Application of chemical, physical and chemometric analytical techniques to the study of ancient ceramic oil lamps

A chemical, mineralogical and morphological characterization of 54 fragments of oil lamps found in two Spanish archaeological sites (Cordoba and Herrera de Pisuerga (Palencia)) has been performed. Flame atomic absorption and emission spectrometry were used for the determination of Al₂O₃, CaO, Fe₂O₃, K₂O, MgO, MnO, Na₂O and TiO₂ as major constituents and Cu, Cr, Ni, Pb and Zn as minor and trace selected elements. Physical, mineralogical and morphological analyses were made by using dilatometry at constant heating rate for the thermal behaviour, X-ray diffraction spectrometry for the mineralogical composition and, in a group of selected samples, scanning electron microscopy and polarizing petrographic microscopy for the observation of thin layers and mineral identification. Separations of light and heavy minerals were carried out with bromoform and X-ray diffraction analysis was applied to both fractions. Multivariate statistical analysis was used to establish correlations between variables and to deduce factors which allow the gathering of oil lamp samples in groups as a function of their composition.The results of these analyses allow the comparison among pieces and the establishment of conclusions about several aspects of their manufacture, the origin of the raw materials and the provenance of the oil lamps (local or imported). They provide information supporting certain archaeological hypothesis. For example, some oil lamps found in Herrera de Pisuerga showed a clearly different physicochemical composition. They were probably brought from Italy by the Roman Legions together with their initial furniture household.     

Archaeological wood characterisation by PY/GC/MS, GC/MS, NMR and GPC techniques

The chemical characterisation of waterlogged archaeological wood is of paramount importance in terms of understanding not only the degradation processes of wood in artistic and archaeological objects but also the development of consolidation and conservation procedures. The two different types of archaeological waterlogged wood were characterized using several analytical techniques. The analytical protocol consists in using PY/GC/MS with in situ derivatisation with hexamethyldisilazane, GC/MS of the extractives, ¹H, ¹³C and ³¹P NMR analysis, and GPC. The main results showed that one of the ancient samples was a gymnosperm wood from the Pinaceae family, whereas the other type of wood was an angiosperm. Lignin from the angiosperm was oxidised in a benzylic position of β-O-4 to give oxo functional groups, in primary alcohol moiety to give carboxylic groups. In addition, the formation of a new intermonomeric bond 5-O-4 was observed.     

Characterization of Egyptian bronze archaeological artifacts

This paper presents the results of in situ non‐destructive X‐ray fluorescence determination of the chemical analysis of a collection of ten bronze statues that are on display at the Egyptian museum of Cairo. The statues are from the late period of the ancient Egyptian history. In addition, destructive technique X‐ray diffraction analysis was applied on 11 damaged archaeological objects to determine the corrosion products and the alloy compositions. Specimens of the latter objects were subjected to metallographic examinations to determine the microstructure of the alloy. Surprisingly, the results indicated that all ten statues and 10 of the 11 damaged objects were made of lead – bronze alloy; the percentage of the lead varied from 3.43 to 18.04, the tin varied from 2.53 to 10.67. The chemical composition of the patina on eight damaged objects is essentially composed of (Cu₂O) cuprite for all objects in addition to other compounds such as (SnO₂) cassiterite in two objects, (PbCO₃) cerussite in three other objects and (Cu₂(OH)₃Cl) atacamite or (Cu(OH)₃Cl) paratacamite in two other objects. The formation of chlorides and carbonate resulted from the interaction between surrounding environment and the alloy. The results of the metallographic examinations indicated a non‐homogenous structure and the increase of the lead content increases the globular lead particles. In spite of this condition, the galvanic corrosion tendency when the alloy is exposed to moist air or soil is not possible as lead compounds are electrically insulating. Another advantage for using leaded bronze in making statues is being heavy and thus leads to stability. Copyright © 2012 John Wiley & Sons, Ltd.     

A standardless approach of INAA for grouping study of ancient potteries

The k ₀ based internal monostandard neutron activation analysis was used to analyze 41 ancient pottery samples from three major locations of Andhra Pradesh state, India, belonging to two different age groups namely Megalithic and Buddhist periods. Samples were irradiated with neutron flux obtained from CIRUS reactor and radioactive assay was carried out using a 40% relative efficiency HPGe detector coupled to 8?k MCA. Concentration ratios of 21 elements were calculated with respect to internal monostandard Sc. Absolute concentrations for six (three each from both Megalithic and Buddhist periods) representative samples along with a modern pottery were obtained for comparison. Elemental concentration ratios with respect to Sc were used for grouping of these archaeological samples. Preliminary grouping of these artifacts was done using La/Ce values, and the grouping was confirmed by statistical cluster analysis using eleven selected trace elements. The IAEA RM SL-3 sample was analysed for validation of the method, where in both concentration ratios and absolute concentrations were calculated.     

Nanosecond and femtosecond Laser Induced Breakdown Spectroscopic analysis of bronze alloys

In the present work we are studying the influence of pulse duration (nanosecond (ns) and femtosecond (fs)) at λ = 248 nm on the laser-induced plasma parameters and the quantitative analysis results for elements such as Sn, Zn and Pb, in different types of bronze alloys adopting LIBS in ambient atmosphere. Binary (Sn–Cu), ternary (Sn–Zn–Cu or Sn–Pb–Cu) and quaternary (Sn–Zn–Pb–Cu) reference alloys characterized by a chemical composition and metallurgical features similar to those used in Roman times, were employed in the study. Calibration curves, featuring linear regression coefficients over 98%, were obtained for tin, lead and zinc, the minor elements in the bronze alloys (using the internal standardization method) as well as for copper, the major element. The effects of laser pulse duration and energy on laser-induced plasma parameters, namely the excitation temperature and the electron density have been studied in our effort to optimize the analysis. Finally, LIBS analysis was carried on three real metal objects and the spectra obtained have been used to estimate the type and elemental composition of the alloys based on the calibration curves produced with the reference alloys. The results obtained are very useful in the future use of portable LIBS systems for in situ qualitative and quantitative elemental analysis of bronze artifacts in museums and archaeological sites.     

Chemical characterization of ancient potteries from Himera and Pestavecchia necropolis (Sicily, Italy) by Inductively Coupled Plasma–Optical Emission Spectrometry (ICP–OES)

Thirty-eight samples of pottery were analyzed for determining chemical composition in order to establish their provenance. The potteries tested in the present research come from Himera and Pestavecchia archaeological sites. After digestion in microwave oven, the samples have been analyzed for fourteen minor elements (Ba, Cd, Co, Cr, Cu, Ga, Li, Mn, Ni, Pb, Sr, Ti, Tl, and Zn) and six major elements (Al, Ca, Fe, K, Mg, and Na). Chemical analysis was carried out by Inductively Coupled Plasma–Optical Emission Spectroscopy (ICP–OES). The most abundant minor elements are Cr, Ba and Ni. Cr concentration ranged from 66 to 3635 mg kg^{− 1}, Ba concentration ranged from 388 to 2677 mg kg^{− 1} and Ni concentration ranged from 35 to 1758 mg kg^{− 1}. The relative standard deviation (RSD) of the replicates on the concentrations of analyzed metals ranged from 0.07% to 14%.The aim of this study is to assign the local or non-local provenance of the examined potteries, in particular validating and clarifying archaeological hypothesis based on the simple visual examination and stylistic characterization of ceramic objects. Principal component analysis performed on the dataset, together with the application of cluster technique and non statistical analysis, allowed the identification of three main groups of samples and a lonely one (R 97). In particular, sample R 97 shows high Cr concentration (3635 mg kg^{− 1}) and high Ni concentration (1758 mg kg^{− 1}), typical of Corinthian pottery. The results of chemical analysis show that the stylistic features are not always sufficient to correctly identify the origin of a ceramic object.     

Mechanism of PbSe y S1 − y film formation in chemical deposition from aqueous solutions

The growth mechanism of PbSe _y S_{1 ? y} films has been studied upon chemical deposition from aqueous solutions using scanning probe microscopy. A comparative morphological analysis of layers deposited at the initial growth stages and the use of fractal formalism shows that the formation of films of PbS, PbSe, and PbSe _y S_{1 ? y} substitutional solid solutions involves cluster-cluster aggregation with self-organization elements.     

A relation between 73Ge chemical shifts and CNDO/2 charges in tetrahalogenogermanes

Using Hojer and Meza's extension of the CNDO/2 method to third row elements, a linear relationship is established between the calculated atomic charges on the Ge atom in germanium tetrahalides GeCl_nBr_4-n (n = 0, 1, 2, 3, 4) and their recently measured ⁷³Ge chemical shifts.     

Characterization of the aeolian aerosol from Cape Verde by k 0-INAA and PIXE

Due to its location on West Coast of Africa, Cape Verde is highly influenced by Sahara Desert dust events being an optimum place to observe and study the African aeolian aerosol. During 2011, particulate matter with an aerodynamic diameter lower than 10 μm (PM₁₀) was sampled in Santiago Island and its chemical composition was evaluated by k ₀-instrumental neutron activation analysis (k ₀-INAA) and particle induced X-ray emission (PIXE). This study showed the existence of a seasonal intrusion of dust from Africa (that occurred from October to March) characterized by significant increases of PM₁₀, mineral elements and anthropogenic particles concentrations. In 2011, the PM₁₀ health-based air quality guidelines defined by WHO, EU and USEPA were exceeded. Cape Verde PM₁₀ composition was characterized essentially by high concentrations of elements originating from the soil (Ca, Ce, Co, Fe, K, Mg, Mn, Rb, S, Sc, Si, Sm, and Ti) and sea (Br, Cl, and Na); and low concentrations of anthropogenic elements (As, Cr, Cu, Ni, Pb, Sb, V, and Zn). k ₀-INAA and PIXE were fundamental tools for the determination of airborne chemical elements in Cape Verde. Their multi-elemental capabilities in association with low detection limits made it possible to determine the majority of the element concentrations of environmental interest.     

Rare earth tungsten bronzes: a new method of synthesis. Perspectives for their application as inert matrices for transmutation of long-life actinide elements

A new method of synthesis of oxide tungsten bronzes containing lanthanide (Ln) Nd and Eu, based on thermal degradation of polyoxotungstate compounds, is proposed. The simplicity of the method allows to consider this class of compounds with chemical formula, Ln_xWO₃, as potential inert target for incineration or transmutation of minor actinides, Am and Cm, in neutron reactors. Nd and Eu were used as analogues of transplutonium elements. Powder X-ray diffraction patterns of compounds synthesized reveal a cubic perovskite structure. The lanthanide content in bronzes was determined by optical spectroscopy analysis. The experimental density of the pressed bronze samples was estimated at 6.58 g cm⁻³, i.e., 89% of the crystallographic value. The thermal stability of the bronzes synthesized was checked up to 900°C in an inert atmosphere. Leaching tests were performed for europium bronzes in nitric acid solutions using luminescence technique.     

Study of series of the M1,M2‖F,Cl,Br quaternary reciprocal systems (M1 and M2 are group 1 s-block elements)

Quaternary reciprocal systems of alkali metal fluorides, chlorides, and bromides were partitioned into simplexes by a geometric method and a graph method. Phase transformations and chemical reactions in the bordering ternary reciprocal systems were described. Conversion lines were experimentally studied, and information on crystallizing phases within the composition prisms of the M₁,M₂‖F,Cl,Br systems (M₁ and M₂ are group 1 s-block elements) was obtained.     

Analysis of lignin from archaeological waterlogged wood by direct exposure mass spectrometry (DE-MS) and PCA evaluation of mass spectral data

The chemical characterisation of waterlogged archaeological wood is of fundamental importance to understand the degradation processes undergone by wooden objects and consequently to develop suitable consolidation and conservation procedures. Lignin extracted from archaeological waterlogged wood samples was characterized using direct exposure electron ionisation mass spectrometry (DE-MS). DE-MS achieves a mass spectral fingerprint of the sample in a few minutes, avoiding any chemical pre-treatment and requiring only few micrograms of material.Mass spectral data were put in relation to the chemical composition of lignin and evaluated by means of principal component analysis (PCA). The preliminary results, presented in this study, demonstrate the feasibility and the potential of DE-MS as a reproducible and rapid screening method for archaeological waterlogged wood samples.     

CO2 production from degraded woods via a novel integrated pyrolysis-combustion process

The process of combustion produces minimal amounts of CO₂ for conventional radiocarbon dating, making it difficult to estimate the age of the archaeological wood. Thus, the objective of this paper is to introduce a novel integrated pyrolysis-combustion process that will maximize the production of CO₂. Degraded wood samples were assumed to be archaeological samples for this study, namely Karas (Aquilaria malaccensis), Meranti (Shorea acuminate) and Setumpol (Hydnocarpus spp.) were used for this process. The process of CO₂ production was optimized by the application of design of experiment (DOE) and response surface method. The mathematical model was examined using the analysis of variance (ANOVA) at 5% level of significance. The temperature during the pyrolysis process, retention time and flow rates for the carrier gas (argon) were found to have a positive influence on the production of CO₂. A second-order model was obtained to predict the production of CO₂ as a function of temperature, retention time and flow rate. Optimum conditions for the production of CO₂ were obtained at a pyrolysis temperature of 300 °C, 20 min retention and 980, 984 and 987.6 ml/min argon flow rate for Karas, Meranti and Setumpol, respectively. The optimized yields of carbon dioxide produced were 82.57, 79.7 and 84% for Karas, Meranti and Setumpol, respectively. The different yields of carbon dioxide were due to the carbon content in the individual samples.     

Stabilization of H3 + in the high pressure crystalline structure of HnCl (n = 2–7)

The particle-swarm optimization method has been used to predict the stable high pressure structures up to 300 GPa of hydrogen-rich group 17 chlorine (H_nCl, n = 2–7) compounds. In comparison to the group 1 and 2 hydrides, the structural modification associated with increasing pressure and hydrogen concentration is much less dramatic. The polymeric HCl chains already present in the low temperature phase under ambient pressure persist in all the high pressure structures. No transfer of electrons from the chlorine atoms into the interstitial sites is found. This indicates the chemical bonding at high pressure in group 17 elements is fundamentally different from the alkali and alkaline elements. It is found that almost perfectly triangular H₃ ⁺ ions can be stabilized in the crystalline structure of H₅Cl.     

Thermally produced ω-(o-alkylphenyl)alkanoic acids provide evidence for the processing of marine products in archaeological pottery vessels

ω-(o-Alkylphenyl)alkanoic acids with 16, 18 and 20 carbon atoms were identified in archaeological pottery vessels from coastal sites in Southern Brazil. Such compounds are presumed to form during heating of triunsaturated fatty acids (C_16:3, C_18:3 and C_20:3), which are commonly found in the tissues of marine animals. The detection of these unusual cyclic compounds together with the isoprenoid fatty acids, 4,8,12-trimethyltetradecanoic acid and phytanic acid and substantial quantities of archaeological bones of fish and mollusca, provides evidence for the processing of marine animal products in archaeological pottery.     

Role of interlayer M k atoms and H2O molecules in the structure formation of M k (VUO6) k · nH2O uranovanadates

M ^k (VUO₆) _k · nH₂O uranovanadates of alkali (Li, Na, K, Rb, Cs), alkaline-earth (Mg, Ca, Sr, Ba), 3d transition (Mn, Fe, Co, Ni, Cu, Zn), and rare-earth (Y, La, Ln) elements were prepared by precipitation from solutions under hydrothermal conditions and in solid-phase reactions. The composition and structure of these compounds and the role of M ^k atoms and H₂O molecules in the formation of their structure were studied by X-ray diffraction, IR-spectroscopy, thermal analysis, and chemical analysis.     

Determination of k 0-factors and validation of k 0-INAA for short-lived nuclides

For standardization of k ₀-based instrumental neutron activation analysis, k ₀-factors for short-lived nuclides (half-lives—11 s to 37 min) of elements F, Se, Sc, Al, V, Ti, Cu, Ca, Mg, I, and Cl with respect to gold (¹⁹⁷Au) were determined using pneumatic carrier facility (PCF) at CIRUS reactor of BARC, Mumbai. Characterization of PCF was carried out by cadmium-ratio method using Au and Zr. The experimental k ₀-factors of the isotopes were found to be in good agreement with the recommended k ₀-factors in most of the cases, as evident from the values of % error and U-score at 95% confidence level. The method was validated by determining concentrations of elements through their short-lived nuclides in one type of the synthetic multielement standards (SMELS-I) obtained from SCK-CEN, Belgium. The method was also applied for determination of concentrations of some of the elements in two reference materials of IAEA, SL-3, and SL-1.     

How to determine accurate chemical ordering in several nanometer large bimetallic crystallites from electronic structure calculations

Chemical and physical properties of binary metallic nanoparticles (nanoalloys) are to a great extent defined by their chemical ordering, i.e. the pattern in which atoms of the two elements are located in a given crystal lattice. The reliable determination of the lowest-energy chemical ordering is a challenge that impedes in-depth studies of several-nm large bimetallic particles. We propose a method to efficiently optimize the chemical ordering based solely on results of electronic structure (density functional) calculations. We show that the accuracy of this method is practically the same as the accuracy of the underlying quantum mechanical approach. This method, due to its simplicity, immediately reveals why one or another chemical ordering is preferred and unravels the nature of the binding within the nanoparticles. For instance, our results provide very intuitive understanding of why gold and silver segregate on low-coordinated sites in Pd₇₀Au₇₀ and Pd₇₀Ag₇₀ particles, while Pd₇₀Cu₇₀ exhibits matryoshka-like structure and Pd₇₀Zn₇₀ features Zn and Pd atoms arranged in layers. To illustrate the power of the new method we optimized the chemical ordering in much larger Pd₇₃₂Au₇₃₁, Pd₇₃₂Ag₇₃₁, Pd₇₃₂Cu₇₃₁, and Pd₇₃₂Zn₇₃₁ nanocrystals, whose size ∼4.4 nm is common for catalytic applications.     

Geochemical studies of Guarani ethnic groups pottery with XRF

Artefacts of pottery belonging to the Guarani ethnic group were investigated by XRF techniques. The Tupi-Guarani, is one of the three main representatives of the Neolithic culture in the Amazonian scope. Such an ethnic group dispersed towards the South; in the Paraguayan area between the Paraguay and the Parana Rivers several Guarani ethnic movements by both rivers and their tributaries are perceived. The lithology and ceramics typology have contributed to support that perception. The archaeological findings help to clarify prehistoric cultural aspects and dispersal areas. In that context, the knowledge of the chemical composition of the found ceramic devices, in particular of the rare earth elements (REE) and other refractory ones provide information on this dispersion and its expansion. Selected trace elements (Rb, Sr, Y, Zr, Nb, Ba, La, Ce, and Nd) were determined in samples from thirteen archaeological sites with XRF using an Am-241 source. Their spidergrams have allowed identifying four different sets of samples according to their areas of provenance.