Potash - a key raw material of glass batch for Bohemian glasses from 14th-17th centuries?

The aim of this work is to verify or refute hypothesis of existence of basic/universal glass batch: quartz sand: potash: limestone, at a ratio of 2: 1: 1 used in Bohemian glass production since the middle ages onwards and to simulate the preparation of a potassium glass type with the composition used in medieval Bohemia. The chemical composition of Bohemian glass, which incorporated in the proposed glass batch for glassmaking on a laboratory scale, was evaluated by (a) findings directly related to glassmaking (samples from glasswork in Moldava dating back to the 15th century) and (b) information from publications.Experimentally produced glasses for the present paper were prepared from raw materials such as ash, leached ash, potash, limestone and quartz sand. The plant raw materials (spruce, beech and bracken ashes, raw and refined potash) were treated and prepared by methods similar to the production procedures used in the pre-industrial era.The main contrast was found in the CaO/K₂O weight ratio, which was determined in glasses that were characteristic of given periods. While this ratio was often below 1 in glasses of the 15th century, it reached values above 1 in glasses at the turn of the 16th-17th centuries. This result may indicate that the composition of the glass batch had changed.The results of the present study reject the current scholarly work dealing with glass batch composition during the 14th-17th centuries and confirm that glass produced in some Bohemian medieval glassworks could have been melted from a batch that included plant ash, making the use of limestone unnecessary. The traditional suggestion of the exact ratios of raw materials, often cited in historical literature, seems to be impossible. The glassmakers had to react to the variable composition of the raw materials, especially plant ash.     

Meteorological influences on the spatial and temporal variability of NO2 in Toronto and Hamilton

The spatial and temporal variability of nitrogen dioxide (NO₂) concentrations and their relationships with meteorology was evaluated in the Toronto–Hamilton urban airshed. NO₂ concentrations were highest in the early morning and late evening. Mean concentrations were highest in winter, although individual one-hour NO₂ concentrations were found to be highest in summer. Wind direction was the strongest control on hourly NO₂ concentration, and temperature and wind speed also had an effect. Our analysis of NO₂ concentration variation by wind direction showed that areas downwind of major highways, urban centres and industry were exposed to higher pollutant concentrations. Seasonal patterns of NO₂ concentration displayed significant spatial heterogeneity, in particular, in Toronto. Onshore winds sheltered coastal inhabitants from the full extent of NO₂ exposure they would otherwise experience. Seasonal variations in meteorology and emissions mean that the degree of spatial variability in NO₂ concentrations changes from season to season. This study will help to improve existing land-use regression-based NO₂ prediction models by incorporating meteorological controls on NO₂ distributions for health effect studies.     

Supply routes and the consumption of glass in first millennium CE Butrint (Albania)

Archaeological, historical and analytical evidence can identify trade patterns and the movement of people and products and thus reveal the cultural and economic connections that existed at a given time. In the case of first millennium CE glass, the manufacture of raw glass in a limited number of glass making installations with unique compositional characteristics makes it possible to trace the likely origin of the raw materials at consumption sites. In this way the analytical characterisation of a large corpus of glass finds can identify changes in the supply routes of high-end industrial products from the Roman to the middle Byzantine period.     

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.     

ROMAN WINDOW GLASS: A COMPARISON OF FINDINGS FROM THREE DIFFERENT ITALIAN SITES

Thirty‐three samples of window glass and five glass lumps coming from three Italian archaeological sites—the Suasa excavations (Ancona, settled from the third century bc to the fifth to sixth centuries ad ), the Roman town of Mevaniola (Forlì‐Cesena, settled from the Imperial Age up to the fourth century ad ) and Theodoric's Villa of Galeata (Forlì‐Cesena, settled from the sixth century ad onwards)—were analysed to track the changes in the chemical composition and manufacturing technology of window glass through the centuries. The aims of this study were: (1) to establish the origin of the raw materials; (2) to verify the chemical homogeneity among samples coming from different sites and/or produced using different techniques; and (3) to sort the samples into the compositional groups of ancient glass. The analysis of all the chemical variables allowed two groups to be distinguished: (a) finds from Mevaniola and Suasa; and (b) finds from Galeata. All the samples had a silica–soda–lime composition, but the analysis of minor elements—in particular, of Fe, Mn, and Ti—made it possible to split the samples into two groups, with the higher levels of these elements always found in the Galeata samples (HIMT glass). In conclusion, it can be asserted that the main differences between the samples are related to their chronology.     

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.     

GLASS BY DESIGN? RAW MATERIALS,RECIPES AND COMPOSITIONAL DATA*

Compositional analyses of ancient and historic glasses have often been interpreted in terms of the use of specific raw materials in glass manufacture. However, the known inhomogeneity of many glass‐making raw materials and the insolubilities of some compounds make any explanation of compositional data problematic. This paper looks at three glass‐making alkalis with a view to understanding how the compositions of these raw materials are carried through to the final glass. The chemistry and variability of the raw materials are discussed, as is their contribution to the final glass composition. In addition, the choices and decisions made by glassmakers are acknowledged in the final glass compositions. This combination of factors addresses the complexity of predicting the use of specific raw materials from the finished glass composition.     

A geochemical study of Roman to early Byzantine Glass from Sagalassos,South-west Turkey

The finding of glass chunks together with fuel ash slag and kiln fragments related to glass processing strongly suggests local secondary production (working) of glass at Sagalassos (SW Turkey) from imperial to early Byzantine times. Chemical evidence shows that different silica raw materials were used in imperial and early Byzantine times for blue and green glass found locally. Colourless glass shows no clear difference in chemical composition and hence in silica raw materials between late Roman and early Byzantine times. Locally found early Byzantine yellow-green glass and chunks correspond to the previously defined Byzantine HIMT glass type. The chemical composition of the glass chunks found, identical to that of the contemporary glass of the same colour, strongly indicates that these chunks were used for the manufacture of early Byzantine green, colourless and yellow-green glass at Sagalassos.The homogenous lead isotopic composition of the chronological groups of blue glass, suggests the use of two distinct but homogenous silica raw materials for the manufacture of this glass. In view of this homogeneity, it is likely that contemporary blue glass was produced at a single location. The linear trend of the heterogeneous lead isotopic composition of the green and colourless glass is a strong indication of recycling effects in the glass composition. The end members of this trend are formed by the isotopic composition of the blue glass on the one hand, and of the yellow-green (HIMT) glass on the other hand. The heterogeneous lead isotopic composition of the yellow-green glass at Sagalassos is probably the result of recycling of this glass, reflecting mixtures of the original lead isotopic signatures of the broken glass and the original HIMT glass chunks.It should be noted that the two main raw materials for primary glass production (silica and soda) were available on the territory of Sagalassos. Moreover, the lead isotopic composition of quartz pebbles sampled from the artisanal quarter of Sagalassos, is similar to that of the local blue glass.     

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.     

Chemical characterisation of glass mosaic tesserae from sixth-century Sagalassos (south-west Turkey): chronology and production techniques

Little is known about the origin, supply pattern and production technology of Byzantine glass mosaic tesserae. In this study, we have analysed forty-eight glass tesserae from Sagalassos (Asia Minor) of different colours and from two archaeological contexts that were stratigraphically dated to the sixth century CE. The main aim was to identify the raw materials, colourants and opacifiers as well as secondary working practices that are reflected in the composition (EPMA, LA-ICP-MS analyses) and the microstructure (XRD, SEM-BSE) of the tesserae. The set of samples retrieved from the Roman Baths complex at Sagalassos is compositionally very homogeneous, representing possibly a single commission, and can be tentatively dated to the late Roman period. In contrast, the assemblage associated with the construction of a Byzantine church around the turn of the sixth century CE is more diverse, suggesting that these tesserae were produced from more than one silica source. This highlights a diversification in the supply and manufacture of glass tesserae during the Byzantine period.     

Considering the effects of the Byzantine–Islamic transition: Umayyad glass tesserae and vessels from the <Emphasis Type="Italic">qasr</Emphasis> of Khirbet al-Mafjar (Jericho,Palestine)

The paper reports and discusses data obtained by archaeological and archaeometric studies of glass vessels and tesserae from the qasr of Khirbet al-Mafjar (near Jericho, Palestine). Archaeological contextualisation of the site and chrono-typological study of glass vessels were associated to EPMA and LA–ICP–MS analyses, performed to characterise the composition of the glassy matrix (major and minor components as well as trace elements). Analyses allowed achieving meaningful and intriguing results, which gain insights into the production and consumption of glass vessels and tesserae in the near East during the Umayyad period (seventh–eighth centuries). Within the analysed samples, both an Egyptian and a Levantine manufacture have been identified: such data provide evidence of a double supply of glass from Egypt and the Syro-Palestinian coast in the Umayyad period occurring not only in the glassware manufacture but also in the production of base glass intended to be used in the manufacture of mosaic tesserae. Thus, the achieved results represent the first material evidence of a non-exclusive gathering of glass tesserae from Byzantium and the Byzantines in the manufacture of early Islamic mosaics.     

Glass from the Archaeological Museum of Adria (North-East Italy): new insights into Early Roman production technologies

In the present study, the first archaeometric data on an ample selection of intentionally coloured (or decoloured) Early Roman glass (1st–2nd centuries AD) from the Archaeological Museum of Adria (Rovigo, Italy) are reported. The analysed samples are 61 in total, both transparent and opaque, and were characterised from the textural (SEM-EDS), mineralogical (XRPD) and chemical (XRF, EPMA, LA-ICP-MS) points of view. This combined approach allowed us to identify the raw materials and production technologies employed in the manufacture of glassware. Results for the transparent samples show that they are all silica-soda-lime glasses. Most of them, independently of colour, have compositions close to those of typical Roman glass, produced with natron as flux. No relationships were identified among chemical compositions, types or production techniques, but a dependence on bulk composition was identified for some particular colours, revealing the careful and intentional selection of raw materials. This is the case of Sb-colourless glass, produced with sand of high purity, a group of intensely coloured objects, mainly emerald green and black, produced with soda ash as flux, and some blue examples produced with various sources of sand or soda ash as flux. Two main types of opacifiers were identified for the opaque samples: calcium antimonate for white, mauve and blue glasses, and lead antimonate for the yellow ones; in one case, a yellow lead-tin antimonate was also identified. As regards the opaque glasses, most of the samples opacified with calcium antimonate are silica-soda-lime in composition, similar to the typical Roman glass. Instead, samples opacified with lead and/or lead-tin antimonates are lead glasses, suggesting different production technologies.     

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 use of oxygen,strontium and lead isotopes to provenance ancient glasses in the Middle East

It is sometimes possible to discriminate between glasses made at different factory sites by using chemical analysis. However, this is not necessarily a means of provenancing them unambiguously because glass of slightly different compositions may have been fused using different proportions of the same raw materials. The determination of oxygen, strontium and lead isotopes can provide the possibility of linking the geological sources of the glass raw materials to the production sites on which the glass was fused. Here we consider the possible isotope contributions made to the raw materials thought to have been used in the manufacture of plant ash and natron glasses found at 8th–9th century al-Raqqa, Syria. The isotopic data from al-Raqqa are compared with published results from other Middle Eastern and German glasses. We show that strontium isotopes, in particular, provide a reliable means of distinguishing between the sources of plant ash glass raw materials and that oxygen and lead isotope signatures are less discriminatory.     

Potassium–Calcium Glass: New Data and Experiments*

The chemical composition of potassium–calcium ‘wood‐ash’ glass reflects the elemental pattern of the involved non‐volatile base materials in quartz sand, wood ash and possibly potash. The essential elemental ratio K₂O/CaO of wood ash varies between 0.2 and 0.8, and depends on the habitat and geological substratum of the wood rather than on the tree species; ratios between 1.0 and 3.0 in wood‐ash glass are only possible when potash is added as a third base material. Melting temperatures of wood‐ash glass sensu stricto, termed K–Ca‐2, produced with the two raw materials quartz sand and wood ash, are between 1250°C and 1400°C, while those of three‐component‐glasses, termed K–Ca‐3, are between 900°C and 1250°C, according to the amount of added potash. Experimentally produced glass displays different hues, from colourless to brown, olive‐green and pink, according to the chemical composition of the wood ash. Elevated MnO concentrations between 0.5 and 3 wt% may originate from wood ash and are hence not necessarily an indicator of colour‐inhibiting additives. Phosphate stemming from wood ash is an essential discriminator between wood‐ash glass and potash–lime glass. Because wood ash contains only minor amounts of sodium, wood‐ash glass with equal concentrations of potassium and sodium is a hybrid glass type, where besides quartz sand, wood ash, possibly potash and also soda‐rich cullet have been applied for glass production.     

RAW MATERIALS OF GLASS FROM AMARNA AND IMPLICATIONS FOR THE ORIGINS OF EGYPTIAN GLASS*

Analysis has been conducted on 19 blue glasses from Amarna in Middle Egypt dated to around 1350 BC. The results suggest that these glasses fall into two distinct types: cobalt coloured glasses with a natron based alkali made from local Egyptian materials, and copper coloured glasses with a plant ash alkali, which follow a Mesopotamian tradition of glass making. It is suggested that at least some of this copper/plant ash glass is imported into Egypt during the Amarna period despite extensive local production of cobalt/natron glass. Existing analyses (Lilyquist and Brill 1995) of the earliest glass from the reign of Tuthmosis III (c. 1450 BC) suggest that during this period the same two types of glass are present. Local Egyptian cobalt and natron in these early glasses implies that, despite the lack of archaeological evidence for production sites, glass was produced from its raw materials in Egypt as early as the reign of Tuthmosis III.     

CHARACTERIZATION OF ARCHAEOLOGICAL AND IN SITU SCOTTISH WINDOW GLASS

Scottish window glass from both archaeological sites and historic buildings was examined using portable X‐ray fluorescence (pXRF) and scanning electron microscopy – energy‐dispersive X‐ray micro‐analysis (SEM–EDX). The elemental composition of the glass provides information regarding the materials used and, subsequently, an approximate range of dates of manufacture. pXRF is shown to be more vulnerable than SEM–EDX to the effects of surface corrosion and matrix effects in archaeological samples. The study showed that the production of window glass in Scotland from the 17th century onwards appears to closely parallel that in England. It also demonstrated the potential of pXRF for in situ studies of window glass in historic buildings. pXRF was used to assess two Scottish buildings; one in state care and one in private ownership. The building in state care, the Abbot's House at Arbroath Abbey, showed a uniform glass type, suggesting that the building was re‐glazed completely at some point during the late 19th or early 20th century. The building in private ownership, Traquair House, had a range of glass types and ages, demonstrating a different maintenance and repair regime. This type of data can be useful in understanding historic buildings in the future, particularly if re‐glazing is being considered.     

Mineralogical And Chemical Investigations Of Bloomery Slags From Prehistoric (8th Century Bc To 4th Century Ad) Iron Production Sites In Upper And Lower Lusatia,Germany

More than 400 fayalitic bloomery slags from prehistoric iron production sites in Upper and Lower Lusatia, eastern Germany, as well as bog iron ore samples and intermediary samples of the smelting process, were analysed by chemical and mineralogical techniques. While the precursor bog iron ores exploited in the two regions under investigation were very similar in composition, consisting of low‐manganese/low‐barium as well as high‐manganese/high‐barium types of ore, pronounced differences in slag composition were detected. Slags from 17 investigated sites in Upper Lusatia showed average P₂O₅ contents between 1 and 3 mass%, whereas slags from 15 investigated sites in Lower Lusatia were generally much richer in phosphorus, reaching values as high as 7 mass% P₂O₅. Since a reasonable correlation exists between calcium and phosphorus contents in the slags of the latter sites, it is conjectured that deliberate addition of CaO to the ore/charcoal charge of the bloomery furnace may have taken place in order to fix the phosphorus in the slags effectively. In many samples, this conjecture is being supported by the detection of a slag mineral Ca–Fe phosphate Ca_9?xFe_1+x(PO₄)₇ that presumably crystallized from a residual phosphorus‐rich melt and shows a cotectic relationship to both Ca‐rich fayalite and wustite, as well as to members of the solid solution series magnetite–hercynite.     

MEDIEVAL GLASS FROM ROCCA DI ASOLO (NORTHERN ITALY): AN ARCHAEOMETRIC STUDY

An archaeometric study was performed on 33 medieval glass samples from Rocca di Asolo (northern Italy), in order to study the raw materials employed in their production, identify analogies with medieval glass from the Mediterranean area and possible relationships between chemical composition and type and/or production technique, contextualize the various phases of the site and extend data on Italian medieval glass. The samples are soda–lime–silica in composition, with natron as flux for early medieval glasses and soda ash for the high and late medieval ones. Compositional groups were identified, consistent with the major compositional groups identified in the western Mediterranean during the first millennium AD . In particular, Asolo natron glass is consistent with the HIMT group and recycled Roman glass; soda ash glass was produced with the same type of flux (Levantine ash) but a different silica source (siliceous pebbles, and more or less pure sand). Cobalt was the colouring agent used to obtain blue glass; analytical data indicate that at least two different sources of Co were exploited during the late medieval period. Some data, analytical and historical, suggest a Venetian provenance for the high/late medieval glass and a relationship between type of object (beaker or bottle) and chemical composition.     

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。