Enrichment of chalcophile elements in seawater accompanying the end-Cretaceous impact event

Chalcophile elements are enriched in the Cretaceous–Paleogene (KPg) boundary clays from Stevns Klint, Denmark. As the concentrations of Cu, Ag, and Pb among several chalcophile elements such as Cu, Zn, Ga, As, Ag, and Pb are correlated with those of Ir, we suggest that these elements were supplied to the oceans by processes related to the end-Cretaceous asteroid impact. Synchrotron X-ray fluorescence images revealed that Cu and Ag exist as trace elements in pyrite grains or as 1–10-µm-sized discrete phases specifically enriched in Cu or Ag. The difference in carrier phases might depend on the materials that transported these elements to the seafloor. Based on their affinities with Cu, Ag, and Ir, iron oxides/hydroxides and organic matter were identified as the potential carrier phases that supplied these elements to the seafloor. Chalcophile elements adsorbed on iron oxides/hydroxides might have been released during reductive dissolution of iron oxides/hydroxides and incorporated into the pyrite produced simultaneously with the reductive dissolution of iron oxides/hydroxides. Both iron oxides/hydroxides and chalcophile elements were possibly released from the KPg target rocks (i.e., sedimentary rocks and/or basement crystalline rocks) by impact heating. Elements with a high affinity to organic matter would have been released upon its degradation and then converted into discrete minerals because of the deficiency in Fe ions. As such discrete minerals include the elements that form acid soluble sulfides such as Cu, Ag, and Pb, enrichment of these elements might have been induced by the intense acid rain just after the end-Cretaceous asteroid impact.