Faecal biomarker and archaeobotanical analyses of sediments from a public latrine shed new light on ruralisation in Sagalassos, Turkey

A public latrine in the ‘Imperial Baths’ of Sagalassos was transformed into a dump site in the early Byzantine period. Several layers of urban waste, including ceramics, bones, glass and perhaps excrements were deposited on the floor. Faecal biomarker analyses and archaeobotanical analyses were conducted to reconstruct the history of the room. 5β-stanols of human origin, such as coprostanol, were found in the sewage channels together with mineralised plant remains, indicating a human faecal context. The botanical remains are furthermore representative of the Roman diet of the Sagalassians. Soil layers, deposited on top of the latrine floor and dating to the early Byzantine period, contained herbivore derived 5β-stanols, such as 5β-stigmastanol and epi-5β-stigmastanol. Additionally, a clear predominance of epi-5β-stanols over 5β-stanols showed that the animal dung has been subject to composting. In this period, the former latrine was clearly used as a manure production site which is further confirmed by stratigraphic evidence of large amounts of urban waste artefacts, which were commonly collected together with manure before application on the fields. The results of the present study support the theory that off-site potsherd scattering can be used as a proxy for manuring events. Additionally, the data show key evidence for vertical migration of 5β-stanols and presumably also for the leaching of bile acids.     

Biomolecular and micromorphological analysis of suspected faecal deposits at Neolithic Çatalhöyük,Turkey

Suspected coprolites from midden, burial and room fill contexts at Çatalhöyük were analysed by GC/MS and thin section micromorphology. Assessment of sterol biomarkers enabled a distinction between faecal and non-faecal sources for the deposits to be made, with bile acid biomarkers indicating that many of the faecal deposits are human coprolites. The relative lack of ruminant faeces could be due to this material being used as a fuel source. Deposits in burials were observed to contain soil and plant derived sterols rather than their faecal counterparts. Further analysis in thin section enabled identification of associated materials and contents. Diagnostic inclusions such as bone and plant fragments were only present in some of the human coprolites, which were observed to have a very similar morphology to decayed plant remains. This study illustrates the difficulties in distinguishing coprolites in the field and under the microscope, and demonstrates the importance of integrating biogeochemical methods, particularly when such deposits are used as the basis for interpreting human health and diet, and use-of-space in settlements.     

Lipid Residues from Low‐Fired Pottery

This paper assesses the fate of lipids associated with low‐temperature and pit‐fired pottery to determine to what degree organic compounds persist or are removed during short‐firing episodes below 800 °C. Three different types of clay were fired using contrasting techniques including at 400 °C for 4 h in a muffle furnace, and pit‐firing in which pottery was fired to higher temperatures but for shorter periods of time. Total lipid extracts obtained by solvent extraction of test sherds were screened using gas chromatography‐flame ionization detection (GC‐FID) to determine the lipid concentrations and gas chromatography–mass spectrometry (GC–MS) to identify the organic compounds present. The results showed that firing of clay removes all naturally occurring alkyl lipids; however, during pit‐firing, diterpenoid lipids were introduced into the clay as a condensate from pine ( Pinus spp.) wood used as fuel. These results confirm that alkyl lipids, e.g., fatty acids, can be reliably associated with the use of vessels, although caution is required when interpreting the origins of lipids that might derive from fuel used in firing.     

GC–MS ANALYSIS OF LIPIDS IN PREHISTORIC ROCK PAINTS AND ASSOCIATED OXALATE COATINGS FROM THE LOWER PECOS REGION,TEXAS*

The presumption that lipids were used as binders/vehicles in pictograph paints from southwestern Texas was tested using gas chromatography–mass spectrometry (GC–MS). A one‐step transesterification/derivatization procedure was used to convert bound and unbound fatty acids to fatty acid methyl esters for the analysis. Approximately 30 organic compounds were detected in the natural rock coating that encapsulates the paints, but there were no compounds unique to the paints. Moreover, the C_16:0 and C_18:0 concentrations in the paint samples were similar to the concentrations of these fatty acids in the rock coating, indicating that the compounds are native to the patina. Thus, lipid binders were either not used in the original paint mixture or have since degraded.     

Heavy Metals in Sediments of the Upper Hawkesbury‐Nepean River

There is little published information on heavy metals in surficial sediments of the upper Hawkesbury‐Nepean River in central New South Wales, Australia. In the current investigation, the fine fraction (<62.5 µm) of 90 sediment samples taken from this section of the river was analysed by flame‐Atomic Absorption Spectroscopy for nine heavy metals (Ag, Cd, Pb, Zn, Cu Co, Fe, Ni and Mn) to determine background and enrichment. Sediment in the upper Hawkesbury‐Nepean River is not heavily polluted by heavy metals. Maximum enrichment over background for Ni and Ag, Cd, Pb, Zn, Cu and Mn is 3x, 5.7x, 6x, 6.7x, 12x and 13.6x, respectively. Mean heavy metal concentrations for this, the upper section of the river, are about half the mean values for the Hawkesbury River between Windsor and Broken Bay in the lower, estuarine section of the river. The highest Cu, Pb and Zn concentrations (214, 108 and 334 mg kg^?1, respectively) occur in surficial sediments in Peachtree Creek at Penrith and the Nepean River near Jacksons Lane, Castlereagh. These metal concentrations are possibly associated with industrial activity at Penrith. Two of the six sewage treatment plants on the upper Hawkesbury‐Nepean River are associated with high metal concentrations (Cu, Zn, Fe and Mn) in sediments, that is, the West Camden and Penrith sewage treatment plants. Other possible sources of heavy metals are coal mining and washing which occurs at several places in the upper catchment. The highest Cd, Co and Fe concentrations (1.7, 27.6 mg kg^?1 and 4.81%, respectively) were found in sediments 400 m downstream of the Nepean Dam and the highest concentrations of Ni and Mn (54 and 790 mg kg^?1, respectively) were located in sediment from the Nepean River at Moresby Hill Road Bridge, near Robertson and at the Avon Dam Road Bridge. The source of these metals is unknown.     

GC/MS ANALYSIS OF FATTY ACIDS FROM ANCIENT HEARTH RESIDUES AT THE SWAN POINT ARCHAEOLOGICAL SITE*

Gas chromatography – mass spectrometry (GC/MS) is used to analyse soil residues from hearth sites in Swan Point, Alaska. An experimental hearth is also prepared by burning animal bones to study the characteristics of bone fires and the lipid residues that they leave embedded in soil. Hearth soil samples are derivatized with HCl in methanol to convert bound and unbound fatty acids into methyl esters. Concentrations of saturated fatty acid methyl esters in the samples are determined and their ratios analysed. The fatty acid patterns found in ancient campfires are consistent with burning bones of large ruminants as well as monogastric herbivores.     

AN EVALUATION OF ANALYTICAL AND INTERPRETATIVE METHODOLOGIES FOR THE EXTRACTION AND IDENTIFICATION OF LIPIDS ASSOCIATED WITH POTTERY SHERDS FROM THE SITE OF SAGALASSOS,TURKEY*

Three lipid analysis methods were applied to extracts of archaeological potsherds from the ancient city of Sagalassos, south‐west Turkey. In the fatty acid methyl ester fraction, obtained by selective transesterification of acylglycerols, the ratio of methyl palmitate to methyl stearate was determined. Secondly, by means of gas chromatography– combustion–isotope ratio mass spectrometry (GC–C–IRMS), stable carbon isotope ratios were measured for the same methyl esters. Finally, triglyceride composition was determined via high‐performance liquid chromatography–mass spectrometry (HPLC–MS). All three methods can be used to trace the origin of animal fat. Agreement between them is reasonable, especially in recognizing ruminant adipose fat. One sample was found to be of dairy origin using both GC–C–IRMS and HPLC–MS. The advantages of the various methods are discussed. Variations in lipid composition were observed between samples from different periods and excavated in diverse areas within the city of Sagalassos.     

Hydrothermal activity associated with the Ries impact event, Germany

Combined field studies, optical and scanning electron microscopy, and electron microprobe studies of impactites from the Ries impact structure, Germany, have allowed a clearer picture of the hydrothermal system associated with the Ries impact event to be made. Hydrothermal alteration is concentrated within impact‐generated suevites in the interior of the crater (crater suevites) and around the periphery (surficial suevites), with minor alteration in the overlying sedimentary crater‐fill deposits. The major heat source for the Ries hydrothermal system was the suevite units themselves. Hydrothermal alteration of crater‐fill suevites is pervasive in nature and comprises several distinct alteration phases that vary with depth. An early phase of K‐metasomatism accompanied by minor albitization of crystalline basement clasts and minor chloritization, was followed by pervasive intermediate argillic alteration (predominantly montmorillonite, saponite, and illite) and zeolitization (predominantly analcite, erionite, and clinoptilolite). Hydrothermal fluids were typically weakly alkaline during the main stage of alteration. In contrast to the crater‐fill suevites, alteration within surficial suevites was typically restricted to montmorillonite and phillipsite deposition within cavities and fractures. The pervasive nature of the alteration within the crater‐fill suevites was likely due to the presence of an overlying crater lake; whereas alteration within surficial suevites typically occurred under undersaturated conditions with the main source of water being from precipitation. There are exceptional outcrops of more pervasively altered surficial suevites, which can be explained as locations where water pooled for longer periods of time. Hydrothermal fluids were likely a combination of meteoric waters that percolated down from the overlying crater lake and groundwaters that flowed in from the surrounding country rocks.     

Fuel For Lamps: Organic Residues Preserved in Iron Age Lamps Excavated at the Site of Sahab in Jordan

Five Iron Age ceramic lamps from a tomb at the site of Sahab in the south‐eastern part of central Jordan were analysed using gas chromatography – mass spectrometry (GC–MS). The results of this study provide data on the type of fuel used in three of these lamps. The study proposes that animal fat, possibly of ruminant origin, was used in three Early Iron Age II lamps. The material used in the other two Iron Age I lamps could not be determined due to the absence of diagnostic biomarkers. The data obtained from the lamps can be put in conjunction with the archaeological evidence on the availability of domestic animals and, most probably, use of their products at the site of Sahab during the Iron Age.     

The Preservation of Invertebrates in 16th‐Century Cesspits at St Saviourgate,York*

The taphonomy of invertebrates from 16th‐century cesspits at St Saviourgate, York, was investigated. Earthworms, fly larvae and puparia are preserved through replication in calcium phosphate, a process facilitated by acidic cesspit pore water and by the presence of abundant organic matter, bones and shells. Features preserved by mineralization include muscles, blood vessels and setae. Non‐mineralized invertebrate remains include puparia and beetles. Py–GC/MS (flash pyrolysis–gas chromatography/mass spectrometry) revealed a very high level of preservation of structural biomolecules, with all the protein and chitin markers that are evident in the living forms still being detectable in the divalent remains.     

LIPIDS FROM SAMPLES OF SKIN FROM SEVEN DUTCH BOG BODIES: PRELIMINARY REPORT

A combination of micro-analytical techniques including thin layer chromatography (TLC), gas chromatography (GC). and combined gas chromatography/mass spectrometry (GCIMS) have been employed to study the lipid compositions of samples of skin from seven Dutch bog bodies. TLC showed that, while phospholipids have been degraded, other acyl lipids, for example triacylglycerols and steryl esters, may remain intact. GC and GC/MS analyses, following treatment of the total lipid extracts with acidified methanol, showed the presence of abundant fatty carboxylic acids and sterols. Molecular analysis by GC/MS allowed distinctions to be drawn between components originating from the bog body and the surrounding peat. Additionally, substances derived from microbial alteration of endogenous skin lipids and from the lipids of the micro-organisms themselves can be distinguished.     

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.     

THE STUDY OF NABATAEAN ORGANIC RESIDUES FROM MADÂ’IN SÂLIH,ANCIENT HEGRA,BY GAS CHROMATOGRAPHY – MASS SPECTROMETRY*

Four Nabataean samples collected in some of the monumental tombs of Madâ’in Sâlih, ancient Hegra, in Saudi Arabia, have been studied by gas chromatography coupled with mass spectrometry. These samples are textile fragments that are either covered with a black layer or bound together with some black amorphous substance. Fatty acids and triterpenoic compounds were detected. Eight triterpenic compounds were identified: ursa‐9(11),12‐dien‐3‐ol, ursa‐9(11),12‐dien‐3‐one, olean‐9(11),12‐dien‐3β‐ol, β‐amyrone, β‐amyrin, α‐amyrone, α‐amyrin and lupeol. The resinous chemical composition and these pentacyclic alcohols, in considerable proportion, indicate a resin of the Burseraceae family, possibly of the genus Canarium.     

Characterization of organic media in the wall-paintings of the “Palace of Nestor” at Pylos,Greece: evidence for a secco painting techniques in the Bronze Age

This paper presents the results of an investigation of organic binding media detected in samples from the Mycenaean wall-paintings at the “Palace of Nestor” in Pylos (Western Messenia, Greece): samples dated from the Late Bronze Age (ca. 1200 BC). This is the first scientific study to be conducted on organic binding media in Mycenanean painting, and it is a study that aims to contribute significantly towards our understanding of the original painting techniques used during the Bronze Age. The analytical procedures employed for the detection and characterization of the organic substances preserved within the paint layers (proteinaceous materials, lipids and plant gums), were based on chromatography/mass spectrometry techniques (PY–GC/MS, GC/MS). The most significant results, highlighting an a secco painting technique, are herein reported and discussed.     

SCIENTIFIC INVESTIGATIONS OF ANTIQUE LACQUERS FROM A 17TH‐CENTURY JAPANESE ORNAMENTAL CABINET

A recent restoration of a 17th‐century Japanese lacquer cabinet revealed various later treatments over the original black coating to maintain and preserve the high gloss of the oriental cabinet over the course of time and to meet changing tastes. The comprehensive investigation on a series of coating samples was executed by means of two hyphenated techniques: gas chromatography – mass spectrometry (GC–MS) and pyrolysis combined with GC–MS (Py‐GC–MS). The results showed that the original lacquer is based on urushi and linseed oil, while the past interventions are composed of sandarac, shellac and dammar. Additional microscopic studies proved the multi‐layer structure of the lacquer and the use of different pigments.     

Evidence of early tobacco in Northeastern North America?

While tobacco use was a widespread and important social practice among Native Americans during the Historic Period, the prehistoric origins of the practice are poorly understood. Smoking pipes significantly predate botanical evidence of tobacco in Eastern North America. A promising technique for addressing this problem is gas chromatography/mass spectroscopy (GC/MS) analysis to identify nicotine or related compounds in smoking pipe residues. GC/MS analysis of a smoking pipe dating to approximately 300 B.C. from the Boucher Site, a Middlesex-complex site from Vermont, has produced evidence of nicotine decay products. This is interpreted as evidence for an Early Woodland Period origin for tobacco use in Eastern North America. The cultural and chronological implications of this finding are discussed.     

A MULTI‐ANALYTICAL APPROACH FOR THE CHARACTERIZATION OF COMMODITIES IN A CERAMIC JAR FROM ANTINOE (EGYPT)*

This paper describes a multi‐analytical chemical study performed on the original, almost totally conserved, content of a small ceramic jar from the Antinoe archaeological site (fifth to seventh centuries ad, Roman Egypt) and now belonging to the archaeological collection of the Istituto Papirologico ‘Girolamo Vitelli’ (Florence, Italy). Scanning electron microscopy with an energy‐dispersive X‐ray spectrometer (SEM–EDX), Fourier transformed infrared spectroscopy (FTIR) and X‐ray diffraction (XRD) were all used to characterize the inorganic components of the archaeological material. The organic substances were analysed using FTIR, direct exposure mass spectrometry (DE–MS) and gas chromatography – mass spectrometry (GC–MS). The inorganic component essentially consisted of halite (NaCl). Among the NaCl crystals, lamellar elements were identified. They were chemically characterized by carbonato‐apatite and showed a concentric morphology typical of the scales of small fish. The most prevalent organic constituents of the sample were monocarboxylic acids, α,ω‐dicarboxylic acids, and cholesterol and its oxidation products. The organic material composition was consistent with the occurrence of lipids of animal origin. In addition, diterpenes related to pine pitch were also identified. The overall results suggest that the material recovered in the small ceramic jar found in Antinoe is a residue of fish‐based pickles such as garum, muria, allex and liquamen, which were commonly used in Roman times.     

Identification of the Residue in the Bolgar Medieval Sphero‐Conical Vessel by Gas Chromatography – Mass Spectrometry

The Golden Horde sphero‐conical vessel retrieved from the ruins of the medieval city of Bolgar (Russia, Republic of Tatarstan) during archaeological excavations, which contained residue in the form of encrustation on the bottom and the wall, was analysed in the NRC ‘Kurchatov Institute’ by X‐ray phase analysis and high‐performance liquid and gas chromatography with MS detectors (HPLC–MS, GC–MS). The GC–MS method established that the residue from the sphero‐conical vessel was comprised primarily of abietic acid derivatives (around 46%) and retene, which is polycyclic aromatic hydrocarbon (around 27%); this means that turpentine exuded from the stems of certain species of coniferous trees, called resin and subsequently heat‐treated, was poured into the vessel. Researchers have been trying to decipher the function of these mysterious vessels for 200 years, and this is the first time that resin stored in a sphero‐conical vessel has been documented. Potentially, this vessel was probably used as a personal ‘medical kit’.     

Palaeobiology of the Medieval Population of Albano (Rome,Italy): A Combined Morphological and Biomolecular Approach

Recent years have seen increased interest in skeletal populations from the Imperial Roman Age in Italy, but much less is known about diet and standards of living in the subsequent medieval period. To fill this gap, we conducted a morphological analysis of human remains from Albano, an Italian town near Rome, as well as a stable isotope analysis of bone collagen to reconstruct diet. The sample was recovered from a Medieval cemetery (1040–1220 cal. yr. BP) located in the gardens of the historical Palazzo Doria Pamphili in Albano. A minimum number of 40 individuals (31 adults and 9 sub‐adults) were examined using standard methods. Though the general health status of the population was good, signs of cribra orbitalia and diffuse enthesopathies were noted during the morphological examination. Stable carbon and nitrogen isotope analyses of the bone collagen from 24 adult humans and three faunal bones indicate that the diet of the population may be described as predominantly terrestrial and C₃‐plant based although the data for some of the individuals suggest a modest consumption of C₄‐(millet) based or aquatic proteins. No evidence of significant dietary differences between the sexes was found. The comparison of the isotope data from Albano with those from populations recovered in the same region is consistent with a shift from a terrestrial, possibly plant foods‐dominated subsistence in the Early Middle Ages to a diet with a higher contribution from animal proteins, both terrestrial and aquatic, in the Later Middle Ages. Copyright © 2013 John Wiley & Sons, Ltd.     

木材中挥发性有机酸的SPMEGC/MS分析研究

采用木材制作的藏展空间,木材释放出的挥发性有机酸,在一定的温湿度条件下,会对文物造成不良的影响,因此需要建立一套对木材挥发性有机酸测定的方法.为此,采用固相微萃取(SPME)样品预处理技术,分离富集木材中的挥发性有机物,结合气相色谱-质谱(GC/MS)联用技术对木材中挥发性有机酸进行半定量分析,研究了9种木材中挥发性有机酸的挥发量和分布规律.结果表明,不同木材有机酸的挥发量差别较大.实验结果可为博物馆在装修和储藏中对材料的筛选提供科学依据.