Léa Drieu

Alexandre Lucquin

Laura Cassard

Sabine Sorin

Oliver E Craig

Didier Binder a , Martine Regert

A Neolithic without dairy? Chemical evidence from the content of ceramics from the Pendimoun rockshelter (Castellar, France, 5750-5150 BCE)

Keywords: Organic residues analysis, Neolithic, pottery use, dairy products, ruminant adipose fat, beeswax

The early phases of Neolithic expansion in the Central and Western Mediterranean are relatively poorly understood with regards to the diversity in the subsistence economy and the degree of interaction with indigenous hunter-gatherers. Recent analysis of pottery manufacturing techniques also points to a surprisingly diverse range of practices across the region. Here, we explore the use of pottery during the early phases of the Neolithic in the North-western Mediterranean, through analysis of organic residues absorbed in the pots of the Pendimoun rock-shelter (Impresso-Cardial complex) in South-eastern France. Using molecular and single-compounds stable carbon isotopes analyses, our study reveals that the majority of pots were used for processing wild or domesticated ruminant carcase fats, although lipids derived from cereals and wild non-ruminant fats, such as hares, cannot be excluded. In addition, a few of the earlier Impressa vessels showed the presence of beeswax and porcine fats. Correlations between the contents of the vessels and their volume were found, suggesting that vessels were manufactured for specific uses. Only one vessel from the Cardial phase showed evidence of dairy fats strengthening the notion that milk was not heavily or systematically exploited by the earliest Neolithic populations of the Mediterranean. Overall, however, our study calls for more detailed regional investigations to fully understand the transition to farming according to the local landscape and environmental context.

Introduction

The arrival of farming in the Mediterranean and the nature of the earliest farming communities is a key theme in European prehistory. In the Central and Western Mediterranean, many prehistorians now dismiss simple models of demic diffusion [START_REF] Ammerman | A population model for the diffusion of early farming in Europe[END_REF] in favour of a more complex mosaic where farming dispersed at a non-uniform rate (e.g. [START_REF] Binder | Modelling the earliest north-western dispersal of Mediterranean Impressed Wares: new dates and Bayesian chronological model[END_REF][START_REF] Guilaine | Going over: the Mesolithic-Neolithic transition in northwest Europe[END_REF][START_REF] Manen | The Neolithic Transition in the Western Mediterranean: a Complex and Non-Linear Diffusion Process -The Radiocarbon Record Revisited[END_REF]. At the heart of understanding of the dispersal of farming is the need to characterise variation in the nature of the earliest Neolithic activity and subsistence practices, as well as interactions, if any, with indigenous hunter-gatherers. Recent analysis of Impresso-Cardial material culture in the Mediterranean reveals great diversity in this respect, for example, in the variety of ceramic decoration [START_REF] Binder | Mésolithique et Néolithique ancien en Méditerranée nord-occidentale entre 7000 et 5500 cal. BCE[END_REF][START_REF] Manen | Premières sociétés paysannes de Méditerranée occidentale. Structures des productions céramiques[END_REF], shaping methods [START_REF] Gomart | Spiralled patchwork in pottery manufacture and the introduction of farming to Southern Europe[END_REF], in the variability of domestic animal exploitation [START_REF] Debono Spiteri | Regional asynchronicity in dairy production and processing in early farming communities of the northern Mediterranean[END_REF][START_REF] Rowley-Conwy | Early domestic animals in Italy, Istria, the Tyrrhenian Islands, and southern France[END_REF] and harvesting technology [START_REF] Mazzucco | Migration, adaptation, innovation: The spread of Neolithic harvesting technologies in the Mediterranean[END_REF]. The first Neolithic communities in the North-western Mediterranean settled as pioneer groups across the Liguro-Provencal arc and in Languedoc at the beginning of the 6 th millennium BC (Figure 1). While animal husbandry and cereal agriculture are well attested, exploitation of molluscs and wild fruits also appear to have been a part of the economy. Analyses of faunal assemblages obtained from the earliest well-dated sites of this region (Arene Candide, Pont-de-Roque-Haute), also show that domesticated animals were initially unlikely to have been heavily exploited for their milk [START_REF] Debono Spiteri | Regional asynchronicity in dairy production and processing in early farming communities of the northern Mediterranean[END_REF], in contrast to pioneer Neolithic settlers in other parts of Europe [START_REF] Copley | Dairying in antiquity. III. Evidence from absorbed lipid residues dating to the British Neolithic[END_REF][START_REF] Ethier | Earliest expansion of animal husbandry beyond the Mediterranean zone in the sixth millennium BC[END_REF]. Such diversity of practice could be the consequence of multiple interactions between Neolithic populations originating from the Aegean and indigenous hunter-gatherers, but also between different Neolithic groups, as shown by the ancient DNA analysis (aDNA) of these populations [START_REF] Rivollat | Ancient genome-wide DNA from France highlights the complexity of interactions between Mesolithic hunter-gatherers and Neolithic farmers in western Europe[END_REF].

Many questions are still outstanding. For example, to what degree was early Neolithic Mediterranean economy dependent on wild resources? Does this reflect strong interactions with the surrounding Mesolithic communities, or an adaptation of the pioneer Neolithic groups to the local environment? What was the nature of early animal husbandry practices? When was a fully agrarian economy established in this region?

Analyses of organic residues preserved in ceramics following their use provides an approach to address some of these issues. Organic residue analysis has revealed a strong association of early Neolithic pottery use for processing milk especially in Northern Europe (e.g. [START_REF] Copley | Dairying in antiquity. III. Evidence from absorbed lipid residues dating to the British Neolithic[END_REF]Cramp et al., 2014;[START_REF] Salque | Earliest evidence for cheese making in the sixth millennium BC in northern Europe[END_REF], a product that can be unambiguously assigned to animal domestication. More recently, this type of approach has contributed to deconstructing the overly simplistic model of sedentary European Neolithic societies relying solely on the economy of production. Recent work has shown that regional variation in the degree to which dairy products were processed in early Neolithic pottery [START_REF] Cubas | Latitudinal gradient in dairy production with the introduction of farming in Atlantic Europe[END_REF] and that other products that had no relation to the productive economy, such as fish, were also processed [START_REF] Craig | Ancient lipids reveal continuity in culinary practices across the transition to agriculture in Northern Europe[END_REF][START_REF] Cramp | Regional diversity in subsistence among early farmers in Southeast Europe revealed by archaeological organic residues[END_REF]. However, very little work has been carried on early pottery of the North-western Mediterranean. The Pendimoun rock-shelter offers a unique opportunity to study the Neolithisation mechanisms in the North-western Mediterranean through the reconstruction of pottery use by organic residue analysis. Pendimoun is one of the few stratified sites that has yielded Impressa and Cardial material, witnessing both pioneering Neolithic incursions and the permanent establishment of farming communities. A new set of recent dates has provided a reliable and detailed sequence of these occupations [START_REF] Binder | Modelling the earliest north-western dispersal of Mediterranean Impressed Wares: new dates and Bayesian chronological model[END_REF]. The Impresso-Cardial pottery assemblage, composed of more than 200 identified vessels, has recently been subjected to an in-depth interdisciplinary study leading to a very detailed understanding of the assemblage in terms of clay pastes, manufacturing method and decoration [START_REF] Gabriele | La circolazione delle ceramiche del Neolitico nel medio e alto Tirreno e nell'area ligure-provenzale[END_REF][START_REF] Gomart | Spiralled patchwork in pottery manufacture and the introduction of farming to Southern Europe[END_REF]. Finally, the site is conveniently situated to study the interactions between local Mesolithic populations, occupying the highlands, and Neolithic groups settling along the coast. Organic remains mainly support an agropastoral Neolithic economy, with the predominance of domestic sheep and domesticated cereals [START_REF] Binder | First farming in the north-western Mediterranean: Evidence from Castellar -Pendimoun during the 6th millennium BCE[END_REF][START_REF] Delhon | Phytoliths as a seasonality indicator? The example of the Neolithic site of Pendimoun, south-eastern France[END_REF][START_REF] Rowley-Conwy | Early domestic animals in Italy, Istria, the Tyrrhenian Islands, and southern France[END_REF]. Excavation of the site also revealed the presence of rocky marine shellfish, fruits and nuts (e.g. acorns, hazelnuts) and some exploitation of wild animals; evidence that collection and hunting activities continued in parallel with the productive economy [START_REF] Binder | First farming in the north-western Mediterranean: Evidence from Castellar -Pendimoun during the 6th millennium BCE[END_REF].

Since the Mediterranean area is known for poor preservation of organic matter associated with ceramic vessels (e.g. [START_REF] Debono Spiteri | Pottery use at the transition to agriculture in the western Mediterranean. Evidence from biomolecular and isotopic characterisation of organic residues in Impressed/Cardial Ware vessels[END_REF], the first aim of these investigations was to assess the degree of lipid preservation in the Impressa and Cardial pottery at the Pendimoun rockshelter. Following this objective, we aimed to determine whether hunted, gathered or fished resources (mainly marine products, which are easily identified by organic residue analysis) were used in ceramics, or whether pottery was exclusively dedicated to processing produced foods (i.e. domesticated animal carcass fats, dairy products and cereals).

Material and methods

Archaeological site and pottery assemblage

The Pendimoun rock-shelter is located in the municipality of Castellar in the Alpes-Maritimes (France) at an altitude of about 690 m on a limestone massif, less than one kilometre from the Italian border [START_REF] Barral | Contribution à la connaissance des populations néo-énéolithiques de Basse-Provence : l'homme cardial de Castellar, abri Pendimoun (A.-M.)[END_REF][START_REF] Binder | L'abri Pendimoun à Castellar (Alpes-Maritimes). Nouvelles données sur le complexe culturel de la céramique imprimée méditerranéenne dans son contexte stratigraphique[END_REF]. Its sedimentary sequence extends from the Epipalaeolithic to the historical periods, with a particularly well-developed stratigraphic sequence between the 6 th and 3 rd millennia BC.

The site was first excavated by L. Barral in 1955and 1956[START_REF] Barral | Contribution à la connaissance des populations néo-énéolithiques de Basse-Provence : l'homme cardial de Castellar, abri Pendimoun (A.-M.)[END_REF], then by D. Binder from 1985to 1992, and from 1997and 2006[START_REF] Binder | L'abri Pendimoun à Castellar (Alpes-Maritimes). Nouvelles données sur le complexe culturel de la céramique imprimée méditerranéenne dans son contexte stratigraphique[END_REF], 2020). Part of the archaeological remains are located under the roof of the shelter (about 15 m²), but the layers of occupation extend beyond the shelter itself. Based on pottery and AMS dating of short-lived samples, the two first phases of Neolithic occupation were during the 6 th millennium BC. The Impressa phase, with finger and instrumental impressed pottery decorations dated to between 5730 and 5430 BCE. The Cardial phase, mainly with cardiidae shell decorated pottery, dated to between 5550 and 5150 BCE [START_REF] Binder | First farming in the north-western Mediterranean: Evidence from Castellar -Pendimoun during the 6th millennium BCE[END_REF].

The economy of the site was based on the cultivation of cereals (naked barley, emmer and einkorn) and the rearing of domestic caprines, mainly sheep [START_REF] Binder | First farming in the north-western Mediterranean: Evidence from Castellar -Pendimoun during the 6th millennium BCE[END_REF][START_REF] Rowley-Conwy | Early domestic animals in Italy, Istria, the Tyrrhenian Islands, and southern France[END_REF]. Due to the small amount of faunal remains, it is not possible to study the livestock management for the Impressa phase. During the Cardial phase, production is mainly centred on meat. The succession of dung layers indicates the use of the shelter for penning small ruminants, probably on a seasonal basis [START_REF] Binder | L'abri Pendimoun à Castellar (Alpes-Maritimes). Nouvelles données sur le complexe culturel de la céramique imprimée méditerranéenne dans son contexte stratigraphique[END_REF][START_REF] Binder | First farming in the north-western Mediterranean: Evidence from Castellar -Pendimoun during the 6th millennium BCE[END_REF]. The hunted fauna is very restricted and mainly represented by hare, deer and wild cats. The wild or domestic status of the suids found at the site remains unclear. The gathering of wild fruits and marine molluscs completes the available resources: acorns, hazelnuts, and shells from rocky environments (mainly limpets, but also Trochidae spp.) have been discovered at the site [START_REF] Binder | L'abri Pendimoun à Castellar (Alpes-Maritimes). Nouvelles données sur le complexe culturel de la céramique imprimée méditerranéenne dans son contexte stratigraphique[END_REF][START_REF] Binder | First farming in the north-western Mediterranean: Evidence from Castellar -Pendimoun during the 6th millennium BCE[END_REF].

Pottery is present in relatively large densities for this period: 126 individual vessels have been identified in the Impressa horizon and 83 in the Cardial horizon. Three groups of pastes were distinguished by mineralogical and petrographic analyses: local glauconitic earths, granitic earths from the Argentera-Mercantour massif (about 30 km as the crow flies from the site) and pastes made from mixtures of the two previous ones, in varying proportions [START_REF] Binder | La séquence de l'Impresso-Cardial de l'abri Pendimoun et l'évolution des assemblages céramiques en Provence[END_REF][START_REF] Gabriele | La circolazione delle ceramiche del Neolitico nel medio e alto Tirreno e nell'area ligure-provenzale[END_REF]. The Impressa and Cardial pottery of Pendimoun rock-shelter was made using the spiral patchwork manufacturing method, specific to the Tyrrhenian area [START_REF] Gomart | Spiralled patchwork in pottery manufacture and the introduction of farming to Southern Europe[END_REF]. The vessels are characterised by a great variability in morphology and volume, suggesting a diversity of function (Figure 2).

Archaeological pottery sampling and capacity measurement

Ceramic samples obtained from fifty-two vessels and one foodcrust, adhering to the inside of a vessel, were investigated. Where possible, potsherds selected for analysis were taken from the upper part of the body of each vessel, which generally accumulates the most amount of lipids during cooking [START_REF] Charters | Quantification and distribution of lipid in archaeological ceramics: implications for sampling potsherds for organic residue analysis and the classification of vessel use[END_REF]. Since all the reconstructed pots and significant isolated sherds were 3D scanned for technological analysis, the destructive sampling for chemical analysis did not cause any loss of information regarding the form and decoration of the vessels.

The ceramics were scanned with a portable 3D scanner Artec Spider, and 3D model without texture was obtained for each potsherd. The reconstructions of the vessels -virtual reshaping and creation of a form model -were carried out with the Cyclone 3DR software. In order to calculate the capacity, the shape of the ceramic was reconstructed by revolution of the profile. The capacity of the vessel was calculated between the inner walls and a maximum capacity level, positioned on the rim. An automatic capacity calculation function was applied, and the result given in litres. Where the entire lower part of the vessels was missing, only the minimum volume was calculated.

Modern products

Single-compounds stable carbon isotopes analyses have been performed on modern cereals (wheat, barley and einkorn) and animal products (goat adipose fat and goat milk). These products, originating from the South of France and Sicily, were purchased in organic supermarkets or collected from producers (Table S2). The diet of the animals was strictly composed of C3 plants (outdoor grazing, barley and alfalfa fodder), to be as close as possible to Neolithic animal diet [START_REF] Roffet-Salque | Impact of modern cattle feeding practices on milk fatty acid stable carbon isotope compositions emphasise the need for caution in selecting reference animal tissues and products for archaeological investigations[END_REF].

Organic residue analysis

Only one sample had charred residues on the surface, which was collected using a clean scalpel. The surfaces of the potsherds were removed using a mini-drill to eliminate any exogenous lipids and the potsherds were drilled to collect around 1g of ceramic powder. Part of the charred residue (around 200 mg) was crushed with a mortar and pestle. An internal standard (n-alkane C34, 10 µg, 1mg mL -1 in n-hexane) was then added to each sample.

The extraction of the samples was performed using 4 mL of methanol to which 800 µL of sulphuric acid was added drop by drop. After sonication for 15 min, the samples were heated for 4 hours at 70°C. The samples were then centrifugated and extracted three times in hexane. The hexane solution containing the lipids were then evaporated and re-dissolved in 100 µL of hexane. A second internal standard (n-alkane C36, 10 µg, 1 mg mL -1 in n-hexane) was added to each sample. An aliquot of this solution was kept for GC-C-IRMS analyses and another was derivatised with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA, 1% trimethylchlorosilane; 70°C, 1h) for GC and GC/MS analyses.

Dichloromethane / methanol (DCM/MeOH) extractions were performed on specific samples to check for the presence of triacylglycerols (TAGs), wax esters and alkylresorcinols. A second sample (1 g) was obtained for this purpose. After drilling, and the addition of 10 µg of n-alkane C34, the samples were extracted in 10 mL of a DCM/MeOH solution (2:1, v/v) with ultrasonication. The samples were centrifuged (10 minutes at 3000 rpm) and the supernatants were collected. These operations were repeated twice more. The combined lipid extracts were evaporated under nitrogen flow and dissolved in 100 µL of DCM/MeOH, before derivatisation with BSTFA. The lipid extracts were analysed on GC-FID and GC/MS after the addition of 10 µg of n-C36.

GC-FID analyses were performed on an Agilent 7890B chromatograph equipped with a flame ionization detector (FID). After injection via split/splitless injector in splitless mode, the molecular compounds were separated into a 15 m DB-1HT (Agilent) apolar capillary column with an internal diameter of 0.32 mm and a phase thickness of 0.1 µm. The temperature program was as follow: 2 min isothermal at 50°C followed by a gradient increase to 375°C at 10°C/min, followed by 10 min at 375°C. GC/MS analysis were performed on an Agilent Technologies 7890A device chromatograph coupled to an Agilent 5977B mass spectrometer. The separation was performed through a high temperature non-polar column (DB5-HT, 30 m x 0.25 mm i.d., 0.1 μm film thickness, Agilent J&W), after injection with a splitless injector. The temperature was set at 50°C for 2 min before an increase to 325°C at 10°C min -1 , and a final isothermal hold for 15 min. The mass spectrometer was running in electron ionization mode (EI, 70 eV) and mass spectra acquired over the range m/z 50-1000. Additional analyses were performed at high temperature on specific solvent extract (DCM/MeOH extractions) using the same column but with a temperature program set as follow: 50°C for 2 min before an increase to 375°C at 10°C min -1 , and a final isothermal hold for 12.5 min.

Additionally, samples were analysed on a DB-23 (50%-cyanopropyl)-methylpolysiloxane column (60m × 0.250mm × 0.25mm; J&WScientific) in Selected Ion Monitoring (SIM) mode to identify aquatic markers (isoprenoid fatty acids and ω-(o-alkylphenyl)alkanoic acids; Cramp and Evershed, 2014;[START_REF] Lucquin | Utilising phytanic acid diastereomers for the characterisation of archaeological lipid residues in pottery samples[END_REF]. The temperature program was set as follow: 50°C for 2 min and increase to 100°C at 10°C min -1 , increase to 140°C at 4°C min -1 , increase to 160°C at 0.5°C min -1 , increase to 250°C at 20°C min -1 , and a final isothermal hold for 10 min. The SIM mode was set to detect 4,8,12-trimethyltridecanoic acid (4,8,12-TMTD) fragmentation (ions m/z 74, 87, 213, 270), pristanic acid (ions m/z 74, 88, 101, 312), phytanic acid (ions m/z 74, 101, 171, 326), and C16to C22-ω-(o-alkylphenyl)alkanoic acids (ions m/z 74,105,262,290,318,346). Helium was used as the carrier gas with a flow rate of 2.4 mL/min. The percentage of phytanic acid diastereoisomer SSR was obtained using the area of the ion m/z 101.

The well-preserved samples (more than 10 µg/g lipid) were analysed by GC-C-IRMS, after removal of sulphur, where present [START_REF] Blumer | Removal of Elemental Sulfur from Hydrocarbon Fractions[END_REF]. These analyses were performed using a Trace Ultra gas chromatograph (Thermo Fisher) with a GC Isolink II interface (Cu/Ni combustion reactor held at 1000°C; Thermo Fisher) coupled to a Delta V Advantage isotope ratio mass spectrometer (Thermo Fisher, Bremen, Germany). The carrier gas was ultrahighpurity-grade helium with a flow rate of 2mL/min. 1 μL of each sample was injected into a DB-5MS fused-silica column (60m × 0.25mm× 0.25 μm; J&W Scientific). The temperature program was as follow: 0.5 min isothermal at 50°C followed by a gradient increase to 175°C at 25°C min -1 , then to 325°C at 8°C min -1 . Temperature was finally held for 20 min at 325°C. After ionization of the eluted compounds by electron impact (70°C), the 13 C/ 12 C ratio of each peak was automatically obtained by measuring the ionic intensities of m/z 44, 45 and 46. Computations were based on comparisons with repeated measurements a standard reference gas (CO2). The results of the analysis were reported in per mile (‰) relative to the Vienna Pee Dee belemnite (VPDB) international standard. For each batch of samples, a curve of expected vs. measured δ 13 C values (international standards, Indiana A6 and F8-3 mixture) was used for calibration (average R 2 = 0.999 ± 0.001 in 6 batches). Control of the accuracy of the instrument was based on n-alkanoic acid ester standards of known isotopic composition and the precision on a laboratory standard mixture that was injected regularly between samples. Stable carbon isotope measurements were performed on the two main fatty acids in archaeological extracts: palmitic (C16:0) and stearic (C18:0) acid methyl esters. Values were corrected subsequent to analysis to account for the methylation of the carboxyl group using a mass balance formula. The Δ 13 C value (δ 13 C18:0δ 13 C16:0) was calculated to overcome the influence of animal feed and the environment on stable carbon isotope values and to facilitate the identification of dairy products, ruminant and non-ruminant adipose fats [START_REF] Evershed | Identification of animal fats via compound specific δ 13 C values of individual fatty acids: assessments of results for reference fats and lipid extracts of archaeological pottery vessels[END_REF]. The archaeological data were compared with the values obtained for modern animal fats published in the literature (Cramp and Evershed, 2014;[START_REF] Debono Spiteri | Pottery use at the transition to agriculture in the western Mediterranean. Evidence from biomolecular and isotopic characterisation of organic residues in Impressed/Cardial Ware vessels[END_REF][START_REF] Dudd | Molecular and isotopic characterisation of animal fats in archaeological pottery[END_REF][START_REF] Outram | The Earliest Horse Harnessing and Milking[END_REF][START_REF] Pääkkönen | Compound-specific stable carbon isotope values of modern terrestrial and aquatic animals from the Baltic Sea and Finland as an aid to interpretations of the origins of fatty acids preserved in archaeological pottery[END_REF][START_REF] Taché | Cooperative harvesting of aquatic resources and the beginning of pottery production in north-eastern North America[END_REF] and the data obtained in this study (cereals and animal fats, Table S2). The 13 C change in the atmosphere due to post-industrial carbon was mitigated by correcting the measured values on modern samples base on the estimated harvest and death date [START_REF] Hellevang | Constraints on natural global atmospheric CO2 fluxes from 1860 to 2010 using a simplified explicit forward model[END_REF].

Results

Forty-six of the 52 pottery samples (88%) yielded enough lipids (> 10 µg/g) to be interpreted. Fatty acids (palmitic, C16:0 and stearic, C18:0), probably from animal fats were the main compounds extracted, generally in similar amounts (C16:0/C18:0 was between 1 and 1.5 in more than half of the samples; Figure 3). Small amounts of C16:1 and C18:1 were also present in many samples. Eight samples (AP_0002, AP_0011, AP_0015, AP_0029, AP_0037, AP_0039, AP_0053 and AP_0164) differed from the others in their high amounts of C16:0 and sometimes C18:1 (C16:0/C18:0 >2.0 and 2.5> C18:1/C18:0>0.2; Figure 3b), which suggest the presence of a plant oils rather than animal fats. Shorter fatty acids such as C12:0 and C14:0 were also sometimes detected. Linear and branched isomers of odd-carbon-numbered fatty acids (C13:0 to C19:0), derived from bacteria, potentially from the rumen of ruminants [START_REF] Christie | The composition, structure and function of lipids in the tissues of ruminant animals[END_REF], were present in 15 samples (Figure 3a). Long chain fatty acids (C20:0 to C32:0), related to plant and insect waxes [START_REF] Dunne | Earliest direct evidence of plant processing in prehistoric Saharan pottery[END_REF][START_REF] Eglinton | Leaf epicuticular waxes[END_REF][START_REF] Roffet-Salque | Widespread exploitation of the honeybee by early Neolithic farmers[END_REF], and some of their unsaturated homologues (C20:1 and C22:1) were detected. AP_0011 displayed large amounts of C24:0 (major long chain fatty acid), C26:0, and C28:0 (Figure 3d) and the long chain fatty acids of AP_0158 were dominated by C26:0 (Figure 3c). Cholesterol (mainly occurring in animal products) and its derivatives (methyl cholesterol, cholesta-3,5-diene, cholest-2-ene) were present in some of the samples. Isoprenoid fatty acids, from phytol transformation in ruminants and aquatic organisms [START_REF] Lucquin | Utilising phytanic acid diastereomers for the characterisation of archaeological lipid residues in pottery samples[END_REF], were identified in 19 samples. 4,8,12-TMTD is detected in 15 samples and phytanic and pristanic acid in four samples (AP_0008, AP_0036, AP_0157, and AP_0175; Figure 4). The ratio of the two isomers of phytanic acid varied from 45 to 76% of SSR diastereoisomer. Markers of thermal transformation of animal fats [START_REF] Bondetti | Investigating the formation and diagnostic value of ω-(oalkylphenyl)alkanoic acids in ancient pottery[END_REF][START_REF] Hansel | Thermally produced w-(o-alkylphenyl)alkanoic acids provide evidence for the processing of marine products in archaeological pottery vessels[END_REF][START_REF] Raven | Formation of long-chain ketones in archaeological pottery vessels by pyrolysis of acyl lipids[END_REF] were also detected occasionally. Traces of ω-(oalkylphenyl)alkanoic acids (APAAs) with 18 carbon atoms were detected in 3 samples (AP_0008, AP_0027, and AP_0036; Figure 4) but no C20-APAAS. Three mid-chain ketones (K31, K33 and K35) were detected in the foodcrust (AP_0176r). Alkanes were generally present in small amounts, as a homologous series of even and oddnumbered chains of carbon atoms (centred around C22). This profile remains difficult to interpret and contamination cannot be excluded. However, four samples had different alkane profiles: AP_0001, AP_0036, and AP_0158 had odd-numbered carbon-dominated alkane profiles dominated by C31, and AP_0011 by C27 (Figure 3c andd), indicating the presence of waxy products [START_REF] Dunne | Earliest direct evidence of plant processing in prehistoric Saharan pottery[END_REF][START_REF] Eglinton | Leaf epicuticular waxes[END_REF][START_REF] Roffet-Salque | Widespread exploitation of the honeybee by early Neolithic farmers[END_REF]. AP_0011 also yielded linear alcohols in significant amounts, dominated by even-carbonnumbered long chains (max C30OH). The other samples exhibited low amounts of a homologous series of linear alcohols with even-and odd-carbon-numbered chains centred on C18OH, possibly resulting from environmental contamination. High temperature chromatographic analyses (GC and GC-MS) revealed the presence of wax esters (palmitic acid wax esters, W40 to W48) in AP_0011 (Figure 3d) and small amounts of palmitoleic and myristic acid wax esters in several other samples. Diterpenes (methyl-dehydroabietic, methyldidehydroabietic and methyl 7-oxo-dehydroabietic acids and phenanthrene), originating from conifer exudates [START_REF] Mills | Natural resins of art and archaeology their sources, chemistry, and identification[END_REF], were also present in very small amounts (0.1 to 1.1 µg/g) in 16 samples. Due to their low amount and the absence of pine in the archaeological record [START_REF] Battentier | L'abri Pendimoun (Castellar, Alpes-Maritimes) : Nouvelles données sur l'évolution du couvert forestier et l'exploitation du milieu au Néolithique (5800-2000 ans cal. BCE)[END_REF], this presence is at the moment difficult to explain and these compounds will not be further discussed.

Many samples yielded significant amounts of phthalates (mass spectrum characterised by the m/z 149 ion) and benzoic acid derivatives (m/z 105 and 123 ions), revealing contamination by plastic products, and sometimes small amounts of squalene from the handling of the potsherds. Molecular sulphur was detected in variable amounts in 25 samples.

Stable carbon isotope measurements of C16:0 and C18:0 gave values mostly in the range of -30 to -28‰ (C16:0) and -31 to -29‰ (C18:0) and an offset around -1‰ (Figure 5). Three samples (AP_0001, AP_0022 and AP_0028) had fatty acids more enriched in 13 C (offset between 0 and 1‰) and one sample has a large Δ 13 C offset (-5‰; AP_0157). Ellipses (95% confidence) are calculated from modern reference substances from the UK, Finland, Russia, Canada, Kazakhstan, Italy and Southern France (Cramp and Evershed, 2014;[START_REF] Debono Spiteri | Pottery use at the transition to agriculture in the western Mediterranean. Evidence from biomolecular and isotopic characterisation of organic residues in Impressed/Cardial Ware vessels[END_REF][START_REF] Dudd | Molecular and isotopic characterisation of animal fats in archaeological pottery[END_REF][START_REF] Outram | The Earliest Horse Harnessing and Milking[END_REF][START_REF] Pääkkönen | Compound-specific stable carbon isotope values of modern terrestrial and aquatic animals from the Baltic Sea and Finland as an aid to interpretations of the origins of fatty acids preserved in archaeological pottery[END_REF][START_REF] Taché | Cooperative harvesting of aquatic resources and the beginning of pottery production in north-eastern North America[END_REF]and this study). b) Plot of the Δ 13 C (difference between the δ 13 C values of the C16:0 and C18:0 fatty acids) and δ 13 C16:0 . B: beeswax; P: plant epicuticular wax.

Discussion

Identification of products contained in Pendimoun rock-shelter ceramics

Molecular analyses of the content of Pendimoun pottery show a predominance of animal fats, in particular from ruminants (largely predominant saturated fatty acids, linear and branched odd carbon-numbered fatty acids, cholesterol and derivatives, %SSR<76%; Figure 3a; [START_REF] Lucquin | Utilising phytanic acid diastereomers for the characterisation of archaeological lipid residues in pottery samples[END_REF][START_REF] Regert | Analytical strategies for discriminating archeological fatty substances from animal origin[END_REF]. These results are consistent with analyses of faunal assemblages that revealed the predominance of domestic sheep [START_REF] Binder | First farming in the north-western Mediterranean: Evidence from Castellar -Pendimoun during the 6th millennium BCE[END_REF][START_REF] Rowley-Conwy | Early domestic animals in Italy, Istria, the Tyrrhenian Islands, and southern France[END_REF]. Isotopic values also support the identification of ruminant adipose fats in many samples (-3.3‰ < Δ 13 C < -1‰). The 13 C values of many other samples are close or higher to the limit between ruminant and non-ruminant adipose fat, but too depleted to be interpreted as porcine fats (Δ 13 C > -1‰; δ 13 C16:0 around -30‰; Figure 5). This shift could be due to the presence of freshwater fats, but neither molecular data nor faunal remains support this hypothesis. The presence of isoprenoids is not sufficient to formally identify fats of aquatic origin, as these lipids also exist in ruminant fats [START_REF] Lucquin | Utilising phytanic acid diastereomers for the characterisation of archaeological lipid residues in pottery samples[END_REF]. When phytanic acid is detected in Pendimoun samples, the % of the SSR isomer corresponds to ruminant fat values (Figure 4; [START_REF] Lucquin | Utilising phytanic acid diastereomers for the characterisation of archaeological lipid residues in pottery samples[END_REF]. In addition, there is no evidence of C20-APAAs that are characteristic of aquatic products (Cramp and Evershed, 2014). Another potential source are wild non-ruminants (e.g. hare) or cereals, both well attested at the site [START_REF] Binder | First farming in the north-western Mediterranean: Evidence from Castellar -Pendimoun during the 6th millennium BCE[END_REF].

The molecular profile, mainly composed of C16:0 and C18:0 in similar amounts, is consistent with both animal fats or degraded cereal lipids (Debono Spiteri, 2012, p. 168). The absence of alkylresorcinols in all samples extracted with DCM/MeOH is not a criterion to rule out the presence of cereals because these molecular markers have shown that they were very poorly preserved in aerobic contexts [START_REF] Hammann | Towards the detection of dietary cereal processing through absorbed lipid biomarkers in archaeological pottery[END_REF].

Isotopic data indicated the presence of dairy products in a single vessel (AP_0157, Δ 13 C < -3.3 ‰; Figure 5; [START_REF] Regert | Analytical strategies for discriminating archeological fatty substances from animal origin[END_REF]. Three containers (AP_0001, AP_0022 and AP_0028) had 13 Cenriched fatty acids, which indicates the presence of either porcine fats or marine products (Δ 13 C < -3.3‰, δ 13 C16:0 > -28‰; Figure 5). The absence of marine molecular markers in these samples (the three isoprenoids together and APAAs; Cramp and Evershed, 2014) suggests the exploitation of porcine fats. This finding correlates with the faunal assemblage that contained either wild or domesticated pigs [START_REF] Binder | First farming in the north-western Mediterranean: Evidence from Castellar -Pendimoun during the 6th millennium BCE[END_REF][START_REF] Rowley-Conwy | Early domestic animals in Italy, Istria, the Tyrrhenian Islands, and southern France[END_REF].

The presence of large amounts of C16:0 and C18:1 in 8 samples suggests the presence of plant oils (Figure 3b). Hazelnuts or acorns, identified in carpological assemblages [START_REF] Binder | First farming in the north-western Mediterranean: Evidence from Castellar -Pendimoun during the 6th millennium BCE[END_REF], are potential candidates to explain such molecular signal. The presence of these oils may be due to a deliberate oil extraction or to cooking episodes, with or without other products. As solvent extraction of some of these samples also revealed the presence of C14:0 and C16:1 wax esters (AP_0002, AP_0029, AP_0037), used in the cosmetics industry (e.g. Takekoshi et al., 2002), modern contamination of these samples cannot be ruled out. One vessel (AP_0158, Figure 3c) shows the exploitation of leafy plants during the Cardial, through the presence of C29, C31 and C33 alkanes and long-chain fatty acids dominated by C26:0 [START_REF] Dunne | Earliest direct evidence of plant processing in prehistoric Saharan pottery[END_REF][START_REF] Eglinton | Leaf epicuticular waxes[END_REF].

Sample AP_0011 shows a very clear beeswax profile (C16:0 wax esters, long-chain alkanes dominated by C27 and long-chain alcohols dominated by C30OH, large amount of C16:0; Figure 3d; Roffet- [START_REF] Roffet-Salque | Widespread exploitation of the honeybee by early Neolithic farmers[END_REF]. The presence of beeswax in an Impressa pot demonstrates the long history of the exploitation of beehive products in the North-western Mediterranean, which had not been identified until now (Roffet- [START_REF] Roffet-Salque | Widespread exploitation of the honeybee by early Neolithic farmers[END_REF]. The presence of C18:0 in the same sample suggests that the pots have contained a fatty product, mixed with the beeswax or used prior to or after the beeswax.

Correspondence between vessel shape and contents

Comparison of vessel capacity with lipid extraction yield (Figure 6b) shows a distinction between small capacity pots (between 1 and 2 L) with high lipid yields (> 200 µg/g) and very large vessels (V > 6 L) with very low lipid yields (between 8 and 22 µg/g). Differential preservation does not seem to be the cause of such a difference, as the lipid concentration shows no correlation with the period (Impressa or Cardial), the location of the potsherds within the site, or the type of ceramic paste. These two groups could correspond respectively to cooking pots and storage/serving vessels. However, AP_0028, one of the small lipid-rich vessels with a closed a shape would seem to be unsuitable for use on a fire (e.g. Rice, 1987, p. 237-240). The difference in lipid yields may be due to the different contents of these vessels. The molecular profile and isotope values of the small lipid-rich vessels clearly point to animal fats (ruminant, porcine or mixtures, depending on the pots; Figure 6a). In contrast, one of the largest vessel (AP_0158) had a clear signal of plant epicuticular waxes and the molecular and/or isotopic data from the other large pots also suggests a plant origin (large dominance of C16:0 over C18:0 and/or isotope values in the cereal range; Figure 6a). Previous experiments demonstrate that the accumulation of animal fats from boiling meat in a single episode is over 150 times that from repeated boiling of leafy vegetables [START_REF] Evershed | Experimental approaches to the interpretation of absorbed organic residues in archaeological ceramics[END_REF]. The difference observed in concentrations may therefore reflect their use, although a difference in the intensity of use of the pots cannot be ruled out.

Small vessels may have served as cooking pots for a single, or limited number of individuals (e.g. household or family group ;[START_REF] Smith | Function from Whole Vessel Shape: A Method and an Application to Anasazi Black Mesa, Arizona[END_REF][START_REF] Henrickson | Ceramic Form and Function: An Ethnographic Search and an Archeological Application[END_REF][START_REF] Tsirtsoni | Les poteries du début du Néolithique Récent en Macédoine. II. Les fonctions des récipients[END_REF] or may reflect specialised use for processing and storage of animal fats (such as lard or tallow). The latter is perhaps most relevant for AP_0028 that also contained red ochre (Pradeau, 2015, p. 270-274). Although reuse cannot be excluded, it is possible that the pot was used to store a mixture of porcine adipose fat and ochre. The co-presence of ochre and animal fat (ruminant adipose fat) has also been identified in another vessel at the site (AP_0163; Pradeau, 2015, p. 270-274). Animal fats could be added to the ochre to facilitate its pliability allowing manipulation for technical, decorative or symbolic activities. Such a preparation could be used, for example, for the finishing treatment or maintenance of leathers, for body care and decoration [START_REF] Audouin | Les ocres et leurs témoins au Paléolithique en France : enquête et expériences sur leur validité archéologique[END_REF][START_REF] Rifkin | Assessing the efficacy of red ochre as a prehistoric hide tanning ingredient[END_REF], or for colouring some objects (such as the sculpted and coloured face discovered at the site; [START_REF] Binder | First sculpted human face in the Western Mediterranean Early Neolithic[END_REF]. In comparison, the very large volume of some of the vessels that contained plant products (> 9 L) suggests use for a larger group than the household. The diversity of shapes indicates that these vessels do not constitute a single functional group but may have been used for cooking and storage of plant substances, especially the bottle (AP_0016) that might have been used to store or serve a plant-or cereal-based liquid. In addition, it is interesting to note that the only pot that unambiguously yielded dairy products is also the shallowest and most open of the vessels tested (AP_0157; Figure 6a). Such a form, also associated with dairy products during the Middle Neolithic period in the Jura [START_REF] Drieu | Defining pottery use and exploitation of natural products at Clairvaux XIV during the Middle Neolithic[END_REF], does not evoke a use as a cooking pot. This vessel could have been employed for milk processing (e.g. for recovering filtered whey during cheesemaking, as has been suggested for Neolithic bowls in Poland; [START_REF] Salque | Earliest evidence for cheese making in the sixth millennium BC in northern Europe[END_REF], or for serving and consuming dairy products.

A distinctive subsistence economy?

The absence of aquatic products in the ceramics of Pendimoun is in-keeping with a terrestrial subsistence economy, similar to other Neolithic sites of the North-western Mediterranean [START_REF] Debono Spiteri | Regional asynchronicity in dairy production and processing in early farming communities of the northern Mediterranean[END_REF][START_REF] Tarifa-Mateo | New insights from Neolithic pottery analyses reveal subsistence practices and pottery use in early farmers from Cueva de El Toro (Málaga, Spain)[END_REF]. This suggests in particular that the shellfish found at the site were not collected to be processed in ceramic vessels and that terrestrial resources, particularly animal fats, constituted the major part of the everyday food prepared in pottery. This pattern, supported by analyses of bone collagen [START_REF] Goude | Alimentation et modes de vie néolithiques en Ligurie[END_REF][START_REF] Bras-Goude | New radiocarbon dates and isotope analysis of Neolithic human and animal bone from the Fontbregoua Cave (Salernes, Var, France)[END_REF], shows that fish, shellfish and marine molluscs were not important dietary components although we cannot rule out low-level consumption and preparation techniques that did not involve ceramics.

Even if domestic ruminants were an important part of the diet, it should be noted that the exploitation of wild ruminants in ceramics, such as deer, identified in small quantities at the site [START_REF] Binder | First farming in the north-western Mediterranean: Evidence from Castellar -Pendimoun during the 6th millennium BCE[END_REF][START_REF] Rowley-Conwy | Early domestic animals in Italy, Istria, the Tyrrhenian Islands, and southern France[END_REF], cannot be completely excluded from use in pottery as these cannot be formally identified using molecular markers or single compound stable carbon isotopes [START_REF] Craig | Distinguishing wild ruminant lipids by gas chromatography/combustion/isotope ratio mass spectrometry[END_REF]. Similarly, the status of pigs, domestic or wild, found in faunal assemblages is still undetermined [START_REF] Binder | First farming in the north-western Mediterranean: Evidence from Castellar -Pendimoun during the 6th millennium BCE[END_REF][START_REF] Rowley-Conwy | Early domestic animals in Italy, Istria, the Tyrrhenian Islands, and southern France[END_REF]. The potential contribution of hunting activities, a possible mark of Mesolithic way of life or interaction with Mesolithic groups, cannot currently be discussed in more detail.

Although the use of perishable containers to process and consume the milk cannot be excluded, the lack of pottery with a clear dairy product signal in Pendimoun (only 1 sample, accounting for 2% of the interpretable samples, and dated from the end of the Impresso-Cardial phase) is in agreement with the archaeozoological data which suggests that the management of the domestic animals (mainly sheep) was oriented towards the exploitation of the meat [START_REF] Rowley-Conwy | Early domestic animals in Italy, Istria, the Tyrrhenian Islands, and southern France[END_REF]. A different pattern seems to emerge from the analysis of pottery from other early Impresso-Cardial sites that delivered enough interpretable results (i.e. more than a few pots with enough lipids to be interpreted). These sites, located in Central and Southern Italy, on the eastern side of the Apennines, yielded a higher proportion of vessels dedicated to dairying (44% in Fondo Azzollini and 23% in Colle Santo Stefano;[START_REF] Debono Spiteri | Regional asynchronicity in dairy production and processing in early farming communities of the northern Mediterranean[END_REF][START_REF] Salque | New insights into the Early Neolithic economy and management of animals in Southern and Central Europe revealed using lipid residue analyses of pottery vessels[END_REF]. The different extraction method that was used in these studies (DCM/MeOH extraction, which generally results in lower extraction yields; Correa-Ascencio & Evershed, 2013) may account for the difference in results, as dairy might yield higher amounts of lipids and therefore have a better chance of being detected using these approaches. However, archaeozoological analyses at Colle Santo Stefano also suggest the exploitation of dairy products [START_REF] Debono Spiteri | Regional asynchronicity in dairy production and processing in early farming communities of the northern Mediterranean[END_REF].

Archaeobotanical and sediments analyses demonstrate that the Pendimoun rock-shelter has been used for penning small domestic ruminants [START_REF] Battentier | L'abri Pendimoun (Castellar, Alpes-Maritimes) : Nouvelles données sur l'évolution du couvert forestier et l'exploitation du milieu au Néolithique (5800-2000 ans cal. BCE)[END_REF][START_REF] Binder | L'abri Pendimoun à Castellar (Alpes-Maritimes). Nouvelles données sur le complexe culturel de la céramique imprimée méditerranéenne dans son contexte stratigraphique[END_REF][START_REF] Delhon | Phytoliths as a seasonality indicator? The example of the Neolithic site of Pendimoun, south-eastern France[END_REF]. The scarcity of pottery specifically dedicated to the processing of dairy products at the site might be related to a complex system of land use, where the rock-shelter was occupied when the animals were not in lactation. Analysis of the phytoliths reveals that Pendimoun was mainly occupied from late spring to early autumn [START_REF] Delhon | Phytoliths as a seasonality indicator? The example of the Neolithic site of Pendimoun, south-eastern France[END_REF]. Stable oxygen isotope composition of enamel of sheep teeth suggests that, during the Neolithic, sheep birth generally occurred throughout the spring in Western and South-eastern Europe [START_REF] Balasse | Animal Board Invited Review: Sheep birth distribution in past herds: a review for prehistoric Europe (6th to 3rd millennia BC)[END_REF]. Because the lactation period is of a few months (at least 4 months; [START_REF] Haenlein | About the evolution of goat and sheep milk production[END_REF], fresh milk would potentially have been available from late winter/early spring until the end of summer. Assuming that the scarcity of dairy products in the Pendimoun pottery is due to a specific occupation season, the combination of archaeobotanical, archaeozoological and organic residue analyses would suggest occupation of the Pendimoun rock-shelter only in early autumn. It cannot be excluded that, in addition to spring lambing, the Pendimoun breeders achieved autumn lambing, as at other Cardial and Epicardial sites in the south of France [START_REF] Tornero | Early evidence of sheep lambing de-seasoning in the Western Mediterranean in the sixth millennium BCE[END_REF]. According to this hypothesis, the occupation window of the rock-shelter would have been very short, between the end of summer and the first autumn births. Assuming that the milk was exploited at other sites, as part of a complex seasonal exploitation of the territory involving transhumance, the vessels used to store and process the milk can be supposed to have been left on site. Such a hypothesis does not preclude possible transport and consumption of dairy products in Pendimoun (in the form of cheeses, for example, which are easier to transport and preserve). On the contrary, Fondo Azzollini and Colle Santo Stefano are open-air sites, which could have been occupied for a longer duration.

The distinction in dairy product exploitation between Impresso-Cardial sites has an interesting parallel in that pottery manufacturing methods also differ between the Pendimoun rock-shelter and Colle Santo Stefano [START_REF] Gomart | Spiralled patchwork in pottery manufacture and the introduction of farming to Southern Europe[END_REF], perhaps indicating that culinary and cultural traditions were closely linked, and each associated with a different pioneer colonisation process. Possible avenues for studying Neolithic expansion routes from the culinary traditions can be found in the comparison with the first phases of the Neolithic in Northern Greece and on the Atlantic coast of the Iberian Peninsula. These two regions, for which a large amount of data on the contents of pottery is available, also appear to be centred on the exploitation of meat rather than dairy products [START_REF] Cubas | Latitudinal gradient in dairy production with the introduction of farming in Atlantic Europe[END_REF][START_REF] Whelton | Strong bias towards carcass product processing at Neolithic settlements in northern Greece revealed through absorbed lipid residues of archaeological pottery[END_REF].

Clearer evidence, both molecular and archaeozoological, for the exploitation of milk is seen during the Late Impresso-Cardial in Southern France and North-eastern Spain [START_REF] Debono Spiteri | Regional asynchronicity in dairy production and processing in early farming communities of the northern Mediterranean[END_REF], representing a potential shift in the subsistence economy towards intensification in the exploitation of dairy products. Interestingly, while goats are absent from the early phases of occupation in Pendimoun, their appearance during the Cardial period is concomitant with the only ceramic vessel providing clear evidence of the exploitation of dairy products. The hypothesis that goats were exploited for their milk from the Cardial period is tempting, but studies on a larger corpus will have to be set up to verify whether milk exploitation really constitutes a turning point starting from the Cardial period.

Conclusion

Analysis of the contents of the Early Neolithic ceramics from the Pendimoun rock-shelter demonstrated, on the one hand, that the pottery was mainly used to process and consume livestock products, particularly ruminants. The fish and shellfish do not appear to have been prepared in pottery, but a contribution of hunting game, such as wild boar, hare or deer, cannot be ruled out. The lack of pottery with a clear dairy signal during the earliest occupation phase of the site contrasts with findings from Southern Italy at the origin of the Western Mediterranean farming dispersal. Therefore, the absence, or scarcity, of dairy at the first step of this spread may suggest the loss of some aspects of the original farming package. However, the seasonal occupation of the Pendimoun rock-shelter during non-lactation periods could also explain this absence, as opposed to open-air sites, which are potentially occupied yearround. This study highlights that the Neolithic "package" varies from one site to another, calling for future investigations to be undertaken at a regional scale in order to more accurately reflect the true diversity of culinary practices by Europe's first farming communities [START_REF] Binder | Une économie de chasse au Néolithique ancien. La Grotte Lombard à Saint-Vallier-de-Thiey[END_REF]. With regard to these questions and their consequences for our perception of the economic and social changes induced by the spread of agriculture in Europe, biomolecular studies should be undertaken on a wider geographical scale, in the light of the detailed chronology recently published [START_REF] Binder | Modelling the earliest north-western dispersal of Mediterranean Impressed Wares: new dates and Bayesian chronological model[END_REF][START_REF] Manen | The Neolithic Transition in the Western Mediterranean: a Complex and Non-Linear Diffusion Process -The Radiocarbon Record Revisited[END_REF].

Period

Figure 1 :

 1 Figure 1: Map of the earliest Neolithic sites in the North-western Mediterranean. In red, the site studied in this paper. Source: Google Maps

Figure 2 :

 2 Figure 2: Examples of pottery shapes from Pendimoun rock-shelter. a) Cardial phase; b) Impressa phase. Reconstructions obtained by 3D scan.

Figure 3 :

 3 Figure 3: Chromatograms representative of the substances identified in the pottery of the Pendimoun rock-shelter. a) ruminant adipose fat (AP_0175), b) plant oil (AP_0037) ; c) plant wax (AP_0158) ; d) beeswax and unidentified fat (AP_0011, solvent extraction). Cxx:x: fatty acids; CxxOH: linear alcohols; Cxx: linear alkanes; Wxx: wax esters; IS: internal standard; *: modern contamination.

Figure 4 :

 4 Figure 4: Example of a chromatogram obtained in SIM mode for the search for aquatic and ruminant biomarkers (AP_0008). The m/z 101 ion is used to indicate the presence of phytanic acid and the m/z 290 and 318 ions, C18-and C20-APAAs respectively.

Figure 5

 5 Figure 5: a) δ 13 C values of fatty acids (C16:0 and C18:0) in pottery from the Pendimoun rock-shelter.Ellipses (95% confidence) are calculated from modern reference substances from the UK, Finland, Russia, Canada, Kazakhstan, Italy and Southern France(Cramp and Evershed, 2014;[START_REF] Debono Spiteri | Pottery use at the transition to agriculture in the western Mediterranean. Evidence from biomolecular and isotopic characterisation of organic residues in Impressed/Cardial Ware vessels[END_REF][START_REF] Dudd | Molecular and isotopic characterisation of animal fats in archaeological pottery[END_REF][START_REF] Outram | The Earliest Horse Harnessing and Milking[END_REF][START_REF] Pääkkönen | Compound-specific stable carbon isotope values of modern terrestrial and aquatic animals from the Baltic Sea and Finland as an aid to interpretations of the origins of fatty acids preserved in archaeological pottery[END_REF][START_REF] Taché | Cooperative harvesting of aquatic resources and the beginning of pottery production in north-eastern North America[END_REF] and this study). b) Plot of the Δ 13 C (difference between the δ 13 C values of the C16:0 and C18:0 fatty acids) and δ 13 C16:0 . B: beeswax; P: plant epicuticular wax.

Figure 6

 6 Figure 6: a) Plot of the Δ 13 C and δ 13 C16:0 representing samples as a function of vessel capacity and lipid yield. The shape of the vessels discussed in the text is displayed; b) Plot of vessel capacity as a function of the amount of lipids extracted. Included are drawings of vessels with specific volume/form/organic content relationships discussed in the text.

δ 13 C 18:0 -δ 13 C 16:0 )

	Earth type Granitic earth Mixed earth Glauconitic earth Glauconitic earth Glauconitic earth Cereal (YM0858 Minimum volume (L) Lipid yield (µg g -1 ) C16:0/C18:0 C18:1/C18:0 other biomarkers δ 13 C16:0 (‰) δ 13 C18:0 (‰) Δ 13 C (‰) (δ 13 C18:0-δ 13 C16:0) Interpretation of vessel contents AP_0001 Impressa 0,6 75,04 0,96 0,18 long chain FA (C20:0-C25:0) -27,27 -25,94 1,33 Porcine adipose fat AP_0002 Impressa 3,2 36,27 2,12 1,04 long chain FA (C20:0-C26:0), cholesterol -29,18 -29,46 -0,29 Plant product? AP_0003 Impressa 6,8 10,59 0,94 0,18 long chain FA (C20:0-C26:0) -30,80 -31,03 -0,23 Undetermine fat (wild non ruminant or cereals). See Discussion part AP_0004 Impressa 2,4 86,77 1,22 0,23 long chain FA (C20:0-C26:0) -28,90 -30,37 -1,47 Ruminant adipose fat AP_0007 Impressa 0,4 64,26 1,15 0,20 long chain FA (C20:0-C24:0), cholesterol -29,19 -29,98 -0,78 Undetermine fat (wild non ruminant or cereals). See Discussion part long chain FA (C20:0-C24:0), linear and branched odd-numbered FA Sample name Provenance Geographical origin δ 13 C 16:0 δ 13 C 18:0 Date collected (‰) (‰) Wheat Local producer (Azienda Agricola biologica San Luca) Castronovo di Sicilia, Italy 2018 -29,6 -31,0	Δ 13 C (‰) -1,4
	AP_0008 AP_0011 YM0861 Impressa Impressa	Granitic earth Granitic earth Barley	1,8 0,9	402,12 59,78 Local producer (Azienda Agricola biologica 0,84 0,13 (C15:0 and C17:0), C18:0 APAAs, 4,8,12-TMTD, pristanic and phytanic acid (76% SSR) 4,51 0,46 long chain FA (C20:0-C32:0), odd-numbered alkanes (C27-C33), linear alcohols (C24OH-C34OH), wax esters (W40-W48) San Luca, Castronovo di Sicilia, Italy) Castronovo di Sicilia, Italy -28,61 -31,90 -3,29 -26,85 -29,23 -2,38	Ruminant adipose fat Beeswax and animal adipose fat 2018	-30,6	-31,2	-0,6
	AP_0014 AP_0015 YM0868 Impressa Impressa	Mixed earth Mixed earth Einkorn	6,0 9,4	5,48 8,95		1,73 2,67 Local organic supermarket 0,27 0,37		n.d. n.d. Provence, France n.d. n.d. n.d. n.d.	Low amount of lipid Plant product? 2019	-31,4	-32,9	-1,5
	AP_0016 AP_0018 YM0869 Impressa Impressa AP_0019 Impressa YM0870 AP_0020 Impressa YM0871	Mixed earth Granitic earth Einkorn Glauconitic earth Einkorn Glauconitic earth Barley	1,9 0,9 2,5 2,7	17,03 256,65 28,15 18,94	1,13 0,25 Local organic supermarket 0,13 long chain FA (C20:0) 0,09 long chain FA (C20:0-C26:0), linear and branched odd-numbered FA (C15:0 and C17:0) 1,09 0,09 4,8,12-TMTD (tr.) Local organic supermarket 0,82 0,16 long chain FA (C20:0) Local organic supermarket	-29,84 -28,39 Provence, France -29,94 -0,10 -29,35 -0,96 -30,20 -30,41 Provence, France -0,21 -30,21 -30,41 -0,20 Provence, France	Undetermine fat (wild non ruminant or cereals). See Discussion part 2019 Undetermine fat (wild non ruminant or cereals). See Discussion part Undetermine fat (wild non ruminant or 2019 cereals). See Discussion part Undetermine fat (wild non ruminant or cereals). See Discussion part 2019	-32,0 -32,2 -36,4	-33,00 -33,9 -35,6	-1,0 -1,7 0,8
	AP_0022 AP_0027 AP_0028 AP_0029 YM0863 Impressa Impressa Impressa Impressa	Granitic earth Mixed earth Granitic earth Mixed earth with chamotte? Goat	3,0 5,6 2,1 1,0	87,62 140,14 546,88 39,22 Local producer (Pierre Pradier) 1,10 0,18 long chain FA (C20:0-C24:0) 0,91 0,17 long chain FA (C20:0-C22:0), C18:0 APAAs, 4,8,12-TMTD (tr.) and 1,25 0,43 long chain FA (C20:0-C26:0) 3,93 2,40 long chain FA (C20:0-C24:0)	-27,37 -27,79 -26,99 -28,41 Simiane-la-Rotonde, -26,36 1,01 -28,97 -1,18 -26,87 0,12 -30,05 -1,64 France	Porcine adipose fat Ruminant adipose fat Porcine adipose fat Ruminant adipose fat, plant product? 2016	-28,7	-31,1	-2,4
	AP_0030 AP_0036 AP_0037 AP_0039 YM0867 Impressa Impressa Impressa Impressa	Glauconitic earth Mixed earth Glauconitic earth Granitic earth Goat milk	4,1 4,1 5,1 5,8	31,94 50,59 32,22 11,45	0,59 0,99 2,06 2,22 Local producer (Pierre Pradier) 0,10 long chain FA (C20:0-C28:0), phytanic acid (tr.) 0,13 long chain FA (C20:0-C26:0), C18:0 APAAs, 4,8,12-TMTD, pristanic 0,51 long chain FA (C20:0-C24:0), 4,8,12-TMTD (tr.), cholesterol 0,44 Simiane-la-Rotonde, -30,02 -30,57 -0,55 -29,08 -31,75 -2,67 -27,64 -28,89 -1,25 -28,16 -28,44 -0,29 France	Undetermine fat (wild non ruminant or cereals). See Discussion part Ruminant adipose fat Ruminant adipose fat, plant product? Plant product? 2016	-26,8	-31,9	-5,1
	AP_0042	Impressa	Glauconitic earth	3,7	17,38		1,48	0,16	long chain FA (C20:0-C26:0), cholesterol		-30,62	-31,38	-0,76	Undetermine fat (wild non ruminant or cereals). See Discussion part
	AP_0045	Impressa	Granitic earth	4,6	182,17	0,57	0,17	long chain FA (C20:0-C24:0), linear and branched odd-numbered FA	-28,33	-29,61	-1,29	Ruminant adipose fat
	AP_0046	Impressa	Glauconitic earth	1,2	5,60		1,70	0,26			n.d.	n.d.	n.d.	Low amount of lipid
	AP_0052	Impressa	Glauconitic earth	2,3	21,57		1,49	0,47	long chain FA (C20:0-C26:0), cholesterol		-30,26	-31,78	-1,52	Ruminant adipose fat
	AP_0053	Impressa	Glauconitic earth	2,5	11,52		2,40	1,01	long chain FA (C20:0-C30:0), 4,8,12-TMTD (tr.)		-29,69	-30,45	-0,76	Plant product?
	AP_0081	Impressa	Granitic earth	n.d.	19,29		1,12	0,26	long chain FA (C20:0), 4,8,12-TMTD		-30,20	-31,05	-0,85	Undetermine fat (wild non ruminant or cereals). See Discussion part
	AP_0137	Impressa	Mixed earth	0,7	80,68		1,37	0,49	long chain FA (C20:0-C26:0), 4,8,12-TMTD		-28,61	-30,15	-1,54	Ruminant adipose fat
	AP_0038	Cardial (transition Impressa/Cardial)	Glauconitic earth	6,7	80,08		1,19	0,47	long chain FA (C20:0-C26:0), cholesterol		-29,26	-30,17	-0,91	Undetermine fat (wild non ruminant or cereals). See Discussion part
	AP_0146	Cardial (transition Impressa/Cardial)	Glauconitic earth	4,4	77,82		1,10	0,25	long chain FA (C20:0-C26:0), 4,8,12-TMTD		-30,56	-31,38	-0,82	Undetermine fat (wild non ruminant or cereals). See Discussion part
	AP_0040	Cardial	Glauconitic earth	1,4	5,21		2,79	0,00			n.d.	n.d.	n.d.	Low amount of lipid
	AP_0148	Cardial	Glauconitic earth	2,0	7,00		1,23	0,11			n.d.	n.d.	n.d.	Low amount of lipid
	AP_0152	Cardial	Glauconitic earth	0,4	151,70	1,85	0,24	long chain FA (C20:0-C26:0), 4,8,12-TMTD, cholesterol		-28,74	-30,80	-2,06	Ruminant adipose fat
	AP_0157	Cardial	Glauconitic earth	2,0	104,91	1,03	0,08	long chain FA (C20:0-C26:0), linear and branched odd-numbered FA (C15:0 and C17:0), pristanic and phytanic acid (61% SSR)	-27,91	-33,00	-5,09	Dairy product
	AP_0158	Cardial	Glauconitic earth	13,6	15,30		1,44	0,39	long chain FA (C20:0-C30:0), 4,8,12-TMTD, odd-numbered alkanes	-28,64	-29,85	-1,21	Ruminant adipose fat
	AP_0163	Cardial	Glauconitic earth	4,9	176,17	0,55	0,03	long chain FA (C20:0-C26:0)		-28,07	-29,03	-0,96	Undetermine fat (wild non ruminant or cereals). See Discussion part
	AP_0164	Cardial	Glauconitic earth	1,0	20,87		3,11	0,21			-27,55	-28,85	-1,30	Ruminant adipose fat, plant product?
	AP_0165	Cardial	Glauconitic earth	3,2	43,24		1,26	0,19	long chain FA (C20:0-C22:0), 4,8,12-TMTD, cholesterol		-29,39	-30,37	-0,99	Undetermine fat (wild non ruminant or cereals). See Discussion part
	AP_0166	Cardial	Glauconitic earth	3,5	13,25		1,33	0,29	long chain FA (C20:0-C26:0)		-29,60	-30,10	-0,49	Undetermine fat (wild non ruminant or cereals). See Discussion part
	AP_0170	Cardial	Glauconitic earth	1,8	43,94		1,09	0,07	long chain FA (C20:0-C25:0)		-29,62	-30,24	-0,63	Undetermine fat (wild non ruminant or cereals). See Discussion part
	AP_0171	Cardial	Glauconitic earth	n.d.	9,12		1,58	0,19	long chain FA (C20:0-C26:0), 4,8,12-TMTD		-28,86	-31,11	-2,25	Ruminant adipose fat
	AP_0174	Cardial	Glauconitic earth	n.d.	34,14		1,08	0,03	long chain FA (C20:0-C22:0)		-29,64	-30,18	-0,54	Undetermine fat (wild non ruminant or cereals). See Discussion part
	AP_0175	Cardial	Glauconitic earth	2,0	358,38	0,45	0,09	long chain FA (C20:0-C28:0), linear and branched odd-numbered FA (C15:0 and C17:0), pristanic and phytanic acid (46% SSR)	-28,07	-30,78	-2,70	Ruminant adipose fat
	AP_0176	Cardial	Glauconitic earth	15,0	22,41		0,91	0,16	long chain FA (C20:0-C26:0)		-28,83	-28,85	-0,03	Undetermine fat (wild non ruminant or cereals). See Discussion part
	AP_0176r	Cardial	Glauconitic earth	-	58,65		1,10	0,33	long chain FA (C20:0-C28:0), ketones (K31, K33, K35)		-27,51	-29,30	-1,79	Heated ruminant adipose fat
	AP_0178	Cardial	Glauconitic earth	2,0	6,48		1,42	0,18	long chain FA (C20:0-C28:0)		n.d.	n.d.	n.d.	Low amount of lipid
	AP_0180	Cardial	Glauconitic earth	1,3	39,57		1,63	0,26	long chain FA (C20:0-C28:0)		-29,83	-31,69	-1,85	Ruminant adipose fat
	AP_0181	Cardial	Glauconitic earth	5,0	13,86		1,32	0,00			-28,33	-29,32	-0,99	Undetermine fat (wild non ruminant or cereals). See Discussion part
	AP_0182	Cardial	Glauconitic earth	3,0	103,98	0,47	0,05	long chain FA (C20:0-C24:0)		-28,98	-29,84	-0,85	Undetermine fat (wild non ruminant or cereals). See Discussion part
	AP_0187	Cardial	Glauconitic earth	4,0	33,75		1,36	0,12	long chain FA (C20:0-C24:6), 4,8,12-TMTD (tr.) and phytanic acid (tr.)	-30,32	-29,93	0,39	Undetermine fat (wild non ruminant or cereals). See Discussion part
	AP_0206	Cardial	Granitic earth	n.d.	14,90		0,95	0,10	long chain FA (C20:0-C22:0)		-30,51	-30,21	0,30	Undetermine fat (wild non ruminant or cereals). See Discussion part
	AP_0207	Cardial	Glauconitic earth	n.d.	66,23		0,44	0,12	long chain FA (C20:0-C26:0)		-29,99	-31,02	-1,03	Ruminant adipose fat
	AP_0212	Cardial	Glauconitic earth	n.d.	11,37		1,34	0,33	4,8,12-TMTD, cholesterol		-28,90	-30,10	-1,20	Ruminant adipose fat

Acknowledgement

This work is carried out within the framework of the ANR CIMO (ANR-14-CE31-009). We thank Pierre Pradier and Egidio Gonzales for providing us with the modern samples of cereals and animal fats. We are grateful to Marie Balasse and Juliette Knockaert for the fruitful discussion on the periods of birth of caprines and lactation season during the Neolithic. Finally, we would like to thank the two reviewers for their constructive suggestions which helped to improve the quality of this article.

Supplementary information

Table S1: List of analysed vessels, period, type of earth and main information from the organic residue analysis. FA: fatty acids; [START_REF] Binder | La séquence de l'Impresso-Cardial de l'abri Pendimoun et l'évolution des assemblages céramiques en Provence[END_REF]8,8, Table S2: List of modern cereals and stable carbon isotope values measured on palmitic (C16:0) and stearic (C18:0) acids.