Jointly published by Journal of Radioanalytical and Nuclear Chemistry, Articles, Elsevier Science S. A., Lausanne and VoL 196, No. 2 (1995) 255-266 Akad~miai Kiadd , Budapest CHEMICAL ANALYSIS OF COPPER AND BRASS SAMPLES FROM CHRISTIAN ISLAND, GEORGIAN BAY, ONTARIO R.G.V. HANCOCK', R.M. FARQUHAR", L.A. PAVLISH", W.D. 17ENLAYSON"*~ "SLOWPOKEReactor Facility and Department of Chemical Engineering and Applied Chemistry, University of Toronto, Toronto, Canada, M5S 1A4 "Department of Physics, University of Toronto, Toronto Canada, MSS 1AS "*London Museum of Archaeology, London, Canada, N6G 3M6 (Received March 1. 1995) One hundred and eighty-seven metal samples, recovered from tlae fortified mission of Ste. Marie II and nearby villages on Christian Island, include 3 samples of native copper, 22 samples of European copper, 19 samplesof brassy copper (~8% Zn), 141 brass samples and 2 samples of lead. The European copper samples form 5 distinct chemical groups, possibly coming from 5 different copper kettles. The brassy COlrpersamples are more difficultto group, When the brass samples are sorted by Ag and As, they form 2 major groupings:group 1 with high Ag and low As contents; group 2 with similar Ag and As contents through to low Ag and high As contents. Group 1 consisted of 11 chemical sub-groups and 6 outliers, while group 2 contributed 14 sub-groups and 14 outliers. This combines to give a total of 45 potentially unrelated brass chemistries, and leads to the possibility of as few as 20 different brass trading items (mainly kettles) from which the samples were cut. The small sub-sets of samples from the sites away from Ste. Marie lI tended to fit within chemical groups found there, suggesting some possible inter-site contemporaneity. When the first Europeans arrived in south-central Ontario in the early 17th century, the area was occupied by the Hurons, a confederacy of four tribes of lroquoian speaking peoples, who built longhouses and lived in villages, which were often palisaded. The Hurons were slash and burn horticulturalists who grew corn, beans and squash. After earlier documented visits by explorers like Samuel de Champlain (1616), and the Recollet priests, the Jesuits established themselves in Huronia in 1634. In 1639, they created a centrafized mission at the site of Ste. Marie I, on the bank of the Wye River near present day Midland, Ontario. This mission flourished until the mid 1640's when, traditional warfare between the Huron and the League of Five Nations Iroquois, who lived south of Lake Ontario, began to intensify. 1-3 Following a series of Iroquoian raids that had devastating effects on both the economy and morale, the Huron confederacy as a social and political entity began to disintegrate. In 1648, the Jesuits reported that they had set up a mission in a Huron village, whose occupants had recently moved to Christian Island to escape the attacks of the Iroquois. TIle following spring, Father Chaumonot and a number of huron refugees from Ossossone arrived at Christian Island. 0236-5731/95/US $ 950 Copyrioht 1995 Akaddmiai Kiad6, Budapest All rights reserved R. G. V. HANCOCKet al.: CHEMICALANALYSIS OF COPPER AND BRASS In June of 1649, the decision was made to abandon Ste. Marie L Discussions between the Huron chiefs and the Jesuits about a new permanent location for the mission finally resulted in the choice of Christian Island (see figure 1) in southern Georgian Bay rather than the more distant and climatically less favourable, but safer, Mauitoulin Island. Ste. Marie I was stripped of usable goods and materials, which were subsequently transported to Christian Island on a large raft Ste. Marie I was burned to prevent it from falling into the hands of the Iroquois. A new fortified mission with a secure water supply, SI~. Marie IT, was built on the lee shore of Christian Island to house the Jesuits and their lay assistants. A large Huron village was established adjacent to the mission. Historical evidence suggests that this village may have comprised up to 100 structures. Estimates suggest a total population on the island of up to 8,000 individuals in the fall and winter of 1649-50. The Huron refugees had not been able to bring adequate food supplies with them to the island. Consequently, during the winter, thousands of Hurons died of starvation and disease. 4 In June of 1650, the Jesuits and their assistants and about 300 Hurons left Christian Island and took refuge in Quebec while another 300 Hurons stayed on the island. In 1651, some of the latter sought refuge on Manitouiin Island while the remainder were taken captive by the Iroquois, or fled. Fig. 1 Loe~m map fo~ thearcha~logieal sil~ Today, Christian Island is the home of the Beausoleil First Nation, a population of mostly Ojibwa and a few Potowatomi. Archaeological Investigations: Ste. Marie 1/ was fin-st investigated in the late 19th centur~ '6. The first modem archaeological excavations were conducted within the stone walled fort in 1965. 7 In 1967 and 1968, excavations were conducted in the village north of the fort 256 R, G. V. HANCOCKet ,'d.: CHEMICALANALYSIS OF COPPER AND BRASS and also in the Huron cemetery) Between 1987 and 1989, archaeological investigations were continued on the Christian Island Indian Reserve. Test excavations were conducted in and adjacent to the Fort Ste. Marie II and in the village nearby. Archaeological survey resulted in the investigation of four Huron sites on Christian Island which produced native and European metal artifacts and metallic debris. Limited excavations were conducted within Ste. Marie 11. It was found to be larger than previously thought, with a European compound located to the north of the stone walled ruins visible today on the shore of the island. Electromagnetic and resistivity surveys supported these findings. 9 Middle Woodland ceramics were also recovered, suggesting a much earlier occupation of this portion of the island. North of the fort, the village was investigated and produced a small sampling of artifacts. The Charity site was discovered on the shore of Lake Douglas and is interpreted as the Huron village associated with the Jesuit mission established in 1647 or 1648. It predated the establishment of Ste. Marie II, but was still occupied after the fort was built. The Omand site is located near the southern tip of Christian Island. It is interpreted as a pre-European contact and European contact period Huron fishing camp, which may have been occupied at the same time as Ste. Marie II to protect the island from attack by the Iroquois from the adjacent shore of the mainland. The Little Sand site is located on the eastern shore of Christian Island and appears to be another fishing camp, which produced both native and European artifacts. One hundred and eighty seven metal artifacts were selected for chemical analysis, the results of which are presented below. Analytical Procedure The metal samples, recovered mainly from trade kettles found in Christian Island archaeological sites, were analyzed by instrumental neutron activation analysis (INAA) at the SLOWPOKE Reactor Facility of the University of Toronto. ~~ Pre-weighed samples were first irradiated serially for three minutes at a neutron flux of 1.0 x l0 n n.cm-2.s1 and assayed for 200 seconds after a delay time of approximately one minute using Ge detector-based gamma ray spectrometers, for Cu, V and A1. Elemental concentrations were calculated using the comparator method. Smaller samples were irradiated with suitably larger neutron doses. After a delay time of about one hour, each sample was re-assayed for Zn, Mn and In. Medium and long half-life radioisotope-producing elements were quantified by batch irradiating between 20 to 30 samples per irradiation container for 16 hours at 2.5 x 10 n n.cm2.s 1. After 6 to 8 days, samples were serially assayed for 1000 to 3000 seconds looking for Sin, Au, La, Cd, As, Sb and Na. A final counting was made after between 10 and 14 days, at which time the samples were counted for 2 to 16 hours each, depending on sample size, to determine the concentrations of Sn, Se, Hg, Th, Cr, Au, As, Sb, Ag, Ni, Sc, Fe, Zn, Co and Eu. This procedure produced replicate measurements of enough elements to guarantee no sampie mix- ups. Analytical precisions ranged from +1% to detection limits. 257 R. G. V. HANCOCK et al.: CHEMICAL ANALYSIS OF COPPER AND BRASS Results and Discussion The analytical results indicate that the distribution of trace elements in copper-based metals from the sites sampled can be used to evaluate the copper and brass distribution. H18 A summary of the general chemical groupings, listed in Table 1, shows that the sample suite consisted of three samples of native copper, 22 samples of European copper, nineteen samples of brassy (.g8% Zn) European copper, I41 brass samples and 2 samples of lead. Table 2 presents the analytical data for the lead and native copper samples. The native copper samples may have come from earlier occupations or may have been brought from Ste. Marie I. The finding of two lead samples was rather surprising, since at the time of sampling, efforts were made to exclude non-copper based metals. Table 1 Distribution of metals from the archaeological sites Site Native European Brassy Brass Lead copper copper copper Ste. Marie II 2 19 18 100 2 Little Sand 1 Omand 2 1 Village 1 7 Charity I 1 32 Table 2 INAA Data for lead and native copper samples from Saint Marie II and the village. Sample Ag As Au Co In Mn Ni Sb Sn Zn Number ppm ppm lYpb ppm ppm ppm ppm ppm ppm % Pb08 190 39 270 <1.8 .~0.3 <9 ~'93 200 2700 fill.007 Pb45 980 660 76 <LI _<0.3 4 -<60 310 370 -~.005 79 160 _<4.1 37 2.7 <1-2 if,5 <18 0.45 2/10 fll.003 184 29 ~42 130 5.3 _<0.9 .~ _<73 t.5 <4(10 .~0.010 v130 13 _<4.1 110 3.2 <1.0 _<4 57.6 2.3 _<64 .gl).001 The data for the 22 European copper samples are shown in Table 3, in which they are sorted by their chemistries.