The Smallest Base and Precious Metal Deposits in the World: Vapor Transport and deposition of Co-Cu-Sn-Ag alloys in vesicles

• Main Author: Hunter, Elizabeth Adele Outdoor
• Format: Others
• Published: BYU ScholarsArchive 2007
• Subjects: Vapor phase; Cu; Sn; Co; Ag; Au; alloys; Vesuvius; Kilauea; Etna; Stromboli; vapor transport of metals; vapor phase deposition; chlorine; chlorine transport; Geology
• Online Access: https://scholarsarchive.byu.edu/etd/1406; https://scholarsarchive.byu.edu/cgi/viewcontent.cgi?article=2405&context=etd

Metallic bronze-Co-Ag alloys ranging from1-90 µm have been discovered in bomb and lava vesicles from the mafic volcanoes of Kilauea in Hawaii and Vesuvius, Stromboli and Etna in Italy. It is inferred that the metals for these alloys were transported (in part) as chloride complexes, and that the metal ratios in the alloys may be a function of S/Cl. Alloy compositions in each system are extremely heterogeneous with Co concentrations from 1% to 94%, Cu from 2% to 89%, Sn from 1% to 22% and Ag from 0.5% to 42%. Maximum abundances (in wt%) of other trace or minor elements are, Fe (3.0), Zn (0.11), As (0.50), Pd (0.05), Pt (0.05), Au (0.05), Hg (0.10) and Pb (.13) Spot analyses and element maps of alloy grains reveal that three major exsolved components exist. They are bronze, Co, and Ag. Kilauean alloys are dominantly Cu-Sn (bronze) with little Co and Ag while a systematic decrease in the bronze component and an increase in Co occurs in grains from Stromboli to Etna to Vesuvius. Element maps show a covariance of Cu and Sn while Co and Ag concentrations vary independently. Element maps of the alloys also reveal that chlorides are occasionally present in the same vesicles as the alloys. Sulphur content of the metal alloys rarely exceed about 0.4 wt%. Electron back-scatter diffraction (EBSD) was employed for lattice characterization of the exsolved phases and shows a FCC structure for the Cu-Sn section of the alloys. Cu-Sn alloys high in Sn are successfully indexed using the Cu6Sn5 pattern (hexagonal), even though the Sn:Cu ratio of our alloys is considerably lower than 5:6. Cu-Sn alloys containing significant subequal amounts of Co and Fe (≈5 wt% each) indexes as body-centered cubic (BCC). The presence of alloys suggests metal transport as complexes in a vapor phase before being reduced to native metals. Our current model for the origin of the alloys suggests that the metals are transported to vesicles as chlorides and then deposited as sulfides and/or native metals. Oxidation and removal of most of the S then occurs. This data suggests that in some circumstances Cu-Sn-Co and Ag are readily partitioned into escaping magmatic volatiles during quenching of mafic magma. Further examination into vesicle-hosted alloys may confirm that the ratio of Cu, Ag, Au, Zn, and Pb in vesicles reflects the ratio of available metals present in the magma and in subsequent ore deposits.