Geological factors impacted cadmium availability and use as an
alternative cofactor for zinc in the carbon fixation pathways of marine
diatoms
Abstract
Transition metal cofactors are crucial for many biological processes.
Despite being primarily considered to be toxic, the transition metal
cadmium (Cd) was discovered to be a substitute for zinc (Zn) in
photosynthetic carbon fixation pathways in marine diatoms. However, it
is not known how conditions in the geosphere impacted Cd availability
and its incorporation as an alternative metal cofactor for
phytoplankton. We employed mineral chemistry network analysis to
investigate which geochemical factors may have influenced the
availability of Cd and Zn during the putative time period that
alternative Cd-based pathway evolved. Our results show that Zn minerals
are more chemically diverse than are Cd minerals, but Zn- and
Cd-containing minerals have similar mean electronegativities when
specifically considering sulfur (S)-containing species. Cadmium and zinc
sulfides are the most common Cd- and Zn-containing mineral species over
the past 500 million years. In particular, the Cd and Zn sulfides,
respectively greenockite and sphalerite, are highly abundant during this
time period. Furthermore, S-containing Cd- and Zn minerals are commonly
co-located in geologic time, allowing them to be weathered and
transported to the ocean in tandem, rather than occurring from separate
sources. We suggest that the simultaneous weathering of Cd and Zn
sulfides allowed for Cd to be a bioavailable direct substitute for Zn in
protein complexes during periods of Zn depletion. The biogeochemical
cycles of Zn and Cd exemplify the importance of the coevolution of the
geosphere and biosphere in shaping primary production in the modern
ocean.