• Structural Characterization of Charcoal Exposed to High and Low pH: Implications for 14C Sample Preparation and Charcoal Preservation

      Rebollo, N. R.; Cohen-Ofri, I.; Popovitz-Biro, R.; Bar-Yosef, O.; Meignen, L.; Goldberg, P.; Weiner, S.; Boaretto, E. (Department of Geosciences, The University of Arizona, 2008-01-01)
      Chemical and structural similarities between poorly preserved charcoal and its contaminants, as well as low radiocarbon concentrations in old samples, complicate 14C age determinations. Here, we characterize 4 fossil charcoal samples from the late Middle Paleolithic and early Upper Paleolithic strata of Kebara Cave, Israel, with respect to the structural and chemical changes that occur when they are subjected to the acid-base-acid (ABA) treatment. Differential thermal analysis and TEM show that acid treatment disrupts the structure, whereas alkali treatment results in the reformation of molecular aggregates. The major changes are ascribed to the formation of salt bridges at high pH and the disruption of the graphite-like crystallites at low pH. Weight losses during the treatments are consistently greater for older samples, implying that they are less well preserved. Based on the changes observed in vitro due to pH fluctuations, various methods for removing contamination, as well as a mechanism for preferential preservation of charcoal in nature, are proposed.
    • Towards a Deeper Understanding of How Carbonate Isotopes (14C, 13C, 18O) Reflect Environmental Changes: A Study with Recent 210Pb-Dated Sediments of the Plitvice Lakes, Croatia

      Horvatinčić, Nada; Barešić, Jadranka; Babinka, Slavica; Obelić, Bogomil; Krajcar Bronić, Ines; Vreča, Polona; Sucrow, Axel (Department of Geosciences, The University of Arizona, 2008-01-01)
      Five short cores (top 40-45 cm of sediment) from 4 lakes of the Plitvice Lakes system (Croatia) were measured for 210Pb, 137Cs, a14C, 13C, and 18O in order to study the influence of environmental changes on the sediment system in small and large lakes. Sediment chronology based on the constant flux (CF) 210Pb model was the most reliable. Lake sediments consisted mainly of autochthonous carbonates with higher sedimentation rates in small lakes. Sediments from 2 large lakes, Proće and Kozjak, showed constant stable isotope profiles for the carbonate fraction and full agreement between the 137Cs and 210Pb chronologies. Sediments from 2 small lakes, Gradinsko and Kaluderovac, showed synchronous increases in 14C and 13C and disturbed 137Cs records. All lakes showed an increase in a14C in the carbonate sediments above the first occurrence of 137Cs, which was interpreted as a damped (~10 pMC increase in a14C) and decades-delayed consequence of the bomb-induced increase in a14C in atmospheric CO2. For the small lakes, increased 13C in the last 2 decades and part of the a14C increase is probably due to an increase in primary productivity, which enhanced biologically induced calcite precipitation with concomitant changes in the carbon isotopic composition of carbonate sediments. 13C values of a near-shore sediment core close to the confluence of one of the tributaries of Lake Kozjak showed that the carbonates in this core are a mixture of autochthonous and eroded allochthonous mineral carbonate. This core had a higher fraction of organic material. The sedimentation rate at this core site was high, but rates could not be quantified by 210Pb, 137Cs, or 14C.