All That Glitters, Experiment 3

A problem with finally picking up this blog a bit is that some of the old stories in it have been sitting idle for really quite some time. Does anyone remember, for example, that while I was working at the Barber Institute we got a small amount of money to zap gold coins with x-rays? If you do, you may remember that I’d already reported on the first two experiments we did in that project when everything here ground to a halt in 2016. Well, now I resume, with a brief account of the third experiment we did, and before long who knows, we may be through the rest!

Bruker S8 TIGER XRF analyser open for business

The S8TIGER WD-XRF spectrometer in the Department of Chemistry, University of Birmingham, with five sample cups waiting and one under analysis

A brief recap may be in order first of all, though. The very short version of the project’s purpose was: we had all seen an increasing amount of work using X-ray fluorescence spectrometry to analyse the fineness of precious-metal coins and sometimes even assign origins to its metal based on the trace elements therein. We had our doubts about this, but the manufacturers of some of the best machinery involved wanted to quell our doubts about this and offered us quite a lot of help with it, so we came up with a plan and, somewhat to our surprise, got both permission from the Henry Barber Trust to muck around with their coins and funding from the Royal Numismatic Society to do it, and so set about it. We began this in December 2014, with two experiments. The first was designed to test the viability of hand-held, portable, energy-dispersive machinery that could be brought to the coins; the second did comparator analyses using a fixed-location wavelength-dispersive spectrometer to which we had to bring the coins. This showed us that to detect anything at all of trace elements we would need the big machine, but also that it was picking up a whole load of stuff that seemed very likely to be extraneous material on the surface of the coins, probably from the soil in which they had long ago been found, rather than the stuff of which they were actually made. And that is about where we come in!

Gold solidus of Emperor Constantine VI and Empress Eirini struck at Constantinople 785-797, Barber Institute of Fine Arts B4599

The coin whose results (and details) are given in the first table below, set up for the test in which it did so

So, the third experiment was very simple. Using the same set of coins as we had previously run, I got hold of some conservation-quality acetone and a toothbrush, took them and the coins down to a workroom in the depths of the Barber and gave them all a careful but thorough scrubbing and let them dry, all except one that we left uncleaned as a check. Then I packed them up again and we bore them off to the Department of Chemistry on 22nd July 2015. There we ran them again, on the shorter of the big machine’s two cycles, and this gave us some results both before and after cleaning.

Unfortunately, if anything, the post-cleaning results showed more extraneous grot. That ‘if anything’ will tell you, though, that consistency was hard to observe. The variation wasn’t vast amounts, you understand, between half and one-and-a-half per cent, but cumulatively certainly enough to push our figures for the actual gold content up or down by two or three per cent, which would for some people be enough on which to found a theory about debasement… Here are the top ten elemental results from just one side of one coin by way of example:

Coin 170 (obverse)1 Percentage observed first time Percentage observed second time
Gold 86.51% 84.49%
Silicon 3.44% 4.63%
Silver 1.61% 1.43%
Aluminium 1.27% 1.19%
Potassium 0.80% 0.63%
Sodium 0.74%
Copper 0.44% 0.34%
Calcium 0.32% 1.96%
Sulphur 0.28% 0.48%
Iron 0.27% 0.50%
Total percentage of coin observed 96.38% 96.70%

Down by two per cent gold, and that mostly gone to silicon and calcium, even though some other small elements had dropped in the readings as well. Also, what this arrangement doesn’t show, the second time small but possible readings showed up for chlorine, magnesium and, way down the scale, platinum, all absent the first time through. Surely cleaning with acetone couldn’t have added calcium to the coin? But each coin we ran had its own little tale of additional mess to tell, even (and this should have told us something) the uncleaned check. Here are its top-ten figures for the obverse:

Coin 21 (obverse)2 Percentage observed first time Percentage observed second time
Gold 82.57% 87.43%
Silicon 1.82% 1.61%
Aluminium 1.01% 0.81%
Silver 0.74% 1.10%
Sodium 0.65%
Potassium 0.47%
Chlorine 0.45%
Calcium 0.44% 1.78%
Iron 0.31% 0.31%
Copper 0.24% 0.26%
Total percentage of coin observed 89.12% 93.80%

Some things are beguilingly similar, yes—iron and copper levels stay about the same—but others are not. The first test picked up sodium, potassium and chlorine but none of those turned up second time even though we’d actually got better readings with more of the sample observed (possibly because we gave it a flatter bit to look at). Were we just looking at a different bit? If so, that bit apparently had less silicon in it, but a whole whack more calcium in it. What can you do with these sorts of data?

Gold solidus of Emperor Anastasius I struck at Constantinople 491-518, Barber Institute of Fine Arts B0006, in an WD-XRF sample cup

The uncleaned check likewise set up for the results above, though I have to say it’s not like it looks dirty

So this was somewhat daunting, especially as we had four solid days of testing booked in for the following week and now somewhat less certainty that it would produce anything. At the time, my best guess was that the acetone had removed only handling patina, thus exposing the actual surface of the coin and everything that had adhered to or reacted into it while it was in the ground. Actually, looking back, I think we were already seeing here the conclusion that the final experiment would necessarily lead us to. But that would be getting ahead of the story, and even though this story is so very far behind, I have hopes of telling it as I wanted to anyway. So, till next post but, er, two, if I have my plans right (and no-one else dies—did you see Mark E. Smith has left us for the bar of the great and final WMC since the last post?), I shall leave the question hanging…

1. We used randomly-allocated running numbers throughout these experiments, so that we couldn’t try and guess what the results should be according to where the coins fitted in Byzantine history (or the previous curves laid down by work like Cécile Morrisson, Jean-Nöel Barrandon and Jean Poirier, “La monnaie d’or byzantine à Constantinople : purification et modes d’altérations (491-1354)” in Morrisson, Claude Brenot, Barrandon, Poirier and Robert Halleux (edd.), L’or monnayé I : purification et altérations de Rome à Byzance, Cahiers Ernest Babelon 2 (Paris: C. N. R. S. 1985), pp. 113–187. This one was actually Birmingham, Barber Institute of Fine Arts B4599, a solidus of Emperor Constantine VI and Empress Eirini struck at Constantinople between 785 and 797, online here. I’m actually almost loath to identify the coins here, though, lest it be thought I’m actually publishing figures for their metal content. As is probably clear, though, that’s something I’m sure we weren’t reliably getting.

2. And this one was Barber Institute of Fine Arts B0006, a solidus of Emperor Anastasius I struck at Constantinople between 491 and 518, online here, with the same reservations as in the previous note.


2 responses to “All That Glitters, Experiment 3

  1. Glad that you have time for the odd post again, but don’t worry if writing which pays in CV entries or money takes precedence! Its good to talk about practical problems with various kinds of experiments in the open.

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