Abstract. Plant biosilica particles (phytoliths) contain small amounts of carbon called phytC. Based on the assumptions that phytC is of photosynthetic origin and a closed system, claims were recently made that phytoliths from several agriculturally important monocotyledonous species play a significant role in atmospheric CO2 sequestration. However, anomalous phytC radiocarbon (14C) dates suggested contributions from a non-photosynthetic source to phytC. Here we address this non-photosynthetic source hypothesis using comparative isotopic measurements (14C and δ13C) of phytC, plant tissues, atmospheric CO2, and soil organic matter. State-of-the-art methods assured phytolith purity, while sequential stepwise-combustion revealed complex chemical-thermal decomposability properties of phytC. Although photosynthesis is the main source of carbon in plant tissue, it was found that phytC is partially derived from soil carbon that can be several thousand years old. The fact that phytC is not uniquely constituted of photosynthetic C limits the usefulness of phytC either as a dating tool or as a significant sink of atmospheric CO2. It additionally calls for further experiments to investigate how SOM-derived C is accessible to roots and accumulates in plant biosilica, for a better understanding of the mechanistic processes underlying the silicon biomineralization process in higher plants.
Abstract. In the rhizosphere, the uptake of low-molecular-weight carbon (C) and nitrogen (N) by plant roots has been well documented. While organic N uptake relative to total uptake is important, organic C uptake is supposed to be low relative to the plant's C budget. Recently, radiocarbon analyses demonstrated that a fraction of C from the soil was occluded in amorphous silica micrometric particles that precipitate in plant cells (phytoliths). Here, we investigated whether and to what extent organically derived C absorbed by grass roots can feed the C occluded in phytoliths. For this purpose we added 13C- and 15N-labeled amino acids (AAs) to the silicon-rich hydroponic solution of the grass Festuca arundinacea. The experiment was designed to prevent C leakage from the labeled nutritive solution to the chamber atmosphere. After 14 days of growth, the 13C and 15N enrichments (13C excess and 15N excess) in the roots, stems and leaves as well as phytoliths were measured relative to a control experiment in which no labeled AAs were added. Additionally, the 13C excess was measured at the molecular level, in AAs extracted from roots and stems and leaves. The net uptake of labeled AA-derived 13C reached 4.5 % of the total AA 13C supply. The amount of AA-derived 13C fixed in the plant was minor but not nil (0.28 and 0.10 % of total C in roots and stems/leaves, respectively). Phenylalanine and methionine that were supplied in high amounts to the nutritive solution were more 13C-enriched than other AAs in the plant. This strongly suggested that part of AA-derived 13C was absorbed and translocated into the plant in its original AA form. In phytoliths, AA-derived 13C was detected. Its concentration was on the same order of magnitude as in bulk stems and leaves (0.15 % of the phytolith C). This finding strengthens the body of evidences showing that part of organic compounds occluded in phytoliths can be fed by C entering the plant through the roots. Although this experiment was done in nutrient solution and its relevance for soil C uptake assessment is therefore limited, we discuss plausible forms of AA-derived 13C absorbed and translocated in the plant and eventually fixed in phytoliths, and implications of our results for our understanding of the C cycle at the soil–plant–atmosphere interface
We report up to 6 wt% storage of H2 at 2 atm and T = 77 K in processed bundles of single-walled carbon nanotubes. The hydrogen storage isotherms are completely reversible; D2 isotherms confirmed this anomalous low-pressure adsorption and also revealed the effects of quantum mechanical zero point motion. We propose that our postsynthesis treatment of the sample improves access for hydrogen to the central pores within individual nanotubes and may also create a roughened tube surface with an increased binding energy for hydrogen. Such an enhancement may be needed to understand the strong adsorption at low pressure. We obtained an experimental isosteric heat qst = 125 ± 5 meV. Calculations are also presented that indicate disorder in the tube wall enhances the binding energy of H2.
Raman spectra of iodine-doped single-walled carbon nanotube ͑I-SWNT͒ bundles excited with 514.5 nm were studied at room temperature and elevated pressure up to 7 GPa. The low frequency modes in I-SWNT exhibit very small pressure-induced frequency shifts, in contrast to the pressure shift of ϳ7 cm Ϫ1 /GPa ͑or larger͒ reported for the radial modes in undoped SWNT samples. This weak pressure dependence and the resonance with 514.5 nm excitation, corroborate the previous assignment of the Raman bands at ϳ110 and 175 cm Ϫ1 in I-SWNT to polyiodide chains. Furthermore, based on a comparison between the pressure behavior of the I-SWNT and undoped SWNT samples, we suggest that the I n Ϫ molecules might reside both in the interstitial channels and inside the pores of the tubes in SWNT bundles.
We report (6 wt %) storage of H2 at T=77 K in processed bundles of single-walled carbon nanotubes at P=2 atmospheres. The hydrogen storage isotherms are completely reversible. D2 isotherms confirm this anomalous low-pressure adsorption and further reveal the effects of quantum mechanical zero point motion. We propose that our post-synthesis treatment of the sample not only improves access for hydrogen to the central pores within individual nanotubes, but also may create a roughened tube surface with an enhanced binding energy for hydrogen. Such an enhancement is needed to understand the strong adsorption at low pressure. We obtain an experimental isosteric heat qst=125 ± 5 meV for processed SWNT materials.
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