Saturday, March 20, 2010

Is There a Common Link Between These Ancient Blue Hues?

I've no idea.  I'm not suggesting that the recipe for either blue travelled from Old World to New World or vice versa.  I'm wondering is there an underlying chemical conection or similarity in the composition of the minerals in the clay and/or rocks that the Maya used to produce their cobalt blue color and the minerals in the rocks the ancient Egytians used to produce their cobalt blue color? 

Mar 16, 2010
Archaeologists: Maya Blue pigment recipe moved around
An archaeologist reports the ingredients of "Maya Blue" pigment beloved by Central America's ancients may have been widely mined, not traded as previously suggested.

In the Journal of Archeological Science report, Leslie Cecil of Stephen F. Austin State University in Nacogdoches, Texas, reports on "palygorskite" minerals, the chief ingredient in the bright and long-lasting pigment, found at the archaeological site of Ixlú in the Petén region of Guatemala. Maya Blue was widely used by the classic Maya of Central America to decorate buildings and wares, making the cobalt color a signature of the pyramid-building culture. (Image: Photo by Lori Polette. Elsevier. JAS)

Rather than emerging from one of seven mines already discovered in Mexico, the mineral traces back to a nearby site in Guatemala, a first sign that the color's recipe was traded widely outside the Yucatan, and that the ritual burning required to manufacture the pigment also was used by Maya further south as well.

"Geochemical analyses demonstrate that the Ixlú pigment has the traditional Maya Blue structure, but it was manufactured from clays in central Petén, Guatemala," says the study. "If Maya Blue was being used in the southern Maya lowlands as it was in the northern Maya lowlands, then it should not seem too shocking that some southern lowland Maya (perhaps ritual specialists) may have learned the technology and specialized knowledge behind the manufacture of Maya Blue."

By Dan Vergano

(History:  Scientists Figure Out Secret of Maya's  Blue Paint, February 27, 2008) 

In Search of Key Blue Ingredient in Ancient Egyptian Pottery
ScienceDaily (Mar. 19, 2010) — Jennifer Smith, PhD, associate professor of earth and planetary sciences in Arts & Sciences at Washington University in St. Louis, was belly crawling her way to the end of a long, narrow tunnel carved in the rock at a desert oasis by Egyptians who lived in the time of the pharaohs.

"I was crawling along when suddenly I felt stabbed in the chest," she says. "I looked down and saw that I was pressing against the broken end of a long bone. That freaked me out because at first I thought I was crawling over bodies, but I looked up and saw a sheep skull not too far away, so I calmed down. At least the bones weren't human."

What was she doing in the tunnel?

The answer: seeking an uncontaminated sample of a mineral that might have been the key ingredient in the blue used to decorate "blue painted pottery" popular among the Egyptian elite during the New Kingdom (1550 to 1079 BCE).

Colleague Colin A. Hope, an expert in blue painted pottery, had asked if she wouldn't help him pin down the source of the blue pigment by sampling and analyzing material fromt he mine.

Hope and Smith, together with Paul Kucera, a doctoral student at Monash University who first identified the mines, describe the pottery, the mines and the mineral in a chapter of Beyond the Horizon, a festschrift for the Egyptologist Barry A. Kemp,

'Generic geologist'

In the wastes of the eastern Sahara, nestled against the limestone escarpment that separates the desert from the Nile Valley, lies the Dakhleh Oasis. This fortunate spot, where deep water is able to reach the surface along fractures and faults under its own pressure, has been continuously inhabited for a very long time -- perhaps as long as 400,000 years.

During that period there were roughly four glacial cycles and, although Egypt itself was ice-free, the local climate oscillated from hyperarid to semi-arid as the Earth's orbital position drove changes in the location of the tropical rainfall belts.

Smith studies the impact of these climate fluctuations on ancient oasis dwellers.

But Smith is also the "generic geologist" as she puts it, for the Dakhleh Oasis Project, a long-term study of the oasis that covers the entire stretch of Dakhleh history, from the Neolithic through the Pharaonic, Roman, Islamic and modern settlements, and employs -- off and on -- more than 50 specialists.

"The dig house is open from November until March," Smith says.

As generic geologist, Smith was asked to help with a material-sourcing puzzle that she says was "way outside her period." During the 2007 season, Colin A. Hope, PhD, associate professor and director of the Center for Archaeology and Ancient History at Monash University in Australia, asked her whether a mineral found at the oasis could have been used to color the blue painted pottery.

It was a small question but an intriguing one.

Blue painted pottery

Most Egyptian pottery is undecorated, but during the New Kingdom, the period when Egypt is at the zenith of its power, a variety of pottery was elegantly decorated in a distinctive pale blue.

The pottery has been found at many sites in Egypt, and also in the Middle East and in Sudan.

The largest deposits, however, were found at New Kingdom sites in Egypt, including Malqata (the palace complex of Amenhotep III), Amarna (the remains of the city built by the Akenaten, the famous pharaoh who moved the capital from Thebes and established his own religion), the cemetary at Deir el-Medineh (the village where artisans who worked on the tombs in the Valley of the Kings during the New Kingdom lived), and the Great Temple of Amun (patron of kingship during the New Kingdom).

"Walking over some sites, it is only a matter of minutes before several shards of blue painted pottery or cobalt blue glass or faience can be collected," Hope, who has written extensively about the pottery, says.

Given the restricted use to which the pigment was put and the archeological sites where remnants were found, Hope believes it was probably available only to artisans associated with major royal residences.

The pale blue is distinguishable at a glance from the brilliant blues and blue-greens of the faience glazes common from the 3000 BC onward. Faience, probably most familiar in the form of the small statue of a hippo nicknamed William that is now in the collection of the Metropolitan Museum of Art in New York, was made by adding ground copper to ground quartz to create what ceramists today call Egyptian paste.

But it is difficult to create durable patterns with copper pigment on pottery, says Hope. "Copper-based pigments must be applied in thick layers and were added after firing, so they tended to flake off when an object was handled. Instead of copper, the colorant used on most of the blue painted pottery is cobalt, which was fired onto the pots.

Where did the cobalt-bearing mineral come from? Analysis of the paint showed that the cobalt was accompanied by trace amounts of zinc, nickel and manganese, a mixture of elements distinctive enough to serve as a chemical fingerprint.

The mines of Dakhleh

At the height of its power, the Egyptian administration of the Nile Valley sponsored mineral exploitation of the Valley and surrounding desert regions. As early as 1980, it was suggested that the cobalt might have come from the desert oases at Dakhleh and Kharga.

In the lower foothills of the oasis escarpment at the western end of Dakhleh, four mine shafts were meticulously hand-cut into the rock. Steps carved along the shafts allowed a safe descent. The shafts provided access to horizontal galleries, some as long as 15 meters, that followed horizontal veins of the mineral alum.

A few centimeters thick, the alum veins are fibrous, pale gray to pink in color and slightly astringent.

Alum is both the term for a specific compound and for a class of compounds, all of which contain two negatively charged sulfate groups and two chemical elements or groups bearing a positive charge. The specific compound is hydrated aluminum potassium sulfate but many other elements or groups can substitute for the aluminum and potassium, and cobalt is one of these.

Alum was probably exploited for a variety of purposes in ancient times, some having nothing to do with color. The Egyptians, for example, used alum both to whiten skins during tanning and to prepare cloth to absorb dye.

Alum is still used today in styptic pencils to stem bleeding and in recipes for pickling cucumbers. More recently, it has been in vogue as a "crystal deodorant" that is sold as more natural than older deodorant products.

Was the Dakhleh Oasis alum used as a general-purpose astringent, or did it have the same chemical fingerprint as the blue paint on the pottery?

Analyzing the alum

To find out, Smith needed to sample the alum and analyze its composition. "I wanted to get relatively unaltered samples," she says, "which is why I was crawling to the end of a gallery. The galleries were small enough you couldn't really crawl on your hand and knees: you had to belly crawl."

Smith brought the samples she collected back to Washington University where she ran them through a variety of sophisticated analytical instruments. "When we characterize a natural mineral," she says, "we want to know two things: its chemical composition and then how the elements that make it up are arranged, or its crystal structure."

In the case of the Dakhleh alum, the crystal structure was of little use because it would have been destroyed in preparing the paint. Only the composition could connect the alum to the pottery.

Smith's results showed that the alum did contain cobalt, although they weren't particularly rich in this element. The cobalt, however, was accompanied by trace amounts of manganese, nickel and zinc, the same mixture of elements found in the blue paint.

Surprised by the low concentration of cobalt, Smith wondered if the ancient artisans hadn't found a way to concentrate it on site. One sample she collected, a crust at the edge of a partially flooded mine shaft, had a higher cobalt content than the others. Because sulphate dissolves easily and the mines were much more likely to have been flooded in the past, she wondered whether the cobalt was mined not by chipping it out of the rock but instead by ladling water out of the mines and collecting the sediment left over when the water evaporated.

"But this is wild arm waving given the amount of data," Smith says.

This small exercise in archeological problem solving left her with a deep respect for the long-vanished miners.

"I look at all these different veins of sulfate and I don't know which are useful for which purposes without doing analyses, but they must have had ways of telling from observable properties which ones to mine. That's impressive," she says.
I found this article that contains chemical formulae for the various blue compounds found in the ancient world - fascinating stuff. Note the comment about the similarity between the ancient Egyptian and ancient Chinese formulae for blue.

Chemical Science Magazine (online)
Instant insight: True blue chemistry
23 November 2006
Heinz Berke, professor of inorganic chemistry at the University of Zürich, Switzerland, looks at the use of manmade blue and purple pigments by ancient civilizations
Colours are an intrinsic part of human life. They produce aesthetic stimulation and they fascinate. They are the means of expression in art and they form part of human culture.

In prehistoric times, only the so-called earth colours, colours provided by the surface soil, could be used as pigments. Blue is not an earth colour and so was not available to prehistoric humans as a pigment, nor is it provided by nature as a stable dye.

Necessity, as the mother of invention, stimulated several ancient civilizations to develop artificial blue and purple materials by chemical synthesis. Egyptian Blue (CaCuSi4O10), the first synthetic pigment, was used in ancient Egypt in the Mediterranean area, Mesopotamia and Persia from around 3000 BC until the end of the Roman Empire. Han Blue (BaCuSi4O10) and Han Purple (BaCuSi2O6) appeared in a relatively small area of northwestern China from around 800 BC until the end of the Han Period in 220 AD. Maya Blue, a chemical intercalation compound of indigo (C16H10N2O2) and the white clay palygorskite (a magnesium aluminosilcate mineral), was used in Central America to paint houses and decorate artifacts from around 400 BC. [I believe Maya Blue predates 400 BCE]

Advances in ancient pottery techniques, for making compact blue objects, and glazing techniques, such as polychromic tile glazing, were closely related to the development of blue pigments. Blue and purple had thus made man's life more pleasant and had become highly esteemed in ancient times.

In recent years, archaeology has profited greatly from progress in science. Advances in microanalytical techniques have allowed historical assignments to be made on the basis of hard scientific facts. The application of scientific techniques and methods to archaeology is called archaeometry.

The archaeometry of ancient pigments has gained support from x-ray analytical methods, Raman spectroscopy and electron microscopy. Many questions about how ancient pigments were made can now be answered. For instance, the mysterious finding of significant amounts of lead in all the samples of Han Blue and Han Purple that have so far been analysed - it is now known that lead additives were used to accelerate the decomposition of the barium mineral starting materials. Such detailed conclusions could only be reached on the basis of laborious scientific analyses applying modern scientific methodologies.

A possible technology transfer from Egypt to China is suggested by the chemical relationship of the Egyptian and Chinese pigments. For any transfer of knowledge and techniques, the areas of distribution of these pigments must have overlapped, but knowledge about the use of Egyptian Blue in Central Asia is still limited, so this question remains open. [I don't agree with the underlying assumptions.  We know there was trade - scattered and intermittent, but evidence exists for it nonetheless, over several thousand years - so it is quite possible the ancient peoples in the northwest area of China decided to develope their own blue pigment based on examples on Egyptian ware that came their way over the years.]

All the pigments described have one thing in common: they were all created by human inventive talent, which is strongest when there are situations of deficiency - even if the invention does not serve vital needs. In the case of blue pigments, chemistry was used as an opportunity. Chemistry was not only an opportunity for the people in ancient times and at the age of industrialisation, but still is an opportunity for the people of today. Seizing opportunities with chemistry means, according to the notable German chemist Justus von Liebig, to use 'silent force' and reach 'copious abundance'.

Read Heinz Berke's review on 'The invention of blue and purple pigments in ancient times' in issue 1, 2007 of Chem. Soc. Rev.

The invention of blue and purple pigments in ancient times
H Berke, Chem. Soc. Rev., 2007

DOI: 10.1039/b606268g

NOTE:  When I followed the DOI link (above) I found the following synopsis of Berke's article:
Heinz Berke

This tutorial review examines manmade blue and purple pigments appearing in antiquity. They were obtained by chemical synthesis from mineral starting materials and refer to chemical compounds: Egyptian Blue (CaCuSi4O10), Han Blue (BaCuSi4O10) and Han Purple (BaCuSi2O6), Maya Blue (x·indigo·(Mg,Al)4Si8(O,OH,H2O)24) and Ultramarine Blue (Na,Ca)8(AlSiO12)(S, SO4,Cl). [What is this Ultramarine Blue - what culture did it come from?  Is it common to all?  I ask because when I first saw the graphic for the example of Maya Blue in the first article in this post, I thought it was "marine blue."] The Egyptian and Chinese copper-based pigments are assumed to have been developed independently and are presumably an outcome of the historical developments in glazing techniques. A technology transfer from Egypt into China cannot be fully excluded but, based on the facts acquired up to now, looks less probable. [Really?]

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