Subsistence practices and pottery use in Neolithic Jordan: molecular and isotopic evidence

This paper presents direct evidence of subsistence practices and pottery use at a Late Neolithic site at al-Basatîn, northern Jordan. Measurable concentrations of C_16:0 and C_18:0 were recovered from 8 of 10 archaeological pottery fragments through use of a microwave-assisted silica gel and aminopropyl solvent protocol developed for the isolation and concentration of free fatty acids in marine sediments. Subsequent isotopic analysis of the surviving C_16:0 and C_18:0 saturated fatty acids revealed ∂¹³C ratios consistent with those of adipose fats of ruminant and non-ruminant animals pastured on lands adjacent to the Jordan Valley. The high recovery of diagnostic compounds from the al-Basatîn material is discussed in context of a wider examination of the initial development and use of pottery in the Fertile Crescent, and the emerging debate concerning the efficacy of stable carbon isotope values in characterizing organic residues embedded in pottery fragments recovered from the earliest ceramic horizons in the Middle East and Europe.     

EXPERIMENTAL EVIDENCE FOR THE PROCESSING OF MARINE ANIMAL PRODUCTS AND OTHER COMMODITIES CONTAINING POLYUNSATURATED FATTY ACIDS IN POTTERY VESSELS*

ω‐(o‐Alkylphenyl)alkanoic acids are known to form in vitro from triunsaturated fatty acids following protracted heating. These compounds have recently been identified in absorbed lipid extracts obtained from archaeological pottery vessels, providing a potentially valuable new class of indicator for the processing of commodities, such as marine oils, which contain high abundances of polyunsaturated fatty acids. Experiments were conducted to assess whether ω‐(o‐alkylphenyl)alkanoic acids form when pure compounds and complex triacylglycerol mixtures are heated with a fired clay. The results demonstrate that ω‐(o‐alkylphenyl)alkanoic acids are only produced following heating of unsaturated fatty acids (tri‐, di‐ and monounsaturated species) or complex unsaturated fatty acyl lipids at around 270°C. Heating saturated fatty acyl lipids does not yield ω‐(o‐alkylphenyl)alkanoic acids. Thus, when searching for evidence for the processing of marine derived animal fats in archaeological pottery vessels, it is essential that: ω‐(o‐alkylphenyl)alkanoic acids of carbon length C₁₈ and C₂₀ should be present, ideally with C₂₂ also detectable (if only in trace abundances), together with at least one of the three isoprenoid fatty acids (phytanic, pristanic or 4,8,12‐tetramethyltridecanoic acid).     

GC–MS ANALYSIS AND FATTY ACID RATIOS OF ARCHAEOLOGICAL POTSHERDS FROM THE WESTERN GREAT BASIN OF NORTH AMERICA*

The study of organic residues in archaeological pottery has focused on fatty acids due to their relative stability and longevity. However, even these compounds are subject to degradation, which makes assignment of residues to original foods problematic. This paper suggests that the use of ratios of fatty acids that degrade at roughly the same rate can be useful to identify very general categories of foods. It compares independent information on pot function based on ethnography and engineering/technological studies to that reconstructed based on extracted fatty acid ratios. The results support the notion that Great Basin pots were used primarily to boil seeds and that pot shape and pot function were related.     

THE SEARCH FOR THE ORIGIN OF BITUMEN EXCAVATED FROM ARCHAEOLOGICAL SITES IN THE NORTHERNMOST ISLAND IN JAPAN BY MEANS OF STATISTICAL ANALYSIS OF FI–MS DATA*

The origin of bitumen excavated from archaeological sites in Hokkaido, the northernmost island in Japan, was sought by means of field‐ionization mass spectrometry (FI–MS) and gas chromatography – mass spectrometry (GC–MS) of the hydrocarbon components. The field‐ionization mass spectra were decomposed by Z‐numbers into several components, where the Z‐number refers to z in the formula C _n H _2n+z . This is equivalent to the deficit number of H atoms, when compared to the corresponding saturated hydrocarbon, which is related to the number of saturated hydrocarbon rings in alkanes. By use of the spectral intensities of the seven alkane components in each sample, multiple discriminant analysis was employed for the data of raw bitumen samples and excavated samples from archaeological sites. Based on this method and the gas chromatogram type, the following bitumen trade in the prehistoric age of Japan was elucidated: bitumen from Niigata, one of the main sources on the main island of Japan, spread to the north in 2000 bc , probably via the coastal zone, and reached a small island near the north end of Hokkaido. Bitumen from Sakhalin reached the central lowland in Hokkaido, but it went no further. Bitumen from Akita, another main source on the main island, spread over northern Honshu much earlier and reached the Oshima peninsula, the southwestern part of Hokkaido. The Akita bitumen scattered into the central lowland after the Niigata and Sakhalin bitumen. This area is believed to be the place where people from the south and the north met in those periods.     

Organic geochemical analysis of archaeological medicine pots from Northern Ghana. The multi-functionality of pottery

Sherds from pots found layered under a granite boulder in the Tong Hills of the Upper East Region of Northern Ghana seem, based on their deposition context to have been used for the preparation of medicines. Organic geochemical and isotopic analyses of these sherds and a modern day analogue reveal an n-alkanoic acid composition that is consistent with their being used in the preparation of plant derived substances. Isotopic analyses of the modern medicine pot indicate a contribution of n-alkanoic acids derived from plants that use C₄ carbon fixation, most likely maize, sorghum and/or millet suggesting that this pot was used for cooking C₄ based plant substances, perhaps, based on current analogy, staple porridge type food. The modern medicine pot could thus have had a prior use. The absence of C₄ plant residues in the archaeological sherds suggests that either staple foodstuffs differed radically to today, or, more likely, were not prepared in vessels that were to be used for medicinal purposes.     

Chemical analyses of organic residues in archaeological pottery from Arbon Bleiche 3, Switzerland – evidence for dairying in the late Neolithic

Fatty acids distribution and stable isotope ratios (bulk δ¹³C, δ¹⁵N and δ¹³C of individual fatty acids) of organic residues from 30 potsherds have been used to get further insights into the diet at the Late Neolithic (3384–3370 BC) site of Arbon Bleiche 3, Switzerland. The results are compared with modern equivalents of animal and vegetable fats, which may have been consumed in a mixed ecology community having agrarian, breeding, shepherd, gathering, hunting, and fishing activities. The used combined chemical and isotopic approach provides valuable information to complement archaeological indirect evidence about the dietary trends obtained from the analysis of faunal and plant remains. The small variations of the δ¹³C and δ¹⁵N values within the range expected for degraded animal and plant tissues, is consistent with the archaeological evidence of animals, whose subsistence was mainly based on C₃ plants. The overall fatty acid composition and the stable carbon isotopic compositions of palmitic, stearic and oleic acids of the organic residues indicate that the studied Arbon Bleiche 3 sherds contain fat residues of plant and animal origin, most likely ruminant (bovine and ovine). In several vessels the presence of milk residues provides direct evidence for dairying during the late Neolithic in central Europe.     

Dairying in antiquity. II. Evidence from absorbed lipid residues dating to the British Bronze Age

Molecular and isotopic analyses were undertaken of absorbed lipid residues from 256 pottery vessels obtained from four southern British Bronze Age sites (Potterne, Brean Down, Black Patch and Trethellan Farm). The results confirm that not only were Ancient Britons utilising dairy products during this period, but also that they were processed in pottery vessels on a large scale. This has been demonstrated through the determination of the compound-specific stable isotope values of the principal fatty acids found in animal fats (C_16:0 and C_18:0) that allows ruminant dairy and ruminant/non-ruminant adipose fats to be distinguished. The proportion of sherds yielding degraded dairy fats at each of the sites is variable, with the highest occurrence being from Potterne, and the lowest occurrence being from Black Patch. The faunal remains, and vessel characteristics (e.g. rim diameter and vessel type) are compared with the organic residue analyses, and intra-site variability is investigated at Trethellan Farm.     

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.     

Dairying in antiquity. III. Evidence from absorbed lipid residues dating to the British Neolithic

Absorbed lipid residue analysis has previously demonstrated that dairying was a major component of animal husbandry in Britain during both the Iron Age and Bronze Age. As a continuation of this research into the antiquity of dairying, the incidence of dairy fats associated with pottery vessels from six Neolithic sites from Southern Britain is presented herein. A total of 438 potsherds from Windmill Hill, Abingdon Causewayed Enclosure, Hambledon Hill, Eton Rowing Lake, Runnymede Bridge and Yarnton Floodplain were submitted for organic residue analysis. To date, this constitutes the largest number of sherds investigated from one particular archaeological period. The compound-specific stable isotope values of the major fatty acid components in animal fats, namely C_16:0 and C_18:0, enable absorbed lipids in pottery vessels to be classified to commodity group, i.e. ruminant adipose, dairy and non-ruminant adipose fats can be distinguished. The lipid extracts were relatively well preserved, and dairy fats were observed in approximately 25% of all of the sherds, demonstrating that milk was a valued commodity in the British Neolithic. These results confirm that dairying was an established component of the agricultural practices that reached Britain in the 5^th Millennium BC.     

CHEMICAL CHARACTERIZATION AND STATISTICAL MULTIVARIATE ANALYSIS OF ANCIENT POTTERY FROM MESSINA,CATANIA, LENTINI AND SIRACUSA (SICILY)*

This paper presents the chemical characterization of 79 fragments of Archaic and Hellenistic fine‐grained pottery from archaeological sites in Messina, Catania, Lentini and Siracusa (Sicily). The sherds were classified as ‘calcidian’, ‘banded’, ‘unvarnished’ and ‘black varnished’ pottery. The major and trace elements identified by X‐ray fluorescence (XRF) were statistically elaborated using the method proposed by J. Aitchinson in 1986 for the analysis of compositional data. From cluster analyses using element/SiO₂ log‐ratios, it was possible to group the pottery found in Catania, Lentini and Siracusa into highly linked clusters. Conversely, the Messina pottery was divided into two clearly distinct groups. With the aim of identifying any possible mineralogical differences between the two Messina groups, Fourier transform infrared (FT–IR) absorption measurements were made, showing only quantitative differences in plagioclase and muscovite. The specific groups of pottery with restricted chemical compositions are considered to be of local production, also on the basis of archaeological and petrographic evidence.     

Dairying in antiquity. I. Evidence from absorbed lipid residues dating to the British Iron Age

The evidence for dairying in antiquity has, until recently, primarily been restricted to the reconstruction of herd structures through the analysis of faunal remains. Using this method alone cannot provide definitive evidence for the presence of dairy herds, due to differences in the recovery of animal bones at sites and the many different farming strategies that can affect herd structures (e.g. dairying, meat production, traction etc.). Absorbed lipid residues have been extracted from 237 pottery vessels from the British Iron Age sites of Maiden Castle, Danebury Hillfort, Yarnton Cresswell Field and Stanwick. The compound-specific stable carbon isotope (δ¹³C values) of the principal fatty acids found in animal fats (C_16:0 and C_18:0) have allowed the direct detection of dairy fats, thus providing evidence that dairying was an important component of farming practices in the British Iron Age. The results are compared to assessments of the faunal remains at each of the sites, and correlations between morphological characteristics of the vessels (e.g. type, form, use wear and rim diameter) and lipid residue discussed.     

Microstructural,chemical and isotopic evidence for the origin of late neolithic leather recovered from an ice field in the Swiss Alps

Archaeological leather samples recovered from the ice field at the Schnidejoch Pass (altitude 2756 m amsl) in the western Swiss Alps were studied using optical, chemical molecular and isotopic (δ¹³C and δ¹⁵N of the bulk leather, and compound-specific δ¹³C analyses of the organic-solvent extracted fatty acids) methods to obtain insight into the origin of the leather and ancient tanning procedures. For comparison, leathers from modern native animals in alpine environment (red deer, goat, sheep, chamois, and calf/cow) were analyzed using the same approach. Optical and electron microscopically comparisons of Schnidejoch and modern leathers showed that the gross structure (pattern of collagen fibrils and intra-fibrils material) of archaeological leather had survived essentially intact for five millennia. The SEM studies of the hairs from the most important archaeological find, a Neolithic leather legging, show a wave structure of the hair cuticle, which is a diagnostic feature for goatskins. The variations of the bulk δ¹³C and δ¹⁵N values, and δ¹³C values of the main fatty acids are within the range expected for pre-industrial temperate C₃ environment. The archaeological leather samples contain a mixture of indigenous (from the animal) and exogenous plant/animal lipids. An important amount of waxy n-alkanes, n-alkan-1-ols and phytosterols (β-sitosterol, sitostanol) in all samples, and abundant biomarker of conifers (nonacosan-10-ol) in the legging leathers clearly indicate that the Neolithic people were active in a subalpine coniferous forest, and that they used an aqueous extract of diverse plant material for tanning leather.     

Molecular evidence for the mixing of Meat,Fish and Vegetables in Anglo‐Saxon coarseware from Hamwic,UK

Absorbed lipid residues from 24 seventh‐ to ninth‐century coarseware potsherds from the major Anglo‐Saxon trading centre of Hamwic (Southampton, UK) were analysed by gas chromatography – mass spectrometry (GC–MS) in order to reconstruct the dietary habits of its population. The results show that the vessels were used for preparing ruminant fats and leafy vegetables. In addition, evidence was found for a minor contribution of aquatic foods. Beeswax was found once and most probably relates to a sealing function or to honey. Remarkable features were: (i) the isomeric mixture of octadecenoic acid (C_18:1 Δ^{7,8,9,10,11,12,13,14,15,16}) and 8‐ to 16‐hydroxyoctadecanoic acid, and (ii) the co‐occurrence of C_17:1, C_19:1 and isoprenoid fatty acids. These features were proposed as biomarkers for ruminant and aquatic food sources, respectively. Furthermore, the carbonyl position distribution in mid‐chain ketones was used to identify mixtures of animal‐ and plant‐derived ketones. The paper highlights the difficulty in interpreting complex lipid signatures that show a mixture of various foods, as observed in the majority of the samples. This was linked to the preparation of stews or the recycling of vessels. The results are considered alongside ceramic usewear data and existing data relating to environmental remains recovered from the Hamwic excavations.     

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.     

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.     

THE DISCOVERY OF ANOMALOUSLY HIGH SILVER ABUNDANCES IN POTTERY FROM EARLY ROMAN EXCAVATION CONTEXTS IN JERUSALEM*

This is the first study on the differential distribution and concentrations of silver in ceramics recovered from archaeological excavations. The chemical compositions of 1174 pottery vessels from 38 Roman‐period sites in Israel have been determined. Unusually high and variable abundances of silver were discovered in pottery samples of all vessel types and chemical compositions from four distinct archaeological contexts dating to late first century bce to 70 ce Jerusalem. The large majority of the Jerusalem vessels could be distinguished by their silver abundances from all analysed pottery pieces recovered at rural sites outside Jerusalem, even when the pottery types and chemical compositions, except for silver, of pottery found within and outside Jerusalem were indistinguishable. The evidence is suggestive of a human origin for the high and variable silver abundances, and dispersion of the silver by aqueous transport. The differential silver concentrations found in excavated pottery from Jerusalem and other urban and rural sites suggest that attention to the distribution of silver in pottery from excavated contexts may be helpful for evaluating the nature and function of archaeological remains and patterns of urban contamination.     

Application of lipid biomarker analysis to evaluate the function of ‘slab-lined pits’ in Arctic Norway

Gas chromatography–mass spectrometry (GC–MS) and bulk carbon isotope determinations have been performed on samples (‘cemented organic residues’, charcoal, sediment and fire-cracked rock) excavated from 12 slab-lined pits from various locations in Arctic Norway to test the premise that these archaeological features were used for the extraction of oil from the blubber of marine mammals, such as seal, whale and walrus. A wide range of lipid compound classes were detected especially in the cemented organic residues and in the charcoal samples. The presence of long-chain unsaturated and isoprenoid fatty acids together with oxidation and thermal alteration products of unsaturated acids such as dicarboxylic acids, dihydroxyfatty acids and ω-(o-alkylphenyl)alkanoic acids suggests that these features were used for marine oil extraction at elevated temperatures. Notably the location of the hydroxyl groups in the dihydroxyfatty acids provides a record of the positional isomer of the precursor fatty acid and allows confirmation that 11-docosenoic (cetoleic) acid, the most abundant C_22:1 isomer in marine oil, was a major component of the original lipid. Further information was provided by the presence of long-chain fatty acyl moieties in surviving triacylglycerols and the presence of cholesterol. A fungal metabolite, mycose (trehalose), was found in all samples apart from a fire-cracked rock and points to microbiological activity in the pits. Bulk isotope analysis conducted on the ‘cemented organic residues’ is consistent with modern reference samples of blubber and oil from seal and whale. These data provide clear analytical evidence of the function of slab-lined pits in the archaeological record and suggest widespread exploitation of marine mammals for producing oil for heating, lighting and myriad other uses in the past.     

Molecular evidence of changing foodways across the Mississippian transition at the George Reeves site (11S650)

ABSTRACT

The George Reeves site (11S650) is a multicomponent village on the bluffs in the central American Bottom, Illinois. The site was occupied from the Late Woodland Rosewood phase through the Mississippian Lohmann phase. Pottery use and dietary variation between the Late Woodland and Emergent Mississippian occupations at the site were explored through stylistic analysis, pottery residue analysis, and compound-specific carbon isotopic analysis of pottery residues. Although more samples should be analyzed, diet and pottery use at George Reeves seems to have been varied, with maize present by cal AD 900–1000, but comprising a relatively small portion of lipid residues in pottery. Residue analysis indicates a C₄ presence in 5 of 16 sampled pots from the early Emergent Mississippian deriving from either maize or from meat from animals consuming maize. Pottery residues were mixed, showing C₃ and C₄ plants as well as meat and fish or shellfish. One residue showed a high incidence of C₄ contribution, most likely from Portulaca oleracea (common purslane), as well as large amounts of fish or shellfish and another C₃ plant. Residue from a ceramic pipestem indicates that maize may have been smoked, probably in the form of maize silk mixed with other nontobacco plants.     

CHEMICAL COMPOSITION OF A BOG BODY ADIPOCERE

Chemical analyses were carried out on adipocere obtained from a bog body recovered from a peat bog at Meenybradden, County Donegal, Ireland. Chromatographic (thin-layer chromatography and gas chromatography) and mass spectrometric analyses, combined with microanalytical chemical transformations, have yielded detailed compositional information. An absence of intact triacylglycerols, diacylglycerols and monoacylglycerols indicates that hydrolysis is complete. Consequently the adipocere is composed mainly of fatty carboxylic acids. The high proportion of palmitic and stearic acids, together with depleted oleic acid content, indicates that extensive reduction and, possibly, β-oxidation have occurred during burial in the peat bog. Hydration of the double-bond in oleic acid has also occurred, as is shown by the formation of 10-hydroxystearic acid. The monoenoic fatty carboxylic acids that are present, composed mainly of C₁₈ and C₁₆ compounds, comprise a mixture of positional isomers. The results are compared and contrasted with those obtained from previous studies of the lipid composition of other adipoceres and cadavers of archaeological interest.     

Probing dietary change of the Kwädąy Dän Ts'ìnchį individual,an ancient glacier body from British Columbia: I. Complementary use of marine lipid biomarker and carbon isotope signatures as novel indicators of a marine diet

The remains of the preserved ice body from the Kwäd?y Dän Ts'ìnch? discovery were recovered from a retreating glacier in the Tatshenshini-Alsek Park, British Columbia in August 1999. Despite the remote location 80 km inland, bone collagen stable isotope analysis indicated that the individual spent much of his life in a region rich in marine foods (δ¹³C −13.7‰ and δ¹⁵N +17.9‰). Since finds of such bodies are exceptionally rare we undertook detailed lipid analyses in order to assess their preservation and determine whether they might provide new insights into the individual’s dietary life history. Molecular fingerprinting and compound-specific carbon isotope analysis were performed on individual lipids extracted from his bone (turnover approximately ≥1 year) and skin (turnover approximately several weeks). A considerable abundance was observed of C_12:0, C_14:0, C_16:0, C_16:1, C_18:0 and C_18:1 fatty acids (FAs), cholesterol and hydroxy FAs (the latter being decay products). Most unusual was the presence of long-chain hydroxy FAs (LCHFAs), 10- and 12-hydroxyeicosanoic acid and 10- and 12-hydroxydocosanoic acid, in the bone. The latter components are most likely the products of microbially mediated hydration of the double-bonds of C_20:1 and C_22:1 FAs, the latter almost certainly originating from the consumption of a largely marine-based diet. A suite of three isoprenoidal lipids, phytanic acid, pristanic acid and 4,8,12-trimethyltetradecanoic (TMTD) acid, was also detected supporting the notion of a significant marine component of the diet for a substantial part of his life. In contrast, the skin lipid composition was dominated by C_{16:0 FA}, with lower abundances being observed of the marine LCHFAs and isoprenoidal compounds, suggesting reduced reliance on coastal marine foods in the last period of life. This interpretation is supported by the enhanced marine dietary signal observed in the bone than skin FA δ¹³C values.