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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 [ABSTRACT FROM AUTHOR]

Serpentinization of ultramafic rocks drives geochemical exchange between the hydrosphere, biosphere and lithosphere in surficial environments and at depth. Precious metals are implicated in these hydration reactions because of the well-known association between peridotite-hosted Au and placer platinum-group mineral (PGM) deposits sourced from serpentinized ophiolite complexes at surface. However, the distribution of precious metals in mantle rocks and their mode of occurrence at the onset of serpentinization are not well understood because early-stage features are typically obliterated with progressive hydration. Herein we report electron probe microanalysis (EPMA) and laser ablation inductively coupled mass spectrometry (LA-ICPMS) spot and mapping results for a suite of base metal sulphide (pentlandite, pyrrhotite, chalcopyrite), native metal (Cu and Fe) and Ni-Fe alloy (awaruite) from variably serpentinized peridotite and pyroxenite (Late Permian to Early Triassic Nahlin ophiolite, Cache Creek terrane; Atlin, British Columbia, Canada). Pentlandite and pyrrhotite occur with magmatic clinopyroxene and Cr-spinel as ultrafine inclusions (few μm) and as coarser interstitial base metal sulphides (≤200 μm) that are enveloped by native metal (Cu and Fe) and Ni-Fe alloy. Because native Fe- and awaruite-bearing mineral assemblages require reduced and/or low- f S 2 conditions, we suggest that these replacement textures document destabilization of base metal sulphide phases during the conversion of olivine to serpentine and magnetite. Desulphurization reactions decoupled precious metals from relict pentlandite at the microscale, with Ag, Pd, Pt and Au partitioning from sulphides into both awaruite and native metal (Cu and Fe) at concentrations up to 100s of ppm. New high-resolution LA-ICPMS maps also point to clusters of ultrafine PGM, tellurides, bismuthides and metal alloys that were either remobilized within the serpentinized mesh and/or represent the completely desulphidized product of ultrafine, intergranular base metal sulphide. Other PGE (Os and Ir) are mostly hosted within relict pentlandite and/or pyrrhotite that were preserved during incomplete desulphurization, along with lesser microscale remobilization of these elements into ultrafine veins. New whole-rock PGE (nickel-sulphide fire-assay; NiS-FA) results demonstrate that precious metal remobilization was limited to the microscale during the earliest stages of serpentinization, which, in the case of Au, is consistent with its low solubility within such reduced, low f S 2 fluids. Precious metal mobility during the early stages of serpentinization may therefore depend on the stability of Ni-Fe alloy, native metal (Cu and Fe) and PGM. Progressive serpentinization, complete replacement of olivine and destabilization of the reduced, low- f S 2 mineral assemblage likely represents an important process to liberate, transport and concentrate precious metals within more oxidized and/or sulphur-bearing fluids in surficial and deep subduction environments. • Alloy and native metal replace base metal mantle sulphide during serpentinization. • Osmium and iridium mostly immobile during serpentinization. • Gold, silver, platinum and palladium partition into alloy and native metal. • Precious metal remobilization mostly limited to the microscale. • New LA-ICPMS geochemical imaging method and data integration tools. [ABSTRACT FROM AUTHOR]

The lithospheric mantle should be depleted in base- and precious-metals as these elements are transferred to the crust during partial melting. However, some melt-depleted mantle peridotites are enriched in these ore-forming elements. This may reflect re-fertilization of the mantle lithosphere and/or sequestering of these elements by residual mantle phase(s). Both processes remain poorly understood because of the low abundances of incompatible elements in peridotite and the nugget-like distribution of digestion-resistant mantle phases that pose analytical challenges for conventional geochemical methods. Herein we report new major and trace element concentrations for a suite of mantle peridotite and pyroxenite samples from the Late Permian to Middle Triassic Nahlin ophiolite (Cache Creek terrane, British Columbia, Canada) using Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICPMS) analysis of nanoparticulate powders and olivine. Compatible to moderately incompatible element concentrations suggest that Nahlin ophiolite peridotites represent residues after ≥20% melt extraction. Pyroxenite dykes and replacive dunite bands are folded and closely intercalated with residual harzburgite. These field relationships, coupled with the presence of intergranular base metal sulphide, clinopyroxene and Cr-spinel at the microscale, point to percolating melts that variably re-fertilized melt-depleted mantle peridotite. Radiogenic Pb (206Pb/204Pb = 15.402–19.050; 207Pb/204Pb = 15.127–15.633; 208Pb/204Pb = 34.980–38.434; n = 45) and Os (187Os/188Os 0.1143–0.5745; n = 58) isotope compositions for a subset of melt-depleted peridotite samples further support metasomatic re-fertilization of these elements. Other ore-forming elements are also implicated in these metasomatic reactions because some melt-depleted peridotite samples are enriched relative to the primitive mantle, opposite to their expected behaviour during partial melting. New LA-ICPMS analysis of fresh olivine further demonstrates that a significant proportion of the highly incompatible element budget for the most melt-depleted rocks is either hosted by, and/or occurs as trapped inclusions within, the olivine-rich residues. Trapped phases from past melting and/or re-fertilization events are the preferred explanation for unradiogenic Pb isotope compositions and Paleozoic to Paleoproterozoic Re-depletion model ages, which predate the Nahlin ophiolite by over one billion years. [ABSTRACT FROM AUTHOR]