Lime plaster and mortar are pyrotechnological materials that have been employed in constructions since prehistoric times. They may nucleate as calcite and/or aragonite under different environmental settings. In nature, aragonite and calcite form through biogenic and geogenic processes that lead to different degrees of atomic order. The latter is a result of defects in the crystal lattice, which affect the properties of crystals, including their interaction with infrared light. Using Fourier transform infrared spectrometry (FTIR) with the KBr pellet method, it is possible to exploit these differences and assess the degree of atomic order of aragonite and calcite crystals and thus their mechanisms of formation. Here we use FTIR to characterize the degree of short-range atomic order of a pyrogenic form of aragonite recently observed in experimental and archaeological lime binders. We show that pyrogenic aragonite has a unique signature that allows its identification in archaeological sediments and lime binders of unknown origin. Based on these results, we developed a new FTIR-based method to assess the integrity and degree of preservation of aragonite and calcite when they occur together in the same material. This method allowed a better assessment of the diagenetic history of an archaeological plaster and finds application in the characterization of present-day conservation materials, such as lime plaster and mortar, where different polymorphs may nucleate and undergo recrystallization processes that can alter the mechanical properties of binders.
14 June 2021 in Proceedings of the National Academy of Sciences
Significance: The Initial Upper Paleolithic (IUP) marks a distinct cultural change possibly related to Homo sapiens dispersals into Eurasia. New radiocarbon and optically stimulated luminescence dates from the recent excavations at Boker Tachtit, Negev, Israel, show that the IUP starts as early as around 50,000 y ago, and the later IUP phase dates to 48,000 y ago. Thus, the Late Middle Paleolithic (MP) and early IUP populations both inhabited the Negev 50,000 y ago. The Negev later IUP phase and the Early UP of the Eastern Mediterranean woodland are contemporaneous. These results also show that the MP to UP transition was a fast-evolving process.
1 January 2020 in Science of The Total Environment
The Arf1-directed GTPase-activating protein ArfGAP1 is a Golgi-localized protein that controls the dynamics of the COPI coat of carriers that mediate transport in the endoplasmic reticulum-Golgi shuttle. Previously the interaction of ArfGAP1 with the Golgi was allocated to a portion of the non-catalytic, carboxyl part of the protein, but the mechanism of this interaction has not been established. In this study we identify a short stretch in the non-catalytic part of ArfGAP1 (residues 204–214) in which several hydrophobic residues contribute to Golgi localization. Even single alanine replacement of two of these residues (Leu-207 and Trp-211) strongly diminished Golgi localization. Mutations in the hydrophobic residues also diminished the in vitro activity of ArfGAP1 on Arf1 bound to Golgi membranes. The stretch containing the hydrophobic residues was recently shown to mediate the binding of ArfGAP1 to loosely packed lipids of highly curved liposomes (Bigay, J., Casella, J. F., Drin, G., Mesmin, B., and Antonny, B. (2005) EMBO J. 24, 2244–2253). Whereas short fragments containing the hydrophobic stretch were not Golgi-localized, a proximal 10-residue in-frame insertion that is present in new ArfGAP1 isoforms that we identified in brain and heart tissues could confer Golgi localization on these fragments. This localization was abrogated by alanine replacement of residues Phe-240 or Trp-241 of the insertion sequence but not by their replacement with leucines. Our findings indicate that ArfGAP1 interacts with the Golgi through multiple hydrophobic motifs and that alternative modes of interaction may exist in tissue-specific ArfGAP1 isoforms.
Radiocarbon (14C) dating of anthropogenic carbonates (CaCO3) such as ash, lime plaster and lime mortar, has proven a difficult task due to the occurrence of a number of contaminants embedded within the CaCO3 pyrogenic binder. These include 14C-free geologic components and/or secondary phases bearing an unknown amount of 14C, and thus the alteration of the original pyrogenic isotopic signature of the material results in major age offsets when carbon recovery is performed through acid hydrolysis. Here we present a characterization/quantification approach to anthropogenic carbonates that includes Fourier transform infrared spectroscopy (FTIR), X-ray diffraction, thin section petrography, thermogravimetric analysis and scanning electron microscopy coupled with high-resolution cathodoluminescence, with which we identified the pyrogenic CaCO3 fraction in an aerial lime plaster and two hydraulic mortars. The preserved pyrogenic component was then isolated by density separation and its purity checked again using FTIR. Carbon was recovered through thermal decomposition in vacuum. The resulting 14C age matches the expected age of the lime plaster, whereas hydraulic mortars are slightly offset due to the carbonation of calcium hydroxide lumps. This approach highlights the importance of a dedicated characterization strategy prior to dating and may be applied to aerial lime plasters to obtain accurate ages.