ANALYTICAL EVIDENCE FOR THE ORGANIZATION OF THE ALEXANDRIAN MINT DURING THE TETRARCHY (III-IV CENTURIES AD)

J.M.COMPANA (A), L. LEN-REINA (B), F.J. FORTES (C), L.M. CABALN (C), J.J. LASERNA(C), M.A.G. ARANDA(A)* The province of Egypt occupied a strategic position within the Roman Empire, and for that reason it was subject to special control under direct government by the Emperor. One of the interventionist measures was to establish a monetary system independent from that of the rest of the empire, so that the commercial exchanges could be supervised. From the reign of Tiberius (AD 14-37) until Diocletians monetary reform in 296 AD the tetradrachm-based monetary system continued without any interruption. There is some numismatic evidence for the mints organization in certain periods. J.G. Milne studied the subject in two detailed papers, concluding that the mint was organized in a variable number of workshops. He established the hypothesis that during the Tetrarchy it had operated with up to four workshops. Here we have analysed a series of late tetradrachms, mainly of the reigns of Diocletian and Maximianus. Several techniques have been used, including Laser-Induced Breakdown Spectroscopy (LIBS) and X-Ray Powder Diffraction (XRPD). The study of the analytical data has shown the existence of several alloy groups that continue throughout the period studied. These rst results allow the conrmation of some of Milnes hypotheses about the organization of the Alexandrian mint and open new possibilities for a deeper understanding. The minting processes in Antiquity were very similar from one mint to another, so the results and methodology discussed in this work will probably be useful in future works. Introduction During the reign of Tiberius (AD 14-37) the tetradrachm-based monetary system, which would continue without any interruption until Diocletians monetary reform in 296 AD, was established in Egypt. During its existence the tetradrachm suffered severe debasements, corresponding to the successive economic crises of the Empire. This involved an evolution of the coins chemical composition through the years. Consequently, the proportion of precious metal is considered fundamental to the comprehension of the history and the economy of Egypt during the Roman Empire. On the other hand, through detailed knowledge of these metal alloys it might be possible to extract some additional conclusions about the technology employed in the monetary workshops. The Alexandrian coins have been studied from this approach, but mainly looking for the precious metal contents (for instance, Cope et al. 1997, Bouyon / Depeyrot / Desnier 2000). Alexandria was the capital of Egypt, so the mint was established there. There is little archaeological information about the mints organization, but there are several works, from a numismatic approach, by J.G. Milne (Milne 1916, 1918 and 1927). In one of his papers studying the coin dies (Milne 1916), the author reached the conclusion that there were up to four mint workshops operat* We thank MICINN (Spain) for nancial support through MAT200611080-C2 research grant. JMC thanks MICINN for his studentship. (A) Departamento de Qumica Inorgnica, Cristalografa y Mineraloga, Facultad de Ciencias; (B) Laboratorio de Difraccin de Rayos-X, Servicios Centrales de Apoyo a la Investigacin; (C) Departamento de Qumica Analtica, Facultad de Ciencias Universidad de Mlaga.

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ing at Alexandria during the Tetrarchy. In several regnal years they are indicated on the coins by the inclusion or omission of a star in the reverse eld, or by Greek numerals, also on the reverse. For Diocletian years 2-6, there are coins of Diocletian with and without star, and the same arrangement is also found for Maximianus. For Diocletian years 7-8, there are coins of Diocletian without star and Maximianus coins with star, so the stars are mint marks. From regnal years 8 to 10, we nd Greek letters as mint marks. The letters A and for Diocletian and his Caesar, Constantius, and the letters B and for Maximianus and his Caesar, Galerius (Milne 1916). In this paper a collection of 26 Alexandrian tetradrachms from the reign of Nero to the Tetrarchy have been analysed to gain a deeper understanding about the nature of the alloy used and about their production technology. Furthermore, this data may be useful to complement archaeological studies in the future. Materials and experimental techniques Samples We had access to a private collection of Alexandrian tetradrachms from which we could select a series of coins for analysis, including microdestructive techniques, but unfortunately the samples which we were permitted to select to do this kind of analysis were those of low grade. The coins selected were from the following reigns: 2 of Nero, 1 of Pius, 2 of Probus, 13 of Diocletian and 8 of Maximianus. Selected information about the coins is found in Table 1. As the obverse legends are very fragmentary and almost illegible in some cases, Table 1 includes reverse type and regnal year but not references to Alexandrian coin catalogues, such as Milnes (Milne 1927). Nevertheless, the attributions are sure in every coin, except in one case (no. 18), as we will see later. Our sample of Tetrarchy coins includes coins of regnal years 2-6 of Diocletian and years 2, 4, and 6-7 of Maximianus. The sample includes coins with and without star for both rulers so, according to Milne, we should expect to nd coins of up to four mint workshops. TABLE 1: General information and chemical characterization of the twenty-six samples analyzed by LIBS.

Number
1 2 3 4 5 6 7 8

Emperor
Nero Nero Pius Probus Probus Diocletian Diocletian Diocletian

Regnal year
LIA LIB LI LS LZ LB LB LB

Reverse
Eagle Eagle Nike Roma Eagle Alexandria Alexandria Alexandria

Metal alloy
Ag, Cu Ag, Cu Ag, Cu Cu, Sn, Pb Cu, Sn, Pb Cu, Sn, Pb Cu, Sn, Pb Cu, Sn, Pb

Traces
Si, Pb, Sn Si, Pb, Sn Si, Pb Fe Fe, Si Si Fe, Si Fe, Si, Ag

ANALYTICAL EVIDENCE FOR THE ORGANIZATION OF THE ALEXANDRIAN MINT DURING THE TETRARCHY (III-IV CENTURIES AD) 597 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 Diocletian Diocletian Diocletian Maximianus Diocletian Diocletian Maximianus Maximianus Maximianus Maximianus Maximianus Diocletian Diocletian Diocletian Diocletian Diocletian Maximianus Maximianus L L L LB L L L L L L LE LE LE LE LS LS LS LZ Tyche Eagle Eagle Eirene Athena Nike Nike Nike Nike Alexandria Tyche Eagle Alexandria Tyche Elpis Eirene Elpis Nike Cu, Sn, Pb Cu, Sn, Pb Cu, Sn, Pb Cu, Sn, Pb Cu, Sn, Pb Cu, Sn, Pb Cu, Sn, Pb Cu, Sn, Pb Cu, Sn, Pb Cu, Sn, Pb Cu, Sn, Pb Cu, Sn, Pb Cu, Sn, Pb Cu, Sn, Pb Cu, Sn, Pb Cu, Sn, Pb Cu, Sn, Pb Cu, Sn, Pb Fe, Si Fe, Si Fe,Si Fe, Si, Ag Si Fe Fe Fe Fe, Ag Fe, Si Fe Fe Fe, Si, Ag Si Fe Fe Fe, Si, Ag

Analytical techniques All the samples were analyzed using Laser-induced breakdown spectrometry. LIBS is an established technique for surface analysis (Vadillo and Laserna 2004). The advantages of LIBS in terms of fast analytical response, no sample preparation, remote sensing capabilities and the possibility to perform in-situ analysis have been extensively investigated in the cultural heritage eld (see for instance: Fortes et al. 2007; Anglos 2001; Giakoumaki / Melessanaki / Anglos 2006). The attributes of LIBS as analytical technique allow the multielemental characterization of any kind of materials with the minimum damage to the object (Fortes et al. 2005). For this reason, LIBS is a good candidate technique in the characterization, restoration and preservation of artworks (Fortes / Cabaln / Laserna 2008). The experimental set-up used for the LIBS analyses is schematized in Fig. 1. The second harmonic (532 nm) of a pulsed Q-Switched Nd:YAG laser (Spectron, model SL 284, pulse width 5 ns, beam diameter 4 mm) was used to generate microplasmas on the sample surface in air at atmospheric pressure and at room temperature. The output energy of the laser beam was 30 mJ per pulse at a repetition rate of 2 Hz. The laser beam was guided by two reective mirrors (diameters = 25.4 mm) both with coating for 532 nm and focused on the surface of the sample by a 100 mm focal length

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quartz lens (diameters = 25.4 mm) for plasma formation. The second mirror placed just before the laser focusing lens was a reective (at 45) quartz mirror (Lambda Research Optics, Inc.) in order to allow plasma recording in the same direction of plasma creation. The sample was placed at 16 mm upwards the beam focal point and the plasma emission was collected by a plano-convex quartz lens (diameter = 25.4 mm) with a focal length of 100 mm onto the entrance slit of a 0.5 m focal length Czerny-Turner imaging spectrograph (Chromex, model 500 IS, f-number 8, tted with indexable gratings of 300, 1200 and 2400 grooves mm-1). Spectral emission was detected by an intensied charge-coupled device (ICCD, Stanford Computer Optics, model 4Quik 05) with 768 x 512 pixels, each 7.8 x 8.7 m2. With an entrance slit width of 50 m, this conguration provides a spectral window of ~15 nm and a spectral resolution of 0.02 nm pixel-1 using the grating of 2400 grooves mm-1. Operation of the detector was controlled by a personal computer with 4Spec software. The experimental conditions for all the samples were 500 ns delay time, 500 ns acquisition time and 680 MCP voltages. For data acquisition, the CCD system was triggered by an output TTL pulse from the laser Q-switch system. The sample was placed on two crossed motorized stages (Physik Instrument) which allowed exact movement of the sample in both x and y directions. Laser trigger was controlled externally by a digital delay/pulse generator (Stanford Research System model DG535). The sample was analysed in several places to get a good representation of the composition. This is particularly important in the leaded bronzes, since there may be very important zone differences due to lead segregation in the liquid phase during the solidication of the blanks. Every site analysed was cleaned with several laser pulses before the analysis. This cleaning eliminates the rst layer of corrosion products to get fresh metal for the analysis. The process leaves a small spot, about 100 m diameter and several microns depth, as we can see in Fig. 2 marked with white circles. A light blackening is also observed around the spot. There is some surface oxidation of the copper due to the laser heating. A sample of the spectrum obtained from a representative sample is shown in Fig. 3.

Fig. 1. Scheme of the LIBS instrumentation used for the study of coins.

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Fig. 2. White circles highlight the marks in the coin after the LIBS analysis.

Fig. 3. Typical LIBS spectrum obtained from an Alexandrian coin with the main emission lines labelled.

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After the LIBS analysis, a coin of Diocletian (no. 9) and one of Maximianus (no. 15) were selected to be studied by X-Ray Powder Diffraction (XRPD). A section of each coin was cut and polished with sandpaper and diamond paste of 6 and 1 m successively. When the section had been fully polished, its X-Ray powder diffraction pattern was recorded. XRPD data were collected on a PANanalytical XPert PRO MPD diffractometer, BraggBrentano reection conguration, by using a Ge(111) primary monochromator (CuK1) and the XCelerator detector. The XRPD patterns were recorded between 40 and 75 in /2 mode with a step size of 0.017 (2). The X-ray tube worked at 45 kV and 40 mA. Results and discussion LIBS is a truly quantitative analytical technique (see for instance Vadillo / Laserna 2004) when the appropriate reference materials are used. This is one of the main drawbacks of this technique. The matrix effects are quite important in LIBS, so we can not obtain accurate compositional data without these reference materials. Nevertheless, even in the absence of this type of study it is possible to get better analytical information than merely qualitative analysis. If the intensity ratios of the same peaks among several samples are used, it is possible to compare the relative presence of one element to another, because in the same sample the matrix effects for both elements are approximately the same. For instance, if a peak for Cu and another for Pb are selected, the intensity ratio for these two peaks gives a good idea of the Cu/Pb ratio in the sample. This is very useful, because it is possible to compare samples of similar bulk compositions without any type of standards (Vadillo et al. 1998). The selected peaks must be the same in every sample. Overlapped peaks, resonant peaks and similar should be avoided, if possible. The spectral lines used in this study were Ag (I) at 237.57 nm, Cu (I) at 249.29 nm, Fe (I) at 250.19 nm, Pb (I) at 247.64 nm and Sn (I) at 248.41 nm. The major and trace elements detected are also shown in Table 1. Our rst analysis conrms that only the coins of Nero and Pius have a high Ag/Cu ratio, as expected (Fig. 4). In the remaining coins, this ratio is close to zero, as silver is only present as a minor element or traces. On the other hand, Pb/Cu ratios are higher in the late coins, but without an apparent clear trend. With the Pb/Cu intensity ratios obtained from the spectra, an ANOVA analysis was carried out. As stated before, lead contents must be considered carefully, but all the coins were analysed in enough points to ensure condence. The result, shown in Fig. 5, shows a statistically signicant difference among the lead contents during the different reigns. This difference is particularly remarkable between the coins of Diocletianus and those of Maximianus, because those coins minted in the same mint at the same time should use a similar alloy.

ANALYTICAL EVIDENCE FOR THE ORGANIZATION OF THE ALEXANDRIAN MINT DURING THE TETRARCHY (III-IV CENTURIES AD) 601

Fig. 4. Plot of Ag/Cu (triangles) and Pb/Cu (squares) intensity ratios. The samples are ordered as given in table 1.

Fig. 5. ANOVA plot for Pb/Cu intensity ratios corresponding to the different reigns, showing the data distribution and the mean value in all the cases. An analysis of Pb/Cu and Sn/Cu ratios was carried out, as they are the major elements in the al-

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loys (Fig. 6). Interestingly, the coins form separate groups corresponding to each reign. The groups of Nero and Pius are very different from the rest, because they are mainly billon coins. The rest are leaded bronze coins, so their Sn and Pb contents are higher. It is more interesting to analyse the Diocletian and Maximianus groups. The Diocletian group seems to have a higher lead content than that of Maximianus, but there is a clear difference between them. There is a coin which seems to be of Diocletians group more than Maximianuss. This coin is that with doubtful attribution (no. 18), and it may also be a Diocletian coin. Milne pointed out that the coins of each ruler are minted in specic mint workshops (one or a pair depending on the regnal year). This evidence on the use of different alloys for each ruler thus seems to be a conrmation of Milnes hypotheses. If the blanks of each ruler are different, and this difference remains over some years, it seems reasonable that there were at least two minting places at Alexandria, each making its own blanks. This is just a hypothesis that needs to be conrmed. One exciting way to do this would be by expanding our study to coins including letters as mint marks, and some coins of Caesars Galerius and Constantius. Unfortunately the studied collection did not include any, but we are looking for some of them to check these preliminary results.

Fig. 6. Plot of Sn/Cu versus Pb/Cu intensity ratios showing grouping of the coins. The XRPD patterns of two selected coins are shown in Fig. 7, with the main peaks labelled. The two patterns are superimposed in Fig. 8, showing the differences. There is a difference in the copper-rich phase peaks between the two samples. The lead-rich phase peak positions are almost identical in both cases. The peak displacement in the copper-rich phase probably arises from its different tin content. The full quantication of the unit cell parameter of the phases in different coins will be carried out by applying the Rietveld method (Rietveld 1969) to the powder patterns of several coins. However, this type of study is outside the scope of this contribution. This work is in progress and will be reported elsewhere.

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Fig. 7. XRPD pattern of one coin of Diocletianus and one of Maximianus.

Fig. 8. Superposed XRPD patterns of the two coins showing the Cu-rich phase displacement. Conclusions A collection of early and late Alexandrian tetradrachms have been studied using LIBS and XRPD. The statistical study of the data obtained shows clear differences between the coins of Diocletianus and Maximianus. These differences agree with Milnes hypotheses about the workshops of the mint and their organisation during the Tetrarchy. The grouping of the Tetrarchy coins suggests that there were at least two minting places at Alexandria, each one making its own blanks. This last hypothesis should be conrmed in future archaeological studies of papyri and excavations at Alexandria.

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