Characterization and genesis interpretation of charcoal-bearing concretions from the early Eocene Ione Formation, CA
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Charcoal core concretions have been discovered in the kaolinitic soil horizons of the Ione formation (early Eocene epoch ~52Ma BP). It is thought that the Ione Formation in the Ione Basin was deposited in delta and estuarine waters that were subsequently exhumed and exposed to a warmer, humid, tropical-like environment during the early Eocene. The formation of concretions is indicative of seasonal dryness, and the charcoal cores are evidence of wildfires and of the existence of a forest ecosystem. The mineral outer shells of the concretions have been characterized by powder X-ray diffraction, Electron Microprobe and Laser Ablation Quadruple Mass Spectrometry (LA-ICP-MS). Micro-computed tomography (MCT) scans indicate that these concretions have at least three distinct shells and a inner core with fragments of charcoal without apparent internal organization. The outer shell is mainly composed of a layered mix of kaolinite, quartz, goethite, hematite and birnessite. Some pyrite and jarosite have also been found, which could indicate that goethite may be post-depositional and a product of the bacteria-mediated oxidation of pyrite. The central shell has a similar composition, but with a higher content of iron oxyhydroxides and jarosite. The inner cores of the concretions are mainly composed of a mixture of kaolinite and quartz which correspond to the layer in which the concretions were found. The concretion cores contain loose charcoal fragments in a unsolidified kaolinite matrix. The charcoal fragments have been characterized by Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), C/N isotope analysis, and Synchrotron radiation FTIR (SR-FTIR). Analysis of the ATR-FTIR spectra showed significant absorbance peaks at wavenumbers that coincided with the chemical functionality of other wood biochars. Charcoal from different concretions display (n =12) extremely similar spectra which suggest that they were originated from similar species and probably during the same event. The study of the microscopic structure of selected charcoal pieces by SR-FTIR suggests that despite their age, the internal structure was preserved. We obtained an average 13C value of -22.79 ( 1.7, n = 12), which correspond to a C3-like photosynthetic pathway. The latter is also confirmation of the good state of preservation of this material and to the best of our knowledge constitutes the first C-isotopic record on this kind of material for the Eocene epoch.
