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Manillas) Via Energy Dispersive X-Ray Fluorescence

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Manillas) Via Energy Dispersive X-Ray Fluorescence AMERICAN JOURNAL OF UNDERGRADUATE RESEARCH VOL. 1 NO. 1 (2002) Chemical Compositions of African Trade Bracelets (Manillas) via Energy Dispersive X-Ray Fluorescence Mike Kuntz, Jennifer Ferguson, Vincent Iduma, Renee Kuzava, and Mark Benvenuto Department of Chemistry and Biochemistry University of Detroit Mercy 4001 W. McNichols Road Detroit, Michigan 48219-0900 USA Received March 4, 2002 Accepted March 13, 2002 ABSTRACT Sixteen small, west African trade bracelets called manillas, and one large, African trade bracelet referred to as a king manilla based on its size, were analyzed via energy dispersive x-ray fluorescence spectrometry and compared for the following elements: copper, zinc, tin, lead, antimony, and arsenic. The composition of the bracelets varied widely in the amount of lead present, especially when compared to the official amounts of lead allowed by the various manufacturing concerns. The king manilla showed a markedly different chemistry than the sixteen smaller manillas, consistent with the belief such large manillas were not manufactured in the same location as the small. I. INTRODUCTION certain differences in style, as can be seen Copper objects have been traded as most obviously when comparing photograph items of money and wealth in sub-Saharan 16 to the others. The king manilla is Africa for hundreds of years [1]. European considerably larger, as seen in photograph trading companies produced millions of 17, being approximately 12" long. The copper bracelets, known as manillas, for use bracelets have been matched to their type in in west African trade; and their use the Opitz reference [1], and are listed in continued in many areas well into the Table 1. Where possible, their presumed twentieth century [1]. While these items city, country, or region of manufacture, as have been of interest to and have been well as possible dates of manufacture, are studied by numismatists who specialize in also listed. non-traditional forms of money, they seem not to have been studied in terms of their II. PROCEDURE metallurgical composition, perhaps because early, published reports simply have stated Bracelets 1 – 10 were purchased for what their compositions should be [1-3]. study, and bracelets 11 – 17 were provided Until this time, there appears to have been as loans from the American Numismatic no attempt to determine the chemical make Association, headquartered in Colorado up of any sampling of these bracelets via a Springs, Colorado. Bracelets 1 – 10 were non-destructive, analytical chemical wiped with a Kimwipe prior to exposure to X- technique. rays, while bracelets 11 – 17 were not The sixteen smaller bracelets cleaned in any way prior to exposure. [See analyzed here vary in size, as shown in the Appendix for photographs of the photographs 1 – 16. In addition, there are manillas.] 29 AMERICAN JOURNAL OF UNDERGRADUATE RESEARCH VOL. 1 NO. 1 (2002) Sample Opitz Type City/County/Region of Date Number Production 1 atoni Birmingham, England 2 atoni Birmingham, England 3 onoudu Birmingham, England 1856 4 onoudu Birmingham, England 1856 5 onoudu Birmingham, England 1856 6 onoudu Birmingham, England 1856 7 onoudu Birmingham, England 1856 8 onoudu Birmingham, England 1856 9 onoudu Birmingham, England 1856 10 popo French 11 atoni Birmingham, England 12 atoni Birmingham, England 13 atoni Birmingham, England 14 atoni Birmingham, England 15 bidda 16 popo French 17 king Africa Table 1. The manillas tested: their type, point of production, and date of production. Beyond this, each bracelet was examined to Spectrace Quanx spectrometer with Si (Li) ensure that the points of exposure to the X- detector for the following elements: Cu, Zn, ray beam were clean and free from Sn, Pb, Fe, Ni, Mn, Sb, Au, Pt, Pd, and Ag. patination. The bracelets all have a torque Excitation conditions for each sample were shape with flared ends. The X-ray beam as follows: 20 kV, 0.10 mA, 100 second was directed at three equally spaced points count, K for Fe, Co, Ni, Cu, Zn, As, Pt, on each side of each bracelet, for a total of Au, Bi, and Pb, followed by 45 kV, 0.72 mA, six points per sample. These were then 60 second count, L lines, for Pd, Ag, Sn, and averaged for each elemental percentage. Sb, using a rhodium target X-ray tube. Pure The samples were examined via energy element standards and fundamental dispersive X-ray fluorescence on a Kevex software were utilized in determining Figure 1: Percent Composition of Copper 90 80 70 60 50 40 77.2 30 58.7 56.1 52 47.4 50.3 43.5 20 37.8 39.4 38.3 39 33.2 34.9 24.3 10 22.3 14.7 Percent Copper/Standard Deviation 0 12345678910111213141516 Bracelet, Sample Number 30 AMERICAN JOURNAL OF UNDERGRADUATE RESEARCH VOL. 1 NO. 1 (2002) all elemental concentrations. Brass Element Standard 1 Standard 2 standard sample disks of known Cu 80.3 % 77.8 % concentrations were run before the samples Zn 2.5 3.7 each day and after each day’s samples. Pb 2.0 6.5 Concentrations (in percent) of the major Sn 14.1 10.5 components of the standards were: Figure 2: Percent Composition of Lead 90 80 n o ati 70 60 50 tandard Devi S 40 65.6 66.9 30 47.8 50.2 51.3 52 46 20 35.5 35.2 rcent Lead/ 31.9 28 33.1 32 e P 10 18.5 19.3 0 0.8 1 2 3 4 5 6 7 8 9 10111213141516 Bracelet, Sample Number Figure 3: Percent Composition of Zinc 25 n o ati 20 evi 15 25.5 tandard D S 10 20.2 nc/ 5 Percent Zi 1. 5 1. 4 1.2 0 0.2 0.1 00 00.1 0.1 0.1 0.5 0.1 0.2 12345678910111213141516 Bracelet, Sample Number III. ELEMENTAL COMPOSITIONS, THE SMALL MANILLAS The compositions of the major eleven of the sixteen samples, as seen in components of bracelets 1-16 are illustrated Figure 1. In addition, it was quite graphically in Figures 1 – 6. It was unexpected to see the lead percentages rise surprising to note that copper was not as high as they did – over 40% in seven of present to the amount of even 50% in the samples, and over 50% in five of those 31 AMERICAN JOURNAL OF UNDERGRADUATE RESEARCH VOL. 1 NO. 1 (2002) seven – as shown in Figure 2. Since prior This appears never to be the case, which reports indicate the bracelets should be indicates other elements are present in copper with no more than 25% lead [4], significant amounts in the alloys of each Figures 1 and 2 should add up to total sample, and which is also consistent with percentages at or close to 100% (allowing similar findings in African copper-based for impurities that were not refined away). artifacts [5]. Figure 4: Percent Compoistion of Tin 50 45 40 35 30 25 20 15 28.6 28 22.2 10 Percent Tin/Standard Deviation 5 9.9 9.8 10 .8 9 5 4 4.8 4.2 2.9 3.1 0 0.6 1. 3 0.1 12345678910111213141516 Bracelet, Sample Number Figure 5: Percent Composition of Antimony 25 ion t a i 20 v rd De 15 nda /Sta 10 12.9 t Animony 12 11.7 n 5 10.1 10.5 e 7.7 rc Pe 2.1 0.9 1.4 0.8 0 0.6 0.3 0.7 0.7 0 0.2 1 2 3 4 5 6 7 8 9 10111213141516 Bracelet, Sample Number Figure 3 graphs zinc percentages, as no more than a trace element, though the and shows that only bracelets 15 and 16 pure element standards and brass have a large percentage of zinc. In standards used as known concentrations bracelets 1 – 14, zinc appears to be present make such trace numbers for zinc and other 32 AMERICAN JOURNAL OF UNDERGRADUATE RESEARCH VOL. 1 NO. 1 (2002) elements semi-quantitative. This does the bracelets. Both zinc and tin however indicate that these fourteen concentrations are lower than lead though, samples cannot be accurately called leaded in all but bracelets 15 and 16. As well, the brass, though 15 and 16 can be. On a standard deviations for lead and tin do related note, the presence of a significant become large in some of the samples. This amount of tin (graphed in Figure 4) would may be a result of long-term storage of indicate the bracelets to be leaded bronze; those samples in a chemically active and it does appear that tin is present in environment, such as being buried in acidic greater amounts than zinc in all but three of soil. Figure 6: Percent Composition of Arsenic 5 4.5 4 3.5 3 2.5 2 3.9 4 3.5 1.5 2.9 1 2.1 1.7 1.4 0.5 1 Percent Arsenic/Standard Deviation 0.8 0.8 0.7 0.4 0.5 0.5 0.3 0 0.1 12345678910111213141516 Bracelet, Sample Number The bracelets were also examined for IV. ELEMENTAL COMPOSITION, THE antimony and arsenic because of the KING MANILLA occurrence of these two elements in conjunction with both lead and tin ores King manilas are significantly rarer throughout the world, as is evidenced by than the small manilas, which makes most their proximity on the periodic table [6]. of them the provenance of museums or While arsenic was present in all the wealthy collectors today. Consequently, this bracelets, it was routinely a trace element, research is only able to compare one king only rising above 2% in five samples, and with a larger number of small manillas.
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