The chemical form of silicon in marine Synechococcus

The widely distributed marine picocyanobacterium Synechococcus is found throughout the upper oceans. Recent observations that Synechococcus accumulates silicon indicate that it may influence the global cycle of this element. While diatoms, the organisms that dominate the marine Si cycle, have absolute Si requirements due to their precipitation of exoskeleton frustules composed of hydrated opal-A (i.e., biogenic silica), no requirements or biological roles are known for the Si associated with Synechococcus. Even less is known about the biochemical form(s) of Si in picocyanobacteria or whether it differs from diatomaceous silica. Using bulk X-ray absorption near-edge spectroscopy (XANES) across the Si K-edge, we investigated the chemical speciation of Si in dried Synechococcus laboratory isolates from several clades, representing both coastal and oligotrophic isolates grown at a range of Si(OH)4 concentrations. Silicon associated with Synechococcus is bound to oxygen and is spectroscopically distinct from opal-A precipitated by diatoms. The closest XANES spectral analogues found in the literature are dried Mg-Si gels precipitated under basic conditions, suggesting that some Synechococcus Si may be present in vivo as a hydrated siliceous network with Mg and/or Ca cations. Slight spectral variations across isolates and growth conditions suggest strain-specificity in Si chemistry and the potential for siliceous phases to bind organic matter.