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Archive for August, 2013

Black-on-white Sherd at Pueblo Alto

Black-on-white Sherd at Pueblo Alto

In keeping with what seems to be the recent pattern around here, my previous post led to some interesting discussion in the comments. Frequent commenter marcaeolog provided a link to a pdf version of Anna Shepard’s Ceramics for the Archaeologist, a classic work that challenges some of Florence Hawley’s theories that I discussed in the post. Andy Ward, who has done extensive experimental work attempting to recreate prehistoric pottery-making techniques, then chimed in with some information on his own efforts, focusing specifically on the question of what keeps carbon-based pigments from burning off during firing. Here’s part of his comment:

I have been doing research in just this area by collecting clays and firing them in open mesquite fires. While it is easier to keep carbon based paint on a pot in a reducing atmosphere this doesn’t account for polychromes. To make polychrome with a carbon based paint, like the ubiquitous Gila Polychrome, requires an oxidizing atmosphere. Certain kinds of clays have the ability to hold these carbon paints through a firing, bentonite clay in particular. Modern pueblo potters have used a slip called Cochiti slip which has these properties, ancient potters in cultures such as the Salado had access to similar slips.

As it turns out, Shepard had the same theory, based on her own experiments, which also provided solid evidence against Hawley’s theory, based on experiments with hydrofluoric acid, that it was compounds in the ash of the organic material that reacted with silica in the clay to protect the pigment from burning away. She acknowledged that this was a reasonable conclusion based on the information available to Hawley at the time, but Shepard’s own experiments comparing organic material with and without this sort of ash showed no substantial difference. Instead the biggest factor was clay type:

The most striking fact brought out by these tests is the effect of the type of clay on the permanence of the carbon. Bentonitic and other highly adsorptive clays retained a good black under firing conditions that completely oxidized the carbon on unnadsorptive, sedimentary clays. All of the clays that held the paint well required a high percentage of wafer to bring them to the plastic state and they had high shrinkage. These clays take up much more of the paint solution than the less adsorptive clays, and on drying, the clay plates are drawn tightly together, protecting the film of paint that surrounds them. The effectiveness of hydrofluoric acid in facilitating oxidation of carbon paints is explained by the fact that it attacks the clay, opening the surface and loosening the bond and thus exposing the carbon to air.

The upshot of this in cultural terms is that, contrary to what I said in an earlier post, it seems like the difference between mineral- and carbon-based black pigments is actually technological rather than cultural. Here’s Shepard again:

The relation of the type of clay to the depth of color of carbon paint from a plant extract is not a matter of merely theoretic interest to the technologist. It has a bearing on the distribution of this class of paint because it could not be produced in regions lacking adsorptive clays unless such clays could be obtained in trade. The use of plant extracts is not open to free choice or established merely by custom; it is limited by ceramic resources.

This is particularly interesting given the well-documented expansion of carbon-based pigments at the expense of mineral ones over the course of the late prehistoric period. If special clays were required to make this work, and those clays had restricted distributions, what accounts for the change? In areas that switched from mineral to carbon paint, such as Chaco, was this the result of a change in clay sources? The discovery, perhaps due to increased contact with other areas that had long used carbon, of which local clay sources worked for this? Importation of clay? Importation of finished pots? This raises a lot of questions, which to my knowledge have not received much attention in the archaeology of these areas, despite the fact that it’s now been several decades since Shepard’s research.

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Black-on-white Potsherd at Kin Bineola

Black-on-white Potsherd at Kin Bineola

“Never read the comments” is generally sage advice, so it’s likely that many of my readers have missed the interesting comment thread in response to my previous post. I won’t try to summarize it all here, but the gist is that a potter showed up and took issue with my use of the word “paint” to describe the pigments applied to prehistoric Pueblo pottery. Apparently, while archaeologists routinely refer to these pigments as paints, that’s not actually an accurate characterization and they are instead best described as types of “slip,” a term that archaeologists usually use only for the underlying layer of thin clay that the “paints” are often applied to. There’s a long history of archaeologists appropriating and misusing terminology from other fields, so it’s not surprising that they would have done this in this case too, but I’m not sure how best to proceed with the terminology, as it is pretty useful in practice to be able to distinguish the underlying “slip” from the “painted” designs on top of it. For now I’ll try using the (hopefully) more neutral term “pigment” for the “paint” and continue to use “slip” for the underlying clay.

Another issue that came up in the discussion, however, is separate from the terminology. This is the question of how the carbon-based pigments that are so well known from many parts of the Southwest could have adhered to pots after firing at all. After all, at the temperatures necessary to create usable ceramics any purely carbon pigment would burn right off. As I started to think about it, I realized that this was indeed a puzzle, and I went looking back into the literature to see if it had been addressed anywhere.

As it turned out, it had, and in the very first research on this subject, that of Florence Hawley in the 1920s. Hawley was an important figure in Southwestern archaeology throughout much of the twentieth century, and her early chemical studies of pottery pigments were fundamental in establishing the classification system by which they have been interpreted ever since. The most important aspect of this system was the division between “carbon-based” and “mineral-based” black pigments, although looking back at her initial publication on this topic from 1929, it’s clear that the dichotomy is more subtle than the terms imply. In fact both types of pigment contain both carbon and mineral elements, the difference being the relative proportions and the specific minerals involved. Both involve the boiling of certain plants, usually Tansy mustard or Rocky Mountain beeweed, to create a thick, black substance that can be applied to an unfired pot with a brush. The carbon type consists only of this substance, while the mineral type involves a subsequent step of adding ground iron oxide before applying it to the pot. Hawley also identifies a third type using manganese, which she speculates was used for certain types of pottery made of clay to which the usual carbon pigment wouldn’t adhere properly. (She also identifies a fourth type, so-called “smudged” pottery, that resulted from adding organic material after firing and letting it sink into the clay. This type is generally associated with the Mogollon culture in the highlands of east-central Arizona and west-central New Mexico and is quite different from the others in appearance.)

The chemical tests Hawley suggests to distinguish among these types of pigment are complicated and involve the use of dangerous acids, so they have not caught on as routine methods for archaeological analysis in more recent years. The tests appear to have been worked out and conducted mainly by Hawley’s father Fred Hawley, who was a chemist at a smelter in one of the mining areas of Arizona. Instead of these tests, archaeologists have generally tried to learn to distinguish the more common types by sight. As one of the papers I discussed earlier found in a test of this method, it works pretty well except in more marginal cases that are difficult to interpret using the standard visual criteria. The methods that have been proposed more recently using modern imaging technology have also not yet become very popular. In general the visual criteria seem to work fine.

As I noted in the previous post, the fact that both organic and mineral pigments seem to work to create black designs, but the mineral type is basically the same as the carbon one, raises the question of why there were two types at all. I suggested that cultural tradition rather than technological considerations probably was the main factor. Hawley doesn’t address the question in those terms, but she does argue that the different pigment types correspond to different cultural traditions, and the second half of the paper consists of her conclusions about cultural provinces and their spheres of influence based on pigment types through time. Her basic scheme of carbon pigments predominating in western areas and mineral pigments further east has generally held up, but otherwise her interpretations show how little was known at the time about Southwestern prehistory. She was clearly writing before tree-ring dating had established a firm foundation for the absolute chronology of cultural developments and pottery types, and the assumptions she makes about which sites were contemporary are strikingly wrong in light of that chronology. This makes her conclusions about changing patterns of cultural influence through time basically useless.

All that said, what about the question I mentioned earlier? How does the carbon pigment survive firing? Hawley’s answer, backed up by the chemical tests, was that it actually contains some mineral inclusions in addition to the carbon, especially silica and carbonates that melt in the process of firing and form a very thin film over the carbon that protects it from burning away. She considers this layer too thin to be considered a glaze, but it appears to serve the same basic function. It only works, however, when firing is in a reducing atmosphere, i.e., with oxygen prevented from reaching the surface of the pot. It’s not totally clear from her explanation where these mineral compounds come from, but the implication seems to be that some are from the plants from which the pigment is made and others are perhaps from the clay of the underlying pot. In the case of the mineral pigments, these potential sources are complemented by the trace silica in the iron oxide. As the more recent papers note, this interpretation has been questioned by others, most significantly Anna Shepard (another pioneering ceramic analyst at the same time as Hawley). It seems clear, however, that getting these pigments to survive firing requires some sort of chemical reaction along these lines, involving compounds in the pigment and/or the clay, along with a reducing atmosphere during the firing process itself.

It turns out pottery is pretty complicated! Archaeologists usually use pottery types primarily as a means to date sites and establish trade relationships, but studying potsherds intently with an eye to technological issues can reveal a lot of additional and potentially useful information.
ResearchBlogging.org
Hawley, FM (1929). Prehistoric Pottery Pigments in the Southwest American Anthropologist, 31 (4), 731-754 DOI: 10.1525/aa.1929.31.4.02a00110

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