Five smithsonite samples from locations in Germany, Mexico and Namibia have been investigated with cathodoluminescence (CL) spectroscopy and trace-element analyses. As with other carbonates, the CL properties of smithsonite are mainly controlled by Mn2+- and Fe2+-incorporation, because these elements are the most important activator and quencher species, respectively. Additional trace elements may have either a quenching effect (Cu) or have only small or no influence (Ca, Pb). A linear correlation exists between the Mn content and the intensity of the Mn-emission band in smithsonite, which can be quantified, if the Cl intensity is related to the number of moles of Mn rather than the weight fraction. A correlation between the Cl intensity and the Mn concentration, which is valid for all trigonal carbonates, is obtained from the published results of calcite, dolomite and smithsonite. Matrix effects due to the different chemical composition of the carbonate minerals seem to be of lesser importance.

A comparative cathodoluminescence (CL) spectroscopic study of extraordinarily well-preserved versus diagenetically altered Turonian (∼92 Ma before present) calcitic and aragonitic microfossils was performed to document the cathodoluminescence characteristics of two common Cretaceous carbonate producers, foraminifera and calcareous dinoflagellates. Unaltered specimens reveal a conspicuous peak in the blue CL band at ∼400 nm that has rarely been previously reported for biogenic carbonates. We interpret this luminescence as an indicative feature of the primary bio-mineralized shells of calcareous dinoflagellates and foraminifera. Orange luminescence as the second important CL emission band (∼620 nm) in calcite generally increases with diagenetic cement overgrowth and recrystallization but can also be present in unaltered material. Thus, orange CL of biogenic calcite is not an unequivocal diagenetic indicator. Accordingly, spectroscopic investigation of both the ∼400 and ∼620 nm peaks represents a more objective criterion to evaluate the degree of diagenetic alteration. The ratio of relative intensities of the blue CL versus orange CL can provide a semiquantitative measure with relative intensity ratios blue:orange >2 occurring in the least diagenetically altered microfossils. Comparison of unaltered specimens of separate species reveals elemental differences that potentially indicate species-specific biomineralization or habitats.