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Altered Paints – Pre-Industrial modification of natural pigments

If you’re not part of the solution, you’re part of the precipitate.

The Oldest Chemistry Joke Known To Exist

A common theme you may have noticed in the science articles on the Pandemic Blog is that a near-infinite variety of colors can be found in nature, but not all of the material that gives rise to these colors are suitable for use in painting or dyeing. However, ancient and medieval artists were not limited to the pure, stable colors found in minerals or mineral earths. Many important pigments and dyes were made throughout recorded history by taking natural products (geological or biological or both) and treating them in some way to change their color, or improve their chemical characteristics, or even to synthesize pigments from entirely different things. Many sophisticated techniques to improve the use of natural products were developed far in advance of the modern understanding of chemical principles that became codified from the 17th century on. But the ancient and medieval world nevertheless had access to many reactive chemicals, both from minerals and biological products, which could be used in making or altering pigments. Vinegar contains acid; aged urine, ammonia; Lye can be had from ash and water; salt deposits can be sources of reactive carbonates or metal salts that can be used as mordants. While ancient and medieval artisans had little notion of what we call chemistry, they were perfectly fine at experimentation and developing sophisticated techniques that had no equal until the modern era.

These rhinos from the Chauvet cave were outlined in charcoal. (Screenshot from the film “Cave of Forgotten Dreams”, Public Domain)

A witty person once said to me that the entire development of science and technology by humans can be summarized by “set fire to it (or, alternately, blow it up) and see what happens.” And indeed, among the earliest pigments used by prehistoric artists was charcoal. Charcoal can be found in the leftovers of wood fires, but from before antiquity it was intentionally made by slowly heating wood twigs to the point of combustion while restricting the access of air. In the absence of a flow of oxygen the wood does not ‘completely’ burn and oxidize to carbon dioxide (a gas of little utility if you are not a plant or a brewer), instead leaving behind a somewhat sticky, hard black residue, nearly pure carbon, that can be used to make black pigment or a very tidy, hot, and nearly smokeless fire when burned in an open fire. A very fine black pigment powder (called lampblack) can be recovered from the smoke of burning of oil in a lamp, another technique known to the ancients. You can also treat some minerals with fire or heat to alter their color. As mentioned previously, the colors burnt sienna and burnt umber are natural earth pigments treated with heat, which causes chemical reactions that reduce some of their more oxidized (and therefore brighter) iron oxides to hematite, a darker mineral. Heating white lead oxide (ceruse) can lead to a yellowish pigment that Theophilus described as a base for making flesh tones (Hawthorne and Smith, 1979). And it should be mentioned at this point that if you treat chalk or limestone with high heat, you get quicklime, a reactive chemical used to make cement or plaster and in some pigment making processes.

Another important property of pigments that artists need to take into account is solubility. Pigments that dissolve readily into water do not necessarily make good paints, as you would rely on the pigment coming out of the water solution to bind to the surface in some way. This is frequently an important part of the fabric dyeing process, where treating a dye solution with a chemical (frequently called a mordant) is required to make the dye turn the proper color and/or bind properly to the fabric. On the other hand, most paints are in fact suspensions of tiny particles of pigment in medium – they do not dissolve, but form an emulsion of sorts with the water, oil, egg yolk, etc. In many cases the same exact pigment can be used for watercolor or oil paints or tempera, because the pigment itself does not dissolve in or react with the medium.

This 14th Century (CE) Chinese dish was made from carved lacquer. That’s right: red bug excretions.
The Metropolitan Museum of Art, New York.

So some natural dyes that dissolve in water can be treated with a mordant to make them insoluble. They then precipitate out of the aqueous solution and become a solid, that can be dried and ground into a pigment powder. These pigments are called lake pigments. The term lake in this context is an English corruption (of course) of the word lac, which refers to the Indian scale insect that makes (like other highly prized bugs) a brilliant red pigment, and also a very useful waxy resin, from which we get lacquer and shellac. Lac in turn has the same root as the Sanskrit word lakh, meaning 100,000 (because there are SO. MANY. BUGS. required to make this). Presumably this also means lac pigments were used in making red lake pigments, but now, like in many bug-derived pigments, there are synthetic alternatives.

A word or two on mordants. Despite what you might think (well; I thought it), the Latin derivation of this word is not “something that makes you dead.” In fact it’s derived from mordēre, which means to “bite.” This makes great sense in the dyeing context, where mordants are used to make the water soluble dyes stay attached to the fabric. A mordant, chemically, is frequently a colorless metal salt that can form a coordination complex (as described in our earlier article) with the organic dye molecule and still have the ability to bind with something else. In the case of lake pigments it changes the dissolved pigment to an insoluble one rather than make it bind to fabric. Common mordants available from ancient times include calcium carbonate (from chalk or bone), lye (from ash), alum (from evaporated salt deposits in Egypt, or ground minerals), and green vitriol (ferrous sulfate, from certain kinds of rust).

The roots of the madder plant yield two quinine-derived dyes which can be used to make madder lake pigments and dyes.
Painting: Franz Eugen Köhler, Köhler’s Medizinal-Pflanzen (1897)

The earliest lake pigments known to be produced were indigo lakes made in ancient Egypt from the woad plant. The exact techniques the Egyptians used are not known, but it is thought that they may have used plants grown in chalky, alkaline soil (so there would be calcium carbonate or other light metal salts at hand). Perhaps the most well known lake pigment is made from madder. Madder is well known as a source of red or yellow dye from the purpurin and alizarin found in the roots. The mordants could be chalk, clay, or crushed bone (all containing calcium salts). The ancient Egyptians used gypsum (calcium sulphate hexahydrate, a brilliant white mineral found in evaporated ocean deposits) with madder to make a pink pigment.

Copper acetate was a source of blue and green color for Renaissance artists, and could be made from copper and vinegar.
(Public Domain, Photo Source)

A variety of natural pigments were made in ancient and medieval times from the oxidation products of metals. In addition to the familiar iron oxide from rust, blue pigments could be made by corroding copper in the presence of calcium carbonate (azurite is a natural mineral of this nature). Theophilus (I:34, in Hawthorne and Smith) describes a particularly nasty concoction of sulfur and mercury heated over coals produced the pigment Renaissance artists called cinnabar (after the natural mercury ore from Spain or California which can make a fine pigment itself; but the smelted metal was far more valuable and was more widely available). The pigments called “salt green” or “Spanish green” were made from copper, salt, and vinegar to produce copper acetate. Ceruse, the white pigment also used in makeup by the ancient Romans, was made from lead heated with vinegar or urine.

The blues in this 15th century manuscript were made from folium, treated with aged urine to turn the red pigment blue.
Hvalov zbornik, 1404. Illustrated Slavic manuscript from medieval Bosnia. (Public Domain image, via Wikipedia)

Finally, it was known that some pigments, in particular folium, as described in the previous article, were known to change color in response to the pH, or the acidity, of their medium. Theophilus (I:33) describes making lye and using quicklime to raise the pH of folium to change its color from red to purple to blue. Similar pH sequences are used to adjust the color of indigo as part of the mordanting process for dyeing. It was not until the 17th century that scientists realized you could turn this around and use changes in colors of certain pigments (called indicators) to determine the acidity of a solution.

To conclude, it can be safely assumed that almost any material you can think of that has color to it was subjected to some kind of attempt at alteration by ancient or medieval artisans. Heat, acid, base, and other reactive chemicals were all tried in attempts to improve natural products. In many cases successes resulted in techniques that were used for thousands of years. But many of these techniques that remained important through the Middle Ages became largely extinct, in part from the globalization of trade providing cheaper substitutes for expensive traditional materials – but in the modern era synthetic chemistry has come to dominate the production of pigments for artistic purposes. Next time we’ll talk about why and how this came to pass.

Thank you for joining us as we do Pandemic Projects, meant to keep you energized, curious and learning!


In this article we referred to the translation of “On Divers Arts” by ‘Theophilus’ (possibly Roger of Helmarshausen, ca. 1100 C.E.) by J.G. Hawthorne and C.S. Smith, Dover Publications, New York, 1979.

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Pigments in the Landscape

Last time we talked about the physics and chemistry of pigments, both natural and synthetic, and how they come to have the colors that we value. This time we’re going to discuss natural earth and mineral pigments, their origins, and their mineral and chemical composition.

The Altamira cave bison paintings date from 20,000 years BCE. The ancient artists used ochre and hematite-containing clays for the red, yellow and brown tones, and charcoal for the black lines. Reproductions at the Museo del Mamut, Barcelona 2011. Photo by Thomas Quine. This file is licensed under the Creative Commons Attribution-Share Alike 2.0 Generic license.

Natural earth pigments are, according to archaeologists, some of the earliest pigments used for art by humans. The earliest paintings known included paints made from earth pigments, and charcoal. Earth pigments are, in their simplest form, soil that lacks organic matter, composed of mixtures of minerals, some of which confer color to the mixture. Soil can be classified by its mineral composition and its particle size, with clay being much smaller than (for example) sand particles. Clays are generally formed in river beds, with the action of flowing water grinding the mineral particles down to tiny sizes. But massive clay deposits, relics of ancient water bodies, are found in rocks on dry land as well. The earliest artists used naturally occuring clay of varying colors as the basis for their pigments, as the fine grains of clay are best for making smooth, regular pigment powders that can be mixed with binders or dispersants to make paints.

The clay deposits found in Roussilon, France, were a major source of ocher pigments in the 18th and 19th centuries.
Photo by “BlueBreezeWiki.” This file is licensed under the Creative Commons Attribution-Share Alike 3.0 Unported license.

The bulk of the material in earth pigments is not the actual mineral that confers the color. The deposits of colorful clay that ancient and modern artists use come from the erosion of rocks into tiny particles, and reflect the origin and chemical composition of the original rocks. For the most part, these are mostly varying degrees of black or white or even crystalline and clear. Take a look at your beach sand. If your beach sand comes from the erosion of mixed continental rocks, you will see individual bits of clear quartz, or black or gray bits of other kinds of rock, mixed in with a few brightly colored grains of minerals. If your beach sand comes from fresh(ish) lava deposits, it could be very black. If your sand comes from coral reefs or limestone, it may be bright white. The famous pink sand beaches in Bermuda are mostly pure white grains of calcium carbonate from coral reefs, with a few bright red shells of a particular foraminiferan (a microorganism that makes a red calcium carbonate shell). If you were to clean and dry and grind Bermuda sand to the consistency of clay, you would have a pale pink pigment powder. Most of the naturally occurring earth pigments are similar sorts of mixtures; a ground of silicate-containing mineral rocks of no particular color, with bright mineral additives. Some synthetic pigments are made this way; a colorless natural earth is doped with a brightly colored synthetic mineral, so that it behaves similarly to a natural earth when used in pigments.

The most common and robust colors in natural earths are of course the reds and yellows and browns. These colors almost all come from various forms of iron oxide, complexed with water and oxygen in various ways that result in different shades, and mixed of course with the background material. Iron is quite abundant in the universe, as it is the heaviest element that can be made by the nuclear reactions of a normal star. To make larger elements requires a supernova explosion, and those are rather rare. So it is no surprise to see the familiar colors of rust and earth pigments in the canyons of Mars, the ice sheets of Europa, and the craggy surface of distant Pluto. Metallic iron, combined with water, leads to the familiar rust, which is one kind of iron oxide. Other iron oxides are formed through geological processes, involving heat or pressure or exposure to oxidixing chemicals other than water.

Purple sand at Pfeiffer Beach, Big Sur, also contains a black magnetic ferrous mineral. Fun stuff!

The mineral that gives yellow ocher its color is called limonite (not surprisingly). It is a hydrated iron oxide, which means the iron oxide (plain old rust) is complexed with water in a more or less permanent way that changes the electronic structure of the metal to change its absorption spectrum. The red in natural pigments often comes from hematite, which is an anhydrous (lacking water) iron oxide. Some hematites look purple (as in the sand at Pfeiffer Beach, in Big Sur), but it is the same mineral, and a feature of the grain size causes the red to have a purplish tone. Grinding the sand down to clay size may, sadly, eliminate the purple. Green colors in some natural earths come from iron in a different oxidation state, complexed with magnesium and aluminum, in minerals like celedonite (also, not surprisingly named).

Historically, natural clays found in the landscape were used by artists for pigments, giving each their local flavor. When trade began moving materials long distances across the Earth, pigments went with them. Desirable colors found in deposits in particular locations the world have become standards. For example, clay deposits found near the city of Siena or the region of Umbria in Italy have given their names to the colors that derive from their pigment powders. Sienna and Umber pigments have more manganese oxides than ocher pigments, leading to darker colors. Heating sienna and umber pigments causes some of the iron oxides to dehydrate, further darkening their color and leading to burnt sienna or burnt umber.

Naturally occuring colored clay is not the only way to obtain a natural mineral pigment, however. Certain minerals that occur in interesting colors and in large enough deposits can be ground finely to make a pigment directly. These minerals generally originate from infrequent and inconveniently located geological processes, deep in the earth. Making them available for use on the surface requires uplift of the regions where they occurred, and erosion to expose them, and perhaps even mining into the earth to find them. Frequently these situations occur in the high mountains of the world, where uplift and erosion can be ongoing processes in the present.

The most precious pigment used in Europe in the ancient world and the middle ages – more expensive than gold! – was ultramarine, made from finely-ground bits of the semiprecious stone lapis lazuli. Lapis lazuli is a metamorphic rock (meaning, transformed by temperatures or pressures deep in the earth) found in several places around the world, but most importantly in the mountains of Afghanistan. Lapis lazuli from Afghanistan traveled very far in the ancient and prehistoric world, with ancient examples of lapis beads found in west Africa, and famously on the coffin of the pharoah Tutankhamen. The mineral that gives lapis lazuli its lovely blue color is called lazurite. The rock itself is often found with inclusions of pyrite (a shiny, gold or brassy iron mineral). The blue itself comes from a particular ionic state of sulfur. Burning sulfur in an oxygen atmosphere can produce blue flames (don’t do this). Another place you can see blue sulfur is erupting from the famous sulfur volcanoes of Jupiter’s moon Io. Iozurite, a blue pigment similar to lapis lazuli, may be a very precious AEP product of the far future.

Green malachite and blue azurite are found in this rock from Arizona.
Photo by Robert Lavinsky. This file is licensed under the Creative Commons Attribution-Share Alike 3.0 Unported license.

As you can imagine, from ancient times people have ground up interesting colored rocks and minerals to try and make pigments (at this point I should caution you not to grind up the gorgeous blue-green serpentine rocks of central California as this could be hazardous; the fibrous minerals are similar to asbestos). The ancients were familiar with the bright green mineral malachite as a copper ore: heating malachite over a hot fire causes it to break down and release the copper metal. But they also ground malachite to make a green pigment. Malachite is found in the deposits of ancient limestone caves, where mineral rich water ran over the calcium carbonate, producing reactions that precipitated the mineral into a solid. Deposits of malachite in the Fertile Crescent supplied the ancient world with copper for making bronze, but malachite is found in many places around the world. Malachite sometimes occurs alongside azurite, also a copper mineral, which is a bright blue. Azurite was also used as a pigment (like ultramarine, it is rare and expensive). Turquoise is another mineral rock whose blue color comes from copper, and whose formation involves the weathering of rocks (igneous, rather than carbonate). Deposits of turquoise are found in many places and it is one of the most important gemstones worldwide. Turquoise can be ground to make pigment, but it is more precious than malachite so this was rare.

Of course, artists have never been limited in the colors they use by what they can dig up from the ground. Next time we’ll talk more about organic pigments, derived from biological materials, and their origins.

Thank you for joining us as we do Pandemic Projects, meant to keep you energized, curious and learning!

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The Annunciation in Many Mediums

The spark of inspiration, combined with artistic skill and patronage by wealthy families or the Church are often the “back story” to many of the world’s great art pieces.

On a trip to Italy, we amused ourselves by capturing the many attitudes and poses of Mary and the Angel as we toured museums.

I’m particularly fond of the story of the Annunciation, where an Angel of the Lord visits a young woman, saying, “Hail, Mary!” Here, I found that angels can have multicolored wings.

As we are avid readers, we were laughing to see how Mary is often seen reading. Sometimes she is surprised, or annoyed, or turning away from the interruption.

Annunciation, Alesssandro Filipepi, called BOTTICELLI c.1489-90 Tempera on wood

The earliest examples we saw of the Annunciation were done as fresco (pigments painted into wet plaster on walls) or egg tempera (pigments bound with egg yolk and/or egg white) on animal skin parchment or painted on wood panels. We were astonished to see how brilliant the egg tempera was even though 600 years had passed!

Only in the later Italian Renaissance were the pigments bound in oil medium, usually upon a ground of gesso on panels or canvas. In contrast to the tempera, some of the oils had darkened. Or, reactions had set up between the lime in the fresco and the pigments themselves.

Annunciation, Alessandro Allori, Firenze, c.1603, Oil on canvas.

In most of these and other paintings of Mary, her gown and robe are painted in the most valuable and expensive pigments of the day. Both she and the angel (and a dove) may have haloes of gold, are surrounded by gold leaf or by rays of shell-gold paint. Great care was taken in depicting her surroundings, whether she is kneeling, sitting by a tapestry, or architectural elements- the artist used the “newest” style of perspective.

Our sincerest thanks and appreciation go to the fine art museums of Italy especially in Rome, The Vatican, Florence and Venice for their exceptional collections and efforts to maintain and restore these treasures for future generations to enjoy!

At Ancient Earth Pigments we strive to make sure that the pure pigments we sell are as versatile as possible. In the individual descriptions of each pigment, you can read whether it will be suitable for the medium you use, today, or the type of art you wish to learn in the future! Families of artists or friends can share a stock of pigments, each artist mixing with the binder or medium of their choice for their project- be it pastel, fresco, egg tempera, watercolor, gouache, oils, acrylics or even ceramics. One of my teachers is using our pigment to tint the grout around her inlaid turquoise jewelry!

Here is one of my works in progress- “The Annunciation” in egg tempera on sheep skin parchment. I’ve completed Mary’s face and headdress. I’ll deepen the values of her blue gown. The archways and background will be detailed now that I’ve established where I want the dove’s beam of light to fall.

The Angel is sometimes depicted as a child. The Angel’s face has had its under-painting of green shadows. Now, I can add the layers of translucent skin tones on top. Lastly, I’ll define the fingers and hands with stronger highlights and shadows. I’ve also shown some of my favorite tools. Wish me luck!

The above image, copyright Linda D. Nelson, 2020. This image may not be used for any purpose without permission by the artist.
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Hello!

I’m the new owner of Ancient Earth Pigments.

Hello!  I’m Linda D. Nelson, an all-ages art teacher, artist in Pastels, Oils and Watercolor, jeweler, activist and lifelong environmentalist. I’ve raised my family of 3 kids into strong adults with a great partner. I’m a woman of color who welcomes diversity.

I’m a co-founder of the Santa Barbara Art Association-Student Art Fund, a Non-Profit 501c3 which provides funding and grants for public Jr. and Sr. High School art classes in Goleta, Santa Barbara and Carpinteria, CA.

I support all forms of education by paying attention to local issues, rallying fellow students by connecting them with each other and sharing appropriate Calls to Action.  I’ve marched in Sacramento to support teachers and met with legislators.

My ‘Superpower’ is the ability to listen and help anyone of any age to become more creative and expand their horizons. My love of teaching arts and enjoyment of art history is a perfect fit with historical art pigments and tools. I’m developing my personal style in period illumination and egg tempera.  Ancient Earth Pigments is an awesome source for all of us to experiment in six or more mediums using one jar of color!

Can I help you experience something new and fun, today? Check out our convenient and affordable Historical Color Sets or the smaller beginner’s Pocket Pigment Kit.