The sinking of organic matter to the deep ocean leaves extremely low concentrations of major and trace nutrients for photosynthetic organisms at the sunlit surface. As a result, marine phytoplankton make use of alternative sources of essential elements and have evolved to substitute some elements by others in various biochemical processes. A particularly intriguing example is that of Zn, which is used in many biochemical functions but is often depleted down to picomolar concentrations in surface seawater. Laboratory data show that many phytoplankton species are able to achieve high growth rates by replacing Zn with Cd or Co in cultures. One documented biochemical replacement occurs in some carbonic anhydrases that are used in the acquisition of inorganic carbon for photosynthesis. Field data show the existence of such enzymes in surface seawater and indicate a replacement of Zn by Cd and Co in the surface waters of the eastern tropical South Pacific. Those results point at interesting opportunities for future research. ▪ The dearth of essential elements in surface seawater has caused marine phytoplankton to substitute some trace metals by others in various biochemical processes. ▪ Many species can substitute Cd and/or Co for Zn as a metal center in carbonic anhydrase enzymes that are used in the acquisition of inorganic carbon for photosynthesis. ▪ Field data show the presence of such enzymes in the sea and indicate a replacement of Zn by Cd and Co in the surface upwelling waters of the eastern tropical South Pacific. ▪ New analytical and molecular tools provide opportunities to elucidate the unusual biochemistry of marine phytoplankton.