Copper isotope ratios in magmatic and hydrothermal ore-forming environments

Multi-collector inductively coupled plasma mass spectrometry now provides for precise and accurate measurements of Cu isotope ratios. Copper minerals prepared by direct dissolution with and without chromatographic purification yield identical Cu isotope ratios within analytic precision of about 0.04 parts per thousand (I sigma). Cut isotope ratios have been measured for copper minerals from worldwide magmatic and hydrothermal copper deposits, and for several weathered deposits. Natural variations in delta(65)Cu values, relative to NBS976, range over 9 parts per thousand. Chalcopyrite samples from mafic intrusions lie within a narrow range of about 1.5 parts per thousand, and most cluster tightly between -0.10 parts per thousand and -0.20 parts per thousand. This range lies within the broader black smoker chalcopyrite and iron meteorite ranges, and possibly represents a bulk mantle Cu isotope ratio. Most values for hydrothermal native copper from the Michigan native copper district also show a narrow range just larger than 0.1 parts per thousand and suggest a common homogeneous source for Cu in this large hydrothermal system. Later copper sulfide and arsenide minerals from this district range to values more than 2 parts per thousand lower than native copper. Ratios for chalcopyrite and bornite from moderate to high-temperature porphyry, skarn, and replacement deposits as a group and within individual deposits exhibit a broad range of values. Variations of nearly I parts per thousand are observed over distances on the order of I in. In some cases, these variations may result from multiple mineralization events or copper remobilization during retrograde or later hydrothermal activity. Fractionations between chalcopyrite and bornite, where they occur in the same sample or in related samples, cluster near 0.4 parts per thousand, suggesting equilibrium Cu isotope fractionation between them at moderate temperatures. In addition, weathering of hydrothermal copper minerals produces a wide range of values in secondary copper phases. In the supergene environment, cuprite typically has higher values than associated native copper. Therefore, redox states appear to exert a significant control over fractionation at low temperatures. Significant questions remain to be answered. Before the source of copper in hydrothermal environments can be fully addressed, source reservoir Cu ratios need to be determined, and chemical and physical factors that control Cu isotope fractionation must be quantitatively defined. (C) 2003 Elsevier B.V. All rights reserved.