ANNEX

HISTORICAL PRODUCTION AND

USES OF LEAD

HISTORICAL ACCOUNTS OF LEAD SMELTING

Primitive lead smelting hearths and furnaces, dating from ancient times, have
been found in many parts of the world. The smelting of pure galena is a simple
operation, and appears to have been discovered independently wherever the ore
was found. (Pulsifer, 1888.)
The ancient Egyptians, Phoenicians and others in the Middle East were well
acquainted with simple metallurgy, and are believed to have imparted their
knowledge to the Hebrews, Greeks and Romans. There are several references to
extraction metallurgy made in the Old Testament of the Bible, showing that this
was known at the time (e.g. Ezekiel, 22:19-20 - dated 593 BC - As they gather
silver, and brass, and iron, and lead, and tin, into the midst of the furnace, to blow
the fire upon it, to melt it . . . - cited by Nriagu, 1983).
Many simple hearths consisted of little more than a low circular wall of stones
built on a hillside, with perhaps a channel to direct the molten metal. This
technology had hardly changed from ancient times until the Industrial
Revolution in Europe. A German scientist, George Agricola, gives exhaustive
descriptions of mining and metallurgy technology in his work (1556, De Re
Metallica). A description of one type of furnace, cited by Tylecote (1992)
follows:
They heap up two wagon loads of charcoal on some hillside which adjoins a
level place, a layer of straw is placed on top and on this is laid as much pure lead
ore as the heap can bear; then the charcoal is kindled and when the wind blows,
it fans the fire so that the ore is smelted. In this way the lead, trickling down from
the heap, falls on to the level and forms broad thin slabs.
This furnace type was also typical of British furnaces of the time. Agricola also
describes some more sophisticated versions, some involving chimneys and
upper chambers to collect some of the metal vapour and dust lost (Pulsifer,
1888).
The interested reader can refer to Pulsifer, 1888, Notes for a history of lead;
Nriagu, 1983, Lead and Lead Poisoning in Antiquity; and Tylecote, 1992, A
History of Metallurgy, for descriptions of simple furnaces and smelting

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techniques used by native American women, ancient Britons, native Peruvians,

and other accounts of smelters in India, Iran and Japan. A more recent example
of the crudest of methods is how early European settlers in Missouri learned how
to smelt lead for bullets. They made a fire in the hollow of a fallen tree or old tree
stump, threw in pieces of galena found on the ground, and recovered the lead
from the ashes. (Pulsifer, 1888, and Nriagu, 1983 citing Schoolcraft, 1819.)
Such simple technology is possible for lead, as lead oxide can be reduced in
charcoal or wood fires below 800C, and more importantly, lead can undergo a
double decomposition reaction, in which lead ore reacts with ore which has been
oxidised at the top of the furnace, to yield lead metal and release sulphur dioxide
gas.
This process was very simple, but had a number of problems. No more than
two thirds of the lead was recovered by such primitive methods (Pulsifer, 1888),
often a lot less. The remainder was lost to the slag (the material which collects
over the top of the molten metal, also called lead ashes by early writers) and as
fume. Thus it was only worthwhile exploiting ores very rich in lead, and even
ores containing 20% lead would probably be discarded. (Pulsifer, 1888.)
It was observed that vegetation was damaged for a considerable distance
around such furnaces, and the soil was poisoned (Tylecote, 1992), probably from
the lead fume and sulphur dioxide liberated.
Old lead workings are a current source of lead in the environment. Some of
these early slags have proved to be a profitable source for lead exploitation by
more modern methods. Smelting is now carried out under more controlled
conditions.

HISTORICAL OVERVIEW OF THE USES OF LEAD

There is evidence of lead workings and artefacts from very early periods, in
excavations dating well before the time of the Roman Empire. The earliest
known example of metallic lead is a metal figure recovered from the Temple of
Abydus in Upper Egypt, considered to date from 4000BC; lead-rich glazes have
also been found on pottery in ancient Egypt. A host of other applications are
described below. However, such finds are generally small in number. Lead was
less prized than the other metals - gold, silver, copper, tin and later iron - known
in antiquity, as its dull lustre and softness did not make it particularly suitable for
jewellery or weapons.
Prior to the time of the Roman Empire, lead extraction appears to have been
principally in order to obtain silver, as the two metals frequently occur together.
(Nriagu, 1983.) However, following the beginning of this era, lead was used on a
large scale, as a useful material in its own right, for plumbing, tank linings,
kitchenware and a host of miscellaneous uses. The use of lead declined after the
collapse of the Roman Empire, but in the Middle Ages in Europe, lead began to

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be used again for many applications. Some of these applications, such as for
water piping and in paints, have recently been phased out, or at least greatly
reduced, in view of the potential for risks to health; however, some continue to
this day.

Lead piping
Lead has been used in water piping in many cultures since ancient times.
Examples include pieces recovered from 4th millenium remains in Mesopotamia
(Aitchison, 1960, cited in Nriagu, 1983), from Persia, dated from 1000-500BC
(Partington, 1935, cited Nriagu, 1983), Egypt (Pulsifer, 1888) and ancient
Greece. However, it was during the Roman Empire, with the large demand for
water supplies, that the demand for lead took off. It is believed that the Romans
could have learnt lead plumbing technology from the Greeks (Nriagu, 1983);
their advances were in terms of implementing large scale application. The
English word plumbing, referring to water piping, derives from the Latin word
for lead, plumbum.
It was known since early times that lead could cause ill health (Pulsifer, 1888),
and an ancient writer Vitruvius recommended that earthenware pipes be used to
ensure wholesome water supply. (Pulsifer, 1888) Another writer, Pausanias
referred to a particular area where the water from the hot springs destroyed the
pipes within a few years - it is assumed by Pulsifer, (1888) that the water
contained hydrogen sulphide, and thus was unusually corrosive. However, this
did not deter the Greeks and Romans from using lead for most of their piping.

Constructional / architectural purposes

Lead used as flashings (the weathering of intersections, for example, between
roof and chimney, or where a drain joins the gutter), covering of cesspools,
roofing, and damp-proofing of foundations, was known in ancient times (Nriagu,
1983). Perhaps the most striking example is the huge hanging gardens of
Babylon, presumed to have been built by King Nebuchadnezzar (605-562BC)
for his wife: these contained lead linings separating the soil from underlying
stone structure, to retain the soils moisture. (Mothes, 1889, cited in Nriagu,
1983; Diodorus, cited in Pulsifer, 1888)
Lead was also widely used for joining masonry, by pouring molten led into the
joints themselves, or around iron or bronze clamps for extra strength. (Nriagu,
1983, Pulsifer, 1888) For more ordinary applications, wire or bands of lead metal
were used to provide reinforcement, for example, for large amphorae used to
store water and wine. (Nriagu, 1983, Pulsifer, 1888)
As already mentioned, extensive usage of lead began with the Roman Empire,
and the great desire for water, and bathing. In addition to piping, water supply
required the construction of tanks, baths and the like, which were commonly
lined with lead. Lead was sometimes used for other purposes, such as the roofing

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of the old senate building in Constantinople, erected by Emperor Constantine,

(306-336 AD).
Later, from Medieval times in Europe, lead was used in cames for stained glass
windows, for roofing, piping, and other uses. Its use was not universal: lead
being abundant in Britain, has traditionally been used there for roofing and even
cladding of furnishings (Pulsifer, 1888); however, some other countries have
traditionally favoured alternative materials, such as copper and zinc, for such
purposes.

Leaded bronzes
Leaded bronze artefacts, dating from bronze age era, have been found in many
areas, including Babylonia, Egypt, Greece and China and Europe. It is believed
that lead was added deliberately, to lower the melting temperature and thus
facilitate casting, and possibly also to harden the copper. It could also have been
added as a cheap diluent in the more expensive copper (Tylecote, 1992), though
in later times highly leaded bronzes were more prized (Pulsifer, 1888) It is
interesting to note that leaded bronze was widely used for statues and statuettes,
but weapons found at such sites contained much smaller amounts of lead.
(Adding tin instead would give much better properties)

Statues, statuettes, figures

Such articles made of lead or lead alloys have been found from many ancient
cultures. Artefacts from ancient Egypt date from earlier than 3000BC; small
figures of soldiers from Sparta and Athens are believed to be even older
(Rhousopoulos, 1909, cited in Nriagu, 1983). Effigies of sacred figures,
particularly animals, were used in Assyria from 1400BC; more recently, Greek
and Roman finds include a great number of figures of nude women, believed to
represent Diana and other goddesses. Small figures were probably also used as
childrens toys. (Nriagu, 1983, Pulsifer, 1888)
Several thousand lead-based axes, found in Brittany (north west France), are
dated to around 700BC (Nriagu, 1983). These would have been useless as tools
or weapons; it is believed they were made for ritualistic purposes (Tylecote,
1992) or possibly as a form of currency (Nriagu, 1983).

Currency and tokens

Lead, and alloys rich in lead, have been used for millenia in the form of weights,
figures, and coins. Its use was widespread in ancient Assyria, from around
2000BC, with lead animal heads being used as currency. (Nriagu, 1983)
Many finds of coins with high lead contents at sites from ancient Greece, India
- the Andraha dynasty, dating from late second century BC to early third century
AD, and ancient China. (Nriagu, 1983) Lead and leaded bronze coins were
widely used in the Roman Empire. A large number of lead medals and tokens

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were also in use, which may also have had a monetary value. (Pulsifer, 1888) The
use of lead for counterfeit purposes, either by addition to bronze, or plating coins
with silver or gold, has also been known since ancient times. It is referred to in
texts from ancient Rome, Greece and China. (Nriagu, 1983, Pulsifer, 1888) Lead
money has also been used in Europe from about the Middle Ages. It was not the
preferred metal for coinage, and some lead coins would have been counterfeit,
plated with silver; others were probably tokens, with presumably little monetary
value. Official money was made from lead, for example, at times of war, when
other metals were in short supply. (Pulsifer, 1888)
Many finds of lead tokens in Medieval France have been made. From 15th to
17th centuries, they were commonly used to denote membership of a
professional guild. (Pulsifer, 1888) Others would have been used for religious
purposes, or as lucky charms.

Vessels, kitchenware
Lead and pewter have been used for such purposes since very early times, in
ancient Persia, Egypt, and later by the Greeks and Romans. A whole assortment
of vases, kettles, tableware and cooking pots were in wide use during the Roman
Empire. Pewter tableware - consisting of about 50% tin, 50% lead, was generally
used by those who could not afford silver, but lead pots were actually preferred
for preparation of certain dishes. The most notable were residues of boiled down
fruit, which were used as cheap sweetening ingredients. Cooking in lead vessels,
rather than copper, was reported by classical authors (Pliny, Cato, Palludius,
cited in Nriagu, 1983) to improve the flavour (sweeten the food) and aid
preservation of the dishes. Lead readily dissolves in organic acids such as those
present in fruit and wine, and some such dishes would have undoubtedly been
contaminated with dangerously high levels of lead.
Similarly, pewter and lead tableware was demanded by the nobility in Europe
in the centuries after the Middle Ages, as silver was scarce. It was certainly in use
in England by the 15th century, and in France before then. Pewter was also used
to make objects of art. (Pulsifer, 1888)
The possibility of plumbism from drinking from cups made of lead, or highly
leaded bronzes, or using these metals for wine storage vessels, is also discussed by
Nriagu (1983). Such vessels were apparently widely used by nobility in several
Chinese dynasties, for drinking fermented wines. Bronze vessels made by
European Celts generally had very high lead contents, and drinking wines from
such vessels was probably not advisable. Early Christian missionaries would have
usually used lead or leaded bronze cups for sacramental wine, again, potentially
dissolving significant amounts of lead. Lead itself was also widely used for
repairing broken pottery jars and pots, including those used for the storage of wine.
A more bizarre application of lead, and also tin and copper, was in the quality
control of wine. Strips of the metals were glued to the inside of the vat lid, the vat

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sealed for 40 days. If the strips were found to be clean, rather than covered with
scale or bubbles, the wine was pronounced good. This practice developed into
leaving metal strips permanently in wine vats, presumably highly contaminating
the beverages. This was performed in Europe until well into the Middle Ages.
(Nriagu, 1983)

Stationery and seals

Lead tablets used for inscriptions were used in Roman and Medieval times. They
were used to provide durable written records, or to record prayers, invocations
and curses. (Pulsifer, 1888) The Phoenicians used inscribed lead sheets, dropped
into the tomb, as a means of sending messages to the dead. (Partington, 1935,
cited in Nriagu, 1983) Lead seals have been attached to messages and
merchandise since ancient times, In fact, their use on bales of cloth was required
by law in England during the reign of Henry VIII. (Nriagu, 1983) Lead and lead
compounds were also used as pencils or incorporated into inks.

Weights
Lead has been used since ancient times as standard weights, because of its high
density, and inertness in air. The metal was used in almost every ancient weight
class known (Nriagu, 1983), and became widely used in the Greek period, and
more so during the Roman Empire. There are numerous references to the use of
lead as anchors for ships. (Pulsifer, 1888) Unscrupulous use of lead to weight
dice in ancient Greece was noted by Aristotle. (Pulsifer, 1888)

Burial of the dead

Lead has been used for coffins and coffin linings because it does not perish.
Many examples have been found in England dating from Roman times, though
few elsewhere from that period; it is thought to have been used here because lead
was abundant and relatively cheap. (Pulsifer, 1888, Nriagu, 1983). The Anglo-
Saxons did not bury their dead in lead, but it was sometimes used after the
Middle Ages for the burial of nobility, for example for King Richard II. Some
tombs included inscriptions and ornamental patterns. (Nriagu, 1983, Pulsifer,
1888)

Warfare, weapons, punishment

One of the earliest weapons of war was the sling, initially used to project stones
at the enemy. Slugs or pellets of lead came in to use by Greek armies in the 5th
century BC; it is reported that slingers from Rhodes could throw their missiles
twice as far as the opposing Persians, who were using rocks. (Xenophon, cited by
Nriagu, 1983) They were cast to shape, and often bore inscriptions such as an
invocation to the gods, an insult or joke about the enemy, or message to
companions. (Nriagu, 1983, Pulsifer, 1888) Other uses of lead in ancient warfare

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were the pouring of molten lead from battlements on to invaders, or dropping

large masses of solid lead on to them or their equipment. (Nriagu, 1983, Pulsifer,
1888) Later applications of lead in battles included cannon balls. Punishment for
crimes in Greek and Roman times included lifetime of labour in the mines, with
large pieces of lead strapped to the convicts body.

Glazes, enamels and glasses

A glaze is a glassy coating applied to ceramics, for reasons of decoration, or to
give a gloss. Examples of pottery glazed with glazes which are rich in lead (in the
chemical form lead oxide) are found in ancient Egypt, China, the Near East, and
Rome. Besides being cheap, readily available, and easily fusible, such glazes
have advantages of good adherence to, and compatibility with the substrate, high
gloss and bright colours are possible, and the glaze lasts without devitrifying
(crystals forming within the glaze, which can spoil it). However, such glazes
were not universally used, and unleaded alkali glazes appear to have been more
widespread. Vessels glazed with lead compounds have the potential to release
lead into contents, particularly acidic wines and fruit juices, and to contribute to
lead poisoning (though modern manufacturing and testing procedures limit this).
Leaded glasses, though sometimes of similar composition to glazes,
apparently developed separately. Many examples of opaque, brightly coloured
glass, have been found in many areas of the Middle East, dating from around the
15th century BC. Lead was added to silicate glasses in order to make melting
easier, and also to add colour, opacity, or increase the brilliance of the glass.

Pigments and paints

Many compounds of lead are strongly coloured, and also durable, and this has
been exploited since very early times. Red and yellow oxides of lead were used
for purposes of decoration, and it is thought that early peoples attributed magical
properties to them. (Nriagu, 1983) Ancient Egyptians, Assyrians and Hindus
decorated their temples with bright colours, which would have included some
compounds of lead. (Nriagu, 1983, Pulsifer, 1888) Galena (lead sulphide) was
widely used as black eye paint in many ancient Middle Eastern cultures (Nriagu,
1983); its use continues to this day in India. (This eye paint was believed to be
able to treat eye diseases.)
There are several forms of lead oxide, and the colour of oxidised lead can
range through white to shades of yellow and red. These were used as cosmetics
in Europe, the Middle East, India and China, and also found use with artists for
painting and decoration. Red lead was less favoured, because it darkened with
time.
White lead, an intimate mixture of lead carbonate, hydroxide, and possibly
oxide, makes a very durable white paint, which has been much exploited from
ancient times until a few decades ago. This compound was manufactured by the

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ancient Greeks, Romans and Chinese. (Nriagu, 1983.) Later, it was

manufactured in many countries in Europe from the late Middle Ages, and
appeared to be the preferred choice of white pigment. (Pulsifer, 1888.)

Medicinal uses of lead

Present day understanding of the effects of lead and its compounds on health, of
both humans and other organisms, is that it does not have any beneficial effects
whatsoever, and that excessive amounts can be very harmful. However, although
the poisonous effects of lead were known even in ancient times, it was actually
prescribed for medicinal purposes. Lead was used in ancient India to treat
indigestion. (Pulsifer, 1888.) The Egyptians, Hippocrates and others, also
considered it therapeutic, and Pliny describes several remedies which use lead:
for the removal of scars . . . and as an ingredient in plasters, for ulcers, and for
the eyes etc. (Pliny, Natural History, book XXXIV chapter 1, cited Pulsifer,
1888.) Lead was generally considered to have cooling properties; even last
century lead acetate was regarded as cooling, and used as a soothing lotion.
Medicinal ointments were believed to work much better if kept in lead
containers. (Pulsifer, 1888.) Lead also found application in dentistry, and was
used in fillings in Europe up to the 17th century. (Nriagu, 1983.)

REFERENCES TO ANNEX

Agricola, 1556 De Re Metallica, translated into English 1950 by Hoover and

Hoover, New York, Dover.
Nriagu, J.O. 1983, Lead and Lead Poisoning in Antiquity, Wiley.
Tylecote, R.F. 1992, A History of Metallurgy, The Institute of Materials,
London.
Pulsifer, 1888, Notes for a History of Lead, New York, University Press.

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