KIMMERIDGE JET—A POTENTIAL NEW SOURCE FOR BRITISH JET

Archaeological artefacts identified as jet are often assumed to have originated from the principal British source, which is at Whitby in Yorkshire. Geological samples of jet have also been found within the Kimmeridge Blackstone in Dorset—a seam of oil shale which has been worked since prehistoric times to produce artefacts similar to those made from jet. This paper discusses the geology and geochemistry of jet samples from both Whitby and Kimmeridge, and shows that the geological samples can be discriminated by differences in their organic components, as elucidated by Fourier transform infrared spectroscopy and pyrolysis-gas chromatography/mass spectrometry.     

THE CHARACTERIZATION OF PAINTS AND WATERPROOFING MATERIALS FROM THE SHIPWRECKS FOUND AT THE ARCHAEOLOGICAL SITE OF THE ETRUSCAN AND ROMAN HARBOUR OF PISA (ITALY)*

This work presents the results of a diagnostic survey on the shipwrecks from the archaeological site of the ancient harbour of San Rossore (Pisa, Italy). The original waterproofing, caulking and painting materials were characterized by Fourier transform infrared spectroscopy (FTIR), gas chromatography – mass spectrometry (GC–MS), energy‐dispersive X‐ray microanalysis (EDX) and X‐ray diffraction (XRD). The major constituents of the waterproofing and caulking materials detected on the planks were tricyclic abietanes showing a high degree of aromatization. These compounds are indicative of a pitch obtained from the wood of trees of the Pinaceae family. The analysis of the organic components of the paint samples revealed diterpenoid acids characteristic of Pinaceae resins together with linear long‐chain alcohols and fatty acids, highlighting the presence of beeswax. Noticeably, the characteristic odd carbon number alkanes that are normally present in beeswax were not detected. The EDX and XRD analyses showed that hematite, calcite, cerussite and kaolinite were employed as pigments to paint the ships’ hulls.     

In situ decarboxylation of acetic and formic acids in aqueous inclusions as a possible way to produce excess CH4

Accurate reconstruction of diagenetic P‐T conditions in petroleum reservoirs from fluid inclusion data relies on valid measurements of methane concentration in aqueous inclusions. Techniques have been developed (Raman spectrometry) to provide sufficiently accurate data, assuming measured methane concentration has not been modified after aqueous inclusion entrapment. This study investigates the likelihood that organic acids derived from petroleum fluids and dissolved in formation water might suffer decarboxylation upon postentrapment heating within the fluid inclusion chamber, thereby generating excess CH₄ in the inclusions. Four different experiments were conducted in fused silica capillary capsules (FSCCs), mimicking fluid inclusions. The capsules were loaded with acetic (CH₃COOH) or formic (HCOOH) acid solution and were heated to 250°C for short durations (<72 h) in closed‐system conditions, with or without applying a fixed P_H2. Reaction products were characterized by Raman and FT‐IR spectrometry. Results indicate that decarboxylation reactions did take place, at variable degrees of progress, and that measurable excess CH₄ was produced in one experiment using acetic acid. This suggests that methane may be produced from dissolved organic acids in natural aqueous inclusions in specific situations, possibly inducing errors in the thermodynamic interpretation.     

Anselm Kiefer: a study of his artistic materials

The style of the contemporary German artist Anselm Kiefer is highly innovative and unconventional and is characterized by the use of diverse materials that he selects and combines according to the emotions that they stir in him. The conservation and preservation of works by Kiefer are particularly difficult tasks because of the heterogeneity and, in some cases, the incompatibility of the materials used; therefore, a thorough characterization is crucial before any intervention is considered. In this paper, we report the results of an investigation on a fragment from a multimaterial work and on samples from the paintings Bohemia Lies by the Sea and Die Größe Fracht. The large fragment was cut by the artist himself from a work in progress and is considered destitute of any artistic value; therefore, it was possible to sample it extensively. This fragment and the samples from the Die Größe Fracht and Bohemia Lies by the Sea paintings were analyzed by ultraviolet (UV) fluorescence imaging, fiber optic reflectance spectroscopy, Fourier transform infrared spectroscopy, nuclear magnetic resonance, Raman spectroscopy, X-ray diffraction, gas chromatography-mass spectrometry, and pyrolysis gas chromatography-mass spectrometry. This multitechnique approach allowed us to fully characterize and identify pigments, dyes, and organic components that reflect the diversity of the materials typically chosen by the artist. The results are evaluated in the context of the interview that Antonio Rava had with the Anselm Kiefer in 2000.     

Ethno-geochemical and Phytolith Studies of Activity Related Patterns: A Case Study from Al Ma’tan,Jordan

ABSTRACT

Understanding Neolithic sites in southwest Asia is often difficult because of the lack of preservation of organic remains and the effects of various taphonomic processes that alter the original record. Here, we use an ethnographic approach to test the potential of using plant phytoliths and geochemistry to aid our interpretation of southwest Asian Neolithic sites. Our study of a recently abandoned stone and mud constructed village in Jordan, shows that for certain activity types, phytoliths and geochemistry can help distinguish different construction methods and functions, particularly for burnt areas, animal use areas and where there has been the addition of a specific construction material. For features constructed from the same source materials distinctions are more problematic. Geochemical and phytolith proxies were individually effective in distinguishing activity areas and construction materials, but signals were diminished when the statistical analysis was run on both forms of evidence combined. It is therefore recommended that the data from plant phytolith and geochemical analyses are subject to separate statistical tests and that the two sets of results are used in combination to interpret archaeological sites and their uses.     

FIELD AND LABORATORY MULTI‐TECHNIQUE ANALYSIS OF PIGMENTS AND ORGANIC PAINTING MEDIA FROM AN EGYPTIAN COFFIN (26TH DYNASTY)

This paper describes the physico‐chemical analyses performed on an Egyptian wood coffin on the occasion of its restoration in the hall of the National Archaeological Museum of Parma (Italy), with the aim of investigating the pigments and organic materials originally used. Pigment determination was performed both in situ by a portable energy‐dispersive X‐ray fluorescence (EDXRF) spectrometer and in the laboratory using a micro‐Fourier‐transform‐infrared (micro‐FTIR) and a Fourier‐transform (FT) Raman spectrometer. The identification of organic materials was performed through gas chromatography – mass spectrometry (GC–MS) and micro‐FTIR analysis. Amongst the pigments, special attention was paid to the green, which appeared to be severely degraded and was examined using powder X‐ray diffraction (XRD) and scanning electron microscopy – energy‐dispersive X‐ray (SEM–EDX) in addition to the above‐cited techniques. Other materials used in the polychromatic decorations are Egyptian blue, cinnabar and possibly orpiment, while calcium carbonate was used for the ground layer. The organic materials were identified as beeswax, mastic and gum arabic, sometimes as mixtures.     

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。     

It’s never too late to join the revolution! – Enabling new modes of production in the contemporary Danish food system

ABSTRACT

The Danish food system has undergone a transition in the past 10–20 years, in which new quality conventions have evolved. Examples include increasing organic production and consumption, and increasing interest in local food, experience, community, taste and gastronomy. This article explores what influences if and how these new food trends are expressed in the food system. We conduct a comparative case study involving three product categories: craft beer, specialty flour and organic broilers. Craft beer and specialty flour have undergone a revolution, in which new flavours, products, practices and social relations are generated; by contrast, organic broilers have remained a relatively stable product category. The case studies demonstrate that the revolution is not just taking place in one domain, but it implies a multidimensional reconfiguration of the food system where an emphasis on multiple quality aspects and diversification of the product category is important. However, food trends are not the invention of the individual producer, but serve as common conventions that products can be related to, although their interpretation is not pre-given. In addition, a transition presupposes a shared vision and a coordination of activities among the actors in the food system or the mobilization of new actors who share this vision.     

Organic-walled microfossils from the Early Cambrian of South Australia

Microfossils which are hollow, possess a two-layered vesicle wall, and occur as single elements or, more rarely, as compound forms, have been recovered from the Early Cambrian Heatherdale Shale, on the Fleurieu Peninsula, South Australia. The microfossils, which range in size from 4 to 14.5 μm, are informally and tentatively assigned to the genus Sphaerocongregus Moorman 1974. Superficially they resemble forms assigned to Pyritosphaera Love 1958 and its probable junior synonym, Bavlinella Shepeleva 1962. Topotypes of these genera, however, have yet to be studied using SEM techniques, and their morphologic details remain uncertain. The organic composition of the present microfossils is supported by energy-dispersive X-ray analyses. Samples of the Heatherdale Shale were also analysed using pyrolysis techniques; the organic matter is, however, over-mature with respect to petroleum generation, and no geochemical assessment of original kerogen type is possible.     

PREHISTORIC WALL PAINTINGS: THE CASE OF THE DOMUS DE JANAS NECROPOLIS (SARDINIA,ITALY)*

The Domus de Janas (Home of the Fairies, or Home of the Witches) are Neolithic hypogea located throughout Sardinia (Italy) and decorated with red and black wall paintings. The objective of this study was to define the painting technique through the analytical characterization of the pigments and binding media. Samples of painting film from different graves have been examined by means of various analytical techniques. XRD, Raman and SEM–EDX analyses identified the red and black pigments respectively as red ochre rich in hematite and carbon black, while GC–MS analyses characterized the organic binder as egg.     

FT-IR measurements of petroleum fluid inclusions: methane, n-alkanes and carbon dioxide quantitative analysis

A recent advancement in petroleum geochemistry is to model fossil oil composition using microthermometric and volumetric data acquired from individual fluid inclusion analysis. Fourier transform infrared (FT‐IR) microspectroscopy can record compositional information related to gas (CH₄ and CO₂) and alkane contents of petroleum inclusions. In this study, a quantitative procedure for FT‐IR microspectrometry has been developed to obtain, from individual fluid inclusions, mol percentage concentrations of methane, alkanes and carbon dioxide as constraints to thermodynamic modelling. A petroleum inclusion in a sample from the Québec City Promontory nappe area was used as standard to record a reference spectrum of methane. The analytical procedure is based on the measurement of CH₄/alkane and CH₄/CO₂ band area ratios. CH₄/alkane infrared band area ratio is obtained after spectral subtraction of the reference methane spectrum. This area ratio, affected by absolute absorption intensities of methane, methyl and methylene, provides a molar CH₄/alkane ratio. Methyl/methylene ratio (CH₂/CH₃) ratio is obtained following procedures established in previous work. CO₂/CH₄ concentration ratio is estimated from relative absolute absorption intensities. Application to natural inclusions from different environments shows good correlation between FT‐IR quantification and PIT (petroleum inclusion thermodynamic) modelling.     

重庆大足大佛湾彩绘绿色和蓝绿色颜料的分析研究

为了确定重庆大足大佛湾彩绘含铜、砷元素的绿色及蓝绿色颜料显色成分,应用便携式X射线荧光光谱仪(XRF)、便携式显微镜等无损调查方法,结合X射线衍射分析仪(XRD)、扫描电镜-能谱仪(SEM-EDX)、X射线光电子能谱分析仪(XPS)、显微拉曼光谱仪(RM)等分析方法,对取自大佛湾塑像的绿色及蓝绿色颜料进行调查和分析。结果表明绿色颜料显色成分为为巴黎绿,蓝绿色颜料显色成分为氯砷钠铜石[NaCaCu₅(AsO₄)₄Cl·5H₂O]。根据研究结论推断,氯砷钠铜石可能为巴黎绿的变色产物。该结果为探讨近代人工合成颜料变色机理提供了新的线索和方法。     

A Qualitative Approach for Assessment of the Burial Environment by Interpreting Soil Characteristics; A Necessity for Archaeological Monitoring

Abstract

Modern-day archaeological monitoring is often hampered by lack of money, lack of time, inadequate measuring equipment, and lack of insight in the conservation potential of a site.

Although in modern archaeological excavations soil characteristics are noted (colour, texture, groundwater level, and sometimes mineralogy), these characteristics are mainly used for the interpretation of a site. However, by looking to these characteristics from a conservational view eventually combined with the conservation status of the archaeological objects, much can be learned about the burial environment. This is essential for optimizing archaeological monitoring.

Degradation processes result from the change of reactive phases in the soil or the site. Reactive phases are soil components such as organic matter, sulfides, iron(hydr)oxides and carbonates (chalk, shells), and, if present, components in the ground or interstitial water such as hydrogen ions and sulphate. The presence of these phases can easily be established by the archaeologist or soil scientist in the field. We propose a simple field-based method for assessing degradation processes essential for in situ preservation and monitoring.     

Interdisciplinary Search for Early Life Forms and for the Beginning of Life on Earth

Abstract

The evolution of life and the nature of the oldest organisms depend on the atmospheric, hydropheric and lithospheric conditions during very early terrestrial history. Specialists, working in different fields of scientific endeavour, assume that the various proposed early atmospheric, hydrospheric and lithospheric models are established; this is not the case as some of the proposed models are contradictory. The results of prebiological chemical evolution simulation experiments, actual chemical analyse of very ancient rocks and ancillary micropaleontological studies also lack agreement.

This article represents the first time a critical interdisciplinary inquiry has been attempted, based on astronomy geophysics, geochemistry, geology, atmospheric physics, oceanography, hydrology, chemistry and biology. Prebiological organic compounds have yet to be found in rocks. The oldest known rock (~3800 million years) of sedimentary origin, found in S.W. Greenland has not yet revealed microfossils and carbon compound other than methane. The (~3400 m years) Onverwacht sedimentary rocks in South Africa may or may not contain biological substances. A Transvaal stromatolite (~2300 m years) contains blue-green algal microfossils having physiologically diversified cells: these fossile algae may have modern living analogs. Artificial compounds in this small rock may well attest complex biochemistry ~2300 m years ago.     

One Colour, (at Least) Two Minerals: A Study of Mulberry Rock Art Pigment and a Mulberry Pigment ‘Quarry’ from the Kimberley,Northern Australia

Distinctive mulberry paintings found in northern Australia, particularly those of the Kimberley region, have been argued to represent some of the oldest surviving rock art on the continent. Significant research efforts continue to focus on resolving the age of these motifs, but comparatively little attention has been given to understanding their physical composition and potential source(s). In a pilot investigation, we conclude that (at least) two mineralogically distinct mulberry pigments occur in Gwion motifs and demonstrate that their major components can be indicatively chemically differentiated, non‐invasively. Characterization of a ‘quarried’ mulberry ochre source demonstrates that these pigments occur locally as natural minerals.     

ORGANIC RESIDUE ANALYSIS IN ARCHAEOLOGY: THE ARCHAEOLOGICAL BIOMARKER REVOLUTION*

Organic residue analysis utilizes analytical organic chemical techniques to identify the nature and origins of organic remains that cannot be characterized using traditional techniques of archaeological investigation (because they are either amorphous or invisible). The field is founded upon the principle that the biomolecular, or biochemical, components of organic materials associated with human activity survive in a wide variety of locations and deposits at archaeological sites. The archaeological information contained in organic residues is represented by the biomolecular components of the natural products that contribute to the formation of a given residue. By applying appropriate separation (chromatographic) and identification (mass spectrometric) techniques, the preserved, and altered, biomolecular components of such residues can be revealed. Once identified, the Archaeological Biomarker Concept can be applied, wherein the structure and even isotopic composition(s) of a given biomolecule or suite of biomolecules (the ‘chemical fingerprint’) can be related to the compositions of organisms exploited by humans in the past. As the organic residue field emerges from its pre‐paradigmatic phase, and the organic residue revolution gathers pace, the way is open for challenging many long‐held archaeological hypotheses and offering new perspectives on the study of human activity in the past.     

IDENTIFYING THE PLANT ORIGIN OF ARTISTS' YELLOW LAKE PIGMENTS BY ELECTROSPRAY MASS SPECTROMETRY

Dyes containing flavonoids are found in yellow lake pigments used as artists' materials. Pre‐treating a sample of a flavonoid‐based lake pigment with an acidic ion exchange resin followed by reversed‐phase HPLC electrospray mass spectrometry enables the identification of key diagnostic yellow compounds, even when the pigment is bound in paint media. Reference raw plant materials of weld and buckthorn berries were also treated similarly for comparison with the lake pigments derived from these plants. This method is suitable for microsamples and thus suitable for analysis of samples that can be ethically removed from works of art in the course of their conservation. The flavonoid content is analysed and plant origins are suggested for yellow lake samples taken from Reclining Tiger by Jean‐Baptiste Oudry and the 1893 version of The Scream by Edvard Munch.     

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.     

Relevance of soil biology and fertility research to archaeological preservation by reburial

Abstract

This paper discusses how soil biological information can help to improve understanding of, and possibly inform decisions about, preservation of organic archaeological remains by reburial. A brief summary of the properties of the soil biological community is followed by an outline of results from recent biological investigations following the recovery of archaeologically relevant materials that had been buried for thirty-three years in one of the experimental earthworks in England UK. Examples from the soil biology and fertility literature are discussed to illustrate the effects of fluctuations in soil wetness and aeration, and of nitrogen availability on decomposition. Finally, the impact of soil handling and physical disruption on biological processes in soil are discussed, as they influence whether soil functions can be restored at a reburial site once the archaeological resources have been ‘protected’ beneath.