Compositions of magmatic hydrothermal fluids determined by LA-ICP-MS of fluid inclusions from the porphyry copper–molybdenum deposit at Butte, MT

Abstract

We analyzed 85 fluid inclusions from seven samples from the porphyry Cu–Mo deposit in Butte, MT, using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). The Butte deposit formed at unusually great depth relative to most porphyry deposits, and fluid inclusions in deep veins trapped a low-salinity, CO 2-bearing, magmatically derived, supercritical fluid as a single aqueous phase. This fluid is interpreted to be the parent fluid that cooled, decompressed, unmixed, and reacted with wall rock to form the gigantic porphyry Cu deposit at Butte. Few previous analyses of such fluids exist. Low-salinity, aqueous fluids from the earliest veins at Butte are trapped in deep veins with biotite-rich alteration envelopes (EDM veins). These veins, and the Butte quartz monzonite surrounding them, host much of the Butte porphyry Cu mineralization. Twenty fluid inclusions in one EDM quartz vein are dominated by Na, K, Fe (from ∼0.1 to ∼1 wt.%) and contain up to 1.3 wt.% Cu. These inclusions contain only small amounts (tens of ppm) of Pb, Zn, and Mn, and typically contain Li, B, Ca, As, Mo, Ag, Sn, Sb, Ba, and W in less than detectable quantities. The abundance of Cu in early fluids indicates that a low-salinity, Cu-rich, aqueous ore fluid can be directly produced by aqueous fluid separation from a granitic magma. Similar inclusions (eight) in an early deep quartz–molybdenite vein with a K-feldspar selvage have similar compositions but contain significantly less Cu than most inclusions in the biotite-altered vein. Analyzed inclusions in both veins contain less than detectable concentrations of Mo even though one is molybdenite-bearing. Low-salinity, CO 2-bearing aqueous fluids are also trapped in pyrite–quartz veins with sericitic selvages. These veins cut both of the above vein types and contain inclusions that were trapped at lower pressure and temperature. Thirty-nine inclusions in two such veins have compositions similar to early fluids, but are enriched by up to a factor of 10 in Mn, Pb, and Zn relative to early fluids, and are slightly depleted in Fe. Many of these inclusions contain as much or more Cu than early fluids, although little chalcopyrite is found in or around pyrite–quartz veins. Eighteen halite-bearing inclusions from three veins from both chalcopyrite-bearing and barren veins with both K-silicate and sericitic selvages were analyzed as well. Halite-saturated inclusions are dominated by Na, K, Fe, and in some inclusions Ca. Whereas these inclusions are significantly enriched in Ca, Mn, Fe, Zn, and Pb, fluids in all three veins contain significantly less Cu than early, high temperature, low-salinity inclusions. Analyses of all inclusion types show that whereas bulk-salinity of the hydrothermal fluid must be largely controlled by the magma, fluid–rock interactions have a significant role in controlling fluid compositions and metal ratios. Cu concentrations range over an order of magnitude, more than any other element, in all four samples containing low-salinity inclusions. We infer that variations are the result of fluid trapping after different amounts of fluid–rock reaction and chalcopyrite precipitation. Enrichment, relative to early fluids, of Mn, Pb, and Zn in fluids related to sericitic alteration is also likely the result of fluid–rock reaction, whereby these elements are released from biotite and feldspars as they alter to sericite. In halite-bearing inclusions, concentrations of Sr, Ca, Pb, and Ba are elevated in inclusions from the pyrite–quartz vein with sericitic alteration relative to halite-bearing inclusions from unaltered and potassically altered samples. Such enrichment is likely caused by the breakdown of plagioclase and K-feldspar in the alteration envelope, releasing Sr, Ca, Pb, and Ba.