ABSTRACT. Chemical and structural similarities between poorly preserved charcoal and its contaminants, as well as low radiocarbon concentrations in old samples, complicate 14 C 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.
Flowering plants possess mechanisms that stimulate positive emotional and social responses in humans. It is difficult to establish when people started to use flowers in public and ceremonial events because of the scarcity of relevant evidence in the archaeological record. We report on uniquely preserved 13,700–11,700-y-old grave linings made of flowers, suggesting that such use began much earlier than previously thought. The only potentially older instance is the questionable use of flowers in the Shanidar IV Neanderthal grave. The earliest cemeteries (
ca
. 15,000–11,500 y ago) in the Levant are known from Natufian sites in northern Israel, where dozens of burials reflect a wide range of inhumation practices. The newly discovered flower linings were found in four Natufian graves at the burial site of Raqefet Cave, Mt. Carmel, Israel. Large identified plant impressions in the graves include stems of sage and other
Lamiaceae
(
Labiatae
; mint family) or
Scrophulariaceae
(figwort family) species; accompanied by a plethora of phytoliths, they provide the earliest direct evidence now known for such preparation and decoration of graves. Some of the plant species attest to spring burials with a strong emphasis on colorful and aromatic flowers. Cave floor chiseling to accommodate the desired grave location and depth is also evident at the site. Thus, grave preparation was a sophisticated planned process, embedded with social and spiritual meanings reflecting a complex preagricultural society undergoing profound changes at the end of the Pleistocene.
The maximum operating temperature of conventional thermal barrier coatings based on yttria-stabilized zirconia is ultimately limited by de-stabilization of the “non-transformable” t phase, rendering it susceptible to the monoclinic transformation upon cooling. Investigations into alternative thermal barrier oxide compositions suggest that Yb offers superior t stability compared with Y, Sc and larger rare earth cations at the same concentration. The present study sheds light on this behavior by comparing the microstructure evolution of specimens with 7.6 and 11.4 % MO1.5 (M = Y or Yb) heat treated at 1450 °C for times up to 512 h. X-ray diffractometry and transmission electron microscopy revealed that the onset of partitioning occurs at short times but then the compositions of the phases evolve slowly over time until sufficient stabilizer is depleted from the t phase to render it transformable. Substitution of Yb for Y delays the onset of monoclinic formation. Differences in the transformation behavior of the Y and Yb rich phases on cooling provide new insight and suggest refinements to the current thermodynamic models for the binary ZrO2 – MO1.5 systems are needed.
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