The Isotope Geochemistry of Zinc and Copper

Copper, a native metal found in ores, is the principal metal in bronze and brass. It is a reddish metal with a density of 8920 kg m−3. All of copper’s compounds tend to be brightly colored: for example, copper in hemocyanin imparts a blue color to blood of mollusks and crustaceans. Copper has three oxidation states, with electronic configurations of Cu([Ar]3 d 104 s 1), Cu+([Ar]3 d 10), and Cu2+([Ar]3 d 9). Cu does not react with aqueous hydrochloric or sulfuric acids, but is soluble in concentrated nitric acid due to its lesser tendency to be oxidized. Cu(I) exists as the colorless cuprous ion, Cu+. Cu(II) is found as the sky-blue cupric ion, Cu2+. The Cu+ ion is unstable, and tends to disproportionate to Cu and Cu2+. Nevertheless, Cu(I) forms compounds such as Cu2O. Cu(I) bonds more readily to carbon than Cu(II), hence Cu(I) has an extensive chemistry with organic compounds. In aqueous solutions, Cu2+ ion occurs as an aquacomplex. There is no clearly predominant structure among the four-, five-, and six-fold coordinated Cu(II) species (Chaboy et al. 2006). Hydrated Cu(II) ion has been represented as the hexaaqua complex Cu(H2O)62+, which shows the Jahn–Teller distortion effect (Sherman 2001; Bersuker 2006), whereby the two Cu–O distances of the vertical axial bond (Cu–Oax) are longer than four Cu–O distances in the equatorial plane (Cu–Oeq). The Jahn–Teller effect lowers the symmetry of Cu(H2O)62+ from octahedral Th to D2h. The sixfold coordination of hydrated Cu(II) species is questioned by a finding of fivefold coordination (Pasquarello et al. 2001; Chaboy et al. 2006; Little et al. 2014b …