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 b Institute of Environmental Science and Technology-UAB, ICREA, Barcelona, Spain c 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 A R T I C L E I N F O A B S T R A C T Keywords: The use of resinous substances, certainly one of the earliest technologies developed by humans, was well-known Early Neolithic by Holocene hunter-gatherers at the onset of the Neolithisation process across Europe. Recent research has Pinaceae resin revealed the use of birch bark tar in the central Mediterranean far from this taxon’s endemic regions both in the Organic residue analysis Paleolithic and Neolithic periods and shows that the first farmers from the Fertile Crescent hafted lithic tools and Iberian Peninsula waterproofed artefacts using bitumen. The generalised absence of these natural products in south-western Europe may have thus forced a refor­ mulation 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 Crescent (ex: Connan and van de Velde, 2010; Breu et al., 2022) which predates the introduction of agriculture and pastoralism (Bar-Yosef, In the Neolithic period (here referring to approx. 7000–3500 cal. 1987; Rosenberg and Chasan, 2021). Nevertheless, in Neolithic Europe, BC), archaeological evidence suggests that resinous substances were mainly birch bark tar and tree resins were chosen for the same appli­ multifunctional materials used as waterproofing agents, adhesives and cations (Chen et al., 2022; Rageot et al., 2016, 2021; Urem-Kotsou et al., decorative materials (Rageot et al., 2021, 2016). There is a significant 2018) although bitumen was still used in southern Italy, where acces­ body of research supporting the widespread use of bitumen in the Fertile sible 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 Available online 10 December 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 northeast of the Iberian Peninsula. The three main aims are: independently or they adopted it after contacts with local communities is a question still unresolved. - To better understand the conditions under which pottery vessels Data on hafting adhesives from hunter-gatherer populations are might have been exposed to resinous substances. scarce in Europe. Analyses indicate birch bark tar was already exten­ - To approximate how intensively were resins used in pottery though sively used (Aveling and Heron, 1998; Fletcher et al., 2018; Mazza et al., vessel lifetime. 2006; Niekus et al., 2019), and studies from southern Italy suggest - To explore which resin-producing species present in the pollen and Pinaceae resins were exploited (Degano et al., 2019) at least in the carpological records might have been exploited. Middle Palaeolithic. Nonetheless, the exact strategies used by Epi­ paleolithic groups remain unknown. The choice of resinous substances Throughout the results, discussion, and conclusion sections of this adopted by Neolithic groups would certainly be affected by the varied paper, we will argue that Neolithic technologies in the northeast of the environment contexts in Europe. As detected for other plant resources, Iberian Peninsula included the infrequent but ubiquitous collection and there were significant differences between Neolithic groups in the use of Pinaceae resins in contact with pottery. western Mediterranean and in Northern Europe and the Balkans (de Vareilles et al., 2020). 2. Materials and methods Archaeological evidence supporting the use of resins from species other than birch is not substantial (Rageot et al., 2021). Before the IVth 2.1. Materials millennium, remains of Pinaceae adhesives in the Mediterranean region are scarce. Only 10 pottery vessels out of 70 (14%) from Greece and the To achieve the stated objectives, 168 ceramic samples (Table 1) were Balkans (Makriyalos, Toumba Kremastis Koliadas, Drenovac and Dikili obtained from 10 Early Neolithic (Cardial and Epicardial) sites (Fig. 1). Tash)(Garnier and Valamoti, 2016; Mitkidou et al., 2008; Urem-Kotsou These were located along the north-eastern coast of the Iberian Penin­ et al., 2018) presented evidence of abietane diterprenoids. In the Pen­ sula and dated between 5500 and 4500 cal BC. (available 14C dates and dimoun rock shelter (southern France), 16 vessels from a sample of 52 chronologically diagnostic pottery types for each site can be found in the (30%) presented minimal amounts of diterpenoids which were not supplementary materials (SI1). In this period, while the most intense analysed further due to the absence of pine in the anthracological record occupations have so far been detected on plains and lowlands (La Draga, from the site (Drieu et al., 2021). Caserna de Sant Pau-Carrer Reina Amàlia, Guixeres de Vilobí, El Molló, The Early Neolithic in the northeast of the Iberian Peninsula is El Cavet), caves in highlands and planes were also frequently used (Cova characterised by small communities comprising round huts with un­ de Sant Llorenç, Cova de Can Sadurní, Cova de la Guineu, Cova de la derground silos to store farming produce and, later, debris from Font major). In consequence, the sites sampled in this study are repre­ everyday life (Prats et al., 2020). Herds were mainly composed of ovi­ sentative of the occupation pattern in the region. caprines and, to a lesser extent, bovines and suines (Saña Seguí et al., Regarding the archaeological context, the first third of the samples 2021). Domestic cereals including wheat and barley were farmed was recovered from pit silo refills at four sites, the second third of the intensively (Antolín et al., 2015). Fruits including Corylus avellana, samples belonged to the refilling of sunken huts from two sites and the Quercus sp. and Pinus sp., amongst others, (Antolín et al., 2018) were last third was recovered from cave (17%) and open air (16%) occupation gathered across the territory. Terrestrial animals, including Cervus ela­ layers at six sites (Table 1). While most of the samples date to the Cardial phus, Sus scrofa, Capreolus capreolus and Capra pyrenaica, were seldom period (n = 102, seven sites), 66 Epicardial vases from four sites were hunted (Antolín et al., 2018). Marine shell was used extensively as raw also studied. material by craftspeople for ornamental purposes and as tools to deco­ The sampled ceramic assemblage, composed of rims and wall frag­ rate vases by potters. ments, presented smoothed surfaces and impressed Cardial decorations The arrival of the Neolithic in the Iberian Peninsula presents a sin­ using toothed seashells. In Epicardial sherds, decoration was incised or gular case regarding resin use, as birch was extremely scarce in this made via the application of cords in orthogonal dispositions. Pottery was region (Revelles et al., 2018; Riera et al., 2016). While Pinaceae resins made using mainly local clays through coiling and was fired completely would have been more readily available, there is an absence of in combustion structures with scarce control over the input of oxygen. compelling evidence proving their use in the Early Neolithic archaeo­ The main forms included small to medium bowls, hemispheric and logical record. Only two visible residues from the site of La Draga subspherical pots and necked S-shaped vases. (Binder et al., 2010; Clop, indicate the presence of a birch bark tar glue in a marble bracelet and a 2005; Gómez et al., 2008; Morales and Oms, 2008; Oms et al., 2016). Pinaceae hafting adhesive (Rageot et al., 2021; Tresserras, 2000). Following the pattern of Pinaceae resin scarcity seen in other Early 2.2. Methods Neolithic Mediterranean regions hitherto, evidence of diterpenoid resins in the Iberian Peninsula has only been reported in two out of 26 ceramic After removal of the vessel’s interior surface (1–2 mm) and collection samples (8%) from layer IV in Cueva del Toro (5280–4780 cal BC) of roughly 1 g of pottery powder, all samples were spiked with 10 μg n- (Tarifa-Mateo et al., 2019). Additional evidence is only found in Bronze tetratriacontane (internal standard 1) and prepared using an acidified Age Argaric pottery: two vessels from Peñalosa (Manzano et al., 2015), methanol extraction (Correa-Ascencio and Evershed, 2014). Before in­ three vessels from La Bastida, one vessel from La Almoloya (Molina, jection, all samples were spiked with 10 μg of n-hexatriacontane. For this 2015) and one vessel from Castro dos Ratinhos (García, 2010) were assemblage, the analysis of the vessel’s exterior to further study poten­ reported to contain diterpenes from Pinaceae resins. tial contamination was not advised. Early Neolithic pottery fragments Therefore, further analyses are necessary to assess whether resins were usually too fragmented to withstand two different extractions, and, were a commonly exploited substance by the first farmers and herders of the destructive nature of the analyses was not compatible with the the Iberian Peninsula. Assessing whether the generalised European necessary preservation of impressed, incised or applied decorations. pattern of birch bark tar use reached Iberia is key to better understand Extracts were screened using gas chromatography with flame ionisation the socioeconomic and technological relationships developed between detection (GC-FID) to identify samples with significant quantities of different Mediterranean regions within the Impressa, Cardial and lipids. These were total lipid extracts above the 5 μg⋅g− 1 stablished Epicardial spheres and possible local preceding hunter-gatherer groups. thereshold (Evershed et al., 2008), which is the most frequently used for To this end, this paper reports on the results of gas chromatography and samples in the Iberian Peninsula (Breu et al., 2021; Cubas et al., 2020; mass spectrometry (GC–MS) analyses evaluating the presence of bio­ Tarifa-Mateo et al., 2019). Selected cases were further analysed through markers from resinous substances in Early Neolithic pottery from the 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 Barcelona plain Cardial Silo pit refilling 24 24 Carrer Reina Amàlia Barcelona plain Epicardial Sunken Hut refilling 52 52 Cova de Sant Llorenç Garraf Cardial + Epicardial Cave occupation layers 4 4 Can Sadurní Garraf Cardial + Epicardial Cave occupation layers 7 7 La Serreta Penedès Cardial Silo pit refilling 12 6 Guixeres de Vilobí Penedès Cardial Settlement occupation layers 22 5 Cova de la Guineu Penedès Cardial Cave occupation layers 13 2 El Cavet Camp de Tarragona Cardial Silo pit refilling and occupation layers 22 7 Cova de la Font Major Conca de Barberà Cardial Cave occupation layers 5 2 El Molló Ebro Epicardial Hut and silo pit refilling 7 7 Total Cardial + Epicardial 168 116 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 methoxydehydroabietic acid (V) (Izzo et al., 2013), which is likely a SI2). methoxy substitution of the hydroxy group in 15-hyroxydehydroabietic While birch bark tar can be identified through the detection of tri­ acid occurring during the extraction process (Lough, 1964). Strong terpenoids such as betulin, lupeol and other related compounds (Aveling heating will produce triaromatic defunctionalised diterpenoids such as and Heron, 1998), the most abundant molecule in aged Pinaceae resins retene (II) (Pollard and Heron, 2008; Robinson et al., 1987) and further is usually dehydroabietic acid (IV), a diterpenoid resulting from the dehydrogenation will also produce additional compounds such as oxidative dehydrogenation of abietane and pimarane (I) acids (Pollard didehydroabietic acid (III) and 7-oxo-didehydroabietic acid (VII) and Heron, 2008; Weser et al., 1998). Further oxidation may lead to the (Baumer et al., 2009; Colombini et al., 2005) The presence of these appearance of 7-oxodehydroabietic acid (VI) and 15- 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 charac­ Table 3 teristic ions (Table 2) and validated using the NIST library. All reported Scoring system used to qualitatively evaluate the presence of diterpenoid resins compounds were identified as their methyl esters. and their heated derivatives in this study. Although diterpenoids originating from aged Pinaceae resins have Score Requirements Compounds been reported in analysis of pottery organic residues using an acidified 0 No evidence of diterpenoids None methanol extraction (Drieu et al., 2021; Oras et al., 2017; Reber et al., 1 Presence of dehydroabietic acid IV 2018; Bondetti et al., 2020), this procedure presents several limitations. 2 The requirements from score 1 and limited evidence of Free diterpenoid acids and methyl esters already present in the sample diagenesis (detection of one oxidised or dehydrogenated compound) cannot be distinguished. Additionally, the existence of false negatives 3 The requirements from score 2 and additional evidence II, III, V, VI, VII should not be ruled out as the technique is not optimised for the single of diagenesis (at least two compounds) extraction of resin biomarkers. To better understand these limitations, 4 The requirements from score 3 and additional evidence 10 samples from Carrer Reina Amàlia (CRA) were extracted using both a of diagenesis (at least three compounds) dichloromethane/methanol (DCM/MeOH) (see supplementary mate­ 5 Detection of five or more diterpenoids including I, II, III, IV, V, VI, extensive evidence of oxidation and dehydrogenation. VII rials 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 sam­ 19 cases, 74% of which already included DA and 7ODA, and retene was ples contained methyl dehydroabietate. This is consistent with the found in 40 vessels always accompanied by DA and, in 72% of the cases, observed higher lipid yields of the second technique as reported in other by other additional compounds (7ODA or DDA). Evidence of pimarane investigations (Correa-Ascencio and Evershed, 2014; Papakosta et al., diterpenoids (8 samples) always coincided with extensive evidence of 2015). oxidation and dehydrogenation and matched with high quantities of A scoring system based on the number of distinct diterpenoid com­ other diterpenes. Additional biomarkers such as 15-methoxydehydroa­ pounds present in the sample was implemented to qualitatively assess bietic acid and 7-oxo-didehydroabietic acid were only detected in the likelihood that an aged Pinaceae resin had been in contact with the samples with a score of 5: CS11 from Can Sadurní (Fig. 2) and CV3003 vessel. This value was used to distinguish samples with a partial or from El Cavet. limited diterpenoid fingerprint from those with a comprehensive suite of Residues with a score of 1 only contained DA. While a score of 2 was compounds potentially degraded by time. Following the criteria laid out reached because of a combination of DA with DDA (19%), 7ODA (28%) in Table 3, a score from 0 to 5 was assigned to each sample. Scores of 3 or or Retene (52%), 94% of the samples with a score of 3 achieved it with a higher, where a suite of at least three distinct compounds is present, combination of DA, 7ODA and Retene. Only a total of 13 samples (9%) were considered an unambiguous resinous residue based on criteria from Caserna de Sant Pau, Guixeres de Vilobí, Can Sadurní, El Cavet and similarly applied elsewhere (Drieu et al., 2021; Oras et al., 2017; Reber Carrer Reina Amàlia (Table 4) reached higher scores. These were ach­ et al., 2018; Bondetti et al., 2020). ieved because of the presence of additional diterpenoids accompanying Additionally, an estimation of abundance within the recovered res­ the common DA-7ODA-Retene pattern, namely DDA (92%) and pimar­ idue was obtained by calculating the proportion of diterpenoids as a anes (61%). percentage of the total lipid extract. This was obtained by dividing the The quantity of diterpenoids in samples scoring 3 or higher varied sum of all the areas of the diterpenoid peaks by the sum of all the areas of between 0.02% and 9.4% of the total lipid extract with a median of 0.7% the lipid peaks and multiplying this figure by 100. 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 3. Results sites (CS11, CV3003 and CSP3) diterpenoids were more than 2% of the lipid extract. Higher diterpenoid scores (4 and 5 compared to 3) coin­ Interpretable amounts of lipids (see 2.2 methods) were recovered cided with higher percentages of diterpenoids in the residue (Mann- from 139 of the 168 studied vessels, 83% of the analysed assemblage. Withney test, N:32, U:63, p(same) = 0.017) (Fig. 3). From these, 116 vessels (69%) were further studied by GC–MS. Lipid High and low diterpenoid scores were equally detected in rim, wall extracts were dominated by free fatty acids (FFA) ranging between 10 and base fragments; decorated and undecorated sherds; straight and and 28 carbons atoms. In all cases, the two main recovered compounds closed rim shapes and both in vessels cooked in reducing, oxidising and were palmitic and stearic acids. The total amount of lipids recovered mixed atmospheres. varied between 1 µg⋅g− 1 to 4832 µg⋅g− 1 (median 17 µg⋅g− 1; standard When describing the presence of diterpenoid resins across different deviation 539 µg⋅g− 1). Modern contamination from phthalate plasti­ regions (Table 1), the percentage of vessels presenting a score of 3 or cisers was minimal and did not interfere with the analysis of the results. higher varied somewhat: Barcelona Plain (21%), Garraf (27%), Penedès Evidence of triterpenoids indicating the presence of birch bark tar (15%) and Southern Catalonia (Camp de Tarragona, Conca de Barberà was not recovered in any of the extracts. Alternatively, dehydroabietic and Ebro) (33%). Notable differences were found at sites in similar acid (DA) was detected in 97 of the studied vessels (70%) while 7-oxo­ environmental contexts. Despite being adjacent sites, 58% of Caserna de dehydroabietic acid (7ODA) was only present in 37 samples, 35 of Sant Pau’s samples had a score of 3 or higher while this figure was only which also contained DA. Didehydroabietic acid (DDA) was identified in 4% at Carrer Reina Amàlia (X2 = 29.33, df = 1, N = 76, p(no associa­ tion) = 1.2⋅10− 7). In other regions, differences were less clear. In the Table 2 Penedès, none of the samples from La Serreta contained high (≥3) Range of diterpenoids detected in archaeological samples in this study (bp = diterpenoid scores, but both Guixeres de Vilobí and Cova de la Guineu base peak; M+ = molecular ion), highlighting characteristic fragment ions cor­ presented at least 2 samples with high values. This was also the case in responding to methyl ester derivatives. Southern Catalonia, where, despite significant landscape and resource Elution order Compound Characteristic ions (m/z) accessibility differences, only one out of seven samples in El Molló contained any diterpenoids while 33% of the samples from El Cavet and I Pimarane diterpenoid 241(bp), 256, 301, 316(M+) two samples from Cova de la Font Major presented high scores for these II Retene 205, 219(bp), 234(M+) III didehydroabietic acid 197, 237(bp), 312(M+) compounds. Therefore, based on this data, a strong correlation between IV Dehydroabietic acid 239(bp), 299, 314(M+) the detection of resin diterpenoids and the location of the site in the V 15-methoxydehydroabietic acid 269, 329(bp), 344(M+) prehistoric landscape should not be assumed. VI 7-oxodehydroabietic acid 187, 253(bp), 328(M+) Diachronically, a statistically significant decrease in the number of VII 7-oxodidehydroabietic acid 211, 251(bp), 326(M+) 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 Table 4 diterpenoid occurrence in this study. 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. 4. Discussion Diterpenoid Score Number of samples Percentage of the studied assemblage ≥1 97 70% The study of the residues preserved in the ceramic matrix of Early ≥2 52 38% Neolithic pottery in the northeast of the Iberian Peninsula has demon­ 31 22% strated the presence of multiple diterpenoids characteristic of aged ≥3 ≥4 13 9% 5 4 3% 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, rep­ resenting 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 sam­ pling. 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 Fig. 3. Box-plot presenting the relation between diterpenoid scores (3 to 5) and of the highest percentages of diterpenoids in this study (2.3%) and the amount of resin as a percentage of the total residue. several samples where Pinaceae resins were completely absent (addi­ tional comparisons between samples originating from the same strati­ samples with high diterpenoid scores was noticed between the Cardial graphic unit can be performed following the data in the supplementary (36%) and Epicardial period (8%) (X2 = 8.54, df = 1, N = 138, p(no materials, SI3). Significant disparities in the abundance and variety of association): 6⋅10− 5), but this apparent change is difficult to assess given diterpenoids between adjacent archaeological sites (Caserna de Sant Pau that 96% of the Epicardial assemblage from Carrer Reina Amàlia and Carrer Reina Amàlia) also suggests that environmental factors alone 5 A. Breu et al. Journal of Archaeological Science: Reports 47 (2023) 103744 cannot explain the Pinaceae resin biomarkers present in the pottery Regardless of the purpose for which Pinaceae resins came into con­ matrix. tact with pottery vessels, the results clearly indicate that this product Recent experimental work by Reber et al. (2018) demonstrated the was part of the Early Neolithic subsistence practices in the northeast of incorporation of diterpenoids from woodsmoke during the vessel’s firing the Iberian Peninsula. Nonetheless, a direct comparison with results process. The reported compounds (18/19-norabieta-8,11,13-triene, obtained by Rageot et al (2021) should proceed with caution as their 1,2,3,4-tetrahydroretene, retene, didehydroabietic acid, dehydroabietic analyses were performed on visible adhesive deposits attached to either acid and 7-oxodehydroabietic acid) were consistent with the thermal lithic or pottery artefacts. It is therefore possible that birch bark tar and dehydrogenation and oxidation of diterpenoids and would partially Pinaceae resins were used for different purposes across the Mediterra­ match the data recovered in this study. Nevertheless, there is a signifi­ nean and that the absence of birch bark tar in the Early Neolithic of the cant lack of evidence supporting the use of Pinaceae wood as fuel in the Iberian Peninsula is the result of research biases rather than an effective Early Neolithic. Pinaceae charcoal represented only 1% of the assem­ substitution of exploited species. Nonetheless, the incidence of Betula sp. blage recovered from layers 17 and 18 in Can Sadurní (Antolín et al., in this region is significantly limited. Pollen records from cores in 2013), 0.81% of the charcoal recovered from El Cavet (Fontanals et al., northern Catalonia and the Pyrenees (Gassiot et al., 2012; Revelles et al., 2008b), 3.9% of the assemblage from layer IIe in Cova de la Guineu 2018) suggests only limited amounts of birch were present at the onset (Allué et al., 2009) and, in the later Postcardial layers at Caserna de Sant of the Neolithic. Furthermore, minimal amounts of Betula sp. charcoal Pau, only 5% of the recovered charcoal remains (Mensua and Piqué, remains have been found in a handful of Early Neolithic sites only, 2008). While Quercus sp. was the main taxon used as fuel from the including Cova 120, Codella and Bauma del Serrat del Pont, which are Mesolithic onwards across the territory (Piqué et al., 2018), Pinaceae all placed in the mountainous region of La Garrotxa (Revelles et al., twigs and branches could have been used as fire starters (Peña and 2018). When looking at other pollen cores and charcoal evidence closer Zapata, 2003) when pottery vases would have been most probably still to the areas where the studied sites are located, birch is completely away from the fire. Regional studies in the northeast of the Iberian absent. There are no traces of Betula sp. in the pollen records from Peninsula suggest pine would only be used as firewood in mountainous Barcelona (Riera et al., 2016), the Font Major cave (Ballesteros Fer­ sites where oak forests were absent (Piqué et al., 2021). Yet, conifers randis, 2009), or in anthracological studies from any of the sites such as Pinus sp. or Juniperus sp. were present in the Early Neolithic included in this research. pollen records in non-negligible quantities (Ballesteros Ferrandis, 2009; Gassiot et al., 2012; Piqué et al., 2018; Revelles et al., 2018; Riera et al., 5. Conclusion 2016) and pine carpological remains including cones were recovered from several sites such as Can Sadurní and Coves del Fem (Antolín et al., This study has integrated biomolecular data from pottery vessels 2013; Palomo et al., 2018), located in the highlands and the lowlands with anthracological, carpological and pollen studies to show that (Antolín et al., 2018; Gassiot et al., 2012). To summarise, while the Pinaceae resins were the most commonly used adhesive by Early carpological and pollen evidence supports the availability and exploi­ Neolithic groups in the northeast of the Iberian Peninsula. This presents tation of the Pinaceae taxa by Early Neolithic societies, anthracological a notable change from birch bark tar, which dominates the results re­ studies indicate they were not used as fuel, thus implying that direct ported by Rageot et al. (2021) for northern Italy and the south of France, human activity would be the best candidate to explain the presence of and Urem-Kotsou et al. (2018) in Greece and the Balkans. The results degraded diterpenoids as residues in pottery from this study. support an exploitation pattern where Pinaceae resins sporadically but There is a range of possible reasons for the accumulation of resinous ubiquitously came into contact with pottery vessels either as contents or deposits in Early Neolithic vessels. Firstly, the vessels could have been as post-firing treatments. Further research is necessary to assess whether used in the acquisition and transformation process of resin itself. They the detected resin practices were an innovation expanding the diversity could have been placed below an open tree wound to gather exudates or of Neolithic technologies or an adaptation from the persistence of used to heat and store the collected product. Alternatively, resins and hunter-gatherer knowledge. their heated derivatives, could have been intentionally applied as a waterproofing agent used to repair broken or cracked vessels (Reber CRediT authorship contribution statement et al., 2018; Reber and Hart, 2008; Regert et al., 2003; Stacey et al., 2010). The co-occurrence of minor quantities of diterpenoids with sig­ A. Breu: Conceptualization, Formal analysis, Investigation, Visuali­ nificant amounts of fatty acids suggests that none of the aforementioned zation, Writing – original draft. A. Rosell-Melé: Supervision, Method­ possibilities should be considered as the container’s only or main pur­ ology, Resources, Writing – original draft. C. Heron: Writing – review & pose. Within the studied assemblage, there is no evidence to support the editing, Resources. F. Antolín: Writing – review & editing, Resources. F. existence of vessels specialised in the management of resinous sub­ Borrell: Resources. M. Edo: Resources. M. Fontanals: Writing – review stances. Yet, all the archaeological sites analysed except for La Serreta & editing, Resources. M. Molist: Writing – review & editing, Resources, and El Molló contained two or more vessels with a diterpenoid score of 3 Project administration. N. Moraleda: Methodology, Validation, Re­ or higher. The evidence is thus scarce, but ubiquitous. sources. F.X. Oms: Writing – review & editing, Resources. C. Tornero: The distribution of aged Pinaceae resin biomarkers in the studied Resources. J.M. Vergès: Writing – review & editing, Resources. O. assemblage suggests that only a limited quantity of resin-related vessels Vicente: Resources. A. Bach-Gómez: Writing – review & editing, Re­ was needed for everyday life. This could mean that only some pottery sources, Project administration. 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 Declaration of Competing Interest need for vessels requiring said post-firing treatment. The low quantity of diterpenoids across all the studied vessels and the consistent presence of The authors declare that they have no known competing financial retene in samples with a high diterpenoid score might support this interests or personal relationships that could have appeared to influence interpretation. Alternatively, it could also mean that some ceramic the work reported in this paper. vessels would have been sporadically used to gather, prepare, and store resinous substances for a limited period before the container was reused Data availability for other purposes. Experimental work exploring diterpenoid degrada­ tion, deposition pattern and distribution across the vessel walls will be All data is available in the supplementary materials. necessary to obtain further information which allows the identification of distinct types of uses. 6 A. Breu et al. Journal of Archaeological Science: Reports 47 (2023) 103744 Acknowledgements de la Península Ibérica procedentes de la Cova del Toll (Moià, Barcelona) y de la Cova de la Font Major (L’Espluga de Francolí, Tarragona). Trabajos de Prehistoria 71, 134–145. Doi: https://doi.org/10.3989/tp.2014.12128. AB has been funded by an FPU grant (2014/00957) and a “La Caixa” Charters, S., Evershed, R.P., Goad, L.J., Leyden, A., Blinkhorn, P.W., Denham, V., 1993. fellowship LCF/BQ/EU14/10310064. Analyses were partially funded by Quantification and distribution of lipid in archaeological ceramics: implications for the following I + D projects awarded by the Spanish Ministry of Edu­ sampling potsherds for organic residue analysis and the classification of vessel use. Archaeometry 35, 211–223. https://doi.org/10.1111/j.1475-4754.1993.tb01036.x. cation and Science (HAR2016- 78416-P and HAR2013-43624-P). ABG, Charters, S., Evershed, R.P., Quye, A., Blinkhorn, P.W., Reeves, V., 1997. Simulation MM and AB are members of the 2017 SGR 1302 Research Group Experiments for Determining the Use of Ancient Pootery Vessels: the Behaviour of recognized by the Generalitat de Catalunya. Nuria Moraleda and Ferran Epicuticular Leaf Wax During Boiling of a Leafy Vegetable. J. Archaeol. Sci. 24, 1–7. https://doi.org/10.1006/jasc.1995.0091. Colomer are acknowledged for their support in the GC-MS analyses at Chen, S., Vahur, S., Teearu, A., Juus, T., Zhilin, M., Savchenko, S., Oshibkina, S., the ICTA-UAB laboratories. Beatriz Bastos, Ben Stern, at the University Asheichyk, V., Vashanau, A., Lychagina, E., Kashina, E., German, K., Dubovtseva, E., of Bradford and Rebecca Stacey and Christopher Mussell at The British Kriiska, A., Leito, I., Oras, E., 2022. Classification of archaeological adhesives from Eastern Europe and Urals by ATR-FT-IR spectroscopy and chemometric analysis. Museum are thanked for their support whilst performing laboratory Archaeometry 64, 227–244. https://doi.org/10.1111/arcm.12686. work. CH thanks the Wellcome Trust for support (Grant ref: 097365/Z/ Clop, X., 2005. Las primeras producciones cerámicas del nordeste de la Península Ibérica: 11/Z). The archaeological fieldwork and research at El Cavet and Cova estudios de caracterización. 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