorkshire, England.
Thomas Chaloner fils, the son,
ended up as an accidental industrial spy.
He traveled to Italy near the end of the 16th century and visited the
alum works in the Papal States.
A cousin, also named Thomas Chaloner because
apparently every male in the Chaloner family got the same name,
had prospected for copper and alum in Ireland.
In 1584 he had published
A Short Discourse of the Most Rare Vertue of Nitre,
a treatise on practical chemistry.
So, there was chemical expertise in the family.
One of these three things happened:
-
Thomas the son returned from his diplomatic mission to
the Papal alum works with some skilled workers,
perhaps hidden in barrels.
-
Thomas the son noticed fossils in the Italian shale deposits.
He thought they were similar to fossils in shale back in Yorkshire,
and assumed that meant similar minerals.
-
Thomas the cousin recognized that certain plants grew where
you find minerals used to produce alum.
Then he noticed these plants in his cousin's land in Guisborough.
Now we realize that it's actually the presence of aluminium silicates
and sulfur compounds in the
Lias
shale deposits along the Yorkshire coast that make them useful.
In 1606–1607 Thomas the son went into a partnership that got a
31-year monopoly on alum manufacturing in England.
There had been several attempts at manufacturing alum in Britain
since 1545, but this became the first successful one.
How to Make Your Own Alum
The deposits in Africa and western Anatolia were actual alum,
those in the Greek islands and Italy were its direct precursors.
Britain had nothing of the sort.
But Thomas Chaloner had access to English deposits similar in some ways
to known alum precursors.
Somehow — and here's the huge unexplained leap in this story —
some English entrepreneurs realized that if you burn the right variety of
local stone for nine months, soak the result in water,
stir in ashes and urine, and boil that mixture, you can get alum crystals.
Shale is a sedimentary rock, formed from clay and tiny
quartz and calcite particles.
It's basically ancient mud turned to rock.
It can contain a variety of elements.
There are large deposits along the Yorkshire coast of Britain.
There is shale in cliffs and steep hillsides along the coast,
where it can be quarried more easily.
And, that shale has the needed chemical composition.
I've read that alum was produced as early as 1604 in Britain,
at Slapewatch, near Guisborough in North Yorkshire.
The large deposits at Ravenscar were discovered in 1640.
The Peak fault, formed around 350 million years ago,
left Lias Group shales accessible well above sea level at Ravenscar.
Two large quarries at Ravenscar yielded over a million tons of grey shale
extracted by workers called pickmen.
Then the barrowmen hauled the stone to where they
built large bonfires they called clamps,
ten to twenty meters tall.
They started with a thick layer of wood, then piled shale on top.
These fires burned at a low rate for nine months.
Chemical reactions called calcination took place within the piles,
joining the wood fuel to keep the piles of stone hot,
while the frequent rain kept it from getting too hot.
They knew it was done when, after about nine months,
the stone had turned pink or red.
At that point a group of workers called liquormen moved the
red mineral into large water pits.
Aluminium sulfate or
Al2(SO4)3
leached out into the water, called the liquor.
After stirring and adequate time for leaching, they pulled the waste
mineral out of the solution and drained the liquor into large pans
in a boiling house.
Now they needed to add potassium.
Although at the time they didn't realize that it was actually potassium
that they needed — potassium wasn't isolated until 1807.
The Arabs had realized that burned plant material had alkali properties,
and that was close as anyone had gotten to figuring out potassium.
There aren't natural deposits of elemental potassium
because it's too reactive,
highly reactive with oxygen and violently so with water.
You have to extract potassium compounds from some material.
Neolithic
Toilets
The English got their potassium from kelp and other seaweed.
It was hauled ashore and dried and burned at Orkney,
the islands off the north coast of Scotland, where
Neolithic people had indoor toilets by 3000 BCE.
The seaweed ashes were transported by boat
down the east coast of Britain to Yorkshire.
Neolithic settlement at Skara Brae in Orkney.
A Neolithic home at Skara Brae in Orkney,
where the homes included indoor toilet chambers.
Ammonia was the last component.
They got that from stale human urine.
One liter of human urine typically contains a little over 8800 milligrams
of nitrogen, as a component of ammonia or NH3
and ammonium or NH4+.
The alum plants started by asking their employees to contribute urine.
Then they placed urine collection barrels outside all the local farmhouses.
Ammonium, NH4+,
formed from ammonia plus an extra hydrogen atom.
Urea, NH2–CO–NH2.
Biochemical decomposition of urea as urine ages
converts urea into ammonia and ammonium.
The seaweed ashes along with the aged urine were added to the
liquor tanks.
Large shipments of coal were hauled up the slope to the processing area,
stoking the fires to boil the liquor.
This would have been the most pungent stage of the process.
After the solution of aluminum sulfate, seaweed ashes, and aged urine had
been boiled for the proper period, it was allowed to cool and alum crystals
formed in the boiling pans.
They would remove the alum crystals and start another boil,
with several cycles maximizing the yield.
Thomas Chaloner (the son of the father with the same name,
with the cousin with the same name) set up an alum manufacturing operation.
Once it seemed promising, the English Crown seized control.
Importation of foreign alum was prohibited,
the native alum sources were claimed as royal mines,
and their operation was rented out for high annual fees.
The result was a mixture of potassium and ammonium alum.
KAl(SO4)2·12H2O
NH4Al(SO4)2·12H2O
At its peak, the English alum industry operated at about 50 sites,
largely along the Yorkshire coast,
and was producing 5,000 tonnes of alum every year.
That production rate required about 200 tonnes of urine per year,
the urine of at least 1,000 people.
The Roman
Urine Tax
The alum plants placed collection barrels in the nearby cities of Hull
and Newcastle,
and then all the way down in London.
The barrels were placed on street corners,
and the urine collected weekly.
The English were reviving a Roman practice of collecting urine
from the population for industrial use.
In Roman times, it was collected by the local government
and sold to businesses.
In this example, the urine-based businesses were government controlled.
Shakespeare
and Toilets
The urine could be stored to age into lant, in which
biochemical decomposition of urea increases ammonium content.
Large casks of aged urine were carried to the Yorkshire coast
by what were called lye boats.
In
Shakespeare's time
people conflated urine with lye, KOH or NaOH, as all were used for
laundry and other cleaning tasks.
The urine casks were hauled up the slope to the chemical processing area,
barrels of the resulting urea were lowered down for shipment to customers.
A simple urine-collecting apparatus and method for cows and heifers
In 1785 an experiment attempted to use cattle urine,
to avoid having to transport aged human urine by sea.
The experiment was a failure, despite what I've seen called
a complicated collection process, which I imagine is an understatement.
Given the description of the experimental apparatus in
this Journal of Dairy Science paper,
I can see how the 1780s experiment in the Yorkshire countryside failed.
The End of the Alum Industry
Wove Paper and the History of Alum in England
Aniline dye was invented in 1856,
soon ending the market for mordants of vegetable dyes.
After about 1880, aluminium sulfate replaced alum
for most other industrial processes.
Visiting the Alum Works
The Peak Alum Works is open for visitors as a part of
Historic England.
It was started by Sir Bryan Cooke of Wheatley, near Doncaster, in 1615.
Next article:
Groom of the King's Stool
