Location, speciation, and quantification of carbon in silica phytoliths using synchrotron scanning transmission X-ray microspectroscopy

PLoS One. 2024 Apr 15;19(4):e0302009. doi: 10.1371/journal.pone.0302009. eCollection 2024.

Abstract

Phytoliths of biogenic silica play a vital role in the silicon biogeochemical cycle and occlude a fraction of organic carbon. The location, chemical speciation, and quantification of this carbon within phytoliths have remained elusive due to limited direct experimental evidence. In this work, phytoliths (bilobate morphotype) from the sugarcane stalk epidermis are sectioned with a focused ion beam to produce lamellas (≈10 × 10 μm2 size, <500 nm thickness) and probed by synchrotron scanning transmission X-ray microspectroscopy (≈100-200 nm pixel size; energies near the silicon and carbon K-absorption edges). Analysis of the spectral image stacks reveals the complementarity of the silica and carbon spatial distributions, with carbon found at the borders of the lamellas, in islands within the silica, and dispersed in extended regions that can be described as a mixed silica-carbonaceous matrix. Carbon spectra are assigned mainly to lignin-like compounds as well as to proteins. Carbon contents of 3-14 wt.% are estimated from the spectral maps of four distinct phytolith lamellas. The results provide unprecedented spatial and chemical information on the carbon in phytoliths obtained without interference from wet-chemical digestion.

MeSH terms

  • Carbon / analysis
  • Silicon Dioxide* / chemistry
  • Silicon*
  • Synchrotrons
  • X-Rays

Substances

  • Silicon Dioxide
  • Silicon
  • Carbon

Grants and funding

Authors acknowledge funding from National Council for Scientific and Technological Development – CNPq (grant 302334/2022-0) and São Paulo Research Foundation – FAPESP (grants 14/50884-5, 18/07033-5, and 20/15505-4). The funders had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscript.