Natural nanoparticles of the Critical Element tellurium Revision 1

Tellurium (Te) is a Critical Element that is toxic to microorganisms and humans alike, most notably in its soluble oxyanionic forms. To date, the biogeochemical behaviour of Te in Earth’s surface environment is largely unknown. Here, we report the discovery of elemental Te nanoparticles (Te NPs) in regolith samples using Single-Particle Inductively Coupled Plasma Mass Spectroscopy. Tellurium NPs were detected in both proximal and distal locations (bulk concentrations >4 ppm) relative to weathering Te ores. Synchrotron X-ray Fluorescence Mapping and X-ray Absorption Spectroscopy showed that bulk Te in the regolith is generally associated with Fe (oxyhydr)oxides and clay minerals, and mostly found in the oxidation states +IV and +VI. Although Te NPs account for less than 2 mole‰ of Te in our samples, their detection provides evidence for the active biogeochemical cycling of Te in surface environments. Te NPs are reactive and are likely to have formed in situ in distal samples, most likely via microbially-mediated reduction. Hence, the presence of Te NPs indicates the potential for release of toxic soluble forms of Te even in environments where most Te is “fixed” in forms such as Fe (oxyhydr)oxides that have low solubility and poor bioavailability. • Tellurium nanoparticles detected in supergene environments by SP-ICP-MS • Te nanoparticles detected in both proximal and distal (>100 m from source) samples • Mixed oxidation state of bulk Te (+IV/+VI) regardless of Te concentration • Te nanoparticles form less than 2‰ total Te, but represent a key reduced Te sink • Detection of distal Te nanoparticles suggests in situ biogenic formation