Thermal effects on cathodoluminescence in forsterite

Cathodoluminescence (CL) spectral analysis has been conducted for luminescent forsterite (olivine) of terrestrial and meteoritic origins. Two emission bands at 3.15 and 2.99 eV in blue region can be assigned to structural defect centres and two emission bands at 1.91 and 1.74 eV in red region to impurity centres of Mn²⁺ and Cr³⁺, respectively. These emissions reduce their intensities at higher temperature, suggesting a temperature quenching phenomenon. The activation energy in the quenching process was estimated by a least-square fitting of the Arrhenius plots using integrated intensity of each component as follows; blue emissions at 3.15 eV: 0.08–0.10 eV and at 2.99 eV: 0.09–0.11 eV, red emissions at 1.91 eV: ～0.01 eV and at 1.74 eV: ～0.02 eV. The quenching process can be construed by the non-radiative transition by assuming the Mott-Seitz model. The values of activation energies for blue emissions caused by structural defects correspond to the vibration energy of Si-O stretching mode in the lattice, and the values for red emissions caused by Mn and Cr impurity centres to Mg-O vibration energy. It implies that the temperature quenching energy might be transferred as a phonon to the specific lattice vibration.     

THE BLUE ENAMELS IN THE BAROQUE DECORATIONS OF THE CHURCHES OF PALERMO,SICILY: FE2+‐COLOURED GLASSES FROM LIME KILNS*

Deep blue glasses coloured by octahedral Fe²⁺ cations are often reported as textbook examples of blue pigmentation. However, despite the possibility of laboratory synthesis under reducing conditions, to date there are no well‐reported occurrences of their production and use in the past. A thorough historical, ethnographic, mineralogical, and chemico‐physical investigation of the ‘smaltini di calcara’ from several baroque churches in Palermo, Sicily, has revealed that the blue enamels widely used for altar decorations in the 17th and 18th centuries are actually a unique case of ancient blue glasses pigmented by divalent iron cations in distorted octahedral coordination. This mixed‐alkali glass was accidentally produced under severely reducing conditions in the local kilns during production of lime.     

氧化铁及分相结构对钧窑蓝色系釉的呈色作用

钧窑大部分产品的基本釉色之一是各种浓淡不一的蓝色乳光釉。为了探讨釉层呈乳光蓝色及其深浅的原因,利用聚焦离子束、场发射扫描电镜(配备EDS)、高分辨率透射电镜(配备EDS)、穆斯堡尔谱仪以及紫外可见分光光度计等手段,对7片出土于河南禹县钧窑遗址的具有深浅不一蓝色釉层的残片样品进行科学分析。结果发现,钧窑蓝色系釉层的主要着色剂为Fe2+,其含量的增加能够使釉面蓝色饱和度增大;此外,釉层中存在着大小不一的分相液滴,小液滴尺寸增大,能够使蓝色釉面颜色偏绿、明度提高。即钧窑蓝色乳光釉的呈色是化学成分和显微结构的共同作用,也是对可见光散射和吸收共同作用的结果。     

Observation and analysis of NI 520.0 nm auroral emissions

The results from the analysis of simultaneous auroral ground-based optical measurements of the N(²D) 520.0 nm, N₂⁺ 1NG 470.9 nm, O(³P) 844.6 nm and the O(¹D) 630.0 nm emission intensities are presented. The data were obtained during auroral observations at Gillam (56.35°N, 265.32°E) over an observation period of about 8 hours, from UT 2:33 hrs to UT 10:06 hrs, on 20 March 1985. The soft electron flux measurements on board the DMSP satellite for the time of the experiment have also been considered in the analysis. The N(²D) density and the N(²D) 520.0 nm integral emission rate I(520.0) were calculated employing a one- and two-dimensional time-dependent ion-chemistry model and the model predictions have been compared with the experimental I(520.0) nm emission rates. It was found that the model predictions of the NI I(520.0) nm intensity based on the electron energy fluxes inferred from the experimental I(844.6)/I(427.8) emission rate ratios are smaller in magnitude than the experimental values by a factor of 5–8 after allowing for horizontal transport of [N(²D)] by neutral winds. Assuming soft electron precipitation, suggested by the OI I(630.0) nm emission measurements and the DMSP satellite electron flux data, provided good agreement between the model and experimental results. Based on the results obtained it was concluded that horizontal transport played a minor role and that the observed N(²D) I(520.0) nm emissions were mostly produced by precipitating soft electron fluxes with energies below about 100 eV.     

The E<Subscript>1</Subscript>’ center in natural quartz: Its formation and applications to dating and provenance researches

Quartz is one of the minerals useful for electron spin resonance (ESR) dating. The E₁′ center is one of well-known paramagnetic defects in crystalline quartz. This center has a unique feature; its intensity increases on heating. An electronic process to explain this increase was found to be controlled not only by the number of oxygen vacancies, which are the precursors, but also by the number of Al hole centers, which depend on the previous radiation dose and on the Al concentration.     

Chemical composition and colouring agents of Roman mosaic and millefiori glass, studied by electron microprobe analysis and Raman microspectroscopy

About 100 fragments of Roman mosaic and millefiori glass were stylistically attributed to a Hellenistic type, a Ptolemaic and Romano-Egyptian period type and an early imperial period type. Twelve representative fragments were studied by electron microprobe analysis and Raman microspectroscopy. Eleven of them display a Na-pronounced recipe with low K, Mg and P contents, typical for the Roman period. Minor differences in composition are unsystematic, not reflecting the stylistic classification. Ionic colouring agents are Mn³⁺ for violet, Cu²⁺ for light blue, Co²⁺ for deep blue and Fe³⁺ for brown translucent colours. Calcium antimonates, lead antimonate and cuprite are the colourants responsible for white, yellow and red colours, respectively, and additionally serve as opacifiers. Mixing of ionic colouring agents and opacifying colourants led to a more differentiated palette of colours. Pb was used as yellow colouring agent, as a flux material and as a stabiliser for the colourant crystals. The remaining fragment consisting of a K-pronounced but still Na-bearing glass matrix was most likely produced during the Middle Ages or later.     

ON THE ORIGIN OF GREY AND BLACK ‘COLOURS’ OF ANCIENT POTTERY: ROLE OF Fe AND Ti4+ IONS

It is shown, from comparisons with the optical absorption of minerals, that the black and grey colours of pottery can arise from Fe²⁺ Fe³⁺ and Fe²⁺ Ti⁴⁺ charge-transfer (or electron-hopping) processes, the cations being located at the centres of adjacent edge-sharing octahedra.     

Optical measurements of a nightside poleward expanding aurora

Coordinated optical observations were performed from the poleward side of the midnight auroral oval. Height measurements of the auroral emissions at 4278, 5577 and 6300 Å, as well as their intensity ratios in the poleward expanded auroral substorm, have been carried out. The findings indicate a significantly softened electron spectrum compared with similar data from the equatorward part of this substorm. Typical values for the poleward expanded aurora are 300 eV and lower, while keV particles dominate the auroras at 10° lower latitudes. Emission altitudes and spectral characteristics are comparable to the transient burst emissions frequently observed from the same site in the post-noon sector, i.e. within the cusp.The 6300 Å atomic oxygen emission is used as a tracer of F-region wind and temperature. Interferometer observations show that there exists a prevailing crosspolar antisunward wind, increasing with geomagnetic activity to several hundred m s⁻¹. The temperature shows an increase of 150 K associated with high geomagnetic activity.     

Optical observations of gravity waves in the auroral zone

Night-time observations of O(¹D) λ630 nm and O(¹S) λ558 nm thermospheric emissions were made at Mawson, Antarctica (67.6°S, 62.9°E) from 1982 to 1989, using a three-field photometer. Crossspectral analysis of the data was used to extract frequencies and horizontal trace velocities of periodic structures. Structures in the λ630 nm emission were characteristic of large-scale waves, and those in the λ558 nm emission were characteristic of medium-scale waves. The results showed distinct polarisation of the propagation azimuths; waves in the λ630 nm emission propagated approximately northwestward throughout the 8 yr period, whilst propagation azimuths of waves in the λ558 nm emission appeared to be solar-cycle-dependent. It is suggested that waves observed in the λ630 nm emission were of predominantly auroral electrojet origin, whilst those observed in the λ558 nm emission were of both auroral and tropospheric origin.     

A non-invasive study of Roman Age mosaic glass tesserae by means of Raman spectroscopy

Ancient mosaic tesserae are a range of materials of very varied and complex nature, including pottery, stone and glass. Raman spectroscopy is a powerful tool for the analysis of all these kinds of materials. In the particular case of glasses, this technique can be used both for a study of surface weathering and for the characterization of bulk structure, but it has not yet been extensively used for the characterization of mosaic glass tesserae. We carried out Raman analyses on a set of Roman and Late Antiquity period mosaic glass samples, which allowed a good characterization of both the glass matrix and the crystalline inclusions. All the samples show the typical Raman signatures of soda-lime-silicate glasses. Several crystalline phases were also identified, being relics of raw materials used during the glass manufacturing process, such as quartz and feldspars, or linked to the glass color/opacification, such as bindheimite and cuprite. The analyses also led to the identification in some blue, turquoise and green tesserae of calcium antimonate, whose Raman signature has only recently been recognized in the scientific literature on mosaic glasses. Some emphasis is given to the analysis of red lead-containing tesserae, colored with Cu⁺ ions or even Cu⁰ (or Au⁰) metal nanoparticles. Samples with peculiar compositions, as well as “modern” (and restoration) samples, could quite easily be distinguished from the ancient ones by their Raman spectra.     

Experimentally produced glass compared with that occurring at The Torr, NW Scotland, UK: vitrification through biotite melting

It is proposed that the vitrification in some Iron Age forts in NW Scotland can be explained through decomposition of micas (largely biotite) giving melts that react with or dissolve quartz and crystallise orthopyroxene and feldspars, so equating with the reaction biotite + quartz = sanidine + orthopyroxene + liquid. A sample of Moine semi-pelite has been experimentally melted at c. 850 °C demonstrating this breakdown reaction. A preserved thermal gradient across the sample reveals the progressive degradation of biotite towards the melting (upper) surface. Degradation is evident from the initial emphasis of mica cleavages in grains at the bottom of the sample, and then appearance and progressive increase in size of bubbles associated with biotite and melt towards the top of the sample. A chocolate-brown melt was produced as a coating on the upper surface and along micaceous layers. A near equivalent sample was located from the fort at The Torr that, whilst being more thoroughly affected by heat, with no unaffected biotite, preserved similar textures. Compositions of original Moine minerals are used to constrain the melts produced and melt evolution is tracked through quenched crystals. These include ternary feldspars as well as sanidine, spinels and orthopyroxene. Spot geochemical evidence demonstrates the heterogeneity of the melts, plus varying contributions of Ca and Na that could be attributed to the onset of reactions involving feldspars and other minerals from the original assemblage. It is thus concluded that a similar temperature to that of c. 850 °C derived in the experiment was reached in the vitrification process at The Torr in order to produce the glass observed.     

Mössbauer Spectroscopic and Chromaticity Analysis on the Colourative Mechanism of Ancient Goryeo Celadon from GangJin and Buan

In ancient Goryeo celadon excavated from the kiln sites in the GangJin and Buan areas, the effect of the chemical composition and ionic state of Fe on the colour was evaluated by Mössbauer spectroscopy and chromaticity analysis. According to chromaticity analysis, the L* value (brightness) of the glaze was shown to be affected more by TiO₂ and MnO than by Fe₂O₃, and the body was affected more by Fe₂O₃ than by TiO₂. The a* value was found to be affected by Fe₂O₃ and TiO₂ in the glaze, whereas there was hardly any change in the body according to the composition. As for the b* value, changes due to the composition were shown to be smaller than those for the L* and a* values. According to the Mössbauer spectroscopy results, as the quantities of TiO₂ and Fe₂O₃ are increased, Fe²⁺/Fe³⁺ decreases; while the changes in Fe²⁺/Fe³⁺ with MnO and P₂O₅ are negligible. As the quantity of Fe²⁺/Fe³⁺ increases, the a* and b* values decrease, which results in the change of colour from red–yellow to blue–green. The characteristic green colour can be attributed to increased L* (brightness) and decreased a* and b* values (blue–green shift) due to the reduced Fe ion, which is mainly determined by the TiO₂ and Fe₂O₃ contents.     

A case study of a high latitude ionospheric electron density depletion

Incoherent scatter measurements inside and outside an ionospheric electron density depletion are described. The density depletion is probably caused by an enhancement of NO⁺-ions and subsequent dissociative recombination. The NO⁺-ions are increased because high electric fields present at the geographical location of the density depletion speed up the reaction O⁺ + N₂ → NO⁺ + N. The electron as well as the ion temperature within the density depletion are strongly enhanced, the latter due to Joule heating, also caused by the electric field.     

The colourless glass of Iulia Felix

The present paper focuses on 85 colourless glass samples selected among the recycling cullet found in the Roman ship Iulia Felix, wrecked off the town of Grado (province of Udine, North Italy) in the first half of the 3rd century AD, with the aim of examining their chemical composition, investigating similarities within and between the three established group types (cups, plates, bottles), and comparing the chemical compositions of the Iulia Felix glass samples with groups reported in the literature for colourless glasses. Chemical analyses, performed by X-ray fluorescence and electron microprobe, indicate that the samples were all soda-lime–silica in composition, with natron as flux, according to typical Roman production technologies. Chemical data are treated by multivariate statistical tools, such as cluster analysis and the NPC test. Statistical analyses allow us to conclude that the Iulia Felix colourless glasses were produced by at least two different production technologies related to group type, confirming the trend recently identified in the literature. In addition, the trace element patterns (particularly those of Sr, Zr and Ba) suggest that beach sand with differing amounts of alkali feldspars was predominantly used as raw material, like those specifically mentioned by Pliny for glass production.     

Ionoluminescence and Cathodoluminescence in Marbles of Historic and Architectural Interest

Ion beam induced luminescence (IBIL) was applied, along with cathodoluminescence (CL), on seven samples of marbles of historic and architectural interest. The CL colours, observed in a cold cathode device, have been related to the IBIL spectra. Moreover, a detailed analysis of the IBIL spectral features has made it possible to disclose the influence of the chemical composition and to emphasize the crystal‐chemical role of the Mn²⁺. Beyond the chemical information and the crystal‐chemical interpretation, the spectra are recognized as being valuable in the field of archaeological studies for their significance as fingerprints of marbles, giving information on their nature and origin.     

Invasion of a karst aquifer by hydrothermal fluids: evidence from stable isotopic compositions of cave mineralization

Mineral deposits in the Cupp‐Coutunn/Promeszutochnaya cave system (Turkmenia, central Asia) record a phase of hydrothermal activity within a pre‐existing karstic groundwater conduit system. Hydrothermal fluids entered the caves through fault zones and deposited sulphate, sulphide and carbonate minerals under phreatic conditions. Locally, intense alteration of limestone wall rocks also occurred at this stage. Elsewhere in the region, similar faults contain economic quantities of galena and elemental sulphur mineralization. Comparisons between the Pb and S isotope compositions of minerals found in cave and ore deposits confirm the link between economic mineralization and hydrothermal activity at Cupp‐Coutunn. The predominance of sulphate mineralization in Cupp‐Coutunn implies that the fluids were more oxidized in the higher permeability zone associated with the karst aquifer. A slight increase in the δ³⁴S of sulphate minerals and a corresponding δ³⁴S decrease in sulphides suggest that partial isotopic equilibration occurred during oxidation. Carbonate minerals indicate that the hydrothermal fluid was enriched in ¹⁸O (δ¹⁸O_SMOW ～ + 10‰) relative to meteoric groundwater and seawater. Estimated values for δ¹³C_DIC (δ¹³C_PDB ～ ? 13‰) are consistent with compositions expected for dissolved inorganic carbon (DIC) derived from the products of thermal decomposition of organic matter and dissolution of marine carbonate. Values derived for δ¹³C_DIC and δ¹⁸O_water indicate that the hydrothermal fluid was of basinal brine origin, generated by extensive water–rock interaction. Following the hydrothermal phase, speleothemic minerals were precipitated under vadose conditions. Speleothemic sulphates show a bimodal sulphur isotope distribution. One group has compositions similar to the hydrothermal sulphates, whilst the second group is characterized by higher δ³⁴S values. This latter group may either record the effects of microbial sulphate reduction, or reflect the introduction of sulphate‐rich groundwater generated by the dissolution of overlying evaporites. Oxygen isotope compositions show that calcite speleothems were precipitated from nonthermal groundwater of meteoric origin. Carbonate speleothems are relatively enriched in ¹³C compared to most cave deposits, but can be explained by normal speleothem‐forming processes under thin, arid‐zone soils dominated by C4 vegetation. However, the presence of sulphate speleothems, with isotopic compositions indicative of the oxidation of hydrothermal sulphide, implies that CO₂ derived by reaction of limestone with sulphuric acid (‘condensation corrosion’) contributed to the formation of ¹³C‐enriched speleothem deposits.     

Application of electron microprobe analysis to identify the origin of ancient pottery production from the Castillo de Huarmey,Peru

A vast amount of ceramics (among other grave goods) were recovered from Castillo de Huarmey, a Wari culture (650–1050 ce ) archaeological site on the north coast of Peru. In order to assess ceramic production area(s) and possible trade, political or cultural interactions with other regions, and to complement earlier petrographic analysis, electron microprobe analysis (EMPA) was conducted following a rarely used methodology in archaeology. The chemical composition of individual minerals in ceramics and sediments samples from the Huarmey Valley was obtained, focusing mainly on amphiboles, feldspars and pyroxenes. The results of the analyses clearly indicate that the majority of the ceramic analysed was made of raw material of local origin.     

Luminescence Properties of Chert and some Archaeological Applications

We have examined the cathodoluminescence (CL) and induced thermoluminescence (TL) properties of chert collected from the Ozark Mountains area of the central United States. The cherts showed predominately orange CL with occasional blue CL. X-ray diffraction indicates that the amount of orange CL correlates closely with the abundance of carbonates within the chert. Previous studies have shown that macroquartz characteristically gives off a weak and transient blue CL. Thermoluminescence studies concentrated on the shape of the radiation induced TL glow curve. The results seem to indicate all of the cherts sampled fall into one of four glow curve categories. The TL categories correspond to quartz crystallinity as measured by X-ray diffraction, which is probably a reflection of quartz grain size. Application of these techniques is somewhat new to chert studies, but may provide a useful criterion in establishing the number of chert varieties or sourcing chert provenience locations for artefacts collected from archaeological sites. Calcite and dolomite are expected to leach from chert surfaces upon exposure to weathering agents, thus making CL a helpful tool for the detection of fake stone artefacts with fresh fracture surfaces. Quartz crystallinity is an important factor in determining chert cleavage characteristics and TL appears to be a useful measure of this property.