Impact of deformation and metamorphism on sphalerite chemistry – Element mapping of sphalerite in carbonate-hosted Zn-Pb sulfide deposits of the Kootenay Arc, southern British Columbia, Canada and northeastern Washington, USA

Sphalerites from the Kootenay Arc in British Columbia and Washington State were selected to represent three types of carbonate-hosted massive sulfide deposits, including Mississippi Valley-type (MVT), Irish-type, and fracture-controlled replacement type (FCR). These deposits were variably deformed and metamorphosed during the Cordilleran orogen. Laser ablation inductively coupled plasma mass spectrometric (LA-ICP-MS) analyses of the trace element distributions within the sphalerites are combined with petrography and sulfur isotope analyses to evaluate the influence of primary trace element signatures, along with the variable influence of post-ore metamorphism and deformation on sulfide remobilization and trace element redistribution. Mississippi Valley-type (Josephine orebodies) and Irish-type (Yellowhead orebodies) at Pend Oreille mine are only weakly deformed and recrystallized, so their sulfide minerals commonly retain primary ore textures. The sphalerite from the Irish-type deposit has positive narrow range of δ34S values (17.9–20.5‰, mean 19.2‰), and it is enriched in Ge, Tl and Pb, but depleted in Cd, Mn, and Cu relative to MVT and FCR deposits. Germanium is concentrated in dark-brown acicular-colloform bands where micro-inclusions of a germanium oxide mineral (argutite (GeO2)) and galena have been detected. Other MVT deposits of the Kootenay Arc (Reeves MacDonald, Jersey-Emerald, HB, Jackpot-Lerwick, Duncan) are more deformed and metamorphosed than the Irish-type deposit of the Pend Oreille mine and primary ore textures are only locally preserved. There is a progressive increase in deformation and degree of recrystallization from Reeves MacDonald, located away from intrusions, to deposits within the contact metamorphic aureoles of intrusions (HB, Jersey-Emerald, Jackpot-Lerwick). Sphalerite from the least metamorphosed Reeves MacDonald deposit has high Cd, Ga, Pb, and Tl contents, high Cd/Ge and Ga/In values, and the lowest δ34S values (7.4 to 11.1‰, mean 8.8‰). In contrast, sphalerites from contact metamorphosed HB, Jersey-Emerald and Jackpot-Lerwick deposits have higher δ34S values (13.3 to 28.5‰, mean 19.2‰), are enriched in Mn and Fe, with higher Zn/Cd and Mn/Fe values relative to Reeves MacDonald deposit. These enrichments and fractionations correspond to the breakdown of pyrite and pyrrhotite and the thermal annealing of sphalerite caused by contact metamorphism. Sulfide minerals from the FCR deposit (Abbott-Wagner) are undeformed (except for microfractures) and only weakly recrystallized. Sphalerite from the FCR Abbott-Wagner deposit is enriched in Cu, Ga, In, and Sn as primary source signatures relative to sphalerite from MVT and Irish-type deposits. This reflects the more complex mineral assemblage of galena, sphalerite, pyrite, chalcopyrite, and tetrahedrite in this deposit. The presence of chalcopyrite and tetrahedrite is consistent with a higher-temperature origin of the FCR deposit relative to the lower-temperature MVT and Irish-type deposits. This study demonstrates that the high spatial resolution of in-situ LA-ICP-MS analyses of trace element within sphalerites, in combination with petrography and other analytical techniques (e.g., electron microprobe, secondary ion mass spectrometry, field emission scanning electron microscopy) characterizes the behavior and distribution of trace elements in sphalerite for three deposit types and variable conditions of regional and contact metamorphism. Understanding the effects of metamorphism and deformation on trace elements can be very useful in exploration for deposits rich in critical metals.