Journal of Archaeological Science: Reports 47 (2023) 103744 Contents lists available at ScienceDirect Journal of Archaeological Science: Reports journal homepage: www.elsevier.com/locate/jasrep Resinous deposits in Early Neolithic pottery vessels from the northeast of the Iberian Peninsula Adrià Breu a, *, Antoni Rosell-Melé b, Carl Heron c, Ferran Antolín d, Ferran Borrell e, Manel Edo f, Marta Fontanals g, i, Miquel Molist a, Núria Moraleda b, Francesc Xavier Oms h, Carles Tornero a, Josep Maria Vergès i, g, Oriol Vicente a, Anna Bach-Gómez a a Department of Prehistory, Autonomous University of Barcelona (UAB), Barcelona, Spain Institute of Environmental Science and Technology-UAB, ICREA, Barcelona, Spain Department of Scientific Research, The British Museum, London, UK d Division of Natural Sciences, German Archaeological Institute & Integrative Prehistory and Archaeological Science, University of Basel, Basel, Switzerland e Institució Milà i Fontanals, Consejo Superior de Investigaciones Científicas (CSIC), C/Egipcíaques 15, Barcelona, Spain f Institut d’Arqueologia de la Universitat de Barcelona, Col⋅lectiu per a la Investigació de la Prehistòria i l’Arqueologia del Garraf (CIPAG), Barcelona, Spain g Institut Català de Paleoecologia Humana i Evolució Social (IPHES-CERCA), Zona Educacional 4, Campus Sescelades (Edifici W3), 43007 Tarragona, Spain h Seminari d’Estudis i Recerques Prehistòriques (SERP), Universitat de Barcelona, Barcelona, Spain i Universitat Rovira i Virgili, Departament d’Història i Història de l’Art, Avinguda de Catalunya 35, 43002 Tarragona, Spain b c A R T I C L E I N F O A B S T R A C T Keywords: Early Neolithic Pinaceae resin Organic residue analysis Iberian Peninsula The use of resinous substances, certainly one of the earliest technologies developed by humans, was well-known by Holocene hunter-gatherers at the onset of the Neolithisation process across Europe. Recent research has revealed the use of birch bark tar in the central Mediterranean far from this taxon’s endemic regions both in the Paleolithic and Neolithic periods and shows that the first farmers from the Fertile Crescent hafted lithic tools and waterproofed artefacts using bitumen. The generalised absence of these natural products in south-western Europe may have thus forced a reformulation of Early Neolithic technologies by exploring and benefitting from existing knowledge in local European hunter-gatherer societies. However, information on resin use from the western Mediterranean is still scarce. Here, we report on the analysis of organic residues from 168 pottery sherds by gas chromatography and gas chromatography-mass spectrometry from 10 archaeological sites in this region dating from the second half of the VIth millennium to the first half of the Vth millennium cal BC. In a limited number of samples, minor amounts of several diterpenoids diagnostic of aged Pinaceae resins were detected as mixtures with fats. The presence of pine in the palynological and carpological record supports the human exploitation of this taxon, but its minimal incidence in the anthracological record suggests that other species were selected as fuelwood. This supports the hypothesis that Pinaceae resins were used in association with pottery sporadically but ubiquitously either as its contents, or as post-firing treatments to waterproof the vessels. This demonstrates the development of adhesive technologies and resin-involved labour processes specific to Early Neolithic societies. 1. Introduction In the Neolithic period (here referring to approx. 7000–3500 cal. BC), archaeological evidence suggests that resinous substances were multifunctional materials used as waterproofing agents, adhesives and decorative materials (Rageot et al., 2021, 2016). There is a significant body of research supporting the widespread use of bitumen in the Fertile Crescent (ex: Connan and van de Velde, 2010; Breu et al., 2022) which predates the introduction of agriculture and pastoralism (Bar-Yosef, 1987; Rosenberg and Chasan, 2021). Nevertheless, in Neolithic Europe, mainly birch bark tar and tree resins were chosen for the same applications (Chen et al., 2022; Rageot et al., 2016, 2021; Urem-Kotsou et al., 2018) although bitumen was still used in southern Italy, where accessible deposits existed (Nardella et al., 2019). Whether newly arrived * Corresponding author. E-mail addresses: adria.breu@uab.cat (A. Breu), ferran.antolin@unibas.ch (F. Antolín). https://doi.org/10.1016/j.jasrep.2022.103744 Received 9 February 2022; Received in revised form 1 September 2022; Accepted 10 November 2022 2352-409X/© 2022 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/). A. Breu et al. Journal of Archaeological Science: Reports 47 (2023) 103744 Neolithic groups developed the technology to produce birch bark tar independently or they adopted it after contacts with local communities is a question still unresolved. Data on hafting adhesives from hunter-gatherer populations are scarce in Europe. Analyses indicate birch bark tar was already extensively used (Aveling and Heron, 1998; Fletcher et al., 2018; Mazza et al., 2006; Niekus et al., 2019), and studies from southern Italy suggest Pinaceae resins were exploited (Degano et al., 2019) at least in the Middle Palaeolithic. Nonetheless, the exact strategies used by Epipaleolithic groups remain unknown. The choice of resinous substances adopted by Neolithic groups would certainly be affected by the varied environment contexts in Europe. As detected for other plant resources, there were significant differences between Neolithic groups in the western Mediterranean and in Northern Europe and the Balkans (de Vareilles et al., 2020). Archaeological evidence supporting the use of resins from species other than birch is not substantial (Rageot et al., 2021). Before the IVth millennium, remains of Pinaceae adhesives in the Mediterranean region are scarce. Only 10 pottery vessels out of 70 (14%) from Greece and the Balkans (Makriyalos, Toumba Kremastis Koliadas, Drenovac and Dikili Tash)(Garnier and Valamoti, 2016; Mitkidou et al., 2008; Urem-Kotsou et al., 2018) presented evidence of abietane diterprenoids. In the Pendimoun rock shelter (southern France), 16 vessels from a sample of 52 (30%) presented minimal amounts of diterpenoids which were not analysed further due to the absence of pine in the anthracological record from the site (Drieu et al., 2021). The Early Neolithic in the northeast of the Iberian Peninsula is characterised by small communities comprising round huts with underground silos to store farming produce and, later, debris from everyday life (Prats et al., 2020). Herds were mainly composed of ovicaprines and, to a lesser extent, bovines and suines (Saña Seguí et al., 2021). Domestic cereals including wheat and barley were farmed intensively (Antolín et al., 2015). Fruits including Corylus avellana, Quercus sp. and Pinus sp., amongst others, (Antolín et al., 2018) were gathered across the territory. Terrestrial animals, including Cervus elaphus, Sus scrofa, Capreolus capreolus and Capra pyrenaica, were seldom hunted (Antolín et al., 2018). Marine shell was used extensively as raw material by craftspeople for ornamental purposes and as tools to decorate vases by potters. The arrival of the Neolithic in the Iberian Peninsula presents a singular case regarding resin use, as birch was extremely scarce in this region (Revelles et al., 2018; Riera et al., 2016). While Pinaceae resins would have been more readily available, there is an absence of compelling evidence proving their use in the Early Neolithic archaeological record. Only two visible residues from the site of La Draga indicate the presence of a birch bark tar glue in a marble bracelet and a Pinaceae hafting adhesive (Rageot et al., 2021; Tresserras, 2000). Following the pattern of Pinaceae resin scarcity seen in other Early Neolithic Mediterranean regions hitherto, evidence of diterpenoid resins in the Iberian Peninsula has only been reported in two out of 26 ceramic samples (8%) from layer IV in Cueva del Toro (5280–4780 cal BC) (Tarifa-Mateo et al., 2019). Additional evidence is only found in Bronze Age Argaric pottery: two vessels from Peñalosa (Manzano et al., 2015), three vessels from La Bastida, one vessel from La Almoloya (Molina, 2015) and one vessel from Castro dos Ratinhos (García, 2010) were reported to contain diterpenes from Pinaceae resins. Therefore, further analyses are necessary to assess whether resins were a commonly exploited substance by the first farmers and herders of the Iberian Peninsula. Assessing whether the generalised European pattern of birch bark tar use reached Iberia is key to better understand the socioeconomic and technological relationships developed between different Mediterranean regions within the Impressa, Cardial and Epicardial spheres and possible local preceding hunter-gatherer groups. To this end, this paper reports on the results of gas chromatography and mass spectrometry (GC–MS) analyses evaluating the presence of biomarkers from resinous substances in Early Neolithic pottery from the northeast of the Iberian Peninsula. The three main aims are: - To better understand the conditions under which pottery vessels might have been exposed to resinous substances. - To approximate how intensively were resins used in pottery though vessel lifetime. - To explore which resin-producing species present in the pollen and carpological records might have been exploited. Throughout the results, discussion, and conclusion sections of this paper, we will argue that Neolithic technologies in the northeast of the Iberian Peninsula included the infrequent but ubiquitous collection and use of Pinaceae resins in contact with pottery. 2. Materials and methods 2.1. Materials To achieve the stated objectives, 168 ceramic samples (Table 1) were obtained from 10 Early Neolithic (Cardial and Epicardial) sites (Fig. 1). These were located along the north-eastern coast of the Iberian Peninsula and dated between 5500 and 4500 cal BC. (available 14C dates and chronologically diagnostic pottery types for each site can be found in the supplementary materials (SI1). In this period, while the most intense occupations have so far been detected on plains and lowlands (La Draga, Caserna de Sant Pau-Carrer Reina Amàlia, Guixeres de Vilobí, El Molló, El Cavet), caves in highlands and planes were also frequently used (Cova de Sant Llorenç, Cova de Can Sadurní, Cova de la Guineu, Cova de la Font major). In consequence, the sites sampled in this study are representative of the occupation pattern in the region. Regarding the archaeological context, the first third of the samples was recovered from pit silo refills at four sites, the second third of the samples belonged to the refilling of sunken huts from two sites and the last third was recovered from cave (17%) and open air (16%) occupation layers at six sites (Table 1). While most of the samples date to the Cardial period (n = 102, seven sites), 66 Epicardial vases from four sites were also studied. The sampled ceramic assemblage, composed of rims and wall fragments, presented smoothed surfaces and impressed Cardial decorations using toothed seashells. In Epicardial sherds, decoration was incised or made via the application of cords in orthogonal dispositions. Pottery was made using mainly local clays through coiling and was fired completely in combustion structures with scarce control over the input of oxygen. The main forms included small to medium bowls, hemispheric and subspherical pots and necked S-shaped vases. (Binder et al., 2010; Clop, 2005; Gómez et al., 2008; Morales and Oms, 2008; Oms et al., 2016). 2.2. Methods After removal of the vessel’s interior surface (1–2 mm) and collection of roughly 1 g of pottery powder, all samples were spiked with 10 μg ntetratriacontane (internal standard 1) and prepared using an acidified methanol extraction (Correa-Ascencio and Evershed, 2014). Before injection, all samples were spiked with 10 μg of n-hexatriacontane. For this assemblage, the analysis of the vessel’s exterior to further study potential contamination was not advised. Early Neolithic pottery fragments were usually too fragmented to withstand two different extractions, and, the destructive nature of the analyses was not compatible with the necessary preservation of impressed, incised or applied decorations. Extracts were screened using gas chromatography with flame ionisation detection (GC-FID) to identify samples with significant quantities of lipids. These were total lipid extracts above the 5 μg⋅g−1 stablished thereshold (Evershed et al., 2008), which is the most frequently used for samples in the Iberian Peninsula (Breu et al., 2021; Cubas et al., 2020; Tarifa-Mateo et al., 2019). Selected cases were further analysed through gas chromatography-mass spectrometry (GC–MS) to identify the 2 A. Breu et al. Journal of Archaeological Science: Reports 47 (2023) 103744 Table 1 Detail of all the studied sites, their chronologies, sampled archaeological contexts and the number of vessels analysed using GC-FID and GC–MS. Archaeological site Region Period Archaeological context Number of samples GC-FID GC–MS Caserna de Sant Pau Carrer Reina Amàlia Cova de Sant Llorenç Can Sadurní La Serreta Guixeres de Vilobí Cova de la Guineu El Cavet Cova de la Font Major El Molló Total Barcelona plain Barcelona plain Garraf Garraf Penedès Penedès Penedès Camp de Tarragona Conca de Barberà Ebro Cardial Epicardial Cardial + Epicardial Cardial + Epicardial Cardial Cardial Cardial Cardial Cardial Epicardial Cardial + Epicardial Silo pit refilling Sunken Hut refilling Cave occupation layers Cave occupation layers Silo pit refilling Settlement occupation layers Cave occupation layers Silo pit refilling and occupation layers Cave occupation layers Hut and silo pit refilling 24 52 4 7 12 22 13 22 5 7 168 24 52 4 7 6 5 2 7 2 7 116 Fig. 1. Map of all the sampled sites from this study. (1) Caserna de Sant Pau, (2) Carrer Reina Amàlia, (3) Cova de Sant Llorenç, (4) Cova de Can Sadurní, (5) La Serreta, (6) Guixeres de Vilobí, (7) Cova de la Guineu, (8) El Cavet, (9) Cova de la Font Major and (10) El Molló. (Breu et al., 2021; Fontanals et al., 2008a; Blasco et al., 2011; Borrell et al., 2014; Cebrià et al., 2014; Gibaja et al., 2018; Gómez and Molist, 2017; González et al., 2011; Molist et al., 2018; Oms et al., 2016, 2014; Piera et al., 2016) and sites mentioned in the text: Coves del Fem (11), La Draga (12), Codella (13), Bauma del Serrat del Pont (14), Cova 120 (15), Pendimoun (16) and Cueva del Toro (17). presence of resin biomarkers (see analytical details in supplementary SI2). While birch bark tar can be identified through the detection of triterpenoids such as betulin, lupeol and other related compounds (Aveling and Heron, 1998), the most abundant molecule in aged Pinaceae resins is usually dehydroabietic acid (IV), a diterpenoid resulting from the oxidative dehydrogenation of abietane and pimarane (I) acids (Pollard and Heron, 2008; Weser et al., 1998). Further oxidation may lead to the appearance of 7-oxodehydroabietic acid (VI) and 15- methoxydehydroabietic acid (V) (Izzo et al., 2013), which is likely a methoxy substitution of the hydroxy group in 15-hyroxydehydroabietic acid occurring during the extraction process (Lough, 1964). Strong heating will produce triaromatic defunctionalised diterpenoids such as retene (II) (Pollard and Heron, 2008; Robinson et al., 1987) and further dehydrogenation will also produce additional compounds such as didehydroabietic acid (III) and 7-oxo-didehydroabietic acid (VII) (Baumer et al., 2009; Colombini et al., 2005) The presence of these compounds was evaluated in all GC–MS analysed samples. 3 A. Breu et al. Journal of Archaeological Science: Reports 47 (2023) 103744 Identifications were performed according to the compound’s characteristic ions (Table 2) and validated using the NIST library. All reported compounds were identified as their methyl esters. Although diterpenoids originating from aged Pinaceae resins have been reported in analysis of pottery organic residues using an acidified methanol extraction (Drieu et al., 2021; Oras et al., 2017; Reber et al., 2018; Bondetti et al., 2020), this procedure presents several limitations. Free diterpenoid acids and methyl esters already present in the sample cannot be distinguished. Additionally, the existence of false negatives should not be ruled out as the technique is not optimised for the single extraction of resin biomarkers. To better understand these limitations, 10 samples from Carrer Reina Amàlia (CRA) were extracted using both a dichloromethane/methanol (DCM/MeOH) (see supplementary materials 2 for further details) and an acidified methanol extraction on separate subsamples. Under DCM/MeOH, 30% of the samples presented only dehydroabietic acid (TMS ester). All the acidified methanol samples contained methyl dehydroabietate. This is consistent with the observed higher lipid yields of the second technique as reported in other investigations (Correa-Ascencio and Evershed, 2014; Papakosta et al., 2015). A scoring system based on the number of distinct diterpenoid compounds present in the sample was implemented to qualitatively assess the likelihood that an aged Pinaceae resin had been in contact with the vessel. This value was used to distinguish samples with a partial or limited diterpenoid fingerprint from those with a comprehensive suite of compounds potentially degraded by time. Following the criteria laid out in Table 3, a score from 0 to 5 was assigned to each sample. Scores of 3 or higher, where a suite of at least three distinct compounds is present, were considered an unambiguous resinous residue based on criteria similarly applied elsewhere (Drieu et al., 2021; Oras et al., 2017; Reber et al., 2018; Bondetti et al., 2020). Additionally, an estimation of abundance within the recovered residue was obtained by calculating the proportion of diterpenoids as a percentage of the total lipid extract. This was obtained by dividing the sum of all the areas of the diterpenoid peaks by the sum of all the areas of the lipid peaks and multiplying this figure by 100. Table 3 Scoring system used to qualitatively evaluate the presence of diterpenoid resins and their heated derivatives in this study. Characteristic ions (m/z) Pimarane diterpenoid Retene didehydroabietic acid Dehydroabietic acid 15-methoxydehydroabietic acid 7-oxodehydroabietic acid 7-oxodidehydroabietic acid 241(bp), 256, 301, 316(M+) 205, 219(bp), 234(M+) 197, 237(bp), 312(M+) 239(bp), 299, 314(M+) 269, 329(bp), 344(M+) 187, 253(bp), 328(M+) 211, 251(bp), 326(M+) None IV 5 II, III, V, VI, VII I, II, III, IV, V, VI, VII 19 cases, 74% of which already included DA and 7ODA, and retene was found in 40 vessels always accompanied by DA and, in 72% of the cases, by other additional compounds (7ODA or DDA). Evidence of pimarane diterpenoids (8 samples) always coincided with extensive evidence of oxidation and dehydrogenation and matched with high quantities of other diterpenes. Additional biomarkers such as 15-methoxydehydroabietic acid and 7-oxo-didehydroabietic acid were only detected in samples with a score of 5: CS11 from Can Sadurní (Fig. 2) and CV3003 from El Cavet. Residues with a score of 1 only contained DA. While a score of 2 was reached because of a combination of DA with DDA (19%), 7ODA (28%) or Retene (52%), 94% of the samples with a score of 3 achieved it with a combination of DA, 7ODA and Retene. Only a total of 13 samples (9%) from Caserna de Sant Pau, Guixeres de Vilobí, Can Sadurní, El Cavet and Carrer Reina Amàlia (Table 4) reached higher scores. These were achieved because of the presence of additional diterpenoids accompanying the common DA-7ODA-Retene pattern, namely DDA (92%) and pimaranes (61%). The quantity of diterpenoids in samples scoring 3 or higher varied between 0.02% and 9.4% of the total lipid extract with a median of 0.7% and a standard deviation of 1.7%. In 15 cases, these represented less than 0.7% of the total residue and only in 3 samples from three different sites (CS11, CV3003 and CSP3) diterpenoids were more than 2% of the lipid extract. Higher diterpenoid scores (4 and 5 compared to 3) coincided with higher percentages of diterpenoids in the residue (MannWithney test, N:32, U:63, p(same) = 0.017) (Fig. 3). High and low diterpenoid scores were equally detected in rim, wall and base fragments; decorated and undecorated sherds; straight and closed rim shapes and both in vessels cooked in reducing, oxidising and mixed atmospheres. When describing the presence of diterpenoid resins across different regions (Table 1), the percentage of vessels presenting a score of 3 or higher varied somewhat: Barcelona Plain (21%), Garraf (27%), Penedès (15%) and Southern Catalonia (Camp de Tarragona, Conca de Barberà and Ebro) (33%). Notable differences were found at sites in similar environmental contexts. Despite being adjacent sites, 58% of Caserna de Sant Pau’s samples had a score of 3 or higher while this figure was only 4% at Carrer Reina Amàlia (X2 = 29.33, df = 1, N = 76, p(no association) = 1.2⋅10−7). In other regions, differences were less clear. In the Penedès, none of the samples from La Serreta contained high (≥3) diterpenoid scores, but both Guixeres de Vilobí and Cova de la Guineu presented at least 2 samples with high values. This was also the case in Southern Catalonia, where, despite significant landscape and resource accessibility differences, only one out of seven samples in El Molló contained any diterpenoids while 33% of the samples from El Cavet and two samples from Cova de la Font Major presented high scores for these compounds. Therefore, based on this data, a strong correlation between the detection of resin diterpenoids and the location of the site in the prehistoric landscape should not be assumed. Diachronically, a statistically significant decrease in the number of Table 2 Range of diterpenoids detected in archaeological samples in this study (bp = base peak; M+ = molecular ion), highlighting characteristic fragment ions corresponding to methyl ester derivatives. Compound Compounds No evidence of diterpenoids Presence of dehydroabietic acid The requirements from score 1 and limited evidence of diagenesis (detection of one oxidised or dehydrogenated compound) The requirements from score 2 and additional evidence of diagenesis (at least two compounds) The requirements from score 3 and additional evidence of diagenesis (at least three compounds) Detection of five or more diterpenoids including extensive evidence of oxidation and dehydrogenation. 4 Interpretable amounts of lipids (see 2.2 methods) were recovered from 139 of the 168 studied vessels, 83% of the analysed assemblage. From these, 116 vessels (69%) were further studied by GC–MS. Lipid extracts were dominated by free fatty acids (FFA) ranging between 10 and 28 carbons atoms. In all cases, the two main recovered compounds were palmitic and stearic acids. The total amount of lipids recovered varied between 1 µg⋅g−1 to 4832 µg⋅g−1 (median 17 µg⋅g−1; standard deviation 539 µg⋅g−1). Modern contamination from phthalate plasticisers was minimal and did not interfere with the analysis of the results. Evidence of triterpenoids indicating the presence of birch bark tar was not recovered in any of the extracts. Alternatively, dehydroabietic acid (DA) was detected in 97 of the studied vessels (70%) while 7-oxodehydroabietic acid (7ODA) was only present in 37 samples, 35 of which also contained DA. Didehydroabietic acid (DDA) was identified in Elution order Requirements 0 1 2 3 3. Results I II III IV V VI VII Score 4 A. Breu et al. Journal of Archaeological Science: Reports 47 (2023) 103744 Fig. 2. Chromatogram of sample CS11 highlighting a range of diterpenoids originating from an aged Pinaceae resin. Numbers 1, 2, 4, 6–12, 14 and 15: saturated free fatty acids. 3 and 5 monounsaturated fatty acids. 13: Cholesterol methylether. ●: alkane series (C24-C33) +: tetatriacontane (internal standard 1), *: hexatriacontane (internal standard 2). See identification and mass spectra of numbered peaks in supplementary 4. presented a score of 2 or less, which is one of lowest percentages of diterpenoid occurrence in this study. Table 4 Number and percentage of samples for each diterpenoid score over the total amount of GC–MS analyses and the GC-FID analyses with no evidence of lipids. Diterpenoid Score Number of samples Percentage of the studied assemblage ≥1 ≥2 ≥3 ≥4 5 97 52 31 13 4 70% 38% 22% 9% 3% 4. Discussion The study of the residues preserved in the ceramic matrix of Early Neolithic pottery in the northeast of the Iberian Peninsula has demonstrated the presence of multiple diterpenoids characteristic of aged Pinaceae resins in up to 31 ceramic vessels, representing 22% of the studied assemblage. This figure is in the range of the 30% of vases found at Pendimoun (Drieu et al., 2021), the 14% from studies in Greece and the Balkans (Garnier and Valamoti, 2016; Urem-Kotsou et al., 2018) and the 8% detected at Cueva del Toro (Tarifa-Mateo et al., 2019). Similar to the yields reported by Drieu et al (2021) and Hjulström et al. (2006), only small amounts of diterpenoids were recovered in the vessels, representing a maximum of 9% of the total lipid extract (CS11). Given their occurrence as mixtures and only in minor quantities, an archaeological interpretation of these results must carefully consider the possibility of soil contamination and the possible introduction of diterpenoids from softwood used in cooking fireplaces and kilns (Reber et al., 2018) given the availability of Pinaceae taxa in the Early Neolithic environment. While diterpenoids can survive in soil for extended periods of time (Simoneit, 1977), its incorporation to the clay matrix would be expected to follow the same mechanisms demonstrated for other hydrophobic matter such as fats and waxes, notably a heating event mobilising the lipids (Charters et al., 1997, 1993; Evershed, 2008). Nonetheless, although this would be unlikely after vessel burial, the immediate inner surface (1–2 mm) of all the studied vessels was removed before sampling. Furthermore, soil contamination would be expected to similarly affect pottery remains from the same stratigraphic unit. Nevertheless, in this study, score values and diterpenoid percentages varied significantly between samples from the same archaeological context. As an example, silo 1 in Caserna de Sant Pau del Camp contained both a sample with one of the highest percentages of diterpenoids in this study (2.3%) and several samples where Pinaceae resins were completely absent (additional comparisons between samples originating from the same stratigraphic unit can be performed following the data in the supplementary materials, SI3). Significant disparities in the abundance and variety of diterpenoids between adjacent archaeological sites (Caserna de Sant Pau and Carrer Reina Amàlia) also suggests that environmental factors alone Fig. 3. Box-plot presenting the relation between diterpenoid scores (3 to 5) and the amount of resin as a percentage of the total residue. samples with high diterpenoid scores was noticed between the Cardial (36%) and Epicardial period (8%) (X2 = 8.54, df = 1, N = 138, p(no association): 6⋅10−5), but this apparent change is difficult to assess given that 96% of the Epicardial assemblage from Carrer Reina Amàlia 5 A. Breu et al. Journal of Archaeological Science: Reports 47 (2023) 103744 cannot explain the Pinaceae resin biomarkers present in the pottery matrix. Recent experimental work by Reber et al. (2018) demonstrated the incorporation of diterpenoids from woodsmoke during the vessel’s firing process. The reported compounds (18/19-norabieta-8,11,13-triene, 1,2,3,4-tetrahydroretene, retene, didehydroabietic acid, dehydroabietic acid and 7-oxodehydroabietic acid) were consistent with the thermal dehydrogenation and oxidation of diterpenoids and would partially match the data recovered in this study. Nevertheless, there is a significant lack of evidence supporting the use of Pinaceae wood as fuel in the Early Neolithic. Pinaceae charcoal represented only 1% of the assemblage recovered from layers 17 and 18 in Can Sadurní (Antolín et al., 2013), 0.81% of the charcoal recovered from El Cavet (Fontanals et al., 2008b), 3.9% of the assemblage from layer IIe in Cova de la Guineu (Allué et al., 2009) and, in the later Postcardial layers at Caserna de Sant Pau, only 5% of the recovered charcoal remains (Mensua and Piqué, 2008). While Quercus sp. was the main taxon used as fuel from the Mesolithic onwards across the territory (Piqué et al., 2018), Pinaceae twigs and branches could have been used as fire starters (Peña and Zapata, 2003) when pottery vases would have been most probably still away from the fire. Regional studies in the northeast of the Iberian Peninsula suggest pine would only be used as firewood in mountainous sites where oak forests were absent (Piqué et al., 2021). Yet, conifers such as Pinus sp. or Juniperus sp. were present in the Early Neolithic pollen records in non-negligible quantities (Ballesteros Ferrandis, 2009; Gassiot et al., 2012; Piqué et al., 2018; Revelles et al., 2018; Riera et al., 2016) and pine carpological remains including cones were recovered from several sites such as Can Sadurní and Coves del Fem (Antolín et al., 2013; Palomo et al., 2018), located in the highlands and the lowlands (Antolín et al., 2018; Gassiot et al., 2012). To summarise, while the carpological and pollen evidence supports the availability and exploitation of the Pinaceae taxa by Early Neolithic societies, anthracological studies indicate they were not used as fuel, thus implying that direct human activity would be the best candidate to explain the presence of degraded diterpenoids as residues in pottery from this study. There is a range of possible reasons for the accumulation of resinous deposits in Early Neolithic vessels. Firstly, the vessels could have been used in the acquisition and transformation process of resin itself. They could have been placed below an open tree wound to gather exudates or used to heat and store the collected product. Alternatively, resins and their heated derivatives, could have been intentionally applied as a waterproofing agent used to repair broken or cracked vessels (Reber et al., 2018; Reber and Hart, 2008; Regert et al., 2003; Stacey et al., 2010). The co-occurrence of minor quantities of diterpenoids with significant amounts of fatty acids suggests that none of the aforementioned possibilities should be considered as the container’s only or main purpose. Within the studied assemblage, there is no evidence to support the existence of vessels specialised in the management of resinous substances. Yet, all the archaeological sites analysed except for La Serreta and El Molló contained two or more vessels with a diterpenoid score of 3 or higher. The evidence is thus scarce, but ubiquitous. The distribution of aged Pinaceae resin biomarkers in the studied assemblage suggests that only a limited quantity of resin-related vessels was needed for everyday life. This could mean that only some pottery was treated with resin or tar/pitch after firing. In this case, this could be the result of a technological choice by the potter or the result of a limited need for vessels requiring said post-firing treatment. The low quantity of diterpenoids across all the studied vessels and the consistent presence of retene in samples with a high diterpenoid score might support this interpretation. Alternatively, it could also mean that some ceramic vessels would have been sporadically used to gather, prepare, and store resinous substances for a limited period before the container was reused for other purposes. Experimental work exploring diterpenoid degradation, deposition pattern and distribution across the vessel walls will be necessary to obtain further information which allows the identification of distinct types of uses. Regardless of the purpose for which Pinaceae resins came into contact with pottery vessels, the results clearly indicate that this product was part of the Early Neolithic subsistence practices in the northeast of the Iberian Peninsula. Nonetheless, a direct comparison with results obtained by Rageot et al (2021) should proceed with caution as their analyses were performed on visible adhesive deposits attached to either lithic or pottery artefacts. It is therefore possible that birch bark tar and Pinaceae resins were used for different purposes across the Mediterranean and that the absence of birch bark tar in the Early Neolithic of the Iberian Peninsula is the result of research biases rather than an effective substitution of exploited species. Nonetheless, the incidence of Betula sp. in this region is significantly limited. Pollen records from cores in northern Catalonia and the Pyrenees (Gassiot et al., 2012; Revelles et al., 2018) suggests only limited amounts of birch were present at the onset of the Neolithic. Furthermore, minimal amounts of Betula sp. charcoal remains have been found in a handful of Early Neolithic sites only, including Cova 120, Codella and Bauma del Serrat del Pont, which are all placed in the mountainous region of La Garrotxa (Revelles et al., 2018). When looking at other pollen cores and charcoal evidence closer to the areas where the studied sites are located, birch is completely absent. There are no traces of Betula sp. in the pollen records from Barcelona (Riera et al., 2016), the Font Major cave (Ballesteros Ferrandis, 2009), or in anthracological studies from any of the sites included in this research. 5. Conclusion This study has integrated biomolecular data from pottery vessels with anthracological, carpological and pollen studies to show that Pinaceae resins were the most commonly used adhesive by Early Neolithic groups in the northeast of the Iberian Peninsula. This presents a notable change from birch bark tar, which dominates the results reported by Rageot et al. (2021) for northern Italy and the south of France, and Urem-Kotsou et al. (2018) in Greece and the Balkans. The results support an exploitation pattern where Pinaceae resins sporadically but ubiquitously came into contact with pottery vessels either as contents or as post-firing treatments. Further research is necessary to assess whether the detected resin practices were an innovation expanding the diversity of Neolithic technologies or an adaptation from the persistence of hunter-gatherer knowledge. CRediT authorship contribution statement A. Breu: Conceptualization, Formal analysis, Investigation, Visualization, Writing – original draft. A. Rosell-Melé: Supervision, Methodology, Resources, Writing – original draft. C. Heron: Writing – review & editing, Resources. F. Antolín: Writing – review & editing, Resources. F. Borrell: Resources. M. Edo: Resources. M. Fontanals: Writing – review & editing, Resources. M. Molist: Writing – review & editing, Resources, Project administration. N. Moraleda: Methodology, Validation, Resources. F.X. Oms: Writing – review & editing, Resources. C. Tornero: Resources. J.M. Vergès: Writing – review & editing, Resources. O. Vicente: Resources. A. Bach-Gómez: Writing – review & editing, Resources, Project administration. Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. 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Poblamiento, explotación y entorno natural de los estadios alpinos y subalpinos del Pirineo central durante la primera mitad del Holoceno. Cuaternario y Geomorfología 26, 29–45. Gibaja, F.J., Oms, F.X., Mestres, J., Mazzucco, N., Palomo, A., 2018. Primeros resultados sobre la función del utillaje lítico de las primeras comunidades neolíticas asentadas en Les Guixeres de Vilobí (Sant Martí Sarroca, Barcelona). SAGVNTVM-PLAV 50, 35–56. Gómez, A., Guerrero, E., Clop, X., Bosch, J., Molist, M., 2008. Estudi de la ceràmica neolítica del jaciment de Caserna de Sant Pau. In: Molist Montaña, M. (Ed.), Estudi Del Jaciment Neolític de La Caserna de Sant Pau. QUARHIS, Barcelona, pp. 25–35. AB has been funded by an FPU grant (2014/00957) and a “La Caixa” fellowship LCF/BQ/EU14/10310064. Analyses were partially funded by the following I + D projects awarded by the Spanish Ministry of Education and Science (HAR2016- 78416-P and HAR2013-43624-P). ABG, MM and AB are members of the 2017 SGR 1302 Research Group recognized by the Generalitat de Catalunya. Nuria Moraleda and Ferran Colomer are acknowledged for their support in the GC-MS analyses at the ICTA-UAB laboratories. Beatriz Bastos, Ben Stern, at the University of Bradford and Rebecca Stacey and Christopher Mussell at The British Museum are thanked for their support whilst performing laboratory work. CH thanks the Wellcome Trust for support (Grant ref: 097365/Z/ 11/Z). The archaeological fieldwork and research at El Cavet and Cova de la Font Font Major sites has been conducted with financial support from the Department of Culture (Projectes Quadriennals de Recerca en Materia d’Arqueologia-CLT009/18/00053) and the AGAUR Agency (SGR 2017 1040) of the Generalitat de Catalunya. 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