All That Glitters, Experiment 2

Somehow my posts about me and my work—and that may not be what you’re here for but, you know, I like it—have got behind my seminar reports in such a way that they’re into February 2015 and I’m still in December 2014. Let me resolve some of that disparity by giving you a short report on the second day of experiments in the collaborative project I’m in for analysing Byzantine gold coinage by X-ray fluorescence, which was 14th December. (If you need background I announced this project ages ago here and dealt with some of our starting questions and the first day’s experiment here.)

Cover of J. O. Jeppson, The Second Experiment

Our results have so far not been this dramatic, but then, I’m guessing that our first experiment wasn’t quite as adventurous as this must have been

To recap, we had established that if our experiments were to tell us anything much about elements other than gold, silver, copper and maybe one or two other pre-determined elements, we were going to need not the energy-dispersive machinery we’d been using on the first day but the bigger, more expensive and, most importantly, immobile wavelength-dispersive machinery in the Department of Chemistry in the University of Birmingham, a machine called the S8 TIGER. I am only just able to describe the difference between these two analytic methods: in so far as I can, it’s to do with what is being used to pick up the energy given off by the things you’re bombarding with x-rays. The WD machinery includes crystal collimators that are sensitive to certain wavelenths of that energy, which therefore get picked up better, where the ED machines, which measure only in terms of intensity of signal, simply wouldn’t see such things among the massive gold return, as we had surmised. The WD machine also scans its samples in a vacuum, which eliminates interference from the air.

Bruker S8 TIGER XRF analyser open for business

The mouth of the TIGER yawning wide, with five sample cups waiting and one under analysis

On the other hand there are also problems with the WD machinery that don’t exist with the ED kit. For us the first of those was simply access; it’s nothing to do with the actual machinery except in so far as it’s immovable, but because we had to take the coins to the kit rather than vice versa, that meant arranging transport and insurance even on campus, and the transport repeatedly went wrong, which cut into our experimental time a lot. But, also, the ED kit works with narrow beams focussed on points; the WD machine scans its samples in masks such as the one below, of which the two sizes relevant to us were 5 mm and 8 mm, and those were therefore the only area sizes that we could analyse. Importantly, this also precluded examining coins at their edges or over piercings, because the sample has to fill the exposed area completely. This also highlights a problem with both ED and WD methods: non-homogeneity. If for some reason your coin had an odd tiny lump of platinum on its surface, say, the ED machinery would either miss it (in which case you’d never know) or find it and report a massive platinum signal (which would be misleading for the coin’s overall composition). The WD machinery, however, would factor it into the average, so that you wouldn’t necessarily realise that it was a coherent inclusion rather than a component of the main alloy. So there was plenty to worry about even if the machine worked perfectly.

Emperor Heraclius just visible on one of his solidi of Constantinople loaded behind an 8 mm mask for analysis in the Bruker S8 TIGER

Emperor Heraclius just visible on one of his solidi of Constantinople loaded behind an 8 mm mask for analysis

Anyway, we had our goals clear for this test. The first was to get our hands on the machinery and find out what the operational considerations in any further planning were, the results of which you sort of see in the musings above. Here I have to acknowledge the tremendous help and general goodwill of Dr Jackie Deans, official keeper of the TIGER, and Dr Adrian Wright, who had first let us involve the Department of Chemistry in the project and had helpful things to say whenever he dropped in. Our second priority was to run the same ten coins around which we’d built our first experiment on the S8 TIGER and see how the results differed from those on the ED kit. And as it turned out, our third one was to determine how we wanted to use the S8 TIGER, because as Jackie explained to us, it could analyse at three levels, a 2-minute cycle that would probably get us no more data than the ED machinery had, an 8-minute one which should do the job, and an 18-minute one which was the very most data it could gather. Adding 10 minutes to each analysis was obviously going to limit the number of coins we could actually analyse in any given timeframe, so we really rather needed to know whether or not it was worthwhile.

Gold solidus of Empress Eirini at Constantinople set up for analysis in a Bruker S8 TIGER XRF analyser

The rather different visage in gold of the Empress Eirini, likewise cruelly cut down to 8 mm of glaring royalty

And so what did we find? Well, this machine certainly had more to tell us. We were now getting returns in terms of many elements, at concentrations of down to parts per thousand or even less. This ineluctably meant a decrease in gold concentration reported, because there was now simply more data to fit into the percentages, but the overall picture of lots of gold, not much silver and less copper was still very apparent in the reported figures. What we hadn’t expected, and had now to deal with, was that copper wasn’t usually the third most detected element, and sometimes silver not the second: instead, we were seeing lots of calcium, silicon and sometimes aluminium beating them out. It seemed a priori unlikely that these were original metallic components of the coins in these quantities. That in turn implied that these elements had got into, or much more likely onto, the coins since striking, be that from use, preservation or anything else that might have happened to them. But, whatever they were, they also seemed to be more consistently detected on the long cycle than the medium-length one, meaning that we were going to need to use the long analysis to have any chance of consistent findings. So now we had two difficult questions to answer in setting up Experiment 3: firstly, what could we get done with less than half the scans that we might have hoped to do in any given day of experiments, but secondly, when we did, could we determine whether these results were merely contamination or do anything about that if they were? And these were things which we attempted to address in the New Year, so I’ll stop here for now.

3 responses to “All That Glitters, Experiment 2

  1. brewerwithout

    Right, yes; this is fascinating and I’ll be keeping an eye out for the next of these. You say calcium, silicon and aluminium and I hear soil.

    • Your instincts may well be sound, as this was also the opinion of the people in Chemistry we were able to consult. As for what we did about that, well, yes, wait for the next one :-)

  2. Pingback: Announcing Buried Treasures | A Corner of Tenth-Century Europe

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