营城子汉墓出土玻璃耳珰的化学成分与制作工艺研究

营城子汉墓位于辽宁省大连市甘井子区,是我国东北地区一处重要的大型汉墓群。营城子汉墓出土了一批玻璃耳珰,为探讨其成型工艺及来源,采用超景深显微系统进行了表面形貌观察,初步认为是模铸成型,并经过打磨。采用便携式X射线荧光光谱仪(XRF)进行了化学成分分析,结果显示,它们分属铅钡硅酸盐和钾硅酸盐玻璃系统,一件由Cu²⁺着色,其余主要由Co²⁺着色。其为我国自制,所用钴料来源相同,钴料的锰钴比特征与国产钴土矿的类似。并对营城子汉墓出土玻璃耳珰造型与化学成分体系间的关系进行了分析,对玻璃耳珰制作模式进行了初步探讨,进一步加深了对我国古代玻璃耳珰制作与传播的认识。     

A STUDY OF GLASS BEADS FROM THE HALLSTATT C–D FROM SOUTHWESTERN POLAND: IMPLICATIONS FOR GLASS TECHNOLOGY AND PROVENANCE*

Eighty‐one samples taken from 68 glass beads found in southwestern Poland on sites of the Lusatian culture from the Hallstatt C and Hallstatt D subphases were analysed by EPMA. A subsample of 18 of these were additionally subjected to analysis by means of LA–ICP–MS in order to validate the results obtained by EPMA. Some glass was made using mineral soda and some using plant ash rich in sodium. Both high‐magnesium soda–lime glass (HMG) and low‐magnesium soda–lime glass (LMG) were identified. A large number of samples are characterized by low MgO content and medium K₂O content (LMMK glass), combined with low concentrations of CaO and high Fe₂O₃ and Al₂O₃. All the LMMK glass contains numerous silica crystals and inclusions composed of a number of elements (most frequently Cu, Co, Sb, As, Ag, Ni and Fe). The LMMK glass was presumably made in Europe during the Hallstatt C.     

The Production and Circulation of Carthaginian Glass Under the Rule of the Romans and the Vandals (Fourth to Sixth Century ad): A Chemical Investigation

Fifty‐seven glass samples from Carthage dating to the fourth to sixth century ad were analysed using the electron microprobe. The results show that these samples are all soda–lime–silica glass. Their MgO and K₂O values, which are below 1.5%, suggest that they were made from natron, a flux that was widely used during the Roman period. The major and minor elements show that these samples can be divided into four groups, three of which correspond to the late Roman period glass groups that were found throughout the Roman Empire: Levantine I, and ‘weak’ and ‘strong’ HIMT. Of particular interest is our Group 2, which is technologically and compositionally similar to HIMT glass and the CaO and Al₂O₃ values of which are similar to those of Levantine I. Glass of similar composition has been reported by several authors and is predominantly found dating from the late fifth to seventh century. This could represent a ‘new’ glass group; therefore further study is needed to determine its origin. Also, this study suggests that the Vandal invasion in North Africa did not disrupt the glass trade between Carthage and the Levantine coast.     

An archaeometric study of Hellenistic glass vessels: evidence for multiple sources

In the present study, 53 glass fragments from core-formed vessels and 3 glass beads are investigated using SEM/EDX, EPMA and LA-ICP-MS. All samples were excavated in the Latin settlement of Satricum in central west Italy and apart from two, were found in the so-called fourth–third c. BC Hellenistic Votive deposit, also known as Votive Deposit III, discovered in front of the sanctuary of Mater Matuta on top of the acropolis. The analytical results indicate that the glass from Satricum is a typical soda-lime-silica type with natron used as a flux. Its chemical compositions display a relatively low compositional variation. Small differences in the concentrations of major and minor oxides (SiO₂, Al₂O₃, CaO and Fe₂O₃) and in trace elements (Sr, Zr and Nd) between individual samples suggest the use of different types of raw materials, especially sand. In turn, this suggests that the glass derived from more than one glass making centre. The combined investigation of colourants (Co, Cu and Mn) reinforces and confirms the idea that glass from Satricum was made using different manufacturing traditions during the Hellenistic period.     

Dry CO2–CO fluid as an important potential deep Earth solvent

Transport properties of reduced carbonic fluid have been studied experimentally at P = 2 kbar and T = 700–1000°C in internally heated pressure vessel (IHPV). Synthetic FeCO₃ and natural siderite were used to generate fluid during experiments using a platinum double‐capsule technique. A natural CaTiSiO₅ aggregate was placed into the inner capsule as an additional source of trace elements. The outer capsule was loaded with albite glass. No water was introduced to the system and oxygen fugacity was established near to graphite–oxygen (CCO) buffer due to transformation of FeCO₃ into a magnetite aggregate during decarbonation to yield CO and CO₂. The carbonates decomposed during initial heating of the experiments, causing their some constituent components to be dissolved in and transferred by the fluid to the pore space of the albite glass matrix. After temperature reached 1000°C glass, the shards annealed and then melted, as evidenced by a vesiculated glass in the quench products. Micro‐Raman investigation of the fluid in bubbles in the albite glass in experiments with decomposition of natural siderite yielded CO–CO₂ mixture where CO mole fraction was 0.15–0.16. We observe significant concentrations of Pt, Mn, P, and REE in the albite glass; in contrast, no Fe or Mg transfer was detected. LA‐ICP‐MS analysis of the albite glass product yielded the average Pt content of 2 ppm. Such high Pt signal came from Pt particles (100–500 nm in size), which were observed on the walls of the bubbles embedded in the glass. Olivines and aluminous spinel were observed in the Fe‐oxide aggregate, demonstrating transfer of SiO₂ and Al₂O₃ from the albite melt by the reduced carbonic fluid from the albite glass (large capsule). Our results demonstrate that dry CO–CO2 fluid can be important agents of dissolution and transport, especially for Pt and other metals. The data imply that metals are chiefly dissolved as carbonyl complexes.     

故宫藏清代挂屏镶嵌玻璃饰件的科学分析

清代镶嵌器物数量巨大且种类繁多,玻璃是其中一种重要的镶嵌材料。为探讨清代镶嵌玻璃饰件的成分特征和加工工艺,本工作采用微区X射线荧光能谱、扫描电子显微镜、显微共聚焦拉曼光谱、激光诱导击穿光谱等方法,对故宫馆藏清代紫檀木边嵌玉石楼阁挂屏上的6件镶嵌玻璃饰件进行了初步分析,结果表明:6件玻璃饰件属于K₂O-CaO-SiO₂体系,以石英岩引入SiO₂作玻璃基体,硝石作助熔剂引入K₂O,CaO有方解石和萤石两个主要来源;深蓝色玻璃着色元素为钴,浅蓝色玻璃着色元素为铜,蓝绿色玻璃为铜和铁共同着色,4件玻璃饰件乳浊剂均为CaF₂;黄色玻璃以铅锡黄为着色剂并乳浊剂。通过显微形貌观察结合档案记载,认为镶嵌玻璃饰件是在熔制好的玻璃块上经过二次加工而成,加工工艺采用了中国古代传统的治玉工艺。研究结果可为清代镶嵌工艺及玻璃制作工艺的研究提供佐证。     

RETENTION OF PHOSPHATE IN BURIED CERAMICS: AN ELECTRON MICROBEAM APPROACH

Elevated concentrations of P₂O₅ of 2–12 wt% absolute were observed in the matrices of a small group of ceramics with the electron microprobe. P₂O₅, CaO and FeO^t are enriched towards the surfaces in some cases and elemental correlations suggest precipitation of a crystalline calcium phosphate with a stoichiometry close to CaO · P₂O₅. Scanning electron microscopy with X-ray mapping showed P₂O₅ to be dispersed in the ceramic matrix on a very fine scale, while X-ray diffraction detected no crystalline phosphate. Parallels are drawn with the precipitation of phosphate in the surfaces of weathered glass. It is concluded that the amorphous phases produced on firing behave as chemically active substrates which facilitate the adsorption or precipitation of very fine grained calcium phosphate from the burial environment.     

Degradation processes in colourless Roman glass: cases from the Bocholtz burial

A group of Roman glass objects from the Bocholtz burial in the SW of Limburg (The Netherlands) was found to have been subject to varying degrees of degradation. Many of the 25 colourless glass objects were fragmented to pieces <0.1 cm (“sugared”), whereas the three transparent blue-green glass objects were in near-pristine state. Analyses using SEM, XRF and EDS revealed that the fragmentation was the direct result of the intense leaching of Na₂O from the glass structure and its replacement with water. The resulting gel layers with low-Na₂O contents and large amounts of water are sensitive to cracking when they dry out. Thin-walled glass appears to be less sensitive to cracking from the resulting stress than thick-walled glass. Local differences in the moisture regime during burial also influence the severity of the glass degradation. Glass with low concentrations of CaO seems to be the most sensitive to this form of degradation. The typical blue-green Roman glass is less sensitive as it generally has considerably higher concentrations of CaO.     

Roman blue-green bottle glass: chemical–optical analysis and high temperature viscosity modelling

Chemical analysis, optical absorption spectroscopy and mathematical modelling of high temperature viscosity have been carried out on five 1st–2nd century AD Roman blue-green bottle glass fragments from Coppergate, York. Modelled viscosities indicate remarkable consistency within the sample set studied and support the suggestion that temperatures of ∼1000–1150 °C were required to remelt these glasses and to provide suitable viscosities for forming articles. Iron redox ratios (Fe²⁺/ΣFe), analysed SO₃ contents and the absence of characteristic Fe³⁺–S²⁻ amber absorption bands suggest that melting conditions for all studied glasses were mildly, rather than strongly, reducing (estimated pO₂ ≈ 10⁻¹–10⁻⁶ bar). These furnace conditions are consistent with the effects of combustion gases and carbonaceous matter contained in the raw materials.     

MOSAIC GLASS FROM ST PETER'S,ROME: MANUFACTURING TECHNIQUES AND RAW MATERIALS EMPLOYED IN LATE 16TH‐CENTURY ITALIAN OPAQUE GLASS

A recent restoration of late 16th‐century mosaics in one of the vaults beneath the dome of St Peter's Basilica in Rome allowed sampling and analysis of a group of glass tesserae. The aim of this work is the characterization of opaque coloured glasses possibly produced in Rome. The characteristics of the glass from St Peter's were compared with those of Venetian and Tuscan production, in order to assess possible common origins. Chemical analysis of 30 samples was carried out by electron microprobe, while the nature and morphology of opacifiers were determined by X‐ray diffraction and scanning electron microscopy. Almost all the opaque samples were characterized by the presence of SnO₂ crystals. In addition, depending on the colour of the glass, other crystalline phases were identified: lead‐tin oxide (PbSnO₃) in yellow glass, cuprite (Cu₂O) in orange glass and two calcium‐tin silicates with different stoichiometry (CaSnSiO₅ and Ca₃SnSi₂O₉) in the green‐yellow variety. A frame of reference for identifying raw materials and glass‐making techniques is provided by textual sources, here examined in comparison with the compositional characteristics of the tesserae from St Peter's.     

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.     

Glass on the Amber Road: the chemical composition of glass beads from the Bronze Age in Poland

The article discusses the chemical composition of 56 glass samples from 52 beads found in Poland at 13 archaeological sites (mainly cemeteries). The artefacts have been dated to the II–V period of the Bronze Age (=phases BzB–HaB; c. 1600–750/700 bc). The LA-ICP-MS method was applied. Two groups were distinguished in this assemblage based on a comparison of the MgO to K₂O ratio in glass: (i) high magnesium glass (HMG)—23; and (ii) low magnesium and high potassium glass (LMHK)—33 (29 matrix glass specimens and 4 decorative). In southern Poland, beads made of HMG and LMHK are often found in the same cemeteries. Analyses have shown that HMG was most probably made in Mesopotamia and that at least one cobalt glass is of Egyptian provenance. LMHK glass was made in Europe, most probably in Italy. Also, Italy was the most probable transit point for artefacts made of HMG en route to East-Central Europe.     

The coloured glass of Iulia Felix

Research on the cargo of glass 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 and composed of recycling cullet carefully selected for colour and type, provided much information on Roman glass production technology. A combined approach, involving analytical, statistical, and archaeological evidence, included chemical analyses (X-ray fluorescence, electron microprobe), which indicated that the coloured samples were all soda-lime-silica in composition, with natron as flux, although cluster analysis identified many compositional groups. Comparisons among the compositional groups of the colourless glass, previously studied, and those of coloured glass showed that the production technologies of the colourless glass vessels constitute two well-defined technological end-members, also related to group types, into which those of the coloured glass samples fall. In particular, coloured glass samples—all bottles, low-status vessels—were produced with mainly beach siliceous-feldspar-calcareous sand. However, unlike the colourless type, strict control of raw materials and decolourising processes was not adopted, and recycling was also practised, as demonstrated by the Sb₂O₃, Cu and Pb patterns. In this context, a “recycling index” (RI)—[(Sb₂O₃)_X/(Sb₂O₃)_Ref] * 100—is proposed here for the first time, in order to quantify the extent of recycling of antimony colourless glass in the batch. RI is valid for glass containing abundant Sb from an end-member of colourless glass. In conclusion, although it cannot be stated unequivocally that the identified compositional trends are related to different production centres or different raw materials, the strong evidence of compositional variability among all the Iulia Felix glass samples, both colourless and coloured, supports the dispersed production model for Roman glassware and the common practice of recycling in Roman imperial times, especially for low-status vessels.     

Rotational temperatures for OH and O2 airglow bands measured simultaneously from El Leoncito (31°48′S)

Some results from 54 nights of simultaneous measurements, performed between 1984 and 1987, of rotational temperatures for the OH(6−2) and O₂(¹∑)(0–l) bands are presented. A summer enhancement by 15 K in O₂ temperature has been found that has not formerly been observed in airglow measurements. At least five nights show prominent tide-like temperature oscillations with a phase shift between layers typical of upward wave propagation at about 10 km h⁻¹, with up to 55 K variation. During other nights, similar oscillations are limited to the O₂ layer. Data for different seasons seem to be characterized by different levels of variability. During the one equinox campaign, nocturnal temperature variations show an exceptionally stable pattern of tide-like oscillations.     

Numerical simulations of the saturated gravity wave spectra in the atmosphere

A two dimensional numerical model is used to compute the saturation of small scale gravity waves in the region near the critical level. The vertical wave number spectrum of horizontal velocity fluctuations in the unstable region (USR) where shear instability develops is found to be governed by wave-shear interaction and follows a theoretical saturation spectrum ~ω_b²/2m³. Wave-shear interaction is also found to be responsible for the observed fact that the variance of vertical velocity fluctuations is significantly lower than the level predicted by linear gravity wave theory. On the other hand, the corresponding spectrum in the stable region (SR) following a much shallower spectrum ~m⁻² is found to result from the combined effects of wave-wave interactions and eddy diffusion. The key step in our simulation is the separate parameterization of horizontal and vertical eddy diffusion coefficients instead of a constant molecular viscosity coefficient.     

Chemical analysis of 17th century Millefiori glasses excavated in the Monastery of Sta. Clara-a-Velha,Portugal: comparison with Venetian and façon-de-Venise production

A set of ten Millefiori glass fragments dating from the 17th century, originated from archaeological excavations carried out at the Monastery of Sta. Clara-a-Velha (Coimbra, Portugal), were characterized by X-ray electron probe microanalysis (EPMA), Raman microscopy and UV–Visible absorption spectroscopy. All glasses are of soda-lime-silica type. The use of coastal plant ash is suggested by the relatively high content of MgO, K₂O and P₂O₅, as well as by the presence of chlorine. Tin oxide or calcium antimonate were the opacifiers used in the opaque glasses, cobalt in the blue glasses, copper in the turquoise glasses, iron in the yellow and greenish glasses, and iron and copper were found in the opaque red and aventurine glasses. Based on the concentrations of alumina and silica four different sources of silica were identified, allowing the classification of the glasses into the following compositional groups: low alumina (<2 wt%), which includes a sub-group of cristallo samples with SiO₂ > 70 wt%, medium alumina (2–3 wt%), high alumina (3–6 wt%) and very high alumina (>6 wt%). Comparison with genuine Venetian and façon-de-Venise compositions showed that two fragments are of Venetian production, one of Venetian or Spanish production and the remaining are of unknown provenance. In two fragments the glass of the decoration is probably Venetian or Spanish but the glass used in the body is also of unknown provenance.     

ROMAN AND MEDIEVAL GLASS FROM THE ITALIAN AREA: BULK CHARACTERIZATION AND RELATIONSHIPS WITH PRODUCTION TECHNOLOGIES*

Compositional investigations were performed on 81 Roman and medieval glass fragments (first to 14th centuries ad ) from four Italian archaeological sites. The samples were soda–lime–silica in composition, with natron as flux for the Roman and early medieval glass samples, and with plant ash as flux for the late medieval ones. The varying colours are due to the differing FeO, Fe ₂ O ₃ , MnO and Sb ₂ O ₃ contents. Hierarchical cluster analysis identified six compositional groups related to age, which were compared with those found in the literature. In this way, technological continuity from the Roman to the early medieval period and the appearance of plant ash technology in the ninth century, 200 years in advance of the period previously believed, are demonstrated.     

THE SECTILIA PANELS OF FARAGOLA (ASCOLI SATRIANO,SOUTHERN ITALY): A MULTI‐ANALYTICAL STUDY OF THE GREEN,MARBLED (GREEN AND YELLOW), BLUE AND BLACKISH GLASS SLABS

Analyses at the Cu–K, Fe–K and Mn–K edge were performed to study the green, marbled (green and yellow), blue and blackish (deep greyish olive green) glass slabs decorating three sectilia panels from the archaeological site of Faragola. Results indicate that all slabs were made by mixing siliceous sand with natron, sometimes probably mixed with small percentages of plant ash. Cu²⁺ and Pb antimonates should be responsible for the opaque green colours. The dark green and yellow portions of the marbled slabs are respectively comparable to the slabs comprising only one of these colours. Cu²⁺ together with Ca antimonates probably produced light blue slabs, whereas cobalt was used to produce dark blue slabs. We consider it possible that the abundance ratio of Fe²⁺/Fe³⁺ and the complex Fe³⁺S^2? would have an effect on the blackish slabs. The contribution of Mn cannot be ascertained even if it could have played a role in darkening glass colour. The comparison between the chemical composition of Faragola samples and several glass reference groups provided no conclusive evidence of provenance; whereas, the presence of a secondary local workshop can be hypothesized.     

Characterization of some ancient glass beads unearthed from the Kizil reservoir and Wanquan cemeteries in Xinjiang,China

A total of 33 ancient glass beads unearthed from the Kizil reservoir cemetery and Wanquan cemetery in Xinjiang are studied using Raman spectroscopy, scanning electron microscopy with energy‐dispersive spectrometry (SEM–EDS) and other methods. The detailed study of the glassy matrices, the crystalline inclusions and the microstructural heterogeneities for these glass beads has revealed some valuable information to help in the understanding of their possible manufacturing technology and provenance. At least two different types of glass were present in the two cemeteries. For the first time, antimony‐based colourant/opacifier—for example, Pb₂Sb₂O₇ or CaSb₂O₆—was systematically identified in some beads of plant‐ash type soda–lime glass dated to about 1000–500 bc . The limited number of potash glass beads from the Kizil reservoir cemetery, which were dated to about 500–300 bc , used tin oxide as an opacifier. The diverse resources of the soda–lime and potash glasses indicate the existence of a complex trade network between China and the West much earlier than the Western Han Dynasty.     

登封南洼遗址出土的宋代玻璃饰品

2004—2006年,登封南洼遗址出土了风化严重的白色项链2004M18:1,发掘者认为是二里头阶段的白陶(高岭土)制品。为验证此出土文物的成分与制作年代,扫描电镜、XRF成分分析显示为铅基玻璃(PbO-Al2O3·K2O-SiO2)。2004M18出土人骨14C测年结果为北宋。又对该遗址有北宋纪年M26:2耳珰进行测试分析,结果显示亦为铅基玻璃(PbO-Al2O3·SiO2)。白色项链、耳珰的扫描电镜、XRF成分分析结果一致,与14C测年结果也基本吻合,故2004M18出土项链应该是北宋时期的。两座墓葬形制规模相对较小,但均随葬玻璃器皿。这从某种程度也说明了玻璃制品随着技术的成熟,其消费群体也开始扩大,玻璃制品消费日益大众化。这种铅基玻璃的出现比文献记载提前了400年左右。