New highlights on phytolith structure and occluded carbon location: 3-D X-ray microscopy and NanoSIMS results
Abstract. Phytoliths contain occluded organic compounds called phytC. Recently, phytC content, nature, origin, paleoenvironmental meaning and impact in the global C cycle has been the subject of increasing debate. Inconsistencies were fed by the scarcity of in-situ characterization of phytC in phytoliths. Here we reconstructed at high spatial resolution the 3-dimensional (3-D) structure of harvested grass short cell (GSC) phytoliths using 3-D X-ray microscopy. While this technic has been widely used for 3-D reconstruction of biological systems it has never been applied in high resolution mode to silica particles. Simultaneously, we investigated the location of phytC using Nano-scale Secondary Ion Mass Spectrometry (NanoSIMS). Our data evidenced that the silica structure contains micrometric internal cavities. These internal cavities were sometimes observed isolated from the outside. Their opening may be an original feature or may result from a beginning of dissolution of silica during the chemical extraction procedure, mimicking the progressive dissolution process that can happen in natural environments. The phytC that may originally occupy the cavities is thus susceptible to rapid oxidation. It was not detected by the nanoSIMS technique. To the contrary another pool of phytC, continuously distributed in and protected by the silica structure was evidenced. Its N/C ratio (0.27) is in agreement with the presence of amino acids. These findings allowed to discuss discrepancies in phytC quantification, evaluate phytC accessibility to oxidation, and reassess the paleo-environmental meaning of opaque features observed in phytoliths by natural light (NL) microcopy. They also should help to reappraise the significance of phytC in the global C cycle.