A laser ablation inductively coupled plasma mass spectrometry study of the distribution of chalcophile elements among sulfide phases in sedimentary and magmatic rocks of the Duluth Complex,Minnesota, USA

Nickel-copper sulfide deposits occur in the basal unit of the Partridge River Intrusion, Duluth Complex (Minnesota, USA). Many lines of evidence suggest that these sulfides are formed after assimilation of the proterozoic S-rich black shales, known as the Bedded Pyrrhotite Unit. In addition to S, black shales are enriched in Te, As, Bi, Sb and Sn (TABS) and the basaltic magma of the intrusion is contaminated by the partial melt of the black shales. The TABS are chalcophile and together with the platinum-group elements, Ni and Cu partitioned into the magmatic sulfide liquid that segregated from the Duluth magma. The TABS are important for the formation of platinum-group minerals (PGM) thus their role during crystallization of the base metal sulfide minerals could affect the distribution of the PGE. However, the concentrations of TABS in magmatic Ni-Cu-PGE deposits and their distribution among base metal sulfide minerals are poorly documented. In order to investigate whether the base metal sulfide minerals host TABS in magmatic Ni-Cu-PGE deposits, a petrographic and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) study has been carried out on base metal sulfide and silicate phases of the Partridge River Intrusion, Duluth Complex.Petrographic observations showed that the proportions of the base metal sulfide minerals vary with rock type. The sulfide assemblage of the least metamorphosed Bedded Pyrrhotite Unit from outside the contact metamorphic aureole consists of pyrite with minor pyrrhotite plus chalcopyrite (<5%), whereas within the contact aureole the sulfide assemblage of the Bedded Pyrrhotite Unit rocks consists dominantly of pyrrhotite (>95%) with small amount of chalcopyrite (<2%). The sulfide mineral assemblage in the xenoliths of the Bedded Pyrrhotite Unit and in the mafic rocks of the basal unit contains two additional sulfides, pentlandite and cubanite.Our LA-ICP-MS study shows that sulfides of the Bedded Pyrrhotite Unit are rich in TABS; consistent with these S-rich black shales being the source of TABS that contaminated the mafic magma. Most of the TABS are associated with sulfides and platinum-group minerals in the rocks of the Bedded Pyrrhotite Unit from the contact aureole, the Bedded Pyrrhotite Unit xenoliths and the mafic rocks of the Duluth Complex. In addition to these phases the laser maps show that silicate phases, i.e., orthopyroxene and plagioclase contain Sn and Pb respectively. In contrast, in the least metamorphosed samples of the Bedded Pyrrhotite Unit from outside the contact aureole although the pyrite contains some TABS mass balance calculations indicates that most the TABS are contained in other phases. In these rocks, galena hosts significant amounts of Te, Bi, Sb, Sn and Ag and few very small grains of Sb-rich phases were also observed. The host phases for As were not established but possibly organic compounds may have contributed.