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.     

On the geochemistry of gases and noble gas isotopes (including 222Rn) in deep crustal fluids: the 4000 m KTB-pilot hole fluid production test 2002–03

The concentrations of H₂, O₂, CO₂, and concentrations and isotopic composition of the noble gases (including ²²²Rn), N₂, CH₄, and higher hydrocarbons dissolved in 4000 m deep‐seated fluids from a 12‐month fluid production test in the KTB pilot hole were analyzed. This determination of the gas geochemistry during the test in combination with the knowledge of the hydraulic data provides relevant information about the fluid hydraulics of the deep system. All gas concentrations and isotopic signatures, except for ²²²Rn, showed constancy during the course of the test. This, in combination with large fluid flow rates at a moderate water table drawdown, imply an almost infinite fluid reservoir in 4000 m depth. From the change in ²²²Rn‐activity as a function of pump rate, the contribution of smaller and wider pores to the overall fluid flow in an aquifer can be deduced. This ²²²Rn‐activity monitoring proved therefore to be a valuable instrument for the qualitative observation of the scavenging of pore and fracture surfaces, a hydraulic feature invisible to standard hydraulic testing tools. The observance of this scavenging effect is due to (i) the continuous on‐line geochemical monitoring, (ii) the durability of the test, (iii) a change in pump rate during the course of the test, and (iv) due to the short half‐life of ²²²Rn. The fluids have a 5.9% mantle He component, and a δ²¹Ne excess of 14%, and a noble gas model age of about (5.5–6.2) ± 2.0 Myr. The mean N₂/Ar‐ratio of 516 and δ¹⁵N‐data of about +1.5‰ indicates sedimentary or metamorphic origin of N₂. The hydrocarbons, amounting to 33 vol.% in the gas phase, are derived from thermal decomposition of marine organic matter of low maturity. But a key question, the identification of the potential source region of the fluids and the migration pathway, is still unidentified.     

Finding a Relatively Flat Archaeological Site with Minimal Ceramics: A Case Study from Iraqi Kurdistan

ABSTRACT

We present a new technique to detect flat archaeological sites with minimal ceramics using an unmanned aerial vehicle that maps surface stone concentrations. Methods deployed include point pattern analysis of stone concentrations and a machine-learning technique using unsupervised classification of visible stone signature qualities, which are used in simple linear regressions to compare with geophysical and ceramic surface survey results of a site in Iraqi Kurdistan. There is a stronger fit (r^2?=?0.77) between surface stone concentrations and architecture identified by geophysical measurement, while surveyed ceramics show a weaker fit to defined architecture (r^2?=?0.31). Surface stone concentrations are potentially a better proxy than ceramics for determining the presence of past settlement in regions where stone was commonly used, sites are relatively flat, and ceramics are found in low concentrations. The methods advanced here can be scaled to wider areas, particularly in mountainous regions, where surface stone features are present.     

On significant quantities of negative ions observed around the mesopause

Significant amounts of negative ions are sometimes observed at altitudes as high as the mesopause region (Kopp E. and Hermann L., 1984, Annales Geophysical2, 83; Ganguly S., 1984, J. atmos. terr. Phys. 46, 633). Using a suitable ion-chemical scheme in which water clustering to negative ions is also considered, the effect of change in temperature, T, and concentrations of NO, O, O₃ and H₂O on the abundance of negative ions in the mesopause region has been examined. It is shown that a drastic increase in the concentration of O₃ or a decrease in neutral temperature by about 20 K. around 85km could make the concentration of total negative ion comparable to that of electron.     

中国古代高温铁釉瓷的呈色研究

中国是最早烧制高温陶瓷的国家,从原始瓷开始,含铁原料制作的颜色釉瓷贯穿了整个中国制瓷的历史,从而产生了呈色各异、品种繁多的铁釉瓷.为研究影响铁釉瓷呈色的各类因素,本工作综合应用成分分析方法,对一些典型的铁釉瓷品种进行定量测定.研究表明:高温铁釉中Fe2O3的含量范围从1％至高达约18％,铁的含量对釉的呈色起着决定性的作用;同时窑炉的烧成气氛和原料中的TiO2含量变化会影响Fe2+、Fe3+的生成比例,从而使釉色发生改变;另外,原料中MnO的含量、施釉工艺等也会对釉色产生影响.研究结果将对我国高温铁釉瓷制作技术的产生、发展有一个更好的诠释.     

Positive and negative ion composition measurements in the D- and E-regions during the 26 February 1979 solar eclipse

Two rockets bearing quadrupole mass spectrometers capable of measuring both positive and negative ion composition were launched from Red Lake, Canada, during the solar eclipse. Both instruments had liquid helium cryopumps and shock-attaching conical samplers. The payloads also contained two Gerdien condensers to measure total positive and negative ion concentrations and ion mobilities. Attitude control systems aligned the payloads with the velocity vector throughout ascent and descent. The first rocket was launched so that the D-region was in darkness 35 ± 8 s on the upleg and about 150 ± 15 s on the downleg for the study of ionospheric decay processes. The second rocket was fired after totality into 75% solar illumination for the study of ionospheric recovery. The positive ion composition above 105 km exhibited a strongly increasing NO⁺/O₂⁺ ratio with time after second contact due to O₂⁺ charge transfer with NO and a sharply diminished ionization rate. However, in both nights, the ionization below 105 km was created mainly by energetic particle deposition as exemplified by the increased ion concentrations and the composition signatures of a particle event: asignificant enhancement of O₂⁺ below 105 km and large amounts of H₅O₂⁺ ions in the D-region which result from the O₂⁺ clustering scheme. H₅O₂ was the major ion in the upper D-region while H₇O⁺₃, H₉O₄⁺ and H₅O₂⁺ were dominant ions at lower altitudes. Numerous minor species were also detected. The negative ion distributions in both flights exhibited a distinct shelf at 83 ± 2 km, decreasing by more than an order of magnitude by 90 km and with minima near 75 km. In the 75–90 km range, a significant percentage of the negative ions had masses exceeding 160 a.m.u. Comparisons are made with prior negative ion measurements during similar daytime auroral zone absorption (AZA) events. Two striking characteristics of the precipitating particles were apparent from these and past observations in daytime AZA events: there is a near absence of low energy electrons capable of ionizing above about 105 km and there is'a significant spatial and/or temporal variability in the electron flux. This paper is devoted principally to a presentation of the ion composition measurements and associated uncertainties.     

Ancient soil resources of the Usumacinta River Region,Guatemala

In this study we present the results of a combination of methods used to identify possible agricultural activity of the ancient Maya in the Usumacinta River Basin in Guatemala. These methods included stable carbon isotope analysis of bulk soil organic matter, soil profile investigations and a spatial model of gentle slopes and well-drained soils to identify favorable agricultural conditions. Stable carbon isotope analysis of bulk soil organic matter in particular offers potentially direct evidence of agricultural activity. The δ¹³C results suggest that there is a strong signature of C₄ plants, such as maize and tropical grasses, throughout the study area. Further, the current soil conditions and extent of relatively gently sloped areas are favorable to agriculture. Overall, the results are supportive of the hypothesis that the area, located between the polities of Piedras Negras and Yaxchilán, was agriculturally important to surrounding areas.     

Atmospheric deterioration of Qin brick in an environmental chamber at Emperor Qin's Terracotta Museum, China

Potential mechanisms for the changing appearance of Qin terracotta was evaluated on simulated bricks with, SO₂, NH₃, O₃, and a NH₃/O₃ mixture for total dosages of 2.2–5.4 ppm-years. Changes in the surface composition and appearance were evaluated with scanning electron microscopy/energy dispersive X-ray analysis (SEM–EDX) and X-ray photoelectron spectroscopy (XPS). No observable changes with O₃ exposure were found. Sulfate as sulfur and ammonium as nitrogen increased by 1.2 at% and 0.8 at% of the surface deposit as determined by XPS. O₃ did not have a detectable effect by itself, but when combined with NH₃, NO₃ as nitrogen increased by 1.5 at%, indicating a strong oxidation of NH₃ to nitric acid. The combination of outdoor O₃ infiltration with indoor NH₃, presumably from the visitors, appears to have a greater potential for damage than either pollutant by itself. SEM–EDX mapping of the surface showed sulfur associated with calcium and magnesium compounds after SO₂ exposure, but not before. More detailed microscopic examination showed this primarily in the form of gypsum, especially near cracks and pits in the surface. Both of these mechanisms are probably among the causes of changes in terracotta appearances since they were unearthed in 1974.     

山东香山汉墓出土陶质彩绘文物材质及制作工艺的初步研究

山东青州香山汉墓陪葬坑出土了数量巨大,种类齐全陶质彩绘文物,尤其是陶马和陶俑上的彩绘保存完好,色彩鲜艳,绘画工艺精湛,非常罕见。为了研究汉代彩绘及其制陶工艺等信息,本研究使用拉曼光谱(RS)、带能谱的扫描电镜(SEM-EDX)、偏光显微镜(PLM)、体式显微镜(OM)、X射线荧光光谱(XRF)、X射线衍射(XRD)、热膨胀仪等分析方法,对出土的陶质彩绘文物进行了分析研究。结果表明这批陶质彩绘文物制作工艺是就地取土,与水混合塑型,在900~1000℃烧制陶胎。其彩绘所使用的颜料均为矿物颜料,其中白色为方解石(CaCO3)、红色为赭石(Fe2O3)和朱砂(HgS)、黑色为炭黑(C)、紫色为人造汉紫(BaCuSi2O6),采用胶料调和颜料调涂刷绘制而成。这批文物的制作工艺属于典型的秦汉时期彩绘陶器的制作方法。研究成果可为相关文物的保护提供科学数据。     

Slag inclusions in iron objects and the quest for provenance: an experiment and a case study

Slag inclusions are found within most archaeological bloomery iron artefacts and are remainders of slag created during the smelting and smithing processes. Although they are widely believed to provide data with the potential for provenancing iron artefacts, previous slag inclusion studies have mostly proven inconclusive. The main aim of the work reported here is to analyse experimental smelting and smithing assemblages (including ore, furnace lining, fuel and slag), to compare these to slag inclusions in the resulting bloom and worked objects, and then explore the relationships between ore, slag and slag inclusions. This study has revealed that the composition of slag inclusions most closely relates to the smelting slag produced, whereas provenance to a specific ore would be difficult due to the chemical variability derived from furnace lining, fuel and any fluxes used. Some compounds in the slag inclusions are particularly affected during smithing of the artefact, i.e. those present in the sand flux and fuel used. However, trends are observed in the K₂O/MgO, MnO/SiO₂, Al₂O₃/SiO₂, Al₂O₃/MgO, Al₂O₃/K₂O and Al₂O₃/CaO ratios that allow comparison between slag inclusions and smelting slag in these experiments, and may therefore be used during other provenancing attempts. The knowledge gained from the experimental assemblages was subsequently applied to an archaeological case study, examining objects from the 900 Cal BC smithing site of Tel Beth-Shemesh, Israel and the 930 Cal BC smelting site of Tell Hammeh, Jordan. The analyses suggest that none of the artefacts examined derived from the Hammeh smelting system.     

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.     

临水窑与介休窑白底彩绘工艺的对比研究

白底黑花装饰风格的瓷器,始终是陶瓷、科技界和陶瓷爱好者关注的热点。临水窑(磁州窑)与介休窑白底黑花风格的瓷器之间有着密切的联系,但是对于两窑产品的科技分析甚少,至于两者的对比研究更是无从谈起。因此,本工作利用岩相分析、SEM-EDS等方法分析了临水窑(磁州窑)、介休窑样品的瓷胎、化妆土及瓷釉的化学成分和显微结构。比较分析显示,两窑样品的瓷胎均为低硅高铝配方,且介休窑瓷胎中的Al2O3含量更高;两窑瓷胎粗糙,Fe2O3、TiO2含量较高,致使其呈浅黄色。瓷胎表面均施有化妆土,所不同的是,介休窑的瓷胎表面施有两层化妆土,其靠近釉的一层化妆土(h2),Fe2O3、TiO2含量极低,靠近胎的一层化妆土(h1),Fe2O3、TiO2含量较高;临水窑样品的瓷胎表面仅施一层化妆土,其Fe2O3、TiO2含量较低,但高于介休窑近釉层化妆土中的相应含量。介休窑瓷釉为典型的高钙釉,而临水窑则为典型的碱钙釉和钙碱釉。不难认识到,介休窑似在临水窑白底黑花及化妆土工艺的基础上,因地制宜,勇于创新,形成了成本低廉、技术先进的两层化妆土工艺,在当地原料较为粗糙的条件下,生产出质量较好的白底釉下彩绘瓷器。     

ANCIENT EGYPTIAN LIMESTONE QUARRIES: A PETROLOGICAL SURVEY*

Ancient Egyptian limestone quarries in the Nile Valley occur in six geological formations of Palaeogene age. Samples were collected from 23 of the 48 known quarries, and analysed by thin-section petrography and X-ray fluorescence spectrometry. Results of the analyses show that the geological formations can be identified from rock texture and allochem types, and a plot of SiO₂/Al₂O₃ versus CaO/[CaO + MgO]. The application of these petrographic and geochemical parameters make it possible to determine the geographic provenance of limestone used in ancient Egyptian sculptures and monuments.     

Does it come from the Pays de Bray? Examination of an origin hypothesis for the ferrous reinforcements used in French medieval churches using major and trace element analyses

A new methodology based on major and trace element analyses of slag inclusions is proposed to determine (or exclude) the provenance of iron artefacts. It is applied to verify if the Pays de Bray, a French area between Rouen and Beauvais, could have been an important supplier for the ferrous reinforcements used in the Middle Ages for the building of churches and cathedrals in these two towns. To this purpose, the behaviour of trace elements during both direct and indirect operating chains is studied combining experimental smelting and different analytical methods, such as SEM–EDS, ICP–MS, LA–ICP–MS and INAA, performed on archaeological samples. The chemical signature of the Pays de Bray iron ore and slag is determined considering MnO and P₂O₅ contents as a first rough filter and seven couples of trace elements. Then, the major and trace elements are analysed using the same methods in the slag inclusions of 32 artefacts from the Beauvais and Rouen churches, made by the bloomery process. The trace element signature of the inclusions from each artefact is compared with the ore from the Pays de Bray area. The iron used in the Rouen and Beauvais churches seems not to come mainly from the Pays de Bray.     

Topside and intelhemispheric ion flows in the mid-latitude plasmasphere

A modelling study has been carried out of field-aligned ion flows in the topside ionospheres of conjugate hemispheres under solstice conditions at mid to low latitudes. In the model calculations coupled time-dependent O⁺, H⁺ and electron continuity, momentum and heat balance equations are solved along dipole magnetic field lines at L = 1.5 and 3.0 Sunspot medium and sunspot minimum atmospheric conditions are considered.It has been found that thermal coupling between conjugate hemispheres gives rise to strong flows of O⁺ in the topside ionosphere of the summer hemisphere that are directed upwards at conjugate sunrise and directed downwards at conjugate sunset. At conjugate sunrise in the winter hemisphere there is a small upward-directed signature in the O⁺ field-aligned flux; there is no observable signature in the O⁺ field-aligned flux in the winter hemisphere at conjugate sunset. There are strong upward and downward flows of O⁺ at local sunrise and local sunset, respectively, in both the summer and winter hemispheres.At both L = 1.5 and 3.0 the 24 h time-integrated interhemispheric H⁺ flux is in the direction summer hemisphere to winter hemisphere. At L = 1.5 its magnitude is in good agreement with the magnitude of the 24 h time-integrated plasma (O⁺ + H⁺) field-aligned flux at 1000 km altitude; there are no such agreements at L = 3.0.A study of the roles played by the individual terms of the O⁺ momentum equation has demonstrated the complex structure of momentum balance. Certain of the terms may be orders of magnitude greater than the combined total of the individual terms, i.e. the O⁺ field-aligned flux.     

Removal of natural organic dyes from wool–implications for ancient textile provenance studies

Ancient wool textiles recovered from archaeological sites are in many cases originally dyed with natural organic dyestuffs from vegetable sources. These include among others woad (Isatis tinctoria L.), weld (Reseda luteola L.), and madder (Rubia tinctorum L.). These dyestuffs could be a threat to the use of the strontium isotopic system as a tracer for provenance studies of ancient wool, because they could potentially contaminate the signature of the textile's raw material. We present a novel method which allows for efficient removal of organic dyestuffs in wool prior to strontium isotopic analysis. Our method is based on an oxidative release of the dyestuff constituents by ammonium peroxodisulfate [(NH₄)₂S₂O₈] solution, combined with hydrofluoric acid (HF) that has shown to effectively remove/dissolve adhering dust micro-particles. Our multi-analytical results show that such a pretreatment is capable of removing >98% of the originally present organic dyestuffs without significantly destroying the wool structure. The strontium isotopic ratios of the residual wool fraction after the application of the pretreatment are sensitive to the origin and, therefore, can be used as tracers for the provenance of the raw material. We propose to apply this method to ancient wool textiles in which positive identification of organic dyestuff constituents by High Performance Liquid Chromatography (HPLC) was made.     

The geochemical evolution of very dilute CO2‐rich water in Chungcheong Province,Korea: processes and pathways

A geochemical study was carried out on the CO₂‐rich water occurring in granite areas of Chungcheong Province, Korea. In this area, very dilute and acidic CO₂‐rich waters [62–242 mg l^?1 in total dissolved solid (TDS), 4.0–5.3 in pH; group I) occur together with normal CO₂‐rich waters (317–988 mg l^?1 in TDS, 5.5–6.0 in pH; group II). The concentration levels and ages of group I water are similar to those of recently recharged and low‐mineralized groundwater (group III). Calculation of reaction pathways suggests that group I waters are produced by direct influx of CO₂ gas into group III type waters. When the groundwater is injected with CO₂, it develops the capacity to accept dissolved solids and it can evolve into water with very high solute concentrations. Whether the water is open or closed to the CO₂ gases becomes less important in controlling the reaction pathway of the CO₂‐rich groundwater when the initial pco ₂ is high. Our data show that most of the solutes are dissolved in the CO₂‐rich groundwater at pH > 5 where the weathering rates of silicates are very slow or independent of pH. Thus, groundwater age is likely more important in developing high solute concentrations in the CO₂‐rich groundwaters than accelerated weathering kinetics because of acidic pH caused by high pco ₂.     

Tetraethylene glycol thermooxidation and the influence of certain compounds relevant to conserved archaeological wood

The degradation of tetraethylene glycol (TEG) was studied at 70 °C under dry air and nitrogen. Degradation products were detected using gas chromatography-mass spectrometry (GC–MS). They were mono-, di- and tri-ethylene glycol, mono- and di-formates of mono-, di-, tri- and tetra-ethylene glycol and formic acid. The rate of TEG degradation was significantly decreased by approximately 10 mmol/l KI, FeCl₃, Cu(CH₃COO)₂, MnO₂ and CuSO₄, small amounts of fresh oak wood sawdust and gypsum-containing scrapings from the wood surface of the Vasa ship in Stockholm. Thus certain salts and natural components of archaeological wood are able to inhibit oxidative degradation of TEG. NaFe₃(SO₄)₂(OH)₆ (Natrojarosite), FeS₂ (pyrite), FeSO₄, Fe₂(SO₄)₃, NiCl₂, NiSO₄, Fe, Cu, Fe₂O₃, CuO, NaHSO₄ and natrojarosite-containing scrapings from the Vasa had no major effect on the rate of oxidation.     

The effects of differential ion flows on EISCAT observations in the auroral ionosphere

During geomagnetic storms different partial pressure gradients in the auroral ionosphere may result in H⁺, He⁺, O⁺ and molecular ions drifting with different velocities along the Earth's magnetic field line. For relative drift velocities ⪡ 400 m s⁻¹ it is shown that differential ion flows may be identified by two signatures in the autocorrelation function (ACF) measured by EISCAT. For larger relative drifts numerical simulations show that these signatures still exist and may result in an asymmetry in the incoherent scatter spectrum for O⁺ and molecular ions. It is demonstrated that UHF data can be reliably analysed for k²λ_D² ≲ 1, but at high altitudes, where O⁺–H⁺ flows are expected, UHF observations will be restricted by large Debye lengths (k²λ_D² > 1). Examples of ACFs based on polar wind theory are presented and discussed for the VHF system and finally it is shown that large ion temperature ratios (T_i(H⁺) >T_i(O⁺)) can significantly affect the velocity determination.     

RESEARCH ON THE PIGMENTS FROM PAINTED CERAMICS EXCAVATED FROM THE YANGQIAOPAN TOMBS OF THE LATE HAN DYNASTY (48 BC – AD 25)

The analysis of pigments on painted ceramics excavated from the Yangqiaopan Tombs of the late Western Han Dynasty was undertaken using optical microscopy (OM), micro‐Raman spectroscopy (μ‐RS), scanning electron microscopy with energy‐dispersive X‐ray spectrometry (SEM–EDS), X‐ray diffraction (XRD) and Fourier‐transform infrared spectroscopy spectra (FTIR). The pigments were identified as red lead (Pb₃O₄), carbon (C), malachite [Cu₂CO₃(OH)₂], Chinese purple (BaCuSi₂O₆) and illite {[K,H₃O]Al₂Si₃AlO₁₀(OH)₂}. Fibrous materials were observed in some pigment samples. When observed by SEM, one showed a large amount of fibre in solidified gum, which indicated that gum of ramie could have been used as the binding medium to make the pigment particles adhere together. These results provide significant insights into the characteristics of these pigments in the Qin and Han Dynasties.