Development of a laser ablation ICP-MS method for the analysis of fluid inclusions associated with volcanogenic massive sulfide deposits

There is increasing acceptance of the presence of variable magmatic contributions to the mineralizing fluids in the formation of volcanogenic massive sulfide (VMS) deposits. The world-class Windy Craggy Cu-Co-Au deposit (>300 MT @ 2.12 wt% Cu) in northwestern British Columbia is of interest because, unlike most VMS deposits, fluid inclusions in quartz from within the deposit range from relatively low to intermediate salinity (most 6–16 wt% equivalent). In this study we used an excimer (193 nm) laser ablation system interfaced to a quadrupole inductively coupled plasma mass spectrometer to quantify key metals and metalloids that are considered by many to be indicative of magmatic contributions to hydrothermal ore deposits. Although LA-ICP-MS signals from these low-salinity inclusions are highly transient, we were able to quantify Na, Mg, K, Ca, Mn, Fe, Co, Cu, Zn, Sr, Sn, Ba, Ce, Pb and Bi consistently – of the 34 elements that were monitored. Furthermore, Cl, Sb, Cd, Mo, Rb, Br and As were also measured in a significant number of inclusions. Comparison of the fluid inclusion chemistry with unaltered and altered mafic volcanic and sedimentary rocks and mineralized samples from the deposit indicate that enrichment in the main ore metals (Cu, Zn, Fe, Pb) in the inclusions reflects that of the altered rocks and sulfides. Metals and metalloids that may indicate a magmatic contribution typically show much greater enrichments in the fluid inclusions over the host rocks at the same Cu concentration; in particular Bi, Sn and Sb are significantly elevated when compared to the host rock samples. These data are consistent with the ore-forming fluids at Windy Craggy having a strong magmatic contribution. Supplementary material: fluid inclusion data for temperature of homogenization and salinity, and full analytical results for laser ablation ICP-MS analyses of individual inclusions for the two analytical sessions are available at https://doi.org/10.6084/m9.figshare.c.5443094