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Anthropogenic calcite is a form of calcium carbonate produced through pyrotechnological activities, and it is the main component of materials such as lime binders and wood ash. This type of calcite is characterized by a significantly lower degree of crystallinity compared with its geogenic counterparts, as a result of different formation processes. The crystallinity of calcite can be determined using infrared spectroscopy in transmission mode, which allows decoupling particle size effect from atomic order and thus effectively distinguish anthropogenic and geogenic calcites. On the contrary, Raman micro-spectroscopy is still in the process of developing a reference framework for the assessment of crystallinity in calcite. Band broadening has been identified as one of the proxies for crystallinity in the Raman spectra of geogenic and anthropogenic calcites. Here we analyze the full width at half maximum of calcite bands in various geogenic and anthropogenic materials, backed against an independent crystallinity reference based on infrared spectroscopy. Results are then used to assess the crystallinity of anthropogenic calcite in archaeological lime binders characterized by different states of preservation, including samples affected by the formation of secondary calcite, and tested on micromorphology thin sections in which lime binders are embedded in sediments.

Electron spin resonance coupled with uranium-series dating (ESR/U-series) of carbonate hydroxyapatite in tooth enamel is the main technique used to obtain age determinations from Pleistocene fossils beyond the range of radiocarbon dating. This chronological information allows to better understand diachronic change in the palaeontological record, especially with regard to the evolution of the genus Homo . Given the relative paucity of human teeth at palaeontological and archaeological localities, ESR/U-series is widely applied to the teeth of ungulate species. However, the accuracy of ESR/U-series ages is greatly affected by the incorporation of uranium in the enamel during burial in sediments. It has been shown that uranium content is positively correlated with an increased degree of atomic order in carbonate hydroxyapatite crystals, the latter determined using infrared spectroscopy. Here we present a reference infrared spectral library of tooth enamel from African ungulates, based on the grinding curve method, which serves as baseline to track the diagenetic history of carbonate hydroxyapatite in different species and thus select the best-preserved specimens for dating.

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.

In nature, calcium carbonate (CaCO 3 ) in the form of calcite and aragonite nucleates through different pathways including geogenic and biogenic processes. It may also occur as pyrogenic lime plaster and laboratory-precipitated crystals. All of these formation processes are conducive to different degrees of local structural order in CaCO 3 crystals, with the pyrogenic and precipitated forms being the least ordered. These variations affect the manner in which crystals interact with electromagnetic radiation, and thus formation processes may be tracked using methods such as X-ray diffraction and infrared spectroscopy. Here we show that defects in the crystal structure of CaCO 3 may be detected by looking at the luminescence of crystals. Using cathodoluminescence by scanning electron microscopy (SEM-CL) and laser-induced fluorescence (LIF), it is possible to discern different polymorphs and their mechanism of formation. We were thus able to determine that pyrogenic calcite and aragonite exhibit blue luminescence due to the incorporation of distortions in the crystal lattice caused by heat and rapid precipitation, in agreement with infrared spectroscopy assessments of local structural order. These results provide the first detailed reference database of SEM-CL and LIF spectra of CaCO 3 standards, and find application in the characterization of optical, archaeological and construction materials.

The relative chronology of the Aegean Iron Age is robust. It is based on minute stylistic changes in the Submycenaean, Protogeometric and Geometric styles and their sub-phases. Yet, the absolute chronology of the time-span between the final stages of Late Helladic IIIC in the late second millennium BCE and the archaic colonization of Italy and Sicily toward the end of the 8(th) century BCE lacks archaeological contexts that can be directly related to events carrying absolute dates mentioned in Egyptian/Near Eastern historical sources, or to well-dated Egyptian/Near Eastern rulers. The small number of radiocarbon dates available for this time span is not sufficient to establish an absolute chronological sequence. Here we present a new set of short-lived radiocarbon dates from the sites of Lefkandi, Kalapodi and Corinth in Greece. We focus on the crucial transition from the Submycenaean to the Protogeometric periods. This transition is placed in the late 11(th) century BCE according to the Conventional Aegean Chronology and in the late 12(th) century BCE according to the High Aegean Chronology. Our results place it in the second half of the 11(th) century BCE.

Accurate radiocarbon (14C) dating of lime mortars requires a thorough mineralogical characterization of binders in order to verify the presence of carbon-bearing contaminants. In the last 20 years, cathodoluminescence (CL) has been widely used for the identification of geologic calcium carbonate (CaCO3) aggregates and unreacted lime lumps within the particle size fraction selected for carbon recovery. These components are major sources of older and younger carbon, respectively, and should be removed to obtain accurate age determinations. More recently, laser-induced fluorescence (LIF) has provided another means of investigating the preservation state and composition of CaCO3 binders. Considered the growing interest of the mortar dating community in the latest advancements of these analytical methods, here we review the principles of CL and LIF of CaCO3, their instrument setup, and their application to the characterization of ancient lime mortars used for 14C dating. In addition, we provide examples of SEM-CL and LIF analyses using high-resolution instrumentation, we discuss current issues and propose future lines of research.

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.

Pyrotechnological activities leave many traces in the archaeological record, most notably ash, which is the powdery residue of the combustion of organics such as wood. These traces have provided important insights into the biological and cultural evolution of humans. Given the common occurrence of ash layers at archaeological sites, the charred remains embedded within these features have been regularly targeted for radiocarbon dating. However, often charcoal does not preserve in sediments, and only the mineral fraction of ash is left. The latter is composed of calcium carbonate derived from the thermal decomposition of calcium oxalates produced by the plants used as fuel, and in principle can be dated using radiocarbon. Past attempts have shown that pyrogenic calcium carbonate in the form of calcite does not always preserve the radiocarbon content of the original plant, and that it is prone to recrystallization. Recently, pyrogenic aragonite (a metastable polymorph of calcium carbonate) in archaeological ash has produced accurate radiocarbon age determinations because its crystals did not recrystallize over time. In this paper, we report on the radiocarbon dating of an ash layer rich in aragonite identified at Tell es-Safi/Gath (Israel). Using a combination of infrared spectroscopy and micro-spectroscopy, X-ray diffraction, scanning electron microscopy, phytolith analysis, micromorphology, and radiocarbon dating, we reconstructed the formation processes of the combustion feature and showed that most of the pyrogenic aragonite crystals in the ash layer exchanged carbon with the environment, and thus cannot be considered a closed system suitable for dating. Therefore, we proposed an improved extraction method to isolate the smallest crystals of pyrogenic aragonite and calcite, which are more likely to keep their original isotopic composition based on independent age controls from the same depositional context.

Obtaining accurate age determinations from minerals in archaeological ash is a major unsolved issue in radiocarbon (14C) dating. This is because the original 14C content of calcite, the main component of ash, is altered by isotopic exchange. Pyrogenic aragonite, another mineral phase recently discovered in ash, might preserve its 14C signature through time. Using a new method based on density separation and step combustion, we were able to isolate and date aragonitic ash from an archaeological destruction horizon of known age. Here we show that the 14C age of aragonite matches the age of the destruction horizon. Our results demonstrate that pyrogenic aragonite is a short-lived material suitable for 14C dating and directly related to human activities involving the use of fire, thus bearing major implications for the establishment of absolute chronologies for the past 50,000 yr.

Lovedale is the only open-air Middle Stone Age site in the Free State dated to early Marine Isotope Stage 4. Framing the chronology of this context, especially by taking into account diagenetic processes that may affect age results, is thus fundamental to understand modern human dynamics in the interior of South Africa. In a recent study, we investigated the effect of diagenesis on teeth samples collected for combined electron spin resonance and uranium-series dating at the site. By combining different characterisation methods, it was shown that the uranium (U) content of enamel varied in the specimens, and that it was positively correlated with the degree of crystallinity of carbonate hydroxyapatite, whereby larger amounts ofUare associated with highly crystalline enamel. The large variability in U content was in contrast with the fact that teeth were found in the same depositional context. High levels of U in some of the samples limit the accuracy of age determinations, since several uncertainties remain regarding U uptake and leaching, which both affect dose rate modelling. In such complex cases, calculating minimum ages is the most cautious option. Newsamples were collected at the site during the excavation campaign in 2021. Enamel was analysed using Fourier transform infrared spectroscopy and scanning electron microscopy coupled with cathodoluminescence in order to determine its degree of atomic order and the presence of foreign ions (especially U), and the correlation between the two. We discuss here the contribution of U-uptake modelling on the age calculation, and present new ESR ages calculated assuming an early uptake of U, ranging from 84 ± 9 ka to 56 ± 5 ka. Together with previous ages obtained on the gravel layer, a weighted mean age of 64 ka can be used as a minimum age estimate for the base of the sequence.